Low metal–insulator transition temperature of Ni-doped vanadium oxide films

Elemental doping is the main means to regulate the phase transition of vanadium oxide (VO₂); however, the effects of low valence elemental (<4+) doping on the phase transition of VO₂ are still controversial. In the present work, Ni-doped VO₂ films were prepared on quartz glass by direct current reactive magnetron sputtering and subsequent annealing. With the increase of the Ni doping content, the phase transition temperature of heating (T_H) of the VO₂ films decreased from 73.4 °C to 52.4 °C. The temperature required for the occurrence of phase transition (T_b) was lower than T_MIT. Different from the undoped VO₂ film, the Ni-doped VO₂ films had a T_b of around 30 °C. XRD and Raman results revealed that some rutile VO₂ microcrystals appeared in the vanadium oxide films because of the lattice distortion by incorporated Ni. Hence, rutile VO₂ micro-crystallinities significantly facilitated the phase transition of monoclinic VO₂ to rutile one.     

Insights into Cu2O thin film absorber via pulsed laser deposition

Cuprous oxide materials are of growing interest for optoelectronic devices and were produced by several chemical and physical methods. Here, we report on the structural, optical, and electrical properties of Cu_xO thin films prepared by the pulsed laser deposition technique. The substrate temperature, as well as the oxygen partial pressure in the deposition chamber, were varied to monitor the copper to oxygen ratio within the deposited films. The growth conditions were carefully optimized to provide the highest conductivity and mobility. Thus, 100 nm thick cuprous oxide films (Cu₂O) deposited at 750 °C exhibited a resistivity of 16 Ω?cm, high mobility of 30 cm²/(V?s), and a bandgap of around 2 eV. The film deposited at the optimized deposition parameters on Nb:STO (001) substrate with Au top electrode showed a photovoltaic response with an open circuit voltage of 0.56 V. These results path the way to efficient solar cells made with Cu₂O films via the pulsed laser deposition technique.     

Phase evolution and thermochromism of vanadium oxide thin films grown at low substrate temperatures during magnetron sputtering

Vanadium oxides (VO_x) have been studied extensively for applications in thermochromic materials, electrochomics, and infrared detectors due to their unique phase transition characteristics. However, various vanadium oxide phases usually occur under different deposition conditions due to their particularly complex vanadium-oxygen system. In this research, V₃O₇, VO₂(B), VO₂(M), and V₂O₅ thin films were obtained as pure or mixed phases by controlling the substrate temperatures between 250 °C and 400 °C during magnetron sputtering. The microstructure and phase composition of vanadium oxide thin films were characterized and analyzed using X-ray diffraction and Raman spectroscopy. The phase evolution was dependent on the substrate temperature and could be clarified. Metastable V₃O₇ and VO₂(B) phases were obtained at substrate temperatures of 250–300 °C, while stable VO₂ and V₂O₅ phases were obtained at 350–400 °C. The surface morphology and optical properties of vanadium oxide thin films with different substrate temperatures were investigated in detail. Our results provide methods for transforming vanadium oxide phases under well controlled substrate temperatures.     

Influence of deposition parameters on the structure and microstructure of Bi12TiO20 films obtained by pulsed laser deposition

The structure, morphology and surface roughness of Bi₁₂TiO₂₀ (BTO) thin films grown on R-sapphire by pulsed laser deposition (PLD) were studied at different substrate temperatures, target-substrate distances, oxygen pressures and laser-pulse repetition rates. Although the substrate temperature seems to be the most important experimental parameter, the gas pressure and the target–substrate distance played important role on the phase formed and film thickness, with a significant effect of the laser-pulse repetition rate on the films thickness and preferred orientation of the deposited film. Single-phase γ-Bi₁₂TiO₂₀ was obtained on substrates at 650?°C, while several BTO metastable phases were observed in films deposited on substrates at temperatures between 500 and 600?°C. By the first time, thin films of pure and textured δ-Bi₁₂TiO₂₀ were successfully growth on substrates at 450?°C. When annealed, all the films deposited at lower temperatures resulted in the thermodynamically stable γ-Bi₁₂TiO₂₀.     

Thickness-dependent switching behavior of 0.8(Bi0.5Na0.5)TiO3-0.2SrTiO3 lead-free piezoelectric thin films

0.8(Bi_0.5,Na_0.5)TiO₃-0.2SrTiO₃ (BNT-0.2ST) thin films, with thicknesses ranging from 90 to 364 nm, were fabricated on platinized silicon substrates by sol-gel method. These films were investigated by switching spectroscopy piezoresponse force microscope (SS-PFM) as a function of frequency at room temperature, revealing the enhanced ferroelectric response in ∼ 210 nm film at all frequencies (0.1 Hz - 1.5 Hz). This enhancement was ascribed to the largest thermally-activated stress at such thicknesses generated during film fabrications. As the temperature of the investigated films increases from room temperature to 200 ^oC, the piezoelectric parameters were obtained from SS-PFM, such as switching polarization (R_s), coercive bias (V₀), work of switching (A_s), maximum strain (S_max), and negative strain (S_neg), indicating an occurrence of phase transition from ferroelectrics to relaxors. This work revealed that thickness plays a crucial role for ferroelectric response and temperature-dependent phase transition in BNT-0.2ST films, since it affects the stress state and switching behavior.     

The novel preparation method of thermochromic VO2 films with a low phase transition temperature by thermal oxidation of V–Mo cosputtered alloy films

Vanadium dioxide (VO₂) has been studied extensively for its unique insulator-metal transition characteristics and potential applications in thermochromic smart windows, switching devices, and infrared detectors. However, how to balance the metal-insulator transition temperature, luminous transmittance (T_lum) and solar modulation ability (ΔT_sol) of VO₂ thin films remains a challenge. In this work, high-quality thermochromic VO₂ thin films were prepared by a two-step method of magnetron sputtering and thermal oxidation annealing. Metallic and alloyed V–Mo layers were first deposited by direct-current reactive magnetron sputtering, and then a thermal oxidation annealing process was used to obtain pure and Mo-doped VO₂ thin films. The Mo content in the films was regulated by changing the sputtering power of the vanadium target, and the effect of Mo doping on the crystallinity, microstructure, phase transition temperature and optical properties of VO₂ thin films was studied. The shift of the VO₂(011) peak to a lower 2θ angle in the XRD patterns showed that Mo was successfully diffused into vanadium dioxide films. The phase transition temperatures were decreased continuously from 57.4 to 32.7 °C by decreasing the sputtering power of vanadium. The thinner Mo-doped VO₂ thin films showed higher luminous transmittance and lower transition temperature. Our results were shown to be an innovative preparation method to fabricate thermochromic VO₂ films with a low phase transition temperature, balanced luminous transmittance and solar modulation ability by thermal oxidation of V–Mo cosputtered alloy films.     

Surface morphology of PECVD fluorocarbon thin films from hexafluoropropylene oxide, 1,1,2,2‐tetrafluoroethane,and difluoromethane

Atomic force microscopy (AFM) measurements have been made on a series of fluorocarbon films deposited from pulsed plasmas of hexafluoropropylene oxide (HFPO), 1,1,2,2‐tetrafluoroethane (C₂H₂F₄), and difluoromethane (CH₂F₂). All of the films give images showing nodular growth (cauliflower‐like appearance), with the size and distribution of the nodules dependent on both the precursor, the degree of surface modification to which the growing film is exposed, and the substrate surface. Films deposited from C₂H₂F₄ showed clusters of smaller nodules around larger nodules, whereas films deposited from CH₂F₂ were characterized by a uniform distribution of smaller nodules, and films deposited from HFPO had the largest observed nodules. Movchan and Demchishin's structure zone model was applied to the observed films, which were all found to be zone 1 structures, indicating that film growth is dominated by shadowing effects. Increased substrate temperature and incident power per nm of film deposited results in decreased rms roughness, consistent with greater atomic mobility during deposition. Larger nodules in the fluorocarbon films developed on silicon wafer substrates than on rougher Al‐coated substrates. Advancing contact angles for all of the films were found to be higher than that of PTFE (108°), indicating both hydrophobic and rough surfaces. Specifically, contact angles of films deposited from HFPO were found to increase with pulse off‐time, the same trend observed for both the CF₂ fraction of the film and the rms roughness. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2439–2447, 1999     

Development of MgO:TiO2 thin films for gas sensor applications

In this study, structural, morphological and optical properties, and gas sensor performance of magnesium oxide (MgO) doped titanium dioxide (TiO₂) thin films were investigated in detail. Gas sensor metallic patterns were fabricated on Si substrate using traditional photolithographic technique. MgO doped TiO₂ thin films were deposited on formed Pt electrode surface by confocal sputtering (co-sputtering) system as the active layer. Thin film characterizations were realized by using secondary ion mass spectroscopy (SIMS), atomic force microscope (AFM) and UV–Vis Spectrometer (UV–Vis). Gas sensing measurements were performed by gas sensing test system against methane gas at working temperature of 300?°C. To evaluate deposition and thermal annealing effects on the sensing performance, sensors were tested under gas. The sensitivity and response/recovery time of gas sensors were measured in 1000?ppm. MgO doped TiO₂ based sensor at substrate temperature of 100?°C has high sensitivity and short response/recovery time.     

Structural and Optical Property of Titanium Oxide Film Prepared by Energy Filtering Magnetron Sputtering Technique

Titanium oxide (TiO₂) film was deposited by an improved direct current magnetron sputtering (DMS) technique. The improved technique was named as energy filtering magnetron sputtering (EFMS) technique. The phase, surface morphology, and optical property of the film were characterized by X‐ray diffraction (XRD), Raman spectrometer, scanning electron microscope (SEM), and spectroscopic ellipsometer, respectively. Results show that the TiO₂ film prepared by the EFMS technique has good crystallization of the anatase phase without subsequent annealing process. The film is denser and the grain size is smaller. The crystallite sizes of the TiO₂ films prepared by the DMS and EFMS techniques are obtained at about 17.3 and 12.5 nm. The TiO₂ film deposited by the EFMS technique has higher refractive index and larger band gap owing to the result of the quantum size effect.     

Hybrid multilayer thin-film fabrication by atmospheric deposition process for enhancing the barrier performance

In this paper, a multilayer barrier thin film, based on polyvinylidene difluoride (PVDF)–silicon dioxide (SiO₂), has been fabricated on a PET substrate through a novel method of joint fabrication techniques. The inorganic SiO₂ thin film was deposited using a roll-to-roll atmospheric atomic layer deposition system (R2R-AALD), while the organic PVDF layer was deposited on the surface of SiO₂ through the electrohydrodynamic atomization (EHDA) technique. The multilayer barrier thin films exhibited very good surface morphology, chemical composition, and optical properties. The obtained values for arithmetic surface roughness and water contact angle of the as-developed multilayer barrier thin film were 3.88 nm and 125°, respectively. The total thickness of the multilayer barrier thin film was 520 nm with a high optical transmittance value (85–90%). The water vapor transmission rate (WVTR) of the barrier thin film was ~?0.9?×?10^?2 g m^?2 day^?1. This combination of dual fabrication techniques (R2R-AALD and EHDA) for the development of multilayer barrier thin films is promising for gas barrier applications.     

Study of Phosphorus Doped Micro/Nano Crystalline Silicon Films Deposited by Filtered Cathodic Vacuum Arc Technique

Phosphorus doped micro/nano crystalline silicon thin films have been deposited by the filtered cathodic vacuum arc technique at different substrate temperatures (T_s) ranging from room temperature (RT) to 350 ^°C. The films have been characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy, secondary ion mass spectroscopy, dark conductivity ( σ _D), activation energy ( ΔE) and optical band gap (E _g). The XRD patterns show that the RT grown film is amorphous in nature but high T_s (225 and 350 ^°C) deposited films have a crystalline structure with (111) and (220) crystal orientation. The crystallite size of the higher T_s grown silicon films evaluated was between 17 to 31 nm. Raman spectra reveal the amorphous nature of the film deposited at RT whereas higher T_s deposited films show a higher crystalline nature. The crystalline volume fraction of the silicon film deposited at higher T_s was estimated as 65.7 % and 74.4 %. The values of σ _D, ΔE and E _g of the silicon films deposited at different T_s were found to be in the range of 8.84 x 10 ^?4? 0.98 ohm ^?1 cm ^?1, 0.06 - 0.31 eV and 1.31-1.93 eV, respectively. A n-type nc-Si/p-type c-Si heterojunction diode was fabricated which showed the diode ideality factor between 1.1 to 1.5.     

Polymer/carbon nanotube composite film formation: A fluorescence study

In this study, the effect of multi‐walled Carbon nanotube (MWNT) on film formation behavior of Polystrene (PS) latex film was investigated by using steady state fluorescence technique. Films were prepared by mixing of pyrene (P)‐labeled PS latex with different amounts of MWNTs varying in the range between 0 and 20 wt%. After drying, MWNT containing films were separately annealed above glass transition temperature (T_g) of PS ranging from 100 to 270°C for 10 min. In order to monitor film formation behavior of PS/MWNT composites, Scattered light (I_s) and fluorescence intensities (I_P) from P were measured after each annealing step to monitor the stages of film formation. At 0–20 wt% range of MWNT content films, minimum film formation (T_o), void closure (T_v), and healing, (T_h) temperatures were determined. Void closure and interdiffusion stages were modeled and related activation energies were determined. It was observed that while void closure activation energies increased, backbone activation energies decreased as the percent of MWNT is increased in the composite films. POLYM. COMPOS., 35:817–826, 2014. © 2013 Society of Plastics Engineers     

Electric field-induced phase transition and energy storage performance of highly-textured PbZrO3 antiferroelectric films with a deposition temperature dependence

Thin PbZrO₃ (PZO) antiferroelectric films with (001)-preferred orientation were deposited on SrRuO₃/Ca₂Nb₃O₁₀-nanosheet/Si substrates using pulsed laser deposition. Variation of the deposition temperature was found to play a key role in the control of the microstructure and strongly influence the energy storage performance of the thin film. The critical phase switching field, where the aligned antiferroelectric (AFE) domains start to transform into the ferroelectric (FE) state, decreased with increasing temperature. On the other hand, the content of the FE phase in the AFE PZO thin films increased with increasing deposition temperature. A large recoverable energy-storage density of 16.8?J/cm³ and high energy-storage efficiency of 69.2% under an electric field of 1000?kV/cm were achieved in the films deposited at 525?°C. This performance was due to the high forward switching field and backward switching field values and the low difference between these two fields. Moreover, the PZO thin films showed great charge-discharge cycling life with fatigue-free performance up to 10¹⁰ cycles and good thermal stability from room temperature to 100?°C.     

A mechanical and modelling study of magnetron sputtered cerium-titanium oxide film coatings on Si (100)

Ce/Ti mixed metal oxide thin films have well known optoelectrical properties amongst several other physio-chemical properties. Changes in the structural and mechanical properties of magnetron sputtered Ce/Ti oxide thin films on Si (100) wafers with different Ce:Ti ratios are investigated experimentally and by modelling. X-ray Photoemission Spectroscopy (XPS) and X-ray diffraction (XRD) confirm the primary phases as trigonal Ce₂O₃ and rutile form of TiO₂ with SiO₂ present in all prepared materials. FESEM imaging delivers information based on the variation of grain size, the mixed Ce/Ti oxides providing much smaller grain sizes in the thin film/substrate composite. Nanoindentation analysis concludes that the pure cerium oxide film has the highest hardness value (20.1?GPa), while the addition of excess titanium oxide decreases the hardness of the film coatings. High temperature in-situ XRD (up to 1000?°C) results indicate high thermal phase stability for all materials studied. The film with Ce:Ti?=?68%:32% has a new additional minor oxide phase above 800?°C. Contact angle experiments suggest that the chemical composition of the surface is insignificant affecting the water contact angle. Results show a narrow band of 87.7–95.7° contact angle. The finite element modelling (FEM) modelling of Ce/Ti thin film coatings based on Si(100); Si(110); silica and steel substrates shows a variation in stress concentration.     

Controlled synthesis of Mg(OH)2 thin films by chemical solution deposition and their thermal transformation to MgO thin films

The chemical solution deposition of Mg(OH)₂ thin films on glass substrates and their transformation to MgO by annealing in air is presented. The chemical solution deposition consists of a chemical reaction employing an aqueous solution composed of magnesium sulfate, triethanolamine, ammonium hydroxide, and ammonium chloride. The as-deposited films were annealed at different temperatures ranging from 325 to 500?°C to identify the Mg(OH)₂-to-MgO transition temperature, which resulted to be around 375?°C. Annealing the as-deposited Mg(OH)₂ films at 500?°C results in homogeneous MgO thin films. The properties of the Mg(OH)₂ and MgO thin films were analyzed by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, UV–Vis spectroscopy, and by circular transmission line model. Results by X-ray diffraction show that the as-deposited thin films have a brucite structure (Mg(OH)₂), that transforms into the periclase phase (MgO) after annealing at 500?°C. For the as-deposited Mg(OH)₂ thin film, a nanowall surface morphology is found; this morphology is maintained after the annealing to obtain MgO, which occurred with the evident formation of pores on the nanowall surface. The assessed chemical composition from X-ray photoelectron spectroscopy yields Mg_0.36O_0.64 (O/Mg ratio of 1.8) for the as-deposited Mg(OH)₂ film, where the expected stoichiometric composition is Mg_0.33O_0.67 (O/Mg ratio of 2.0); the same assessment yields Mg_0.60O_0.40 (O/Mg ratio of 0.7) for the annealed thin film, which indicates the obtainment of a MgO material with oxygen vacancies, given the deviation from the stoichiometric composition of Mg_0.50O_0.50 (O/Mg ratio of 1.0). These results confirm the deposition of Mg(OH)₂ films and the obtainment of MgO after the heat-treatment. The energy band gap of the films is found to be 4.64 and 5.10?eV for the as-deposited and the film annealed at 500?°C, respectively. The resistivity of both Mg(OH)₂ and MgO thin films lies around 10⁸?Ω·cm.     

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.     

Ferroelectric yttrium doped hafnium oxide films from all-inorganic aqueous precursor solution

We report a unique aqueous solution deposition method to prepare yttrium doped hafnium oxide (Y:HfO₂) thin films using all-inorganic reagents. The composition and chemical bonding features of the films were investigated using X-ray photoelectron spectroscopy. The Y:HfO₂ film was integrated into metal-insulator-semiconductor (MIS) structure capacitors for electrical measurements. A transition of the polarization behavior from apparent ferroelectric-type to linear dielectric-type was observed for films with thickness increasing from 25?nm to 80?nm, which is correlated to the dominant crystal structure change from high-symmetry phase to monoclinic phase evidenced by grazing incidence X-ray diffraction analysis.     

Mechanically stable flat anodic titania membranes for gas transport applications

Anodic titanium oxide (ATO) membranes were produced by two-step anodic oxidation of titanium foil in ethylene glycol electrolyte containing NH₄F at the anodization voltage of 60?V. To provide the mechanical strength necessary for applying tubular anodic films as gas membranes, we utilized the formation of protective continuous TiO₂ layer at the top film surface prior to second anodization. As compared to conventional two-step anodic oxidation this technique decreases dissolution rates of titanium oxide phases with oxidation states lower than +4 (Ti₂O₃, Ti₃O₅), which are forming between titania nanotubes during anodization. The structural parameters of anodic titania films were determined by small-angle X-ray scattering and scanning electron microscopy techniques. According to SEM the proposed method resulted in growth of ATO films with a flat surface without nanotube endings, which enabled to use the films as gas separation membranes. The permeance of individual gases through ATO membranes were found to depend on gas molecular weight (M^?0.5), with absolute values twice exceeding theoretical permeabilities as it was predicted by Knudsen diffusion (up to 63?m³/(m²?×?bar?×?h) for nitrogen at 298?K). Here we ascribe this phenomenon to diffusion according to Knudsen-Smoluchoski mechanism (diffusion with slip, involving specular reflections of molecules), which is appropriate for membranes with straight pores and smooth internal pore surfaces.     

Sol-gel derived low temperature HfO2-GPTMS hybrid gate dielectric for a-IGZO thin-film transistors (TFTs)

In this study, we prepared inorganic-organic HfO₂-GPTMS hybrid films by a simple sol-gel method at low temperature for high-k dielectric gate applications. The hybrid films were deposited by spin coating process, followed by annealing at 150?°C. The hybrid dielectric material was characterized by Spectroscopic ellipsometry (SE), AFM, FESEM, FTIR, TGA, and XPS techniques. The resulting hybrid films exhibit homogeneous and smooth surface with high optical transparency. Their dielectric properties were analysed by measuring leakage current and capacitance versus voltage of metal-insulator-metal (MIM) capacitor structures. From this analysis, the leakage current density at ??5?V, capacitance and dielectric constant at 1?MHz measured on the hybrid films were 10^?7 A/cm², 51.3?nF/cm² and of 11.4 respectively. Finally, to investigate the electrical performance of the hybrid thin films as a dielectric gate in thin film transistors (TFTs), bottom-gate TFTs were fabricated by depositing the HfO₂-GPTMS dielectric gate layer on ITO-coated glass substrate and subsequently a sputtered a-IGZO thin film as the channel layer. The electrical response of the resulting TFTs demonstrated good saturation mobility of 4.74?cm² V^?1 s^?1, very low threshold voltage of 0.3?V and I_on/I_off current ratio of 10⁴, with low operating voltage under 8?V.     

Low‐Temperature Deposition of Hexagonal Boron Nitride via Sequential Injection of Triethylboron and N2/H2 Plasma

Hexagonal boron nitride (hBN) thin films were deposited on silicon and quartz substrates using sequential exposures of triethylboron and N₂/H₂ plasma in a hollow‐cathode plasma‐assisted atomic layer deposition reactor at low temperatures (≤450°C). A non‐saturating film deposition rate was observed for substrate temperatures above 250°C. BN films were characterized for their chemical composition, crystallinity, surface morphology, and optical properties. X‐ray photoelectron spectroscopy (XPS) depicted the peaks of boron, nitrogen, carbon, and oxygen at the film surface. B 1s and N 1s high‐resolution XPS spectra confirmed the presence of BN with peaks located at 190.8 and 398.3 eV, respectively. As deposited films were polycrystalline, single‐phase hBN irrespective of the deposition temperature. Absorption spectra exhibited an optical band edge at ~5.25 eV and an optical transmittance greater than 90% in the visible region of the spectrum. Refractive index of the hBN film deposited at 450°C was 1.60 at 550 nm, which increased to 1.64 after postdeposition annealing at 800°C for 30 min. These results represent the first demonstration of hBN deposition using low‐temperature hollow‐cathode plasma‐assisted sequential deposition technique.