Chem. Mater.

2010, 22, 3983–3987 3983

DOI:10.1021/cm1005604

An Epitaxial Transparent Conducting Perovskite

Oxide: Double-Doped SrTiO3
Jayakanth Ravichandran,*,† Wolter Siemons,‡ Herman Heijmerikx,‡,§

)
Mark Huijben,§ Arun Majumdar, and Ramamoorthy Ramesh‡,^
Applied Science and Technology Graduate Group, University of California, Berkeley California 94720,
Department of Physics, University of California, Berkeley California 94720, Faculty of Science and
Technology, University of Twente, P. O Box 217, 7500 AE, Enschede (The Netherlands), Advanced Research
Projects Agency - Energy, U.S. Department of Energy, Washington, DC 20585, and Department of
Materials Science and Engineering, University of California, Berkeley California 94720. †Applied Science
and Technology Graduate Group, University of California. ‡Department of Physics, University of
California. § University of Twente. Department of Energy. ^Department of Materials Science and
)
Engineering, University of California.
Received February 23, 2010. Revised Manuscript Received May 11, 2010

Epitaxial thin films of strontium titanate doped with different concentrations of lanthanum
and oxygen vacancies were grown on LSAT substrates by pulsed laser deposition technique. Films
grown with 5-15% La doping and a critical growth pressure of 1-10 mTorr showed high transparency
(>70-95%) in the UV-visible range with a sheet resistance of 300-1000 Ω/0. With the aid of
UV-visible spectroscopy and photoluminescence, we establish the presence of oxygen vacancies
and the possible band structure, which is crucial for the transparent conducting nature of these
films. This demonstration will enable development of various epitaxial oxide heterostructures for both
realizing opto-electronic devices and understanding their intrinsic optical properties.

Introduction oxides, most notably InxCd3TeO6,5 Sb-doped SrSnO3,6

ZnSnO3,7 La- and Sb-doped BaSnO3,8 and Cd-In-
Transparent conducting oxides (TCOs) are an interest-
Sn-O.9 SrTiO3 (STO) is a model functional perovskite
ing class of materials which combine two conflicting
oxide and widely used as substrate material for the growth
properties, namely electrical conduction and optical
of oxide thin films. It has a wide band gap and can be easily
transparency. The guiding principle in designing a trans-
doped on cationic sites or with oxygen vacancies. Heavy
parent conductor is the creation of defect levels close to
doping of STO using La or Nb has been demonstrated in
conduction or valence bands of a wide band gap semi-
both bulk10 and thin films,11 leading to metallic conductivi-
conductor. Ionization of these defects produces a degen-
ties. In the past, efforts have been made to produce a
erate electron gas causing only free carrier absorption in
transparent conducting oxide using STO by tuning the
far-infrared regime but maintains good optical transpar-
oxygen vacancies in amorphous or polycrystalline films12 or
ency in the UV-visible region by retaining the band gap
antimony (Sb) doping13 with no significant success. Recently,
of the material.1 Perovskite oxides show a wide range of
it was discovered that a very thin surface layer (1-3 nm)
exotic phenomena namely superconductivity,2 thermoelec-
of STO becomes conducting by Ar ion bombardment while
tricity,3 and colossal magneto-resistance.4 However, there
maintaining excellent transparency, presumably due to
are very few reports of transparent conducting perovskite
oxygen vacancies.14 Another report on La0.5Sr0.5TiO3þδ15

*Author to whom correspondence should be addressed. Tel.: þ1-510-643-

8202. Fax þ1-510-643-5792. E-mail: jayakanth@berkeley.edu. (8) Wang, H. F.; Liu, Q. Z.; Chen, F.; Gao, G. Y.; Wu, W.; Chen, X. H.
(1) Edwards, P. P.; Porch, A.; Jones, M. O.; Morgan, D. V.; Perks, J. Appl. Phys. 2007, 101, 106105.
R. M. Dalton Trans. 2004, 2995. (9) Mason, T. O.; Kammler, D. R.; Ingram, B. J.; Gonzalez, G. B.;
(2) Schooley, J. F.; Hosler, W. R.; Cohen, M. L. Phys. Rev. Lett. 1964, Young, D. L.; Coutts, T. J. Thin Solid Films 2003, 445, 186.
12, 474. (10) Ohta, S.; Nomura, T.; Ohta, H.; Koumoto, K. J. Appl. Phys. 2005,
(3) Frederikse, H. P. R.; Thurber, W. R.; Hosler, W. R. Phys. Rev. 97, 034106.
1964, 134, A442. (11) Ohta, S.; Nomura, T.; Ohta, H.; Hirano, M.; Hosono, H.;
(4) Jin, S.; Tiefel, T. H.; McCormack, M.; Fastnacht, R. A.; Ramesh, Koumoto, K. Appl. Phys. Lett. 2005, 87, 092108.
R.; Chen, L. H. Science 1994, 264, 413. (12) Campet, G.; Geoffroy, C.; Manaud, J. P.; Portier, J.; Sun, Z. W.;
(5) Tetsuka, H.; Shan, Y. J.; Tetsuka, K.; Imoto, H.; Wasa, K. Salardenne, J.; Keou, P. Mater. Sci. Eng. B 1991, 8, 45.
J. Mater. Res. 2005, 20, 2256. (13) Wang, H. H.; Chen, F.; Dai, S. Y.; Zhao, T.; Lu, H. B.; Cui, D. F.;
(6) Liu, Q. Z.; Wang, H. F.; Chen, F.; Wu, W. J. Appl. Phys. 2008, 103, Zhou, Y. L.; Chen, Z. H.; Yang, G. Z. Appl. Phys. Lett. 2001, 78,
093709. 1676.
(7) Minami, T.; Sonohara, H.; Takata, S.; Sato, H. Jpn. J. Appl. Phys. (14) Reagor, D. W.; Butko, V. Y. Nat. Mater. 2005, 4, 593.
1994, 33, L1693. (15) Cho, J. H.; Cho, H. J. Appl. Phys. Lett. 2001, 79, 1426.

r 2010 American Chemical Society Published on Web 06/04/2010 pubs.acs.org/cm

3984 Chem. Mater., Vol. 22, No. 13, 2010 Ravichandran et al.

speculated the role of oxygen content in controlling the

filling in Ti-3d states and hence the transparent conduct-
ing nature of La doped STO at the Mott-Hubbard limit
(La doping . 20%). These reports and theoretical pre-
dictions of a defect band formation due to oxygen vacan-
cies in STO16,17 suggest oxygen vacancies can be crucial
for creating a TCO of doped STO. A doped STO based
TCO will have far reaching implications in fabricating
optoelectronics devices, for example photo detectors,
solar cells, and light emitting diodes (LED) based on
epitaxial perovskite oxide heterostructures, and also a
single crystalline transparent bottom electrode will be
crucial to understand the optoelectronic properties of
such perovskite heterostructures. It is important to note
that STO substrate has been the preferred substrate for a
variety of single crystalline epitaxial perovskite hetero-
structures and a functional transparent conducting layer
of doped STO can be easily integrated into such hetero- Figure 1. Schematic of sample structure is shown on top. Typically 150
nm thick STO film was grown on a 0.5 mm thick LSAT substrate and Ti/
structures. In this article, we report a heteroepitaxial TCO Pt contacts with 10/100 nm thicknesses were deposited for transport
based on doped STO and establish the role of oxygen measurements in Van der Pauw geometry. Below is the photograph of
vacancies under the simple band picture using optical STO thin films on LSAT substrate which are (a) transparent and
insulating (0% La grown at 10-3 Torr), (b) transparent and conducting
spectroscopy and transport measurements. (15% La grown at 10-3 Torr), (c) nontransparent and conducting (15%
La grown at 10-7 Torr), (d) bare LSAT substrate, and (e) bare MgO
Experimental Section substrate.

Thin films of double-doped STO (LaxSr1-xTiO3-δ, x = grown at 10-3 Torr), (b) transparent and conducting
0-0.15) were grown on (LaAlO3)0.3-(Sr2AlTaO6)0.7 (LSAT) (15% La grown at 10-3 Torr), and (c) nontransparent
substrates (<1% lattice mismatch with bulk STO) using pulsed and conducting (15% La grown at 10-7 Torr). Substrates
laser deposition (PLD). An excimer laser (λ = 248 nm) with of (d) LSAT and (e) magnesium oxide (MgO) are shown
laser fluence of 1.5 J cm-2 per pulse and repetition rate of 8 Hz for comparison. The inset of Figure 1 shows the schematic
was used to ablate commercial polycrystalline STO targets with of the device structure used for the transport and optical
nominal La doping of 0, 10, and 15%. The substrate tempera-
spectroscopic measurements.
ture was maintained at 850 C during the deposition. X-ray
Figure 2 shows the X-ray diffraction (XRD) pattern for
diffraction (XRD) was carried out on these films with a Pana-
lytical X’Pert Pro thin film diffractometer using Cu KR radia- the transparent conducting sample grown at 10-3 Torr
tion. Low temperature resistivity and Hall measurements were with 15% La doping. The diffraction pattern clearly
performed in Van der Pauw geometry using a Quantum Design demonstrates the absence of any secondary phase. The
physical property measurement system (PPMS). Thermopower inset shows the rocking curve with full-width-at-half-
measurements at room temperature were done using a home-built maximum (fwhm) of ∼0.12, indicating the high quality
setup with T type thermocouples. UV-visible transmission and nearly single crystalline nature of the film. The out of
reflection measurements were obtained from a Perkin-Elmer plane lattice parameter for the TCO films was
Lambda 950 spectrometer and Hitachi U-3010 spectrometer, ∼3.926-3.934 Å and the reciprocal space map (not shown
respectively. The photoluminescence (PL) data were acquired here) showed that all the films were strained in-plane to
using a setup with a 325 nm laser excitation source.
approximately the bulk STO’s lattice parameter (3.905 Å).
The observed tetragonal distortion is a clear signature of
Results and Discussion
oxygen vacancies as predicted by earlier theoretical
The electrical properties of the grown films can be calculations.16,18 Rutherford backscattering measure-
tuned from insulating to metallic based on the La doping ments show that the films contain the nominal 15% of
and growth pressure. It was observed that a critical La substituting Sr sites, maintaining a (La þ Sr)/Ti ∼ 1.
amount of La doping and oxygen vacancies are required RBS-channeling experiments on the films confirmed the
for producing a TCO and at the extreme limits of oxygen single crystalline nature, as observed by the rocking curve
vacancies, STO acts either as an insulator (very high measurements. Even though it will be interesting to learn
growth pressure or low oxygen vacancies) or a nontran- about the relationship between oxygen vacancy concen-
sparent metallic conductor (very low growth pressure or tration and growth pressure using RBS, due to the limited
high oxygen vacancies). Figure 1 shows 150 nm thick sensitivity for vacancies of lighter atoms like oxygen,
films of doped STO which are (a) insulating (0% La a reliable estimation of oxygen vacancy concentration
cannot be made.
The transmission of the various doped thin films of
(16) Luo, W.; Duan, W.; Louie, S. G.; Cohen, M. L. Phys. Rev. B. 2004, STO (corrected for the absorption of the substrate) over
70, 214109.
(17) Wunderlich, W.; Ohta, H.; Kuomoto, K. Physica B 2009, 404,
2202. (18) Astala, R.; Bristowe, P. D. Comput. Mater. Sci. 2001, 22, 81.
Article Chem. Mater., Vol. 22, No. 13, 2010 3985

Figure 2. Thin film X-ray diffraction pattern of 15% La doped STO film grown at 10-3 Torr (marked as SrTiO3). The pattern shows only peaks
corresponding to strained STO thin film apart from the substrate peaks (marked as LSAT). The inset shows the rocking curve for the (002) peak of the STO
thin film. The fwhm measured was ∼0.12, which suggests the high quality, nearly single crystalline nature of the film. The fwhm measured for the substrate
was 0.02 (not shown here).

conducting and insulating films. The insulating film

showed the maximum possible transmission over the
whole range of the spectrum. Tauc plot of the films
showed that the indirect band gap of the films was
∼3.2-3.3 eV for all the doping levels, very similar to
the bulk indirect gap of 3.27 reported in the literature.19
Figure 4b depicts the measured sheet resistance of the
TCO films as a function of transmission of the film at 600
nm. A logarithmic scaling behavior was observed between
the sheet resistance and transmission. The growth pressure
influenced the sheet resistance or transmission more than
the La doping, emphasizing the role of the oxygen vacan-
cies in forming the defect band below the conduction
Figure 3. Transmission of various 150 nm double-doped STO films on band. The resistivity, carrier concentration, and mobility
LSAT substrate over the UV-visible part of the electromagnetic spec- of the 15% La doped film grown at 10-3 Torr as a function
trum. Apart from the transparent conducting films, the plots for the
insulating (0% La grown at 10-3 Torr) and nontransparent but conduct-
of temperature are shown in Figure 4a. The resistivity fit
ing (15% La grown at 10-7 Torr) films are also shown for comparison. indicated the presence of small polaron conduction me-
chanism as reported in the literature.20 The small polaron
the whole UV-visible range of the electromagnetic spec- equation used for the fitting is shown in eq 1.
trum is shown in Figure 3. The figure clearly shows the  
2 A
transparent nature of the films with either 10 or 15% La F ∼ sinh ð1Þ
T
doping grown in the pressures ranging from 10-2 to 10-3
Torr. The transmission of the films with 15% La grown at It is interesting to note that the sample remains metallic
10-7 Torr (Figure 1c) and no La doping grown at 10-3 throughout the temperature range, implying degenerate
Torr (Figure 1a) are shown as comparison. As shown in
(19) Capizzi, M.; Frova, A. Phys. Rev. Lett. 1970, 25, 1298.
Figure 1, the nontransparent conducting samples shows (20) Liang, S.; Wang, D. J.; Sun, J. R.; Shen, B. G. Solid State Commun.
much lower transmission compared to the transparent 2008, 148, 386.
3986 Chem. Mater., Vol. 22, No. 13, 2010 Ravichandran et al.

Figure 4. (a) Resistivity, Hall carrier concentration, and Hall mobility of

the transparent conducting film with 15% La doping and grown at 10-3
Torr. The red line is the small polaron fit for the resistivity. (b) Sheet
resistance of various transparent conducting films against their transmis-
sion for an incident radiation with a wavelength of 600 nm. The dashed
line is a logarithmic fit.

doping. Hall measurements and thermopower measure-

ments (not shown here) revealed electrons as the major
transport carriers irrespective of the dopant (La or oxygen
vacancies). Due to the small polaron behavior, double-
doped STO has very low mobility (1-5 cm2 V-1 s-1) Figure 5. (a) PL spectrum for 15% La doped film grown at 10-3 Torr.
compared to conventional TCOs like Sn doped In2O3 The red arrow indicates the peak corresponding to the oxygen vacancy
(ITO), Nb doped TiO2, and Al doped ZnO (AZO), which defect band (∼ 420 nm). (b) Tauc plot for the same sample. The derived
optical indirect band gap is 3.3 eV. (c) Schematic of the optical band
have much larger mobilities (∼100 cm2 V-1 s-1). This also structure derived for the transparent conducting films. The chemical
leads to much larger sheet resistances (∼100-1000 Ω/0) as potential lies in the defect band, which is crucial for a transparent
compared to lower sheet resistances for conventional TCOs conductor.
(1-100 Ω/0) for similar transparency.21
To confirm the role of oxygen vacancies in forming the structure as mapped by these spectroscopic techniques
defect band, we performed optical spectroscopic mea- for the TCO samples.
surements, in this case, photoluminescence (PL) and
UV-visible (UV-vis) absorption. These measurements Conclusion
provide information about the optical band structure of
the material; PL and UV-vis absorption provide infor- In summary, we have demonstrated a transparent
mation about the in-gap states and band edges, respec- conducting oxide in double-doped STO over a range of
tively. The typical Tauc plot derived from UV-vis doping levels. Based on the optical band structure and
absorption and the PL spectra for 15% La doped sample transport measurements, we substantiate the forma-
grown at 10-3 Torr are shown in Figure 5. The PL tion of a defect band due to the oxygen vacancies. This
spectrum shows a peak at ∼420 nm, which indicates the defect band is the most important component of the
presence of an oxygen vacancy defect band, approxi- guiding principle behind TCO formation, as discussed
mately 2.9 eV above the valence band, as reported earlier. The filling of this band can be accurately con-
elsewhere.22 Figure 5c summarizes the optical band trolled by varying both the La doping and the oxygen
partial pressure during growth to produce a controlled
(21) Gordon, R. G. MRS Bull. 2000, 25(8), 52. TCO in the double-doped STO. Double-doped STO can
(22) Mochizuki, S.; Fujishiro, F.; Minami, S. J. Phys.: Condens. Matter
2005, 17, 923. be used in conjugation with a wide range of complex
Article Chem. Mater., Vol. 22, No. 13, 2010 3987

oxides, particularly perovskite oxides for the demonstra- Acknowledgment. We acknowledge the help of Dr. Martin
tion of various opto-electronic and photonic devices. This Gajek in hall measurements and Dr. Kin Man Yu’s help in
work also emphasizes the versatility of STO, a model RBS measurements. This work was supported by the Division
oxide system, capable of showing myriad properties of Materials Sciences and Engineering, Office of Basic Energy
relevant for various technological applications. Sciences, U.S. Department of Energy.