CN100509994C - Light emitting film, luminescent device, method for manufacturing light emitting film and method for manufacturing luminescent device - Google Patents

Light emitting film, luminescent device, method for manufacturing light emitting film and method for manufacturing luminescent device Download PDF

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CN100509994C
CN100509994C CN 200480006816 CN200480006816A CN100509994C CN 100509994 C CN100509994 C CN 100509994C CN 200480006816 CN200480006816 CN 200480006816 CN 200480006816 A CN200480006816 A CN 200480006816A CN 100509994 C CN100509994 C CN 100509994C
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light emitting
light
phosphor
emitting element
resin
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CN1764707A (en
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武市顺司
泉野训宏
玉置宽人
祖父江慎介
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日亚化学工业株式会社
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Abstract

本发明为防止荧光体的经年黑化,提供长寿命且可靠性高的荧光体等。 The present invention is prevented by blackening of phosphor, high reliability, long life and to provide a phosphor and the like. 发光装置具有发光元件和荧光体层,荧光体层具有用发光元件发出的光来进行激发的荧光体和附载荧光体的粘结剂。 A light emitting device having a light emitting element and a phosphor layer, the phosphor layer having a light emitting element to excite the phosphor and the binder annexed phosphor. 粘结剂是一种水合氧化物凝胶,该凝胶由水合氧化物的溶胶固化而成,所述溶胶则由含有Al、Y、Gd、Lu、Sc、Ga、In、B之中的任一种金属元素的溶胶混合而成。 Hydrous oxide binder is a gel which is solidified by a hydrated oxide sol is made by the sol comprising any from among Al, Y, Gd, Lu, Sc, Ga, In, B sol one metal element are mixed. 水合氧化物在凝胶状态下的透过率较进一步进行溶胶-凝胶反应而得到的多晶体为高。 Hydrated oxide in gel state transmittance further than the sol - gel reaction polycrystalline obtained is high. 另外,水合氧化物中羟基或结晶水的含量为10重量%或以下。 Further, the hydroxyl group content of the hydrated oxide or water of crystallization is 10% or less by weight.

Description

发光膜、发光装置、发光膜的制造方法以及发光装置的制造方法技术领域 TECHNICAL FIELD The light emitting film, the light emitting device, a method of manufacturing the light emitting device and a light emitting film

本发明涉及可以用于照明用光源、LED显示器、背光光源、信号机、照明式开关、各种传感器以及各种指示器等方面的发光膜、发光装置以及这些发光膜、发光装置的制造方法。 The present invention relates to a method for manufacturing a light emitting film illumination light source, LED displays, backlight sources, traffic signal, an illuminated switch, various sensors and various indicators and other aspects, the light emitting device and a light emitting film, the light emitting device.

背景技术 Background technique

人们已经开发出了这样一种发光装置,该装置借助于荧光体对发光元件的光的一部分进行波长转换,并将进行过波长转换的光和未进行过波长转换的发光元件的光混合后使之发射出来,藉此发出发光颜色与发光元件的光不同的光(例如特开2002-198573号公报)。 After it has been developed a light emitting apparatus by means of a fluorescent substance emitting part of the light wavelength conversion element, and light subjected to wavelength conversion element is not emitting light mixing is carried out so that the wavelength conversion the emitted, thereby emitting different light emission color of a light emitting element (e.g., Laid-open Patent Publication No. 2002-198573). 例如, —种白色LED发光装置已经实用化,该装置将使用InGaN系材料的蓝色发光二极管(以下也称为"LED")用作发光元件,并在发光元件表面涂覆有荧光构件,所述荧光构件由含有可以用组成式(Y、 Gd)3(Al、 Ga)5012表示的钇铝石榴石(以下也称为"YAG")系荧光体的环氧树脂等透光性材料构成。 For example, - kind of white LED device has practical use, the device will use the blue light emitting diode of InGaN-based material (hereinafter also referred to as "LED") is used as a light emitting element and a fluorescent member emitting element coated surface, the said yttrium aluminum garnet phosphor containing member can be represented by the composition formula (Y, Gd) 3 (Al, Ga) 5012 (hereinafter also referred to as "YAG") such as epoxy resin-based phosphor light-transmissive material. 白色LED发光装置的发光颜色可以通过光的混合原理而得到。 Emission color white LED light emitting device can be obtained by mixing principle of light. 从LED发射出来的蓝色发光入射到突光构件之中以后,在层内反复进行吸收和散射,然后向外发射出来。 Emitted from the LED emitting blue light is incident into the projection member after repeated scattering and absorption within the layer, and then emitted outwardly. 另一方面,被荧光体吸收的蓝色光作为激发源产生作用,发出黄色的荧光。 On the other hand, the phosphor absorbs the blue light as an excitation source generating effect, emits yellow fluorescence. 使该荧光体的黄色光和LED的蓝色光混合,人的眼睛便可以看到白光。 The LED light and the yellow phosphor mixing the blue light, the human eye can see the white light.

使用这样的LED的LED发光装置,其特点是小型、电力效率高以及发出颜色鲜艳的光。 The use of such an LED LED lighting apparatus, which is characterized by small size, high power efficiency, and emit bright color light. 另夕卜,LED因为是半导体元件,所以不用担心产生烧坏(bum out)等现象。 Another Bu Xi, LED as a semiconductor element, there is no fear to generate burned (bum out) and so on. 再者,LED发光装置还具有初期激励特性优良、振动和通-断点灯的反复能力较强这样的特征。 Further, LED light emitting device also has excellent initial characteristics of excitation, and the via vibration - repeated lamp break strong ability of such features. 因为具有这样优良的特征,所以LED发光装置可以作为各种光源加以利用。 Because having such excellent features, the LED light emitting device may be used as various light sources. 但是,以前的白色发光装置因为大量使用树脂,所以当用于输出功率高、波长短的发光元件时,存在树脂发生退化的问题。 However, because the white light emitting device before a large amount of a resin, when the light-emitting element for outputting a high-power, short-wavelength, there is a problem of degradation of the resin occurs. 另外,在使用无机系粘结剂的情况下,特别在使用由二氧化硅凝胶形成的固化膜的情况下,当曝露在高输出功率和紫外线的环境中时,存在着色退化并产生黑化的问题。 Further, in the case where an inorganic binder, in particular in the case of using a cured film formed from the silica gel when exposed to ultraviolet light and a high output environments, where the colored degradation and blackening The problem. 虽然其原因尚不清楚,但一般认为这是因为二氧化硅溶胶中所含的有机基团在固化后仍有残留,这些有机基团因强烈的光激发作用而被还原。 Although the reason is not clear, it is thought this is because the organic group contained in the silica sol still remain after curing, these organic groups by the strong action of excitation light is reduced.

另外,为了改善发光装置的光取出效率,可以考虑提高发光膜的透过率。 Further, in order to improve the light extraction efficiency of the light emitting device, the light emitting film may be considered to increase the transmittance. 发光膜的透过率依赖于在发光膜中附载荧光体的粘结剂的透过率。 Transmittance of the film depends on the transmittance of light emission in the light emitting film annexed binder phosphor. 当使用在粘结剂中使溶胶热固化而形成的凝胶时,如图1所示, 一般可以认为随着溶胶-凝胶反应的进行,越是接近多晶体,发光膜的 When using the sol-gel manipulation thermosetting adhesive is formed, shown in Figure 1, can generally be considered as a sol - gel reaction, the closer polycrystal, the light emitting film

透过率像图中A所示的那样就越上升。 Like FIG transmittance rises as shown in the more A.

但是,如果使凝胶接近多晶体,则溶胶-凝胶反应成为在高温下进行的反应,因而需要更多的时间和能量。 However, if the gel close to the polycrystal, the sol - gel reaction be carried out at a reaction temperature, thus requiring more time and energy. 再者,因为高温,所以存在对半导体发光元件和荧光体产生不良影响的问题。 Further, because the high temperature, there is a problem of adverse effect on the semiconductor light emitting element and a phosphor. 例如连接LED芯片的引线因热而破损,或者荧光体产生退化。 E.g. lead connecting the LED chip due to heat damage or degradation of the phosphor produced. 为了提高光的取出效率, 随着溶胶-凝胶反应的进行而产生多晶体的无机玻璃化,这从反应温度方面来看,伴随着困难的发生。 In order to improve the light extraction efficiency, as the sol - gel reaction to produce polycrystalline inorganic glass, and from this point of view the reaction temperature, along with the problems occur.

再者,即使随着溶胶-凝胶反应的进行而产生无机玻璃化,发光膜与发光元件的界面也会产生各种问题。 Moreover, even with the sol - gel reaction to produce the inorganic glass, the light emitting element and the light emitting film interface also have various problems. 例如在玻璃化的界面产生全反射,导致光的取出效率低下,或者产生如下的问题,即发生固化而在发光元件的界面与荧光体的界面形成空间层,空间层成为阻挡层而使光的取出变得困难。 For example, total reflection occurs at the glass interface, resulting in low light extraction efficiency, the following problems arise or that cures to form a space layer at the interface with the interface of the phosphor light-emitting element, the space layer becomes the light blocking layer remove difficult.

另外,在使用LED等发光元件激发发光层的结构中,也存在发光层因曝露在LED的激发光的强大能量中而产生退化的问题。 Further, in the configuration using a light emitting element such as an LED excitation light emitting layer, an emitting layer and also due to exposure to strong light excitation energy of the LED and degradation problems. 退化的发光层着色为带有黑色,因而有损于本来的透光性,导致光的取出效率恶化。 The light emitting layer with a black colored degradation, and thus be detrimental to the translucent original, resulting in deterioration of light extraction efficiency. 这样黑化的着色退化的原因尚不清楚,但一般认为原因在于用作发光层的粘结剂的二氧化硅。 The reason for this blackening colored degradation is not clear, but it is generally believed that the reason that the light emitting layer is used as a binder of silica. 体的密封材料,即使想利用一般的树脂, 也因曝露在强光中而明显退化,因而难以将树脂用作密封材料。 The sealing material, even if he wanted using a general resin, also due to the exposure to light significantly degraded, it is difficult to be used as the sealing resin material. 为此, to this end,

使用二氧化硅(Si02)等具有透光性的粘结剂。 Silica (Si02) and the like having a light-transmitting adhesive. 凝胶状的二氧化硅即 I.e. silica gel

二氧化硅凝胶因粘结性良好、透光性优良、光的取出效率高以及在工业方面廉价而容易获得应用。 Silica gel, due to good adhesion, excellent in light transmittance, high light extraction efficiency and a cheap and readily available in industry applications.

但是,当长时间曝露于LED的强光中时,二氧化硅粘结剂层发生着色退化。 However, when prolonged exposure to the LED light, the silica binder layer is colored degradation. 特别在高输出功率的发光装置中,因高光密度和热而导致二氧化硅粘结剂层的退化,并着色成黑色或黑褐色。 In particular, the light emitting device of high output power, due to the high optical density and thermal degradation caused by the silica binder layer, and a black-colored or dark brown. 本发明者进行研究的结果,可以推测其原因在于:Si02即二氧化硅因氧的缺损而生成SiOx (x<2) 。 The present inventors conducted study, presumably is because: Si02 i.e. silica defects due to oxygen generated SiOx (x <2). 二氧化硅粘结剂在250'C或以下的热固化温度下, 处于在Si02骨架中残存一部分羟基、有机基团的二氧化硅凝胶的状态。 Silica binder at a heat curing temperature or below 250'C, in the remaining part of the hydroxyl Si02 skeleton, the state of silica gel, organic group. 在这样的二氧化硅凝胶的状态中,当由LED入射高密度的光时, 将产生氧的缺损,从而使Si02变成SiOx (x<2)。 In such a state of silica gel, when the LED light incident on the high density, the oxygen defect is generated, so that the Si02 into SiOx (x <2). 这样一来,因为Si 容易产生氧化还原,所以一般认为二氧化硅凝胶产生氧的缺损是着色退化的原因。 Thus, since the Si prone to redox, silica gel, it is generally considered to generate oxygen defect is the cause of degradation colored. 一旦产生着色退化,就会产生源于发光元件的光输出功率下降的问题。 Once the colored degradation problem arises from the light emitting element of the optical output power decrease.

近年来,正在进行使用高输出功率的发光元件的发光装置的开发, 但发光元件产生的光具有促进树脂退化的倾向。 In recent years, the use of the ongoing development of high output light emitting element of the light-emitting device, the light emitting element generating light having a tendency to promote degradation of the resin. 另外, 一方面,正在进行从蓝色到可见光的短波区域、进而到紫外光区域这样的短波长发光元件的开发,另一方面,能够长期经受这些紫外线等的涂膜还没冇发现。 Further, on the one hand, to the blue visible light from being short-wavelength region, and further development of such a short wavelength light emitting element to the ultraviolet range, on the other hand, the long-term coating film is subjected to the ultraviolet Nuisance not found. 即使想利用一般的树脂,也因为曝露在强光中而明显退化,所以难于将树脂用作涂膜。 Even using a general resin like, but also because of the exposure to light significantly degraded, it is difficult to be used as the resin coating film.

发明内容 SUMMARY

本发明是为解决这样的问题而完成的。 The present invention is made to solve such problems accomplished. 本发明的主要目的在于: 提供一种光的取出效率得以改善、且可靠性优良的发光膜、发光装置、 发光膜的制造方法以及发光装置的制造方法,进而提供一种这样的可靠性高的发光装置及其制造方法,其中所述发光装置具有难以因源于 The main object of the present invention is: to provide an improved light extraction efficiency, and has high reliability light emitting film, the light emitting device, a method of manufacturing the light emitting film, and a method of manufacturing a light emitting device, thereby providing high reliability One such the method of manufacturing the light emitting device, wherein the light emitting device having a difficult because from

8紫外线等的发光元件的光而产生退化的涂膜。 The light emitting element 8 such as ultraviolet rays generated coating degradation.

本发明的发光膜是用于覆盖发光元件的发光膜,其至少由含有发光材料的填料构件和粘结剂构件构成,其中粘结剂构件至少含有金属元素的水合氧化物(又称氧化物-氢氧化物)。 Light emitting film of the present invention is a light emitting film for covering the light emitting element, which consists of at least a filler component and a binder component containing a luminescent material, wherein the adhesive member comprises at least a hydrated oxide of metal elements (also known as oxide - hydroxide). 该发光膜也可以作为不含荧光体的扩散层来使用。 The light emitting film may be used as a diffusion layer containing no phosphor is used.

另外,本发明的另一发光膜的特征在于:发光材料为无机荧光体, 填料构件为无机填料,粘结剂构件为以恒定价数的金属元素的水合氧 Further, another feature of light emitting film of the present invention: a light emitting material is an inorganic phosphor, an inorganic filler member fillers, binders member hydrated oxide of a metal element at a constant number of pricing

化物为主体的无机粘结剂。 An inorganic compound as a main binder.

因为发光膜以无机物为主体形成,且构成水合氧化物的金属元素具有恒定的价数,所以成膜后的化合物的氧化还原反应受到抑制,发光膜变得稳定,因此,可以得到高光密度、高温下的激励也不会退化的发光膜。 Since the light emitting body is formed as the inorganic film and the hydrated oxide of a metal element constituting a constant valence, the oxidation of the compound after the deposition of the reduction reaction is inhibited, the light emitting film becomes stable, and therefore, it is possible to obtain a high optical density, excitation luminescent film at a high temperature can not be degraded.

另外,本发明的又一发光膜的特征在于:发光材料为无机荧光体, 填料构件为无机填料,粘结剂构件为以金属元素的水合氧化物为主体 Further, another feature of light emitting film of the present invention: a light emitting material is an inorganic phosphor, an inorganic filler as the filler member, the binder is hydrated oxide of a metal member as a main element

的无机粘结剂,金属元素的水合氧化物至少是niA族或IIIB族元素的 Inorganic binder, hydrated oxide of a metal element is at least niA or Group IIIB elements

水合氧化物。 Hydrous oxides.

通过使用3价的金属元素,具有较大的氧化还原反应的抑制效果, 可以获得更为稳定的发光膜。 Reduction reaction by using a trivalent metal element, has a large effect of suppressing the oxidation, the light emitting film can be obtained more stable.

另外,本发明的又一发光膜的特征在于:IIIA族或IIIB族元素含 Further, another feature of light emitting film of the present invention is characterized in: IIIA or Group IIIB element-containing

有Sc、 Y、 Gd、 Lu或B、 Al、 Ga、 In之中的至少l种。 There are Sc, Y, Gd, Lu, or B, Al, Ga, at least among species l In.

这些元素的水合氧化物,其透明性高而且稳定,也比较容易弄到手。 Hydrated oxides of these elements, which is highly transparent and stable and relatively easy to procure.

另外,本发明的又一发光膜的特征在于:粘结剂构件中含有的金属元素的水合氧化物为至少具有勃姆石结构或伪勃姆石结构的Al的水合氧化物。 Further, another feature of light emitting film of the present invention is characterized in: a hydrated oxide of a metal element contained in the binder component having at least Al stone structure or pseudo-boehmite structure hydrated oxide boehmite.

另外,本发明的又一发光膜的特征在于,粘结剂构件含有:铝的水合氧化物,和相对于粘结剂构件含量为0.5重量%〜50重量%的、 与铝不同的IIIA族元素或IIIB族元素的水合氧化物。 Further, another feature of light emitting film of the present invention, the adhesive member comprising: a hydrated oxide of aluminum, and the content of the binder component with respect to 0.5 wt% ~ 50 wt% of aluminum different IIIA element or hydrated oxide of a group IIIB element.

另外,本发明的又一发光膜的特征在于:粘结剂构件含有相对于 Further, another feature of light emitting film of the present invention is that: with respect to the adhesive member comprising

9粘结剂构件含量为0.5重量%〜50重量%的氧化硼或硼酸。 9 binder content of 0.5 wt% member ~ 50 wt% of boron oxide or boric acid.

另外,本发明的又一发光膜的特征在于:粘结剂构件中含有的金 Further, another feature of light emitting film of the present invention: gold contained in the adhesive member

属元素的水合氧化物为钇的水合氧化物。 Hydrated metal element oxide is a hydrous oxide of yttrium.

另外,本发明的又一发光膜的特征在于,粘结剂构件含有:钇的 Further, another feature of light emitting film of the present invention, the adhesive member comprising: yttrium

水合氧化物,和相对于粘结剂构件含量为0.5重量%〜50重量%的、 与钇不同的IIIA族元素或IIIB族元素的水合氧化物。 Hydrated oxide, and the content of the binder component with respect to 0.5 wt% ~ 50 wt% of yttrium and a hydrous oxide of a different element or group IIIA IIIB elements.

另外,本发明的又一发光膜的特征在于:粘结剂构件含有相对于 Further, another feature of light emitting film of the present invention is that: with respect to the adhesive member comprising

粘结剂构件含量为0.5重量%〜50重量%的氧化硼或硼酸。 The binder component content of 0.5 wt.% ~ 50 wt% of boron oxide or boric acid.

另外,本发明的又一发光膜的特征在于:粘结剂构件是由含有水 Further, another feature of light emitting film of the present invention is that: the adhesive member is a water-containing

合氧化物的粒子的集合体形成交联结构、网状结构或聚合物结构的多孔体。 Aggregate particles together forming a porous oxide crosslinked structure, a mesh structure or a polymeric structure.

发光膜的粘结剂构件的脱水、固化没有完全进行到成为氧化物的状态,由此发光膜较之于结晶质处于非晶质的状态,可以形成粘结力得以增加、光取出效率良好的发光膜。 A light emitting member dehydration adhesive film is not completely cured to become an oxide state, thereby emitting light compared to the crystalline film is an amorphous state, adhesion can be formed is increased, good light extraction efficiency luminescent film.

另外,本发明的又一发光膜的特征在于:粘结剂构件呈凝胶状, 其中填充着含有水合氧化物的无机粒子。 Further, another feature of light emitting film of the present invention is characterized in: a gelatinous adhesive member, wherein the inorganic particles include filled with hydrated oxides.

另外,本发明的又一发光膜的特征在于:发光膜的光透过率比溶胶-凝胶反应后进行烧结这一情况下的多晶体或非晶体的透过率更高。 Further, another feature of light emitting film of the present invention is characterized in: emitting light transmittance than the sol film - polycrystalline or amorphous for higher transmittance in this case after sintering gel reaction.

另外,本发明的又一发光膜的特征在于:粘结剂构件相对于粘结剂构件含有10重量°/。 Further, another feature of light emitting film of the present invention is that: the adhesive member 10 with respect to the binder component comprising by weight ° /. 或以下的羟基或结晶水。 Or less crystal water or a hydroxyl group.

另外,本发明的又一发光膜的特征在于:构成发光膜的填料构件和粘结剂构件的重量比以填料/粘结剂计为0.05〜30。 Further, another feature of light emitting film of the present invention: weight of the filler and binder components constituting the light emitting member film ratio of filler / binder in terms of 0.05~30.

另外,本发明的发光装置具有发光元件和吸收发光元件发出的光 Further, the light emitting device of the present invention has a light emitting element and a light-emitting element of the absorbent

的至少一部分而发光的发光层。 At least a portion of the light emitting layer to emit light. 该发光装置的特征在于:发光层为上述发光膜。 Wherein the light emitting device comprising: a light emitting layer serving as the luminescent film.

再者,本发明的另一发光装置的特征在于:发光层直接覆盖发光元件。 Further, the light emitting device according to another feature of the present invention: a light-emitting layer to directly cover the light emitting element.

另外,本发明的又一发光装置具有发光元件和吸收发光元件发出的光的至少一部分而发出不同波长的光的发光层。 Further, the light emitting device of the present invention further includes a light emitting element and a light-emitting element absorbing at least part of the light emitting layer emits light of different wavelengths. 该发光装置的特征在于:发光层具有用发光元件的光来激发的荧光体粒子和在该层内分散并附载着荧光体粒子的粘结剂构件。 Wherein the light emitting device comprising: a light emitting layer having a light emitting phosphor particles excited element and to the binder member of the phosphor particles dispersed in the layer together with carrying.

另外,本发明的又一发光装置的特征在于,该发光装置包括:具 Further, the light emitting device according to still another feature of the present invention, the light emitting device comprising: having

有550nm或以下的发光波长的半导体发光元件、和用该波长的光来激 The semiconductor light emitting element has an emission wavelength of 550nm or less, and a light to the laser wavelength

发发光的荧光体。 Hair emitting phosphor.

另外,本发明的又一发光装置的特征在于,该发光装置包括:具 Further, the light emitting device according to still another feature of the present invention, the light emitting device comprising: having

有410nm或以下的发光波长的半导体发光元件、和用该波长的光来激发发光的荧光体。 There 410nm or less semiconductor light emitting element emission wavelength, and the wavelength of light used to excite the luminescent phosphor.

另外,本发明的又一发光装置的特征在于:发光层在温度为5(TC 或以上的条件下发光。 Further, the light emitting device according to still another feature of the present invention: a light emitting layer at a temperature of (TC 5 or more light emitting conditions.

发光层的粘结剂产生退化的原因一般认为在于光、热或它们之间的相互作用。 Cause adhesive luminescent layer is generally believed that the degradation generated light, heat or interaction between them. 上述构成的发光装置即使是可见光的大功率激励、紫外光、高温激励等也难以使粘结剂产生退化,因而在这些激发密度高的激励方面是特别有效的。 The light emitting device of the above-described configuration, even if the excitation power is visible, ultraviolet, and so it is difficult to motivate high temperature adhesive to produce degradation, thus high excitation density of these incentives are particularly effective.

另外,本发明的又一发光装置的特征在于:发光层粘结形成在半导体发光元件上,半导体发光元件激励时的投入电力为0.1W/cn^或以上。 Further, the light emitting device according to still another feature of the present invention: a light emitting layer is adhered is formed on the semiconductor light emitting element, when the input power to the semiconductor light emitting element excited 0.1W / cn ^ or more. 特别在高达lW/cr^或以上的投入电力下是有效的。 Especially in high lW / cr ^ at or above the input power is valid.

另外,本发明的又一发光装置的特征在于:半导体发光元件的发光波长为410nm或以下,在lW/cn^或以上的投入电力下激励半导体发光元件时,IOOO小时后的发光层的辉度维持率为80%或以上。 Further, the light emitting device according to still another feature of the present invention is characterized in: emission wavelength of the semiconductor light emitting element is 410nm or less, the excitation light emitting element, the luminance of the light emitting layer after the semiconductor IOOO hours or more at a power input of lW / cn ^ retention rate of 80% or more.

另外,本发明的又一发光装置的特征在于:发光装置的发光层的填料中含有的荧光体具有包含蓝色发光荧光体、蓝绿色发光荧光体、 绿色发光荧光体、黄绿色发光荧光体、黄色发光荧光体、黄红色发光荧光体、橙色发光荧光体以及红色发光荧光体之中的至少一种的白色系或中间色系的发光。 Further, the light emitting device according to still another feature of the present invention is: a phosphor layer emitting filler contained in the light-emitting device comprising a blue emitting phosphor having a blue-green emitting phosphor, a green emitting phosphor, a yellow-green light emitting phosphor, at least one intermediate color or white-based light emission among the yellow-emitting phosphor, a yellow-red light emitting phosphor, an orange light emitting phosphor and a red emitting phosphor.

另外,本发明的又一发光装置的特征在于:发光层的填料中含有的荧光体具有峰值波长在510nm〜600nm之间的从绿色到黄红色的发光,是至少用Ce活化的稀土类铝酸荧光体。 Further, the light emitting device according to still another feature of the present invention is: a phosphor layer containing a filler emission having a peak wavelength of the rare earth aluminate from yellow green to red light emission, activated with Ce is at least between the 510nm~600nm phosphor.

另外,本发明的又一发光装置的特征在于:发光装置的发光层的 Further, the light emitting device according to still another feature of the present invention: a light-emitting layer of the device

填料中含有的荧光体具有峰值波长在580nm〜650nm之间的从黄红色到红色的发光,是至少用Eu活化的碱土类氮化硅荧光体。 Filler contained in the phosphor having a peak wavelength in the alkaline-earth silicon nitride phosphor from yellow to red light emission is at least between 580nm~650nm Eu-activated.

另外,本发明的又一发光装置的特征在于:发光层的填料中含有的荧光体具有峰值波长在500nm〜600nm之间的从蓝绿色到黄红色的发光,是至少用Eu活化的碱土类氧氮化硅荧光体。 Further, the light emitting device according to still another feature of the present invention is: a phosphor layer containing a filler emission having a peak wavelength of oxygen from an alkaline earth blue yellow green to red light emission, at least between a 500nm~600nm Eu activated in silicon nitride phosphor.

另外,本发明的又一发光装置的特征在于:它是发光元件以发光波长在410nm或以下进行发光的半导体发光元件,发光层的填料屮含有的荧光体具有蓝色发光,包含选自至少用Eu活化的碱土类卤素磷灰石荧光体、至少用Eu活化的碱土类卤素硼酸荧光体以及至少用Eu 活化的碱土类铝酸荧光体之中的一种,进而与具有从绿色到黄红色发光的至少用Ce活化的稀土类铝酸荧光体混合,从而显示出白色系的发光。 Further, the light emitting device according to still another feature of the present invention is that: it is a semiconductor light-emitting elements to emit light in the emission wavelength of 410nm or less, Che emitting phosphor layer containing a filler having a blue light emission, comprising at least a selected Eu-activated alkaline earth halogen apatite fluorescent material activated with at least Eu alkaline earth borate halogen phosphor, and activated with Eu among at least an alkaline earth aluminate phosphor of one kind, further having the light emitting from green to yellow-red Ce-activated with rare earth aluminate fluorescent materials are mixed at least, thereby displaying a white color luminescence.

另外,本发明的又一发光装置的特征在于:它是发光元件以发光波长在410nm或以下进行发光的半导体发光元件,发光层的填料屮含有的荧光体具有蓝色发光,包含选自至少用Eu活化的碱土类卤素磷灰石荧光体、至少用Eu活化的碱土类卤素硼酸荧光体以及至少用Eu 活化的碱土类铝酸荧光体之中的一种,进而与具有从绿色到黄红色发光的至少用Ce活化的稀土类铝酸荧光体和具有从黄红色到红色发光的至少用Eu活化的碱土类氮化硅荧光体混合,从而显示出白色系的发光。 Further, the light emitting device according to still another feature of the present invention is that: it is a semiconductor light-emitting elements to emit light in the emission wavelength of 410nm or less, Che emitting phosphor layer containing a filler having a blue light emission, comprising at least a selected Eu-activated alkaline earth halogen apatite fluorescent material activated with at least Eu alkaline earth borate halogen phosphor, and activated with Eu among at least an alkaline earth aluminate phosphor of one kind, further having the light emitting from green to yellow-red Ce-activated with at least a rare earth aluminate fluorescent material activated with Eu and at least an alkaline earth silicon nitride phosphor is mixed from yellow to red light emission, thereby displaying a white color luminescence.

另外,本发明的又一发光装置的特征在于:它是发光元件的以发光波长在440nm〜480nm的蓝色区域进行发光的半导体发光元件,发光层的填料中含有的荧光体与至少用Ce活化的稀土类铝酸荧光体混合,从而显示出白色系的发光。 Further, the light emitting device according to still another feature of the present invention is that: it is a semiconductor light emitting element emits light in the blue region 440nm~480nm to the emission wavelength of the light emitting element, the phosphor of the filler contained in the light-emitting layer and at least activated with Ce the rare earth aluminate fluorescent materials are mixed, thereby displaying a white color luminescence.

另外,本发明的又一发光装置的特征在于:它是发光元件的以发光波长在440nm〜480nm的蓝色区域进行发光的半导体发光元件,发 Further, the light emitting device according to still another feature of the present invention: it is the emission wavelength to emit light of a semiconductor light-emitting elements in the blue region of 440nm~480nm, hair

12光层的填料中含有的荧光体与具有从绿色到黄红色发光的至少用Ce 活化的稀土类铝酸荧光体和具有从黄红色到红色发光的至少用Eu活化的碱土类氮化硅荧光体混合,从而显示出白色系的发光。 The phosphor layer of filler 12 contained in the light from green to yellow and red light emission is activated with at least Ce rare-earth aluminate phosphor having a yellow-red to red light emission from at least activated with Eu alkaline earth silicon nitride phosphor having mixed, thereby displaying a white color luminescence.

另外,本发明的发光膜的制造方法是至少由包含发光材料的填料构件和粘结剂构件构成的、用于覆盖发光元件的发光膜的制造方法, 其特征在于,包括以下步骤:将作为粘结剂构件的含有金属元素的金属氧烷溶胶和填料构件混合而调配料浆的步骤,将料浆形成为膜状的步骤,以及通过对形成为膜的料桨进行热固化、使含有金属元素的水合氧化物的粒子聚集在一起、从而用由该集合粒子的结构体构成的粘结剂构件附载填料构件的步骤。 Further, a method of manufacturing the light emitting film of the present invention is at least composed of a binder and a filler component member comprising a light emitting material, a method of manufacturing the light emitting film for covering the light emitting element, characterized by comprising the steps of: a stick the metal oxide sol and an alkoxy filler member comprising a metal element member caking agent formulated by mixing slurry step, the step of forming a slurry of a film, and is formed by thermally curing the film feed pitch, containing a metal element hydrous oxide particles together, so that the binder formed of a structure member of the collection of particles is the step of filler-carrying member.

另外,本发明的另一发光膜的制造方法的特征在于:金属氧烷溶胶至少为铝氧垸溶胶或钇氧烷溶胶。 Further, the method of manufacturing the light emitting characteristics of another film of the invention is characterized in: at least a metal oxide sol or sol alkyl alumoxane yttrium aluminum oxide sol embankment.

另外,本发明的又一发光装置的制造方法是具有发光元件和根据上述制造方法覆盖发光元件的至少一部分而得到的发光膜的发光装覽的制造方法,其特征在于:在形成为膜状的步骤中,于热处理条件下采用料浆覆盖发光元件和/或隔开发光元件的区域,从而形成为膜状。 Further, another method for manufacturing the light emitting device according to the present invention is a method for producing light-emitting device having a light emitting element and laid light emitting film covering at least a portion of the light emitting element obtained according to the above manufacturing method, comprising: forming a film of step using the slurry under treatment conditions cover the light emitting element and / or spaced apart from the light emitting element region, thereby forming a film.

根据本发明,可以获得光取出效率高的发光膜、发光装置、发光膜的制造方法以及发光装置的制造方法。 The manufacturing method of the present invention, the light emitting film can be obtained with high light extraction efficiency, a light emitting device, a method of manufacturing the light emitting device and a light emitting film. 这是因为:通过在发光膜中使用水合氧化物,即使在没有达到多晶体状态的凝胶状态下,也能使发光膜的透过率受到较少的抑制,从而获得较高的光取出效率。 This is because: in the light emission by using a hydrated oxide film, even in a gel state has not reached a polycrystalline state, the transmittance of the light emitting film can also be suppressed less, thereby obtaining high light extraction efficiency . 再者, 根据本发明,由于使用具有恒定价数的金属元素的水合氧化物,所以能够获得因使用而引起的着色退化少、耐久性好、可靠性优良的发光膜、发光装置、发光膜的制造方法以及发光装置的制造方法。 Further, according to the present invention, since the hydrated oxide having a metal element of a constant number of price, it is possible to obtain a colored degradation caused by use of small, good durability, excellent in reliability of the light emitting film, the light emitting device, the light emitting film and a method of manufacturing a manufacturing a light emitting device. 这是因为:作为荧光体的粘结剂,本发明不使用可以取多种价数的、像二氧化硅那样的金属元素,因而不会产生氧缺损,从而由氧缺损产生的粘结层的着色退化也可以避免。 This is because: as a binder of the phosphor, the present invention does not use the number may take a variety of divalent, as metal elements such as silicon dioxide, and thus will not generate oxygen deficiency, so that oxygen defects generated in the adhesive layer coloring degradation can be avoided. 由此可以避免因粘结层的着色而产生的光输出功率的低下,可以获得长期稳定的性能,即使使用动力型发光元件,也可以获得优良的可靠性,并实现长寿命化。 Low optical output power can thus be avoided due to the colored adhesive layer is generated, can be long-term stable performance, even if the power light-emitting element, high reliability can be obtained, and a long life. 另外,还可以获得耐热性优良、荧光体的耐久性得以提高、可靠性极高的发光膜、发光装置、发光膜的制造方法以及发光装置的制造方法。 Further, excellent heat resistance can be obtained, the durability of the phosphor is improved, a method for producing the high reliability light emitting film, the light emitting device, a method of manufacturing the light emitting device and a light emitting film.

另外,本发明涉及一种发光装置,其具有发光元件和承载所述发光元件的基体,该发光装置的特征在于:所述发光元件被无机粘结剂所覆盖,所述无机粘结剂被树脂所覆盖,所述无机粘结剂用所述树脂来浸渍,所述无机粘结剂形成有覆盖所述发光元件及所述基体的至少一部分的无机粘结剂层。 Further, the present invention relates to a light emitting device having a light emitting element and the base body carrying said light emitting element, the light emitting device is characterized in that: said light emitting element is covered with an inorganic binder, the inorganic binder is a resin covered, the inorganic binder is impregnated with the resin, the inorganic binder is an inorganic binder layer is formed to cover at least a portion of the light emitting element and the base body.

无机粘结剂优选的是可以通过树脂将无机粘结层所具有的空隙填埋起来。 The preferred inorganic binder is an inorganic adhesive layer has voids filled up by resin.

另外,无机粘结剂优选的是可以通过树脂将无机粘结层所具有的 The inorganic binder is preferably an inorganic resin through the adhesive layer has

约95%或以上的空隙填埋起来。 About 95% or more voids filled up.

采用树脂覆盖无机粘结剂优选使用浇灌手段或喷涂喷雾手段,使无机粘结剂浸渍上树脂。 A resin covering the inorganic binder is preferably used in watering or spraying means to spray means, so that the inorganic binder is impregnated resin.

再者,无机粘结剂优选含有荧光体。 Further, the inorganic binder preferably contains a phosphor.

脂优选的是可以形成覆盖无机粘结剂的至少一部分的树脂i: The preferred aliphatic resins can be formed i covering at least part of the inorganic binder:

<formula>formula see original document page 14</formula> <Formula> formula see original document page 14 </ formula>

树脂层的表面优选的是平滑的表面。 Preferably, the surface of the resin layer is a smooth surface.

树脂优选含有油料、凝胶以及橡胶之中的至少任一种。 Resin preferably contains oil, a gel and at least any one among rubber. 树脂优选在成型前及成型后的任一种情况下,是具有二烷基硅氧 Resin is preferably in any case before and after the forming and molding, having a dialkyl siloxane

烷骨架的硅树脂。 Alkyl silicone backbone. 以下的化学式1表示二垸基硅氧烷骨架,式中R表不院基。 Represented by the following chemical formula 1 alkyl with two siloxane skeleton, wherein R represents no group homes.

<formula>formula see original document page 14</formula> <Formula> formula see original document page 14 </ formula>

化学式1 Formula 1

树脂优选成型前在主链上具有二甲基硅氧烷。 Preferably before molding resin having a dimethylsiloxane chain in the main. 二甲基硅氧烷是二烷基硅氧垸骨架之中的1种形态。 Dimethicone in one form is a dialkyl siloxane backbone embankment. 以下的化学式2表示二甲基硅氧垸。 Represented by the following chemical formula 2 dimethylsiloxane embankment.

<formula>formula see original document page 14</formula>化学式2树脂在红外光谱的键吸收强度中,优选树脂组成中的C一Si — O 键与Si—0—Si键的强度比为1.2 / 1或以上。 <Formula> formula see original document page 14 </ formula> Chemical Formula 2 resin bond infrared absorption intensity, the resin composition of the C-Si - intensity ratio O bond and Si-0-Si bonds was 1.2 / 1 or above.

本发明涉及一种发光装置的制造方法,其具有:将发光元件承载在基体上的第一工序;将该发光元件用无机粘结剂覆盖的第二工序; 将该无机粘结剂用树脂覆盖的第三工序,其中第三工序使用浇灌手段或喷涂喷雾手段使树脂覆盖无机粘结剂。 The present invention relates to a method of manufacturing a light emitting device, comprising: a first step of carrying the light emitting element on a substrate; a second step of the light emitting element is covered with an inorganic binder; the inorganic binder resin covered a third step, wherein the third means of watering or spraying step of spraying using the resin covered with an inorganic binder means.

第三工序优选的是在真空中进行浸渍。 The third step is preferably carried out in vacuum impregnation.

因为具有上面所说明的构成,所以本发明产生出如下所述的效果。 Having a configuration as described above, the present invention produces the following effects. 本发明涉及一种发光装置,其具有发光元件和承载该发光元件的基体,在该发光装置中,所述发光元件被无机粘结剂所覆盖,所述无机粘结剂被树脂所覆盖,以所述树脂覆盖所述无机粘结剂的步骤使用浇灌手段或喷涂喷雾手段,使所述无机粘结剂浸渍所述树脂。 The present invention relates to a light emitting device having a light emitting element and the carrier matrix of the light emitting element, the light emitting device, the light emitting element is covered with an inorganic binder, the inorganic binder being covered with resin, the resin covering step using the inorganic binder spraying means watering or spraying means, so that the resin impregnating the inorganic binder. 由此, 即使在使用高输出功率的发光元件或放出紫外线的发光元件的情况下,可以提供一种树脂退化的促进受到抑制、能够长时间耐紫外线等的涂膜。 Accordingly, even in the case where the light emitting elements emit high-output light emitting elements or ultraviolet light may be provided to promote a resin degradation is suppressed, and the like can be UV resistant coating film for a long time. 另外,可以不发生覆盖发光元件的无机粘结剂的退化而谋求光取出效率的提高。 Further, the light emitting element may cover the degradation of the inorganic binder be improved light extraction efficiency does not occur. 再者,因为整个无机粘结剂都采用树脂来漫渍, 所以无机粘结剂不会产生裂纹和缺陷,可以形成耐冲击的涂膜。 Further, because the entire inorganic binder resin are used to diffuse stain, the inorganic binder so that no cracks and defects, impact resistant coating film may be formed. 这是由以下作用所决定的。 This is determined by the following action.

无机粘结剂固化时,有形成空隙的部分。 When the inorganic binder is cured, some void formation. 在现有技术中,由于该空隙的作用,光的取出受到抑制,而在本发明中,采用树脂将该空隙填埋起来,由此可谋求光取出效率的改善。 In the prior art, due to the gap, the light extraction is suppressed, whereas in the present invention, a resin to fill up the gap, thereby seeking to improve the light extraction efficiency.

作为采用树脂将该空隙填埋起来的手段,使用的是浇灌手段或喷涂喷雾手段。 The resin employed as a means to fill up voids, using a means of watering or spraying means for spraying. 浇灌手段、喷涂喷雾手段之外的手段例如一次性地往整个无机粘结剂注入树脂的手段,要向外排出的气体或者残存在无机粘结层中,或者侵入树脂中而将气体保存下来。 Means watering, spraying means other means such as spraying once to the entire inorganic binder resin injection means, the gas to be discharged outwardly or remains in the inorganic adhesive layer, and the resin invasion or preserved gas. 存在于该无机粘结层中的气体被封闭在层中,保存在层中的气体因发光装置激励时发光元件的发热而膨胀。 Present in the adhesive layer of the inorganic gas is enclosed in the layer, the gas stored in the layer due to the heating element when the light emitting device emitting excitation expands. 由此,往往发生光取出效率低下的情况。 Accordingly, where the low light extraction efficiency tends to occur. 与此相对照, 在浇灌手段、喷涂喷雾手段中,树脂一边将无机粘结剂的空隙中含有的气体向外部挤出, 一边向无机粘结剂中渗透,所以无机粘结剂的空隙中几乎没有残存气体,树脂几乎可以完全填埋无机粘结剂所具有的空隙。 In contrast to this, the irrigation means, spray means for spraying the resin while the gas contained in the voids of the inorganic binder out to the exterior, while the inorganic binder to penetrate, so there is almost void inorganic binder no residual gas, can be almost completely filled with resin, the inorganic binder has a void. 因此,即使在激励发光装置时,在空隙和无机粘结层界面的反射也受到抑制,不会产生光取出效率低下的情况,而涂膜本身是稳定的。 Accordingly, even when the excitation light emitting device, the reflective inorganic adhesion layer and the interface gap is also suppressed, no case of low light extraction efficiency, and the film itself is stable.

由于无机粘结剂所具有的空隙中有柔软的有机类树脂的侵入,所以因热引起的气体的体积膨胀所导致的裂纹的发生可以受到抑制。 Since the inorganic binder has voids have invaded a soft organic resin, the volume of the gas due to heat expansion caused by the occurrence of cracks can be suppressed.

无机粘结剂优选形成有覆盖发光元件及基体的至少一部分的无机粘结层。 The inorganic binder is preferably an inorganic adhesion layer is formed covering at least a portion of the light emitting element and the base body. 这是因为:通过形成为层结构,能够容易地采用树脂浸渍无机粘结剂所具有的空隙。 This is because: The layer structure is formed, a resin can be easily impregnated with the inorganic binder has a void. 另外,从光取出的角度来看,可以几乎均匀地向外部发出源于发光元件的光。 Further, from the point of view of light extraction, light can be uniformly emitted from the light emitting element to the outside almost.

无机粘结剂优选采用树脂将无机粘结层所具有的空隙填埋起来。 The inorganic binder is preferably a resin layer having inorganic adhesive voids filled up. 由此,无机粘结层的空隙消失,可以谋求光取出效率的提高。 Thus, the void disappears inorganic adhesion layer, can be improved light extraction efficiency. 因此, 所使用的树脂量仅够填埋无机粘结层的空隙就行。 Thus, the amount of resin used is just enough to fill the voids of the inorganic adhesive layer on the line.

另外,无机粘结剂优选的是可以通过树脂将无机粘结层所具有的95%或以上的空隙填埋起来。 The inorganic binder is preferably an inorganic adhesion layer having a void of 95% or more by the resin filled up. 这是因为:如果只是无机粘结层所具冇的空隙的一部分被树脂填埋,则空隙部分抑制光的取出。 This is because: if only part of the void Nuisance inorganic adhesion layer is filled with a resin, the space portion to suppress the light extraction. 在无机粘结层离开发光元件的情况下,因为不会从发光元件直接进行热传导,所以不要特别考虑因热引起的退化,因而树脂也可以不填埋该空隙。 In the case of the inorganic adhesive layer away from the light emitting element, as there is no direct heat conduction from the light emitting element, it is not considered particularly degradation due to heat, and the resin can not be filled the void. 但是,如果需要考虑源于发光元件的光,则优选采用树脂将该空隙几乎完全填埋起来。 However, if the light from the light emitting element needs to be considered, it is preferable to use the resin is almost completely filled up the gap.

无机粘结剂优选在其中含有荧光体。 Wherein the inorganic binder preferably contains a phosphor. 由此,该荧光体吸收源于发光元件的光的一部分并进行波长转换,从而向外部发出与发光元件的光不同的光,将源于发光元件的光的一部分与源于荧光体的光的一部分混合,藉此便可以提供一种具有所希望的色调的发光装置。 Thereby, the phosphor absorbs the light from the light emitting element and a wavelength conversion portion, to emit light with different light emitting element to the outside from a portion of the light from the phosphor light emitting element mixing portion, whereby it is possible to provide a light emitting device having a color tone desired. 另外, 通过设计成含有荧光体的无机粘结层,可以使色调调节变得容易,并提供一种发出均匀光线的、合格率高的发光装置。 Further, by designing the adhesive layer containing an inorganic phosphor, the color tone can be easily adjusted, and provide, high pass rate of the light emitting device emits light uniformly.

树脂优选的是可以形成覆盖无机粘结剂的至少一部分的树脂层。 The preferred resin is a resin layer covering at least part of the inorganic binder.

16通过形成为层结构,可以形成膜厚均匀的涂膜,从而谋求光取出效率的提高。 16 is formed by a layer structure, a coating film may be formed in a uniform thickness, thereby seeking to improve the light extraction efficiency.

树脂层的表面优选的是平滑的表面。 Preferably, the surface of the resin layer is a smooth surface. 无机粘结剂固化时,其表而存在凹凸。 When the inorganic binder is cured, the presence of tables which irregularities. 因此,当由发光元件发出的光透过无机粘结剂向外部发出时,由于该凹凸部分的作用,光的指向性产生偏差。 Accordingly, when sent to the outside from the light emitting element transmits light emitted by the inorganic binder, due to the uneven portion, the directivity of light variation generated. 与此相对照, 在无机粘结剂中浸渍树脂时,涂膜表面变得平滑,可以降低光的指向性的偏差。 In contrast, when the inorganic binder in the impregnating resin, the coating film surface becomes smooth, it can reduce the deviation of the directivity of the light.

树脂优选含有油料、凝胶以及橡胶之中的至少任一种。 Resin preferably contains oil, a gel and at least any one among rubber. 这是为了使树脂浸渍到无机粘结剂中。 This is because the resin is impregnated into an inorganic binder. 特别是使用处于油料状态的树脂将树脂浸渍到无机粘结剂中的情况,因加热等而产生凝胶化,藉此可以提高一种光取出效率高的发光装置。 In particular resin oil in the state of the impregnating resin to the inorganic binder, and the like due to heating gelation, whereby a high efficiency can be improved light extraction emitting device. 另外,在凝胶状或橡胶状的形态中, 能够容易地控制树脂的硬度。 Further, gel-like or rubber-like in shape, the hardness of the resin can be easily controlled. 再者,与发光元件上设置的电极和外部电极进行电连接的引线,即使对树脂进行固化,引线也不会被切断。 Further, a lead electrically connected to the electrode and the external electrode disposed on the light emitting element, even if the resin is cured, the leads will not be cut off. 在现有技术中,当固化环氧树脂时,由于引线与环氧树脂的热膨胀系数存在差异,引线被切断。 In the prior art, when a cured epoxy resin, due to difference in thermal expansion coefficient of the epoxy resin and the lead, the lead is cut off. 而在本发明中,由于树脂呈油料状、或者凝胶状、橡胶状,引线不会被切断。 In the present invention, since the resin is in the oil-like, gel-like or rubber-like, the lead will not be cut off. 另外,单凭无机粘结剂,耐冲击能力较弱,而用呈橡胶状等的树脂填埋,藉此可以赋予涂膜以柔软性, 可以形成耐冲击能力强的涂膜。 Further, the inorganic binder alone, impact resistance is weak, and the like with a rubbery resin filled, whereby flexibility can be imparted to the coating, it can form a strong coating film impact resistance.

树脂优选在成型前及成型后的任一种情况下,是具有二烷基硅氧垸骨架的硅树脂。 Resin is preferably in any case before and after the forming and molding, a dialkyl silicone having a silicone skeleton embankment. 通过使用该树脂,可以提供一种树脂的退化进一步受到抑制、可以长时间耐紫外线等的涂膜得以使用的发光装置。 By using the resin, the resin can be provided a further degradation is suppressed, long-time resistance to ultraviolet light emitting apparatus is used for coating film.

树脂优选成型前在主链上具有二甲基硅氧烷。 Preferably before molding resin having a dimethylsiloxane chain in the main. 由此可以提供一种树脂的退化进一步受到抑制、可以长时间耐紫外线等的涂膜得以使用的发光装置。 Thereby to provide a further deterioration of the resin is suppressed, long-time resistance to ultraviolet light emitting apparatus is used for coating film.

树脂在红外光谱的键吸收强度中,优选树脂组成中的C一Si—O 键与Si—O—Si键的强度比为1.2/1或以上。 Resin bond absorption intensity of the infrared spectrum, C a Si-O bond strength of the resin is preferably in the bond Si-O-Si was 1.2 / 1 or more. 通过设定为1.2 / 1或以上,由于树脂保持为油料状、或者凝胶状、橡胶状,可以形成应力得以缓和、裂纹或缺陷难以产生的涂膜。 By setting 1.2 / 1 or more, since the resin remains oil-like, gel-like or rubber-like, may be formed in the stress relaxation film, cracks or difficult to produce a defect. 本发明涉及一种发光装置的制造方法,其具有:将发光元件承载在基体上的第一工序;将该发光元件用无机粘结剂覆盖的第二工序; 将该无机粘结剂用树脂覆盖的第三工序,其中第三工序使用浇灌树脂的手段或对树脂进行喷涂喷雾手段来覆盖无机粘结剂。 The present invention relates to a method of manufacturing a light emitting device, comprising: a first step of carrying the light emitting element on a substrate; a second step of the light emitting element is covered with an inorganic binder; the inorganic binder resin covered a third step, the third step wherein the resin using a means of watering or spraying means for spraying the resin to cover the inorganic binder. 通过使用浇灌树脂的手段或对树脂进行喷涂喷雾手段,可以填埋无机粘结剂所具有的空隙。 By means of the use of resins or resin pouring spraying means for spraying, can be filled with inorganic binder has voids. 另外,可以防止该空隙中存在的气体侵入树脂之中。 Further, the gap can be prevented from being present in the gas intrusion resin. 再者, 可以稳定且均匀地涂布覆盖粘结剂的树脂。 Further, the coating can be stably and uniformly covered with the binder resin. 特别地,通过使用在溶胶-凝胶反应过程中不会发生价数的变化而氧化状态稳定的Al和Y元素等水合氧化物的凝胶,可以谋求光取出效率的提高。 In particular, by using a sol - gel reaction process and change the valence oxidation state of stable gel hydrated oxide of Y element and Al and the like do not occur, can be improved light extraction efficiency.

第三工序也可以在真空中进行浸渍。 The third step of the impregnation may be carried out in vacuum. 由此,树脂可以容易地浸渍到无机粘结层中的空隙里。 Accordingly, the resin can be easily impregnated into the voids of the inorganic adhesive layer inside. 虽然其原因尚不清楚,但一般认为起因于毛细管现象。 Although the reason is not clear, but it is generally believed that due to capillary action. 在这里,所谓"凝胶"是指由溶胶失去流动性的固体和液体构成的胶态体系。 Here, the term "gel" refers to a colloidal sol loses flowability system composed of solids and liquids.

附图说明 BRIEF DESCRIPTION

图1表示溶胶-凝胶反应的进行和发光膜的透光率的变化之间的关系。 1 shows the sol - the relationship between the change of light transmittance and the light emitting film were gel reaction.

图2是表示本发明的实施方案1的发光装置的示意图。 FIG 2 is a schematic view showing a light emitting device according to the embodiment of the present invention.

图3是示意表示本发明的实施方案2的发光装置的平面图。 FIG 3 is a schematic plan view showing a light emitting device according to embodiment 2 of the present invention.

图4是图3的发光装置的剖面图。 FIG 4 is a sectional view of a light emitting device of FIG.

图5是本发明的又一实施方案的发光装置的示意剖面图。 FIG 5 is a schematic sectional view showing an embodiment of the device according to still another embodiment of the present invention. 图6示意表示了形成本发明的实施方案的发光装置的工序。 FIG 6 schematically shows a step of forming a light emitting device according to the embodiment of the present invention. 图7示意表示了形成本发明的实施方案的发光装置的装置。 7 schematically shows an apparatus forming an embodiment of the light emitting device of the present invention. 图8是示意表示本发明的实施方案3的发光装置的平面图。 8 is a schematic plan view showing a light emitting device according to the embodiment 3 of the invention. 图9是图8的发光装置的A—A'向剖面图。 FIG 9 is a light-emitting device of FIG. 8 A-A 'cross-sectional view to FIG. 图10是示意表示本发明的实施方案4的发光装置的剖面图。 FIG 10 is a schematic sectional view showing a light emitting device according to the embodiment 4 of the present invention. 图11是示意表示本发明的实施方案5的发光装置之制造过程的剖面图。 FIG 11 is a schematic sectional view showing a manufacturing process of the light emitting device of the embodiment 5 of the present invention.

18图12是示意表示本发明的实施方案5的发光装置之制造过程的剖面图。 18 FIG. 12 is a schematic sectional view showing a manufacturing process of the light emitting device of the embodiment 5 of the present invention.

图13是示意表示本发明的实施方案5的发光装置之制造过程的剖面图。 FIG 13 is a schematic sectional view showing a manufacturing process of the light emitting device of the embodiment 5 of the present invention.

图14是示意表示本发明的实施方案5的发光装置之制造过程的剖面图。 14 is a schematic sectional view showing a manufacturing process of the light emitting device of the embodiment 5 of the present invention.

图15是示意表示本发明的实施方案5的发光装置之制造过程的剖面图。 FIG 15 is a schematic sectional view showing a manufacturing process of the light emitting device of the embodiment 5 of the present invention.

图16是示意表示本发明的实施方案5的发光装置之制造过程的剖面图。 FIG 16 is a schematic sectional view showing a manufacturing process of the light emitting device of the embodiment 5 of the present invention.

图17是示意表示本发明的实施方案5的发光装置之制造过程的剖面图。 FIG 17 is a schematic sectional view showing a manufacturing process of the light emitting device of the embodiment 5 of the present invention.

图18是示意表示本发明的实施方案5的发光装置之制造过程的剖面图。 FIG 18 is a schematic sectional view showing a manufacturing process of the light emitting device of the embodiment 5 of the present invention.

图19是示意表示本发明的实施方案5的发光装置的剖面图。 FIG 19 is a schematic sectional view showing a light emitting device according to the embodiment 5 of the invention.

图20是示意表示本发明的实施方案5的其它发光装置的平面阁。 FIG 20 is a schematic plane Court other light-emitting device of Embodiment 5 of the present invention.

图21是图20的发光装置的B—B'向剖面图。 FIG 21 is a light-emitting device of FIG 20 B-B 'cross-sectional view to FIG.

图22是图21的发光装置的主要部分的放大剖面图。 FIG 22 is an enlarged sectional view of a main portion of the light-emitting device 21 of FIG.

图23是表示本发明的实施例15〜23的荧光体的色度的色度图。 FIG 23 is a chromaticity diagram showing the chromaticity of the phosphor of an embodiment of the present invention. 15~23.

图24是用波长365nm的LED激发本发明的实施例23的三波L<: FIG 24 is an embodiment of the present invention, the excitation wavelength of 365nm LED 23 three-wave L <:

白色荧光体的谱图。 Spectrum of the white phosphor.

图25是用波长400nrn的LED激发本发明的实施例19的三波长 FIG 25 is an embodiment of the present invention the excitation wavelength of 19 three-wavelength LED of 400nrn

白色荧光体的谱图。 Spectrum of the white phosphor.

图26表示本发明的实施例的荧光体的可靠性试验结果。 26 shows results of reliability test of the phosphor of an embodiment of the present invention. 图27表示本发明的实施例的荧光体的可靠性试验结果。 27 shows results of reliability test of the phosphor of an embodiment of the present invention. 图28表示本发明的实施例的荧光体的可靠性试验结果。 28 shows results of reliability test of the phosphor of an embodiment of the present invention. 图29表示本发明的实施例的荧光体的可靠性试验结果。 29 shows results of reliability test of the phosphor of an embodiment of the present invention. 图30表示本发明的实施例的荧光体的可靠性试验结果。 30 shows results of reliability test of the phosphor of an embodiment of the present invention. 20 20

图31是表示本发明的实施方案6的发光装置的示意平面图。 FIG 31 is a schematic plan view showing a light emitting device according to embodiment 6 of the present invention. 图32 (a)是表示本发明的实施方案的发光装置的示意剖面图, FIG 32 (a) is a schematic cross-sectional view showing a light emitting device according to an embodiment of the present invention,

图32 (b)是放大基体凹部的示意剖面图。 FIG. 32 (b) is an enlarged schematic sectional view of the base of the recess.

图33是表示本发明的实施方案的发光装置之制造工序的一部分 33 is a part of a manufacturing process of the light emitting device of an embodiment of the present invention.

的示意图。 FIG.

图34是表示本发明的实施方案的发光装置之其它制造工序的一部分的示意图。 FIG 34 is a schematic diagram showing a part of another manufacturing process of the light emitting device of an embodiment of the present invention.

图35是表示本发明的实施方案的发光装置之另一个其它制造工序的一部分的示意图。 FIG 35 is a schematic diagram showing a portion of another embodiment of the light emitting device of another embodiment of the present invention is a manufacturing process.

图36 (a)是放大本发明的实施方案7的发光装置之基体凹部的示意剖面图,图36 (b)是表示发光装置的立体图。 FIG 36 (a) is an enlarged embodiment of the present invention a schematic cross-sectional view of the base of the recessed portion 7 of the light emitting device, FIG. 36 (b) is a perspective view of a light emitting device.

图37 (a)是放大本发明的实施方案8的发光装置之基体凹部的示意剖面图,图37 (b)是表示发光装置的立体图。 FIG 37 (a) is a schematic cross-sectional view of the base of the recess of the light-emitting device according to the present invention, an enlarged embodiment 8, FIG. 37 (b) is a perspective view of a light emitting device.

图38是表示本发明的实施方案9之发光装置的一部分的示意剖而图。 FIG 38 is a schematic of a portion of the light emitting device according to Embodiment 9 of the present invention and a cross-sectional FIG.

图39表示实施例的发光装置的耐久性试验结果。 39 shows the results of durability test of the light emitting device of the embodiment.

图40表示实施例的发光装置的光取出效率的结果。 FIG 40 shows the results of light extraction efficiency of the light emitting device according to the embodiment.

图41是表示实施例的涂膜的红外光谱图。 FIG 41 is a coating film of the infrared spectra embodiment.

图42是表示比较例的发光装置的示意剖面图。 FIG 42 is a schematic sectional view showing a light emitting device of a comparative example.

图43是表示比较例的涂膜的红外光谱图。 FIG 43 is a coating film of the infrared spectra of the Comparative Example.

图44是表示本发明的实施方案10的发光装置的示意构成图。 FIG 44 is a schematic configuration diagram showing a light emitting device according to the embodiment 10 of the present invention.

具体实施方式 Detailed ways

下面以附图为基础就本发明的实施方案进行说明。 Below it will be described based on the drawings embodiments of the present invention. 但是,以下所示的实施方案仅用于使本发明的技术思想具体化,是发光膜、发光装置、发光膜的制造方法以及发光装置的制造方法的例示,而并不是将本发明的发光膜、发光装置、发光膜的制造方法以及发光装置的制造方法特定为以下的内容。 However, the embodiments shown below only for the technical idea of ​​the present invention is embodied, a light emitting film, the light emitting device, illustrating the light emitting film, and a method for manufacturing the light emitting device manufacturing, rather than the light emitting film of the present invention , a light emitting device, method of manufacturing a light emitting film and a method of manufacturing the light emitting device is specified as the following. 另外,也决不是将权利要求书所示的构件特定为实施方案的构件。 Further, the member is never shown in the specific member of the claims embodiment. 而且各附图所示的构件的大小和位置关系等, 为使说明变得明确,有时进行了夸张。 The size and positional relationship of each member shown in the accompanying drawings and the like, become clear, it may be exaggerated for the explanation. 再者,构成本发明的各要素也可以设定为用同一构件构成多个要素或用一个构件兼用多个要素的形式。 Further, each element constituting the present invention may be configured to set a plurality of elements with the same member or a combination of a plurality of elements with a form member.

在本发明的实施方案中,将水合氧化物的凝胶用作粘结剂。 In an embodiment of the present invention, the gel of the hydrous oxide as a binder. 图1 表示的是随着溶胶-凝胶反应的进行,在从溶胶状态经过含结晶水的凝胶、或水合氧化物和氧化物至非晶质或多晶体氧化物的过程中,发光膜的透光率和光的取出效率所发生的变化。 Figure 1 shows that as the sol - gel reaction, in the process from a sol state through a gel containing water of crystallization, and an oxide or hydrated oxide to an amorphous or polycrystalline oxides, luminescent film and the change in transmittance of light extraction efficiency that takes place. 如图1所示,在将凝胶川作粘结剂的情况下,一般可以认为随着溶胶-凝胶反应的进行,越是接 1, in the case of plain gel as the binder may generally be considered as a sol - gel reaction, then more

近多晶体结构,发光膜的透过率像图中A所示的那样就越上升。 Near polycrystalline structure, the transmittance of the light emitting film image pattern as shown in more rising A. 但是, 在采用溶胶-凝胶反应获得多晶体方面,需要相当多的能量。 However, the sol - gel reaction to obtain polycrystalline aspect requires considerable energy. 在分离凝胶状态的结构所含有的羟基和有机基团的过程中需要相当高的温设, 所以并不那么容易。 It requires a fairly high temperature is provided during a hydroxyl group and an organic group of the structure of the separation gel contained in a state, it is not so easy.

本发明者经过潜心的研究,结果发现:在特定的金属元素中,即使不提高结晶性,也能在凝胶状态下获得高的光取出效率,从而成就了本发明。 After the present inventors have intensively studied and found that: even if the crystallinity is not increased, it is possible to obtain a high light extraction efficiency in a gel state in a specific metal element, thus accomplishing the present invention. 特别地,如果使用在溶胶-凝胶反应过程中不会发生价数的 Particularly, if used in the sol - gel reaction does not occur during the valence of

变化而氧化状态稳定的Al和Y元素等水合氧化物的凝胶,则如图1 中的B所示的那样,发现处于凝胶状态的光取出效率具有比溶胶-凝胶反应进行中的多晶体状态的光取出效率更高的倾向。 Change the oxidation state of stable gel hydrated oxide of Al and Y elements or the like, as shown in FIG. 1 B is found in the gel state light extraction efficiency than a sol - gel reaction plurality higher efficiency tends to crystalline state light extraction. 例如在钇之类的非晶体中, 一般认为其中的一个原因是由光的散射引起的。 For example, in amorphous yttrium or the like, it is generally considered one of the reason is caused by the scattered light. 也就是说, In other words,

在通过高温加热进行的结晶化阶段,在从化学结构方面来看形成多分子的从a到b的结晶化过程中,从微观方面来看, 一般认为部分结晶的部分和处于凝胶状态的部分发生相分离而形成为多相结构。 By high-temperature heating for the crystallization stage, from a to b in the crystallization process of forming a plurality of molecules in terms of the chemical structure point of view, from the microscopic point of view, the general portion and the portion is partially crystalline gel state that phase separation to form a multiphase structure. 因此, 从微观方面来看,相与相之间是不均匀的,因而在相的界面发生光的散射,从整体上说使透过率降低。 Accordingly, from the microscopic point of view, between the phase to phase it is not uniform, and therefore scattering of light occurs with an interface that the transmittance decreased as a whole. 作为另一项理由, 一般认为是山结晶结构引起的。 As another reason, generally considered to be caused by mountain crystal structure. 也就是说,在从a到b的状态下,由于以球晶的形成为基础的结晶区域和非晶区域的形成,引起各区域的密度和折射率不同。 That is, in the state from a to b, since formation to form spherulites based crystalline region and an amorphous region caused by the different density and refractive index of each region. 即使在微观方面是均匀的,在光学方面也形成多分子结构,因而 Even in the micro level is uniform, also formed in the optical multi-molecular structures, and thus

21从整体上说使透过率降低。 21 On the whole the decrease in transmittance. 因此,即使没有形成多晶体,也通过在凝胶状态下形成发光膜,使溶胶-凝胶反应不会继续下去而能够以短时间、低能量容易地获得光取出效率高的发光膜。 Therefore, even without forming the polycrystal, but also in the light emitting film is formed by the gel state, the sol - gel reaction and can not continue for a short time, low energy light emitting film easily obtained with high light extraction efficiency.

再者,凝胶状态为含有水合氧化物中的羟基或结晶水的状态,可以推测依其含量的不同,光取出效率将会发生变化。 Furthermore, the gel state containing hydroxyl or hydrous oxide in the state of water of crystallization, presumably according to their different levels of light extraction efficiency will change. 本发明者进行了反复的实验,结果发现:羟基或结晶水的含量占水合氧化物的10重量%或以下时,确认可以获得更高的光取出效率。 The present inventors conducted repeated experiments, and found that: a hydroxyl group or water of crystallization content accounted for 10% by weight of the hydrated oxide or less, confirmation can achieve higher light extraction efficiency. 这样一来,通过设定为含有结晶水的凝胶状态,可以获得致密的膜,而且与完全进行了固化的、实现了结晶化的膜相比,其光的取出效率更好。 Thus, by setting the gel state containing water of crystallization, a dense film can be obtained, but with a completely cured, to achieve crystallization of the film compared to its better light extraction efficiency. 这一般认为是由于在凝胶状态下,水合氧化物具有包含部分氧化物的交联结构,提高了荧光体和元件的粘结性。 It is generally considered that the state in the gel, hydrated oxide having a crosslinked structure comprising portions of the oxide to improve the adhesion and the phosphor elements.

另外,通过采用水合氧化物的凝胶构成粘结剂构件,可以提高形成的发光膜和发光层的品质。 Further, by constituting the hydrous oxide gel binder member, and a light emitting film can improve the quality of the light emitting layer is formed. 含有水合氧化物的粘结剂构件,其粒子状物质通过溶胶-凝胶法来聚集,从而成为形成有交联结构、网状结构或聚合物结构的多孔体。 Hydrous oxide of member contains a binder which the particulate matter by the sol - gel method to aggregate, making a crosslinked structure, a mesh structure or a porous polymer structure is formed.

如果水合氧化物的粒子集合的骨架结构是具有孔隙的网状结构, 则因为是多孔性的结构体而可以提高发光膜的柔软性。 If the particles of the skeleton structure is a set of hydrous oxide network structure having pores, since the structure is porous and can improve the flexibility of the light emitting film. 另外,发光层在成膜时,即使附载着荧光体粒子等填料构件,同时被涂覆的对象形状复杂,也可以与此相适应进行成膜,可以获得富有粘结性的发光股。 Further, when forming the light emitting layer, even if the phosphor particles attached to the filler carrying member, while the complex shape of the object to be coated, may also be adapted to this film formation, adhesive properties can be obtained rich in the light emitting unit. 再者,由于是水合氧化物,因而可以获得对热和光稳定且不变质的膜。 Further, since the hydrated oxide, it is possible to obtain heat and light stabilizers do not deteriorate the film.

形成的发光膜因为曝露在源于发光元件的光中,所以通过发光装置的使用而产生退化。 Because the luminescent film formed from exposure to the light emitting element, so that the degradation is generated by using the light emitting device. 一般认为该退化的原因在于:因源于发光元件的光输出功率和发热之中的任一种或两者而导致反应的发生。 It is generally believed that the cause of the degradation: result from either or both of the optical output power in the light emitting element and the heat caused by the occurrence of the reaction. 因此, 当将光能量高的紫外线用于发热以及热阻抗值大的大型元件时,就容易产生退化。 Thus, when the high-energy ultraviolet light to heat and a large thermal resistance value large member, it is prone to degradation. 正如后面所叙述的那样,制作本发明的实施例的试样进行了耐久试验,结果确认具有极高的耐性。 As later described the above, the present invention produced samples of the examples were endurance test, it was confirmed with a high resistance. 虽然其理由尚不明确,但一般认为原因在于选择了这样一种结构,即具有恒定价数的水合氧化物在热能和光能的作用下,难以发生氧化还原反应。 Although the reason is not clear, but is generally believed that the reason for selecting such a configuration, i.e., having a constant number of pricing hydrated oxides under the action of heat and light, oxidation-reduction reaction is difficult to occur. 因此,优选利用在水合氧化物中价数不会发生变化的金属元素。 Thus, preferably using a metal element that does not change the valence of hydrated oxides. 例如,在使用可以取 For example, in can take

得多种离子价态的Si等作为凝胶或固化膜的情况下,可以推测因光密 More ions have a valence of Si or the like as the case of a gel or a cured film, presumably because the optical density

度和由元件的发热产生的热传导而容易引起价数的变化,因而导致着 And thermal conduction generated by the heat generating element causes a change readily valence, resulting in the

色退化的产生。 Produce color degradation. 与此相对照,以本发明的实施方案得到的3价水合争t 化物为粘结剂的发光层,则难以发生氧化还原反应。 In contrast to trivalent embodiment of the present invention obtained hydrated compound contention t binder light-emitting layer, it is difficult to redox reactions. 因此,本发明的发光装置即使在接触或靠近光照射密度例如为0.1 W/cm2〜1000W/cm2 的高输出功率的半导体发光元件的情况下,也可以具有充分的耐性。 Thus, the light emitting device of the present invention, even in contact with or near the irradiation optical density, for example, at high output power of 0.1 W / cm2~1000W / cm2 in the semiconductor light emitting element may have a sufficient resistance. (粘结剂) (Binder)

作为附载着在高温下或紫外线激发下使用的荧光体的粘结剂,所采用的是二氧化硅(Si02)。 As the binder is attached at a high temperature or carrying UV excitation using the phosphor used it is silica (Si02). 当继续使用二氧化硅粘结剂时,混合冇对发光元件的发光进行转换的荧光体和透光性材料的荧光构件慢慢黑化。 When continuing to use silica binder, mixing Nuisance for converting light emission element and a fluorescent phosphor material is light-transmissive member gradually blackening. 本发明者研究了这样的着色退化的原因,结果查明:其原因在于在二氧化硅粘结层中产生氧的缺损而生成了SiOx (x<2)。 The present inventors have studied the cause of such degradation of the coloring result found that: The reason is that the oxygen defects generated in the adhesive layer and the silicon dioxide generated SiOx (x <2).

二氧化硅粘结剂在25(TC或以下的热固化温度下,呈二氧化硅凝 Silica binder at a thermosetting temperature (TC 25 or less, as a silica agglomerates

胶状,在Si02骨架中残存一部分羟基和有机基团。 Gum, and the remaining part of the hydroxyl groups in the organic backbone Si02. 在这样的二氧化硅 In such silica

凝胶的状态下,当由LED入射高密度的光时,则由光能或热能产牛载的缺损,从而由Si02生成SiOx (x<2: x为1.4〜1.9左右)。 A gel state, when a high-density light from the LED is incident, by light or heat energy contained in cattle production defects, thereby generating a Si02 SiOx (x <2: x is approximately 1.4~1.9). 一般认为因该SiOx被着色而产生黑化。 SiOx is generally believed that because of the coloring blackening. 这样,二氧化硅凝胶一般认为是因为成为主体的金属元素Si可以取得各种价数,Si容易产生价数的变化而发生氧化还原,从而产生着色退化。 Thus, the silica gel is generally considered to be the metal element is Si because the body can be obtained various valence, Si prone to change the valency and oxidation-reduction occurs, resulting in degradation of coloring. 于是,在本发明的实施方案屮, 使用含有金属元素不会发生价数变化的水合氧化物或氧化物的粘结剂。 Thus, in embodiments of the present invention Cao, a binder containing a hydrous oxide or oxide of a metal element does not change in valence. 下面就利用氧化铝、氧化钇的实例进行说明。 Here the use of alumina, yttria examples will be described. (氧化铝) (Alumina)

将无定形氧化铝或微粒子水合氧化铝均匀分散在水中,并将这样形成的氧化铝溶胶用作粘结剂,在这种情况下,在加热氧化铝溶胶而固化形成为具有稳定的勃姆石结构的水合氧化铝之前,经历一个伪勃姆石结构的阶段。 The amorphous alumina or hydrated alumina fine particles uniformly dispersed in water, and the resulting alumina sol as a binder so that, in this case, the heating cures to form an alumina sol having boehmite stable before the structure of hydrated alumina, pseudo-boehmite undergoes phase structure. 水合氧化铝的勃姆石结晶结构和水合氧化铝的伪勃姆石结构可以分别用化学式A100H或A1203 'H20和(A100H) 'xI^O Pseudo-boehmite crystalline structure and a boehmite structure hydrated alumina are hydrated alumina may be a chemical formula A100h or A1203 'H20 and (A100H)' xI ^ O

23或A1203 • 2H20等来表示。 23 or A1203 • 2H20, to present. 具体地说,作为中间体取A1203 • 2H20、 A1203 *xCH3COOH 'yH20、 A1203 'xHCl 'yH20、 A1203 'xHN03 'yH20 More specifically, taking as an intermediate A1203 • 2H20, A1203 * xCH3COOH 'yH20, A1203' xHCl 'yH20, A1203' xHN03 'yH20

等形态,最后形成稳定的勃姆石结构。 Like shape, and finally to form a stable boehmite structure. 进一步提高勃姆石结构的结品性,则成为Y-氧化铝(A1203)或a-氧化铝(A1203)。 Further improve the junction resistance boehmite structure, it becomes Y- alumina (A1203) or a- alumina (A1203). 将具有这样性质的氧化铝溶胶用作粘结剂,从而形成发光膜。 The alumina sol having such properties as a binder, thereby forming a light emitting film.

作为发光膜的具体的主材料,可以使用按如下方法制备的溶胶溶液,即以少量的无机酸、有机酸以及碱为稳定剂,将无定形金属氧化物、超微粒子金属水合氧化物以及超微粒子氧化物等均匀分散在水或有机溶剂中。 Specific examples of the main material of the light emitting film, a sol solution prepared in the following manner, i.e., a small amount of an inorganic acid, organic acid and alkali as a stabilizer, the amorphous metal oxide, metal hydrous oxide ultrafine particles and ultrafine particles oxide uniformly dispersed in water or an organic solvent. 作为合成无定形金属氧化物、超微粒子金属水合氧化物以及超微粒子氧化物等的初始原料,可以利用的有:烷氧基金属、双二酮基金属(metal diketonate)、金属卤化物、或金属羧酸盐、金属烷基化合物的水解产物以及将它们混合后进行水解的产物。 As the synthetic amorphous metal oxide starting materials for ultrafine particles and the metal oxide ultrafine particles of hydrous oxides and the like, may be utilized are: metal alkoxide, double metal-dione (metal diketonate), metal halides, metal, or hydrolyzate carboxylates, and metal alkyl compounds will be hydrolyzed after they were mixed. 另外,也可以使用将金属氢氧化物、金属氯化物、金属硝酸盐以及金属氧化物微粒子均匀分散在水和有机溶剂、或者水和水溶性有机溶剂的混合溶剂中所制备的胶体(溶胶)溶液。 It is also possible to use colloidal (sol) mixed solvent of a metal hydroxide, a metal chloride, metal nitrate and metal oxide fine particles uniformly dispersed in an organic solvent and water, or water and a water-soluble organic solvent solution prepared . 它们总称为铝氧烷。 They are collectively referred to as aluminoxane. 铝氧烷的'it架中具有[AlO]x的重复单元。 Aluminoxane 'it rack having the repeating unit [AlO] x a.

作为烷氧基金属,可以利用的有:甲氧基铝、乙氧基铝、正丙試基铝、异丙氧基铝、正丁氧基铝、仲丁氧基铝、异丙氧基铝、叔丁氧 As the metal alkoxide, can be used are: aluminum methoxide, aluminum ethoxide, aluminum n-propyl group test, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum isopropoxide , tert-butoxy

基铝、甲氧基钇、乙氧基钇、正丙氧基钇、异丙氧基钇、正丁氧基钇、 仲丁氧基钇、异丙氧基钇、叔丁氧基钇等。 Aluminum group, a methoxy group yttrium, yttrium ethoxy, n-propoxy, yttrium, yttrium isopropoxy, n-butoxy, yttrium, sec-butoxy, yttrium, yttrium isopropoxy, tert-butoxy and yttrium.

作为双二酮基金属,可以利用的有:三乙基乙酰乙酸铝、烷基乙酰乙酸二异丙氧基铝、乙基乙酰乙酸二异丙氧基铝、单乙酰基丙酮酸双乙基乙酰乙酸铝、三乙酰基丙酮酸铝、三乙酰基丙酮酸钇以及三乙基乙酰乙酸钇等。 As the double metal-dione, may be utilized are: acetyl triethyl aluminum acetate, alkyl acetoacetate aluminum diisopropoxy ethyl acetoacetate, diisopropoxy aluminum, mono- acetylacetonate bis ethylacetoacetate aluminum acetate, aluminum triacetylacetonate, triacetylacetonate yttrium and yttrium acetyl triethyl acetate.

作为金属羧酸盐,可以利用的有:醋酸铝、丙酸铝、2-乙基己酸铝、醋酸钇、丙酸钇以及2-乙基己酸钇等。 As the metal carboxylate, may be utilized are: aluminum acetate, aluminum propionate, aluminum 2-ethylhexanoate, yttrium acetate, propionate, 2-ethylhexanoate, yttrium and yttrium.

另外,作为金属卤化物,可以利用的有:氯化铝、溴化铝、碘化铝、氯化钇、溴化钇以及碘化钇等。 Further, as the metal halides, may be utilized are: aluminum chloride, aluminum bromide, aluminum iodide, yttrium chloride, yttrium bromide, yttrium iodide, and the like.

24作为有机溶剂,可以利用的有:甲醇、乙醇、正丙醇、异丙醇、 正丁醇、仲丁醇、叔丁醇、四氢呋喃、二噁烷、丙酮、乙二醇、甲乙酮、N,N-二甲基甲酰胺以及N,N-二甲基乙酰胺等。 24 The organic solvent can be used are: methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, tetrahydrofuran, dioxane, acetone, ethylene glycol, methyl ethyl ketone, N, N- dimethylformamide and N, N- dimethylacetamide and the like.

作为形成发光层的粘结剂加以使用的除了这些以外,也可以混合作为填料的荧光体和扩散粒子。 As the binder forming the light emitting layer to be used in addition to these, may be mixed as a filler and diffusing the phosphor particles. 再者,作为它们的复合体,也可以使 Moreover, as their complexes, can also

基体和发光元件的线膨胀系数保持一致。 Linear expansion coefficient of the base body and the light emitting element consistent. 作为填料,混入荧光体而产生发光自不必说,同时还产生出固化时的水分蒸发等的微细通路,具有加快粘结剂的固化干燥的效果。 As the filler, is mixed to produce the luminescence phosphor Needless to say, and also produce a fine passage of water evaporation during curing, the adhesive has cured to accelerate the drying effect. 另外,还具有将荧光体的发光扩散开来、增加发光层的粘结强度和物理强度的作用。 Further, the light emitting phosphor having the spread, the effect of increasing the bonding strength of the light emitting layer and physical strength. 此外,发光层和发光膜也可以作为不含荧光体的扩散层加以使用。 Further, the light emitting layer and the light emitting film may also be used as the diffusion layer does not contain a phosphor. 另外,在作为粘结剂加以使用的复合材料中,除3价金属元素以外,也可以少量含有具有多种价数的元素。 Further, to be used as a binder in the composite material, in addition to trivalent metal element, may contain a small amount of an element having a plurality of valences. 再者,粘结剂构件可以包含水合氧化物作为主要的化合物,即使包含一部分金属氧化物和金属氢氧化物以及它们的结合也可以发挥作用。 Further, the adhesive member may comprise a hydrated oxide as a main compound, even if it contains a portion of the metal oxides and metal hydroxides, and combinations thereof may also play a role. (填料) (filler)

填料就是填充剂,可以利用的有:钛酸钡、氧化钛、氧化铝(三氧化二铝)、氧化钇(三氧化二钇)、二氧化硅、碳酸钙以及其它水合氧化物等。 Filler is a filler, may be utilized are: barium titanate, titanium oxide, aluminum oxide (alumina), yttrium oxide (yttria), silica, calcium carbonate and other hydrous oxide. 例如,也可以有相对于至少包含选自Al、 Ga、 Ti、 Ge、 P、 B、 Zr、 Y或碱土金属之中的一种或多种元素的无色水合氧化物、 或至少包含选自Si、 Al、 Ga、 Ti、 Ge、 P、 B、 Zr、 Y或碱土金属之屮的一种或多种元素的氧化物具有更高热传导系数的填料。 For example, there may be selected with respect to at least comprising Al, Ga, Ti, among Ge, P, B, Zr, Y, or an alkaline earth metal is one or more elements as a colorless hydrated oxide, or selected from the group comprising at least si, oxide of Al, Ga, Ti, Ge, P, one kind of B, Zr, Y, or an alkaline earth metal Che or more elements of a filler having a higher thermal conductivity coefficient. 通过添加这样的填料,发光装置的排热效果得以提高。 By adding such a filler, the effect of exhaust heat emitting device is improved. 作为这样的填料,在釆用上述无机粘结剂形成粘结层而对LED芯片进行芯片焊接(die bond) 时,可以列举出氧化铝、Ag等金属粉。 As such fillers, when the die-bonding the LED chips (die bond) preclude the adhesive layer is formed by the inorganic binder include alumina, Ag metal powder and the like.

在粘结剂的溶胶中,除荧光体及低级醇之外,通过事先混合分散剂,可以借助于固化时与低级醇的共沸脱水在低温形成致密的涂膜。 In the sol binder, in addition to the phosphor and a lower alcohol, by previously mixing the dispersant, when cured by means of azeotropic dehydration with a lower alcohol to form a dense film at low temperature. 另外,也可以含有光稳定化材料、着色剂以及紫外线吸收剂等。 In addition, it may contain a light stabilizer material, a coloring agent and an ultraviolet absorber.

进而在形成发光膜时,也可以添加硼酸和氧化硼。 Further, in forming a light emitting film, it may be added to boric acid and boron oxide. 由于硼酸和氧化硼的添加,导致发光膜的弹性降低,所以膜的品质得以提高。 Due to the addition of boric acid and boron oxide, resulting in the elastic light emitting film decreases, the film quality is improved. 例如可以抑制发光膜的裂纹的产生并形成致密的膜。 Generation of cracks can be suppressed, for example, the light emitting film is formed and a dense film. 硼酸和氧化硼相对于 Boric acid and boron oxide with respect to

粘结剂构件优选含有0.5重量%〜50重量%。 The binder component preferably contains ~ 50 wt%, 0.5 wt.%. 再者,在发光膜中,也可以添加除硼酸和氧化硼以外的增粘剂。 Further, in the light emitting film, a tackifier may be added in addition to boron oxide and boric acid. 这样一来,作为粘结剂构件, 除铝等水合氧化物以外,也可以含有用于控制料浆粘度的添加剂。 Thus, as the binder component, other than aluminum hydrous oxide and the like, it may also contain additives for controlling the viscosity of the slurry. 因此,在成膜时控制粘度、提高触变性,便可以成形出形状复杂的膜。 Thus, during the film formation to control the viscosity, to improve thixotropy, can complicated shapes formed film. 另外,在膜形成后,由于粘结剂是水合氧化物,因而可以提高对添加剂的许用能力,而且可以在控制粘结剂结构体的结构方面发挥作用。 Further, after the film formation, because the binder is hydrous oxide, the additives can be improved for the allowable capacity, and may play a role in the control structure of a binder structure.

发光层用料浆溶液来形成。 The light emitting layer is formed with a slurry solution. 料浆溶液是这样调制而成的,即以无定形金属水合氧化物、微粒子金属水合氧化物以及金属氢氧化物为主要成分,将该主要成分进而将无定形金属氧化物、微粒子金属氧化物均匀分散在水中,由此制得溶胶溶液,然后在该溶胶溶液中,混合荧光体和填料。 The slurry solution thus prepared is formed, i.e. an amorphous hydrated metal oxide, metal hydrous oxide fine particles and a metal hydroxide as a main component, the main component of the amorphous metal oxide and further, the metal oxide fine particles uniformly dispersed in water, thereby preparing a sol solution, and then the sol solution, the mixed phosphor and a filler. 溶胶溶液中的有效固体成分与荧光体的重量比、或者溶 The weight ratio of the sol solution of the solid active ingredient with the phosphor, dissolving or

胶溶液中的有效固体成分与荧光体和填料混合物的重量比优选为0.05〜30。 By weight of active ingredient and solid filler mixture of the phosphor in the gum solution is preferably from 0.05~30. 例如可以在相对于20g有效固体成分浓度为15%的溶胶溶液、荧光体为90g到相对于600g有效固体成分浓度为15%的溶胶溶液、荧光体为4.5g的比率范围内进行调整。 90g may be, for example, with respect to 600g active solid content concentration of 15% in the sol solution 20g of the effective concentration of the solid content of 15% with respect to the sol solution, the phosphor, the phosphor is adjusted within a ratio range of 4.5g. (氧化钇) (Yttrium oxide)

将无定形氧化钇或微粒子氧化钇均匀分散在水中,并将这样形成的氧化钇溶胶用作粘结剂,在这种情况下,即使加热固化氧化钇溶胶, 结晶结构的主体也是无定形。 Amorphous yttrium oxide or yttrium oxide particles uniformly dispersed in water, and the resulting yttrium oxide sol such as a binder, in this case, even if the heat curing yttria sol, the main crystal structure is amorphous. 水合氧化钇和氧化钇可以分别用YOOH • xH20和Y203 "xH20等化学式来表示。具体地说,作为中间体,经过YOOH • xCH3COOH , yH20或Y203 • xCH3COOH • yH20 的形态,最后形成为部分含有水合氧化钇或氧化钇的形式。氧化钇即使在这样的凝胶状态下也可以形成稳定的膜。 一般认为其原因在于各自的成分具有交联结构,可以实现稳定化。 Hydrous yttrium oxide and yttrium oxide can be respectively YOOH • xH20 and Y203 "xH20 chemical formula. In particular, as an intermediate, after YOOH • xCH3COOH, yH20 form or Y203 • xCH3COOH • yH20 finally formed containing partially hydrated in the form of yttrium oxide or yttrium oxide. yttria even in such a stable gel state may be formed of a film is generally believed that the reason is that each component having a crosslinked structure, can be stabilized.

氧化钇与氧化铝相比,具有难以形成结晶结构的性质。 Compared with yttria alumina, it has a property difficult to form a crystalline structure. 这样一来, 即使是不具结晶性的无定形的非晶结构也可以是稳定的化合物,Y保持3价不变而不会发生价数的变化。 Thus, even if the amorphous non-crystalline amorphous structure may be a stable compound, Y remains unchanged trivalent valence number change does not occur. 即具有的长处是难以发生氧化还原反应,没有着色退化。 I.e., it is difficult to have strengths redox reaction, no coloring degradation.

关于其它,则是与上述的氧化铝一样地形成发光层。 On the other, are formed in the same manner as the above-described light-emitting layer of alumina. 正如以上所叙述的那样,荧光体作为粘结剂加以使用的溶胶,也可以利用市售的无机系粘结剂和陶瓷粘结剂等。 As described above, as the phosphor to be used as a binder sol, it may be a commercially available inorganic binders and ceramic adhesive or the like. 此外,在可以作为粘结剂加以利用的材质中,并不限于氧化铝和氧化钇之类的含有Al和Y元素的水合氧化物,也可以利用其它的IIlA族元素和niB族元素的水合氧化物、氧化物以及氢氧化物等。 Further, the can be utilized as a binder material, it is not limited to the hydrated oxide aluminum and yttrium oxide containing Y and Al elements, may be utilized hydrated oxide of other elements IIlA group element and niB , oxides and hydroxides. 选择的金属元素优选不会发生价数变化。 The metal element is preferably selected valence change does not occur. 特别地,优选的是表现为3价且稳定的金属元素。 In particular, it is preferable that the stable performance of trivalent metal element. 另外,也优选是无色透明的。 In addition, it is also preferably transparent and colorless. 例如除A1和Y之外,还可以利用包含Gd、 Lu、 Sc、 Ga以及In等金属元素的金属化合物,优选可以利用Sc和Lu。 For example, in addition to A1 and Y, it can be utilized further comprising Gd, metal compound Lu, Sc, Ga, and In like metal element, and preferably may be utilized Sc Lu. 或者也可以利用将多种的这些元素进行组合的复合氧化物和复合水合氧化物。 Or you may be using a plurality of composite oxides of these elements in combination, and a composite hydrous oxide. 不单是铝和钇,通过含有其它III族元素的水合氧化物等,也可以将发光股的折射率等光学性能以及膜的柔软性、粘结性等膜的物性之类的各种特性控制为所希望的值。 Not only is aluminum, and yttrium oxide and the like by hydration contain other group III elements may be various properties was Softness Unit emitting optical refractive index and film properties, adhesion and other film or the like is controlled to desired value. 这样一来,通过具有由本发明的实施方案得到的含有价数恒定、优选为3价的水合氧化物凝胶的无机粘结剂,所形成的发光层可以设计为稳定、光取出效率良好的发光层。 Thus, by having a constant-containing monovalent obtained by embodiments of the present invention, the number of, preferably an inorganic binder trivalent hydrated oxide gel, a light emitting layer is formed may be designed to stabilize, good light extraction efficiency of the light emitting Floor. 另外,山于用无机材料构成,因此可以制成不随时间变化的、稳定的发光层与发光膜。 Further, the inorganic material constituting the mountain, and therefore may be made not change with time, stable emission layer and the light emitting film.

实施方案l L embodiment

下面采用图2就本发明的实施方案1的发光装置进行说明。 2 will be described below embodiments of the light emitting device 1 of the present invention using FIG. 实施方案1的发光装置包括:发光元件10,由荧光体1 la和包含荧光体1 la 的透光性粘结剂llb构成的荧光构件ll。 1 embodiment, a light emitting device comprising: a light emitting element 10, a fluorescent member ll made of a phosphor and the translucent adhesive llb La contains La in phosphor 1.

用炮弹型的LED构成的发光元件10焊接在罩体(cup)的大致中央部位并由该罩体所承载,其中罩体配置在管脚引线(mount lead) 13a 的上部。 The light emitting element 10 is welded with a bullet-shaped LED constituting a substantially central portion in the cover body (Cup) is carried by the cover, wherein the cover body is arranged in an upper pinouts (mount lead) 13a of. 发光元件10上形成的电极通过导电性引线14与引线框(lead frame) 13的管脚引线13a以及内部引线(inner lead) 13b进行电连接。 Electrodes formed on the light emitting element 10 and the inner lead pin lead 13a (inner lead) 13 are electrically connected through 13b of the conductive leads 14 of the lead frame (lead frame).

27荧光体lla含有YAG系荧光体和氮化物系荧光体,这些荧光体吸收发光元件10发出的光的至少一部分,同时发出不同于吸收光波长的光。 27 containing the phosphor lla YAG phosphor and the nitride-based phosphor, at least a portion of the light emitted by these phosphors absorbing a light emitting element 10, and emits light of a different wavelength of light absorption. 再者,氮化物系荧光体可以用微胶囊等覆盖材料覆盖起来。 Further, the nitride-based phosphor may be covered up with a microcapsule coating material. 在粘结剂lib中含有该荧光体lla的荧光构件11配置在承载发光元件10的罩体上。 Phosphor member containing the phosphor in the binder lla lib, the cover 11 is disposed on the light emitting element 10 of the carrier. 这样,为了保护LED芯片和荧光体免受外部应力、水分以及尘垢的侵害,以及为了改善光的取出效率,配置发光元件IO和荧光构件11的引线框13被模压在铸模构件15中,从而形成发光装置。 Thus, in order to protect the LED chip and the phosphor from external stress, moisture and dust violations, as well as to improve the light extraction efficiency, a light emitting element disposed IO and the lead frame 11 of the fluorescent member 13 is molded in the mold member 15, so as to form the light emitting device. 这样一来,在形成含有由水合氧化物构成的粘结剂的发光层后,也可以以树脂制铸模的形式形成透镜等。 Thus, after forming the light emitting layer contains a binder made of hydrated oxide, and the like may be formed in the form of a lens made of a resin mold. (发光元件) (Light emitting element)

在本说明书中,所谓发光元件除半导体发光元件以外,还包括用于获得由真空放电产生的发光、以及由热发光产生的发光的元件。 In the present specification, the term light-emitting element other than the semiconductor light emitting element further includes means for obtaining light emission discharge is generated by a vacuum, and the light emitting element is generated by thermal emission. 例如,由真空放电产生紫外线等的元件也可以用作发光元件。 For example, vacuum ultraviolet rays are generated by a discharge element or the like may be used as the light emitting element. 在本发明的实施方案中,作为所利用的发光元件,其波长为550nm或以下,优选为460nm或以下,进一步优选为410nm或以下。 In an embodiment of the present invention, the light-emitting element utilized, a wavelength of 550nm or less, preferably 460nm or less, and further preferably 410nm or less. 例如可以加以利用的有:作为紫外光发出波长为250nm〜365nm的光的紫外光LED和波长为253.7nm的高压水银灯。 For example there may be utilized: As emits ultraviolet light having a wavelength ultraviolet LED 250nm~365nm a high pressure mercury lamp and a wavelength of 253.7nm. 特别地,正如后面所叙述的那样,本发明的实施例所具有的优点是:耐久性优良,可以适用输出功率大的动力型发光元件。 In particular, as is described later, embodiments of the present invention has advantages are: excellent durability, a large power can be applied to the light emitting element output power type.

下面说明将III族氮化物系半导体发光元件用作发光元件10的实例。 The following description will be based Group III nitride semiconductor light-emitting element as a light emitting element of Example 10. 发光元件IO例如是在蓝宝石基板上、隔着GaN缓冲层依次层叠下列层所形成的层叠结构,这些层依次为:未掺杂Si或Si浓度低的第1 n型GaN层;由掺杂Si或Si浓度比第1 n型GaN层更高的n型GaN构成的n型接触层;未掺杂或Si浓度比n型接触层更低的第2 GaN层;多重量子阱结构的发光层(GaN阻挡层/InGaN阱层的量子阱结构);由P型GaN构成的p包层,其中P型GaN由掺杂Mg的P型GaN构成;由掺杂Mg的P型GaN构成的P型接触层。 IO emitting element, for example, on a sapphire substrate, a GaN buffer layer are stacked via structure formed by laminating the following layers, these layers are as follows: a low concentration of 1 n-type GaN layer of undoped Si or Si; Si doped or n-type contact layer composed of Si concentration higher than the first n-type GaN n-type GaN layer; undoped Si or a lower concentration than the n-type contact layer of GaN layer 2; a light emitting layer of multiple quantum well structure ( quantum well layer / InGaN well layer is GaN barrier); P P-type clad layer made of GaN, wherein the P-type GaN Mg-doped P-type GaN; P-type contact Mg-doped P-type GaN Floor. 并按下述的方法形成电极。 Forming an electrode in accordance the following method. 当然,也可以使用不同于该构成的发光元件。 Of course, different from the configuration of the light emitting element may be used.

28P欧姆电极几乎在P型接触层的整个面上形成,在一部分该P欧 28P ohmic electrode almost the entire surface of the P-type contact layer is formed in a part of the European P

姆电极上形成p焊盘电极(padelectrode)。 Ohmic electrode are formed p-pad electrode (padelectrode) on.

另外,通过浸蚀从P型接触层除去第1 GaN层而露出n型接触层的一部分,n电极便在该露出部分上形成。 Further, removing by etching the first layer is from 1 GaN P-type contact layer to expose a portion of the n-type contact layer, n electrodes will be formed on the exposed portion.

此外,本实施方案使用多重量子阱结构的发光层,但本发明并不限定于此,例如利用InGaN的单量子阱结构和多重量子阱结构都可以,也可以利用掺杂Si和Zn的GaN。 Further, the present embodiment uses a light emitting layer of multiple quantum well structure, but the present invention is not limited thereto, for example using a single quantum well structure and multiple quantum well structure of InGaN may be, may be doped with Si and Zn using GaN.

另外,发光元件10的发光层通过改变In的含量,可以在420nm〜490nm的范围内改变主发光峰。 Further, the light emitting layer of the light emitting element 10 by changing the content of In, may be varied within the scope of the main emission peak of 420nm~490nm. 而且发光波长并不限于上述范围,口T以使用发光波长为360nm〜550nm的发光元件。 But is not limited to the above-described emission wavelength range, port T is a light-emitting wavelength of the light emitting element 360nm~550nm. 特别地,当将本发明的实施方案的发光装置适用于紫外光LED发光装置时,可以提高激发光的吸收转换效率,可以降低紫外光的透过。 Particularly, when the light emitting device according to the embodiment of the present invention is applied to an ultraviolet LED light-emitting device, it can increase the absorption efficiency of the excitation light can be reduced through the ultraviolet light. (荧光体) (Phosphor)

荧光体将从发光元件发出的可见光和紫外光转换为其它波长的发光。 Visible and ultraviolet light from the light emitting element emits a phosphor converted light emitting other wavelengths. 例如,用从LED的半导体发光层发出的光进行激发以产生其它波长的发光。 For example, the excitation light emitted from the LED with a semiconductor light-emitting layer to produce light emission at other wavelengths. 作为优选的荧光体,可以利用的有:YAG系、碱土类氮化硅荧光体等氮化物系、碱土类氧化氮化硅荧光体等氧氮化物系。 Preferred phosphors may be utilized are: YAG nitride-based oxynitride-based, alkaline earth silicon nitride fluorescent material, alkaline earth silicon oxynitride-based fluorescent material thereof. 在本实施方案中,作为荧光体使用的是由紫外光激发产生预定颜色的光的荧光体。 In the present embodiment, it is used as a phosphor excited by ultraviolet light to produce a predetermined color phosphors. 具体地说,可以利用的荧光体举例如下: Specifically, the phosphor can be utilized for example as follows:

(1) Ca10(PO4)6FCl: Sb, Mn (1) Ca10 (PO4) 6FCl: Sb, Mn

(2) M5(P04)3C1: Eu (其中:M为选自Sr、 Ca、 Ba以及Mg之中的至少一种) (2) M5 (P04) 3C1: Eu (wherein: M is at least one selected from among Sr, Ca, Ba and Mg)

(3) BaMg2All6027: Eu (3) BaMg2All6027: Eu

(4) BaMg2Al16027: Eu, Mn (4) BaMg2Al16027: Eu, Mn

(5) 3.5MgO • 0.5MgF2 • Ge02: Mn (5) 3.5MgO • 0.5MgF2 • Ge02: Mn

(6) Y202S: Eu (6) Y202S: Eu

(7) Mg6As2Ou: Mn (7) Mg6As2Ou: Mn

(8) Sr4Al14025: Eu (8) Sr4Al14025: Eu

29(9) (Zr、 Cd)S: Cu 29 (9) (Zr, Cd) S: Cu

(10) SrAl204: Eu (10) SrAl204: Eu

(11) Ca10(PO4)6ClBr: Mn, Eu肪Zn2Ge04: Mn (11) Ca10 (PO4) 6ClBr: Mn, Eu fatty Zn2Ge04: Mn

03) Gd202S: Eu 03) Gd202S: Eu

(14) U202S: Eu (14) U202S: Eu

(15) Ca2Si5N8: Eu(1© Sr2Si5N8: Eu(17) SrSi202N2: Eu(恥BaSi202N2: Eu (15) Ca2Si5N8: Eu (1 © Sr2Si5N8: Eu (17) SrSi202N2: Eu (shame BaSi202N2: Eu

另外,除上述荧光体以外,毫无疑问,也可以利用产生黄色区域的发光的、用(Y, Gd)3(Al, Ga)5Ol2: Ce等表示的稀土类铝酸盐即YAG系荧光体。 Further, in addition to the phosphor, no doubt, may also be utilized to produce a yellow light emitting region, with (Y, Gd) 3 (Al, Ga) 5Ol2: Ce and other rare-earth aluminate represented by the YAG phosphor i.e. .

当LED芯片发出的光和荧光体发出的光成互补颜色关系等时,通过将各自的光混色便可以发出白色的光。 When the light in a complementary color relationship phosphor LED chip emits light emitted by the respective light color mixing can emit white light. 具体地说,可以列举出LED芯片发出的光和由该光激发而发光的荧光体的光分别相当于3原色(红色系、绿色系、蓝色系)的情况、以及LED芯片发出的蓝色光和 Specifically, the light may include light emitted from the LED chip and excited by the light emitting phosphors correspond to the case of the three primary colors of blue light (red, green-based, blue), and the LED chip emits with

由该光激发而发光的荧光体的黄色光。 Excited by the light and yellow light emitting phosphor. 特别是在使用紫外光的情况下,因为可以单独利用由紫外光激发发光的荧光体的发光颜色,因而获得 Especially in the case of using ultraviolet light, the emission color can be utilized as a phosphor excited by ultraviolet light to emit light singly, thus obtaining

信号用的蓝绿色、黄红色、红色等以及浅色等各种中间色的发光装置也是可能的。 Signal for the cyan, yellow, red and other light emitting devices other intermediate colors are possible.

通过对作为荧光体与荧光体之间的粘结剂发挥作用的各种树脂和玻璃等无机粘结构件、与填料等的比率、荧光体的沉降时间、荧光体的形状等进行各种调整以及对LED芯片的发光波长进行选择,发光装置的发光颜色可以提供灯泡颜色(electric bulb color)等任意的白色系的色调。 Various settling time is adjusted by the ratio of various binder resins and inorganic glass member functions as a binder between the phosphor and the phosphor, the filler, etc., phosphors, and the like, and the shape of the phosphor the emission wavelength of the LED chip is selected, the color of the light emitting device can provide the light emitting lamp colors (electric bulb color) hue and the like of any of the white-based. 在发光装置的外部,优选LED芯片发出的光和和荧光体发出的光有效地透过铸模构件。 Light external light and the phosphor, the light emitting device of the LED chips emit efficiently emitted through the mold member.

作为有代表性的荧光体,可以列举出用铜活化的硫化镉锌和用铈活化的YAG系荧光体。 As a representative of the phosphor can include cadmium zinc sulfide activated with copper and cerium-activated YAG phosphor. 特别在高辉度且长时间使用时,优选的是(ReLxSmx) 3 (Ah.yGay) 50i2: Ce (0《x<l, 0《y《l,其中:Re 是选自Y、 Gd、 La以及Lu之中的至少一种元素。 Particularly at high luminance and a long time, it is preferable that (ReLxSmx) 3 (Ah.yGay) 50i2: Ce (0 "x <l, 0" y "l, wherein: Re is selected from Y, Gd, La and at least one element of Lu.

(Rei.xSmx) 3 (Al!.yGay) 5012: Ce荧光体因为是石榴石结构,所以对热、光以及水分具有很强的耐性,激发谱峰可以达到470nm左右。 (Rei.xSmx) 3 (! Al .yGay) 5012: Ce phosphor as garnet structure, has a strong resistance to heat, light and moisture may reach peak excitation 470nm. 另外,也可能具有宽的发光谱,其发光峰在530nm附近,峰的末端延伸到720nrn处。 Further, it may also have a broad emission spectrum, the emission peak at 720nrn extending into, the end of the peak near 530nm.

在本发明的实施方案的发光装置中,荧光体也可以是2种或更多种荧光体混合而成的。 In an embodiment of the light emitting device of the present invention, the phosphor may be two or more kinds of phosphors are mixed. 即可以将2种或更多种Al、 Ga、 Y、 La、 Lu 以及Gd和Sm的含量不同的(Re,.xSmx) 3 (A"Gay) 5012: Ce变光体进行混合,从而增加RGB的波长成分。另外,使用具有黄〜红色发光的氮化物荧光体等增加红色的成分,也可以获得平均演色评价指数高的照明或灯泡颜色的LED等。具体地说,混配发光元件的发光波长,调整CIE色度图上的色度点不同的荧光体的含量,藉此可以发出色度图上任意点的光,其中色度图用发光元件将该荧光体之间连接起来。 I.e., it may be two or more different kinds of Al, Ga, Y, La, Lu and Gd and Sm content (Re, .xSmx) 3 (A "Gay) 5012: Ce were mixed variant light, thereby increasing the RGB wavelength components. in addition, the nitride fluorescent material having a yellow-to-red emitting red component is increased, it can be obtained a high average color rendering index of LED lighting color of the lamp or the like. specifically, the light emitting element emitting compounding wavelength, the content of different points on the adjustment of chromaticity CIE chromaticity chart of the phosphor, whereby light can be emitted at any point on the chromaticity diagram, the chromaticity diagram wherein the light-emitting element is connected between the phosphor up.

这样荧光体可以分散在气相和液相中并均匀地发光。 Such a phosphor may be dispersed in the gas phase and the liquid phase and uniformly emit light. 分散在气相和液相中的荧光体因自身的重量而下降。 Phosphor is dispersed in the gas and liquid phases due to its own weight decreases. 特别在液相中,通过使悬浊液静置,可以形成具有均一性更高的荧光体的膜。 Particularly in the liquid phase, by allowing the suspension to stand, a film may be formed of a phosphor having a higher uniformity. 根据要求进行多次反复,由此可以形成所要求的荧光体量。 Repeatedly performed according to the requirements, whereby the amount of the fluorescent body may be formed as required.

在发光装置的表面上,像以上那样形成的荧光体可以在由一层构成的发光层中存在二种或更多种,也可以在由二层构成的发光层屮分别存在一种、二种或更多种。 On the surface of the light emitting device, the phosphor is formed as described above there may be two or more light emitting layer composed of one layer, or may be in the presence of a luminescent layer comprising two layers, respectively Cao, two kinds of or more. 这样一来,通过源于不同荧光体的光的混色可以得到白色光。 Thus, it is possible to obtain white light by mixing light from different phosphors. 此时,为了使各荧光体发出的光更好地混色并减少颜色不均,优选各荧光体具有类似的平均粒径和形状。 In this case, in order to make each of the light emitted by the phosphor better color mixing and reduced color unevenness, preferably each phosphor has a similar average particle size and shape. 另外,也可以考虑受形状影响的沉降特性来形成发光层。 Further, the light emitting layer may be formed also conceivable characteristics influenced by the shape of the settlement. 作为不容易受沉降特性影响的发光层的形成方法,可以列举出喷涂法、丝网印刷法以及浇灌法等。 As a method of forming a light emitting layer is not susceptible to sedimentation characteristics can include a spray method, a screen printing method and the watering method. 在本实施方案中,无机粘结剂可以具有1%〜80%的有效固体 In the present embodiment, the inorganic binder may have a 1% ~ 80% of active solids

31成分,可以在lcps〜5000 cps的宽范围内进行粘度调整,而且也可以调整触变性,所以,能够与这些发光层的形成方法相适应。 Component 31 may be within a wide range lcps~5000 cps of a viscosity modifier, thixotropic but may be adjusted, it is possible to adapt the method of forming the light emitting layer. 如上所述, 填料和无机粘结剂的重量比优选设定为0.05〜30的范围,另外,通过调整填料的配合量和粒径来增强粘结力。 As described above, the weight ratio of inorganic binder and a filler preferably in the range of 0.05~30, further, to enhance the adhesion by adjusting the amount and particle size of the filler.

本实施方案中使用的荧光体也可以将YAG系荧光体、可能发出红色系光的荧光体、特别是碱土类氮化硅荧光体等氮化物荧光体组合起来加以使用。 Phosphor used in the present embodiment may be a YAG-based phosphor, nitride phosphor may emit red light of the phosphor, especially the alkaline earth silicon nitride fluorescent material to be used in combination. 这些YAG系荧光体以及荧光体可以混合并包含在发光层中,也可以分别包含在由多层构成的发光层中。 These YAG-based phosphor and a phosphor may be mixed and contained in the light emitting layer, it may be included in the light emitting layer composed of a plurality of layers, respectively. 下面就各自的荧光体进行详细的说明。 The following detailed description on their respective phosphor. (YAG系荧光体) (YAG-based phosphor)

所谓本实施方案使用的YAG系荧光体是用铈或Pr等稀土类元素活化的荧光体,它含有Y和Al,并且含有选自Lu、 Sc、 La、 Gd、 Tb、 Eu以及Sm之中的至少一种元素和选自Ga以及In之中的一种元素, 是受LED芯片发出的可见光或紫外线激发而发光的荧光体。 The so-called YAG fluorescent material used in the present embodiment is cerium or other rare earth element activated Pr phosphor which contains Y and Al, and contains selected from among Lu, Sc, La, Gd, Tb, Eu and Sm, and at least one element selected from Ga and one element of in, by visible light or ultraviolet light is emitted from the LED chip and emitting light excited the phosphor. 特别在本实施方案中,也可以利用用铈或Pr活化的、组成不同的2种或更多种钇•铝氧化物系荧光体。 In this particular embodiment, may also be used with Ce or Pr is activated to form two or more different kinds • yttrium aluminum oxide phosphor. 如果将使用氮化物系化合物半导体作为发光层的发光元件发出的蓝色系光、和由因吸收蓝色光而体色(body color) 呈黄色的荧光体发出的绿色系以及红色系光、或者为黄色系光但史接近绿色系和更接近红色系的光混合显示出来,则可以显示出所要求的白色系发光色。 If the nitride-based compound semiconductor as a light greenish blue and red light, and blue light due to absorption by the body color (body color) as a yellow light emitting phosphor layer is emitted from the light emitting element is emitted, or a yellowish green light but the history-based and closer proximity mixing red light is displayed, it may exhibit a desired luminescent color including white. 发光装置因为产生混色,所以也可以在环氧树脂、丙烯酸树脂或硅树脂等各种树脂和本实施方案的无机粘结剂之类的透光性无机物中含有荧光体的粉体和块。 Because the color mixture light emitting apparatus, the block may contain a phosphor powder and a translucent inorganic material in an inorganic binder of various resins epoxy, acrylic or silicone and the like of this embodiment of the class. 这样,含有荧光体的发光层可以根据荧光体呈点状或呈层状等用途而以各种方式使用,其中发光层形成得较薄,足以使LED芯片发出的光得以透过。 Thus, a light emitting layer containing a phosphor may be used in various ways according to the fluorescent material has a layered dot or other purposes, wherein the light emitting layer is formed thin enough to allow light emitted from the LED chip is transmitted. 通过对荧光体和透光性无机物的比率和涂布、填充量进行各种调整以及对发光元件的发光波长进行选择,可以提供包括白色在内的灯泡颜色等任意的色调。 And by coating ratio, filling amount of the phosphor and the translucent inorganic material and make various adjustments to the emission wavelength of the light emitting element is selected may be provided in any color including white bulb color.

另外,相对于源于发光元件的入射光,各自按顺序配置2种或更多种荧光体,由此可以获得能够有效发光的发光装置。 Further, with respect to the incident light from the light emitting element, each arranged in the order of two or more kinds of fluorescent material, thereby obtaining a light-emitting device can efficiently emit light. 也就是说,在 In other words,

32具有反射构件的发光元件上,以层叠等方式配置含有在长波长侧有吸收波长且可以发出长波长光的荧光体的颜色转换构件即含有荧光体作为填料的发光层、以及较之于该发光层在更长的波长侧有吸收波长且可以发出更长波长的光的颜色转换构件,藉此可以有效利用反射光。 32, the light emitting element having a reflection member, arranged in a stacked like color conversion member contains a phosphor absorption wavelengths and may emit long wavelength light, i.e., light emitting layer containing a phosphor as a filler in the long-wavelength side, and compared to the a longer wavelength light-emitting layer side and the absorption wavelength of the color conversion member can emit light in a longer wavelength, whereby the reflection light can be effectively utilized.

如果使用YAG系荧光体,那么即使以接触或靠近的方式配置辐射光密度为0.1W'cm'2〜1000 W'cn^的LED芯片,也可以获得高效率且具有充分耐光性的发光装置。 If a YAG-based phosphor, even if in contact or close to the density of radiation arranged 0.1W'cm'2~1000 W'cn ^ LED chip, high efficiency can be obtained having sufficient light resistance and a light emitting device.

本实施方案使用的用铈活化的钇•铝氧化物系荧光体即能够发出绿色系光的YAG系荧光体因为是石榴石结构,所以对热、光以及水分具有很强的耐性,激发吸收谱峰的波长可以在420nm〜470nm附近。 The present embodiment • cerium-activated yttrium-aluminum oxide phosphor capable of emitting green, i.e. the use of light and a YAG phosphor as garnet structure, has a strong resistance to heat, light and moisture, the excitation absorption spectrum peak wavelength may be near the 420nm~470nm. 另外,具有宽的发光谱,其发光峰峰值波长入p在510nm附近,峰的末端延伸到700nm附近。 Further, having a broad emission spectrum, the emission peak wavelength near 700nm to extend into the p, a peak near the end of 510nm. 另一方面,用铈活化的钇•铝氧化物系荧光体即能够发出红色系光的YAG系荧光体也因为是石榴石结构,所以对热、光以及水分具有很强的耐性,激发吸收谱峰的波长可以在420nm〜470nm附近。 On the other hand, • cerium activated yttrium aluminum oxide fluorescent material that is capable of emitting YAG phosphor red light because of garnet structure, has a strong resistance to heat, light and moisture, the excitation absorption spectrum peak wavelength may be near the 420nm~470nm. 另外,具有宽的发光谱,其发光峰峰值波长入p 在600nm附近,峰的末端延伸到750nm附近。 Further, having a broad emission spectrum, the emission peak wavelength near 750nm to extend into the p, a peak near the end of 600nm.

在具有石榴石结构的YAG系荧光体的组成内,用Ga置换Al的一部分,由此使发光谱向短波长侧移动,而用Gd和域La置换组成中的Y的一部分,由此使发光谱向长波长侧移动。 In the composition of YAG fluorescent material having garnet structure, with Ga substituting a part of Al, whereby the emission spectrum is moved to the short wavelength side, and replaced with a part of Y, La and Gd composition in the domain, whereby the hair spectrum shifted to the long wavelength side. 这样一来,通过改变组成,可以连续调节发光颜色。 Thus, by altering the composition, the emission color can be continuously adjusted. 因此,氮化物半导体能够以Gd的组成比来连续改变长波长侧的强度,利用这样的氮化物半导体的蓝色系发光具有转换成白色系发光的理想条件。 Thus, the nitride semiconductor can Gd composition ratio continuously varying the intensity of the long wavelength side, the use of such blue light emitting nitride semiconductor is converted into the ideal conditions having a white light-emitting. 当Y的置换不足2成时, 绿色成分增多而红色成分减少,为8成或以上时,虽然红色成分增加但辉度急剧下降。 When the Y displacement of less than 2 percent, the green component increased to reduce the red component, it is 80% or more, although the red component increases but a sharp decline in brightness. 另外,关于激发吸收谱也同样,在具有石榴石结构的YAG系荧光体的组成内,用Ga置换Al的一部分,由此使激发吸收谱向短波长侧移动,而用Gd和/或La置换组成中的Y的一部分, 由此使激发吸收谱向长波长侧移动。 Further, with respect to the excitation absorption spectrum similarly, in the composition of YAG fluorescent material having garnet structure, with Ga substituting a part of Al, thereby moving the excitation absorption spectrum toward the short wavelength side, and with Gd and / or La substitution portion Y of the composition, and thereby the excitation absorption spectrum shifted to the long wavelength side. YAG系荧光体的激发吸收谱的峰值波长优选的是与发光元件的发光谱的峰值波长相比位于短波长侧。 Peak wavelength of the YAG phosphor excitation absorption spectrum is preferably the emission spectrum peak wavelength of the light emitting element compared to a shorter wavelength side. 如果是这样的构成,则当供给发光元件的电流增加时,激发吸收谱的峰值波长因为与发光元件的发光谱的峰值波长基本一致,所以可以形成荧光体的激发效率不会降低、色度偏移的发生得以抑制的发光装置。 If this is the configuration, when the current supplied to the light emitting element is increased, the peak wavelength of the excitation absorption spectrum as substantially coincides with a peak wavelength of emission spectrum of the light emitting element, it is possible to form the phosphor excitation efficiency is not reduced, partial color the light emitting device is suppressed occurrence of shift.

这样的荧光体将Y、 Gd、 Ce、 La、 Lu、 Al、 Sm以及Ga的氧化物或在高温下容易成为氧化物的化合物用作原料,将它们按化学计量比充分混合便得到原料。 This phosphor will Y, Gd, Ce, La, Lu, Al, Sm and Ga or an oxide at a high temperature tends to be used as starting material a compound oxide, the stoichiometric they will obtain a raw material mixed thoroughly. 或者按化学计量比将Y、 Gd、 Ce、 La、 Lu、 Al、 Sm的稀土类元素溶解在酸中,然后用草酸使这样得到的溶解液产生共沉积,再对这样得到的共沉积产物进行烧结便得到共沉积氧化物,继而将该共沉积氧化物与氧化铝、氧化镓混合便得到混合原料。 Or a stoichiometric ratio Y, Gd, Ce, La, Lu, Al, Sm rare earth elements are dissolved in an acid, and oxalic acid to make lysates thus obtained produce the co-deposition, and then the co-deposited product thus obtained was then co-sintered to obtain the oxide deposition, followed by the co-deposition of aluminum oxide, gallium oxide, then mixed to obtain a mixed raw material. 在该混合原料中适量添加氟化铵等氟化物作为助熔剂并将其装入坩埚中,然后于空气中在1350'C〜145(TC的温度范围内烧结2小时〜5小时,从而得到烧结品,接着在水中对烧结品进行球磨,然后进行洗净、 分离、干燥,最后过筛,由此便可以得到荧光体。另外,其它实施方案的荧光体的制造方法优选分两个阶段进行烧结,该两个阶段由第一烧结工序和第二烧结工序构成,其中第一烧结工序将由混合了荧光休原料的混合原料和助熔剂构成混合物在大气中或弱还原气氛中进行烧结,第二烧结工序在还原气氛中进行烧结。在此,所谓弱还原气氛指的是在由混合原料形成所要求的荧光体的反应过程中,所设定的至少含有必要氧量的较弱的还原气氛,在该弱还原气氛中,进行第一烧结工序直至所要求的荧光体的结构形成得以完成,由此可以防止荧光体的黑变,而 In the raw material mixing an appropriate amount of a fluoride such as ammonium fluoride as a flux and charged in a crucible, and then in air at 1350'C~145 (TC sintering temperature range for 2 hours ~ 5 hours to obtain a sintered product, followed by a ball mill in water, the sintered product, and then washed, separated, dried, and finally sieved, whereby we can obtain the phosphor. Further, the method for producing the phosphor of the other preferred embodiments two stages sintering the two phases constituted by a first sintering step and the second firing step, wherein the sintering step by mixing a first fluorescent material and the flux raw material mixing Hugh constituting the mixture in the air or weakly reducing atmosphere sintering, sintering second the sintering step is performed in a reducing atmosphere. here, the weakly reducing atmosphere refers to a weak reducing atmosphere containing at least the necessary amount of oxygen during the reaction from a mixed phosphor material formed in a desired, set in the weakly reducing atmosphere, a first sintering step until the desired structure is formed of the phosphor to be completed, thereby preventing the blackening of the phosphor, and 防止光吸收效率的下降。另外,所谓第二烧结工序的还原气氛,指的是比弱还原气氛更强的还原气氛。如果这样分两个阶段进行烧结,则可以得到激发波长的吸收效率高的荧光体。因此,在采用这样形成的荧光体形成发光装置的情况下,为得到所要求的色调可以减少必要的荧光体用量,可以形成光取出效率高的发光装置。 Preventing light absorption efficiency decrease. Further, the so-called second reducing atmosphere sintering process, refers to a weakly reducing atmosphere stronger than a reducing atmosphere. If this two-stage sintering, it is possible to obtain a high absorption efficiency of excitation wavelength phosphor. Thus, in the case where the phosphor formed using the thus formed light-emitting device, to obtain the desired color tone may reduce the necessary amount of phosphor with high light extraction efficiency of the device can be formed.

组成不同的2种或更多种用铈活化的钇*铝氧化物系荧光体,可以混合使用,也可以各自独立地进行配置。 Different compositions of two or more of cerium-activated yttrium-aluminum oxide phosphor *, can be mixed, may be configured independently. 在各自独立地配置荧光体的情况下,优选按如下的顺序进行配置,先配置在短波波长侧容易吸 In the case where the phosphor is independently arranged, preferably configured in the following order, to a short wavelength side disposed easy to suck

34收源于发光元件的光并发光的荧光体,再配置在相对长波长侧容易吸收源于发光元件的光并发光的荧光体。 34 received from the light emitting element and a light emitting phosphor, and then arranged in a relatively long wavelength side from readily absorbs light emitting element and a light-emitting phosphor. 由此,荧光体能够有效地吸收发光元件发出的光并发光。 Accordingly, the phosphor can be effectively absorbed light emitting element and emits light. (氮化物荧光体) 作为本实施方案使用的荧光体,除了上述用铈活化的钇•铝•氧 (Nitride phosphor) as the phosphor used in the present embodiment, in addition to the cerium-activated yttrium oxide • aluminum •

化物系荧光体以外,还适用具有黄红〜红色发光波长的用Eu或稀土类活化的碱土类氮化物系荧光体。 Other than the compound-based phosphor, but also for having a red emission wavelength of the yellow - red with Eu activated alkaline earth or rare earth nitride-based phosphor. 该荧光体是通过吸收由LED芯片发出的可见光和紫外线、以及由YAG系荧光体发出的光而受激发光的。 The phosphor by absorbing ultraviolet light and visible light emitted by the LED chip and the light emitted by the YAG-based phosphor by the excitation light. 本发明的实施方案的荧光体特别是:Sr-Ca-Si-N:R、 Ca-Si-N:R、 Sr -Si-N:R、 Sr-Ca-Si-ON:R、 Ca-Si-ON:R以及Sr -Si-ON:R系硅氮化物。 Phosphor of embodiments of the present invention is in particular: Sr-Ca-Si-N: R, Ca-Si-N: R, Sr -Si-N: R, Sr-Ca-Si-ON: R, Ca-Si -ON: R and Sr -Si-ON: R-based silicon nitride. 这些荧光体的基本构成元素可以用通式LxSiYN,x+4/3Y):R或LxSiYOz N(2/3X+4/3Y-2/3Z): R (L为Sr、 Ca以及Sr和Ca之中的任一组)来表示。 These phosphors may be represented by the formula basic elements LxSiYN, x + 4 / 3Y): R or LxSiYOz N (2 / 3X + 4 / 3Y-2 / 3Z): R (L is Sr, Ca and Sr and Ca, any of a group) is represented. 在通式中,X以及Y优选的是X-2、 ¥=5或乂=1、 Y=7,但也可以是任意的数值。 In the formula, X and Y are preferably X-2, ¥ = 5 or qe = 1, Y = 7, but may be any value. 另外,R是必须含有Eu的稀土类元素,N为氮,O为轼。 Further, R is a rare earth element containing Eu, and must, N is nitrogen, O is Shi. 具体地说,优选使用基本构成元素可以用(SrxCai.x)2Si5N8:Eu 、 Sr2Si5N8:Eu、 Ca2Si5N8:Eu、 SrxCaLxSi?NK):Eu、 SrSi7N10:Eu、 CaSi7N10:Eu 表示的荧光体,但在该荧光体的组成中,也可以含有选自Mg、 B、 Al、 Cu、 Mn、 Cr以及Ni之中的至少l种或多种。 Specifically, it is preferable to use basic elements can be used (SrxCai.x) 2Si5N8: Eu, Sr2Si5N8: Eu, Ca2Si5N8:? Eu, SrxCaLxSi NK): Eu, SrSi7N10: Eu, CaSi7N10: Eu phosphor represented, but in this phosphor composition may also contain selected from Mg, l or more at least from among B, Al, Cu, Mn, Cr and Ni. 但本发明并不限于该实施方案以及实施例。 However, the present invention is not limited to the embodiments and examples.

L为Sr、 Ca以及Sr和Ca之中的任一组。 It is L, Ca, and Sr in any one of a group of Ca and Sr. Sr和Ca可以根据要求来改变配比。 Sr and Ca can be changed according to the ratio requirements.

发光中心主要使用作为稀土类元素的铕Eu。 Europium Eu luminescent center is used as the rare earth element. 铕主要具有2价和3 价的能级。 Europium mainly has a divalent and trivalent energy levels. 本发明的实施方案的荧光体对于作为母体的碱土类金属系氮化硅,将Eu"用作活化剂。另外,也可以将Mn用作添加物。 Phosphor according to the embodiment of the present invention as the parent alkaline earth metal silicon nitride-based, the Eu "used as an activator. Additionally, Mn can also be used as an additive.

下面就本发明的实施方案中使用的荧光体((SrxCai-X)2Si5N8:Eu) 的制造方法进行说明,但本发明并不限于本制造方法。 The following ((SrxCai-X) 2Si5N8: Eu) phosphor can be used in embodiments of the present invention is a manufacturing method will be described, but the present invention is not limited to the manufacturing method. 在上述荧光体中含有Mn和O。 Containing Mn and O. In the above-described phosphor

将作为原料的Sr、 Ca进行粉碎。 As starting material Sr, Ca pulverized. 作为原料的Sr、 Ca优选使用单质,但也可以使用酰亚胺化合物、酰胺化合物等化合物。 As a raw material Sr, Ca is preferably used a simple substance, but may be a compound of an imide compound, an amide compound used. 通过粉碎得 Obtained by pulverization

到的Sr、 Ca,优选的平均粒径约为0.1um〜15um,但本发明并不限于该范围。 To Sr, Ca, preferred average particle size of about 0.1um~15um, but the present invention is not limited to this range. Sr、 Ca的纯度优选为2N或以上,但本发明并不限定于此。 Sr, Ca or a purity of preferably 2N or more, but the present invention is not limited thereto.

将作为原料的Si进行粉碎。 Si as a raw material is pulverized. 作为原料的Si优选使用单质,但也可以使用氮化物化合物、酰亚胺化合物、酰胺化合物等。 Si is preferably used as a single feedstock, it is also possible to use a nitride compound, an imide compound, an amide compound and the like. 原料Si的纯度优选为3N或以上。 Purity of the Si raw material is preferably 3N or more. Si也进行粉碎,优选的Si化合物的平均粒径约为0.1 ym〜15 U m。 Si is also pulverized, the average particle diameter of the Si compound is preferably from about 0.1 ym~15 U m.

接着在氮气氛中将作为原料的Sr、 Ca进行氮化。 Next, in a nitrogen atmosphere as a raw material of Sr, Ca nitriding. 该反应式分别如化学式3和4所示。 The reaction formula, respectively, as shown in Chemical Formula 3 and 4.

3Sr+N2—Sr3N2 化学式3 3Sr + N2-Sr3N2 Chemical Formula 3

3Ca+N2—Ca3N2 化学式4 3Ca + N2-Ca3N2 Chemical Formula 4

在氮气氛中,于60(TC〜900。C的温度下,将Sr、 Ca氮化约5个小时。Sr、 Ca的氮化物优选的是具有高纯度,也可以使用市售的Sr、 Ca氮化物。 In a nitrogen atmosphere at 60 (at a temperature TC~900.C will Sr, Ca for about 5 hours .sr nitride, Ca nitride preferably has a high purity may be commercially available as Sr, Ca nitride.

在氮气氛中将作为原料的Si进行氮化。 Si in a nitrogen atmosphere as a raw material is nitrided. 该反应式如化学式5所示。 The reaction formula of Chemical Formula 5 as shown in FIG. 3Si+2N2—Si3N4 化学式5 3Si + 2N2-Si3N4 Chemical Formula 5

在氮气氛中,于80(TC〜120(TC的温度下,硅Si也氮化约5个小时。氮化硅优选的是具有高纯度,也可以使用市售的氮化硅。 In a nitrogen atmosphere, to 80 ((the lower the temperature TC TC~120, silicon nitride Si also about 5 hours is preferable that a silicon nitride having a high purity can be commercially available silicon nitride.

将Sr、 Ca或Sr-Ca的氮化物粉碎。 The Sr, Ca, or Sr-Ca nitride pulverized. 同样,将Si的氮化物粉碎。 Similarly, the nitride of Si is pulverized. 另外,还同样将Eu的化合物Eu203粉碎。 Further, a Eu compound Eu203 same pulverization. 作为Eu的化合物,所使用的是氧化铕,但金属铕、氮化铕等也可以使用。 As the Eu compound, europium oxide is used, but metal europium, europium nitride and the like may also be used. 此外,作为原料的Eu, 也可以使用酰亚胺化合物和酰胺化合物。 Further, Eu as a raw material may be used an amide compound and the imide compound. 氧化铕优选的是具有高纯度, 也可以使用市售的氧化铕。 Europium oxide having high purity are preferred, it can be a commercially available europium oxide. 粉碎后的碱土类金属的氮化物、氮化硅以及氧化铕的平均粒径优选的是0.1 nm〜15 " m左右。 The pulverized alkaline earth metal nitride, silicon nitride and europium oxide average particle diameter is preferably 0.1 nm~15 "about m.

在上述原料中,也可以含有选自Mg、 B、 Al、 Cu、 Mn、 Cr、 0 以及Ni之中的至少l种或多种。 In the raw material may also contain selected from Mg, B, Al, Cu, Mn, Cr, 0 and l or more at least in being Ni. 另外,也可以在以下的混合工序中, 调节Mg、 Mn、 B等上述元素的配比而进行混合。 Further, the mixing may be in the following step, adjusting the ratio of the above elements Mg, Mn, B and the like are mixed.

上述粉碎结束后,将Sr、 Ca、 Sr-Ca的氮化物,Si的氮化物以及 After completion of the pulverization, the Sr, Ca, Sr-Ca nitride, Si nitride and

36Eu的化合物Eu203进行混合,并且添加Mn进行混合。 Eu203 36Eu compounds were mixed and Mn is added and mixed.

最后在氨气氛中,将Sr、 Ca、 Sr-Ca的氮化物、Si的氮化物以及Eu的化合物Eu203的混合物进行烧结。 Finally, in an ammonia atmosphere, Sr, Ca, Sr-Ca nitride, Si nitride and Eu in the mixture of compounds Eu203 sintered. 通过烧结,可以得到添加了Mn的以(SrxC^x)2Si5Ns:Eu表示的荧光体。 By sintering, it can be added to the Mn (SrxC ^ x) 2Si5Ns: Eu phosphor represented. 通过该烧结得到的基本构 The basic configuration obtained by sintering

成元素的反应式如以下的化学式6所示。 Reactive elements such as the following chemical formula 6.

Ze v a.97-X)^ Ar 5C. Ar 0.03 。 Ze v a.97-X) ^ Ar 5C. Ar 0.03. Eight

332 3 323h223 、 332 3 323h223,

—S/>C。 -S /> C. (197—^£"0 03 ^5〃79800.。45 化学式6 (197- ^ £ "0 03 ^ 6 5〃79800..45 formula

其中,通过改变各原料的配比,可以改变目标荧光体的组成。 Wherein, by changing the ratio of each raw material, the composition may be varied target phosphor. 关于烧结温度,可以在1200'C〜170(TC的范围内进行烧结,但优选的是1400'C〜170(TC的烧结温度。荧光体的原料优选用氮化硼(BN)材质的坩埚、舟皿进行烧结。除氮化硼材质的坩埚以外,也可以使用氧化铝(A1203)材质的坩埚。 About sintering temperature, it can be (in the range of TC 1200'C~170 sintering, but preferably 1400'C~170 (sintering temperature TC of the raw materials of the phosphor is preferably boron nitride (BN) crucible material, sintering boat. other than a boron nitride crucible, it may also be used alumina (A1203) material of the crucible.

通过使用以上的制造方法,可以得到目标荧光体。 By using the above manufacturing method, it is possible to obtain a phosphor target. 在本发明的实施例中,作为发出带红色光的荧光体,特别使川飄化物系荧光体,而在本实施方案中,也可以获得具有上述YAG系荧光体和可能发出红色系光的荧光体的发光装置。 In an embodiment of the present invention, the phosphor emits reddish light, in particular to make plain float compound-based phosphor in the present embodiment, it can be obtained with the above-described YAG phosphor and the phosphor may emit red light the light emitting device body. 这样的可能发出红色系光的荧光体是由波长为250nm〜600nm的光激发而发光的荧光体, 例如可以列举出Y202S:Eu、 La202S:Eu、 CaS:Eu、 SrS:Eu、 ZnS:Mn、 ZnCdS:Ag,Al以及ZnCdS:Cu,Al等。 Eu, La202S:: Eu, CaS: Eu, SrS: Eu, ZnS: this may emit red light emitting phosphor is excited to emit light 250nm~600nm phosphor Y202S Examples include wavelength is Mn, ZnCdS: Ag, Al and ZnCdS: Cu, Al and the like. 这样,通过使用可能与YAG系荧光体一起发出红色系光的荧光体,可以提高发光装置的演色性。 Thus, it may be sent by using the YAG-base phosphor with a phosphor of red light can be improved color rendering property of the light emitting device.

在本发明的各实施方案的发光装置中,荧光体可以使用各种各样的荧光体。 In various embodiments of the light emitting device of the present invention, the phosphor can use various phosphors. 例如,可以列举出的有:产生蓝色区域的发光的、以BaMgAl1()017: Eu表示的、用铕活化的铝酸钡镁系荧光体,产生蓝色区域的发光的、以(Ca、 Sr、 Ba)5(P04)3Cl: Eu表示的、用铕活化的&j 素磷酸钙系荧光体,产生蓝色区域的发光的、以(Ca、 Sr、 Ba)2B509Cl:Eu 表示的、用铕活化的碱土类氯硼酸盐系荧光体,产生蓝绿色区域的发光的、以(Sr、 Ca、 Ba)Al204: Eu或(Sr、 Ca、 Ba)4Al14025: Eu表示的、 用铕活化的碱土类铝酸盐系荧光体,产生绿色区域的发光的、以(Mg、Ca、 Sr、 Ba)Si202N2: Eu表示的、用铕活化的碱土类硅氧氮化物系荧光体,产生绿色区域的发光的、以(Ba、 Ca、 Sr)2Si04: Eu表示的、用铕活化的碱土类硅酸镁系荧光体,产生黄色区域的发光的、以(Y、 Gd)3(Al、 Ga)5Ol2: Ce表示的稀土类铝酸盐即YAG系荧光体以及产生红色区域的发光的、以(Y、 La、 Gd、 Lu)202S: Eu表示的、用铕活 For example, there may include: generating a blue light emitting region, to BaMgAl1 () 017:, with europium-activated barium magnesium aluminate-based phosphor represented by Eu, to generate blue light emitting region, to (Ca, Sr, Ba) 5 (P04) 3Cl:, & j europium-activated calcium-based pigment represented by Eu phosphor, the blue emission region is generated, in (Ca, Sr, Ba) 2B509Cl: Eu represented by europium alkaline earth chloride-activated borate-based phosphor, a blue-green light emitting region is generated to (Sr, Ca, Ba) Al204: Eu or (Sr, Ca, Ba) 4Al14025: Eu represented by europium-activated alkaline earth aluminate-based phosphor, the green emission region is generated to (Mg, Ca, Sr, Ba) Si202N2: Eu represented by europium-activated alkaline earth silicon oxynitride phosphor, a green emission region is generated to (Ba, Ca, Sr) 2Si04: Eu represented by europium-activated alkaline earth silicate based phosphor, a yellow light emitting region is generated to (Y, Gd) 3 (Al, Ga) 5Ol2: , europium Eu which live: Ce rare-earth aluminate represented i.e. YAG phosphor and the red light emitting region is generated to (Y, La, Gd, Lu) 202S 的稀土类氧硫化物系荧光体等,但本发明并不限于这些,前述的荧光体和其它的荧光体也可以在本发明的实施方案的发光层中使用。 Rare earth oxysulfide phosphor the like, but the present invention is not limited, and the phosphor of other phosphors may be used in an embodiment of the light-emitting layer in the present invention. 再者, 也可以使用具有断裂面的荧光体,其中在断裂面上采取了防止涂层退化的对策。 Further, also possible to use a phosphor having a fracture surface, wherein the fracture surface of the coating to take countermeasures to prevent degradation.

上述荧光体例如用铕活化的碱土类氯硼酸盐系荧光体、用铕活化的碱土类铝酸盐系荧光体、用铕活化的碱土类硅氧氮化物系荧光休、 YAG系荧光体以及用铕活化的碱土类硅氮化物系荧光体等优选含有B,从而使结晶性变得良好,增大粒径,或调整结晶形状。 For example, with the phosphor of the europium-activated alkaline earth chloro-borate-based phosphor, europium-activated alkaline earth aluminate phosphor, europium-activated alkaline earth silicon oxynitride phosphor off, a YAG-based phosphor, and europium-activated alkaline earth silicon nitride fluorescent material preferably contains B, so that the crystallinity becomes better, increasing the particle size, crystal form or adjust. 由此可谋求发光辉度的提高。 Thus can be improved emission brightness. 这些荧光体作为本实施方案的荧光体的填料也是有效的。 These phosphors as a phosphor filler present embodiment is also effective.

关于结晶结构,例如Ca2SisN8为单斜晶,Sr2Si5N8、(SrQ.5Cao.5)2Sr5N8 为斜方晶,Ba2SisNs取单斜晶。 About the crystalline structure, it is monoclinic Ca2SisN8 e.g., Sr2Si5N8, (SrQ.5Cao.5) 2Sr5N8 orthorhombic, Ba2SisNs take monoclinic.

再者,本荧光体是结晶在其组成中占60%或以上、优选为80%或以上的准晶质。 Furthermore, the present crystalline phosphor is 60% or more in its composition, preferably 80% or more quasi-crystalline. 一般地说,优选X-2、 Y-5或X4、 Y=7,但也可以是任意的数值。 In general, preferred X-2, Y-5 or X4, Y = 7, but it may be any value.

在微量添加物中,B等不降低发光特性而可以提高结晶性,而且Mn、 Cu等也表现出同样的效果。 In minor additives, B is the light emission characteristics and the like without reducing the crystallinity can be improved, and Mn, Cu, also exhibited the same effects. 另外,La、 Pr等也具有改善发光特性的效果。 Further, La, Pr, also has the effect of improving light emission properties. 除此以外,Mg、 Al、 Cr、 Ni等具有縮短余辉的效果,可以适宜使用。 In addition, Mg, Al, Cr, Ni and the like have the effect of shortening afterglow, can be suitably used. 此外,即使是本说明书没有明示的元素,只要在10〜 1000ppm左右,不明显降低辉度就可以添加。 Further, even if the specification is not explicitly element, as long as about 10~ 1000ppm, significant loss of luminance can be added.

R中含有的稀土类元素优选包括Y、 La、 Ce、 Pr、 Nd、 Gd、 Tb、 Dy、 Ho、 Er、 Lu之中的l种或以上,但也可以包括Sc、 Sm、 Tm以及Yb。 Rare earth element R contained preferably comprises one or more l among Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu, but may also include Sc, Sm, Tm and Yb. 另外,除上述元素以外,还可以含有B、 Mn等具有改善辉皮 Further, in addition to the above elements, it may contain B, Mn and the like having improved luminance sheath

38的效果的元素。 Effect element 38. 这些稀土类元素除单质外,还以氧化物、酰亚胺、酰 These rare earth elements other than a single substance, but also to oxides, imides, acid

胺等状态混合在原料中。 Amines, etc. mixed in the raw material state. 稀土类元素主要具有稳定的3价的电子排列, 但Yb、 Sm等也具有2价、Ce、 Pr、 Tb等也具有4价的电子排列。 Major rare-earth element having stable electron arrangement trivalent, but Yb, Sm, also a divalent, Ce, Pr, Tb, also an electronic arrangement tetravalent. 在使用氧化物的稀土类元素的情况下,氧的参与对荧光体的发光特性产生影响。 In the case of using a rare-earth element oxide, oxygen participation affect the emission characteristics of the phosphor. 也就是说,由于含有氧,有时也发生辉度的降低。 That is, because it contains oxygen, sometimes to reduce the occurrence of luminance. 但是,在使用Mn的情况下,由于Mn与O产生的作为助熔剂的效果,使粒径得以增大,从而可谋求发光辉度的提高。 However, in the case of Mn, Mn and O is generated since a flux effect, so that the particle size is increased, thereby seeking to improve the luminance of the hair.

作为发光中心,适于使用作为稀土类元素的铕Eu。 As a luminescent center, europium Eu is suitable for use as the rare earth element. 具体列举出基本构成元素的实例,则有:添加了Mn、 B的Ca2Si5OaiN7.9:Eu、 Sr2Si50(uN7.9:Eu、 (CaxSr卜x)2 Si5OaiN7.9:Eu、 CaSi7Oo.5N9.5:Eu、进而添加了稀土类元素的Ca2Si50(nN7.9:Eu、 Sr2Si5O0.5N7.7:Eu、 (CaxSr卜x)2 SisOo美9:Eu等。 Specific examples include basic constituent element, there are: Added Mn, Ca2Si5OaiN7.9 B's: Eu, Sr2Si50 (uN7.9: Eu, (CaxSr BU x) 2 Si5OaiN7.9: Eu, CaSi7Oo.5N9.5: Eu, Ca2Si50 further added rare earth element (nN7.9: Eu, Sr2Si5O0.5N7.7: Eu, (CaxSr BU x) 2 SisOo US 9: Eu and the like.

以上说明的氮化物系荧光体,吸收由发光元件发出的蓝色光的一部分而发出从黄色到红色区域的光。 The nitride-based fluorescent material described above, absorbs a portion of blue light emitted from the light emitting element emits light from yellow to red region. 将该荧光体用于具有上述构成的 The phosphor having the above-described configuration for

发光装置,便可以提供一种由发光元件发出的蓝色光和荧光体的纟n色 A light emitting device, it is possible to provide n Si-color phosphor a blue light emitted from the light emitting element

光通过混色而发出暖色系的白光的发光装置。 The light emitting device emits white light by mixing warm colors. 特别在白光发光装贾_屮, 优选含有氮化物系荧光体和稀土类铝酸盐荧光体即用铈活化的钇•铝 In particular, a white light emitting apparatus Jia _ Cao, preferably comprising a nitride-based phosphor, and rare earth aluminate phosphor activated with cerium i.e. yttrium aluminum •

氧化物荧光体。 Oxide phosphor. 这是因为:通过含有上述的钇•铝氧化物荧光体,"了以调节所要求的色度。用铈活化的钇•铝氧化物荧光体,可以吸收由发光元件发出的蓝色光的一部分而发出黄色区域的光。在这里,由发光元件发出的蓝色光和和钇•铝氧化物荧光体的发色光通过混色而可以发出蓝白色的白色光。因此,通过组合将该钇•铝氧化物荧光休以及所述氮化物荧光体与粘结剂一起混合的荧光体和由发光元件发出的蓝色光,可以提供一种暖色系的白光的发光装置。该暖色系的白光的发光装置,其平均演色评价指数Ra可以达到75〜95,色温度可以设定为2000K〜8000K。特别优选的是平均演色评价指数Ra较高、色温度位于色度图的黑体辐射的轨迹上的白色发光装置。但是,为了提供具有所要求的色温度以及平均演色评价指数的发光装置,也可以适当改变钇•铝氧化物荧光体和荧光体 This is because: • by containing the yttrium aluminum oxide phosphor, a part of "the adjustment to the desired chromaticity • cerium activated yttrium aluminum oxide phosphor, can absorb the blue light emitted by the light emitting element and emits light of the yellow region. here, light hair, and blue color light • yttrium aluminum oxide phosphor emitted by the light emitting element may emit white light by the blue-white color mixture. Thus, by combining the yttrium-aluminum oxide • phosphor and a phosphor off the nitride phosphor together with a binder and mixing the blue light emitted from the light emitting element, the light emitting device can provide a warm color white light emitting device of the warm color white, the average color rendering index Ra can be achieved 75~95, the color temperature may be set to 2000K~8000K. particularly preferred are the higher average color rendering index Ra, color white light emitting device on the chromaticity diagram is located in the temperature of the black body radiation locus. However, , in order to provide an average color temperature and a light emitting device having a color rendering index required, may be appropriately changed • yttrium aluminum oxide phosphor and the phosphor 的配合量和各荧光体的组成比。该 The amount and composition ratio of each phosphor. The

暖色系的白光的发光装置特别谋求特殊演色评价指数R9的改善。 Warm color white emitting apparatus is particularly special seeking to improve the color rendering index R9. 以前的由蓝色发光元件和用铈活化的钇•铝氧化物荧光体组合而成的发出白色光的发光装置,其特殊演色评价指数R9低下,红色成分不足。 The light emitting device emits white light by a combination of blue light emitting element and cerium-activated yttrium-aluminum oxide phosphor • previously formed, its special color rendering index R9 is low, insufficient red component. 因此,提高特殊演色评价指数R9就成了需要解决的课题,而在用钸活化的钇•铝氧化物荧光体中含有用Eu活化的碱土类氮化硅系荧光体,藉此可以将特殊演色评价指数R9提高到40〜卯。 Therefore, a special object to improve the color rendering index R9 has become to be solved, and activated with Eu-containing alkaline earth silicon nitride-based phosphors activated with cerium • yttrium aluminum oxide phosphor, whereby the special color rendering may be R9 evaluation index increased to 40~ d. 另外,还可以制作发出灯泡颜色的LED发光装置。 Further, the lamp can create a color emitted LED light emitting device. (发光装置) (Light emitting device)

发光元件(LED芯片)IO通过焊接在罩体的大致中央部位而很好地由该罩体所承载,其中罩体配置在管脚引线13a的上部。 A light emitting element (LED chip) by the IO good welding is carried by the cover in a substantially central portion of the cover, wherein the cover body is disposed in the upper portion 13a of the lead pins. 引线框13 例如由铜-铁合金(copper-ironalloys)构成。 For example, a copper lead frame 13 - composed of an iron alloy (copper-ironalloys). 发光元件10上形成的屯极通过导电性引线14与引线框进行电连接。 Tun light emitting element 10 is formed on the conductive electrode lead 14 is electrically connected to the leadframe through. 导电性引线14用金构成, 而且在用于将电极和导电性引线14进行电连接的凸缘(bump)上适当地镀覆了Ni镀层。 Electrically conductive wire configuration 14 with gold, and in which the electrodes and the conductive leads 14 on the flange (Bump) appropriately electrically connected to the plated Ni plating.

将充分混合上述荧光体lla和粘结剂llb而成为料浆的荧光构件11注入承载着发光元件10的罩体中。 The fluorescence of the phosphor mixed member lla and llb binder slurry 11 to become injected into the shell carrying the light emitting element 10. 然后,加热含有荧光体lla的凝胶而使之固化。 Then, the phosphor-containing gel is heated to the curing lla. 料浆的热固化优选为50'C〜500'C。 Heat curing the slurry is preferably 50'C~500'C. A1和Y的热固化温度约为10(TC〜500'C。在这里,于150。C或以下进行热固化。在凝胶的热固化中可以照射紫外线。例如可以利用水银灯、VUV等,而且也可以并用多个光源与热源。通过照射像VUV那样的强光,可以有效地切断羧酸等有机基团的键合,从而可以使固化反应实现稳定化。 当用VUV照射料浆状的荧光构件时,使02以及N2的混合气体流过, 在VUV的照射下,使一部分氧与隔离的羟基和有机基团反应而成为<:02和&0,这也可以促进这些羟基、有机基团等的除去。在本实施方案中,通过组合254nm或以上的真空紫外线照射和加热,在膜固化的膜形成阶段,粘结剂与荧光体、填料界面的附着力、在LED等发光元件上的附着力变得良好,可以形成微孔少的膜。这样,在LED芯片 Y A1 and heat-curing temperature of about 10 (TC~500'C. Here, in the following 150.C or thermally cured. In the thermal curing of the gel may be irradiated with ultraviolet rays. For example, using a mercury lamp, and so the VUV, and a plurality of light sources may be used with a heat source. VUV as image light, can be effectively cut off the organic groups bonded to the carboxylic acid by irradiation, so that the curing reaction can be stabilized. when the fluorescent material is irradiated with VUV slurry when the member, so that a mixed gas of 02, and N2 flows at the irradiation VUV, so that part of oxygen and isolation of a hydroxyl group and an organic group is reacted to form <: 02 and & 0, which may also facilitate the hydroxyl group, the organic group and the like removed. in this embodiment, by a combination of heating and vacuum ultraviolet irradiation 254nm or more, adhesion formation stage, the binder and the phosphor, the filler in the film interface of the cured film is attached on the light emitting element such as an LED focus becomes good, fewer microporous film can be formed. Thus, the LED chip

40上形成由包含荧光体的粘结剂构成的荧光构件11而使LED芯片得以固定。 Forming the fluorescent member of the LED chip 11 made of phosphor containing binder 40 is fixed. 此后,为了保护LED芯片和荧光体免受外部应力、水分以及尘垢的侵害,进一步以铸模构件15的形式适当地对透光性环氧树脂进行成形。 Thereafter, in order to protect the LED chip and the phosphor from external stress, moisture and dust against the further mold member 15 in the form of appropriately translucent epoxy resin for molding. 将形成有颜色转换构件的引线框13插入炮弹型的模框中,混入透光性环氧树脂进行固化。 The lead frame is formed with a color conversion member 13 is inserted into the bullet-shaped mold box, sealed with translucent epoxy resin is cured.

另外,荧光构件11可以直接与LED芯片接触并覆盖在LED芯片上,也可以使透光性树脂等介于其间而进行设置。 Further, the fluorescent member 11 may contact and cover the LED chip may be made translucent resin or the like interposed therebetween and is set directly with the LED chip. 不用说,此时优选使用耐光性高的透光性树脂。 Needless to say, this time using a high light resistance is preferably translucent resin.

本发明的实施方案的荧光体,即使曝露在高温下使得发光装置发生软熔时,也可以延缓发光效率的急剧下降。 Phosphor of embodiments of the present invention, even when exposed to elevated temperatures such that the light emitting device reflow occurs, the sharp decline in light emission efficiency can delay. 特别是对于引线和荧光构件接触或靠近、热容易通过引线传递给荧光体的发光元件,本发明的实施方案的荧光体也是有用的。 And particularly for lead in contact with or close to the fluorescent member, heat is easily transferred to the light emitting element by wire phosphor, the phosphor of the embodiment of the present invention are also useful.

实施方案2 Embodiment 2

其次,作为本发明的实施方案2的发光装置的一个实例,图3及图4分别为示意平面图和示意剖面图,均表示在金属壳体上安装作为发光元件的LED的状态。 Next, the light emitting device as one example embodiment of the present invention 2, 3 and 4 are schematic plan view and a schematic sectional view showing the state of each LED as a light emitting element mounted on the metal housing.

壳体105由金属构成,在其中央部具有凹部a。 Housing 105 is made of metal, having a recess in its central portion. 另外,在所述四部的周围即基底部b有2个贯通厚度方向的贯通孔,各自的贯通孔夹持着所述凹部a相向设置。 Further, around the four, i.e., the base b has two through holes penetrating in the thickness direction, each of the through holes of the holding recess portion is provided facing a. 正的和负的引线电极102隔着作为绝缘构件103的硬质玻璃分别插在该贯通孔内。 Positive and negative lead electrodes 102 via the insulating member as a hard glass 103 are inserted in the through hole. 另外,在金属壳体105的—i-: 面侧具有透光性窗部107和由金属部构成的引线106,通过焊接金弒部和金属壳体105的接触面,发光元件等与氮气一起便被气密在壳休内。 Further, the metal case 105 -i-: a light-transmissive window portion 107 and side portions 106 by a lead made of metal, together with the nitrogen through the contact surface, the light emitting element, such as welding metal and the metal housing portion killing 105 it off hermetically in the casing. 收容在凹部a内的LED芯片101是发出蓝色光或紫外线的发光元件,LED芯片101与金属壳体105的粘结是通过粘结层IIO进行的, 其中粘结层110是将硅酸乙酯的水解溶液进行干燥并烧结而得到的。 Accommodated in the recess portion of the LED chip 101 is a light emitting element emits blue light or ultraviolet light, the LED chip 101 and the bonding metal housing 105 is performed by the IIO adhesive layer, wherein the adhesive layer 110 is a tetraethylorthosilicate the hydrolysis solution was obtained by drying and sintering.

再者,如图4所示,在与引线电极102绝缘的凹部a内,在发光元件上形成了由A100H将CCA-Blue (化学式为Ca10(PO4)6aBr,活 Further, as shown in the insulating recess 102 and the lead electrode portion a, it is formed on the light emitting element 4 by a A100H the CCA-Blue (chemical formula Ca10 (PO4) 6aBr, live

41化材料为Mn、 Eu)荧光体粘结而成的发光层109,再在发光层109 上形成了由AIOOH、 YOOH等将YAG系荧光体粘结而成的发光层108。 41 light-emitting layer material is Mn, Eu) phosphor obtained by binding 109, then the adhesive layer 108 is formed by a AIOOH, YOOH YAG fluorescent material or the like is formed on the light emitting layer 109. 下面参照附图详细叙述本发明的实施方案的构成构件。 The following detailed description of embodiments of the constituting member of the present invention with reference to the accompanying drawings. (发光层108、 109) (Light emitting layer 108, 109)

除铸模构件以外,发光层设置在管脚引线的罩体内和壳体的开口部内等处,是含有对LED芯片101的发光进行转换的荧光体以及对荧光体进行粘结的材料层。 In addition to the mold member, the light emitting layer is disposed in the opening portion of the housing body and the housing of pinouts, etc., containing the light-emitting LED chip 101 is phosphor-converted, and the phosphor material layer be bonded. 另外,正如图5所示的那样,本发明的实施方案的发光层,其在LED芯片101的上面、侧面以及角部上设置的发光层109A的厚度与在LED芯片101以外的支持体上设置的发光层108A的厚度大致相等。 Further, as shown in FIG. 5, as the light emitting layer according to the present embodiment of the invention, which is above the LED chip 101 is provided on a support other than the thickness of the LED chip 101 and the light emitting layer side surface provided on the corner portion 109A the thickness of the light-emitting layer 108A is substantially equal. 另外,发光层即使在LED芯片101的角部的部分也没有间断,发光层是连续的。 Further, corner portions of the light-emitting layer even in a LED chip 101 is not interrupted, the light emitting layer is continuous.

由于壳体等产生的反射,从LED芯片发出的高能光等在发光层屮 Since the housing like reflections, high energy emitted from the LED chip light emitting layer and the like Che

变成高密度。 It becomes a high density. 再者,由荧光体也产生漫反射,发光层有时曝露在高密度的高能光中。 Further, also diffuse reflection by the phosphor, the light emitting layer is sometimes exposed to a high density of high-energy light. 因此,当将发光强、能够发出高能光的氮化物系半导体用作LED芯片时,优选将对这些高能光有耐光性的、含有A1、 Y、 Gd、 Lu、 Sc、 Ga、 In、 B之中的任一种的金属元素的水合氧化物作为粘接剂或粘结剂加以利用。 Thus, when the luminous intensity, is capable of emitting high-energy light nitride-based semiconductor is used as the LED chip, these high-energy light will preferably have light resistance, comprising A1, Y, Gd, Lu, Sc, Ga, In, B of any of a hydrous oxide of a metal element to be used as an adhesive or binder.

作为发光层的具体的主材料之一,适合使用的有在Al(OH)3、 Y(OH)3等透光性无机构件中含有荧光体的材料。 As one specific light-emitting layer host material, suitable for use with a material containing the phosphor 3, Y (OH) 3 and the like inorganic translucent member Al (OH) in. 荧光体彼此之间借助于透光性无机构件进行粘结,而且荧光体在LED芯片和支持体上堆积成层状并与之粘结。 By means of a light transmissive member for bonding the inorganic phosphor with each other, and the phosphor on the LED chip and the support is deposited in layers and bonded thereto. 在本实施方案中,水合氧化物由以如下水合氧化物为主体的化合物所形成,其中成为主体的水合氧化物由Al、 Y、 Gd、 Lu、 Sc、 Ga、 In、 B之中的任一种的有机金属化合物所形成。 In the present embodiment, the hydrous oxide is formed by the following compounds hydrous oxide as a main component, wherein the body has become hydrated oxide among Al, Y, Gd, Lu, Sc, Ga, In, B is any one of different kinds of organic metal compound formed. 在此, 所谓有机金属化合物包含通过氧原子与金属键合的垸基和芳基。 Here, the organometallic compound comprising the metal through an oxygen atom bonded to the embankment and aryl. 作为这样的有机金属化合物,例如可以列举出垸基金属、烷氧基金属、双二酮基金属、双二酮基金属的络合物以及金属羧酸盐等。 As such organic metal compound may include embankment based metal, metal alkoxide, metal-bis-dione, bis-dione-based metal complexes, and metal carboxylates and the like. 在这样的有机金属化合物中,如果特别使用在常温下呈液态的有机金属化合物, 则通过添加有机溶剂,可以容易地从工艺性的角度调节粘度并防止有机金属化合物等的凝固物的发生,从而能够使工艺性得以提高。 In such an organometallic compound, if used in particular are liquid at room temperature, the organic metal compound is by adding an organic solvent, can easily regulate the viscosity from the viewpoint of manufacturability and prevent coagulum organometallic compound, whereby enabling improved manufacturability. 另外, 这样的有机金属化合物因为容易发生水解等化学反应,所以容易四处飞散,可以形成使荧光体得以粘结的发光层。 Further, because of such organometallic compounds are readily hydrolyzed by chemical reaction, it is easy to be scattered, the light emitting layer is bonded to the phosphor can be formed. 因此,使用有机金属化 Thus, using the organometallic

合物的方法与在350'C或以上的温度下或者在施加静电的状态下在LED上形成发光层的其它方法不同,不会降低作为LED发光元件的性能而可以容易地在LED芯片上形成发光层,从而使生产合格率得以提高。 The method or other method and composition is formed on the LED light emitting layer at a temperature of 350'C or more in a state of static electricity is applied, it would not decrease and can be easily formed on the LED chip as the LED light emitting element performance a light emitting layer, so that the production yield is improved.

另外,发光层虽然以无机物为主体构成,但也可以含有一部分以羧酸为主体的有机物。 Further, although the light emitting layer composed of an inorganic material as the main body, but may contain a portion of organic acids as a main component. 有机物的含量优选设定为1重量%或以下。 Organic content is preferably set to 1% by weight or less. 另外,发光层优选在250nm〜800nm的波长区域至少具有50%或以上的透光性。 Further, the light emitting layer preferably has at least 50%, or translucent in the wavelength region of 250nm~800nm.

作为发光层中含有的具体的主材料,下面以AIOOH为例进行说明。 Specific examples of the host material contained in the luminescent layer, will be described as an example below to AIOOH.

(由AIOOH将荧光体粘结而成的发光层109) 由A100H将荧光体粘结而成的发光层是通过以下方法形成的, 即在有机溶剂中以预定的比例使垸基醇铝或烷氧基铝水解,在水解得到的铝氧烷溶胶或氧化铝溶胶溶液中,使荧光体(粉体)均匀分散而得到涂布液,调整该涂布液并以喷涂或撒布的方式涂覆该荧光体得以分散的氧化铝溶胶溶液,从而使之覆盖整个发光元件,然后进行加热和固化,从而由AIOOH成分使荧光体彼此之间得以固定,而且固定在发光元件的表面。 (Light-emitting layer is bonded by a phosphor formed AIOOH 109) by a A100H luminescent layer is formed by bonding the phosphor formed by the following method, i.e., in an organic solvent at a predetermined ratio so that the aluminum alkyl with an alcohol or an alkoxy aluminum alkoxide hydrolysis, the alumoxane sol or alumina sol obtained by hydrolyzing the solution, the phosphor (powder) was uniformly dispersed to obtain a coating solution, and adjusting the coating solution so as to spray or dusting the coated the phosphor is dispersed in an alumina sol solution, so as to cover the entire light emitting element, and then cured by heating, whereby a phosphor composition AIOOH be fixed to each other, and fixed to the surface of the light emitting element.

烷基醇铝或烷氧基铝是作为涂料的增粘剂、凝胶化剂、固化剂、 聚合催化剂以及颜料的分散剂使用的有机铝化合物。 Alkyl aluminum alkoxides or aluminum alkoxide as a paint thickener, gelling agent, a curing agent, a polymerization catalyst and an organic aluminum compound used in the pigment dispersant.

作为烷基醇铝或烷氧基铝之一的异丙氧基铝、乙氧基铝以及丁氧基铝非常富有反应性,借助于空气中的水分生成氢氧化铝或垸基铝酸盐,生成具有勃姆石结构的水合氧化铝。 Aluminum isopropoxide as an aluminum alkyl alcohol or one of aluminum alkoxide, aluminum ethoxide, aluminum butoxide and very high reactivity, moisture in the air by means of production of hydrogen or alkyl with aluminum aluminates, generating a hydrated alumina having a boehmite structure. 例如异丙氧基铝如以下的化学式7所示的那样,容易与水反应,最终成为以水合氧化铝为主成分、 具有与氢氧化铝或氧化铝(矾土)进行交联的交联结构的混合物。 E.g. aluminum isopropoxide as the following chemical formula 7 as shown, easily reacts with water, to eventually become hydrated alumina as a main component, a crosslinked structure crosslinked with aluminum hydroxide or aluminum oxide (alumina) mixture.

43因此,使异丙氧基铝与空气中的水分反应后,采用加热生成的AIOOH粘结荧光体,从而可以将由含有荧光体的AIOOH粘结荧光休而成的发光层作为发光层形成在发光元件的表面上以及发光元件的表面以外的支持体上。 After 43 Thus, the reaction of aluminum isopropoxide moisture in the air, using heat generated AIOOH bonded phosphor, and can be bonded by the light emitting layer containing a fluorescent phosphor AIOOH Hugh formed as a light emitting layer formed on the light emitting the upper surface of the support member and the upper surface other than the light emitting element.

以上由AIOOH粘结荧光体而成的发光层,也可以组合由Y、 Gd、 Lu、 Sc、 Ga、 In、 B等其它水合氧化物粘结荧光体而成的发光层和由A100H粘结荧光体而成的发光层,从而在同一发光元件上形成2种或2种以上的层。 More light emitting layer body formed by bonding AIOOH fluorescent, light emitting layer material may be combined by other hydrated oxide formed by bonding phosphor Y, Gd, Lu, Sc, Ga, In, B, etc., and a fluorescent binding A100H emitting layer body formed thereby or more kinds of two kinds of layer are formed on the same light-emitting element. 根据本实施方案的采用喷涂的发光层的形成方法,l大l 为也可以控制两层的膜厚,故而容易形成同样形状的发光层。 The method for forming the light emitting layer by spraying the present embodiment, the large-l l is the thickness of the two layers can be controlled, and therefore the light emitting layer is easily formed the same shape. 例如在同一发光元件上,首先形成¥203发光层,然后在其上形成八1203发光层。 For example, in the same light emitting element, the light emitting layer is first formed ¥ 203, and the light emitting layer 1203 is formed eight thereon. 在此,荧光体可以包含在两层双方之中,也可以只包含在一层中, 而且也可以在两层双方之中都不包含。 Here, the phosphor may be included in the two sides may be included only in one layer, but also not included in the two sides. 如果采用这样的构成,则具有通过荧光层的折射率的大小以提高光取出效率等效果。 With this configuration, it has a light extraction efficiency by improving the refractive index of the phosphor layer size effect. 当形成由一/S 构成的发光层时,则在该发光层与外界气氛或氮化物半导体发光元件的界面产生折射率的急剧变化,从发光元件取出的光的一部分可能在该界面发生反射,因而导致光取出效率的低下。 When forming the light emitting layer composed of a / S, is an abrupt change in refractive index at the interface between the light emitting layer from the outside atmosphere or a nitride semiconductor light emitting element, the light emitting element extracted from a portion of the reflected light may occur at the interface, thereby resulting in low light extraction efficiency. 另外,通过形成例如混合有A100H和YOOH的发光层,也可以调整线膨胀系数和折射率。 Further, for example, by forming the mixed layer and the light emitting A100H YOOH may also adjust the refractive index and linear expansion coefficient.

由这样形成的AIOOH粘结荧光体而成的发光层,因为是与以前的树脂不同的无机物,所以与树脂相比,由紫外线引起的退化极小, 也可以组合使用发出紫外光的发光元件和高输出功率的动力型LED 等。 Emitting layer body formed by bonding AIOOH phosphor thus formed, as is different from the previous inorganic resin, as compared with the resin minimal degradation caused by ultraviolet rays, may be used in combination of the light emitting element emits ultraviolet light and other high-powered LED output power.

(LED芯片101) (LED chip 101)

在本实施方案中,作为发光元件使用的LED芯片101能够激发荧光体。 In the present embodiment, used as the light emitting element 101 can be an LED chip excites the phosphor. 作为发光元件的LED芯片101是采用MOCVD等方法在基休上形成GaAs、 InP、 GaAlAs、 InGaAlP、 InN、 A1N、 GaN、 InGaN、 AlGaN、 InGaAlN等半导体作为发光层。 An LED chip emitting element 101 is formed GaAs, InP, GaAlAs, InGaAlP, InN, A1N, GaN, InGaN, AlGaN, InGaAlN semiconductor such as a light emitting layer on the substrate off the MOCVD method and the like. 作为半导体的结构,可以列举出具有MIS结、PIN结和PN结等的均质结结构、异质结结构或双 As the structure of the semiconductor may include a homojunction structure having MIS junction, PIN junction and the PN junction or the like, or a double heterojunction structure

44异质结结构。 44 heterojunction structure. 可以根据半导体层的材料及其混晶度对发光波长进行各种选择。 Can be variously selected depending on the material of the emission wavelength of the semiconductor layer and the crystallinity thereof. 另外,也可以设定为在产生量子效果的薄膜上形成有半导体活性层的单量子阱结构或多重量子阱结构。 Further, there may be set to the semiconductor active layer is formed of a single quantum well structure or a multiple quantum well structure in the film quantum effect. 优选的是能够高效激发突光体且能够高效地发出波长较短的光的氮化物系化合物半导体(通式 Preferably the projections can be efficiently excited and capable of emitting light nitride-based compound semiconductor light of shorter wavelength (Formula efficiently

为IiiiGajAlkN,其中,0《i、 0《j、 0《k, i+j+k=l)。 Is IiiiGajAlkN, where, 0 "i, 0" j, 0 "k, i + j + k = l).

在使用氮化镓系化合物半导体的情况下,适于用作半导体基体的材料有:蓝宝石、尖晶石、SiC、 Si、 ZnO、 GaN等。 In the case where the material gallium nitride-based compound semiconductor, suitable for use as the semiconductor substrate include: sapphire, spinel, SiC, Si, ZnO, GaN and the like. 为了形成结晶性良好的氮化镓,更优选使用蓝宝石基板。 In order to form gallium nitride of good crystallinity, and more preferably to use a sapphire substrate. 当在蓝宝石基板上生长半导体膜时,优选形成GaN、 A1N等缓冲层后,再在缓冲层上形成具有PN 结的氮化镓半导体。 When a semiconductor film is grown on a sapphire substrate, preferably formed of GaN, A1N, etc. after the buffer layer, and then forming gallium nitride semiconductor having a PN junction on the buffer layer. 另外,也可以将GaN单晶本身用作基板,其屮GaN单晶是在蓝宝石基板上以Si02为掩模进行选择生长而成的。 Further, the GaN single crystal itself may be used as the substrate, which is to Si02 Che GaN single crystal obtained by growth selection on a sapphire substrate as a mask. 在这种情况下,在各半导体层形成后,也可以通过浸蚀并除去Si02而使发光元件与蓝宝石基板分离。 In this case, after forming the semiconductor layers, may be removed by etching and the light emitting element Si02 separated from the sapphire substrate. 氮化镓系化合物半导体在不掺杂的情况下表现出n型导电性。 Gallium nitride compound semiconductor exhibits n-type conductivity without doping. 在形成包括提高发光效率等要求的n型氮化镓半导体的情况下,作为n型惨杂剂,优选适当导入Si、 Ge、 Se、 Te以及C等元素。 In the case of forming including improved luminous efficiency requirements of n-type gallium nitride semiconductor, an n-type suffer heteroaryl, preferably suitably introduced Si, Ge, Se, Te and C and other elements. 另一方面,在形成p型氮化镓半导体的情况下,则掺杂作为p型掺杂剂的Zn、 Mg、 Be、 Ca、 Sr以及Ba等。 On the other hand, in the case of forming a p-type gallium nitride semiconductor, the Zn-doped p-type dopant, Mg, Be, Ca, Sr and Ba and the like.

氮化镓系化合物半导体如果只是掺杂p型掺杂剂,则难以实现p 型化,所以在导入p型掺杂剂以后,优选采用炉子加热、低速电子束照射以及等离子体照射的方法进行退火,由此实现p型化。 If only the gallium nitride compound semiconductor doped with p-type dopants, p-type is difficult to achieve, so after introducing the p-type dopant, preferably using a heating furnace, low speed electron beam irradiation method and a plasma irradiation annealing , thereby achieving p-type. 作为具体的发光元件的层构成,可以举出的适当的例子是由以下层层叠而成的, 即在具有于低温下形成有氮化镓、氮化铝等缓冲层的蓝宝石基板或碳化硅上,层叠作为氮化镓半导体的n型接触层,作为氮化铝*镓半导体的n型包层,作为掺杂Zn及Si的氮化铟镓半导体的活性层,作为氮化铝•镓半导体的p型包层以及作为氮化镓半导体的p型接触层。 As a specific layer constituting the light emitting element, suitable examples may be mentioned are the following layers are laminated, at low temperature i.e. having formed on a sapphire substrate has a gallium nitride or silicon carbide, aluminum nitride buffer layer stacking an n-type contact layer is gallium nitride semiconductor, the n-type cladding layer * aluminum gallium nitride semiconductor, doped with Zn as an active layer of indium gallium nitride, and Si semiconductor as a semiconductor is gallium nitride aluminum • the p-type cladding layer and a p-type contact layer is gallium nitride semiconductor. 为了形成LED芯片101,对于具有蓝宝石基板的LED芯片101的怙况,在通过浸蚀等形成p型半导体以及n型半导体的露出面后,在半导体层上使用溅射法和真空蒸镀法等形成具有所要求形状的各个电 In order to form the LED chip 101, the status of the LED chip to presume the sapphire substrate 101 has, after forming the p-type semiconductor and n-type semiconductor surface exposed by etching and the like, using a sputtering method and a vacuum deposition method and the like on the semiconductor layer, forming respective electrical connection having a desired shape

45极。 45 poles. 对于SiC基板的情况,利用基板本身的导电性也可以形成一对电极。 In the case of the SiC substrate, a conductive substrate itself may be formed a pair of electrodes.

接着对形成的半导体晶片等进行划片,划片或者是采用钻石轮划 Next, the semiconductor wafer is formed dicing, scribing using a diamond wheel or zoned

片机进行的直接的完全切割(fliU cut),其中钻石轮划片机的刀片具有金刚石制刀刃,切割时刀刃旋转;或者是在切出比刀刃宽度更宽的槽后(halfcut),利用外力分开半导体晶片。 Direct completely cut (fliU cut) sheet machine, wherein the diamond blade wheel machine having designated a diamond blade, rotating cutting blade; or after cutting out the groove wider than the width of the blade (halfcut), by an external force separated from the semiconductor wafer. 或者借助于顶端的金刚石针作往复直线运动的钻石轮划片机在半导体晶片上划出极细的划线(经线),例如划成网纹状,然后利用外力分开晶片,从而由半导体晶片切割成芯片状。 Or by means of a diamond needle tip reciprocating linear motion dicing saw machine draw on the semiconductor wafer fine scribe (meridian), for example, classified into a wavy, then an external force to separate the wafer to cut the semiconductor wafer into chips. 这样,便可以形成作为氮化物系化合物半导体的LED芯片101。 Thus, they may be formed as a nitride-based compound semiconductor LED chip 101.

在本实施方案的发光装置中,在发光的情况下,考虑到与荧光体的发光颜色互补,LED芯片101的主发光波长优选为350nm〜530腿。 In the light emitting device of the present embodiment, the light emission in the case, taking into account the complementary colors of the light emitting phosphor, the main emission wavelength of the LED chip 101 is preferably 350nm~530 leg. (金属壳体105) (Metal case 105)

本发明的一实施方案的发光装置中使用的金属壳体105由收容发光元件的凹部a和配置了引线电极的基底部b所构成,金属壳体105 作为发光元件的支持体发挥作用。 A metal case the light emitting device of the embodiment of the present invention is used in the light emitting element 105 by a receiving recess portion and a base portion arranged lead electrode b formed, the metal housing 105 as a support of the light emitting element functioning. 所述凹部的底面与所述引线电极的底面大致位于同一面上。 The bottom surfaces of the concave portions of the lead electrode is located substantially in the same plane.

在发光装置中,考虑的散热性和小型化,壳体优选用薄膜来形成。 In the light-emitting device, and miniaturization of the heat dissipation considerations, the housing is preferably formed with a thin film. 另一方面,绝缘构件设置在与引线电极的界面上,为了缓和与该绝缘构件的诸如热膨胀率之差并提高可靠性,有必要增大各自的接触而。 On the other hand, an insulating member is provided at the interface between the lead electrode, in order to mitigate the difference in thermal expansion coefficient between the insulating member and is such as to improve the reliability, it is necessary to increase the respective contact. 于是,本发明者在金属壳体中,区分配置发光元件的部分和固定引线电极的部分,与各自的区域相适应设定形状和膜厚,藉此谋求可靠性的提高。 Thus, the present inventors in a metal case, the distinction between the light emitting element part of the configuration of the fixed portion and the lead electrode, the respective shape and area adapted to set the film thickness, thereby to seek improvement in reliability.

(引线电极102) (Lead electrodes 102)

本发明的实施方案的发光装置具有正的以及负的引线电极102, 引线电极102隔着绝缘构件插在设置于金属壳体的基底部的贯通孔内。 The light emitting device of the embodiment of the present invention, having a positive lead and a negative electrode 102, the lead electrode 102 provided via an insulating member is inserted in the base through hole of the metal shell. 所述引线电极的顶端部从所述基底部的表面突出出来,且所述引线电极的底面与所述凹部的安装面侧的底面大致处在同一平面上。 Mounting the bottom surface of the tip portion of the side surface of the lead electrodes protrude from a surface of said base portion out, and a bottom surface of the lead electrode and the concave portion is substantially in the same plane. 200480006816.X 200480006816.X

(引线106) (Lead 106)

本发明的一实施方案的发光装置在金属壳体105的主面侧,具有透光性窗部107和由金属部构成的引线106。 The light emitting device of one embodiment of the present invention, the main surface side of the metal housing 105, having a light-transmissive window portions 107 and 106 by the lead portion formed of metal. 窗部107优选为发光装置的发光面且配置在发光装置的中央部。 Window portion 107 is preferably a light emitting surface and the light emitting device arranged in the center portion of the light emitting device.

在本实施例中,所述窗部位于配置在所述金属壳体凹部的发光元件的上面,并与所述凹部内壁的延长线相交。 In the present embodiment, the window portion is located above the light emitting element disposed in the recess portion of the metal housing, and intersects an extension line of the inner wall of the recess. 从所述发光元件的端部发出的光在所述凹部的侧面产生漫反射并于正面方向取出。 Light emitted from the light emitting element is an end portion of the diffuse reflection on the side surface of the recess and taken out to the front direction. 这些漫反射光的存在范围一般认为大致在所述凹部侧面的延长线内。 The present scope of diffuse reflected light is generally considered to be within an extension line substantially in the concave portion side surface. 于是,通过像上述那样调整作为发光面的窗部的面积,所述漫反射光可以有效地聚焦在所述窗部,从而可以得到能够发出高辉度光的发光装置。 Thus, by adjusting the like that as the area of ​​the window portion of the light-emitting surface, the diffuse reflection light can be efficiently focused on the window portion, can be obtained a light emitting device capable of emitting light of high luminance. (壳体114) (Housing 114)

如图5所示,在本发明的又一实施方案中使用的壳体114作为在凹部内固定并保护LED芯片101的支持体发挥作用。 5, a further embodiment of the housing used in the embodiment of the present invention 114 as a fixed support and protect the LED chip 101 to play a role in the recess portion. 另外,还具冇能够与外部进行电接触的外部电极102A。 Further, the external electrode also has Nuisance 102A can be electrically contact with the outside. 与LED芯片101的数量与人小相适应,壳体114也可以设计为具有多个开口部。 And the number of human small LED chip 101 is adapted to, the housing 114 may be designed to have a plurality of openings. 为使之具冇合适的遮光机能,壳体114被着色成黑色或灰色等暗色系,或者壳体114 的发光观测表面侧被着色成暗色系。 To make this device suitable Nuisance shielding function, like the housing 114 is colored in black or gray dark color, or the emission observation surface side of the housing 114 is colored in a dark color. 为了进一步保护LED芯片101 免受外部环境的侵害,除涂层1U、 112以外,还可以设置作为透光性保护体的铸模构件113。 To further protect against the LED chip 101 from the external environment, in addition to the coating 1U, 112, 113 may be provided as a translucent mold member of the protector. 壳体114优选的是与涂层111、 112以及铸校构件113的粘结性好且刚性强。 Preferably the housing 114 with a coating 111, 112, and adhesion member 113 cast correction and good rigidity. 为了对LED芯片101和外部迸行电绝缘,壳体114优选具有绝缘性。 To the LED chip 101 and electrically insulated from the outside into line, the housing 114 preferably has insulating properties. 再者,壳体114在受到源于LED芯片101等的热的影响的情况下,考虑到与铸模构件113的附着力,优选具有较小的热膨胀率。 Further, the housing 114 in the case of affected by the heat from the LED chip 101 and the like, taking into account the adhesion of the mold member 113, preferably having a small thermal expansion coefficient.

LED芯片101与壳体114的粘结也可以采用热固性树脂等进行。 Bonding the LED chip 101 and the housing 114 may also be a thermosetting resin or the like. 具体地说,可以列举出环氧树脂、丙烯酸树脂以及酰亚胺树脂等。 Specifically, it includes epoxy resin, acrylic resin and imide resin. 在发光装置使用发出含有紫外线的光的LED芯片并于高输出功率下加以使用的情况下,对于LED芯片101与壳体114的粘结部分,因为由LED芯片发出的紫外线等也被作为密封构件的树脂或包含在其中的 In the case of containing the ultraviolet light emitted in the light emitting device using an LED chip and used in a high output power for the LED chip 101 and the bonding portion of the housing 114, because ultraviolet rays emitted by the LED chips is used as a sealing member resins contained therein or

47荧光体等所反射,光特别在壳体内变成高密度,因此,粘结部分的树脂因紫外线而退化,故而可以认为因树脂的黄变等而导致发光效率的低下以及因粘结强度的低下而导致发光装置寿命的降低。 47 reflected by the fluorescent material, light becomes particularly high density in the housing, and therefore, resin-bonded portions due to UV degradation, and therefore can be considered due to yellowing caused by the resin, and emission efficiency due to low bond strength low resulting in reduced life of the light emitting device. 为防止这样的因紫外线而引起的粘结部分的退化,可以使用含有紫外线吸收剂的树脂,更优选的可以使用本发明的实施方案的无机物等。 To prevent degradation of the bonding portion due to such ultraviolet rays cause, a resin containing an ultraviolet absorber, an inorganic material may be used and more preferably an embodiment of the present invention, and the like. 特别地,在 In particular,

壳体使用金属材料的情况下,LED芯片101与壳体114的粘结除了使用本发明的实施方案的无机物以外,也可以使用Au-Sn等的共晶软钎料等。 A case where a metal housing material, bonding the LED chip 101 and the housing 114 except for using an inorganic substance embodiments of the present invention may also be used such as Au-Sn eutectic solder and the like. 因此,与使用树脂进行粘结的情况不同,本发明即使在发光装置使用发出含有紫外线的光的LED芯片并于高输出功率下加以使用的情况下,其粘结部分也不会退化。 Under Thus, unlike the case using a resin for bonding with the present invention, even if ultraviolet rays emitted light contained in the light-emitting device using an LED chip and used under high output power, the bonding portion thereof is not degraded.

另外,在配置并固定LED芯片101的同时,为了与壳体114内的外部电极102A进行电接触,适合使用Ag浆料、碳浆料、ITO浆料以及金属凸缘等。 Further, in the configuration fixing the LED chip 101 and at the same time, in order to perform electrical connection with the external electrode 114 in contact with the housing 102A, suitably used Ag paste, carbon paste, the ITO and metal paste such as a flange.

(外部电极102A) (External electrode 102A)

图5所示的外部电极102A是用于从壳体114的外部向配置在内部的LED芯片IOI供给电力的电极。 External electrodes 102A shown in FIG. 5 for supplying electric power to the electrode disposed inside the LED chip from outside the housing 114 of the IOI. 因此,可以列举出利用了设置在壳体114上的、具有导电性的图案和引线框的各种电极。 Thus, it includes use of various electrode having a conductive pattern and the lead frame 114 is disposed on the housing. 另外,考虑到外部电极102A的散热性、电传导性以及LED芯片101的特性等, 可以形成为各种各样的大小。 Further, considering the heat dissipation of the outer electrode 102A, and the electrical conductivity characteristics of the LED chip 101 may be formed in various sizes. 外部电极102A在配置各LED芯片101 的同时,为了将LED芯片IOI放出的热传递到外部,优选具有良好的热传导性。 External electrodes 102A arranged in each of the LED chip 101 while the LED chip to the heat emitted IOI transferred to the outside, preferably has good thermal conductivity. 作为外部电极102A的具体的电阻,优选为300" Q • cm 或以下,更优选为3U Q 'cm或以下。另外,具体的热传导系数优选为0.01cal/(s)(cm2)(。C/cm)或以上,更优选为0.5cal / (s)(cm2)rC/cm) 或以上。 As a specific resistance of the external electrode 102A is preferably 300 "Q • cm or less, more preferably 3U Q 'cm or less. Further, the thermal conductivity particularly preferably 0.01cal / (s) (cm2) (. C / cm) or more, more preferably 0.5cal / (s) (cm2) rC / cm) or more.

作为这样的外部电极102A,适合使用的有在铜或磷青铜板表面镀覆了钯或金等的金属或者进行了焊镀(soldering plating)的材料。 Examples of such external electrodes 102A, suitable for use with a copper or phosphor bronze plate surfaces of the metal plating palladium or gold, or the like were plated solder (soldering plating) material. 在将引线框用作外部电极102A的情况下,可以根据电导率、热传导系数的不同而以各种方式加以利用,但从加工性的角度考虑,板厚优选为0.1mm〜2 mm。 In the case where the lead frame is used as the external electrodes 102A, may be utilized in various ways according to the different conductivity of the thermal conductivity, but in view of workability, the thickness is preferably 0.1mm~2 mm. 作为在玻璃环氧树脂和陶瓷之类的支持体等的上面设置的外部电极102A,可以形成铜箔和钨层。 External electrodes 102A above a glass epoxy resin and a ceramic is provided to support the like, may be formed of copper foil and a tungsten layer. 当在印刷电路板上使用金属箔时,作为铜箔等的厚度,优选设定为18um〜70um。 When a metal foil on a printed circuit board, the thickness of the copper foil, is preferably set to 18um~70um. 另外, 也可以在铜箔等的上面镀覆金或进行悍镀。 In addition, gold may be plated on top of copper foil or plating defended. (导电性引线104) 作为导电性引线104,要求与LED芯片101之电极的接触电阻小, 并具有良好的机械连接性、电传导性以及热传导性。 (Conductive lead 104) The conductive wires 104, the contact resistance with the requirements of the LED chip 101 of the electrode is small, and has a good mechanical connectivity, electrical conductivity and thermal conductivity. 作为热传导系数, 优选为O.Olcal / (s)(cm2)(。C/cm)或以上,更优选为0.5cal / (s)(cm2)(°C /cm)或以上。 As the thermal conductivity, preferably O.Olcal / (s) (cm2) (. C / cm) or more, more preferably 0.5cal / (s) (cm2) (° C / cm) or more. 另外在形成高输出功率的发光装置的情况下,考虑到工艺性等因素,导电性引线104的直径优选为4)10um〜(b70um。作为这样的导电性引线104,具体地可以列举出使用金、铜、铂金以及铝等金属及其合金的导电性引线。这样的导电性引线104借助于引线接合设备很容易将各LED芯片101的电极、内部引线以及管脚引线等 Also in case of forming the light emitting device of high output power, taking into account factors such as processability, diameter of the conductive wire 104 is preferably 4) 10um~ (b70um. Examples of the electrically conductive wire 104, in particular may be used include gold conductive leads of copper, platinum and metal such as aluminum and its alloys. such a conductive wire 104 by means of a wire bonding apparatus is easy electrode of each LED chip 101, inner leads and the like pinouts

连接起来。 connect them.

(铸模构件U3) (Mold member U3)

铸模构件113可以根据发光装置的使用用途而设置,以用于保护LED芯片101、导电性引线104以及含有荧光体的涂层111、 112等免受外界的侵害或用于提高光取出效率。 Mold member 113 may be provided a light emitting device according to the intended use, for protecting the LED chip 101, a conductive lead 104 and a coating 111 comprising phosphor 112 from external damage or the like to improve light extraction efficiency. 铸模构件113可以用各种树脂和玻璃来形成。 Mold member 113 may be formed of various resins and glass. 作为铸模构件113的具体材料,适合使用的主要有: 环氧树脂、尿素树脂、硅树脂以及氟树脂等耐侯性优良透明树脂和玻璃等。 As a specific material of the mold member 113, suitable for use are: epoxy resin, urea resin, silicone resin, fluorine resin or the like and excellent in weather resistance transparent resin and glass. 另外,通过在铸模构件中含有扩散剂,也可以缓和来自于LED 芯片101的光的指向性以及增加视场角。 Further, by containing a diffusing agent in the mold member, it is possible to mitigate the directivity of light from the LED chip 101 and increasing viewing angle. 这样的铸模构件113可以使用与涂层的粘接剂、粘结剂相同的材料,也可以使用不同的材料。 Such a mold member 113 may be used with the adhesive coating layer, the same binder material, different materials may be used.

此外,当使用金属壳体、使LED芯片101与氮气一起被气密时, 铸模构件113不是本发明必须的构成。 Further, when a metal housing, the LED chip 101 and the nitrogen together hermetically, the mold member 113 is not an essential constituent of the present invention. (喷涂装置300) (Spray apparatus 300)

如图6以及图7所示,本实施方案使用喷涂装置300,该喷涂装置300分别使用输送管307、 308、 309将收容涂布液的容器301、调 6 and FIG. 7, the present embodiment uses the spray apparatus 300, the spray device 300, respectively, using the delivery tube 307, 308, 309 of the coating liquid storage container 301, transfer

49节涂布液的流量的阀302、把涂布液输送到喷嘴201后再从喷嘴201 输送到容器301的循环泵303以及使涂布液203以螺旋状的形式喷出的喷嘴201连接起来。 Section 49 of the flow valve 302 of the coating liquid, the coating liquid supplied to the delivery nozzle 201 from the nozzle 201 and then the circulation pump 303 to the container 301 and the coating liquid 203 discharged in the form of a spiral nozzle 201 connected . (容器301) (Container 301)

在收容涂布液的容器301内安装着搅拌机304,在涂布作业中经常搅拌涂布液。 Mixer 304 is mounted within the container 301 accommodating the coating solution, the coating solution was stirred constantly during the coating operation. 被容器301收容的涂布液203采用搅拌机304经常搅拌,从而涂布液203中所含的荧光体202常常均匀分散在溶液中。 The container 301 is accommodated coating solution using a stirrer 203 304 regular stirring, whereby the phosphor 202 contained in the coating liquid 203 is often uniformly dispersed in the solution. (阀302) (Valve 302)

阀302借助于阀的开闭调节由容器301通过输送管309输送来的涂布液的流量。 Valve opening and closing valve 302 by means of adjusting the flow rate of the coating liquid container 301 through the delivery tube 309 of delivery.

(循环泵303) (Circulation pump 303)

循环泵303通过输送管309将涂布液从容器301经由阀302和压縮机305输送到喷嘴201的顶端部,此后,将没有从喷嘴201喷出的而残留下来的涂布液通过输送管308输送到容器301。 A circulation pump 303 conveyed by the coating liquid 309 delivered from the container 301 via the valve 302 and the compressor 305 to the tip portion of the nozzle 201, thereafter, the remaining not discharged from the nozzle 201 through the coating liquid down the delivery tube 308 delivered to the container 301. 涂布液由于借助于循环泵303通过输送管309从容器301经由阀302被输送到喷嘴201的顶端部,此后,通过输送管308被输送到容器301,所以,涂布液常常处于在喷涂装置内循环的状态。 Since the coating solution by means of a circulation pump 303,309 is transported from the container 301 via the valve 302 to the nozzle 201 by a tip portion of the delivery tube, thereafter, is conveyed to the vessel 308 through the feed pipe 301, therefore, the coating solution is usually in the spray device circulating state. 因此,涂布液因为处于遍及整个喷涂装置的搅拌或循环的状态,所以涂布液中含有的荧光体在涂布作业中经常处于均匀的分布状态。 Thus, because the coating liquid is stirred or circulated state throughout the spraying device, so that the phosphor coating liquid contained in the coating operation are often in a uniform distribution. (压縮机305) (Compressor 305)

压缩机305通过输送管307或309设置在装置内,压縮通过输送管307输送来的空气,调节通过输送管309输送来的涂布液的压力。 The compressor 305 through the delivery tube 307 or 309 is provided within the device, the delivery tube 307 is compressed by the air conveyed, by adjusting the pressure delivery tube 309 conveyed coating solution. 借助于压缩机305,压縮空气和进行过压力调节的涂布液分别输送到喷嘴201。 By means of a compressor 305, compressed air and the pressure regulating been conveyed to the coating liquid nozzle 201, respectively. 在此,压缩空气的压力通过压力计306进行监视。 Here, the compressed air is monitored by a pressure gauge 306. 使用以上的喷涂装置300,与高压气体一起高速喷出涂布液,喷涂在发光元件的上面、侧面以及角上。 Using the above coating apparatus 300, the high-speed high-pressure gas discharged together with the coating liquid sprayed on the light emitting element above, the sides and corners. (喷嘴201) (Nozzle 201)

在本实施方案中,所使用的装置的特征在于:涂布液和气体(在 In the present embodiment, features of the apparatus used in that: the coating liquid and the gas (

50这里为空气)通过喷嘴201以螺旋状的形式喷出。 50 here, air) is ejected through a nozzle in a spiral form 201. 该装置的喷嘴的周围设置若干个气体喷出口,从这些喷出口喷出的气体的喷出方向相对于被涂布的表面各自成某一角度。 Nozzle means disposed around the plurality of gas discharge ports, the discharge direction from the discharge port of the gas discharged with respect to each of the coated surface at an angle. 因此,当同时向以涂布液的喷出口为中心旋转的这些气体喷出口送入气体时,将从各自的喷出口喷出的气体集中在一起的整个气体的流动,成为颠倒过来的涡壳状的流动、 螺旋状的流动或龙巻风中的空气的流动。 Thus, when the gas fed to the discharge port while the gas discharge port of the coating liquid for the center of rotation, the discharge from the discharge port of each gas concentration throughout the gas flow together, become reversed volute shaped flow, spiral flow of air flow or long Volume wind. 另外,在该装置的喷嘴的中心设置有涂布液的喷出口,当与气体的喷出同时喷出涂布液时,成为雾状的涂布液趁颠倒过来的涡壳状的流动、螺旋状的流动或龙巻风屮的空气的流动而扩散开来。 Further, in the center of the nozzle of the apparatus is provided with the coating liquid discharge outlet, when the discharge gas while discharging the coating liquid, the coating liquid into a mist while upside down scroll-shaped flow, spiral shaped flow of air flow or wind Che Long Volume of the spread.

扩散成螺旋状的整个喷雾的直径从发光元件上方的喷射起始点开始,越靠近发光元件的表面,直径变得越大。 Spread into the entire diameter of the spiral spray injection start point above the beginning of the light emitting element, the light emitting element closer to the surface, the diameter becomes larger. 另外,从发光元件上方的喷射起始点开始,越靠近发光元件的表面,由涂布液构成的喷雾的旋转速度越小。 Further, the injection start point starting from the top of the light emitting element, the light emitting element closer to the surface, the rotation speed of the coating solution consisting of spraying smaller. 也就是说,当雾状的涂布液从喷嘴喷出并在空气屮扩散时,在喷射起始点即喷嘴的附近,喷雾呈圆锥状扩散开来,而在离开喷嘴的地方,喷雾呈圆柱状扩散开来。 That is, when the atomized coating liquid is discharged from the nozzle and spread in the air Cao, i.e. starting in the vicinity of the injection nozzle, spray conical spread, while leaving the nozzle in place, cylindrical spray spread. 于是,本实施例优选对发光元件的上面到喷嘴的下端之间的距离进行调节并进行设置,使得发光元件的表面出现在喷雾处于呈圆柱状扩散开来这一状态的地方。 Thus, the present preferred embodiment of the above embodiment the light emitting element is adjusting the distance between the lower end of the nozzle and disposed so that the surface of the light emitting element appear where the spray is spread to the cylindrical state. 此时的喷雾呈螺旋状旋转,且速度较慢,因此,喷雾能够绕到处于导电性引线阴影之下的发光元件表面上,不仅整个发光元件上面、而且整个侧面都能充分喷到。 At this time, the rotation of spiral spray, and slow, thus, can be sprayed on the surface around the light emitting element is electrically conductive wires under the shadow, not only the entire light-emitting element above, but can be adequately sprayed onto the entire side. 由此,可以在固定发光元件或喷嘴的状态下进行作业。 Thus, work can be performed in a fixed state light-emitting elements or nozzles. 另外,因为在喷雾处于呈圆柱状扩散开来这一状态的地方,喷雾的速度较慢,所以当喷雾喷涂在发光元件的表面时,发光元件的表面不会受到喷雾中所含有的荧光体粒子的冲击。 Further, since the spray is diffused by cylindrical state where the spray slower, when the spray coating on the surface of the light emitting element, the light emitting element of the surface will not be sprayed in the phosphor particles contained in the impact. 另外,不会产生导电性引线的变形和断线,从而使产品合格率和工艺性提高。 Further, no distortion and disconnection of the electrically conductive wire, so that the product yield of the process and improved. (加热器205) (Heater 205)

如图6所示,本实施方案的涂布后的发光元件在加热器205上处于温度为50。 6, the light emitting element after coating in this embodiment on the temperature of the heater 50 in 205. C〜500。 C~500. C的加热状态。 C in a heated state. 作为这样地使发光元件处于加热状态的方法,也可以使用在烘箱等加热装置内加热发光元件的方法。 As the light emitting element in such a way that the process in a heated state may be used a method of heating the light emitting element in an oven or other heating means.

51通过加热,使乙醇、微量包含在处于凝胶状态的水解液中的水分以及 51 by heating, ethanol, trace moisture contained in the hydrolysis solution in a gel state as well as

溶剂蒸发,而且由处于凝胶状态的涂布液203可以得到非晶质的Al(OH)3禾卩A100H。 The solvent was evaporated, and the coating solution is in a gel state 203 can be obtained amorphous Al (OH) 3 Wo Jie A100H. 再者,本实施方案的涂布液203由于进行了粘度调节,所以喷涂在发光元件的上面、侧面以及角上、进而在支持休204 的表面之后,不会从喷涂的场所流出来。 Further, the coating slurry 203 of this embodiment as a result of adjusting the viscosity, it is sprayed in the above light emitting element, the sides and corners, and thus the support surface after the break 204, the spray will not flow out from the place. 于这些场所在涂布之后不久便进行加热,这样通过由AIOOH将荧光体粘结而成的涂层可以覆盖发光元件的上面、侧面以及角上的部分。 In these locations will be shortly after the coating is heated, so that the adhesion by the coating formed AIOOH phosphor may cover the light emitting portion of the above elements, and the angular side.

在本实施方案中,使粘结液处于温度为50'C〜50(TC的加热状态, 藉此发光元件可焊接在支持体204上。作为这样地处于加热状态的方法,可以将发光元件设置在加热器上,也可以使用在烘箱等加热装置内加热发光元件的方法。当通过加热、使乙醇、微量包含在处于凝胶状态的水解液中的水分以及溶剂蒸发时,就可以由处于凝胶状态的粘结液得到粘结层,该粘结层以A100H为主成分,由许多粒径为儿个纳米的粒子密集形成。该粘结层是由以无机物为主成分的、粒径为儿个纳米的粒子密集在一起而形成的,在粒子间存在空隙。如果在粘结层上施加的温度发生急剧变化,则由于热应力的作用,各自粒子的休积发生膨胀或收縮。因此,和不存在上述粒子而由热膨胀系数与支持体材料有很大差异的熔融玻璃或树脂粘结发光元件的情况不同,本实施方案的粘结层作为 In the present embodiment, the bonded liquid at a temperature of 50'C~50 (TC heated state, whereby the light emitting element 204 may be welded on a support. As a method in this manner in a heated state, the light emitting element may be provided the heater may be used a method of heating the light emitting element in an oven or other heating device. when heated, ethanol, contained in trace amounts in the gel state of the hydrolyzate in water and the solvent was evaporated, the condensate can be made in liquid glue bonding adhesive layer to give a state, the adhesive layer A100H main component, by a number of particle diameter of child particles nanometers densely formed is dominated by the bonding layer to the inorganic component, the particle size child particle nanometers formed close together, the presence of voids between the particles. If the abrupt change in temperature applied on the adhesive layer occurs due to thermal stress, the product off their particles expands or contracts. Thus and a case where the molten resin bonded glass or absence of the light emitting element of the particles are very different from the thermal expansion coefficient different support materials, the adhesive layer of the present embodiment as 个整体不会因热应力而受到太大的影响,粘结层的剥离和龟裂等也不会发生。因此,即使发光装置在施加的温度发生急剧变化的状态下使用,本实施方案的发光装置也可以维持其可靠性。 Full thermal stress will not be greatly affected, cracking and peeling the adhesive layer or the like does not occur. Thus, even when the light emitting device used in a state changed dramatically at the applied temperature, the present embodiment is a light emitting apparatus reliability can be maintained.

再者,在本实施方案中,由于粘结液被调整为高粘度,所以该粘结液介于发光元件的基板面和支持体表面之间,而且不会从扩展到发光元件侧面的场所产生流动。 Further, in the present embodiment, since the adhesive liquid is adjusted to a high viscosity, the adhesive was interposed between the substrate surface and the support surface of the light emitting element, and no place to extend from the side of the light emitting element flow. 在这些场所进行芯片焊接后,加热粘结液进行固化。 After die bonding in these locations, heat bonding was cured. 由此,发光元件不会偏离最初被承载的位置而可以形成被AIOOH焊接在支持体上的发光装置。 Accordingly, the light emitting device without departing from the position initially be carried on a light-emitting device AIOOH welded support body may be formed. (屏蔽挡板206) (Shielding shutter 206)

52在本实施方案中,在排列多个壳体的情况下,把发光元件分别焊接在壳体内,并将发光元件的电极与外部电极进行引线接合,然后从 52 in the present embodiment, in a case where a plurality of housing arrangement, the light-emitting element are respectively welded to the housing, and the electrode of the light emitting element is wire-bonded to the external electrodes, and then from

发光元件的上方喷涂涂布液203。 Above the light emitting element 203 of the spray coating solution. 但是,壳体的凹部侧面被设计圆锥形状,当将壳体的凹部侧面作为提高壳体正面方向的光取出效率的反射部加以使用时,如果该凹部的侧面附着涂布液203,则由发光元件发出的光在该侧面产生漫发射,因而难以谋求壳体正面方向的光取出效率的提高。 However, the side surface of the housing recess is designed conical shape when the recessed portion of the side surface of the housing to be used as a front direction of the housing to improve the light extraction efficiency of the reflecting portion, if the side surface of the recessed portion 203 is attached a coating liquid, by light emission improved light generating element emits the diffuse emission side, it is difficult to seek housing front direction of the light extraction efficiency. 于是,在本实施方案中,为防止在壳体的凹部侧面以及外部电极上附着涂布液203,从屏蔽挡板206的上方将涂布液203喷涂在发光元件的表面上。 Accordingly, in the present embodiment, in order to prevent adhesion of the coating liquid 203 on the concave portion side surface of the housing and the external electrodes, the shielding flap 206 from above the coating solution sprayed on the surface of the light emitting element 203 in. 屏蔽挡板206是完全遮盖壳体的凹部侧面以及外部电极的、设置有大小可以使涂布液203喷涂在发光元件的上面、 侧面以及角上的贯通孔的板,具有金属制屏蔽挡板、强化塑料制屏蔽挡板等。 A concave portion side surface and the external electrode 206 is a shield completely covers the flap of the housing is provided with a size coating liquid 203 may be sprayed on the top, sides and a through-hole on the corner of the light-emitting element panel having a metallic shield baffles, reinforced plastic shield baffles and the like.

(粘结层110) (Adhesive layer 110)

本实施方案所使用的粘结层110是通过处于凝胶状态的有机材料将发光元件与支持体粘贴在一起后、进行加热干燥所形成的非晶质无机物层。 After the adhesive layer 110 used in this embodiment is an organic material in the gel state of the light emitting element are pasted together with the support, for heating and drying the amorphous inorganic material layer is formed. 进一步说,本实施方案的粘结层是存在于支持体上面和发光元件的的基体面之间的连续的无色透明层,而且扩展到发光元件的上面。 Further, the adhesive layer of the present embodiment is continuous between a colorless and transparent layer is present in the base face above the support and the light emitting element, but also to the above light-emitting element.

由于壳体等产生的反射,由LED芯片发出的高能光等在粘结层中变成高密度。 Since the housing like reflections, and other high-energy light emitted from the LED chip into a high density in the adhesive layer. 当将发光强度高、能够发出高能光的氮化物系半导体用作LED芯片时,优选将对这些高能光有耐光性的、含有Si、 Al、 Ga、 Ti、 Ge、 P、 B、 Zr、 Y以及碱土类金属之中的1种、2种或更多种的氧化物作为发光元件和支持体的粘接液加以利用。 When the high luminous intensity, high-energy light is capable of emitting nitride-based semiconductor used as the LED chip, these high-energy light will preferably have light resistance, containing Si, Al, Ga, Ti, Ge, P, B, Zr, Y and one kind, two kinds or more from among an oxide of an alkaline earth metal to be used as an adhesive solution to a support and a light emitting element. 另外,也可以将上述的水合氧化物作为粘结层加以使用。 Further, the above may be used as a binder to be hydrated oxide layer.

作为粘结层的具体的主材料之一,适合使用的有Si02、 A1203、 Zr02、 Y203、 MSi03 (其中,作为M,可以列举出Zn、 Ca、 Mg、 Ba 以及Sr等)等透光性无机构件。 As one specific main material of the adhesive layer, suitable for use with a Si02, A1203, Zr02, Y203, MSi03 (where, as M, include Zn, Ca, Mg, Ba and Sr and the like) non-translucent body parts. 通过这些透光性无机构件,以发光元件的基体面和支持体表面相互对置的方式,使发光元件相对于支持体得以固定。 These inorganic translucent member, the base face manner and the support surface of the light emitting element opposed to each other, the light emitting element is fixed with respect to the support. 在本实施方案中,至少含有选自Si、 Al、 Ga、 Ti、 Ge、 P、B、 Zr、 Y或者碱土类金属之中的1种或多种元素的氧化物,与形成涂层的材料一样,均采用有机金属化合物来形成。 In the present embodiment, at least selected from Si, Al, Ga oxide, one or more elements among Ti, Ge, P, B, Zr, Y, or an alkaline earth metal, and forming the coating material Like, are employed to form the organic metal compound. 如果使用这样的在常温下呈液态的有机金属化合物,则通过添加有机溶剂,可以容易地从工艺性的角度调节粘度并防止有机金属化合物等的凝固物的发生,从而能够使工艺性得以提高。 If such is liquid at normal temperature an organic metal compound, then by adding an organic solvent, can be easily adjusted from a process point of viscosity and prevent coagulation thereof an organometallic compound or the like, thereby enabling the process is improved. 另外,这样的有机金属化合物因为容易发生水解等化学反应而生成氧化物和氢氧化物等无机物,所以借助于至少含有选自Si、 Al、 Ga、 Ti、 Ge、 P、 B、 Zr、 Y或者碱土类金属之中的1种或多种元素的氧化物等,可以不降低LED作为发光元件的性能而容易形成粘结层。 Further, because of such organometallic compounds are readily hydrolyzed to generate a chemical reaction such as inorganic oxides and hydroxides, it is selected by means comprises at least Si, Al, Ga, Ti, Ge, P, B, Zr, Y an oxide of one or more elements from among alkaline earth metal or the like, may not reduce the performance of the light emitting element LED as easily form an adhesive layer. 但是,这些元素中也含有不易着色的物质,所以需要根据用途进行适当的选择。 However, these elements also contain a coloring material can not easily, it is necessary appropriately selected depending on the use. 另外,本实施方案的水合氧化物即粘结剂也具有耐光性和耐热性,因而它们也可以作为粘结层加以使月j。 Further, hydrated oxides i.e. binder present embodiment also has light resistance and heat resistance, and thus they can also be used as the adhesive layer so that month j. 再者,在粘结层扩展到发光元件侧面的情况下,如果用金属软钎料焊接发光元件,则吸收由发光元件发出的从近紫外到蓝色光的金属往往包含在金属软钎料中。 Further, in the case where the adhesive layer to the light emitting element side is extended, if the weld metal solder the light emitting element is absorbed from the near ultraviolet to blue light emitted from the light emitting metal contained in the metal element often solders. 例如,当用Au-Sn共晶软钎料焊接发光元件时,由于Au吸收了由发光元件发出的从近紫外到蓝色的光,因而具有使发光装置的输出功率下降的问题,但基于本实施方案的粘结层不会吸收由发光元件发出的从近紫外到蓝色的光,因而可以形成发光效率高的发光装置。 For example, when using Au-Sn eutectic solder welding the light emitting element, since Au absorbs blue light emitted from the near-ultraviolet to the light-emitting element, the light emitting device thus has a problem of the decrease in output power, but based on the present embodiment of the adhesive layer does not absorb from near ultraviolet to blue light emitted from the light emitting element, therefore a light emitting device with high emission efficiency can be formed.

实施方案3 Embodiment 3

下面使用图8和图9就本发明的实施方案3的发光装置进行说明。 Below using FIGS. 8 and 9 will be described a light emitting device according to the embodiment 3 of the invention. 图8和图9分别表示发光装置的平面图和图8的A-A'向剖面图。 Figures 8 and 9 are a plan view and a light emitting device A-A 'sectional view of FIG. 8 to. 在实施方案3的发光装置中,所使用的荧光构件可以是与实施方案1相同的荧光构件。 In the light emitting device of Embodiment 3, the fluorescent member may be used with embodiments of the same fluorescent member 1. 这里使用的是具有发光峰在蓝色区域、发光波长为460nm的InGaN系半导体层作为发光层的发光元件401 。 As used herein, the emission peak in the blue region having an emission wavelength of 460nm InGaN-based semiconductor layer as a light emitting element emitting layer 401. 在发光元件4G1上形成有p型半导体层和n型半导体层(图中未示出),在p型半导体层和n型半导体层上形成有连接引线电极402的导电性引线404。 A p-type semiconductor layer and n-type semiconductor layer (not shown), electrically conductive wire 404 connecting the lead electrode 402 is formed on the p-type semiconductor layer and n-type semiconductor layer is formed on the light emitting element 4G1. another

54外,以覆盖引线电极402的外周的方式形成有绝缘密封材403,从而使短路得以防止。 54, the outer periphery of the cover 402 is formed with a lead electrode insulating sealing member 403 so that a short circuit is prevented. 在发光元件401的上方,设置着由位于壳体405上部的引线406延伸出来的透光性窗部407。 Above the light emitting element 401 is provided with a translucent window portion 407 extending from the upper housing 405 is located out of the lead 406. 在透光性窗部407的内面,大致整个面都涂布均匀含有荧光体408的粘结剂410。 In the surface of the transparent window portion 407, are substantially the entire surface of the phosphor containing the binder is applied uniformly to 410,408.

这样,图8和图9的发光装置在LED芯片的上方并与LED芯片保持距离那样地配置着含有荧光体的发光膜409。 Thus, the light emitting device of FIGS. 8 and 9 and held above the LED chip as the LED chip is disposed with the light emitting phosphor film 409 containing distance. 这一点与上述图3、图4的发光装置的结构不同,而其它部分大致一样,荧光体和粘结剂也可以使用同样的材料。 This is described above in FIG. 3, the light emitting device of a different structure in FIG. 4, while the other portion is substantially the same as the phosphor and the binder may be used the same material. 发光膜作为多层结构,各层可以混入不同的荧光体,也可以将没有混入荧光体的膜组合进去。 Light emitting film as a multilayer structure, the layers of different phosphors may be mixed, it may be not mixed into the phosphor film composition. 图8和图9的发光膜是可以从发光装置上分离下来并能够进行更换的,从而也可能变更发光颜色或者把退化的发光膜更换下来。 Luminescent film 8 and FIG. 9 is separated off from the light emitting device and can be replaced, which may also change the emission color of the light emitting film, or degradation of the replaced.

实施方案4 Embodiment 4

再者,图10是表示本发明的实施方案4的发光装置。 Further, FIG. 10 shows a light emitting device according to embodiment 4 of the present invention. 该图中所示的发光装置与上述的发光装置相反,将LED配置在上方作为发光元件501,而在下方的壳体505上形成弯曲的凹部并在其表面设置发光层509。 The light emitting device shown in the figure opposite to the above-described light-emitting device, disposed above the LED 501 as a light emitting element, a concave curved portion is formed on the housing 505 and beneath the light emitting layer 509 disposed on the surface thereof. 在该构成中,也可以利用由上述荧光体和粘结剂构成的多层结构。 In this configuration, the multilayer structure may also be used by the phosphor and a binder thereof. 另外,层构成也与上述同样,可以设计为多层结构。 Further, the layer configuration is also similar to the above can be designed as a multi-layer structure.

实施方案5 Embodiment 5

另外,图U〜图22是表示本发明的实施方案5的发光装置。 Further, FIG. U~ FIG. 22 is a light-emitting device of Embodiment 5 of the present invention. 这些图中所示的发光装置正如图19所示的那样,以设置着发光元件的电极的一侧与基体相对置的方式进行配置。 The light emitting device as shown in these figures as shown in FIG. 19, in the manner provided with the base electrode side of the light emitting element opposite configuration. 下面以图U〜图18为基础就图19所示的发光装置的制作方法进行说明。 FIG 18 to FIG U~ below based on FIG method for manufacturing the light emitting device shown in FIG. 19 will be described.

首先,如图11所示,在基座(sub-mount)用基板601的表而配置导电性构件602。 First, as shown in FIG. 11, in the base (sub-mount) substrate 601 Table conductive member 602 is arranged. 其次,如图12所示,在基体601的表面设置了形成有绝缘部603的导电性图案,其中绝缘部603用于分离连接发光元件600的正电极和负电极的导电性构件602。 Next, as shown in FIG. 12, the surface of the substrate 601 is provided an insulating portion 603 of the conductive pattern, wherein an insulating portion connecting the light emitting element 603 for separating the positive electrode 600 and negative electrode conductive member 602.

基座用基板601的材料优选的是与半导体发光元件的热膨胀系数 The base substrate 601 is preferably a material with a thermal expansion coefficient of the semiconductor light emitting element

55大致相等的材料例如氮化铝等。 55 is substantially equal to a material such as aluminum nitride. 通过使用这样的材料,可以缓和基座 By using such a material, the base can be alleviated

用基板601和发光元件600之间产生的热应力。 Thermal stress generated between the substrate 600 and the light emitting element 601. 基座用基板601的材料有时优选能形成保护元件的、和廉价的硅。 Preferably the base may be formed of the protective element, and inexpensive silicon substrate 601 material. 另外,导电性构件602优选使用反射率高的银和金。 Further, the conductive member 602 is preferably of high reflectance silver and gold.

为了提高发光装置的可靠性,在发光元件600的正负两电极间与绝缘部603之间产生的间隙内,填充底填料(underfill) 604。 In order to improve the reliability of the light emitting device, the gap created between the insulating portion between the light emitting element 603 and the positive and negative electrodes 600, underfill filling (underfill) 604. 如图13所示,在上述基座用基板601的绝缘部603的周边配置有底填料604。 13, in the periphery of the base substrate 601 with an insulating filler having a bottom portion 603 disposed 604. 底填料604的材料例如为环氧树脂等热固化性树脂。 Underfill material 604, for example, a thermosetting resin such as epoxy. 为了缓和底填料604的热应力,也可以进一步将氮化铝、氧化铝以及它们的复合混合物等混入环氧树脂中。 In order to alleviate thermal stress underfill 604 may further aluminum nitride, alumina, and mixtures thereof and the like mixed into the composite in an epoxy resin. 底填料604的用量为可以跨过绝缘部603而填埋发光元件600的正负两电极与基座用基板601之间产生的间隙的量。 The amount of the underfill 604 to be filled across the insulating portion 603 and the light emitting element 600 and the positive and negative electrodes with the amount of gap created between the base substrate 601.

其次,如图14所示,以分别与上述导电性图案的正负两电极相对置的方式将采用另外的方法制成的LED芯片等发光元件600的正负两电极固定下来。 Then, 14 to respectively the positive and negative electrodes of the conductive pattern opposite manner using LED chip emitting element made of another method of the positive and negative electrode 600 is fixed. 首先,使导电性材料605附着在发光元件600的正负两电极上。 First, the conductive material 605 deposited on the light emitting element 600 of the positive and negative electrodes. 导电性材料605的材料例如有Au、共晶软钎料(Au-Sn)、Pb-Sn、无铅软钎料等。 The material of the conductive material 605 for example, Au, eutectic solder (Au-Sn), Pb-Sn, Pb-free solders and the like. 在底填料604处于软化状态的情况下,通过导电性材料605,使发光元件600的正负两电极与上述导电性图案的正负两电极相对置,然后将发光元件600的正负两电极、导电性材料605以及上述导电性图案热压接在一起。 In the case of the underfill 604 in a softened state, the conductive material 605, the light emitting element 600 of the positive and negative electrodes negative electrode and the opposite conductive pattern, and the light emitting element 600 of the positive and negative electrodes, conductive material 605 and the conductive patterns together thermocompression. 此时,导电性材料和上述导电性图案的正负两电极间的底填料604得以排除。 At this time, the underfill 604 positive and negative electrodes of the conductive material and the conductive pattern can be ruled out.

再者,如图15所示,从发光元件600的基板恻配置着筛板606。 Further, as shown in FIG 15, disposed from the deck 606 of the light emitting element substrate 600 sad. 此外,也可以在导电性引线的球焊(ball bonding)位置、分型线(partingline)的形成位置等不想形成荧光体层的位置配置金属掩模以取代筛板。 Further, we do not want to position the phosphor layer is formed is disposed in a metal mask instead of the electrically conductive wire sieve ball bonding (ball bonding) position, the parting line (partingline) forming location.

接着如图16所示,调整在具有触变性的氧化铝溶胶中含有荧光体的荧光体层形成材料607,使用刮浆板(圆头刮刀)进行丝网印刷。 Next, as shown in FIG. 16, in an alumina sol comprising adjusting the thixotropic phosphor layer of the phosphor material 607 is formed using a squeegee (spatula) screen printing.

进而如图17所示,取下筛板,使荧光体层形成材料607固化。 Further shown in FIG. 17, remove the sieve, the phosphor layer forming material 607 is cured. 然后如图18所示,沿着分型线609切割每一个发光元件,便得到如图 Then, as shown in FIG. 18, each light emitting element cut along the parting line 609, as shown to give

5619所示的带荧光体层的发光装置610。 The light emitting device 610 with a phosphor layer 5619 as shown.

进而也可以制作出将这样的带荧光体层的发光装置610固定在支持体等上面的发光装置。 In addition to the above may produce such a light emitting device with a phosphor layer on a support 610 fixed to the light emitting device and the like. 图20〜图22的示例的是将带荧光体层的发光装置610固定在具有凹部612的支持体611上的发光装置。 FIG example 20~ 22 with a light emitting device is the phosphor layer having the light emitting device 610 is fixed on the recess portion 611 of the support 612. 图20 是发光装置的平面图,图21是图20的B—B,向剖面图,而且图22 是图21的放大图。 FIG 20 is a plan view of a light emitting device, FIG. 21 is a view of B-B 20, the cross-sectional view, and FIG. 22 is an enlarged view 21. 这些图中所示的发光装置是用Ag涂膏等粘结剂将带荧光体层的发光装置610固定在凹部612的底面而成的,其中问部612设置在壳体等支持体611的金属基体615上。 The bottom surface of the light emitting device 610 is fixed to the recessed portion 612 of the light emitting device shown in these figures is coated with Ag paste, an adhesive tape formed phosphor layer, wherein the intermetallic portion 612 is provided on a support 611 such as a housing 615 on the substrate. 进而将露出的引线电极613用导电性引线614与设置在基座用基板601上的导电性图案相连接。 Further exposed lead electrode 613 is connected with the electrically conductive wires disposed in the base 614 with a conductive pattern on the substrate 601.

在以上说明的发光装置中,也可以使用由被覆材料涂覆或被覆的荧光体。 In the light emitting device described above may be made using a phosphor coated or coated with the coating material. 具有由以上述水合氧化物为主体的无机粘结剂和填料构成的发光层的发光装置,并不限定发光装置的构成。 A light emitting device having a light emitting layer composed of the above-described hydrated oxide as a main component an inorganic binder and a filler composed of a light emitting device is not limited. 例如,除了向下安装上述发光元件而在蓝宝石基板等的上面形成发光层的例子以外,也可以适用在高压水银灯的灯管表面形成发光层的例子等。 Outside example, examples of the light emitting layer in addition to the light emitting element is mounted downwardly is formed above the sapphire substrate or the like, may be applied to the surface of the high-pressure mercury lamp, etc. Examples of the luminescent layer is formed.

实施例1〜29 Example 1~29

下面就本发明的实施例进行说明。 Here will be described embodiments of the present invention. 首先,用氧化铝溶胶、钇溶胶调配荧光体料浆,从而制作出荧光体/溶胶料漿。 First, alumina sol, yttria sol formulations phosphor slurry, thereby producing a phosphor / sol slurry. (实施例1) (Example 1)

取10g市售商品氧化铝溶胶(日产化学制A1520)盛在100ml的烧杯中,然后相对于氧化铝溶胶添加50重量%的乙醇并进行混合。 Taking 10g of commercially available alumina sol (manufactured by Nissan Chemical A1520) served in a 100ml beaker, and with respect to the alumina sol was added 50 wt% ethanol and mixed. 在该混合液中添加10g荧光物质YAG,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 10g of YAG fluorescent substance in the mixture, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. (实施例2) (Example 2)

取10g市售商品氧化铝溶胶(日产化学制A1200)盛在100ml的烧杯中,然后相对于氧化铝溶胶添加70重量%的乙醇并进行混合。 Taking 10g of commercially available alumina sol (manufactured by Nissan Chemical A1200) served in a 100ml beaker, and with respect to the alumina sol was added 70 wt% ethanol and mixed. 在该混合液中添加10g荧光物质YAG,充分搅拌而混合后,便得到荧光 10g of YAG fluorescent substance in the mixture, sufficiently stirred and mixed, then to obtain a phosphor

57体/溶胶的料浆。 57 bodies / sol slurry.

(实施例3) (Example 3)

取10g市售商品氧化铝溶胶(触媒化成制力夕口一KAS3)盛在100ml的烧杯中,然后相对于氧化铝溶胶添加50重量%的乙醇并进行混合。 Taking 10g of commercially available alumina sol (Shokubai Kasei Co., Ltd. Tokyo opening force a KAS3) served in a 100ml beaker, and an alumina sol was added with respect to 50 wt.% Ethanol and mixed. 在该混合液中添加10g荧光物质YAG,充分搅拌而混合后,便得到荧光体/溶胶的料桨。 10g of YAG fluorescent substance in the mixture, sufficiently stirred and mixed, then obtain a phosphor / sol material paddle. (实施例4) (Example 4)

取10g市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml 的烧杯中,然后相对于氧化钇溶胶添加50重量°/。 Taking 10g of commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and then added with respect to 50 ° by weight of yttrium oxide sol /. 的乙醇并进行混合。 Ethanol and mixed. 在该混合液中添加10g荧光物质YAG,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 10g of YAG fluorescent substance in the mixture, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. (实施例5) (Example 5)

取10g市售商品氧化铝溶胶(日产化学制A1520)盛在100ml的烧杯中,然后相对于氧化铝溶胶添加50重量%的乙醇并进行混合。 Taking 10g of commercially available alumina sol (manufactured by Nissan Chemical A1520) served in a 100ml beaker, and with respect to the alumina sol was added 50 wt% ethanol and mixed. 在该混合液中添加10g荧光物质SAE,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 10g of the fluorescent substance in the SAE mixture, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. (实施例6) (Example 6)

取10g市售商品氧化铝溶胶(日产化学制A1200)盛在100ml的烧杯中,然后相对于氧化铝溶胶添加70重量%的乙醇并进行混合。 Taking 10g of commercially available alumina sol (manufactured by Nissan Chemical A1200) served in a 100ml beaker, and with respect to the alumina sol was added 70 wt% ethanol and mixed. 在该混合液中添加10g荧光物质SAE,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 10g of the fluorescent substance in the SAE mixture, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. (实施例7) (Example 7)

取10g市售商品氧化铝溶胶(触媒化成制力夕口吖KAS3)盛在100ml的烧杯中,然后相对于氧化铝溶胶添加50重量%的乙醇并进行混合。 Taking 10g of commercially available alumina sol (Shokubai Kasei Co., Ltd. Tokyo opening force acridine KAS3) served in a 100ml beaker, and an alumina sol was added with respect to 50 wt.% Ethanol and mixed. 在该混合液中添加10g荧光物质SAE,充分搅拌而混合后,便 10g of the fluorescent substance in the SAE mixture, sufficiently stirred and mixed, then

得到荧光体/溶胶的料浆。 To obtain a slurry of the phosphor / sol. (实施例8) (Example 8)

取10g市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml的烧杯中,然后相对于氧化钇溶胶添加70重量°/。 Taking 10g of commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and then added with respect to 70 ° by weight of yttrium oxide sol /. 的乙醇并进行混合。 Ethanol and mixed. 在该混合液中添加10g荧光物质SAE,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 10g of the fluorescent substance in the SAE mixture, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. (实施例9) (Example 9)

取10g市售商品氧化铝溶胶(日产化学制A1200)盛在100ml的烧杯中,然后相对于氧化铝溶胶添加50重量%的乙醇并进行混合。 Taking 10g of commercially available alumina sol (manufactured by Nissan Chemical A1200) served in a 100ml beaker, and with respect to the alumina sol was added 50 wt% ethanol and mixed. 在该混合液中添加10g荧光物质BAM,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 10g of the fluorescent substance in the BAM mixture, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. (实施例10) (Example 10)

取10g市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml 的烧杯中,然后相对于氧化钇溶胶添加50重量%的乙醇并进行混合。 Taking 10g of commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and yttria sol was added with respect to 50% by weight of ethanol and mixed. 在该混合液中添加10g荧光物质CCA-l,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 10g of CCA-l fluorescent substance in the mixture, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. (实施例11) (Example 11)

取10g市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml 的烧杯中,然后相对于氧化钇溶胶添加50重量%的乙醇并进行混合。 Taking 10g of commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and yttria sol was added with respect to 50% by weight of ethanol and mixed. 在该混合液中添加10g荧光物质CCA-2,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 10g of the fluorescent substance CCA-2 in the mixture, sufficiently stirred and mixed, then obtain a phosphor / sol slurry. (实施例12) (Example 12)

取10g市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml 的烧杯中,然后相对于氧化钇溶胶添加50重量%的乙醇并进行混合。 Taking 10g of commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and yttria sol was added with respect to 50% by weight of ethanol and mixed. 在该混合液中添加10g荧光物质CCBE,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 10g of the fluorescent substance CCBE mixture, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. (实施例13) (Example 13)

取10g市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml 的烧杯中,然后相对于氧化钇溶胶添加50重量%的乙醇并进行混合。 Taking 10g of commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and yttria sol was added with respect to 50% by weight of ethanol and mixed. 在该混合液中添加10g荧光物质SAE,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 10g of the fluorescent substance in the SAE mixture, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol.

59(实施例14) 59 (Example 14)

取10g市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml 的烧杯中,然后相对于氧化钇溶胶添加50重量%的乙醇并进行混合。 Taking 10g of commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and yttria sol was added with respect to 50% by weight of ethanol and mixed. 在该混合液中添加10g荧光物质CESN,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 10g of the fluorescent substance CESN mixture, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol.

另外,作为实施例15〜23,以下表示的是在各种条件下制作LED 的例子。 Further, as an embodiment 15~23, the following shows an example of fabrication of the LED under various conditions.

(实施例15-1) (Example 15-1)

将市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml的烧杯中,然后相对于氧化钇溶胶添加50重量%的乙醇并进行混合。 The commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and yttria sol was added with respect to 50% by weight of ethanol and mixed. 在该混合液中以预定的比例添加荧光物质YAG,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 It was added to the mixture at a predetermined ratio fluorescent material YAG, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. 由此,与波长为460nm的半导体发光元件组合,便得到发出白色光的LED。 Accordingly, the light emitting element in combination with a semiconductor having a wavelength of 460nm, to give LED will emit white light. (实施例15-2) (Example 15-2)

将市售商品氧化铝溶胶(日产化学制氧化铝溶胶200)盛在100ml 的烧杯中,然后相对于氧化铝溶胶添加50重量%的乙醇并进行混合。 The commercially available alumina sol (alumina sol manufactured by Nissan Chemical 200) filled in a 100ml beaker, and an alumina sol was added with respect to 50 wt.% Ethanol and mixed. 在该混合液中以预定的比例添加荧光物质YAG,充分搅拌而混合后, 便得到荧光体/溶胶的料浆。 It was added to the mixture at a predetermined ratio fluorescent material YAG, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. 将该荧光体/溶胶的料浆与波长为460nm 的半导体发光元件组合,便得到发出白色光的LED。 The phosphor / sol slurry with a wavelength of 460nm semiconductor light emitting element of the combination, it will have LED to emit white light. (实施例16) (Example 16)

将市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml的烧杯中,然后相对于氧化钇溶胶添加50重量%的乙醇并进行混合。 The commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and yttria sol was added with respect to 50% by weight of ethanol and mixed. 在该混合液中以预定的比例添加荧光物质YAG和用铕活化的钙硅氮化物,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 To this mixture is added at a predetermined ratio and the YAG fluorescent material activated with europium nitride, calcium silicon, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. 将该荧光体/溶胶的料浆与波长为460nm的半导体发光元件组合,便制作出发出灯泡颜色的光的LED。 The phosphor / sol slurry with a wavelength of 460nm semiconductor light emitting element combination, produce light emitted by the LED bulb colors. (实施例17-1) (Example 17-1)

将市售商品氧化铝溶胶(日产化学制氧化铝溶胶200)盛在100ml The commercially available alumina sol (alumina sol manufactured by Nissan Chemical 200) served in 100ml

60的烧杯中,然后相对于氧化铝溶胶添加50重量%的乙醇并进行混合。 Beaker 60, and with respect to the alumina sol was added 50 wt% ethanol and mixed. 在该混合液中以预定的比例添加荧光物质YAG和用铕、锰活化的钙氯磷灰石,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 In the mixture to a predetermined ratio and adding a fluorescent material YAG with europium and manganese-activated calcium chlorapatite, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. 将该荧光体/溶胶的料浆与波长为400mn的半导体发光元件组合,便制作出发出白色光的LED。 The phosphor / sol slurry wavelength semiconductor light emitting element 400mn combination, they produce an LED that emits white light. (实施例17-2) (Example 17-2)

将市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml的烧杯中,然后相对于氧化钇溶胶添加50重量%的乙醇并进行混合。 The commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and yttria sol was added with respect to 50% by weight of ethanol and mixed. 在该混合液中以预定的比例添加荧光物质YAG和用铕、锰活化的钙氯磷灰石,充分搅拌而混合后,便得到荧光体/溶胶的料桨。 In the mixture to a predetermined ratio and adding a fluorescent material YAG with europium and manganese-activated calcium chlorapatite, sufficiently stirred and mixed, then the paddle to obtain the phosphor material / sol. 将该荧光体/溶胶的料浆与波长为400nm的半导体发光元件组合,便制作出发出白色光的LED。 The phosphor / sol slurry with a wavelength of 400nm semiconductor light emitting element combination, produce an LED that emits white light. (实施例18) (Example 18)

将市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml的烧杯中,然后相对于氧化钇溶胶添加50重量%的乙醇并进行混合。 The commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and yttria sol was added with respect to 50% by weight of ethanol and mixed. 在该混合液中以预定的比例添加荧光物质YAG和用铕、锰活化的钙氯磷灰石以及用铕活化的钙硅氮化物,充分搅拌而混合后,便得到荧光体/溶胶的料桨。 In the mixture to a predetermined ratio and adding a fluorescent material YAG with europium and manganese-activated calcium chloride and calcium apatite with the silicon nitride europium-activated, sufficiently stirred and mixed, then the paddle to obtain the phosphor material / sol . 将该荧光体/溶胶的料浆与波长为400nm的半导体发光元件组合,便制作出发出灯泡颜色的光的LED。 The phosphor / sol slurry with a wavelength of 400nm semiconductor light emitting element combination, produce light emitted by the LED bulb colors. (实施例19) (Example 19)

将市售商品氧化铝溶胶(日产化学制氧化铝溶胶200)盛在100ml 的烧杯中,然后相对于氧化铝溶胶添加50重量%的乙醇并进行混合。 The commercially available alumina sol (alumina sol manufactured by Nissan Chemical 200) filled in a 100ml beaker, and an alumina sol was added with respect to 50 wt.% Ethanol and mixed. 在该混合液中以预定的比例添加荧光物质即用铕活化的钙氯磷灰石、 用铕、锰活化的铝酸钡镁以及用铕活化的锶硅氮化物,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 After adding a fluorescent substance that is a europium-activated calcium chlorapatite predetermined ratio in the mixture, europium, manganese-activated barium magnesium aluminate activated by Europium and strontium silicon nitride, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. 将该荧光体/溶胶的料浆与波长为400nm的半导体发光元件组合,便制作出发出白色光的LED。 The phosphor / sol slurry with a wavelength of 400nm semiconductor light emitting element combination, produce an LED that emits white light. (实施例20) (Example 20)

将市售商品氧化铝溶胶(日产化学制氧化铝溶胶200)盛在100ml The commercially available alumina sol (alumina sol manufactured by Nissan Chemical 200) served in 100ml

61的烧杯中,然后相对于氧化铝溶胶添加50重量°/。 Beaker 61, then added with respect to 50 ° by weight of alumina sol /. 的乙醇并进行混合。 Ethanol and mixed. 在该混合液中以预定的比例添加荧光物质即用铕活化的铝酸锶,充分搅拌而混合后,便得到荧光体/溶胶的料桨。 In the mixture to a predetermined ratio by adding a fluorescent substance that is europium-activated strontium aluminate, sufficiently stirred and mixed, then the paddle to obtain the phosphor material / sol. 将该荧光体/溶胶的料浆与波长为365nm的半导体发光元件组合,便制作出发出信号用蓝绿色光的LED。 The phosphor / sol slurry with a wavelength of 365nm semiconductor light emitting element combination, they produce a signal emitted by the blue-green light LED.

(实施例21) (Example 21)

将市售商品氧化铝溶胶(日产化学制氧化铝溶胶200)盛在100ml的烧杯中,然后相对于氧化铝溶胶添加50重量°/。 The commercially available alumina sol (alumina sol manufactured by Nissan Chemical 200) filled in a 100ml beaker, and then added with respect to 50 ° by weight of alumina sol /. 的乙醇并进行混合。 Ethanol and mixed. 在该混合液中以预定的比例添加荧光物质即用铕活化的钡硅氮化物,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 In the mixture to a predetermined ratio by adding a fluorescent substance that is europium-activated barium silicon nitride, sufficiently stirred and mixed, then obtain a phosphor / sol slurry. 将该荧光体/溶胶的料浆与波长为365nm的半导体发光元件组合,便制作出发出信号用黄色光的LED。 The combination of the light emitting element of the phosphor / sol slurry with a wavelength of 365nm semiconductor, will produce a signal emitted by the LED light yellow.

(实施例22) (Example 22)

将市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml的烧杯中,然后相对于氧化钇溶胶添加50重量%的乙醇并进行混合。 The commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and yttria sol was added with respect to 50% by weight of ethanol and mixed. 在该混合液中以预定的比例添加荧光物质YAG和用铕活化的铝酸钡镁以及用铕活化的钙锶硅氮化物,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 To this mixture is added at a predetermined ratio and the YAG fluorescent material activated with europium barium magnesium aluminate and calcium strontium silicon nitride activated by Europium, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. 将该荧光体/溶胶的料浆与波长为365nm的半导休发光元件组合,便制作出发出灯泡颜色的光的LED。 The phosphor / sol slurry with a wavelength of 365nm as semiconductor light-emitting element off compositions, it creates the light emitted by the LED bulb colors. (实施例23) (Example 23)

将市售商品氧化钇溶胶(多木化学制氧化钇溶胶)盛在100ml的烧杯中,然后相对于氧化钇溶胶添加50重量%的乙醇并进行混合。 The commercially available yttrium oxide sol (manufactured by Taki Chemical yttria sol) served in a 100ml beaker, and yttria sol was added with respect to 50% by weight of ethanol and mixed. 在该混合液中以预定的比例添加荧光物质即用铕活化的钙氯磷灰石、用铕、锰活化的铝酸钡镁以及用铕活化的钙硅氮化物,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 After adding a fluorescent substance that is a europium-activated calcium chlorapatite predetermined ratio in the mixture, europium, manganese-activated barium magnesium aluminate activated by Europium and calcium silicon nitride, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol. 将该荧光体/溶胶的料浆与波长为365nm的半导体发光元件组合,便制作出发出白色光的LED。 The phosphor / sol slurry with a wavelength of 365nm semiconductor light emitting element combination, produce an LED that emits white light.

表1表示了组合上述实施例15-1到23的荧光体、粘结剂以及LED的实例。 Table 1 shows the phosphor 23 to 15-1, the binder and examples of LED combinations of the above embodiments. 另外,发光颜色表示在图23的色度图上。 Further, the luminescent color indicates chromaticity diagram 23 in FIG. 这些实施例的LED These embodiments of the LED

62的发光颜色分别为:实施例15-1、 15-2为白色,实施例16为灯泡颜色,实施例17-1、 17-2为高演色白色,实施例18、 22为灯泡颜色,实施例19、 23为三波长白色,实施例20为信号用蓝绿色,实施例21为信号用黄色。 Emission color were 62: Example 15-1, 15-2 is white, the color of the lamp in Example 16, Example 17-1, 17-2 for the high color rendering white, Example 18, the lamp 22 is color, embodiment Example 19, 23 is a three-wavelength white, as in Example 20 with the cyan signals, Example 21 as a yellow signals.

表1 Table 1

实施例 粘结剂 荧光体 LED 色X 调y EXAMPLE binder phosphor LED color tone y embodiment X

实施例15-1 氧化钇 ①YAG 460 0.283 0.305 Example 15-1 yttria embodiment ①YAG 460 0.283 0.305

实施例15-2 氧化铝 实施例16 氧化钇 ① YAG ② 用铕活化的钙硅氮化物 460 0.439 0.419 Example 16 Example yttrium oxide ① YAG ② europium-activated calcium silicon nitride 460 0.439 0.419 15-2 alumina embodiment

实施例17-1 氧化铝 ① YAG ② 用铕、锰活化的钙氯磷灰石 400 0.330 0.328 Example 17-1 alumina ① YAG ② europium, manganese-activated calcium chlorapatite embodiment 400 0.330 0.328

实施例17-2 氧化钇 实施例18 氧化钇 ① YAG ② 用铕、锰活化的钙氯磷灰石③ 用铕活化的钙硅氮化物 400 0.430 0.420 Example 18 ① YAG ② with yttrium oxide, europium manganese-activated calcium chloride with apatite ③ calcium europium-activated yttrium oxide silicon nitride 17-2 0.430 0.420 Example 400

实施例19 氧化铝 ① 用铕活化的钙氯磷灰石② 用铕、锰活化的铝酸钡镁③ 用铕活化的锶硅氮化物 400 0.330 0.335 Example 19 Alumina ① europium-activated calcium chlorapatite embodiment ② europium, manganese-activated barium magnesium aluminate activated by Europium ③ strontium silicon nitride 400 0.330 0.335

实施例20 氧化铝 ①用铕活化的铝酸锶 365 0.150 0.420 Example 20 Alumina ① The europium-activated strontium aluminate embodiment 365 0.150 0.420

实施例21 氧化铝 ①用铕活化的钡硅氮化物 365 0.586 0.409 Example 21 Alumina ① The europium-activated barium silicon nitride embodiment 365 0.586 0.409

实施例22 氧化钇 ① YAG ② 用铕活化的钙锶硅氮化物③ 用铕活化的铝酸钡镁 365 0.449 0.407 22 ① YAG ② embodiment yttria europium-activated calcium strontium silicon nitride ③ with europium-activated barium magnesium aluminate embodiment 365 0.449 0.407

实施例23 氧化钇 ① 用铕活化的钙氯磷灰石② 用铕、锰活化的铝酸钡镁③ 用铕活化的钙硅氮化物 365 0.332 0.331 Example 23 ① The europium-activated yttrium oxide calcium chlorapatite ② europium, manganese-activated barium magnesium aluminate activated by Europium ③ calcium silicon nitride embodiment 365 0.332 0.331

再者作为本发明优选的实施例,也可以制作高输出功率的发光元件。 Note that the present preferred embodiments of the invention, may be prepared emitting element with high output power. 高输出功率的发光元件例如适用于照明用途等。 High-output light emitting device for lighting purposes, for example, and the like. 组合用于制作在 In combination used to make

实用方面具有优选特性的LED的荧光体、粘结剂以及LED的实例作为实施例24〜实施例29表示在下表2中。 LED phosphor, a binder and preferred examples of the practical aspect having characteristics of an LED as Example 29 Example 24~ represented in Table 2 below. 这些实施例的LED的发光 These embodiments of the LED light emission

63颜色(色调)分别为:实施例24为白色,实施例25、 26、 27为灯泡颜色,实施例28为三波长白色。 63 color (hue), respectively: Example 24 as a white, Examples 25, 26, 27 for the light bulb color, Example 28 as a white three-wavelength.

另外,实施例19、实施例23使用的三波长白色的荧光体谱图数据如图24以及图25所示。 Further, Example 19, Example 23 using the three-wavelength white phosphor Spectral Data embodiment shown in FIG. 24 and FIG. 25. 图24和图25分别表示用实施例23使用的波长为365mn的LED激发的谱图和用实施例19使用的波长为400nm的LED激发的谱图。 Figures 24 and 25 are represented by Example 23 using a wavelength of 365mn and a LED excitation wavelength spectrum used in Example 19 was 400nm excitation spectrum of the LED.

表2 Table 2

<table>table see original document page 64</column></row> <table> <Table> table see original document page 64 </ column> </ row> <table>

(比较例1) (Comparative Example 1)

作为比较例1,制作使用了二氧化硅溶胶的样品获得了比较数据。 As Comparative Example 1, samples prepared using a silica sol obtained comparative data.

取10g市售商品二氧化硅溶胶(〕々〕一卜制HAS10)盛在】00ml的烧杯中,然后在其中添加10gCESN作为荧光物质,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 Taking 10g of commercially available silica sol (manufactured Bu] 々] a HAS10) filled in a beaker of 00ml] then added 10gCESN fluorescent material, sufficiently stirred and mixed, then to obtain a slurry of the phosphor / sol . (比较例2) (Comparative Example 2)

作为比较例2,制作不使用荧光体的样品获得了比较数据。 As Comparative Example 2, the sample prepared without using a phosphor obtained comparative data. 在此,仅使用400nm的LED。 Here, only the 400nm LED. (荧光体层的形成) (Formation of the phosphor layer)

使用以上得到的实施例1〜14的荧光体/溶胶料浆、形成荧光体层的方法表示如下:首先将实施例1〜5的荧光体/溶胶料浆分别填充在喷涂装置(乂一K、/y制)的喷罐中。 The method of the phosphor of Example 1~14 / sol slurry, the phosphor layer is formed using the above obtained as follows: First, the phosphor of Example 1 ~ 5 / sol slurry were filled in the spray apparatus (qe a K embodiment, / y) was spray tank. 在喷嘴的下方,设置波长为400nm的LED (9巾管座封装(stem package) 、 0.35mm芯片)作为发光元件。 Below the nozzle is provided as a wavelength of 400nm LED (9 towel package header (stem package), 0.35mm chips) as the light emitting element. 在此,为了只在LED芯片上涂布荧光体/溶胶料浆,事先对LED芯片进行掩蔽。 Here, only the coating to the phosphor / sol slurry on the LED chip, the LED chip prior to masking. 进而从LED芯片的下方,用热板加热到9(TC左右。喷涂成形后,荧光体借助于混合的溶胶粘结在LED芯片上,从而可以形成发光层。 Further from the lower side of the LED chip, a hot plate heated to about 9 (TC. After the spray forming, by means of the phosphor mixed sol adhered on the LED chip, the light emitting layer can be formed.

其次,为了使固化充分地进行,在氮气氛、24(TC的温度下进行30min的正式固化。最后,采用氮气气密密封技术将LED芯片覆盖在辉光盒(glow box)内,这样便得到了具有包含荧光体的发光层的LED。 Secondly, in order to sufficiently cured, the cured formal 30min in a nitrogen atmosphere, 24 (at a temperature of TC Finally, LED chips with nitrogen cover a hermetic seal technique in the glow box (glow box), this will give LED having a light emitting layer containing phosphor.

表3为实施例使用的荧光体的一览表。 Table 3 is a list of the phosphor used in Example embodiment.

表3 table 3

简称 正式名称 组成 平均粒径Om) ^苗* 乏谋& 发光颜色(400nm 激发) Official Name Acronym average particle size composition Om) ^ * spent seeking & seedlings emission colors (400nm excitation)

YAG 用铈活化的钇铝石榴石 (Y0.79Gd02Ce0.0i)3Al5O12 3.8 6.4 黄色 YAG is cerium-activated yttrium aluminum garnet (Y0.79Gd02Ce0.0i) 3Al5O12 3.8 6.4 Yellow

SAE 用铕活化的铝酸锶 (Sr0.9Euo.i)4 Al"O25 9 14 蓝绿色 SAE europium-activated strontium aluminate (Sr0.9Euo.i) 4 Al "O25 9 14 cyan

CCA-1 用铕活化的钙氯磷灰石 (Cao.95Eu005) (P04)3C1 15.9 18 蓝色 CCA-1 europium-activated calcium chlorapatite (Cao.95Eu005) (P04) 3C1 15.9 18 blue

CCA-2 用铕、锰活化的钙氯磷灰石 (Cao.94Euo.05Mno.01) (P04)3C1 22 25 蓝色 CCA-2 with europium and manganese activated calcium chlorapatite (Cao.94Euo.05Mno.01) (P04) 3C1 22 25 Blue

CCBE 用铕活化的钙氯硼酸盐 (Ca^EiKuhBACl 12 19.1 蓝色 CCBE europium-activated calcium chloride borate (Ca ^ EiKuhBACl 12 19.1 Blue

BAM 用铕活化的铝酸钡镁 (Bao.45Euo.25Sr0.3) • Mg05Al203 3.9 8.7 蓝色 BAM with europium-activated barium magnesium aluminate (Bao.45Euo.25Sr0.3) • Mg05Al203 3.9 8.7 Blue

CESN 用铕活化的钙硅氮化物 (Cao.97Eu0.03)2Si5N8 4.7 7.5 红〜橙 CESN europium-activated calcium silicon nitride (Cao.97Eu0.03) 2Si5N8 4.7 7.5 ~ red orange

65(耐久试验) 65 (endurance test)

下面进行耐久试验以确认制作的发光装置的可靠性。 The following durability test was carried out to confirm the reliability of the light emitting device is fabricated. 耐久试验是 Endurance test is

使用波长为400nm、输出功率为14.5mW、 一边的大小为350 um的LED芯片,在常温下使其以60mA的电流工作,以确认耐久性。 With a wavelength of 400 nm, output power of 14.5mW, while the size is 350 um LED chip, so that work at room temperature at a current of 60mA, to confirm the durability. 此时, 投入到发光装置的发光层的光照射密度,如果假设光的一半从芯片的侧面输出,则为86.3W/cm'2左右。 In this case, the density of the irradiation light into the light emitting layer of a light emitting device, assuming half of the light output from the side of the chip, compared with about 86.3W / cm'2. 另外,结温约为80'C,整个壳体的热阻值为230'C/ W。 Further, the junction temperature of about 80 'C., the thermal resistance value of the entire housing 230'C / W. 太阳光的光照射密度在14点的东京约为0.1 W/cm々,所以通过计算,照射光的能量密度为太阳光的863倍左右。 Sunlight photoirradiation Tokyo density of about 14:00 0.1 W / cm々, so by calculation, the energy density of the irradiation light is about 863 times that of sunlight. 该耐久试验的结果如图26〜图28所示。 The results of the endurance test is shown in FIG. 28 26~.

图26是使用YAG系荧光体的实施例1〜4的耐久试验结果。 FIG 26 is a durable test results of Example YAG-based phosphor is 1 ~ 4. 关于涂布有上述进行过调整的荧光体/溶胶之内的实施例1〜4调配的荧光体/溶胶,投入点灯试验前和经过1000小时点灯后的输出功率相比较,结果完全没有发现输出功率的退化。 The coating has been adjusted in the above-described embodiment of the phosphor / sol within the phosphor formulation ~ 4 / sol, and testing before commissioning the lighting lapse of 1000 hours after lighting output power compared to the output power was found no result degradation. 另一方面,作为比较例1, 使用二氧化硅溶胶的荧光体的LED,其输出功率则慢慢降低,经过1000小时点灯后的输出功率降低为原来的85%。 On the other hand, as Comparative Example 1, silica sol LED using a phosphor, which gradually decreases the output power, the output power after the lapse of 1000 hours of lighting decreased to 85% of the original. 此外,在各图中,比较例2因为只是400nm的LED而没有涂布荧光体,当然不能确汄发生了退化。 Further, in the drawings, as Comparative Example 2 except 400nm LED is a phosphor coating without, of course, not really Ze degradation occurs.

图27表示使用铝酸锶荧光体的实施例5〜8的耐久试验结果。 27 shows the endurance test results of Example using strontium aluminate phosphor of 5 ~ 8. 涂布有实施例5〜8调配的荧光体/溶胶的荧光体/LED,其1000小时后的输出功率正如图27所示的那样,实施例5为88%,实施例6为89%, 实施例7为92%,实施例8为93%。 Example 5 ~ 8 formulations coated with phosphor / sol phosphor / the LED, its output after 1000 hours, as shown in FIG. 27 as Example 5 88% Example 6 89% Embodiment Example 7 92% Example 8 93%. 其中涂布有实施例5调配的荧光体/溶胶的荧光体/LED正如图27所示的那样,由荧光体层的退化引起的输出功率的降低在进行到300小时时降低至88%,但此后没有看到输出功率的降低,在1000小时仍然维持88%的输出功率。 Wherein the phosphor is coated with a formulation of Example 5 / phosphor sol / LED as shown in FIG. 27 as reduced to 88% when the output power decreases due to the degradation of the phosphor layer is performed to 300 hours, Since no decrease in output power, still maintain 88% of the output power at 1000 hours.

再者,图28表示三波长白色的实施例9〜12的耐久试验结果,其中三波长白色是将用氧化钇溶胶形成了含有RGB各荧光体的发光层的LED组合而成的,同时,图29和图30分别表示实施例13、实施例14的耐久试验结果。 Further, FIG. 28 shows a three-wavelength white endurance test results of Example 9~12, wherein the three-wavelength white LED is formed a light emitting layer containing the RGB phosphor combination, at the same time, yttrium oxide sol FIG. 29 and 30, respectively Example 13, the results of endurance test of Example 14. 在这些实施例中,涂布了调配的荧光体/溶胶的荧光体/LED在1000小时后的输出功率正如图28所示的那样,实施例9为94°/。 In these embodiments, the formulation of the coating the phosphor / sol phosphor / LED 28 just as in FIG output after 1,000 hours as shown in Example 9 was 94 ° /. ,实施例10为88%,实施例11为94%,实施例12为94%。 Example 10 88% Example 11 94% Example 12 94%. 另夕卜,图29所示的实施例13为94%,图30所示的实施例14为96%。 Another Bu Xi, shown in FIG. 29 embodiment 13 embodiment 94%, in the embodiment 30 shown in FIG. 14 was 96%. 此外,涂布了图29的实施例13调配的荧光体/溶胶的荧光体/LED在1000小时后的输出功率维持在94%。 Further, the coating 29 of the embodiment of FIG. 13 formulated phosphor / phosphor sol / LED output power is maintained after 1000 hours at 94%.

这样一来,业已判明上述实施例制作调配的荧光体/溶胶与使用二氧化硅等的以前的荧光体相比,可以获得极高的耐久性。 As a result, it has been revealed that the above-described embodiment can be obtained than the formulations produced a very high durability of the phosphor / silica sol or the like before the phosphor. 并且已经确认作为在410nm或以下的波长区域使用的发光膜和发光层是特别有效的。 And it has been confirmed as a luminescent film and the light emitting layer used in the wavelength region of 410nm or less is particularly effective. 另外,将发出紫外线的半导体发光元件用作发光元件时,因为条件更加苛刻,因而上述实施方案利用的无机粘结剂是有效的。 Further, the emitted ultraviolet semiconductor light emitting element as a light emitting element, because the conditions are more severe, and thus the above-described embodiments utilize an inorganic binder is effective. 另一方面,以前在发光层中使用树脂的LED和使用二氧化硅的荧光体,即使波长比较长而达到520nm左右,也会产生退化现象,通过使用上述实施方案的无机粘结剂,可以获得即使长时间使用也比较稳定且可靠性高的发光装置。 On the other hand, before the resin is used in the light emitting LED and a phosphor layer of silica, even if relatively long wavelength of 520 nm or so achieved, will produce degradation, by using the above-described embodiments of an inorganic binder, may be obtained even if prolonged use is relatively stable and highly reliable light-emitting device. 另外,在半导体发光元件与粘贴在元件上形成的荧光体的组合以及输入电量大的发光元件中,上述实施方案可以有效地加以利用。 Further, in the combination of the semiconductor light emitting element formed on the element attached to the phosphor and the input power of a large light-emitting element, the above-described embodiments may be used effectively. 因为在输入电量大的发光装置中,作用于发光层的发热量、 光照射密度等能量较大,所以以前的树脂粘结层和二氧化硅凝胶退化得特别快。 Because a large amount in the input light-emitting device, the light emitting layer is applied to the heat, light irradiation energy density is large, the adhesive resin layer and the previous silica gel, degradation much faster. 与此相对照,正如以上所叙述的那样,本实施方案即使长时间使用也几乎看不到有退化的发生,可以获得高输出功率得以维持且可靠性高的发光装置。 In contrast, as described above, as the present embodiment even if prolonged use is hardly visible degradation has occurred, a high output can be obtained with high reliability is maintained and the light emitting device.

实施方案6 Embodiment 6

下面以图31〜32为基础就本发明的实施方案6的发光装置进行说明。 FIG 31~32 below to a light emitting device will be described with embodiment 6 of the present invention is based. 图31是表示实施方案6的发光装置的示意平面图,图32 (a)是表示实施方案6的发光装置的示意剖面图,图32 (b)是放大基体凹部的示意剖面图。 FIG 31 is a schematic plan view showing a light emitting device according to Embodiment 6, FIG. 32 (a) is a schematic cross-sectional view showing a light emitting device according to Embodiment 6, FIG. 32 (b) is a schematic sectional view of an enlarged portion of the recess base. 本发明的实施方案6的发光装置1包括发光元件60、 承载该发光元件60的基体20以及在该基体20上形成的盖体26。 Embodiments of the present invention is a light-emitting device 6 comprises a light emitting element 60, the carrier 20 and the cover member is formed on the substrate 20 26 base 60 of the light emitting element. 以承载发光元件60的一侧为主面,将其反面称为背面。 In carrying side of the light emitting element 60 as a main surface, which is referred to as negative back surface. 基体20由金属构成,在其中央部具有凹部20a。 The base 20 is made of metal, it has a recess portion 20a at its central portion. 另外,在凹部20a 的周围即基底部有2个贯通厚度方向的贯通孔,各自的贯通孔夹持着所述凹部20a相向设置。 Further, around the concave portion 20a, i.e., the base has two through holes penetrating in the thickness direction of the bottom, each of the through holes of the holding portion 20a facing the recess is provided. 金属制正的和负的引线电极22隔着作为绝缘构件23的硬质玻璃分别插在该贯通孔内。 Metal positive and negative lead electrodes 22 via an insulating member 23 of hard glass are inserted in the through hole. 另外,在金属基体20的主面侧具有包含透光性窗部25和由金属部构成的引线24的盖体26,并将金属制的引线24和金属制的基体20的接触面焊接在一起。 Further, the main surface of the metal substrate 20 having a light-transmissive window comprises a lead portion 25 and metal portion 24 constituting the lid body 26 and the base 24 made of a metal wire and a contact surface 20 made of metal are welded together . 通过辉接基体20和盖体26,该发光元件60便被气密起来。 Hui contact base 20 and a cover member 26, the light emitting element 60 is hermetically together through it. 气密可以使用氮气等不活泼的气体。 Airtightness may be used inert gases such as nitrogen. 收容在凹部20a内的发光元件60是发出蓝色光或紫外线的发光元件,发光元件60粘结在基体20的凹部20a内。 Housed in the concave portion 20a of the light emitting element 60 is a light emitting element emits blue light or ultraviolet light emitting element 60 is bonded to the base 20a of the recess 20 thereof. 作为该粘结剂的一个例子,可以使用的有将硅酸乙酯的水解溶液进行干燥并烧结而得到的材料。 As an example of the binder, there may be used a hydrolyzed solution of ethyl silicate is dried and sintered material obtained. 承载在基体20的凹部20a内的发光元件60被含有荧光体的无机粘结剂30所覆盖。 The light emitting element 60 in the recess 20a of the base portion 20 of the carrier is covered with an inorganic adhesive 30 containing the phosphor. 该无机粘结剂30的表面被树脂40所覆盖。 The surface of the inorganic binder 30 is coated with a resin 40.

对于发光装置601,在特定的金属元素中,即使不提高结晶性, 在凝胶状态下也不会招致光取出效率的降低,通过在无机粘结剂30 中浸渍树脂40,可以提供一种光取出效率高的发光装置。 For the light emitting device 601, the specific metal element, without increasing the crystallinity, also in a gel state without degradation of light extraction efficiency, 40, may be provided by an optical resin impregnated in the inorganic binder 30 a high efficiency light-emitting device taken out. 特别地,如果使用在溶胶-凝胶反应过程中不会发生价数的变化而氧化状态稳定的Al和Y元素等水合氧化物的凝胶,则即使涂膜中有一部分处于凝胶状态,也通过进一步浸渍树脂形成发光膜,可以不会继续进行溶胶-凝胶反应而能够以短时间、低能量容易地获得光取出效率高的涂膜。 In particular, if a sol - gel reaction valence change does not occur during the oxidation state of stable gel hydrated oxide of Y element and Al and the like, even if a part of the coating film in a gel state, light emitting film is formed by further impregnating resin can not proceed with the sol - gel reaction can be short, low energy easily obtain a high efficiency of light extraction film.

另外,通过采用水合氧化物的凝胶构成无机粘结剂30,可以提高 Further, the inorganic binder constituting the gel 30 by using hydrous oxide can be increased

形成的涂膜的品质。 The quality of coating film formation. 含有水合氧化物的无机粘结剂构件,其粒子状物质通过溶胶-凝胶法来聚集,从而成为形成有交联结构、网状结构或聚合物结构的多孔体。 Comprising an inorganic binder member hydrous oxide, which particulate matter by the sol - gel method to aggregate, thus becoming porous crosslinked structure, a mesh structure or a polymer structure formed. 如果水合氧化物的粒子集合的骨架结构是具有孔隙的网状结构,则因为是多孔性的结构体而可以提高涂膜的柔软性。 If the skeleton structure hydrous oxide particles is set in a mesh structure having a porosity, since the porous structure is the flexibility of the coating film can be improved. 另外,无机粘结剂30在成膜时,即使附载着荧光体粒子等填料构件, 同时被涂覆的对象形状复杂,也可以与此相适应进行成膜,可以获得富有粘结性的涂膜。 Further, when forming the inorganic binder 30, even if the phosphor particles attached to the filler carrying member, while the complex shape of the object to be coated, may also be adapted to this film formation, adhesive properties can be obtained rich coating film . 再者,由于是水合氧化物,因而可以获得对热和光稳定且不变质的膜。 Further, since the hydrated oxide, it is possible to obtain heat and light stabilizers do not deteriorate the film.

从前的发光装置中形成的涂膜因为曝露在源于发光元件的光中, 所以通过发光装置的使用而产生退化。 Coating film formed in the light emitting device because the previous exposure light from the light emitting element, so that the degradation is generated by using the light emitting device. 一般认为该退化的原因在于-因源于发光元件的光输出功率和发热之中的任一种或两者而导致反应的发生。 The reason for this is believed that the degradation - result from either or both of the optical output power in the light emitting element and the heat caused by the occurrence of the reaction. 因此,当将光能量高的紫外线用于发热以及热阻抗值大的大型元件时,就容易产生退化。 Thus, when the high-energy ultraviolet light to heat and a large thermal resistance value large member, it is prone to degradation. 与此相对照,正如后面所叙述的那样, 制作本发明的实施例的试样进行了耐久试验,结果确认具有极高的耐 In contrast, as described later, as the produced samples of the examples of the present invention conducted the endurance test, it was confirmed with a high resistance to

性。 Sex. 本发明的实施方案6的发光装置具有以下的构成,下面参照附图就本实施方案的构成构件进行详细说明。 The light emitting device of Embodiment 6 of the present invention has the following configuration, described in detail below with reference to the accompanying drawings constitute part of this embodiment. (无机粘结剂) (Inorganic binder)

设置在基体20上的发光元件20被无机粘结剂30所覆盖。 The light emitting element 20 disposed on the base 20 is covered by the inorganic binder 30. 通过浇灌、浇注以及喷涂喷雾等手段使处于溶胶状态的无机粘结剂30进入基体20的凹部20a内,从而使其覆盖发光元件60的表面以及凹部20a。 By watering, spraying, and pouring the inorganic binder spraying means 30 is in a sol state into the recess 20a of the base 20, so that it covers the surface of the light emitting element 60 and the concave portion 20a. 在该无机粘结剂30中含有荧光体50。 50 contains a phosphor 30 of the inorganic binder.

无机粘结剂30在进行喷涂或者浇灌、丝网印刷之后,因凝胶化而得以固化。 Inorganic binder during spraying or watering 30, after screen printing, and is solidified by gelling. 该固化导致在无机粘结剂30中产生空隙31。 This curing results in voids 31 in the inorganic binder 30. 由于该空隙的存在,无机粘结剂30变脆并产生裂纹和缺陷。 The presence of the voids, and the inorganic binder 30 brittle cracks and defects.

除铸模构件以外,无机粘结剂30设置在管脚引线的罩体内和基休的开口部内等处,是含有对发光元件60的发光进行转换的荧光体以及对荧光体进行粘结的材料等的层。 In addition to the mold member, the inorganic binder 30 disposed within the housing body and the opening portion pinouts group, etc. Hugh, containing a light-emitting element 60 is emitting phosphor-converted phosphor materials and the like be bonded layers. 关于无机粘结剂30的层,其在发光元件60的上面、侧面设置的无机粘结剂30的层的厚度与在凹部20a 的内面设置的无机粘结剂30的层的厚度大致相等。 About 30 layers of inorganic binder, the inorganic binder in which the light emitting element 60 disposed above the side thickness of the layer 30 and the layer thickness of the inorganic binder in the inner surface of the concave portion 20a provided substantially equal to 30. 另外,无机粘结剂30即使在发光元件60的角部的部分也没有间断,无机粘结剂30的层是连续的。 Further, the inorganic binder 30 without interruption even in the corner portions of the light emitting element 60, the inorganic binder layer 30 is continuous.

由于基体20和引线21等产生的反射,从发光元件60发出的高能光等在无机粘结剂30中变成高密度。 Since reflections 20 and the lead 21 other matrix, like high-energy light emitted from the light emitting element 60 becomes a high density in the inorganic binder 30. 再者,由荧光体50也产生漫反射,无机粘结剂30有时曝露在高密度的高能光中。 Further, 50 also diffuse reflection by the phosphor, the inorganic binder 30 is sometimes exposed to a high density of high-energy light. 因此,当将发光强度大、能够发出高能光的氮化物系半导体用作发光元件60时,优选将对这些高能光有耐光性的、含有A1、 Y、 Gd、 Lu、 Sc、 Ga、 In、 B之中的任一种的金属元素的水合氧化物作为无机粘接剂30加以利用。 Thus, when the light emission intensity, high-energy light is capable of emitting a nitride-based semiconductor as a light emitting element 60, the high-energy light will preferably have light resistance, comprising A1, Y, Gd, Lu, Sc, Ga, In, any of a hydrous oxide of a metal element among B is utilized as the inorganic adhesive 30.

作为无机粘结剂30的具体的主材料之一,适合使用的有在A1(0H)3、 Y(OH)3等透光性无机构件中含有荧光体的材料。 As the inorganic binder, one specific host material 30, there are suitably used (0H) 3, Y (OH) 3 and the like inorganic light transmissive member containing a phosphor material A1. 荧光体50 彼此之间借助于这些透光性无机构件进行粘结,而且荧光体50在发光元件60和支持体上堆积成层状并与之粘结。 By means of the phosphor 50 to each other such inorganic translucent member for bonding, and the phosphor on the light emitting element 50 and the support 60 is deposited in layers and bonded thereto. 在本实施方案中,水合轼化物由以如下水合氧化物为主体的化合物所形成,其中成为主体的水合氧化物由A1、 Y、 Gd、 Lu、 Sc、 Ga、 In、 B之中的任一种的有机金属化合物所形成。 In the present embodiment, the hydrated Shi compound formed from a compound of the following hydrous oxide as a main component, wherein the body has become hydrated oxide by either among A1, Y, Gd, Lu, Sc, Ga, In, B a different kinds of organic metal compound formed. 在此,所谓有机金属化合物包含通过氧原子与金属键合的垸基和芳基。 Here, the organometallic compound comprising the metal through an oxygen atom bonded to the embankment and aryl. 作为这样的有机金属化合物,例如可以列举出烷基金属、烷氧基金属、双二酮基金属以及金属羧酸盐等。 As such organic metal compound may include a metal alkyl, metal alkoxide, metal bis dione based metal carboxylates and the like. 在这样的有机金属化合物中,对有机溶剂溶解性强的化合物在水解后容易成为均匀的溶胶溶液。 In such an organometallic compound, of strong organic solvent solubility of the compound after the hydrolysis tends to be a homogeneous sol solution. 另外,这样的有机金属化合物因为容易发生水解等化学反应,所以容易四处飞散,可以形成使荧光体50得以粘结的无机粘结剂30。 Further, because of such organometallic compounds are readily hydrolyzed by chemical reaction, it is easy to be scattered, the adhesive may be formed to make the fluorescent material 30 of the inorganic binder 50. 因此,使用有机金属化合物的方法与在35(TC或以上的温度下或者在施加静电的状态下在发光元件60上形成无机粘结剂30的其它方法不同,不会降低作为发光元件的性能而可以容易地在发光元件60上形成无机粘结剂30,从而使生产合格率得以提高。 Thus, methods of using the organometallic compound with or formed at a temperature (TC 35 or more in a state of static electricity is applied on the light emitting element 60 of the inorganic binder 30 is different from the other methods, it does not reduce the properties as the light emitting element inorganic binder can be easily formed on the light emitting element 30 60, so that the production yield is improved.

无机粘结剂30优选形成为薄膜状态的层结构。 The inorganic adhesive 30 is preferably formed as a layer structure of the thin-film state. 这是因为:通过形成为层结构,无机粘结剂30中含有的荧光体50可以均匀地发光。 This is because: a layer structure, the phosphor 30 contained in the inorganic binder 50 may uniformly emit light by forming. 另外,由于呈薄膜状态,树脂40容易浸透无机粘结剂30。 Further, since a thin film state, the resin 40 easily permeates the inorganic binder 30. 作为形成无机粘结剂30的层的手段,可以采用浇灌手段或喷涂喷雾手段。 As a means of forming the inorganic binder layer 30 may be employed watering or spraying means spray means. 但是, 无机粘结剂30也可以采用薄膜状态以外的形式。 However, the inorganic binder 30 may adopt a form other than a thin film state.

无机粘结剂30可以使用氧化铝、氧化钇、二氧化硅或它们的复合物等。 The inorganic adhesive 30 may be used alumina, yttria, silica, or a composite thereof and the like. 它们也由固体状态分散在水等中,形成为溶胶-凝胶状态,山此可以形成各种各样的形状。 They are also in a solid state by the water dispersion or the like, is formed sol - gel state, this mountain can be formed in various shapes. 另外,也可以使荧光体均匀分散在无机粘结剂30中。 Further, the phosphor may be uniformly dispersed in the inorganic binder 30. 下面将氧化铝、氧化钇作为无机粘结剂30的例子进行说明,但本发明并不周限于此。 Below alumina, yttria Examples of the inorganic binder 30 will be described, but the present invention is not limited thereto weeks. 此外,以前在涂膜中使用无机系的粘结剂。 In addition, the previously used inorganic binder in the coating film. 在使用该无机系的粘 In using the inorganic adhesive is

结剂的情况下,特别在使用由二氧化硅凝胶(Si02)形成的固化膜的 Case-caking agent, in particular a cured film formed by using a silica gel (Si02)

情况下,当曝露在高输出功率和紫外线的环境中时,存在着色退化并产生黑化的问题。 A case where, when exposed to ultraviolet light and a high output environments, where the colored degradation and blackening problem. 特别在高输出功率的发光装置中,因高光密度和热而导致二氧化硅粘结剂层的退化,并着色成黑色或黑褐色。 In particular, the light emitting device of high output power, due to the high optical density and thermal degradation caused by the silica binder layer, and a black-colored or dark brown. 本发明者 The present inventors

进行研究的结果,可以推测其原因在于:Si02即二氧化硅因氧的缺 The results of the study, the reason is presumed to be that: Si02 silica due to lack of oxygen i.e.

损而生成SiOx (x<2) 。 Loss generated SiOx (x <2). 二氧化硅粘结剂在250'C或以下的热固化温度下,处于在Si02骨架中残存一部分羟基、有机基团的二氧化硅凝胶的状态。 Silica binder at a heat curing temperature or below 250'C, in the remaining part of the hydroxyl Si02 skeleton, the state of silica gel, organic group. 在这样的二氧化硅凝胶的状态中,当由LED入射高密度的光时,将产生氧的缺损,从而使Si02变成SiOx (x<2)。 In such a state of silica gel, when the LED light incident on the high density, the oxygen defect is generated, so that the Si02 into SiOx (x <2). 这样一来,因为Si容易产生氧化还原,所以一般认为二氧化硅凝胶产生氧的缺损是着色退化的原因。 Thus, since the Si prone to redox, silica gel, it is generally considered to generate oxygen defect is the cause of degradation colored. 一旦产生着色退化,就会产生源于发光元件的光输出功率下降的问题。 Once the colored degradation problem arises from the light emitting element of the optical output power decrease. 另外,无机系的粘结剂还具有因空隙的存在而容 Further, inorganic binder also has the capacity due to the presence of voids

易产生裂纹和缺陷、耐冲击性弱这样的问题。 Easy to produce cracks and defects, weak impact resistance is a problem. 可以认为这是由于无机系的粘结剂与树脂不同,其缺乏耐冲击性。 This is considered because the binder resin and the inorganic different, the lack of impact resistance. (氧化铝) (Alumina)

将无定形氧化铝或微粒子水合氧化铝均匀分散在水中,并将这样形成的氧化铝溶胶用作粘结剂,在这种情况下,在加热氧化铝溶胶而固化形成为具有稳定的勃姆石结构的水合氧化铝之前,经历一个伪勃姆石结构的阶段。 The amorphous alumina or hydrated alumina fine particles uniformly dispersed in water, and the resulting alumina sol as a binder so that, in this case, the heating cures to form an alumina sol having boehmite stable before the structure of hydrated alumina, pseudo-boehmite undergoes phase structure. 水合氧化铝的勃姆石结晶结构和水合氧化铝的伪勃姆石结构可以分别用化学式AIOOH或A1203 'H20和(AIOOH) 'xH20 或A】203 • 2H20等来表示。 Pseudo-boehmite crystalline structure and a boehmite structure hydrated alumina may be alumina hydrate respectively the formula AIOOH or A1203 'H20 and (AIOOH)' xH20] A 203 • 2H20 or the like. FIG. 具体地说,作为中间体取A1203 • 2H20、 A1203 *xCH3COOH 'yH20、 A1203 'xHCl 'yl^CK A1203 'xHN03 'yH20 等形态,最后形成稳定的勃姆石结构。 More specifically, taking as an intermediate A1203 • 2H20, A1203 * xCH3COOH 'yH20, A1203' xHCl 'yl ^ CK A1203' xHN03 'yH20 like shape, and finally to form a stable boehmite structure. 进一步提高勃姆石结构的结晶性,则成为Y-氧化铝(A1203)或a-氧化铝(A1203)。 To further improve the crystallinity of the boehmite structure, it becomes Y- alumina (A1203) or a- alumina (A1203). 将具有这样性质的氧化铝溶胶用作粘结剂,从而形成发光膜。 The alumina sol having such properties as a binder, thereby forming a light emitting film.

作为无机粘结剂30的具体的主材料,可以使用按如下方法制备的溶胶溶液,即以少量的无机酸、有机酸以及碱为稳定剂,将无定形金属氧化物、超微粒子金属水合氧化物以及超微粒子氧化物等均匀分散在水或有机溶剂中。 Specific examples of the host material of the inorganic binder 30, may be used sol solution prepared in the following manner, i.e., a small amount of an inorganic acid, organic acid and alkali as a stabilizer, the amorphous metal oxide, metal hydrous oxide ultrafine particles and oxide ultrafine particles uniformly dispersed in water or an organic solvent. 作为合成无定形金属氧化物、超微粒子金属水合氧化物以及超微粒子氧化物等的初始原料,可以利用的有:烷氧基金属、双二酮基金属、金属卤化物、或金属羧酸盐、金属烷基化合物的水解产物以及将它们混合后进行水解的产物。 As the synthetic amorphous metal oxide starting materials for ultrafine particles and the metal oxide ultrafine particles of hydrous oxides and the like, may be utilized are: metal alkoxide, bis dione based metal, a metal halide, or metal carboxylates, hydrolysates of the metal alkyl compound will be hydrolyzed and after they were mixed. 另外,也可以使用将金属氢氧化物、金属氯化物、金属硝酸盐以及金属氧化物微粒子均匀分散在水和有机溶剂、或者水和水溶性有机溶剂的混合溶剂中所制备的胶体(溶胶)溶液。 It is also possible to use colloidal (sol) mixed solvent of a metal hydroxide, a metal chloride, metal nitrate and metal oxide fine particles uniformly dispersed in an organic solvent and water, or water and a water-soluble organic solvent solution prepared . 它们总称为铝氧烷。 They are collectively referred to as aluminoxane. 铝氧垸的骨架中具有[A10]x Framework aluminum oxide having embankment [A10] x

的重复单元。 Repeating units.

作为烷氧基金属,可以利用的有:甲氧基铝、乙氧基铝、正丙氧基铝、异丙氧基铝、正丁氧基铝、仲丁氧基铝、异丙氧基铝、叔丁氧基铝、甲氧基钇、乙氧基钇、正丙氧基钇、异丙氧基钇、正丁氧基钇、 仲丁氧基钇、异丙氧基钇、叔丁氧基钇等。 As the metal alkoxide, can be used are: aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum isopropoxide , tert-butoxy aluminum, yttrium methoxy, ethoxy yttrium, yttrium n-propoxy, isopropoxy, yttrium, yttrium n-butoxy, sec-butoxy, yttrium, yttrium isopropoxy, tert-butoxy yttrium base.

作为双二酮基金属,可以利用的有:三乙基乙酰乙酸铝、烷基乙酰乙酸二异丙氧基铝、乙基乙酰乙酸二异丙氧基铝、单乙酰基丙酮酸双乙基乙酰乙酸铝、三乙酰基丙酮酸铝、三乙酰基丙酮酸钇以及三乙基乙酰乙酸钇等。 As the double metal-dione, may be utilized are: acetyl triethyl aluminum acetate, alkyl acetoacetate aluminum diisopropoxy ethyl acetoacetate, diisopropoxy aluminum, mono- acetylacetonate bis ethylacetoacetate aluminum acetate, aluminum triacetylacetonate, triacetylacetonate yttrium and yttrium acetyl triethyl acetate.

作为金属羧酸盐,可以利用的有:醋酸铝、丙酸铝、2-乙基已酸铝、醋酸钇、丙酸钇以及2-乙基己酸钇等。 As the metal carboxylate, may be utilized are: aluminum acetate, aluminum propionate, 2-ethylhexanoate, aluminum, yttrium acetate, propionate, 2-ethylhexanoate, yttrium and yttrium.

另外,作为金属卤化物,可以利用的有:氯化铝、溴化铝、碘化铝、氯化钇、溴化钇以及碘化钇等。 Further, as the metal halides, may be utilized are: aluminum chloride, aluminum bromide, aluminum iodide, yttrium chloride, yttrium bromide, yttrium iodide, and the like.

作为有机溶剂,可以利用的有:甲醇、乙醇、正丙醇、异丙醇、 正丁醇、仲丁醇、叔丁醇、四氢呋喃、二噁烷、丙酮、乙二醇、甲乙酮、N,N-二甲基甲酰胺以及N,N-二甲基乙酰胺等。 The organic solvent can be used are: methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, tetrahydrofuran, dioxane, acetone, ethylene glycol, methyl ethyl ketone, N, N - dimethylformamide and N, N- dimethylacetamide and the like.

在无机粘结剂30中,也可以混入填料和扩散粒子以取代荧光体50,或者除荧光体50外,还可以混入填料和扩散粒子。 In the inorganic binder 30, and the filler may be mixed into the phosphor-diffusing particles 50 in place, or in addition to the phosphor 50, may also be mixed with filler particles and diffusion. 再者,作为它 Furthermore, as it

们的复合材料,也可以使涂布基体和发光元件的线膨胀系数保持一致。 Their composite material may be made coating a substrate and the light emitting element of the linear expansion coefficient consistent. 作为填料,混入荧光体50而产生发光自不必说,同时还产生出固化时的水分蒸发等的微细通路,具有加快粘结剂的固化干燥的效果。 As the filler, mixed with the phosphor 50 and produce light emission Needless to say, and also produce a fine passage of water evaporation during curing, the adhesive has cured to accelerate the drying effect. 另外, In addition,

还具有将荧光体50的发光扩散开来、增加无机粘结剂30的粘结强度和物理强度的作用。 Emitting phosphor 50 also has a spread, and increasing the physical strength as a bonding strength of the inorganic binder 30. 此外,无机粘结剂30的层和无机粘结剂30的膜也可以作为不含荧光体的扩散层加以使用。 Further, an inorganic binder and a film layer 30 of the inorganic binder 30 may also be used as the diffusion layer does not contain a phosphor. 另外,在作为粘结剂加以使用的复合材料中,除3价金属元素以外,也可以少量含有具有多种价数的元素。 Further, to be used as a binder in the composite material, in addition to trivalent metal element, may contain a small amount of an element having a plurality of valences. 再者,在本实施方案中,粘结剂构件可以包含水合氧化物作为主要的化合物,即使包含一部分金属氧化物和金属氢氧化物以及它们的结合也可以发挥作用。 Further, in the present embodiment, the adhesive member may comprise a hydrated oxide as a main compound, even if it contains a portion of the metal oxides and metal hydroxides, and combinations thereof may also play a role.

作为无机粘结剂30中含有的具体的主材料,下面以氧化铝的AIOOH为例进行说明。 Specific examples of the host material contained in the inorganic binder 30, AIOOH below to alumina as an example. (A】OOH) (A] OOH)

由AIOOH将荧光体50粘结而成的无机粘结剂30是通过以下方法形成的,即在有机溶剂中以预定的比例使烷基醇铝或烷氧基铝水解, 在水解得到的铝氧垸溶胶或氧化铝溶胶溶液中,使荧光体50 (粉体) 均匀分散而得到涂布液,调整该涂布液并以浇灌、喷涂或撒布的方式涂覆该荧光体50得以分散的氧化铝溶胶溶液,从而使之覆盖整个发光元件60,然后进行加热和固化,从而由A100H成分使荧光体彼此之间得以固定,而且固定在发光元件60的表面。 AIOOH by the phosphor 50 obtained by bonding the inorganic binder 30 is formed by the following method, i.e., in an organic solvent at a predetermined ratio an alkyl aluminum alkoxide or hydrolysis of aluminum alkoxide, hydrolysis of aluminum in oxygen embankment sol or an alumina sol solution, so that 50 (powder) to obtain a uniform dispersion of the phosphor coating liquid, and adjusting the coating liquid drench, spraying or coating the phosphor spreading manner is dispersed alumina body 50 sol solution, so as to cover the entire light emitting element 60, and then cured by heating, whereby a phosphor composition A100H be fixed to each other, and fixed to the surface of the light emitting element 60.

烷基醇铝或烷氧基铝是作为涂料的增粘剂、凝胶化剂、固化剂、 聚合催化剂以及颜料的分散剂使用的有机铝化合物。 Alkyl aluminum alkoxides or aluminum alkoxide as a paint thickener, gelling agent, a curing agent, a polymerization catalyst and an organic aluminum compound used in the pigment dispersant.

作为垸基醇铝或烷氧基铝之一的异丙氧基铝、乙氧基铝以及丁氧 Aluminum isopropoxide as aluminum alkoxide group or embankment one aluminum alkoxide, and aluminum ethoxide butoxy

基铝非常富有反应性,借助于空气中的水分生成氢氧化铝或垸基铝酸 Aluminum group very high reactivity, moisture in the air generated by means of aluminum hydroxide or aluminum alkyl with an acid

盐,生成具有勃姆石结构的水合氧化铝。 Salt, hydrated alumina having a boehmite generating structure. 例如异丙氧基铝如以下的化 As example of aluminum isopropoxide of

学式8所示的那样,容易与水反应,最终成为以水合氧化铝为主成分、 As shown in the chemical formula 8, easily reacts with water, to eventually become hydrated alumina as a main component,

具有与氢氧化铝或氧化铝(矾土)进行交联的交联结构的混合物。 The mixture having a crosslinked structure crosslinked with aluminum hydroxide or aluminum oxide (alumina). W ~>刀(0〃)3~151~^/(%W"lsir^力/2(93 化学式8 W ~> knife (0〃) 3 ~ 151 ~ ^ / (% W "lsir ^ force / 2 (Chemical Formula 93 8

因此,使异丙氧基铝与空气中的水分反应后,采用加热生成的AIOOH粘结荧光体50,从而可以将由含有荧光体50的AIOOH粘结荧光体50而成的无机粘结剂30作为无机粘结剂30形成在发光元件60的表面上以及发光元件60的表面以外的支持体上。 Therefore, the reaction of aluminum isopropoxide moisture in the air, using heat generated by the phosphor 50 AIOOH adhesive, by containing an inorganic binder can be obtained by the phosphor 30 50 AIOOH bond as the phosphor 50 the inorganic adhesive 30 is formed on a surface of the light emitting element 60 and the upper surface of the support than the light emitting element 60.

以上由A100H粘结荧光体50而成的无机粘结剂30,也可以组合由Y、 Gd、 Lu、 Sc、 Ga、 In、 B等其它水合氧化物粘结荧光体50而成的无机粘结剂30和由A100H粘结荧光体50而成的无机粘结剂30, 从而在同一发光元件60上形成2种或2种以上的层。 The inorganic binder is more than 30 50 A100H formed by bonding phosphor, an inorganic binder may be combined by a body 50 made of Y, Gd, Lu, Sc, Ga, In, B and other phosphor binder hydrous oxide agent and an inorganic binder 30 30 50 A100H bonded together by fluorescence, or more kinds of such two kinds of layer are formed on the same light-emitting element 60. 根据本实施方案的采用喷涂喷雾手段的无机粘结剂30的形成方法,因为也可以控制两层的膜厚,故而能够容易形成同样形状的无机粘结剂30。 The method for forming a spray means for spraying the inorganic binder 30 of the present embodiment, since the thickness of the two layers can be controlled, and therefore can be easily formed in the same shape as the inorganic binder 30. 例如在同一发光元件60上,首先形成¥203无机粘结剂30,然后在其上形成A1203 无机粘结剂30。 For example, the light emitting element 60 on the same, first forming the inorganic binder 30 ¥ 203, and the inorganic binder A1203 30 formed thereon. 在此,荧光体50可以包含在两层双方之中,也可以只包含在一层中,而且也可以在两层双方之中都不包含。 Here, the phosphor 50 may be included in both layers, it may be included only in one layer, but may be not included in the both layers. 如果采用这样的构成,则具有通过无机粘结剂30的折射率的大小以提高光取出效率等效果。 With this configuration, the size having a refractive index of inorganic binder by 30 to improve light extraction efficiency and other effects. 当形成由一层构成的无机粘结剂30时,则在该无机粘结剂30与外界气氛或氮化物半导体发光元件的界面产生折射率的急剧变化,从发光元件60取出的光的一部分可能在该界面发生反射,因而导致光取出效率的低下。 When the inorganic binder is composed of one layer 30 is formed, then an abrupt change in refractive index at the interface of the inorganic binder 30 from the outside atmosphere or a nitride semiconductor light emitting device, taken from the part of the light emitting element 60 may be reflection occurs at the interface, thus resulting in low light extraction efficiency. 另外,通过形成例如混合有AIOOH和YOOH 的无机粘结剂30,也可以调整线膨胀系数和折射率。 Further, for example, is formed by mixing an inorganic binder and 30 AIOOH YOOH can also adjust the refractive index and linear expansion coefficient.

由这样形成的A100H粘结荧光体50而成的无机粘结剂30,因为与以前只用环氧树脂进行密封的情况不同而为无机物,所以与环轼树脂相比,由紫外线引起的退化极小,也可以组合使用发出紫外光的发光元件和高输出功率的动力型发光元件等。 Inorganic binder 30 formed by the body 50 thus formed A100H adhesive fluorescence, because, unlike the case where only previously sealed with an epoxy resin and inorganic substances, as compared with the ring Shi resin degradation caused by ultraviolet very small power type can be used in combination and the light-emitting elements emits ultraviolet light of high output power and the like. (氧化钇) (Yttrium oxide)

将无定形氧化钇或微粒子氧化钇均匀分散在水中,并将这样形成的氧化钇溶胶用作无机粘结剂30,在这种情况下,即使加热固化氧化钇溶胶,结晶结构的主体也是无定形。 Yttria sol as the inorganic binder 30 amorphous yttrium oxide or yttrium oxide particles uniformly dispersed in water, and formed such, in this case, even if the heat curing yttria sol, the main crystal structure is amorphous . 水合氧化钇和氧化钇可以分别用YOOH • xH20和Y203 • xH20等化学式来表示。 Hydrous yttrium oxide and yttrium oxide can be respectively YOOH • xH20 and Y203 • xH20 chemical formula. 具体地说,作为中间体,经过YOOH 'xCHsCOOH 'yHzO或Y203 'xCH^COOH 'yHiO 的形态,最后形成为部分含有水合氧化钇或氧化钇的形式。 More specifically, as an intermediate, after YOOH 'xCHsCOOH' yHzO yHiO or morphology of Y203 'xCH ^ COOH', formed as part of the final hydrated form containing yttria or yttrium. 氧化钇即使在这样的凝胶状态下也可以形成稳定的膜。 Even in such a yttria gel state may be formed in a stable film. 一般认为其原因在于各自的成分具有交联结构,可以实现稳定化。 This was because that each component having a crosslinked structure can be stabilized.

氧化钇与氧化铝相比,具有难以形成结晶结构的性质。 Compared with yttria alumina, it has a property difficult to form a crystalline structure. 这样一来, Thus,

即使是不具结晶性的无定形的非晶结构也可以是稳定的化合物,Y保持3价不变而不会发生价数的变化。 Even the amorphous structure of the amorphous non-crystalline compound may also be stable, Y remains unchanged trivalent valence number change does not occur. 即具有的长处是难以发生氧化还原反应,没有着色退化。 I.e., it is difficult to have strengths redox reaction, no coloring degradation.

关于其它,则是与上述的氧化铝一样地形成无机粘结剂30。 For other, the inorganic binder 30 are formed as described above with alumina. 正如以上所叙述的那样,荧光体作为粘结剂加以使用的溶胶,也可以利川市售的无机系粘结剂和陶瓷粘结剂等。 As described above, as the phosphor to be used as a binder sol, it may be a commercially available Icheon inorganic binders and ceramic adhesive or the like. 此外,在可以作为粘结剂加以利用的材质中,并不限于氧化铝和氧化钇之类的含有Al和Y元素的水合氧化物,也可以利用其它的IIIA族元素和IIIB族元素的水合氧化物、氧化物以及氢氧化物等。 Further, the can be utilized as a binder material, it is not limited to the hydrated oxide aluminum and yttrium oxide containing Y and Al elements, may be utilized hydrated oxide of other elements of group IIIA and IIIB elements , oxides and hydroxides. 选择的金属元素优选不会发生价数变化。 The metal element is preferably selected valence change does not occur. 特别地,优选的是表现为3价且稳定的金属元素。 In particular, it is preferable that the stable performance of trivalent metal element. 另外,也优选是无色透明的。 In addition, it is also preferably transparent and colorless. 例如除A1和Y之外,还可以利用包含Gd、 Lu、 Sc、 Ga以及In等金属元素的金属化合物,优选可以利用Sc和Lu。 For example, in addition to A1 and Y, it can be utilized further comprising Gd, metal compound Lu, Sc, Ga, and In like metal element, and preferably may be utilized Sc Lu. 或者也可以利用将多种的这些元素进行组合的复合氧化物和复合水合氧化物。 Or you may be using a plurality of composite oxides of these elements in combination, and a composite hydrous oxide.

不单是铝和钇,通过含有其它m族元素的水合氧化物等,也可以将无 Not only is aluminum and yttrium, through hydrous oxides containing other elements of Group m, may be no

机粘结剂30的层的折射率等光学性能以及膜的柔软性、粘结性等膜的物性之类的各种特性控制为所希望的值。 Various characteristics of the organic binder refractive index layer 30 of the optical properties and the like softness, adhesion and other physical properties of the film such film is controlled to a desired value. 这样一来,具有由本发明的实施方案得到的含有价数恒定、优选为3价的水合氧化物凝胶的无机粘结剂30,可以设计出稳定、光取出效率良好的无机粘结剂30。 Thus, having a constant value, preferably an inorganic binder 30 trivalent hydrous oxide gel may be devised stable, good light extraction efficiency of an inorganic binder containing 30 obtained by embodiments of the present invention. 另外,由于用无机材料构成,因此可以制成不随时间变化的、稳定的无机粘结剂层与无机粘结剂膜。 Further, since the inorganic material constituting, it can be made does not change with time, stable inorganic binder and the inorganic layer adhesive film. (树脂) (Resin)

树脂覆盖着无机粘结剂30的表面。 The resin to cover the surface of the inorganic binder 30. 该涂膜在无机粘结剂30的层的表面形成树脂40的层。 The coating resin layer 40 is formed on the surface of the inorganic binder layer 30. 但也可以让树脂40填充在具有凹部20a的基体20内,并覆盖着无机粘结剂30。 It may be filled with the resin body 40 so that the base 20 has a recess portion 20a and covering with the inorganic binder 30. 此外,虽然可以采用各种方法,但优选用树脂40浸渍无机粘结剂30。 Furthermore, although various methods can be employed, but preferably the resin 40 impregnated with the inorganic binder 30. 所谓浸渍是指在无机粘结剂30浸入并包含树脂40。 The so-called dipping means 30 is immersed in the inorganic binder comprising a resin and 40.

当固化前的树脂40的粘度过高时,树脂流动不起来,不能形成均匀的涂膜。 When the viscosity of the resin 40 before curing is too high, the resin does not flow up, a uniform coating film can not be formed. 与此相对照,当固化前的树脂40的粘度过低时,树脂滞留在低洼部分,凸部没有树脂的残留,也不能形成均匀的涂膜。 In contrast, when the viscosity of the resin 40 before curing is too low, the resin staying in the low-lying portion of the convex portion no residual resin, can not form a uniform coating film. 因此,优选使用的是具有预定粘度的树脂。 Thus, preferably used is a resin having a predetermined viscosity.

树脂40优选为层结构。 Resin 40 is preferably a layer structure. 通过设计为层结构,可以谋求从发光元件60发出的光的取出效率的提高和对指向性加以控制。 By designing a layer structure, it may seek the light emitted from the light emitting element 60 and to improve the extraction efficiency of the controlled directivity. 另夕卜,由发光元件60产生的热不会蓄积在树脂40中而可以排放到外部。 Another Bu Xi, heat generated from the light emitting element 60 does not accumulate in the resin 40 can be discharged to the outside.

树脂40优选为凝胶状。 Preferably a gel-like resin 40. 通过凝胶可以缓和由热膨胀产生的应力,因而可以防止由发光元件60延伸出来的引线21的切断。 Can relax the stress generated by the thermal expansion of the gel, it can be prevented by the light emitting element cutting wire 60 extending out of 21. 另外,树脂40也可以呈油状。 Further, the resin 40 may be an oil.

覆盖无机粘结剂30的树脂40的表面是平滑的。 Inorganic binder 30 covering the surface of the resin 40 is smooth. 如果只将无机粘结剂30固化,则用电子显微镜观察其表面时,可以看到许多粒状的l"l凸。为此,从发光元件60发出的光在该粒状的凹凸上产生反射,或者产生散射,抑制光的取出。因此,通过在该无机粘结剂30的表面覆盖树脂40,可以使树脂40的表面变得平滑。由此可以使发光元件60发出的光有效地向外部发射,从而可以谋求光取出效率的提高。另外,因为无机粘结剂30的表面形成有粒状的凹凸,与树脂40的表面积增大,从而在树脂40与无机粘结剂30的界面具有增大附着力等的效果。 If only the inorganic binder 30 cured, the surface was observed with an electron microscope, can see many granular l "l convex. For this reason, the light reflection irregularities on the particulate emitted from the light emitting element 60, or scattering, light is extracted suppressed. Thus, by covering the surface of the resin 40 of the inorganic binder 30, the surface of the resin 40 becomes smooth, thereby the light emitting element 60 can be emitted efficiently emitted to the outside, whereby the light extraction efficiency can be improved Further, since the surface of the inorganic binder 30 are formed granular irregularities, increasing the surface area of ​​the resin 40, thereby increasing the adhesion with the resin 40 at an interface 30 with the inorganic binder and the like Effect.

树脂40的气体含有率在常压下为3体积%或以下。 40 resin content of the gas at atmospheric pressure was 3% by volume or less. 优选为1体积%或以下,更优选为0.01。 Preferably 1 vol% or less, more preferably 0.01. /。 /. 体积或以下。 Volume or less. 在无机粘结剂30所具有的空隙31中,含有空气等气体。 In the inorganic binder 30 having a void 31, containing gas such as air. 该气体在浸渍树脂40时被排放到外部。 The gas in the impregnating resin 40 is discharged to the outside. 此时,在无机粘结剂30的表面覆盖着树脂40,所以空隙31中的气体有时也溶解在树脂40中,由于该气体溶解在树脂40中,所以在树脂40中含有气体。 At this time, the surface of the inorganic adhesive 30 is covered with the resin 40, the voids 31 may be a gas dissolved in the resin 40, since the gas dissolved in the resin 40, the resin 40 contained in the gas. 该树脂40中含有的气体,伴随着发光元件60的激励而发热,因发热而产生热膨胀,因热膨胀有时在树脂40中产生气泡。 The gas contained in the resin 40, along with the excitation of the light emitting element 60 generates heat, thermal expansion due to heat, air bubbles may occur in the resin 40 due to thermal expansion. 由于该气泡的作用,从发光元件60发出的光有时产生反射,从而导致树脂40的材料是往无机粘结剂30中渗透的材料,优选的是具有优良的耐热性、耐光性以及耐侯性。 Since the effect of the air bubbles, light emitted from the light emitting element 60 may produce reflections, resulting in a material of the resin is 40 to 30 in the inorganic binder permeable material, preferably having excellent heat resistance, light resistance and weather resistance . 由于发光元件60的发热达12(TC或以上,温度极高,所以树脂40必须是能够承受该温度的耐热性树脂。另外,树脂40因为要受到蓝色光或紫外线等发光强度高的光的照射以及使其通过,因而必须是耐光性的树脂。另一方面,优选吸水性、吸潮性低的树脂。在使用吸水性、吸潮性高的树脂的情况下,该树脂中的水分因发光元件60的发热而使水蒸气爆发,在发光元件60和无机粘结剂30或树脂40的界面产生剥离,从而招致光取出效率的低下。因此,使用吸水性、吸潮性低的树脂,优选的是在该树脂40中不含有水分。 The light emitting element 60 due to heat up to 12 (TC or more, extreme temperatures, the resin 40 must be able to withstand the temperature of heat-resistant resin. Further, since the resin 40 is subjected to high light like blue or ultraviolet light emission intensity and passed through the irradiation, and must be light resistance resin. on the other hand, preferably water absorption, low moisture absorption of the resin. in the case of water absorption, high moisture absorption of the resin, the resin due to moisture the light emitting element 60 of the steam heat outbreak, peeling at the interface between the light emitting element 30 or 60 and an inorganic binder resin 40, thereby leading to low light extraction efficiency. Thus, the use of water absorption, low moisture absorption of the resin, preferably it does not contain water in the resin 40.

作为粘结着荧光体50的无机粘结剂30的层中浸渍的有机系树脂材料,可以列举出硅树脂、丙烯酸系树脂以及环氧树脂等。 As the adhesive layer is impregnated with the inorganic binder 30 of the phosphor 50 in the organic resin material can include a silicone resin, acrylic resin and epoxy resin. 作为树脂40的材料,优选为硅树脂。 As the material 40 is a resin, preferably a silicone.

硅树脂具有耐热性、耐侯性、耐光性等化学性质稳定的特性。 Silicone has stable properties and chemical properties of heat resistance, weather resistance, light resistance and the like. 硅树脂由Si-O-Si骨架构成。 Silicone resins composed of Si-O-Si backbone. 因为Si-O的硅氧垸键的结合能较大,所以是稳定的,而且对从可见到紫外的光都具有优良的透明性。 Because the Si-O binding silicone embankment bond can be large, it is stable, but also can be seen from the ultraviolet light have excellent transparency. 因此,一般认为由于树脂40本身并不吸收这些光,因而难以产生退化。 Thus, the resin 40 is generally believed that itself does not absorb light, it is difficult to produce degradation. 另外,硅树脂的表面张力小,粘度也低,渗透性优良,可以均匀地渗透到无机粘结剂30中的微细之处。 Further, the surface tension and the silicone resin, a low viscosity, high permeability, can be uniformly infiltrated into the fine inorganic binder of 30. 硅树脂有加成固化型、UV固化型、缩合反应型、UV阳离子聚合型,其中优选加成固化型。 An addition curable silicone resins, UV curable type, condensation reaction type, UV cationic polymerization type, wherein the addition curing type is preferred. 这是因为:加成固化型在树脂中几乎没有挥发成分,热固化后几乎不产生体积收縮。 This is because: in the addition curing type resin is almost no volatile component, almost no volume shrinkage after thermal curing. 因为不产生体积收縮,所以不会产生因体积收縮引起的裂纹。 Because volume shrinkage does not occur, so that no cracks caused by volume shrinkage. 另外,在树脂40和无机粘结剂30的界面不会发生剥离。 Further, the peeling does not occur at the interface between the resin 40 and 30 of the inorganic binder. 树脂40由于几乎没有挥发成分,所以在作为气密基体加以使用的情况下,不用担心因为与发光元件60的发热相伴的内部压力的上升而引起基体的破损。 Since the resin 40 almost no volatile component, so in the case to be used as a gastight matrix, without fear of increase in the internal pressure of the heat accompanying the light emitting element 60 caused breakage of the base body. 树脂40优选的是,固化后的树脂状态相对于硬质状态而言为软质的凝胶或硬度较低的橡胶。 Preferably the resin 40 is a resin cured state with respect to the rigid state in terms of low hardness soft gel or rubber. 由于树脂40以软质状态存在,因而可以缓和由热、冲击等作用于树脂40的应力和外部压力,使树脂40的柔软性得以提高。 Since the resin 40 is present in the soft state, and thus can be alleviated by the action of heat, shock stress and external pressure of the resin 40 in the flexible resin 40 is improved. 例如,树脂40在成形前或成形后的任一种情况下可以使用具有二烷基硅氧烷骨架的硅树脂。 For example, the resin 40 may be a silicone resin having a dialkyl siloxane backbone in any case before and after the molding or forming. 硅树脂交联后具有凝胶、橡胶状等结构。 Silicone resin after crosslinking has a gel, a rubber-like structure and the like. 特别地,树脂40优选在成形前具有二甲基硅氧烷的主链。 In particular, the resin 40 preferably has a main chain of dimethylsiloxane before molding. 但并不局限于二甲基硅氧垸,也可以使用苯基甲基硅氧烷。 But not limited to, dimethyl silicone embankment, phenylmethyl siloxane may be used.

无机粘结剂30事先不是完全的氧化物结晶和多晶,而是以多孔的凝胶状态保存。 Inorganic binder 30 in advance is not completely crystalline and polycrystalline oxides, but stored in a porous gel state. 特别地,软熔工序等因为需要施加由热冲击作用于无机粘结剂30的应力,因而在浸渍硅树脂40等时,由于硅树脂40和无机粘结剂30的热膨胀系数不同而招致开裂和剥离。 In particular, since the reflow process or the like to be applied to a thermal shock by the stress of the inorganic binder 30, thus the silicone resin during impregnation and the like 40, 40 and the silicone resin due to the different thermal expansion coefficients of the inorganic binder 30, and cracking incurred peel off.

多孔质凝胶由于形成为交联结构、网状结构或聚合物结构,所以热膨胀系数比结晶、多晶状态为大,由于接近于硅树脂的热膨胀系数,因而不会产生开裂和剥离。 The porous gel is formed due to a crosslinked structure, a mesh structure or a polymeric structure, the coefficient of thermal expansion than crystalline, polycrystalline state is large, the coefficient of thermal expansion close to silicon resin, and thus will not produce cracks and detachment.

采用縮合型树脂40进行固化时,将产生小分子成分。 When using a condensation resin 40 is cured, it will produce small molecular constituents. 此时,树脂40发生体积收縮,在无机粘结剂30中产生龟裂,而且在无机粘结剂30与荧光体50的接触面产生剥离。 At this time, volume shrinkage of the resin 40 occurs, cracks in the inorganic binder 30, and peeling the inorganic binder on the contact surface 30 and the phosphor 50.

UV固化型树脂40因为导入了吸收紫外线的有机官能基团,所以树脂40因吸收激发光以及产生的光而导致光取出效率的降低。 UV curable resin 40 is introduced as an organic UV absorbing functional groups, the resin 40 by the absorption of light and excitation light generated by resulting in reduced light extraction efficiency. (填料) (filler)

填料(图中未示出)就是填充剂,可以利用的有:钛酸钡、氧化钛、氧化铝(三氧化二铝)、氧化钇(三氧化二钇)、氧化硅、碳酸钙以及其它水合氧化物等。 A filler (not shown) that fillers can be utilized are: barium titanate, titanium oxide, aluminum oxide (alumina), yttrium oxide (yttria), silica, calcium carbonate, and other hydrated oxides. 例如,也可以有相对于至少包含选自Al、Ga、 Ti、 Ge、 P、 B、 Zr、 Y或碱土金属之中的一种或多种元素的无色水合氧化物、或至少包含选自Si、 Al、 Ga、 Ti、 Ge、 P、 B、 Zr、 Y或碱土金属之中的一种或多种元素的氧化物具有更高热传导系数的埙料。 For example, there may be selected with respect to at least comprising Al, Ga, Ti, among Ge, P, B, Zr, Y, or an alkaline earth metal is one or more elements as a colorless hydrated oxide, or selected from the group comprising at least si, oxide of Al, Ga, Ti, Ge, one kind among P, B, Zr, Y, or one or more alkaline earth metal elements having a higher thermal conductivity material Xun coefficient. 通过添加这样的填料,发光装置601的排热效果得以提高。 By adding such a filler, the effect of exhaust heat emitting device 601 is improved. 作为这样的填料,在采用上述无机粘结剂30形成粘结层而对发光元件60进行芯片焊接时,可以列举出氧化铝、Ag等金属粉。 Such as a filler, an adhesive layer is formed using the inorganic adhesive 30 for die bonding of the light emitting element 60 may include aluminum oxide, Ag metal powder and the like.

在无机粘结剂30的溶胶中,除荧光体50及低级醇之外,通过—啦先混合分散剂,可以借助于固化时与低级醇的共沸脱水在低温形成致密的涂膜。 In the sol of the inorganic binder 30, in addition to the phosphor 50 and the lower alcohol, by - mixing it first dispersing agent, a lower alcohol and azeotropic dehydration to form a dense film at low temperatures by means of curing. 另外,也可以在无机粘结剂30中含有光稳定化材料、着色剂以及紫外线吸收剂等。 In addition, it may contain a light stabilizer material, a coloring agent and an ultraviolet absorber and the like in the inorganic binder 30.

无机粘结剂30用料浆溶液来形成。 30 with the inorganic binder to form a slurry solution. 料浆溶液是这样调制而成的, 即以无定形金属水合氧化物、微粒子金属水合氧化物以及金属氢氧化物为主要成分,将该主要成分进而将无定形金属氧化物、微粒子金属氧化物均匀分散在水中,由此制得溶胶溶液,然后在该溶胶溶液中, 混合荧光体50和填料。 The slurry solution thus prepared is formed, i.e. an amorphous hydrated metal oxide, metal hydrous oxide fine particles and a metal hydroxide as a main component, the main component of the amorphous metal oxide and further, the metal oxide fine particles uniformly dispersed in water, thereby preparing a sol solution, and then the sol solution, mixed phosphor 50 and a filler. 溶胶溶液中的有效固体成分与荧光体50的s: 量比、或者溶胶溶液中的有效固体成分与荧光体50和填料混合物的重量比优选为0.05〜30。 Sol solution the active ingredient with solid phosphor S 50: the ratio, by weight, and a filler or a mixture of active sol solution a solid content ratio of the phosphor 50 is preferably 0.05~30. 例如可以在从相对于20g有效固体成分浓度为15%的溶胶溶液、荧光体为90g到相对于600g有效固体成分浓度为15%的溶胶溶液、荧光体为4.5g的比率范围内进行调整。 For example the ratio may be adjusted within a range from 20g active solid concentration of 15% with respect to the sol solution, the phosphor is 90g to 600g active with respect to a solid content concentration of 15% of the sol solution, the phosphor is 4.5g. (发光元件) (Light emitting element)

发光元件60并不限于能够发出可见光的发光元件,也可以使用能够发出紫外光的发光元件。 The light emitting element 60 is not limited to the light emitting element capable of emitting visible light, a light-emitting element may be capable of emitting ultraviolet light. 另外,发光元件60可以与荧光体50组合使用。 Further, the light emitting element 60 may be used 50 in combination with a phosphor. 也就是说,将由发光元件60发出的光照射荧光体50,使荧光体50激发,便可以发出与发光元件60不同的光。 That is, the light irradiation by the light emitting element 60 emits the fluorescent body 50, so that the excitation of the phosphor 50, the light emitting element can emit different light 60. 发光元件60采用MOCVD等方法,在基板上形成GaAs、 InP、 GaAlAs、 InGaAlP、 InN、 A1N、 GaN、 InGaN、 AlGaN、 InGaAlN等半导体作为发光层。 The light emitting element 60 like the MOCVD method, forming GaAs, InP, GaAlAs, InGaAlP, InN, A1N, GaN, InGaN, AlGaN, InGaAlN semiconductor such as a light emitting layer on the substrate. 作为半导体的结构,可以列举出具有MIS结、PIN结和PN结等的均质结结构、异质结结构或双异质结结构。 As the structure of the semiconductor may include a homojunction structure having MIS junction, PIN junction and the PN junction or the like, heterojunction structure or double heterojunction structure. 可以根据半导体层的材料及其混晶度对发光波长进行各种选择。 Can be variously selected depending on the material of the emission wavelength of the semiconductor layer and the crystallinity thereof. 另外,也可以设定为在产生量子效果的薄膜上形成有半导体活性层的单量子阱结构或多重量子阱结构。 Further, there may be set to the semiconductor active layer is formed of a single quantum well structure or a multiple quantum well structure in the film quantum effect. 优选的是能够高效激发荧光体且能够高效地发出波长较短的光的氮化物系化合物半导体(通式为IniGajAlkN,其中,0《i、 0《j、 0《k, i+j+k二l)。 Preferred is possible to efficiently excite the phosphor efficiently and capable of emitting light of shorter wavelength nitride-based compound semiconductor (formula IniGajAlkN, where, 0 "i, 0" j, 0 "k, i + j + k two l).

在将氮化镓系化合物半导体用作发光元件60的情况下,适于用作半导体基板的材料有:蓝宝石、尖晶石、SiC、 Si、 ZnO、 GaN等。 In the case where the material is gallium nitride-based compound semiconductor light emitting element 60, it is suitable for use as a semiconductor substrate: sapphire, spinel, SiC, Si, ZnO, GaN and the like. 为了形成结晶性良好的氮化镓,更优选使用蓝宝石基板。 In order to form gallium nitride of good crystallinity, and more preferably to use a sapphire substrate. 当在蓝宝石基板上生长半导体膜时,优选形成GaN、 A1N等缓冲层后,再在缓冲层上形成具有PN结的氮化镓半导体。 When a semiconductor film is grown on a sapphire substrate, preferably formed of GaN, A1N, etc. after the buffer layer, and then forming gallium nitride semiconductor having a PN junction on the buffer layer. 另外,也可以将GaN单晶本身用作基板,其中GaN单晶是在蓝宝石基板上以Si02为掩模进行选择生长而成的。 Further, the GaN single crystal itself may be used as the substrate, wherein the GaN single crystal is grown from selection to Si02 on a sapphire substrate as a mask. 在这种情况下,在各半导体层形成后,也可以通过浸蚀并 In this case, after forming the semiconductor layers, it may be by etching and

除去Si02而使发光元件与蓝宝石基板分离。 Si02 removing the separated light emitting element and the sapphire substrate. 氮化镓系化合物半导体在 The gallium nitride-based compound semiconductor

不掺杂的情况下表现出n型导电性。 Without doping exhibit n-type conductivity. 在形成包括提高发光效率等要求的n型氮化镓半导体的情况下,作为n型掺杂剂,优选适当导入Si、 Ge、 Se、 Te以及C等元素。 In the case of forming including improved luminous efficiency requirements of the n-type gallium nitride semiconductor, and an n-type dopant is preferably introduced into a suitable Si, Ge, Se, Te and C and other elements. 另一方面,在形成p型氮化镓半导体的情况下,则掺杂作为p型掺杂剂的Zn、 Mg、 Be、 Ca、 Sr以及Ba等。 On the other hand, in the case of forming a p-type gallium nitride semiconductor, the Zn-doped p-type dopant, Mg, Be, Ca, Sr and Ba and the like.

氮化镓系化合物半导体如果只是掺杂p型掺杂剂,则难以实现p 型化,所以在导入p型掺杂剂以后,优选采用炉子加热、低速电子朿照射以及等离子体照射的方法进行退火,由此实现p型化。 If only the gallium nitride compound semiconductor doped with p-type dopants, p-type is difficult to achieve, so after introducing the p-type dopant, preferably using a heating furnace, and a method of irradiating low-energy electrons Bouquet plasma irradiation annealing , thereby achieving p-type. 作为具体的发光元件的层构成,可以举出的适当的例子是由以下层层叠而成的, 即在具有于低温下形成有氮化镓、氮化铝等缓冲层的蓝宝石基板或碳化硅上,层叠作为氮化镓半导体的n型接触层,作为氮化铝'镓半导体的n型包层,作为掺杂Zn及Si的氮化铟镓半导体的活性层,作为氮化铝•镓半导体的p型包层以及作为氮化镓半导体的P型接触层。 As a specific layer constituting the light emitting element, suitable examples may be mentioned are the following layers are laminated, at low temperature i.e. having formed on a sapphire substrate has a gallium nitride or silicon carbide, aluminum nitride buffer layer stacking an n-type contact layer is gallium nitride semiconductor, an n-type cladding layer of aluminum nitride 'gallium semiconductors as Si and Zn-doped InGaN active layer of the semiconductor, a gallium nitride aluminum semiconductor • the p-type cladding layer and a P-type contact layer is gallium nitride semiconductor. 为了形成发光元件60,对于具有蓝宝石基板的发光元件60的情况, 在通过浸蚀等形成P型半导体以及n型半导体的露出面后,在半导休层上使用溅射法和真空蒸镀法等形成具有所要求形状的各个电极。 To form the light emitting element 60, in the case of the light emitting element having a sapphire substrate 60, after forming the P-type semiconductor and n-type semiconductor surface exposed by etching and the like, using a sputtering method and a vacuum deposition method in the semiconductor layer off like each electrode having a desired shape. 对于SiC基板的情况,利用基板本身的导电性也可以形成一对电极。 In the case of the SiC substrate, a conductive substrate itself may be formed a pair of electrodes.

接着对形成的半导体晶片等进行划片,划片或者是采用钻石轮划片机进行的直接的完全切割,其中钻石轮划片机的刀片具有金刚石制刀刃,切割时刀刃旋转;或者是在切出比刀刃宽度更宽的槽后,利用外力分幵半导体晶片。 Next, the semiconductor wafer is formed of scribing, dicing, or is a direct fully cut dicing saw machine, wherein the dicing saw machine blade having a diamond blade, the blade rotating cutting; or tangentially after the blade width wider than the groove, the semiconductor wafer with an external force divided Jian. 或者借助于顶端的金刚石针作往复直线运动的钻石轮划片机在半导体晶片上划出极细的划线(经线),例如划成网纹状,然后利用外力分开晶片,从而由半导体晶片切割成芯片状。 Or by means of a diamond needle tip reciprocating linear motion dicing saw machine draw on the semiconductor wafer fine scribe (meridian), for example, classified into a wavy, then an external force to separate the wafer to cut the semiconductor wafer into chips. 这样,便可以形成作为氮化物系化合物半导体的发光元件60。 Thus, it may be formed of a nitride-based compound semiconductor light emitting element 60.

在本实施方案的发光装置601中,在发光的情况下,考虑到与荧光体的发光颜色互补,发光元件60的主发光波长优选为350nm〜 530腦。 In the light emitting device 601 of this embodiment, the case where light emission, considering the complementary color emission phosphor, the main emission wavelength of the light emitting element 60 is preferably 350nm~ 530 brain.

另外,发光元件除半导体发光元件以外,还包括用于获得由真空放电产生的发光、以及由热发光产生的发光的元件。 Further, the light emitting elements other than the semiconductor light emitting element further includes means for obtaining light emission by the vacuum generated by the discharge, and the light emitting element is generated by thermal emission. 例如,由真空放电产生紫外线等的元件也可以用作发光元件。 For example, vacuum ultraviolet rays are generated by a discharge element or the like may be used as the light emitting element. 在本发明的实施方案中, 作为所利用的发光元件,其波长为550nm或以下,优选为460nm或以下,进一步优选为410nm或以下,但本发明并不局限于此。 In an embodiment of the present invention, the light-emitting element utilized, a wavelength of 550nm or less, preferably 460nm or less, and further preferably 410nm or less, but the present invention is not limited thereto. 特别地, 正如后面所叙述的那样,本发明的实施例所具有的优点是:耐久性优良,可以适用输出功率大的动力型发光元件。 In particular, as is described later, embodiments of the present invention has advantages are: excellent durability, a large power can be applied to the light emitting element output power type.

下面说明将m族氮化物系半导体发光元件用作发光元件60的实例。 The following description will be m-nitride-based semiconductor light-emitting element as a light emitting element of Example 60. 发光元件60例如是在蓝宝石基板上、隔着GaN缓冲层依次层叠下列层所形成的层叠结构,这些层依次为:未掺杂Si或Si浓度低的第1 n型GaN层;由掺杂Si或Si浓度比第1 n型GaN层更高的n型GaN构成的n型接触层;未掺杂或Si浓度比n型接触层更低的第2 GaN 层;多重量子阱结构的发光层(GaN阻挡层/InGaN阱层的量子阱结构);由P型GaN构成的p包层,其中P型GaN由掺杂Mg的P型GaN构成;由掺杂Mg的P型GaN构成的P型接触层。 The light emitting element 60, for example, on a sapphire substrate, a GaN buffer layer are stacked via structure is formed the following layers are stacked, these layers as follows: a low concentration of 1 n-type GaN layer of undoped Si or Si; Si doped or n-type contact layer composed of Si concentration higher than the first n-type GaN n-type GaN layer; undoped Si or a lower concentration than the n-type contact layer of GaN layer 2; a light emitting layer of multiple quantum well structure ( quantum well layer / InGaN well layer is GaN barrier); P P-type clad layer made of GaN, wherein the P-type GaN Mg-doped P-type GaN; P-type contact Mg-doped P-type GaN Floor. 并按下述的方法形成电极。 Forming an electrode in accordance the following method. 当然,也可以使用不同于该构成的发光元件。 Of course, different from the configuration of the light emitting element may be used.

p欧姆电极几乎在p型接触层的整个面上形成,在一部分该P欧姆电极上形成p焊盘电极。 p-ohmic electrode substantially the entire surface of the p-type contact layer is formed, p-pad electrode is formed on a portion of the P-ohmic electrode.

另外,通过浸蚀从P型接触层除去第1 GaN层而露出n型接触层的一部分,n电极便在该露出部分上形成。 Further, removing by etching the first layer is from 1 GaN P-type contact layer to expose a portion of the n-type contact layer, n electrodes will be formed on the exposed portion.

此外,本实施方案使用多重量子阱结构的发光层,但本发明并不限定于此,例如利用InGaN的单量子阱结构和多重量子阱结构都可以, 也可以利用掺杂Si和Zn的GaN。 Further, the present embodiment uses a light emitting layer of multiple quantum well structure, but the present invention is not limited thereto, for example using a single quantum well structure and multiple quantum well structure of InGaN may be, may be doped with Si and Zn using GaN.

另外,发光元件60的发光层通过改变In的含量,可以在420nm〜 490nm的范围内改变主发光峰。 Further, the light emitting layer of the light emitting element 60 by changing the content of In, may be varied within the scope of the main emission peak of 420nm~ 490nm. 而且发光波长并不限于上述范围,可以使用发光波长为360nm〜550nm的发光元件。 But is not limited to the above-described emission wavelength range, it may be used for the emission wavelength of the light emitting element 360nm~550nm. 特别地,当将本发明的发光装置适用于紫外光LED发光装置时,可以提高激发光的吸收转换效率,可以降低紫外光的透过。 Particularly, when the light-emitting device of the present invention is applied to an ultraviolet LED light-emitting device, it can increase the absorption efficiency of the excitation light can be reduced through the ultraviolet light. (荧光体) (Phosphor)

荧光体50将从发光元件60发出的可见光和紫外光转换为与发光元件60不同发光波长的发光。 Visible and ultraviolet light from the phosphor 50 emits the light emitting element 60 is converted into the light emitting element 60 emitting different emission wavelengths. 例如,用从发光元件60的半导体发光层发出的光进行激发而发光。 For example, excitation light emitted from the light emitting layer of the semiconductor light emitting element 60 to emit light. 作为优选的荧光体,可以利用的有:至少用Ce活化的稀土类石榴石系荧光体例如钇铝石榴石(以下称为"YAG")系、碱土类氮化硅荧光体等氮化物系、碱土类氧化氮化硅荧光体等氧氮化物系。 Preferred phosphors may be utilized are: activated with at least Ce rare earth garnet phosphor such as yttrium aluminum garnet (hereinafter, referred to as "YAG") based, alkaline earth silicon nitride fluorescent material-based composition, alkaline earth silicon oxynitride phosphor oxide-based material and the like. 在本实施方案中,作为荧光体50使用的是由紫外光激发产生预定颜色的光的荧光体。 In the present embodiment, used as the phosphor 50 is excited by ultraviolet light of a predetermined color phosphors. 具体地说,可以利用的荧光体举例如下: Specifically, the phosphor can be utilized for example as follows:

(1) Ca10(PO4)6FCl: Sb, Mn (1) Ca10 (PO4) 6FCl: Sb, Mn

(2) M5(P04)3C1: Eu (其中:M具有选自Sr、 Ca、 Ba以及Mg之 (2) M5 (P04) 3C1: Eu (wherein: M is selected from Sr, Ca, Ba and Mg of

中的至少一种的碱土类金属) At least one of alkaline earth metals)

(3) BaMg2Al16027: Eu (3) BaMg2Al16027: Eu

(4) BaMg2Al16027: Eu, Mn (4) BaMg2Al16027: Eu, Mn

(5) 3.5MgO • 0.5MgF2 • Ge02: Mn (5) 3.5MgO • 0.5MgF2 • Ge02: Mn

(6) Y202S: Eu (6) Y202S: Eu

(7) Mg6As2Ou: Mn (7) Mg6As2Ou: Mn

(8) Sr4Al14025: Eu (8) Sr4Al14025: Eu

(9) (Zr、 Cd)S: Cu 卿SrAl204: Eu (9) (Zr, Cd) S: Cu Qing SrAl204: Eu

(U) Ca10(PO4)6ClBr: Mn, Eu (②Zn2Ge04: Mn (U) Ca10 (PO4) 6ClBr: Mn, Eu (②Zn2Ge04: Mn

(13) Gd202S: Eu (13) Gd202S: Eu

(14) La202S: Eu (14) La202S: Eu

(15) Ca2Si5N8: Eu (15) Ca2Si5N8: Eu

(16) Sr2Si5N8: Eu(17) SrSi202N2: Eu (16) Sr2Si5N8: Eu (17) SrSi202N2: Eu

(18) BaSi202N2: Eu (18) BaSi202N2: Eu

卿M2Si04: Eu (其中:M具有选自Sr、 Ca、 Ba以及Mg之巾的至少一种的碱土类金属) Qing M2Si04: Eu (wherein: M is selected from Sr, Ca, Ba, and Mg of at least one towel alkaline earth metal)

另外,除上述荧光体以外,还可以利用产生黄色区域的发光的、 用(Y, Gd)3(Al, Ga)5012: Ce等表示的稀土类铝酸盐即YAG系荧光体。 Further, in addition to the phosphor, light emission may also be generated using a yellow region, with (Y, Gd) 3 (Al, Ga) 5012: Ce and other rare-earth aluminate represented i.e. YAG phosphor.

当发光元件60发出的光和荧光体50发出的光成互补颜色关系等时,通过将各自的光混色便可以发出白色的光。 When a complementary color relationship to light 50 emitted from a phosphor light emitting element 60 emitted by the respective light color mixing can emit white light. 作为发出白色光的发光元件60与荧光体50的组合,具体地说,可以列举出发光元件60 发出的光和由该光激发而发光的荧光体50的光分别相当于3原色(红色系、绿色系、蓝色系)的情况、以及发光元件60发出的蓝色光和由该光激发而发光的荧光体的黄色光。 As a combination of light-emitting element 60 emits white light and fluorescent body 50, in particular, it may include an optical element 60 starting the fluorescent light emitted by the excitation light and the light emitting body 50 correspond to the three primary colors (red, greenish yellow light blue, blue case), and the light emitting element 60 is excited by the light emitted from the light emitting phosphors. 特别是在发光元件60使用紫外光的情况下,因为发光颜色仅由荧光体50的发光颜色来决定,因而获得信号用的蓝绿色、黄红色、红色等以及浅色等各种中间色的发光装置也是可能的。 Especially in the case of using ultraviolet light emitting element 60, since only the emission color of the emission color of the phosphor 50 is determined, thereby obtaining a cyan signal for the yellow, red and other light emitting colors other intermediate the device is also possible.

通过对作为荧光体50与荧光体50之间的粘结剂发挥作用的各种树脂和玻璃等无机粘结剂、与填料等的比率、荧光体50的沉降时间、 荧光体的形状等进行各种调整以及对LED芯片的发光波长进行选择, 发光装置601的发光颜色可以提供灯泡颜色等任意的白色系的色调。 By the ratio of acting as a binder between the phosphor 50 and the phosphor 50 and the various glass inorganic binder resins, fillers and the like, fluorescent settling time 50, the shape of the phosphor for each peer such adjustment and the emission wavelength of the LED chip is selected, the light emission color of the light emitting device 601 may provide any hue bulb whitish color. 在发光装置601的外部,优选发光元件6O发出的光和和荧光体50发出的光有效地透过铸模构件。 The light can be transmitted efficiently emitted outside the mold member 50, preferably a light emitting element and the light emitted 6O light emitting device and a phosphor 601.

作为有代表性的荧光体50,可以列举出用铜活化的硫化镉锌和川铈活化的YAG系荧光体。 As a representative of the phosphor 50 may include cadmium zinc sulfide activated with copper and cerium-activated River YAG phosphor. 特别在高辉度且长时间使用时,优选的是(ReLxSmx) 3 (Al^Gay) 5012: Ce (0《x<l, 0《y《l,其中:Re 是选自Y、 Gd、 La、 Lu、 Tb以及Pr之中的至少一种元素=。 Particularly at high luminance and a long time, it is preferable that (ReLxSmx) 3 (Al ^ Gay) 5012: Ce (0 "x <l, 0" y "l, wherein: Re is selected from Y, Gd, La , Lu, Tb, and at least one element selected from among = Pr.

(Rei.xSmx) 3 (Ah-yGay) 5012: Ce荧光体因为是石榴石结构,所以对热、光以及水分具有很强的耐性,激发谱峰可以达到470nm左右。 (Rei.xSmx) 3 (Ah-yGay) 5012: Ce phosphor as garnet structure, has a strong resistance to heat, light and moisture may reach peak excitation 470nm. 另外,也可能具有宽的发光谱,其发光峰在530nm附近,峰的末端延伸到720nm处。 Further, it may have a wide emission spectrum, which extends to the emission peak at 720nm, the peak in the vicinity of the end of 530nm.

在本实施方案的发光装置601中,荧光体50也可以是2种或更多种荧光体混合而成的。 In the light emitting device 601 of this embodiment, the phosphor 50 may be two or more kinds of phosphors are mixed. 即可以将2种或更多种Al、 Ga、 Y、 La、 Lu、 Tb、 Pr以及Gd和Sm的含量不同的(Rei-xSmx) 3 (Al,.yGay) 5012: Ce荧光体进行混合,从而增加RGB的波长成分。 I.e. two or more different kinds of Al,,,,,, Pr, Sm and Gd content of the Ga Y La Lu Tb (Rei-xSmx) 3 (Al, .yGay) 5012 may be: Ce phosphor are mixed, thereby increasing the wavelength components of RGB. 另外,使用具有黄〜 红色发光的氮化物荧光体等增加红色的成分,也可以获得平均演色评价指数高的照明或灯泡颜色的发光装置等。 Further, having a yellow-to-red emitting phosphor is a nitride red component increases the like, can be obtained a high average color rendering index or bulb color light emitting means for illuminating the like. 具体地说,混配发光元件的发光波长,调整CIE色度图上的色度点不同的荧光体的含量,藉此可以发出色度图上任意点的光,其中色度图用发光元件将该荧光体之间连接起来。 Specifically, the emission wavelength of the light emitting element is compounded, adjusting the content of the different points on a chromaticity CIE chromaticity chart of the phosphor, whereby light can be emitted at any point on the chromaticity diagram, the chromaticity in which the light-emitting element in FIG. connected between the phosphor.

这样荧光体50可以均匀地分散在无机粘结剂30中并均匀地发光。 Such a phosphor 50 may be uniformly dispersed in the inorganic binder 30 and uniformly emit light. 在无机粘结剂30中的荧光体因自身的重量而沉降或浮起来。 Inorganic binder and a phosphor 30 by its own weight settling or float.

在发光装置601的表面上,像以上那样形成的荧光体50可以在由一层构成的无机粘结剂30中存在二种或更多种,也可以在由二层构成的无机粘结剂30中分别存在一种、二种或更多种。 On the surface of the light emitting device 601, the phosphor 50 is formed as described above may be present in one layer composed of the inorganic binder 30 in two or more, the inorganic binder 30 may be composed of two layers respectively in the presence of one, two or more species. 再者,在树脂40 中也可以存在一种、二种或更多种的荧光体。 Further, there may be one, two or more of the phosphor in the resin 40. 这样一来,通过源于不同荧光体50的光的混色可以得到白色光。 Thus, it is possible to obtain white light by mixing light from different phosphors 50. 此时,为了使各荧光体50 发出的光更好地混色并减少颜色不均,优选各荧光体具有类似的平均粒径和形状。 In this case, in order to make the light emitted from each phosphor 50 to better color mixing and reduced color unevenness, preferably each phosphor has a similar average particle size and shape. 另外,也可以考虑受形状影响的沉降特性来形成无机粘结剂30。 Further, the inorganic binder to form 30 may also be considered affected by the shape of the settling characteristics. 作为不容易受沉降特性影响的粘结剂30的形成方法,可以列举出喷涂法、丝网印刷法以及浇灌法等。 As a method for forming the binder 30 is not susceptible to sedimentation characteristics can include a spray method, a screen printing method and the watering method. 在本实施方案中,无机粘结剂可以具有1%〜80%的有效固体成分,可以在lcps〜5000 cps的宽范围内进行粘度调整,而且也可以调整触变性,所以,能够与这些无机粘结剂的形成方法相适应。 In the present embodiment, the inorganic binder may have a 1% ~ 80% of an effective solid content, the viscosity can be adjusted over a wide range lcps~5000 cps, but also can adjust the thixotropy, it is possible with the inorganic adhesive the method of forming caking agent compatible. 如上所述,填料和无机粘结剂的重量比优选设定为0.05〜30的范围,另外,通过调整填料的配合量和粒径来增强粘结力。 As described above, the weight ratio of inorganic binder and a filler preferably in the range of 0.05~30, further, to enhance the adhesion by adjusting the amount and particle size of the filler.

本实施方案中使用的荧光体也可以将YAG系荧光体、可能发出红色系光的荧光体、特别是碱土类氮化硅荧光体等氮化物荧光体组合起来加以使用。 Phosphor used in the present embodiment may be a YAG-based phosphor, nitride phosphor may emit red light of the phosphor, especially the alkaline earth silicon nitride fluorescent material to be used in combination. 这些YAG系荧光体以及荧光体可以混合并包含在发光层中,也可以分别包含在由多层构成的无机粘结剂中。 These YAG-based phosphor and a phosphor may be mixed and contained in the light emitting layer, an inorganic binder may be included in a plurality of layers respectively.

下面就各自的荧光体进行详细的说明。 The following detailed description on their respective phosphor. (YAG系荧光体) (YAG-based phosphor)

所谓本实施方案使用的YAG系荧光体是用铈或Pr等稀土类元素活化的荧光体,它含有Y和Al,并且含有选自Lu、 Sc、 La、 Gd、 Tb、 Pr、 Eu以及Sm之中的至少一种元素和选自Ga以及In之中的一种元素,是受LED芯片发出的可见光或紫外线激发而发光的荧光体。 The so-called YAG fluorescent material used in the present embodiment is cerium or other rare earth element activated Pr phosphor which contains Y and Al, and contains selected from Lu, Sc, La, Gd, Tb, Pr, Eu, and Sm of and at least one element of Ga, and one element selected from among in, the phosphor is a visible or an ultraviolet LED chip by excitation of luminescence emitted. 特别在本实施方案中,也可以利用用铈、Tb或Pr活化的、组成不同的2 种或更多种钇•铝氧化物系荧光体。 In this particular embodiment, may also be used with Ce, Tb or Pr activated, different compositions of two or more kinds of yttrium aluminum oxide phosphor •. 如果将使用氮化物系化合物半3 体作为发光层的发光元件发出的蓝色系光、和由因吸收蓝色光而体色(bodycolor)呈黄色的荧光体发出的绿色系以及红色系光、或者为黄色系光但更接近绿色系和更接近红色系的光混合显示出来,则可以显示出所要求的白色系发光色。 If the nitride-based compound semiconductor body 3 as a blue light emitting layer is emitted from the light emitting element, and a green-based yellow phosphor and the red light emitted as a result of absorption of blue light by the body color (bodycolor), or as a yellow-based light which is closer to the green line and closer to the light mixing red is displayed, it is possible to exhibit the desired white light-emitting color. 发光装置因为产生混色,所以也可以在环氧树脂、丙烯酸树脂或硅树脂等各种树脂和本实施方案的无机粘结剂之类的透光性无机物中含有荧光体的粉体和块。 Because the color mixture light emitting apparatus, the block may contain a phosphor powder and a translucent inorganic material in an inorganic binder of various resins epoxy, acrylic or silicone and the like of this embodiment of the class. 这样,含有荧光体的发光层可以根据荧光体呈点状或呈层状等用途而以各种方式使用, 其中发光层形成得较薄,足以使发光元件发出的光得以透过。 Thus, a light emitting layer containing a phosphor may be used in various ways according to the fluorescent material has a layered dot or other purposes, wherein the light emitting layer is formed thin enough to allow light to be emitted through the light emitting element. 通过对荧光体和透光性无机物的比率和涂布、填充量进行各种调整以及对发光元件的发光波长进行选择,可以提供包括白色在内的灯泡颜色等任意的色调。 And by coating ratio, filling amount of the phosphor and the translucent inorganic material and make various adjustments to the emission wavelength of the light emitting element is selected may be provided in any color including white bulb color.

另外,相对于源于发光元件的入射光,各自按顺序配置2种或更多种荧光体,由此可以获得能够有效发光的发光装置。 Further, with respect to the incident light from the light emitting element, each arranged in the order of two or more kinds of fluorescent material, thereby obtaining a light-emitting device can efficiently emit light. 也就是说,在具有反射构件的发光元件上,以层叠等方式配置含有在长波长侧有吸收波长且可以发出长波长光的荧光体的颜色转换构件即含有荧光体作为填料的发光层、以及较之于该发光层在更长的波长侧有吸收波长且可以发出更长波长的光的颜色转换构件,藉此可以有效利用反射光。 That is, on the light emitting element having a reflective member, arranged in a stacked like color conversion member contains a phosphor absorption wavelengths and may emit long wavelength light, i.e., light emitting layer containing a phosphor as a filler in the long-wavelength side, and compared to the light emitting layer in the longer wavelength side of the absorption wavelength conversion member and can emit color light of longer wavelength, thereby effectively utilizing reflected light.

本实施方案使用的用铈活化的钇•铝氧化物系荧光体即能够发出绿色系光的YAG系荧光体因为是石榴石结构,所以对热、光以及水分具有很强的耐性,激发吸收谱峰的波长可以在420nm〜470nm附近。 The present embodiment • cerium-activated yttrium-aluminum oxide phosphor capable of emitting green, i.e. the use of light and a YAG phosphor as garnet structure, has a strong resistance to heat, light and moisture, the excitation absorption spectrum peak wavelength may be near the 420nm~470nm. 另外,具有宽的发光谱,其发光峰峰值波长Ap在510nm附近,峰的末端延伸到700nm附近。 Further, having a broad emission spectrum, the emission peak wavelength of 700nm in the vicinity of Ap extending into, the end of the peak near 510nm. 另一方面,用铈活化的钇•铝氧化物系荧光体即能够发出红色系光的YAG系荧光体也因为是石榴石结构,所以对热、光以及水分具有很强的耐性,激发吸收谱峰的波长可以在420nm〜470nm附近。 On the other hand, • cerium activated yttrium aluminum oxide fluorescent material that is capable of emitting YAG phosphor red light because of garnet structure, has a strong resistance to heat, light and moisture, the excitation absorption spectrum peak wavelength may be near the 420nm~470nm. 另夕卜,具有宽的发光谱,其发光峰峰值波长入p 在600nm附近,峰的末端延伸到750nm附近。 Another Bu Xi, having a broad emission spectrum, the emission peak wavelength near 750nm to extend into the p, a peak near the end of 600nm.

在具有石榴石结构的YAG系荧光体的组成内,用Ga置换Al的一部分,由此使发光谱向短波长侧移动,而用Gd和/或La置换组成中的Y的一部分,由此使发光谱向长波长侧移动。 In the composition of YAG fluorescent material having garnet structure, with Ga substituting a part of Al, whereby the emission spectrum toward the short wavelength side movement, and with the portion of Gd / La or Y in the composition of the substitution, whereby emission spectrum shifted to the long wavelength side. 这样一来,通过改变组成,可以连续调节发光颜色。 Thus, by altering the composition, the emission color can be continuously adjusted. 因此,氮化物半导体能够以Gd的组成比来连续改变长波长侧的强度,利用这样的氮化物半导体的蓝色系发光具有转换成白色系发光的理想条件。 Thus, the nitride semiconductor can Gd composition ratio continuously varying the intensity of the long wavelength side, the use of such blue light emitting nitride semiconductor is converted into the ideal conditions having a white light-emitting. 当Y的置换不足2成吋, 绿色成分增多而红色成分减少,为8成或以上时,虽然红色成分增加但辉度急剧下降。 When Y is less than 2 percent of the replacement inches, increasing the green component to reduce the red component for 8 percent or more, although the red component increases but a sharp decline in brightness. 另外,关于激发吸收谱也同样,在具有石榴石结构的YAG系荧光体的组成内,用Ga置换Al的一部分,由此使激发吸收谱向短波长侧移动,而用Gd和/或La置换组成中的Y的一部分, 由此使激发吸收谱向长波长侧移动。 Further, with respect to the excitation absorption spectrum similarly, in the composition of YAG fluorescent material having garnet structure, with Ga substituting a part of Al, thereby moving the excitation absorption spectrum toward the short wavelength side, and with Gd and / or La substitution portion Y of the composition, and thereby the excitation absorption spectrum shifted to the long wavelength side. YAG系荧光体的激发吸收谱的峰值波长优选的是与发光元件的发光谱的峰值波长相比位于短波长侧。 Peak wavelength of the YAG phosphor excitation absorption spectrum is preferably the emission spectrum peak wavelength of the light emitting element compared to a shorter wavelength side. 如果是这样的构成,则当供给发光元件的电流增加时,激发吸收谱的峰值波长因为与发光元件的发光谱的峰值波长基本一致,所以可以形成荧光体的激发效率不会降低、色度偏移的发生得以抑制的发光装置。 If this is the configuration, when the current supplied to the light emitting element is increased, the peak wavelength of the excitation absorption spectrum as substantially coincides with a peak wavelength of emission spectrum of the light emitting element, it is possible to form the phosphor excitation efficiency is not reduced, partial color the light emitting device is suppressed occurrence of shift.

这样的荧光体将Y、 Gd、 Tb、 Pr、 Ce、 La、 Lu、 Al、 Sm以及Ga的氧化物或在高温下容易成为氧化物的化合物用作原料,将它们按化学计量比充分混合便得到原料。 This phosphor will Y, Gd, Tb, Pr, Ce, La, Lu, Al, Sm and Ga or an oxide at a high temperature tends to be used as starting material a compound oxide, they will stoichiometrically mixed ratio obtain raw materials. 或者按化学计量比将Y、 Gd、 Ce、 La、 Lu、 Al、 Sm的稀土类元素溶解在酸中,然后用草酸使这样得到的溶解液产生共沉积,再对这样得到的共沉积产物进行烧结便得到共沉积氧化物,继而将该共沉积氧化物与氧化铝、氧化镓混合便得到混合原料。 Or a stoichiometric ratio Y, Gd, Ce, La, Lu, Al, Sm rare earth elements are dissolved in an acid, and oxalic acid to make lysates thus obtained produce the co-deposition, and then the co-deposited product thus obtained was then co-sintered to obtain the oxide deposition, followed by the co-deposition of aluminum oxide, gallium oxide, then mixed to obtain a mixed raw material. 在该混合原料中适量添加氟化铵等氟化物作为助熔剂并将其 An appropriate amount of fluoride such as ammonium fluoride as the raw material in the mixed flux and

装入坩埚中,然后于空气中在135(TC〜1450'C的温度范围内烧结2小时〜5小时,从而得到烧结品,接着在水中对烧结品进行球磨,然后进行洗净、分离、干燥,最后过筛,由此便可以得到荧光体。另外, 其它实施方案的荧光体的制造方法优选分两个阶段进行烧结,该两个阶段由第一烧结工序和第二烧结工序构成,其中第一烧结工序将由混合了荧光体原料的混合原料和助熔剂构成混合物在大气中或弱还原气氛中进行烧结,第二烧结工序在还原气氛中进行烧结。在此,所谓弱还原气氛指的是在由混合原料形成所要求的荧光体的反应过程中,所设定的至少含有必要氧量的较弱的还原气氛,在该弱还原气氛中,进行第一烧结工序直至所要求的荧光体的结构形成得以完成,由此可以防止荧光体的黑变,而且防止光吸收效率的下降。另外,所谓第二烧结工序的还原 Was charged in a crucible, and then in air (sintering temperature range for 2 hours TC~1450'C ~ 5 hours to obtain a sintered product, followed by 135 in the water ball on the sinter and then washed, separated, dried , and finally sieved, whereby we can obtain the phosphor. Further, the method for producing the phosphor of the other preferred embodiments sintering in two stages, the two stages is constituted by a first sintering step and the second firing step, wherein the first a sintering step and the mixed raw material by mixing the phosphor raw material constituting the flux mixture is sintered in air or weakly reducing atmosphere in the second sintering step is sintered in a reducing atmosphere. here, the weakly reducing atmosphere refers to the weak reducing atmosphere is formed during the reaction from a mixed phosphor raw materials required, the set containing at least the necessary amount of oxygen in the weakly reducing atmosphere, the structure of a first sintering step performed until the desired phosphor formation is complete, thereby preventing the blackening of the phosphor, but also prevent a reduction in light absorption efficiency. Further, a second sintering step of reducing the so-called 氛,指的是比弱还原气氛更强的还原气氛。如果这样分两个阶段进行烧结,则可以得到激发波长的吸收效率高的荧光休。 因此,在采用这样形成的荧光体形成发光装置的情况下,为得到所要求的色调可以减少必要的荧光体用量,可以形成光取出效率高的发光装置。 Atmosphere, refers to a weakly reducing atmosphere stronger than a reducing atmosphere. If this two-stage sintering, it is possible to obtain a high absorption efficiency of the excitation wavelength of a fluorescent off. Accordingly, the use of the phosphor thus formed light-emitting device is formed case, in order to obtain the desired color tone may reduce the necessary amount of phosphor with high light extraction efficiency of the device can be formed.

组成不同的2种或更多种用铈活化的钇•铝氧化物系荧光体,可以混合使用,也可以各自独立地进行配置。 Different compositions of two or more of cerium-activated yttrium-aluminum oxide phosphor •, can be mixed, may be configured independently. 在各自独立地配置荧光体的情况下,优选按如下的顺序进行配置,先配置在短波波长侧容易吸收源于发光元件的光并发光的荧光体,再配置在相对长波长侧容易吸收源于发光元件的光并发光的荧光体。 In the case where the phosphor is independently arranged, preferably configured in the following order, to the short wavelength side disposed easily absorbs the light emission from the light emitting element and a phosphor, and then arranged in a relatively long wavelength side is easily absorbed from the light emitting element and a light-emitting phosphor. 由此,荧光体能够有效地吸收发光元件发出的光并发光。 Accordingly, the phosphor can be effectively absorbed light emitting element and emits light. (氮化物荧光体) (Nitride phosphor)

作为本实施方案使用的荧光体,除了上述用铈活化的钇•铝•氧化物系荧光体以外,还适用具有黄红〜红色发光波长的用Eu或稀土类活化的碱土类氮化物系荧光体。 As the phosphor used in the present embodiment, in addition to the cerium-activated yttrium • aluminum • oxide phosphor, but also for having a red emission wavelength of Eu with yellow and red - or a rare earth activated alkaline earth phosphor nitride . 该荧光体是通过吸收由LED芯片发出的可见光和紫外线、以及由YAG系荧光体发出的光而受激发光的。 The phosphor by absorbing ultraviolet light and visible light emitted by the LED chip and the light emitted by the YAG-based phosphor by the excitation light. 本发明的实施方案的荧光体特别是:Sr-Ca-Si-N:R、 Ca-Si-N:R、 Sr -Si-N:R、 Sr-Ca-Si-ON:R、 Ca-Si-ON:R以及Sr -Si-ON:R系硅氮化物。 Phosphor of embodiments of the present invention is in particular: Sr-Ca-Si-N: R, Ca-Si-N: R, Sr -Si-N: R, Sr-Ca-Si-ON: R, Ca-Si -ON: R and Sr -Si-ON: R-based silicon nitride. 这些荧光体的基本构成元素可以用通式LxSiYN(2/3X+4/3Y):R或LxSiYOz N(2/3X+4/3Y-2/3Z): R (L为Sr、 Ca以及Sr和Ca之中的任一组)来表示。 The basic elements of the phosphor can be represented by the formula LxSiYN (2 / 3X + 4 / 3Y): R or LxSiYOz N (2 / 3X + 4 / 3Y-2 / 3Z): R (L is Sr, Ca and Sr, and among any of a group of Ca) is represented. 在通式中,X以及Y优选的是X-2、 Y-5或X-1、 Y=7,但也可以是任意的数值。 In the formula, X and Y are preferably X-2, Y-5, or X-1, Y = 7, but may be any value. 另外,R是必须含有Eu的稀土类元素,N为氮,O为氧。 Further, R is a rare earth element containing Eu, and must, N is nitrogen, O is oxygen. 具体地说,优选使用基本构成元素可以用(SrxCai_x)2Si5N8:Eu 、 Sr2Si5N8:Eu、 Ca2Si5N8:Eu、 SrxCauSirN^Eiu SrSi7N10:Eu、 CaSi7N10:Eu 表示的荧光体,但在该荧光体的组成中,也可以含有选自Mg、 B、 Al、 Cu、 Mn、 Cr以及Ni之中的至少l种或多种。 Specifically, it is preferable to use basic elements can be used (SrxCai_x) 2Si5N8: Eu, Sr2Si5N8: Eu, Ca2Si5N8: Eu, SrxCauSirN ^ Eiu SrSi7N10: Eu, CaSi7N10: Eu phosphor is represented, but the composition of the phosphor, may also contain selected from Mg, l or more at least from among B, Al, Cu, Mn, Cr and Ni. 但本发明并不限于该实施方案以及实施例。 However, the present invention is not limited to the embodiments and examples.

L为Sr、 Ca以及Sr和Ca之中的任一组。 It is L, Ca, and Sr in any one of a group of Ca and Sr. Sr和Ca可以根据要求 Sr and Ca may request

来改变配比。 To change the ratio.

发光中心主要使用作为稀土类元素的铕Eu。 Europium Eu luminescent center is used as the rare earth element. 铕主要具有2价和3 价的能级。 Europium mainly has a divalent and trivalent energy levels. 本发明的实施方案的荧光体对于作为母体的碱土类金属系氮化硅,将E^+用作活化剂。 Phosphor according to the embodiment of the present invention as an alkaline earth metal silicon nitride-based precursor, the E ^ + as an activator. 另外,也可以将Mn用作添加物。 Further, Mn may be used as the additive.

下面就本发明的实施方案中使用的荧光体((SrxCai.x)2Si5N8:Eu) 的制造方法进行说明,但本发明并不限于本制造方法。 Here phosphor ((SrxCai.x) 2Si5N8: Eu) used in embodiments of the present invention will be described manufacturing method, but the present invention is not limited to the manufacturing method. 在上述荧光体中含有Mn和O。 Containing Mn and O. In the above-described phosphor

在本发明的实施例中,作为发出带红色光的荧光4本,特别使用氮化物系荧光体,而在本实施方案中,也可以获得具有上述YAG系荧光体和可能发出红色系光的荧光体的发光装置。 In an embodiment of the present invention, as fluoresces reddish light 4, in particular nitride-based phosphor in the present embodiment, it can be obtained with the above-described YAG phosphor and the phosphor may emit red light the light emitting device body. 这样的可能发出红色系光的荧光体是由波长为250nm〜600nm的光激发而发光的荧光体, 例如可以列举出Y202S:Eu、 La202S:Eu、 CaS:Eu、 SrS:Eu、 ZnS:Mn、 ZnCdS:Ag,Al以及ZnCdS:Cu,Al等。 Eu, La202S:: Eu, CaS: Eu, SrS: Eu, ZnS: this may emit red light emitting phosphor is excited to emit light 250nm~600nm phosphor Y202S Examples include wavelength is Mn, ZnCdS: Ag, Al and ZnCdS: Cu, Al and the like. 这样,通过使用可能与YAG系荧光体一起发出红色系光的荧光体,可以提高发光装置的演色性。 Thus, it may be sent by using the YAG-base phosphor with a phosphor of red light can be improved color rendering property of the light emitting device.

在本发明的各实施方案的发光装置中,荧光体可以使用各种各样的荧光体。 In various embodiments of the light emitting device of the present invention, the phosphor can use various phosphors. 例如,可以列举出的有:产生蓝色区域的发光的、以 For example, there may include: a blue light emitting region is generated to

BaMgAh。 BaMgAh. 0,7: Eu表示的、用铕活化的铝酸钡镁系荧光体,产生蓝色区域的发光的、以(Ca、 Sr、 Ba)5(P04)3Cl: Eu表示的、用铕活化的卤素磷酸钙系荧光体,产生蓝色区域的发光的、以(Ca、 Sr、 Ba)2B509Cl:Eu 表示的、用铕活化的碱土类氯硼酸盐系荧光体,产生蓝绿色区域的发光的、以(Sr、 Ca、 Ba)Al204: Eu或(Sr、 Ca、 Ba)4Al14025: Eu表示的、 用铕活化的碱土类铝酸盐系荧光体,产生绿色区域的发光的、以(Mg、 Ca、 Sr、 Ba)Si202N2: Eu表示的、用铕活化的碱土类硅氧氮化物系荧光体,产生绿色区域的发光的、以(Ba、 Ca、 Sr)2Si04: Eu表示的、用铕活化的碱土类硅酸镁系荧光体,产生黄色区域的发光的、以(Y、 Gd)3(Al、 Ga)5012: Ce等表示的稀土类铝酸盐即YAG系荧光体以及产生红色区域的发光的、以(Y、 La、 Gd、 Lu)202S: Eu表示的、用铕活化的稀土类氧硫化物系荧光体等,但本发明并不限于这些 0,7: Eu represented by europium-activated barium magnesium aluminate-based phosphor, a blue emission region is generated, in (Ca, Sr, Ba) 5 (P04) 3Cl: Eu represented by europium-activated halo calcium phosphate-based phosphor, a blue emission region is generated, in (Ca, Sr, Ba) 2B509Cl: Eu represented by europium-activated alkaline earth chloro-borate-based phosphors, produce emission of blue-green region to (Sr, Ca, Ba) Al204: Eu or (Sr, Ca, Ba) 4Al14025: Eu represented by europium-activated alkaline earth aluminate phosphor, the green emission region is generated to (Mg, Ca, Sr, Ba) Si202N2:, with the europium-activated alkaline earth silicon oxynitride phosphor of Eu which produce emission in a green region to (Ba, Ca, Sr) 2Si04: Eu represented by europium-activated alkaline earth silicate based phosphor, a yellow light emitting region is generated to (Y, Gd) 3 (Al, Ga) 5012: Ce and other rare-earth aluminate represented by the YAG phosphor and that is generated in the red region light, to (Y, La, Gd, Lu) 202S: Eu represented by europium-activated rare earth oxysulfide phosphor the like, but the present invention is not limited ,前述的荧光体和其它的荧光体也可以在本发明的实施方案的无机粘结剂中使用。 , The phosphor and other phosphors may be used in embodiments of the inorganic binder of the present invention. 再者,也可以使用具有断裂面的荧光体,其中在断裂面上采取了防止涂层退化的对策。 Further, also possible to use a phosphor having a fracture surface, wherein the fracture surface of the coating to take countermeasures to prevent degradation.

上述荧光体例如用铕活化的碱土类氯硼酸盐系荧光体、用铕活化的碱土类铝酸盐系荧光体、用铕活化的碱土类硅氧氮化物系荧光体、 YAG系荧光体以及用铕活化的碱土类硅氮化物系荧光体等优选含有B元素,从而使结晶性变得良好,增大粒径,或调整结晶形状。 For example, with the phosphor of the europium-activated alkaline earth chloro-borate-based phosphor, europium-activated alkaline earth aluminate phosphor, europium-activated alkaline earth silicon oxynitride phosphor, a YAG-based phosphor, and europium-activated alkaline earth silicon nitride fluorescent material preferably contains B element, so that the crystallinity becomes better, increasing the particle size, crystal form or adjust. 由此可谋求发光辉度的提高。 Thus can be improved emission brightness. 这些荧光体作为本实施方案的荧光体的填料也是有效的。 These phosphors as a phosphor filler present embodiment is also effective.

关于结晶结构,例如Ca2Si5N8为单斜晶,Sr2Si5N8、 (SrQ.5Cao.5)2Sr5N8 为斜方晶,Ba2SisN8取单斜晶。 About the crystalline structure, such as Ca2Si5N8 monoclinic, Sr2Si5N8, (SrQ.5Cao.5) 2Sr5N8 orthorhombic, Ba2SisN8 take monoclinic.

再者,本荧光体是结晶在其组成中占60%或以上、优选为80%或以上的准晶质。 Furthermore, the present crystalline phosphor is 60% or more in its composition, preferably 80% or more quasi-crystalline. 一般地说,优选x:2、 "5或f1、 y=7,但也可以是任意的数值。 In general, preferably x: 2, "5 or f1, y = 7, but may be any value.

在微量添加物中,B等不降低发光特性而可以提高结晶性,而且Mn、 Cu等也表现出同样的效果。 In minor additives, B is the light emission characteristics and the like without reducing the crystallinity can be improved, and Mn, Cu, also exhibited the same effects. 另外,La、 Pr等也具有改善发光特性的效果。 Further, La, Pr, also has the effect of improving light emission properties. 除此以外,Mg、 Al、 Cr、 Ni等具有縮短余辉的效果,可以适宜使用。 In addition, Mg, Al, Cr, Ni and the like have the effect of shortening afterglow, can be suitably used. 此外,即使是本说明书没有明示的元素,只要在10〜 1000ppm左右,不明显降低辉度就可以添加。 Further, even if the specification is not explicitly element, as long as about 10~ 1000ppm, significant loss of luminance can be added.

R中含有的稀土类元素优选包括Y、 La、 Ce、 Pr、 Nd、 Gd、 Tb、 Dy、 Ho、 Er、 Lu之中的1种或以上,但也可以包括Sc、 Sm、 Tm以及Yb。 Rare earth element R contained preferably comprises one or more among Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu, but may also include Sc, Sm, Tm and Yb. 另外,除上述元素以外,还可以含有B、 Mn等具有改善辉度的效果的元素。 Further, in addition to the above elements, it may contain an element having an effect of improving luminance of B, Mn and the like. 这些稀土类元素除单质外,还以氧化物、酰亚胺、酰胺等状态混合在原料中。 These rare earth elements other than a single substance, but also to oxides, imides, amides, etc. mixed in the raw material state. 稀土类元素主要具有稳定的3价的电子排列, 但Yb、 Sm等也具有2价、Ce、 Pr、 Tb等也具有4价的电子排列。 Major rare-earth element having stable electron arrangement trivalent, but Yb, Sm, also a divalent, Ce, Pr, Tb, also an electronic arrangement tetravalent. 在使用氧化物的稀土类元素的情况下,氧的参与对荧光体的发光特性产生影响。 In the case of using a rare-earth element oxide, oxygen participation affect the emission characteristics of the phosphor. 也就是说,由于含有氧,有时也发生辉度的降低。 That is, because it contains oxygen, sometimes to reduce the occurrence of luminance. 但是,在使用Mn的情况下,由于Mn与O产生的作为助熔剂的效果,使粒径得以增大,从而可谋求发光辉度的提高。 However, in the case of Mn, Mn and O is generated since a flux effect, so that the particle size is increased, thereby seeking to improve the luminance of the hair.

作为发光中心,适用作为稀土类元素的铕Eu。 As a luminescence center for europium Eu as rare earth element. 具体列举出基本构成元素的实例,则有:添加了Mn、 B的Ca2Si5OaiN7.9:Eu 、 Sr2SisO(uN7.9:Eu、 (CaxSr10()2 SisO(uN7.9:Eu、 CaSi7O0.5N9.5:Eu、进而添加了稀土类元素的Ca2Si5O0.5N7.9:Eu、 Sr2Si5Oo.5N7.7:Eu、 (CaxSri-X)2 SisOo美9:Eu等。 Specific examples include basic constituent element, there are: Added Mn, B of Ca2Si5OaiN7.9: Eu, Sr2SisO (uN7.9: Eu, (CaxSr10 () 2 SisO (uN7.9: Eu, CaSi7O0.5N9.5 : Eu, and further added a rare earth element Ca2Si5O0.5N7.9: Eu, Sr2Si5Oo.5N7.7: Eu, (CaxSri-X) 2 SisOo US 9: Eu and the like.

以上说明的氮化物系荧光体,吸收由发光元件发出的蓝色光的--部分而发出从黄色到红色区域的光。 The nitride-based fluorescent material described above, absorbs blue light emitted from the light emitting element - while the portion of the light emitted from the yellow to red region. 将该荧光体用于具有上述构成的发光装置,便可以提供一种由发光元件发出的蓝色光和荧光体的红色光通过混色而发出暖色系的白光的发光装置。 The phosphor for a light emitting device having the above structure can provide a red phosphor is a blue light emitted from the light emitting element and the light emitting device emits white light by mixing warm colors. 特别在白光发光装置中, 优选含有氮化物系荧光体和稀土类铝酸盐荧光体即用铈活化的钇•铝氧化物荧光体。 In particular, a white light emitting device, preferably a nitride-based phosphor containing a rare-earth aluminate phosphor activated with cerium i.e. • yttrium aluminum oxide phosphor. 这是因为:通过含有上述的钇•铝氧化物荧光体,可以调节所要求的色度。 This is because: • by containing the yttrium aluminum oxide phosphor, the chromaticity can be adjusted as required. 用铈活化的钇•铝氧化物荧光体,可以吸收由发光元件发出的蓝色光的一部分而发出黄色区域的光。 • cerium-activated yttrium-aluminum oxide phosphor that can absorb the blue light emitted from the light emitting element emits light in the yellow part of the region. 在这里,由发光元件发出的蓝色光和和钇•铝氧化物荧光体的发色光通过混色而可以发出蓝白色的白色光。 Here, light hair, and blue color light • yttrium aluminum oxide phosphor emitted by the light emitting element may emit white light by the blue-white color mixture. 因此,通过组合将该钇,铝氧化物荧光体以及所述氮化物荧光体与粘结剂一起混合的荧光体和由发光元件发出的蓝色光,可以提供一种暖色系的白光的发光装置。 Thus, by combining the yttrium-aluminum oxide phosphor and a phosphor of said nitride phosphor is mixed together with a binder and blue light emitted from the light emitting element, the light emitting device can provide white light of a warm color. 该暖色系的白光的 The warm color white

发光装置,其平均演色评价指数Ra可以达到75〜95,色温度可以设定为2000K〜8000K。 A light emitting device, the average color rendering index Ra can be achieved 75~95, the color temperature may be set to 2000K~8000K. 特别优选的是平均演色评价指数Ra较高、色温度位于色度图的黑体辐射的轨迹上的白色发光装置。 Particularly preferred are higher average color rendering index Ra, color white light emitting device on the chromaticity diagram is located in the temperature of the black body radiation locus. 但是,为了提供具有所要求的色温度以及平均演色评价指数的发光装置,也可以适当改变钇•铝氧化物荧光体和荧光体的配合量和各荧光体的组成比。 However, in order to provide an average color temperature and a light emitting device having a color rendering index required, it may be appropriately changed • yttrium composition ratio of each phosphor and the amount of aluminum oxide phosphor and the phosphor. 该暖色系的白光的发光装置特别谋求特殊演色评价指数R9的改善。 The warm white light emitting devices based in particular seek to improve special color rendering index of R9. 以前的由蓝色发光元件和用铈活化的钇•铝氧化物荧光体组合而成的发出白色光的发光装置,其特殊演色评价指数R9低下,红色成分不足。 The light emitting device emits white light by a combination of blue light emitting element and cerium-activated yttrium-aluminum oxide phosphor • previously formed, its special color rendering index R9 is low, insufficient red component. 因此,提高特殊演色评价指数R9就成了需要解决的课题,而在用铈活化的钇•铝氧化物荧光体中含有用Eu活化的碱土类氮化硅系荧光体,藉此可以将特殊演色评价指数R9提高到40〜90。 Therefore, a special object to improve the color rendering index R9 has become to be solved, and activated with Eu-containing alkaline earth silicon nitride-based phosphors activated with cerium • yttrium aluminum oxide phosphor, whereby the special color rendering may be R9 evaluation index increased to 40~90. 另外,还可以制作发出灯泡颜色的LED发光装置。 Further, the lamp can create a color emitted LED light emitting device. (基体) (Base)

基体20由收容发光元件60的凹部20a和配置了引线电极22的基底部所构成,它作为发光元件60的支持体发挥作用。 Base body 20 by the recess 20a receiving the light emitting element 60 and the lead electrodes disposed constituted the base 22, as the support 60 of the light emitting element functioning. 所述凹部20a 的底面与所述引线电极的底面优选大致位于同一面上。 A bottom surface of the lead electrode portion 20a of the bottom surface of the recess preferably substantially in the same plane.

基体20优选用金属制造,从加工性和生产性等角度考虑也可以是树脂。 20 is preferably made of a metal substrate, from the viewpoint of workability and productivity may be equal angular resin. 基体20从光取出面侧看,其形状可以形成为大致正方形、大致矩形、大致圆形、大致椭圆形等各种形状。 Substrate 20 from the light extraction surface side look, the shape may be formed in various shapes substantially square, substantially rectangular, substantially circular, substantially oval shape. 承载发光元件60的部分优选形成凹部20a。 Preferably the carrier portion of the light emitting element 60 of the recess portion 20a is formed. 这是因为:通过将发光元件60收容在凹部20a内, 可以使从发光元件60发出的光在凹部20a的开口侧发射出来,从而可以谋求光输出功率的提高。 This is because: the light emitting element 60 through the housed in the recess portion 20a, the light can be emitted from the light emitting element 60 emitted at the opening side of the concave portion 20a, so that the light can be improved output power.

在发光装置601中,考虑的散热性和小型化,基体20优选用薄脱 In the light emitting device 601, preferably 20 and heat dissipation considerations miniaturized, thin-off base

来形成。 Is formed.

与发光元件60的数量与大小相适应,也可以将基体设计为具有多个开口部。 Number and size of the light emitting element 60 is adapted, the base may also be designed with a plurality of openings. 为使之具有合适的遮光机能,基体20被着色成黑色或灰色等暗色系,或者基体20的发光观测表面侧被着色成暗色系。 To make this function with suitable light shielding matrix 20 is colored dark color like black or gray, or substrate side of the light emitting surface 20 of the observer is colored in a dark color. 为了进-一步保护发光元件60免受外部环境的侵害,除涂层以外,还可以设置作为透光性保护体的铸模构件。 In order to feed - further protection against the light emitting element 60 from the external environment, in addition to the coating may also be provided as a light-transmitting protective body mold member. 再者,当基体20受到源于发光元件60 的热的影响时,考虑到与铸模构件的附着力,优选基体20具有较小的热膨胀率。 Further, when the substrate 20 is subjected to the influence of heat from the light emitting element 60, taking into account the adhesion of the mold member, the base member 20 preferably has a smaller thermal expansion coefficient.

发光元件60与基体20的粘结也可以采用热固性树脂等进行。 Bonding the light emitting element 60 and the base 20 may also be a thermosetting resin or the like. 具体地说,可以列举出环氧树脂、丙烯酸树脂以及酰亚胺树脂等。 Specifically, it includes epoxy resin, acrylic resin and imide resin. 在发光装置601使用发出含有紫外线的光的发光元件60并于高输出功率下加以使用的情况下,对于发光元件60与基体20的粘结部分,因为由发光元件60发出的紫外线等也被作为密封构件的无机粘结剂30或包含在其中的荧光体50等所反射,光特别在基体20内变成高密度,因此,粘结部分的树脂因紫外线而退化,故而可以认为因树脂的黄变等而导致发光效率的低下以及因粘结强度的低下而导致发光装置寿命的降低。 A case where a light-emitting element light containing ultraviolet rays in the 601 light-emitting device 60 and used under high output power, for the bonding portion emitting element 60 and the base 20, since the ultraviolet rays emitted from the light emitting element 60 is also used as inorganic binder comprising a sealing member 30 or the like in which the phosphor 50 is reflected, in particular light in the matrix 20 becomes a high density, and therefore, resin-bonded portions due to UV degradation, and therefore can be considered by resin yellowing varying the like results in a reduction of the emission efficiency is low due to poor adhesive strength and the result of the lifetime of the light emitting device. 为防止这样的因紫外线而引起的粘结部分的退化,可以使用含有紫外线吸收剂的树脂,更优选的可以使用本发明的无机物等。 To prevent degradation of the bonding portion due to such ultraviolet rays caused by a resin containing an ultraviolet absorber may be used, more preferably an inorganic material may be used according to the present invention, and the like. 特别地,在基体使用金属材料的情况下,发光元件60与基体20的粘结除了使用本发明的无机物以外,也可以使用Au-Sn等的共晶软钎料等。 In particular, in the case of using a metal material substrate, bonding the light emitting element 60 and the base body 20 except for using an inorganic substance of the present invention may also be used such as Au-Sn eutectic solder and the like. 因此,与使用树脂进行粘结的情况不同,本发明即使在发光装置601 使用发出含有紫外线的光的发光元件60并于高输出功率下加以使用的情况下,其粘结部分也不会退化。 Thus, unlike the case using a resin for bonding with the present invention, even if the light emitting device 601 emits light containing an ultraviolet light emitting element of the case and to be used at high output power of 60, which the adhesive portion is not degraded.

另外,在配置并固定发光元件60的同时,为了与基体20内的外部电极进行电接触,适合使用Ag浆料、碳浆料、ITO浆料以及金属凸缘等。 Further, the light emitting element 60 arranged and fixed at the same time, 20 to the external electrode in electrical contact with the substrate, suitable for use Ag paste, carbon paste, the ITO and metal paste such as a flange.

(引线电极) (Lead electrode)

发光装置601具有正的以及负的引线电极22,引线电极22隔着绝缘构件23插在设置于金属基体20的基底部的贯通孔内。 The light emitting device 601 having a positive and a negative electrode lead 22, the lead electrode 22 via an insulating member 23 is inserted is provided in the base portion 20 of the metal base through hole. 所述引线电极22的顶端部从所述基底部的表面突出出来,且所述引线电极22的底面与所述凹部的安装面侧的底面大致处在同一平面上。 The tip portion of the lead electrode 22 protrudes from the surface of the base portion, and a bottom surface of the lead electrode 22 of the mounting surface side of the bottom surface of the concave portion is substantially in the same plane. (盖体) (The cover)

发光装置601在基体20的主面侧具有包含透光性窗部25和由金属部构成的引线24的盖体26。 The light emitting device 601 on the main surface side of the base 20 has a portion 25 comprising a light-transmissive window and a cover portion 24 made of a metal wire 26. 窗部25为发光装置601的发光面,优选配置在中央部。 Window portion 25 of the light emitting surface of the light emitting device 601, preferably arranged in the center portion.

窗部25位于配置在基体20的凹部20a内的发光元件60的上面, 并与凹部20a的内壁的延长线相交。 Window portion 25 is located above the light emitting element disposed on the base 60 in the recess portion 20a of the body 20 and intersects with the concave portion 20a of the extension line of the inner wall. 从发光元件60的端部发出的光在凹部20a的侧面产生漫反射并于正面方向取出。 Light emitted from the light emitting element 60 of the end portion of diffuse reflection on the side surface of the concave portion 20a and removed in the front direction. 这些漫反射光的存在范围一般认为大致在凹部20a的侧面的延长线内。 The present scope of diffuse reflected light is generally considered to be within a substantially extended line of the side surface of the concave portion 20a. 于是,通过像上述那样调整作为发光面的窗部25的面积,所述漫反射光可以有效地聚焦在窗部25,从而可以得到能够发出高辉度光的发光装置601。 Thus, by adjusting the like as a light emitting surface area of ​​the window portion 25, the diffuse reflection light can be effectively focused on the window section 25, so as to obtain the light emitting device 601 can emit light of high luminance.

窗部25具有透光性。 Portion 25 having a light-transmitting window. 在窗部25中,可以含有荧光体50,另外也可以粘贴荧光体50的膜。 In the window portions 25, 50 may contain a phosphor, the film may additionally be attached to the phosphor 50.

窗部25可以使用玻璃、环氧树脂、聚丙烯等各种材料,但从耐热性的角度考虑,优选的是玻璃。 Window portion 25 may use a variety of materials such as glass, epoxy resin, polypropylene or the like, but from the viewpoint of heat resistance, preferred are glass.

盖体26以气密的方式设置在基体20上。 Lid 26 in an airtight manner is disposed on the base 20. 由于进行了气密,因而可以防止水分侵入发光装置601的内部。 As a result of airtightness, it is possible to prevent the intrusion of water into the interior of the light emitting device 601. (引线) (lead)

引线21要求具有良好的与发光元件60的电极的欧姆性、机械连接性、电传导性以及热传导性。 Wire 21 having excellent ohmic electrode of the light emitting element 60, the mechanical connection, electrical conductivity and thermal conductivity. 作为引线21,具体地可以列举出使川金、铜、铂金以及铝等金属及其合金的导电性引线。 As a lead 21, specific examples thereof include conductive leads ambassador River gold, copper, platinum and metal such as aluminum and its alloys. 这样的引线21 借助于引线接合设备很容易将各发光装置60的电极、内部引线以及管脚引线等连接起来。 Such a lead 21 by means of a wire bonding device is easy to connect the electrodes of the light emitting device 60, the inner lead and the lead pins and the like.

(发光装置的制造方法) (Method of manufacturing a light emitting device)

下面以图31〜图35为基础就发光装置的制造方法进行说明。 FIG. 31~ 35 below to a method for manufacturing the light emitting device will be described on the basis of. 如上所述,图31是本发明的实施方案6的发光装置的示意平面图,图32 (a)是同一发光装置的示意剖面图,图32 (b)是放大基体凹部的示意剖面图。 As described above, FIG. 31 is a schematic plan view of a light emitting device according to embodiment 6 of the present invention, and FIG. 32 (a) is a schematic cross-sectional view of the same light-emitting device, FIG. 32 (b) is a schematic sectional view of an enlarged portion of the recess base. 再者,图33是表示本发明的实施方案的发光装置之制造工序的一部分的示意图,图34是表示实施方案的发光装置之其它制造工序的一部分的示意图,图35是表示实施方案的发光装置之另一个其它制造工序的一部分的示意图。 Further, FIG. 33 is a schematic view showing part of a manufacturing process of the light emitting device of an embodiment of the present invention, FIG 34 is a schematic diagram of a portion of the other manufacturing process of the light-emitting device of the embodiment represented, FIG. 35 is a light-emitting device of the embodiment another schematic of a portion of the other manufacturing processes. 具体地说,图34是表示采用喷涂喷雾手段的无机粘结剂30的层或树脂40的形成方法的示意图,图35表示釆用丝网印刷手段的无机粘结剂30的层或树脂40的形成方法。 More specifically, FIG. 34 is a schematic diagram showing a method of spray coating using an inorganic binder means a resin layer 30 or 40 is formed, FIG. 35 shows a screen printing preclude the use of an inorganic binder means a resin layer 30 or 40 forming method. 下而以这些图为基础说明发光装置的制造方法。 These figures and to the basic method for manufacturing the light emitting device. 但是,以下的工序只是一个实施方案,本发明并不局限于此。 However, the following embodiment is only one step, the present invention is not limited thereto. (第一工序) (First step)

在基体20上承载着发光元件60。 Carrying the light emitting element 60 on the base 20. 基体20形成有凹部20a,在该凹部20a上承载着发光元件60。 The base 20 is formed with a recess portion 20a, the light emitting element 60 carries in the recess portion 20a. 发光元件60使用环氧树脂等粘结剂进行焊接。 The light emitting element 60 such as epoxy adhesive welding. 承载发光元件60的工序完成后,发光元件60的电极和引线电极22通过引线21进行电连接。 After the step of carrying the light emitting element 60 is completed, the light emitting element 60 and the electrode lead electrodes 22 are electrically connected by wire 21. (第二工序) (Second step)

用无机粘结剂30覆盖发光元件60。 With an inorganic binder covering the light emitting element 6030. 无机粘结剂30优选事先含冇荧光体50。 The inorganic binder is preferably 30 Nuisance containing the phosphor 50 in advance. 该荧光体50事先混合并均匀分散在无机粘结剂30中。 The phosphor 50 mixed in advance and uniformly dispersed in the inorganic binder 30. 无机粘结剂30可以采用浇灌手段、喷涂喷雾手段、丝网印刷手段以及浇注手段等,但优选的是浇灌手段或者喷涂喷雾手段。 The inorganic binder may be employed watering means 30, means for spraying the spray, and screen printing methods like casting means, it is preferred that the spray means spraying or watering means. 无机粘结剂30 覆盖着发光元件60的整个上面以及整个侧面。 The inorganic adhesive 30 covers the entire upper side and the entire light emitting element 60. 而且覆盖承载发光元件60的凹部20a的底面以及侧面。 It covers the recess and carrying the light emitting element 60 of the bottom surface and the side surface 20a. 无机粘结剂30形成薄膜状的层结构。 Inorganic binder 30 is formed of a thin film layer structure. 无机粘结剂30在固化后进行第三工序,但也可以在固化前进行第三工序,使树脂40与无机粘结剂30同时进行固化。 Inorganic binder 30 after curing the third step, the third step may be performed before curing the resin 40 is cured simultaneously with the inorganic binder 30.

例如以丝网印刷的手段用无机粘结剂30覆盖发光元件60。 For example, a screen printing means covering the light emitting element 60 with an inorganic adhesive 30. 相对于发光元件60,将具有图案的筛板97加工成带状、格子状、同心岡状、涡壳状、三角形状以及点状等所希望的形状。 With respect to the light emitting element 60, the sieve 97 having a pattern is processed into a band shape, a lattice shape, a concentric shape Gang, scroll shape, triangular shape or the like, and a desired dot shape. 导电性构件91配置在基座基板92的上面,在该导电性构件91上,朝下(facedown)安装着发光元件60。 The conductive base member 91 disposed on the upper substrate 92, on which the conductive member 91, downward (facedown) the light emitting element 60 is mounted. 此时,为使正极和负极不发生短路,在基座基板92 上事先设置预定的沟。 In this case, the negative electrode and the positive electrode is not short-circuited, a predetermined groove is provided in advance on the base substrate 92. 另外,在发光元件60的各电极之间,事先将绝缘性构件94设置在基座基板92侧,之后通过凸缘96将发光元件60焊接在该基座基板92的上面。 Further, between the electrodes of the light emitting element 60, the insulating member 94 in advance is provided on the base substrate 92 side, after the light emitting element 96 through the flange 60 welded to the upper surface of the base substrate 92. 然后使用刮浆板用含有荧光体的无机粘结材料进行丝网印刷。 Then using a squeegee for screen-printing an adhesive material containing an inorganic phosphor. 由此可以形成涂覆了经常具有恒定厚度的无机粘结剂30的发光元件60。 The inorganic binder can be formed thereby often coated with a light-emitting element having a constant thickness of 60 30. 此后沿分型线93切断基座基板92。 After cutting the base substrate 92 along a parting line 93. 该工序优选在真空中进行,但也可以在不活泼气体气氛中进行。 This step is preferably performed in a vacuum, but may be carried out in an inert gas atmosphere. (第三工序) (Third Step)

采用树脂40覆盖无机粘结剂30。 A resin 40 covers the inorganic binder 30. 在树脂40中也可以事先含有荧光体50。 In the resin 40 may contain a phosphor 50 in advance. 树脂40可以采用浇灌手段、喷涂喷雾手段、丝网印刷手段以及浇注手段等,但优选的是浇灌手段或者喷涂喷雾手段。 Resin may be employed watering means 40, means for spraying the spray, screen printing means and other means of casting, it is preferred that the spray means spraying or watering means. 树脂40 覆盖着无机粘结剂30的表面。 Resin 40 to cover the surface of the inorganic binder 30. 树脂40优选形成薄膜状的层结构。 A film-like resin 40 is preferably formed in a layer structure. 树脂40往无机粘结剂30中渗透,无机粘结剂30所具有的空隙则由树脂40所填埋。 30 resin 40 to infiltrate the inorganic binder, the inorganic binder 30 has a void 40 filled by the resin. 由此便可以制造出发光装置61。 Whereby the light-emitting device can be manufactured 61. 该工序优选在真空中进行, 但也可以在不活泼气体气氛中进行。 This step is preferably performed in a vacuum, but may be carried out in an inert gas atmosphere. (浇灌手段、喷涂喷雾手段) (Means watering, spraying spray means)

图33是表示本发明的实施方案的发光装置之制造工序的一部分的示意图。 FIG 33 is a diagram showing a part of a manufacturing process of a light-emitting device of an embodiment of the present invention. 浇灌手段可以使用公知的浇灌手段。 Pouring means may be a known watering means. 在图33(a)中,说明了采用浇灌手段将树脂40涂覆在无机粘结剂30上的方法。 In FIGS. 33 (a), the use of irrigation means described resin 40 in the coating method of the inorganic binder 30. 往浇灌装置(图中未示出)上安装的浇灌工具66内注入要涂布的树脂40。 To watering device (not shown) installed on the tool 66 injection poured resin 40 to be coated. 树脂40根据粘度、润湿性、对禾机粘结剂30的渗透性以及附着力等因素来调整材质、温度和浇灌速度。 The viscosity of the resin 40, the wettability, and permeability to organic binder Wo adhesion factors and the like to adjust the material 30, the temperature and speed of pouring. 从浇灌工具66的嘴67的尖端部将树脂40的溶胶往作为目标物的无机粘结剂30的上面进行浇灌。 Watering nozzle portion from the tip 67 of the tool 66 will sol resin 40 to be poured as above, the inorganic binder of the target object 30. 此时, 浇灌树脂40优选不与引线21接触。 In this case, pouring resin 40 preferably does not contact leads 21.

在图33(b)中,从发光元件60的上面浇灌树脂40,树脂40从该浇灌处渗透进入无机粘结剂30中。 In FIG 33 (b), the resin 40 is poured from above the light emitting element 60, the resin 40 penetrating into the inorganic binder 30 from the watering place. 此时,在无机粘结剂30所具有的空隙中浸渍有树脂40,该空隙中存在的气体从容易向外排出的树脂40 的侧面侧拔出来。 At this time, the inorganic binder 30 having a void 40 is impregnated with a resin, the side surface of the side discharge of the gas from the voids present in the resin 40 is easy to pull out outwardly. 树脂40慢慢地流向发光元件60的周围部。 Slowly resin 40 to the light emitting element 60 of the peripheral portion. 此时, 一边将处在发光元件60的周围部的无机粘结剂30的空隙内存在的气体向外部挤出, 一边使树脂流进空隙内。 At this time, while the inorganic binder in the peripheral portion of the light emitting element 60 in the recess 30 of the memory out to the outside of the gas, while the resin flows into the voids.

在图33(c)中,树脂40从发光元件60的周围部继续沿凹部20a的侧面侧往上爬。 In FIG 33 (c), the resin 40 continues along the side surface 20a of the recess portion periphery side climb from the light emitting element portion 60. 这起因于毛细现象。 This is due to the capillary phenomenon. 此时,树脂40也将空隙31中的基体往外挤,这样可以防止气体侵入树脂40中。 At this time, the resin substrate 40 will squeeze out of the recess 31, which prevents gas from entering the resin 40.

在图33(d)中,可以形成覆盖无机粘结剂30层的树脂40层。 In FIG. 33 (d) can be formed to cover the resin layer 40 of the inorganic binder layer 30. 树脂40层的膜厚大致均匀。 Thickness of the resin layer 40 is substantially uniform. 另外树脂40层的表面是平滑的。 Further surface of the resin layer 40 is smooth.

采用浇灌手段将无机粘结剂30覆盖在无机粘结剂30上以代替树脂40的方法与上面所叙述的同样。 The use of irrigation means 30 covers the inorganic binder in the same manner as the inorganic binder resin in place of 30 and 40 as described above.

图34是表示本发明的发光装置之其它制造工序的一部分的示意图。 FIG 34 is a schematic diagram showing a part of another manufacturing process of the light-emitting device of the present invention. 喷涂喷雾手段可以使用公知的喷涂喷雾手段。 Spray spray means may be any known means of spray painting. 本发明使用如下的喷涂装置(图中未示出),该喷涂装置分别使用输送管(图中未示出) 将收容涂布液即树脂40的容器(图中未示出)、调节涂布液的流量的阀(图中未示出)、把涂布液输送到喷嘴70后再从喷嘴70输送到容器的循环泵(图中未示出)以及使涂布液以螺旋状的形式喷出的喷嘴70连接起来。 Spraying means (not shown) of the present invention is used as the spray means were used delivery pipe (not shown) i.e. the coating liquid accommodating container 40 of a resin (not shown), adjusting coating the fluid flow valve (not shown), the coating liquid supplied to the circulation pump nozzle 70 from the nozzle 70 and then conveyed to the container (not shown), and the coating was sprayed in the form of a spiral a nozzle 70 connected together.

在收容涂布液的容器内安装着搅拌机(图中未示出),在涂布作业中经常搅拌涂布液。 A stirrer mounted (not shown) housed within the coating solution vessel, a coating solution was stirred constantly during the coating operation. 被容器收容的涂布液采用搅拌机经常搅拌,从而在涂布液中含有荧光体的情况下,涂布液中所含的荧光体常常均匀分散在溶液中。 The coating liquid container is accommodated using a stirrer stirring frequently, so that the case containing the phosphor, the phosphor contained in the coating liquid always uniformly dispersed in the solution in the coating liquid. 阀借助于阀的开闭调节由容器通过输送管输送来的涂布液的流量。 Valve opening and closing the valve by means of adjusting the flow rate of the coating liquid from the vessel through a delivery pipe conveyed. 循环泵通过输送管将涂布液从容器经由阀和压縮机输送到喷嘴70的顶端部,此后,将没有从喷嘴70喷出的而残留下来的涂布液通过输送管输送到容器。 The coating liquid circulating pump tubing conveyed by the conveying from the vessel to the compressor via the valve and the nozzle tip portion 70, and thereafter, the delivery tube to the container is not delivered from the nozzle 70 by the discharged coating liquid left over. 涂布液由于借助于循环泵通过输送管从容器经由阀被输送到喷嘴的顶端部,此后,通过输送管被输送到容器, 所以,涂布液常常处于在喷涂装置内循环的状态。 Since the coating solution by means of a circulating pump from the vessel via the delivery pipe is delivered to the valve tip portion of the nozzle, thereafter, it is conveyed through the delivery tube to the container, so that the coating liquid is often circulated in the state in the spraying device. 因此,涂布液因为处于遍及整个喷涂装置的搅拌或循环的状态,所以涂布液中含有的荧光体在涂布作业中经常处于均匀的分布状态。 Thus, because the coating liquid is stirred or circulated state throughout the spraying device, so that the phosphor coating liquid contained in the coating operation are often in a uniform distribution. 压縮机通过输送管设笠在装置内,压縮通过输送管输送来的空气,调节通过输送管输送来的涂布液的压力。 Li compressor through the delivery tube disposed within the device, the compressed air delivery tube conveyed, by adjusting the delivery tube to the delivery pressure of the coating liquid. 借助于压縮机,压缩空气和进行过压力调节的涂布液分别输送到喷嘴70。 By means of compressors, compressed air and coating liquid subjected to the pressure regulator 70 are supplied to the nozzle. 在此,压缩空气的压力通过压力计进行监视。 Here, the compressed air is monitored by a pressure gauge. 使用以上的喷涂装置,与高压气体一起高速喷出涂布液,喷涂在发光元件的上面、侧面以及凹部内面上。 Using the above coating apparatus, a high-speed high-pressure gas discharged together with the coating solution sprayed on top, and an inner side surface of the concave portion of the light emitting element.

涂布液和气体(本实施方案为空气)通过喷嘴70以螺旋状的形式喷出。 The coating liquid and a gas (air in this embodiment) is ejected through a nozzle in the form of a spiral 70. 该装置的喷嘴的周围设置若干个气体喷出口,从这些喷出口喷出的气体的喷出方向相对于被涂布的表面各自成某一角度。 Nozzle means disposed around the plurality of gas discharge ports, the discharge direction from the discharge port of the gas discharged with respect to each of the coated surface at an angle. 因此,当同时向以涂布液的喷出口为中心旋转的这些气体喷出口送入气体时, 将从各自的喷出口喷出的气体集中在一起的整个气体的流动,成为颠倒过来的涡壳状的流动、螺旋状的流动或龙巻风中的空气的流动。 Thus, when the gas fed to the discharge port while the gas discharge port of the coating liquid for the center of rotation, the discharge from the discharge port of each gas concentration throughout the gas flow together, become reversed volute shaped flow, spiral flow of air flow or long Volume wind. 另外,在该装置的喷嘴的中心设置有涂布液的喷出口,当与气体的喷出同时喷出涂布液时,成为雾状的涂布液趁颠倒过来的涡壳状的流动、 螺旋状的流动或龙巻风中的空气的流动而扩散开来。 Further, in the center of the nozzle of the apparatus is provided with the coating liquid discharge outlet, when the discharge gas while discharging the coating liquid, the coating liquid into a mist while upside down scroll-shaped flow, spiral shaped flow of air flow or wind and Lung Volume spread.

扩散成螺旋状的整个喷雾的直径从发光元件上方的喷射起始点开始,越靠近发光元件的表面,直径变得越大。 Spread into the entire diameter of the spiral spray injection start point above the beginning of the light emitting element, the light emitting element closer to the surface, the diameter becomes larger. 另外,从发光元件上方的喷射起始点开始,越靠近发光元件的表面,由涂布液构成的喷雾的旋转速度越小。 Further, the injection start point starting from the top of the light emitting element, the light emitting element closer to the surface, the rotation speed of the coating solution consisting of spraying smaller. 也就是说,当雾状的涂布液从喷嘴喷出并在空气屮扩散时,在喷射起始点即喷嘴的附近,喷雾呈圆锥状扩散开来,而在离开喷嘴的地方,喷雾呈圆柱状扩散开来。 That is, when the atomized coating liquid is discharged from the nozzle and spread in the air Cao, i.e. starting in the vicinity of the injection nozzle, spray conical spread, while leaving the nozzle in place, cylindrical spray spread. 于是,本实施例优选对发光元件的上面到喷嘴的下端之间的距离进行调节并进行设置,使得发光元件的表面出现在喷雾处于呈圆柱状扩散开来这一状态的地方。 Thus, the present preferred embodiment of the above embodiment the light emitting element is adjusting the distance between the lower end of the nozzle and disposed so that the surface of the light emitting element appear where the spray is spread to the cylindrical state. 此时的喷雾呈螺旋状旋转,且速度较慢,因此,喷雾能够绕到处于导电性引线阴影之下的发光元件表面上,不仅整个发光元件上面、而且整个侧面都能充分喷到。 At this time, the rotation of spiral spray, and slow, thus, can be sprayed on the surface around the light emitting element is electrically conductive wires under the shadow, not only the entire light-emitting element above, but can be adequately sprayed onto the entire side. 由此,可以在固定发光元件或喷嘴的状态下进行作业。 Thus, work can be performed in a fixed state light-emitting elements or nozzles. 另外,因为在喷雾处于呈圆柱状扩散开来这一状态的地方,喷雾的速度较慢,所以当喷雾喷涂在发光元件的表面时,发光元件的表面不会受到喷雾中所含有的荧光体粒子的冲击。 Further, since the spray is diffused by cylindrical state where the spray slower, when the spray coating on the surface of the light emitting element, the light emitting element of the surface will not be sprayed in the phosphor particles contained in the impact. 另外,不会产生导电性引线的变形和断线,从而使产品合格率和工艺性提高。 Further, no distortion and disconnection of the electrically conductive wire, so that the product yield of the process and improved.

涂布后的发光装置在加热器上处于温度为5(TC〜50(TC的加热状态。作为这样地使发光元件处于加热状态的方法,也可以使用在烘筘等加热装置内加热发光元件的方法。通过加热,使乙醇、微量包含在处于凝胶状态的水解液中的水分以及溶剂蒸发,而且由处于凝胶状态 The light emitting device after coating at a temperature of 5 (TC~50 (TC heated state of the heater as the light emitting element in such a way that the process in a heated state, the light emitting element may be used in a heating oven or other heating means reed the method by heating, ethanol, and the solvent was evaporated trace water contained in the hydrolyzate is in a gel state, and the gel state

的涂布液可以得到非晶质的A1(0H》和AIOOH。再者,本实施方案的涂布液由于进行了粘度调节,所以喷涂在发光元件的上面、侧面以及角上、进而在支持体表面之后,不会从喷涂的场所流出来。于这些场所在涂布之后不久便进行加热,这样通过由AIOOH将荧光体粘结而成的涂层可以覆盖发光元件的上面、侧面以及角上的部分。 The coating liquid can be obtained amorphous A1 (0H "and AIOOH. Further, the coating solution of the present embodiment as a result of adjusting the viscosity, it is sprayed onto the above light-emitting element, and a corner side surface, and further a support after the surface, does not flow out from the sprayed place. in these locations will be shortly after the coating is heated, so that the adhesion by coating the phosphor AIOOH formed on the light emitting element may cover the top, side and corner section.

在本实施方案中,在排列多个基体20的状态下,把发光元件60 分别焊接在基体20内,并将发光元件60的电极与引线电极22进行引线接合,然后用无机粘结剂30覆盖发光元件60,并从无机粘结剂30 的上方喷涂树脂40。 In the present embodiment, in the state of arrangement of the plurality of base body 20, the light emitting elements 60 are welded to the base body 20, electrode 60 and electrode 22 and the lead wire bonding the light emitting element, and then covered with an inorganic adhesive 30 the light emitting element 60, 40 and sprayed from above the resin in the inorganic binder 30. 在预定的场所以外,例如为防止在凹部20a内而以外附着树脂40,从屏蔽挡板80的上方将树脂40喷涂在无机粘结剂30的表面。 Other than a predetermined place, for example, in the concave portion 20a to prevent the outside of the resin-coated 40 from the shield 80 above the baffle 40 of the surface of the resin coating 30 in the inorganic binder. 屏蔽挡板80是完全遮盖基体20的凹部20a外侧的、设胃有大小可以使树脂40喷涂在无机粘结剂30的表面上的贯通孔的板, 具有金属制屏蔽挡板、强化塑料制屏蔽挡板等。 A shielding baffle 80 completely covers the outside of the recess 20a of the base 20, there are provided the size of the stomach the resin can be sprayed through hole 40 on the surface of the inorganic binder of the plate 30, the shutter having a metallic shield, the shield-reinforced plastic baffles and so on.

当使用喷涂喷雾手段时,树脂40被喷成粒状,所以存在于空隙31中的气体从粒子彼此之间的间隙向外部排出。 When using spray coating methods, the resin 40 is injected into a granular form, there is a void 31 in the gas discharged from the gap between particles to the outside. 由此可以使溶解亍树脂40中的气体量得以减少,可以减少树脂40中的气体含量。 Whereby the amount of gas dissolved in the right foot of the resin 40 is reduced, the gas content in the resin 40 can be reduced.

实施方案7 Embodiment 7

下面以图36为基础就本发明的实施方案7的发光装置进行说明。 In FIG 36 will be described below on the light emitting device of embodiment 7 of the present invention is based. 图36 (a)是放大实施方案7的发光装置之基体凹部的示意剖面图, 图36 (b)是表示该发光装置的立体图。 FIG 36 (a) is a schematic cross-sectional view of the base of the recess of the light-emitting device 7 is an enlarged embodiment, FIG. 36 (b) is a perspective view of the light emitting device. 如这些图所示的发光装置, 具体地说是炮弹型的发光装置。 As the light emitting device shown in these figures, specifically, shell-type light-emitting device. 发光装置700具有:发光元件710、 承载发光元件710的引线框(基体)720、覆盖发光元件710的无机粘结剂730、包含在无机粘结剂730中的荧光体750、覆盖无机粘结剂730的树脂740以及铸模构件760。 The light emitting device 700 includes: a light emitting element 710, a lead frame carrying the light emitting element 710 (base) 720, 710 cover the light emitting element 730 of the inorganic binder, the inorganic binder included in the phosphor 730 of the body 750, cover the inorganic binder a resin mold member 740 and 730 760. 另外,因无机粘结剂730的固化而产生空隙731。 Further, since the inorganic binder is cured voids 731 and 730. 在与上述部分具有同一机能的情况下,其说明予以省略。 In the case of having the same function with the above-described portions are omitted from description. 用炮弹型的发光装置700构成的发光元件710焊接在凹部720a 的大致中央部位并由该凹部720a所承载,其中凹部720a配置在成为基体的管脚引线的上部。 710 welded to a substantially central portion of the concave portion 720a by the light-emitting element 700 emitting device bullet-shaped configuration of the recess 720a of the carrier, wherein the concave portion 720a disposed at an upper portion of the base body becomes the pinouts. 发光元件710上形成的电极通过引线721与引线框720的管脚引线720a以及内部引线720b进行电连接。 Electrodes formed on the light emitting element 710 are electrically connected by wire leads 721 and 720 of the lead frame through inner lead 720a and 720b. 荧光体750含有YAG系荧光体和氮化物系荧光体,这些荧光体吸收发光元件710发出的光的至少一部分,同时发出不同于吸收光波长的光。 750 containing the phosphor YAG phosphor and the nitride-based phosphor, the phosphor absorbs at least a portion of light 710 emitted from the light emitting element, and emits light while absorbing light having a wavelength different from that. 再者, 氮化物系荧光体可以用微胶囊等覆盖材料覆盖起来。 Further, the nitride-based phosphor may be covered up with a microcapsule coating material. 在无机粘结剂730中使该荧光体750均匀分散。 The inorganic binder in the phosphor 730 is uniformly dispersed manipulation 750. 含有荧光体750的无机粘结剂730 配置在承载发光元件710的凹部内。 A phosphor containing an inorganic binder 730,750 disposed in the recess 710 of the light emitting element carrier. 这样,为了保护发光元件710和荧光体750免受外部应力、水分以及尘垢的侵害,以及为了改善光的取出效率,配置发光元件710和荧光体750的引线框720被模压在铸模构件760中,从而形成发光装置700。 Thus, in order to protect the light emitting element 710 and the phosphor 750 from external stress, moisture and dust violations, as well as to improve the light extraction efficiency, light emitting element 710 and the lead frame 750 of the phosphor 720 is molded in the mold member 760, thereby forming the light emitting device 700. 也可以以铸模构件的形式形成透镜等。 And the like may be formed in the form of a lens mold member.

树脂740采用喷涂喷雾手段或者浇灌手段覆盖无机粘结剂730以及发光元件710。 Resin 740 spraying means spray watering or inorganic binder cover means 730 and the light emitting element 710. 树脂740填充在引线框720的凹部720a内。 A resin filled in the lead frame 740 within the recessed portion 720a 720. 通过使树脂740的表面成为平面,可以控制指向性,并谋求光取出效率的提高。 If the surface of the resin 740 becomes a plane, the directivity can be controlled, and seek to improve the light extraction efficiency.

(铸模构件) (Mold member)

铸模构件760可以根据发光装置700的使用用途而设置,以用于保护发光元件710、导电性引线721、含有荧光体750的无机粘结剂730的层以及树脂740免受外界的侵害或用于提高光取出效率。 Mold member 760 may be provided in accordance with the intended use of the light emitting device 700, for protecting the light emitting element 710, the conductive leads 721, 750 an inorganic binder containing a phosphor layer 730 and the resin 740 from external damage, or for improve light extraction efficiency. 铸模构件760可以用各种树脂和玻璃来形成。 Mold member 760 may be formed of various resins and glass. 作为铸模构件760的具体材料,适合使用的主要有:环氧树脂、尿素树脂、硅树脂以及氟树脂等耐侯性优良透明树脂和玻璃等。 As a specific material of the mold member 760, suitable for use are: epoxy resin, urea resin, silicone resin, fluorine resin or the like and excellent in weather resistance transparent resin and glass. 另外,通过在铸模构件中含有扩散剂, 也可以缓和来自于发光元件710的光的指向性以及增加视场角。 Further, by containing a diffusing agent in the mold member, it can be alleviated to increase the directivity of light and angle of view from the light emitting element 710. 这样的铸模构件760可以使用与树脂740相同的材料,也可以使用不同的材料。 Such a mold member 760 with the resin 740 may be used the same material, different materials may be used. 实施方案8 Embodiment 8

再者,以图37为基础就本发明的实施方案8的发光装置进行说明。 Further, FIG. 37 to be described on the basis of the light emitting device of Embodiment 8 of the present invention. 图37 (a)是放大发光装置之基体凹部的示意剖面图,图37 (b)是表示该发光装置的立体图。 FIG 37 (a) is an enlarged schematic cross-sectional view of the base of the recess of the light-emitting device, FIG. 37 (b) is a perspective view of the light emitting device. 在该实例中,发光装置具体地说也是炮弹型发光装置800。 In this example, the light emitting device is in particular shell-type light-emitting device 800. 发光装置800具有:发光元件810、承载发光元件810的引线框(基体)820、覆盖发光元件810的无机粘结剂830、包含在无机粘结剂830中的荧光体850、覆盖无机粘结剂830的树脂840以及罩826。 The light emitting device 800 includes: a light emitting element 810, the inorganic binder is a lead frame 830 carrying the light emitting element 810 (base) 820, 810 cover the light emitting element, the phosphor comprising the inorganic binder 850 830, covering the inorganic binder 830 resin 840 and a cover 826. 另外,因无机粘结剂830的固化而产生空隙831。 Further, since the inorganic binder cured voids 831 and 830. 而且电极通过引线821与引线框820进行电连接。 And electrode 821 are electrically connected by a lead 820 to the lead frame. 在各部分与上述实施方案7具有同一机能的情况下,其说明予以省略。 In the case of the above-described embodiment, each portion 7 having the same function, description thereof is omitted.

发光装置800用罩826对承载着发光元件810的引线框820进行密封。 The light emitting device 800 with a cover 826 pairs of the light emitting element 810 carries the lead frame 820 is sealed. 该密封优选为气密。 The hermetic seal is preferably. 罩826的上面设置着窗部825,使源于发光元件810的光得以透过。 The above cover 826 is provided with a window portion 825, the light from the light emitting element 810 is transmitted. 引线824支持着窗部825。 Lead 824 supports the window 825.

实施方案9 Embodiment 9

另外,还以图38为基础就本发明的实施方案9的发光装置进行说明。 Further, the light emitting device will be described embodiments of the present invention in FIG. 9 based on 38. 图38是表示发光装置的一部分的示意剖面图。 FIG 38 is a schematic sectional view of a portion of the light emitting device. 特别涉及图35所示的、采用丝网印刷手段涂覆无机粘结剂30和树脂40的发光元件60附近的示意剖面图。 Particularly to FIG. 35, a schematic sectional view near the light emitting element 60 is coated by screen printing means 30 and the inorganic binder resin 40. 在基座基板92上,朝下安装着发光元件60,并采用丝网印刷手段在发光元件60的表面设置无机粘结剂30。 On the base substrate 92, the light emitting element 60 is mounted down, and means provided by screen printing on the surface of the inorganic binder 30 of the light emitting element 60. 之后将承载发光元件60的基座基板92安装在发光装置上,并将引线21焊接在导线性构件91上。 After the base substrate 60 carrying the light emitting element 92 is mounted on the light emitting device, and a lead wire 21 welded to the member 91. 继而采用浇灌等手段使树脂40浸渍在该无机粘结剂30中。 Then use other means watering the resin 40 is immersed in the inorganic binder 30. 由此可以提供一种在无机粘结剂30的表面浸渍有树脂40的发光装置。 Thereby to provide a surface-impregnated inorganic binder resin 30 has a light-emitting device 40. 其中,也可以在采用浇灌等手段将树脂40涂覆在无机粘结剂30上之后,再焊接引线21。 Wherein, irrigation may be employed other means after the resin 40 is coated on the inorganic binder 30, and then solder tails 21.

实施例30〜32 Example 30~32

(实施例30及31)作为与上述实施方案6〜9相对应的实施例,下面就实施例30〜32所得到的结果进行说明。 (Examples 30 and 31) as the above-described embodiment corresponding to Example 6~9 embodiment, described for Examples 30~32 The following results are obtained will be described. 实施例30及31是炮弹型的发光装置。 Example 30 and 31 are shell-type light-emitting device. 图33是表示实施例30及31的发光装置之制造工序的一部分的示意图,图34是表示实施例30及31的发光装置之制造工序的一部分的示意图。 FIG 33 is a diagram showing a part of a manufacturing process of a light-emitting device of Example 30 and 31 embodiment, FIG. 34 is a schematic diagram of a portion of a manufacturing process of the light emitting device of Example 30 and 31 of FIG. 图37 (a)是放大实施例30及31之基体凹部的示意剖面图,图37 (b)是表示实施例30及31的发光装置800的立体图。 FIG 37 (a) is an enlarged schematic cross-sectional view of the base of the recessed portion 31 of the embodiment and Example 30, FIG. 37 (b) is a perspective view showing a light emitting device 30 and the embodiment 31 800 embodiment. 图42是表示比较例3的发光装置的示意剖面图。 FIG 42 is a schematic sectional view showing a light emitting device of Comparative Example 3.

实施例30及31具有以下构成:发光元件810使用在400nm处贝.有主发光波长的、口0.35mm见方的管芯(dies)。 Example 30 and 31 has the following configuration: a light emitting element 810 in the shell main emission wavelength of 400nm, the die orifice 0.35mm square (dies).. 弓|线821使用以Au为主成分材料。 Bow | 821 using Au as a main component material. 无机粘结剂830使用氧化钇溶胶(多木化学制氧化钇溶胶)。 Inorganic binder 830 yttrium oxide sol (manufactured by Taki Chemical yttria sol). 荧光体850使用(Y0.8Gdo.2) 3AlsO,2:Ce的YAG荧光体。 850 phosphor used (Y0.8Gdo.2) 3AlsO, 2: Ce phosphor of YAG. 关于树脂840,实施例30为浸渍用硅树脂(商品名:KJF816,信越、>y^ — y株式会社制造),实施例31为浸渍用硅树脂(商品名:KJF816L,信越^!; ^一y株式会社制造)。 For the resin 840, Example 30 is impregnated with a silicone resin (trade name: KJF816, Shin-Etsu,> y ^ - y Co., Ltd.) Example 31 is impregnated with a silicone resin (trade name: KJF816L, Shin-Etsu ^ !; ^ a y Corporation). 实施例30的浸渍用硅树脂的基本物性是:粘度为100 (mmVsec),比重(25°C)为0.97,挥发成分(105'C/3小时)为0.5,固化状态为橡胶状膜,硬度(邵尔C型硬度)为60。 The basic physical properties of Example 30 is impregnated with a silicone resin are: viscosity 100 (mmVsec), specific gravity (25 ° C) of 0.97, a volatile component (105'C / 3 hr) was 0.5, the cured rubber film state, hardness (Shore C hardness) of 60. 实施例31的浸渍用硅树脂的基本物性是:粘度为60(mm2/sec),比重(25°C)为0.97,挥发成分(105°C/3小时)为0.5,固化状态为橡胶状膜,硬度(邵尔C型硬度)为60。 Basic properties embodiment impregnated Example 31 with a silicone resin are: viscosity 60 (mm2 / sec), a specific gravity (25 ° C) 0.97, volatile content (105 ° C / 3 hr) was 0.5, the cured state of the rubber-like membrane hardness (Shore C hardness) of 60.

实施例30及31根据以下的制造方法来制造。 Examples 30 and 31 produced according to the following manufacturing method. 首先,让发光元件810承载在引线框(基体)820上。 First, let the light emitting element 810 is carried on a lead frame (substrate) 820. 弓l线框820形成有包括广口开口部的凹部820a,在该凹部820a的底面承载着发光元件810。 L bow frame 820 includes a recess portion 820a is formed with a wide-mouth opening portion, the bottom surface of the recess portion 820a of the light emitting element 810 carries. 进行焊接以便使发光元件810的基板侧与凹部820a的底面相接触。 Welding so that the light emitting element substrate side portion 820a of the recess 810 and the bottom surface of the contact. 发光元件810使用Au-Sn等的共晶软钎料等粘接剂进行焊接。 The light emitting element 810 and the like using the Au-Sn eutectic solder adhesive such as welding. 承载发光元件810的工序完成后,发光元件810的电极和引线电极通过引线821进行电连接。 The light emitting element carrier after step 810 is completed, the light emitting element and the lead electrode 810 is electrically connected to an electrode by wire 821.

其次,在荧光体850称量好后,在预定量的无机粘结剂830中投入预定量的荧光体850并混合均匀。 Next, after the phosphor 850 good weighed into a predetermined amount in a predetermined amount of a fluorescent inorganic binder 830 body 850 and mixed well. 详细地说,是氧化钇溶胶和YAG荧光体各取10g,盛在100ml的烧杯中,然后相对于氧化钇溶胶添加50重量%的乙醇,充分搅拌而混合后,便得到荧光体/溶胶的料浆。 Specifically, yttria sol, and from each of the YAG phosphor 10g, filled in a 100ml beaker and then with respect to the yttrium oxide sol was added 50 wt% of ethanol, sufficiently stirred and mixed, then obtain a phosphor / sol material pulp.

接着利用喷涂喷雾手段向引线框820所承载的发光元件810上喷涂无机粘结剂830,从而使无机粘结剂830得以固定。 Spraying means for spraying using the spray is then the inorganic binder 830 to the light emitting element 810 on a lead frame 820 carried, so that the inorganic binder 830 is secured. 通过采用喷涂喷雾手段固定无机粘结剂830,可以使发光元件810的上面、侧面、 引线框820的凹部820a的底面、侧面以大致均匀的厚度形成无机粘结剂830的层。 By spraying the inorganic binder spraying means 830 is fixed, the light emitting element 810 can top, side, bottom of the recess 820a of the lead frame 820, the side surface to a substantially uniform thickness the inorganic binder layer 830. 除预定的场所以外,为了使无机粘结剂830不能固定, 设置了屏蔽挡板80进行喷涂喷雾。 Other than a predetermined place, in order to make the inorganic binder 830 can not be fixed, the shutter 80 is provided for spraying a spray shield. 用无机粘结剂830进行喷涂喷雾而使之固定后,在约24(TC的温度下进行30分钟的热固化。 After spraying with an inorganic binder spray 830 of the fixed thermally cured for 30 minutes at a temperature (TC about 24.

接着使用浇灌工具将树脂840浇灌在无机粘结剂830的层表面。 Watering tool is then used on the surface of the resin 840 poured inorganic binder layer 830. 树脂840的浇灌是在发光元件810的正上方以及无机粘结剂830的层的大致中央部滴下。 Pouring the resin 840 is dropped at a substantially central portion of the layer immediately above and an inorganic binder 830 of the light emitting element 810. 该树脂840从无机粘结剂830的层表面的中央部迅速渗透并向外周部方向扩展开来,使无机粘结剂830内部的空隙得以填埋,并覆盖表面直至无机粘结剂830的整个层表面发出树脂840 的光亮。 The rapid penetration of the resin 840 from the central portion of the surface of the layer 830 and the inorganic binder is spread to the outer peripheral portion of the direction of the interior of the void 830 is filled with an inorganic binder, and cover the entire surface of the inorganic binder until 830 a resin surface layer 840 emits light. 树脂840沿着引线框820的凹部侧面的无机粘结剂830的层表面往上爬, 一般认为这起因于毛细现象。 Resin climbing along the surface of the lead frame 840 recess 820 side surface 830 of the inorganic binder layer, it is generally believed that due to the capillary phenomenon. 由此在无机粘结剂830的层表面形成了均匀的薄膜状的树脂840的层。 Thereby forming a uniform layer of film-like resin 840 on the surface of the inorganic binder layer 830. 浇灌结束后,发光元件810被无机粘结剂830的层和树脂840的层所覆盖,然后将承载巻该发光元件810的引线框820在150'C左右的温度下,加热约3个小时, 从而使树脂840得以固化。 After watering, the light emitting element 810 is an inorganic binder and a resin layer 840 covered by layer 830, and then the light emitting element carrier Volume lead frame 820,810 at a temperature of about 150'C, for about 3 hours, so that the resin 840 is cured.

最后在氮气气氛中将该引线框820用罩826进行密封。 Finally, the lead frame in a nitrogen atmosphere 820 sealing cover 826. 罩826内被氮气所填充。 A nitrogen gas is filled within the housing 826. 在罩826的窗部825的下面,配置着引线框820的凹部820a。 In the following the window portion 825 of the cover 826, the lead frame is disposed in the recess portion 820a 820. 这样一来,便制造出实施例30及31的发光装置800。 As a result, they produce a light emitting Example 30 and 31 of device 800. (耐久性试验的测定结果) (Measurement Results of durability test)

就实施例30及31的发光装置进行了耐久性试验。 30 and the light emitting device 31 on the durability test was implemented. 图39表示实施例30及31、比较例3的发光装置的耐久性试验结果。 39 shows an embodiment 30 and 31, the results of durability test of the light emitting device of Comparative Example 3. 比较例3没有被无机粘结剂830和树脂840所覆盖,只是将发光元件810承载在引线框820的凹部820a内。 Comparative Example 3 is not an inorganic binder and a resin 840 covering 830, except that the light emitting element 810 carried within the recess portion 820a of the lead frame 820. 除此以外,与实施例30相同。 In addition, the same as in Example 30.

将实施例30及31的发光装置投入常温下进行的100mA的激励试验。 The light emitting device of Example 30 and 31 into the excitation 100mA tests conducted at room temperature. 将刚刚投入O小时时的输出功率设定为100%,测定100小时后、 200小时后、350小时后、500小时后以及700小时后输出功率。 The output power at O ​​hours just put as 100%, measured after 100 hours, 200 hours, after 350 hours, 500 hours and 700 hours after the output power. 其结果,实施例30及31的、比较例3的发光装置在经过700小时后均维持较高的输出功率。 As a result, Examples 30 and 31, a light emitting device of Comparative Example 3 are maintained at a high output power after 700 hours.

(光取出效率的测定结果) (Measurement result of the light extraction efficiency)

就实施例30及31的发光装置进行了光取出效率的测定。 The light emitting device 30 and the embodiment 31 was measured on the light extraction efficiency. 图40 表示实施例30及31、比较例4的发光装置的光取出效率的结果。 40 shows an embodiment of FIG. 30 and 31, Comparative Example result of the light extraction efficiency of the light emitting device 4.

图42是表示比较例4的发光装置的示意剖面图。 FIG 42 is a schematic sectional view showing a light emitting device of Comparative Example 4. 比较例4不用树脂覆盖无机粘结剂,而只使用无机粘结剂330。 Comparative Example 4 not covered with resin an inorganic binder, an inorganic binder 330 only. 在比较例4的无机粘结剂330中,使用与实施例30同样的YAG荧光体850。 In Comparative 4, 330 cases of the inorganic binder in Example 30 using the same embodiment of the YAG phosphor 850. 比较例4的发光装置用无机粘结剂330覆盖在发光元件310的上面。 The light emitting device of Comparative Example 4 310 overlies the light emitting element 330 with an inorganic binder. 在该无机粘结剂330中,包含许多空隙331。 In the inorganic binder 330, 331 contains many voids.

在该实施例30及31、比较例4的发光装置中,投入预定的电流, 测定其光的输出功率。 In this embodiment 30 and embodiment 31, the light emitting device of Comparative Example 4 was charged with a predetermined current, measuring the output power of its light. 其结果可以看到:实施例30为比较例4的】.91 倍,光取出效率得以提高,实施例31为比较例4的1.75倍,光取出效率也得到提高。 The results can be seen: Example 30 Comparative Example 4] 0.91 times the light extraction efficiency is improved, as Comparative Example 31 Example 4 1.75 times the light extraction efficiency is improved. 一般认为这是因为:比较例4的无机粘结剂330的层中含有的空隙331反射源于发光元件310的光。 This is considered because: the gap layer Comparative Example 4 inorganic binder contained in 330 331 310 reflected from the light emitting element. 也就是说,这是因为:在空隙331中含有氮等空气,由于无机粘结剂330与空气存在折射率上的差异,所以在空气和无机粘结剂330的界面产生反射。 That is, this is because: air containing nitrogen or the like in the space 331, since the difference in refractive index is present on the inorganic binder 330 with air, the air reflection interface 330 and an inorganic binder. 由此, 实施例30及31所提供的发光装置是富有耐久性、光取出效率高的发光装置。 Accordingly, the light emitting device 30 and 31 embodiment is provided rich durability, high light extraction efficiency of the light emitting device.

(红外光谱的测定结果) (IR spectrum measurement result)

就实施例30的浸渍用硅树脂测定了红外光谱。 Example 30 was immersed to the IR spectrum of a silicone resin. 另外,作为比较, 就比较例5的硅树脂测定了红外光谱。 For comparison, a silicone resin Comparative Example 5 was measured by FTIR. 图41是表示实施例30的涂股的红外光谱图。 FIG 41 shows IR spectra of coated strands of Example 30. 图43是表示比较例5的涂膜的红外光谱图。 FIG 43 is a diagram of an infrared spectrum of the coating film of Comparative Example 5. 该红外光谱是釆用傅立叶变换红外分光法(FT-IR)进行测定的结果。 The results of infrared spectra preclude Fourier transform infrared spectroscopy (FT-IR) was measured in. 作为傅立叶变换红外分光法的测定装置,使用了Nexus 870<主体>和Continu UnK显微〉(均为二^3—• ^亇六y公司制造)。 The measuring apparatus of Fourier transform infrared spectroscopy using the Nexus 870 <body> and microscopic Continu UnK> (two are six Ma ^ 3- • ^ y Inc.). 使用实施例30的浸渍用硅树脂的发光装置与使用比较例5的硅树脂的发光装置相比,具有优良的光取出效率以及耐热性、耐久性等。 Example 30 was immersed embodiment using a light emitting device as compared with Comparative Example 5 silicone light-emitting device using a silicone resin, having excellent light extraction efficiency and heat resistance, durability and the like. 另外,树脂退化的促进也受到抑制。 Further, promoting the degradation of the resin is suppressed. 一般认为其原因在于C-Si-O键的比例低于Si-O-Si键的比例。 The reason is generally believed that the proportion of C-Si-O bond is less than the ratio of Si-O-Si bond. 也就是说, 一般认为其原因在于:如果C-Si-O键的比例较小,则形成交联密度低的三元网络结构,从而可以形成橡胶状或凝胶状的比较富于柔软性的树脂涂膜。 That is, it is generally believed that the reason: If the proportion of bonds C-Si-O is small, a low crosslink density three yuan network structure is formed, can be formed of a rubber or gel comparative high flexibility resin coating film. 通过形成为橡胶状膜或凝胶状,可以促进内部应力的缓和,可以防止因热膨胀产生的剥离。 By forming the rubber-like or gel-like film can be promoted to alleviate internal stress can be prevented from peeling due to thermal expansion.

比较例5的涂膜在其树脂组成中,C-Si-O键相对于Si-O-Si键的强度比为1.16/1。 Coating Film of Comparative Example 5 in which the resin composition, C-Si-O bonds relative intensity ratio of Si-O-Si bond is 1.16 / 1. 与此相对照,实施例30的涂膜的强度比为2.21/1。 In contrast, the strength of the coating film of Example 30 ratio of 2.21 / 1. 此外,比较例5的硅树脂为一般的硅树脂。 In addition, the silicone resin of Comparative Example 5 for a typical silicone. (实施例32) (Example 32)

实施例32是炮弹型的发光装置。 Example 32 is a shell-type light-emitting device. 图35是表示实施例32的发光装置之制造工序的一部分的示意图。 FIG 35 is a schematic view showing part of a manufacturing process of the light-emitting device of Example 32. 图38是表示本发明的实施方案9 的发光装置的一部分的示意剖面图。 FIG 38 is a schematic sectional view of a portion of the light-emitting device of the present embodiment 9 of the invention. 特别是图35所示的、采用丝网印刷手段将含有荧光体的无机粘结材料99覆盖在发光元件60上这一工序的示意剖面图。 In particular FIG. 35, by screen printing means to an inorganic binding material containing the phosphor 99 is a schematic sectional view showing a cover step on the light emitting element 60. 另外,如图38所示,表示的是将无机粘结剂30覆盖在发光元件60上、再在无机粘结剂30的表面浸渍树脂40时的发光元件60附近的示意剖面图。 Further, as shown in FIG. 38, represented by the inorganic binder 30 is coated on the light emitting element 60, a schematic sectional view near the light emitting element 60 when the resin 40 and then immersing the surface of the inorganic binder 30. 实施例32除了与实施例30及31的发光元件810的承载状态不同以外,其余大致采用同样的构成。 Example 32 except in Example 30, and the light emitting element 31 of the embodiment different bearer status 810, substantially the same configuration as the rest. 图37(a)、 (b)是表示实施例30及31的发光装置的立体图,虽然与实施例32存在符号上的不同,但表示的是与实施例32大致同样的构成。 FIG 37 (a), (b) is a perspective view of a light emitting device of Example 30 and 31 in the embodiment, although the presence of Example 32 on a different symbol, but the embodiment shown is substantially the same configuration as in Example 32. 下面就实施例32与实施例30及31主要不同的部分进行说明。 The following Examples 30 and 32 with the main portions different from embodiment 31 will be described.

无机粘结剂30使用氧化铝溶胶(日产化学株式会社制,商品名: A1-520)。 30 using the inorganic binder of alumina sol (Nissan Chemical Industries, Ltd., trade name: A1-520). 用离子交换树脂对该氧化铝溶胶进行处理,藉此可以使作为稳定剂的硝酸根离子实现低浓度化。 Ion exchange resins treated in this alumina sol, whereby a nitrate ion can be made as a stabilizer of low concentration. 在10g该氧化铝溶胶中,添加20g (YG.8Gda2) 3AlsO,2:Ce的YAG荧光体,充分混合并搅拌。 In this alumina sol 10g, was added 20g (YG.8Gda2) 3AlsO, 2: Ce phosphor is a YAG, sufficiently mixed and stirred. 使用这样调配的荧光体糊剂,采用丝网印刷手段,用丝网印刷在管芯晶片(dies wafer)上形成荧光体层。 Phosphor paste using this deployment, by screen printing means, forming a phosphor layer by screen printing on the wafer die (dies wafer). 树脂40可以使用浸渍用硅树脂(商 40 may be impregnated with resin using a silicone resin (trade

品名:kjf816,信越^i; 〕一y株式会社制造)或浸渍用硅树脂(商 Name: kjf816, Shin-Etsu ^ i; y a] Ltd.) or impregnated with a silicone resin (trade

品名:kjf816l,信越V!J 3 — y株式会社制造)。 Name: kjf816l, Shin-Etsu V J 3 - y Corporation)!.

实施例32的发光元件60朝下安装在基座基板92的上面。 Example 32 light emitting element 60 is mounted face down on top of the base substrate 92. 在朝下安装着的发光元件60的表面采用丝网印刷手段设置无机粘结剂30。 Means provided by screen printing on the surface of the inorganic binder 30 of the light emitting element 60 is mounted downwardly. 承载着发光元件60的基座基板92通过导电性构件91以及凸缘96进行电连接,并通过基座基板92与引线21焊接在一起。 Carrying the light emitting element 60 of the base substrate 92 are electrically connected via the conductive member 91 and flange 96, with the solder tails 21 and 92 together through the base substrate. 无机粘结剂30 的表面浸渍有树脂40。 30 is surface-impregnated inorganic binder resin 40. 浸渍树脂40后的无机粘结剂30的表面具有光泽。 Surface 30 of the inorganic binder 40 impregnated with the resin has a gloss.

下面详细说明实施例32的发光装置的制造方法之无机粘结剂30 的形成方法。 The following detailed description of a method of forming an inorganic light-emitting device manufacturing method according to embodiment 32 of the adhesive 30. 首先,在基座基板92的表面配置导电性构件91,然后设置具有隔离正极和负极的绝缘部94的导电性图案。 First, the surface of the base substrate 92 is disposed a conductive member 91 and conductive pattern having a separator disposed positive and negative insulating portion 94.

基座用基板92的材料优选的是与半导体发光元件的热膨胀系数大致相等的材料例如对氮化物半导体发光元件而言为氮化铝。 Base substrate 92 is preferably a material with a thermal expansion coefficient of the semiconductor light emitting element is substantially equal to the material such as nitride semiconductor light-emitting element in terms of aluminum nitride. .通过使用这样的材料,可以缓和基座用基板92和发光元件60之间产生的热应力。 By using such a material, the thermal stress can be relaxed by between base substrate 92 and the light emitting element 60 is produced. 基座用基板92的材料有时优选能形成具有p型半导体区域和n 型半导体区域的保护元件的、排热性比较良好的、同时也廉价的硅。 Base material for the substrate 92 may preferably have a protective element capable of forming a p-type semiconductor region and an n-type semiconductor region, the exhaust heat relatively good, but also an inexpensive silicon. 另外,导电性构件91优选使用反射率高的银、金和铝。 Further, the conductive member 91 is preferably silver, gold, aluminum, high reflectance.

为了提高发光装置的可靠性,在发光元件60的正负两电极间与绝缘部94之间产生的间隙内,填充底填料材料95。 In order to improve the reliability of the light emitting device, the gap created between the insulating portion 94 and between the positive and negative electrodes of the light emitting element 60, filling the underfill material 95. 首先,在上述基座基板92的绝缘部94的周边配置有底填料材料95。 First, at the periphery of the base portion 94 of the insulating substrate 92 is disposed filler material 95 having a bottom. 底填料材料95例如为硅树脂和环氧树脂等热固化性树脂。 Underfill material 95, for example, a silicone resin, and epoxy thermosetting resin. 为了缓和底填料材料95的热应力,也可以进一步将氮化铝、氧化铝以及它们的复合混合物等混入环氧树脂中。 In order to alleviate thermal stress in the underfill material 95 may further be aluminum nitride, alumina, and mixtures thereof and the like mixed into the composite in an epoxy resin. 底填料的用量为可以填埋发光元件的正负两电极与基座基板92之间产生的间隙的量。 The amount of the underfill amount generated between the gap 92 may be filled with positive and negative electrodes of the light emitting element and the base substrate.

以分别与在基座基板92上设置的上述导电性图案的正负两电极相对置的方式将发光元件60的正负两电极用凸缘96接合并固定下来。 Positive and negative electrodes, respectively, to the positive and negative electrodes and the conductive pattern disposed on the base substrate 92 in a manner opposed to the light emitting element 60 is engaged with the flange 96 fixed. 此外,将基座作为保护元件时,发光元件的正极和负极分别与保护元件的n型半导体区域和p型半导体区域相连接。 Further, as the protective element, positive and negative electrodes are connected to the light emitting element, the base and the n-type semiconductor region and a p-type semiconductor region of the protective element. 首先,相对于发光元件60的正负两电极形成作为导电性构件的凸缘96。 First, with respect to the positive and negative electrodes of the light emitting element 60 is formed as a flange 96 of the conductive member. 此外,也可以相对于基座基板92的导电性图案的正负两电极形成凸缘96。 Further, with respect to the positive and negative electrode base substrate, a conductive pattern 92 is formed flange 96. 当配置在基座基板92的绝缘部94附近的底填料材料95软化时,发光元件60 的正负两电极通过凸缘96与上述导电性图案的正负两电极相对置。 When softened 95 disposed in the vicinity of the base portion of the insulating substrate 92 of the bottom 94 of filler material, the positive and negative electrodes of the light emitting element 60 opposite to the positive and negative electrodes 96 through the flange and the conductive pattern. 其次,借助于载荷、热以及超声波使发光元件的正负两电极、凸缘96 以及上述导电性图案热压接在一起。 Secondly, by means of load, heat, and ultrasonic wave emitting element of the positive and negative electrodes, flange 96 and the conductive patterns together thermocompression. 此时,凸缘96和上述导电性图案的正负两电极间的底填料得以排除,可以谋求发光元件的电极和上述导电性图案的导通。 At this time, the underfill between the flange 96 and the positive and negative electrodes of the conductive pattern can be ruled out, can achieve conduction electrode and the conductive pattern of the light emitting element. 作为导电性材料凸缘96的材料例如有Au、共品软钎料(Au-Sn) 、 Pb-Sn、无铅软钎料等。 As the conductive material of the flange material 96 of for example Au, eutectic solder (Au-Sn), Pb-Sn, Pb-free solders and the like.

从发光元件60的基板侧配置着筛板97。 Sieve 97 is disposed from the substrate side of the light emitting element 60. 此外,也可以在导电性引线的球焊位置、分型线的形成位置等不想形成含有荧光体的无机粘结剂的位置配置金属掩模以取代筛板97。 Furthermore, the ball did not want the electrically conductive wire welding position, the position of the parting line is formed like a position of an inorganic binder containing a phosphor is disposed instead of the metal mask 97 sieve.

调整在具有触变性的氧化铝溶胶中含有荧光体的材料,使用刮浆板(圆头刮刀)98进行丝网印刷。 Adjusting a phosphor-containing material in the alumina sol having thixotropic properties, a squeegee (spatula) 98 for screen printing.

取下筛板97,使含有荧光体的材料固化,然后沿着分型线切割每一个发光元件,便得到具有包含荧光体的无机粘结材料的发光装置60。 Remove the sieve 97, so that a cured material containing a phosphor, a light emitting element and then cut along each parting line 60 will obtain a light emitting device having an inorganic bond material comprises phosphor.

再者,可以设计这样一种发光装置:以Ag糊剂为粘接剂将上述 Further, it is possible to design a light emitting device: Ag paste as an adhesive in the above-described

发光元件60固定在壳体的凹部底面,然后用导电引线将在凹部底面露 The light emitting element 60 is fixed to the bottom of the recess of the housing, the conductive leads and then recesses in the bottom cheeky

出一部分的引线电极和设置在基座基板上的导电性图案连接起来。 A part of a lead electrode disposed on the base substrate and the conductive patterns are connected together. example

如,本实施例可以使用的发光装置具有:用于控制发光装置的配光性的透镜,以及在用于提高发光元件的排热性、承载发光元件的凹部底面的一部分形成的金属基体。 For example, the present embodiment may use the light emitting device having: a light emitting device for controlling the light distribution of a lens, as well as for improving the exhaust heat of the light emitting element, a part of the metal matrix formed of the bottom of the recess carrying the light emitting element. 另外,在透镜的下面和壳体凹部的内壁面之间的间隙中优选配置硅树脂等的铸模构件。 Further, the gap between the inner wall surface of the concave portion of the housing and below the lens mold member is preferably arranged in the silicone resin or the like. 由于采用这样的构成, 可以获得源于发光元件的光的取出效率得以提高、且具有高可靠性的发光装置。 Due to such a configuration, the light emitting element can be obtained from the extraction efficiency is improved, and the light emitting device with high reliability.

下面就实施例32的发光装置的制造方法进行说明。 Here a method of manufacturing a light emitting device according to the embodiment 32 will be described. 实施例32采用与实施例30及31大致同样的构成的地方,其说明予以省略。 Example 32 and 30 using the same place and substantially the configuration of embodiment 31 embodiment, description thereof is omitted.

首先,在基座基板92上,朝下安装着发光元件60。 First, the base substrate 92, the light emitting element 60 is mounted face down. 基座基板92 和发光元件60通过凸缘96进行电连接。 The base substrate 92 and the light emitting element 60 is electrically connected by a flange 96. 在基座基板92上设置有沟部以便使之成为异种电极,使绝缘部流入该沟部从而防止异种电极间的短路。 On the base substrate 92 is provided with a groove portion so as to become dissimilar electrodes, the insulating portion to flow into the groove portion so as to prevent a short circuit between the electrodes heterogeneous.

接着在朝下安装的发光元件60和基座基板92上,采用筛板97 进行丝网印刷。 Then on the light emitting element 60 and the base board 92 is mounted downward, deck 97 using screen printing. 丝网印刷所使用的无机粘结剂30的层使用含有荧光体的无机粘结材料99。 Layer 30 of the inorganic binder used in the screen printing using an inorganic bond material 99 containing the phosphor. 但是,也可以使用不含荧光体的无机粘结材料99。 However, it may also be used an inorganic binding material 99 containing no phosphor. 使用丝网印刷手段在发光元件60的上面以及侧面形成均匀的无机粘结剂30的层。 Screen printing means for forming a uniform layer 30 of the inorganic binder in the light emitting element 60 and the upper side. 含有荧光体的无机粘结材料99使用的是在10g氧化铝溶胶中添加20gYAG荧光体、然后充分搅拌并混合而成的材料。 An inorganic binding material containing the phosphor 99 is used to add 20gYAG phosphor 10g of alumina sol, and then sufficiently stirred and mixed material. 在发光元件60的上面以及侧面形成无机粘结剂30后,在氮气氛中于80'C 左右30分钟、150。 After the formation of the inorganic binder in the light emitting element 30 and side surfaces 60 above, at about 80 'C. 30 min in a nitrogen atmosphere 150. C左右30分钟、240。 C for about 30 minutes, 240. C左右30分钟的加热条件下, 对无机粘结剂30进行固化。 C at about 30 minutes heating, inorganic adhesive 30 is cured. 这是为了除去无机粘结剂30中含有的冇机成分等。 Nuisance This is to remove organic components contained in the inorganic binder 30, and the like. 但是,本发明并不特别局限于该加热条件,也可以在100 t:左右加热30分钟后,再于240'C加热1个小时。 However, the present invention is not limited to this particular heating conditions may be 100 t: about 30 minutes heating, then heated at 240'C 1 hours.

接着使朝下安装在上述基座基板92上的发光元件60 (210)承载在引线框(基体)820上。 Then the light emitting element 60 (210) downward is mounted on the base substrate 92 is carried on a lead frame (substrate) 820. 引线框820形成有包括广口开口部的凹部820a,在该凹部820a的底面承载着发光元件60 (210)。 Lead frame 820 includes a recess 820a is formed wide-mouth opening portion, carrying the light emitting element 60 (210) in the bottom surface of the recessed portion 820a. 进行焊接以便使发光元件60 (210)的基板侧与凹部820a的底面相接触。 Contacting the bottom surface of the recess portion 820a and the substrate-side welding is performed so that the light emitting element 60 (210). 发光元件60 (210)使用Au-Sri等的共晶软钎料等粘接剂进行焊接。 60 light emitting element (210) and the like using the Au-Sri eutectic solder adhesive such as welding. 承载发光元件60 (210)的工序完成后,基座基板92的导电性构件91和引线电极通过引线821进行电连接。 After step 60 carrying the light emitting element (210) is completed, the base substrate 92 of the conductive member and the lead electrode 91 are electrically connected by a lead 821.

接着使用浇灌工具将树脂40 (240)浇灌在无机粘结剂30 (230) 的层表面。 The resin is then used watering tool 40 (240) surface of the inorganic binder is poured in 30 (230) layer. 树脂40 (240)的浇灌是在发光元件60 (210)的正上方以及无机粘结剂30 (230)的层的大致中央部滴下。 40 resin (240) is watered dropped at a substantially central portion of the light emitting element layer 60 (210) immediately above and the inorganic binder 30 (230). 该树脂40 (240)从无机粘结剂30 (230)的层表面的中央部迅速渗透并向外周部方向扩展开来,使无机粘结剂30 (230)内部的空隙得以填埋,并覆盖表面直至无机粘结剂30 (230)层的整个表面发出树脂40 (240)的光亮。 The resin 40 (240) from the central portion of the rapid penetration of the surface of the inorganic binder 30 (230) layer and extending to the outer peripheral portion of the opening direction of the inorganic binder 30 (230) inside the air space to be filled, and cover surface until the entire surface of the inorganic binder 30 (230) emits the resin layer 40 (240) light. 由此在无机粘结剂30 (230)层的表面形成了均匀的薄膜状的树脂40(240)。 Whereby the inorganic binder 30 (230) forms a surface layer of a uniform thin film-shaped resin 40 (240). 焊接结束后,用无机粘结剂30 (230)的层和树脂40 (240)的层覆盖发光元件60 (210),将承载该发光元件60 (210)的引线框820在15(TC左右的温度下加热约3小时,使树脂840得以固化。在此,硅树脂使用浸渍用硅树脂(商品名:KJF816,信越、乂y3 — 乂株式会社制造)。 After welding, the light emitting element 60 covered with the inorganic binder 30 layer (230) and the resin layer 40 (240) (210), the light emitting element 60 the carrier (210) of the lead frame 820 at 15 (TC about heating at a temperature of about 3 hours to cure the resin 840 in this case, the use of the silicone resin is impregnated with a silicone resin (trade name: KJF816, Shin-Etsu, qe y3 - qe Corporation).

最后在氮气气氛中将该引线框820用罩826进行密封。 Finally, the lead frame in a nitrogen atmosphere 820 sealing cover 826. 罩826内被氮气所填充。 A nitrogen gas is filled within the housing 826. 在罩826的窗部825的下面,配置着引线框820的凹部820a。 In the following the window portion 825 of the cover 826, the lead frame is disposed in the recess portion 820a 820. 这样一来,便制造出实施例32的发光装置。 As a result, they produce a light emitting device of Example 32.

实施方案10 Embodiment 10

继而以图44为基础就本发明的实施方案10的发光装置进行说明。 In turn, FIG. 44 will be described embodiments of the light emitting device 10 of the present invention is based. 图44表示实施方案10的具有发光膜的发光装置1000的示意结构阁。 44 shows a schematic embodiment of a light emitting device light emitting film structure Court 1000 10. 该发光装置1000包括,激发光源44:用于射出激发光42;发光材料54:它吸收由激发光源44射出的激发光42,进行波长转换后而发出预定波长区域的照明光43;光导纤维46:它一端连接激发光源44,另一端连接发光材料54,并相对于周边部(包层)提高断面中心部(芯)的折射率,从而将由激发光源44射出的激发光42导向发光材料54。 The light emitting device 1000 includes an excitation light source 44: 42 for emitting excitation light; a light emitting material 54: 42 it absorbs light, excited by the excitation light source 44 emits the illumination wavelength converted to emit light of a predetermined wavelength region 43; 46 fiber : excitation light source 44 which connects the other end connected to the light emitting material 54, and the peripheral portion (cladding) increase the refractive index of the central part section (core), so that excited by the excitation light source 44 emits light 42 of the guide 54 with respect to the light emitting material.

激发光源44具有发光元件47,将由发光元件47射出的光从射出部48导向光导纤维46。 Excitation light source 44 having a light emitting element 47, light emitted by the light emitting element 47 of the light 46 emitted from the optical fiber guide section 48. 为了有效地将由发光元件47射出的光导向射出部48,在发光元件47与射出部48之间设有透镜49。 In order to effectively emitted by the light emitting element 47 emitting light guide portion 48, between the light emitting element 47 and the exit portion 48 with lens 49.

光导纤维46的一端与射出部48连接,另一端具有将光导向外部的输出部52。 One end portion of the optical fiber 46 and the exit 48 and the other end portion 52 with an output of the light guided to the outside. 输出部52具有发光材料54。 Output unit 52 having the light emitting material 54. 作为发光材料54,在本实例中使用无机荧光体55。 As the light emitting material 54, 55 used in the present example an inorganic phosphor. 发光材料54吸收由激发光源44射出的激发光42,进行波长转换后而发出预定波长区域的照明光43。 After 54 absorbs the light emitting material 42, 44 for the excitation light emitted by the wavelength conversion of excitation light source that emits illumination light 43 of a predetermined wavelength region. 荧光体55事先混合在填料构件56和粘结剂构件57中,在输出部52配置该填料构件56和粘结剂构件57。 A phosphor 55 mixed in advance in the packing member 56 and the adhesive member 57, 52 disposed at the output portion of the filler member 56 and the adhesive member 57. 荧光体55的用量可以根据该填料构件56和粘结剂构件57的量来调整。 The amount of the phosphor 55 may be adjusted according to the amount of the filler member 56 and the adhesive member 57. 填料构件56是无机填料,粘结剂构件57为至少含有金属元素的水合氧化物的无机化合物。 The filler is an inorganic filler member 56, member 57 is a binder containing at least an inorganic hydrous oxide compound of the metal element. 粘结剂构件57中含有的金属元素的水合氧化物可以使用具有勃姆石结构或伪勃姆石结构的A1、 Y的水合氧化物等。 Hydrous oxide of a metal element contained in the adhesive member 57 may be used having a boehmite structure A1 or pseudo-boehmite structure, Y hydrated oxide.

当使用在可见光的短波区域400nm附近具有发光峰值波长的发光元件47、以及由发出蓝色光的荧光体和发出黄色光的荧光体混合而成的荧光体55时,由荧光体55发出的白色光主要成为照明光43。400nm附近的光难以进行视觉辨认,因而使其成为容易进行视觉辨认的蓝色光、黄色光和白色光。 When the light emitting element having an emission peak wavelength in the vicinity of visible light short-wavelength region 400nm 47, and emits yellow light from the phosphor emitted blue light and the phosphor mixture of a phosphor 55, the white light 55 emitted from the fluorescent body the main illumination light become close 43.400nm visibility difficult, thus making it easy to visually recognize the blue light, the yellow light and white light.

当使用在可见光的短波区域460mn附近具有发光峰值波长的发光元件47、发出黄色光的荧光体和发出红色光的荧光体时,由发光元件47射出的激发光42和由荧光体55发出的光的混色光作为照明光43导向外部。 Light when the light emitting element having an emission peak wavelength in the vicinity of visible light short-wavelength region 460mn 47, phosphor that emits yellow light and emits red light fluorescent material by emitting element 47 of the excitation light 42 and is composed of fluorescence 55 emitted the external illumination light as mixed light guide 43. 该照明光43成为带红色的白色光。 43 the illumination light reddish white light.

当使用在紫外线区域365mn附近具有发光峰值波长的发光元件47、以及由发出蓝色光的荧光体和发出黄色光的荧光体混合而成的荧光体55时,由荧光体55发出的白色光成为照明光43。 When the light emitting element having an emission peak wavelength near ultraviolet region 365mn 47, and emits yellow light from the phosphor emitted blue light and the phosphor mixture of a phosphor 55, a white fluorescent body 55 becomes the illumination light emitted light 43. 因为紫外线用人的肉眼看不到,所以只是由荧光体55发出的光成为照明光43,其中荧光体55用于进行波长转换而使紫外线成为可见光。 Because the human eye can not see ultraviolet light, so that only the light 55 becomes the illumination light emitted by the phosphor 43, wherein the phosphor 55 for converting the ultraviolet wavelength to become visible. 因此,由荧光体55发出的白色光成为照明光43。 Thus, the white phosphor emitted by the illumination light 55 becomes light 43.

但是,考虑到荧光体55的各种组合,则有利用光的三原色(蓝色、绿色、红色)得到广范围的色调的情况、以及利用成为补色关系的蓝色和黄色、蓝绿色和红色、绿色和红色、蓝紫色和黄绿色等2种颜色得到各种色调的情况。 However, considering the various combinations of the fluorescent body 55, there are three primary colors (blue, green, red) to give color tone of light using a wide range, and the use of complementary colors become blue and yellow, blue green and red, green and red, green, blue purple and yellow colors to give two kinds of the case of various hues. 也可以将这些颜色的一方置换成由发光元件射出的光。 It is also one of these colors may be replaced with the light emitted from the light emitting element. 这里所谓的补色指的是一方的发光峰值波长的光与另一方的发光峰值波长的光混合时,能够得到白色区域的光的2种颜色。 Here, the term refers to the complementary color mixing light emission peak wavelength of the emission peak wavelength of one light and the other, it is possible to obtain two kinds of color light of white areas. 在此,色名和波长范围的关系参见JISZ8110。 Here, the relationship between the name and the color wavelength range See JISZ8110. 另外,为了获得高的演色性,有时也对荧光体55进行各种组合。 Further, in order to obtain a high color rendering, the phosphor 55 may also be various combinations thereof.

所谓演色性是左右对由某一光源照明的物体颜色之视度的该光源的性质。 The so-called color rendering properties of the light source about the color of an object depends on a degree of the illumination light. 色温度是在心理物理方面表现光源本身的颜色的,以具有与 Representing color is the color temperature of the light source itself psychophysical terms, to have a

某一光源的色度相等的色度的完全辐射体的绝对温度(K)来表示。 Full radiator absolute temperature equal chromaticities of a light source (K) is represented. 一般地说,在某一光源下对看到的物体颜色的视度,由它与在具有同一色温度的基准光下对看到的物体颜色的视度之差异来表示。 In general, in a light source of the visual color of an object seen, it is represented by a view of the differences seen in the color of an object reference light having the same color temperature. 平均演色评价指数(Ra)是以8种比色图表分别由试料光源和基准光源照射时的色差的平均值为基础而求出的。 The average color rendering index (Ra) is 8 kinds of the average value of each color chart color when irradiated with sample light source and the light source based on the reference and determined. 特殊演色评价指数是上面8种比色图表以外的其它7种比色图表各自的色差为基础而求出的,不是7 种的平均值。 Special color rendering index is based on the respective color is obtained than seven other than colorimetric color chart graph, not the average of 7 kinds of the above eight kinds. 其中R9表示红色。 Where R9 represents red.

该发光装置1000可以在照射被拍摄物体而对其进行摄像的内窥镜等医疗领域、用多个激发光源44获得各种颜色的照明装置、显示器等方面使用。 The light emitting device 1000 may be photographed object subjected to irradiation imaging endoscope in the medical field, aspects obtain various colors light source 44 illuminating device, a display, etc. using a plurality of excitation. 由发光装置IOOO射出的光除直接由人进行视觉辨认外, 有时也在CCD摄像机等中进行摄像。 IOOO emitted from the light emitting device in addition to the light directly from people outside visibility, and sometimes also the CCD camera imaging. 与CCD摄像机等显像器的感度相一致,可以适当选择激发光源44和荧光体55。 Consistent with the sensitivity of a CCD camera imaging device may be appropriately selected excitation light source 44 and a phosphor 55.

下面就发光装置1000的作用进行说明。 Here will be described the role of the light emitting device 1000. 由激发光源44所具有的发光元件47射出的激发光42透过透镜49而导向射出部48。 44 by the excitation light source having a light emitting element 47 emits excitation light 42 is emitted through the lens 49 and the guide portion 48. 透镜49 在射出部48将由发光元件47射出的激发光42聚焦。 48 by the lens 49 is emitted from the light emitting element portion 47 of the excitation light 42 emitted from focus. 从射出部48射出的激发光42被导向光导纤维46。 48 is emitted from the portion of the excitation light 42 emitted from the optical fiber 46 is guided. 激发光42在光导纤维46内反复产生全反射并导向另一端的输出部52。 Excitation light 42 is totally reflected repeatedly inside the optical fiber 46 and the other end of the guide portion 52 of the output. 将导出来的激发光42照射在输出部52上设置的荧光材料54即荧光体55上,该激发光42的至少一部分被荧光体55吸收而进行波长转换后,发出预定波长区域的光。 The fluorescent material 54 guided by the irradiation of excitation light 42 is provided on the output section 52, i.e., on the phosphor 55, the excitation after the absorbent body 55 at least a portion of the fluorescent light 42 and converting the wavelength of the emitted light of a predetermined wavelength region. 该光作为照明光而导向外部,或者作为由荧光体55发出的光和激发光42混合而成的照明光而导向外部。 The light guided to the outside as illumination light or the excitation light and the illumination light 42 are mixed as a 55 emitted by the fluorescent body light guided to the outside. 在输出部52由荧光体55产生光的吸收和散射,从而使光密度得以提高。 An output section 5255 in the absorption and scattering of light generated by the phosphor, so that the light density is increased. 因此,使用无机填料32和粘结剂构件57需要耐热性、耐光性优良的构件。 Thus, using an inorganic filler member 32 and a binder 57 requiring heat resistance, light resistance member. 由此,至少用l个发光元件47可以得到白色光。 Accordingly, at least one light emitting element 47 with l white light can be obtained. 另外,因为仅用l个发光元件47就可以得到白色光,所以可以提供一种色调偏差少、富有颜色重现性的发光装置。 Further, since the light emitting element 47 l only can obtain white light, it is possible to provide a small deviation tone, full color reproducibility of the light emitting device. 另外,因为使用发光元件47和荧光体55,所以可以提供一种容易混色且演色性高的发光装置。 Further, since the light emitting element 47 and a phosphor 55, it is possible to easily provide a high color rendering and color mixing light emitting device. 另外,还可以提供一种发光强度高的发光 It is also possible to provide a highly luminous intensity

110装置。 110 apparatus. 由于没有在发光元件47上涂布荧光体55,所以不会因伴随着发光元件47的激励所产生的发热而引起荧光体55的退化。 Since there is no body on the light emitting element 55 is coated with phosphor 47, the light emitting element is not accompanied by heat generated by the excitation caused by degradation of the phosphor 47 to 55. 再者,当将激光二极管元件用作激发光源44时,因为光密度极高,所以不能将混合有荧光体55的树脂用于输出部52。 Further, when the laser diode elements used as the excitation light source 44, since the high optical density, the resin can not be mixed with a phosphor 55 for outputting section 52. 与此相对照,当将混合有荧光体55的氧化铝溶胶和钇溶胶等粘结剂构件57用于输出部52时,因为耐光性、耐热性极其优良,所以可以提供一种即使对比较高的光密度也不会退化且耐侯性优良的发光装置。 In contrast, when mixed with alumina sol and yttrium sol binder member 55 phosphor output section 57 for 52, since the light resistance, heat resistance and extremely excellent, even if it is possible to provide a comparison high optical density and excellent weather is not light-emitting device degradation. (激发光源) (Excitation light source)

激发光源44可以射出用于激发荧光体55的光,可以将半导体发光元件、灯、电子束、等离子体以及EL等作为能源加以使用。 The light source 44 may emit excitation light for exciting the phosphor 55, a semiconductor light emitting element, light, electron beam, plasma, and EL or the like may be used as the energy. 本发明没有特别加以限定,但因为小型且发光强度高,所以优选使用发光元件47。 The present invention is not particularly be limited, because a small size and high emission intensity, the light emitting element 47 is preferably used. 发光元件47可以使用发光二极管元件(LED)和激光二极管元件(LD)。 The light emitting element 47 may be a light emitting diode element (LED) and laser diode elements (LD). (发光材料) (Luminescent material)

发光材料54只要吸收由激发光源44射出的激发光、且进行波长 Luminescent material 54 so long as the wavelength absorbed by the excitation light source 44 emits the excitation light, and

转换后发出预定波长区域的照明光就没有特别的限制,可以使用荧光体55和颜料等。 Emits a predetermined wavelength region of the illumination light after the conversion is not particularly limited, and the phosphor 55 and pigments. 激发光源44的发光谱与发光材料54的发光谱不同。 The excitation emission spectrum and emission spectrum of the luminescent material 54 different from the light source 44. 因为将由激发光源44射出的光作为激发光,所以发光材料54在激发光源44所具有的发光峰值波长的更大波长侧具有发光峰值波长。 Because the excitation light source 44 will be emitted as excitation light, the light emitting material 54 having a light emission peak wavelength in the excitation wavelength side greater emission peak wavelength of the light source 44 has. 特别地,即使在将激光二极管元件用作发光元件47的情况下,也因为照明光为半峰宽非常宽的发光谱而容易进行视觉辨认。 In particular, even in the case where a laser diode as a light emitting element 47 of the element, and because the illuminating light emission spectrum is very broad half-value width of easily visually recognize. 可以使用上述的荧光体55、填料构件56以及粘结剂构件57。 Can 55, the filler member 56 and the adhesive member 57 using the phosphor. 作为在输出部55进行涂布的方法,除了可以混合荧光体55、填料构件56以及粘结剂构件57、 并将其配置在预定的容器内、然后用玻璃和透光性树脂等做盖进行密封以外,也可以混合荧光体55、填料构件56以及粘结剂构件57、并将其配置在预定的容器内、然后浸渍树脂,它们并没有特别的限定。 As a method for applying the output unit 55, in addition to the mixed phosphor 55, the filler member 56 and the adhesive member 57, and which is disposed in a predetermined vessel, and the resin and the translucent glass lid do outside the seal, it may be mixed with the phosphor 55, the filler member 56 and the adhesive member 57, and which is disposed in a predetermined vessel, and then impregnated with a resin, and they are not particularly limited. 另外,为了提高排热性,也可以配置热传导性优良且具有透光性的无机填料。 In order to improve heat discharge, it may be arranged having excellent thermal conductivity and translucency inorganic filler.

m(光导纤维) m (optical fiber)

光导纤维46可以具有将由激发光源44射出的光导向发光材料54 的作用。 It may have a role in the optical fiber 46 by excitation light emitted from the guide light source 44 emitting material 54. 从能量效率的角度考虑,特别优选使由激发光源44射出的光不衰减地导向发光材料54。 From the viewpoint of energy efficiency, it is particularly preferable that the light emitted from the excitation light source 44 is guided without attenuation luminescent material 54. 例如可以使用的有:将具有高折射率的材料和具有低折射率的材料组合起来的材料和使用了反射率高的构件的材料。 For example there may be used: a material having a high refractive index and a material having a low refractive index material and the use of a combination of high reflectance material members. 具体地说,可以使用光导纤维46。 Specifically, the optical fiber 46 may be used.

光导纤维46在传输光时,是作为光的传输路径使用的极细的玻璃纤维。 When the optical fiber 46 transmitting light, the optical glass fiber as a transmission path used for extremely fine. 以石英玻璃和塑料为材料,相对于周边部(包层)提高断面'l, 心部(芯)的折射率,由此可以使光信号不衰减便进行传输。 As quartz glass and plastics materials, with respect to the peripheral portion (cladding) improved 'l, a cross-sectional refractive index core portion (core), thereby attenuating the optical signal will not be transmitted.

光导纤维46因为是可动的,所以能够将照明光43照射在预定的位置。 Since the optical fiber 46 is movable, it is possible to irradiate the illumination light 43 at a predetermined position. 另外,光导纤维46也可以弯成曲线的形状。 Further, the optical fiber 46 can be bent into the shape of the curve. 光导纤维46可以设计为单线纤维。 Optical fiber 46 can be designed as a single-line fiber. 单线纤维的芯的直径优选为400H m或以下。 Diameter of the core of the fiber is preferably a single line 400H m or less. (遮断构件) (Shielding member)

遮断构件也可以使用能够遮断90%或以上的源于激发光源的光的材料。 Blocking member may also be capable of blocking 90% or more of the excitation light from the source material. 例如,在使用发出对人体有害的紫外线的发光元件47的情况下, For example, in the case where the issue of harmful ultraviolet light emitting element 47,

为了遮断该紫外线,可以将紫外线吸收剂用作遮断构件。 In order to block the ultraviolet rays, an ultraviolet absorber may be used as the blocking member. 另外,在输出部52设置预定的填料,也可以遮断预定的波长。 Further, the output portion 52 is provided a predetermined filler, the predetermined wavelength may be blocked.

如上所述,本发明的发光膜、发光装置、发光膜的制造方法以及发光装置的制造方法可以用于照明用光源、LED显示器、背光光源、 信号机、照明式开关、各种传感器以及各种指示器等方面。 As described above, the light emitting film of the present invention, the light emitting device, a method of manufacturing the light emitting film, and a method of manufacturing the light emitting device can be used for illumination light sources, LED displays, backlight sources, traffic signal, an illuminated switch, various sensors and various indicators and so on.

112 112

Claims (34)

1. 一种发光膜,其是用于覆盖半导体发光元件的发光膜,所述发光膜的特征在于:至少由含有发光材料的填料构件和粘结剂构件构成,所述粘结剂构件至少含有金属元素的水合氧化物。 A light emitting film, which is a film for covering a light-emitting semiconductor light emitting element, the light emitting film is characterized in that: at least composed of a binder and a filler component member comprising a light emitting material, the binder component comprising at least the hydrated oxide of a metal element.
2. 根据权利要求1所述的发光膜,其特征在于:所述发光材料为无机荧光体,所述填料构件为无机填料,所述粘结剂构件为以恒定价数的金属元素的水合氧化物为主体的无机粘结剂。 The light emitting film according to claim 1, wherein: said emissive material is an inorganic phosphor, an inorganic filler said filler member, the adhesive member is a metallic element at a constant number of pricing hydrated oxide inorganic binder as the main product.
3. 根据权利要求1所述的发光膜,其特征在于:所述发光材料为无机荧光体,所述填料构件为无机填料,所述粘结剂构件为以金属元素的水合氧化物为主体的无机粘结剂,所述金属元素的水合氧化物是IIIA族或IIIB族元素的水合氧化物。 The light emitting film according to claim 1, wherein: said emissive material is an inorganic phosphor, an inorganic filler said filler member, said adhesive member is a hydrated oxide of a metal element as a main component inorganic binder, said hydrous oxide is a hydrous oxide of a metal element or a group IIIA IIIB elements.
4. 根据权利要求3所述的发光膜,其特征在于:所述IIlA族或mB族元素含有Sc、 Y、 Gd、 Lu或B、 Al、 Ga、 In之中的至少l种。 4. The light emitting film according to claim 3, wherein: said IIlA containing group or mB elements Sc, Y, Gd, Lu, or B, and l kind among Al, Ga, In.
5. 根据权利要求1〜4的任一项所述的发光膜,其特征在于:所述粘结剂构件中含有的金属元素的水合氧化物为具有勃姆石结构或伪勃姆石结构的Al的水合氧化物。 The light emitting film according to any one of claim 1 ~ 4 claims, wherein: the hydrated oxide of a metal element contained in the binder member having a boehmite structure or a pseudo-boehmite structure hydrous oxide of Al.
6. 根据权利要求5所述的发光膜,其特征在于,所述粘结剂构件含有:铝的水合氧化物,和相对于粘结剂构件含量为0.5重量%〜50重量%的、与所述铝不同的IIIA族元素或niB族元素的水合氧化物。 The light emitting film according to claim 5, wherein said adhesive member comprises: a hydrated oxide of aluminum, and the content of the binder component with respect to 0.5 wt% ~ 50 wt%, and the hydrated oxides of different group IIIA element or elements niB said aluminum.
7. 根据权利要求1〜4的任一项所述的发光膜,其特征在于:所述粘结剂构件中含有的金属元素的水合氧化物为钇的水合氧化物。 The light emitting film according to any one of claim 1 ~ 4 claims, wherein: the hydrated oxide of a metal element contained in the binder component of a hydrous oxide of yttrium.
8. 根据权利要求7所述的发光膜,其特征在于,所述粘结剂构件含有:钇的水合氧化物,和相对于粘结剂构件含量为0.5重量%〜50重量°/。 8. The light emitting film according to claim 7, wherein said adhesive member comprising: a hydrated oxide of yttrium, and the content of the binder component with respect to 0.5 wt% ~ 50 wt ° /. 的、与所述钇不同的IIIA族元素或IIIB族元素的水合氧化物。 The hydrated oxide of the Group IIIA elements yttrium or different IIIB elements.
9. 根据权利要求5所述的发光膜,其特征在于:所述粘结剂构件含有相对于粘结剂构件含量为0.5重量°/。 9. The light emitting film according to claim 5, characterized in that: said member comprises an adhesive member with respect to the binder content of 0.5 wt ° /. 〜50重量%的氧化硼或硼酸。 ~ 50 wt% of boron oxide or boric acid.
10. 根据权利要求1〜4的任一项所述的发光膜,其特征在于:所述粘结剂构件是由含有所述水合氧化物的粒子的集合体形成交联结构、网状结构或聚合物结构的多孔体。 10. The light emitting film according to any one of claims 1 ~ 4, wherein: said adhesive member is a mass of particles containing the hydrous oxide form a crosslinked structure, a mesh structure or a polymeric structures of the porous body.
11. 根据权利要求1〜4的任一项所述的发光膜,其特征在于:所述粘结剂构件呈凝胶状,其中填充着含有所述水合氧化物的无机粒子。 11. The light emitting film according to any one of claims 1 ~ 4, wherein: said member is a gelatinous binder, wherein the inorganic filler particles comprising the hydrated oxide.
12. 根据权利要求ll所述的发光膜,其特征在于:所述发光膜的光透过率比溶胶-凝胶反应后进行烧结这一情况下的多晶体或非晶体的透过率更高。 12. The light emitting film according to claim ll, characterized in that: the ratio of light transmittance of luminescent film sol - be polycrystalline or amorphous higher transmittance in this case after the gel reaction sintering .
13. 根据权利要求1〜4的任一项所述的发光膜,其特征在于:所述粘结剂构件相对于粘结剂构件含有10重量%或以下的羟基或结晶水。 13. The light emitting film according to any one of claim 1 ~ 4 claims, wherein: said adhesive member comprises an adhesive member with respect to 10% by weight or less hydroxyl group or water of crystallization.
14. 根据权利要求1〜4的任一项所述的发光膜,其特征在于:构成所述发光膜的填料构件和粘结剂构件的重量比以填料/粘结剂计为0.05〜30。 14. The light emitting film according to any one of claim 1 ~ 4 claims, wherein: said light emitting film composed by weight of a filler and a binder component ratio filler member / binder in terms of 0.05~30.
15. —种发光装置,其具有发光元件和吸收所述发光元件发出的光的至少一部分而发光的发光层,所述发光装置的特征在于:所述发光层为权利要求1〜14的任一项所述的发光膜。 15 - light-emitting layer and the characteristic of, at least part of the light emitting device means a light emitting species, which absorb light having a light emitting element and the light emitting element is characterized in that: the light-emitting layer according to any one of claims 1~14 the light emitting film according to item.
16. 根据权利要求15所述的发光装置,其特征在于:所述发光层直接覆盖所述发光元件。 The light emitting apparatus according to claim 15, wherein: the light emitting layer to directly cover the light emitting element.
17. 根据权利要求2所述的发光膜,其特征在于:所述无机粘结剂以被覆盖的状态而被树脂所浸渍。 17. The light emitting film according to claim 2, wherein: said inorganic binder in a state of being covered with a resin to be impregnated.
18. —种发光膜的制造方法,其是至少由包含发光材料的填料构件和粘结剂构件构成的用于覆盖发光元件的发光膜的制造方法,所述制造方法的特征在于,包括以下步骤:将作为粘结剂构件的含有金属元素的金属氧垸溶胶和填料构件混合而调配料浆的步骤,将所述料浆形成为膜状的步骤,以及通过对所述形成为膜的料浆在50°C〜500°C 进行热固化、使含有所述金属元素的水合氧化物的粒子聚集在一起、 从而用由该集合粒子的结构体构成的无机粘结剂构件附载填料构件的步骤。 18. - The method of manufacturing a luminescent film, characterized in that the filler is at least composed of a binder component comprising a member and a method for manufacturing a light-emitting material covering the light emitting element of the light emitting film, the manufacturing method comprising the steps of : the formulated slurry and the step of mixing the metal oxide sol embankment member containing a metal element and a filler adhesive member, the step of a film forming slurry, and the slurry is formed by a film of carried out at 50 ° C~500 ° C heat curing, the particles comprising the hydrated oxide of a metal element together, so that the inorganic binder is composed of a structure member of the collection of particles is the step of filler-carrying member.
19. 根据权利要求18所述的发光膜的制造方法,其特征在于:所述金属氧垸溶胶为铝氧烷溶胶或钇氧垸溶胶。 19. A method of manufacturing a light emitting film according to claim 18, wherein: said metal oxide sol embankment aluminoxane yttrium oxide sol or sol embankment.
20. 根据权利要求18所述的发光膜的制造方法,其特征在于:所述无机粘结剂以被覆盖的状态而被树脂所浸渍。 20. A method of manufacturing a light emitting film according to claim 18, wherein: said inorganic binder in a state of being covered with a resin to be impregnated.
21. —种发光装置的制造方法,其是具有发光元件和根据权利要求18或19所述制造方法覆盖发光元件的至少一部分而得到的发光膜的发光装置的制造方法,所述制造方法的特征在于:在所述形成为膜状的步骤中,于热处理条件下采用所述料浆覆盖所述发光元件和/或隔开发光元件的区域,从而形成为膜状。 21. - The method of manufacturing a luminescent device, which is characterized in having a light emitting element and a method of manufacturing a light emitting device emitting film covering at least a portion of the light emitting element obtained, according to the manufacture or the method of claim 18 19 A method of producing wherein: the step of a film, employed in the formed under heat treatment conditions of the slurry to cover the light emitting element and / or spaced apart from the light emitting element region, thereby forming a film.
22. —种发光装置,其具有发光元件和承载所述发光元件的基体,所述发光装置的特征在于:所述发光元件被无机粘结剂所覆盖,所述无机粘结剂至少含有金属元素的水合氧化物,并被树脂所覆盖,所述无机粘结剂用所述树脂来浸渍,所述无机粘结剂形成覆盖所述发光元件及所述基体的至少一部分的无机粘结层。 22. - A luminous device, having a base body carrying said light emitting element and the light emitting element, the light emitting device is characterized in that: said light emitting element is covered with an inorganic binder, the inorganic binder contains at least a metal element hydrated oxide, and is covered with a resin, the inorganic binder is impregnated with the resin, the inorganic binder is formed covering the light emitting element and the inorganic layer of at least a portion of the adhesive matrix.
23. 根据权利要求22所述的发光装置,其特征在于:所述无机粘结剂通过所述树脂将所述无机粘结剂层所具有的空隙填埋起来。 23. The light-emitting device according to claim 22, wherein: said inorganic binder resin to the inorganic by said adhesive layer has voids filled up.
24. 根据权利要求22所述的发光装置,其特征在于:所述无机粘结剂通过所述树脂将所述无机粘结剂层所具有的95%或以上的空隙填埋起来。 24. The light-emitting device according to claim 22, wherein: the inorganic binder of the inorganic binder layer having a void of 95% or more by the resin filled up.
25. 根据权利要求22所述的发光装置,其特征在于:采用所述树脂覆盖所述无机粘结剂的步骤使用浇灌手段或喷涂喷雾手段,使所述无机粘结剂浸渍所述树脂。 25. The light-emitting device according to claim 22, wherein: the step of covering the inorganic binder resin employing the use of watering or spraying means spray means, so that the resin impregnating the inorganic binder.
26. 根据权利要求22〜25的任一项所述的发光装置,其特征在于: 所述无机粘结剂含有荧光体。 26. A light emitting device according to any one of claims 22~25, wherein: said inorganic binder contains a phosphor.
27. 根据权利要求22所述的发光装置,其特征在于:所述树脂形成覆盖所述无机粘结剂的至少一部分的树脂层。 27. The light-emitting device according to claim 22, wherein: a resin layer covering at least part of the inorganic binder of the resin.
28. 根据权利要求27所述的发光装置,其特征在于:所述树脂层的表面是平滑的表面。 28. The light emitting apparatus according to claim 27, wherein: a surface of the resin layer is a smooth surface.
29. 根据权利要求22所述的发光装置,其特征在于:所述树脂含有油料、凝胶以及橡胶之中的至少一种。 29. The light-emitting device according to claim 22, wherein: said resin contains at least one from among the oil, and rubber gel.
30. 根据权利要求22所述的发光装置,其特征在于:所述树脂在成型前及成型后的任一种情况下,是具有二垸基硅氧烷骨架的硅树脂。 30. The light-emitting device according to claim 22, wherein: said resin prior to molding the case, and either after molding, the silicone resin having a siloxane skeleton two embankment.
31. 根据权利要求22所述的发光装置,其特征在于:所述树脂成型前在主链上具有二甲基硅氧烷。 31. The light-emitting device according to claim 22, wherein: the resin molding having a front polydimethylsiloxane in the main chain.
32. 根据权利要求22所述的发光装置,其特征在于:所述树脂在红外光谱的键吸收强度中,树脂组成中的C一Si—O键与Si—O—Si 键的强度比为1.2/l或以上。 32. The light-emitting device according to claim 22, wherein: said resin bond absorption in the infrared spectral intensity, the intensity ratio of the resin composition C Si-O bond and a Si-O-Si bond is 1.2 / l or more.
33. —种发光装置的制造方法,其具有:将发光元件承载在基体上的第一工序;将所述发光元件用无机粘结剂覆盖的第二工序;将所述无机粘结剂用树脂覆盖的第三工序,所述制造方法的特征在于:所述第三工序使用浇灌手段或喷涂喷雾手段使所述树脂覆盖至少含有金属元素的水合氧化物的所述无机粘结剂。 33. - The method of manufacturing a luminescent device, comprising: a first step of carrying the light emitting element on a substrate; the light emitting element is covered with a second step of the inorganic binder; the inorganic binder resin a third step coverage characteristics, the manufacturing method wherein: said third means of watering or spraying step of spraying using the resin covering means comprising at least an inorganic binder of hydrous oxide of a metal element.
34. 根据权利要求33所述的发光装置的制造方法,其特征在于: 所述第三工序是在真空中进行浸渍。 34. The method of manufacturing the light emitting device according to claim 33, characterized in that: said third step is immersed in vacuo.
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