CN115172566A - 波长转换部件以及使用其的发光器件 - Google Patents
波长转换部件以及使用其的发光器件 Download PDFInfo
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- CN115172566A CN115172566A CN202210789175.XA CN202210789175A CN115172566A CN 115172566 A CN115172566 A CN 115172566A CN 202210789175 A CN202210789175 A CN 202210789175A CN 115172566 A CN115172566 A CN 115172566A
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- phosphor
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- conversion member
- light
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 73
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000011521 glass Substances 0.000 claims abstract description 68
- 239000011159 matrix material Substances 0.000 claims abstract description 32
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 150000004767 nitrides Chemical class 0.000 claims abstract description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 7
- DGWFDTKFTGTOAF-UHFFFAOYSA-N P.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl DGWFDTKFTGTOAF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001263 acyl chlorides Chemical class 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
- 230000005284 excitation Effects 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 7
- 238000005286 illumination Methods 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 26
- 238000010304 firing Methods 0.000 description 16
- 230000007423 decrease Effects 0.000 description 13
- 239000000395 magnesium oxide Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 9
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- 229910001413 alkali metal ion Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
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- 230000000694 effects Effects 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 4
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- 239000011812 mixed powder Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
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- 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
- 238000000576 coating method Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- -1 oxygen ions Chemical class 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
- 238000000137 annealing Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 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
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002223 garnet 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
- 239000006060 molten glass Substances 0.000 description 1
- 230000003287 optical effect Effects 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
- 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
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Abstract
本发明提供在照射LED、LD的光的情况下,经时的发光强度的降低少的波长转换部件以及使用其的发光器件。该波长转换部件的特征在于,其为在玻璃基质中分散有无机荧光体的波长转换部件,上述玻璃基质以摩尔%计,含有30~85%的SiO2、0~20%的B2O3、0~25%的Al2O3、0~3%的Li2O、0~3%的Na2O、0~3%的K2O、0~3%的Li2O+Na2O+K2O、0~35%的MgO、0~35%的CaO、0~35%的SrO、0~35%的BaO、0.1~45%的MgO+CaO+SrO+BaO、和0~4%的ZnO,上述无机荧光体为选自氧化物荧光体、氮化物荧光体、氧氮化物荧光体、氯化物荧光体、酰氯化物荧光体、卤化物荧光体、铝酸盐荧光体和卤磷酸盐化物荧光体中的至少1种。
Description
技术领域
本发明涉及用于将发光二极管(LED:Light Emitting Diode)或激光二极管(LD:Laser Diode)等发光元件发出的光的波长转换成其他波长的波长转换部件。
背景技术
近年来,作为代替荧光灯或白炽灯的下一代光源,从低消耗电力、小型轻量、容易光量调节的观点出发,对使用LED、LD的光源的关注提高。作为这样的下一代光源的一个例子,例如专利文献1公开了在射出蓝色光的LED上,配置有将来自LED的光的一部分吸收并转换成黄色光的波长转换部件的光源。该光源发出作为从LED射出的蓝色光与从波长转换部件射出的黄色光的合成光的白色光。
作为波长转换部件,一直以来使用在树脂基质中分散有无机荧光体的部件。然而,在使用该波长转换部件的情况下,存在因来自LED的光而使树脂劣化、光源的亮度容易变低的问题。特别是存在因LED发出的热或高能的短波长(蓝色~紫外)光而使树脂基质劣化、引起变色、变形的问题。
因此,提出了代替树脂而在玻璃基质中分散固定无机荧光体的由完全无机固体构成的波长转换部件(例如参照专利文献2和3)。该波长转换部件具有如下特征,即,成为母材的玻璃不易因LED芯片的热或照射光而劣化、不易产生变色和变形的问题。
然而,专利文献2和3中记载的波长转换部件存在由于制造时的烧制而使无机荧光体劣化、亮度容易劣化的问题。特别是在一般照明、特殊照明等的用途中,要求高的演色性,因此需要使用红色、绿色这样的耐热性比较低的无机荧光体,存在无机荧光体的劣化明显的倾向。因此,提出了在玻璃组成中含有碱金属氧化物,由此使玻璃粉末的软化点降低的波长转换部件(例如、参照专利文献4)。该波长转换部件能够通过比较低温的烧制制造,因此能够抑制在烧制时的无机荧光体的劣化。
现有技术文献
专利文献
专利文献1:日本特开2000-208815号公报
专利文献2:日本特开2003-258308号公报
专利文献3:日本专利第4895541号公报
专利文献4:日本特开2007-302858号公报
发明内容
发明所要解决的课题
专利文献4中记载的波长转换部件存在发光强度容易经时地降低(温度消光)的问题。伴随近年来的LED、LD等光源的输出功率进一步增大,发光强度的经时的降低越发明显。
鉴于以上情况,本发明的目的在于提供在照射LED、LD的光时,发光强度的经时降低少的波长转换部件以及使用该波长转换部件的发光器件。
用于解决课题的方法
本发明的波长转换部件,其特征在于,其为在玻璃基质中分散有无机荧光体的波长转换部件,玻璃基质以摩尔%计,含有30~85%的SiO2、0~20%的B2O3、0~25%的Al2O3、0~3%的Li2O、0~3%的Na2O、0~3%的K2O、0~3%的Li2O+Na2O+K2O、0~35%的MgO、0~35%的CaO、0~35%的SrO、0~35%的BaO、0.1~45%的MgO+CaO+SrO+BaO、和0~4%的ZnO,无机荧光体为选自氧化物荧光体、氮化物荧光体、氧氮化物荧光体、氯化物荧光体、酰氯化物荧光体、卤化物荧光体、铝酸盐荧光体和卤磷酸盐化物荧光体中的至少1种。其中,“○+○+···”是指该各成分的总量。
本发明的发明人研究发现,波长转换部件的发光强度的经时降低的原因特别在于玻璃组成中所含的碱金属成分。推测其机理如下。
可以认为如果对组成中含有碱金属元素的玻璃基质照射激发光,则由于激发光的能量,存在于玻璃基质中的氧离子的最外层的电子被激发,从氧离子脱离。其一部分与玻璃基质中的碱金属离子结合形成着色中心(其中,在碱金属离子脱离后形成空孔)。另一方面,由于电子脱离所生成的空穴在玻璃基质中移动,一部分被碱金属离子脱离后所形成的空孔捕获而形成着色中心。在玻璃基质中所形成的这些着色中心成为激发光、荧光的吸收源,使波长转换部件的发光强度降低。进而,由于由无机荧光体产生的热(因波长转换损失而产生的热),存在玻璃基质中的电子、空穴、碱金属离子的移动变得活跃的倾向。由此,会加速着色中心的形成,发光强度容易降低。
在本发明的波长转换部件中,通过如上所述尽量减少玻璃基质中的碱金属成分的含量,抑制着色中心的产生。另外,通过尽量减少玻璃基质中的碱金属成分的含量,还能够抑制高温高湿下的经时的玻璃基质劣化。
此外,本发明的波长转换部件中的玻璃基质含有碱土类氧化物(MgO、CaO、SrO、BaO)作为必须成分。碱土类氧化物不会如碱金属离子那样对波长转换部件的发光强度的经时降低造成影响,同时能够使玻璃基质的软化点降低。由此,能够抑制制造时由于烧制造成的无机荧光体的特性劣化。
在本发明的波长转换部件中,优选玻璃基质以摩尔%计,含有30~85%的SiO2、0~20%的B2O3、0~25%的Al2O3、0~3%的Li2O、0~3%的Na2O、0~3%的K2O、0~3%的Li2O+Na2O+K2O、0~35%的MgO、0~35%的CaO、0~35%的SrO、0~35%的BaO、0.1~45%的MgO+CaO+SrO+BaO和0以上且低于1.8%的ZnO。
在本发明的波长转换部件中,优选玻璃基质的软化点为600~1100℃。
本发明的波长转换部件优选含有0.01~70质量%的无机荧光体。
本发明的波长转换部件优选由粉末烧结体形成。
本发明的发光器件的特征在于,包括上述波长转换部件、以及对波长转换部件照射激发光的光源。
本发明的车载用照明的特征在于,使用了上述发光器件。
本发明的车载用照明的特征在于,作为前照灯使用。
发明的效果
本发明的波长转换部件在照射LED、LD的光的情况下,经时的发光强度的降低少。因此,使用本发明的波长转换部件的发光器件的长期可靠性优异,适合作为车载用照明、特别适合作为车载用前照灯。
附图说明
图1是本发明的一个实施方式的发光器件的示意性的侧视图。
具体实施方式
本发明的波长转换部件是在玻璃基质中分散有无机荧光体而成。玻璃基质以摩尔%计,含有30~85%的SiO2、0~20%的B2O3、0~25%的Al2O3、0~3%的Li2O、0~3%的Na2O、0~3%的K2O、0~3%的Li2O+Na2O+K2O、0~35%的MgO、0~35%的CaO、0~35%的SrO、0~35%的BaO、0.1~45%的MgO+CaO+SrO+BaO、和0~4%的ZnO。以下说明这样限定玻璃组成范围的理由。此外,在以下的说明中,只要没有特别说明,“%”就是指“摩尔%”。
SiO2是形成玻璃网络的成分。SiO2的含量为30~85%,优选为35~80%。如果SiO2的含量过少,则存在耐候性、机械强度降低的倾向。另一方面,如果SiO2的含量过多,则烧结温度变高,因此在制造波长转换部件时,无机荧光体容易劣化。
B2O3是使熔融温度降低而显著改善熔融性的成分。B2O3的含量为0~20%,优选为0.1~18%。如果B2O3的含量过多,则耐候性容易降低。
Al2O3是使耐候性、机械强度提高的成分。Al2O3的含量为0~25%,优选为0.1~20%。如果Al2O3的含量过多,则存在熔融性降低的倾向。
Li2O、Na2O和K2O是使熔融温度降低并改善熔融性、同时使软化点降低的成分。然而,如果这些成分的含量过多,则耐候性容易降低,且由于LED、LD的光照射,发光强度容易经时地降低。因此,Li2O+Na2O+K2O的含量为0~3%,优选为0~2%。另外,Li2O、Na2O和K2O的各成分的含量分别为0~3%,优选分别为0~2%。在含有Li2O、Na2O、K2O的情况下,优选混合使用2种以上、特别优选混合使用3种。如果这样设置,通过混合碱效果,能够抑制因LED、LD的光照射造成的发光强度的经时降低。
MgO、CaO、SrO和BaO是使熔融温度降低并改善熔融性、同时使软化点降低的成分。此外,如上所述,这些成分与碱金属成分不同,不影响波长转换部件的发光强度的经时降低。MgO+CaO+SrO+BaO的含量为0.1~45%,优选为0.1~40%、0.1~35%、1~30%,特别优选为5~25%。如果MgO+CaO+SrO+BaO的含量过少,则软化点难以降低。另一方面,如果MgO+CaO+SrO+BaO的含量过多,则耐候性容易降低。此外,MgO、CaO、SrO和BaO的各成分的含量分别优选为0~35%、0.1~33%、特别优选为1~30%。如果这些成分的含量过多,则存在耐候性降低的倾向。
ZnO是使熔融温度降低并改善熔融性的成分。ZnO的含量为0~4%,优选为0~3%,更优选为0以上且低于1.8%,更加优选为0.1~1.5%。如果ZnO的含量过多,则存在耐候性降低的倾向。另外会分相且透过率降低,作为结果存在发光强度降低的倾向。
另外,在上述成分以外,在不损害本发明的效果的范围还可以含有各种成分。例如,可以分别以15%以下、进而10%以下、特别是5%以下、以总量计30%以下的范围含有P2O5、La2O3、Ta2O5、TeO2、TiO2、Nb2O5、Gd2O3、Y2O3、CeO2、Sb2O3、SnO2、Bi2O3、As2O3和ZrO2等。另外,也可以含有F。由于F具有降低软化点的效果,所以通过代替作为着色中心形成的原因之一的碱金属成分而含有F,能够在维持低软化点的状态下,抑制发光强度的经时的降低。F的含量以阴离子%计优选为0~10%、0~8%、特别优选为0.1~5%。
Fe和Cr是使可见光透过率降低、成为发光强度降低的原因的成分。因此,Fe的含量优选为1000ppm以下,特别优选为500ppm以下。另外,Cr的含量优选为500ppm以下,特别优选为100ppm以下。其中,为了使玻璃中不含Fe和Cr,需要使用昂贵的高纯度原料,因此制造成本容易大涨。因此,从降低制造成本的观点出发,Fe和Cr的含量分别优选为5ppm以上,特别优选为10ppm以上。
玻璃基质的软化点优选为600~1100℃、630~1050℃、特别优选为650~1000℃。如果玻璃基质的软化点过低,则机械强度和耐候性容易降低。另一方面,如果软化点过高,则烧结温度也变高,因此在制造时的烧制工序中,无机荧光体容易劣化。
本发明的无机荧光体为选自氧化物荧光体(包括YAG荧光体等的石榴石系荧光体)、氮化物荧光体、氧氮化物荧光体、氯化物荧光体、酰氯化物荧光体、卤化物荧光体、铝酸盐荧光体和卤磷酸盐化物荧光体中的至少1种。这些无机荧光体中,氧化物荧光体、氮化物荧光体和氧氮化物荧光体的耐热性高,烧制时比较不易劣化,因此优选。此外,氮化物荧光体和氧氮化物荧光体将近紫外~蓝色的激发光转换成绿~红的宽范围的波长区域,而且具有发光强度也比较高的特征。因此,氮化物荧光体和氧氮化物荧光体特别是作为用于白色LED元件用波长转换部件的无机荧光体是有效的。为了抑制由无机荧光体产生的热传导至玻璃基质,也可以使用包覆处理过的无机荧光体。由此,能够抑制玻璃基质中的电子、空穴、碱金属离子的移动的活跃化,作为结果能够抑制着色中心的形成。作为包覆材料优选氧化物。此外,作为上述以外的荧光体可以列举硫化物荧光体,但硫化物荧光体由于会经时地劣化、或与玻璃基质反应而发光强度容易降低,所以在本发明中不使用。
作为上述无机荧光体,可以列举在波长300~500nm具有激发带在波长380~780nm具有发光峰的荧光体,特别是在蓝色(波长440~480nm)、绿色(波长500~540nm)、黄色(波长540~595nm)、红色(波长600~700nm)发光的荧光体。
作为照射波长300~440nm的紫外~近紫外的激发光而发出蓝色的发光的无机荧光体,可以列举(Sr,Ba)MgAl10O17:Eu2+、(Sr,Ba)3MgSi2O8:Eu2+等。
作为照射波长300~440nm的紫外~近紫外的激发光而发出绿色的荧光的无机荧光体,可以列举SrAl2O4:Eu2+、SrBaSiO4:Eu2+、Y3(Al,Gd)5O12:Ce3+、SrSiON:Eu2+、BaMgAl10O17:Eu2+,Mn2+、Ba2MgSi2O7:Eu2+、Ba2SiO4:Eu2+、Ba2Li2Si2O7:Eu2+、BaAl2O4:Eu2+等。
作为照射波长440~480nm的蓝色的激发光而发出绿色的荧光的无机荧光体,可以列举SrAl2O4:Eu2+、SrBaSiO4:Eu2+、Y3(Al,Gd)5O12:Ce3+、SrSiON:Eu2+、β-SiAlON:Eu2+等。
作为照射波长300~440nm的紫外~近紫外的激发光而发出黄色的荧光的无机荧光体,可以列举La3Si6N11:Ce3+等。
作为照射波长440~480nm的蓝色的激发光而发出黄色的荧光的无机荧光体,可以列举Y3(Al,Gd)5O12:Ce3+、Sr2SiO4:Eu2+。
作为照射波长300~440nm的紫外~近紫外的激发光而发出红色的荧光的无机荧光体,可以列举MgSr3Si2O8:Eu2+,Mn2+、Ca2MgSi2O7:Eu2+,Mn2+等。
作为照射波长440~480nm的蓝色的激发光而发出红色的荧光的无机荧光体,可以列举CaAlSiN3:Eu2+、CaSiN3:Eu2+、(Ca,Sr)2Si5N8:Eu2+、α-SiAlON:Eu2+等。
此外,也可以根据激发光和发光的波长域,而混合使用多种无机荧光体。例如,在照射紫外域的激发光要得到白色光的情况下,混合使用发出蓝色、绿色、黄色、红色的荧光的无机荧光体即可。
此外,一般而言,大多情况下,无机荧光体比玻璃的折射率高。在波长转换部件中,如果无机荧光体与玻璃基质的折射率差大,则激发光容易在无机荧光体与玻璃基质的界面散射。其结果,激发光相对于无机荧光体的照射效率提高,发光效率容易升高。只是如果无机荧光体与玻璃基质的折射率差过大,则激发光的散射变得过度,成为散射损失,反而有发光效率降低的倾向。鉴于以上情况,无机荧光体与玻璃基质的折射率差优选为0.001~0.5左右。另外,玻璃基质的折射率(nd)优选为1.45~1.8,更优选为1.47~1.75,更加优选为1.48~1.6。
波长转换部件的发光效率(lm/W)根据无机荧光体的种类、含量、进而波长转换部件的厚度等的不同而变化。无机荧光体的含量和波长转换部件的厚度以发光效率达到最优的方式适当调整即可。如果无机荧光体的含量过多,则有可能产生难以烧结、气孔率变大而激发光难以高效地照射到无机荧光体、波长转换部件的机械强度降低等问题。另一方面,如果无机荧光体的含量过少,则难以得到所希望的发光强度。从这样的观点出发,本发明的波长转换部件中无机荧光体的含量优选为0.01~70质量%,更优选为0.05~50质量%,更加优选为0.08~30质量%。
此外,在以使波长转换部件中产生的荧光向激发光入射侧反射、主要仅将荧光取出到外部为目的的波长转换部件中,并不限于上述内容,能够以发光强度达到最大的方式,增多无机荧光体的含量(例如、30~80质量%、进而40~75质量%)。
本发明的波长转换部件中,在无机荧光体以外,氧化铝、氧化硅、氧化镁等的光扩散材料可以以总量计含有到30质量%。
本发明的波长转换部件优选由粉末烧结体形成。具体而言,优选由包含玻璃粉末和无机荧光体粉末的混合粉末的烧结体形成。这样一来,就能够容易制作在玻璃基质中均匀分散有无机荧光体的波长转换部件。
玻璃粉末的最大粒径Dmax优选为200μm以下、150μm以下、特别优选为105μm以下。玻璃粉末的平均粒径D50优选为0.1μm以上、1μm以上、特别优选为2μm以上。如果玻璃粉末的最大粒径Dmax过大时,则在所得到的波长转换部件中,激发光难以散射,发光效率容易降低。另外,如果玻璃粉末的平均粒径D50过小,则在所得到的波长转换部件中,激发光过度散射而发光效率容易降低。
此外,在本发明中,最大粒径Dmax和平均粒径D50是指通过激光衍射法测定得到的值。
包含玻璃粉末和无机荧光体的混合粉末的烧制温度优选在玻璃粉末的软化点±150℃以内,特别优选在玻璃粉末的软化点±100℃以内。如果烧制温度过低,则玻璃粉末无法充分流动,难以得到致密的烧结体。另一方面,如果烧制温度过高,则有可能无机荧光体成分在玻璃中溶出而发光强度降低,或由于无机荧光体成分在玻璃中扩散而玻璃着色且发光强度降低。
烧制优选在减压气氛中进行。具体而言,烧制中的气氛优选低于1.013×105Pa、1000Pa以下、特别优选在400Pa以下。由此,能够减少波长转换部件中残留的气泡的量。其结果,能够降低波长转换部件内的散射因素,能够使发光效率提高。此外,既可以在减压气氛中进行全部烧制工序,也可以例如在减压气氛中仅进行烧制工序,其前后的升温工序、降温工序在非减压气氛的气氛(例如大气压下)下进行。
本发明的波长转换部件的形状没有特别限制、例如不仅可以为片状、柱状、半球状、半球圆顶状等其自身具有特定形状的部件,还包括形成在玻璃基板或陶瓷基板等基材表面的覆膜状的烧结体等。
此外,也可以在波长转换部件表面设置防反射膜或微细凹凸结构层。通过这样设置,波长转换部件表面的光反射率降低,改善光提取效率,能够使发光强度提高。
作为防反射膜,可以列举包含氧化物、氮化物、氟化物等的单层膜或多层膜(电介质多层膜),能够由溅射法、蒸镀法、涂布法等形成。防反射膜的光反射率在波长380~780nm时优选为5%以下、4%以下,特别优选为3%以下。
作为微细凹凸结构层,可以列举由可见光的波长以下的尺寸构成的蛾眼结构等。作为微细凹凸结构层的制作方法,可以列举纳米压印法、光刻法。或者,也可以利用喷砂、蚀刻、研磨等将波长转换部件表面糙面化而形成微细凹凸结构层。凹凸结构层的表面粗糙度Ra优选为0.001~0.3μm、0.003~0.2μm,特别优选为0.005~0.15μm。如果表面粗糙度Ra过小,则难以得到所希望的防反射效果。另一方面,如果表面粗糙度Ra过大,则光散射变大,发光强度容易降低。
图1示出本发明的发光器件的实施方式的一例。如图1所示,发光器件1包括波长转换部件2和光源3而成。光源3对波长转换部件2照射激发光L1。射入波长转换部件2的激发光L1被转换成其他波长的荧光L2,从光源3的相反侧射出。此时,也可以射出没有被波长转换而透过的激发光L1与荧光L2的合成光。
实施例
以下,根据实施例详细说明本发明,但本发明不限于这些实施例。
(1)玻璃粉末的制作
表1~3示出实施例中使用的玻璃粉末(试样1~39)和比较例中使用的玻璃粉末(试样40、41)。
[表1]
[表2]
[表3]
[表4]
[表5]
以成为表1~5所示的玻璃组成的方式调配原料,使用铂坩埚,在1200~1700℃熔融1~2小时进行玻璃化。通过将熔融玻璃倒出到一对冷却辊之间而以膜状成型。将所得到的膜状玻璃成型体用球磨机粉碎后,分级得到平均粒径D50为2.5μm的玻璃粉末。对所得到的玻璃粉末,用下述方法,测定热膨胀系数、密度、应变点、退火点、软化点和耐候性。
热膨胀系数利用膨胀计,测定30~380℃的范围的值。
密度利用阿基米德法测定。
应变点、退火点和软化点使用纤维伸长率法,采用粘度分别为1014.5dPa·s、1013.0dPa·s和107.6dPa·s的温度。
耐候性如下评价。将玻璃粉末用模具加压成型,制作直径1cm的圆柱状预成型体,以表1~5中记载的烧制温度烧制,由此得到圆柱状的烧结体试样。使用平山制作所制HAST试验机PC-242HSR2,将试样在121℃、95%RH、2气压的条件下保持300小时,观察表面,由此评价耐候性。具体而言,用光学显微镜观察(×500),将试验前后试样表面没有变化的试样评价为“○”,将在试样表面析出了玻璃成分、或丧失光泽的试样评价为“×”。
(2)波长转换部件的制作
表6~14示出本发明的实施例(试样A-1~A-39、B-1~B-39)和比较例(A-40、A-41、B-40、B-41)。
[表6]
[表7]
[表8]
[表9]
[表10]
[表11]
[表12]
[表13]
[表14]
在表1~5中记载的各玻璃粉末试样中将表6~14所示的无机荧光体粉末以规定的质量比混合,得到混合粉末。将混合粉末用模具加压成型,制作直径1cm的圆柱状预成型体。对预成型体进行烧制后,对所得到的烧结体实施加工,由此得到1.2mm见方、厚度0.2mm的波长转换部件。此外,烧制温度根据使用的玻璃粉末,采用表1~5中记载的烧制温度。
将上述波长转换部件载置在以650mA通电的发光波长445nm的LED芯片上,进行100小时连续光照射。关于光照射前和光照射后的波长转换部件,使用通用的发光光谱测定装置测定积分球内从波长转换部件上表面发出的光的能量分布谱。通过在所得到的发光光谱乘以标准相对可见度,算出全光束值。全光束值的变化率用将光照射后的全光束值除以光照射前的全光束值并乘以100得到的值(%)表示。将结果示出于表6~14。
由表6~14可知,在使用YAG作为无机荧光体的情况下,作为实施例的A-1~A-39的波长转换部件即使在100小时的光照射后,也维持着光照射前的99.5%以上的全光束值,相对于此,作为比较例的A-40、A-41的波长转换部件的100小时的光照射后的全光束值降低为光照射前的98%以下。
另外,在使用α-SiAlON作为无机荧光体时,作为实施例的B-1~B-39的波长转换部件即使在100小时的光照射后,也维持着光照射前的99%以上的全光束值,相对于此,作为比较例的B-40、B-41的波长转换部件的100小时的光照射后的全光束值降低为光照射前的94%以下。
产业上的可利用性
本发明的波长转换部件适合作为白色LED等的一般照明或特殊照明(例如、投影仪光源、车载用前照灯等的车载用照明)等的构成部件。
符号说明
1 发光器件
2 波长转换部件
3 光源
Claims (7)
1.一种波长转换部件,其特征在于:
其为玻璃基质中分散有无机荧光体的波长转换部件,
所述玻璃基质以摩尔%计,含有30~85%的SiO2、0~20%的B2O3、0~25%的Al2O3、0~3%的Li2O、0~3%的Na2O、0~3%的K2O、0~3%的Li2O+Na2O+K2O、0~35%的MgO、0~35%的CaO、0~35%的SrO、0~35%的BaO、0.1~45%的MgO+CaO+SrO+BaO、和0~4%的ZnO,
所述玻璃基质的软化点为829~1100℃,
所述无机荧光体为选自氧化物荧光体、氮化物荧光体、氧氮化物荧光体、氯化物荧光体、酰氯化物荧光体、卤化物荧光体、铝酸盐荧光体和卤磷酸盐化物荧光体中的至少1种。
2.如权利要求1所述的波长转换部件,其特征在于:
所述玻璃基质以摩尔%计,含有30~85%的SiO2、0~20%的B2O3、0~25%的Al2O3、0~3%的Li2O、0~3%的Na2O、0~3%的K2O、0~3%的Li2O+Na2O+K2O、0~35%的MgO、0~35%的CaO、0~35%的SrO、0~35%的BaO、0.1~45%的MgO+CaO+SrO+BaO和0以上且低于1.8%的ZnO。
3.如权利要求1或2所述的波长转换部件,其特征在于:
含有0.01~70质量%的所述无机荧光体。
4.如权利要求1或2所述的波长转换部件,其特征在于:
由粉末烧结体形成。
5.一种发光器件,其特征在于,包括:
权利要求1~4中任一项所述的波长转换部件、和对所述波长转换部件照射激发光的光源。
6.一种车载用照明,其特征在于:
使用了权利要求5所述的发光器件。
7.如权利要求6所述的车载用照明,其特征在于:
作为前照灯使用。
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- 2017-06-08 KR KR1020237033686A patent/KR20230146113A/ko not_active Application Discontinuation
- 2017-06-08 KR KR1020227023957A patent/KR102588722B1/ko active IP Right Grant
- 2017-06-08 CN CN201780039736.1A patent/CN109415622B/zh active Active
- 2017-06-08 CN CN202210789175.XA patent/CN115172566A/zh active Pending
- 2017-06-08 WO PCT/JP2017/021377 patent/WO2018003454A1/ja unknown
- 2017-06-08 US US16/091,115 patent/US11034609B2/en active Active
- 2017-06-08 EP EP17819819.8A patent/EP3476914B1/en active Active
- 2017-06-23 TW TW106121072A patent/TWI711189B/zh active
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2021
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US11912621B2 (en) | 2024-02-27 |
JP6906277B2 (ja) | 2021-07-21 |
JP2018002762A (ja) | 2018-01-11 |
TW201817043A (zh) | 2018-05-01 |
CN109415622B (zh) | 2024-04-02 |
EP3476914B1 (en) | 2024-08-21 |
KR102422065B1 (ko) | 2022-07-18 |
US20230159375A1 (en) | 2023-05-25 |
CN109415622A (zh) | 2019-03-01 |
KR20220104272A (ko) | 2022-07-26 |
JP2021121850A (ja) | 2021-08-26 |
TWI711189B (zh) | 2020-11-21 |
US11584682B2 (en) | 2023-02-21 |
EP3476914A4 (en) | 2020-01-15 |
EP3476914C0 (en) | 2024-08-21 |
WO2018003454A1 (ja) | 2018-01-04 |
EP3476914A1 (en) | 2019-05-01 |
KR20190023047A (ko) | 2019-03-07 |
US20210230047A1 (en) | 2021-07-29 |
US20190119148A1 (en) | 2019-04-25 |
KR20230146113A (ko) | 2023-10-18 |
KR102588722B1 (ko) | 2023-10-13 |
US11034609B2 (en) | 2021-06-15 |
JP7022398B2 (ja) | 2022-02-18 |
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