2008年第16卷合成化学
Vol .16,2008 第1期,1～7Chinese Journal of Synthetic Che m istry No .1,1～7
·综合评述·
层状类钙钛矿结构有机-无机杂合物的制备
3
郭丽玲,刘韩星
(武汉理工大学材料复合新技术国家重点实验室,湖北武汉 430070)
摘要:综述了近年来层状类钙钛矿结构有机-无机杂合物的制备方法,包括有机元、无机元的选择及其合成。参考文献66篇。
关 键 词:钙钛矿;有机-无机杂合物;组成;合成;综述中图分类号:O611.6;T B34
文献标识码:A
文章编号:100521511(2008)0120001207
Proparati on M ethods of
Layered Perovskite 2type Organ i c 2i n organ i c Hybr i ds
G UO L i 2ling, L I U Han 2xing
(State Key Laborat ory of Advanced Technol ogy forMaterials Synthesis and Pr ocessing,
W uhan University of Technol ogy,W uhan 430070,China )
Abstract:Pr oparati on methods of layered per ovskite 2type organic 2inorganic hybrids,including choice and synthesis of organic and inorganic components,were revie wed with 66references .Keywords:per ovskite;organic 2inorganic hybrid;component;synthesis;revie w
层状类钙钛矿结构的有机-无机杂合物是一
种分子尺度的、单相的有机-无机复合材料,具有典型的层状结构:无机金属离子和卤素离子构成的八面体在二维方向上共顶连接成无机层(可以是半导体层),在两相邻的钙钛矿层间排列着有机阳离子(可以是绝缘层),有机层与无机层交替在第三维方向上伸展排列而成“三明治”样多量子阱结构。因可以用变换无机和有机元的组成来改变或调节量子阱的阱深、阱宽、势垒高度和宽度,从而可以连续地调节和控制材料的电子学性能,近十几年来吸引了更多的研究者。此外,有机-无机元在分子尺度上的复合可能综合有机、无机物的性能优势,如既保留无机元高的载流子传导性又保留有机元良好的易成膜性,因此,该类材料在制作轻小器件上有广泛的应用前景。多种
杂合物被合成出来并在其结构、性能、应用等方面得到了进一步的研究。其中<100>取向的层状类钙钛矿结构有机-无机杂合物报道的数量较多,涉及的无机金属元素范围较广,既有过渡金属元素,又有主族金属元素,还有稀土元素
[1～3]
。
<110>和<111>取向的类钙钛矿杂合物报道数
量相对较少,涉及的金属只有少数几种主族元素(如Pb,Sn,Sb 和B i )[4～10],如<110>取向的[N H 2C (I )=NH 2]2(CH 3NH 3)n Sn n I 3n +2(n =1～3),[NH 2C (Ⅰ)=NH 2]2(NH 2CH =NH 2)Sn I 5或[NH 2C (Ⅰ)=NH 2]3Pb I 5
[2,5,6]
和<111>取向的(CH 3N
H 3)3B i 2B r 9,[NH 2(CH 3)2]3Sb 2Cl 9[7,8]
。
含多个钙钛矿层的结构,被报道的杂合物种
3
收稿日期:2007207226
基金项目:国家自然科学基金重大资助项目(NSFC90206047);湖北省自然科学基金资助项目(2006ABA306)
作者简介:郭丽玲(1964-),女,汉族,江西吉安人,博士,副教授,主要从事功能材料的研究。E 2mail:jgcgsg@yahoo https://www.doczj.com/doc/d413056944.html, 通讯联系人:刘韩星,博士生导师,E 2mail:lhxhp@mail .whut .edu .cn
类也相对有限。从金属元素看,目前只有第Ⅳ主族的元素Sn和Pb参与形成的<100>取向的杂合物(其中卤素为I或B r)的报道,如(C
4
H9N
H3)2(CH3NH3)n-1Sn I3n+1,(C6H5C2H5NH3)2(C H3NH3)n-1Pb I3n+1(n=1～5),(C6H5C2H4NH3)2
(CH
3
NH3)n-1Pb n B r3n+1(n=1～3)等[9～14],未见过渡金属类似物的报道。此外,由于含多钙钛矿层的有机-无机杂合物在合成时有两种以上的有机阳离子参与反应,可同时生成各以其中一种有机阳离子为有机组元的单钙钛矿层杂合物及含多钙钛矿层的杂合物,此时的反应产物可以是两种以上杂合物的混合物。虽然可以通过改进合成工艺如改变原料的化学配比来抑制其中某个化学平
衡的移动,但这些改进并不总是有效的,如(C
9
H19 NH3)2(CH3NH3)Pb n I3n+1当n≥3时,无法得到含无机钙钛矿层数为某一定值的纯净产物[15,16]。
本文主要介绍<100>取向、含单钙钛矿层的
有机-无机杂合物(RNH
3)
2
MX4(简称O I H)的制
备方法(包括有机元、无机元的选择及其合成)研究进展。
1 无机元和有机元的选择
1.1 无机元的选择
文献[17,18]报道的已被合成出的O I H中,所选用的金属主要有过渡金属元素、第Ⅳ和第Ⅴ主族元素,还有少量稀土元素。这些元素作为无机组元与被适当选取的有机组元形成了预期的层状类钙钛矿结构,但还有很多理论上可以形成的结构,其相应的杂合物如第四周期中元素Sc,Ti,V的体系却从未见过报道。
层状类钙钛矿有机-无机杂合物的合成在选择无机金属元素时充分体现了对该类材料应用前景的预期。选择过渡金属的原因是基于其磁性能,选择第Ⅳ,Ⅴ主族元素则基于其半导性,而选择稀土元素则是希望利用其发光性能。这些元素参与构成的层状类钙钛矿结构杂合物被预期形成二维磁性材料、二维半导材料和二维发光材料。
1.2 有机元的选择
有机组分因其结构的丰富性和多变性,选择范围比无机组分的还要大得多。典型的阳离子有直链烷基胺[19～29]或二者的衍生物[30～32],双胺有机组元[33]也常有报道。对O I H来说,有机胺阳离
子为正二价,因此每相邻的两个钙钛矿层间只有一层有机胺阳离子,化学通式变为(NH
3
RNH3) MX4,与单胺杂合物对照的结构示意图[34]如图1所示。单胺与双胺的明显差异在于,位于两相邻钙钛矿层间的单胺有两层,相互间没有化学键而只有弱的范德华作用力,而双胺阳离子只有一层,各原子都由共价键结合。因此,在相同条件下,双胺的杂合物可能有更好的热稳定性,例如直链烷基胺中的碳原子数都为4,无机组分都是氯化锰
时,单胺的杂合物(C
4
H9NH3)2MnCl4的热分解温
度比双胺杂合物(H
2
NC4H8NH3)MnCl4的低[35]
。
(RNH
3
)
2
MX4 (NH3RNH3)MX4
图1 O I H的平面示意图[34]
F i gure1 Plane sketch map of O I H
图2 复杂有机胺或其铵盐的例子[41～47]
F i gure2 Exa mp les of the comp lex a m ine or
a mmoniu m salt in hybrids
近年来,低聚物胺或含氮的非胺也被采用,如
甲脒[NH
2
CH=NH2Sn I3][36],咪唑类(含氮杂原子
的环烷)如2,2′2氮对二咪唑[(C
6
H8N4)M I4(M 为Pb和Sn)][37]等。还有一些含杂原子的有机
胺如{Cu[O
2
C(CH2)3NH3]}+[38],[(CH3O)3Si
(CH
2
)
3
NH3]+[39]等。美国I B M公司的M itzi[40]首先选用染料分子合成出其层状类钙钛矿杂合
—
2
— 合成化学 Vol.16,2008
物,此后更多较大较复杂的染料分子胺(图2)的杂合物被合成出来[41～47]。日本研究者Yuko Takeoka[48]和Masanao Era[49]还成功地在两相邻钙钛矿层间使含双键的有机胺阳离子聚合,得到了聚合物胺阳离子为有机组元的O I H。
这些有机组元的变化是非常富有意义的:其一,有机组元的分子比最初采用的分子大得多,它与钙钛矿层如何能稳定地结合、形成什么类型的结构是一个新课题,这对类钙钛矿结构的有机-无机分子组装体的结构设计与结构控制意义重大;其二,染料类分子都有较大的电子共轭基团,因而在可见区发光性能上可能具有明显优势。采用染料分子,就有可能把无机层的载流子高迁移率与有机层的高发光效率结合起来,对这些材料在电致发光或光致发光中的应用来说意义重大;其三,有机层为不饱和烃的聚合物时,可认为有机层形成的是二维共轭体系,此时有机层是电子的通道。从载流子的输运行为来看,若无机层是空穴为多子或无机层是p型半导体,那么这样的层状类钙钛矿杂合物就成为分子尺度、多层交替的、一层是电子为多子一层是空穴为多子的通道材料。
1.3 三价金属离子和掺杂的体系
无机组元的变化相对于有机组元似乎非常有限,因为电价的限制,所用金属阳离子都是二价的。这种状况已经有了改变,M itzi等[50,51]创造性地合成了含三价阳离子的、有空位的类钙钛矿结构有机-无机分子组装体(H
2
AEQT)M2/3I4(M为B i或Sb),(H3NRNH3)B iI5(R1=C18H24S2,R2= C12H24)。这里,(H2AEQT)M2/3I4是第一个有阳离子空位的层状类钙钛矿有机-无机杂合物,其
无机八面体层的化学表达可写作[(M n+)
2/n V(n-2)/n X4]2-,其中的V表示金属阳离子空位,n (n≥2)为金属阳离子的价态。例如三价B i构成
的无机层为[(B i3+)
2/3
V1/3X4]2-,即共顶连接的八面体无机钙钛矿层中,有三分之一的金属阳离子空位存在。理论上可类推当金属阳离子为+4价时,无机层有二分之一金属阳离子空位[(M4+)1/2V1/2X4]2-,+5价金属则有五分之三的空位产生。但从结构稳定性角度看,空位缺陷超过一定浓度,结构会变得非常不稳定,这应该是目前为止还未看到三价以上金属阳离子这类杂合物的报道的原因
。
图3 杂合物中共存的多种阳离子[56]
F i gure3 The organic cati ons in
hybrids
a b
图4 有机元之间插入中性有机分子的杂合物[57]3
F i gure4 The hybrids with intercalated
neutral molecules bet w een the organic and organic cati ons 3a=(C
6
H5C2H4NH3)2Sn I4·(C6F6);
b=(C6F5C2H42NH3)2Sn I4·(C6H6);
A=neutral molecule
缺陷对材料的半导性质意义重大,半导体“掺杂”的研究方法也出现在层状类钙钛矿杂合
物中:有金属掺杂[52]的产物[(C
4
H9NH3)2Fe x Pb1-x Cl4],也有卤素掺杂[53～55]的产物[(C6H5C2
H4NH3)2Pb(B r,I)4和(C6H5C2H4NH
3
)
2
Pb(Cl, B r)4]。有趣的是,有机元也有了“掺杂”的成功
例子[36],如(CH
3
NH3)1-x(NH2CH=NH2)x Sn I3。有机元的掺杂的可变性又比无机元的要大得多,如Xu和M itzi[56]合成出了有5种阳离子共存的体系,其采用的5种阳离子和其中的2种阳离子按1∶1比例形成的产物结构(图3)。M itzi[57]还
合成出了“插层”的杂合物(C
6
H5C2H4NH3)2Sn I4·(C6F6)和(C6F5C2H4NH3)2Sn I4·(C6H6)———
—
3
—
第1期 郭丽玲等:层状类钙钛矿结构有机-无机杂合物的制备
在有机元之间再插入中性有机分子的杂合物(图4)。这种结构不仅丰富了钙钛矿家族,也为研究有机元之间的相互作用在层状类钙钛矿结构形成和稳定中的性质与作用提供了全新的机会。
2 合成方法
目前报道的绝大多数杂合物的合成方法都是
液相反应法。对O I H中的(RNH
3)
2
MX4,其合成
反应方程式可写为:
2RNH2+2HX+2MX
2(RNH
3
)
2
MX4
反应大多在室温附近就能进行,而且反应速度很快,反应也比较彻底,可以达到很高的产率(>90%)[58,59]。尽管有时也采用各种溶剂,但氢卤酸常常既是反应物,又是反应的溶液介质,因不引入其它化学组分,对生成纯净的目标产物有利[60]。
采用溶剂基于以下两个原因:其一,无机元和有机元溶解性能有差异。如氯化铅在37%盐酸中的溶解度不高,而饱和脂肪胺则能与盐酸反应生成胺盐并易于溶解在盐酸或水中。为保证反应是均相的,或为保证反应确实按所设计的计量比进行,采用溶剂可增加无机元、有机元在反应液中的溶解性。其二,溶剂能使某些产物的溶解度对温度变化更敏感,从而在冷却溶液得到产物时能显著提高反应的产率[46,51]。有时,某种组分对目标产物而言是不良溶剂,则反应后可加入该溶剂使产物沉淀下来[16,33]。对Sn和Pb为金属元素的杂合物,最常用的溶剂有甲醇、乙醇、甲苯、甲基氰、丙酮、N,N2二甲基甲酰胺(DMF),22丙醇、22丁醇或它们的混合物[22,23,35]。
液相反应法也常常用于制备能满足结构测试的单晶,可以通过冷却制度的控制(通常都是非常缓慢地冷却)来控制晶体的生长。利用多相界面处各反应组分的缓慢扩散、再继而缓慢地反应可达到此目的,典型的代表有溶胶-凝胶法[61]和层溶液生长法[62]。如文献[62]方法是先制成PbCl4的盐酸溶液与甲醇的相界面,再加入有机胺C
6
H5C2H4NH3,让有机胺通过甲醇层稀释后在
界面处与PbCl
4
相互扩散,从而得到线度大于4 mm的单晶。
层状类钙钛矿有机-无机杂合物也可以方便地用固相法合成[63～65],因为有机组分的熔点很低,通常固相反应的温度都在200℃以下。常用的方法是先用相应的有机胺与氢卤酸反应并去掉其中的水分制得有机胺盐,把有机胺盐加热至熔融并将充分研磨的无机卤化物粉料与之混合,或直接混合有机胺盐与无机卤化物再按一定温度制度保温一定时间(通常需要几十小时至几天)即得目标产物。这里并不需要将无机组分全部熔融因而也大大降低了预期的反应温度。
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第1期 郭丽玲等:层状类钙钛矿结构有机-无机杂合物的制备