Appl. Phys. A 75, 629632 (2002) / Digital Object Identier (DOI) 10.

1007/s003390101140

Applied Physics A
Materials Science & Processing

Room-temperature photoluminescence in amorphous SrTiO3 the inuence of acceptor-type dopants

L.E.B. Soledade1, , E. Longo1 , E.R. Leite1 , F.M. Pontes1 , F. Lanciotti Jr.2 , C.E.M. Campos2 , P.S. Pizani2 , J.A. Varela3
1 CMDMC, LIEC, Department of Chemistry, UFSCar, Federal University of So Carlos, 13565-905, So Carlos, C. 2 Department of Physics, UFSCar, Federal University of So Carlos, So Carlos, SP, Brazil 3 CMDMC, LIEC, Institute of Chemistry, UNESP, So Paulo State University, 13560-905, Araraquara, SP, Brazil

Postal 676, SP, Brazil

Received: 20 November 2001/Accepted: 22 November 2001/Published online: 27 March 2002 Springer-Verlag 2002

Abstract. Room-temperature photoluminescence (PL) was observed in undoped and 2 mol % Cr-, Al- and Y-doped amorphous SrTiO3 thin lms. Doping increased the PL, and in the case of Cr signicantly reduced the associated PL wavelength. The optical bandgaps, calculated by means of UVvis absorption spectra, increased with crystallinity and decreased with the doping level. It was considered that yttrium and aluminum substituted Sr2+ , whereas chromium replaced Ti4+ . It is believed that luminescence centers are oxygen-decient BO6 complexes, or the same centers with some other defects, such as oxygen or strontium vacancies, or BO6 complexes with some other defects placed in their neighborhood. The character of excitation and the competition for negatively charged non-bridging oxygen (NBO) among numerous types of BO6 defect complexes in doped SrTiO3 results in various broadband luminescence peak positions. The results herein reported are an indicative that amorphous titanates are sensitive to doping, which is important for the control of the electro-optic properties of these materials. The probable incorporation of Cr into the Ti site suggests that the existence of a double network former can lead to materials displaying a more intense photoluminescence. PACS: 78.55.m; 78.55.Hx; 78.66.W; 78.66.Jg; 81.20.Fw

limited due the instability of these structures and their fragile mechanical properties. Amorphous materials of the ABO3 family (A and B are cations and O is the oxygen anion), such as BaTiO3 , PbTiO3 and SrTiO3 have recently attracted a good deal of attention due to their ferroelectric and electro-optic properties [24]. In crystalline form, ABO3 compounds are typically wide-bandgap semiconductors. Photoluminescence in crystalline titanates [5] is well known, but this property has only recently been identied in amorphous titanates synthesized at low temperatures as thin lms and powders [68]. The study of PL in ABO3 amorphous compounds, i.e. SrTiO3 thin lms, has so far been reported in only a few papers. This paper describes the characterization of intense photoluminescence observed at room temperature in amorphous SrTiO3 thin lms, either undoped or doped with Cr, Al and Y, prepared by the polymeric precursor method [911]. 1 Experimental In this method, the desired metal cations are chelated in a solution using a hydroxycarboxylic acid, such as citric acid, as the chelating agent. This solution is then mixed with a polyhydroxy alcohol, such as ethylene glycol, and heated to promote esterication reactions in the solution. The metal ions are chelated by the carboxyl groups and remain homogeneously distributed within the polymeric network. In this work, all the dopants were added in order to obtain a constant 2 mol % doping level. The viscosity of the deposition solution was adjusted to 13 mPa s by controlling the water content. The dip coating was conducted by immersing the clean glass substrates into the solutions and then pulling them up at a constant speed of 0.76 cm/min. After deposition, each layer was dried at 150 C on a hot plate for 20 min to remove residual solvents. The heat treatment was carried out in a tube furnace under oxygen ow, at a heating rate of 1 C/min at 300 C for 8 h to pyrolyze the organic materials. This temperature is sufciently high to promote polymer pyrolysis, but not crystallization. An undoped SrTiO3 thin lm was submitted to heat treatment at 550 C to promote its crystallization.

The development of new semiconductor materials with wide bandgaps (2.04.0 eV) may give rise to new optoelectronic devices, particularly to materials for application in the development of green or blue light-emission diodes (LEDs) or laser diodes. In many optoelectronic devices, amorphous semiconductors can replace single crystal semiconductors, particularly when cost is an important factor [1]. Light emission from porous silicon has been a matter of much interest since the rst observation of its visible photoluminescence (PL) at room temperature by Canham. However, the use of light-emitting structures based on porous silicon has been
Corresponding

author. (Fax: +55-16/261-5215; E-mail: plebs@iris.ufscar.br)

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The amorphous character of the lms was assessed by means of X-ray diffraction (XRD) (Siemens, D5000) using grazing incident angle. Scanning electron microscopy (Zeiss, model DSM 940-A) was used to evaluate the thickness of the lms. The UVvis absorption spectra of the doped and undoped lms were taken at room temperature, using Cary 5G equipment. The photoluminescence spectra were performed using a U 1000 JobinYvon double monochromator coupled to a cooled GaAs photomultiplier and conventional photon counting system. The 514.5 nm exciting wavelength of an argon ion laser was used. The maximum output of the laser was 500 mW and a cylindrical lens was provided to prevent the sample overheating. The slit used was 250 m. All measurements were taken at room temperature.

(d) (c) (a) (b)

2 Results and discussion The lms were deposited on the glass substrates and their thickness ranged from 200 to 650 nm (see Table 1), according to the SEM microphotographs. XRD results conrmed the amorphous structure of the undoped and doped (Cr, Al and Y) thin lms, heat treated at 300 C. No peaks were observed, neither the ones related to the presence of SrTiO3 , TiO2 or SrO, nor those indicating the presence of dopants. Heat treatment at 550 C under oxygen ow was sufcient to display the peaks characteristic of crystalline SrTiO3 , see Fig. 1. In Fig. 1, as the amorphous lms presented very similar diffractograms, they are represented by 2 mol % Cr-doped amorphous SrTiO3 .

Fig. 2. Effect of the addition of dopants on the thickness-normalized PL spectra of amorphous SrTiO3 thin lms. Excitation with the 514.5 nm line of an argon ion laser: (a) undoped; (b) 2 mol % Al-doped; (c) 2 mol % Cr-doped; (d) 2 mol % Y-doped

Table 1. Maximum normalized PL intensity and the corresponding wavelength of undoped and Y-, Al- and Cr-doped SrTiO3 lms SrTiO3 thin lm Film thickness (nm) Wavelength of maximum normalized intensity (nm) 583 575 562 578 Maximum normalized intensity (a.u.)

2 mol % Y-doped 2 mol % Al-doped 2 mol % Cr-doped Undoped

200 350 350 650

3.8 3.9 2.4 1.9

Fig. 1. X-ray diffractogram of crystalline and amorphous SrTiO3 lms. Upper graph: Undoped crystalline SrTiO3 lm, heat treated at 550 C. Lower graph: Amorphous 2 mol % Cr-doped SrTiO3 lm, heat treated at 300 C

Figure 2 displays the PL spectra of all four amorphous lms excited with the 514.5 nm line. The photoluminescence intensity values obtained were normalized for the thickness presented in Table 1 and calculated as intensity per unit thickness. It should also be noted that all the dopants increased the photoluminescence of the undoped SrTiO3 . The next in the rank of normalized PL intensity was the chromium-doped lm and the Al and the Y doped lms presented the highest PL intensities. These PL intensities are also shown in Table 1, as well as their corresponding wavelengths. Doping with chromium was shown to signicantly reduce the wavelength, i.e. increase the energy corresponding to maximum PL intensity. The other dopants seemed to have only a slight effect thereon. A conrmatory PL study was carried out at 457.9 nm excitation wavelength, using a maximum output of 40 mW, in which the PL spectra were only taken for the three doped lms. Although some oscillation was observed in terms of the normalized intensities, the order of the maximum peak wavelength was the same in both cases: the Cr-doped lm presented the smaller wavelength, followed respectively by Al- and Y-doped lms. The PL spectra of the Cr-doped thin lm, taken as example, as a function of the exciting wavelength (457.9 and 514.5 nm) are shown in Fig. 3a. The Stokes shift is about 35 nm and the same behavior was observed for the Al- and the Y-doped lms. Figure 4 displays the UVvis spectra of the thin lms. The primary transmittance values of the amorphous lms (doped or undoped) are also quite similar and therefore they were represented in this gure by the 2 mol % Al-doped SrTiO3 lm. These data were transformed to absorbance data, by means of Lamberts law and the known thickness of each individual lm (Table 1). As stated by Wood and Tauc [12], the absorbance photon energy curve can be divided into three regions, A, B and C, respectively, for high, medium and low photon energies. In this work, the UVvis absorption spectra of the thin lms agreed with the pattern previously described by Wood

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Fig. 3. Normalized photoluminescence spectra of an amorphous 2 mol % Cr-doped SrTiO3 thin lm at different irradiation wavelengths

Fig. 5. Determination of the optical bandgap of a SrTiO3 thin lm, amorphous and crystalline. The bandgap was deduced by extrapolation of the straight line region of the plot of the Th index against photon energy (eV). The Th index is the square root of the product of absorbance (in cm1 ) and photon energy (in eV)

(a) (b)

Table 2. Energy constant data obtained from UVvisible absorption spectra Dopant Heat treatment temperature ( C) 300 300 300 300 550 Eg (eV) 3.66 3.64 3.66 3.71 3.73 E1 (eV) 0.2 0.26 0.2 0.19 Et (eV) 1.51 1.12 1.21 1.52

2 mol % Al 2 mol % Cr 2 mol % Y Undoped (amorphous) Undoped (crystalline)

Fig. 4. UVvisible transmittance spectra of SrTiO3 thin lms. (a) Undoped crystalline SrTiO3 lm heat treated at 550 C. (b) Amorphous 2 mol % Crdoped SrTiO3 lm heat treated at 300 C

and Tauc [12], allowing us to follow their procedure for calculating the three energy constants for each lm. Figure 5 displays for each lm, the region A, in which the square root of the product of the absorbance (in cm1 ) and photon energy (in eV) varies linearly with the photon energy. The optical energy gap, E g (eV), was obtained from this gure by extrapolating the straight lines at high energies to the x-axis. These values are displayed in Table 2. The absorbance increases exponentially with the photon energy in regions B and C, previously described. E 1 (eV) is the energy constant that represents region B, whereas E t (eV) describes region C [12]. These values were calculated from the absorbance curves and are also displayed in Table 2. The optical bandgaps obtained for the thin lms (Table 2) decreased with doping and increased with crystallinity, as one might expect. The value for undoped crystalline SrTiO3 , 3.73 eV, agrees with the value of about 3.7 obtained by Thielsch and co-workers [13], but is higher than the 3.43 eV reported by Kamalasanan et al. [14]. Different thin lm processing methods may be responsible for differences like these in the optical bandgaps.

Ab initio quantum mechanics calculations on titanates of the ATiO3 type, cited by Leite [7], suggest that the chemical bond between titanium and oxygen (TiO) has a highly covalent character, while the bond between the A cation and oxygen is basically ionic. This result, coupled to SAED and XANES results, led Leite [16] to suggest that the amorphous titanate is formed by a TiO network. The charge of the A cation must be compensated by negatively charged nonbridging oxygen (NBO). Besides NBO, other defects can be present in the amorphous structure, such as oxygen vacancies. The photoluminescence in amorphous titanates, such as PbTiO3 , was explained by Leite and co-workers [7]. They studied the structure of amorphous PbTiO3 by means of XANES spectroscopy. They found that these amorphous compounds are formed basically through sixfold oxygenTi coordination (TiO6 octahedra) and vefold oxygenTi coordination (TiO5 square-base pyramids). They also pointed out that the TiO5 square-base pyramid structure, to which the photoluminescence was related, is not found in wellcrystallized titanates. Akhtar and co-workers [15] performed a theoretical study on SrTiO3 defects. They studied the undoped SrTiO3 and found that the main defects were Schottky or Schottky-like defects. They also studied the effect of dopants and different mechanisms were presented for different dopants. For instance, for monovalent and divalent dopants, they concluded that their substitution of Sr2+ needed to be compensated for by the formation of oxygen vacancies in the former (monova-

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lent) case. Tetravalent dopants substituted either Sr2+ or Ti4+ according to the ion radius. Higher valence dopants were not studied. The composition disordering of SrTiO3 is caused by nonstoichiometric content of SrO, presence of vacancies, modiers and site-to-site disordering in the B sub-lattice. Al3+ or Y3+ replace Sr2+ in A sites of the crystal structure. The charge equilibrium is maintained by the creation of lattice vacancies on B sites and by releasing some SrO [16]. At the same time, according to ESR data on the related ABO3 compounds with, for example, BaTiO3 [17], PZT [18, 19] and PLZT : Mn [20], the charge compensation results in the appearance of Ti3+ in the B octahedral position. The Cr impurity is usually placed also in the B site, not only as Cr3+ but sometimes also as Cr5+ in PbTiO3 [21], BaTiO3 [22] and PT [7, 8]. Pure amorphous SrTiO3 of ABO3 structure gives luminescence due to ions at A and B sites. In addition, the presence of color centers should be considered (including vacancies of VO , VSr , etc.), donor-acceptor pairs and impurity (Y, Al and Cr) centers. These occupy either the substitutional site in [AO12 ] or [BO6 ] complexes and/or interstitial sites. In the case of chromium impurities in perovskite (SrTiO3 ), one chromium ion substitutes a titanium ion to form an octahedral CrO6 complex, but the other ion substitutes a titanium ion in a different octahedron, forming a CrO5 complex plus an oxygen vacancy, VO . If these two different structures coexist in the amorphous material, the charge of two holes is compensated by one oxygen vacancy. This model should also be applicable for the case of Al3+ or Y3+ substituting Sr2+ sites in an [AO12 ] complex. If Cr3+ ions substitute the Ti4+ site or if Al3+ or Y3+ ions substitute the Sr2+ site, the presence of the [CrO6 ] and [CrO5 VO ] complexes or [AlO12 VSr ] and [YO12 VSr ] complexes will stabilize defect domains by charge compensation. It is believed that luminescence centers are oxygendecient BO6 complexes, or the same centers with some other defects, or BO6 complexes with some other defects placed in their neighborhood. The character of excitation and the competition for negatively charged non-bridging oxygen (NBO) among numerous types of BO6 defect complexes in doped SrTiO3 results in various broadband luminescence peak positions.

and the unbalancing of the electronic density in the structure of this system will lead to an increase in the number of NBOs (non-bridging oxygens). The results herein reported are an indication that amorphous titanates are sensitive to doping, which is important for the control of the electro-optic properties of these materials. The probable incorporation of Cr into the Ti site suggests that the existence of a double network former can lead to materials displaying a more intense photoluminescence.
Acknowledgements. The authors wish to thank the Brazilian agencies FAPESP/CEPID, CAPES and CNPq/PRONEX for their nancial support.

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3 Summary In summary, the structure of the amorphous SrTiO3 lms studied can be understood by similarity to amorphous PT [7],