Giant pyroelectric coefficient of Mn-doped PLT thin films epitaxially grown on (001) Pt/MgO

The c-axis-oriented epitaxial thin films of Mn-doped Pb_1−xLa_xTi_1−x/4O₃ (PLT) on (001) Pt/MgO substrates were prepared by rf-magnetron sputtering. To investigate the effect of the doped ion, 0-1.7 mol% MnO₂ added to the PLT target powder. The temperature dependence of the relative dielectric constant ?_r measurements and modified Curie-Weiss plots suggested that the increasing of diffuseness n was induced by high-La substitution and the diffuseness n of PLT thin films decreased by the addition of Mn, considerably. Inner stress and thermodynamic analysis were carried out and the results propose that the increasing of γ with Mn doping caused by increasing the misfit strain of the c-axis-oriented epitaxial PLT thin films and substrate. As a result, giant pyroelectric coefficient (γ = 15.8 × 10⁻⁸ C/cm² K) of Mn-doped epitaxial PLT thin film was achieved.     

Optical and ferromagnetic characteristics of Mn doped ZnO thin films grown by filtered cathodic vacuum arc technique

Mn doped ZnO (ZnO:Mn) thin films with ~ 10 at.% of Mn were grown on quartz substrates by filtered cathodic vacuum arc (FCVA) technique at low substrate temperature (≤ 200 °C). The influence of substrate temperature and oxygen flow rate on the optical, electrical and magnetic properties of the ZnO:Mn thin films was studied. Both room temperature ferromagnetism and ultraviolet photoluminescence were observed in all films. A maximum saturation moment of 2.9 × 10⁻²⁴ A m²/Mn can be achieved for the films grown in an optimum condition. This suggests that the fabrication of high-quality ZnO:Mn films by FCVA technique has the potential to realize efficient magneto-optic devices operating at ultraviolet regime.     

Effect of lattice matching on microstructure and electrical conductivity of epitaxial ARuO3 (A = Sr, Ca and Ba) thin films prepared on (001) LaAlO3 substrates by laser ablation

(001) SrRuO₃ (SRO), (001) CaRuO₃ (CRO) and (205) BaRuO₃ (BRO) thin films were epitaxially grown on (001) LaAlO₃ substrates by laser ablation, and the effect of lattice matching on the microstructure and electrical conductivity was investigated. (001) SRO and (001) CRO thin films had a terrace with orthogonal step structure, whereas (205) BRO thin film had an orthogonal structure with tetragonal grains. Epitaxial thin films showed metallic conduction, and the (001) CRO thin films exhibited the highest electrical conductivity, i.e. 1.5 × 10⁵ S m^− 1, among the (001) SRO, (001) CRO and (205) BRO thin films. The smaller misfit between thin film and substrate could be associated with the higher electrical conductivity.     

Effect of dopant concentration on the structural, electrical and optical properties of Mn-doped ZnO films

The Mn-doped ZnO (Zn_1 − xMn_xO) thin films with manganese compositions in the range of 0-8 at.% were deposited by radio-frequency (RF) magnetron sputtering on quartz glass substrates at room temperature (RT). The influence of Mn concentration on the structural, electrical and optical properties of Zn_1 − xMn_xO films has been investigated. X-ray diffraction (XRD) measurements reveal that all the films are single phase and have wurtzite structure with (002) c-axis orientation. The chemical states of Mn have been identified as the divalent state of Mn²⁺ ions in ZnO lattice. As the content of Mn increases, the c-lattice constant and the optical band gap of the films increase while the crystalline quality deteriorates gradually. Hall-effect measurements reveal that all the films are n-type and the conductivity of the films has a severe degradation with Mn content. It is also found that the intensity of RT photoluminescence spectra (PL) is suppressed and saturates with Mn doping.     

Preparation and characterization of Mn-doped BaTiO<Subscript>3</Subscript> thin films by magnetron sputtering

Barium titanate (BaTiO₃) thin films doped with Mn (0.1–1.0 at%) were prepared by r.f. magnetron sputtering technique. Oxygen/argon (O₂/Ar) gas ratio is found to influence the sputtering rate of the films. The effects of Mn doping on the structural, microstructural and electrical properties of BaTiO₃ thin films are studied. Mn-doped thin films annealed at high temperatures (700 °C) exhibited cubic perovskite structure. Mn doping is found to reduce the crystallization temperature and inhibit the grain growth in barium titanate thin films. The dielectric constant increases with Mn content and the dielectric loss (tan δ) reveals a minimum value of 0.0054 for 0.5% Mn-doped BaTiO₃ films measured at 1 MHz. The leakage current density decreases with Mn doping and is 10⁻¹¹ A/cm⁻² at 6 kV/cm for 1% Mn-doped thin films.     

Transparent p-AgCoO2/n-ZnO diode heterojunction fabricated by pulsed laser deposition

Transparent diode heterojunction on ITO coated glass substrates was fabricated using p-type AgCoO₂ and n-type ZnO films by pulsed laser deposition (PLD). The PLD of AgCoO₂ thin films was carried out using the pelletized sintered target of AgCoO₂ powder, which was synthesized in-house by the hydrothermal process. The band gap of these thin films was found to be ∼ 3.89 eV and they had transmission of ∼ 55% in the visible spectral region. Although Hall measurements could only indicate mixed carrier type conduction but thermoelectric power measurements of Seebeck coefficient confirmed the p-type conductivity of the grown AgCoO₂ films. The PLD grown ZnO films showed a band gap of ∼ 3.28 eV, an average optical transmission of ∼ 85% and n-type carrier density of ∼ 4.6 × 10¹⁹ cm^− 3. The junction between p-AgCoO₂ and n-ZnO was found to be rectifying. The ratio of forward current to the reverse current was about 7 at 1.5 V. The diode ideality factor was much greater than 2.     

Lead-free piezoelectric thin films of Mn-doped NaNbO3-BaTiO3 fabricated by chemical solution deposition

Lead-free piezoelectric thin films of NaNbO₃-BaTiO₃ were fabricated on Pt/TiO_x/SiO₂/Si substrates by chemical solution deposition. Perovskite NaNbO₃-BaTiO₃ single-phase thin films with improved leakage-current and ferroelectric properties were prepared at 650 °C by doping with a small amount of Mn. The 1.0 and 3.0 mol% Mn-doped 0.95NaNbO₃-0.05BaTiO₃ thin films showed slim ferroelectric P-E hysteresis and field-induced strain loops at room temperature. The 1.0 and 3.0 mol% Mn-doped 0.95NaNbO₃-0.05BaTiO₃ films showed remanent polarization values of 6.3 and 6.2 μC/cm², and coercive field of 41 and 55 kV/cm, respectively. From the slope of the field-induced strain loop, the effective piezoelectric coefficient (d₃₃) was found to be 40-60 pm/V.     

Annealing effect on dielectric and leakage current characteristics of Mn-doped Ba0.6Sr0.4TiO3 thin films as gate insulators for low voltage ZnO thin film transistor

We report on the dielectric properties and leakage current characteristics of 3 mol% Mn-doped Ba_0.6Sr_0.4TiO₃ (BST) thin films post-annealed up to 600 °C following room temperature deposition. The suitability of 3 mol% Mn-doped BST films as gate insulators for low voltage ZnO thin film transistors (TFTs) is investigated. The dielectric constant of 3 mol% Mn-doped BST films increased from 24 at in-situ deposition up to 260 at an annealing temperature of 600 °C due to increased crystallinity and the formation of perovskite phase. The measured leakage current density of 3 mol% Mn-doped BST films remained on the order of 5 × 10^− 9 to 10^− 8 A/cm² without further reduction as the annealing temperature increased, thereby demonstrating significant improvement in the leakage current characteristics of in-situ grown Mn-doped BST films as compared to that (5 × 10^− 4 A/cm² at 5 V) of pure BST films. All room temperature processed ZnO-TFTs using a 3 mol% Mn-doped BST gate insulator exhibited a field effect mobility of 1.0 cm²/Vs and low voltage device performance of less than 7 V.     

Raman scattering studies of Mn-doped ZnO thin films deposited under pure Ar or Ar + N2 sputtering atmosphere

This paper investigates the anomalous and specific Raman modes present in Mn-doped ZnO thin films deposited using the magnetron co-sputtering method. To trace these peaks, we prepared Mn-doped ZnO films with different Mn concentrations by altering the sputtering power of the Mn target in a pure Ar or Ar + N₂ sputtering atmosphere. A broad band observed in the Raman spectra of heavily Mn-doped ZnO films ranges from 500 to 590 cm^− 1. This band involves the enhanced A₁ longitudinal mode and activated silent modes of ZnO, as well as a characteristic mode of Mn₂O₃. Four anomalous Raman peaks at approximately 276, 510, 645 and 585 cm^− 1 are present in pure and Mn-doped ZnO films deposited under the Ar + N₂ sputtering atmosphere. The peaks at 276 cm^− 1 and 510 cm^− 1 may originate from the complex defects of Zn_i-N_O and Zn_i-O_i, respectively, while the peak at approximately 645 cm^− 1 could be due to a complex defect of Zn_i coupled with both the N and Mn dopants. The results of this study suggest classifying the origins of anomalous and specific Raman peaks in Mn-doped ZnO films into three major types: structural disorder and morphological changes caused by the Mn dopant, Mn-related oxides and intrinsic host-lattice defects coupled with/without the N dopant.     

Magnetic properties and photoabsorption of the Mn-doped CeO2 nanorods

Mn-doped CeO₂ nanorods have been prepared from CeO₂ particles through a facile composite-hydroxide-mediated (CHM) approach. The analysis from X-ray photoelectron spectroscopy indicates that the manganese doped in CeO₂ exists as Mn²⁺. The magnetic measurement of the Mn-doped CeO₂ nanorods exhibits an enhanced ferromagnetic property at room temperature with a remanence magnetization (Mr) of 1.36 × 10⁻³ emu/g and coercivity (Hc) of 22 Oe. Comparative UV-visible spectra reveal the shift of the absorption peak of the CeO₂ from ultraviolet region to visible light region after being doped with Mn. The room temperature ferromagnetic properties and light absorption of the Mn-doped CeO₂ nanorods would have potential applications in photocatalysis and building of photovoltaic devices.     

Dielectric and structural characterization of KNbO3 ferroelectric thin films epitaxially grown by pulsed laser deposition on Nb doped SrTiO3

KNbO₃ thin films were deposited on SrTiO₃ substrates by pulsed laser deposition. The X-ray diffraction patterns highlight an epitaxial growth according to the (011) orientation. This epitaxial growth was then confirmed by Electron Channeling Pattern. In agreement with the structural characteristics the dense microstructure consists in regular and ordered grains. Dielectric measurements were performed in the 20 Hz to 1 MHz frequency range on a KNbO₃ thin film grown on 2 at.% Nb doped (100)SrTiO₃ substrate in a large range of temperature in order to investigate the paraelectric-ferroelectric transition. Measurements at room temperature revealed a dielectric constant of 450 at 10 kHz and a minimum value of the loss tangent of 0.075 at 100 kHz. Dielectric study in the 20-600 °C temperature range showed a maximum of permittivity at the Curie temperature T_c = 410 °C and evidenced a “progressive” first-order phase transition, different from the classical “diffuse” transition.     

Effect of Ga doping on micro/structural, electrical and optical properties of pulsed laser deposited ZnO thin films

Undoped and Ga doped ZnO thin films (1% GZO, 3% GZO and 5% GZO) were grown on c-Al₂O₃ substrates using the 1, 3 and 5 at. wt.% Ga doped ZnO targets by pulsed laser deposition. X-ray diffraction studies revealed that highly c-axis oriented, single phase, undoped and Ga doped ZnO thin films with wurtzite structure were deposited. Micro-Raman scattering analysis showed that Ga doping introduces defects in the host lattice. The E₂^High mode of ZnO in Ga doped ZnO thin film was observed to shift to higher wavenumber indicating the presence of residual compressive stress. Appearance of the normally Raman inactive B₁ modes (B₁^Low, 2B₁^Low and B₁^High) due to breaking of local translational symmetry, also indicated that defects were introduced into the host lattice due to Ga incorporation. Band gap of the Ga doped ZnO thin films was observed to shift to higher energy with the increase in doping concentration and is explicated by the Burstein-Moss effect. Electrical resistivity measurements of the undoped and GZO thin films in the temperature range 50 to 300 K revealed the metal to semiconductor transition for 3 and 5% GZO thin films.     

Enhanced ferroelectric properties of Mg doped (Ba,Sr)TiO3 thick films grown on (001) SrTiO3 substrates

Highly (001)-oriented 1 mol% Mg doped (Ba_0.67,Sr_0.33)TiO₃ (BST) films with a thickness of 1.25 μm were grown on (110) SrRuO₃/(001) SrTiO₃ substrates by pulsed laser deposition. X-ray diffraction measurements reveal that the BST thick films have very high crystalline quality, and have a distorted lattice with a large tetragonality a/c = 1.012. The BST thick films have a remanent polarization (P_r) value as large as 10.1 μC/cm² and a coercive electric field (E_c) value of 65.0 kV/cm. The films possess dielectric constant and loss values of ε_r = 385.36 and tgδ = 0.038 at 1 kHz and room temperature. The leakage currents of the films are on the order of 10^− 5 A/cm² at ± 150 kV/cm. The mechanism for enhancing electric properties of the Mg doped BST films was also discussed.     

CdS thin films doped with metal-organic salts using chemical bath deposition

CdS thin films doped with metal-organic salts were grown on glass substrates at 90 °C by the chemical bath deposition technique. Metal-organic salts such as zinc acetate, chromium acetylacetonate, ammonium fluoride, aluminum nitrate, tin acetate and indium acetate were used. The chemical bath was prepared with cadmium acetate, ammonium acetate, thiourea and ammonium hydroxide. In the case of un-doped films, the S/Cd ratio was varied by changing the thiourea in the range 1-12. The best optical, structural and electrical properties were found for S/Cd = 2. The doped films were prepared by always keeping the ratio S/Cd constant at 2. The band gap (E_g) of doped and un-doped films was evaluated from transmittance spectra, where films with lower sulfur concentration exhibited higher E_g. X-ray analysis showed that both un-doped and doped films were polycrystalline with preferential orientation along the (111) direction and with the zincblende structure in all cases. The dark electrical results showed that CdS doped with Zn (1 at.%) exhibited the lowest resistivity values of 10 Ω cm.     

Low temperature growth and properties of Cu-In-Te based thin films for narrow bandgap solar cells

Cu-In-Te based thin films were grown onto soda-lime glass (SLG) substrates at 200 °C by co-evaporation using a molecular beam epitaxy system. The microstructural properties were examined by means of scanning electron microscopy, X-ray diffraction and Raman scattering. The crystalline quality of Cu-In-Te based thin films with high Cu/In ratios is superior to that of films with low Cu/In ratios. The films with Cu/In ratios of 0.69 ± 0.04 exhibited a single chalcopyrite phase with random orientation, whereas a defect chalcopyrite phase with a preferred (112) orientation was obtained for thin films with Cu/In ratios of 0.26 ± 0.02. However, the films with high Cu/In ratios of 0.69 ± 0.04 showed nearly constant low resistivity (∼ 10^− 2 Ω cm) at temperatures from 80 to 400 K due to high hole concentration (> 10¹⁹ cm^− 3), resulting in semi-metallic behavior. The hole conduction mechanism of the film (Cu/In atomic ratios = 0.26 ± 0.02) with semi-conductive properties was found to be variable-range-hopping of the Mott type in the wide range of 80-300 K. The optical bandgaps of Cu-In-Te based thin films are determined to be 0.93-1.02 eV at 300 K from transmission and reflection measurements. A solar cell with a ZnO/CdS/CuIn₃Te₅/Mo/SLG structure showed a total area (0.50 cm²) efficiency of 5.1% under AM1.5 illumination (100 mW/cm²) after light soaking. The conduction band offset at the CdS/CuIn₃Te₅ interface was estimated to be − 0.14 eV from X-ray photoelectron spectroscopy analysis.     

Stable p-type conductivity and enhanced photoconductivity from nitrogen-doped annealed ZnO thin film

We report on the growth of p-type ZnO thin films with improved stability on various substrates and study the photoconductive property of the p-type ZnO films. The nitrogen doped ZnO (N:ZnO) thin films were grown on Si, quartz and alumina substrates by radio frequency magnetron sputtering followed by thermal annealing. Structural studies show that the N:ZnO films possess high crystallinity with c-axis orientation. The as-grown films possess higher lattice constants compared to the undoped films. Besides the high crystallinity, the Raman spectra show clear evidence of nitrogen incorporation in the doped ZnO lattice. A strong UV photoluminescence emission at ~ 380 nm is observed from all the N:ZnO thin films. Prior to post-deposition annealing, p-type conductivity was found to be unstable at room temperature. Post-growth annealing of N:ZnO film on Si substrate shows a relatively stable p-type ZnO with room temperature resistivity of 0.2 Ω cm, Hall mobility of 58 cm²/V s and hole concentration of 1.95 × 10¹⁷ cm^− 3. A homo-junction p-n diode fabricated on the annealed p-type ZnO layer showed rectification behavior in the current-voltage characteristics demonstrating the p-type conduction of the doped layer. Doped ZnO films (annealed) show more than two orders of magnitude enhancement in the photoconductivity as compared to that of the undoped film. The transient photoconductivity measurement with UV light illumination on the doped ZnO film shows a slow photoresponse with bi-exponential growth and bi-exponential decay behaviors. Mechanism of improved photoconductivity and slow photoresponse is discussed based on high mobility of carriers and photodesorption of oxygen molecules in the N:ZnO film, respectively.     

Investigation on Mn doped ZnO thin films grown by RF magnetron sputtering

In this paper, we have investigated the Zn_1 − x Mn_xO (x = 0.05, 0.10 and 0.15) thin films grown by RF magnetron sputtering. The grown films on sapphire [Al₂O₃(0001)] substrates have been characterized using X-ray Diffraction (XRD), Photoluminescence (PL) and Vibrating Sample Magnetometer (VSM) in order to investigate the structural, optical and magnetic properties of the films respectively. It is observed from XRD that all the films are single crystalline with (002) preferential orientation along c-axis. PL spectra reveal that the addition of Mn marginally shifts the Near Band Edge (NBE) position towards the higher energy side. The magnetic measurements of the films using VSM clearly indicate the ferromagnetic nature.     

Sputter-epitaxy and electric properties of multiferroic Bim + 1Fem-3Ti3O3m + 3 thin films

Growth conditions suitable for sputter-epitaxy of Bi_m + 1Fe_m-3Ti₃O_3m + 3 (BFTO) thin films with layered structure have been investigated. The amount of oxygen during deposition was found to be specifically essential for obtaining a good-quality thin film of BFTO with a large m. The (001) epitaxial thin films of BFTO with m of nearly 10 which is expected to retain magnetic order up to room temperature have been successfully grown on (001) SrTiO₃ substrates under the determined optimum condition. The film exhibited leakage current as low as order of 10⁻²-10⁻¹ A/m² limited by Schottky emission at the interfaces between the electrodes and the film. In addition, the film showed a ferroelectric polarization curve with Pr = 6 μC/cm² for applied field of 35 MV/m at room temperature though the curve was unsaturated. These indicate that the BFTO (m = 10) thin films are promising as multiferroics at room temperature.     

Reduced leakage current and enhanced ferroelectric properties in Mn-doped Bi0.5Na0.5TiO3-based thin films

Bi_0.5(Na_0.76K_0.2Li_0.04)_0.5TiO₃ thin films were deposited on SrRuO₃-coated (001)-SrTiO₃ substrates by pulsed laser deposition. The effects of oxygen pressure and Mn doping on the leakage current and ferroelectric and dielectric properties were investigated. The remnant polarization and dielectric constant (at 10 kHz) of Mn-doped film deposited at 400 mtorr were measured to be 23 μC cm^?2 and 660, respectively. The leakage current density of Mn-doped films was suppressed by more than two orders of magnitude and the polarization was considerably enhanced. The XPS results showed coexistence of Mn²⁺, Mn³⁺, and Mn⁴⁺ in doped films. Oxidation of Mn²⁺ to higher valence states by absorbing holes along with occupation of A-site vacancies was suggested as the possible reason for a reduced leakage current and dielectric loss in Mn-doped films.     

Photoelectrochemical properties of nitrogen-doped indium tin oxide thin films prepared by reactive DC magnetron sputtering

Nitrogen-doped indium tin oxide (N-ITO) thin films are deposited on unheated ITO glass substrates in this study. The structural properties of the N-ITO thin films, determined by X-ray diffraction (XRD) and Raman scattering, show that the indium nitride (InN) phase is liable to form in N-ITO films prepared in 20% N₂. A broad XRD peak around 2θ = 33° and Raman peak around 490 cm^− 1 are assigned to the InN phase, but no such peak is observed from the ITO film. Hence, the bandgap is narrowed by N-doping for absorbing light of longer wavelengths of ~ 500 nm. However, under illumination by ultraviolet, the N-ITO film prepared in 20% N₂ exhibits the least photocurrent response, which is less than one third that of the N-ITO catalyst that was doped in 16.4% N₂. This result is attributed mostly to the fact that the valence and conduction band potentials are not positioned properly between the newly formed InN and host ITO phases, rendering inefficient inter-semiconductor electron transfer. Therefore, higher N-doped samples exhibit a lower photocurrent response. Interestingly, the N-ITO film prepared in 16.4% N₂ exhibits the highest photocurrent density of about 165.5 μA/cm² at an applied bias of 1.2 V. This implies that the N-ITO films should be prepared at a low N₂ ratio to ensure a favorable photoelectrochemical activity.