CN116084019A - 一类基于取代基调控的杂化有机-无机钙钛矿晶体及合成方法 - Google Patents
一类基于取代基调控的杂化有机-无机钙钛矿晶体及合成方法 Download PDFInfo
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Abstract
一类基于取代基调控的杂化有机‑无机钙钛矿晶体及合成方法，属于功能杂化材料技术领域。是将有机胺和PbBr2以2：1的物质的量计量比溶于HBr水溶液中，并在80℃条件下搅拌20min，待溶液完全澄清后缓慢降温，数日后得到块状晶体，异丙醇洗涤后于烘箱烘干得到两个杂化有机‑无机钙钛矿晶体[3‑MeO‑PEA]2PbBr4和[3,5‑DMeO‑PEA]2PbBr4。本发明以有机胺配体在取代基数量和位置的不同为出发点，合成的两个杂化有机‑无机钙钛矿晶体具有宽的可见光光谱范围和稳定的结构。本发明的制备方法简单高效，产物稳定。在白光固态照明、探测等光电领域具有广泛的应用前景。
Description
技术领域
本发明属于功能杂化材料技术领域，涉及两个杂化有机-无机钙钛矿晶体及其合成方法。
背景技术
杂化有机-无机钙钛矿因其优异的物理性能和在光电领域的应用潜力而引起了广泛的研究兴趣。在室内照明所需的高质量白光方面，单一的材料很难达到如此广泛的发射。在商用白光光源中，通常使用多个发光波段二极管或涂上一种或多种荧光粉，进而产生显示白光的混合发射。然而，由于器件内荧光粉的降解率不同，以及不同组分的吸收和发射能量重叠而导致效率损失，发光颜色和亮度会随时间而变化。杂化有机-无机钙钛矿的有机部分选择丰富而多样，极大拓展了杂化有机-无机钙钛矿体系。通过对有机组分的调控，可实现不同程度的白光发射，为寻找高质量白光钙钛矿材料设计提供了新的思路，并对其合成和实际应用具有重要意义。
钙钛矿材料通常化学式为ABX3。典型的钙钛矿材料是CaTiO3，相继出现无机金属卤化物钙钛矿和杂化有机-无机金属卤化物钙钛矿等。通常阳离子A+是一个小的有机分子或单个的无机原子(如：CHN3NH3 +、Cs+等)，阳离子B2+是二价的金属，(如Pb+、Sn+)而阴离子X-是单价的卤素(如Cl-、Br-、I-)。钙钛矿结构的组成很大程度上受A位阳离子的大小影响，大的A位阳离子使得三维骨架破裂而形成低维钙钛矿。维度的改变使得钙钛矿的性质发生剧烈变化，显著反映了钙钛矿的结构可调性，使其具有高的光吸收系数，良好的溶液可加工性，长的载流子扩散长度，发光效率高、范围窄、合成成本低等优异特性，被广泛应用于发光二极管，光电探测器，光伏发电等领域。
现有的实验和理论研究证明，杂化有机-无机钙钛矿宽白光发射主要来源于晶格中结构维度和畸变程度。结构维度的降低，畸变程度的增大导致荧光从窄发射向宽发射转变。主要影响因素是有机阳离子改变了无机骨架的结构尺寸和扭曲。因此，有机阳离子的组成选取在荧光性质的调控中起着至关重要的作用，拓展该材料在白光发射领域的合成应用是新功能材料发展的重大挑战之一。
发明内容
本发明目的是解决现有技术存在的上述问题，提供了两个基于取代基调控的杂化有机-无机钙钛矿晶体及其合成方法。本发明利用具有不同取代基数量及位置的有机胺配体为原料合成具有不同光谱范围的白光钙钛矿晶体：
[3-MeO-PEA]2PbBr4和[3,5-DMeO-PEA]2PbBr4。该反应不需要高温高压的苛刻条件，实验过程安全，对实验设备要求低，操作简单。
为实现上述目的，本发明提供了如下方案：
基于取代基调控的杂化有机-无机钙钛矿晶体的合成制备。因有机胺配体取代基数量和位置影响，合成两个杂化有机-无机钙钛矿晶体(晶体Ⅰ：3-甲氧基-苯乙胺溴化铅[3-MeO-PEA]2PbBr4和晶体Ⅱ：3，5-双甲氧基-苯乙胺溴化铅[3,5-DMeO-PEA]2PbBr4)。结构保持在二维，其空间群分别为正交和单斜，在对称性上发生不同。
所述有机胺配体3-甲氧基-苯乙胺和3,5-双甲氧基-苯乙胺的结构式如下：
进一步地，所述两个杂化有机-无机钙钛矿晶体均是二维的块状晶体：
晶体Ⅰ(Pnma)：α＝90°，β＝90°，γ＝90°。
晶体Ⅱ(P21/c)：α＝90°，β＝103.490(2)°，γ＝90°。
所述两个杂化有机-无机钙钛矿晶体分别为无色块状晶体和灰色块状晶体，在365nm的紫外灯照射下钙钛矿晶体Ⅰ发黄白光，钙钛矿晶体Ⅱ发淡黄白光。且具有很好的热稳定性，钙钛矿晶体Ⅰ分解温度为250℃，钙钛矿晶体Ⅱ分解温度为260℃。
本发明提供了杂化有机-无机钙钛矿晶体的合成方法，所述两个钙钛矿晶体均是以48％HBr水溶液作为溶剂，溶解后挥发制备而成，具体步骤如下：
步骤一、将溴化铅溶解于氢溴酸中，超声使溴化铅溶解，得到溶液A；
步骤二、将3-甲氧基苯乙胺和3,5双加氧基苯乙胺分别加入两瓶溶液A中，立即产生粉晶，放置加热台80℃下搅拌20分钟，待完全溶解均得到澄清的溶液；
步骤三、将溶液在加热台上以5℃/1h缓慢降温，降至室温静置数日后分别析出无色块状晶体和灰色块状晶体；
步骤四、将步骤三中的块状晶体从溶液中取出，异丙醇洗涤抽滤，放置于烘箱中55℃干燥，制得两个杂化有机-无机钙钛矿晶体，取出待用。
与现有技术相比，公开了以下技术效果：单晶生长采用的是饱和溶液挥发法，该实验操作过程简单、成本低，目标产物的纯度高且无副产物、对环境污染小；合成的杂化有机-无机溴化铅钙钛矿材料因有机组分的多样可调，可形成多波段和半峰宽的发光性能。为获得目标白光效果，我们提供了一种改变同类有机胺的取代基，增加有机无机层间位阻来实现具有宽的可见光光谱范围，表现出不同程度的白光发射的技术思路。极大推动新型白光发射杂化有机-无机溴化铅钙钛矿晶体的合成研究及应用。
附图说明
图1为本发明合成的两个杂化有机-无机钙钛矿晶体的XRD图。其中，Obs＝真实值、Calc＝计算值、Diff＝真实值和计算值之间的差值；
图2为本发明两个杂化有机-无机钙钛矿晶体的合成路线图；
图3为本发明合成的两个杂化有机-无机钙钛矿晶体的结构图；
图4为本发明合成的两个杂化有机-无机钙钛矿晶体的形貌图；
图5为本发明合成的两个杂化有机-无机钙钛矿晶体的热重图；
图6为本发明合成的两个杂化有机-无机钙钛矿晶体的紫外吸收图；
图7为本发明合成的两个杂化有机-无机钙钛矿晶体的荧光发射图；
图8为本发明合成的两个杂化有机-无机钙钛矿晶体的低温荧光发射图。
具体实施方式
现详细说明本发明的多种示例性实施方式，该详细说明不应认为是对本发明的限制，而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式，并非用于限制本发明。另外，对于本发明中的数值范围，应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明，否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料，但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入，用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时，以本说明书的内容为准。
在不背离本发明的范围或精神的情况下，可对本发明说明书的具体实施方式做多种改进和变化，这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本发明说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等，均为开放性的用语，即意指包含但不限于。
杂化有机-无机钙钛矿晶体制备是简单易操作，安全的实验制备方法。无需复杂严苛的实验条件，可在一般实验室内通过少量原料和温和条件即可制备出稳定无杂质的产物晶体。采用的方法溶液挥发法生长单晶，该方法因操作简单，成本低，无污染等优点被广泛用于晶体制备中。
参见附图2，本发明杂化有机-无机钙钛矿晶体的制备：
称取0.5mmol(0.185mg)的溴化铅分别放于25mL的小烧杯A和B中，用移液枪取10mL的氢溴酸，缓慢加入两个小烧杯中，封口超声10min，使溴化铅完全溶解。
有机胺和溴化铅的摩尔比为2:1。两个有机胺在室温下均为液体。A烧杯加入1mmol的3-甲氧基苯乙胺，B烧杯加入1mmol的3，5-双甲氧基苯乙胺，均立即产生粉晶，随后将两个烧杯放在加热台上80℃搅拌至完全溶解，并以5℃/h缓慢降至室温，静置3-4天，烧杯A得到无色块状晶体，烧杯B得到灰色块状晶体。将晶体从母液中抽滤并用异丙醇洗涤，随后放入55℃的真空烘箱中干燥6h，所得目标产物即为所需杂化有机-无机钙钛矿晶体Ⅰ和晶体Ⅱ。所合成的两个杂化有机-无机钙钛矿晶体(晶体Ⅰ：3-甲氧基-苯乙胺溴化铅和晶体Ⅱ：3，5-双甲氧基-苯乙胺溴化铅)的结构图如附图3所示，其形貌如附图4所示。
利用XRD粉末衍射对上述制备的杂化有机-无机钙钛矿晶体进行表征，最大电压为40KV。打开仪器开关，紧接着打开软件并进行初始化。将所制得的单晶利用研钵压成粉末状，取适量粉末样品放在洁净的硅片上并压平，接着将硅片放入衍射仪中，关闭仓门。设置测试条件为扫速为5deg/min，2θ为3-50°。测试结果如图1所示，从图中可以很明显看出，两个钙钛矿晶体的XRD图与其对应的单晶X射线衍射拟合的结果几乎一致，表明所得晶体纯度很高。
利用热重分析仪对上述制备的杂化有机-无机钙钛矿晶体的热稳定性测试，测试在空气氛围进行，称取8mg粉末样品于坩埚内，软件设置扫描范围为28.7-700℃，扫速10℃/min。.结果如图5所示，从图中可以很明显看出，两个钙钛矿晶体均具有很好的热稳定，钙钛矿晶体Ⅰ分解温度为250℃，钙钛矿晶体Ⅱ分解温度为260℃。
利用紫外可见吸收光谱对上述制备的两个杂化有机无机钙钛矿晶体进行测试，取适量粉末样品于槽内，在200-750nm之间进行固体紫外测试，测试结果见图6所示。
利用荧光光谱仪对对上述制备的两个杂化有机无机钙钛矿晶体进行室温和低温荧光发射测试。室温测试：取适量粉末样品于固体槽内，激发波长设置为365nm，测得结果如图7所示。低温测试：取适量样品于低温测试装置固体槽内，加入液氮使得温度稳定控制在100k，激发波长设置为365nm，测试结果如图8所示，均出现较大的荧光增强。
具体的应用：
白光杂化有机无机钙钛矿钙材料主要用于固态照明，是LED灯里所用的发光材料。现在常用的LED灯传统白光材料由两种以上的材料复合而成，长时间使用会发黄。此次研究的白光钙钛矿材料，是单一发白光材料，使用寿命显著增长。
同时，此类层状结构杂化有机无机钙钛矿材料由于其具有较高的载流子迁移率、长扩散长度和高稳定性，使其在光电探测器中表现出可调谐的光响应以及较短的响应时间(毫秒)。
申请人声明，本发明利用上述实施例进一步说明杂化有机无机钙钛矿晶体的制备方法及应用，但不局限于具体工艺步骤，本领域其它技术人员，在本发明的启发下，利用添加或替换等手段对本发明进行的任何改进，均属于本发明的保护范围之内。
Claims (9)
1.一类基于取代基调控的杂化有机-无机钙钛矿晶体，其特征在于，利用具有不同取代基数量及位置的有机胺配体为原料合成得到，所述的有机胺为3-甲氧基-苯乙胺和3,5-双甲氧基-苯乙胺，合成两个杂化有机-无机钙钛矿晶体Ⅰ：3-甲氧基-苯乙胺溴化铅[3-MeO-PEA]2PbBr4和晶体Ⅱ：3,5-双甲氧基-苯乙胺溴化铅[3,5-DMeO-PEA]2PbBr4，所得晶体Ⅰ和晶体Ⅱ结构保持在二维，其空间群分别为正交和单斜，在对称性上发生不同。
2.根据权利要求1所述的基于取代基调控的杂化有机-无机钙钛矿晶体，其特征在于，所述两个杂化有机-无机钙钛矿晶体均是二维的块状晶体：
晶体Ⅰ(Pnma)：α＝90°，β＝90°，γ＝90°。
晶体Ⅱ(P21/c)：α＝90°，β＝103.490(2)°，γ＝90°。
3.根据权利要求1所述的基于取代基调控的杂化有机-无机钙钛矿晶体，其特征在于，有机胺配体3-甲氧基-苯乙胺和3,5-双甲氧基-苯乙胺的结构如下：
4.根据权利要求1所述的基于取代基调控的杂化有机-无机钙钛矿晶体，其特征在于，所得取代基调控的钙钛矿晶体Ⅰ和晶体Ⅱ分别为无色块状晶体和灰色块状晶体，在365nm的紫外灯照射下钙钛矿晶体Ⅰ发黄白光，钙钛矿晶体Ⅱ发淡黄白光。
5.根据权利要求1所述的基于取代基调控的杂化有机-无机钙钛矿晶体，其特征在于，钙钛矿晶体Ⅰ分解温度为250℃，钙钛矿晶体Ⅱ分解温度为260℃。
6.根据权利要求1所述的基于取代基调控的杂化有机-无机钙钛矿晶体，其特征在于，所得取代基调控的钙钛矿晶体Ⅰ和晶体Ⅱ在低温条件下受紫外光激发，其荧光强度增强。
7.一种权利要求1至6任一项所述杂化有机-无机钙钛矿晶体的合成方法，其特征在于，以48％HBr水溶液作为溶剂，溶解后挥发结晶得到两个钙钛矿晶体，具体步骤如下：
步骤一、将溴化铅溶解于氢溴酸中，超声使溴化铅溶解，得到溶液A；
步骤二、将有机胺3-甲氧基苯乙胺和3,5双加氧基苯乙胺分别加入两瓶溶液A中，均立即产生粉晶，放置加热台80℃下搅拌20分钟，待完全溶解均得到澄清的溶液；
步骤三、将溶液在加热台上以5℃/1h缓慢降温，降至室温静置数日后分别析出无色块状晶体和灰色块状晶体；
步骤四、将步骤三中的块状晶体过滤放置于烘箱中，干燥，制得两个杂化有机-无机钙钛矿晶体，取出待用。
8.权利要求7所述杂化有机-无机钙钛矿晶体的合成方法，其特征在于，在合成过程中所用原料有机胺和溴化铅的物质的量比为2：1。
9.一种权利要求1至6任一项所述杂化有机-无机钙钛矿晶体的应用，其特征在于，基于取代基调控的钙钛矿晶体表现出宽的可见光光谱范围，用于研究物质结构与内部能量相关性，应用于照明探测领域。
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