TWI387635B - A phosphor particle group and a light-emitting device using the same - Google Patents

A phosphor particle group and a light-emitting device using the same Download PDF

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TWI387635B
TWI387635B TW097124430A TW97124430A TWI387635B TW I387635 B TWI387635 B TW I387635B TW 097124430 A TW097124430 A TW 097124430A TW 97124430 A TW97124430 A TW 97124430A TW I387635 B TWI387635 B TW I387635B
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light
phosphor
particle group
diameter
emitting device
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TW200920817A (en
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Tetsuya Hanamoto
Masatsugu Masuda
Kenji Terashima
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Sharp Kk
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Description

螢光體粒子群及使用其之發光裝置
本發明係關於適用於發光裝置之螢光體粒子之粒子群(螢光體粒子群)及將其用在波長變換部之發光裝置。
半導體發光元件與螢光體組合而成之發光裝置，作為期待成為低耗電、體積小、高輝度、廣範圍色再現性及高演色性之次世代發光裝置而廣受矚目，積極研究、開發。發光元件所發出之一次光，通常在長波長之紫外線到藍光之範圍，即可使用380~480 nm之光。另，還有適用於該用途之各種螢光體之波長變換部之提案。
現在，作為該種白色發光裝置，主要使用發藍色光之發光元件(峰值波長：460 nm左右)與因該藍色光激發而發出黃色光之以3價鈰賦活之(Y,Gd)3 (Al,Ga)5 O12 螢光體或以2價銪賦活之2(Sr,Ba,Ca)O．SiO2 螢光體之組合。但，該等發光裝置，色再現性(NTSC比)僅為70%左右，近年，即使是小型LCD也要求有更好的色再現性。
此外，最近對於該種發光裝置不僅嘗試變換功率(亮度)，且嘗試更提高輸入能量、進而嘗試提高亮度。於提高輸入能量之情形，有必要對包含波長變換部在內之發光裝置整體進行有效散熱。因此，雖然發光裝置整體之構造、材質等不斷進行開發，但現在依然無法避免作動時發光元件及波長變換部之溫度上昇。
但，特別是以3價鈰賦活之(Y,Gd)3 (Al,Ga)5 O12 螢光體， 於以25℃時之亮度(明亮度)作為100%時，由於在100℃時之亮度低至85%左右，故存在輸入能量無法調高之技術課題。因此，對於該種發光裝置，所使用之螢光體之溫度特性之改善是當務之急。
對於該等技術課題，已知使用以Eua Sib Alc Od Ne 實質表示之β型SiAlON，即藉由使用2價銪賦活氮氧化物綠色系發光螢光體，可得到具有良好色再現性(NTSC比)及溫度特性之發光裝置。
但，作為β型SiAlON之2價銪賦活氮氧化物綠色系發光螢光體，基本為柱狀結晶體，於螢光體之粒子群(螢光體粒子群)而言，易生成長徑對短徑比之值超過5之粒子。使用長徑對短徑比之值超過5之粒子占多數之螢光體粒子群之情形，存在下述技術課題，該螢光體粒子群分散至樹脂中時，會發生推測為形狀因數之凝集等現象，無法均質分佈，無法得到良好特性(亮度)。
因此，形狀受到控制之以Eua Sib Alc Od Ne 實質表示之β型SiAlON之2價銪賦活氮氧化物綠色系發光螢光體粒子，及使用其之高效發光裝置之開發是當務之急。例如特開2005－255895號公報(專利文獻1)中，關於β型SiAlON，記載有橫縱比(粒子之長軸長度對短軸長度比之值)之平均值在1.5以上20以下。但，專利文獻1之實施例中，並未記載各實施例之螢光體粒子之橫縱比，且完全未提及橫縱比與特性。此處長軸相當於本案之長徑，短軸相當於本案之短徑。另，專利文獻1中，於圖2中，僅顯示柱狀形狀(照 片)。
專利文獻1：特開2005－255895號公報
本發明係用以解決前述課題之發明，目的在於提供一種使用β型SiAlON之既高效又穩定之發光裝置，及所使用之螢光體粒子群。
本發明人等，為解決前述課題而積極調查、探討及開發之結果，發現使用結晶形狀受控制之β型SiAlON粒子群，可得到特性(亮度)良好之發光裝置。即，本發明如下所述。
本發明之螢光體粒子群之特徵為：以通式Eua Sib Alc Od Ne (式中，各符號係滿足下列之數：0.005≦a≦0.4，b＋c＝12，d＋e＝16)實質表示之β型SiAlON，即2價銪賦活氮氧化物綠色系發光螢光體粒子之粒子群，由長徑對短徑比之值大於1.0且3.0以下之螢光體粒子占60%以上所構成。
本發明之螢光體粒子群中，較好由其長徑對短徑比之值較好大於0.1且0.3以下之螢光體粒子占80%以上所構成。
本發明之螢光體粒子群中，在前述式中最好是0.01≦a≦0.2。
另，本發明之螢光體粒子群中，中值粒徑最好在6~20 μm之範圍內。
本發明亦提供一種發光裝置，其具備發出峰值波長 430~480 nm之一次光之氮化鎵系半導體發光元件，及吸收前述一次光、發出具有比一次光之波長更長之二次光之波長變換部，其中前述波長變換部係以通式Eua Sib Alc Od Ne (式中，各符號滿足下述之數：0.005≦a≦0.4，b＋c＝12，d＋e＝16)實質表示之β 型SiAlON，即2價銪賦活氮氧化物綠色系發光螢光體粒子群，該發光裝置含有由其長徑對短徑比之值大於1.0且3.0以下之螢光體粒子占60%以上所構成之螢光體粒子群。
本發明之發光裝置中，前述螢光體粒子群最好是由長徑對短徑比之值大於1.0且3.0以下之螢光體粒子占80%以上所構成。
於本發明之發光裝置中，前述螢光體粒子群，在前述式中最好是0.01≦a≦0.2。
另，本發明之發光裝置中，前述螢光體粒子群，中值粒徑最好在6~20 μm之範圍內。
 [發明之效果]
根據本發明，可提供可有效率地吸收來自發光元件之一次光，得到具有高效且優異色再現性(NTSC比)及良好溫度特性之白色光之發光裝置，與適用於該發光裝置之螢光體粒子群。
本發明之螢光體粒子群係由下述通式實質表示之β型SiAlON(賽隆)，即2價銪賦活氮氧化物綠色系發光螢光體之粒子構成。
通式：Eua Sib Alc Od Ne
前述式中，a值為滿足0.005≦a≦0.4之數，b值及c值為滿足b＋c＝12之數，d值及e值為滿足d＋e＝16之數。前述式中，a值若小於0.005，則會產生亮度不足之問題，而a值若超過0.4，則因濃度消光等，會產生亮度大幅降低之問題。另，Eu之添加量小於0.01之情形，螢光體粒子群中可能會有不含Eu之螢光體粒子，而Eu之添加量超過0.2之情形，可能會發生Eu之偏析使得螢光體粒子群中出現含有過多Eu之螢光體粒子，從作為粉體特性之安定性，維持母體均一性之觀點考慮，前述式中之a值最好是滿足0.01≦a≦0.2之數。
以前述通式實質表示之β型SiAlON(賽隆)，即2價銪賦活氮氧化物綠色系發光螢光體，具體來說，可舉例為Eu0.05 Si11.50 Al0.50 O0.05 N15.95 、Eu0.10 Si11.00 Al1.00 O0.10 N15.90 、Eu0.30 Si9.80 Al2.20 O0.30 N15.70 、Eu0.15 Si10.00 Al2.00 O0.20 N15.80 、Eu0.01 Si11.60 Al0.40 O0.01 N15.99 、Eu0.005 Si11.70 Al0.30 O0.03 N15.97 、Eu0.25 Si11.65 Al0.35 O0.06 N15.94 、Eu0.40 Si11.35 Al0.65 O0.15 N15.85 等，但並不局限於此。
此處，圖1係構成本發明之螢光體粒子群之螢光體粒子1之模式示意圖。本發明之螢光體粒子群，其特徵係由如圖1所示之柱狀形狀之粒子，其長徑x(沿長軸之直線距離)對短徑y(沿短軸之直線距離)比之值(縱橫比)大於1.0且3.0以下之螢光體粒子占60%以上構成。長徑對短徑比之值大於1.0且3.0以下之螢光體粒子未達螢光體粒子群之60%時， 使用該等螢光體粒子群之發光裝置之波長變換部(後述)無法使螢光體粒子緻密分散，從而無法得到足夠亮度。另，若要形成螢光體粒子非常緻密分散之良好波長變換部，實現特性非常安定之發光裝置，長徑對短徑比之值大於1.0且3.0以下之螢光體粒子較好占螢光體粒子群之80%以上，更好占90%以上。
另，構成前述螢光體粒子群之螢光體粒子之長徑對短徑比之值，可使用例如掃描電子顯微鏡(SEM)、透射型電子顯微鏡(TEM)或光學顯微鏡進行測定。另，螢光體粒子群中，長徑對短徑比之值大於1.0且3.0以下之螢光體粒子占多少比例也可使用例如掃描電子顯微鏡(SEM)、透射型電子顯微鏡(TEM)或光學顯微鏡進行測定。
本發明之螢光體粒子群，中值粒徑(D50值)較好在6~20 μm範圍內，更好在7~12 μm範圍內。於本發明之螢光體粒子群之中值粒徑不足6 μm之情形，有結晶成長不充分，使用該等螢光體粒子之發光裝置可能無法得到足夠亮度之虞，而若大於20 μm時，有較難形成螢光體粒子均質分散之波長變換部之虞。另，前述中值粒徑(D50值)係使用粒度分佈測定裝置(LA－920，崛場製造所製)進行測定之數值。
本發明之螢光體粒子群，除控制為由長徑對短徑比之大於1.0且3.0以下之螢光體粒子占60%以上構成以外，可使用先前公知之適當方法進行製造。對於構成本發明之螢光體粒子群之60%以上之螢光體粒子，控制其長徑對短徑比 之值大於1.0且3.0以下之方法，例如可藉由例如高精度控制氧濃度、高精度控制繞成容器中之原材料之密度與體積(繞成容器中原材料之填入狀態)，使合成時之溫度分佈達到最佳，但並不局限於此。
本發明亦提供使用前述本發明之螢光體粒子群之發光裝置。即，本發明之發光裝置，基本上具備發出一次光之發光元件，及吸收前述一次光發出具有比一次光之波長更長之二次光之波長變換部，該波長變換部中含有前述本發明之螢光體粒子群。此處，圖2係本發明之較佳例之發光裝置11之模式斷面圖。圖2所示之發光裝置11，基本上具備發光元件12與波長變換部13，波長變換部13含有多個螢光體粒子1。該多個螢光體粒子1構成前述本發明之螢光體粒子群。
本發明之發光裝置，具備含有由長徑對短徑比之值大於1.0且3.0以下之螢光體粒子占60%以上所構成之本發明之螢光體粒子群之波長變換部。該等本發明之發光裝置，可有效吸收發光元件所發出之一次光，得到具有高效且優異色再現性(NTSC比)及進而良好溫度特性之白色光。
本發明之發光裝置11所使用之發光元件12，從效率觀點觀之，可使用氮化鎵(GaN)系半導體。另，本發明之發光裝置11中之發光元件12，使用可發出峰值波長在430~480 nm範圍內之一次光之發光元件。使用峰值波長不足430 nm之發光元件時，獲得藍色成分之貢獻小，演色性差，無實用性，而，使用峰值波長超過480 nm之發光元件時，白色 時之亮度不足，無實用性。從效率性觀點觀之，本發明之發光裝置11中之發光元件12最好使用可發出440~470 nm範圍內之一次光之發光元件。
圖2所示之本發明之發光裝置11中，波長變換部13只要係含有前述本發明之螢光體粒子群，吸收發光元件12所發出之一次光之一部分，發出比一次光之波長更長之二次光之部件，則對介質並無特殊限定。介質(透明樹脂)可使用環氧樹脂、矽氧樹脂、尿素樹脂等，但並不局限於此。另，波長變換部13，在不妨礙本發明之效果之範圍內，還可適當含有SiO2 、TiO2 、ZrO2 、Al2 O3 、Y2 O3 等添加劑。
本發明之發光裝置11之波長變換部13中，如圖2所示，可含有除前述本發明之螢光體粒子群以外之螢光體粒子14。本發明之螢光體粒子群以外之波長變換部13中所含之螢光體粒子，雖無特殊限定，但由於本發明之螢光體粒子群係由綠色系發光螢光體粒子構成，故從可實現藉由混色呈現白色光之發光裝置觀之，最好是如下通式所表示之2價銪賦活氮化物紅色系發光螢光體粒子。
通式：(MI1－f Euf )MIISiN3
前述式中，MI表示鹼土類金屬，係選自Mg、Ca、Sr及Ba中之至少1種元素。另，前述式中，MII表示3價金屬元素，係選自Al、Ga、In、Sc、Y、La、Gd及Lu中之至少1種元素。其中，從可更高效率發出紅色系光而言，MII較好是選自Al、Ga及In中之至少1種元素。另，前述式中，f值為0.001≦f≦0.10，較好是0.005≦f≦0.05。f值若小於 0.001，則有無法得到足夠亮度之傾向；f值若大於0.10，則因為濃度消光等，有造成亮度大幅降低之傾向。
作為該等2價銪賦活氮化物紅色系發光螢光體，具體來說，可舉例為Ca0.99 Eu0.01 SiAlN3 、(Ca0.97 Mg0.02 Eu0.01 )(Al0.99 Ga0.01 )SiN3 、(Ca0.98 Eu0.02 )AlSiN3 、(Ca0.97 Sr0.01 Eu0.02 )(Al0.98 In0.02 )SiN3 、(Ca0.999 Eu0.001 )AlSiN3 、(Ca0.895 Mg0.100 Eu0.005 )AlSiN3 、(Ca0.79 Sr0.20 Eu0.01 )AlSiN3 、(Ca0.98 Eu0.02 )(Al0.95 Ga0.05 )SiN3 等，但並不局限於此。
另，使用前述2價銪賦活氮化物紅色系發光螢光體時，波長變換部13中與本發明之螢光體粒子群之混合比率，雖無特殊限定，但相對於本發明之螢光體粒子群，重量比較好是在1~35%範圍內，更好在5~25%範圍內。
本發明之發光裝置11中之波長變換部13，在不妨礙本發明之效果之範圍內，還可含有除前述2價銪賦活氮化物紅色系發光螢光體以外之本發明之螢光體粒子群以外之螢光體粒子。另，如此之本發明之螢光體粒子群、前述2價銪賦活氮化物紅色系發光螢光體以外之螢光體粒子，可加入本發明之螢光體粒子群及前述2價銪賦活氮化物紅色系發光螢光體中，進而可含於波長變換部13中。
本發明之發光裝置11，可通過先前公知之適當方法製造，對其製造方法並無特殊限定。係例示例如使用作為介質之熱硬化型矽氧樹脂製封裝材，於其中混練本發明之螢光體粒子群(以及視需要之本發明之螢光體粒子群以外之螢光體粒子)，將發光元件12封裝成形、製造之情形。
以下，例舉實施例及比較例對本發明進行詳細說明，但本發明並不局限於此。
<實施例1、比較例1>
發光元件使用具有450 nm峰值波長之氮化鎵(GaN)系半導體。波長變換部中使用具有Eu0.05 Si11.50 Al0.50 O0.05 N15.95 (β型SiAlON)(D50值：7.8 μm)組成之綠色系發光螢光體粒子之粒子群，長徑對短徑比之值大於1.0且3.0以下之粒子占85%之螢光體粒子群。該螢光體粒子群可藉由使氧濃度最適化進行調製。另，粒子分佈測定裝置使用LA－920(崛場製造所製)。該螢光體粒子群，藉由以一定比例分散於作為介質之熱硬化型矽樹脂製封裝材中，封裝發光元件，製作波長變換部，製作實施例1之發光裝置。對如此製作而成之實施例1之發光裝置，藉由順電流(IF)20 mA點燈，測定來自發光裝置之光輸出(光電流)，評價其特性(亮度)。
另一方面，除使用具有Eu0.05 Si11.50 Al0.50 O0.05 N15.95 (β型SiAlON)(D50值：7.6 μm)組成之綠色系發光螢光體粒子之粒子群，長徑對短徑比之值大於1.0且3.0以下之粒子占40%之螢光體粒子群以外，與前述同樣，製作比較例1之發光裝置，同樣進行特性評價。
實施例1、比較例1之結果如表1所示。從表1可知，實施例1之發光裝置與比較例1之發光裝置相比，其特性(亮度)更優良。
<實施例2~7、比較例2~7>
除使用如表2所示之長徑對短徑比之值大於1.0且3.0以下之粒子之比例(%)、D50值及發光元件以外，與實施例1同樣，分別製作實施例2~7、比較例2~7之發光裝置。將與實施例1同樣測定之特性(亮度)結果，一起列於表2。從表2中可知，實施例2~7之發光裝置與比較例2~7之發光裝置相比，其特性(亮度)更優良。
<實施例8、比較例8>
發光元件使用具有460 nm峰值波長之氮化鎵(GaN)系半導體。波長變換部中使用具有Eu0.01 Si11.80 Al0.20 O0.04 N15.96 (β型SiAlON)(D50值：10.5 μm)組成之綠色系發光螢光體粒子之粒子群，長徑對短徑比之值大於1.0且3.0以下之粒子占85%之螢光體粒子群，與具有(Ca0.99 Eu0.01 )AlSiN3 (D50值：10.5 μm)組成之2價銪賦活氮化物紅色系發光螢光體粒子。前述螢光體粒子群可藉由使合成時之溫度分佈最適化進行調製。另，粒子分佈測定裝置使用LA－920(崛場製造所製)。該螢光體粒子群及紅色系發光螢光體，藉由以一定比例分散於作為介質之熱硬化型矽樹脂製封裝材中，封裝發光元件，製作波長變換部，製作實施例8之發光裝置。
另一方面，除使用具有Eu0.05 Si11.50 Al0.50 O0.05 N15.95 (β型SiAlON)(D50值：7.6 μm)組成之綠色系發光螢光體粒子之粒子群，長徑對短徑比之值大於1.0且3.0以下之粒子占40%之螢光體粒子群以外，與實施例8同樣，製作比較例8之發光裝置。
對該實施例8、比較例8之發光裝置，進行與實施例1同樣之特性(亮度)評價。另，於順電流(IF)20 mA之條件下點燈，使用MCPD－2000(大塚電子公司製)測定來自發光裝置之白色光，亦對Tc－duv進行評價。結果如表3所示。由表3可了解實施例8之發光裝置，相較於比較例8之發光裝置，其特性(亮度)更優良。
此次所揭示之實施形態、實施例及比較例之所有特點均為示例而非局限於此。本發明之範圍並不局限於前述說明，而是由申請專利範圍界定，包含與申請專利範圍均等之意思及範圍內之所有變更。
1‧‧‧螢光體粒子
11‧‧‧發光裝置
12‧‧‧發光元件
13‧‧‧波長變換部
14‧‧‧本發明之螢光體粒子群以外之螢光體粒子
圖1係構成本發明之螢光體粒子群之螢光體粒子1之模式示意圖。
圖2係本發明之較佳例之發光裝置11之模式斷面圖。
(無元件符號說明)

Claims (9)

  1. 一種螢光體粒子群，其係以通式Eua Sib Alc Od Ne (式中，各符號為滿足下列之數：0.005≦a≦0.4，b+c=12，d+e=16)實質表示之β型SiAlON，即2價銪賦活氮氧化物綠色系發光螢光體粒子之粒子群，由長徑對短徑比之值大於1.0且3.0以下之柱狀螢光體粒子(1)占60%以上所構成。
  2. 如請求項1之螢光體粒子群，其中由長徑對短徑比之值大於1.0且3.0以下之螢光體粒子(1)占80%以上構成。
  3. 如請求項1之螢光體粒子群，其中前述式中，0.01≦a≦0.2。
  4. 如請求項1之螢光體粒子群，其中值粒徑在6~20 μm之範圍內。
  5. 一種發光裝置(11)，其係具備發出峰值波長430~480 nm之一次光之氮化鎵系半導體之發光元件(12)，及吸收前述一次光、發出比一次光之波長更長之二次光之波長變換部(13)，前述波長變換部(13)包含：以通式Eua Sib Alc Od Ne (式中，各符號為滿足下列之數：0.005≦a≦0.4，b+c=12，d+e=16)實質表示之β型SiAlON，即2價銪賦活氮氧化物綠色系發光螢光體粒子群，由長徑對短徑比之值大於1.0且3.0以下之柱狀螢光體粒子占60%以上構成之螢光體粒子群。
  6. 如請求項5之發光裝置(11)，其中前述螢光體粒子群由長 徑對短徑比之值大於1.0且3.0以下之螢光體粒子(1)占80%以上構成。
  7. 如請求項5之發光裝置(11)，其中前述式中，0.01≦a≦0.2。
  8. 如請求項5之發光裝置(11)，其中前述螢光體粒子群之中值粒徑在6~20 μm之範圍內。
  9. 如請求項5之發光裝置(11)，其中前述波長變換部(13)進一步包含：以通式：(MI1-f Euf )MIISiN3 (式中，MI表示鹼土類金屬，係選自Mg、Ca、Sr及Ba中之至少1種元素；MII表示3價金屬元素，係選自Al、Ga、In、Sc、Y、La、Gd及Lu中之至少1種元素；f值為0.001≦f≦0.10)所表示之2價銪賦活氮化物紅色系發光螢光體粒子。
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