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MODELLING AND SIMULATION IN MATERIALS SCIENCE AND ENGINEERING doi:10.1088/0965-0393/18/2/025004

Modelling Simul. Mater. Sci. Eng. 18 (2010) 025004 (9pp)

First principles study of the size effect of TiO2 anatase nanoparticles in dye-sensitized solar cell
Yinkai Lei, Huijun Liu and Wei Xiao1
Department of Physics, Wuhan University, Wuhan, Hubei, 430072, People’s Republic of China E-mail: weixiao@whu.edu.cn

Received 18 September 2009, in final form 27 November 2009 Published 18 January 2010 Online at stacks.iop.org/MSMSE/18/025004 Abstract Density of states of eight TiO2 anatase nanoparticles have been studied. The size effect of the TiO2 nanoparticles on the electron transport in dye-sensitized solar cell (DSSC) has been investigated. For the small size nanoparticles (R < 2 nm), the smaller the particle is, the more the acceptable states locate at the bottom of the conduction band. As a result, the electron injection rate to the particles from the dye is higher in the smaller nanoparticles DSSC. (Some figures in this article are in colour only in the electronic version)

1. Introduction TiO2 mesoporous films dye-sensitized solar cells (DSSCs) were developed in 1991 [1]. As low cost alternatives to the conventional solid state semiconductor solar cells, DSSCs have been intensively studied [1–8]. The power efficiencies of DSSCs can reach 11% or higher [6, 7]. In DSSCs, the mesoporous dye-sensitized TiO2 photoanode receives electrons from the photoexcited dye. At the same time, the dye is oxidized. In turn the dye oxidizes the redox species in the electrolyte. The electrolyte is reduced by the electrons from the external circuit [3]. When sunlight enters, a dye molecule attached on the thin film of TiO2 absorbs a photon, then an electron is excited from the ground state S to an excited state S∗ . If the energy of the excited state S∗ is higher than the bottom of the conduction band of TiO2 , the electron can be injected into the semiconductor and transported to the conducting glass and becomes the electric current in the outside circuit. The schematic of the DSSC is shown in figure 1. The incident photon to current conversion efficiency of DSSCs with single crystal anatase electrode is much lower than that of cells with nanocrystalline electrode [3]. It is interesting to study the TiO2 size effect on the DSSCs. Recently computational simulations and calculations have been used to understand the mechanisms of the DSSCs [9–12]. TiO2 particles
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Figure 1. Schematic of the DSSC.

structural properties have been studied with molecular dynamics (MD) simulations [13]. The structural, electronic and surface properties of anatase TiO2 nanocrystals were studied by first principles calculations [14]. Different size TiO2 nanoparticles electronic properties were calculated by tight-binding and density functional theory (DFT) [15]. Structural and electronic properties of bare and dye-sensitized TiO2 clusters and nanoparticles have been studied by DFT calculations [16]. But the relation between the particle size and the efficiency of the DSSC is not clear. Electronic properties of different types of TiO2 nanoparticles are studied in this work. The density of states (DOSs) and integrated DOS results show that the excited electrons can be injected to the small particles faster from the dye. Not only can TiO2 be used in the DSSCs, it has also been widely used in photocatalysis, biomaterials and many other fields [17–20]. The TiO2 bulk, surfaces and particles properties have been studied with computational methods [13–15, 21–24]. Titanium dioxide has three major different structures: rutile (tetragonal, P 42 /mnm), anatase (tetragonal, I 41 /amd) and brookite (rhombohedral, P bca). In bulk materials, rutile is the only stable phase, whereas anatase and brookite are metastable at all temperatures. Anatase and brookite can transfer to rutile at high temperature. But when the particle diameter is decreased to about 13 or 14 nm, anatase is more stable [25, 26]. In this work, different TiO2 anatase nanoparticles are studied by first principles calculations. 2. Calculation methods 2.1. DFT calculation methods DFT [27, 28] calculations are carried out to investigate the electronic properties of different TiO2 particles. The size effect on the electronic property is studied. The calculations are performed using the Vienna Ab-Initio Simulation Package (VASP) [29–31]. The projected augmented wave (PAW) method [32, 33] is used in this work. TiO2 bulk structure is relaxed with both local density approximation (LDA) of Ceperly and Alder parametrized by Perdew and Zunger (CA) [34] and generalized gradient approximation (GGA) of Perdew and Wang (PW91) [35]. The TiO2 lattice constants from LDA are closer to the experimental data than the lattice constants from GGA (see table 1). So, LDA is used in this work. The energy cutoff is set to 400 eV. For the electronic relaxation calculations, the residual minimization method
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Table 1. The calculated TiO2 anatase lattice constants with LDA and GGA, compared with the experimental data [38]. a and c are the lattice constants and d is the Ti–O bond length. a (Å) LDA GGA Expt (15 K) 3.77 3.83 3.78 c/a 2.51 2.51 — c (Å) 9.46 9.61 9.50 d (Å) 1.97 2.00 1.98

(a) Side view of the particles

(b) Top view of the particles

Figure 2. Structure of three bipyramid particles with 30, 78, 105 atoms after relaxation. The small (red) circles are oxygen atoms and the big (gray) circles are titanium atoms.

with direct inversion in the iterative subspace (RMM-DIIS) [36] is used while the energy convergence criterion is set to 10−4 eV. The conjugate gradient method is used to minimize the Hellmann–Feynman forces in the ionic relaxations with the same energy convergence criterion of 10−4 eV. In bulk TiO2 calculations, summations over the Brillouin zone (BZ) are performed with a 8 × 8 × 8 Monkhorst–Pack k-point mesh. The tetrahedron method with Bl¨ chl corrections o is used in the electronic DOS calculation. In the DOS calculation, a 21 × 21 × 21 -centered k-point mesh is used. TiO2 (1 0 1), (0 0 1) and (1 0 0) surfaces properties are calculated with a 36 atom unit cell and a 20 Å thick vacuum layer on the top. An 8 × 8 × 1 Monkhorst–Pack k-point mesh is used in the surface calculations. Eight TiO2 particles separated into three groups are calculated in this work. The particles 3 are placed in a 22.62×22.62×28.39 Å box which is much larger than the size of the particles. Particle calculations are performed at the point. 2.2. Structures of nanoparticles Minimizing the system energies including the cohesive energies and the calculated surface energies, eight stoichiometric TiO2 anatase nanoparticles are constructed. According to the shape of the particles, they are separated into three categories. Because the anatase surface energy for the (1 0 1) surface is lower than that for the (1 0 0) and (0 0 1) surfaces (see section 3.1), the bipyramid particles with eight {1 0 1} facets [15] are studied first. Three type 1 particles with 30, 78 and 105 atoms are shown in figure 2. Another type of particle is a truncated bipyramid which has {0 0 1} facets at the apices of the bipyramid nanoparticle [14, 15]. Three type 2 particles with 24, 72 and 99 atoms are listed in figure 3. The third type of particles
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Figure 3. Structure of three relaxed type 2 nanoparticles with 24, 72 and 99 atoms.

Figure 4. Structure of three relaxed type 3 particles with 72, 102 and 132 atoms.

has both {1 0 1} and {0 0 1} facets and it extends in the [1 0 0] direction. This type of particle looks like a lamina with two large {1 0 1} facets [11]. Three type 3 particles with 72, 102 and 132 atoms are plotted in figure 4. Because the type 2 particle with 72 atoms is the same as the type 3 particle with 72 atoms, in total eight nanoparticles are studied in this work. TiO2 anatase nanoparticles of types 2 and 3 have two dangling oxygen atoms at the edge of {0 0 1} facets. These oxygen atoms are used to keep the atomic number ratio between Ti and O as 1 : 2. As a result, the total charge of the particles is zero. 3. Results and discussion 3.1. Bulk and surface calculations The anatase TiO2 has a body-centered tetragonal (bct) structure (space group is I 41 /amd). The anatase TiO2 lattice constants are calculated and listed in table 1. The calculated lattice constants from LDA exchange-correlation functional are closer to the experimental data than those from GGA are. The DOS of bulk anatase TiO2 is calculated and the band gap is about 2.0 eV which agrees with other calculations [21, 22]. The calculated gap is 1.2 eV lower than the experimental data [37] because DFT calculations underestimate the band gap width.
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Modelling Simul. Mater. Sci. Eng. 18 (2010) 025004 Table 2. Anatase (1 0 1), (1 0 0) and (0 0 1) surface energies. Esurf (1 0 1) (J m−2 ) This work Lazzeri et al [23] 0.91 0.84 Esurf (1 0 0) (J m−2 ) 1.28 0.96

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Esurf (0 0 1) (J m−2 ) 1.43 1.38

Figure 5. DOS of type 1 particles: (a) 105 atoms, (b) 78 atoms and (c) 30 atoms. Vacuum energy is set as zero, the solid lines are the Fermi energy of the particles.

The anatase surface energies for the (1 0 1), (1 0 0) and (0 0 1) surfaces are calculated in order to set up the TiO2 nanoparticles. The surface energy calculations for the (1 0 1) and (1 0 0) surfaces employ a six layer slab of 36 atoms and each layer has two (TiO2 ) units. The periodical repeated slabs are separated by vacuum regions about 20 Å wide to eliminate the interaction between the nearest neighbor slabs. Periodic boundary conditions are applied in the X and Y directions and the surfaces are free to relax in the Z direction. The unit cell used in the (0 0 1) surface calculation is composed of 12 (TiO2 ) layers (36 atoms). In the (1 0 1) and (1 0 0) surfaces calculations, the two middle layers are fixed, while the four middle layers are fixed in the (0 0 1) surface calculation to simulate the bulk materials, other atoms are free to relax along the direction perpendicular to the surfaces. The surface energies are listed in table 2 and compared with other published data [23]. It shows that the surface energies in this work are close to Lazzeri et al’s works. 3.2. DOSs of nanoparticles In order to evaluate the size effect on the electronic structures of the TiO2 particles, the DOSs per TiO2 of the particles are calculated. The DOSs of the particles are shown in figures 5, 6 and 7. The vacuum energy is set as zero to compare the DOSs of different particles. The quantum effect on the small particle is very clear, the energy bands of the small particle split into a number of small peaks. The band gaps of type 1 particles are about 2 eV, but the band gaps of types 2 and 3 particles are about 1 eV. At the top of the valence band of the particles of types 2 and 3, a small peak appears. This small peak narrows the band gap. The detailed local DOS information on each atom shows that these peaks are from the compensating oxygen atoms. For example, figure 8 shows the total DOS and the DOS contributions from one dangling O atom and its nearest neighbor Ti atom of the type 2 particle with 99 atoms. It suggests that if there are some dangling oxygen atoms on the {0 0 1} facets, the light absorption of TiO2 anatase may change. The oxygen absorption on TiO2 particle may change its photo-catalytic property
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Figure 6. DOS of type 2 particles: (a) 99 atoms, (b) 72 atoms and (c) 24 atoms. Vacuum energy is zero, the solid lines are the Fermi energy of the particles.

Figure 7. DOS of type 3 particles: (a) 132 atoms, (b) 102 atoms and (c) 72 atoms. Vacuum energy is zero, the solid lines are the Fermi energy of the particles.

or the solar cell property. The surface absorption can increase the visible light absorption and the excited electron from the TiO2 may reduce the dye. For small particles, the influence of the dangling oxygen atom is more serious since the number of dangling atoms is fixed and the number of total atoms is smaller. Therefore, the peak from the dangling atom is relatively higher for small particles (see figures 6 and 7). Define the integrated DOS as intDOS(E) =
E

D(ε) dε,
−∞

(1)

where D(ε) is the DOS. The integrated DOSs of the particles are calculated and shown in figure 9. Since the 1s electrons of O atoms and 1s, 2s, 2p, 3s, 3p electrons of Ti atoms are the core electrons, there are 16 electrons per TiO2 . The horizontal lines at around −6 eV correspond to the band gaps of the DOS. For energy higher than the gap, the value (intDOS(E)−16) is the number of states in the range from the bottom of the conduction band to the energy E. From the bottom of the conduction band to energy about 1.5 eV above, the smaller the particle size is, the more electron states there are. For the DSSC, the excited electrons will be injected into the TiO2 particle from the dye. The injection rates are proportional to the number of empty states which can be used to accept electrons. If the excited state of the dye molecular is located in this
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120 Density of States 100 80 60 40 20 0 –20 –15

total DOS dangling O nearest Ti

–10 –5 Energy(eV)

0

5

Figure 8. Total DOS, local DOS from one dangling O atom and its nearest neighbor Ti atom. The small peak on the top of the valence band comes from the two dangling O atoms and their two nearest Ti neighbor atoms. Fermi energy is set as zero.

Figure 9. Integrated DOS of the nanoparticles near the band gap: (a) type 1 particles, (b) type 2 particles and (c) type 3 particles. Vacuum energy is set to zero.

energy range. The smaller the TiO2 particle is, the faster the electrons could be injected. The conduction bands of the small semiconductor particles split into several energy levels. This makes the DOS of the conduction band of a smaller particle spread in a wider energy range. So, near the bottom of the conduction band, there is an energy range in which the smaller particles have more states than the bigger particles. The ideal sensitizer for a single junction photovoltaic cell should absorb all light below a threshold wavelength of about 920 nm [4]. The energy corresponding to this wavelength is about 1.35 eV. So, the energy gap between the LUMO and HOMO of the dye cannot be larger than 1.35 eV. Because the HOMO of the dye is lower than the conduction band of the TiO2 particles, the energy difference between the LUMO of the dye and the bottom of the conduction band of the TiO2 particle is smaller than 1.35 eV. Consequently, the excited electrons from the dye can be injected into the small particles faster.
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4. Conclusions First principles calculation has been used to study the DOS of different type TiO2 anatase nanoparticles. The dangling O atoms located on the {0 0 1} facets can raise the top of the valence band and narrow the band gap. This narrowing of the band gap affects the light absorption of TiO2 particles. The photon excited electrons in TiO2 anatase may reduce the dye attached on the particle and shorten the lifetime of the solar cell. The size effect on the particle DOS is observed from the study of the three types of TiO2 anatase particles. For small nanoparticles (R < 2 nm), if the excited state of the dye on the DSSC is in the energy range between the conduction band bottom and around 1.5 eV above, the smaller the particle is, the faster the electrons can be injected. N886 0H and N719 [39] are such kinds of dye molecules. If they are on the TiO2 anatase particles, the electron injection rates may be higher for the small TiO2 particles. Because the particle sizes used in this DFT calculation are small, especially for the 30 atom and 24 atom cases, larger size particle calculations are needed in future work. The particle size in the experimental work is larger than the simulation particle size. Although the injection rates are faster for small particles, the small particle solar cell efficiency may not be higher. Because the small particles will increase the grain boundary, the electron transport at the grain boundary may decrease the whole electron transport properties. How to find the best grain size which can balance the two aspects is still a challenge. Acknowledgments This work is supported by the Chinese National Science Foundation project 10704058 and the Chinese National Basic Research Program (973 Program) project 2009CB939705. Part of the work is supported by the Chinese National Fundamental Science Training Foundation, Project J0830310. Reference
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