Interaction of YD2 and TiO2 in dye-sensitized solar cells (DSSCs): a density functional theory study

Abstract

The interaction of the dye YD2 with a cluster of (anatase-phase) TiO2 (which is utilized in dye-sensitized solar cells, DSSCs) and electron injection by the dye into the cluster were studied by performing density functional theory (DFT) calculations at the B3LYP, PBE, and TPSS levels of theory, including dispersion effects. We studied and quantified the interaction of the metallomacrocycle with the TiO2 cluster and the electronic spectrum of the complex. TDDFT calculations using the B3LYP functional were found to be the most suitable for describing the observed absorption energy bands of YD2 and YD2-TiO2. Our calculations show that the diarylamino groups act as electron donors in the photon-induced injection that occurs in DSSCs. The free-energy changes that take place during electron injection support the good performance of YD2 on TiO2 clusters.

Electronic and optical properties of metalloporphyrins of zinc on TiO2 cluster in dye-sensitized solar-cells (DSSC). A quantum chemistry study

“…25,26 Small TiO 2 clusters have successfully been used in studies of the interactions between TiO 2 and different dyes such as N749, N3, C101, J3, YD2, LD14, ZnPBAT, ZnPBA and WW3m-WW8m. [25][26][27][28][29][30][31][32][33][34][35][36] The excitation energies have been calculated for the optimized structures at the DFT level using the time-dependent perturbation theory approach (TDDFT). 42,43 The B3LYP, 39 CAM-B3LYP 40 and BHLYP 44 functionals have been employed in the TDDFT calculations.…”

“…5,13 The interaction of the two zinc porphyrin-based dyes, LD13 and YD2-o-C8, with the (101) plane of TiO 2 (anatase) or a TiO 2 nanocluster has been previously modelled showing that the dyes are attached to TiO 2 via the carboxylate group. [25][26][27][28][29][33][34][35][36] The aim of this work is to extend the study to systems using the known coordination preference of the LD13 (h ¼ 8.4%) and YD2-o-C8 (h ¼ 12.1%) dyes. We use these two dyes because of their medium sized in comparison to other compounds and their high values of h. We employ computational methods for elucidating which anchor groups should be used for obtaining an improved conjugation of the MP ring with the TiO 2 surface.…”

“…[8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] The DSSC model systems considered in the present calculations consist of a dye attached to a TiO 2 cluster representing the TiO 2 surface. [25][26][27][28][29][30][31][32][33][34][35][36] The molecular structures of the DSSC models have been optimized at density functional theory (DFT) levels for identifying and characterizing suitable light-capturing molecules. The ground-state calculations show how the dye binds to TiO 2 , whereas single-point quantum chemical calculations of the excitation energies provide information about the vertical excitation processes.…”

Charge Transfer Enhancement in the D-π-A Type Porphyrin Dyes: A Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) Study

“…The B3LYP method has been reported as a reliable method of calculating the geometry of YD2-o-C8 [34][35][36]. Vibrational frequencies were further calculated at the same level to confirm that each ground geometry was a minimum on the potential energy surface.…”

Insights into the role of D‐A‐π‐A type pro‐aromatic organic dyes with thieno[3,4‐b]pyrazine as A acceptor group into dye‐sensitized solar‐cells. A TD‐DFT/periodic DFT study

“…These are conducted through time‐dependent density functional theory (TD‐DFT), which identifies the orbital contributions of electronic states that participate in the electronic transition when absorbing UV‐Vis light dye. The most employed functionals tested in these systems are hybrid and meta‐hybrid‐GGA, such as B3LYP, CAM‐B3LYP, and M06 . Moreover, computational studies analyze the electron injection step in the solar cell, modeling the dye@TiO 2 interaction.…”