JP4187033B2 - Light emitting device - Google Patents

Description

    The present invention relates to a light emitting device using a light emitting element and a fluorescent material that can be used for a signal lamp, illumination, a display, an indicator, various light sources, and the like. An object of the present invention is to provide a light emitting device capable of emitting white light or the like using a fluorescent material.

Today, various light emitting diodes and laser diodes have been developed as semiconductor light emitting devices. Such a semiconductor light emitting device takes advantage of low voltage drive, small size, light weight, thin shape, long life, high reliability and low power consumption, and as a light source such as a display, backlight, indicator, etc. Some are being replaced.
In particular, a light emitting element that can emit light efficiently from the ultraviolet region to the short wavelength side of visible light has been developed using a nitride semiconductor. Blue and green LEDs having a quantum well structure having a nitride semiconductor (for example, InGaN mixed crystal) as an active (light emitting) layer and having 10 candela or more are being developed and commercialized.

By combining such light from the LED chip 1 and a fluorescent material that is excited and emits fluorescence, it is possible to display mixed colors including white. Examples include Patent Documents 1, 2, and 3.
More specifically, the light emitting element emits blue light having a relatively short wavelength among ultraviolet rays and visible light. A light emitting diode that emits visible light having a longer wavelength than light emitted from the light emitting element by exciting the fluorescent material by light emitted from the light emitting element. When a part of light from the light emitting element is transmitted and used, there is an advantage that the structure itself can be simplified and the output can be easily improved.

On the other hand, when a light emitting element that emits ultraviolet light is used, white or the like is emitted by combining fluorescent materials capable of emitting RGB (red, green, and blue). Since only light emitted from the fluorescent material is basically used, color adjustment can be performed relatively easily. In particular, when a wavelength in the ultraviolet region is used, the chromaticity is absorbed only by the emission color of the fluorescent material by absorbing variations such as the wavelength of the semiconductor light emitting device as compared with the case where a semiconductor light emitting device emitting visible light is used. Since it can be determined, mass productivity can be improved.
JP 05-152609 A JP 09-153645 A Japanese Patent Laid-Open No. 10-242513

However, in order to utilize the advantages of the semiconductor light emitting element and to be used as a light source including lighting, the conventional light emitting device is not sufficient, and further improvement in luminance and improvement in mass productivity are required.
Especially for fluorescent materials that can emit blue and green light, they can be excited in the long wavelength ultraviolet region and the short wavelength region of visible light, and can emit red light with sufficient brightness compared to other blue and green light. The fluorescent material is not known. For this reason, the luminescent color obtained from the three primary colors only from the fluorescent material has few reddish components, and the red color illuminated with such a luminescent color is hardly reproduced and is perceived as a dull color. On the other hand, if the mixing ratio of the red fluorescent material is increased so as to improve the color rendering, the relative luminance decreases.

In addition, when the excitation spectrum curve of the fluorescent substance itself changes greatly with respect to the emission spectrum from the light-emitting element, a slight variation in the excitation spectrum emitted from each light-emitting element when combined with a light-emitting element with a wide emission peak is fluorescent. Even if the emission spectrum emitted from the light emitting element is visible light having an ultraviolet region or very low visibility, color variations may occur between the light emitting devices.
Further, when the excitation light spectrum width of the fluorescent material is narrow, the reliability of the light emitting device is impaired by light in the ultraviolet or near ultraviolet region that is not absorbed by the fluorescent material among the light emitted from the light emitting element. . When an organic member is used for a sealing member for protecting a light emitting element, a binder member of a fluorescent material, or a package containing the light emitting element, these organic members are deteriorated and colored by light that is not absorbed by the fluorescent material. As a result, the output decreases and the color shift occurs with the progress of use.
Moreover, in order to improve mass productivity, it is required that various desired colors can be realized by adjusting the composition of one fluorescent substance.

  Accordingly, an object of the present invention is to solve the above-described problems, and to provide a light-emitting device that has extremely little reduction in light emission output and color misregistration and is excellent in color rendering.

  The inventor of the present invention has completed the present invention as a result of intensive studies to achieve this object.

The light-emitting device of the present invention includes a semiconductor light-emitting element, a first fluorescent material that converts at least a part of an emission spectrum from the semiconductor light-emitting element, and any emission spectrum of the semiconductor light-emitting element and the first fluorescent material. A second fluorescent material having a different emission spectrum, and a light emitting device comprising:
The semiconductor light-emitting element has an emission spectrum at least between the near-ultraviolet region and the short-wavelength visible region, and the first fluorescent substance has a general formula (M _1-xy Eu _x M ′ _y ) ₂ B ₅ O ₉ M ″ (where M is at least one selected from Mg, Ca, Ba, Sr, and M ′ is at least one selected from Mn, Fe, Cr, Sn, and 0.0001 ≦ x ≦ 0.5 and 0.0001 ≦ y ≦ 0.5. M ″ has at least one selected from halogen elements of F, Cl, Br, and I.) It is a metal borate phosphor, and the second fluorescent material is excited by light emitted from the first fluorescent material, and is emitted from the light emitted from the first fluorescent material and the second fluorescent material. It is characterized by a complementary color relationship with the emitted light To.

In the light-emitting device according to the present invention, the second fluorescent substance,
(A) a nitrogen-containing CaO—Al ₂ O ₃ —SiO ₂ phosphor activated with Eu and / or Cr ,
(B) M _x Si _y N _z : Eu (where M has at least one selected from Mg, Ca, Ba, Sr and Zn, and z = 2 / 3x + 4 / 3y).
_{(C) (Y z Gd 1} -z) 3 Al 5 O 12: Ce ( where, 0 <z ≦ 1),
(D) (Re _1-a Sm _a ) ₃ Re ′ ₅ O ₁₂ : Ce (where 0 ≦ a <1, 0 ≦ b ≦ 1, Re is at least one selected from Y, Gd, La, Sc) , Re ′ is at least one selected from Al, Ga, and In.)
It may be at least one selected from the group consisting of

In the light emitting device of the present invention, in addition to the first and second fluorescent materials,
(A) Alkaline earth halogen apatite phosphor activated by Eu or Eu and Mn ((Sr, Ca, Ba, Mg, Zn) ₅ (PO ₄ ) ₃ (F, Cl, Br): Eu, Mn),
_{(B) SrAl 2 O 4:} Eu, Sr 4 Al 14 O 25: Eu, Mn, CaAl 2 O 4: Eu, Mn, BaMg 2 Al 16 O 27: Eu, BaMg 2 Al 16 O 27: Eu, Mn, And an alkaline earth metal aluminate-based phosphor selected from the group consisting of BaMgAl ₁₀ O ₁₇ : Eu, Mn,
(C) Nitrogen-containing CaO—Al ₂ O ₃ —SiO ₂ phosphor (oxynitride fluorescent glass) activated with Eu and / or Cr,
(D) MxSiyNz: Eu (where M has at least one selected from Mg, Ca, Ba, Sr, Zn, and z = 2 / 3x + 4 / 3y).
(E) an Eu-activated rare earth oxysulfide phosphor selected from the group consisting of La ₂ O ₂ S: Eu, Y ₂ O ₂ S: Eu, and Gd ₂ O ₂ S: Eu,
(F) (Sr, Ca, Ba, Mg) ₅ (PO ₄ ) ₃ Cl: Eu,
(G) ZnS: Cu,
(H) Zn ₂ GeO ₄ : Mn,
(I) (Sr, Ca, Ba, Mg) Ga ₂ S ₄ : Eu, and (j) (Sr, Ca, Ba, Mg) ₂ Si ₅ N: Eu)
It may have at least one fluorescent substance selected from the group consisting of

  The specific configuration of the present invention will be described in detail below with reference to FIG. A surface mount type light emitting device as shown in FIG. 2 is formed. As the light emitting element, the LED chip 1 uses a nitride semiconductor light emitting element having an InGaN semiconductor with an emission peak wavelength of about 400 nm as the light emitting layer as shown in FIG. 6B. As a more specific LED element structure, an n-type GaN layer that is an undoped nitride semiconductor on a sapphire substrate, a GaN layer that is formed with an Si-doped n-type electrode and becomes an n-type contact layer, and an undoped nitride semiconductor A single quantum well structure includes an n-type GaN layer, an n-type AlGaN layer that is a nitride semiconductor, and then an InGaN layer that constitutes a light-emitting layer. An AlGaN layer as a p-type cladding layer doped with Mg and a GaN layer as a p-type contact layer doped with Mg are sequentially stacked on the light emitting layer (note that the GaN layer is formed on the sapphire substrate at a low temperature. (The p-type semiconductor is annealed at 400 ° C. or higher after the film formation.) The surface of the p-type contact layer and the n-type contact layer is exposed by etching on the same surface on the nitride semiconductor lamination side on the sapphire substrate. An n-electrode is formed in a strip shape on the exposed n-type contact layer, and a translucent p-electrode made of a metal thin film is formed on almost the entire surface of the p-type contact layer that remains without being cut. A pedestal electrode is formed on the p-electrode in parallel with the n-electrode by sputtering.

  Next, the light emitting element chip 1 is mounted on an iron package having a thin part and a thick part. The package has a concave portion which is a thin portion at the center portion, and a Kovar lead electrode 3 whose surface is Ni / Au plated is integrally formed on a thick portion extending around the concave portion via an insulating member 2. It is fixed to. The bottom surface of the concave portion of the thin portion and the bottom surface of the lead electrode 3 are located on substantially the same plane, and both are designed to be able to contact the mounting substrate. The LED chip 1 is die-bonded with an Ag—Sn alloy in the recess. Thereby, the heat | fever emitted from LED chip 1 at the time of lighting can be efficiently radiated | emitted from the thin part of the said recessed part bottom face to the mounting substrate side. Each electrode of the LED chip 1 is connected to the main surface of the lead electrode 3 by an Ag wire 4 to be electrically connected.

Next, an alkaline earth metal chlorate phosphor 8 activated with Eu containing Mn on the surface of the LED chip 1 and the inner wall of the recess (Sr _0.90 Eu _0.05 Mn _0.05 ) ₂ B ₅ A continuous color conversion layer having O ₉ Cl and SiO ₂ is formed by spray coating. Here, a method for forming the color conversion layer will be described in detail.

Step 1.
Although methyl silicate, ethyl silicate, N-propyl silicate, and N-butyl silicate can be used as the alkyl silicate, a colorless and transparent oligomer liquid obtained by condensing ethyl silicate containing 40 wt% of SiO ₂ is used in this embodiment. . In addition, ethyl silicate is used that has been made into a sol by reacting with water in the presence of a catalyst in advance to cause a hydrolysis reaction.
First, a coating solution is prepared by stirring a solution in which sol-form ethylsilicate, ethylene glycol, and fluorescent substance 8 are mixed at a weight ratio of 1: 1: 1. Here, since sol-like ethylsilicate is easy to dry, it is preferable to prevent gelation by mixing with a high boiling point (100 ° C. to 200 ° C.) organic solvent such as butanol or ethylene glycol. When mixed with a high-boiling organic solvent in this way, clogging of the nozzle tip due to gelation of the sol-like ethyl silicate can be prevented and work efficiency can be improved.

Step 2.
The coating liquid is placed in a container, and the coating liquid is conveyed from the container to the nozzle by a circulation pump. The flow rate of the coating solution is adjusted by a valve. Here, the mist-like coating liquid ejected from the nozzle is sprayed while being rotated in a mist-like and spiral manner. Specifically, the spray spreads in a conical shape in the vicinity of the nozzle, and spreads in a cylindrical shape as the distance from the nozzle increases. As a result, the upper surface, side surfaces, and corners of the light emitting element can be covered with a continuous color conversion layer in which the film thickness is substantially equal and the fluorescent material 8 is uniformly dispersed, thereby improving color unevenness. be able to. In the color conversion layer, the fluorescent material 8 is preferably a single particle layer in which the fluorescent material particles 8 are arranged in parallel, thereby improving the light extraction efficiency. In this embodiment, the distance from the upper surface of the light emitting element to the lower end of the nozzle is set to 40 to 50 mm so that the surface of the light emitting element is placed in a state where the spray spreads in a columnar shape, and the coating liquid and gas are emitted. A continuous color conversion layer having a substantially uniform film thickness can be formed by spraying on the upper surface, side surfaces and corners of the element, and further on the in-recess plane.

  Moreover, the said process is performed in the state which heated the place to apply | coat. As a result, the ethanol or solvent generated by the sol-formation of ethyl silicate can be instantaneously blown onto the light emitting element. Accordingly, the color conversion layer can be provided without adversely affecting the light emitting element. Specifically, in a state where the package is placed on a heated heater, the coating liquid and gas are sprayed onto the upper surface, side surfaces and corners of the light emitting element, and further on the plane in the recess. It is preferable that the temperature of the heater is adjusted to a temperature of 50 ° C. or higher and 300 ° C. or lower.

Step 3.
Next, it is allowed to stand at room temperature (25 ° C.), the sol-form ethylsilicate is reacted with moisture in the air, and the fluorescent substance 8 is fixed by SiO ₂ .

Step 4.
Next, it is dried at a temperature of 300 ° C. for 2 hours. When a nitride-based light emitting device is placed at a temperature of 350 ° C. or higher, the performance as the light emitting device is degraded. Therefore, an alkyl silicate that can be fixed to the surface of the light emitting device at a temperature of 300 ° C. It can be preferably used as a fixing agent.
In this way, after the moisture in the package recess to which the fluorescent material 8 has been applied is sufficiently removed, it is hermetically sealed with a Kovar lid provided with a light extraction portion made of glass at the center, and seam welding is performed. In the present embodiment, the fluorescent material 8 is fixed in the vicinity of the LED chip 1, but may be applied to the back surface or the main surface of the light extraction portion. As a result, the distance between the fluorescent material 8 and the light emitting element can be kept constant, and the reliability of the light emitting device can be maintained even when the fluorescent material 8 that is relatively weak against heat is used.

  The light emitting device thus formed can be a light emitting diode capable of emitting white light with high luminance. An emission spectrum of the light emitting device is shown in FIG. As a result, it is possible to obtain a light emitting device that is extremely easy to adjust chromaticity and has excellent mass productivity and reliability. Hereafter, each structure of this invention is explained in full detail.

<Light emitting element 1>
In the present invention, the light emitting element 1 has a light emitting layer capable of emitting a light emission wavelength capable of exciting the fluorescent substance 8 used together. Examples of such a semiconductor light emitting device include various semiconductors such as ZnSe and GaN, but a nitride semiconductor capable of efficiently exciting the fluorescent material 8 and capable of emitting a short wavelength (In _X Al _Y Ga _1-XY N , 0 ≦ X, 0 ≦ Y, X + Y ≦ 1). If desired, the nitride semiconductor may contain boron or phosphorus. Examples of the semiconductor structure include a homostructure having a MIS junction, a PIN junction, and a pn junction, a heterostructure, and a double heterostructure. Various emission wavelengths can be selected depending on the material of the semiconductor layer and the degree of mixed crystal. In addition, a single quantum well structure or a multiple quantum well structure in which the semiconductor active layer is formed in a thin film in which a quantum effect is generated can be used.
When a nitride semiconductor is used, materials such as sapphire, spinel, SiC, Si, ZnO, and GaN are preferably used for the semiconductor substrate. In order to form a nitride semiconductor with good crystallinity with high productivity, it is preferable to use a sapphire substrate. A nitride semiconductor can be formed on the sapphire substrate by MOCVD or the like. A buffer layer made of GaN, AlN, GaAIN or the like is formed on the sapphire substrate, and a nitride semiconductor having a pn junction is formed thereon.

As an example of a light emitting device having a pn junction using a nitride semiconductor, a first contact layer formed of n-type gallium nitride, a first cladding layer formed of n-type aluminum nitride / gallium, and a nitride layer on a buffer layer Examples include a double hetero structure in which an active layer formed of indium gallium, a second cladding layer formed of p-type aluminum nitride / gallium, and a second contact layer formed of p-type gallium nitride are sequentially stacked.
Nitride semiconductors exhibit n-type conductivity without being doped with impurities. When forming a desired n-type nitride semiconductor, for example, to improve luminous efficiency, it is preferable to appropriately introduce Si, Ge, Se, Te, C, etc. as an n-type dopant. On the other hand, when forming a p-type nitride semiconductor, the p-type dopants such as Zn, Mg, Be, Ca, Sr, and Ba are doped. Since nitride semiconductors are not easily converted to p-type by simply doping with a p-type dopant, it is preferable to reduce resistance by heating in a furnace or plasma irradiation after introducing the p-type dopant. After the electrodes are formed, the light emitting element 1 made of a nitride semiconductor can be formed by cutting the semiconductor wafer into chips.

  In the present invention, a fluorescent element that uses a light-emitting element having a main emission wavelength between the near-ultraviolet region and the short-wavelength visible region, and can absorb part of light from the light-emitting element and emit other wavelengths. By combining with the substance 8, a color conversion type light emitting device with less uneven color tone is formed. Here, when binding the fluorescent material 8 to a light emitting device, it is preferable to use a resin that is relatively resistant to ultraviolet rays, glass that is an inorganic substance, or the like.

<Metal package 5>
The metal package 5 used in the light-emitting device of the present embodiment includes a thin-walled concave portion that houses the light-emitting element and a thick-walled portion where the lead electrode 3 is disposed. The bottom surface of the recess and the bottom surface of the lead electrode 3 are substantially on the same plane.
In the light emitting device, the metal package 5 is preferably formed to be thin in consideration of the heat dissipation of the heat generated from the light emitting element 1 and the miniaturization of the package. On the other hand, in order to alleviate the difference in coefficient of thermal expansion between the metal of the package material and the insulating member 2 adjacent to the metal and to improve the reliability, it is necessary to enlarge the respective contact surfaces. It is preferable to be formed thick. Therefore, in the present invention, a highly reliable light emitting device is formed by using a metal package having a thin portion where the light emitting element is disposed and a thick portion where the lead electrode 3 is fixed.

(Fluorescent substance 8)
The fluorescent substance 8 used in the light emitting device of the present invention can emit light efficiently by the emission spectrum from the semiconductor light emitting element. The fluorescent substance 8 preferably has an excitation region in at least the ultraviolet region. Further, the fluorescent material 8 absorbs at least a part of the emission spectrum in the ultraviolet region having a main emission wavelength longer than 360 nm from the semiconductor light emitting device, and a red light emitting activator is present on the base of the fluorescent material emitting blue light. It is added. As such a specific fluorescent substance 8, for example, an alkaline earth metal borate fluorescent substance containing at least Mn as an activator of red light emission in a matrix of a phosphor activated with Eu showing blue light emission. 8 is mentioned.

This fluorescent substance 8 can be obtained by the following method. A predetermined amount of an oxide of constituent elements of the fluorescent substance 8 or various compounds that can be converted into oxides by thermal decomposition and ammonium chloride are weighed and mixed with a ball mill or the like, and then put into a crucible and reduced in an atmosphere of N ₂ and H ₂ . Baked at a temperature of 500 to 1000 ° C. for 3 to 7 hours. The obtained fired product can be pulverized wet, sieved, dehydrated and dried to obtain a powder of an alkaline earth metal borate phosphor.

When represented by ((M _1-xy Eu _x M ′ _y ) ₂ B ₅ O ₉ M ″ as an alkaline earth metal halogen borate phosphor, where M is selected from Mg, Ca, Ba, and Sr Having at least one, M ′ is a red light-emitting activator, and has at least one selected from Mn, Fe, Cr, Sn, 0.0001 ≦ x ≦ 0.5, 0.0001 ≦ y ≦ 0.5. M ″ has at least one selected from the halogen elements F, Cl, Br, and I.), x represents the composition ratio of the first activator Eu element, and is 0. 0001 ≦ x ≦ 0.5 is preferable, and when x is less than 0.0001, the emission luminance decreases, and even when x exceeds 0.5, the emission luminance tends to decrease due to concentration quenching. 005 ≦ x ≦ 0.4, more preferably 0.01 ≦ x ≦ 0.2. Indicates the composition ratio of at least one element of Mn, Fe, Cr, and Sn, preferably 0.0001 ≦ y ≦ 0.5, more preferably 0.005 ≦ y ≦ 0.4. More preferably, 0.01 ≦ y ≦ 0.3 When y exceeds 0.5, the emission luminance tends to decrease due to concentration quenching.

This fluorescent material 8 is blue to white (for example, white in a conventional color of JIS Z8110 or a color of a system color name) by excitation light in a visible region having a relatively short wavelength from the ultraviolet region (for example, the main wavelength is 440 nm or less). The light emission color of white) to red can be shown.
In particular, as shown in FIG. 6A and FIG. 6B, the average color rendering index can be obtained because the main wavelength can be efficiently emitted with high luminance by ultraviolet rays or short-wavelength visible light having a relatively long wavelength and also sufficiently contains a red component. A good color rendering property of Ra of 90 or more can also be obtained.

  FIG. 3 is a CIE chromaticity diagram showing an example of the color of light emitted by excitation at 365.0 nm of the fluorescent substance 8 used in Examples 1 to 4 of the present invention. From this figure, it can be seen that by changing the composition ratio of the fluorescent material 8 used in the present invention, the light emitted from the light emitting device can be variously changed from blue to white to red to adjust the color tone.

That is, when M is Sr, the emission color is blue due to the emission of Eu ²⁺ having a peak near 450 nm, but when the value of y is increased with M ′ of M ′, the emission color of the fluorescent substance 8 is caused by the red emission of Mn. Indicates blue-white-red emission colors. When M is Ca, the same amount of Eu and Mn is shown, but when M is Ba, the emission color changes little.

  4A shows an emission spectrum of the fluorescent material 8 used in Example 1 by 400 nm excitation, and FIG. 5A shows an excitation spectrum of the fluorescent material 8 used in Example 1 of the present invention with respect to 455 nm emission, which is 590 nm. A similar excitation spectrum can be obtained even when excited by light emission. From this figure, this fluorescent substance 8 used in the present invention is efficiently excited by a relatively short wavelength visible light (for example, 250 to 425 nm) from a long wavelength ultraviolet ray, and the emission color is the basic color name in JIS Z8110. It can be seen that it is included in the area. In addition, since this fluorescent substance 8 is efficiently excited in the entire ultraviolet region, it can be expected that it can be effectively used even for short wavelength ultraviolet rays.

FIG. 4B shows an emission spectrum of the fluorescent substance 8 used in Example 9 of the present invention by 400 nm excitation, and FIG. 5B shows an excitation spectrum of the fluorescent substance 8 used in Example 9 of the present invention with respect to 455 nm emission. The same excitation spectrum can be obtained even when excited by 590 nm emission.
Furthermore, the fluorescent material 8 used in the light emitting device of the present invention is selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, Ti, and Pr in addition to Eu as desired 1 Seeds can also be included.

  In addition, the light emitting device of the present invention is a first fluorescent material that can be excited by at least ultraviolet light emitted from a semiconductor light emitting element, and has a blue light emitting phosphor added with a red light emitting activator. In addition, a second fluorescent material having an emission spectrum different from the emission spectra of both the semiconductor light emitting element and the first fluorescent material may be used. The excitation source of the second fluorescent material may be a semiconductor light emitting device or a first fluorescent material, or both the semiconductor light emitting device and the first fluorescent material. The second fluorescent material preferably emits light between the blue region and the red region, thereby obtaining a light emitting device capable of emitting various intermediate colors.

  In addition, the first fluorescent material and the second fluorescent material may each be one type, or two or more types may be used. As a result, a combination of emission spectra is infinitely widened, and a light emitting device having excellent characteristics such as color rendering properties and light emission luminance can be obtained. Moreover, when they are complementary colors, it is possible to emit white light efficiently. In addition, when the second fluorescent material is excited by the first fluorescent material and two or more types of the first fluorescent material are used, all of the first fluorescent materials are the second fluorescent material. It does not have to be an excitation source of the fluorescent material, and any one of the first fluorescent materials only needs to excite the second fluorescent material. In addition, the first fluorescent material and the second fluorescent material may be complementary colors regardless of whether the first and second fluorescent materials are one kind or two kinds or more. Thereby, it can be set as the light-emitting device more excellent in color rendering. In addition, color unevenness can be suppressed as compared with the case where two or more of the first and second fluorescent materials are used and complementary colors are obtained. For example, when two types of first fluorescent materials are used and they are complementary colors, if one of the fluorescent materials deteriorates due to heat or the like, the color tone balance is lost and the color tone changes over time. The same applies to the case where two or more kinds of second fluorescent materials are used and they are complementary to each other.

As a specific example of the second fluorescent material, a sapphire (aluminum oxide) phosphor activated by Eu and / or Cr, which is a fluorescent material capable of absorbing blue to blue-green to green light and emitting red light, Eu And / or a nitrogen-containing CaO—Al ₂ O ₃ —SiO ₂ phosphor activated with Cr (oxynitride fluorescent glass), MxSiyNz: Eu (where M is selected from Mg, Ca, Ba, Sr, Zn) And z = 2 / 3x + 4 / 3y.) And the like. As a result, by mixing the light emitted from the first fluorescent material and the light emitted from the second fluorescent material that can be excited by the light emitted from the first fluorescent material, the red component is further reduced. Full luminescence with high color rendering properties can be obtained. Thus, white light excellent in color rendering can be preferably used for applications such as a medical lighting device and a flash in a copying machine.

As another specific example of the second fluorescent material, a general formula (Y _z Gd _1-z ) ₃ Al ₅ O ₁₂ : Ce (provided that absorbs blue to blue green to green light and can emit yellow light) , 0 <z ≦ 1) and general formula _{(Re 1-a Sm a)} 3 Re '5 O 12: Ce ( where, 0 ≦ a <1,0 ≦ b ≦ 1, Re is, Y, Gd, La, And at least one selected from Sc, Re ′ is at least one selected from Al, Ga, and In.) An yttrium-aluminum oxide-based fluorescent material photoluminescent phosphor activated by Ce be able to. This fluorescent substance can increase the excitation emission efficiency in a long wavelength region of 460 nm or more by containing Gd (gadolinium) in the crystal. As the Gd content increases, the emission peak wavelength shifts to a longer wavelength, and the entire emission wavelength also shifts to the longer wavelength side. That is, when a strong reddish emission color is required, it can be achieved by increasing the amount of Gd substitution. Furthermore, in addition to Ce, Tb, Cu, Ag, Au, Fe, Cr, Nd, Dy, Co, Ni, Ti, Eu, Pr, and the like can be contained as desired.

  Moreover, in the composition of the yttrium / aluminum / garnet phosphor having a garnet structure, the emission wavelength is shifted to the short wavelength side by replacing a part of Al with Ga. Further, by substituting part of Y in the composition with Gd, the emission wavelength is shifted to the longer wavelength side. When a part of Y is substituted with Gd, it is preferable that the substitution with Gd is less than 10%, and the Ce content (substitution) rate is 0.03 to 1.0. If the substitution with Gd is less than 20%, the green component is large and the red component is small. However, by increasing the Ce content, the red component can be supplemented and a desired color tone can be obtained without lowering the luminance. With such a composition, the temperature characteristics are good and the reliability of the light emitting diode can be improved. In addition, when a photoluminescent phosphor adjusted to have a large amount of red component is used, a light emitting device capable of emitting an intermediate color such as pink can be formed.

  Such photoluminescent phosphors use oxides or compounds that easily become oxides at high temperatures as raw materials for Y, Gd, Al, and Ce, and mix them well in a stoichiometric ratio. Get raw materials. Alternatively, a mixed raw material obtained by mixing a coprecipitation oxide obtained by firing a solution obtained by coprecipitation of a solution obtained by dissolving a rare earth element of Y, Gd, and Ce in an acid in a stoichiometric ratio with oxalic acid and aluminum oxide. Get. A suitable amount of fluoride such as barium fluoride or ammonium fluoride is mixed as a flux and packed in a crucible, and fired in air at a temperature range of 1350 to 1450 ° C. for 2 to 5 hours to obtain a fired product, and then fired. The product can be obtained by ball milling in water, washing, separating, drying and finally passing through a sieve.

In the light emitting device of the present invention, in addition to the fluorescent material, alkaline earth halogen apatite phosphor ((Sr, Ca, Ba, Mg) ₅ (PO ₄ ) ₃ (F, Cl, Br): Eu, Mn), alkaline earth metal aluminate phosphor (SrAl ₂ O ₄ : Eu, Sr ₄ Al ₁₄ O ₂₅ : Eu (Mn), CaAl ₂ O ₄ : Eu (Mn), BaMg ₂ Al ₁₆ O ₂₇ : Eu, BaMg ₂ Al ₁₆ O ₂₇ : Eu, Mn, and BaMgAl ₁₀ O ₁₇ : Nitrogen-containing CaO—Al ₂ O ₃ —SiO ₂ activated by Eu (Mn), Eu and / or Cr Phosphor (oxynitride fluorescent glass), MxSiyNz: Eu (where M has at least one selected from Mg, Ca, Ba, Sr, Zn, and z = 2 / 3x . A 4 / 3y), Eu-activated rare earth oxysulfide phosphor _{(La 2 O 2 S: Eu} , Y 2 O 2 S: Eu, and _{Gd 2 O 2 S: Eu)} , Eu -activated organic complex phosphor Bodies ((Sr, Ca, Ba, Mg) ₅ (PO ₄ ) ₃ Cl: Eu, ZnS: Cu, Zn ₂ GeO ₄ : Mn, (Sr, Ca, Ba, Mg) Ga ₂ S ₄ : Eu, and ( It is also possible to use at least one fluorescent material selected from Sr, Ca, Ba, Mg) ₂ Si ₅ N: Eu), whereby various desired emission colors can be easily obtained. .

In the light emitting device of the present invention, when a plurality of fluorescent substances are used, the plurality of fluorescent substances may be mixed and arranged, or each fluorescent substance may be stacked and arranged.
The particle size of the fluorescent material is preferably in the range of 1 μm to 100 μm, more preferably 5 μm to 50 μm. More preferably, it is 10 μm to 30 μm. A fluorescent material having a particle size smaller than 15 μm tends to form an aggregate relatively easily. Depending on the particle size range, the fluorescent material has high light absorption and conversion efficiency and a wide excitation wavelength range. Thus, by including a large particle size fluorescent material having optically excellent characteristics, light around the dominant wavelength of the light emitting element can be converted and emitted well, improving the mass productivity of the light emitting device. You can also

  Here, the particle size is a value obtained from a volume-based particle size distribution curve. The volume-based particle size distribution curve is obtained by measuring the particle size distribution by a laser diffraction / scattering method, and specifically, hexametaphosphoric acid having a concentration of 0.05% in an environment of an air temperature of 25 ° C. and a humidity of 70%. Each substance can be dispersed in a sodium aqueous solution and measured with a laser diffraction particle size distribution analyzer (SALD-2000A) in a particle size range of 0.03 μm to 700 μm. In this volume-based particle size distribution curve, the particle size value when the integrated value is 50% is referred to as the center particle size, and the center particle size of the fluorescent material used in the present invention is preferably in the range of 15 μm to 50 μm. Luminous light is obtained. Moreover, it is preferable that the fluorescent substance which has this center particle size value is contained frequently, and the frequency value is preferably 20% to 50%. By using a fluorescent material with small variations in particle size in this way, a light-emitting device having a favorable color tone with further reduced color unevenness can be obtained.

The fluorescent substance can be arranged at various places in the positional relationship with the light emitting element. That is, the light emitting element may be directly mounted on the light emitting surface side, or the light emitting element may be contained in a die bond material for die bonding to the package or a mold material for covering the light emitting element, or may be a package or a sealing member. You may apply | coat to the surface of a lid. As described above, the fluorescent substance can be directly or indirectly placed on the light emitting element.
In the light-emitting device of the present invention, the fluorescent substance can be attached with various binders such as a resin that is an organic material and glass that is an inorganic material.

  When an organic substance is used as the binder, a transparent resin excellent in weather resistance such as an epoxy resin, an acrylic resin, or a silicone resin is suitably used as a specific material. In particular, it is preferable to use a silicone resin because it is excellent in reliability and can improve the dispersibility of the fluorescent substance. When an elastomeric or gel-like member is used, a light emitting device having excellent heat stress can be obtained.

Moreover, an inorganic substance can also be used as a binder. As a specific method, a precipitation method, a sol-gel method, or the like can be used. For example, a phosphor, silanol (Si (OEt) ₃ OH), and ethanol are mixed to form a slurry. After the slurry is discharged from a nozzle, the slurry is heated at 300 ° C. for 3 hours to change the silanol to SiO ₂ . The fluorescent material can be fixed to a desired place. In particular, when the fluorescent material is attached to the window portion 7 of the lid, it is preferable to use an inorganic substance that is close to the thermal expansion coefficient of the window portion 7 because the fluorescent material can be satisfactorily adhered to the window portion.

Further, an inorganic binder can be used as a binder. The binder is a so-called low-melting glass, is a fine particle, and is preferably very stable in the binder with little absorption with respect to radiation in the ultraviolet to visible region, and was obtained by a precipitation method. Alkaline earth borates, which are fine particles, are suitable.
In addition, when attaching a fluorescent substance having a large particle size, a binder whose particle is an ultrafine powder even if the melting point is high, such as silica, alumina, or a fine-sized alkaline earth metal obtained by a precipitation method Pyrophosphate, orthophosphate, etc. are preferably used. These binders can be used alone or mixed with each other.

Here, a method of applying the binder will be described. In order to sufficiently enhance the binding effect, it is preferable to use a binder slurry that is wet pulverized in a vehicle to form a slurry. A vehicle is a high viscosity solution obtained by dissolving a small amount of a binder in an organic solvent or deionized water. For example, an organic vehicle can be obtained by adding 1 wt% of nitrocellulose as a binder to butyl acetate as an organic solvent.
A fluorescent substance is contained in the binder slurry thus obtained to prepare a coating solution. The added amount of the slurry in the coating solution can be such that the total amount of the binder in the slurry is about 1 to 3% by weight with respect to the amount of the fluorescent substance in the coating solution. In order to suppress a decrease in the luminous flux maintenance factor, a method with a small amount of binder is preferred. Such a coating solution is applied to the back surface of the window portion. After that, hot air or hot air is blown to dry. Finally, baking is performed at a temperature of 400 ° C. to 700 ° C., and the vehicle is scattered to adhere the fluorescent material layer to the desired place with a binder.

<Diffusion agent>
Furthermore, in this invention, you may contain a diffusing agent with said fluorescent substance in said color conversion member. Specific examples of the diffusing agent include barium titanate, titanium oxide, aluminum oxide, silicon oxide, light or heavy calcium carbonate, and the like. As a result, a light emitting device having good directivity can be obtained.
Here, in this specification, the diffusing agent refers to those having a center particle diameter of 1 nm or more and less than 5 μm. A diffusing agent having a particle size of 1 μm or more and less than 5 μm is preferable because it can diffuse irregularly the light from the light emitting element and the fluorescent material, and can suppress uneven color that tends to occur when a fluorescent material having a large particle size is used. In addition, the half width of the emission spectrum can be narrowed, and a light emitting device with high color purity can be obtained. In addition, a diffusing agent having a wavelength of 1 nm or more and less than 1 μm has a low interference effect on the light wavelength from the light emitting element, but has a high transparency and can increase the resin viscosity without reducing the luminous intensity. As a result, when the color conversion member is arranged by potting or the like, it becomes possible to disperse the fluorescent substance in the resin almost uniformly in the syringe and maintain the state, and the fluorescent substance having a large particle size that is relatively difficult to handle. Even when a substance is used, it is possible to produce with good yield. Thus, the action of the diffusing agent in the present invention varies depending on the particle size range, and can be selected or combined according to the method of use.

<Filler>
Furthermore, in the present invention, the color conversion member may contain a filler in addition to the fluorescent material. The specific material is the same as that of the diffusing agent, but the diffusing agent has a central particle size different from that of the diffusing agent. When the filler having such a particle size is contained in the translucent resin, the chromaticity variation of the light emitting device is improved by the light scattering action, and the thermal shock resistance of the translucent resin can be enhanced. As a result, even when used at high temperatures, it is possible to prevent disconnection of the wire that electrically connects the light emitting element and the external electrode, separation from the bottom surface of the light emitting element and the bottom surface of the concave portion of the package, etc. with high reliability. A light emitting device is obtained. Furthermore, the fluidity of the resin can be adjusted to be constant for a long time, and a sealing member can be formed in a desired place, enabling mass production with a high yield.

  The filler preferably has a particle size and / or shape similar to that of the fluorescent material. Here, in the present specification, the similar particle size means a case where the difference in the center particle size of each particle is less than 20%, and the similar shape means a circularity representing the approximate degree of each particle size with a perfect circle. A case where the difference in the value of (circularity = perimeter length of a perfect circle equal to the projected area of the particle / perimeter length of the projected particle) is less than 20%. By using such a filler, the fluorescent material and the filler interact with each other, the fluorescent material can be favorably dispersed in the binder, and uneven color is suppressed. Furthermore, it is preferable that both the fluorescent substance and the filler have a central particle diameter of 15 μm to 50 μm, more preferably 20 μm to 50 μm. Thus, by adjusting the particle diameter, a preferable interval is provided between the particles. be able to. As a result, a light extraction path is ensured, and the directivity can be improved while suppressing a decrease in luminous intensity due to filler mixing.

  Hereinafter, the light-emitting device of the Example which concerns on this invention is explained in full detail. In addition, this invention is not limited only to the Example shown below.

Example 1.
A surface mount type light emitting device as shown in FIG. 2 is formed. The LED chip 1 uses a nitride semiconductor element having a 400 nm InAlGaN semiconductor having an emission peak in the ultraviolet region as a light emitting layer. More specifically, the LED chip 1 flows a TMG (trimethylgallium) gas, TMI (trimethylindium) gas, nitrogen gas and a dopant gas together with a carrier gas onto a cleaned sapphire substrate to form a nitride semiconductor by MOCVD. It can be formed by forming a film. A layer to be an n-type nitride semiconductor or a p-type nitride semiconductor is formed by switching between SiH ₄ and Cp ₂ Mg as the dopant gas.

  The element structure of the LED chip 1 is an n-type GaN layer that is an undoped nitride semiconductor on a sapphire substrate, a GaN layer that forms an n-type contact layer by forming an Si-doped n-type electrode, and an undoped nitride semiconductor. One set of an n-type GaN layer, an AlGaN layer containing Si serving as an n-type cladding layer, an AlInGaN layer constituting a well layer as a light emitting layer, and an AlInGaN layer serving as a barrier layer having a higher Al content than the well layer And a multi-quantum well structure in which five sets are stacked. On the light emitting layer, an AlGaN layer as a p-type cladding layer doped with Mg, a GaN layer for increasing electrostatic withstand voltage, and a GaN layer as a p-type contact layer doped with Mg are sequentially laminated. (Note that a GaN layer is formed on the sapphire substrate at a low temperature to serve as a buffer layer. The p-type semiconductor is annealed at 400 ° C. or higher after film formation).

More specifically, a buffer layer made of GaN is grown at 200 ° C. on a sapphire substrate having a 2 inch φ, (0001) C plane as the main surface, and then the temperature is raised to 1050 ° C. An undoped GaN layer is grown to a thickness of 5 μm. Note that the film thickness to be grown is not limited to 5 μm, and it is desirable to grow the film thicker than the buffer layer and adjust the film thickness to 10 μm or less. Next, after the growth of the undoped GaN layer, the wafer is taken out of the reaction vessel, a striped photomask is formed on the surface of the GaN layer, and a SiO 2 having a stripe width of 15 μm and a stripe interval (window) of 5 μm is formed by a CVD apparatus. _A mask made of ₂ is formed to a thickness of 0.1 μm. After forming the mask, the wafer is set again in the reaction vessel, and undoped GaN is grown to a thickness of 10 μm at 1050 ° C. The crystal defect of the undoped GaN layer is 10 ¹⁰ / cm ² or more, but the crystal defect of the GaN layer is 10 ⁶ / cm ² or more.

Next, an n-type contact layer and an n-type gallium nitride compound semiconductor layer are formed. First, an n-type contact layer made of GaN doped with Si of 4.5 × 10 ¹⁸ / cm ³ is grown to a thickness of 2.25 μm at 1050 ° C. using silane gas as the source gas TMG, ammonia gas, and impurity gas. Let Next, the silane gas alone is stopped, TMG and ammonia gas are used at 1050 ° C., an undoped GaN layer is grown to a thickness of 75 mm, and then silane gas is added at the same temperature to add Si to 4.5 × 10 ¹⁸ / A GaN layer doped with cm ³ is grown to a thickness of 25 mm. In this manner, a pair consisting of an A layer made of 75 ア ン undoped GaN and a 25 Ｂ B layer having a Si doped GaN layer is grown. Then, 25 pairs are laminated to a thickness of 2500 mm, and an n-type gallium nitride compound semiconductor layer made of a multilayer film having a superlattice structure is grown.

  Next, a barrier layer made of undoped GaN is grown to a thickness of 250 mm, and then the temperature is raised to 800 ° C., and a well layer made of undoped InGaN is grown to a thickness of 30 mm using TMG, TMI, and ammonia. . Then, seven barrier layers and six well layers are alternately laminated in the order of barrier + well + barrier + well + ... + barrier to grow an active layer having a multiple quantum well structure with a total thickness of 1930 mm. Let

Next, a p-type layer including a p-side multilayer clad layer and a p-type contact layer is formed. First, using TMG, TMA, ammonia, Cp ₂ Mg (cyclopentadienyl magnesium) at a temperature of 1050 ° C., Mg-doped 1 × 10 ²⁰ / cm ³ doped p-type Al _0.2 Ga _0.8 N 3 nitride semiconductor layer is grown to a thickness of 40 mm, subsequently the temperature is set to 800 ° C., TMG, TMI, ammonia, Cp ₂ Mg are used, and Mg is doped with 1 × 10 ²⁰ / cm ³ _{. A} fourth nitride semiconductor layer made of ₀₃ Ga _0.97 N is grown to a thickness of 25 mm. Then, these operations are repeated, and five layers are alternately stacked in the order of 3 + 4, and finally, a third nitride semiconductor layer is grown to a thickness of 40 mm. A side multilayer clad layer is grown to a thickness of 365 mm. Subsequently, at 1050 ° C., a p-side contact layer made of p-type GaN doped with 1 × 10 ²⁰ / cm ^{3 of} Mg using TMG, ammonia, and Cp 2 Mg is grown to a thickness of 700 mm.

After completion of the reaction, the temperature is lowered to room temperature, and the wafer is annealed in a reaction vessel at 700 ° C. in a nitrogen atmosphere to further reduce the resistance of the p-type layer.
Next, the surface of each pn contact layer is exposed on the same side as the nitride semiconductor on the sapphire substrate by etching. Specifically, the wafer is taken out from the reaction vessel, a mask having a predetermined shape is formed on the surface, and etching is performed from the p-type gallium nitride compound semiconductor layer side by an RIE (reactive ion etching) apparatus, and the n-type contact layer To expose the surface.

  Positive and negative pedestal electrodes are formed on each contact layer by sputtering. A metal thin film is formed on the entire surface of the p-type nitride semiconductor as a translucent electrode, and then a pedestal electrode is formed on a part of the translucent electrode. Specifically, after etching, a light-transmitting p-electrode (Ni / Au = 60/50) having a thickness of 110 mm so as to cover almost the entire surface of the p-type layer, and a film thickness of 0.5 μm on the p-electrode. A pedestal electrode made of Au and having three extended conductor portions is formed along the side at the corner of the light emitting element. On the other hand, an n-electrode containing W and Al is formed on the surface of the n-side contact layer exposed by etching so as to face the pedestal electrode. After the scribe line is drawn on the completed semiconductor wafer, the LED chip 1 is formed by being divided by an external force.

  On the other hand, the casing of the light emitting device has a concave thin-walled portion at the center and a thick film portion extending from the thin-walled portion to the edge, and the glass 2 is inserted into the through-hole provided in the thick-walled portion. An iron package 5 in which the lead electrode 3 is inserted and fixed in an airtight manner is used. Further, the iron package has a support portion 14 on the bottom surface side of a place symmetrical to the lead electrode through the recess. The support portion can be easily formed by pressing from the main surface side of the iron package. Thereby, the stability of the package is improved, and stable optical characteristics can be obtained. The surface of the lead electrode 3 is plated with a Ni / Ag layer.

The LED chip 1 is die-bonded with an Ag—Sn alloy in the recess of the package thus configured. Next, each electrode of the die-bonded LED chip 1 and each lead electrode 3 exposed from the bottom of the package recess are electrically connected by an Ag wire 4.
Next, SrCO ₃ , H ₃ BO ₃ , Eu ₂ O ₃ , MnCO ₃ , NH ₄ Cl are used as the fluorescent material as raw materials (Sr _0.90 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ O ₉ Adjust and mix so as to have a composition ratio of Cl. However, NH ₄ Cl is preferably charged twice as much as the composition ratio (SrCO ₃ : 265.7 g, H ₃ BO ₃ : 309.1 g, Eu ₂ O ₃ : 17.6 g, MnCO ₃ : 11 0.5 g, NH ₄ Cl: 106.9 g).

The raw materials are weighed and mixed thoroughly by a dry method using a mixer such as a ball mill. This mixed raw material is packed in a crucible made of SiC, quartz, alumina or the like, heated to 1000 ° C. at 500 ° C./hr in a reducing atmosphere of N ₂ and H ₂ , and fired at a constant temperature part 1000 ° C. for 3 hours. The obtained fired product is pulverized, dispersed, sieved, separated, washed with water and dried in water to obtain the target phosphor powder 8.

  The LED chip 1 was placed on a coating solution prepared by stirring a solution in which the weight ratio of the obtained fluorescent substance 8, sol-form ethyl silicate, and ethylene glycol was mixed at a ratio of 1: 1: 1. The package 5 is spray-coated on the surface of the LED chip 1 and the inner wall of the recess of the package 5 in a state where the package 5 is placed on a heater adjusted to a temperature of 200 ° C. Once left at room temperature, the color conversion member is constituted by heating and drying at 300 ° C. for 2 hours.

Next, after the moisture in the recesses of the package 5 is sufficiently removed, the recesses are sealed with a Kovar lid 6 having a glass window 7 at the center, and seam welding is performed to form a light emitting device. . Since all the light emitting devices configured as described above are made of an inorganic material, the light emitting device has high heat dissipation and also has excellent light resistance to near vision and ultraviolet light.
The chromaticity coordinates of such a light emitting device can have a color tone of (x, y) = (0.329, 0.271). The luminous efficiency is 25.2 m / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 2 using 400 nm excitation has about 217%. In a light emitting device using a light emitting element that emits excitation light of 365 nm, the chromaticity coordinates can be (x, y) = (0.330, 0.272), and the light emission luminance is about 147%.

Comparative Example 1
Instead of the fluorescent substance of the present invention, the emission color is blue to achieve the same chromaticity _{BaMg 2 Al 16 O 27: Eu} , green _{BaMg 2 Al 16 O 27: Eu} , Mn, red _Y 2 _O 2 S : A light-emitting device is configured in the same manner as in Example 1 except that Eu is mixed so as to have the same chromaticity as that in Example 1 to be 100%.

Example 2
In the phosphor of Example 1, the composition ratio of (Sr _0.94 , Eu _0.05 , Mn _0.01 ) ₂ B ₅ O ₉ Cl was changed by changing the amounts of raw materials SrCO ₃ , MnCO ₃ and Eu ₂ O _3. When the light emitting device is formed in the same manner as in Example 1 except that adjustment and mixing are performed, a color tone with chromaticity coordinates of (x, y) = (0.210, 0.103) is obtained. The luminous efficiency is 23.9 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 2 with excitation of 400 nm is about 206%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.211, 0.105), and the light emission luminance is about 139%.

Example 3
In the fluorescent material of Example 1, the composition ratio of (Sr _0.92 , Eu _0.05 , Mn _0.03 ) ₂ B ₅ O ₉ Cl was changed by changing the amounts of raw materials SrCO ₃ , MnCO ₃ and Eu ₂ O _3. When the light emitting device is formed in the same manner as in Example 1 except that adjustment and mixing are performed, a color tone with chromaticity coordinates of (x, y) = (0.284, 0.210) is obtained. The luminous efficiency is 24.7 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 3 with excitation of 400 nm is about 213%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.285, 0.212), and the light emission luminance is about 144%.

Example 4
In the phosphor of Example 1, the composition ratio of (Sr _0.85 , Eu _0.05 , Mn _0.10 ) ₂ B ₅ O ₉ Cl was changed by changing the amounts of raw materials SrCO ₃ , MnCO ₃ and Eu ₂ O _3. If the light emitting device is formed in the same manner as in Example 1 except that adjustment and mixing are performed, a color tone with chromaticity coordinates of (x, y) = (0.374, 0.321) is obtained. The luminous efficiency is 26.1 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 4 with excitation of 400 nm is about 225%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.375, 0.323), and the light emission luminance is about 148%.

Example 5 FIG.
In the phosphor of Example 1, the composition ratio of SrCO ₃ , MnCO ₃ and Eu ₂ O ₃ (Sr _0.92 , Eu _0.03 , Mn _0.05 ) ₂ B ₅ O ₉ Cl was changed in the raw material. If the light emitting device is formed in the same manner as in Example 1 except that adjustment and mixing are performed, a color tone with chromaticity coordinates of (x, y) = (0.314, 0.263) is obtained. The luminous efficiency is 24.4 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 5 with excitation of 400 nm is about 210%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.315, 0.265), and the light emission luminance is about 140%.

Example 6
In the phosphor of Example 1, the composition ratio of (Sr _0.85 , Eu _0.10 , Mn _0.05 ) ₂ B ₅ O ₉ Cl was changed by changing the amounts of raw materials SrCO ₃ , MnCO ₃ and Eu ₂ O _3. When the light emitting device is formed in the same manner as in Example 1 except that adjustment and mixing are performed, a color tone with chromaticity coordinates of (x, y) = (0.337, 0.278) is obtained. The luminous efficiency is 25.8 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 6 with excitation of 400 nm is about 222%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.338, 0.280), and the light emission luminance is about 150%.

Example 7
Using CaCO ₃ , H ₃ BO ₃ , Eu ₂ O ₃ , MnCO ₃ , NH ₄ Cl as raw materials (Ca _0.90 , Eu _0.05 , Mn _0.05 ), the composition ratio of ₂ B ₅ O ₉ Cl is obtained. Adjust and mix as follows.
CaCO ₃ : 180.1 g, H ₃ BO ₃ : 309.1 g, Eu ₂ O ₃ : 17.6 g, MnCO ₃ : 11.5 g, NH ₄ Cl: 106.9 g
The raw materials are weighed and mixed thoroughly by a dry method using a mixer such as a ball mill. This combined raw material is packed in a crucible made of SiC, quartz, alumina or the like, heated to 1000 ° C. at 500 ° C./hr in a reducing atmosphere of N ₂ and H ₂ , and fired at a constant temperature part 1000 ° C. for 3 hours. The obtained fired product is pulverized, dispersed, sieved, separated, washed with water, and dried in water to obtain the desired phosphor powder.
When the light emitting device is formed in the same manner as in Example 1 except that this fluorescent material is used, the chromaticity coordinates can be set to (x, y) = (0.318, 0.247). The luminous efficiency is 23.5 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 7 with excitation of 400 nm is about 202%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.320, 0.250), and the light emission luminance is about 132%.
This embodiment is obtained by using CaCO ₃ instead of SrCO ₃ raw fluorescent substance in Example 1, even when using MgCO ₃ instead of SrCO ₃ as a raw material, by the same method as above (Mg _0.90 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ O ₉ Cl can be obtained, and can also be used in a light emitting device.

Example 8 FIG.
In the phosphor of Example 7, the composition of (Ca _0.94 , Eu _0.05 , Mn _0.01 ) ₂ B ₅ O ₉ Cl by changing the amounts of the raw materials CaCO ₃ , MnCO ₃ , and Eu ₂ O ₃ When the light emitting device is formed in the same manner as in Example 7 except that the ratio is adjusted and mixed, a color tone with a chromaticity coordinate of (x, y) = (0.190, 0.091) is obtained. The luminous efficiency is 21.8 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 8 with excitation of 400 nm is about 188%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.191, 0.092), and the light emission luminance is about 124%.

Example 9
In the phosphor of Example 7, the composition of (Ca _0.92 , Eu _0.05 , Mn _0.03 ) ₂ B ₅ O ₉ Cl by changing the amount of raw materials CaCO ₃ , MnCO ₃ , and Eu ₂ O ₃ When the light emitting device is formed in the same manner as in Example 7 except that the ratio is adjusted and mixed, a color tone with a chromaticity coordinate of (x, y) = (0.263, 0.193) is obtained. The luminous efficiency is 22.9 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 9 with excitation of 400 nm is about 197%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.265, 0.195), and the light emission luminance is about 139%.

Example 10
In the phosphor of Example 7, the composition of (Ca _0.85 , Eu _0.05 , Mn _0.10 ) ₂ B ₅ O ₉ Cl by changing the amounts of raw materials CaCO ₃ , MnCO ₃ , and Eu ₂ O ₃ When the light emitting device is formed in the same manner as in Example 7 except that the ratio is adjusted and mixed, a color tone with a chromaticity coordinate of (x, y) = (0.352, 0.300) is obtained. The luminous efficiency is 23.3 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 10 using 400 nm excitation has about 201%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.355, 0.302), and the light emission luminance is about 133%.

Example 11
In the phosphor of Example 7, the composition of (Ca _0.92 , Eu _0.03 , Mn _0.05 ) ₂ B ₅ O ₉ Cl by changing the amounts of raw materials CaCO ₃ , MnCO ₃ , and Eu ₂ O ₃ When the light emitting device is formed in the same manner as in Example 7 except that the ratio is adjusted and mixed, a color tone with a chromaticity coordinate of (x, y) = (0.293, 0.241) is obtained. The luminous efficiency is 22.2 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 11 with excitation of 400 nm is about 191%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.295, 0.243), and the light emission luminance is about 128%.

Example 12 FIG.
In the phosphor of Example 7, the composition of (Ca _0.85 , Eu _0.10 , Mn _0.05 ) ₂ B ₅ O ₉ Cl by changing the amounts of raw materials CaCO ₃ , MnCO ₃ , and Eu ₂ O ₃ When the light emitting device is formed in the same manner as in Example 7 except that the ratio is adjusted and mixed, a color tone with a chromaticity coordinate of (x, y) = (0.326, 0.252) is obtained. The luminous efficiency is 23.8 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 12 with excitation of 400 nm is about 205%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.328, 0.255), and the emission luminance is about 136%.

Example 13
BaCO ₃ , H ₃ BO ₃ , Eu ₂ O ₃ , MnCO ₃ , NH ₄ Cl are used as raw materials (Ba _0.90 , Eu _0.05 , Mn _0.05 ), and the composition ratio becomes ₂ B ₅ O ₉ Cl. Adjust and mix as follows.
BaCO ₃ : 355.2 g, H ₃ BO ₃ : 309.1 g, Eu ₂ O ₃ : 17.6 g, MnCO ₃ : 11.5 g, NH ₄ Cl: 106.9 g
The raw materials are weighed and mixed thoroughly by a dry method using a mixer such as a ball mill. This combined raw material is packed in a crucible made of SiC, quartz, alumina or the like, heated to 900 ° C. at 500 ° C./hr in a reducing atmosphere of N ₂ and H ₂ , and fired at 900 ° C. for 3 hours. The obtained fired product is pulverized, dispersed, sieved, separated, washed with water, and dried in water to obtain the desired phosphor powder.
When the light emitting device is formed in the same manner as in Example 1 except that this fluorescent material is used, the chromaticity coordinates can be set to (x, y) = (0.362, 0.284). The luminous efficiency is 16.8 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, it is about 145% in the light emitting device of Example 13 using 400 nm excitation. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.365, 0.287), and the light emission luminance is about 95%.

Example 14
SrCO ₃ , BaCO ₃ , CaCO ₃ , H ₃ BO ₃ , Eu ₂ O ₃ , MnCO ₃ , NH ₄ Cl were used as raw materials (Sr _0.60 , Ba _0.10 , Ca _0.20 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ O ₉ Cl The composition ratio is adjusted and mixed.
SrCO ₃ : 177.1 g, BaCO ₃ : 39.5 g, CaCO ₃ : 40.0 g, H ₃ BO ₃ : 309.1 g, Eu ₂ O ₃ : 17.6 g, MnCO ₃ : 11.5 g, NH ₄ Cl: 106.9g
The raw materials are weighed and mixed thoroughly by a dry method using a mixer such as a ball mill. This combined raw material is packed in a crucible made of SiC, quartz, alumina or the like, heated to 1000 ° C. at 500 ° C./hr in a reducing atmosphere of N ₂ and H ₂ , and fired at a constant temperature part 1000 ° C. for 3 hours. The obtained fired product is pulverized, dispersed, sieved, separated, washed with water, and dried in water to obtain the desired phosphor powder.
When a light emitting device is formed in the same manner as in Example 1 except that this fluorescent material is used, the chromaticity coordinates can be set to (x, y) = (0.324, 0.262). The luminous efficiency is 24.3 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 14 with excitation of 400 nm is about 209%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.325, 0.265), and the light emission luminance is about 141%.

In the present embodiment, a fluorescent part material in which three kinds of elements Sr, Ba, and Ca are selected as M in the general formula (M _{1 -xy} Eu _x M ′ _y ) ₂ B ₅ O ₉ M ″ is used. However, it is sufficient that at least one selected from the group of Mg, Ca, Ba, and Sr is selected, and the number of selected elements and selected elements are not limited to this. A light-emitting device can be formed by a similar method.

Example 15.
In the fluorescent material of Example 14, the amounts of SrCO ₃ , MnCO ₃ , and Eu ₂ O ₃ as raw materials were changed (Sr _0.64 , Ba _0.10 , Ca _0.20 , Eu _0.05 , Mn _{0. 01} ) When a light emitting device is formed in the same manner as in Example 14 except that the composition ratio is adjusted and mixed so as to have a composition ratio of ₂ B ₅ O ₉ Cl, the chromaticity coordinates are (x, y) = (0.203, 0 0.097) is obtained. The luminous efficiency is 22.3 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 15 using 400 nm excitation has about 192%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.204, 0.098), and the light emission luminance is about 134%.

Example 16
In the fluorescent material of Example 14, the amounts of SrCO ₃ , MnCO ₃ , and Eu ₂ O ₃ as raw materials were changed (Sr _0.62 , Ba _0.10 , Ca _0.20 , Eu _0.05 , Mn _{0. 03} ) When a light emitting device is formed in the same manner as in Example 14 except that the composition ratio is adjusted and mixed so as to be ₂ B ₅ O ₉ Cl, the chromaticity coordinates are (x, y) = (0.276, 0 . 201) is obtained. The luminous efficiency is 23.7 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 16 with excitation of 400 nm is about 204%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.278, 0.203), and the light emission luminance is about 139%.

Example 17.
In the fluorescent material of Example 14, the amounts of SrCO ₃ , MnCO ₃ , and Eu ₂ O ₃ as raw materials were changed (Sr _0.55 , Ba _0.10 , Ca _0.20 , Eu _0.05 , Mn _{0. 10} ) When the light emitting device is formed in the same manner as in Example 14 except that the composition ratio is adjusted and mixed so that the composition ratio is ₂ B ₅ O ₉ Cl, the chromaticity coordinates are (x, y) = (0.363, 0 .313) is obtained. The luminous efficiency is 25.2 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, in the light emitting device of Example 17 using 400 nm excitation, it is about 217%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.365, 0.316), and the light emission luminance is about 143%.

Example 18
In the fluorescent material of Example 14, the amounts of SrCO ₃ , MnCO ₃ , and Eu ₂ O ₃ as raw materials were changed (Sr _0.62 , Ba _0.10 , Ca _0.20 , Eu _0.03 , Mn _{0. 05} ) When the light-emitting device is formed in the same manner as in Example 14 except that the composition ratio is adjusted and mixed so as to have a composition ratio of ₂ B ₅ O ₉ Cl, the chromaticity coordinates are (x, y) = (0.317, 0). 256). The luminous efficiency is 23.0 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 18 using 400 nm excitation has about 198%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.319, 0.258), and the light emission luminance is about 131%.

Example 19.
In the fluorescent material of Example 14, the amounts of SrCO ₃ , MnCO ₃ , and Eu ₂ O ₃ were changed (Sr _0.55 , Ba _0.10 , Ca _0.20 , Eu _0.10 , Mn _{0. 05} ) When the light emitting device is formed in the same manner as in Example 14 except that the composition ratio is adjusted and mixed so that the composition ratio is ₂ B ₅ O ₉ Cl, the chromaticity coordinates are (x, y) = (0.328, 0). .269) is obtained. The luminous efficiency is 25.0 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 19 using 400 nm excitation has about 215%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.330, 0.272), and the light emission luminance is about 144%.

Example 20.
In the fluorescent material of Example 14, in addition to the raw materials SrCO ₃ , BaCO ₃ , CaCO ₃ , H ₃ BO ₃ , Eu ₂ O ₃ , MnCO ₃ , and NH ₄ Cl, SnO ₂ was used as a raw material, and (Sr _{0 .59} , Ba _0.10 , Ca _0.20 , Eu _0.05 , Mn _0.05 , Sn _0.01 ) Example except that the composition ratio is adjusted so as to be ₂ B ₅ O ₉ Cl and mixed. When the light emitting device is formed in the same manner as in 14, a color tone with a chromaticity coordinate of (x, y) = (0.322, 0.261) is obtained. The luminous efficiency is 21.8 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 20 with excitation of 400 nm is about 188%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.324, 0.263), and the light emission luminance is about 133%.

Example 21.
In the fluorescent material of Example 14, in addition to the raw materials SrCO ₃ , BaCO ₃ , CaCO ₃ , H ₃ BO ₃ , Eu ₂ O ₃ , MnCO ₃ , and NH ₄ Cl, Fe ₂ O ₃ is used as a raw material. Sr _0.59 , Ba _0.10 , Ca _0.20 , Eu _0.05 , Mn _0.05 , Fe _0.01 ) ₂ B ₅ O ₉ Cl except that the composition ratio is adjusted and mixed. When the light emitting device is formed in the same manner as in Example 14, a color tone with chromaticity coordinates of (x, y) = (0.342, 0.281) is obtained. The luminous efficiency is 21.9 lm / W when driven at 20 mA. Assuming that the emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 21 by excitation at 400 nm is about 189%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.345, 0.285), and the light emission luminance is about 121%.

Example 22.
In the fluorescent material of Example 14, in addition to the raw materials SrCO ₃ , BaCO ₃ , CaCO ₃ , H ₃ BO ₃ , Eu ₂ O ₃ , MnCO ₃ , and NH ₄ Cl, Cr ₂ O ₃ was used, and (Sr _{0 .59} , Ba _0.10 , Ca _0.20 , Eu _0.05 , Mn _0.05 , Cr _0.01 ) ₂ B ₅ O ₉ Cl, except that the composition ratio is adjusted and mixed. When the light emitting device is formed in the same manner as in FIG. 14, a color tone with a chromaticity coordinate of (x, y) = (0.343, 0.278) is obtained. The luminous efficiency is 22.3 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 22 with excitation of 400 nm is about 192%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.345, 0.280), and the light emission luminance is about 125%.

Example 23.
In the fluorescent material of Example 1, the entire amount of NH ₄ Cl as one raw material was replaced with NH ₄ Br, and the composition ratio of (Sr _0.90 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ O ₉ Br When the light emitting device is formed in the same manner as in Example 1 except that adjustment and mixing are performed, a color tone with chromaticity coordinates of (x, y) = (0.344, 0.291) is obtained. The luminous efficiency is 27.4 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, it is about 236% in the light emitting device of Example 23 using 400 nm excitation. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.345, 0.293), and the light emission luminance is about 155%.
In this embodiment, NH ₄ Br is used as a raw material for substitution of NH ₄ Cl as a raw material, but NH ₄ F or NH ₄ I can be used in the same manner as the substitution raw material.

Example 24.
In the fluorescent material of Example 1, half of NH ₄ Cl as one raw material was replaced with NH ₄ F, and (Sr _0.90 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ O ₉ Cl _{0. When} the light emitting device is formed in the same manner as in Example 1 except that the composition ratio is adjusted to ₅ F _0.5 , the chromaticity coordinates are (x, y) = (0.313, 0.255). ) Is obtained. The luminous efficiency is 23.3 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 24 with excitation of 400 nm is about 201%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.315, 0.257), and the light emission luminance is about 138%.

Example 25.
In the fluorescent material of Example 1, half of NH ₄ Cl as one raw material was replaced with NH ₄ I, and (Sr _0.90 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ O ₉ Cl _{0. When} the light emitting device is formed in the same manner as in Example 1 except that the composition ratio is adjusted to ₅ I _0.5 , the chromaticity coordinates are (x, y) = (0.327, 0.270). ) Is obtained. The luminous efficiency is 20.7 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 25 using 400 nm excitation has a value of about 178%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.329, 0.271), and the light emission luminance is about 120%.

Example 26.
In the fluorescent material of Example 1, a part of NH ₄ Cl as one raw material was replaced with NH ₄ Br and NH ₄ F, and (Sr _0.90 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ When the light emitting device is formed in the same manner as in Example 1 except that the composition ratio is adjusted to O ₉ Cl _0.4 Br _0.3 F _0.3 and mixed, the chromaticity coordinates are (x, y). = (0.326, 0.266). The luminous efficiency is 24.9 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, it is about 214% in the light emitting device of Example 26 using 400 nm excitation. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.328, 0.268), and the light emission luminance is about 144%.

Example 27.
In the fluorescent material of Example 7, the whole amount of NH ₄ Cl as one raw material was replaced with NH ₄ Br, and the composition ratio of (Ca _0.90 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ O ₉ Br When the light emitting device is formed in the same manner as in Example 7 except that adjustment and mixing are performed, a color tone with a chromaticity coordinate of (x, y) = (0.337, 0.285) is obtained. The luminous efficiency is 258 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 27 with excitation of 400 nm is about 222%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.339, 0.287), and the light emission luminance is about 147%.

Example 28.
In the fluorescent material of Example 7, half of NH ₄ Cl as one raw material was replaced with NH ₄ F, and (Ca _0.90 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ O ₉ Cl _{0. When} the light emitting device is formed in the same manner as in Example 7 except that the composition ratio is adjusted to ₅ F _0.5 , the chromaticity coordinates are (x, y) = (0.308, 0.250). ) Is obtained. The luminous efficiency is 22.1 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 28 with excitation of 400 nm is about 130%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.310, 0.252), and the light emission luminance is about 190%.

Example 29.
In the fluorescent material of Example 7, half of NH ₄ Cl as one raw material was replaced with NH ₄ I, and (Ca _0.90 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ O ₉ Cl _{0. When} the light emitting device is formed in the same manner as in Example 7 except that the composition ratio is adjusted to ₅ I _0.5 , the chromaticity coordinates are (x, y) = (0.321, 0.264). ) Is obtained. The luminous efficiency is 19.4 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 29 using 400 nm excitation has about 167%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.324, 0.266), and the light emission luminance is about 112%.

Example 30. FIG.
In the fluorescent material of Example 7, a partial amount of NH ₄ Cl as one raw material was replaced with NH ₄ Br and NH ₄ F, and (Ca _0.90 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ When the light emitting device is formed in the same manner as in Example 7 except that the composition ratio is adjusted to O ₉ Cl _0.4 Br _0.3 F _0.3 and mixed, the chromaticity coordinates are (x, y). = (0.321, 0.260) is obtained. The luminous efficiency is 23.8 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 30 with excitation of 400 nm is about 205%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.323, 0.263), and the light emission luminance is about 136%.

Example 31.
In the fluorescent material of Example 14, replacing the total amount of _NH 4 Cl is one raw material _{NH 4 Br, (Sr 0.60,} Ba 0.10, Ca 0.20, Eu 0.05, Mn 0.05 ) When a light emitting device is formed in the same manner as in Example 14 except that the composition ratio is adjusted and mixed so as to have a composition ratio of ₂ B ₅ O ₉ Br, the chromaticity coordinates are (x, y) = (0.338, 0. 286) is obtained. The luminous efficiency is 24.6 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 31 with excitation of 400 nm is about 227%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.340, 0.288), and the light emission luminance is about 149%.

Example 32.
In the phosphor of Example 14, half of NH ₄ Cl as one raw material was replaced with NH ₄ F, and (Sr _0.60 , Ba _0.10 , Ca _0.20 , Eu _0.05 , Mn _{0. 05} ) When the light emitting device is formed in the same manner as in Example 14 except that the composition ratio is adjusted and mixed so that the composition ratio is ₂ B ₅ O ₉ Cl _0.5 F _0.5 , the chromaticity coordinates are (x, y). = (0.310, 0.249) is obtained. The luminous efficiency is 22.9 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 32 using 400 nm excitation has about 197%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.312, 0.251), and the light emission luminance is about 133%.

Example 33.
In the phosphor of Example 14, half of NH ₄ Cl as one raw material was replaced with NH ₄ I, and (Sr _0.60 , Ba _0.10 , Ca _0.20 , Eu _0.05 , Mn _{0. 05} ) ₂ B ₅ O ₉ Cl _0.5 I _0.5 except that the composition ratio is adjusted and mixed, and the light emitting device is formed in the same manner as in Example 14, the chromaticity coordinates are (x, y ) = (0.320, 0.264). The luminous efficiency is 19.9 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 33 using 400 nm excitation has a wavelength of about 171%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.322, 0.266), and the light emission luminance is about 116%.

Example 34.
In the fluorescent material of Example 14, a part of NH ₄ Cl as one raw material was replaced with NH ₄ Br and NH ₄ F, and (Sr _0.60 , Ba _0.10 , Ca _0.20 , Eu _{0. 05} , Mn _0.05 ) ₂ B ₅ O ₉ Cl _0.4 Br _0.3 F _{0.3 When} the light emitting device is formed in the same manner as in Example 14 except that the composition ratio is adjusted and mixed, The chromaticity coordinates can have a color tone of (x, y) = (0.320, 0.262). The luminous efficiency is 24.3 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 34 using 400 nm excitation has about 209%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.322, 0.264), and the light emission luminance is about 139%.
In the present embodiment, a fluorescent substance material in which, in the general formula (M _1-xy Eu _x M ′ _y ) ₂ B ₅ O ₉ M ″, M ″ is selected from three elements of Cl, Br, and F is used. Although it is used, it is sufficient that at least one kind is selected from the halogen elements, and the number of selected elements and the kind of the selected elements are not limited thereto. Regardless of which element is selected, a light emitting device can be formed by the same method as in this embodiment.

Example 35.
In Example 1, the color conversion member is green with (Sr _0.90 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ O ₉ Cl phosphor and excitation light of the LED chip 1 as the second fluorescent material. When the light-emitting device is formed in the same manner as in Example 1 except that the light-emitting device is formed of a coating solution in which SrAl ₂ O ₄ : Eu phosphor that can emit light is mixed and dispersed, the chromaticity coordinates are ( A color tone of x, y) = (0.325, 0.333) is obtained. The luminous efficiency is 32.1 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 35 with excitation of 400 nm is about 242%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.323, 0.335), and the light emission luminance is about 162%.

Example 36.
In Example 4, the color conversion member emits blue-green light by the (Sr _0.85 , Eu _0.05 , Mn _0.10 ) ₂ B ₅ O ₉ Cl phosphor and the excitation light of the LED chip 1. When the light-emitting device is formed in the same manner as in Example 4 except that the light-emitting device is formed in the same manner as in Example 4 except that the Sr ₄ Al ₁₄ O ₂₅ : Eu phosphor is mixed and dispersed, the chromaticity coordinates are (x, y ) = (0.324, 0.330). The luminous efficiency is 30.8 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 36 using 400 nm excitation has a value of about 255%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.328, 0.333), and the light emission luminance is about 171%.

Example 37.
In Example 7, the color conversion member can emit green light by (Ca _0.90 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ O ₉ Cl phosphor and the excitation light of the LED chip 1. When the light emitting device is formed in the same manner as in Example 7 except that the light emitting device is formed in the same manner as in Example 7 except that the SrAl ₂ O ₄ : Eu phosphor is mixed and dispersed, the chromaticity coordinates are (x, y) = ( 0.320, 0.327) is obtained. The luminous efficiency is 31.1 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 37 with excitation of 400 nm is about 240%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.318, 0.330), and the light emission luminance is about 158%.

Example 38.
In Example 10, the color conversion member emits blue-green light by the excitation light of the (Ca _0.85 , Eu _0.05 , Mn _0.10 ) ₂ B ₅ O ₉ Cl phosphor and the LED chip 1. When the light emitting device is formed in the same manner as in Example 10 except that the light emitting device is formed in the same manner as in Example 10 except that it is formed of a coating solution in which a possible Sr ₄ Al ₁₄ O ₂₅ : Eu phosphor is mixed and dispersed, the chromaticity coordinates are (x, y ) = (0.324, 0.328). The luminous efficiency is 29.8 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 38 with excitation of 400 nm is about 239%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.324, 0.329), and the light emission luminance is about 160%.

Example 39.
In Example 14, the color conversion member comprises (Sr _0.06 , Ba _0.10 , Ca _0.20 , Eu _0.05 , Mn _0.05 ) ₂ B ₅ O ₉ Cl phosphor and the second phosphor material. As described in Example 14, except that it is formed of a coating liquid in which SrAl ₂ O ₄ : Eu phosphor capable of emitting green light by the excitation light of the LED chip 1 is mixed and dispersed. When the apparatus is formed, a color tone with chromaticity coordinates of (x, y) = (0.320, 0.327) is obtained. The luminous efficiency is 31.5 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, it is about 259% in the light emitting device of Example 39 using 400 nm excitation. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.320, 0.328), and the light emission luminance is about 169%.

Example 40.
In Example 17, the color conversion member includes (Sr _0.55 , Ba _0.10 , Ca _0.20 , Eu _0.05 , Mn _0.10 ) ₂ B ₅ O ₉ Cl phosphor, and a second phosphor material. As in Example 17, except that it is formed of a coating solution in which Sr ₄ Al ₁₄ O ₂₅ : Eu phosphor capable of emitting blue-green light by the excitation light of the LED chip 1 is mixed and dispersed. When the light emitting device is formed, the chromaticity coordinates can have a color tone of (x, y) = (0.319, 0.330). The luminous efficiency is 30.8 lm / W when driven at 20 mA. Assuming that the light emission luminance of Comparative Example 1 is 100%, the light emitting device of Example 40 using 400 nm excitation has about 256%. In the light emitting device by excitation at 365 nm, the chromaticity coordinates can be (x, y) = (0.320, 0.333), and the light emission luminance is about 167%.

Example 41.
In Example 8, the color conversion member is a first phosphor that is (Ca _0.94 , Eu _0.05 , Mn _0.01 ) ₂ B ₅ O ₉ Cl, and the first phosphor as the second phosphor material. It is formed by a coating liquid in which (Y _0.08 Gd _0.200 ) ₃ Al ₅ O ₁₂ : Ce is mixed and dispersed by being excited by light emitted from the phosphor and capable of emitting yellow light. Except for the above, when the light emitting device is formed in the same manner as in Example 8, the chromaticity coordinates can be set to (x, y) = (0.325, 0.334). The luminous efficiency is 25.8 lm / W when driven at 20 mA. In this example, the light emitting device formed by adding the second fluorescent material in Example 8 was formed. However, in the light emitting devices described in Examples 1 to 40, the color conversion member also includes the second light emitting device. The fluorescent material can be contained in the same manner.

Example 42.
In Example 41, Example 41 except that the first phosphor is (Ca _0.64 , Ba _0.10 , Sr _0.20 , Eu _0.50 , Mn _0.01 ) ₂ B ₅ O ₉ Cl. When the light emitting device is formed in the same manner as described above, a color tone with chromaticity coordinates of (x, y) = (0.323, 0.338) is obtained. The luminous efficiency is 25.7 lm / W when driven at 20 mA.

Example 43.
Example 41 except that the first phosphor is (Ca _0.64 , Ba _0.10 , Sr _0.20 , Eu _0.50 , Sn _0.01 ) ₂ B ₅ O ₉ Cl in Example 41. When the light emitting device is formed in the same manner as described above, a color tone with chromaticity coordinates of (x, y) = (0.323, 0.338) is obtained. The luminous efficiency is 23.5 lm / W when driven at 20 mA.

Example 44.
In Example 41, except that the first phosphor is (Ca _0.64 , Ba _0.10 , Sr _0.20 , Eu _0.50 , Fe _0.01 ) ₂ B ₅ O ₉ Cl When a light emitting device is formed in the same manner as in 41, a color tone with chromaticity coordinates of (x, y) = (0.322, 0.333) is obtained. The luminous efficiency is 24.8 lm / W when driven at 20 mA.

Example 45.
In Example 41, except that the first phosphor is (Ca _0.64 , Ba _0.10 , Sr _0.20 , Eu _0.50 , Cr _0.01 ) ₂ B ₅ O ₉ Cl When a light emitting device is formed in the same manner as in 41, a color tone with chromaticity coordinates of (x, y) = (0.324, 0.335) is obtained. The luminous efficiency is 23.9 lm / W when driven at 20 mA.

  By employing the structure of the present invention, a light-emitting device capable of emitting light with high luminance and excellent color rendering can be obtained with high yield, taking advantage of the semiconductor light-emitting element. As a result, it can be used as a light source for lighting applications that require color rendering properties, such as medical lighting equipment and copying machine flashes. In particular, since the fluorescent material of the present invention has an excitation spectrum in which the curve near the wavelength having a wide peak half-width and a high relative light emission efficiency is substantially flat, it is caused by variations in the emission spectrum from the semiconductor light emitting device. Color unevenness can be improved. In addition, a light emitting device can be configured with a relatively simple configuration and high productivity. A long wavelength component can be extracted relatively easily and a light emitting device with excellent color rendering can be obtained. A light-emitting device that can emit white light and can produce a desired intermediate color with high luminance and can adjust a delicate color tone can also be obtained.

The example of the emission spectrum light-emitted from the light-emitting device of this invention is shown. 1 is a schematic cross-sectional view showing a surface-mounted light-emitting device that is a light-emitting device of the present invention. It is typical sectional drawing which shows the surface mount type light-emitting device which is a light-emitting device of this invention. It is a CIE chromaticity diagram showing the chromaticity of the fluorescent material used in the light emitting device of the present invention. The emission spectrum by 400 nm excitation of the fluorescent substance used for Example 1 is shown. The emission spectrum by 400 nm excitation of the fluorescent substance used for Example 9 is shown. The excitation spectrum with respect to 455 nm light emission of the fluorescent substance used for Example 1 is shown. The excitation spectrum with respect to 455 nm light emission of the fluorescent substance used for Example 9 is shown. An example of the emission spectrum of the semiconductor light-emitting element used for this invention is shown. An example of the emission spectrum of the semiconductor light-emitting element used for this invention is shown.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Light emitting element, 2 Insulating member, 3 Lead electrode, 4 Wire, 5 Metal package, 6 Lid, 7 Window part, 8 Fluorescent substance.

Claims (3)

A semiconductor light emitting device, a first fluorescent material that converts at least part of an emission spectrum from the semiconductor light emitting device, and a first light emitting spectrum that is different from any of the light emitting spectra of the semiconductor light emitting device and the first fluorescent material. A light emitting device having two fluorescent materials,
The semiconductor light emitting device has an emission spectrum at least between the near ultraviolet region and the short wavelength visible region,
It said first fluorescent material, the general formula _{(M 1-x-y Eu} x M 'y) 2 B 5 O 9 M "( although, M is at least one member selected Mg, Ca, Ba, Sr, , M ′ include at least one selected from Mn, Fe, Cr, and Sn, and 0.0001 ≦ x ≦ 0.5 and 0.0001 ≦ y ≦ 0.5. An alkaline earth metal borate phosphor represented by the following formula: at least one selected from halogen elements of Cl, Br, I.
The second fluorescent material is excited by light emitted from the first fluorescent material,
The light emitting device, wherein the light emitted from the first fluorescent material and the light emitted from the second fluorescent material have a complementary color relationship. The second fluorescent material is
(A) a nitrogen-containing CaO—Al ₂ O ₃ —SiO ₂ phosphor activated with Eu and / or Cr,
(B) M _x Si _y N _z : Eu (where M has at least one selected from Mg, Ca, Ba, Sr and Zn, and z = 2 / 3x + 4 / 3y).
_{(C) (Y z Gd 1} -z) 3 Al 5 O 12: Ce ( where, 0 <z ≦ 1),
(D) (Re _1-a Sm _a ) ₃ Re ′ ₅ O ₁₂ : Ce (where 0 ≦ a <1, 0 ≦ b ≦ 1, Re is at least one selected from Y, Gd, La, Sc) , Re ′ is at least one selected from Al, Ga, and In.)
The light emitting device according to claim 1, wherein the light emitting device is at least one selected from the group consisting of: In addition to the first and second fluorescent materials,
(A) Alkaline earth halogen apatite phosphor activated with Eu or Eu and Mn ((Sr, Ca, Ba, Mg, Zn) ₅ (PO ₄ ) ₃ (F, Cl, Br): Eu, Mn),
_{(B) SrAl 2 O 4:} Eu, Sr 4 Al 14 O 25: Eu, Mn, CaAl 2 O 4: Eu, Mn, BaMg 2 Al 16 O 27: Eu, BaMg 2 Al 16 O 27: Eu, Mn, And an alkaline earth metal aluminate-based phosphor selected from the group consisting of BaMgAl ₁₀ O ₁₇ : Eu, Mn,
(C) Nitrogen-containing CaO—Al ₂ O ₃ —SiO ₂ phosphor (oxynitride fluorescent glass) activated with Eu and / or Cr,
(D) MxSiyNz: Eu (where M has at least one selected from Mg, Ca, Ba, Sr, Zn, and z = 2 / 3x + 4 / 3y).
(E) an Eu-activated rare earth oxysulfide phosphor selected from the group consisting of La ₂ O ₂ S: Eu, Y ₂ O ₂ S: Eu, and Gd ₂ O ₂ S: Eu,
(F) (Sr, Ca, Ba, Mg) ₅ (PO ₄ ) ₃ Cl: Eu,
(G) ZnS: Cu,
(H) Zn ₂ GeO ₄ : Mn,
(I) (Sr, Ca, Ba, Mg) Ga ₂ S ₄ : Eu, and (j) (Sr, Ca, Ba, Mg) ₂ Si ₅ N: Eu)
The light emitting device according to claim 1, comprising at least one fluorescent material selected from the group consisting of:

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