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Applied Physics Express 1 (2008) 111203

Electronic Band Structure of Transparent Conductor: Nb-Doped Anatase TiO2


Taro Hitosugi1;2 , Hideyuki Kamisaka3 , Koichi Yamashita3 , Hiroyuki Nogawa4 , Yutaka Furubayashi2 , Shoichiro Nakao2 , Naoomi Yamada2 , Akira Chikamatsu5 , Hiroshi Kumigashira5 , Masaharu Oshima5 , Yasushi Hirose2;4 , Toshihiro Shimada2;4 , and Tetsuya Hasegawa2;4
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Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan Kanagawa Academy of Science and Technology (KAST), Kawasaki 213-0012, Japan 3 Department of Chemical System Engineering, The University of Tokyo, Tokyo 113-8656, Japan 4 Department of Chemistry, The University of Tokyo, Tokyo 113-0033, Japan 5 Department of Applied Chemistry, The University of Tokyo, Tokyo 113-8656, Japan Received October 6, 2008; accepted October 25, 2008; published online November 14, 2008 We have investigated electronic band structure of a transparent conducting oxide, Nb-doped anatase TiO2 (TNO), by means of firstprinciples band calculations and photoemission measurements. The band calculations revealed that Nb 4d orbitals are strongly hybridized with Ti 3d ones to form a d-nature conduction band, without impurity states in the in-gap region, resulting in high carrier density exceeding 1021 cm3 and excellent optical transparency in the visible region. Furthermore, we confirmed that the results of valence band and corelevel photoemission measurements are consistent with prediction by the present band calculations. # 2008 The Japan Society of Applied Physics DOI: 10.1143/APEX.1.111203

se of titanium dioxide (TiO2 ) has spread over a wide range of application elds, including photocatalysts,1) pigments, and sensors.2) Recently, TiO2 has also oered potentials as a mother compound of electronic materials, such as resistive memories,3) diluted magnetic semiconductors,4) and transparent conductors.5) In particular, Nb- or Ta-doped6) anatase TiO2 have attracted much attention as promising candidates for practical transparent electrode materials.710) Anatase TiO2 lms doped with Nb, Ti1x Nbx O2 (TNO), exhibit metallic behavior with low electrical resistivity  down to $2 104  cm at 300 K and positive temperature coecient, d=dT > 0, in contrast to Nb-doped rutile indicating semiconducting transport properties.11,12) This minimum  value is comparable to those of highlyconducting oxides, such as ReO3 , Nax WO3 , SrRuO3 , and La or Nb-doped SrTiO3 .13) Another interesting feature of TNO is high ionization eciency of Nb, >90%. This implies that each Nb dopant releases one electron into the conduction band. Furthermore, TNO shows high optical transparency in the visible region with optical absorbance < 10%,5) suggesting that doped Nb atoms do not generate in-gap states. In order to understand the carrier transport mechanism in TNO, detailed information about its electronic band structure is of essential importance, however, such attempts from both experimental and theoretical sides, have been scarcely made so far. In this paper, we report on the rst-principles band calculations of anatase TNO and pure anatase TiO2 . Comparing both, we argue how Nb doping modies the band structure of TiO2 and generates carriers in the conduction band. We also performed photoemission measurements of TNO, for comparison, and conrmed that photoemission spectrum near the Fermi level and valence states of Ti and Nb are consistent with prediction by the present band calculations. In our calculations, anatase TiO2 was modeled by eight times larger than the primitive cells with all three vectors being doubled.14) Nb doping was introduced by substituting

E-mail address: hitosugi@wpi-aimr.tohoku.ac.jp

one of the sixteen Ti atoms in unit cell with Nb atom. Geometry optimization was performed using density-functional theory (DFT) calculations employing a standard generalized gradient approximation (GGA; PW91) function. The nuclear positions were updated using the conjugatedgradient method. Vanderbilts ultrasoft pseudopotentials (USPP),15,16) and plane-wave basis sets with a cuto energy of 29.08 Ry were employed. All the atomic positions were simultaneously optimized, while the cell size and shape were xed. Initially, the k points were sampled according to the MonkhorstPack 2 2 2 scheme,17) and the structures obtained were improved using the analogous 4 4 4 scheme. Using sampled k points, the tetrahedron method was employed to carryout integrations over the entire Brillouin zone. All the calculations were carried out using the VASP software package.18,19) Ti0:94 Nb0:06 O2 epitaxial lms with  $ 4:4 104  cm (carrier density $ 1:5 1021 cm3 , Hall mobility 9.2 cm2 V1 s1 ) were grown on LaAlO3 (100) substrates by using pulsed-laser deposition method. The substrate temperature and oxygen partial pressure during deposition were set to 650  C and 1 105 Torr, respectively. Typical thickness of the obtained lms was approximately 100 nm. X-ray diraction (XRD) measurements conrmed epitaxial growth of anatase phase in all lms used in this study. Transport measurements were conducted with six-probe Hall bar geometry. Resonant photoemission spectra were measured using synchrotron radiation at BL2C of the Photon Factory, Tsukuba. We utilized a Scienta SES-100 electron energy analyzer with energy resolution of 0.15 eV in a photon energy range of 400 600 eV. The Fermi level of the samples was referred to that of a gold foil which was in electrical contact with a sample. Core level photoemission spectra of Nb and Ti were characterized by monochromatic Al K X-ray photoemission spectroscopy (XPS; PerkinElmer 5400MC). The resolution of the core-level XPS is estimated to be 1 eV, and the energy oset was calibrated using the C signal. Figure 1(a) shows density of states (DOS) as a function of electron energy calculated for undoped anatase TiO2 . The gure clearly exhibits a band gap of about 2.24 eV, which is
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Appl. Phys. Express 1 (2008) 111203

(a)

(b)

(c)

Fig. 1. Total DOS of (a) stoichiometric pure anatase TiO2 and (b) stoichiometric Nb-doped anatase TiO2 (doping amount correspond to x 0:625). (c) Partial DOS of Ti d (blue line), Nb d (red line) in stoichiometric Nb-doped anatase TiO2 .

somewhat smaller than the experimentally observed value, of 3.2 eV. Such underestimation of band gap is a well-known limitation of the GGA calculation. The Fermi energy (EF ) lies in the middle of the band gap, reecting insulating behavior of pure anatase TiO2 . Total DOS proles computed for Ti1x Nbx O2 are shown in Fig. 1(b), where the central Ti atom in the supercell is substituted for Nb, corresponding to doping content of x $ 0:0625. Notably, EF is located inside the conduction band, indicating that TNO can be categorized as a metal. This is consistent with experimentally observed metallic behavior, i.e., positive temperature coecient of  and almost temperature-independent carrier density.5) Furthermore, no in-gap structure is visible from Fig. 1(b). Figure 1(c) compares partial DOS of Ti d and Nb d states. Remarkably, both DOS proles above EF show essentially identical shapes. That is, the Nb 4d orbital spreads over the entire region of the conduction band, implying that Nb is strongly hybridized with Ti and O. Furthermore, electron charge density distributions around Ti and Nb atoms coincide well with each other, being another support for the strong hybridization between Ti and Nb (data not shown). These results might explain high solubility of Nb into anatase, up to $20%.5) As a consequence of strong Ti Nb hybridization, each Nb atom releases one electron to the conduction band, being consistent with experimentally observed high ionization eciency of >90% and resulting high carrier density exceeding 1021 cm3 . It is interesting to note that the hybridization is a unique feature to the anatase structure. Indeed, Nb-doped rutile TiO2 shows dierent behavior, i.e., formation of shallow Nb-impurity states and semiconductive carrier transport with d=dT < 0.12) According to the present GGA calculation for TNO, the bottom of the conduction band consists of Ti 3dxy and Nb 4dxy orbitals, and EF lies at 0.49 eV from the bottom of the conduction band. As seen from Fig. 1, Nb-doping to anatase does not aect the shape of conduction band, indicating that TNO is well described by rigid band model. It is important to note that the conductivity in TiO2 is due to delocalization of Ti 3d states, and electrons generated by Nb doping lls the Ti 3dxy -nature conduction band, which is nearly parabolic. Kurita et al. observed BursteinMoss shift in TNO, and evaluated EF $ 0:2 eV at x 0:06, which is fairly in good agreement with the present GGA results. In

Intensity (arb. unit)

Onresonance

Intensity (arb. unit)

On- resonance

Off-resonance

Offresonance

-15

-10
(a)

-5

EF

Binding Energy (eV)

EF 3 1 2 Binding Energy (eV)


(b)

Fig. 2. (a) Valence band spectra of highly-conductive anatase Ti0:94 Nb0:06 O2 thin film measured with h 461:2 eV (on resonance: red curve) and 600 eV (off resonance: blue curve). (b) Close up view of the spectra near Fermi energy of (a).

addition we have evaluated EF $ 0:15 eV at x 0:03 from Seebeck coecient.20) This DOS at EF was clearly resolved by resonant photoemission spectroscopy, where the photoionization cross section for Ti 3d states is strongly enhanced.21) Figure 2(a) shows o-resonant (h 600 eV) and Ti 2p3d resonant (h 461:2 eV) valence spectra of Ti0:94 Nb0:06 O2 . Figure 2(b) is a close-up view near the valence band gap edge of Fig. 2(a). The resonant spectrum clearly exhibits a peak at EF , corresponding to the bottom of Ti 3d-nature conduction band, whereas o-resonant spectra show negligible peak at EF . This result proves that the conducting electrons are indeed d-electrons as predicted by calculations. Moreover, we could not detect any impurity state inside the band gap, being consistent with the present GGA calculations. Figures 3(a) and 3(b) shows core-level photoemission spectra of Ti 2p and Nb 3d, respectively. The former exhibits a major Ti4 peak at a binding energy of $458:7 eV together with a minor Ti3 one at lower energy side by 1.8 eV ($456:9 eV). The latter is characterized by a pronounced Nb5 peak at $207:5 eV with a weak shoulder structure around 206.5 eV, which can be assigned as Nb4 . The fact that doped Nb mainly exists as Nb5 is consistent with the present GGA calculation, predicting that each Nb atom substituted for Ti releases one delocalized electron. As
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Normalized intensity (arb. unit) Normalized intensity (arb. unit)

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Ti4+

Nb5+

Nb4+

Ti3+

-10 -5 0 5 Relative binding energy (eV)


(a)

-6 -4 -2 0 2 Relative binding energy (eV)


(b)

Fig. 3. (a) Ti 2p and (b) Nb 3d core-level spectra obtained with photon energy of 1486.6 eV (monochromatic Al K X-ray). Binding energies are calibrated using C peak. Zero energy corresponds to 458.7 and 207.5 eV for (a) and (b), respectively. Blue and red curves denote the fitted composition of Ti4 and Ti3 , respectively for (a), and Nb5 and Nb4 , respectively for (b). Green line is a fitted curve of background.

In summary, we have investigated electronic structure of anatase Nb-doped TiO2 based on the rst-principles band calculations and photoemission measurements. From comparison of Nb and Ti partial density of states, it is concluded that Ti 3d, Nb 3d, and Ti 3d states are strongly hybridized with each other to form d-nature conduction band. Carrier doping by Nb substitution is well described a rigid-band picture: substituted Nb atoms are ionized and release electrons into the hybridized conduction band without forming midgap state. Nb doping does not essentially aect the band dispersion, and thus the eective electron mass. These results provide consistent interpretation on the remarkable features of TNO, i.e., high carrier density of the order of 1021 cm3 , high electron mobility, and excellent optical transparency in the visible region.
Acknowledgments This work was supported by the Ministry of Education, Culture, Sports, Science and Technology (MEXT): Elements Science and Technology Project, New Energy and Industrial Technology Development Organization (NEDO), Global Center of Excellence (COE) Program for Chemistry Innovation, and a Grant-in-Aid for Young Scientists (B).

(a)

(b)

Fig. 4. Calculated electron energy band structure of (a) undoped and (b) Nb-doped TiO2 .

described above, the delocalized electrons occupy the states near the bottom of the conduction band contributed from Ti 3d and Nb 4d orbitals, resulting in the formation of minor components Ti3 and Nb4 . Finally, we discuss on the electron mobility. Figures 4(a) and 4(b) shows the band structure of undoped and Nb-doped anatase TiO2 , respectively. Nb doping changes the band lling, but it does not essentially aect the band dispersions. Observable eect of Nb doping is the slight lift or lowering of bands which would lose degeneracy of the bands. The electron eective mass values, m , near the point were estimated to be 0.42m0 in the M direction (parallel to a,b-axes) and 4.05m0 in the Z (c-direction), where m0 is the free electron mass. These m values are almost independent of Nb content, and are equivalent to those of pure anatase TiO2 , 0.42m0 and 4.05m0 in the a- and c-directions, respectively. Furthermore, they are in good agreement with the experimental data, 0.2 0.6m0 and 2 3m0 in the x- and z-directions, respectively, derived from Drude analyses of transmittance and reectance spectra of (012)-oriented epitaxial TNO lms.22) The relatively low m values, compared to that of rutile TiO2 , 10 16m0 and 2 4m0 in the a- and c-directions, respectively, are responsible for high conductivity of anatase TNO.

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# 2008 The Japan Society of Applied Physics