Structural,optical and morphological evolution of Ga2O3/Al2O3 (0001) films grown at various temperatures by pulsed laser deposition

This study systematically investigated the structural, optical, and morphological evolution of Gallium oxide (Ga₂O₃) films deposited at different substrate temperatures on Al₂O₃(0001) using pulsed laser deposition (PLD). The thickness of the Ga₂O₃ films was standardized in order to eliminate its effect on the film properties. The effect of substrate temperature from room temperature to 600 °C on the film's transmittance, crystalline structure, chemical composition and surface morphology, was explored. The plasma species generated during the deposition of the PLD process were monitored and analyzed employing in situ optical emission spectroscopy. The deposition rate of the films decreased with increasing substrate temperature. X-ray photoelectron spectroscopy was used to detect both Ga³⁺ and Ga ⁺ oxidation states in all prepared films, which indicated substoichiometric Ga₂O₃ films deficient in oxygen. The percentage of non-lattice oxygen decreased with increasing substrate temperature. At optimal condition, mono-crystaline β-Ga₂O₃ was produced with a high visible and near-infrared transmittance, large grain size and smooth surface, which is suitable for the application in high-performance power electric devices and photoelectronic devices.     

Vacancy-engineered V2O5-x films for ultrastable electrochromic applications

In the present study, we prepared vacancy-engineered V₂O_5-x films for electrochromic (EC) applications. To investigate the vacancy effect of V₂O_5-x films with high EC performance capabilities, precursor concentrations of V-based sol solutions were varied at 1 wt%, 5 wt%, and 10 wt%. Among them, V₂O_5-x films with a precursor concentration of 5 wt% (V₂O₅-5wt%) showed superior EC performance outcomes due to the (001)-plane-oriented crystal structure, which provides high electrical conductivity with the oxygen vacancy (V_o). In addition, the gravel-like uniform surface morphology with the optimized film thickness provides a stable electrochemical reaction during the EC measurement. As a result, V₂O₅-5wt% exhibited fast switching speeds (2.1 s for coloration and 3.6 s for bleaching), high transmittance modulation (ΔT) (51.32%), high coloration efficiency (CE) (52.3 cm²/C), and excellent cycle stability (85.85% ΔT retention after 500 cycles). In addition, V₂O₅-5wt% showed energy storage capability of 443.7 F/g at a current density of 2 A/g, thus proving its potential for use in multi-functional applications. Therefore, these results provide valuable insight related to the engineering of vacancies in EC films to achieve high-performance EC devices and additional multi-functional applications.     

The novel positive colossal electroresistance in PbPdO2 thin film with (002) preferred orientation

Doped PbPdO₂ materials have attracted much attention as a spin gapless semiconductor (SGS) with the important properties of colossal electroresistance (CER) and giant magnetoresistance (GMR). In this study, the PbPdO₂ thin films with (002) preferred orientation were prepared by pulsed laser deposition (PLD), and the temperature dependences of resistance and resistivity, R (T) and ρ_I (T), were measured under different applied DC currents. Remarkably, a positive CER effect induced by the current was firstly observed in the PbPdO₂ films. In particular, it is novelty found that the positive CER value of PbPdO₂ with I = 10 μA and T = 10 K reached about 300%. Moreover, the cyclic ρ_I (T) curves were also measured for I = 0.01 and 10 μA going back and forth between 10 K and 400 K. The time dependences of ρ_t/ρ₀ ratio with T = 100 K, 300 K, 400 K and I = 0.01 and 0.1 μA were also obtained. A critical temperature T_c with about T = 260 K for all applied currents was found. As T > T_c，the band gap of the film is enhanced by the combined effect of the temperature and current. At the same time, Pb and O vacancies, and the evolution of oxygen valence states in the PbPdO₂ film were observed by energy dispersive spectrometer (EDS), electron paramagnetic resonance (EPR) and in-situ x-ray photoelectron spectroscopy (XPS). Especially, the charge transport between O¹⁻ and O²⁻ was confirmed by in-situ XPS. Finally, based on first-principles calculation, an internal electric field model and its induced potential barrier were established, which well explains the positive CER effect and the critical temperature T_c.     

Ultrahigh electric breakdown strength,excellent dielectric energy storage density,and improved electrocaloric effect in Pb-free (1-x)Ba(Zr0.15Ti0.85)O3-xNaNbO3 ceramics

In this study, NaNbO₃ (NN) was introduced into Ba(Zr_0.15Ti_0.85)O₃ (BZT) to form a solid solution with relaxor ferroelectric characteristics. The dielectric breakdown strength (BDS) of the specimen with 6 mol.% NN reached 680 kV/cm, the corresponding recoverable energy storage density (W_rec) was 5.15 J/cm³, and the energy storage efficiency (η) was 77%. The dissolution of Na ⁺ ions at the A position and Nb⁵⁺ ions at the B position of the perovskite structure reduced the concentration of oxygen vacancies in the lattice and compensated for defects. The doped ceramics exhibited lower dielectric loss and better thermal stability: the W_rec value was 2 ± 1% J/cm³ at 30–120 °C. In particular, in the 0.02NN ceramics, a ΔT of 1.81 K was achieved at 130 kV/cm, and the operating temperature zone expanded with the increase in doping concentration. The introduction of NN resulted in BZT ceramics that possess excellent energy storage performance and electrocaloric effect properties.     

Electrical conduction behavior in nonstoichiometric BaBixNb5O15±δ tungsten bronze ceramics

The BaBi_xNb₅O_15±δ (BB_xN, 0.98 ≤ x ≤ 1.02) ceramics were synthesized via solid-state reaction to investigate the effect of Bi³⁺ nonstoichiometry on their microstructure and electrical conduction behavior. The study of the relationship between structure and conductive behavior revealed two main conclusions: (1) as the concentration of Bi³⁺ content increased, from deficiency to excess, the oxygen vacancies decreased, and the lattice unit volume V gradually increased; (2) there was a low-frequency Warburg electrode response besides the medium-frequency grain boundary response and high-frequency grain response, and the Bi³⁺ introduction could reduce conductivity. In addition, the dielectric anomalies indicated by the T₁ peak and the T₂ peak at 300 °C and 500 °C are related to the Warburg electrode response and to the Bi vacancy and oxygen vacancy defects, respectively.     

Ultra-low power consumption and favorable reliability Mn-doped BiFeO3 resistance-switching devices via tunable oxygen vacancy

Due to the instability of Fe valence and the existence of a large number of oxygen vacancies in BFO films, a large leakage current, and comparatively low resistance value usually appear in BFO-based devices and high operating voltage and power consumption are demanded to form regular oxygen vacancy conductive channels, which restricts the application of BFO in resistive memory and memristor devices. In this paper, a series of Pt/BiFe_1-xMn_xO₃/TiN (BFMO, x = 0, 0.05, 0.1, 0.15, 0.2) devices with different Mn doping concentrations were prepared by magnetron sputtering and lithography, and the microstructure and electrical characteristics of BFMO-based devices were investigated. As the amount of Mn doping increases, the resistive switching properties including operating voltage, power consumption, cycle stability, and retention of BFMO device first improve and then degrade. Interestingly, with the increase of Mn doping concentrations, the ratio of Fe²⁺ to Fe³⁺ and oxygen vacancies to lattice oxygen in BFMO devices analyzed by X-ray photoelectron spectroscopy initially diminishes reaching the minimum and then rises. Notably, BiFe_0·9Mn_0·1O₃ device presents low DC operating voltage of ?0.7 V and 0.8 V, preferable endurance of 10⁴ pulse cycles, and low power consumption of only 0.45 pJ in a single set process. The remarkable electrical performance in BFMO-based devices likely originated from the inhibition of initial oxygen vacancies caused by Mn doping with appropriate content.     

Understanding the change in electrical resistance of TiO2 thin film irradiated with YVO4 third-harmonic generation pulse laser

To selectively control the electrical resistance, thin films of TiO₂ were irradiated with a YVO₄ third-harmonic generation pulse laser in various power conditions. It was observed that when the laser power was less than 0.26 W, the electrical resistance of thin films decreased with the increase in laser power, whereas when the laser power was more than 0.26 W, the electrical resistance increased as the laser power increases. The minimum electrical resistance of the irradiated thin film was found to be four orders of magnitude lower than that of the unirradiated thin film. X-ray absorption fine structure analysis revealed that the valence of Ti ions in the thin films was reduced after laser irradiation, indicating the formation of oxygen vacancies with electron doping. The cross-sectional observation by a scanning electron microscope revealed that high laser power irradiation caused the thin films to become porous, and the percolation theory explains the origin of the increase in electrical resistance with developing porous structure. We propose a phase diagram to completely explain the relationship between electrical resistance and laser power, which supply a guideline on laser modification in TiO₂ electrical resistance.     

High-speed deposition of silicon nitride thick films via halide laser chemical vapor deposition

Silicon nitride shows significant potential in the field of surface protection for electronic devices owing to its excellent insulation performance and mechanical properties. In this study, silicon nitride films were fabricated via halide laser chemical vapor deposition (LCVD). The effects of deposition parameters on the crystallinity, microstructure, deposition rate (R_dep), Vickers microhardness, nano-hardness and electrical resistivity were investigated. The maximum R_dep of the silicon nitride thick films was 972 µm/h at T_dep of 1573 K and P_tot of 10 kPa, which is the highest value compared with those obtained via conventional CVD. As T_dep increased, the Vickers microhardness and nano-hardness of the films increased to the highest value of 25.1 GPa and 34.8 GPa at 1573 K, respectively. The electrical resistivity of the films decreased with increasing T_dep and showed a maximum value of 1.49 × 10¹⁴ Ω·cm at T_dep of 1273 K.     

Electric field dependence of ferroelectric stability in BiFeO3 thin films co-doped with Er and Mn

Bi_0.9Er_0.1Fe_1−xMn_xO₃ (BEFM_xO, x = 0.00–0.03) films are synthesized by a sol–gel technique. The BEFO film exhibits a conduction mechanism based on electron tunneling. The high applied electric field causes dissociation of the defect complex, and the resulting oxygen vacancies contribute to fake polarization. Consequently, the BEFO film has poor polarization stability at high applied electric fields. Coexistence of two phases (with space groups R3c:H and R3m:R) and reduced concentrations of oxygen vacancies and Fe²⁺ in BEFM_xO are achieved by co-doping with Er and Mn. The presence of bulk-based conduction in the BEFM_xO films then leads to ferroelectric domain switching contributing to the real polarization and to excellent ferroelectric stability. In addition, the BEFM_0.02O film shows a typical symmetrical butterfly curve, the highest remnant polarization of ~109 μC/cm², and the highest switching current of ~1.66 mA. It also has the smallest oxygen vacancy concentration and thus the smallest amount of defect complex, which means that there are fewer pinning effects on ferroelectric domains and therefore excellent ferroelectric stability. This excellent ferroelectric stability makes the BEFM_xO films obtain good stability and reliability in the application of ferroelectric memory devices.     

High-speed epitaxial growth of SrTiO3 films on MgO substrates by laser chemical vapor deposition

Epitaxial (100) and (111) SrTiO₃ films were prepared on (100) and (111) MgO single-crystal substrates, respectively, using laser chemical vapor deposition. The effect of deposition temperature (T_dep) on the orientation and microstructure of the SrTiO₃ films was investigated. On the (100) MgO substrates, SrTiO₃ films showed a (111) orientation at a low T_dep of 1023 K. (100) SrTiO₃ films, which were epitaxially grown at T_dep=1123–1203 K, had dense cross sections and flat surfaces with rectangular-shaped terraces. On the (111) MgO substrates, (111) SrTiO₃ films were epitaxially grown at T_dep=983–1063 K; however, these films' orientations became random at high T_dep of 1063–1113 K. The (111) SrTiO₃ films consisted of columnar grains with triangular pyramidal caps. The deposition rates of the epitaxial (100) and (111) SrTiO₃ films were 13–25 and 18–32 μm h⁻¹, respectively, which is 5–530 times higher than those obtained by MOCVD.     

Effect of argon-oxygen ratio on dielectric and energy storage properties of Ba(Zr0.35Ti0.65)O3 thin films

Lead-free Ba(Zr_0.35Ti_0.65)O₃(short as BZT35) ferroelectric thin films are prepared by RF magnetron sputtering on Pt/Ti/SiO₂/Si substrates. Effects of argon-to-oxygen (short as Ar/O₂) ratios on phase transition, dielectric and energy storage properties are studied. The research found that all thin films are perovskite structures. With the decrease of Ar/O₂, the oxygen vacancies (OVs) in the film are effectively suppressed, which promotes the film to obtain a larger dielectric constant, smaller dielectric loss, and lower leakage current density. The BZT35 film prepared under Ar/O₂ = 40:10 has excellent energy storage density (48.03 J/cm³) and efficiency (87.7%) because of its elongated hysteresis loop, the largest polarization difference (ΔP = 22.91 μC/cm²), higher breakdown field strength (E_b = 4.50 MV/cm) and lower leakage current density (J = 2.3 × 10^?5 A/cm²) and high power density of 7.94 MW/cm³. In addition, the BZT35 film also has excellent frequency stability (500 Hz-20 kHz). These excellent properties show that BZT35 has very broad application prospects in energy storage.     

The effects of pulse repetition rate on the structural,surface morphological and UV photodetection properties of pulsed laser deposited Mg-doped ZnO nanorods

The Mg_0.05Zn_0.95O (MZO) nanorod array (NRA) films have been successfully grown onto SiO₂/ n-Si substrates by pulsed laser deposition (PLD) without any template or seed layer and the influence of pulse repetition rate (3 to 15 Hz) of a 248 nm KrF excimer laser on their crystallinity, surface morphology and UV photodetection properties were systematically investigated. All the samples show the hexagonal wurtzite phase with a preferential c-axis orientation and the optimum crystallization of the MZO NRAs occurs at 5 Hz. FE-SEM analysis revealed that the growth of MZO NRAs is strongly influenced by the pulse repetition rate. It was observed that the average film thickness increases almost linearly with the pulse repetition rate and the MZO nanorod arrays grown at 5 Hz exhibits best surface area. Moreover, the room temperature UV photodetection properties of the samples were investigated in metal–semiconductor–metal (MSM) planar configurations and are found to be strongly driven by the pulse repetition rate dependent crystalline and surface morphological features. The device current–voltage (I–V) characteristics were measured under dark and UV light conditions. Then, the photocurrent and responsivity were measured with the variation of optical power density and applied voltage, respectively. Transient photoresponse studies show an exceedingly stable and fast switching UV photoresponse for the photodetector having MZO nanorods grown at 5 Hz, which demonstrates highest responsivity of 17 mA/W upon 2 mW/cm² UV illumination (365 nm), at 5 V bias.     

Impact of oxygen partial pressure on resistive switching characteristics of PLD deposited ZnFe2O4 thin films for RRAM devices

In this paper we show resistive switching characteristics of ZnFe₂O₄ thin films grown by pulsed laser deposition at various oxygen partial pressures. We discuss how the microstructure, surface roughness, oxidation condition, and resistive switching properties of ZnFe₂O₄ thin films are influenced by the oxygen partial pressure prevalent in the chamber during the deposition process. The films were deposited at oxygen partial pressure (pO₂) of 0.0013, 0.013, 0.13 and 1.3 mbar. The ZnFe₂O₄ thin film deposited at the lowest pO₂ (0.0013 mbar) did not display a resistive switching characteristic. The ZnFe₂O₄ device deposited at 0.13 mbar yielded the best results. These devices have a low SET variance and a large memory window (more than 2 orders of magnitude) due to an optimum amount of oxygen vacancies/ions contained in the ZnFe₂O₄ film, which is helpful for better resistive switching, than devices deposited at other oxygen pressures. We also find that the migration of oxygen vacancies is linked to the resistive switching process.     

Dielectric and optical properties of electroceramic PBZNZT thin films prepared by pulsed laser deposition process

The 0.6[0.94Pb(Zn_1/3Nb_2/3)O₃ + 0.06BaTiO₃] + 0.4[0.48(PbZrO₃) + 0.52(PbTiO₃)], PBZNZT, thin films were synthesized by pulsed laser deposition (PLD) process. The PBZNZT films possess higher insulating characteristics than the PZT (or PLZT) series materials due to the suppressed formation of defects, therefore, thin-film forms of these materials are expected to exhibit superior ferroelectric properties as compared with the PZT (or PLZT)-series thin films. Moreover, the Ba(Mg_1/3Ta_2/3)O₃ thin film of perovskite structure was used as buffer layer to reduce the substrate temperature necessary for growing the perovskite phase PBZNZT thin films. The PBZNZT thin films of good ferroelectric and dielectric properties (remanent polarization P_r = 26.0 μC/cm², coercive field E_c = 399 kV/cm, dielectric constant K = 737) were achieved by PLD at 400 °C. Such a low substrate temperature technique makes this process compatible with silicon device process. Moreover, thus obtained PBZNZT thin films also possess good optical properties (about 75% transmittance at 800 nm). These results imply that PBZNZT thin films have potential in photonic device applications.     

Low threshold voltage,highly stable electroforming-free threshold switching characteristics in VOx films-based device

Threshold switching (TS) devices have evolved as one of the most promising elements in memory circuit due to their important significance in suppressing crosstalk current in the crisscross array structure. However, the issue of high threshold voltage (V_th) and low stability still restricts their potential applications. Herein, the vanadium oxide (VO_x) films deposited by the pulsed laser deposition (PLD) method are adopted as the switching layer to construct the TS devices. The TS devices with Pt/VO_x/Pt/PI structure exhibit non-polar, electroforming-free, and volatile TS characteristics with an ultralow V_th (+0.48 V/−0.48 V). Besides that, the TS devices also demonstrates high stability, without obviously performance degradations after 350 cycles of endurance measurements. Additionally, the transition mechanism is mainly attributed to the synergistic effect of metal-insulator transition of VO₂ and oxygen vacancies. Furthermore, the nonvolatile bipolar resistance switching behaviors can be obtained by changing oxygen pressure during the deposition process for switching films. This work demonstrates that vanadium oxide film is a good candidate as switching layer for applications in the TS devices and opens an avenue for future electronics.     

Oxygen vacancy enhanced room temperature ferromagnetism in Ar+ ion irradiated WO3 films

Room-temperature ferromagnetism in WO₃ films was enhanced by 130 keV Ar⁺ ion irradiation. The X-ray diffraction (XRD) and Raman measurements not only confirmed the monoclinic phase of the irradiated WO₃ films, but also showed that oxygen vacancy (V_O) defects were formed. The analysis of photoluminescence spectra strongly reconfirmed the presence of oxygen vacancy. X-ray photoelectron spectroscopy (XPS) measurements revealed that the contents of V_O and induced W⁵⁺ ions increase with increasing irradiation fluence and rich W⁵⁺-V_O defect complexes in the irradiated WO₃ films were formed. Further, the magnetic measurements exhibited a 2-fold enhancement in the saturation magnetization at the largest fluence of 3 × 10¹⁶ ions/cm². At lower irradiation fluence, a bound magnetic polaron model was proposed to reveal the ferromagnetic exchange coupling resulting from overlapping of V_O⁺ and V_O⁺⁺ defect states, and 5d¹ states of W⁵⁺. At high irradiation fluence, the carrier concentration reaches 1.02 × 10²⁰/cm³ and carrier-mediated exchange interactions result in the film's ferromagnetism.     

Effect of oxygen vacancies on the microstructure and multiferroic behavior of Bi4.25La0.75Fe0.5Co0.5Ti3O15 ceramics

In order to reveal the solid relationship between oxygen vacancies and multiferroic properties, polycrystalline Bi_4.25La_0.75Fe_0.5Co_0.5Ti₃O₁₅ (BLFCT) ceramics were sintered in argon (BLFCT-Ar), air (BLFCT-air) and oxygen (BLFCT-O₂) by conventional solid state reaction, respectively. Their microstructures, ferroelectric, magnetic properties and valence states of magnetic ions were investigated and compared. X-ray diffraction patterns confirmed a single phase crystal structure in all samples. The lattice constants were calculated and the minor variation of the lattice constants is attributed to the different oxygen vacancy concentration. Furthermore, different oxygen vacancy concentration may be responsible for the different values of RT-recorded remanant magnetization (2M_r), remanent polarization (2P_r) as well as magnetic phase transition temperatures (T_CM). The magnetic response of sample sintered in argon (2M_r =0.52 emu/g, T_CM=392 K) is significantly superior to that of the others, while the sample sintered in oxygen exhibits a better remnant polarization (2P_r =11.6 µC/cm²) at an applied electric field of 160 kV/cm. The BLFCT-Ar sample was then annealed in oxygen to further justified the dependence of 2P_r and 2M_r on oxygen vacancies. Finally, outcome of the XPS measurement manifested the ratios of Fe²⁺/Fe³⁺ and Co²⁺/Co³⁺, and reconfirmed the different oxygen vacancy concentration in three samples.     

Structures,morphological control,and antibacterial performance of tungsten oxide thin films

The present work describes structural, morphological, and antibacterial properties of thin film coatings based on tungsten oxide material on stainless-steel substrates. Thin films were prepared by RF magnetron sputtering of W targets in the oxygen/argon plasma environment in 60 W sputtering power. The characterization of the specimens was made on the basis of microstructure and antibacterial properties of the thin films surface. The effect of O₂/Ar ratio on the structure, morphology, and antibacterial properties of the tungsten oxide thin films was studied. Methods such as X-ray diffraction (XRD), scanning electron microscope (SEM), and Fourier Transform Infrared Spectroscopy (FTIR) were used to assess the properties of deposited thin films. XRD peak analysis indicates (100) and (200) of WO₃ phase with hexagonal structure. Moreover, the micro-strain, grain size, and dislocation density were obtained. It is noteworthy that by increasing the oxygen percentage from 10% to 20%, the grain size decreases from 81 to 23 nm while the film micro-strain and dislocation density increases. The SEM results illustrates that tungsten oxide thin films are made of interconnected nano-points in a chain shape with sphere-shaped grains with diameter variation from 10 to 100 nm. The FTIR spectra displays four distinct bands corresponds to O–W–O bending modes of vibrations and W–O–W stretching modes of the WO₃ films. The antibacterial effects of tungsten oxide thin films on steel stainless substrate against Escherichia coli bacteria are also examined for the first time and our observation shows that the number of bacteria on all tungsten oxide samples decreases after 24 h. The samples exhibit an excellent antibacterial performance. This paper renders a strategy through which the tungsten oxide thin films for antibacterial purpose and proposes that WO₃ thin films are ideal for various medical applications including stainless steel medical tools, optical coatings, and antibacterial coatings.     

Stable anatase phase with a bandgap in visible light region by a charge compensated Ga–V (1:1) co-doping in TiO2

A series of charge compensated Ga–V co-doped TiO₂ samples (Ti_(1-x)(Ga_0.5V_0.5)_xO₂) have been synthesized by a modified sol-gel process. X-ray diffraction pattern shows that the anatase to rutile (A→R) onset temperature (T_O) shifts to a higher temperature, whereas the complete phase transformation temperature (T_C) shifts to a low-temperature region as compared to pure TiO₂, due to Ga–V incorporation. Ga–V co-doping helps in the transformation of some smaller sized Ti⁴⁺ to a relatively larger Ti³⁺. In the anatase phase, oxygen content also increases with increasing doping concentration, which along with the larger size of Ti³⁺ results in lattice expansion and thereby delays the T_O. In the rutile phase, oxygen vacancy increases with increasing doping concentration, which results in lattice contraction and accelerates phase transition. Grain growth process is hindered in the anatase phase (crystallites size reduces from ~15 nm (x = 0.00) to 8 nm (0.10)), whereas it is accelerated in the rutile phase as compared to pure TiO₂. In both phases bandgap (E_g) reduces to the visible light region (anatase: E_g = 3.16 eV (x = 0.00) to 2.19 eV (x = 0.10) and rutile: 3.08 eV (x = 0.00) to 2.18 eV (x = 0.10)) in all co-doped samples. The tail of the absorption edge reveals lattice distortion and increase of Urbach energy proofs the same due to co-doping. All these changes (grain growth, phase transition, and optical properties) are due to lattice distortion created by the combined effect of substitution, interstitials, and oxygen vacancies due to Ga–V incorporation in TiO₂.