Abstract
Surface doping has emerged as a promising approach to enhance the reactivity and optoelectronic properties of titanium dioxide (TiO2) and other inorganic oxide semiconductors. This strategy has significant potential to improve the efficiency and long-term stability of dye-sensitized solar cells (DSSCs). The present study employs density functional theory (DFT) calculations to investigate, for the first time, the adsorption behavior of the organometallic N719 dye on pristine and carbon-doped ultrathin TiO2(B) films. Initially, the interaction between the N719 dye and the pristine TiO2(B) (100) surface is examined, considering various molecular orientations and anchoring configurations. The adsorption energies and the resultant changes in the semiconductor’s electronic structure are determined. Subsequently, the impact of carbon doping on the preferential adsorption configurations is analyzed. The results reveal that the adsorption of the N719 dye is energetically favorable on both the pristine and C-doped TiO2(B) (100) surfaces. Notably, all adsorption-related properties are significantly enhanced after carbon doping, with the adsorption energy increasing by up to 300% compared to the undoped surface. This substantial increase in adsorption performance is critical for achieving highly efficient and long-lasting DSSCs.
Data availability
The datasets used and/or analyzed during the current study are available from the corresponding author upon reasonable request.
References
O’Regan, B. & Grätzel, M. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films. Nature 353, 737–740 (1991).
Grätzel, M. Dye-Sensitized solar cells. J. Photochem. Photobiol C. 4, 145–153 (2003).
Freitag, M. et al. Dye-sensitized solar cells for efficient power generation under ambient lighting. Nat. Photon. 11, 372–378 (2017).
Ren, Y. et al. Hydroxamic acid pre-adsorption raises the efficiency of cosensitized solar cells. Nature 613, 60–65 (2023).
Vougioukalakis, G. C., Philippopoulos, A. I., Stergiopoulos, T. & Falaras, P. Contributions to the development of ruthenium-based sensitizers for dye-sensitized solar cells. Coord. Chem. Rev. 255, 2602–2621 (2011).
Qin, Y. & Peng, Q. Ruthenium Sensitizers and Their Applications in Dye-Sensitized Solar Cells. Int. J. Photoenergy 2012, 291579 (2012).
Naik, P., Abdellah, I. M., Abdel-Shakour, M., Keremane, K. S. & Adhikari, A. V. Enhancing the photoelectrochemical performance of Ru(II)-Sensitized Dye-Sensitized solar cells using Cyanopyridine-Based cosensitizers. Energy Technol. 13, 2500294 (2025).
Shamsaldeen, A. A. et al. Influence of TiO2 surface defects on the adsorption of N719 dye molecules. Phys. Chem. Chem. Phys. 23, 22160–22173 (2021).
German, E., Faccio, R. & Mombrú, Á. W. Theoretical study of new potential semiconductor surfaces performance for dye sensitized solar cell usage: TiO2-B (001), (100) and H2Ti3O7 (100). Appl. Surf. Sci. 426, 1182–1189 (2017).
Xie, F. et al. TiO2-B as an electron transporting material for highly efficient perovskite solar cells. J. Power Sources. 415, 8–14 (2019).
Liu, H. et al. Mesoporous TiO2–B microspheres with superior rate performance for lithium ion batteries. Adv. Mater. 23, 3450–3454 (2011).
Kim, N., Raj, M. R. & Lee, G. Nitrogen-doped TiO2(B) nanobelts enabling enhancement of electronic conductivity and efficiency of lithium-ion storage. Nanotech 31, 415401 (2020).
Abbasi, A., Sardroodi, J. J. & Ebrahimzadeh, A. R. Chemisorption of CH2O on N-doped TiO2 anatase nanoparticle as modified nanostructure media: A DFT study. Surf. Sci. 654, 20–32 (2016).
May Ix, L. A., Estrella González, A., Cipagauta-Díaz, S. & Gómez, R. Effective electron–hole separation over N-doped TiO2 materials for improved photocatalytic reduction of 4-nitrophenol using visible light. J. Chem. Technol. Biotechnol. 95, 2694–2706 (2020).
Heffner, H., Marchetti, J. M., Faccio, R. & López-Corral, I. A theoretical exploration of catechol sensitization of C-doped bronze TiO2 surfaces for photochemical systems. Comput. Mater. Sci. 230, 112523 (2023).
Singh, J. et al. XPS, UV–Vis, FTIR, and EXAFS Studies to Investigate the Binding Mechanism of N719 Dye onto Oxalic Acid Treated TiO2 and Its Implication on Photovoltaic Properties. J. Phys. Chem. 117, 21096–21104 (2013).
De Angelis, F., Fantacci, S., Selloni, A., Nazeeruddin, M. K. & Grätzel, M. First-Principles modeling of the adsorption geometry and electronic structure of Ru(II) dyes on extended TiO2 substrates for Dye-Sensitized solar cell applications. J. Phys. Chem. C. 114, 6054–6061 (2010).
Schiffmann, F. et al. Protonation-Dependent binding of ruthenium bipyridyl complexes to the Anatase(101) surface. J. Phys. Chem. C. 114, 8398–8404 (2010).
Sodeyama, K. et al. Protonated carboxyl anchor for stable adsorption of Ru N749 dye (Black dye) on a TiO2 anatase (101) surface. J. Phys. Chem. Lett. 3, 472–477 (2012).
Klein, M., Pankiewicz, R., Zalas, M. & Stampor, W. Magnetic field effects in dye-sensitized solar cells controlled by different cell architecture. Sci. Rep. 6, 30077 (2016).
Sheng, L., Liao, T., Kou, L. & Sun, Z. Single-crystalline ultrathin 2D TiO2 nanosheets: A Bridge towards superior photovoltaic devices. Mater. Today Energy. 3, 32–39 (2017).
Jiang, L. et al. Niobium-Doped (001)-Dominated anatase TiO2 nanosheets as photoelectrode for efficient Dye-Sensitized solar cells. ACS Appl. Mater. Interfaces. 9, 9576–9583 (2017).
Shahroosvand, H., Abbasi, P. & Bideh, B. N. Dye-Sensitized Solar Cell Based on Novel Star-Shaped Ruthenium Polypyridyl Sensitizer: New Insight into the Relationship between Molecular Designing and Its Outstanding Charge Carrier Dynamics. ChemistrySelect 3, 6821–6829 (2018).
Selvaraj, P. et al. Soft-template synthesis of high surface area mesoporous titanium dioxide for dye-sensitized solar cells. Int. J. Energy Res. 43, 523–534 (2019).
Kong, X. et al. Enhancement of photocatalytic H2 production by metal complex electrostatic adsorption on TiO2(B) nanosheets. J. Mater. Chem. A. 7, 3797–3804 (2019).
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B. 59, 1758–1775 (1999).
Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for Ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B. 54, 11169–11186 (1996).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).
Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B. 13, 5188–5192 (1976).
Deák, P., Gali, A., Aradi, B. & Frauenheim, T. Accurate gap levels and their role in the reliability of other calculated defect properties. Phys. Stat. Sol (B). 248, 790–798 (2011).
Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA + U study. Phys. Rev. B. 57, 1505–1509 (1998).
Heffner, H. & Faccio, R. López–Corral, I. C–doped TiO2(B): A density functional theory characterization. Appl. Surf. Sci. 551, 149479 (2021).
Heffner, H., Marchetti, J. M., Faccio, R. & López-Corral, I. Density functional evaluation of catechol adsorption on pristine and reduced TiO2(B)(100) ultrathin sheets for Dye-Sensitized solar cell applications. Inorg. Chem. 61, 19248–19260 (2022).
German, E., Faccio, R. & Mombrú, A. W. A DFT + U study on structural, electronic, vibrational and thermodynamic properties of TiO2 polymorphs and hydrogen titanate: tuning the Hubbard ‘U-term’. J. Phys. Commun. 1, 055006 (2017).
Arrouvel, C., Parker, S. C. & Islam, M. S. Lithium insertion and transport in the TiO2–B anode material: A computational study. Chem. Mater. 21, 4778–4783 (2009).
Gao, D. et al. First-principles study on screening doped TiO2(B) as an anode material with high conductivity and low lithium transport resistance for lithium-ion batteries. Phys. Chem. Chem. Phys. 21, 17985–17992 (2019).
Morgan, B. J. & Madden, P. A. Lithium intercalation into TiO2(B): A comparison of LDA, GGA, and GGA + U density functional calculations. Phys. Rev. B. 86, 035147 (2012).
Cococcioni, M. & de Gironcoli, S. Linear response approach to the calculation of the effective interaction parameters in the LDA + U method. Phys. Rev. B. 71, 035105 (2005).
Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).
Izumi, F. & Momma, K. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).
Ganose, A. M., Jackson, A. J. & Scanlon, D. O. Sumo: Command-line tools for plotting and analysis of periodic *ab initio* calculations. J. Open. Source Softw. 3, 717 (2018).
Niu, M. The adsorption geometry and electronic structure of organic dye molecule on TiO2(101) surface from first principles calculations. MATEC Web Conf. 88, 03002 (2017).
Vittadini, A., Casarin, M. & Selloni, A. Structure and stability of TiO2-B surfaces: A density functional study. J. Phys. Chem. C. 113, 18973–18977 (2009).
Liu, W. et al. A shortcut for evaluating activities of TiO2 facets: water dissociative chemisorption on TiO2-B (100) and (001). Phys. Chem. Chem. Phys. 12, 8721–8727 (2010).
Vittadini, A., Selloni, A., Rotzinger, F. P. & Grätzel, M. Formic acid adsorption on dry and hydrated TiO2 anatase (101) surfaces by DFT calculations. J. Phys. Chem. B. 104, 1300–1306 (2000).
Zhang, Y. et al. Copper-Doped titanium dioxide bronze nanowires with superior high rate capability for lithium ion batteries. ACS Appl. Mater. Interfaces. 8, 7957–7965 (2016).
Ooyama, Y. & Harima, Y. Molecular Designs and Syntheses of Organic Dyes for Dye-Sensitized Solar Cells. Eur. J. Org. Chem. 2009, 2903–2934 (2009).
Meng, S. & Kaxiras, E. Electron and hole dynamics in Dye-Sensitized solar cells: influencing factors and systematic trends. Nano Lett. 10, 1238–1247 (2010).
Zhang, Q. & Cao, G. Nanostructured photoelectrodes for dye-sensitized solar cells. Nano Today. 6, 91–109 (2011).
Zhang, L., Mohamed, H. H., Dillert, R. & Bahnemann, D. Kinetics and mechanisms of charge transfer processes in photocatalytic systems: A review. J. Photochem. Photobiol C. 13, 263–276 (2012).
German, E., Faccio, R. & Mombrú, A. W. Comparison of standard DFT and Hubbard-DFT methods in structural and electronic properties of TiO2 polymorphs and H-titanate ultrathin sheets for DSSC application. Appl. Surf. Sci. 428, 118–123 (2018).
Chang, S. & Liu, W. Surface doping is more beneficial than bulk doping to the photocatalytic activity of vanadium-doped TiO2. Appl. Catal. B Environ. 101, 333–342 (2011).
Subalakshmi, K. & Senthilselvan, J. Effect of fluorine-doped TiO2 photoanode on electron transport, recombination dynamics and improved DSSC efficiency. Sol Energy. 171, 914–928 (2018).
Hamann, T. W., Jensen, R. A., Martinson, A. B. F., Ryswyk, H. V. & Hupp, J. T. Advancing beyond current generation dye-sensitized solar cells. Energy Environ. Sci. 1, 66–78 (2008).
Acknowledgements
The simulations were performed using resources provided by UNINETT Sigma2 – the National Infrastructure for High Performance Computing and Data Storage in Norway. R. Faccio acknowledges CSIC-UdelaR, PEDECIBA, and ANII, Uruguayan institutions.
Funding
Open Access funding enabled and organized by Projekt DEAL. I. López-Corral is a member of CONICET. H. Heffner is a fellow researcher at that institution. This work was supported by PGI-SGCyT-UNS 24/Q140.
Author information
Authors and Affiliations
Contributions
H. Heffner: Conceptualization, Investigation, Formal analysis, Data curation, Visualization, Methodology, Writing – original draft. J.M. Marchetti: Resources, Software. R. Faccio: Validation, Writing – review & editing. I. López-Corral: Conceptualization, Resources, Supervision, Writing – review & editing, Funding acquisition.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
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.
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
About this article
Cite this article
Heffner, H., Marchetti, J.M., Faccio, R. et al. Computational study of carbon-doped TiO2(B) nanomaterials for improved dye-sensitized solar cells. Sci Rep (2026). https://doi.org/10.1038/s41598-026-38897-7
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41598-026-38897-7
