Abstract
This work presents an analysis of the evolution of the structural, electronic and optical properties of a series of benzotrithiophene (BTT) derivatives, decorated with peripheral electron-donor bulky groups, with potential as hole-transporting materials (HTMs) in perovskite solar cells. The analysis is performed on the basis of density functional theory calculations. Theoretical calculations show that the bulky p-methoxydiphenylamine (OMeDPA) and p-methoxydiphenylamine-substituted carbazole (OMeDPAC) groups give rise to highly congested molecular structures. In contrast, the incorporation of p-methoxytriphenylamine (OMeTPA) groups leads to an almost planar structure that is suited for an optimal stacking aggregation with beneficial implications in the charge transport and in the performance of the photovoltaic device. The electronic properties calculated for neutral and cation species reveal the good electron-donor behavior of the BTT derivatives. The small reorganization energies calculated for the BTT derivatives are similar to those reported for other excellent HTMs and support the potential of the sulfur-rich BTT core to design new π-conjugated HTMs. Calculations properly account for the changes observed in the absorption spectra of the BTT derivatives as a function of the peripheral groups attached. Whereas the OMeDPA and OMeTPA groups produce an intensity increase and a red shift of the main absorption band, the OMeDPAC group shifts this band to the blue.
Similar content being viewed by others
References
N. R. E. L. National Renewable Energy Laboratory (2016)
Hsiao Y-C, Wu T, Li M, Liu Q, Qin W, Hu B (2015) J Mater Chem A 3:15372
Motta C, El-Mellouhi F, Sanvito S (2015) Sci Rep 5:12746
Stranks SD, Eperon GE, Grancini G, Menelaou C, Alcocer MJP, Leijtens T, Herz LM, Petrozza A, Snaith HJ (2013) Science 342:341
Dong Q, Fang Y, Shao Y, Mulligan P, Qiu J, Cao L, Huang J (2015) Science 347:967
Eperon GE, Stranks SD, Menelaou C, Johnston MB, Herz LM, Snaith HJ (2014) Energy Environ Sci 7:982
Noh JH, Im SH, Heo JH, Mandal TN, Seok SII (2013) Nano Lett 13:1764
Liang P-W, Chueh C-C, Williams ST, Jen AK-Y (2015) Adv Energy Mater 5:1402321
Calió L, Kazim S, Grätzel M, Ahmad S (2016) Angew Chemie Int Ed 55:14522
Teh CH, Daik R, Lim EL, Yap CC, Ibrahim MA, Ludin NA, Sopian K, Mat Teridi MA (2016) J Mater Chem A 4:15788
Zhou H, Chen Q, Li G, Luo S, Song T, Duan H-S, Hong Z, You J, Liu Y, Yang Y (2014) Science 345:542
Zimmermann I, Urieta-Mora J, Gratia P, Aragó J, Grancini G, Molina-Ontoria A, Ortí E, Martín N, Nazeeruddin MK (2017) Adv Energy Mater 7:1601674
Saliba M, Orlandi S, Matsui T, Aghazada S, Cavazzini M, Correa-Baena J-P, Gao P, Scopelliti R, Mosconi E, Dahmen K-H, De Angelis F, Abate A, Hagfeldt A, Pozzi G, Graetzel M, Nazeeruddin MK (2016) Nat Energy 1:15017
Molina-Ontoria A, Zimmermann I, Garcia-Benito I, Gratia P, Roldán-Carmona C, Aghazada S, Graetzel M, Nazeeruddin MK, Martín N (2016) Angew Chemie Int Ed 55:6270
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Fox DJ, et al (2009) Gaussian 09. Revision D01. Gaussian, Inc, Wallingford
Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785
Becke A (1993) J Chem Phys 6:5648
Francl MM, Pietro WJ, Hehre WJ, Binkley JS, Gordon MS, DeFrees DJ, Pople J (1982) J Chem Phys 77:3654
Tomasi J, Persico M (1994) Chem Rev 94:2027
Tomasi J, Mennucci B, Cammi R (2005) Chem Rev 105:2999
Casida ME, Jamorski C, Casida KC, Salahub DR (1998) J Chem Phys 108:4439
Jamorski C, Casida M, Salahub D (1996) J Chem Phys 104:5134
Petersilka M, Gossmann U, Gross E (1996) Phys Rev Lett 76:1212
Casida ME (2009) J Mol Struct THEOCHEM 914:3
Tozer DJ, Amos RD, Handy NC, Roos BO, Serrano-Andres L (1999) Mol Phys 97:859
Dreuw A, Weisman JL, Head-Gordon M (2003) J Chem Phys 119:2943
Dreuw A, Head-Gordon M (2004) J Am Chem Soc 126:4007
Peach MJG, Benfield P, Helgaker T, Tozer DJ (2008) J Chem Phys 128:44118
Le Bahers T, Adamo C, Ciofini I (2011) J Chem Theory Comput 7:2498
Etienne T, Assfeld X, Monari A (2014) J Chem Theory Comput 10:3896
Etienne T (2015) J Chem Phys 142:244103
Etienne T, Assfeld X, Monari A (2014) J Chem Theory Comput 10:3906
Yanai T, Tew DP, Handy NC (2004) Chem Phys Lett 393:51
Brédas J-L, Beljonne D, Coropceanu V, Cornil J (2004) Chem Rev 104:4971
Chemcraft: http://www.chemcraftprog.com
Aragó J, Viruela PM, Gierschner J, Ortí E, Milián-Medina B (2011) Phys Chem Chem Phys 13:1457
García-Benito I, Zimmermann I, Urieta-Mora J, Aragó J, Molina-Ontoria A, Ortí E, Martín N, Nazeeruddin MK (2017) J Mater Chem A 5:8317
Yao Y, Dong H, Hu W (2016) Adv Mater 28:4513
Sokolov AN, Atahan-Evrenk S, Mondal R, Akkerman HB, Sánchez-Carrera RS, Granados-Focil S, Schrier J, Mannsfeld SCB, Zoombelt AP, Bao Z, Aspuru-Guzik A (2011) Nat Commun 2:437
Taerum T, Lukoyanova O, Wylie RG, Perepichka DF (2009) Org Lett 11:3230
Acknowledgements
This work was supported by the Spanish Ministry of Economy and Competitiveness MINECO (CTQ2015-71154-P and Unidad de Excelencia María de Maeztu MDM-2015-0538), the Generalitat Valenciana (PROMETEO/2016/135) and European FEDER funds (CTQ2015-71154-P). J.A. is grateful to MINECO for a “JdC-incorporación” postdoctoral fellowship. J.C. acknowledges the Ministerio de Educación, Cultura y Deporte (MECD) of Spain for a predoctoral FPU grant.
Author information
Authors and Affiliations
Corresponding authors
Additional information
Published as part of the special collection of articles derived from the 10th Congress on Electronic Structure: Principles and Applications (ESPA-2016).
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Calbo, J., Viruela, R., Aragó, J. et al. Theoretical insights into the structural, electronic and optical properties of benzotrithiophene-based hole-transporting materials. Theor Chem Acc 136, 73 (2017). https://doi.org/10.1007/s00214-017-2100-4
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00214-017-2100-4