Skip to main content
SpringerLink
Log in

Design, Synthesis, and Optical and Electrochemical Properties of D–π–A Type Organic Dyes with Carbazole-Based Donor Units for Efficient Dye-Sensitized Solar Cells: Experimental and Theoretical Studies

  • Original Research Article
  • Published:
Journal of Electronic Materials Aims and scope Submit manuscript

Abstract

Significant progress has been made in developing organic compounds by modifying carbazole (Cz) based donor–spacer–acceptor (D–π–A) type dye molecules. The Cz-1–Cz-3 dyes were theoretically designed and experimentally synthesized successfully. Herein, we report the synthesis, photophysical properties and electrochemical characterization (quasi-reversible oxidation processes) of three Cz-based compounds. The calculated results agree well with the available experimental data of absorption spectra, HOMO–LUMO energy levels and band gaps using the time-dependent density functional theory. Furthermore, the results from natural bond orbital calculations were analyzed with the computational electronic structure and charge transfer (conjugative interaction) in molecular systems. The result shows fluorescence time-correlated single-photon counting between 4.32 ns, 4.25 ns, and 13.2 ns, and green to blue (λPL = 431–881 nm) emission for complexes Cz-1–Cz-3 in DMF solution. The Cz-3 compound showed excellent photovoltaic properties, with power conversion efficiency of 5.68%. These results clearly reveal that modification of the electron-withdrawing capability in D–π–A conjugated metal-free organic dyes is an effective way to improve the optical and electrical properties of organic photovoltaic (PV) devices.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Scheme 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

Data Availability

The raw/processed data required to reproduce these findings cannot be shared at this time as the data also form part of an ongoing study.

References

  1. B. O’Regan and M. Grätzel, A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films. Nature 353(6346), 737–740 (1991).

    Article  Google Scholar 

  2. X. Zhang, F. Gou, J. Shi, H. Gao, C. Xu, Z. Zhu, and H. Jing, Molecular engineering of new phenothiazine-based D-A–π–A dyes for dye-sensitized solar cells. RSC Adv. 6(108), 106380–106386 (2016).

    Article  CAS  Google Scholar 

  3. Z.S. Wang, Y. Cui, K. Hara, Y. Dan-oh, C. Kasada, and A. Shinpo, A high-light-harvesting-efficiency coumarin dye for stable dye-sensitized solar cells. Adv. Mater. 19(8), 1138–1141 (2007).

    Article  CAS  Google Scholar 

  4. B. Liu, W. Zhu, Q. Zhang, W. Wu, M. Xu, Z. Ning, Y. Xie, and H. Tian, Conveniently synthesized isophorone dyes for high efficiency dye-sensitized solar cells: tuning photovoltaic performance by structural modification of donor group in donor–π–acceptor system. Chem. Commun. 13, 1766–1768 (2009).

    Article  Google Scholar 

  5. C. Zafer, M. Kus, G. Turkmen, H. Dincalp, S. Demic, B. Kuban, Y. Teoman, and S. Icli, New perylene derivative dyes for dye-sensitized solar cells. Sol. Energy Mater. Sol. Cells 91(5), 427–431 (2007).

    Article  CAS  Google Scholar 

  6. X. Ma, J. Hua, W. Wu, Y. Jin, F. Meng, W. Zhan, and H. Tian, A high-efficiency cyanine dye for dye-sensitized solar cells. Tetrahedron 64(2), 345–350 (2008).

    Article  CAS  Google Scholar 

  7. S. Hayashi, M. Tanaka, H. Hayashi, S. Eu, T. Umeyama, Y. Matano, Y. Araki, and H. Imahori, Naphthyl-fused π-elongated porphyrins for dye-sensitized TiO2 cells. J. Phys. Chem. C 112(39), 15576–15585 (2008).

    Article  CAS  Google Scholar 

  8. P. Shen, Y. Liu, X. Huang, B. Zhao, N. Xiang, J. Fei, L. Liu, X. Wang, H. Huang, and S.T. Tan, Efficient triphenylamine dyes for solar cells: effects of alkyl-substituents and π-conjugated thiophene unit. Dyes Pigm. 83(2), 187–197 (2009).

    Article  CAS  Google Scholar 

  9. F. Sanda, T. Nakai, N. Kobayashi, and T. Masuda, Synthesis of polyacetylenes having pendant carbazole groups and their photo-and electroluminescence properties. Macromolecules 37(8), 2703–2708 (2004).

    Article  CAS  Google Scholar 

  10. L. Zhao, P. Wagner, A.B.S. Elliott, M.J. Griffith, T.M. Clarke, K.C. Gordon, S. Moric, and A.J. Mozer, Enhanced performance of dye-sensitized solar cells using carbazole-substituted di-chromophoric porphyrin dyes. J. Mater. Chem. A 2, 16963–16977 (2014).

    Article  CAS  Google Scholar 

  11. J. Sivanadanam, P. Ganesan, P. Gao, M.K. Nazeeruddin, A. Emeline, D. Bahnemann, and R. Rajalingam, Impact of strength and size of donors on the optoelectronic properties of D–π–A sensitizers. RSC Adv. 6(44), 37347–37361 (2016).

    Article  CAS  Google Scholar 

  12. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, J. Honda, O. Kitao, H. Nakai, T. Vreven Jr., J.A. Montgomery, J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.M. Iyengar, J. Tomasi, M. Cossi, R. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, and D.J. Fox, Gaussian 09 Revision A02 (Wallingford: Gaussian Inc, 2009).

    Google Scholar 

  13. A.D. Becke, Density-functional thermochemistry. I. The effect of the exchange-only gradient correction. J. Chem. Phys. 96(3), 2155–2160 (1992).

    Article  CAS  Google Scholar 

  14. A.D. Becke, Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 38, 3098 (1988).

    Article  CAS  Google Scholar 

  15. C. Lee, W. Yang, and R.G. Parr, Development of the Colle–Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 37, 785 (1988).

    Article  CAS  Google Scholar 

  16. A.E. Reed and F. Weinhold, Natural localized molecular orbitals. J. Chem. Phys. 83(4), 1736–1740 (1985).

    Article  CAS  Google Scholar 

  17. S. Miertuš, E. Scrocco, and J. Tomasi, Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects. Chem. Phys. 55(1), 117–129 (1981).

    Article  Google Scholar 

  18. S. Miertus and J. Tomasi, Approximate evaluations of the electrostatic free energy and internal energy changes in solution processes. Chem. Phys. 65(2), 239–245 (1982).

    Article  CAS  Google Scholar 

  19. M. Cossi, V. Barone, R. Cammi, and J. Tomasi, Ab initio study of solvated molecules: a new implementation of the polarizable continuum model. Chem. Phys. Lett. 255(4–6), 327–335 (1996).

    Article  CAS  Google Scholar 

  20. R.I. Dennington, T. Keith, and J. Millam, GaussView, Version 508 (Shawnee: Semichem. Inc, 2009).

    Google Scholar 

  21. R.G. Pearson, Absolute electronegativity and hardness correlated with molecular orbital theory. Proc. Natl. Acad. Sci. 83(22), 8440–8441 (1986).

    Article  CAS  Google Scholar 

  22. R.V. Solomon, P. Veerapandian, S.A. Vedha, and P.A. Venuvanalingam, Tuning nonlinear optical and optoelectronic properties of vinyl coupled triazene chromophores: a density functional theory and time-dependent density functional theory investigation. J. Phys. Chem. A 116(18), 4667–4677 (2012).

    Article  CAS  Google Scholar 

  23. Y. Xue, Y. Dou, L. An, Y. Zheng, L. Zhang, and Y. Liu, Electronic structure and spectral properties of aurones as visible range fluorescent probes: a DFT/TDDFT study. RSC Adv. 6(9), 7002–7010 (2016).

    Article  CAS  Google Scholar 

  24. G. Gece, The use of quantum chemical methods in corrosion inhibitor studies. Corros. Sci. 50(11), 2981–2992 (2008).

    Article  CAS  Google Scholar 

  25. R.G. Parr, L.V. Szentpaly, and S. Liu, Electrophilicity index. J. Am. Chem. Soc. 121(9), 1922–1924 (1999).

    Article  CAS  Google Scholar 

  26. P.K. Chattaraj, B. Maiti, and U. Sarkar, Philicity: a unified treatment of chemical reactivity and selectivity. J. Phys. Chem. A 107(25), 4973–4975 (2003).

    Article  CAS  Google Scholar 

  27. R.G. Parr, R.A. Donnelly, M. Levy, and W.E. Palke, Electronegativity: the density functional viewpoint. J. Chem. Phys. 68(8), 3801–3807 (1978).

    Article  CAS  Google Scholar 

  28. R.G. Parr and R.G. Pearson, Absolute hardness: companion parameter to absolute electronegativity. J. Am. Chem. Soc. 105(26), 7512–7516 (1983).

    Article  CAS  Google Scholar 

  29. R.G. Parr and P.K. Chattaraj, Principle of maximum hardness. J. Am. Chem. Soc. 113(5), 1854–1855 (1991).

    Article  CAS  Google Scholar 

  30. T. Iijima, A. Momotake, Y. Shinohara, T. Sato, Y. Nishimura, and T. Arai, Excited-state intramolecular proton transfer of naphthalene-fused 2-(2′-hydroxyaryl) benzazole family. J. Phys. Chem. A 114(4), 1603–1609 (2010).

    Article  CAS  Google Scholar 

  31. X. Ren, J. Li, R.J. Holmes, P.I. Djurovich, S.R. Forrest, and M.E. Thompson, Ultrahigh energy gap hosts in deep blue organic electrophosphorescent devices. Chem. Mater. 16(23), 4743–4747 (2004).

    Article  CAS  Google Scholar 

  32. C. Fan, Y. Wei, D. Ding, and H. Xu, Linkage engineering in hosts for dramatic efficiency enhancement of blue phosphorescent organic light-emitting diodes. Opt. Express 23(10), 12887–12899 (2015).

    Article  CAS  Google Scholar 

  33. T. Daeneke, T.-H. Kwon, A.B. Holmes, N.W. Duffy, U. Bach, and L. Spiccia, High-efficiency dye-sensitized solar cells with ferrocene-based electrolytes. Nat. Chem. 3(3), 211–215 (2011).

    Article  CAS  Google Scholar 

  34. S.J. Su, C. Cai, and J. Kido, RGB phosphorescent organic light-emitting diodes by using host materials with heterocyclic cores: effect of nitrogen atom orientations. Chem. Mater. 23(2), 274–284 (2010).

    Article  Google Scholar 

  35. E. Scrocco and J. Thomasi, Electronic molecular structure, reactivity and intermolecular forces: an euristic interpretation by means of electrostatic molecular potentials. J. Adv. Quantum Chem. 11, 115–193 (1978).

    Article  CAS  Google Scholar 

  36. S.S. Amiri, S. Makarem, H. Ahmar, and S. Ashenagar, Theoretical studies and spectroscopic characterization of novel 4-methyl-5-((5-phenyl-1,3,4-oxadiazol-2-yl) thio) benzene-1, 2-diol. J. Mol. Struct. 1119, 18–24 (2016).

    Article  Google Scholar 

Download references

Acknowledgments

We are greatly thankful to I. Ragavan, Research Scholar, Department of Physics, Periyar University, Salem-11, Tamilnadu, India, for his valuable suggestions and strong encouragement to the work. The authors extend their appreciation to the Research Center for Advanced Materials Science (RCAMS), King Khalid University, Saudi Arabia, for funding this work under Grant Number RCAMS/KKU/020-22.

Author information

Authors and Affiliations

  1. Selvamm Arts and Science College, Namakkal, Tamilnadu, 637 033, India

    K. Periyasamy & P. Sakthivel

  2. Vaigi Arts and Science Women College, Valapady, Salem, Tamilnadu, 636 011, India

    K. Periyasamy

  3. Department of Physics, Periyar University, Salem, Tamilnadu, 636 011, India

    I. Ragavan, P. M. Anbarasan, A. Arunkumar & C. Vidya

  4. Research Center for Advanced Materials Science (RCAMS), King Khalid University, P.O. Box 9004, Abha, 61413, Saudi Arabia

    Mohd Shkir

  5. Department of Physics, King Khalid University, P.O. Box 9004, Abha, 61413, Saudi Arabia

    Mohd Shkir

  6. University Center for Research and Development (UCRD), Chandigarh University, NH95, Chandigarh-Ludhiana Highway, Gharuan, Mohali, Punjab, 140413, India

    Mohd Shkir

  7. Department of Physics, Saveetha School of Engineering, Saveetha Institute of Medical and Technical Sciences, Chennai, Tamilnadu, 602105, India

    V. Balasubramani

  8. School of Chemical Engineering, Yeungnam University, Gyeongsan, 38541, Republic of Korea

    Vasudeva Reddy Minnan Reddy & Woo Kyoung Kim

Authors
  1. K. Periyasamy
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. P. Sakthivel
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. I. Ragavan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. P. M. Anbarasan
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. A. Arunkumar
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Mohd Shkir
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. C. Vidya
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. V. Balasubramani
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Vasudeva Reddy Minnan Reddy
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Woo Kyoung Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

KP, IR, AA and CV: Design work, experimental processes, conceptualization; computational investigation; methodology; data curation; formal analysis; writing—original draft. PS and PMA: Supervision; software; review and editing; conceptualization; validation; data curation, formal analysis. MS, VRMR and VB, WKK: English language in the revisions to the manuscript; funding acquisition, writing—review and editing.

Corresponding authors

Correspondence to P. Sakthivel, Vasudeva Reddy Minnan Reddy or Woo Kyoung Kim.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOC 401 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Periyasamy, K., Sakthivel, P., Ragavan, I. et al. Design, Synthesis, and Optical and Electrochemical Properties of D–π–A Type Organic Dyes with Carbazole-Based Donor Units for Efficient Dye-Sensitized Solar Cells: Experimental and Theoretical Studies. J. Electron. Mater. 52, 2525–2543 (2023). https://doi.org/10.1007/s11664-023-10210-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11664-023-10210-6

Keywords

Search

Navigation