卤素、 氰基及N原子修饰对四硫富瓦烯衍生物载流子传输性质影响的理论研究

doi:10.7503/cjcu20140210

摘要/Abstract

摘要：

基于密度泛函理论结合跳跃模型和能带理论研究了氟、氯、氰基和N原子的引入对四硫富瓦烯(TTF)衍生物载流子传输性质的影响. 计算结果表明, 嵌N修饰会降低分子重组能, 特别是当N原子靠近TTF主体环时作用更明显. 与引入卤素修饰相比, 引入氰基修饰的分子具有更小的电子和空穴重组能及更低的前线分子轨道(FMO)能级. 同时迁移率的计算结果显示, 分子6具有1.15 cm²·V^-1·s^-1的高电子迁移率, 考虑其较低的LUMO能级, 推测其有望成为潜在的优异电子传输材料, 而相似的电子和空穴迁移率使分子2有望成为潜在的双极性传输材料. 同时还考察了S和N原子之间的弱相互作用, 当S或N原子对分子HOMO(或LUMO)有贡献时, 其相应的空穴(或电子)传输能力会有所提高.

关键词: 四硫富瓦烯衍生物, 载流子传输, 密度泛函理论, 跳跃模型, 能带理论, 重组能

Abstract:

The density functional theory and hopping model with band theory were employed to calculate the charge carrier transport properties of six planar polycyclic aromatic hydrocarbon fused tetrathiafulvalene(TTF) derivatives. The effects of halogen, cyan substitutions and nitrogen were investigated in details. It was confirmed that the introduction of N-atoms reduced the molecular reorganization energy especially when the N-atoms were modified next to the TTF core. Comparing to the halogen the cyan group modified molecules behave lower reorganization energy and lower frontier energy level. The calculated electron drift mobility of molecule 6 is 1.15 cm²·V^-1·s^-1. More over the molecule maintains the lowest LUMO energy level, implying that the molecule may exhibit good electron transport property. The calculated electron dirft mobility(0.37 cm²·V^-1·s^-1) of molecule 2 is very close to hole dirft mobility(0.34 cm²·V^-1·s^-1), indicating molecule 2 is suitable for bipolar devices. Moreover, the weak interactions of S…S, S…N and N…N between molecules in crystal were inspected. The results show that the introduction of S or N atom contributes to HOMO(or LUMO), leading to an increase of hole(or electron) transport property.

Key words: Trathiafulvalene derivative, Carrier transport, Density functional theory, Hopping model, Band theory, Reorganization energy

中图分类号:

O641

TrendMD:

李倩, 耿允, 段雨爱, 王光宇, 苏忠民. 卤素、氰基及N原子修饰对四硫富瓦烯衍生物载流子传输性质影响的理论研究. 高等学校化学学报, 2014, 35(7): 1471.

LI Qian, GENG Yun, DUAN Yuai, WANG Guangyu, SU Zhongmin. Theoretical Studies on the Carrier Transport Properties of Halogen, Cyan Group and N-atom Modified Tetrathiafulvalene Derivatives^†. Chem. J. Chinese Universities, 2014, 35(7): 1471.

图/表 8

Fig.1 Molecular structures of TTF derivatives

Table 1 Calculated λh and λe of molecules 1—6

Molecule	λ_h/meV	λ_e/meV	Molecule	λ_h/meV	λ_e/meV
1	236	137	4	236	202
2	225	186	5	227	184
3	252	227	6	215	163

Fig.2 Contribution of the vibration modes to cationic(λh) and anionic(λe) elaxation energy for TTF derivatives

Fig.3 Frontier molecular orbitals of olecules 1—6

Fig.4 Carrier transport pathways of molecules 1—6

Table 2 Calculated transfer integrals in TTF derivatives(Th and Te in meV) with different hopping pathway, centriod-centriod distance(CD in nm) and calculated hole and electron mobilities(μh and μe in cm2·V-1·s-1)

	1			2			3			4			5			6
Path	CD	T_h	T_e	CD	T_h	T_e	CD	T_h	T_e	CD	T_h	T_e	CD	T_h	T_e	CD	T_h	T_e
P1	19.6	1.1	-4.9	5.8	-26.0	-3.0	6.6	-12.9	-1.4	13.0	38.9	-44.7	8.1	-0.3	-1.2	9.1	0.0	1.8
P2	18.2	-0.7	-2.9	14.7	-3.0	10.7	19.4	0.7	-4.2	10.3	-26.2	-40.4	8.9	-13.9	-7.5	10.9	1.3	4.4
P3	19.4	-0.1	2.7	14.8	-3.9	11.6	17.8	0.5	1.4	22.2	-2.4	2.6	14.8	-2.8	-0.6	9.7	-3.2	-1.7
P4	5.9	65.6	1.1	6.5	68.9	6.5	7.0	30.2	-3.5	12.8	-3.4	-5.2	8.9	-0.1	1.8	13.7	-2.4	0.8
P5	4.7	52.0	-55.9	4.9	46.0	60.6	3.9	-12.1	-98.2	6.1	41.8	11.5	3.9	-80.9	-0.6	6.0	-55.5	76.1
P6	5.1	-10.5	19.8				20.8	0.3	0.4	12.9	-5.3	-6.3
P7										21.5	0.9	-1.7
μ_h	0.28			0.37			0.06			0.31			0.24			0.32
μ_e	0.49			0.34			0.36			0.85			0.02			1.15
μ_exp	0.38—0.42(p)^[10]			0.08—0.20(p)^[32]			0.10(n)^[32]			0.11(n)^[32]

Fig.5 Weak contacts including S…S, S…N and N…N of all molecules together with the hole and electron transfer integrals of the paths

Fig.6 Band structures of molecules 1—6(A—F) The energies are all plotted along directions in the first Brillouin zone connecting the point: G(0, 0, 0), R(0.5, 0.5, 0.5), Z(0, 0, 0.5), X(0.5, 0, 0), T(0, 0.5, 0.5), U(0.5, 0, 0.5), Y(0, 0.5, 0), Z(0, 0, 0.5), V(0.5, 0.5, 0), Y(0, 0.5, 0), R(0.5, 0.5, 0.5), X(0.5, 0, 0), U(0.5, 0, 0.5), R(0.5, 0.5, 0.5), for compounds 1—4 and 6. Z(0, 0, 0), G(0.5, 0, 0), Y(0, 0.5, 0), A(0, 0, 0.5), B(0, 0.5, 0.5), D(0, 0.5, 0.5), E(0, 0.5, 0.5), C(0, 0.5, 0.5), for compound 5. The fermi energy is set to 0. The energy gap and the dispertion of conduction and valence band are also marked.

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