CN105793389B - 制备颜色稳定的锰掺杂的络合氟化物磷光体的方法 - Google Patents
制备颜色稳定的锰掺杂的络合氟化物磷光体的方法 Download PDFInfo
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Abstract
制备式(I)Ax(M(1‑m),Mnm)Fy的颜色稳定的Mn4+掺杂的络合氟化物磷光体的方法,其包括:使包含(1‑m)份式HxMFy的化合物的第一含水HF溶液和包含m*n份式Ax[MnFy]的化合物的第二含水HF溶液与包含(1‑n)份式Ax[MnFy]的化合物和式AaX的化合物的第三含水HF溶液接触,以产生包含颜色稳定的Mn4+掺杂的络合氟化物磷光体的沉淀物;其中A是Li、Na、K、Rb、Cs、NR4或它们的组合;M是Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd或它们的组合;R是H、低级烷基或它们的组合;X是阴离子;a是X阴离子的电荷的绝对值;x是[MFy]离子的电荷的绝对值;y是5、6或7;0<m≤<0.05;0.1≤n≤1。
Description
背景
基于通过Mn4+活化的络合氟化物材料的红光发射磷光体,例如GB 1360690、US 3,576,756、US 7,358,542、US 7,497,973和US 7,648,649中描述的那些,可与黄光/绿光发射磷光体(例如YAG:Ce或其它石榴石组合物)组合使用,以从蓝光LED获得暖白光(在黑体曲线上CCTs<5000K,显色指数(CRI)>80),等效于现有荧光灯、白炽灯和卤素灯产生的光。这些材料强烈地吸收蓝光和有效发射约610-635nm,具有很少深红/NIR发射。因此,与发红光磷光体相比光效能最大化,所述发红光磷光体在视觉灵敏度差的较深红色有显著发射。在蓝光(440-460nm)激发下量子效率可超过85%。
虽然使用Mn4+掺杂的的氟化物主体的照明系统的效能和CRI可相当高,但一个潜在的限制是它们对使用条件下劣化的敏感性。有可能使用合成后加工步骤减少该劣化,如US8,252,613所述。然而,期望开发改进所述材料稳定性的备选方法。
发明简述
简而言之,本发明涉及制备式I的颜色稳定的Mn4+掺杂的络合氟化物磷光体的方法,
Ax(M(1-m), Mnm) Fy (I)
使包含(1-m)份式HxMFy的化合物的第一含水HF溶液和包含m*n份式Ax[MnFy]的化合物的第二含水HF溶液与包含(1-n)份式Ax[MnFy]的化合物和式AaX的化合物的第三含水HF溶液接触,以产生包含颜色稳定的Mn4+掺杂的络合氟化物磷光体的沉淀物;
其中
A是Li、Na、K、Rb、Cs、NR4或它们的组合;
M是Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd或它们的组合;
R是H、低级烷基或它们的组合;
X是阴离子;
a是X阴离子的电荷的绝对值;
x是[MFy]离子的电荷的绝对值;
y是5、6或7;0<m≤0.08;
0.1≤n≤1。
在另一方面,本发明涉及通过所述方法制备的具有改进的稳定性的Mn4+掺杂的络合氟化物磷光体,和包括布置于LED芯片表面的通过所述方法制备的络合氟化物磷光体的LED照明设备。
附图简述
当参考附图阅读以下详述时,本发明的这些和其它特征、方面和优点将变得更好理解,在附图中类似的附图标记在所有附图代表类似的部分,其中:
图1是本发明的照明设备的示意截面图;
图2是本发明的照明设备的示意截面图;
图3是本发明的另一实施方案的照明设备的示意截面图;
图4是本发明的实施方案的照明设备的剖面侧透视图;
图5是表面安装的设备(SMD)背光LED的示意透视图。
详述
可通过本发明的方法制备的络合氟化物磷光体是含有配位中心M的配位化合物,所述配位中心M被作为配体的氟离子包围和通过反离子A电荷平衡。主晶格材料AxMFy与活化剂材料AxMnFy组合,且Mn4+活化剂或掺杂离子也作为配位中心,取代部分主晶格M的中心。主晶格,包括反离子,可进一步改变活化剂离子的激发和发射性质。
由于重金属或2+或3+氧化态的锰的污染,制备活化剂材料的方法通常产生低于期望纯度的产物。可期望在制备磷光体之前纯化活化剂材料。因此,在又一个方面,本发明涉及去除杂质的方法,所述杂质在氢氟酸中的溶解度显著不同于活化剂离子,且净效果是可制备改进的络合氟化物磷光体。式AxMnFy的化合物溶于含水HF以形成饱和或几乎饱和的溶液。溶液可经过滤去除任何不溶性材料。然后,活化剂材料沉淀,和将沉淀物分离,并可洗涤、过滤和干燥。沉淀可受到过量的式AF的化合物(在具体实施方案中,KF)的影响。诱导沉淀的其它方法包括降低溶液的温度和添加反溶剂,例如乙酸或丙酮。也可使用所述方法的组合。
根据本发明,制备式I的颜色稳定的Mn4+掺杂的络合氟化物磷光体的方法包括:使含有式HxMFy的酸(其为MFy离子的来源)的第一含水HF溶液和含有式Ax[MnFy]的活化剂材料的第二含水HF溶液,与包含活化剂材料和式AaX的化合物的第三含水HF溶液接触,以产生颜色稳定的Mn4+掺杂的磷光体作为沉淀物。在一些实施方案中,可使用含有A+离子(K+,在许多实施方案中)的另外来源的第四溶液。在根据本发明的方法中,反应物作为单独的溶液提供和组合以逐渐地(即经过一段时间)产生颜色稳定的磷光体产物,与以上引用的专利中描述的制备磷光体的方法相反,以上方法中反应物溶于普通的含水氢氟酸溶液,和通过添加非溶剂或共同离子、或简单地蒸发溶剂,来沉淀所述磷光体产物。尽管本发明人不希望受限于任何特定理论来解释使用本发明的方法可产生的颜色稳定性的改进,但相信本发明的方法允许掺入Mn4+掺杂物遍及磷光体颗粒,而所述方法中产物全部同时沉淀,可产生具有分级组成的颗粒,锰优先的布置于颗粒表面或附近。锰的均匀分布可防止掺杂离子群集导致的浓度猝灭和由此引起的量子效率(QE)损失。
本发明的方法可按间歇模式或连续进行。对于间歇方法,将第一和第二溶液逐渐地添加至第三溶液,和随时间形成产物。对于连续方法,可逐渐混合三种溶液。
三种溶液的浓度经选择使得产物在反应介质中具有低溶解度和易于沉淀。活化剂材料在第二溶液中的量m*n,和在第三溶液中的量1-n,通过两种溶液之间的期望比率n,和通过产物中掺入的Mn的量确定。Mn在第二溶液中的量与第三溶液中的量的比范围为大于0.1至小于1,特别地≤0.25至≤0.9,更特别地≤0.5至≤0.9,和最特别地≤0.6至≤0.8。在具体实施方案中,n为约0.7。Mn在产物中的量是m,和m范围为0至小于0.08。用于制备的活化剂材料的量为至少m,和在一些实施方案中附加量的活化剂材料可包括在第二或第三溶液中,或第二和第三溶液两者中,使得加入溶液中的Mn的总量大于m,因为一些起始活化剂材料可能不掺入产物中。在具体实施方案中,颜色稳定的Mn4+掺杂的络合氟化物磷光体是K2(Si(1-m), Mnm)F6。
式AaX的化合物是可用作A+离子来源的离子化合物。适合的材料的实例包括KF、KHF2、KNO3和CH3COOK。在具体实施方案中,化合物选自KF、KHF2和它们的组合。用于第三溶液的化合物的量范围为约1份(摩尔)至至少约3份。在一些实施方案中,含有化合物的第四溶液可另外与第一、第二和第三溶液接触。
根据本发明的一个实施方案的照明设备或光发射组件或灯10显示在图1中。照明设备10包括半导体辐射源,显示为发光二极管(LED)芯片12,和导线14电连接于LED芯片。导线14可为由较厚的导线框16支撑的细线,或导线可为自支撑的电极和可省略导线框。导线14提供电流至LED芯片12和因此导致其发出辐射。
灯可包括任何半导体蓝光或UV光源,当它发出的辐射引导至磷光体上时能产生白光。在一个实施方案中,半导体光源是掺杂有各种杂质的蓝色发光LED。因此,LED可包含基于任何适合的III-V、II-VI或IV-IV半导体层和具有约250-550nm发射波长的半导体二极管。特别地,LED可包含含GaN、ZnSe或SiC的至少一个半导体层。例如,LED可包含通过式IniGajAlkN(其中0≤i;0≤j;0≤k和i+j+k=1)表示的氮化物化合物半导体,具有大于约250nm和小于约550nm的发射波长。在具体实施方案中,芯片是具有约400-约500nm峰发射波长的近紫外或蓝色发光LED。这样的LED半导体在本领域已知。为了方便起见,辐射源在本文描述为LED。然而,如本文所用,该术语是指包括全部半导体辐射源,其包括例如半导体激光二极管。此外,尽管本文讨论的本发明的示例性结构的一般论述涉及无机LED基光源,应理解LED芯片可被另一种辐射源替换,除非另外说明,且对半导体、半导体LED或LED芯片的任何提及仅代表任何适当的辐射源,包括但不限于有机发光二极管。
在照明设备10中,磷光体组合物22辐射耦合至LED芯片12。辐射耦合是指所述元件彼此相连,因此辐射从一个传输到另一个。磷光体组合物22包括通过本方法制备和通过任何适当的方法在LED 12上沉积的颜色稳定的Mn4+掺杂的络合氟化物磷光体。例如,可形成磷光体的水基悬浮液,和其作为磷光体层涂敷至LED表面。在一个这样的方法中,围绕LED布置磷光体颗粒随机悬浮在其中的硅酮浆料。该方法仅为磷光体组合物22和LED 12的可能位置的示例。因此,通过将磷光体悬浮液涂布覆盖LED芯片12并干燥,磷光体组合物22可涂布覆盖LED芯片12的发光表面或直接涂布在其上。在硅酮基悬浮液的情况下,悬浮液在适当的温度下固化。壳18和密封剂20两者应该是透明的,以允许白光24传输通过那些元件。尽管不期望限制,在一些实施方案中,磷光体组合物的中值粒径范围为约1-约50微米,特别地约15-约35微米。
在其它实施方案中,磷光体组合物22散布在密封剂材料20内,而不是直接形成在LED芯片12上。磷光体(粉末形式)可散布在密封剂材料20的单一区域内或遍及密封剂材料的整个体积。LED芯片12发射的蓝光与磷光体组合物22发射的光混合,且混合光显现为白光。如果磷光体散布在密封剂材料20内,则磷光体粉末可添加到聚合物或硅酮前体,围绕LED芯片12装载,然后聚合物前体可固化以使聚合物或硅酮材料固化。还可使用其它已知的磷光体散布方法,例如转移装载。
在一些实施方案中,密封剂材料20是具有折射率R的硅酮基体,和除磷光体组合物22之外,还含有具有小于约5%吸光度和R±0.1的折射率的稀释剂。稀释剂具有≤1.7的折射率,特别地≤1.6,和更特别地≤1.5。在具体实施方案中,稀释剂为式II,和具有约1.4的折射率。添加无光学活性的材料至磷光体/硅酮混合物,可产生更平缓的跨带通量分布和可对磷光体产生较少的损害。用于稀释剂的适合的材料包括具有约1.38(AlF3和K2NaAlF6)-约1.43(CaF2)的折射率的立方氟化物化合物,例如LiF、MgF2、CaF2、SrF2、AlF3、K2NaAlF6、KMgF3、CaLiAlF6、KLiAlF6和K2SiF6,和具有约1.254-约1.7折射率的聚合物。适合用作稀释剂的聚合物的非限制实例包括聚碳酸酯、聚酯、尼龙、聚醚酰亚胺、聚醚酮和源自以下的聚合物:苯乙烯、丙烯酸酯、甲基丙烯酸酯、乙烯树脂、乙酸乙烯酯、乙烯、环氧丙烷和环氧乙烷单体,和它们的共聚物,包括卤化和非卤化衍生物。这些聚合物粉末可在硅酮固化之前直接加入至硅酮密封剂。
在又一个实施方案中,磷光体组合物22涂布在壳18的表面上,而不是形成覆盖LED芯片12。磷光体组合物优选地涂布在壳18的内表面上,但是如果期望,磷光体可涂布在壳的外表面上。磷光体组合物22可涂布在壳的整个表面上或仅涂布在壳表面的顶部。LED芯片12发射的UV/蓝光与磷光体组合物22发射的光混合,且混合光显现为白光。当然,磷光体可位于任意两个或全部三个位置或在任何其它适合的位置,例如与壳分离或与LED结合。
图2说明本发明的系统的第二结构。图1-4中相应的数字(例如图1中的12和图2中的112)涉及每一个图中对应的结构,除非另有说明。图2实施方案的结构类似于图1,除了磷光体组合物122散布在密封剂材料120内,而不是直接形成在LED芯片112上。磷光体(粉末形式)可散布在密封剂材料的单一区域内或遍及密封剂材料的整个体积。LED芯片112发射的辐射(由箭头126表示)与由本发明的方法制备的颜色稳定的Mn4+掺杂的络合氟化物磷光体122发射的光混合,且混合光显现为白光124。如果磷光体散布在密封剂材料120内,则磷光粉可添加到聚合物前体,和围绕LED芯片112装载。聚合物或硅酮前体然后可固化以使聚合物或硅酮固化。还可使用其它已知的磷光体散布方法,例如转移模塑。
图3说明了本发明的系统的第三种可能结构。图3显示的实施方案的结构类似于图1,除了包括通过本发明的方法制备的颜色稳定的Mn4+掺杂的络合氟化物磷光体的磷光体组合物222涂布在包封218的表面上,而不是形成覆盖LED芯片212。磷光体组合物222优选地涂布在包封218的内表面上,但是如果期望,磷光体可涂布在包封的外表面上。磷光体组合物222可涂布在包封的整个表面上,或仅涂布在包封表面的顶部。LED芯片212发射的辐射226与磷光体组合物222发射的光混合,且混合光显现为白光224。当然,图1-3的结构可组合,且磷光体可位于任意两个或全部三个位置,或在任何其它适合的位置,例如与包封分离,或结合进LED。
在以上任何结构中,灯还可包括多个散射颗粒(未显示),其包埋在密封剂材料内。散射颗粒可包含例如氧化铝或氧化钛。散射颗粒有效散射LED芯片发射的定向光,优选地具有可忽略的吸收量。
如图4中的第四结构所示,LED芯片412可安装在反射杯430内。杯430可由介电材料制造或涂布有介电材料,例如氧化铝、氧化钛或本领域已知的其它的介电粉末,或涂布有反射金属,例如铝或银。图4的实施方案的结构的剩余部分与任何前述附图的那些相同,和可包括两个导线416、导电线432和密封剂材料420。反射杯430通过第一导线416支撑,且导电线432用来将LED芯片412与第二导线416电连接。
另一个结构(特别用于背光应用)是表面安装设备(“SMD”)类型的发光二极管550,例如如图5所示。该SMD是“侧发射类型”和在光导元件554的突出部分具有光发射窗552。SMD包可包含如上限定的LED芯片,和通过LED芯片发射的光激发的磷光体材料。
当使用350-550nm的LED发射和一种或多种其它适合的磷光体时,得到的照明系统将产生白色的光。灯10还可包括散射颗粒(未显示),其包埋在密封剂材料内。散射颗粒可包含例如氧化铝或氧化钛。散射颗粒有效散射LED芯片发射的定向光,优选地具有可忽略的吸收量。
除颜色稳定的Mn4+掺杂的络合氟化物磷光体以外,磷光体组合物22可包括一种或多种其它磷光体。当用于与在约250-550nm范围的蓝色或接近UV的LED发射辐射组合的照明设备时,通过所述组件发射的所得的光为白光。其它的磷光体例如绿色、蓝色、橙色或其他颜色的磷光体可用于共混以定制得到的光的白色和产生更高的CRI源。
与式I的磷光体一起使用的适合的磷光体包括但不限于:
((Sr1-z (Ca, Ba, Mg, Zn) z)1-(x+w)( Li, Na, K, Rb)wCex)3(Al1-ySiy)O4+y+3(x-w)F1-y-3(x-w),0<x≤0.10,0≤y≤0.5,0≤z≤0.5, 0≤w≤x;
(Ca, Ce)3Sc2Si3O12 (CaSiG);
(Sr,Ca,Ba)3Al1-xSixO4+xF1-x:Ce3+ ((Ca, Sr, Ce)3(Al, Si)(O, F)5 (SASOF));
(Ba,Sr,Ca)5(PO4)3(Cl,F,Br,OH):Eu2+,Mn2+;(Ba,Sr,Ca)BPO5:Eu2+,Mn2+;(Sr,Ca)10(PO4)6*νB2O3:Eu2+ (其中0<ν≤1);Sr2Si3O8*2SrCl2:Eu2+;(Ca,Sr,Ba)3MgSi2O8:Eu2+,Mn2+;BaAl8O13:Eu2+;2SrO*0.84P2O5*0.16B2O3:Eu2+;(Ba,Sr,Ca)MgAl10O17:Eu2+,Mn2+;(Ba,Sr,Ca)Al2O4:Eu2+;(Y,Gd,Lu,Sc,La)BO3:Ce3+,Tb3+;ZnS:Cu+,Cl-;ZnS:Cu+,Al3+;ZnS:Ag+,Cl-;ZnS:Ag+,Al3+;(Ba,Sr,Ca)2Si1-ξO4-2ξ:Eu2+ (其中0≤ξ≤0.2);(Ba,Sr,Ca)2(Mg,Zn)Si2O7:Eu2+;(Sr,Ca,Ba)(Al,Ga,In)2S4:Eu2+;(Y,Gd,Tb,La,Sm,Pr,Lu)3(Al,Ga)5-αO12-3/2α:Ce3+ (其中0≤α≤0.5);(Ca,Sr)8(Mg,Zn)(SiO4)4Cl2:Eu2+,Mn2+;Na2Gd2B2O7:Ce3+,Tb3+;(Sr,Ca,Ba,Mg,Zn)2P2O7:Eu2+,Mn2+;(Gd,Y,Lu,La)2O3:Eu3+,Bi3+;(Gd,Y,Lu,La)2O2S:Eu3+,Bi3+;(Gd,Y,Lu,La)VO4:Eu3+,Bi3+;(Ca,Sr)S:Eu2+,Ce3+;SrY2S4:Eu2+;CaLa2S4:Ce3+;(Ba,Sr,Ca)MgP2O7:Eu2+,Mn2+;(Y,Lu)2WO6:Eu3+,Mo6+;(Ba,Sr,Ca)βSiγNμ:Eu2+ (其中2β+4γ=3μ);Ca3(SiO4)Cl2:Eu2+;(Lu,Sc,Y,Tb)2-u-vCevCa1+uLiwMg2-wPw(Si,Ge)3-wO12-u/2 (其中-0.5≤u≤1, 0<v≤0.1, 和0≤w≤0.2);(Y,Lu,Gd)2-ψCaψSi4N6+ψC1-ψ:Ce3+, (其中0≤ψ≤0.5);(Lu,Ca,Li,Mg,Y), α-SiAlON掺杂有Eu2+和/或Ce3+;β-SiAlON:Eu2+;(Ca,Sr,)AlSiN3:Eu2+ (Ca,Sr,Ba)SiO2N2:Eu2+,Ce3+;3.5MgO*0.5MgF2*GeO2:Mn4+;Ca1-c-fCecEufAl1+cSi1-cN3, (其中0≤c≤0.2, 0≤f≤0.2);Ca1-h-rCehEurAl1-h(Mg,Zn)hSiN3, (其中0≤h≤0.2, 0≤r≤0.2); Ca1-2s-tCes(Li,Na)sEutAlSiN3, (其中0≤s≤0.2, 0≤f≤0.2, s+t>0);和Ca1-σ-χ-φCeσ(Li,Na)χEuφAl1+σ-χSi1-σ+χN3, (其中0≤σ≤0.2, 0≤χ≤0.4, 0≤φ≤0.2)。
特别地,用于与式I的磷光体共混的适合的磷光体是
(Ca, Ce)3Sc2Si3O12 (CaSiG);
(Sr,Ca,Ba)3Al1-xSixO4+xF1-x:Ce3+ ((Ca, Sr, Ce)3(Al, Si)(O, F)5 (SASOF));
(Ba,Sr,Ca)2Si1-ξO4-2ξ:Eu2+ (其中0≤ξ≤0.2);
(Y,Gd,Tb,La,Sm,Pr,Lu)3(Al,Ga)5-αO12-3/2α:Ce3+ (其中0≤α≤0.5);
(Ba,Sr,Ca)βSiγNμ:Eu2+ (其中2β+4γ=3μ);(Y,Lu,Gd)2-ψCaψSi4N6+ψC1-ψ:Ce3+, (其中0≤ψ≤0.5);β-SiAlON:Eu2+;和(Ca,Sr,)AlSiN3:Eu2+。
更特别地,在被LED芯片激发时发射黄绿光的磷光体可包括在与本发明的方法制备的颜色稳定的Mn4+掺杂的络合氟化物磷光体的磷光体共混物中,例如(Y,Gd,Tb,La,Sm,Pr,Lu)3(Al,Ga)5-αO12-3/2α:Ce3+ (其中0≤α≤0.5)。
本发明的颜色稳定的Mn4+掺杂的磷光体可用于除了以上描述的那些以外的应用。例如,所述材料可用作荧光灯中、阴极射线管中、等离子体显示设备或液晶显示器(LCD)中的磷光体。所述材料还可用作电磁热量计中、γ射线照相机中、计算机断层扫描仪或激光器中的闪烁器。这些用途仅为示例性而不是限制性。
实施例
实施例1 K2MnF6合成
K2MnF6由KMnO4、KF、H2O2和含水HF通过一步一锅法合成,基于Bode(Angew. Chem.65 (11): 304):
2KMnO4 + KF + 10 HF + 3H2O2 → 2K2MnF6 ↓ +8H2O + 3O2.
4-L聚乙烯烧杯,装备有聚四氟乙烯涂布的磁性搅拌棒,装入50%含水HF(1L)和用冰浴冷却。然后添加KF(240g,4.13mol)和细粉状KMnO4(15g,94.9mmol),并将混合物强烈搅拌15分钟。停止搅拌和使任何不溶材料沉降。将上清液倾倒至第二烧杯以保证不存在任何不溶的KMnO4(其可使在后续滴定步骤中的终点识别变困难)。用滴管缓慢添加30%含水H2O2至冷的暗紫色溶液。添加各5-10滴之后,暂停进一步添加直到停止O2释放。添加约20mL的H2O2之后,接近终点。形成呈金褐色沉淀物,和通过停止搅拌并观察上清液颜色可判断终点。当溶液颜色由紫色变为中等红棕色时判断反应完成。使用带有聚四氟乙烯过滤纸的塑料布氏漏斗收集金黄色的K2MnF6沉淀物。用冷丙酮(各10mL)洗涤沉淀物两次并泵吸至干,产生18.44g (78.6%,基于KMnO4)黄色K2MnF6。
实施例2 K2MnF6纯化
使用20.3g的K2MnF6和282mL 48重量%的HF制备K2MnF6在HF中的饱和或几乎饱和的溶液,并真空过滤所述产物。还制备40.6g KF溶于41mL的48%HF中的处理溶液。KF溶液逐滴至K2MnF6溶液中,搅拌以形成沉淀物。倒出上清液,然后用真空过滤器真空过滤浆料,用冷丙酮洗涤四次,和在真空干燥器中干燥。
实施例3 K2MnF6纯化
使用10克K2MnF6在40ml 70重量%的HF中制备K2MnF6在70%HF中的饱和或几乎饱和的溶液。还制备10g KHF2溶于10ml 48%HF中的处理溶液。在搅拌下,将KHF2溶液添加到K2MnF6溶液中。得到的浆料经真空过滤和用丙酮覆盖4次,和在真空干燥器中干燥K2MnF6产物。
实施例4:通过ICP-MS进行元素分析
测定Al、Ca、Cr、Cu、Fe、Na、Ni和Zr在刚合成的和实施例2中的磷光体样品中的水平。结果显示在表1中。通过纯化过程,污染物的水平显著减少。
实施例5-18 K2SiF6: Mn4+磷光体的制备
一般程序
磷光体制备
将氟硅酸H2SiF6和HF搅拌混合以形成第一溶液。通过将氢氟酸倒入含有KF或KHF2和六氟锰酸钾(PFM)、K2MnF6的烧杯中,搅拌以溶解固体,制备含有K+源的氢氟酸溶液。这称作接受溶液。制备含有含水HF和K2MnF6的第三溶液;这称作PFM溶液。氟硅酸和PFM溶液单独和逐渐地在约10分钟内添加至接受溶液中,带有搅拌。在PFM添加之前,通常早1-2分钟,开始添加氟硅酸溶液。添加完成之后,将悬浮液搅拌几分钟,然后停止搅拌,使磷光体沉降并倾倒上清液。
通过将K2SiF6添加至含有48%HF的聚丙烯烧杯中,制备K2SiF6在HF中饱和或几乎饱和的溶液组成的处理溶液。盖上烧杯,搅拌至少15分钟和使用0.65微米孔径的聚四氟乙烯过滤器真空过滤所述溶液。将处理溶液添加到含有磷光体的烧杯中并搅拌约15分钟。搅拌停止之后,使磷光体沉降和倾倒处理溶液。磷光体经真空过滤,用丙酮漂洗三次,在真空中干燥和过滤以产生Mn掺杂的K2SiF6。
实施例7的磷光体的详细制备
通过将65mL 48%的氢氟酸倒入含有8.1克KHF2的烧杯(烧杯A)中制备KHF2在48%氢氟酸中的溶液。将K2MnF6(0.219g,0.00089mol)添加到所述溶液中,搅拌以溶解固体。将H2SiF6(15mL 35%的H2SiF6,0.036mol)和60mL 48%的HF倒入第二烧杯(烧杯B)中并搅拌。将HF(21mL 48%的HF)倒入含有K2MnF6(0.219g,0.00089mol)的第三烧杯(烧杯C)中,搅拌以溶解固体。当搅拌烧杯A时,烧杯B和C的内含物经过约7分钟逐滴添加。添加完成之后,另外搅拌悬浮液5分钟,然后停止搅拌,使磷光体沉降和倾倒上清液。处理溶液(80mL)然后添加到烧杯,并搅拌产物15分钟。停止搅拌,使磷光体沉降和倾倒处理溶液。磷光体经真空过滤,用丙酮漂洗三次,在真空中干燥和过滤以产生Mn掺杂的K2SiF6。
通过将23g K2SiF6添加至含有500mL 48%HF的聚丙烯烧杯中制备处理溶液。盖上烧杯,搅拌至少15分钟和使用0.65微米孔径的聚四氟乙烯过滤器真空过滤所述溶液,以产生处理溶液,其为K2SiF6在HF中的饱和溶液。
虽然在此说明和描述本发明的仅某些特征,但本领域技术人员应想到许多修改和变化。因此,应理解所附权利要求旨在涵盖落在本发明的真实精神内的所有这些修改和变化。
Claims (16)
1.制备式I的颜色稳定的Mn4+掺杂的络合氟化物的方法:
Ax(M(1-m),Mnm)Fy (I)
所述方法包含使包含(1-m)份式HxMFy的化合物的第一含水HF溶液,和
包含m*n份式Ax[MnFy]的化合物的第二含水HF溶液,与包含(1-n)份式Ax[MnFy]的化合物和式AaX的化合物的第三含水HF溶液接触,
以产生包含颜色稳定的Mn4+掺杂的络合氟化物的沉淀物;
其中
A是Li、Na、K、Rb、Cs、NR4或它们的组合;
M是Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd或它们的组合;
R是H;
X是阴离子;
a是X阴离子的电荷的绝对值;
x是[MFy]离子的电荷的绝对值;
y是5、6或7;
0<m≤0.05;
0.1≤n≤1。
2.权利要求1的方法,其中n范围为0.25-0.95。
3.权利要求1的方法,其中n范围为0.5-0.9。
4.权利要求1的方法,其中n范围为0.6-0.8。
5.权利要求1的方法,其中n为约0.7。
6.权利要求1的方法,其中所述式I的Mn4+掺杂的络合氟化物是K2(Si(1-m),Mnm)F6。
7.权利要求1的方法,其中式AaX的盐选自KF。
8.权利要求1的方法,其中将所述第一和第二含水HF溶液逐渐地添加至所述第三溶液。
9.权利要求1的方法,在所述接触步骤前另外包含,从浓缩的含水HF溶液沉淀式Ax[MnFy]的化合物,和分离沉淀物。
10.包含通过权利要求1的方法制备的络合氟化物的LED照明设备。
11.LED照明设备,其包含:
LED芯片;和
通过权利要求1的方法制备的络合氟化物,布置于所述LED芯片的表面。
12.制备式K2(Si(1-m),Mnm)F6的颜色稳定的Mn4+掺杂的络合氟化物磷光体的方法,所述方法包含:
使包含(1-m)份式H2SiF6的化合物的第一含水HF溶液,和
包含m*n份式K2MnF6的化合物的第二含水HF溶液,与包含(1-n)份式K2MnF6的化合物和选自式KF、KHF2和它们的组合的化合物的第三含水HF溶液接触;
以产生包含颜色稳定的Mn4+掺杂的络合氟化物的沉淀物;
其中
0<m≤0.08;和
0.1≤n≤1。
13.权利要求12的方法,其中n范围为0.6-0.8。
14.权利要求12的方法,所述方法另外包含从浓缩的含水HF溶液中沉淀式K2(Si(1-m),Mnm)F6的化合物,和分离所述沉淀物。
15.制备式I的颜色稳定的Mn4+掺杂的络合氟化物的方法:
Ax(M(1-m),Mnm)Fy (I)
所述方法包含使包含(1-m)份式HxMFy的化合物的第一含水HF溶液,和
包含m*n份式Ax[MnFy]的化合物的第二含水HF溶液,与包含(1-n)份式Ax[MnFy]的化合物和KHF2的第三含水HF溶液接触,
以产生包含颜色稳定的Mn4+掺杂的络合氟化物的沉淀物;
其中
A是Li、Na、K、Rb、Cs、NR4或它们的组合;
M是Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd或它们的组合;
R是H;
x是[MFy]离子的电荷的绝对值;
y是5、6或7;
0<m≤0.05;
0.1≤n≤1。
16.制备式I的颜色稳定的Mn4+掺杂的络合氟化物的方法:
Ax(M(1-m),Mnm)Fy (I)
所述方法包含使包含(1-m)份式HxMFy的化合物的第一含水HF溶液,和
包含m*n份式Ax[MnFy]的化合物的第二含水HF溶液,与包含(1-n)份式Ax[MnFy]的化合物以及KHF2和KF的第三含水HF溶液接触,
以产生包含颜色稳定的Mn4+掺杂的络合氟化物的沉淀物;
其中
A是Li、Na、K、Rb、Cs、NR4或它们的组合;
M是Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd或它们的组合;
R是H;
x是[MFy]离子的电荷的绝对值;
y是5、6或7;
0<m≤0.05;
0.1≤n≤1。
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JP2017501268A (ja) | 2017-01-12 |
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MY183192A (en) | 2021-02-18 |
KR102434076B1 (ko) | 2022-08-19 |
US9388336B2 (en) | 2016-07-12 |
CA2932616C (en) | 2022-11-01 |
CN105793389A (zh) | 2016-07-20 |
CA2932616A1 (en) | 2015-06-18 |
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US20150166887A1 (en) | 2015-06-18 |
KR20160096709A (ko) | 2016-08-16 |
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