TWI715784B - 波長轉換構件及使用其而成之發光裝置 - Google Patents
波長轉換構件及使用其而成之發光裝置 Download PDFInfo
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- TWI715784B TWI715784B TW106121063A TW106121063A TWI715784B TW I715784 B TWI715784 B TW I715784B TW 106121063 A TW106121063 A TW 106121063A TW 106121063 A TW106121063 A TW 106121063A TW I715784 B TWI715784 B TW I715784B
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- phosphors
- wavelength conversion
- conversion member
- light
- glass
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 77
- 239000011521 glass Substances 0.000 claims abstract description 67
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011159 matrix material Substances 0.000 claims abstract description 34
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 8
- 150000004767 nitrides Chemical class 0.000 claims abstract description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 4
- 150000004645 aluminates Chemical class 0.000 claims abstract description 4
- 150000004820 halides Chemical class 0.000 claims abstract description 4
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000005284 excitation Effects 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 23
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 230000007423 decrease Effects 0.000 description 27
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 21
- 239000000395 magnesium oxide Substances 0.000 description 11
- 238000010304 firing Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000001354 calcination Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000036962 time dependent Effects 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 229910017639 MgSi Inorganic materials 0.000 description 3
- 229910003564 SiAlON Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910003668 SrAl Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910015999 BaAl Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- DGWFDTKFTGTOAF-UHFFFAOYSA-N P.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl DGWFDTKFTGTOAF-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
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Abstract
本發明提供一種波長轉換構件及使用其而成之發光裝置,該波長轉換構件於照射LED或LD之光之情形時,經時性之發光強度降低較少。 本發明係一種波長轉換構件,其特徵在於:其係將無機螢光體分散於玻璃基質中而成者,並且上述玻璃基質以莫耳%計含有SiO2
30~85%、B2
O3
4.3~20%、Al2
O3
0~25%、Li2
O 0~3%、Na2
O 0~3%、K2
O 0~3%、Li2
O+Na2
O+K2
O 0~3%、MgO 0~35%、CaO 0~35%、SrO 0~35%、BaO 0~35%、MgO+CaO+SrO+BaO 0.1~45%、及ZnO 0~5%, 上述無機螢光體為選自由氧化物螢光體、氮化物螢光體、氮氧化物螢光體、氯化物螢光體、氧氯化物螢光體、鹵化物螢光體、鋁酸鹽螢光體及鹵磷酸鹽化物螢光體所組成之群中之至少1種。
Description
本發明係關於一種波長轉換構件,其係用以將發光二極體(LED:Light Emitting Diode)或雷射二極體(LD:Laser Diode)等發光元件所發出之光之波長轉換為其他波長者。
近年來,作為替代螢光燈或白熾燈之下一代光源,就低消耗電力、小型輕量、容易調節光量之觀點而言,業界對於使用LED或LD之光源之關注高漲。作為此種下一代光源之一例,例如專利文獻1中揭示有於出射藍光之LED上配置有吸收來自LED之光之一部分並轉換為黃色光之波長轉換構件的光源。該光源發出自LED所出射之藍光與自波長轉換構件所出射之黃色光之合成光即白色光。 作為波長轉換構件,先前使用將無機螢光體分散於樹脂基質中而成者。然而,於使用該波長轉換構件之情形時,存在如下問題:樹脂因來自LED之光而劣化,光源之亮度容易降低。尤其存在如下問題:樹脂基質因LED所發出之熱或高能量之短波長(藍色~紫外)光而劣化,引起變色或變形。 因此,業界提出有包含如下完全無機固體之波長轉換構件,該完全無機固體係將無機螢光體分散固定於玻璃基質中而代替樹脂(例如參照專利文獻2及3)。該波長轉換構件具有如下特徵:成為母材之玻璃不易因LED晶片之熱或照射光而劣化,不易產生變色或變形等問題。 然而,專利文獻2及3中所記載之波長轉換構件存在如下問題:無機螢光體因製造時之煅燒而劣化,亮度容易劣化。尤其於一般照明、特殊照明等用途中,由於要求較高之演色性,故而需要使用紅色或綠色等耐熱性相對較低之無機螢光體,而有無機螢光體之劣化變得明顯之傾向。因此,提出有藉由使玻璃組成中含有鹼金屬氧化物,而使玻璃粉末之軟化點降低之波長轉換構件(例如參照專利文獻4)。該波長轉換構件由於能夠藉由在相對低溫下之煅燒而製造,故而能夠抑制煅燒時之無機螢光體之劣化。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2000-208815號公報 [專利文獻2]日本專利特開2003-258308號公報 [專利文獻3]日本專利第4895541號公報 [專利文獻4]日本專利特開2007-302858號公報
[發明所欲解決之問題] 專利文獻4中所記載之波長轉換構件存在發光強度容易經時性地降低(熱淬滅)之問題。隨著近年來LED或LD等之光源之輸出進一步增大,發光強度之經時性降低日益變得明顯。 鑒於以上情況,本發明之目的在於提供一種波長轉換構件及使用其而成之發光裝置,該波長轉換構件於照射LED或LD之光之情形時,經時性之發光強度降低較少。 [解決問題之技術手段] 本發明之波長轉換構件之特徵在於:其係將無機螢光體分散於玻璃基質中而成者,並且玻璃基質以莫耳%計含有SiO2
30~85%、B2
O3
4.3~20%、Al2
O3
0~25%、Li2
O 0~3%、Na2
O 0~3%、K2
O 0~3%、Li2
O+Na2
O+K2
O 0~3%、MgO 0~35%、CaO 0~35%、SrO 0~35%、BaO 0~35%、MgO+CaO+SrO+BaO 0.1~45%、及ZnO 0~5%,無機螢光體為選自由氧化物螢光體、氮化物螢光體、氮氧化物螢光體、氯化物螢光體、氧氯化物螢光體、鹵化物螢光體、鋁酸鹽螢光體及鹵磷酸鹽化物螢光體所組成之群中之至少1種。此處,「○+○+……」意指相應之各成分之合計量。 本發明者等人查明:波長轉換構件之發光強度之經時性降低之原因尤其在於玻璃組成中所包含之鹼金屬成分。其機制推測如下。 若對組成中含有鹼金屬元素之玻璃基質照射激發光,則玻璃基質中之存在於氧離子之最外殼之電子因激發光之能量而被激發,自氧離子脫離。其一部分與玻璃基質中之鹼離子鍵結形成著色中心(此處,於鹼離子脫落之後會形成空位)。另一方面,因電子脫落而生成之電洞於玻璃基質中移動,一部分被鹼離子脫落後所形成之空位捕捉而形成著色中心。認為玻璃基質中所形成之該等著色中心成為激發光或螢光之吸收源,波長轉換構件之發光強度降低。進而,有如下傾向:由於自無機螢光體產生之熱(因波長轉換損耗產生之熱),玻璃基質中之電子、電洞、鹼離子之移動變得活躍。因此,會加速著色中心之形成,發光強度變得容易降低。 本發明之波長轉換構件係藉由如上述般極力減少玻璃基質中之鹼金屬成分之含量,而抑制著色中心之產生。又,藉由極力減少玻璃基質中之鹼金屬成分之含量,亦能夠抑制高溫高濕下之經時性玻璃基質劣化。 再者,本發明之波長轉換構件之玻璃基質含有鹼土金屬氧化物(MgO、CaO、SrO、BaO)作為必須成分。鹼土金屬氧化物不會如鹼金屬離子般對波長轉換構件之發光強度之經時性降低產生影響,能夠使玻璃基質之軟化點降低。因此,能夠抑制無機螢光體之特性因製造時之煅燒而劣化。 於本發明之波長轉換構件中,較佳為玻璃基質之軟化點為600~1100℃。 本發明之波長轉換構件較佳為含有無機螢光體0.01~70質量%。 本發明之波長轉換構件較佳為包含粉末燒結體。 本發明之發光裝置之特徵在於:其係具備上述波長轉換構件、及向波長轉換構件照射激發光之光源而成。 本發明之車輛用照明之特徵在於:其使用上述發光裝置。 本發明之車輛用照明之特徵在於:其係用作前照燈。 [發明之效果] 本發明之波長轉換構件於照射LED或LD之光之情形時,經時性之發光強度降低較少。因此,使用本發明之波長轉換構件而成之發光裝置於長期可靠性方面優異,適合作為車輛用照明、尤其是車輛用前照燈。
本發明之波長轉換構件係將無機螢光體分散於玻璃基質中而成者。玻璃基質以莫耳%計含有SiO2
30~85%、B2
O3
4.3~20%、Al2
O3
0~25%、Li2
O 0~3%、Na2
O 0~3%、K2
O 0~3%、Li2
O+Na2
O+K2
O 0~3%、MgO 0~35%、CaO 0~35%、SrO 0~35%、BaO 0~35%、MgO+CaO+SrO+BaO 0.1~45%、及ZnO 0~5%。如此限定玻璃組成範圍之原因於下文加以說明。再者,於以下之說明中,只要無特別說明,則「%」意指「莫耳%」。 SiO2
係形成玻璃網絡之成分。SiO2
之含量為30~85%,較佳為35~80%。若SiO2
之含量過少,則有耐候性或機械強度降低之傾向。另一方面,若SiO2
之含量過多,則由於燒結溫度成為高溫,故而於製造波長轉換構件時,無機螢光體變得容易劣化。 B2
O3
係使熔融溫度降低而顯著改善熔融性之成分。B2
O3
之含量為4.3~20%,較佳為4.3~18%。若B2
O3
之含量過少,則製造波長轉換構件時之煅燒步驟中之玻璃之流動性變差,變得容易於玻璃基質中殘留氣泡。另一方面,若B2
O3
之含量過多,則耐候性變得容易降低。 Al2
O3
係使耐候性或機械強度提昇之成分。Al2
O3
之含量為0~25%,較佳為0.1~20%。若Al2
O3
之含量過多,則有熔融性降低之傾向。 Li2
O、Na2
O及K2
O係使熔融溫度降低而改善熔融性並且使軟化點降低之成分。然而,若該等成分之含量過多,則耐候性變得容易降低,且發光強度變得容易因LED或LD之光照射而經時性地降低。因此,Li2
O+Na2
O+K2
O之含量為0~3%,較佳為0~2%。又,Li2
O、Na2
O及K2
O之各成分之含量分別為0~3%,較佳為分別為0~2%。於含有Li2
O、Na2
O、K2
O之情形時,較佳為將2種以上、尤其是3種混合而使用。若如此,則能夠藉由混合鹼效果而抑制因LED或LD之光照射引起之發光強度之經時性降低。 MgO、CaO、SrO及BaO係使熔融溫度降低而改善熔融性從而使軟化點降低之成分。再者,如上所述,該等成分與鹼金屬成分不同,不會對波長轉換構件之發光強度之經時性降低產生影響。MgO+CaO+SrO+BaO之含量為0.1~45%,較佳為0.1~40%、0.1~35%、1~30%、尤其是5~25%。若MgO+CaO+SrO+BaO之含量過少,則軟化點變得難以降低。另一方面,若MgO+CaO+SrO+BaO之含量過多,則耐候性變得容易降低。再者,MgO、CaO、SrO及BaO之各成分之含量分別為0~35%,較佳為0.1~33%、尤其是1~30%。若該等成分之含量過多,則有耐候性降低之傾向。 ZnO係使熔融溫度降低而改善熔融性之成分。ZnO之含量為0~5%,較佳為1~4.5%,更佳為1.8~4%。若ZnO之含量過多,則有耐候性降低之傾向。又,會發生分相,導致透過率降低,結果有發光強度降低之傾向。 又,除上述成分以外,亦可於無損本發明之效果之範圍內含有各種成分。例如,可含有P2
O5
、La2
O3
、Ta2
O5
、TeO2
、TiO2
、Nb2
O5
、Gd2
O3
、Y2
O3
、CeO2
、Sb2
O3
、SnO2
、Bi2
O3
、As2
O3
及ZrO2
等各15%以下,進而10%以下,尤其是5%以下,以合計量計為30%以下之範圍內。又,亦可含有F。F由於具有降低軟化點之效果,故而藉由含有其而代替作為著色中心形成之原因之一的鹼金屬成分,能夠於維持低軟化點之情況下抑制發光強度之經時性降低。F之含量較佳為以陰離子%計為0~10%、0~8%、尤其是0.1~5%。 Fe及Cr係使可見透光率降低、引起發光強度降低之成分。因此,Fe之含量較佳為1000 ppm以下,尤其是500 ppm以下。又,Cr之含量較佳為500 ppm以下,尤其是100 ppm以下。但是,為了使玻璃中不含有Fe及Cr,需要使用昂貴之高純度原料,因此製造成本容易變得高昂。因此,就降低製造成本之觀點而言,Fe及Cr之含量較佳為分別為5 ppm以上,尤其是10 ppm以上。 玻璃基質之軟化點較佳為600~1100℃、630~1050℃、尤其是650~1000℃。若玻璃基質之軟化點過低,則機械強度及耐候性變得容易降低。另一方面,若軟化點過高,則燒結溫度亦會變高,因此無機螢光體變得容易在製造時之煅燒步驟中發生劣化。 本發明之無機螢光體為選自由氧化物螢光體(包含YAG螢光體等石榴石系螢光體)、氮化物螢光體、氮氧化物螢光體、氯化物螢光體、氧氯化物螢光體、鹵化物螢光體、鋁酸鹽螢光體及鹵磷酸鹽化物螢光體所組成之群中之至少1種。該等無機螢光體之中,較佳為氧化物螢光體、氮化物螢光體及氮氧化物螢光體,其原因在於:耐熱性較高,於煅燒時相對不易劣化。再者,氮化物螢光體及氮氧化物螢光體具有如下特徵:將近紫外~藍色激發光轉換為綠色~紅色等較廣之波長區域,並且發光強度亦相對較高。因此,氮化物螢光體及氮氧化物螢光體尤其是作為白色LED元件用波長轉換構件中所使用之無機螢光體有效。為了抑制自無機螢光體所產生之熱傳導至玻璃基質,可使用經被覆處理之無機螢光體。藉此抑制玻璃基質中之電子、電洞、鹼離子之移動之活躍化,結果能夠抑制著色中心之形成。作為被覆材,較佳為氧化物。再者,作為上述以外之螢光體,可列舉硫化物螢光體,但硫化物螢光體由於經時性地劣化、或與玻璃基質反應而容易使發光強度降低,故而於本發明中不使用。 作為上述無機螢光體,可列舉於波長300~500 nm具有激發帶且於波長380~780 nm具有發光峰者,尤其是發出藍色(波長440~480 nm)、綠色(波長500~540 nm)、黃色(波長540~595 nm)、紅色(波長600~700 nm)光者。 作為照射波長300~440 nm之紫外~近紫外之激發光則發出藍色光之無機螢光體,可列舉:(Sr,Ba)MgAl10
O17
:Eu2+
、(Sr,Ba)3
MgSi2
O8
:Eu2+
等。 作為照射波長300~440 nm之紫外~近紫外之激發光則發出綠色螢光之無機螢光體,可列舉:SrAl2
O4
:Eu2+
、SrBaSiO4
:Eu2+
、Y3
(Al,Gd)5
O12
:Ce3+
、SrSiON:Eu2+
、BaMgAl10
O17
:Eu2+
,Mn2+
、Ba2
MgSi2
O7
:Eu2+
、Ba2
SiO4
:Eu2+
、Ba2
Li2
Si2
O7
:Eu2+
、BaAl2
O4
:Eu2+
等。 作為照射波長440~480 nm之藍色激發光則發出綠色螢光之無機螢光體,可列舉:SrAl2
O4
:Eu2+
、SrBaSiO4
:Eu2+
、Y3
(Al,Gd)5
O12
:Ce3+
、SrSiON:Eu2+
、β-SiAlON:Eu2+
等。 作為照射波長300~440 nm之紫外~近紫外之激發光則發出黃色螢光之無機螢光體,可列舉La3
Si6
N11
:Ce3+
等。 作為照射波長440~480 nm之藍色激發光則發出黃色螢光之無機螢光體,可列舉:Y3
(Al,Gd)5
O12
:Ce3+
、Sr2
SiO4
:Eu2+
。 作為照射波長300~440 nm之紫外~近紫外之激發光則發出紅色螢光之無機螢光體,可列舉:MgSr3
Si2
O8
:Eu2+
,Mn2+
、Ca2
MgSi2
O7
:Eu2+
,Mn2+
等。 作為照射波長440~480 nm之藍色激發光則發出紅色螢光之無機螢光體,可列舉:CaAlSiN3
:Eu2+
、CaSiN3
:Eu2+
、(Ca,Sr)2
Si5
N8
:Eu2+
、α-SiAlON:Eu2+
等。 再者,亦可根據激發光或發光之波長區域而混合使用複數種無機螢光體。例如,於照射紫外光區域之激發光而獲得白色光之情形時,混合使用發出藍色、綠色、黃色、紅色之螢光的無機螢光體即可。 再者,一般而言,無機螢光體之折射率高於玻璃之情形較多。於波長轉換構件中,若無機螢光體與玻璃基質之折射率差較大,則於無機螢光體與玻璃基質之界面,激發光變得容易散射。其結果為,激發光對無機螢光體之照射效率變高,發光效率變得容易提昇。但是,若無機螢光體與玻璃基質之折射率差過大,則有如下傾向:激發光之散射變得過度,成為散射損耗,發光效率反而降低。鑒於以上情況,無機螢光體與玻璃基質之折射率差較佳為0.001~0.5左右。又,玻璃基質之折射率(nd)較佳為1.45~1.8,更佳為1.47~1.75,進而較佳為1.48~1.6。 波長轉換構件之發光效率(lm/W)根據無機螢光體之種類或含量、進而波長轉換構件之厚度等而變化。無機螢光體之含量及波長轉換構件之厚度以發光效率成為最佳之方式進行適當調整即可。若無機螢光體之含量變得過多,則有產生如下問題之擔憂:變得難以進行燒結,或氣孔率增大而變得難以對無機螢光體照射激發光,或波長轉換構件之機械強度降低等。另一方面,若無機螢光體之含量過少,則變得難以獲得所需發光強度。就此種觀點而言,本發明之波長轉換構件之無機螢光體之含量較佳為0.01~70質量%,更佳為0.05~50質量%,進而較佳為0.08~30質量%。 再者,於以使波長轉換構件中產生之螢光向激發光入射側反射、主要僅將螢光取出至外部為目的之波長轉換構件中,並非限於上述,為了使發光強度成為最大,可增多無機螢光體之含量(例如,30~80質量%,進而40~75質量%)。 於本發明之波長轉換構件中,除無機螢光體以外,亦可含有以合計量計至多30質量%之氧化鋁、二氧化矽、氧化鎂等光擴散材。 本發明之波長轉換構件較佳為包含粉末燒結體。具體而言,較佳為包含含有玻璃粉末及無機螢光體粉末之混合粉末之燒結體。若如此,則變得能夠容易地製作無機螢光體均勻地分散於玻璃基質中之波長轉換構件。 玻璃粉末之最大粒徑Dmax
較佳為200 μm以下、150 μm以下、尤其是105 μm以下。玻璃粉末之平均粒徑D50
較佳為0.1 μm以上、1 μm以上、尤其是2 μm以上。若玻璃粉末之最大粒徑Dmax
過大,則於所獲得之波長轉換構件中,激發光變得難以散射,發光效率變得容易降低。又,若玻璃粉末之平均粒徑D50
過小,則於所獲得之波長轉換構件中,激發光過度散射,發光效率變得容易降低。 再者,於本發明中,最大粒徑Dmax
及平均粒徑D50
係指藉由雷射繞射法所測得之值。 包含玻璃粉末及無機螢光體之混合粉末之煅燒溫度較佳為玻璃粉末之軟化點±150℃以內,尤其是玻璃粉末之軟化點±100℃以內。若煅燒溫度過低,則玻璃粉末不會充分地流動,導致難以獲得緻密之燒結體。另一方面,若煅燒溫度過高,則有如下擔憂:無機螢光體成分溶出至玻璃中使發光強度降低,或因無機螢光體成分擴散至玻璃中,使玻璃著色,導致發光強度降低。 煅燒較佳為於減壓環境中進行。具體而言,煅燒中之環境較佳為未達1.013×105
Pa、1000 Pa以下、尤其是400 Pa以下。藉此,能夠減少殘留於波長轉換構件中之氣泡之量。其結果為,能夠減少波長轉換構件內之散射因子,能夠使發光效率提昇。再者,可使整個煅燒步驟於減壓環境中進行,亦可例如僅使煅燒步驟於減壓環境中進行,且使其前後之升溫步驟或降溫步驟於非減壓環境之環境(例如大氣壓下)下進行。 本發明之波長轉換構件之形狀並無特別限制,例如不僅包括板狀、柱狀、半球狀、半球圓頂狀等其自身具有特定形狀之構件,亦包括形成於玻璃基板或陶瓷基板等基材表面之覆膜狀之燒結體等。 再者,於波長轉換構件表面亦可設置反射防止膜或微細凹凸構造層。若如此,則於波長轉換構件表面之光反射率會降低,光取出效率得到改善,能夠使發光強度提昇。 作為反射防止膜,可列舉包含氧化物、氮化物、氟化物等之單層膜或多層膜(介電多層膜),可藉由濺鍍法、蒸鍍法、塗佈法等而形成。反射防止膜之光反射率較佳為於波長380~780 nm中為5%以下、4%以下、尤其是3%以下。 作為微細凹凸構造層,可列舉包含可見光之波長以下之大小的蛾眼構造等。作為微細凹凸構造層之製作方法,可列舉奈米壓印法或光微影法。或者亦可藉由利用噴砂、蝕刻、研磨等將波長轉換構件表面進行粗面化而形成微細凹凸構造層。凹凸構造層之表面粗糙度Ra較佳為0.001~0.3 μm、0.003~0.2 μm、尤其是0.005~0.15 μm。若表面粗糙度Ra過小,則變得難以獲得所需反射防止效果。另一方面,若表面粗糙度Ra過大,則光散射變大,發光強度變得容易降低。 圖1表示本發明之發光裝置之實施形態之一例。如圖1所示,發光裝置1係具備波長轉換構件2及光源3而成。光源3對波長轉換構件2照射激發光L1。入射至波長轉換構件2之激發光L1轉換為其他波長之螢光L2,並自與光源3相反之側出射。此時,亦可出射不進行波長轉換而透射之激發光L1與螢光L2之合成光。 [實施例] 以下,基於實施例對本發明詳細地進行說明,但本發明並不限定於該等實施例。 (1)玻璃粉末之製作 表1~3揭示實施例中使用之玻璃粉末(試樣1~23)及比較例中使用之玻璃粉末(試樣24、25)。 [表1]
[表2]
[表3]
以成為表1~3所示之玻璃組成之方式調配原料,並使用鉑坩堝於1200~1700℃下熔融1~2小時進行玻璃化。藉由使熔融玻璃於一對冷卻輥之間流出而成形為膜狀。將所獲得之膜狀玻璃成形體利用球磨機進行粉碎,其後進行分級而獲得平均粒徑D50
為2.5 μm之玻璃粉末。對所獲得之玻璃粉末,藉由下述方法對熱膨脹係數、密度、應變點、緩冷點、軟化點及耐候性進行測定。 熱膨脹係數係使用膨脹計測定30~380℃之範圍之值。 密度係藉由阿基米德法(Archimedes method)進行測定。 應變點、緩冷點及軟化點係使用纖維伸長法,並採用黏度分別成為1014.5
dPa・s、1013.0
dPa・s及107.6
dPa・s之溫度。 耐候性係藉由如下方式進行評價。將玻璃粉末利用模具進行加壓成型而製作直徑1 cm之圓柱狀預成型體,以於表1~3記載之煅燒溫度進行煅燒,藉此獲得圓柱狀之燒結體試樣。使用平山製作所製造之HAST試驗機PC-242HSR2,將試樣於121℃、95%RH、2個大氣壓之條件下保持300小時,對表面進行觀察,藉此對耐候性進行評價。具體而言,藉由光學顯微鏡觀察(×500),將試驗前後試樣表面無變化者評價為「○」,將試樣表面析出有玻璃成分、或失去光澤者評價為「×」。 (2)波長轉換構件之製作 表4~8係揭示本發明之實施例(試樣A-1~A-23、B-1~B-23)及比較例(A-24、A-25、B-24、B-25)。 [表4]
[表5]
[表6]
[表7]
[表8]
以特定之質量比對表1~3記載之各玻璃粉末試樣混合表4~8所示之無機螢光體粉末,而獲得混合粉末。將混合粉末利用模具進行加壓成型而製作直徑1 cm之圓柱狀預成型體。將預成型體進行煅燒,其後,對所獲得之燒結體實施加工,藉此獲得1.2 mm見方、厚度0.2 mm之波長轉換構件。再者,煅燒溫度係根據所使用之玻璃粉末而採用表1~3記載之煅燒溫度。 將上述波長轉換構件載置於接通650 mA之發光波長445 nm之LED晶片上,並進行連續光照射100小時。針對光照射前及光照射後之波長轉換構件,使用通用之發光光譜測定裝置對在積分球內自波長轉換構件上表面發出之光之能量分佈光譜進行測定。藉由將標準比視感度乘以所獲得之發光光譜,而算出總光束值。總光束值之變化率以光照射後之總光束值除以光照射前之總光束值乘以100所獲得之值(%)表示。將結果示於表4~8。 由表4~8明確:於使用YAG作為無機螢光體之情形時,作為實施例之A-1~A-23之波長轉換構件即便於100小時之光照射後,亦維持光照射前之99.5%以上之總光束值,相對於此,作為比較例之A-24、A-25之波長轉換構件於100小時之光照射後之總光束值降低為光照射前之98%以下。 又,於使用α-SiAlON作為無機螢光體之情形時,作為實施例之B-1~B-23之波長轉換構件即便於100小時之光照射後亦維持光照射前之99%以上之總光束值,相對於此,作為比較例之B-24、B-25之波長轉換構件於100小時之光照射後之總光束值降低為光照射前之94%以下。 [產業上之可利用性] 本發明之波長轉換構件適宜作為白色LED等一般照明或特殊照明(例如投影光源、車輛用前照燈等車輛用照明)等構成構件。
1‧‧‧發光裝置2‧‧‧波長轉換構件3‧‧‧光源L1‧‧‧激發光L2‧‧‧螢光
圖1係本發明之一實施形態之發光裝置的模式性側視圖。
1‧‧‧發光裝置
2‧‧‧波長轉換構件
3‧‧‧光源
L1‧‧‧激發光
L2‧‧‧螢光
Claims (7)
- 一種波長轉換構件,其特徵在於:其係將無機螢光體分散於玻璃基質中而成者,並且上述玻璃基質以莫耳%計含有SiO2 30~85%、B2O3 4.3~20%、Al2O3 0~25%、Li2O 0~1%、Na2O 0~1%、K2O 0~1%、Li2O+Na2O+K2O 0~1%、MgO 0~35%、CaO 0~35%、SrO 0~35%、BaO 0~35%、MgO+CaO+SrO+BaO 0.1~45%、及ZnO 0~5%,上述無機螢光體為選自由氧化物螢光體、氮化物螢光體、氮氧化物螢光體、氯化物螢光體、氧氯化物螢光體、鹵化物螢光體、鋁酸鹽螢光體及鹵磷酸鹽化物螢光體所組成之群中之至少1種。
- 如請求項1之波長轉換構件,其中上述玻璃基質之軟化點為600~1100℃。
- 如請求項1或2之波長轉換構件,其含有上述無機螢光體0.01~70質量%。
- 如請求項1或2之波長轉換構件,其包含粉末燒結體。
- 一種發光裝置,其特徵在於:其係具備如請求項1至4中任一項之波長轉換構件、及向上述波長轉換構件照射激發光之光源而成。
- 一種車輛用照明,其特徵在於:其使用如請求項5之發光裝置。
- 如請求項6之車輛用照明,其係用作前照燈。
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2016
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2017
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- 2017-06-08 KR KR1020187023761A patent/KR102422069B1/ko active IP Right Grant
- 2017-06-08 CN CN202210949694.8A patent/CN115172569A/zh active Pending
- 2017-06-08 KR KR1020237033685A patent/KR20230144121A/ko not_active Application Discontinuation
- 2017-06-08 CN CN202210949707.1A patent/CN115312651A/zh active Pending
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TW201542766A (zh) * | 2014-04-01 | 2015-11-16 | 日本電氣硝子股份有限公司 | 波長變換構件及使用其而成之發光裝置 |
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US20240174916A1 (en) | 2024-05-30 |
EP3477187A4 (en) | 2020-01-15 |
EP3477187C0 (en) | 2023-08-02 |
KR20220104069A (ko) | 2022-07-25 |
CN115172569A (zh) | 2022-10-11 |
WO2018003453A1 (ja) | 2018-01-04 |
EP3477187B1 (en) | 2023-08-02 |
JP2021121855A (ja) | 2021-08-26 |
CN115312651A (zh) | 2022-11-08 |
JP2022184915A (ja) | 2022-12-13 |
JP2018002491A (ja) | 2018-01-11 |
KR20190022441A (ko) | 2019-03-06 |
CN109417118B (zh) | 2022-08-30 |
JP7538482B2 (ja) | 2024-08-22 |
US20220081612A1 (en) | 2022-03-17 |
EP3477187A1 (en) | 2019-05-01 |
US20190112524A1 (en) | 2019-04-18 |
US12031069B2 (en) | 2024-07-09 |
KR20230144121A (ko) | 2023-10-13 |
US11254862B2 (en) | 2022-02-22 |
CN109417118A (zh) | 2019-03-01 |
KR102588721B1 (ko) | 2023-10-12 |
KR102422069B1 (ko) | 2022-07-15 |
JP6880528B2 (ja) | 2021-06-02 |
TW201815717A (zh) | 2018-05-01 |
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