TW200911962A - Green fluorescent materials, methods of fabricating the same and emission devices using the green fluorescent materials - Google Patents
Green fluorescent materials, methods of fabricating the same and emission devices using the green fluorescent materials Download PDFInfo
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Abstract
Description
200911962 九、發明說明： 【發明所屬之技術領域】 本發明有關於綠色發光螢光體、其製造方法以及使用 該螢光體的發光元件。 【先前技術】 發光一極體的發光效率良好且發出鮮艷的顏色的光 線°因此，可利用於各種指示器或光源。 然而，發光二極體具有良好的單色性尖峰波長，所以 作為白色系發光有困難。 因此，組合藍色發光二極體或紫外線發光二極體與螢 光物質’且藉由將來自藍色發光二極體5戈紫外線發光二極 體的光與以此光激發而變色的螢光物質的發色的混色，而 產生白色系光的技術已被揭示。例如使藍色發光二極體與 吸收來自藍色發光二極體的光而發出黃色光的螢光物質組 合，而藉由將來自藍色發光二極體的藍色發光與螢光物質 的黃色發光混色，可產生白色系的光。例#，由特許文獻 1可得知，（Y’Gd)3(Al，Ga)5〇12的組成式所知將摻入以於 YAG系氧化物母體格子中的螢光體（YAG : Ce螢光體）分散於 包圍藍色發光二極體（藍色led)的封止樹脂中的物質。 然而，以此方式製作的白色光使用於照明時，以自然 雰圍氣的紅色看到紅色系物質有困難。因此，具有呈色性 低的缺點。 因此，如特許文獻2所示，使紫外線發光二極體與藍 2138-9623-PF;Jessica 5 200911962 色、綠色、紅色螢光體組合的3波長型的白色發光元件已 被開發。紅色發光螢光體可列舉Y2〇2S:Eu^等。藍色發光營 光體可列舉BaMgAl1D〇17:Eu2+等’而綠色發光螢光體可列舉 ZnS.Cu，Al、BaMgAliQ〇i7:Eu，Mri 等。 然而’紫外線發光二極體在390nm附近具有高發光效 率的波長區域，另一方面，上述紅色、藍色以及綠色發光 螢光體在波長3 7 0nm附近的光吸收良好。因此，以此方式 製作的白色發光元件’在紫外線發光二極體的高發光效率 的波長區域的39Onm附近的光，不能高效率地吸收而發光。 因此’特許文獻3已揭示含有鈣、鎂、矽、氧且以銪 作為賦活劑的綠色發光螢光體。 因此’將此文獻揭示的綠色發光螢光體、紅色發光螢 光體、藍色發光螢光體以既定比例混合，相對於此混合的 發光體’使紫外線發光二極體組合的白色發光元件已被開 發。 但是’此文獻揭示的螢光體的發光光譜的發光尖峰的 寬度並非充分地寬廣，因此，以此方式得到的白色發光元 件的白色光，具有自然感受淡薄而呈色性低的問題。 【特許文獻1】特許第2900928號說明書 【特許文獻2】特表2000-5099 1 2號公報 【特許文獻3】特開2004-292569號公報 【發明内容】 本發明為了解決上述問題而提出。亦即，本發明提供 2138-9623-PF;Jessica 6 200911962 以i外線發光二極體或藍色發光二極體作為激發源發 光，而發光光譜的發光尖峰寬.的綠色發光螢光體及上述綠 色發光螢光體的製造方法。再者，本發明提供使用如上所 述的綠色發光螢光體而發出自然感受的光線的發光元件。 為達上述目的，本發明的第〗觀點的綠色發光螢光體 的特徵在於包括：鈣（Ca)、鎂（Mg)、氧化矽、賦活劑以及 鹵素。 再者’也可以更包括勰（Sr)與鋇（Ba)之中至少一種。 再者’上述賦活劑也可以含有銪（Eu)。 再者也了以更包括猛（Μη)，且滿足Mgi-xMnx(式中，X 滿足下列所示的數值：0 S χ<0· 3)的比例。 再者’上述南素也可以含有氯。 再者’本發明的綠色發光螢光體，也可以為（Caa、Srb、200911962 IX. Description of the Invention: TECHNICAL FIELD The present invention relates to a green light-emitting phosphor, a method of manufacturing the same, and a light-emitting element using the same. [Prior Art] The luminous efficiency of the light-emitting body is good and the light of the vivid color is emitted. Therefore, it can be utilized for various indicators or light sources. However, since the light-emitting diode has a good monochromatic peak wavelength, it is difficult to emit light as white. Therefore, the blue light-emitting diode or the ultraviolet light-emitting diode and the fluorescent substance are combined and the light which is discolored by exciting the light from the blue light-emitting diode 5 ohm ultraviolet light-emitting diode The technique of color mixing of matter and the generation of white light has been revealed. For example, the blue light-emitting diode is combined with a fluorescent substance that absorbs light from the blue light-emitting diode and emits yellow light, and the yellow light from the blue light-emitting diode is yellowed with the fluorescent substance. Luminous color mixing produces white light. Example #, from Patent Document 1, it is known that the composition formula of (Y'Gd)3(Al,Ga)5〇12 is incorporated into the phosphor of the YAG-based oxide matrix (YAG: Ce). The phosphor is dispersed in a sealing resin surrounding the blue light-emitting diode (blue LED). However, when white light produced in this manner is used for illumination, it is difficult to see the red substance in red in a natural atmosphere. Therefore, it has the disadvantage of low color rendering. Therefore, as shown in Patent Document 2, a three-wavelength type white light-emitting element in which an ultraviolet light-emitting diode is combined with a blue 2138-9623-PF; Jessica 5 200911962 color, green, and red phosphor has been developed. Examples of the red luminescent phosphor include Y2〇2S: Eu^ and the like. The blue light-emitting camp may be BaMgAl1D〇17:Eu2+ or the like, and the green light-emitting phosphor may be ZnS.Cu, Al, BaMgAliQ〇i7:Eu, Mri or the like. However, the ultraviolet light-emitting diode has a high light-emitting efficiency in the vicinity of 390 nm, and on the other hand, the red, blue, and green light-emitting phosphors have good light absorption at a wavelength of around 370 nm. Therefore, the white light-emitting element 'made in the vicinity of 39 Onm in the wavelength region of the high luminous efficiency of the ultraviolet light-emitting diode cannot be efficiently absorbed and emits light. Therefore, Patent Document 3 discloses a green light-emitting phosphor containing calcium, magnesium, barium, and oxygen as an activator. Therefore, the green light-emitting phosphor, the red light-emitting phosphor, and the blue light-emitting phosphor disclosed in this document are mixed at a predetermined ratio, and the white light-emitting element in which the ultraviolet light-emitting diode is combined with respect to the mixed light-emitting body has been developed. However, the width of the luminescence peak of the luminescence spectrum of the phosphor disclosed in this document is not sufficiently broad. Therefore, the white light of the white illuminating element obtained in this manner has a problem that the natural feeling is light and the color is low. [Patent Document 1] Japanese Patent Publication No. 2900928 [Patent Document 2] Japanese Patent Application Publication No. JP-A No. 2004-292569 [Patent Document 3] The present invention has been made to solve the above problems. That is, the present invention provides 2138-9623-PF; Jessica 6 200911962 is an green light-emitting phosphor with an external light-emitting diode or a blue light-emitting diode as an excitation source, and a light-emitting peak width of the light-emitting spectrum. A method of manufacturing a green light-emitting phosphor. Furthermore, the present invention provides a light-emitting element that emits light that is naturally felt using the green light-emitting phosphor as described above. In order to achieve the above object, the green light-emitting phosphor of the present invention is characterized by comprising calcium (Ca), magnesium (Mg), cerium oxide, an activator, and a halogen. Further, at least one of sputum (Sr) and strontium (Ba) may be further included. Further, the above-mentioned activator may contain ruthenium (Eu). Furthermore, it also includes a ratio of Mji-xMnx (where X satisfies the numerical value shown below: 0 S χ < 0·3). Furthermore, the above-mentioned Nansu may also contain chlorine. Furthermore, the green luminescent phosphor of the present invention may also be (Caa, Srb,
Bae' EUd)8Mgl-xMnxSi4〇i6Cl2(式中，a〜d滿足下列所示數值： 〇<a<l.〇s 〇^b<〇.5' 0^c<0.5' 0<d<0.2> a+b + c + d=l. 0 > x滿足下列所示數值：〇Sx<〇 3)。 再者’本發明的綠色發光螢光體也可以為發光光譜的 發光尖峰的半值寬為52nm以上、60nm以下。 再者’本發明的綠色發光螢光體也可以在波長 33 0 340nm、波長385〜3 9 0ηηι以及波長465〜475nm具有激發 光譜的尖峰。 再者為達上述目的，本發明的第2觀點之綠色發光 勞光體的製造方;4 1 万击包括：混合鈣（Ca)、鎂（Mg)、氧化矽、 賦活劑與鹵音，制仏 % Λ製作原料粉末的混合步驟；以及在加壓 ；JessicaBae' EUd) 8Mgl-xMnxSi4〇i6Cl2 (wherein a to d satisfy the following values: 〇<a<l.〇s 〇^b<〇.5' 0^c<0.5' 0<d<0.2 > a+b + c + d=l. 0 > x satisfies the following values: 〇Sx<〇3). Further, the green light-emitting phosphor of the present invention may have a half-value width of a light-emitting peak of the light-emitting spectrum of 52 nm or more and 60 nm or less. Further, the green light-emitting phosphor of the present invention may have a peak of an excitation spectrum at a wavelength of 33 0 340 nm, a wavelength of 385 to 390 ηηι, and a wavelength of 465 to 475 nm. Further, in order to achieve the above object, the green light-emitting luminous body of the second aspect of the present invention is produced; 410,000 hits include: mixed calcium (Ca), magnesium (Mg), cerium oxide, an activator, and a halogen sound.仏% Λ mixing step of making raw material powder; and under pressure; Jessica
2138-9623-PF 200911962 狀態下燒成上述原料粉末的燒成步驟。 再者’上述混合步驟也可以更增加勰（Sr)與鋇（Ba)之 中至少一種以進行混合。 再者，上述賦活劑也可以含有銪（EU)。 再者’上述混合步驟也可以更包括混合錳（Mn)，且滿 足MghMnx(式中’ X滿足下列所示的數值：χ<〇. 3)的比 例。 再者’上述_素也可以含有氯。 i 再者，上述混合步驟製作的原料粉末為（Caa、Srb、、2138-9623-PF 200911962 The firing step of firing the above raw material powder. Further, the above mixing step may further increase at least one of strontium (Sr) and barium (Ba) for mixing. Further, the above activating agent may also contain cerium (EU). Further, the above mixing step may further include mixing manganese (Mn) and satisfying the ratio of MghMnx (wherein 'X satisfies the numerical value shown below: χ < 〇. 3). Further, the above-mentioned element may also contain chlorine. i, the raw material powder produced by the above mixing step is (Caa, Srb,
Eud)8Mg1-xMnxSi4〇i6Cl2) (式中，a~d滿足下列所示數值：〇<a<1. 〇、〇gb<〇. 5、〇‘ c<0. 5、〇<d<〇· 2，a + b + c + d=l. 0 , x 滿足下列所示數值：〇 S x<〇. 3)。 再者，上述燒成步驟也可以在1.00大氣壓以上、1.50 大氣壓以下的加壓狀態下進行。 V 再者，上述燒成步驟也可以在9001：以上、1 3001：以 下的溫度下進行。 再者，上述燒成步驟也可以在混合氯氣以及氮氣的還 原環境氣體下進行。 再者其中上述燒成步驟終了後，更包括：將藉由粉 碎且混合得到的燒成物所得到的混合物，再度於加壓狀態 下再燒成此混合物的再燒成步驟。 為了上述目0，本發明的第3觀點的發光元件包括： 綠色發光螢光體；以及作為愁伞# & I &卜、π 及作马螢光體的激發光源的紫外線發 2138-9623-PF；Jessica 〇 200911962 光二極體。 為了上述目的，本發明的第4觀點的發光元件包括： 綠色發光螢光體；以及作為螢光體的激發光源的藍色發光 二極體。 再者，上述發光元件也可以更包括：紅色發光螢光體 以及藍色發光螢光體。 再者，上述發光元件也可以更包括紅色發光發光體。 「 #者’上述發光元件之中，上述紅色發光螢光體的特 % 徵在於含有 SrS:Eu、CaS:Eu、CaAlSiN3:Ell 以及 La2〇2S:Eu 之中至少一種；上述藍色發光螢光體的特徵在於含有 (Ba,Sr)MgAh〇On：Eu,Mn > (Ba, Sr, Ca, Mg)10(P〇4)6ci2：Eu ^Eud) 8Mg1-xMnxSi4〇i6Cl2) (wherein, a~d satisfies the following values: 〇<a<1. 〇, 〇gb<〇. 5, 〇' c<0. 5, 〇<d< 〇· 2,a + b + c + d=l. 0 , x satisfies the following values: 〇S x<〇. 3). Further, the calcination step may be carried out under a pressurized state of 1.00 atm or more and 1.50 atm or less. V Further, the calcination step may be carried out at a temperature of 9001: or more and 13001: or less. Further, the calcination step may be carried out under a reducing atmosphere of a mixture of chlorine gas and nitrogen gas. Further, after the completion of the calcination step, the mixture obtained by pulverizing and mixing the calcined product is further subjected to a re-firing step of re-firing the mixture under pressure. In order to achieve the above object, the light-emitting element of the third aspect of the present invention includes: a green light-emitting phosphor; and an ultraviolet light 2138-9623-PF which is an excitation light source of the umbrellas # & I &; Jessica 〇 200911962 light diode. In order to achieve the above object, a light-emitting element according to a fourth aspect of the present invention includes: a green light-emitting phosphor; and a blue light-emitting diode as an excitation light source of the phosphor. Furthermore, the light-emitting element may further include a red light-emitting phosphor and a blue light-emitting phosphor. Furthermore, the above-mentioned light-emitting element may further include a red light-emitting light-emitting body. Among the above-mentioned light-emitting elements, the red light-emitting phosphor has a characteristic value of at least one of SrS:Eu, CaS:Eu, CaAlSiN3:E11, and La2〇2S:Eu; The body is characterized by containing (Ba,Sr)MgAh〇On:Eu,Mn > (Ba, Sr, Ca, Mg)10(P〇4)6ci2:Eu ^
Sr5(P〇4)3ci:Eu 以及 ZnS:Ag 之中至少一样。 再者，上述紅色發光螢光體的特徵在於含有Sd : Eu、 CaS:Eu 以及 CaAlSiN3:Eu 至少一種。 本發明的申請是以曰本申請特願2 〇 〇 7 _ 1313 〇 4 (申請曰 《 2 〇 〇 7年5月17曰）為基礎，而包含所有此基礎申請中揭示 的内容。 【發明效果】 本發明的綠色發光螢光體的發光光譜的發光尖峰寬 廣。再者，使用本發明的綠色發光螢光體的發光元件可發 出賦予觀看者自然感受的光線。 【實施方式】 (實施例1之綠色發光螢光體） 2138-9623-PF;Jessica 9 200911962 本發明的發明人重複致力研究的結果，發現以紫外線 發光二極體或藍色發光二極體的激發源的情況’具有鈣 (Ca) '鎂（Mg)、氧化矽與賦活劑與鹵素的綠色發光螢光體 的發光光譜的發光尖峰寬廣。 首先’將本實施例的綠色發光螢光體（組成式 的激發光譜與發光光譜顯示於第 1圖’作為實施例1。激發光譜以虛線表示，發光光譜以實 線表示。 务、外至备色區域的波長3〇〇~480nm附近具有激發帶， 而分別以紫外線發光二極體以及藍色發光二極體能有效率 地發光。 發光光譜的發光尖峰在5〇5ηπι附近，而半值寬為54nm 且寬廣。 (實施例2~6之綠色發光螢光體） 其次’實施例2〜6為變更實施例1之綠色發光螢光體 (組成式（Ca〇.98Eu〇.()2)8MgSi4〇16Cl2)的 Eu 元素的濃度。 實施例2之綠色發光螢光體為組成式（Cao.snEuo.n) 8MgSl4〇lsCl2的螢光體。實施例3之綠色發光螢光體為組成 式（CaGjEuD.o+MgSL^d2的螢光體。實施例4之綠色發光 螢光體為組成式（Cai) g5Eu〇_ odWgShOuCh的螢光體。實施例 5之、4色么光發光體為組成式（cae.93EUfl.”）8MgSi4〇i6ci2的螢 光體。貫施例6之綠色發光螢光體為組成式（Cat) 3()Eu(( 1〇) 8MgSi4〇ieCl2 的營光體。 第2圖分別顯示實施例2〜6之綠色發光螢光體的激發 2138-9623-PF;Jessica 10 200911962 光譜。由實施例2至實施例6, Eu濃度依序變高，隨著Eu 元素的濃度變高，在藍色LED區域之中的激發強度會變高。 第3圖顯示分別顯示賁施例2〜6之綠色發光蟹光體的 發光光譜。由實施例2至實施例6，Eu濃度依序變高，隨 著Eu元素的濃度變高，發光波長往長波長側移動，且發光 光增也逐漸地變寬。 (貫施例7 ~ 1 0之綠色發光螢光Sr5(P〇4)3ci: at least the same as Eu and ZnS:Ag. Further, the red light-emitting phosphor is characterized by containing at least one of Sd : Eu, CaS:Eu, and CaAlSiN3:Eu. The application of the present invention is based on the application of the present application 2 〇 〇 7 _ 1313 〇 4 (application 曰 2 〇 5 May 17 曰), and includes all the contents disclosed in this basic application. [Effect of the Invention] The green light-emitting phosphor of the present invention has a broad emission peak of an emission spectrum. Further, the light-emitting element using the green light-emitting phosphor of the present invention can emit light which gives the viewer a natural feeling. [Embodiment] (Green luminescent phosphor of Example 1) 2138-9623-PF; Jessica 9 200911962 The inventors of the present invention repeated the results of research and found that ultraviolet light emitting diodes or blue light emitting diodes were found. In the case of an excitation source, the luminescence peak of the luminescence spectrum of the green luminescent phosphor having calcium (Ca) 'magnesium (Mg), cerium oxide, and an activator and halogen is broad. First, the green light-emitting phosphor of the present embodiment (the excitation spectrum and the light-emitting spectrum of the composition formula are shown in Fig. 1) is used as the first embodiment. The excitation spectrum is indicated by a broken line, and the light emission spectrum is indicated by a solid line. The color region has an excitation band near the wavelength of 3 〇〇 to 480 nm, and the ultraviolet light emitting diode and the blue light emitting diode can emit light efficiently. The luminescence peak of the luminescence spectrum is around 5〇5ηπι, and the half value width is 54 nm and wide. (Green light-emitting phosphors of Examples 2 to 6) Next, 'Examples 2 to 6 are green light-emitting phosphors of the modified example 1 (composition formula (Ca〇.98Eu〇.() 2) 8MgSi4 The concentration of the Eu element of 〇16Cl2) The green luminescent phosphor of Example 2 is a phosphor of the composition formula (Cao.snEuo.n) 8MgSl4〇lsCl2. The green luminescent phosphor of Example 3 is a composition formula (CaGjEuD a phosphor of .o+MgSL^d2. The green light-emitting phosphor of Example 4 is a phosphor of the composition formula (Cai) g5Eu〇_ odWgShOuCh. The four-color photoluminescence of Example 5 is a composition formula ( Cae.93EUfl.") 8MgSi4〇i6ci2 phosphor. Green light of Example 6 The phosphor is a camping body of the composition (Cat) 3()Eu((1〇) 8MgSi4〇ieCl2. Fig. 2 shows the excitation 2138-9623-PF of the green luminescent phosphors of Examples 2-6, respectively; Jessica 10 200911962 Spectrum. From Example 2 to Example 6, the Eu concentration increases sequentially, and as the concentration of the Eu element becomes higher, the excitation intensity in the blue LED region becomes higher. Fig. 3 shows the respective display The emission spectrum of the green light-emitting crab light body of Examples 2 to 6. From Example 2 to Example 6, the Eu concentration was sequentially increased, and as the concentration of the Eu element became higher, the emission wavelength shifted to the longer wavelength side, and The illuminating light is also gradually widened. (The green luminescent fluorescent light of Example 7 ~ 1 0
ί 其次，實施例7〜10是使組成式（Ca() 98Em。2) 8、MghM、nxSi4〇16Cl2)之中的χ變化。實施例7之綠色發光螢 光體為組成式（CamEm.oOsMgG.MMno.osShOBClO 的螢光 體。實施％ 8之綠色發光螢光體為级成式（〜遍。。2) 8Mg:.95Mn°.〇5Si4〇16Cl2)的螢光體。實施例9之綠色發光螢光 體為組成式<^。.9而。.。2)8^^。.9 —。.。心4〇16[：12)的螢光體。實 :例10之綠色發光榮光體為組成式―:) 8Mgfl.9„MnD.1()Si4〇16Cl2)的螢光體。 第4圖分別顯示實施例7〜1〇之綠色發光螢光體的發光 /晋。發光光譜可在544nm附近看到。隨著實施们至實 施例、:〇的Μη濃度依序增加，發光光譜成為變寬的發光。 、，有=，貫施例7〜1〇的綠色發光螢光體各別的激發光譜 ::有/化’顯示與實施例1的激發光譜略為同樣的形狀。 (比較例的螢光體） 譜顯示：第將5螢：體:MgAll°〇17:EU的激發光譜與發光光 發光光譜以實線表^例1。激發光譜以虛線表示， 2138-9623~PF；Jessica 200911962Next, Examples 7 to 10 are enthalpy changes in the composition formula (Ca() 98Em. 2) 8, MghM, nxSi4 〇 16Cl2). The green light-emitting phosphor of Example 7 is a phosphor of the composition formula (CamEm.oOsMgG.MMno.osShOBClO. The green light-emitting phosphor of % 8 is a graded formula (~ times.. 2) 8Mg: .95Mn°萤5Si4〇16Cl2) phosphor. The green luminescent phosphor of Example 9 is a composition formula <^. .9 and. . . . 2) 8^^. .9 -. . . . The fluorescent body of the heart 4〇16[:12). Real: The green illuminating glaze of Example 10 is a phosphor of the composition formula::) 8Mgfl.9 „MnD.1()Si4〇16Cl2). Fig. 4 shows the green luminescent phosphor of Example 7~1〇, respectively. The luminescence spectrum can be seen in the vicinity of 544 nm. As the exemplified by the implementation of the 、 浓度 实施 , , , , , , , , 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光The respective excitation spectra of the green light-emitting phosphor of yttrium: the presence/absence 'shows a shape slightly the same as that of the excitation spectrum of Example 1. (The phosphor of the comparative example) The spectrum shows: the fifth will be: Fire: MgAll °〇17: The excitation spectrum and luminescence spectrum of EU are shown by solid line in Example 1. The excitation spectrum is indicated by the dotted line, 2138-9623~PF; Jessica 200911962
BaMgAl〗〇0”：Eu在波長3〇〇〜42〇四附近具有激發帶，而 在紫外線區域的激發區顯示高的發光強度。 然而’發光光譜的半值寬為27nm的狭窄發光形狀，並 非寬廣的發光光譜。 . 其次’將螢光體SrGa?S4: Eu的激發光譜與發光光譜顯 示於第6圖’作為比較例2。激發光譜以虛線表示，發光 光譜以實線表示。SrGazS4: Eu的激發光譜中，激發帶延伸 至波長300mn〜520nm附近，而由紫外至藍色區域的發光。 然而’發光光暗的半值寬為48nm左右，並非充分寬廣 的發光光譜。 再者，SrGasS4: Eu為硫化物螢光體。此硫化物螢光體 的而f濕性等化學安定性低，且有使樹脂、LED晶片、金屬 導線等腐蝕之虞。因此’使用SrGad4: Eu等硫化物榮光體 時’最好設置腐蝕防止措施。 其次，表1顯示比較例1、2與實施例1〜1 〇之中的螢 光體組成式、其發光波長、其CIE色度座標。 表1 螢光體組成式 發光波長 CIE色度座標 [nm] X y 比較例1 BaMgAli〇〇27:Eu、Μη 515 0· 134 0.682 比較例2 SrGa2S4: Eu 535 ^ 0.270 0. 690 貫施例1 (Ca〇. 98Eu〇. 02 ) eMgS ί 4〇 16〇 1 2 ) 505 0.141 0.590 實施例2 (Ca〇. 99E110.01 )eMgS i 4O16C12) 505 0.140 0.575 實施例3 (Ca〇. 97E110.03) eMgS i 4O1 eC 12) 506 卜 0.159 ^Χδ94 實施例4 (Ca〇. 95EU0.05) sMgS i 4O16C12) 508 0.172 0.600 實施例5 (Ca〇. 93E110.07) sMgS i 4O16〇 12) 509 0. 185 0.602 實施例6 (Ca〇. 9〇Eu〇. 1 〇) MgS i 4Ο16〇 12) 510 0.203 0.597 實施例7 (Ca〇. 98Eu〇. 02) eMgo. 97Mn〇. 03S i 4Ο16〇 12 505 0. 178 0.569 2138-9623-pf；Jessica 12 200911962 實施例8 (Ca〇. 98Eu〇. 02 )8Mg〇. 95MII0· 05S i 4〇ieC 12 505 0.198 實施例9 (Ca〇. 98Eu〇. 02 ) eMgO. 93ΜΓΙ0. 〇?S 14〇16〇 12 505 0.217 ' 實施例10 (Ca〇. 9βΕιι〇. 〇2) sMgo. 9〇Mn〇. i〇S i 4Ο16〇 12 505 0.244 . 本貴施、例的綠色發光螢光體具有寬的發光光譜。 本實施例的綠色發光螢光體的激發光譜具有波手 3OOnm以上、48Onm以下的激發帶。因此，不論是使用於結 色發光二極體或者是紫外線發光二極體，皆能夠發光。 本實施例的綠色發光螢光體可針對紫外線發光二極體 以及藍色發光二極體有效率地激發。BaMgAl 〇0": Eu has an excitation band around the wavelength of 3 〇〇 to 42 〇, and shows a high luminescence intensity in the excitation region of the ultraviolet region. However, the narrow luminescence shape of the luminescence spectrum having a half-value width of 27 nm is not A broad luminescence spectrum. Next, the excitation spectrum and luminescence spectrum of the phosphor SrGa?S4: Eu are shown in Fig. 6 as Comparative Example 2. The excitation spectrum is indicated by a broken line, and the luminescence spectrum is indicated by a solid line. SrGazS4: Eu In the excitation spectrum, the excitation band extends to a wavelength of around 300 nm to 520 nm, and emits light from the ultraviolet to the blue region. However, the half value width of the luminescent light is about 48 nm, which is not a sufficiently broad luminescence spectrum. Furthermore, SrGasS4: Eu is a sulfide phosphor. This sulfide phosphor has low chemical stability such as wetness and has corrosion of resin, LED wafer, metal wire, etc. Therefore, 'SrGad4: Eu and other sulfides are used. In the case of the body, it is preferable to provide corrosion prevention measures. Next, Table 1 shows the composition formula of the phosphors in Comparative Examples 1, 2 and 1 to 1 、, the emission wavelength thereof, and the CIE chromaticity coordinates. Table 1 Fluorescence Body composition Luminous wavelength CIE chromaticity coordinates [nm] X y Comparative Example 1 BaMgAli〇〇27: Eu, Μη 515 0· 134 0.682 Comparative Example 2 SrGa2S4: Eu 535 ^ 0.270 0. 690 Example 1 (Ca〇. 98Eu〇. 02) eMgS ί 4〇16〇1 2 ) 505 0.141 0.590 Example 2 (Ca〇. 99E110.01) eMgS i 4O16C12) 505 0.140 0.575 Example 3 (Ca〇. 97E110.03) eMgS i 4O1 eC 12) 506卜 0.159 ^Χδ94 Example 4 (Ca〇. 95EU0.05) sMgS i 4O16C12) 508 0.172 0.600 Example 5 (Ca〇. 93E110.07) sMgS i 4O16〇12) 509 0. 185 0.602 Example 6 (Ca〇 9〇Eu〇. 1 〇) MgS i 4Ο16〇12) 510 0.203 0.597 Example 7 (Ca〇. 98Eu〇. 02) eMgo. 97Mn〇. 03S i 4Ο16〇12 505 0. 178 0.569 2138-9623-pf Jessica 12 200911962 Example 8 (Ca〇. 98Eu〇. 02 ) 8Mg〇. 95MII0· 05S i 4〇ieC 12 505 0.198 Example 9 (Ca〇. 98Eu〇. 02 ) eMgO. 93ΜΓΙ0. 〇?S 14〇 16〇12 505 0.217 'Example 10 (Ca〇. 9βΕιι〇. 〇2) sMgo. 9〇Mn〇. i〇S i 4Ο16〇12 505 0.244 . The green luminescent phosphor of the present invention has a wide width Luminescence spectrum. The excitation spectrum of the green light-emitting phosphor of the present embodiment has an excitation band of 300 nm or more and 48 Onm or less. Therefore, it can emit light whether it is used for a color light-emitting diode or an ultraviolet light-emitting diode. The green light-emitting phosphor of this embodiment can be efficiently excited for the ultraviolet light emitting diode and the blue light emitting diode.
再者，本實施例的綠色發光螢光體可藉由適當地變更 Eu濃度或適當地變更Mn濃度，而細微地變更發光色。例 如，實施例1的綠色發光螢光體的CIE色度座標X為 〇· 14卜y為0.5 90，發出些微偏藍的綠色的光線。相對於 此，實施例ίο的綠色發光螢光體的的ΠΕ色度座標χ為 〇· 244 y為〇. 5 75 ’發出微橙的綠色的光線。照明的用途'、 使用樣態的需求有多樣化，要多樣的色調設計。本實 施例的綠色發光榮光體可因應上述的多樣化的需求。Λ (本發明的綠色發光螢光體的製造方法 準備碳酸鈣（CaCO〇及氯化钮印Γ1、山 乳化鈣（CaCl〇、碳酸鎂 (MgC〇3)、氧化矽（Si〇2)以及作 、 為销化合物的軋化銪（Eu2〇3) 以作為原料。銪化合物也可 rp 』以疋乳化銪（EuC13)、氟化銪 (EuFd專。再者，銪化合物也 θ 也了此疋胺化合物或亞胺化合 物。雖然氧化銪（Eu2〇3)可使用 口 ,, .. ^ Φ。°口，然而較佳為高純度 的軋化銪。虱化鈣（CaCl2)與 ώ , θ , 、乳化矽⑻也可以秤量比起 由化學计置比預定的量略 2138-9623-PF；je ssica 13 200911962 再者’準備氯化銨⑽4ci)，以作為加熱處理時，促進 螢光體粒子結晶成長的添加物之助溶材料。並且’助溶材 料也可以使用氟化銘⑷F3)等的鹵化銘；MW、等 鹼金屬碳酸鹽；LlC1、㈣、们等鹼金屬由化物；CaCl2、 CaF2' BaF2等鹼土族金屬的齒化物、β2〇3、M〇3、NaB4〇7等 硼酸鹽化合物；LisP〇4、NM2P〇4等磷酸鹽等。 其次，以濕式方式充分良好地混合這些原料。用來渴 式混合的有機溶媒可使用丙剩、異丙醇或乙醇等有機溶 媒。雖然也能夠以水混合，然而使用有機溶媒較佳。可將 有機命媒與已秤置的原料，再加上氧化錯球放入陶究製等 的球磨機混合。混合時間較佳為1小時以下、24小時以下 ㈣圍進行。混合終了後，以篩子分離氧化錯球，之後， 乾燥洛媒而得到原料粉末。 ^濕式混合原料以外，也可以利用乾式方式混合。 是利用氧化銘製或猶的研蛛或研杵將已秤量 的材料良好地混合。雖然比人 行里 夺間，然而，與濕式混合比較， 、 利。 小而乾秌步驟這點較為有 其次，將得到的原料粉末填充於氮 掛禍或氧化銘托盤、石炭_或 β乳化銘 熱容器内，再設定電爐。 氮化縣盤等的耐 接著，也可以在混合氫 面 ^ i ff ϊ® λ虱的還原環境氣體下 成。 丹者也可以在-氧化碳氣流t燒 2138-9623-PF；jessica 200911962 燒成時的壓力較佳為1.〇〇~1·50大氣壓。這是由於壓 力低於1 · 00大氣壓的話，則有無法充分地促進反應的可能 性，y > 力—方面，壓办於高於丨· 50大氣壓的話，則有必須使 封閉亂氣的容器變得.堅固，而具有使其製造裝置成為高價 格裝置的可能性。燒成時的壓力較佳為1. 02〜1 · 〇3大氣 壓’更佳為1.05〜1.2大氣壓。 k成Λ度較佳為9 〇 〇 °c ~ 13 0 〇。這是由於燒成溫度低於 的話，反應進行度會遲緩而有反應上花費時間之虞， 另方面，燒成溫度高於130(TC的話，則有產生非預期的 副反應之虞。燒成的溫度較佳為1〇〇〇〜125〇。〇，更佳為 °C ~1 200°C。 燒成時間較佳為3 ~ 1 〇小時Further, in the green light-emitting phosphor of the present embodiment, the luminescent color can be finely changed by appropriately changing the Eu concentration or appropriately changing the Mn concentration. For example, the green luminescent phosphor of Example 1 has a CIE chromaticity coordinate X of 90·14 y of 0.590, and emits a slightly bluish green light. In contrast, the green illuminating phosphor of the embodiment ί 座 座 244 y is 〇 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 The use of lighting, the use of the form of the demand for diversification, to a variety of color design. The green illuminating glaze of this embodiment can meet the diverse needs described above. Λ (The method for producing a green light-emitting phosphor of the present invention prepares calcium carbonate (CaCO〇 and chlorinated button Γ1, mountain emulsified calcium (CaCl〇, magnesium carbonate (MgC〇3), yttrium oxide (Si〇2) and The ruthenium compound (Eu2〇3) is used as a raw material. The ruthenium compound can also be emulsified with ruthenium (EuC13) or ruthenium fluoride (EuFd. Further, the ruthenium compound also has ruthenium. a compound or an imine compound. Although ruthenium oxide (Eu2〇3) can be used as a mouth, .. ^ Φ.° mouth, it is preferably a high-purity rolled bismuth. Calcium telluride (CaCl2) and ώ, θ, , The emulsified enamel (8) can also be weighed in proportion to the predetermined amount by the chemistry meter 2138-9623-PF; je ssica 13 200911962 and then 'prepared ammonium chloride (10) 4 ci) to promote the growth of the phosphor particles during heat treatment. The auxiliary material is a solubilizing material, and the 'solvent material can also be halogenated with fluorinated Ming (4) F3); MW, etc. alkali metal carbonate; LlC1, (4), and other alkali metal-based compounds; CaCl2, CaF2' BaF2 Tooth compounds of alkaline earth metals, borate compounds such as β2〇3, M〇3, NaB4〇7; LisP〇 4. Phosphate such as NM2P〇4, etc. Next, these raw materials are sufficiently mixed in a wet manner. The organic solvent used for the thirst mixing may be an organic solvent such as residual, isopropanol or ethanol. Mixing, however, it is preferred to use an organic solvent. The organic medium can be mixed with the scaled raw material, and the oxidized wrong ball is placed in a ball mill such as a ceramics system. The mixing time is preferably 1 hour or less and 24 hours or less (4). After the mixing is completed, the oxidized ball is separated by a sieve, and then the monomer is dried to obtain a raw material powder. The wet mixed material may be mixed by a dry method.良好 Mix the weighed materials well. Although it is better than the crowd, it is better than wet mixing. The small and dry steps are second to none, and the raw material powder obtained is filled with nitrogen. Oxidation in the tray, charcoal _ or β emulsified in the heat container, and then set the electric furnace. The resistance of the nitriding county plate, etc., can also be formed under the reducing atmosphere of the mixed hydrogen surface ^ i ff ϊ 虱 虱Dan can also burn 2138-9623-PF in the oxidized carbon gas stream; the pressure at the time of firing in jessica 200911962 is preferably 1. 〇〇~1·50 atm. This is because the pressure is lower than 1.00 atmosphere. There is a possibility that the reaction cannot be sufficiently promoted, and if the pressure is higher than 丨·50 atm, it is necessary to make the closed gas container firm. The possibility of the price device. The pressure at the time of firing is preferably 1. 02~1 · 〇 3 atm. 'More preferably 1.05 to 1.2 atm. The k degree of twist is preferably 9 〇 〇 °c ~ 13 0 〇. This is because if the firing temperature is lower, the reaction progress is slow and it takes time to react. On the other hand, if the firing temperature is higher than 130 (TC, there is an unexpected side reaction. The temperature is preferably from 1 〇〇〇 to 125 〇. 〇, more preferably from ° C to 1 200 ° C. The firing time is preferably from 3 to 1 〇 hours.
燒成終了時，慢慢地冷卻’接著，也可以藉由將得到 的乜成物畚碎再混合得到的混合物再度於加壓狀態下進行 得到的混合物再燒成的再燒成步驟。混合物的再燃燒可以 在氮氣的環境氣體下進行，例如使壓力成為丨丨大氣壓左 右’且在1100。。進行3小時的燒成。再燒成終了後，粉碎 且混合慢慢地冷卻而得的再燒成物，可得到本實施例的綠 色發光螢光體。 得到的綠色發光螢光體的平均粒徑為 別是80〜160# m較佳。若平均粒徑超過22〇 20-220 β m > // m的話，有 特 無 法得到螢光體均一地分散之虞，再者， 併使用時’有引起色斑之虞。另一方面 20#ιη時，有螢光體強度降低之虞。 若與其他螢光體合 ’若平均粒徑小於 2138—9623-PF;Jessica 15 200911962 (貫施例1的綠色發光螢光體的製造方法） 秤量碳酸鈣（CaC〇3)11· 4知、氯化約（caCl2)1.68g、碳 酸鎂（MgC〇3)l. 4.〇g、氧化矽（Si〇2)4· 5〇g以及氧化= (Eu2〇3)0. llg。秤量氯化銨（NH4C1)0, 5g。 使用丙酮作為有機溶媒，以濕式方式充分地混合這些 原料。再將氧化錯球加入有機溶媒與秤量的原料之中，再 放入陶瓷製的球磨機内，混合12小時。 將得到原料粉末填充於硼化氮坩堝，再設定電爐，然 後於混合氫氣以及氮氣的還原環境氣體下，使壓力= 大氣壓，燒成溫度為π 0 0。(3，燒成時間為3小時。 燒成終了後，慢慢地冷卻，再將得到燒成物粉碎、混 合。之後再於氮氣環境氣體下，使磨力成為hi大氣壓2 右’於110(TC再度燒成3小時’再燒成終了後，慢慢冷卻 而將得到的再燒成物粉碎、混合。藉A，以得到本二例 的綠色發光螢光體。 (實施例2〜6的綠色發光螢光體的製造方法） 實施例2中，與實施例1不同的是，準備碳酸約 (CaC〇3)46. 18g、氯化飼（㈤2)6.心、碳酸鎮 5.61g、氧化石夕（Si〇2)i8.00g以及氧化销（Eu2〇3)〇.叫。其 他濕式混合條件、燒成溫度、燒成壓力、燒成時間等，與 實施例1相同。 實施例3與實施例2不同的是，準備氧化销 (EwOOOJOg。實施例4與實施例2不同的是，準備氧化銪 (EU2〇3)hl7g。實施例5與實施例2不同的是，準備氧化銪 2138-9623-PF;Jessica 16 200911962 (EU2〇3)1_64g。實施例6舆實施例2不同的是，準備氧化銪 (Eu2〇3)2.34g。其他部分，實施例3〜6與實施例2相同。 (實施例7〜1 〇的綠色發光螢光體的製造方法） 貫施例7中’與實施例1不同的是，準備碳酸鈣 (CaC〇3)45. 71g、氯化鈣（CaC1〇6. 74g、碳酸鎂（MgC〇3) 5· 44g、碳酸錳（MnC〇3)0. 23g、氧化矽（Si〇2)i8. 〇〇g 以及氧 化銪（Eu2Ch)〇.47g。其他濕式混合條件、燒成溫度、燒成壓 力、燒成時間等，與實施例1相同。 貝靶例8中，與實施例7不同是，碳酸鎂（MgC〇3)為 5. 33g、碳酸錳（MnC〇3)4 〇_ 38g。實施例9中，與實施例7 不同是，碳酸鎂（MgC〇3)為5. 22g、碳酸錳（MnC〇3)為〇. 54g。 實施例ίο中，與實施例7不同是，碳酸鎂（％(：〇3)為5 〇5运、 石反酸錳（MnCOd為〇· 77g。其他的部分，實施例8〜1〇與實施 例7相同。 (使用本實施例的綠色發光螢光體的發光元件） 第7圖為使用本發明的實施例的綠色發光螢光體的發 光元件111的剖面圖。發光元件丨丨丨在前面設置透明基板 101。再者’發光元件111在形成為半球狀的透明樹脂體 103的内側配置發光二極體1〇5。 透明樹脂體103是以環氧樹脂、聚氨酯樹脂、聚矽氧 k树月曰、笨乙烯樹脂、聚乙烯系（p〇 1 y V i 1)樹脂、聚乙 稀系（polyethylene)樹脂、聚丙烯系樹脂等構成。使用聚 石夕氧烧樹脂或者聚環氧樹脂作為透明樹脂體丨〇3的話，螢 光體粉末的分散性較佳。 2138-9623-PF;Jessica 17 200911962 使螢光體粉末分散於透明樹脂中時，相對於螢光體粉 末與透明樹脂的總重，螢光體粉末的重量比例通常為 0.1〜20重量％ ’較佳為〇_3〜15重量％。這是由於螢光體粉 末超過此範圍時’會因為螢光體粉末的凝集而使發光效率 降低，另m少的話，同樣會因為樹脂的光吸收或 散亂而使發光效率降低。在透明樹脂之中，也可以添加防 止色斑（mura)的增量劑。 f 發光二極體105可使用紫外線發光二極體inGaN或At the end of the calcination, the mixture is slowly cooled. Next, the mixture obtained by pulverizing and mixing the obtained hydrazine product may be re-fired in a pressurized state. The re-combustion of the mixture can be carried out under an ambient atmosphere of nitrogen, for example, by making the pressure about about atmospheric pressure and at 1100. . The firing was carried out for 3 hours. After the completion of the calcination, the green calcined phosphor of the present example can be obtained by pulverizing and mixing the re-fired product which is gradually cooled. The average particle diameter of the obtained green light-emitting phosphor is preferably 80 to 160 # m. If the average particle size exceeds 22 〇 20-220 β m > // m, there is no way to uniformly disperse the phosphor, and in addition, when used, there is a problem of causing stains. On the other hand, when 20#ιη, there is a decrease in the intensity of the phosphor. If combined with other phosphors, 'If the average particle size is less than 2138—9623-PF; Jessica 15 200911962 (Manufacturing method of green luminescent phosphor according to Example 1) Weigh calcium carbonate (CaC〇3) 11.4 Chlorinated (caCl2) 1.68 g, magnesium carbonate (MgC〇3) 1. 4. g, yttrium oxide (Si 〇 2) 4 · 5 〇 g and oxidation = (Eu 2 〇 3) 0. llg. Weigh ammonium chloride (NH4C1) 0, 5g. These raw materials were sufficiently mixed in a wet manner using acetone as an organic solvent. The oxidized wrong ball was added to the organic solvent and the weighed raw material, and placed in a ceramic ball mill for 12 hours. The raw material powder was filled in a lanthanum boride, and then an electric furnace was set, and then under a reducing atmosphere of hydrogen and nitrogen, pressure = atmospheric pressure, and the firing temperature was π 0 0 . (3) The firing time is 3 hours. After the completion of the firing, the mixture is slowly cooled, and the obtained calcined product is pulverized and mixed. Then, under a nitrogen atmosphere, the grinding force becomes hi atmospheric pressure 2 right 'at 110 ( The TC was fired again for 3 hours. After the completion of the calcination, the obtained re-fired product was pulverized and mixed by slow cooling. The green luminescent phosphor of the present two examples was obtained by A. (Examples 2 to 6) In the second embodiment, in the second embodiment, the carbonic acid (CaC〇3) 46.18g, the chlorinated feed ((5)2), the heart, the carbonic acid town 5.61g, and the oxidation are prepared. Shi Xi (Si〇2) i8.00g and oxidation pin (Eu2〇3) 。. Other wet mixing conditions, firing temperature, firing pressure, firing time, etc., are the same as in Example 1. Example 3 Unlike Example 2, an oxidation pin (EwOOOJOg was prepared. Example 4 differs from Example 2 in that cerium oxide (EU2〇3) hl7g was prepared. Example 5 differs from Example 2 in that yttrium oxide 2138 is prepared. -9623-PF; Jessica 16 200911962 (EU2〇3) 1_64g. Example 6 differs from Example 2 in that 2.34g of cerium oxide (Eu2〇3) is prepared. In some embodiments, Examples 3 to 6 are the same as in Example 2. (Method for Producing Green Luminescent Phosphor of Example 7 to 1) In Example 7, 'In contrast to Example 1, calcium carbonate (CaC) was prepared. 〇3) 45. 71g, calcium chloride (CaC1〇6. 74g, magnesium carbonate (MgC〇3) 5. 44g, manganese carbonate (MnC〇3) 0. 23g, yttrium oxide (Si〇2) i8. 〇〇 g and cerium oxide (Eu2Ch) 〇.47 g. Other wet mixing conditions, firing temperature, firing pressure, firing time, and the like are the same as in Example 1. In the shell example 8, unlike the example 7, carbonic acid The magnesium (MgC〇3) is 5.22g, manganese carbonate (MgC〇3) is 5.22g, manganese carbonate (MgC〇3) is 5.22g, manganese carbonate (MgC〇3) is 5.23g, manganese carbonate (MgC〇3) is 5.23g, manganese carbonate (MgC〇3) MnC〇3) is 〇. 54g. In the example ίο, unlike Example 7, magnesium carbonate (%(:〇3) is 5 〇5 transport, manganese citrate (MnCOd is 〇·77g. Other parts) Example 8 to 1 is the same as Example 7. (Light-emitting element using the green-emitting phosphor of the present embodiment) FIG. 7 is a cross-section of the light-emitting element 111 using the green-emitting phosphor of the embodiment of the present invention. Figure. The element 丨丨丨 is provided with a transparent substrate 101 on the front side. Further, the light-emitting element 111 is provided with a light-emitting diode 1〇5 inside the transparent resin body 103 formed in a hemispherical shape. The transparent resin body 103 is an epoxy resin or a urethane resin. A polyoxynium k-tree, a stupid vinyl resin, a polyethylene-based (p〇1 y V i 1) resin, a polyethylene resin, a polypropylene resin, or the like. When the polyoxoxime resin or the polyepoxy resin is used as the transparent resin body 3, the dispersibility of the phosphor powder is preferable. 2138-9623-PF; Jessica 17 200911962 When the phosphor powder is dispersed in the transparent resin, the weight ratio of the phosphor powder is usually 0.1 to 20% by weight based on the total weight of the phosphor powder and the transparent resin. Good for 〇3~15% by weight. This is because when the phosphor powder exceeds this range, the luminous efficiency is lowered by the aggregation of the phosphor powder, and if the amount of m is small, the luminous efficiency is also lowered due to light absorption or scattering of the resin. Among the transparent resins, an extender for preventing mura may also be added. f Light-emitting diode 105 can use ultraviolet light-emitting diode inGaN or
GaN ° 在透明樹脂體1 03分別混入紅、綠、藍色發光的三種 發光體粉末102 ’並且施以鏡面加工，使得透明樹脂的表 面能夠具有鏡Φ 104 $作用。紅色發光螢光體使用 CaAlSiUu。藍色發光螢光體使用Sr5(p〇4)3Cl.E卜其a， 綠色發光螢光體是使用（Cafl wEuo.whMg。。 並且’為了加強補色’也可以含有 -Sialon:Eu 等 a 紫外線發光二極體105可在波長37〇〜41〇nm的紫外 域，特別是390nm附近以最高效率發出紫外線。紅 '綠 藍色的各色螢光體會被此紫外線激發，藉此，可由透明 板101放射白色光。因此，發光元件lu為白色發光元件 藉由使透明樹脂體103含有擴散劑，也可能緩：來 紫外線發光二極體1 〇 5的指向性而進—步增加視角 劑例如可使用鈦酸鋇、氧化鈦、氧化鋁、氧化石夕等。’、 透明樹脂It 1。3是形成為半球狀’‘然而藉由形成為想要 2138-9623-PF;Jessica 18 200911962 形狀，能夠達成一邊收斂、一邊擴散來自紫外線發光二極 體105的發光等的透鏡效果。 本實施例的綠色發光螢光體具有寬廣的發光光譜。因 此’使用本實施例的綠色發光螢光體的發光元件，可發出 能夠賦予自然感受的光線。 .' . (其他實施例） 並且，本實施例的發光元件，不限於白色的發光元件， f ；也可以是發光暖色系或寒色系等的色調的光線的發光元 件。當然’也可以是綠色單色的發光元件。 上述實施例中，為含有Ca、Mg、氧化矽 '銪與氣的綠 色發光螢光體，其顯示發光光譜的發光尖峰寬廣。再者， .s有Sr或Ba時，能維持發光光譜的發光尖峰寬廣，並且 藉由調整Sr或Ba的含有量，能夠使發光色改變為微藍的 綠色或者接近黃色的綠色等的各種微妙的色度。 具體而έ ’含有S r . ή6邀止a,丨丄„ ..GaN ° is mixed with three kinds of illuminant powders 102' of red, green, and blue light in the transparent resin body 103, and mirror-finished so that the surface of the transparent resin can have the effect of the mirror Φ 104 $ . The red luminescent phosphor uses CaAlSiUu. The blue luminescent phosphor uses Sr5(p〇4)3Cl.Eb, a, green luminescent phosphor is used (Cafl wEuo.whMg. and 'in order to enhance the complementary color' may also contain -Sialon:Eu, etc. a UV The light-emitting diode 105 emits ultraviolet light at a maximum efficiency in the ultraviolet region of a wavelength of 37 〇 to 41 〇 nm, particularly around 390 nm. The red-green-blue color phosphors are excited by the ultraviolet light, whereby the transparent plate 101 can be used. Therefore, the light-emitting element lu is a white light-emitting element. By causing the transparent resin body 103 to contain a diffusing agent, it is also possible to slow down the directivity of the ultraviolet light-emitting diode 1 〇5 and to increase the viewing angle agent, for example, can be used. Barium titanate, titanium oxide, aluminum oxide, oxidized stone, etc. ', transparent resin It 1.3 is formed into a hemispherical shape'' However, by forming into the shape of 2138-9623-PF; Jessica 18 200911962, it can be achieved The lens effect of light emission from the ultraviolet light-emitting diode 105 is diffused while converging. The green light-emitting phosphor of the present embodiment has a broad light-emitting spectrum. Therefore, the green light-emitting phosphor of the present embodiment is used. The light element emits light capable of imparting a natural feeling. (Other Embodiments) Further, the light-emitting element of the present embodiment is not limited to a white light-emitting element, f; and may be a color tone such as a warm color system or a cold color system. Light-emitting element of light. Of course, it can also be a green monochromatic light-emitting element. In the above embodiment, it is a green-emitting phosphor containing Ca, Mg, yttrium oxide and yttrium, which exhibits a broad luminescent peak of luminescence spectrum. Further, when .s has Sr or Ba, the illuminating peak of the luminescence spectrum can be kept wide, and by adjusting the content of Sr or Ba, the luminescent color can be changed to a blueish green color or a yellowish green color or the like. Subtle shades. Specific and έ ' contains S r . ή 6 invites a, 丨丄 „..
發光光譜，發光尖峰寬廣。The luminescence spectrum has a wide illuminating peak.
-^ ^ ^ ^ ^a〇.97ba〇.〇，Euo 〇2) ^Euo.oOsMgSi.O^Cl, ^ (Ca〇.94Ba〇.〇3 2138-9623-PF;Jessica 19 200911962-^ ^ ^ ^ ^a〇.97ba〇.〇, Euo 〇2) ^Euo.oOsMgSi.O^Cl, ^ (Ca〇.94Ba〇.〇3 2138-9623-PF; Jessica 19 200911962
Eu〇.〇3)8MgSi4〇uCl2 ' (Ca〇.9〇Ba〇.〇5Eu〇.〇5)8MgSi4〇i6Cl2 ' (Ca〇 »6 Ba〇.〇7Eu'〇.〇7)8MgSi4〇16Cl2 . (Ca〇.8〇Ba〇. i〇Eu〇. i〇)8MgSi4〇16Gh ' (Ca〇.96Ba〇.〇2Eu〇.〇2)8Mgo.97Mn〇.〇3Si4〇i6Cl2 ^ (Ca〇. 9eBa〇. 〇2Bu〇. 〇〇 sMg〇.95Mn〇. 〇5Si4〇ieCl 2 ' (Ca〇：96Ba〇.〇zEii〇.〇2)8Mg〇.93Mn〇. 〇?Si4〇i6Eu〇.〇3)8MgSi4〇uCl2 '(Ca〇.9〇Ba〇.〇5Eu〇.〇5)8MgSi4〇i6Cl2 '(Ca〇»6 Ba〇.〇7Eu'〇.〇7)8MgSi4〇16Cl2 . (Ca〇.8〇Ba〇. i〇Eu〇. i〇)8MgSi4〇16Gh ' (Ca〇.96Ba〇.〇2Eu〇.〇2)8Mgo.97Mn〇.〇3Si4〇i6Cl2 ^ (Ca〇. 9eBa 〇. 〇2Bu〇. 〇〇sMg〇.95Mn〇. 〇5Si4〇ieCl 2 ' (Ca〇:96Ba〇.〇zEii〇.〇2)8Mg〇.93Mn〇. 〇?Si4〇i6
Ch、（Ca〇.96Ba(ij2EuD.D2)8Mg(i.9DMn(i.iDSi4〇i6Cl2檢測發光光譜’ 發光尖峰寬廣。 再者’含有Sr以及Ba的螢光體例如為，針對 (Ca〇.96Sr〇.〇iBa〇.〇1Eu〇.〇2)8MgSi4〇i6Cl2 ' (Ca〇. 95Sr〇. 〇2Ba〇. 〇2Eu〇. 〇 8MgSi4〇ieCl2 ' (Ca〇. 9iSr〇. osBao. 〇3Eu〇. 〇3)sMgSi4〇i6C1 2 ' (Ca〇.«5 Sr〇.〇5Ba〇.〇5Eu〇.〇5)8MgSi4〇 i6Cl2'(Ca〇.79Sr〇.〇7Ba〇.〇7Eu〇.〇7)8MgSi4 OieCh (Ca〇.7〇Sr〇.i〇Ba〇.i〇Eu〇.i〇)8MgSi4〇i6Cl2 ' (Ca〇.94Sr〇·02 Ba〇. 02EU0. 〇2)8Mg〇.97Mn〇. 03S14O16CI2 (Cao.94Sro.d2Bao.02Eu。.。2) 8MgD.93Mn〇.()5Si4〇16Cl2、（Ca〇.94Ba〇.G2Sr〇.0 2EU(l.0 2)8Mg(l.93MnG.0 7Si4 OieCh、（CamSrusBauJud.dOsMgD.soMno.ioSiAOuCh 檢測發 光光譜，發光尖峰寬廣。 含有Sr的情況，可使原料之中含有碳酸锶（SrCOO、 氣化銘（SrCh)、溴化锶（SrBr)或硫酸锶（SrS〇4)等。 再者’含有Ba的情況，可使原料之中含有偏磷酸鋇 (Ba(P〇3)2)、草酸鋇（BaC2〇4)、硝酸鋇（BaN〇3)或氣化鋇 (BaCl2)等。 再者，上述實施例之中’是使碳酸鈣（CaC〇3)、氯化鈣 (CaCh)、碳酸鎂（MgC〇3) '氧化矽（Si〇〇以及作為氧化銪 (EmO3)混合。然而，本發明的綠色發光螢光體不限於上述 實施例。然而’也可以使用亞氯酸鈣（Ca(cl〇2)2)、亞硫酸 2138-9623-Pf；jeSSica 20 200911962 鈣（CaS〇3)、亞磷酸鈣（CaPH〇3)、鋁矽酸鈣（Ca〇.Al2〇3)、過 氯酸詞（Ca(Cl〇4)2)、氮化終（caaN2)作為飼化合物。 上述貫施例的發光元’件Π 1的紅色發光螢光體是使用 CaAlSiN3:Eu、藍色發光螢光體使用Sr5(p〇4)3C1:Eu、綠色 發光螢光體是使用。 但是’不限於此’紅色發光螢光體可使用Srs : Eu、 CaS:Eu或La^SiEu等。再者，藍色發光螢光體可使用 (Ba, SrOMgAhoOwEu、Mn、（Ba，Sr，Ca，Mg)1()(P〇4)6ci2:Eu 或Ch, (Ca〇.96Ba(ij2EuD.D2)8Mg(i.9DMn(i.iDSi4〇i6Cl2 detection luminescence spectrum' The luminescent peak is broad. Further, the phosphor containing Sr and Ba is, for example, for (Ca〇. 96Sr〇.〇iBa〇.〇1Eu〇.〇2)8MgSi4〇i6Cl2 ' (Ca〇. 95Sr〇. 〇2Ba〇. 〇2Eu〇. 〇8MgSi4〇ieCl2 ' (Ca〇. 9iSr〇. osBao. 〇3Eu〇 〇3)sMgSi4〇i6C1 2 ' (Ca〇.«5 Sr〇.〇5Ba〇.〇5Eu〇.〇5)8MgSi4〇i6Cl2'(Ca〇.79Sr〇.〇7Ba〇.〇7Eu〇.〇7 8MgSi4 OieCh (Ca〇.7〇Sr〇.i〇Ba〇.i〇Eu〇.i〇)8MgSi4〇i6Cl2 ' (Ca〇.94Sr〇·02 Ba〇. 02EU0. 〇2) 8Mg〇.97Mn〇 03S14O16CI2 (Cao.94Sro.d2Bao.02Eu.. 2) 8MgD.93Mn〇.()5Si4〇16Cl2, (Ca〇.94Ba〇.G2Sr〇.0 2EU(l.0 2)8Mg(l.93MnG. 0 7Si4 OieCh, (CamSrusBauJud.dOsMgD.soMno.ioSiAOuCh detects luminescence spectrum, broad luminescent peaks. In the case of Sr, the raw material contains strontium carbonate (SrCOO, gasification (SrCh), strontium bromide (SrBr) or Barium sulfate (SrS〇4), etc. In addition, when Ba is contained, the raw material may contain barium metaphosphate (Ba(P〇3)2) or barium oxalate ( BaC2〇4), barium nitrate (BaN〇3) or gasified barium (BaCl2), etc. Further, in the above embodiment, 'calculated calcium carbonate (CaC〇3), calcium chloride (CaCh), magnesium carbonate ( MgC〇3) '矽 矽 (Si〇〇 and 铕 (EmO3) are mixed. However, the green luminescent phosphor of the present invention is not limited to the above examples. However, 'calcium chlorite (Ca(cl〇) may also be used. 2) 2), sulfite 2138-9623-Pf; jeSSica 20 200911962 calcium (CaS〇3), calcium phosphite (CaPH〇3), calcium aluminum citrate (Ca〇.Al2〇3), perchloric acid ( Ca(Cl〇4)2) and nitriding end (caaN2) are used as feed compounds. The red-emitting phosphor of the above-mentioned embodiment of the luminescent element 'member Π 1 is a CaAlSiN3:Eu, blue luminescent phosphor using Sr5 (p〇4) 3C1: Eu, green light-emitting phosphor is used. However, 'not limited to this' red-emitting phosphor can use Srs: Eu, CaS: Eu or La^SiEu. Further, a blue luminescent phosphor can be used (Ba, SrOMgAhoOwEu, Mn, (Ba, Sr, Ca, Mg) 1 () (P 〇 4) 6 ci 2 : Eu or
ZnS : Ag等。再者’綠色發光螢光體可使用本實施例的各種 綠色發光螢光體。 再者’發光元件111之中’除了本實施例的綠色發光 螢光體以外，也可以混合使用以下所示的綠色發光螢光 體。也可以在本實施例的綠色發光螢光體另使用例如 BaMg2Al16〇27:Eu、Μη 或 BaMgAhoOwEu ' Μη 所表示的銪賦活 紹酸鹽螢光體或（MgCaSrBa)Si2〇2N2:Eu所表示的銪賦活驗 土族氧化矽氮化物螢光體、BhSiO^Eu所表示的賦活驗土 族金屬矽酸鹽螢光體等。 再者’上述貫施例的發光元件111之中，可使用紫外 線發光二極體作為發光二極體1 05。 但是，不限於此，可使用藍色發光二極體GaN作為發 光二極體105。此情況下’可在透明樹脂體1〇3分別混入 紅、綠色發光的兩種類的螢光體粉末1 〇2。例如在綠色發 光螢光體使用（CaD.98EllD.D2)8MgD.9〇MnD.lClSi4〇16Cl2)。在紅色發 光螢光體使用SrS:Eu、CaS:Eu或CaAlSiN3:Eu等。再者， 2138-9623-PF;Jessica 21 200911962 為了進一步增加補色，也可以含有YAG : Ce、CaGa2S4或α _ 賽隆（α.-Sialon)等。 上述實施例之冲，使用InGaN或GaN作為紫外線二極 體6再者，使用GaN作為藍色發光二極體。但是，不限於 此’可使用 InAlGaN、AlGaN、BAlGaN、BlnAlGaN 等。 綠色發光螢光體為（Caa、Srb、Ba。、EUd)8Mgl-xMnxSi4 OieCh) (式中a〜d滿足下列所示數值0<a<1. 〇、〇 $ b<〇. 5、〇 $ c<〇· 5、〇<d<〇· 2，a+b + c + d=l. 0，x 滿足下列所示數值：〇 S χ<0·3)。 當然也可能為 ’ 〇.〇〇1^3$〇.999、〇SbS〇.499、〇 ^c^〇.499' 0.001^d^0.199> a + b + c + d=l.〇5 Ο.Ο^χ^ 0.299。 【產業上利用的可能性】 本發明的螢光體為以紫外線發光二極體或藍色發光二 極體作為激發源發光，而發光光譜的發光尖峰寬廣的綠色 發光螢光體’適用於使用白色發光二極體或電激發光元件 的發光裝置’可發出自然感受的光線，極為有用。 【圖式簡單說明】 第1圖為說明實施例1之綠色發光螢光體的激發光譜 與發光光譜的圖。 第2圖為說明實施例2~6之綠色發光螢光體的激發光 2138-9623-PF;Jessica 22 200911962 譜的圖。 第3圖為說 譜的圖 明實施例2〜6之綠色發光螢光體的發光光 第4圖為說 譜的圖。 第5圖為說 譜的圖。 明實施例7〜1 〇之綠色發光螢光 體的發光光 月比較例1之螢光體的激發光譜與發光光 ，弟6圖為說明比較例2之螢光體的激發光譜與發光光 昏的圖。 、私庀尤 的例子之一的概略構 第7圖為顯示本發明的發光元件 【主要元件符號說明】 101〜透明基板； 102〜二種類的螢光體粉末； 103〜透明樹脂體； 104~鏡子； 1 05〜發光二極體； 111〜本實施例之發光元件。 2138-9623-PF;Jessica 23ZnS : Ag, etc. Further, the green light-emitting phosphor of the present embodiment can be used as the green light-emitting phosphor. Further, in addition to the green light-emitting phosphor of the present embodiment, the green light-emitting phosphor shown below may be used in combination. It is also possible to use, in the green light-emitting phosphor of the present embodiment, for example, an endowurance phosphor or a (MgCaSrBa)Si2〇2N2:Eu represented by BaMg2Al16〇27:Eu, Μη or BaMgAhoOwEu' Μη. The living soil oxidized cerium nitride phosphor, the living earth metal silicate phosphor represented by BhSiO^Eu, etc. are activated. Further, among the light-emitting elements 111 of the above-described embodiments, an ultraviolet light-emitting diode can be used as the light-emitting diode 105. However, the present invention is not limited thereto, and blue light-emitting diode GaN may be used as the light-emitting diode 105. In this case, two kinds of phosphor powders 1 〇 2 in which red and green light are emitted are mixed in the transparent resin body 1〇3. For example, in a green light-emitting phosphor (CaD.98EllD.D2) 8MgD.9〇MnD.lClSi4〇16Cl2). In the red-emitting phosphor, SrS:Eu, CaS:Eu or CaAlSiN3:Eu or the like is used. Further, 2138-9623-PF; Jessica 21 200911962 may further contain YAG: Ce, CaGa2S4 or α_Sialon (α.-Sialon) in order to further increase the complementary color. In the above embodiment, InGaN or GaN was used as the ultraviolet diode 6, and GaN was used as the blue light-emitting diode. However, it is not limited to this, and InAlGaN, AlGaN, BAlGaN, BlInAlGaN, or the like can be used. The green luminescent phosphor is (Caa, Srb, Ba., EUd) 8Mgl-xMnxSi4 OieCh) (wherein a to d satisfy the following numerical values 0 < a < 1. 〇, 〇 $ b < 〇. 5, 〇 $ c<〇·5, 〇<d<〇· 2, a+b + c + d=l. 0,x satisfies the following numerical values: 〇S χ<0·3). Of course, it may also be '〇.〇〇1^3$〇.999, 〇SbS〇.499, 〇^c^〇.499' 0.001^d^0.199> a + b + c + d=l.〇5 Ο.Ο^χ^ 0.299. [Possibility of Industrial Use] The phosphor of the present invention is a green light-emitting phosphor that emits light with an ultraviolet light-emitting diode or a blue light-emitting diode as an excitation source, and a broad emission peak of an emission spectrum is suitable for use. The white light-emitting diode or the light-emitting device of the electroluminescence element is extremely useful for emitting natural light. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an excitation spectrum and an emission spectrum of a green light-emitting phosphor of Example 1. Fig. 2 is a view showing the spectrum of excitation light 2138-9623-PF of the green light-emitting phosphors of Examples 2 to 6; Jessica 22 200911962. Fig. 3 is a view showing the spectrum of the green light-emitting phosphor of the second to sixth embodiments. Fig. 4 is a view showing the spectrum. Figure 5 is a diagram of the spectrum. The emission spectrum of the phosphor of the green light-emitting phosphor of Example 7 to 1 is compared with that of the phosphor of Comparative Example 1, and the emission spectrum of the phosphor of Comparative Example 2 is shown. Figure. Fig. 7 is a schematic view showing one of the examples of the private sector. Fig. 7 is a view showing a light-emitting element of the present invention [main element symbol description] 101 to a transparent substrate; 102 to two types of phosphor powder; 103 to a transparent resin body; 104~ Mirror; 1 05~light emitting diode; 111~ light emitting element of the present embodiment. 2138-9623-PF; Jessica 23
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| JP5326777B2 (en) * | 2009-04-27 | 2013-10-30 | 日亜化学工業株式会社 | Phosphor and method for producing the same |
| JP5391946B2 (en) * | 2009-09-07 | 2014-01-15 | 日亜化学工業株式会社 | Phosphor, light emitting device using the same, and method for producing phosphor |
| JP5532769B2 (en) * | 2009-09-07 | 2014-06-25 | 日亜化学工業株式会社 | Phosphor, light emitting device using the same, and method for producing phosphor |
| KR101098006B1 (en) * | 2009-09-29 | 2011-12-23 | 한국화학연구원 | The phosphor based on (halo-)silicate and manufacturing method for the same |
| WO2013035332A1 (en) * | 2011-09-08 | 2013-03-14 | パナソニック株式会社 | Plasma display panel and phosphor |
| JP2015188050A (en) * | 2014-03-12 | 2015-10-29 | 株式会社東芝 | light-emitting device |
| US9923126B2 (en) * | 2014-04-30 | 2018-03-20 | Sharp Kabushiki Kaisha | Light emitting device having high color rendering using three phosphor types |
| DE102015202159B4 (en) | 2015-02-06 | 2023-06-15 | OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung | semiconductor lighting device |
| KR102514150B1 (en) * | 2016-01-05 | 2023-04-04 | 쑤저우 레킨 세미컨덕터 컴퍼니 리미티드 | Light emitting device and lighting unit having thereof |
| JP6912728B2 (en) | 2018-03-06 | 2021-08-04 | 日亜化学工業株式会社 | Light emitting device and light source device |
| US11732187B2 (en) | 2018-10-25 | 2023-08-22 | Nichia Corporation | Chlorosilicate fluorescent material, method for producing the same, and light emitting device |
| KR102159984B1 (en) * | 2020-06-22 | 2020-09-28 | 주식회사 네오스라이트 | LED lighting source for high-rendering vision safeguard |
| KR102166276B1 (en) * | 2020-06-22 | 2020-10-16 | 주식회사 네오스라이트 | LED lighting device for high-rendering vision safeguard |
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| JP5145934B2 (en) * | 2005-03-04 | 2013-02-20 | 三菱化学株式会社 | Phosphor and method for producing the same, and light emitting device using the phosphor |
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