Role of growth temperature and oxygen partial pressure on the structural and electrical properties of pulsed laser deposited La1−xSrxnO3−δ thin films

The paper presents the fabrication and characterization of La_0.65Sr_0.35MnO_3−δ (LSMO) polycrystalline thin films deposited directly on Si (1 0 0) substrates using pulsed laser deposition technique. Various deposition parameters like substrate temperature and oxygen partial pressure have been varied systematically to obtain stoichiometric, crack-free films with smooth surface morphology having nearly monodisperse grain size distribution. The substrate temperature variation from 600 to 800 °C had profound effects on the microstructure and topography of the deposited film, with optimum result being obtained at 700 °C. The variation of partial pressure of oxygen controls the deposition kinetics as well as the stoichiometry of the film in terms of oxygen vacancy, which influences the magnetic and electrical transport properties of the manganate films. The microstructure and crystallinity of the deposited films have been studied using X-ray diffraction, scanning electron microscopy and atomic force microscopy. A correlation between the oxygen stoichiometry and micro-structural and transport properties of the deposited films has been obtained.     

Modulating microstructure and optical properties of hydrogenated nanocrystalline silicon photovoltaic materials prepared under hydrogen diluted silane PECVD by various DC bias

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films were fabricated by plasma enhanced chemical vapor deposition under the various negative substrate bias voltages with hydrogen as a diluent of silane. The microstructure and optical properties of nc-Si:H thin films were studied by Raman scattering spectroscopy, X-ray diffraction (XRD), transmission electron microscopy, and optical transmission spectroscopy. Raman spectra and XRD pattern reveal that applying negative bias voltages at the moderate level favors the enhancement of crystalline volume fraction, increase of crystallite sizes and decrease of residual stress. We also demonstrated that the negative direct current bias can be used to modulate the volume fraction of voids, refractive index, absorption coefficient, compactness and ordered degree of nc-Si:H films. It is found that the film deposited at −80 V shows not only high crystallinity, size of crystallite, and static index n₀ but also low residual stress and volume fraction of voids. Furthermore, the microstructural evolution mechanism of nc-Si:H thin films prepared at different bias voltages is tentatively explored.     

RETRACTED ARTICLE: Hydrogenated nanocrystalline silicon germanium thin films

Hydrogenated nanocrystalline silicon germanium thin films (nc-SiGe:H) is an interesting alternative material to replace hydrogenated nanocrystalline silicon (nc-Si:H) as the narrow bandgap absorber in an a-Si/a-SiGe/nc-SiGe(nc-Si) triple-junction solar cell due to its higher optical absorption in the wavelength range of interest. In this paper, we present results of optical, structural investigations and electrical characterization of nc-SiGe:H thin films made by hot-wire chemical vapor deposition (HW-CVD) with a coil-shaped tungsten filament and with a disilane/germane/hydrogen gas mixture. The optical band gaps of a-SiGe:H and nc-SiGe:H thin-films, which are deposited with the same disilane/germane/hydrogen gas mixture ratio of 3.4 : 1.7 : 7, are about 1.58 eV and 2.1 eV, respectively. The nc-SiGe:H thin film exhibits a larger optical absorption coefficient of about 2–4 in the 600–900 nm range when compared to nc-Si:H thin film. Therefore, a thinner nc-SiGe:H layer of ∼500 nm thickness may be sufficient for the narrow bandgap absorber in an a-Si based multiple-junction solar cell. We enhanced the transport properties as measured by the photoconductivity frequency mixing technique. These improved alloys do not necessarily show an improvement in the degree of structural heterogeneity on the nanometer scale as measured by smallangle X-ray scattering. Decreasing both the filament temperature and substrate temperature produced a film with relatively low structural heterogeneity while photoluminescence showed an order of magnitude increase in defect density for a similar change in the process.      

Infrared optical properties of Ba(Zr0.20Ti0.80)O3 and Ba(Zr0.30Ti0.70)O3 thin films prepared by sol-gel method

Ba(Zr_xTi_1−x)O₃ (BZT) (x = 0.20 and 0.30) thin films are deposited on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrate by sol-gel method. X-ray diffraction patterns show that the thin films have a good crystallinity. Optical properties of the films in the wavelength range of 2.5-12 μm are studied by infrared spectroscopic ellipsometry (IRSE). The optical constants of the BZT thin films are determined by fitting the IRSE data using a classical dispersion formula. As the wavelength increases, the refractive index decreases, while the extinction coefficients increase. The effective static ionic charges are derived, which are smaller than that in a purely ionic material for the BZT thin films.     

Effect of oxygen pressure on structure and properties of Bi1.5Zn1.0Nb1.5O7 pyrochlore thin films prepared by pulsed laser deposition

The Bi₂O₃-ZnO-Nb₂O₅ (BZN) cubic pyrochlore thin films were prepared on Pt/TiO₂/SiO₂/Si(1 0 0) substrates by using pulsed laser deposition process. The oxygen pressure was varied in the range of 5-50 Pa to investigate its effect on the structure and dielectric properties of BZN thin films. It is found that oxygen pressure during deposition plays an important role on structure and other properties of BZN films. The BZN films deposited at temperature of 650 °C and at O₂ pressure of 5 Pa have an amorphous BZN and Nb₂O₅ phases but exhibits a cubic pyrochlore structure with a preferential (2 2 2) orientation when the oxygen pressure increases to 10 Pa. Dielectric constant and loss tangent of the films deposited at 10 Pa are 185 and 0.0008 at 10 kHz, respectively. The dielectric tunability is about 10% at a dc bias field of 0.9 MV/cm.     

Influence of Si substrate preparation on surface chemistry and morphology of L-CVD SnO2 thin films studied by XPS and AFM

Results of experimental studies of the influence of substrate preparation on the surface chemistry and surface morphology of the laser-assisted chemical vapour deposition (L-CVD) SnO₂ thin films are presented in this paper. The native Si(1 0 0) substrate cleaned by UHV thermal annealing (TA) as well as thermally oxidized Si(1 0 0) substrate cleaned by ion bombardment (IBA) have been used as the substrates. X-ray photoemission spectroscopy (XPS) has been used for the control of surface chemistry of the substrates as well as of deposited films. Atomic force microscopy (AFM) has been used to control the surface morphology of the L-CVD SnO₂ thin films deposited on differently prepared substrates. Our XPS shows that the L-CVD SnO₂ thin films deposited on thermally oxidized Si(1 0 0) substrate after cleaning with ion bombardment exhibit the same stoichiometry, i.e. ratio [O]/[Sn] = 1.30 as that of the layers deposited on Si(1 0 0) substrate previously cleaned by UHV prolonged heating. AFM shows that L-CVD SnO₂ thin films deposited on thermally oxidized Si(1 0 0) substrate after cleaning with ion bombardment exhibit evidently increasing rough surface topography with respect to roughness, grain size range and maximum grain height as the L-CVD SnO₂ thin films deposited on atomically clean Si substrate at the same surface chemistry (nonstoichiometry) reflect the higher substrate roughness after cleaning with ion bombardment.     

Photoluminescence in amorphous (PbLa)TiO3 thin films deposited on different substrates

Pb_1−XLa_XTiO₃ thin films, (X=0.0; 13 and 0.27 mol%) were prepared by the polymeric precursor method. Thin films were deposited on Pt/Ti/SiO₂/Si (1 1 1), Si (1 0 0) and glass substrates by spin coating, and annealed in the 200-300°C range in an O₂ atmosphere. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used for the microstructural characterization of the thin films. Photoluminescence (PL) at room temperature has been observed in thin films of (PbLa)TiO₃. The films deposited on Pt/Ti/SiO₂/Si substrates present PL intensity greater than those deposited on glass and silicon substrates. The intensity of PL in these thin films was found to be dependent on the thermal treatment and lanthanum molar concentration.     

Quantum emission efficiency of nanocrystalline and amorphous Si quantum dots

The paper presents the comparison of emission efficiencies for crystalline Si quantum dots (QDs) and amorphous Si nanoclusters (QDs) embedded in hydrogenated amorphous (a-Si:H) films grown by the hot wire-CVD method (HW-CVD) at the variation of technological parameters. The correlations between the intensities of different PL bands and the volumes of Si nanocrystals (nc-Si:H) and/or an amorphous (a-Si:H) phase have been revealed using X-ray diffraction (XRD) and photoluminescence (PL) methods. These correlations permit to discuss the PL mechanisms in a-Si:H films with embedded nc-Si QDs. The QD parameters of nc-Si:H and a-Si:H QDs have been estimated from PL results and have been compared (for nc-Si QDs) with the parameters obtained by the XRD method. Using PL and XRD results the relations between quantum emission efficiencies for crystalline (η_cr) and amorphous (η_am) QDs have been estimated and discussed for all studied QD samples. It is revealed that a-Si:H films prepared by HW-CVD with the variation of wire temperatures are characterized by better passivation of nonradiative recombination centers in comparison with the films prepared at the variation of substrate temperatures or oxygen flows.     

Study of structural and optical properties of ZnO films grown by pulsed laser deposition

Wurtzite zinc oxides films (ZnO) were deposited on silicon (0 0 1) and corning glass substrates using the pulsed laser deposition technique. The laser fluence, target-substrate distance, substrate temperature of 300 °C were fixed while varying oxygen pressures from 2 to 500 Pa were used. It is observed that the structural properties of ZnO films depend strongly on the oxygen pressure and the substrate nature. The film crystallinity improves with decreasing oxygen pressure. At high oxygen pressure, the films are randomly oriented, whereas, at low oxygen pressures they are well oriented along [0 0 1] axis for Si substrates and along [1 0 3] axis for glass substrates. A honeycomb structure is obtained at low oxygen pressures, whereas microcrystalline structures were obtained at high oxygen pressures. The effect of oxygen pressure on film transparency, band gap E_g and Urbach energies was investigated.     

Substrate effect on electronic sputtering yield in polycrystalline fluoride (LiF, CaF2 and BaF2) thin films

Influence of substrate on electronic sputtering of fluoride (LiF, CaF₂ and BaF₂) thin films, 10 and 100 nm thin, under dense electronic excitation of 120 MeV Ag²⁵⁺ ions irradiation is investigated. The sputtering yield of the films deposited on insulating (glass) and semiconducting (Si) substrates are determined by elastic recoil detection analysis technique. Results revealed that sputtering yield is higher, up to 7.4 × 10⁶ atoms/ion for LiF film on glass substrate, than that is reported for bulk materials/crystals (∼10⁴ atoms/ion), while a lower value of the yield (2.3 × 10⁶ atoms/ion) is observed for film deposited on Si substrate. The increase in the yield for thin films as compared to bulk material is a combined effect of the insulator substrate used for deposition and reduced film dimension. The results are explained in the framework of thermal spike model along with substrate and size effects in thin films. It is also observed that the material with higher band gap showed higher sputtering yield.     

Selective MOCVD of titanium oxide and zirconium oxide thin films using single molecular precursors on Si(1 0 0) substrates

Titanium oxide (TiO₂) and zirconium oxide (ZrO₂) thin films have been deposited on modified Si(1 0 0) substrates selectively by metal-organic chemical vapor deposition (MOCVD) method using new single molecular precursor of [M(OⁱPr)₂(tbaoac)₂] (M=Ti, Zr; tbaoac=tertiarybutyl-acetoacetate). For changing the characteristic of the Si(1 0 0) surface, micro-contact printing (μCP) method was adapted to make self-assembled monolayers (SAMs) using an octadecyltrichlorosilane (OTS) organic molecule which has -CH₃ terminal group. The single molecular precursors were prepared using metal (Ti, Zr) isopropoxide and tert-butylacetoacetate (tbaoacH) by modifying standard synthetic procedures. Selective depositions of TiO₂ and ZrO₂ were achieved in a home-built horizontal MOCVD reactor in the temperature range of 300-500 °C and deposition pressure of 1×10⁻³-3×10⁻² Torr. N₂ gas (5 sccm) was used as a carrier gas during film depositions. TiO₂ and ZrO₂ thin films were able to deposit on the hydrophilic area selectively. The difference in surface characteristics (hydrophobic/hydrophilic) between the OTS SAMs area and the SiO₂ or Si-OH layer on the Si(1 0 0) substrate led to the site-selectivity of oxide thin film growth.     

Optical characterization and microstructure of BaTiO3 thin films obtained by RF-magnetron sputtering

BaTiO₃ thin films were deposited on Pt/Ti/SiO₂/Si by rf planar-magnetron sputtering. The films thickness increases with the decrease of both deposition pressure and sample-discharge centre distance. The films annealed at 900 °C, for 8 h, present direct band gap energy ranged between 3.57 and 3.59 eV. The dependence of the structure and microstructure (texture, degree of crystallinity), as well as of the optical characteristics on the deposition parameters, was analysed. Using spectroscopic ellipsometry (SE) measurements coupled with the Bruggeman Effective Medium Approximation (B-EMA), the layer structure and the surface roughness, were determined. The root mean square roughness values of the surface layer, estimated by atomic force microscopy (AFM) analyses, are ranged between 10 and 20 nm and were in good agreement with SE data.The obtained films have tetragonal unit cell and show densely packed, non-columnar morphology and hexagon-like crystallite shape.     

Properties of a-Si:H films deposited by RF magnetron sputtering at 95 °C

In this work we have investigated the dependence of optical and electrical properties of RF sputtered undoped a-Si:H films and B or P doped a-Si:H films on hydrogen flow rate (F_H). Low deposition temperature of 95 °C was used, a process compatible with low-cost plastic substrates. FTIR spectroscopy and ESR measurements were used for the investigation of Si-H_x bonding configurations, and concentrations of hydrogen and dangling bonds. We found that there is a strong correlation between the total hydrogen concentration, the dangling bonds density and the optoelectronic properties of the films. The best photosensitivity value was found to be 1.4 × 10⁴ for the undoped films. The dark conductivity (σ_D) of the doped layers varied from 5.9 × 10⁻⁸ to 6.5 × 10⁻⁶ (Ω cm)⁻¹ for different ratios F_Ar/F_H. These variations are attributed to both the different B and P concentrations in the films (according to SIMS measurements) and the enhanced disorder of the films introduced by the large number of inactive impurities. The B doping efficiency is lower compared to the P one. A small photovoltaic effect is also observed in n-i-p solar cells fabricated on polyimide (PI) substrates having ITO as antireflective coating, with an efficiency of 1.54%.     

Luminescent characteristics of CaTiO3:Pr thin films prepared by pulsed laser deposition method with various substrates

CaTiO₃:Pr³⁺ films were deposited on different substrates such as Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica using pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by XRD and SEM measurements. The films grown on the different substrates have different crystallinity and morphology. The FWHM of (2 0 0) peak are 0.18, 0.25, 0.28, and 0.30 for Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica, respectively. The grain sizes of phosphors grown on different substrates were estimated by using Scherrer's formula and the maximum crystallite size observed for the thin film grown on Al₂O₃ (0 0 0 1). The room temperature PL spectra exhibit only the red emission peak at 613 nm radiated from the transition of (¹D₂ → ³H₄) and the maximum PL intensity for the films grown on the Al₂O₃ (0 0 0 1) is 1.1, 1.4, and 3.7 times higher than that of the CaTiO₃:Pr³⁺ films grown on MgO (1 0 0), Si (1 0 0), and fused Sillica substrates, respectively. The crystallinity, surface morphology and luminescence spectra of thin-film phosphors were highly dependent on substrates.     

Epitaxial growth of Ba8Ga16Ge30 clathrate film on Si substrate by RF helicon magnetron sputtering with evaluation on thermoelectric properties

Epitaxial Ba₈Ga₁₆Ge₃₀ clathrate thin films were successfully grown on Si substrate by using helicon magnetron sputtering. The (1 0 0) lattice of Ba₈Ga₁₆Ge₃₀ was identified grown on four Si(2 0 0) lattices in small mismatch (0.1%). Both the color of samples and XRD results suggest 600 °C is the optimal substrate temperature for the growth of high quality Ba-Ga-Ge clathrate film on Si substrates. High Seebeck coefficients and electrical resistivities for the deposited clathrate thin films in comparison with those of bulk are obtained. The high crystal quality and thermionic effects in heterostructures may contribute to the larger Seebeck coefficients, while the increasing of interface scattering for electrons probably is the reason for large electrical resistivities. Although the thermoelectric (TE) results are not ideal as designed, our results are significant due to the first successful work on epitaxial growth of Ba₈Ga₁₆Ge₃₀ clathrate thin films on Si substrate with large Seebeck coefficient.     

Nanocrystalline formation and optical properties of germanium thin films prepared by physical vapor deposition

Amorphous and nanocrystalline germanium thin films were prepared on glass substrates by physical vapor deposition (PVD). The influence of thermal annealing on the characteristics of the Ge thin films has been investigated. X-ray diffraction (XRD) and SEM show amorphous structure of films deposited at room temperature. After thermal annealing, the crystallinity was improved when the annealing temperature increases. The Ge thin films annealed at different temperatures in air were nanocrystalline, having the face-centered cubic structure with preferred orientation along the 〈1 1 1〉 direction. The nanostructural parameters have been evaluated by using a single-order Voigt profile analysis. Moreover, the analysis of the optical transmission and reflection behavior was carried out. The values of direct and indirect band gap energies for amorphous and nanocrystalline phases are 0.86±0.02, 0.65±0.02 and 0.79±0.02, 0.61±0.02 eV, respectively. In addition, the complex optical functions for the wavelength range 600-2200 nm are reported. The refractive index of the nanocrystalline phase drops from 4.80±0.03 to 2.04±0.02, and amorphous phase changes from 5.18±0.03 to 2.42±0.02 for the whole wavelength range. The dielectric functions ε₁ and ε₂ of the deposited films were recorded as a function of wavelength within the range from 600 to 2200 nm.     

Fabrication of p-type ZnMgO films via pulsed laser deposition method by using Li as dopant source

p-Type Zn_0.9Mg_0.1O thin films have been realized via monodoping of Li acceptor by using pulsed laser deposition. The Li-doped Zn_0.9Mg_0.1O thin films possessed a good crystallinity with a (0 0 0 2) preferential orientation and a high transmittance in the visible region. Secondary ion mass spectroscopy revealed that Li has been successfully incorporated into the Zn_0.9Mg_0.1O films. The obtained films with the best electrical properties show a hole concentration in the order of 10¹⁷ cm⁻³ and a room-temperature resistivity in the range of 58-72 Ω cm.     

Effect of deposition temperature on orientation and electrical properties of (K0.5Na0.5)NbO3 thin films by pulsed laser deposition

Lead-free ferroelectric K_0.5Na_0.5NbO₃ (KNN) thin films have been prepared on Pt/TiO₂/SiO₂/Si substrates by pulsed laser deposition process. The structures, crystal orientations and electrical properties of thin films have been investigated as a function of deposition temperature from 680 °C to 760 °C. It is found that the deposition temperature plays an important role in the structures, crystal orientations and electrical properties of thin films. The crystallization of thin films improves with increasing deposition temperature. The thin film deposited at 760 °C exhibits strong (0 0 1) preferential orientation, large dielectric constant of 930 and the remnant polarization of 8.54 μC/cm².     

Effect of post-annealing temperature on the microstructure and magnetic properties of Ce:YIG thin films deposited on Si substrates

Amorphous Ce₁Y₂Fe₅O₁₂ (Ce:YIG) thin films deposited on single crystal Si(1 0 0) and thermally oxidized Si(1 0 0) substrates by pulsed laser deposition were annealed in the temperature range of 700-1000 °C in air. The annealing temperature dependence of microstructure and magnetic properties of Ce:YIG films was studied using X-ray diffraction combined with vibrating sample magnetometer. The results show that single phase of polycrystalline Ce:YIG thin films can be obtained by the post-annealing of as-deposited films at the temperature of 700 °C. However, two steps of phase segregation of Ce:YIG occur as the post-annealing temperature increases: at first, Ce:YIG is decomposed into YIG and non-magnetic CeO₂ when annealed at 800 °C; then YIG continues to be decomposed forming Fe₂O₃ when the temperature is increased up to 900 °C. Consequently, the saturation magnetization of Ce:YIG films decreases first and then increases with the post-annealing temperature going up, which indicates that the saturation magnetization of Ce:YIG films is mainly related to the phase composition of the films. Meanwhile, the presence of SiO₂ buffer layer can significantly enhance the saturation magnetization of Ce:YIG films.     

Synthesis and materials properties of transparent conducting In2O3 films prepared by sol-gel-spin coating technique

Transparent conducting indium oxide (In₂O₃) thin films have been prepared on glass substrates by the simple sol-gel-spin coating technique. These films have been characterized by X-ray diffraction, resistivity and Hall effect measurements, optical transmission, scanning electron microscopy and atomic force microscopy for their structural, electrical, optical and morphological properties. The influence of spin parameters, number of coating, process temperature on the quality of In₂O₃ films are studied. In the operating range of deposition, 400-475 °C, all the films showed predominant (2 2 2) orientation. Films deposited at optimum process conditions exhibited a resistivity of 2×10⁻² Ω cm along with the average transmittance of about 80% in the visible spectral range (400-700 nm).