1234294 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種高亮度白光半導體發光 置，特別關於一種利’用藍光或藍綠光發光二極體配 二種分別可發出黃色螢光及紅色螢光之螢光粉，以 作南免度白光發光裝置之技術。 【先前技術】 白光係為多顏色之混合光，可被人眼感覺為白 者，至少包括二種以上波長之混合光。例如，當人 同時受紅、藍、綠光的刺激時、或同時受到藍光與 光的刺激時，均可感受為白光。因此，可依照此種 理，來製作一可發出白光之半導體發光裝置。習知 白光半，導體發光裝置的製造方式主要有五種，分述 下。 第一種方式係使用以磷化鋁鎵銦（AlinGaP )、 化鎵（InGaN )與磷化鎵（GaP )為材質的三顆發 二極體，控制通過各發光二極體之電流，而使其分 發出紅、綠及藍光。將此三顆發光二極體晶粒配置 同一個燈泡（1 a m p )中，並利用透鏡將三種顏色之 加以混合而產生白光。 第二種方式係使用InGaN與AlInGaP或GaP為 質的二顆發光二極體，控制通過各發光二極體之 流，使其分別發出藍及黃綠光，然後加以混合以產 白光。以目前之技術水準而言，上述二種方式的發 裝 合 製 光 眼 黃 原 之 如 氮 光 別 於 光 材 電 生 光 6 1234294 效率可達到約2 Ο 1 m / W。 第三種方式為 1996 年曰本日亞化學 C h e m i c a 1 )公司所發展出之技術，其係以氮 光發光二極體配合受激發可發出黃光之記 型螢光粉，來製成一白光光源。目前，此種 光效率以可達到 20 lm/W以上。再者，由 式僅須使用一組發光二極體晶片，可大幅地 成本。現今其所搭配之螢光粉調製技術已辣 已有商品呈現。 第四種方式為日本住友電工（Sumitomc Industries，Ltd.)於1991年 1月所研發出 用硒化鋅（ZnSe )材料的白光發光二極體 術係先在ZnSe單晶基板上形成一 CdZnSe 電後薄膜會發出藍光，同時部分的藍光照射 而發出黃光，使藍、黃光互補色混合而形成 種法亦僅需使用單顆發光二極體晶粒，其操 2.7 V，I G aN之發光二極體的3 . 5 V要低 需使用螢光物質即可得到白光。 第五種方式係目前仍在開發中的紫外光 二極體技術。此種技術的原理是利用紫外光 體激發三種或三種以上的螢光粉發出不同 光，經混色後產生白光。 前述第一與第二種方式的共同缺點在於， 色發光二極體其中之一發生故障時，將無法 (N i c h i a 化銦鎵藍 鋁石榴石 技術的發 於此種方 降低製造 成熟’故 Electric 之一種使 。此種技 薄膜，通 在基板上 白光。此 作電壓僅 ，並且不 白光發光 發光二極 顏色的螢 當不同光 得到正常 7 1234294 的白光。此外，由於各發光二極體之正向偏壓均 同，故須設置多組控制電路，致使成本較高，此 實際應用上之不利因素。 第二與第三種方式皆利用互補色原理以產 光，其光譜波長分布之連續性不如真實的太陽夫 此色光混合後會在可見光光谱範圍（4 0 0 n m -n m )出現色彩的不均勻，導致色彩飽合度較低 然人類的眼睛可忽略此現象而只看見白色光，但 些精密度較高之光學偵檢器的感測下，例如攝影 相機等，其演色性在實質上仍偏低，亦即，物體 在還原時會產生誤差。所以，此等方式所產生之 光源只適合作為簡單的照明用途。 至於第四種方式之缺點，則在於其發光效率 lm/W，使用壽命也只有8000小時，在實用層面 量上，仍須更進一步地突破。 最後，第五種方式係採取三波段可見光組 光光源，以提高其演色性，因此須使用三種或三 上的螢光粉方可達成。欲同時利用多種螢光粉體 發出不同波長之螢光，先決條件之一乃是所選用 發光必須恰可被此等螢光粉所吸收，並且，各螢 體對此波長的光之吸收係數不可相差太多，此外 能轉換的量子效率亦需盡可能接近為佳。此等因 幅限制適用之螢光材料種類，造成選用螢光材料 難。 【發明内容】 緣是，本發明人特潛心研究並配合學理運用， 不相 皆為 生白 ，因 -700 。雖 在一 機或 色彩 白光 僅 8 的考 成白 種以 使其 之激 光粉 ，光 素大 的困 針對 8 1234294 習知技術之缺點，突破上述習知技術之限制，以降低 製作之難度，乃提出只利用二種螢光粉體搭配一發光 二極體做為激發光源即可製得一白光發光裝置之技 術。 根據本發明之白光發光裝置係包含：一可發出藍光 或藍綠光之發光二極體；一第一螢光體，其可受發光 二極體所發出之光激發，而產生主波長範圍為 5 2 0 至580nm之黃色螢光；及一第二螢光體，其可受發 光二極體所發出之光激發，而產生主波長範圍為5 8 0 至640nm之紅色螢光。如前所述，白光乃為多種色 光之混合後所形成者，故依此光學混色之原理，發光 二極體所發出之藍光或藍綠光可與黃色螢光及紅色 螢光混合，刺激人眼產生白光之視覺。 上述第一螢光體之化學式較佳係為 (YxMyCez)Al5〇12，其中 X + y = 3，且 X、y#0，0.5 > z > 0，Μ係選自铽（Tb )、錙（Lu )及镱（Yb )等 金屬元素所組成之群組，其中（YxMy)Al5012為其主體 結構，Ce為發光中心。 又，上述第二螢光體之化學式較佳係為 (M’aEub)S，其中 a + b 二 1 〜1.2，且 a、b关0，M，係 選自鈣（C a )、勰（S r )及鋇（B a )等金屬元素所組 成之群組，其中Μ ’ S為其主體結構，Eu為發光中心。 【發明特點】 本發明之白光發光裝置中，藍光或藍綠光光源乃由 具省電特性之發光二極體所產生，配合二種以適當比 9 1234294 例調配之螢光材料，經封裝後施以極低之電流即可獲 得一發光特性佳之南免度白光發光二極體。 本發明之白光發光裝置中所使用的螢光粉體，具有 藉由改變主體晶格組成即可調整其發光波長之特 性，因此可利於搭配各種適當波長之藍或藍綠光發光 二極體混合形成白光。此外，所使用的螢光粉體係利 用簡單之固態反應法即可合成，適於大量生產，極具 產業應用價值。 與習知之白光發光裝置中所使用之多種螢光材料 相較，本發明又具有下列幾項優點： 一、目前發光二極體製程上，短波長之高亮度藍光 製造較為困難，而，本發明白光發光裝置中使用之螢 光粉體所需搭配的藍光可調整至較長波長。其另一好 處在於，以較長波長之藍或藍綠光激發，發光效率可 高於波長較短之藍光（470 nm以下）。 二、本發明白光發光裝置中使用之螢光粉體的 調整光色方法，係為改變其主體晶格。相較於習知之 改變異質離子之添加量的方式，由於後者所需添加之 異質離子比例較低，極易因原料之秤取誤差產生光色 之改變。本發明所使用之螢光粉體則無此項缺點，於 製程上有較佳之穩定性。 【實施方式】 本發明之白光發光裝置係以一發光二極體做為激 發光源，並包含二種可受此激發光源激發而分別產生 不同光色之螢光體，藉由三種色光之混合以產生高亮 10 1234294 度白色光源。做為激發光源之發光二極體係為一藍光 或藍綠光發光二極體，其發光波長較佳為4 5 0至5 0 0 nm之範圍，更佳為470至5 00 nm。二種螢光體分別 為一黃色螢光體與一紅色螢光體，其受到激發光源激 發時，可分別發出主波長範圍為5 2 0至5 8 0 nm之黃 色螢光與主波長範圍為5 8 0至640 nm之紅色螢光。 黃色螢光體與紅色螢光體可與一封裝材料依不同比 例混合或組合，配合可發出藍光或藍綠光之發光二極 體，而獲得不同色溫、輝度或演色性等發光特性之白 光發光裝置。 黃色螢光體之化學式較佳係為（YxMyCez)Al5012， 其中x + y二3，且X、y參0，0_5>z>0，Μ係選自試 (Tb )、錙（Lu )及鏡（Yb )等金屬元素所組成之群 組，其中（YxMy)Al5〇12為其主體結構，Ce為發光中 心。紅色螢光體之化學式較佳係為（M’aEub)S，其中a + b = 1〜1 _2，且a、b关0，M，係選自鈣（Ca )、勰（Sr ) 及鋇（Ba)等金屬元素所組成之群組，其中M’S為 其主體結構，Eu為發光中心。上述二螢光體均利用 異質離子摻雜於其主體結構中，以做為可受外部光源 激發而發出螢光之發光中心。此外，其亦皆具一特 點，即，此等螢光體所呈現之光色乃利用微調螢光體 主體結構之元素組成，以調變化合物之晶格場 (crystal field)強度，進而改變發光中心之電子能 態分布，導致其受特定波段之光激發時，由激發態躍 1234294 遷回基態的能階差高低之不同，而發生發光波長之改 變〇 關於本發明白光發光裝置之製作方法，包括所選擇 之螢光粉與其調配及封裝之技術，以下例舉一具體實 施例之製作步驟進行說明： 一、 合成一化學式為（YxMyCez)Al5012之黃色螢光 - 體，其中x + y = 3，且X、y关0，0.5>z>0，Μ係選 自铽（Tb )、錙（Lu )及鏡（Yb )等金屬元素所組成 w 之群組。其合成方法可利用化學合成法、固體反應法 與有機金屬熱分解法等。本例中，所合成之黃色螢光 體係為（Y〇.8Tb2.2Ce〇.〇5)Al5〇12。 二、 合成一化學式為（M’aEnb)S之紅色螢光體，其 中a + b二1〜1 .2，且a、b參0，M，係選自鈣（Ca)、锶 (Sr)及鋇（Ba)等金屬元素所組成之群組。其合成方法 可利用化學合成法、固體反應法與有機金屬熱分解法 等。本例中，所合成之紅色螢光體係為（Sro.9Euo.OS。 鲁 三、 將上述二種螢光粉與環氧樹脂混合，再搭配主 波長為4 8 0 nm之藍綠光發光二極體做為激發光源， 並進行封裝而獲得一白光發光裝置。 # 第一圖顯示上述實施例之光譜圖，其中，光譜 A ' 係為測量上述實施例之白光發光裝置所獲得之發射 · 光諸。所得之白光發光裝置光譜亦可利用電腦程式將 各發光源（發光二極體與螢光體）之單獨光譜組成實 際光譜之配適情形計算出，如第一圖中，光譜B係 12 1234294 為發光二極體之光譜，光譜c係為黃色螢光體受激 發所產生之光譜，而光譜D係為紅色螢光體受激發 所產生之光譜。 如第二圖所示，於CIE色度座標圖中標示此白光 發光裝置混合色光之座標 A點，可發現其顏色確實 座落於圖中之白色區域。 雖然本發明已參照實施例及附圖說明如上，惟 其應被視為舉例性而非限制性者。本發明之範圍為由 隨附之申請專利範圍所限定而非由上述說明所限 制。所有根據本發明之精神所做成之修改與變化，均 應包含於本發明之範圍中。 【圖式簡單說明】 第一圖係為本發明白光發光裝置之實施例的發射 光譜圖。 第二圖係為第一圖之實施例的CIE色度座標圖。 131234294 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a high-brightness white-light semiconductor light-emitting device, and particularly to a light-emitting diode using blue light or blue-green light, which can emit yellow fluorescent light and The red fluorescent powder is used as the technology of white light emitting device of Nandu degree. [Previous technology] White light is a multi-color mixed light, which can be perceived by the human eye as white, and includes at least two kinds of mixed light with different wavelengths. For example, when people are stimulated by red, blue, and green light at the same time, or when they are stimulated by blue and light at the same time, they can feel white light. Therefore, a semiconductor light-emitting device capable of emitting white light can be manufactured in accordance with this principle. There are five main methods of manufacturing white light and conductive light-emitting devices, which are described below. The first method is to use three emitting diodes made of aluminum gallium indium phosphide (AlinGaP), gallium (InGaN), and gallium phosphide (GaP) as materials to control the current passing through each light emitting diode, so that It emits red, green and blue light. The three light-emitting diode crystals are arranged in the same bulb (1 a m p), and the three colors are mixed by a lens to generate white light. The second method is to use two light-emitting diodes of InGaN and AlInGaP or GaP, control the flow through each light-emitting diode to make it emit blue and yellow-green light, and then mix them to produce white light. According to the current technical level, the above two methods of combining the light-emitting eyes with yellow light, such as nitrogen light, are different from light-emitting materials. 6 1234294 The efficiency can reach about 205 m / W. The third method is a technology developed by Benichi Chemical Co., Ltd. in 1996. It uses a nitrogen light-emitting diode in combination with a fluorescent phosphor that emits yellow light when excited to make a white light source. At present, such light efficiency can reach more than 20 lm / W. Furthermore, since only one set of light-emitting diode chips is required, the cost can be greatly increased. Nowadays, the fluorescent powder modulation technology that it is equipped with has already been hot and has been presented. The fourth method is a white light emitting diode system developed by Sumitomc Industries, Ltd. in Japan in January 1991 using zinc selenide (ZnSe) material to first form a CdZnSe electrode on a ZnSe single crystal substrate. The rear film emits blue light, and at the same time, part of the blue light is irradiated to emit yellow light, and the complementary colors of blue and yellow light are mixed to form a method. Only a single light-emitting diode crystal is used, which operates at 2.7 V and IG aN. If the diode's 3.5 V is low, a fluorescent substance can be used to obtain white light. The fifth method is UV diode technology that is still under development. The principle of this technology is to use ultraviolet light to excite three or more kinds of phosphors to emit different light, and produce white light after color mixing. The common disadvantage of the first and second methods mentioned above is that when one of the color light-emitting diodes fails, it will not be possible (Nichia Indium Gallium Blue Aluminum Garnet technology is developed in this way to reduce manufacturing maturity, so Electric This kind of technology film, through the white light on the substrate. This operation voltage is only, and not white light emitting light emitting diode color fluorescent when the different light to obtain normal 7 1234294 white light. In addition, because each light emitting diode is positive The bias voltages are the same, so multiple sets of control circuits must be set up, resulting in higher costs. This is a disadvantageous factor in practical application. The second and third methods use the complementary color principle to produce light and the continuity of its spectral wavelength distribution. It is not as good as a real sun husband. After mixing this color light, color unevenness will appear in the visible light spectral range (400 nm -nm), resulting in low color saturation. However, human eyes can ignore this phenomenon and only see white light, but some Under the detection of a high-precision optical detector, such as a photographic camera, the color rendering is still substantially low, that is, an error occurs when the object is restored Therefore, the light source produced by these methods is only suitable for simple lighting purposes. As for the shortcomings of the fourth method, its luminous efficiency is lm / W, and its service life is only 8000 hours. Further breakthrough. Finally, the fifth method is to adopt a three-band visible light group light source to improve its color rendering. Therefore, three or three phosphors can be used to achieve this. To use multiple phosphors at the same time to emit different One of the prerequisites for wavelength fluorescence is that the selected light must be absorbed by these phosphors, and the absorption coefficients of the phosphors for this wavelength must not differ too much. In addition, the quantum efficiency can be converted. It is also necessary to be as close as possible. These types of fluorescent materials are difficult to select due to the types of fluorescent materials that are applicable. [Abstract] The reason is that the inventors have dedicated themselves to research and cooperate with scientific applications, not everything. White, due to -700. Although only 8 in a machine or color white light have been tested as white powder to make it a laser powder, the difficulty of large photons is aimed at the lack of 8 1234294 conventional technology In order to reduce the difficulty of the above-mentioned conventional technology to reduce the difficulty of production, a technology for producing a white light-emitting device by using only two kinds of fluorescent powders and a light-emitting diode as an excitation light source is proposed. The white light emitting device includes: a light emitting diode capable of emitting blue light or blue green light; and a first phosphor which can be excited by light emitted by the light emitting diode to generate a main wavelength range of 5 2 0 to 580nm yellow fluorescent light; and a second phosphor, which can be excited by the light emitted by the light-emitting diode to produce red fluorescent light with a main wavelength ranging from 580 to 640nm. As mentioned earlier, white light is It is formed by the mixing of multiple colors, so according to the principle of optical mixing, the blue or blue-green light emitted by the light-emitting diode can be mixed with yellow fluorescent light and red fluorescent light, which stimulates the human eye to produce white light vision. The chemical formula of the first phosphor is preferably (YxMyCez) Al5012, where X + y = 3, and X, y # 0, 0.5 > z > 0, and M is selected from 铽 (Tb), A group of metal elements such as lutetium (Lu) and ytterbium (Yb), where (YxMy) Al5012 is the main structure and Ce is the luminous center. In addition, the chemical formula of the second phosphor is preferably (M'aEub) S, where a + b 2 1 to 1.2, and a, b are 0, M, and is selected from calcium (C a), europium ( S r) and barium (B a) and other metal elements, where M ′S is its main structure and Eu is its light-emitting center. [Features of the invention] In the white light emitting device of the present invention, the blue or blue-green light source is generated by a light-emitting diode with power saving characteristics, and it is combined with two kinds of fluorescent materials prepared in an appropriate ratio of 9 1234294 cases. A very low current can be applied to obtain a South-free white light-emitting diode with excellent light-emitting characteristics. The fluorescent powder used in the white light emitting device of the present invention has the property that the light emitting wavelength can be adjusted by changing the composition of the host lattice, so it can be used to mix blue or blue-green light emitting diodes with various appropriate wavelengths. Forms white light. In addition, the phosphor system used can be synthesized by a simple solid state reaction method, which is suitable for mass production and has great industrial application value. Compared with the conventional fluorescent materials used in white light emitting devices, the present invention has the following advantages: 1. At present, the production of high-brightness blue light with a short wavelength is difficult in the current light-emitting diode system, and the present invention The blue light required for the fluorescent powder used in the white light emitting device can be adjusted to a longer wavelength. Another advantage is that the light emission efficiency can be higher than that of shorter blue light (below 470 nm) when excited with longer wavelength blue or blue-green light. 2. The method for adjusting the light color of the fluorescent powder used in the white light emitting device of the present invention is to change its main crystal lattice. Compared with the conventional method of changing the amount of heterogeneous ions, the latter requires a lower proportion of heterogeneous ions to be added, which is likely to cause light color changes due to the weighing error of the raw materials. The fluorescent powder used in the present invention does not have this disadvantage, and has better stability in the manufacturing process. [Embodiment] The white light emitting device of the present invention uses a light emitting diode as an excitation light source, and includes two kinds of phosphors that can be excited by the excitation light source to generate different light colors, respectively. Produces a white light source with a highlight of 10 1234294 degrees. The light emitting diode system used as the excitation light source is a blue or blue-green light emitting diode, and its light emission wavelength is preferably in the range of 450 to 500 nm, more preferably 470 to 500 nm. The two phosphors are a yellow phosphor and a red phosphor. When excited by an excitation light source, they can emit yellow fluorescent light with a main wavelength range of 5 2 0 to 5 8 0 nm and 5 8 0 to 640 nm red fluorescence. The yellow phosphor and the red phosphor can be mixed or combined with a packaging material in different proportions, and combined with a light-emitting diode that can emit blue or blue-green light, to obtain white light emission with different color temperature, brightness, or color rendering characteristics. Device. The chemical formula of the yellow phosphor is preferably (YxMyCez) Al5012, where x + y is 2 and 3, and X and y are 0, 0_5 > z > 0, and M is selected from the group consisting of Tb, Lu, and mirror. (Yb) and other metal elements, in which (YxMy) Al5012 is the main structure and Ce is the light-emitting center. The chemical formula of the red phosphor is preferably (M'aEub) S, where a + b = 1 ~ 1 _2, and a, b are 0, M, which is selected from calcium (Ca), europium (Sr), and barium (Ba) and other metal elements, where M'S is its main structure and Eu is its light-emitting center. The two phosphors mentioned above are all doped into the main structure with hetero ions as the light emitting center which can be excited by an external light source to emit fluorescence. In addition, they all have a feature that the light color presented by these phosphors is made by fine-tuning the elemental composition of the phosphor's main structure to adjust the intensity of the crystal field of the compound, thereby changing the luminescence The distribution of the energy state of the electron at the center causes it to change from the excited state transition to the ground state when the energy level of the specific wavelength band is 1234294, and the light emission wavelength changes. Regarding the manufacturing method of the white light emitting device of the present invention, Including the selected phosphor and its preparation and packaging technology, the following is a description of the manufacturing steps of a specific embodiment: 1. Synthesis of a yellow fluorescent body with the chemical formula (YxMyCez) Al5012, where x + y = 3 And X, y are 0, 0.5 > z > 0, M is selected from the group w consisting of metal elements such as thorium (Tb), thorium (Lu), and mirror (Yb). The synthesis method can be chemical synthesis method, solid reaction method and organometal thermal decomposition method. In this example, the synthesized yellow fluorescent system was (Y0.88Tb2.2Ce0.05) Al5012. 2. Synthesis of a red phosphor with the formula (M'aEnb) S, where a + b 2 1 to 1.2, and a, b reference 0, M, selected from calcium (Ca), strontium (Sr) And barium (Ba) and other metal elements. The synthesis method can use chemical synthesis method, solid reaction method and organometal thermal decomposition method. In this example, the synthesized red fluorescent system is (Sro.9Euo.OS. Lu III. Mix the two fluorescent powders described above with epoxy resin, and then match the blue-green light with a dominant wavelength of 480 nm. The polar body is used as the excitation light source and packaged to obtain a white light emitting device. # The first figure shows the spectrum diagram of the above embodiment, where the spectrum A 'is the emission and light obtained by measuring the white light emitting device of the above embodiment The obtained spectrum of the white light emitting device can also be calculated by using a computer program to fit the individual spectrums of the individual light emitting sources (light emitting diodes and phosphors) into the actual spectrum. 1234294 is the spectrum of the light-emitting diode, spectrum c is the spectrum generated by the excitation of the yellow phosphor, and spectrum D is the spectrum generated by the excitation of the red phosphor. As shown in the second figure, in the CIE color The coordinate A of the white light-emitting device is marked in coordinate graph A, and its color is indeed located in the white area in the figure. Although the present invention has been described above with reference to the embodiments and drawings, it should be regarded as an example. It is not a limitation. The scope of the present invention is defined by the scope of the accompanying patent application and not by the above description. All modifications and changes made according to the spirit of the present invention should be included in the scope of the present invention [Brief description of the drawings] The first diagram is an emission spectrum diagram of the embodiment of the white light emitting device of the present invention. The second diagram is the CIE chromaticity coordinate diagram of the embodiment of the first diagram. 13