Theoretical Studies on the Carrier Transport Properties of Halogen, Cyan Group and N-atom Modified Tetrathiafulvalene Derivatives†

doi:10.7503/cjcu20140210

Abstract

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

CLC Number:

O641

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2014, 35(7): 1471.

Figures/Tables 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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