Theoretical Investigation on the Effect of Extra Donor on the Performance of D-π-A Sensitizer in Dye-sensitized Solar Cell†

doi:10.7503/cjcu20150214

Abstract

Abstract:

In order to explore the effect of extra donor on the performance of sensitizer in dye-sensitized solar cell(DSSC), we have analysized geometrical and electronic structures, absorption spectra, electrochemical properties, charge recombination and conduction band shift for four dyes based on density functional theory(DFT) and time-dependent density functional theory(TD-DFT) calculations. The results show that compared with the classical D-π-A sensitizer 1, although the introduction of extra donor has no significant effect on the conduction band shift, it could change the degree of molecular conjugation and increase their molar absorption coefficients. Importantly, the introduction of extra donors could increase significantly the dye cation hole-conduction surface distance, and thus reduce the charge recombination between the injected electron and dye cation. The introduction of extra donors also make I₂ locate at the outside of sensitizer, thus lower the recombination rate between the injected electron and electrolyte. We hope our calculations could provide a clear strategy for experimental synthesis of high performance dyes.

Key words: Dye-sensitized solar cell, D-D-π-A dye, Density functional theory, Charge recombination, Donor

CLC Number:

O641

TrendMD:

WU Shuixing, ZHANG Jianzhao, SU Xin, ZHANG Ji, WU Yong, GENG Yun, SU Zhongmin. Theoretical Investigation on the Effect of Extra Donor on the Performance of D-π-A Sensitizer in Dye-sensitized Solar Cell^†[J]. Chem. J. Chinese Universities, 2015, 36(10): 2002.

Figures/Tables 9

Fig.1 Molecular structures of isolated organic dyes 1—4

Table 1 Effects of the functionals used on the lowest vertical excitation energy(λ) of dye 2 with the 6-31G* basis set in acetonitrile solution

Functional	λ/eV	Functional	λ/eV
B3LYP	1.90	MPW1K	2.53
BHandHLYP	2.67	CAM-B3LYP	2.70
PBE0	2.05	wB97X	3.01
M06HF	3.14	LC-BLYP	3.13
MPWPW91	1.37	Expt.	3.05

Table 2 Main bond lengths, bond length alternations(BLA) and dihedral angels for dyes 1—4

Dye	Bond length/nm					BLA/nm	∠C1—C2—C3—S/(°)
Dye	C2—C3			C3—C4	C4—C5	C5—C6	C6—C7
1	0.1458	0.1390	0.1403	0.1393	0.1424	0.0037	20.42
2	0.1455	0.1392	0.1401	0.1394	0.1422	0.0033	19.09
3	0.1460	0.1389	0.1404	0.1392	0.1425	0.0039	21.28
4	0.1457	0.1391	0.1402	0.1393	0.1423	0.0035	19.10

Fig.2 Distribution of frontier molecular orbitals for dyes 1—4

Table 3 Calculated maximum absorption wavelength(λmax), oscillator strength(f), light harvesting efficiency(LHE) and transition nature corresponding to S0→S1 for dyes 1—4

Dye	State	Main configuration	λ_max/nm(eV)	f	LHE
1	S₀ → S₁	HOMO-1→LUMO(26%), HOMO→LUMO(65%)	396(3.14)	1.33	0.953
2	S₀ → S₁	HOMO-2→LUMO(30%), HOMO→LUMO(53%)	412(3.01)	1.49	0.967
3	S₀ → S₁	HOMO-5→LUMO(19%), HOMO-2→LUMO(25%), HOMO→LUMO(47%)	390(3.18)	1.43	0.962
4	S₀ → S₁	HOMO-2→LUMO(38%), HOMO→LUMO(41%)	407(3.05)	1.47	0.966

Table 4 Oxidation potential of ground and excited state and corresponding deducing injection and regeneration driving force for dyes 1—4

Dye	E_dye/eV	λ_max/eV	$E dye *$ /eV	ΔG_inj/eV	ΔG_reg/eV
1	-6.39	3.14	-3.25	0.75	1.55
2	-5.64	3.01	-2.63	1.37	0.80
3	-6.12	3.18	-2.94	1.06	1.28
4	-5.63	3.05	-2.58	1.42	0.79

Table 4 Oxidation potential of ground and excited state and corresponding deducing injection and regeneration driving force for dyes 1—4

Dye	E_dye/eV	λ_max/eV	$E dye *$ /eV	ΔG_inj/eV	ΔG_reg/eV
1	-6.39	3.14	-3.25	0.75	1.55
2	-5.64	3.01	-2.63	1.37	0.80
3	-6.12	3.18	-2.94	1.06	1.28
4	-5.63	3.05	-2.58	1.42	0.79

Table 5 Conduction band energy level shift(ΔCB), hole-surface distance(r) and interaction energy of dye-I2 interaction site(Eint) for dyes 1—4

Dye	ΔCB/eV	r/nm	E_int/(kJ·mol^-1)
1	0.2614	1.127	-35.61(1-CN-I₂), -20.63(1-S-I₂)
2	0.2724	1.423	-41.51(2-CN-I₂), -21.71(2-S-I₂)
3	0.2557	1.460	-46.86(3-CN-I₂), -20.17(3-S-I₂)
4	0.2664	1.469	-42.26(4-CN-I₂), -20.84(4-S-I₂)

Fig.3 Optimized molecular structures of dye-I2 complexes and corresponding interaction energies(kJ/mol) for dyes 1—4

Fig.4 Optimized molecular structures of dye-I2 complexes and corresponding interaction energy(kJ/mol) for dye 2

References 37

[1]	Mathew S., Yella A., Gao P., Humphry-Baker R., Curchod B. F. E., Ashari-Astani N., Tavernelli I., Rothlisberger U., Nazee-ruddin M. K., Grätzel M., Nature Chem., 2014, 6(3), 242—247
[2]	Yu Q., Wang Y., Yi Z., Zu N., Zhang J., Zhang M., Wang P., ACS Nano, 2010, 4(10), 6032—6038
[3]	Nazeeruddin M. K., Zakeeruddin S. M., Humphry-Baker R., Jirousek M., Liska P., Vlachopoulos N., Shklover V., Fischer C. H., Grätzel M., Inorg. Chem., 1999, 38(26), 6298—6305
[4]	Chang Y. C., Wang C. L., Pan T. Y., Hong S. H., Lan C. M., Kuo H. H., Lo C. F., Hsu H. Y., Lin C. Y., Diau E. W. G., Chem. Commun., 2011, 47(31), 8910—8912
[5]	Zeng W., Cao Y., Bai Y., Wang Y., Shi Y., Zhang M., Wang F., Pan C., Wang P., Chem. Mater., 2010, 22(5), 1915—1925
[6]	Mishra A., Fischer M. K. R., Bäuerle P., Angew. Chem. Int. Ed., 2009, 48(14), 2474—2499
[7]	Liu J., Li R., Si X., Zhou D., Shi Y., Wang Y., Jing X., Wang P., Energy Environ. Sci., 2010, 3(12), 1924—1928
[8]	Chang D. W., Tsao H. N., Salvatori P., De Angelis F., Gratzel M., Park S. M., Dai L., Lee H. J., Baek J. B., Nazeeruddin M. K., RSC Adv., 2012, 2(15), 6209—6215
[9]	Xu M., Wenger S., Bala H., Shi D., Li R., Zhou Y., Zakeeruddin S. M., Grätzel M., Wang P., J. Phys. Chem. C, 2009, 113(7), 2966—2973
[10]	Tang J., Hua J., Wu W., Li J., Jin Z., Long Y., Tian H., Energy Environ. Sci., 2010, 3(11), 1736—1745
[11]	Tang J., Wu W., Hua J., Li J., Li X., Tian H., Energy Environ. Sci., 2009, 2(9), 982—990
[12]	Zhang J., Li H. B., Zhang J. Z., Wu Y., Geng Y., Fu Q., Su Z. M., J. Mater. Chem. A, 2013, 1, 14000—14007
[13]	Zhang J., Li H. B., Sun S. L., Geng Y., Wu Y., Su Z. M., J. Mater. Chem., 2012, 22(2), 568—576
[14]	Zhang J., Kan Y. H., Li H. B., Geng Y., Wu Y., Duan Y. A., Su Z. M., J. Mol. Model., 2013, 19(4), 1597—1604
[15]	Zhang J., Kan Y. H., Li H. B., Geng Y., Wu Y., Su Z. M., Dyes Pigm., 2012, 95(2), 313—321
[16]	Su X., Zhang J., Wu Y., Geng Y., Su Z. M., Chem. J. Chinese Universities, 2013, 34(8), 1945—1952
	(苏欣, 张吉, 吴勇, 耿允, 苏忠民. 高等学校化学学报,2013, 34(8), 1945—1952)
[17]	Zhang J., Li H. B., Wu Y., Geng Y., Duan Y. A., Liao Y., Su Z. M., Chem. J. Chinese Universities, 2011, 32(6), 1343—1348
	(张吉, 李海斌, 吴勇, 耿允, 段雨爱, 廖奕, 苏忠民. 高等学校化学学报,2011, 32(6), 1343—1348)
[18]	Li H. B., Zhang J., Wu Y., Jin J. L., Duan Y. A., Su Z. M., Geng Y., Dyes Pigm., 2014, 108, 106—114
[19]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., J. A. Montgomery J., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas O., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09W, Revision A.02, Gaussian, Inc., Wallingford CT, 2009
[20]	Wan Z., Jia C., Duan Y., Zhou L., Lin Y., Shi Y., J. Mater. Chem., 2012, 22(48), 25140—25147
[21]	Boys S. F., Bernardi F., Mol. Phys., 1970, 19(4), 553—566
[22]	Newton M. D., Kestner N. R., Chem. Phys. Lett., 1983, 94(2), 198—201
[23]	José M. S., Emilio A., Julian D. G., Alberto G., Javier J., Pablo O., Daniel S. P., J. Phys.: Condens. Matter, 2002, 14(11), 2745—2779
[24]	Cossi M., J. Chem. Phys., 2001, 115(10), 4708—4717
[25]	Persson P., Bergström R., Lunell S., J. Phys. Chem. B, 2000, 104(44), 10348—10351
[26]	Vittadini A., Selloni A., Rotzinger F. P., Grätzel M., J. Phys. Chem. B, 2000, 104(6), 1300—1306
[27]	De Angelis F., Chem. Phys. Lett., 2010, 493(4—6), 323—327
[28]	Wang Z. S., Hara K., Dan-oh Y., Kasada C., Shinpo A., Suga S., Arakawa H., Sugihara H., J. Phys. Chem. B, 2005, 109(9), 3907—3914
[29]	Srinivas K., Yesudas K., Bhanuprakash K., Rao V. J., Giribabu L., J. Phys. Chem. C, 2009, 113(46), 20117—20126
[30]	Lu T., Chen F., J. Comput. Chem., 2012, 33(5), 580—592
[31]	Preat J., Jacquemin D., Michaux C., Perpète E. A., Chem. Phys., 2010, 376(1—3), 56—68
[32]	Islam A., Sugihara H., Arakawa H., J. Photochem. Photobiol., A, 2003, 158(2/3), 131—138
[33]	Daeneke T., Mozer A. J., Uemura Y., Makuta S., Fekete M., Tachibana Y., Koumura N., Bach U., Spiccia L., J. Am. Chem. Soc., 2012, 134(41), 16925—16928
[34]	Clifford J. N., Palomares E., Nazeeruddin M. K., Grätzel M., Nelson J., Li X., Long N. J., Durrant J. R., J. Am. Chem. Soc., 2004, 126(16), 5225—5233
[35]	Clark T., WIREs. Comput. Mol. Sci., 2013, 3(1), 13—20
[36]	Planells M., Pelleja L., Clifford J. N., Pastore M., De Angelis F., Lopez N., Marder S. R., Palomares E., Energy Environ. Sci., 2011, 4(5), 1820—1829
[37]	Pastore M., Mosconi E., De Angelis F., J. Phys. Chem. C, 2012, 116(9), 5965—5973