CN112779003A - 锰卤荧光粉材料及制备方法和利用锰卤荧光粉材料的发光装置 - Google Patents
锰卤荧光粉材料及制备方法和利用锰卤荧光粉材料的发光装置 Download PDFInfo
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Abstract
本发明涉及一种锰卤荧光粉材料及制备方法和利用锰卤荧光粉材料的发光装置,所述荧光粉为含有锰离子(Mn2+)和卤素离子的AnMnXn+2荧光粉,其中:n=1时,AMnX3为红色荧光粉,其Mn2+为八面体配位;n=3时,A3MnX5为绿色荧光粉,其Mn2+为四面体配位;A为正一价无机阳离子、正一价有机阳离子或者其中几种阳离子的混合;X为F‑、Cl‑、Br‑和I‑其中的一种或者几种的阴离子混合;所述荧光粉材料包括AMnX3和A3MnX5中的至少一种。所述锰卤荧光粉材料发光颜色纯、荧光量子效率高,热稳定性良好,适宜于在LED照明、显示器件背光源和医用探测器等方面应用。
Description
技术领域
本发明涉及发光技术领域,特别是涉及荧光粉材料及其制备方法和用途。
背景技术
白光发光二极管LED是一种将电能转换为白光的固态半导体器件,又称半导体照明,具有效率高、体积小、寿命长、安全、低电压、节能和环保等诸多优点,被人们看成是继白炽灯、荧光灯、高压气体放电灯之后第四代照明光源,是未来照明市场上的主流产品。为了提高白光LED的显色性,各国科学家另外研发了蓝光LED芯片与红、绿色荧光材料组合和紫光LED芯片与红、绿、蓝三基色荧光材料组合这两种实现白光LED的方法。目前InGaN芯片的发射波长已经移至近紫外区域 ,能为荧光粉提供更高的激发能量,进一步提高白光LED的光强。由于紫外光不可见 ,紫外线激发白光LED的颜色只由荧光粉决定,因此颜色稳定,显色指数高,使用近紫外InGaN芯片和蓝、黄荧光粉或者与三基色荧光粉组合来实现白光的方案成为目前白光LED行业发展的重点。荧光粉是该方案中不可缺少的成分。传统稀土荧光粉,大多具有较宽的半峰宽(60-80 nm),或者有多个发射峰并存,造成绿光和红色单色性低从而降低显色色域。
全无机APbX3钙钛矿材料因为高的荧光量子效率且线宽窄的发光特性,近年来成为半导体发光领域的研究热点之一。铅卤钙钛矿量子点因其较高的载流子迁移率、高的量子效率、高的色纯度,以及易调节的带隙等特点,在光电探测、太阳能电池、照明、显示等领域有着广泛的应用。但是,全无机APbX3钙钛矿稳定性较差,且全无机CsPbBr3钙钛矿纳米晶体的发射峰位大多位于510 nm附近,而目前通用显示用绿色荧光粉的发光峰在515-545nm,因此510 nm的发光不利于显示应用。同时全无机APbX3钙钛矿含有重金属铅,对环境以及人类身体健康均有威胁。
闪烁体是一类吸收高能x射线和γ射线后能够发光的材料,在辐射探测领域发挥着十分重要的作用。在医学上,闪烁体是核医学影像设备的核心部件,通过它医生可以快速诊断出人体各器官的病变、肿瘤组织的大小和位置。从而帮助病人及早发现疾病并及时预防和治疗。最常用的无机晶体是用铊激活的碘化钠晶体,即NaI(Tl);其他还有CsI(Tl)、ZnS(Ag)等,锗酸铋,陶瓷闪烁体,如:Lu(2-x)GdxO3:Ac,有机闪烁体蒽、茋、萘等。传统的闪烁体的发光效率不高,发光峰较宽。用于x射线/γ射线探测器检测时的灵敏度有待提高。此外,闪烁体晶体的往往含有剧毒元素,如铊(Tl)和钆(Gd),对坏境有不利影响,晶体的制作成本高。
发明内容
本发明要解决的技术问题在于避免现有技术的不足之处而提出一种有着高量子效率,窄的绿光和红光发射峰,具有更高的绿光和红光色纯度,能提高色域的锰卤荧光粉材料及其制备方法和含有锰卤荧光粉材料的发光装置。
本发明解决所述技术问题所采用的技术方案为:
提供一种锰卤荧光粉材料,所述荧光粉为含有锰离子(Mn2+)和卤素离子的AnMnXn+2荧光粉,其中:n=1时,AMnX3为红色荧光粉,其Mn2+为八面体配位;n=3时,A3MnX5为绿色荧光粉,其Mn2+为四面体配位;A为正一价无机阳离子、正一价有机阳离子或者其中几种阳离子的混合;X为F-、Cl-、Br-和I-其中的一种或者几种的阴离子混合;所述荧光粉材料包括AMnX3和A3MnX5中的至少一种。
进一步地:
所述无机阳离子为铵离子NH4 +、铯离子Cs+、铷离子Rb+、钾离子K+、钠离子Na+或锂离子Li+ ,所述有机阳离子为甲胺CH3NH3 +、甲脒CH2(NH2)2 +、胍CH(NH2)3 +、吡啶(C5H6N+)、乙胺CH3CH2CH2NH3 +、丙胺CH3CH2CH2NH3 +、丁胺CH3CH2CH2CH2NH3 +、戊胺CH3CH2CH2CH2CH2NH3 +或者有机胺CH3(CH2)nNH3 + (n=0-20)。
一种如上述锰卤荧光粉材料的制备方法,包括步骤:
1.前驱体混合溶液的制备:将A盐、锰盐以及卤源加入到有机溶剂中充分混合;其中A盐是乙酸铯,碳酸铯或油酸铯;锰盐是乙酸锰、碳酸锰、硝酸锰、硫酸锰或溴化锰;卤源是卤硅烷或氢卤酸;有机溶剂是正己烷、乙醇、异丙醇、丙酮、乙酸乙酯、二甲亚砜或者是以上溶剂的混合溶剂;
2.反应:将前驱体混合溶液超声反应1分钟至1小时;
3.纯化:将反应得到的荧光粉离心分离,并加热烘干保存。
其中,制备AMnX3红色荧光粉时,其中A盐和锰盐的摩尔比为0.5:1至1.5:1,锰盐和卤源的摩尔比优选为1:2至1:4。
制备A3MnX5的绿色荧光粉时,其中A盐和锰盐的摩尔比为2:1至4:1,锰盐和卤源的摩尔比为1:4至1:6。
有机溶剂为丙酮或异丙醇。
一种利用上述锰卤荧光粉材料的发光装置,该发光装置还包括光源,所述荧光粉与光源辐射耦合将光源辐射能量转化为可见光,所述光源包括蓝光LED、紫外光、x射线或γ射线,其辐射能量范围在约2.5eV至约 2.5MeV之间。
所述发光装置为白光LED照明装置,所述荧光粉材料包括AMnX3红色荧光粉和A3MnX5绿色荧光粉中的至少一种,所述光源为蓝光LED。
所述发光装置为显示器背光源装置,所述荧光粉材料包括AMnX3红色荧光粉和A3MnX5绿色荧光粉中的至少一种,所述光源为蓝光LED。
所述发光装置为医用探测器,所述光源为x射线或γ射线。
与现有技术相比,本发明的技术效果在于:
本专利绿色荧光粉发光峰位在525 nm,半峰宽42 nm,发红光荧光粉材料发光峰位在655 nm,发光颜色纯,发光半峰宽为50 nm。和传统荧光粉相比具有更高的单色性以及更高的荧光量子效率。并且A3MnX5绿色和AMnX3红色荧光粉材料具有较好的热稳定性。
和经典CsPbBr3钙钛矿材料相比,本绿色荧光材料发光峰在525nm更利于显示,且本专利荧光粉材料不含铅,是一种环境友好材料。
本发明锰卤荧光粉材料制备方法简单,易于制备。
由于不含重金属,对环境更友好,并且热稳定性良好,因此适宜于在LED照明,液晶显示器件背光源,x射线和γ射线医用探测器上的应用。用于x射线/γ射线医用探测器时的检测灵敏度高,降低了制作成本。
附图说明
图1是本发明实施例发光装置的横断面示意图,其中,标号①代表锰卤荧光粉材料,②代表封装胶,③代表光发射层,④代表光源。
图2是A3MnX5型绿色荧光粉的发射光谱图,右上方为A3MnX5型绿色荧光粉在365nm紫外灯辐照下的实物图。
图3是A3MnX5型绿色荧光粉的发射光谱图,右上方为A3MnX5型绿色荧光粉在x射线辐照下的实物图。
图4是本发明A3MnX5绿色荧光粉的色度坐标图“2”,同时标出了绿色CsPbBr3 (CPB)钙钛矿量子点“1”和传统稀土YAG荧光粉“3”的坐标点作为对比。
图5 是AMnX3型荧光粉的发射光谱图,左上方为AMnX3型红色荧光粉在365nm紫外灯辐照下的实物图。
图6是用绿色A3MnX5荧光粉和红色AMnX3荧光粉制作的基于蓝光氮化镓发光二极管的白光LED的色度坐标图。
具体实施方式
以下对本发明的实施例作详细说明。
一种锰卤荧光粉材料,所述荧光粉为含有锰离子(Mn2+)和卤素离子的AnMnXn+2荧光粉,其中:n=1时,AMnX3为红色荧光粉,其Mn2+为八面体配位;n=3时,A3MnX5为绿色荧光粉,其Mn2+为四面体配位;A为正一价无机阳离子、正一价有机阳离子或者其中几种阳离子的混合;X为F-、Cl-、Br-和I-其中的一种或者几种的阴离子混合。所述荧光粉材料包括AMnX3和A3MnX5中的至少一种。
所述无机阳离子可以为铵离子NH4 +、铯离子Cs+、铷离子Rb+、钾离子K+、钠离子Na+或锂离子Li+ ,所述有机阳离子可以为甲胺CH3NH3 +、甲脒CH2(NH2)2 +、胍CH(NH2)3 +、吡啶(C5H6N+)、乙胺CH3CH2CH2NH3 +、丙胺CH3CH2CH2NH3 +、丁胺CH3CH2CH2CH2NH3 +、戊胺CH3CH2CH2CH2CH2NH3 +或者有机胺CH3(CH2)nNH3 + (n=0-20)。
所述锰卤荧光粉材料的基本原理是:荧光粉把辐射能量转化为可见光。产生的可见光颜色取决于荧光粉材料的特定化学成份。根据晶体场理论,如果一个Mn2+离子被四个配体包围形成一个独立的 [MnX4]2-四面体单元,该单元按照一定的方式排列,周围的空间被其他有机分子填满,则弱磁场强度的四面体配位Mn2+离子通常表现为绿色发光。在这种情况下,Mn2+离子之间的距离很大足以消除直接的自旋耦合,因此它的光学跃迁是由独立的锰离子控制的。在八面体配位化合物中,[MnX6]4-八面体(被六个配体包围)面对面共享,沿晶体方向形成线性链状结构,其中Mn-Mn间距离在一个方向上显著减小,在其正交方向上由于有机或无机A位分子的阻隔而变大。这种各向异性结构对Mn2+离子链具有限制作用,对不同尺寸的d-d跃迁规律和跃迁能量具有重要影响。因此,强场环境下的八面体配位Mn2+离子通常显示红光发射。
A3MnX5由Mn-X四面体形成,由于晶体中的MnX4配位单元,造成整个晶体发绿色荧光。在紫外光和x射线的辐照下,A3MnX5晶体荧光粉的发光峰位在525nm,半峰宽42nm,如图2和图3所示。并且A3MnX5相比稀土YAG荧光粉以及APbX3钙钛矿来说,在绿光上更适宜于显示,该三种材料的色坐标对比图具体见图4。如图5所示,AMX3的发射峰位于655 nm,表现出红光发射。热重分析表明A3MnX5晶体在加热到400℃以上才开始失重,说明A3MnX5晶体有着比较好的热稳定性。将该A3MX5绿色荧光粉与红色商用氟化物KSF粉混合,封装在蓝光GaN LED芯片中,得到了发白光LED。如图6所示,白光的坐标点为(0.29,0.33),色温为7575K。适合于照明和显示产品。
一种如上述的锰卤荧光粉材料的制备方法,包括步骤:
1.前驱体混合溶液的制备:将A盐、锰盐以及卤源加入到有机溶剂中充分混合;其中A盐是乙酸铯,碳酸铯或油酸铯;锰盐是乙酸锰、碳酸锰、硝酸锰、硫酸锰或溴化锰;卤源是卤硅烷或氢卤酸;有机溶剂是正己烷、乙醇、异丙醇、丙酮、乙酸乙酯、二甲亚砜或者是以上溶剂的混合溶剂;
2.反应:将前驱体混合溶液超声反应1分钟至1小时;
3.纯化:将反应得到的荧光粉离心分离,并加热烘干保存。
其中,制备AMnX3红色荧光粉时,其中A盐和锰盐的摩尔比为0.5:1至1.5:1,锰盐和卤源的摩尔比优选为1:2至1:4。制备A3MnX5绿色荧光粉时,其中A盐和锰盐的摩尔比为2:1至4:1,锰盐和卤源的摩尔比为1:4至1:6。有机溶剂优选为丙酮或异丙醇。
AMnX3具体制备实施例如下:
实施例1:称取268mg五水乙酸铯,343mg四水乙酸锰,取580μL溴硅烷加入20mL丙酮中,震荡混合。将混合溶液放入超声中反应30min,将溶液取出,8000rpm离心10min,去除上清液。将剩余产物放入70℃烘箱中烘干,产物取出保存。
实施例2:称取268mg五水乙酸铯,343mg四水乙酸锰,取580μL溴硅烷加入20mL异丙醇中,震荡混合。将混合溶液放入超声中反应30min,将溶液取出,8000rpm离心10min,去除上清液。将剩余产物放入70℃烘箱中烘干,产物取出保存。。
实施例3:称取376mg五水乙酸铯,343mg四水乙酸锰,取320μL溴硅烷加入15mL丙酮与5mL异丙醇中,震荡混合将混合溶液放入超声中反应30min,将溶液取出,8000rpm离心10min,去除上清液。将剩余产物放入70℃烘箱中烘干,产物取出保存。
A3MnX5具体制备实施例如下:
实施例4:268mg溴化铯溶于20mL甲醇;146mg溴化锰溶于20mL四氢呋喃中。5mL溴化铯溶液加入溴化锰溶液中。将混合溶液放入超声中反应30min,将溶液取出,8000rpm离心10min,去除上清液。将剩余产物放入70℃烘箱中烘干,产物取出保存。
实施例5:268mg溴化铯溶于20mL水;146mg溴化锰溶于20mL乙酸乙酯中。将混合溶液放入超声中反应30min,将溶液取出,8000rpm离心10min,去除上清液。将剩余产物放入70℃烘箱中烘干,产物取出保存。。
实施例6:268mg溴化铯溶于20mL二甲亚砜;146mg溴化锰溶于20mL异丙醇中。将混合溶液放入超声中反应30min,将溶液取出,8000rpm离心10min,去除上清液。将剩余产物放入70℃烘箱中烘干,产物取出保存。
一种利用上述锰卤荧光粉材料的发光装置,如图1所示,包括锰卤荧光粉材料①、封装胶②、光发射层③和光源④,所述锰卤荧光粉材料①与光源④辐射耦合将光源辐射能量转化为可见光,所述光源包括蓝光LED、紫外光、x射线或γ射线,其辐射能量范围在约2.5eV至约 2.5MeV之间。锰卤荧光粉材料①分散在封装胶②中。
所述发光装置为白光LED照明装置或显示器背光源装置,所述荧光粉材料包括AMnX3红色荧光粉和A3MnX5绿色荧光粉中的至少一种,所述光源为蓝光LED。
锰卤荧光粉材料把范围在约2.5 eV至约 2.5 MeV之间的光源辐射能量,如:蓝光(400-500 nm),紫外光(10-400 nm),x射线(0.001-10 nm)和γ射线(<0.001 nm),转化为可见光。锰卤荧光粉材料可以提供不同颜色的光发射。荧光粉组合物和共混物,以及它们在发光二极管(LED),紫外光(UV),x射线和γ射线等光源中的应用。单一颜色的锰卤荧光粉、两个或多个基本颜色锰卤荧光粉,或者锰卤荧光粉与普通荧光粉组合可以发不同颜色的光。例如:LED灯中,蓝光LED和绿色锰卤荧光粉和红色锰卤荧光粉混合发出白光。医用探测器中X射线照射绿色锰卤荧光粉产生绿光。产生的可见光的颜色取决于荧光粉材料的特定成分。
应当理解的是,以上实施例仅用以说明本发明的技术方案,而非对其限制,其部分细节可通过相应设计变更以其它的形式来实现。对本领域技术人员来说,可以对上述实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改和替换,都应属于本发明所附权利要求的保护范围。
Claims (10)
1.一种锰卤荧光粉材料,其特征在于:所述荧光粉为含有锰离子(Mn2+)和卤素离子的AnMnXn+2荧光粉,其中:
n=1时,AMnX3为红色荧光粉,其Mn2+为八面体配位;n=3时,A3MnX5为绿色荧光粉,其Mn2+为四面体配位;
A为正一价无机阳离子、正一价有机阳离子或者其中几种阳离子的混合;
X为F-、Cl-、Br-和I-其中的一种或者几种的阴离子混合;
所述荧光粉材料包括AMnX3和A3MnX5中的至少一种。
2.根据权利要求1所述的锰卤荧光粉材料,其特征在于:所述无机阳离子为铵离子NH4 +、铯离子Cs+、铷离子Rb+、钾离子K+、钠离子Na+或锂离子Li+ ,所述有机阳离子为甲胺CH3NH3 +、甲脒CH2(NH2)2 +、胍CH(NH2)3 +、吡啶(C5H6N+)、乙胺CH3CH2CH2NH3 +、丙胺CH3CH2CH2NH3 +、丁胺CH3CH2CH2CH2NH3 +、戊胺CH3CH2CH2CH2CH2NH3 +或者有机胺CH3(CH2)nNH3 + (n=0-20)。
3.一种如权利要求1或2所述的锰卤荧光粉材料的制备方法,其特征在于:包括步骤:
(1)前驱体混合溶液的制备:将A盐、锰盐以及卤源加入到有机溶剂中充分混合;其中A盐是乙酸铯,碳酸铯或油酸铯;锰盐是乙酸锰、碳酸锰、硝酸锰、硫酸锰或溴化锰;卤源是卤硅烷或氢卤酸;有机溶剂是正己烷、乙醇、异丙醇、丙酮、乙酸乙酯、二甲亚砜或者是以上溶剂的混合溶剂;
(2)反应:将前驱体混合溶液超声反应1分钟至1小时;
(3)纯化:将反应得到的荧光粉离心分离,并加热烘干保存。
4.根据权利要求3所述的锰卤荧光粉材料的超声反应制备方法,其特征在于:制备AMnX3红色荧光粉时,其中A盐和锰盐的摩尔比为0.5:1至1.5:1,锰盐和卤源的摩尔比优选为1:2至1:4。
5.根据权利要求3所述的锰卤荧光粉材料的超声反应制备方法,其特征在于:制备A3MnX5的绿色荧光粉时,其中A盐和锰盐的摩尔比为2:1至4:1,锰盐和卤源的摩尔比为1:4至1:6。
6.根据权利要求3所述的锰卤荧光粉材料的超声反应制备方法,其特征在于:有机溶剂为丙酮或异丙醇。
7.一种利用如权利要求1或2所述的锰卤荧光粉材料的发光装置,该发光装置还包括光源,其特征在于:所述荧光粉与光源辐射耦合将光源辐射能量转化为可见光,所述光源包括蓝光LED、紫外光、x射线或γ射线,其辐射能量范围在2.5 eV至 2.5 MeV之间。
8.根据权利要求7所述的发光装置,其特征在于:所述发光装置为白光LED照明装置,所述荧光粉材料包括AMnX3红色荧光粉和A3MnX5绿色荧光粉中的至少一种,所述光源为蓝光LED。
9.根据权利要求7所述的发光装置,其特征在于:所述发光装置为显示器背光源装置,所述荧光粉材料包括AMnX3红色荧光粉和A3MnX5绿色荧光粉中的至少一种,所述光源为蓝光LED。
10.根据权利要求7所述的发光装置,其特征在于:所述发光装置为医用探测器,所述光源为x射线或γ射线。
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