CN115612487B - 一种零维锌基蓝光钙钛矿纳米材料及其制备方法和应用 - Google Patents
一种零维锌基蓝光钙钛矿纳米材料及其制备方法和应用 Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 93
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 26
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- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 7
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 4
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 3
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- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 6
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
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- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种零维锌基钙钛矿纳米材料,所述纳米材料为锌掺杂的CsmZnXn纳米颗粒,所述X为卤素,选自Cl、Br和I中的任意一种,所述m为2或3,所述n为4或5,所述CsmZnXn零维钙钛矿纳米材料为Cs3ZnX5或Cs2ZnX4;所述CsmZnXn零维钙钛矿纳米材料为零维结构,所述CsmZnXn零维钙钛矿纳米材料具有蓝光发射。本发明使用锌元素取代铅,有效解决了含铅钙钛矿毒性的问题,有望实现在人类电子产品等方面的应用,在发光显示、光电子器件等领域有着巨大的发展潜力。
Description
技术领域
本发明属于纳米发光材料技术领域,尤其涉及一种零维锌基蓝光钙钛矿纳米材料及其制备方法和应用,锌基蓝光钙钛矿纳米材料为Cs3ZnX5和Cs2ZnX4零维蓝光钙钛矿纳米材料。
背景技术
金属卤化物钙钛矿纳米材料由于具有高的量子效率、可调的带隙、出色的电荷传输及高的载流子迁移率等优异的光学性质,在高亮度、高色纯度的下一代显示和照明器件中具有应用前景,同时在太阳能电池、光电探测器和生物探针等领域也有着广阔的应用前景。
但目前金属卤化物钙钛矿纳米材料主要为铅基卤化物钙钛矿,其暴露在湿空气中或紫外线辐射下会降解出含铅的有毒物质,可能对人类肾脏、生殖和神经系统造成危害,同时,还会对生态环境造成巨大影响,极大制约了钙钛矿材料在电子产品等方面的应用。
发明内容
为解决上述技术问题,本发明提供一种零维锌基钙钛矿纳米材料,所述纳米材料为锌掺杂的CsmZnXn零维钙钛矿纳米颗粒,所述X为卤素,选自Cl、Br和I 中的任意一种,所述m为2或3,所述n为4或5,
优选地,所述CsmZnXn零维钙钛矿纳米材料为Cs3ZnX5或Cs2ZnX4。
优选地,所述CsmZnXn零维钙钛矿纳米材料为零维结构。
优选地,所述CsmZnXn零维钙钛矿纳米材料具有蓝光发射。
根据本发明的实施方案,所述Cs3ZnX5零维钙钛矿纳米材料为四方相纳米颗粒,所述Cs2ZnX4零维钙钛矿纳米材料为正交相纳米颗粒。
优选地,所述Cs3ZnX5零维钙钛矿纳米材料为Cs3ZnCl5、Cs3ZnBr5或Cs3ZnI5。
根据本发明的实施方案,所述Cs3ZnCl5零维钙钛矿纳米材料的平均粒径为 20~50nm,优选为20-40nm,更优选为25-30nm,例如为25.6nm。
根据本发明的实施方案,所述Cs3ZnBr5零维钙钛矿纳米材料的平均粒径为 20-80nm,优选为30-60nm,更优选为40-55nm例如为40.5nm。
根据本发明的实施方案,所述Cs3ZnX5零维钙钛矿纳米材料具有基本如图1 (a)、图2(a)所示的XRD衍射图谱。
根据本发明的实施方案,所述Cs3ZnX5零维钙钛矿纳米材料具有基本如图1 (b)、图2(b)所示的形貌图。
根据本发明的一个实施方案,所述Cs3ZnCl5零维钙钛矿纳米材料在260nm激发光照射下呈现如图4(a)所示的天蓝色发光(发射峰波长为484nm);
根据本发明的一个实施方案,所述Cs3ZnBr5零维钙钛矿纳米材料在275nm 激发光照射下呈现如图4(b)所示的亮蓝色发光(发射峰波长为468nm)。
根据本发明的实施方案,所述Cs2ZnX4零维钙钛矿纳米材料为Cs2ZnCl4、 Cs2ZnBr4或Cs2ZnI4,例如为Cs2ZnBr4零维钙钛矿纳米材料,所述Cs2ZnBr4零维钙钛矿纳米材料的平均粒径为20-100nm,优选为20-80nm,更优选为30-60nm。
优选地,所述Cs2ZnX4零维钙钛矿纳米材料具有如图图3a所示的XRD衍射图谱。
优选地,所述Cs2ZnX4零维钙钛矿纳米材料具有如图3b所示的形貌图。
所述Cs2ZnBr4零维钙钛矿纳米材料在277nm激发光照射下呈现如图4(c)所示的亮蓝色发光(发射峰波长为470nm)。
本发明还提供一种上述零维锌基钙钛矿CsmZnXn的制备方法,其包括:
1)将碳酸铯、醋酸锌、油酸、油胺和十八烯混合,得到混合溶液;
2)将HX加入上述混合溶液中反应至结束,得到反应液;
3)冷却所述反应液,得到CsmZnXn零维钙钛矿纳米材料。
根据本发明的实施方案,所述碳酸铯、醋酸锌的摩尔比为(1-2):(1-2),示例性为1.5:1或1:1。
优选地,所述HX为HCl、HBr或HI。
根据本发明的实施方案,所述油酸、油胺和十八烯的体积比为 (0.5-1.5):(0.5-1.5):(5-10),优选为1:(0.5-1):5,示例性为1:0.5:5。
根据本发明的实施方案,所述步骤1)中,所述混合是在氮气气氛和搅拌条件下进行。
根据本发明的实施方案,所述步骤1)中,所述混合在温度为100-200℃的条件下进行,优选为100-150℃,示例性为120℃。
根据本发明的实施方案,所述步骤1)中,所述混合的时间为0.5-1.5小时,优选为0.8-1.2小时,示例性为1小时。
根据本发明的实施方案,所述步骤2)中,HX的体积为50-200μl,示例性为 100μl氢氯酸、150μl氢溴酸或100μl氢溴酸。
根据本发明的实施方案,所述步骤2)中,所述混合溶液的温度为 160℃-220℃,示例性为160℃或220℃。
优选地,对于Cs3ZnCl5零维钙钛矿纳米材料,所述氢氯酸的体积为100μl;对于Cs3ZnBr5零维钙钛矿纳米材料,所述氢溴酸的体积为150μl;对于Cs2ZnBr4零维钙钛矿纳米材料,所述氢溴酸的体积为100μl。
优选地,对于Cs3ZnCl5零维钙钛矿纳米材料,所述混合溶液温度为160℃;
优选地,对于Cs3ZnBr5零维钙钛矿纳米材料,所述混合溶液温度为220℃;
优选地,对于Cs2ZnBr4零维钙钛矿纳米材料,所述混合溶液温度为220℃。根据本发明的实施方案,所述步骤2)中,反应时间为5-60s,示例性为30s。
根据本发明的实施方案,所述步骤3)中,所述冷却为将反应溶液在冰水浴中迅速冷却至室温。
根据本发明的实施方案,所述步骤3)还包括对冷却后的反应液进行后处理,例如进行离心分离,得到所述Cs3ZnX5和Cs2ZnX4零维钙钛矿纳米材料。
本发明还提供上述零维锌基钙钛矿纳米材料CsmZnXn在发光显示、光电子器件等领域的应用,优选作为发光二极管的活性发光层。
本发明还提供一种含有上述零维锌基钙钛矿纳米材料CsmZnXn的光电子器件,优选所述光电子器件为发光二极管。
有益效果
本发明提供了几种锌基的蓝色发光的Cs3ZnX5和Cs2ZnX4零维钙钛矿纳米材料及其制备方法和应用,使用非铅无毒的前驱物,采用热注射法制备出形貌均一,分散性好的Cs3ZnX5和Cs2ZnX4相零维钙钛矿纳米材料。
制备出的Cs3ZnX5和Cs2ZnX4零维钙钛矿纳米材料有不同的蓝色发光,合成方法简便,反应条件易控制,具有较高的可重复性;同时Cs3ZnX5和Cs2ZnX4零维钙钛矿纳米材料使用锌元素取代铅,有效解决了含铅钙钛矿毒性的问题,有望实现在人类电子产品等方面的应用,在发光显示、光电子器件等领域有着巨大的发展潜力。
附图说明
图1为实施例1中Cs3ZnCl5零维钙钛矿纳米材料的X射线粉末衍射图(a)和透射电镜图(b)。
图2为实施例2中Cs3ZnBr5零维钙钛矿纳米材料的X射线粉末衍射图(a)和透射电镜图(b)。
图3为实施例3中Cs2ZnBr4零维钙钛矿纳米材料的X射线粉末衍射图(a)和透射电镜图(b)。
图4为实施例1中Cs3ZnCl5零维钙钛矿纳米材料在260nm激发下的发射光谱(a);实施例2中Cs3ZnBr5零维钙钛矿纳米材料在275nm激发的发射光谱(b);实施例3中Cs2ZnBr4在277nm激发下的发射光谱(c)。
具体实施方式
下文将结合具体实施例对本发明的化合物及其制备方法和应用做更进一步的详细说明。应当理解,下列实施例仅为示例性地说明和解释本发明,而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明,以下实施例中使用的原料和试剂均为市售商品,或者可以通过已知方法制备。
实施例1
天蓝色发光的Cs3ZnCl5零维钙钛矿纳米材料的制备
室温下称取摩尔比为1.5:1的碳酸铯与醋酸锌,体积比为1:0.5:5的油酸、油胺、十八烯,加入到50ml三口烧瓶中,通N2搅拌10分钟后,升温至120℃并保温1小时,再将所述溶液快速升温至160℃,迅速注入100μl氢氯酸,反应30秒后立即冰水浴处理冷却至室温,离心即可得到天蓝色发光的Cs3ZnCl5零维钙钛矿纳米材料。
参见图1(a)所示,本实施例得到的天蓝色发光的Cs3ZnCl5零维钙钛矿纳米材料具有良好的结晶性,其衍射峰位置和相对强度与Cs3ZnCl5的ICSD标准卡片 (ICSD-240876)一致,属于四方晶系。
参见图1(b)所示,本实施例得到的天蓝色发光的Cs3ZnCl5零维钙钛矿纳米材料分散性好、形貌均一,平均粒径约为25.6nm。
参见图4(a)所示,在260nm紫外光激发下,本实施例得到的Cs3ZnCl5零维钙钛矿纳米材料呈现天蓝光(484nm)发射。
实施例2
亮蓝色发光的Cs3ZnBr5零维钙钛矿纳米材料的制备
室温下称取摩尔比为1.5:1的碳酸铯与醋酸锌,体积比为1:0.5:5的油酸、油胺、十八烯,加入到50ml三口烧瓶中,通N2搅拌10分钟后,升温至120℃并保温1小时,再将所述溶液快速升温至220℃,迅速注入150μl氢溴酸,反应30秒后立即冰水浴处理冷却至室温,离心即可得到亮蓝色发光的Cs3ZnBr5零维钙钛矿纳米材料。
参见图2(a)所示,本实施例得到的亮蓝色发光的Cs3ZnBr5零维钙钛矿纳米材料具有良好的结晶性,其衍射峰位置和相对强度与Cs3ZnBr5的ICSD标准卡片 (ICSD-180053)一致,属于四方晶系。
参见图2(b)所示,本实施例得到的亮蓝色发光的Cs3ZnBr5零维钙钛矿纳米材料分散性好、形貌均一,平均粒径约为40.5nm。
参见图4(b)所示,在275nm紫外光激发下,本实施例得到的Cs3ZnBr5零维钙钛矿纳米材料呈现亮蓝光(468nm)发射。
实施例3
亮蓝色发光的Cs2ZnBr4零维钙钛矿纳米材料的制备
室温下称取摩尔比为1:1的碳酸铯与醋酸锌,体积比为1:0.5:5的油酸、油胺、十八烯,并加入到50ml三口烧瓶中,通N2搅拌10分钟后,升温至120℃并保温1 小时,再将所述溶液快速升温至220℃,迅速注入100μl氢溴酸,反应30秒后立即冰水浴处理冷却至室温,离心即可得到亮蓝色发光的Cs3ZnBr5零维钙钛矿纳米材料。
参见图3(a)所示,本实施例得到的亮蓝色发光的Cs2ZnBr4零维钙钛矿纳米材料具有良好的结晶性,其衍射峰位置和相对强度与Cs2ZnBr4的ICSD标准卡片 (ICSD-69139)一致,属于正交晶系。
参见图3(b)所示,本实施例得到的亮蓝色发光的Cs2ZnBr4零维钙钛矿纳米材料分散性好、形貌均一,平均粒径约为41nm。
参见图4(c)所示,在277nm紫外光激发下,本实施例得到的Cs2ZnBr4零维钙钛矿纳米材料呈现亮蓝光(470nm)发射。
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (15)
1.一种零维锌基钙钛矿纳米材料的制备方法,其特征在于,包括如下步骤:
1)将碳酸铯、醋酸锌、油酸、油胺和十八烯混合,得到混合溶液;
2)将HX加入混合溶液中反应至结束,得到反应液;
3)冷却所述反应液,得到Cs3ZnX5零维钙钛矿纳米材料;
所述碳酸铯、醋酸锌的摩尔比为1.5: 1,所述油酸、油胺和十八烯的体积比为1:(0.5-1):5,所述步骤1)中,所述混合在温度为100-200℃的氮气氛围和搅拌条件下进行,所述混合的时间为0.5-1.5小时;步骤2)中,所述混合溶液的温度为160℃-220℃,反应时间为5-60s,所述X为卤素,选自Cl、Br和I中的任意一种。
2.根据权利要求1所述的零维锌基钙钛矿纳米材料的制备方法,其特征在于,所述步骤2)中,HX的体积为50-200μl。
3.根据权利要求1或2所述的零维锌基钙钛矿纳米材料的制备方法,其特征在于,所述步骤3)中,所述冷却为将反应溶液在冰水浴中迅速冷却至室温。
4.根据权利要求3所述的零维锌基钙钛矿纳米材料的制备方法,其特征在于,所述步骤3)还包括对冷却后的反应液进行后处理,得到所述零维钙钛矿纳米材料。
5.一种采用权利要求1-4任一项所述方法制备的零维锌基钙钛矿纳米材料,其特征在于,Cs3ZnX5零维钙钛矿纳米材料为零维结构。
6. 根据权利要求5所述的零维锌基钙钛矿纳米材料,其特征在于,Cs3ZnX5零维钙钛矿纳米材料为Cs3ZnCl5、Cs3ZnBr5或Cs3ZnI5, Cs3ZnX5钙钛矿纳米材料为四方相纳米颗粒,所述Cs3ZnCl5零维钙钛矿纳米材料的平均粒径为20~50 nm,所述Cs3ZnBr5零维钙钛矿纳米材料的平均粒径为20-80 nm。
7.根据权利要求5所述的零维锌基钙钛矿纳米材料,其特征在于,Cs3ZnX5零维钙钛矿纳米材料具有蓝光发射。
8. 根据权利要求6所述的零维锌基钙钛矿纳米材料,其特征在于,所述Cs3ZnCl5零维钙钛矿纳米材料的平均粒径为20-40 nm。
9. 根据权利要求6所述的零维锌基钙钛矿纳米材料,其特征在于,所述Cs3ZnBr5零维钙钛矿纳米材料的平均粒径为30-60 nm。
10. 根据权利要求6任一项所述的零维锌基钙钛矿纳米材料,其特征在于,所述Cs3ZnCl5零维钙钛矿纳米材料在260 nm激发光照射下,发射峰波长为484 nm。
11. 根据权利要求6所述的零维锌基钙钛矿纳米材料,其特征在于,Cs3ZnBr5钙钛矿纳米材料在275 nm激发光照射下,发射峰波长为468 nm。
12.一种权利要求1-4任一项所述方法制备的零维锌基钙钛矿纳米材料或权利要求5-11任一项所述的零维锌基钙钛矿纳米材料的用途,其特征在于,其在发光显示、光电子器件领域的应用。
13.根据权利要求12所述的用途,其特征在于,所述零维锌基钙钛矿纳米材料Cs3ZnX5作为发光二极管的活性发光层的应用。
14.一种光电子器件,其特征在于:其包括权利要求1-4任一项所述方法制备的零维锌基钙钛矿纳米材料或5-11中任一项所述的零维锌基钙钛矿纳米材料Cs3ZnX5。
15.根据权利要求14所述的光电子器件,其特征在于:所述光电子器件为发光二极管。
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