CN113185970B - 窄带绿光发射有机无机杂化卤化铅钙钛矿材料、制备方法及其应用 - Google Patents
窄带绿光发射有机无机杂化卤化铅钙钛矿材料、制备方法及其应用 Download PDFInfo
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Abstract
本发明属于材料制备技术领域,具体涉及一种高纯度窄带绿光发射有机无机杂化卤化铅钙钛矿材料、制备方法及其应用,其分子式为[TMDAP]2Pb3Br10(TMDAP=N,N,N’,N’,‑四甲基‑1,3‑丙二胺),采用水热合成法制备,该材料可应用于绿光LED、高分辨显示器以及白光LED。本发明首次证明了结构固化策略在低维金属卤化物钙钛矿中实现纯绿光发射的可行性,得到了首例光纯度高达91.1%的一维[TMDAP]2Pb3Br10钙钛矿材料,该化合物拥有极理想的光致发光性能,包括合适的发射位置,仅有25nm的极窄半峰宽,高达71.59%的光致发光量子产率(PLQY和)121.5%的超宽色域,实现了符合Rec.2020标准的超纯绿色背光材料合成,同时在高分辨率液晶显示器等方面具有优异的应用前景。
Description
技术领域
本发明属于材料制备技术领域,具体涉及一种窄带绿光发射有机无机杂化卤化铅钙钛矿材料、制备方法及其应用。
背景技术
近年来,白光发射二极管(WLEDs)凭借高效率、长寿命、低能耗等优良特性,成为固体照明和液晶显示技术中最有潜力的光电器件之一。根据新定义的国际电信联盟(ITU)推荐的BT 2020 (Rec. 2020)标准,为了实现WLEDs的组装,探索具有极窄半峰宽(FWHM < 25nm)的高纯度单色红、绿、蓝基色至关重要。其中,绿光是人眼最敏感的波段,与红色和蓝色发光的荧光粉相比,实现绿光高效高纯的窄带发射是目前研究的热点与难点。传统的绿色发光荧光粉(如SiAlON:Eu2+)最初由于其高的发光效率被用作绿光基色,但因为半峰宽过宽使其在应用于背景光源中达不到较大的色域范围(>90% NTSC = 国家电视系统委员会)。随着卤化物钙钛矿组装工艺的日渐成熟,以及对三维卤化物钙钛矿光电色性质的系统研究,逐步实现了对三维钙钛矿的发射位置,半峰宽和发光效率的可调谐组装。例如,在准二维MAPbBr3 (MA = CH3NH3 +)和FAPbBr3 (FA = CH(NH2)2 +)纳米片中实现了接近Rec. 2020标准的超纯绿光。然而,精准调控三维钙钛矿结构-性能之间的关系依然存在很大困难,如纳米三维钙钛矿的化学性质和光学性质不稳定,导致其貌和结构难以控制,严重阻碍了发光器件的研发运用。更为严重的是,根据Goldschmidt容差因子,[PbX3]框架中狭小的八面体腔限制了结构组成的调控,只有少数体积较小的阳离子如Cs+、MA+和FA+能满足如此严格的要求,这严重限制了高纯度绿光发射钙钛矿材料的合成。
令人振奋的是,实验证明有机阳离子的引入使得结构更易趋向二维层,一维链甚至零维单元等低维结构,可以从中获得绿光发射。然而在低维钙钛矿结构中存在着由于晶格畸变引起的强电子-声子耦合效应,导致了具有宽半峰宽的宽带发射,从而产生了纯度过低的绿光发射。所以在低维钙钛矿中进一步探索高效高纯窄带绿光发射逐渐成为目前的研究热点。我们组装出一例新型高效(71.59%)高纯(91.1%)的窄带(25 nm)绿光发射的一维有机无机杂化卤化铅钙钛矿,并研究了其发光性能。高纯绿光发射实现高达121.5% NTSC和90.7%的国际电信联盟(ITU)推荐BT 2020 (Rec. 2020)标准的超宽色域,表明其具有作为高质量背光显示的重要潜力。相关工作至今未见文献报道。本发明提供了该化合物的潜在用途,其特征在于:该晶体实现了同时具有超高量子产率和超高色纯度的绿光超窄带发射,实现了正白光发射WLED组装且性能良好。
发明内容
本发明的目的在于提供了一种窄带绿光发射有机无机杂化卤化铅钙钛矿材料、制备方法及其应用。
为了实现上述目的,本发明采用的技术方案为:
本发明窄带绿光发射有机无机杂化卤化铅钙钛矿材料,其分子式为[TMDAP]2Pb3Br10(TMDAP = N,N,N’,N’,-四甲基-1,3-丙二胺),属于单斜晶系空间群为
P21/
c,晶胞参数为
a = 11.7112(10) Å,
b = 15.6589(13) Å,
c = 11.8912(10) Å,α=γ= 90 º,
β= 118.7447(10),
Z = 2,晶胞体积为
V = 1911.94 Å3。
本发明所述的窄带绿光发射有机无机杂化卤化铅钙钛矿材料的制备方法,包括以下步骤:
1)将溴化铅和N,N,N’,N’-四甲基1,3-丙二胺溶解于氢溴酸、乙醇和N-甲基甲酰胺混合液中,充分混合;将混合液装入反应容器;
2)将密封好的反应容器放入带有程序控温的电热鼓风干燥箱中,进行水热反应,反应结束后,自然冷却至室温,静置,用上层清液和乙醇洗涤,干燥后得到目标产物。
步骤1)中溴化铅和的N,N,N’,N’-四甲基1,3-丙二胺的摩尔比为3:2~3:8。
步骤2)中反应温度为80~120 ℃,水热反应时间为12-100小时,静置3-8天。
本发明所述的窄带绿光发射有机无机杂化卤化铅钙钛矿材料的应用,该材料可应用于绿光 LED、高分辨显示器以及白光 LED。
化合物表现出强烈的窄带绿光发射,量子产率高达71.95 %,色纯度高达85.11 %,半峰宽仅25 nm。而且表现出非常优异的稳定性,在潮湿环境(RH ≈ 80 %)中放置180天后依然表现出强烈的绿光发射。这些优异的性质使得该化合物在很多现实应用中具有很大的潜能,尤其是在现代科技中有重要的应用价值。一方面,绿光是人眼最敏感的波段,比传统的红色激光定位更加柔和也更易被人眼分辨,可以运用在在矿山巷道掘进时指向定位,爆炸性气体环境下煤矿的绿光定位系统。其次,在休闲娱乐场所中,如布置舞台效果,城市夜景的装点等方面也有重要应用前景,例如:我们将粉末样品涂覆在365 nm的UV-LED灯上,制成绿色发光二极管,连续照明几天后,LED灯发出明亮的绿光,没有明显的变暗。另一方面更为重要的是,将化合物与蓝红商用荧光粉按照一定质量比例调配适合后,可以得到正白光发射的WLED系统,因为该化合物完美的达到了NTSC和ITU对基色光源的要求(121.5 %NTSC,FWHM<25 nm),所以该白光系统表现出优异的光学性质。测试该系统的各项发光性质及光学参数,得到了非常接近正白光(0.33,0.33)的色坐标(0.3282,0.3403),而且该系统在不同电流强度下都表现出优异的稳定性,随着电流强度的增大,发射强度增强。这表明该化合物不但在单色发光方面具有广泛的应用,而且还能通过进一步组装实现白光照明,符合低成本高效率的市场价值要求。
本发明的有益效果为:本发明首次证明了结构固化策略作为色度工程在所有LDHPs中实现纯绿光发射的有效性,我们得到了具有发射纯度高达91.1%的新型钙钛矿一维结构[TMDAP]2Pb3Br10。该化合物拥有极理想的光致发光性能,包括合适的发射位置,仅有25nm的极窄半峰宽,高达71.59 %的PLQY和121.5 %的超宽色域,使超纯绿色背光实现Rec.2020标准,在高分辨率LCD具有引人注目的潜力。该结构原型具有弱电子-声子相互作用和强量子约束的最佳峰525 nm,从而达到色纯度和发射效率的同步双优化。作为一项重大突破,该工作为实现超纯发光提供了一种新的结构设计策略,得到了稳定性超高的片状晶体,具有很大的应用前景,弥补了胶体三维钙钛矿因为光学化学稳定性差带来形貌结构难以控制的不足。我们相信,这一发现将为开发新型卤化钙钛矿高纯度单色源提供基本指导。
附图说明
图1为实施例2所得[TMDAP]2Pb3Br10的晶体结构图;
图2为实施例2所得[TMDAP]2Pb3Br10的粉末X射线衍射结构图;
图3为实施例2所得[TMDAP]2Pb3Br10的固态紫外-可见吸收光谱;
图4为实施例2所得基于Tauc’s函数在直接和间接跃迁假设下计算的带隙图谱;
图5为实施例2所得[TMDAP]2Pb3Br10在300K时的激发谱与发射谱;
图6为390nm激发,实施例2所得[TMDAP]2Pb3Br10在100-300 K时的发射谱;
图7为实施例2所得[TMDAP]2Pb3Br10晶体的系统特性表征图;
图8为白光WLED在120 mA驱动电流下的发射谱(插图:装配式WLED的照片);
图9为 WLED设备依赖驱动电流的发光光谱;
图10为发光二极管, NTSC标准颜色空间(黑线)和WLED设备(紫色)的1931CIE的色坐标;
图11为WLED系统在不同驱动电流下归一化峰值强度变化;
图12为在20 mA工作电流下,WLED系统随时间变化的发光光谱。
具体实施方式
本发明所采用的原材料均为阿拉丁试剂公司提供:PbBr2 (纯度99.9 %),N,N,N’,N’-四甲基-1,3-丙二胺 (99 %), 乙醇 (99 %), 氢溴酸(浓度48 %),N-甲基甲酰胺 (纯度99.9 %)。水热釜为济南恒化科技公司提供,容量为25 mL。电热鼓风干燥箱为上海一恒科学仪器有限公司提供,型号为DHG-9240(A)。晶体结构通过X-射线单晶衍射仪(德国Bruker公司,SMART APEXII)测试,粉末衍射采用X-射线粉末衍射仪(Bruker D8 ADVANCE)测试,紫外-可见吸收光谱通过紫外-可见分光光度计(PE Lambda 900)测试。PL光谱在爱丁堡FLS980荧光光谱仪上进行。光致发光量子产率是通过在FLS980荧光光谱仪中加入积分球来实现的。发光寿命数据使用爱丁堡FLS980荧光光谱仪与皮秒脉冲二极管激光器进行。利用CIE计算机软件,根据发射光谱计算了CIE国际委员会(CIE)的色度坐标和显色指数(CRI)。XPS数据在Thermo ESCALAB 250XI电子能谱测试仪上测试。SEM图像来自ZEISS MERLINCompact 扫描电子显微镜。白光二极管的测试在虹谱HP9000光电系统测试仪上完成。
实施例 1
本发明窄带绿光发射有机无机杂化卤化铅钙钛矿材料,其分子式为[TMDAP]2Pb3Br10(TMDAP = N,N,N’,N’,-四甲基-1,3-丙二胺),属于单斜晶系空间群为
P21/
c,晶胞参数为
a = 11.7112(10) Å,
b = 15.6589(13) Å,
c = 11.8912(10) Å,α=γ= 90 º,
β= 118.7447(10),
Z = 2,晶胞体积为
V = 1911.94 Å3。
化合物具有一维的链状结构,结构中包含阴离子链 [Pb3Br10]4-。[PbBr6]八面体通过共面形成[Pb3Br12]6-三聚体,三聚体又通过边连接形成了[Pb3Br10]4-一维链。各个一维链之间平行存在,[TMDAP]2+作为平衡电荷均匀分布在一维链周围。
实施例2
本发明所述的窄带绿光发射有机无机杂化卤化铅钙钛矿材料的制备方法,包括以下步骤:
1)将质量比为1:1的溴化铅(0.110 g, 0.3 mmol)和N,N,N’,N’-四甲基1,3-丙二胺(0.110 g,0.83 mmol)与1 mL氢溴酸、2 mL乙醇、4 mL N-甲基甲酰胺于25 mL玻璃瓶中中混合,磁力搅拌5分钟使之充分混合,将混合液装入玻璃瓶中密封;
2)将上述玻璃瓶置于鼓风干燥箱中,以20℃/h-1升温速率升温至80 ℃,持续恒温加热12小时之后取出,在空气中冷却至室温,静置三天后,用上层清液和乙醇洗涤干燥后得到无色透明的片状晶体。
图1为[TMDAP]2Pb3Br10的晶体结构图:a. [Pb3Br12]6-三聚体;b. [Pb3Br12]6-三聚体通过边连接形成的[Pb3Br10]4-一维链。
图2为[TMDAP]2Pb3Br10的粉末X射线衍射结构图:[TMDAP]2Pb3Br10的粉末衍射图与单晶结构模拟的数据相同,说明为单相的[TMDAP]2Pb3Br10,纯度接近于100 %。
图3为[TMPDA]Pb3Br10的固态紫外-可见吸收光谱,图4为基于Tauc’s函数在直接和间接跃迁假设下计算的带隙图谱:[TMDAP]2Pb3Br10在200-800 nm之间有较强的光学吸收,光学带隙为3.26 eV,属于半导体材料。带隙通过使用Tauc’s函数在直接和间接跃迁的假设下计算,Tauc’s图表明[TMPDA]Pb3Br10最适合直接带隙模型,因此[TMPDA]Pb3Br10被指定为3.30 eV的直接带隙。
图5为[TMDAP]2Pb3Br10在300K时的激发谱与发射谱[:TMDAP]2Pb3Br10在300 K,390nm激发下,最强的发射峰位置约为519 nm,斯托克斯位移为129 nm,半峰宽为26 nm。390 nm处激发,伴随着温度从300 K降低到100 K,发射峰强度越来越强,半峰宽越来越窄,且最大发射峰不存在分裂行为,这说明发射来源于单激发态,而不是多重辐射机制。
图6为390nm激发,[TMDAP]2Pb3Br10在100-300 K时的发射谱;
图7为[TMPDA]Pb3Br10晶体的系统特性表征图:
(a)模拟和实验的XRD谱,包括在氙灯光照、潮湿和加热到不同温度后的XRD谱,单晶的稳定性XRD图谱(a)表明:氙灯光照后的单晶,潮湿环境中存放了约180天的单晶,以及从50℃加热到250℃的单晶均表现出优异的稳定性;
(b)单晶的SEM照片:晶体的SEM扫描图像(b)显示了表面生长良好的片状结构;
(c - f) Pb、Br、C和N原子的XPS光谱:Pb-4
f,Br-3
d,C-1
s, N-1
s轨道都能够清晰识别
(g) Pb和Br元素的EDX元素映射图像:EDX元素映射证实,所有的Pb和Br元素在[TMDAP]2Pb3Br10中均匀分布。
实施例3
本发明所述的窄带绿光发射有机无机杂化卤化铅钙钛矿材料的制备方法,包括以下步骤:
1) 将0.1468 g (0.4 mmol)溴化铅和0.792 g (0.6 mmol) N,N,N’,N’-四甲基1,3-丙二胺溶解于1.4 mL氢溴酸中,加入2 mL乙醇和3 mL N-甲基甲酰胺,磁力搅拌5分钟使之充分混合;将混合液装入聚四氟乙烯的的不锈钢反应釜中密封;
2)将上述反应釜置于鼓风干燥箱中,以20℃/h-1升温速率升温至120 ℃,持续恒温加热100小时,在空气中冷却到室温,静置8天后,用上层清液和乙醇洗涤,干燥后得到无色透明的片状晶体。
实施例4
本发明所述的窄带绿光发射有机无机杂化卤化铅钙钛矿材料的制备方法,包括以下步骤:
1) 将0.10 g (0.27 mmol)溴化铅和0.05 g (0.37 mmol) N,N,N’,N’-四甲基1,3-丙二胺溶解于1.1 mL氢溴酸中,加入2 mL乙醇和4 mL N-甲基甲酰胺,磁力搅拌5分钟使之充分混合,将混合液装入玻璃瓶中密封;
2)将上述玻璃瓶置于鼓风干燥箱中,以20℃/h-1升温速率升温至100 ℃,持续恒温加热72小时,在空气中冷却到室温,静置4天后,用上层清液和乙醇洗涤,干燥后得到无色透明的片状晶体。
实施例5
[TMDAP]2Pb3Br10组装的绿光LED:
将晶体样品用球磨机研磨15min,得到的粉末样品分散在商用胶水中,形成均匀混合物;然后,将该混合物在商业紫色365 nm UV-LED上旋涂3-5次,在LED表面形成均匀的薄膜,并于真空干燥箱中50℃烘干,使之形成稳定包覆材料;接通1~3V电源后,LED发出明亮绿光并能持续发光数日没有明显变暗。
实施例6
[TMDAP]2Pb3Br10组装的白光WLED:
将荧光粉按照如下质量比例调配均匀后([TMDAP]2Pb3Br10绿光发射粉末:商业红色荧光粉K2SiF6: Mn4 +:蓝色磷光BaMgAl10O17 = 2.5:0.6:1.6),与395 nm紫外LED芯片组合成白光发射的WLED。测试WLED在不同驱动电流(20-120 mA)下的发射谱,随着电流强度的增强,其发射强度随之增强,在120 mA驱动电流下的发射谱,其色坐标为(0.3282,0.3403),非常接近正白光的色坐标位置(0.33, 0.33);随后测试了20 mA工作电流下随着通电时间变化的稳定性发射谱,通电5小时后,发射谱稍有降低,表明WLED系统在实际应用中将具有良好的稳定性。
图8为白光WLED在120 mA驱动电流下的发射谱(插图:装配式WLED的照片):与其他两种荧光粉组装为白光WLED灯泡,在120mA的驱动电流下,表现出覆盖整个可见光范围的白光发射,色温为5689K,色坐标为(0.3282,0.3403),非常接近正白光发射。
图9为 WLED设备依赖驱动电流的发光光谱:随着驱动电流的增强,在120ma电流范围内,发射光谱轮廓没有明显变化,WLED的发射强度单调增强,表现出优异的稳定性。
图10为发光二极管, NTSC标准颜色空间(黑线)和WLED设备(紫色)的1931CIE的色坐标:即使没有精心选择红色和蓝色荧光粉以及精心组装技术,所制作的WLED显示超宽色域,远远超过ITU-R BT.709标准(171.6%)。
图11为WLED系统在不同驱动电流下归一化峰值强度变化:光谱稳定性较好,在120ma电流范围内,发射强度单调增加,表明其在大功率光电器件中具有潜在的应用前景。
图12为在20 mA工作电流下,WLED系统随时间变化的发光光谱:所制作的WLED器件在至少5小时的恒定工作时间下可以保持较高的稳定性,发射强度而不会明显减弱,进一步证明了热和光稳定性。
Claims (5)
1.一种窄带绿光发射有机无机杂化卤化铅钙钛矿材料,其特征在于,其分子式为[TMDAP]2Pb3Br10,TMDAP = N,N,N’,N’,-四甲基-1,3-丙二胺,属于单斜晶系,空间群为P21/c,晶胞参数为 a = 11.7112(10) Å,b = 15.6589(13) Å,c = 11.8912(10) Å,α=γ= 90º,β= 118.7447(10),Z = 2,晶胞体积为V = 1911.94 Å3。
2.一种如权利要求1所述的窄带绿光发射有机无机杂化卤化铅钙钛矿材料的制备方法,其特征在于,包括以下步骤:
将溴化铅和N,N,N’,N’-四甲基1,3-丙二胺溶解于氢溴酸、乙醇和N-甲基甲酰胺混合液中,充分混合;将混合液装入反应容器;
将密封好的反应容器放入带有程序控温的电热鼓风干燥箱中,进行水热反应,反应结束后,自然冷却至室温,静置,用上层清液和乙醇洗涤,干燥后得到目标产物。
3.根据权利要求2所述的步骤窄带绿光发射有机无机杂化卤化铅钙钛矿材料的制备方法,其特征在于,步骤1)中溴化铅和N,N,N’,N’-四甲基1,3-丙二胺的摩尔比为3:2~3:8。
4.根据权利要求2所述的步骤窄带绿光发射有机无机杂化卤化铅钙钛矿材料的制备方法,其特征在于,步骤2)中反应温度为80~120 ℃,水热反应时间为12-100小时,静置3-8天。
5.一种如权利要求1所述的窄带绿光发射有机无机杂化卤化铅钙钛矿材料的应用,其特征在于,该材料应用于绿光LED以及白光LED。
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