CN114410304A - 一种新型稀土基无铅钙钛矿纳米晶材料及其制备方法与应用 - Google Patents
一种新型稀土基无铅钙钛矿纳米晶材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种新型稀土基无铅钙钛矿纳米晶材料及其制备方法与应用,包括以下步骤:步骤一:将乙酸钠、乙酸铯、稀土乙酸盐在油酸、油胺、十八稀中加热溶解,得到澄清的前驱体溶液;步骤二:向澄清的前驱体溶液中加入TMSCl、TMSBr或TMSI,反应过后,在冰水浴中冷却,离心清洗,最后分散在甲苯溶剂中,得到Cs2NaLnX6无铅钙钛矿纳米晶材料,该Cs2NaLnX6无铅钙钛矿纳米晶材料可应用于光电器件领域。
Description
技术领域
本发明属于光学材料技术领域,具体涉及一种新型稀土基无铅钙钛矿纳米晶材料及其制备方法与应用。
背景技术
近年来,卤化铅钙钛矿纳米晶体(NCs)APbX3(A=CH3NH3,CH(NH2)2,Cs,Rb;X=Cl,Br,I)以其高的载流子迁移率、大的吸收系数、带隙可调等优点被广泛的应用在太阳能电池、发光二极管、激光器和光电探测器等领域。铅卤钙钛矿在光电性能上可与传统半导体材料相媲美,同时它们可以通过简单、低成本的方式合成。与体晶材料相比,铅卤钙钛矿纳米晶体材料具有更大的激子结合能、更强的激子吸收,因此在室温下具有更高的光致发光量子产率(PLQY)。铅卤钙钛矿材料的这些优点使其受到广泛的关注。但是重金属铅的毒性和材料的湿热稳定性成为其实际应用的阻碍。因此,寻找低毒、高效、稳定的无铅钙钛矿型纳米晶材料引起了研究人员的广泛关注。
近年来关于无铅胶体钙钛矿量子点(PQDs)或纳米晶体的研究已经报道,如锡和铋基的PQDs或NCs,具有与卤化铅钙钛矿类似的光学性质,如可调节的发射波长范围。然而,一些重要问题仍未得到解决,如PLQY低,湿度和热稳定性差,所以在寻求低毒、高效、稳定的钙钛矿型纳米晶材料方面的工作还需进一步的探索和研究。
稀土离子在钙钛矿结构中具有丰富的跃迁能级和独特的5d-4f发射、以及其较长的荧光寿命等迷人的特性。但是目前稀土离子只是少量的掺杂在铅卤钙钛矿材料中,其性质和作用还远远没有得到发展。如果用稀土材料作为钙钛矿材料的主体,既可以得到高效的钙钛矿发光,又可以得到高效的稀土发光,既解决了毒性问题,又丰富了发光的颜色和范围。
发明内容
本发明的目的是为了解决背景技术中存在的问题,提供了一种环保无毒且合成方法操作简单,耗时少;合成的Cs2NaLnX6无铅钙钛矿纳米晶材料样品相稳定,形貌尺寸均一,发光色纯度高,表面缺陷少,量子效率高,具有良好的湿热以及光照稳定性的一种新型稀土基无铅钙钛矿纳米晶材料及其制备方法与应用。
为实现上述发明目的,本发明的技术方案是:
一种新型稀土基无铅钙钛矿纳米晶材料的制备方法,包括以下步骤:
步骤一:将乙酸钠、乙酸铯、稀土乙酸盐在油酸、油胺、十八稀中加热溶解,得到澄清的前驱体溶液,其中乙酸铯∶乙酸钠∶稀土乙酸盐的摩尔比为7∶5∶5;
步骤二:向澄清的前驱体溶液中加入TMSCl、TMSBr或TMSI(三甲基氯硅烷、三甲基溴硅烷或三甲基碘硅烷),反应过后,在冰水浴中冷却,离心清洗,最后分散在甲苯溶剂中,得到Cs2NaLnX6无铅钙钛矿纳米晶材料。
作为优选,所述步骤一中油酸、油胺和十八稀的体积比为1:1:5~6。
作为优选,所述步骤一中加热溶解的温度为120~140℃。
作为优选,所述步骤一中稀土乙酸盐为镧、铈、钐、铕、铽、铒、镱中任意一种的乙酸盐,需要说明的是,稀土乙酸盐也可以选用其他稀土元素的乙酸盐,并不限于此。
作为优选,所述步骤一中保护气体为氮气或氩气中的一种,氮气和氩气主要起到保护作用,防止反应物被氧化。
作为优选,所述步骤一具体包括:将乙酸钠、乙酸铯、稀土乙酸盐、油酸、油胺、十八稀在100mL实验容器中混合,在保护气体的保护下,升温至120~140℃,保温一个小时,使其充分溶解得到澄清的前驱体溶液。
作为优选,所述步骤二中向前驱体溶液中加入TMSCl、TMSBr或TMSI时的温度为240℃,TMSCl、TMSBr或TMSI的量为0.4~0.5mL。
作为优选,所述步骤二中离心清洗的转速和时间分别为9500转/s和10min。
作为优选,所述步骤二中甲苯溶剂的量为3mL,需要说明的是,分散溶剂可以选用环己烷、苯、正己烷等溶剂,但不限于此,最优选的溶剂为甲苯。
作为优选,所述步骤二具体包括:在氮气保护下,将前驱体溶液升温至240℃,然后注入0.4~0.5mL的TMSCl、TMSBr或TMSI;反应2分钟后,快速的将反应的混合物放入到冰水中快速降温结晶;将冷却的混合物放入到离心机中,以9500转/s的转速离心10分钟;然后倒出离心的上清液,将沉淀分散在3mL甲苯溶剂中,得到Cs2NaLnX6无铅钙钛矿纳米晶材料。
一种利用本方法制备得到的新型稀土基无铅钙钛矿纳米晶材料,可应用在制备光电器件中。
本发明的有益效果是:
环保无毒且合成方法操作简单,耗时少;合成的Cs2NaLnX6无铅钙钛矿纳米晶材料样品相稳定,形貌尺寸均一,发光色纯度高,表面缺陷少,量子效率高,具有良好的湿热以及光照稳定性;同时能够实现蓝光(445nm)、绿光(545nm)、红光(617nm)的多色发射,以及单一基质钙钛矿材料的白光发射,是很好的白光照明应用的材料。
附图说明
图1为本发明实施例的Cs2NaLnX6(Ln=La,Ce,Sm,Eu,Tb,Er,Yb;X=Cl,Br,I)无铅钙钛矿纳米晶材料的晶体结构图。
图2为本发明实施例的Cs2NaLnX6无铅钙钛矿纳米晶材料的X射线(X-raydiffraction,XRD)衍射图。
图3为本发明实施例的Cs2NaLnCl6无铅钙钛矿纳米晶材料的透射电子显微镜(Transmission Electron Microscope,TEM)图。
图4为本发明实施例的Cs2NaLnBr6无铅钙钛矿纳米晶材料的TEM图。
图5为本发明实施例的Cs2NaLnI6铅钙钛矿纳米晶材料的TEM图。
图6为本发明实施例的Cs2NaLnX6无铅钙钛矿纳米晶材料的吸收图谱。
图7为本发明实施例的Cs2NaLnX6无铅钙钛矿纳米晶材料的光致发光(Photoluminescence Spectroscopy,PL)光谱图和量子效率(PLQY)图。
图8为本发明实施例的Cs2NaLnX6无铅钙钛矿纳米晶材料的湿热以及光照稳定性的测试。
图9为本发明实施例的Cs2Na(Tb:Eu=25:1)Cl6无铅钙钛矿纳米晶材料的PL图和激发(Photoluminescence excitation Spectrum)谱。
图10为本发明实施例的基于Cs2Na(Tb:Eu=25:1)Cl6无铅钙钛矿纳米晶材料白光LED的色坐标和白光LED(Light-emitting diode)通电的照片。
具体实施方式
下面结合附图对本发明进行详细的说明,所列举的实施例,只是用于帮助理解本发明,不应理解为对本发明保护范围的限定,对于本技术领域的普通技术人员来说,在不脱离本发明思想的前提下,还可以对本发明进行改进和修饰,这些改进和修饰也落入本发明权利要求保护的范围内。
根据本申请包含的信息,对于本领域技术人员来说可以轻而易举地对本发明的精确描述进行各种改变,而不会偏离所附权利要求的精神和范围。应该理解,本发明的范围不局限于所限定的过程、性质或组分,因为这些实施方案以及其他的描述仅仅是为了示意性说明本发明的特定方面。实际上,本领域或相关领域的技术人员明显能够对本发明实施方式作出的各种改变都涵盖在所附权利要求的范围内。
为了更好地理解本发明而不是限制本发明的范围,在本申请中所用的表示用量、百分比的所有数字、以及其他数值,在所有情况下都应理解为以词语“大约”所修饰。因此,除非特别说明,否则在说明书和所附权利要求书中所列出的数字参数都是近似值,其可能会根据试图获得的理想性质的不同而加以改变。各个数字参数至少应被看作是根据所报告的有效数字和通过常规的四舍五入方法而获得的。
实施例1,稀土基无铅钙钛矿纳米晶材料Cs2NaLnX6(Ln=La,Ce,Sm,Eu,Tb,Er,Yb;X=Cl,Br,I)的合成。
采用改进的热注入法合成材料:将摩尔比为7∶5∶5的乙酸铯、乙酸钠、稀土乙酸盐和1:1:5~6体积比的油酸、油胺、十八稀在100mL实验容器(如三颈烧瓶)中混合,在氮气的保护下,升温至120~140℃,保温一个小时,使其充分溶解得到澄清的前驱体溶液。
然后在氮气保护下,将前驱体溶液升温至240℃,然后注入0.4~0.5mL的TMSCl、TMSBr或TMSI(该成分的作用是引入卤素,如果选择TMSCl,则X=Cl;如果选择TMSBr,则X=Br;如果选择TMSI,则X=I);反应2分钟后,快速的将反应的混合物放入到冰水中快速降温结晶;将冷却的混合物放入到离心机中,以9500转/s的转速离心10分钟;然后倒出离心的上清液,将沉淀分散在3mL甲苯溶剂中,得到Cs2NaLnX6无铅钙钛矿纳米晶材料。
如图1所示,已知两个Pb2+可以被一个一价M+和一个三价M'3+取代,形成三维双钙钛矿A2MM'X6;MX6八面体与M'X6八面体以共同的顶角交替排列在三维空间中,形成三维框架;A位离子被8个八面体包围在空隙中心。在有序双钙钛矿中,M和M'位在晶格中交替出现。本发明实例的双钙钛矿材料A2MM'X6(A=Cs(橙色球);M+=Na+(紫色球);M'3+=Ln3+(黄色球);X-=Cl-,Br-,I-(黑球))是用一个Na+和一个稀土离子(Ln3+)取代两个铅离子而形成的。
实施例2,对Cs2NaLnX6无铅钙钛矿纳米晶材料进行XRD的测试。
如图2所示,图a,b,c分别为Cs2NaLnCl6,Cs2NaLnBr6,Cs2NaLnI6的XRD图谱。从图中可以明显的看出三种体系的材料都具有较高结晶性,而且同一个体系内材料的XRD数据基本相同,这证明了材料都具有相同的结构;同时能够发现随着La-Yb的元素变化,XRD数据有轻微的向大角度移动到的趋势,这可能是由于La-Yb随着原子序数(57-70)的增加,离子半径(0.106nm,0.103nm,0.096nm,0.095nm,0.092nm,0.088nm,0.086nm)逐渐减小,使得钙钛矿材料的晶格间距逐渐变小。因此,XRD的数据有轻微的向大角度方向移动。
实施例3,对Cs2NaLnX6无铅钙钛矿纳米晶材料进行TEM的测试。
如图3,4,5所示,分别为Cs2NaLnCl6,Cs2NaLnBr6,Cs2NaLnI6的TEM图。Cs2NaLnCl6钙钛矿材料呈现出单分散的四方块形貌,且尺寸分布比较均匀,大小在11-12nm左右;Cs2NaLnBr6钙钛矿材料的形貌是正六边形的纳米片,尺寸在35±7nm;Cs2NaLnl6钙钛矿材料的形貌是纳米圆片,尺寸在27±5nm。
实施例4,对Cs2NaLnX6无铅钙钛矿纳米晶材料进行光吸收的测试。
如图6所示,研究了Cs2NaLnX6无铅钙钛矿纳米晶材料的光吸收特性。Cs2NaLnCl6和Cs2NaLnBr6具有明显的带边吸收,带边吸收峰的位置为306nm,几乎不受镧系离子的影响。Cs2NaLnI6纳米晶材料的的吸收峰红移至362nm,而且也不随镧系元素的变化而变化。
实施例5,对Cs2NaLnX6无铅钙钛矿纳米晶材料进行PL的测试。
如图7所示,a,b,c为别为Cs2NaLnCl6,Cs2NaLnBr6,Cs2NaLnI6无铅钙钛矿纳米晶材料的发射光谱。在365nm光的激发下,Cs2NaLnCl6系列纳米晶体均表现出438nm的宽发射带,半宽为78nm±3nm,而且不同的稀土基双钙钛矿结构具有相似的激子发光特性;在545nm处可以观察到稀土Tb3+绿光发射,在593nm和617nm处可以观察到Eu3+特征红光发射,这是Eu3+的5D0→7FJ(1,2)跃迁所致,从而能够实现钙钛矿材料的多色发光。Br和I基双钙钛矿材料也表现出与Cl基双钙钛矿相似的发光性质,且Tb和Eu的特征发光出现在Cs2NaLnBr6和Cs2NaLnI6无铅钙钛矿纳米晶体中。
实施例6,对Cs2NaLnX6无铅钙钛矿纳米晶材料进行PLQY的测试。
如图7所示,d,e,f为别为Cs2NaLnCl6,Cs2NaLnBr6,Cs2NaLnI6无铅钙钛矿纳米晶材料的量子效率图谱。不同的卤素带来不同的量子效率。在三种无铅钙钛矿纳米晶中,Cs2NaLnCl6纳米晶的量子效率最高,Cs2NaLnI6纳米晶的量子效率最低。这可能是由于Cl-,Br-和I-的离子半径逐渐增大(0.181nm、0.196nm、0.22nm),导致钙钛矿纳米材料的晶格失配更严重,缺陷更多。此外,在三种卤素系列样品中,由Eu3+组成的无铅钙钛矿Cs2NaEuX6(X=Cl,Br,I)的量子效率最高。Cs2NaEuCl6纳米晶的量子效率高达68.5%。
实施例7,对Cs2NaLn(La,Eu,Tb)Cl6无铅钙钛矿纳米晶材料进行湿热以及光照稳定性的测试。
如图8所示,a,b,c分别为Cs2NaLn(La,Eu,Tb)Cl6无铅钙钛矿纳米晶材料的水稳定性,热稳定性以及光照稳定性的测试。以CsPbBr3铅卤钙钛矿材料做对比。
通过对比能够发现Cs2NaLn(Ln=La,Eu,Tb)Cl6纳米晶材料在水中能够稳定的存在8个月以上,荧光强度仍然能够维持初始值的60%以上。然而CsPbBr3材料在两个小时后,荧光强度就下降为初始值的5%。
Cs2NaLnCl6纳米晶系列材料具有相似的性质,后期只对其中Cs2NaEuCl6一个材料表征就能够代表整个系列材料的性质。
Cs2NaEuCl6纳米晶材料在60℃条件下连续加热500h后,材料的荧光强度能够维持在初始值的80%以上。CsPbBr3材料在20个小时后,荧光强度就下降为初始值的20%。
Cs2NaEuCl6纳米晶材料在1mW/cm2紫外光连续辐照500h后荧光强度仍能够维持初始值的87%。CsPbBr3材料在5个小时后,荧光强度就下降为初始值的5%以下。
以上的测试表明Cs2NaLnX6无铅钙钛矿纳米晶材料具有良好的湿热稳定性以及光照稳定性。
实施例8,对Cs2Na(Tb:Eu=25:1)Cl6无铅钙钛矿纳米晶材料进行PL和PLE的测试。
照明用电占全球电力消耗的五分之一,当前白光照明的主流技术是蓝光二极管搭配黄光荧光粉,但存在蓝光成分过强易损伤视网膜,以及显色指数不够高的问题,紫外二极管搭配白光荧光粉有希望解决此问题。Cs2NaLnX6钙钛矿是一种极具白光应用潜力的材料,其自陷激子导致的宽带发射,稀土离子的多色发光,发光色纯度高,荧光产率高,稳定性好,非铅基的环保材料等优势。如图9所示,通过调节Tb,Eu在钙钛矿材料中组成的比例,最终实现了单一基质的Cs2Na(Tb∶Eu=25:1)Cl6的白光发射,发射峰的位置为435nm,545nm和617nm;而且,545nm和617nm位置处的激发光谱和基质435nm处的激发光谱能够很好的重合,证明了稀土离子的发光主要是通过基质材料对其传能导致的。
实施例9,对基于Cs2Na(Tb:Eu=25:1)Cl6无铅钙钛矿纳米晶材料的白光LED器件进行通电点亮和色坐标的测试。
如图10所示,将Cs2Na(Tb∶Eu=25:1)Cl6溶液和紫外固化封装胶混合,然后涂到芯片表面,用紫外灯固化2min后测试。调节Tb与Eu的比例来调节CIE色坐标的组分,最终实现色坐标从(0.207,0.170),(0.227,0.212),(0.249,0.236),(0.302,0.297),到(0.328,0.322)白光发射的调制。插图为器件在3V电压驱动下的照片。
Claims (9)
1.一种新型稀土基无铅钙钛矿纳米晶材料的制备方法,其特征在于:包括以下步骤:
步骤一:将乙酸钠、乙酸铯、稀土乙酸盐在油酸、油胺、十八稀中加热溶解,在保护气体的保护下,反应得到澄清的前驱体溶液,其中乙酸铯:乙酸钠:稀土乙酸盐的摩尔比为7:5:5;
步骤二:向澄清的前驱体溶液中加入TMSCl、TMSBr或TMSI,反应过后,在冰水浴中冷却,离心清洗,最后分散在甲苯溶剂中,得到Cs2NaLnX6无铅钙钛矿纳米晶材料。
2.如权利要求1所述的一种新型稀土基无铅钙钛矿纳米晶材料的制备方法,其特征在于:所述步骤一中油酸、油胺和十八稀的体积比为1:1:5~6。
3.如权利要求1所述的一种新型稀土基无铅钙钛矿纳米晶材料的制备方法,其特征在于:所述步骤一中加热溶解的温度为120~140℃。
4.如权利要求1或3所述的一种新型稀土基无铅钙钛矿纳米晶材料的制备方法,其特征在于:所述步骤一中稀土乙酸盐为镧、铈、钐、铕、铽、铒、镱中任意一种的乙酸盐。
5.如权利要求1所述的一种新型稀土基无铅钙钛矿纳米晶材料的制备方法,其特征在于:所述步骤一中保护气体为氮气或氩气中的一种。
6.如权利要求1所述的一种新型稀土基无铅钙钛矿纳米晶材料的制备方法,其特征在于:所述步骤二中向前驱体溶液中加入TMSCl、TMSBr或TMSI时的温度为240℃,TMSCl、TMSBr或TMSI的量为0.4~0.5mL。
7.如权利要求1所述的一种新型稀土基无铅钙钛矿纳米晶材料的制备方法,其特征在于:所述步骤二中离心清洗的转速和时间分别为9500转/s和10min,所述甲苯溶剂的量为3mL。
8.一种新型稀土基无铅钙钛矿纳米晶材料,其特征在于:所述新型稀土基无铅钙钛矿纳米晶材料由权利要求1至7任意一项所述的制备方法制备得到。
9.一种如权利要求8所述的新型稀土基无铅钙钛矿纳米晶材料的应用,其特征在于:将所述新型稀土基无铅钙钛矿纳米晶材料应用在光电器件领域中。
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Cited By (3)
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CN115627302A (zh) * | 2022-10-24 | 2023-01-20 | 陕西科技大学 | 一种自蒙囿型锆基卤化物钙钛矿纳米鞣剂及其制备方法 |
CN115627302B (zh) * | 2022-10-24 | 2024-02-02 | 陕西科技大学 | 一种自蒙囿型锆基卤化物钙钛矿纳米鞣剂及其制备方法 |
CN116875313A (zh) * | 2023-06-21 | 2023-10-13 | 西北大学 | 一种窄带绿色荧光材料及其应用 |
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