CN105839187B - 一种有机-无机杂化半导体晶体材料及其合成方法与应用 - Google Patents

一种有机-无机杂化半导体晶体材料及其合成方法与应用 Download PDF

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CN105839187B
CN105839187B CN201610297408.9A CN201610297408A CN105839187B CN 105839187 B CN105839187 B CN 105839187B CN 201610297408 A CN201610297408 A CN 201610297408A CN 105839187 B CN105839187 B CN 105839187B
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范乐庆
吴季怀
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Abstract

本发明公开了一种有机‑无机杂化半导体晶体材料及其合成方法与应用，该半导体晶体材料为[Pb3I10Cu2(phen)4]n，是通过温和水热制得。该半导体晶体材料在340nm的紫外光照射下，产生波长近410nm的荧光，实际上是将紫外光转化为可见光，故可广泛地应用于光能转换，可用于制作荧光发光器件。该半导体晶体材料可用于太阳能电池和光电开关。而且该半导体晶体材料具有磁铁性，研究它的合成可以有助于磁自旋器件的设计。

Description

一种有机-无机杂化半导体晶体材料及其合成方法与应用
技术领域
本发明涉及半导体材料领域，具体涉及一种有机-无机杂化半导体晶体材料及其合成方法与应用。
背景技术
有机-无机杂化半导体晶体材料具有独特的拓扑结构和性质，以及潜在的应用价值，可作为功能材料应用到光、电、磁等领域，因此受到了人们的广泛关注并且得到突飞猛进的发展。
基于Pb/I骨架的有机-无机杂化半导体晶体材料具有丰富的光电性能，如光致发光、电致发光、光致变色、热致变色、非线性光学性质等，可应用于太阳能电池、光电开关等领域。由于材料的性质与结构存在必然的联系，所以材料及化学学家通过选择适当的合成方法和有机配体，合成出大量的具有0D、1D、2D、3D该类半导体材料。
在Pb/I骨架引入第二金属离子，除了形成新颖的结构，还将改变Pb/I骨架的电子结构，这将势必影响材料的光电性能。而如果第二金属离子是磁性离子，将可获得磁性Pb/I半导体材料，拓宽它的应用范围，而关于这方面的报道非常少。本专利正是涉及通过简易的水热法成功引入磁性金属离子Cu2+到Pb/I骨架而形成的一种有机-无机杂化半导体晶体材料。
发明内容
本发明的目的在于提供一种易于制备，配体原料便宜，产率高的有机-无机杂化半导体晶体材料。
为了实现上述目的，本发明采用如下技术方案：
一种有机-无机杂化半导体晶体材料，该半导体晶体材料的化学式为[Pb3I10Cu2(phen)4]n，空间群为P21/n，晶胞参数为 β＝112.263(5)°，单胞体积
一种有机-无机杂化半导体晶体材料的合成方法，室温下，将PbI2，KI，CuI，邻菲罗啉和水，搅拌混合均匀，密封加热到120－200℃，保温12－72h，再冷却到室温，得到的沉淀用水洗涤多次后，得到所述的半导体晶体材料。
本发明一种有机-无机杂化半导体晶体材料用于制作荧光发光器件的用途。
本发明一种有机-无机杂化半导体晶体材料用于太阳能电池的用途。
本发明一种有机-无机杂化半导体晶体材料用于光电开关的用途。
采用上述方案后，与现有技术相比，本发明的优点和积极效果为：本发明的半导体晶体材料易于制备，配体原料便宜，产率高。
通过X射线单晶衍射实验得到本发明的半导体晶体材料的单晶结构，同时证明了此半导体晶体材料为高度结晶的晶体材料。应用红外吸收光谱证明了结构中存在的邻菲罗啉。通过热重分析证明该材料可在温度30-250℃范围内保持稳定，具有较宽温度范围应用的价值。该半导体晶体材料在340nm的紫外光照射下，产生波长近410nm的荧光。另外还具有磁铁性。
附图说明
图1为本发明中[Pb3I10Cu2(phen)4]n的结构图。
具体实施方式
一种有机-无机杂化半导体晶体材料，如图1所示，该半导体晶体材料的化学式为[Pb3I10Cu2(phen)4]n，空间群为P21/n，晶胞参数为 β＝112.263(5)°，单胞体积
本发明一种有机-无机杂化半导体晶体材料可用于制作荧光发光器件、太阳能电池和光电开关。
实施例1：
一种有机-无机杂化半导体晶体材料的合成方法：室温下，将46mg PbI2，17mg KI，19mg CuI，18mg邻菲罗啉和16mL水加入到20mL的高压釜中，并搅拌混合均匀。将该混合溶液加热到180℃，并保温36h，然后以3℃/h冷却到室温。得到的沉淀用水洗涤多次后，得到灰黄色块状晶体。根据使用的PbI2计算得到其产率为55.2％。
实施例2：
一种有机-无机杂化半导体晶体材料的合成方法：室温下，将46mg PbI2，33mg KI，19mg CuI，18mg邻菲罗啉和16mL水加入到20mL的高压釜中，并搅拌混合均匀。将该混合溶液加热到160℃，并保温36h，然后以2℃/h冷却到室温。得到的沉淀用水洗涤多次后，得到灰黄色块状晶体。根据使用的PbI2计算得到其产率为48.3％。
实施例3：
一种有机-无机杂化半导体晶体材料的合成方法：室温下，将46mg PbI2，33mg KI，38mg CuI，54mg邻菲罗啉和14mL水加入到20mL的高压釜中，并搅拌混合均匀。将该混合溶液加热到120℃，并保温72h，然后以2℃/h冷却到室温。得到的沉淀用水洗涤多次后，得到灰黄色块状晶体。根据使用的PbI2计算得到其产率为47.6％。
实施例4：
一种有机-无机杂化半导体晶体材料的合成方法：室温下，将46mg PbI2，50mg KI，57mg CuI，18mg邻菲罗啉和14mL水加入到20mL的高压釜中，并搅拌混合均匀。将该混合溶液加热到200℃，并保温12h，然后以3℃/h冷却到室温。得到的沉淀用水洗涤多次后，得到灰黄色块状晶体。根据使用的PbI2计算得到其产率为54.8％。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以作出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (5)

1.一种有机-无机杂化半导体晶体材料，其特征在于：该半导体晶体材料的化学式为[Pb3I10Cu2(phen)4]n，空间群为P21/n，晶胞参数为 β＝112.263(5)°，单胞体积
2.如权利要求1所述的一种有机-无机杂化半导体晶体材料的合成方法，其特征在于：室温下，将PbI2，KI，CuI，邻菲罗啉和水，搅拌混合均匀，密封加热到120－200℃，保温12－72h，再冷却到室温，得到的沉淀用水洗涤多次后，得到所述的半导体晶体材料。
3.如权利要求1所述的一种有机-无机杂化半导体晶体材料用于制作荧光发光器件的用途。
4.如权利要求1所述的一种有机-无机杂化半导体晶体材料用于太阳能电池的用途。
5.如权利要求1所述的一种有机-无机杂化半导体晶体材料用于光电开关的用途。
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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107098926B (zh) * 2017-05-15 2019-08-06 青岛大学 异金属碘化物框架材料及其制备方法
CN108103582B (zh) * 2017-12-13 2020-06-02 江南大学 一种低温可逆热致变色晶体材料，其制备方法及用途
CN108329356A (zh) * 2018-01-22 2018-07-27 天津师范大学 一种用于介电可调器件的金属有机杂化铁电体晶体及其应用
CN108948089B (zh) * 2018-07-16 2021-06-22 天津师范大学 一种具有光电效应的金属有机杂化钙钛矿材料及应用
CN109879880A (zh) * 2019-04-10 2019-06-14 济宁学院 一种近红外固态发光半导体材料及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101190925A (zh) * 2007-12-26 2008-06-04 首都师范大学 一种铜配合物及其制备方法与应用
CN101781323A (zh) * 2010-02-10 2010-07-21 河北工业大学 一种发光过渡金属有机骨架结构化合物及其制备方法
CN102924486A (zh) * 2012-10-19 2013-02-13 宁波大学 邻菲罗啉丙二酸铜铁电功能材料及其制备方法
CN103965222A (zh) * 2013-01-28 2014-08-06 首都师范大学 三核铜咪唑-4,5-二羧酸邻菲啰啉配合物及其制备方法和应用
CN104230967A (zh) * 2014-09-09 2014-12-24 桂林理工大学 荧光材料Zn2(hfoac)4(phen)2及合成方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101190925A (zh) * 2007-12-26 2008-06-04 首都师范大学 一种铜配合物及其制备方法与应用
CN101781323A (zh) * 2010-02-10 2010-07-21 河北工业大学 一种发光过渡金属有机骨架结构化合物及其制备方法
CN102924486A (zh) * 2012-10-19 2013-02-13 宁波大学 邻菲罗啉丙二酸铜铁电功能材料及其制备方法
CN103965222A (zh) * 2013-01-28 2014-08-06 首都师范大学 三核铜咪唑-4,5-二羧酸邻菲啰啉配合物及其制备方法和应用
CN104230967A (zh) * 2014-09-09 2014-12-24 桂林理工大学 荧光材料Zn2(hfoac)4(phen)2及合成方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Guan-E Wang,et al..Haloplumbate hybrids with organically coordinated halometal complexes as templates and mixed halo atoms: Solvothermal syntheses, crystal structures, and optical properties.《Inorganic Chemistry Communications》.2012,第23卷 *
Le-Qing Fan,et al..Novel lead iodine dialkyldithiocarbamates with different dimensions:[PbI(S2CNR2)]n (R2=Me2, (CH2)4, and (CH2)5).《Inorganic Chemistry Communications》.2015,第57卷 *
Meredith A. Tershansy,et al..Syntheses and crystal structures of new chain-containing iodometallate compounds: [H1,10-phen](H2O)1.41[AgI2],[H1,10-phen](H2O)1.42[CuI2];[Co(tpy)2][Bi2I8],[Fe(tpy)2][Bi2I8];[Co(1,10-phen)3][Pb3I8].H2O,and [Fe(1,10-phen)3][Pb3I8].0.5(H2O).《Solid State Sciences》.2007,第9卷 *

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