CN1337988A - 日光荧光颜料 - Google Patents
日光荧光颜料 Download PDFInfo
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- 239000000049 pigment Substances 0.000 title claims abstract description 29
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 229910052788 barium Inorganic materials 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 17
- 238000001228 spectrum Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 7
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 241001062009 Indigofera Species 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 229910016066 BaSi Inorganic materials 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000006862 quantum yield reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002310 reflectometry Methods 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 229910052693 Europium Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- -1 rare-earth activated silicon nitride class Chemical class 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
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- 238000005424 photoluminescence Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006360 Si—O—N Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- 239000005084 Strontium aluminate Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
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- 239000000428 dust Substances 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010442 halite Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004577 thatch Substances 0.000 description 1
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Abstract
一种颜料,尤其是黄至红光发射的荧光材料,具有次氮基硅酸盐型MxSiyNz∶Eu的主晶格,其中M是选自Ca、Sr、Ba族的至少一种碱土金属,而其中z=2/3x+4/3y。
Description
技术领域
本发明涉及一种日光荧光的颜料，更具体涉及，但非仅仅涉及在日光或人造光源激发下，吸收兰至绿光并发射黄至红光谱区荧光的一种颜料。此外，其它谱区，尤其紫外光区的吸收也是可能的。更具体地说，这样的颜料可作为光源磷光体，尤其用于光激发二极管(LED)或电灯的光源磷光体。这种颜料属于稀土激活氮化硅类。
技术背景
对于掺杂Eu2+材料观察到通常紫外(UV)-蓝光发射(见：布拉舍(Blasse)及格拉布密尔(Grabmeier)著：“莹光材料”一书(斯普林格出版社(Springer Verlag)，海德拜尔(Heidelberg)，1994)。有些研究表明，在可见光谱范围的绿及黄区的发射也是可能的[见布拉舍著：“二价镧化物发射的几个特例”，欧洲固态无机化学杂志(Eur.J.Solid State Inorg，Chem.)，33(1996)，p 175；普耳特(Poort)、布洛克波尔(Blokpoel)及布拉舍著：“在钡及锶的铝酸盐及镓酸盐中Eu2+的荧光性”，化学材料(Chem.Mater.)，7(1995)，p 1547；普耳特、赖恩豪特(Reijnhoudt)、范德库普(Van der Kuip)及布拉舍)著：“硅酸盐主晶格中Eu2+与列中碱土金属离子的荧光”，合金及组合物杂志(J.Alloys and Comp.)，241(1996)，p75]。迄今，仅在某些特殊情况下观察到了Eu2+红荧光，诸如在碱土金属硫化物及相关石盐型(rock-salt type)晶格中(见：中尾著：“由Eu2+离子激活后的MgS、CaS及CaSe磷光体的荧光中心”，日本物理协会会志(J.Phys.Soc.Jpn.)48(1980)，p534)；在碱土金属硫代镓酸盐中(见：达沃洛斯(Davolos)、加西亚(Garcia)、福阿塞尔(Fouassier)及哈根缪勒(Hagenmuller)著：“锶及钡的硫代镓酸中Eu2+的荧光”，固态化学杂志，83(1989)，p 316)及在某些硼酸盐中(见：迪亚兹(Diaz)及凯斯蔡尔(keszier)著“固态硼酸盐中的红、绿及蓝Eu2+荧光：结构-特性关系”，材料研究简报(Mater.Res.Bull)，31(1996)，p147)。在碱土金属四氮化三硅中的Eu2+荧光迄今只报道有对于MgSiN2：Eu的(见：盖多(Gaido)、杜布洛夫斯基(Dubrovskii)和朱可夫(Zykov)著：“由铕激活的MgSiN2光致荧光”，苏联科学院简报，无机材料(Izv.Akad.Nauk SSSR，Neorg.Mater.，)10(1974)，p.564)；杜布洛夫斯基、朱可夫和切尔诺维茨(Chernovets)著：“稀土激活MgSiN2的荧光”，苏联科学院简报，无机材料(lzv.Akad.Nauk SSSR，Neorg.Mater.)，17，(1981)p.1421)及对于Mg1-xZnxSiN2：Eu的(见：利姆(Lim)，李(Lee)，张(Chang)著：“用于薄膜电致荧光器件的Mg1-xZnxSiN2：Tb的光致荧光特征，无机和有机电致荧光(Inorganic and OrganicElectroluminescent)，柏林，Berlin，科学及技术出版社(Wissenschaft und Technik Verlag)，(1996)，p.363)。对于二者，在光谱中绿和绿/蓝部分中均发现了Eu2+荧光。
次氮基硅酸盐的新主晶格是基于交联的SiN4四面体的三维网络，其中结合了碱土金属离子(M＝Ca、Sr和Ba)。这种晶格例如有Ca2Si5N8(见：施列佩尔(Schlieper)和施利克(Schlick)著：“次氮基矽酸盐I，Ca2Si5N8高温合成及晶体结构”，无机实用(宇宙)化学杂志(Z.Anorg.Allg.Chem.)621，(1995)，p.1037)、Sr2Si5N8及Ba2Si5N8(见：施列佩尔、密卢斯(Millus)和施利克著：“次氮基矽酸盐II，Sr2Si5N8和Ba2Si5N8的高温合成及晶体结构”，无机实用化学杂志621，(1995)，p.1380)和BaSi7N10(见：胡泊尔茨(Huppertz)和施尼克(Schnick)著：“高缩次氮基硅酸盐BaSi7N10中边缘分享的SiN4四面体，欧洲化学杂志3(1997)，p 249)。晶格类型表述于表1中。
硫化物基磷光体(例如碱土硫化物)对于发光应用是不太如意的，尤其对于LED场合，因为它们与包囊树脂体系互相作用，而部分遭受水解腐蚀。红发射Eu2+激活的硼酸盐已表明在LED的操作温度下温度骤冷(temperature quenching)到某种程度。
发明披露
因此，本发明目的在于避免已有技术的弊端。本发明另一目的在于提供一种日光荧光的颜料。还有一个目的在于提供一种可在波长约200至500纳米，优选在300至500纳米激发且化学及热稳定性高的黄至红光发射荧光材料。
对于LED场合高达至少100℃时特别高的稳定性是非常希望的。其典型操作温度约80℃。
这些目的是通过按照权利要求1表征的特征实现的。在从属权利要求中均可找到有利的实施方案。
该新颜料表明至少在蓝绿光谱范围吸收。而且它们还表明吸收时发射荧光。那些掺杂Eu2+的莹光材料表明了在黄至红光谱区的发射，尤其在长波长的红、橙或黄色发射。这些颜料是基于碱土金属的四氮化三硅材料作为主晶格。当用作磷光体时，它们非常有希望，尤其对于LED的应用。迄今，白色LED是通过将蓝发射二极管与黄发射磷光体结合而实现的。这种结合只是彩色重显不佳。可通过采用多色(例如红-绿-蓝色)体系来达到更好的性能。典型地，可将该新材料与绿发射(或黄色发射)的磷光体一起使用，该磷光体例如铝酸锶SrAl2O4：Eu2+，其发射最大值是在520纳米附近。
详细而言，该日光荧光新颜料采用了一种次氮基硅酸盐型MxSiyNz：Eu的主晶格，其中M是选自Ca、Sr、Ba族的至少一种碱土金属，而且其中z＝2/3x+4/3y。氮的加入增加了共价键与配体领域分裂的比例。从而与氧化物晶格相比，导致激发与发射谱带明显向更长波长位移。
该颜料优选属于其中x＝2及y＝5的类型。在另一优选实施方案中，该颜料属于其中x＝1及y＝7的类型。
颜料中金属M优选为锶，因为所得磷光体是发射 较短的黄至红波长。因此其效率比大部分其它所选金属M的更高。
在进一步实施方案中，该颜料采用不同金属的混合物，例如采用Ca(10原子％)与Ba(余量)一起作为组分M。
这些材料表明，在UV和蓝色可见光谱中(高达450纳米以上)吸收强和激发好，量子效率高和骤冷温度低至100℃。
它可用作为着色商品的颜料，或作为荧光转化LED的磷光体，尤其与蓝光发射主源连同一种或多种其它磷光体(红和绿)一起时。
附图简述
图1：未经掺杂的Ba2Si5N8和Ba2Si5N8：Eu的漫反射光谱；
图2：未经掺杂的BaSi7N10和BaSi7N10：Eu的漫反射光谱；
图3：Ba2Si5N8：Eu的发射光谱；
图4：BaSi7N10：Eu的发射光谱
图5-7：Sr2Si5N8：Eu的几个实施方案的发射光谱；
图8：Ca2Si5N8：Eu的发射光谱。
详细实施方案
对Eu2O3(纯度99.99％)、或Eu(铕)金属(99.99％)、Ba金属(＞99％)；Sr金属(99％)、Ca3N2(98％)，或Ca粉末(99.5％)和Si3N4(99.9％)均使用市售的原材料。Ba和Sr为在550和800℃氮气氛下灼烧的氮化物。随后，在研钵中对Ca3N2或氮化的Ba、Ca或Sr加以研磨，并在氮气氛下按化学计量使之与Si3N4混合。与碱土金属离子相比，Eu-浓度为10原子％。将该粉末混合物置于钼坩埚中，在氮/氢气氛下，在约1300-1400℃的水平管式炉中加以灼烧。灼烧后，用粉末X射线衍射(Cu、Kα线)对该粉料加以表征，X射线衍射表明所有化合物均已形成。
该未经掺杂的Ba2Si5N8、Ca2Si5N8及BaSi7N10均为灰白粉料。这些未经掺杂的稀土激活四氮化三硅表明，在可见区(400-650纳米)反射强，而在250-300纳米间(图1和2)反射急剧减弱。反射的下降是由于主晶格的吸收。Eu-掺杂过的样品是橙红色，但BaSi7N10：Eu除外，它是橙黄色的(表1)。对于Eu2+掺杂的稀土激活四氮化三硅，强彩色是独特的，并因此使这些材料成为引人兴趣的橙红色颜料。Ba2Si5N8：Eu反射光谱的典型实例说明，Eu的吸收迭加在主晶格吸收上，并延伸达至500-550纳米(图1)。这解释了这些化合物的红-橙色。对于Sr2Si5N8：Eu及Ca2Si5N8：Eu也观察到了同样反射光谱。
对于BaSi7N10：Eu，铕的吸收在远可见部份更小(图2)，这解释了该化合物的橙黄色颜色。
所有样品表明，紫外线(UV)激发下有效荧光在可见光谱橙红色部分中发射最大值(见表1)。发射光谱的二个典型实例可见图3及4。它们表明，对于BaSi7N10：Eu，该发射是在最大值高达660纳米的极长波长(对于Eu2+发射)处(见图4)。激发带是在低能处观察到的，这是由于Eu2+5d带在低能量下的重力中心及Eu2+5d带的强配体域分裂的结果，正如对于含N3-晶格可以预计到的(见：范克雷维尔(vanKrevel)、欣芩(Hintzen)、梅泽拉尔(Metselaar)和迈杰林克(Meijerink)著：“Y-Si-O-N材料中长波Ce3+-荧光”，合金和组合物杂志(J.Alloys and Comp.)，168(1998)，272)。
由于这些材料可因低能激发带将蓝光转变为红光，所以可将它们用于白光源，例如用于基于与红、黄及/或绿磷光体结合的主蓝发射光激发二极管(LED)(典型CaN或InGaN)光源。
表1
| 化合物 | 晶体结构 | 颜色 | 发射最大值(纳米)* |
| Ca2Si5N8：Eu | 单晶 | 橙红色 | 600至630 |
| Sr2Si5N8：Eu | 斜方晶 | 橙红色 | 610至650 |
| Ba2Si5N8：Eu | 斜方晶 | 橙红色 | 620至660 |
| Ba2Si7N10：Eu | 单晶 | 橙黄色 | 640至680 |
*注：取决于激活剂的制备及浓度条件；一般与碱土的离子相比，Eu-浓度典型值可变化1-10％。
这些发射最大值都显著远在长波长侧。Sr1.8Eu0.2Si5N8型的磷光体是一个具体实施例。其发射谱如图5所示。
实现M的另一实施方案是应用锌。它可全部或部分替换Ba、Sr或Ca。
另一完全或部分替换硅的实施方案是锗。一个具体实施方案是Sr1.8Eu0.2Ge5N8。
对另外一些具体实施例进行了研究：
研究了红发射磷光体Sr2Si5N8：Eu2+的制备条件和光学性质。最佳化表明量子效率约70％。该发射在610和650纳米之间是和谐的，这取决于样品中Eu2+浓度和加热条件。400和460纳米下的吸收强(反射仅15-40％)和80℃下荧光的温度骤冷(temperature quenching)低(仅4％)。未研磨磷光体的粒度在5微米以下。这些性质使该磷光体用于UV及蓝LED非常有意义。
对于氮化物的合成，原材料是Si3N4(99.9％(主要为α相)，阿尔法埃沙(Alfa Aesar)公司)，Sr金属(枝晶片粒99.9％，阿尔法埃沙公司)及Eu2O3(4N)。Sr金属必须经过氮化，而且如用Eu金属替代Eu2O3，也必须加以氮化。
在玛瑙研钵中在氩手套箱中用手研磨该Sr金属，氮化在800℃下用氮进行。这可使之氮化80％以上。
在再研磨后，将氮化后金属与Si3N4及Eu2O3放在一起，也在该手套箱中用手加以研磨及混合。对该化合物加热的典型参数如下：
18℃/分升至800℃
在800℃下5小时
18℃/分升至Tend(1300-1565℃)
在Tend(1300-1565℃)下5小时
H2(3.75％)/N2，400升/小时
用Ca3N2作为原材料制备Ca2Si5N8：Eu2+的样品。
所有样品的概述列于表1.一般，先将这些样品加热至800℃，然后在升温(1300-1600℃)下对它们第二次加热同样时间。然后研磨这些样品(在空气中)、过筛及测定。
表1：(Ca，Sr)2Si5N8：Eu2+样品的加热周期参数
| 代码 | Ca/Sr | Eu2+(％) | 时间1(小时) | 温度1(℃) | 时间2(小时) | 温度2(℃) |
| EC/HU 31/00 | Ca | 10 | 5 | 800 | 5 | 1400 |
| EC/HU 42/00 | Ca0.4Sr1.4 | 1 | 5 | 800 | 5 | 1565 |
| EC/HU 41/00 | Sr | 10 | 5 | 800 | 5 | 1565 |
| EC/HU 62/00 | Sr | 1 | 5 | 800 | 5 | 1400 |
| EC/HU 63/00 | Sr | 2 | 5 | 800 | 5 | 1400 |
| EC/HU 64/00 | Sr | 3 | 5 | 800 | 5 | 1400 |
| EC/HU 65/00 | Sr | 5 | 5 | 800 | 5 | 1400 |
| EC/HU 66/00 | Sr | 8 | 5 | 800 | 5 | 1400 |
| EC/HU 67/00 | Sr | 10 | 5 | 800 | 5 | 1400 |
加热后获得的样品表明，对含10％Eu2+的Sr2Si5N8样品为深橙色。样品Eu2+越少，颜色越淡。Ca样品呈黄橙色。
还有另一个有趣的特征：粉粒非常细，平均粒度d50在约0.5-5微米之间，一般d50＝1.3微米。细微粒尺寸有利于用荧光材料加工LED。例如可在树脂中均匀分布它们。
表2：(Ca，Sr)2Si5N8：Eu2+样品的光学数据
| 代码 | Ca/Sr | Eu2+％ | 发射最大值(纳米) | 反射率400(％) | 反射率460(％) | 量子效率(％) | X | Y |
| EC/Hu31/00 | Ca | 10 | 619 | 12 | 19 | 26 | 0.600 | 0.396 |
| EC/HU42/00 | Ca0.4Sr1.4 | 1 | 603 | 47 | 58 | 37 | 0.555 | 0.435 |
| EC/HU41/00 | Sr | 10 | 660 | 17 | 22 | 59 | 0.636 | 0.354 |
| EC/HU62/00 | Sr | 1 | 609 | 53 | 58 | 70 | 0.600 | 0.393 |
| EC/HU63/00 | Sr | 2 | 618 | 43 | 48 | 73 | 0.615 | 0.381 |
| EC/HU64/00 | Sr | 3 | 621 | 36 | 41 | 72 | 0.622 | 0.374 |
| EC/HU65/00 | Sr | 5 | 624 | 26 | 32 | 67 | 0.632 | 0.365 |
| EC/HU66/00 | Sr | 8 | 636 | 21 | 26 | 67 | 0.641 | 0.356 |
| EC/HU67/00 | Sr | 10 | 644 | 17 | 22 | 64 | 0.642 | 0.354 |
关于表2，所有样品一般都先在第一周期加热(例如800℃5小时)，如已以上所述。
表2所包括的是发射最大值的位置，平均波长，在400和460纳米的反射率，量子效率和最后x及y色坐标。
由表2可得出，纯Ca样品不如Sr样品有利。令人惊讶的是Sr-Ca化合物发射波长大于纯Sr化合物的。
具体实施例示于图6至8中。图6说明样品HU 64/00(Sr2Si5N8：Eu2+)的能量分布(任意单位)及反射率(以百分数表示)，该样品含有3％比例的Eu及72％的量子效率。图7说明，样品HU 65/00(Sr2Si5N8：Eu2+)的能量分布(任意单位)及反射率(以百分数表示)，该样品含有5％比例的Eu及67％的量子效率。图8说明样品HU 42/00(Ca2Si5N8：Eu2+))的能量分布(任意单位)及反射率(以百分数表示)，该样品含有1％比例的Eu及37％的量子效率。
Claims (10)
1.一种日光荧光颜料，其特征在于一种次氮基硅酸盐型MxSiyNz：Eu的主晶格，其中M是选自Ca、Sr、Ba、Zn族的至少一种碱土金属，其中z＝2/3x+4/3y。
2.按照权利要求1的颜料，其中x＝2及y＝5。
3.按照权利要求1的颜料，其中x＝I及y＝7。
4.按照权利要求1的颜料，其中M是锶。
5.按照权利要求I的颜料，其中M是一种所述族的至少两种金属的混合物。
6.按照权利要求1的颜料，其中Si是全部或部分以Ge替代的。
7.按照权利要求1的颜料，其中所述颜料在蓝至绿光光谱范围内是吸收的。
8.按照权利要求7的颜料，其中所述颜料在黄至红光光谱范围内是荧光的。
9.按照权利要求1的颜料作为着色颜料的应用。
10.按照权利要求1的颜料作为由光源激发的磷光体的应用，所述磷光体在黄至红光光谱范围内发射。
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| CN101629077A (zh) * | 2009-08-14 | 2010-01-20 | 上海芯光科技有限公司 | 多元系氧氮化物基或氮化物基荧光粉及其制备方法 |
| CN102544326A (zh) * | 2010-11-02 | 2012-07-04 | 台湾积体电路制造股份有限公司 | 带有Ce3+ /Ce3+,Li+掺杂发光材料的荧光物质 |
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