Synthesis and Properties of Gallium Naphthalene Phthalocyanine Imide Electron Acceptor Materials

doi:10.19894/j.issn.1000-0518.230084

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (11): 1531-1538.DOI: 10.19894/j.issn.1000-0518.230084

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Synthesis and Properties of Gallium Naphthalene Phthalocyanine Imide Electron Acceptor Materials

Lei LI¹, Li LI¹, Jun-Jie MA¹, Ju-Biao FU², Chun-Sheng CAI¹, Mei-Ling CHEN², Xue-Yan QIN², Zhong-Yi YUAN¹(), Yi-Wang CHEN¹

^1.School of Chemistry and Chemical Engineering Nanchang University，Jiangxi Provincial Key Laboratory of New Energy Chemistry，Nanchang 330031，China
^2.Jiujiang Shanshui Technology Co. ，LTD，Jiujiang 332700，China

Received:2023-04-03 Accepted:2023-08-22 Published:2023-11-01 Online:2023-12-01
Contact: Zhong-Yi YUAN
About author:yuan@ncu.edu.cn
Supported by:
the National Natural Science Foundation of China(22161029);the Natural Science Foundation of Jiangxi Province(20213BCJ22033)

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Abstract

Abstract:

Five gallium naphthalocyanines， Cl-GaNcTl， OH-GaNcTl， OSiR₃-GaNcTI， F₅Ph-GaNcTI and QL-GaNcTI， have been designed and synthesized as acceptor materials for bulk heterojunction organic solar cells （BHJ OSCs）. They exhibit strong near-infrared absorption at 300~1100 nm， a high maximum extinction coefficient of 6.18×10⁵ L/（mol·cm）， a low minimum unoccupied molecular orbital （LUMO） energy level of -3.9 eV， and good thermal stability （T_d＞320 ℃）. The introduction of long chain substituents in the axial direction of naphthalocyanine is found to be effective in decreasing molecular aggregation. All of them could be used as acceptor materials for bulk-phase heterojunction organic solar cells.

Key words: Naphthalocyanine, Organic solar cell, Electron acceptor material, Near-infrared absorption

CLC Number:

O621.3

Lei LI, Li LI, Jun-Jie MA, Ju-Biao FU, Chun-Sheng CAI, Mei-Ling CHEN, Xue-Yan QIN, Zhong-Yi YUAN, Yi-Wang CHEN. Synthesis and Properties of Gallium Naphthalene Phthalocyanine Imide Electron Acceptor Materials[J]. Chinese Journal of Applied Chemistry, 2023, 40(11): 1531-1538.

Figures/Tables 13

Fig.1 Molecular structures of CuPcTIs， 3BSO-SiNcTI and R-GaNcTI

Fig.2 Synthesis of target compounds：（ⅰ） quinolone， GaCl3， 200 ℃， 2 h， 35%；（ⅱ） ammonium hydroxide， DMAC， 100 ℃， 4 h， 60%；（ⅲ） 4a： pentafluorophenol， mesitylene， 180 ℃， 1 h， 50%； 4b： 8-hydroxyquinoline， mesitylene， 180 ℃， 1 h， 70%； 4c： triisopropylsilyl chloride， mesitylene， 180 ℃， 1 h， 60%

Fig.3 UV-Vis absorption of GaNcTI in （A） CHCl3 （1×10-6 mol/L） and （B） in the solid-state

Fig.4 Fluorescence spectra of GaNcTI molecules

Fig.5 TGA curves of GaNcTI molecules

Fig.6 Cyclic voltammetry diagram of GaNcTl molecules

Table 1 Summary of GaNcTIs solution and film absorptions， fluorescence and electrochemical data

Materials	λ_max/nm		10^-5ε/（L·mol^-1·cm^-1）	Φ_f	E $g o p t$ /eV	LUMO/eV	HOMO/eV
Materials	Solution	Film	10^-5ε/（L·mol^-1·cm^-1）	Φ_f	E $g o p t$ /eV	LUMO/eV	HOMO/eV
Cl-GaNcTI	803	780	5.21	0.026	1.51	-3.92	-5.43
OH-GaNcTI	804	783	3.75	0.008	1.51	-3.89	-5.40
R₃SiO-GaNcTI	798	803	6.18	0.038	152	-3.91	-5.43
F₅Ph-GaNcTI	806	785	3.82	0.018	1.50	-3.95	-5.45
QL-GaNcTI	804	788	3.83	0.027	1.51	-3.93	-5.44

Table 1 Summary of GaNcTIs solution and film absorptions， fluorescence and electrochemical data

Materials	λ_max/nm		10^-5ε/（L·mol^-1·cm^-1）	Φ_f	E $g o p t$ /eV	LUMO/eV	HOMO/eV
Materials	Solution	Film	10^-5ε/（L·mol^-1·cm^-1）	Φ_f	E $g o p t$ /eV	LUMO/eV	HOMO/eV
Cl-GaNcTI	803	780	5.21	0.026	1.51	-3.92	-5.43
OH-GaNcTI	804	783	3.75	0.008	1.51	-3.89	-5.40
R₃SiO-GaNcTI	798	803	6.18	0.038	152	-3.91	-5.43
F₅Ph-GaNcTI	806	785	3.82	0.018	1.50	-3.95	-5.45
QL-GaNcTI	804	788	3.83	0.027	1.51	-3.93	-5.44

Fig.7 Device structure of bulk heterojunction organic solar cell

Table 2 Device optimization with different ratios of PTB7-Th （D）∶R3SiO-GaNcTI （A）

D∶A/（mg·mL^-1）	V_OC/V	J_SC/（mA·cm^-2）	FF/%	PCE/%
30∶10	0.500	2.03	38.15	0.46
20∶10	0.502	2.74	38.73	0.83
10∶10	0.521	3.68	41.25	1.10
10∶20	0.518	4.71	40.37	1.01
10∶25	0.523	4.86	40.48	0.85

Table 3 Device optimization under different rotational speeds and thermal annealing conditions

Active materials	Speed/（r·min^-1）	Time ^a /min	V_OC/V	J_SC/（mA·cm^-2）	FF/%	PCE/%
PTB7-Th∶R₃SiO-GaNcTI	2 000	0	0.55	4.97	40.05	1.10
	2 000	10	0.55	5.23	40.43	1.14
	3 000	0	0.55	5.02	39.90	1.10
	3 000	10	0.54	5.24	39.77	1.17

Fig.8 J-V curves of the cell based on GaNcTI active layer receptor material

Table 4 Photoelectric properties of target molecule GaNcTI

Active layer	V_OC/V	J_SC/（mA· cm^-2）	FF/%	PCE/%
PTB7-Th/GaNcTI-Cl	0.468	4.81	35.46	0.80
PTB7-Th/GaNcTI-OH	0.463	4.52	35.35	0.56
PTB7-Th/GaNcTI-QL	0.472	4.13	35.67	0.88
PTB7-Th/GaNcTI-OPhF₅	0.460	2.06	35.72	0.34
PTB7-Th/GaNcTI-OSiR₃	0.595	5.81	36.97	1.28

Fig.9 Electron mobility （A） and hole mobility （B） of PTB7-Th∶R3SiO-GaNcTI/Al device

References 20

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Synthesis and Properties of Gallium Naphthalene Phthalocyanine Imide Electron Acceptor Materials

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