CN114369058B - 一种基于1-丁基-4甲基吡啶鎓阳离子的铋碘簇杂化半导体类钙钛矿材料 - Google Patents
一种基于1-丁基-4甲基吡啶鎓阳离子的铋碘簇杂化半导体类钙钛矿材料 Download PDFInfo
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
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Abstract
本发明公开了一种基于1‑丁基‑4‑甲基吡啶鎓阳离子的铋碘簇杂化类钙钛矿材料及其制备方法。本发明的类钙钛矿化合物杂化材料，由1‑丁基‑4‑甲基氯化吡啶、碘化铋、碘化钾合成得到，其分子结构为(BMPY)3(Bi2I9)，式中BMPY为1‑丁基‑4‑甲基吡啶鎓阳离子。所述杂化半导体材料是禁带宽度适中、光电响应效果好的类钙钛矿半导体材料，DFT计算表明其为一种电荷转移盐。所述材料既具备廉价、完全无铅和易于纯化的优点，而且具有很好的溶解性和稳定性。该材料可作为卤化物基钙钛矿光电器件中的半导体材料。
Description
技术领域
本发明涉及有机无机杂化材料技术领域和光电材料技术领域，尤其是杂化半导体光电材料技术领域。
背景技术
钙钛矿型有机-无机杂化材料很早就有报道，但近年来因其独特的结构组成和电子（能带）结构，尤其是在电子、光学、新能源方面的优异表现而成了研究热点。从从发表首个工作以来，新一代有机无机杂化钙钛矿太阳能电池很快就展现出了相当高的光电转换效率（>25%），而且其还具备材料成本低和制作工艺简易等优势，被认为是最有应用前景的新一代光伏技术，有望成为未来的可持续新能源。很多金属卤化物基杂化材料有着高吸光系数，较长的光致激子寿命，较高的载流子迁移率等优点，也就是说作为新型半导体，相关结构的有机-无机杂化钙钛矿材料具备良好的光电性能。钙钛矿太阳能电池和量子点发光器件领域都有一批研究人员在开展基于杂化钙钛矿材料的应用工作，经过几年努力目前虽然尚没有完全解决光降解的问题，但是前景诱人是不争的事实，人们在钙钛矿半导体相关应用领域的探索热情也始终不减。当下，基于其它金属卤化物开发更稳定和毒性更小的杂化钙钛矿材料，并利用作为潜在的光吸收剂替代材料的研究，正日益受到研究开发人员的重视。
实际上，金属卤化物基钙钛矿杂化材料因其出色的光电性能、低成本和高转换效率而成著称，在太阳能电池、LED、激光器和光催化中已经显示出广泛的应用前景。但是，这些材料的大规模使用受到铅等有毒重金属使用的潜在制约，另外也受到材料在环境条件下的长期稳定工作难以实现的困扰。为克服这些问题，A3M2X9 型无铅金属卤化物类钙钛矿材料因其具有独特的低毒性和更好的化学稳定性（A 为一价金属或有机基团，M 为三价主族金属，X 为与金属配位的卤素阴离子），受到了研究人员的关注，初步研究结果也给出了正面的评价。但目前的这类材料带隙太大，难以满足实际应用的需求。因此，利用清洁又有效的方法对类钙钛矿材料进行带隙调控，并探索其晶体结构与光电特性之间的关系，这可为此材料今后的大范围应用提供坚实的理论支撑。
研究发现，基于锑和铋的碘化物，它们性质与碘化铅相似，可用于开发杂化钙钛矿材料，而且较易形成低维结构的半导体材料。且铋碘酸盐杂化材料具有丰富的化学结构，其杂化方式多变，在不同制备工艺条件下可受控得到所需杂化方式的材料，也具有较为明确的结构性能关系规律研究，这些都为有机-无机杂化钙钛矿材料的研究开发提供了较好的应用基础。总之，开发新型廉价环保的类钙钛矿材料具有重大的实际应用价值，而人们对有机阳离子在半导体带隙控制中的影响认识不足，这也是该类材料开发的一个潜在生长点。
发明内容
本发明内容的目的是提供一种基于1-丁基-4-甲基吡啶鎓阳离子的铋碘簇杂化类钙钛矿材料及其制备方法。通过碘化铋、碘化钾与1-丁基-4-甲基氯化吡啶的溶液发生反应，方便且廉价地制备获得了一种热稳定性较好且光电响应效果也好的类钙钛矿杂化半导体材料。
本发明的技术方案之一，是提供一种新的铋碘簇杂化类钙钛矿材料，由碘化铋、碘化钾与1-丁基-4-甲基氯化吡啶反应得到，其分子结构为(BMPY)3(Bi2I9)，式中BMPY为1-丁基-4-甲基吡啶鎓阳离子，其分子结构如式（I）：
（I）；
上述类钙钛矿材料的晶体为三斜晶系，P-1空间群，晶胞参数为a=19.5542(6)Å，b=22.1063(7)Å，c=26.4190(10)Å，α=65.5044(11)°，β=75.8191(13)°，γ=88.4150(13)°，V=10040.2(6)Å3 , Z=2，ρC=2.660g/cm3 , 材料的晶体颜色为棕红色；该材料结构表现为离子型化合物，其中铋碘簇(Bi2I9 3-)为抗衡阴离子，而阳离子则是1-丁基-4-甲基吡啶鎓阳离子；其分子结构如式（II）：
（II）。
对本发明材料晶态粉末进行测试发现，该材料的光学带隙值（半导体禁带宽度）约为1.86eV，能强烈吸收光子能量大于该阈值的可见光和紫外光；DFT（密度泛函理论）计算揭示了材料的电荷转移盐本质特征。而对该材料的瞬态光电流测试表明，在模拟太阳光的氙灯光照下材料呈现明显光电导响应特性的时间-电流曲线，其瞬态光电流响应较好；另外该材料也具有很好的稳定性，放置数月未见变质；可见，该有机无机杂化材料是较好的中等禁带宽度的半导体材料，而且该材料既具备廉价和完全无铅的优点，也具有很好的稳定性，该材料可应用为卤化物基钙钛矿光电器件中的半导体材料。
本发明的技术方案之二，是提供一种铋碘簇杂化类钙钛矿材料(BMPY)3(Bi2I9)的制备方法。该制备方法是由BiI3、KI与1-丁基-4-甲基氯化吡啶的乙腈溶液混合发生反应，最后过滤旋蒸得到粉末的产物而实现。其具体实施方案分为四步骤：
（1）室温下将1-丁基-4-甲基氯化吡啶溶解在乙腈与水混合溶液中；
（2）室温下将碘化铋和碘化钾粉末混合溶解在乙腈中；
（3）将所述述两种溶液混合，并搅拌使之充分反应，过滤得到棕红色溶液A；
（4）将滤液A减压旋蒸至干，洗涤并干燥，最终得到红棕色晶态粉末产物。
本发明制备方法中，所述的三种反应物的摩尔比1-丁基-4-甲基氯化吡啶:BiI3 :KI为3 : 2 : 3。
本发明的有益效果首先是所提供的铋碘簇杂化类钙钛矿材料(BMPY)3(Bi2I9)，其中使用了碘铋簇作为阴离子团，以1-丁基-4-甲基吡啶为有机阳离子，原料都价廉易得。DFT（密度泛函理论）计算揭示材料中的电子态密度特征很有特色，其价带的顶部与其它铋碘酸盐材料类似都基本来自于碘，但是该材料的导带底部却不是来自铋碘反键成分，而是几乎完全由阳离子的π*反键成分组成，计算结果表明该材料为电荷转移盐。材料通过降低其带隙也大大地提高了材料的光吸收性能。该杂化材料是禁带宽度适中、光电响应效果好的类钙钛矿半导体材料。该杂化材料既具备廉价和易于纯化的优点，而且具有很好的溶解性和热稳定性，为有机-无机钙钛矿材料的进一步应用提供了技术支持。
本发明的有益效果，其次是制备铋碘簇杂化类钙钛矿材料(BMPY)3(Bi2I9)的方法，具有工艺简便，所用设备简单，生产成本低等优点。
附图说明
图1. 类钙钛矿杂化材料(BMPY)3(Bi2I9)的结晶学独立单元的单晶结构图。
图2. 类钙钛矿杂化材料(BMPY)3(Bi2I9)的单胞及其周边空间的堆积图。
图3. 类钙钛矿杂化材料(BMPY)3(Bi2I9)粉末的红外吸收光谱图。
图4. 类钙钛矿杂化材料(BMPY)3(Bi2I9)的光学带隙表征，即粉末紫外漫反射光谱图。
图5. 根据密度泛函计算得到杂化材料(BMPY)3(Bi2I9)的态密度图，表明材料为电荷转移盐半导体。
图6. 类钙钛矿杂化材料(BMPY)3(Bi2I9)薄膜样品的光电导表征，在模拟太阳光的氙灯光照下的时间-电流曲线图。
具体实施方式
本发明的实现过程和材料的性能由实施例说明：
实施例1
大量的类钙钛矿材料(BMPY)3(Bi2I9)粉末样品的制备：称量117.9mg（0.2mmol）的BiI3，83mg（0.5mmol）的KI，92.8mg（0.5mmol）的1-丁基-4-甲基氯化吡啶；分别用5ml的乙腈溶解后依次混合，充分搅拌使之充分反应，得到红棕色色澄清溶液；将上述溶液在35℃下减压旋蒸除去所有溶剂，用水和乙醇多次洗涤后干燥，最终得到红棕色粉末产物，产率为83%。
实施例2
合成类钙钛矿材料(BMPY)3(Bi2I9)的单晶：称量117.9mg（0.2mmol）的BiI3，83mg（0.5mmol）的KI，92.8mg（0.5mmol）的1-丁基-4-甲基氯化吡啶；分别用5ml的乙腈溶解后依次混合，充分搅拌使之充分反应，得到红棕色色澄清溶液；过滤后，在溶液上层覆盖正己烷促使产物结晶，静置几天后有大量红棕色块状晶体析出。挑选一颗0.18mm×0.05mm×0.04mm尺寸的红棕色块状晶体用于X-射线单晶结构测试。该化合物的分子结构图示于附图1，其晶胞堆积结构图示于附图2。
对类钙钛矿材料(BMPY)3(Bi2I9)的纯相粉末样品进行了一些列性能测试。对本发明材料粉末进行了紫外漫反射测试，结果表明该材料具有不错的光学带隙（半导体禁带宽度），带隙值为1.86eV，材料能强烈吸收光子能量大于该阈值的可见光和紫外光，具体的图谱如附图4所示。对该材料进行了理论计算分析，DFT（密度泛函理论）计算揭示材料中的电子态密度特征很有特色，其价带的顶部与其它铋碘酸盐材料类似都基本来自于碘，但是该材料的导带底部却不是来自铋碘反键成分，而是几乎完全由阳离子的π*反键成分组成，该结果表明该材料为电荷转移盐，具体的态密度图如附图5所示。而对该材料的瞬态光电流测试表明，其瞬态光电流响应较好，具体的图谱如附图6所示。另外该材料也具有很好的稳定性，放置数月未见变质。可见，该有机无机杂化材料是较好的中等禁带半导体材料，而且该材料既具备廉价和易于纯化的优点，也具有很好的稳定性，该材料可应用于卤化物基钙钛矿光电器件材料。该发明为类钙钛矿型的杂化半导体材料的进一步应用提供了技术支持。
Claims (4)
1.一种基于1-丁基-4-甲基吡啶鎓阳离子的铋碘簇杂化类钙钛矿材料，其特征在于：该铋碘簇杂化类钙钛矿材料的结构式为(BMPY)3(Bi2I9)，式中BMPY为1-丁基-4-甲基吡啶鎓阳离子，其分子结构如式(I)：
上述类钙钛矿材料的晶体为三斜晶系，P-1空间群，晶胞参数为 α＝65.5044(11)°，β＝75.8191(13)°，γ＝88.4150(13)°，/>Z＝2，ρC＝2.660g/cm3,材料的晶体颜色为棕红色；该材料结构表现为离子型化合物，其中铋碘簇(Bi2I9 3-)为抗衡阴离子，阴离子中的两个BiI6八面体呈共面型连结形式，而阳离子则是1-丁基-4-甲基吡啶鎓阳离子；因为阳离子中丁基的构象变化极其多样，因此该晶体结构的结晶学独立单元中包括四个构象稍有差异的(Bi2I9 3-)阴离子，和12个构象有差异的1-丁基-4-甲基吡啶阳离子，其分子结构如式(II)：
2.根据权利要求1所述基于1-丁基-4-甲基吡啶鎓阳离子的铋碘簇杂化类钙钛矿材料的制备方法，其方法包括以下步骤：
(1)室温下将1-丁基-4-甲基氯化吡啶溶解在乙腈与水混合溶液中；
(2)室温下将碘化铋和碘化钾粉末混合溶解在乙腈中；
(3)将所述述两种溶液混合，并搅拌使之充分反应，得到棕红色溶液A；
(4)将滤液A减压旋蒸至干，洗涤并干燥，最终得到红棕色晶态粉末产物；上述三种反应物的摩尔比1-丁基-4-甲基氯化吡啶:BiI3:KI为3:2:3。
3.根据权利要求1所述基于1-丁基-4-甲基吡啶鎓阳离子的铋碘簇杂化类钙钛矿材料的应用，其特征在于：是中等禁带宽度的无铅型类钙钛矿杂化半导体材料，经粉末紫外漫反射光谱测试得到该材料的光学带隙值，即半导体禁带宽度为1.86eV。
4.根据权利要求3所述基于1-丁基-4-甲基吡啶鎓阳离子的铋碘簇杂化类钙钛矿材料的应用，其特征在于：作为无铅型类钙钛矿杂化半导体材料应用于光电器件中。
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