Influence of hydrogenation on electrical conductivity of vanadium dioxide thin films

The influence of hydrogenation on electrical conductivity of vanadium dioxide thin films has been investigated. It has been shown using measurements of the electrical conductivity that the hydrogenation of vanadium dioxide thin films leads to a decrease in the temperature of the phase transition from the tetragonal phase (with “metallic” conductivity) to the semiconducting monoclinic phase. It has been found that, upon doping of vanadium dioxide with hydrogen, the electrical conductivity of the monoclinic phase can increase by several orders of magnitude. Nonetheless, the temperature dependence of the electrical conductivity of hydrogenated films exhibits a typical semiconducting behavior in the temperature range where the monoclinic phase is stable.     

Specific features of hydrogenation of chromium-doped polycrystalline thin vanadium dioxide films

It has been found that hydrogen penetration into chromium-doped polycrystalline thin vanadium dioxide films occurs with a lower rate than in the case of pure vanadium dioxide films. It has been shown that hydrogenation of films with low chromium concentrations is accompanied by a decrease in the phase transition temperature below T _c = 340 K. However, at room temperature in these hydrogenated films, no traces of M1 monoclinic phase have been observed. As the chromium concentration increases, hydrogenation ceases to be accompanied by the decrease in the phase transition temperature.     

Hydrogenation of Pd-capped Mg thin films prepared by DC magnetron sputtering

Structural and optical properties of pure Mg thin film coated with Pd have been investigated. Pd-capped Mg thin films had been prepared by DC magnetron sputtering. This work presents an ex situ study on hydrogenation and dehydrogenation kinetics of Pd/Mg films at different conditions using XRD, AFM and optical spectrophotometer. We have succeeded to load thin films of Mg to MgH₂ at normal temperature and normal pressure of hydrogen gas. In hydrogenation, α-MgH₂ phase of magnesium hydride was observed in hydrogenated films at 200 °C and γ-MgH₂ at 250 °C respectively. The desorption kinetics in vacuum also revealed the phase transformation α-MgH₂ to γ-MgH₂. A reflectance change was observed in hydrogenated films in comparison of as deposited thin film. Hydrogenated (H loaded) samples were observed partially transparent in comparison of as deposited.     

Effect of hydrogenation on the metal-semiconductor phase transition in vanadium dioxide thin films

Hydrogen penetration into thin films of vanadium dioxide from aqueous solutions of mono-, di-, and tribasic alcohols is studied. It is shown that this process is reversible, has a catalytic character, and brings about a lowering of the metal-semiconductor phase transition temperature. It is established that the phase transition in a hydrogenated H_xVO₂ film is completely suppressed for x> 0.04.     

Morphological transformations of vanadium oxide films during low-temperature reduction in hydrogen electron cyclotron resonance plasma

Morphological transformations of amorphous vanadium oxide films obtained by the sol-gel method and polycrystalline V₂O₅ films are studied during their low-temperature (295–623 K) reduction in a hydrogen electron cyclotron resonance plasma. The morphology of films is analyzed using atomic force microscopy and high-resolution electron microscopy. It is found that a homogeneous amorphous film during the reduction process transforms to an island film and then bulk amorphous islands of a regular shape appear. These islands resemble microcrystals, and their concentration depends on the temperature and the reduction time. The low-temperature reduction of polycrystalline V₂O₅ films leads to their amorphization; however, the microcrystals in the polycrystalline film do not change their shape in this process. A mechanism of the reduction process is proposed. This mechanism explains the regularities of morphological transformations in amorphous sol-gel films of vanadium oxides based on the suggestion of a competition between the ion-stimulated nucleation and growth of nuclei of the crystalline phase and the amorphization of the growing nuclei.     

Influence of the deposition parameters on the transition region of hydrogenated silicon films growth

Hydrogenated microcrystalline and amorphous silicon thin films were prepared by very high frequency plasmaenhanced chemical vapour deposition （VHF PECVD） by using a mixture of silane and hydrogen as source gas. The influence of deposition parameters on the transition region of hydrogenated silicon films growth was investigated by varying the silane concentration （SC）, plasma power （Pw）, working pressure （P）, and substrate temperature （Ts）. Results suggest that SC and Ts are the most critical factors that affect the film structure transition from microcrystalline to amorphous phase. A narrow region in the range of SC and Ts, in which the rapid phase transition takes place, was identified. It was found that at lower P or higher Pw, the transition region is shifted to larger SC. In addition, the dark conductivity and photoconductivity decrease with SC and show sharp changes in the transition region. It proposed that the transition process and the transition region are determined by the competition between the etching effect of atomic hydrogen and the growth of amorphous phase.     

Nanomechanical characterization of amorphous hydrogenated carbon thin films

Amorphous hydrogenated carbon (a-C:H) thin films deposited on a silicon substrate under various mixtures of methane-hydrogen gas by electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MPCVD) was investigated. Microstructure, surface morphology and mechanical characterizations of the a-C:H films were analyzed using Raman spectroscopy, atomic force microscopy (AFM) and nanoindentation technique, respectively. The results indicated there was an increase of the hydrogen content, the ratio of the D-peak to the G-peak (I_D/I_G) increased but the surface roughness of the films was reduced. Both hardness and Young's modulus increased as the hydrogen content was increased. In addition, the contact stress-strain analysis is reported. The results confirmed that the mechanical properties of the amorphous hydrogenated carbon thin films improved using a higher H₂ content in the source gas.     

MoSi2薄膜电子性质的第一性原理研究

采用第一性原理计算方法, 研究了四方MoSi₂薄膜的电子性质. 计算结果表明, 各种厚度的薄膜都是金属性的, 并且随着厚度的增加, 其态密度与能带结构都逐渐趋近于MoSi₂块体的特性. 通过对MoSi₂薄膜磁性的分析, 发现三个原子层厚的薄膜具有磁性, 其原胞净磁矩为0.33 μ_B; 而当薄膜的厚度大于三个原子层时, 薄膜不具有磁性. 此外, 进一步对单侧加氢饱和以及双侧加氢饱和结构下三原子层MoSi₂薄膜的电子性质进行了研究, 发现单侧加氢饱和的三原子层MoSi₂薄膜具有磁性, 其原胞净磁矩为0.26 μ_B, 而双侧加氢饱和三原子层MoSi₂薄膜是非磁性的. 双侧未饱和与单侧加氢饱和的三原子层MoSi₂薄膜的自旋极化率分别为30%和33%. 这些研究结果表明, 三原子层厚的MoSi₂ 超薄薄膜在悬空或者生长于基底之上时具有金属磁性, 预示着它在纳米电子学和自旋电子学器件等方面都有潜在的应用前景.     

Characteristics and properties of metal aluminum thin film prepared by electron cyclotron resonance plasma-assisted atomic layer deposition technology

Metal aluminum (Al) thin films are prepared by 2450-MHz electron cyclotron resonance plasma-assisted atomic layer deposition on glass and p-Si substrates using trimethylaluminum as the precursor and hydrogen as the reductive gas. We focus our attention on the plasma source for thin-film preparation and annealing of as-deposited films related to the surface square resistivity. The square resistivity of as-deposited Al film is greatly reduced after annealing and almost reaches the value of bulk metal. Through chemical and structure analysis we conclude that the square resistivity is determined by neither contaminant concentration nor surface morphology, but by both crystallinity and crystal size in this process.     

Hydrogenation effect on electrical,optical and magnetic properties of ZnSe/Co bilayer DMS thin films

This paper reports ZnSe/Co bilayer diluted magnetic semiconductor thin films have been prepared by using thermal evaporation technique. The bilayer DMS thin films were hydrogenated at different pressures (15–45 psi) for a constant time of 30 min. Before and after hydrogenations of these bilayer thin films the electrical, optical and magnetic properties have been investigated. Electrical resistivity and optical band gap were found to be increased with respect to hydrogenation pressure. X-ray diffraction (XRD) and magnetic measurements confirmed the formation of DMS ZnSe/Co bilayer DMS thin films. Raman spectra show the presence of hydrogen in these thin films. Surface topography study of as-grown, annealed and hydrogenated ZnSe/Co bilayer thin films indicates uniform deposition, mixing of layers and increment in roughness at the surface due to hydrogen passivation effect respectively.     

Structural changes of diamond-like carbon films due to atomic hydrogen exposure during annealing

We have deposited diamond-like carbon (DLC) films by radio-frequency magnetron sputtering, and have annealed the films under various conditions to investigate the effects of annealing on the structural properties by visible Raman spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy. The structural ordering of hydrogenated DLC films occurs during annealing below 400 °C in a vacuum and a hydrogen gas atmosphere, while unhydrogenated DLC films are not ordered during annealing even at 700 °C. On the other hand, the ordering and the decrease of the sp³ content are observed for both the films after annealing under an atomic hydrogen exposure. The ordering progresses as the annealing temperature and time are increased. The reduction of the film thickness after annealing is suppressed with increasing annealing temperature. The results suggest that both the preferential etching by atomic hydrogen and the hydrogen evolution encourage the structural changes under an atomic hydrogen exposure.     

Femtosecond pulse crystallization of thin amorphous hydrogenated films on glass substrates using near ultraviolet laser radiation

Femtosecond laser treatments (second harmonic of Ti-sapphire laser, λ ≈ 400 nm wavelength, <30 fs pulse duration) were applied for crystallization of thin hydrogenated amorphous silicon films on glass substrates. The concentration of atomic hydrogen in the films was varied from 10 to ≈35%. The energy densities (laser fluences) for crystallization of the films with thicknesses from 20 to 130 nm were found. Assumedly, non-thermal processes (plasma annealing) take place in phase transition caused ultra-fast pulses. The developed approach can be used for creation of polycrystalline silicon films on non-refractory substrates.     

纳米VOx薄膜在空气中的电学特性退化研究

采用射频磁控溅射法在氮化硅衬底上沉积纳米VO_x薄膜,利用X射线衍射、原子力显微镜分别对薄膜的结晶形态及表面形貌进行表征.研究了纳米VO_x薄膜在空气中长时间暴露后的方块电阻、热滞回线等电学特性的变化情况,并分析这些变化给器件带来的影响.利用X射线光电子能谱仪、傅里叶变换红外光谱仪分析对比新制与久置薄膜的组分及分子结构差异.研究表明,暴露在空气中的纳米VO_x薄膜方块电阻增大是因为低价钒离子被吸附氧原子氧 关键词： x薄膜')" href="#">纳米VO_x薄膜 磁控溅射 电学特性 退化     

Effect of hydrogen on surface texturing and crystallization of a-Si:H thin film irradiated by excimer laser

Hydrogenated amorphous silicon (a-Si:H) thin films have been considered for use in solar cell applications because of their significantly reduced cost compared to crystalline bulk silicon. However, their overall efficiency and stability are lower than that of their bulk crystalline counterpart. Limited work has been performed on simultaneously solving the efficiency and stability issues of a-Si:H. Previous work has shown that surface texturing and crystallization on a-Si:H thin film can be achieved through a single-step laser processing, which can potentially alleviate the disadvantages of a-Si:H in solar cell applications. In this study, hydrogenated and dehydrogenated amorphous silicon thin films deposited on glass substrates were irradiated by KrF excimer laser pulses and the effect of hydrogen on surface morphologies and microstructures is discussed. Sharp spikes are focused only on hydrogenated films, and the large-grained and fine-grained regions caused by two crystallization processes are also induced by presence of hydrogen. Enhanced light absorptance is observed due to light trapping based on surface geometry changes of a-Si:H films, while the formation of a mixture of nanocrystalline silicon and original amorphous silicon after crystallization suggests that the overall material stability can potentially improve. The relationship between crystallinity, fluence and number of pulses is also investigated. Furthermore, a step-by-step crystallization process is introduced to prevent the hydrogen from diffusing out in order to reduce the defect density, and the relationship between residue hydrogen concentration, fluence and step width is discussed. Finally, the combined effects show that the single-step process of surface texturing and step-by-step crystallization induced by excimer laser processing are promising for a-Si:H thin-film solar cell applications.     

Second harmonic generation in α-Si:H thin films: Thickness dependence

The second harmonic generation (SHG) technique has been applied to investigate the nonlinear optical properties of thin films of hydrogenated amorphous silicon on a glass substrate. SHG measurements have been performed in two transmission experimental schemes. Modeling of a film as a three-layer structure and considering the interference and absorption at the SH wavelength have been carried out. The dependence of the nonlinear susceptibility on the film thickness was used to separate the bulk electric dipole contribution.     

Improvement of the PLD process assisted by RF plasma for AlN growth

The pulsed-laser-deposition (PLD) method is particularly well suited for the growth of oxide thin films, but in the case of other compounds, such as nitrides, PLD presents some limitations which are mainly due to the low reactivity of nitrogen in comparison with oxygen. A possible way to overcome this problem is to increase the reactivity of the constituent species, via plasma assisted-pulsed-laser deposition. A plasma is coupled to the ablation chamber, in order to increase the density of reactive atomic species, which can be further incorporated in the growing film. This approach is described in this paper as well as the nature, energy, and concentration of the atomic and molecular species in the plasma as determined by various plasma diagnostics. These results are correlated to the growth of thin films in the particular case of the aluminum nitride compound. The composition and structure of the films are studied as a function of the growth conditions, and the positive effects of the additional discharge are evidenced on the film purity and properties. The fundamental problem with the PLD technique, especially with metallic targets, is the production of unwanted droplets that significantly worsen the properties of the films. To eliminate these droplets, a thin film has been grown with an experimental setup using two targets and crossed laser beams which gave positive results. PACS 81.15.Fg; 52.80.Pi; 77.84.Bw     

Investigations on non-stoichiometric zirconium nitrides

Non-stoichiometric zirconium nitride thin films were prepared by reactive dc magnetron sputtering. Structural, optical and electrical properties were investigated with respect to nitrogen gas flow. The film characterization was obtained through various techniques: Rutherford back scattering (RBS), X-ray diffraction (XRD), reflectometry and a four probe method. We found that the deposition rate decreases while the nitrogen flow increases. Also it was shown that a stoichiometric compound (ZrN) is formed at a 4 sccm nitrogen flow. It has a rock-salt structure and presents a minimum of resistivity and a gold-like color. As nitrogen flow increases, films become more and more amorphous, semi-transparent and electrically resistive. Furthermore, at a nitrogen flow of 9 sccm, the nitrogen to zirconium atomic concentration ratio is near 1.33 and the film exhibits properties close to those of a Zr₃N₄ phase.     

Structure and catalytic properties of MoSe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> thin films containing Mo nanoparticles in electrochemical production of hydrogen in solution

The introduction of molybdenum nanoparticles in MoSe _x thin films formed by pulsed laser deposition led to changes in the film structure. The base planes of the layered atomic packing of the MoSe _х matrix around Mo nanoparticles rotated; as a consequence, the edge sites that formed during the “breaking” of the Se–Mo–Se layered atomic packing came out to the film surface. At high nanoparticle concentrations, this effect led to high density of edge sites possessing increased catalytic activity (compared with that of the base planes) for initiating the electrochemical evolution of hydrogen in a 0.5 M H₂SO₄ solution. Voltammetric measurements at room temperature showed that when the carbon cathode was coated with MoSe _x thin films under optimum conditions, the hydrogen overvoltage considerably decreased, and the cathodic current increased. The results indicate that developments in the field of preparation of nanostructured electrodes based on layered transition metal dichalcogenides show promise as an alternative to expensive electrodes based on platinum group metals for electrocatalysts of hydrogen evolution.     

Interaction of hydrogen with InN thin films elaborated on InP(1 0 0)

III-V semiconductor compound structures are widely applied in technology of advanced microelectronics, optoelectronics, and gas sensors. In this paper, we report on the use of XPS to characterize in situ the interaction of thermally activated hydrogen atoms and hydrogen molecules with InP(1 0 0) surfaces covered by thin InN overlayers. XPS spectra were taken with an ESCALAB-210 spectrometer after repeated hydrogenation cycles at temperatures up to 350 °C. The evolution of the In 3d, In 4d, P 2p, N 1s, O 1s and C 1s photoelectron spectra was carefully monitored. The XPS spectra of the hydrogen exposed surface revealed significant differences compared to those from the non-hydrogenated surface. InN films were found to be weakly reactive to hydrogen under experimental conditions explored. The behavior of P atoms at the hydrogenated surface was dependent on the parameters characterizing each hydrogenation (exposure, hydrogen species used, annealing temperature). Moreover, the heavily hydrogenated surface exhibited a phosphorus enrichment.     

Surface and bulk phenomena in the process of GdHx (0.01 < x < 3) formation in thin Gd films: Transition from metal to transparent semiconductor

The aim of this work was to answer the question whether in the process of gadolinium hydride formation the negatively charged hydrogen adspecies arise directly on the surface at some coverage, or a transition from protonic to anionic hydrogen occurs in the bulk. Thin gadolinium films were deposited on glass under UHV conditions and transformed “in situ” into GdH_x (0.01 < x < 3) by introducing H₂ in successive calibrated doses. Work function changes ΔΦ and pressure P were recorded continuously. Knowing the weight of the thin Gd film and the amount of hydrogen consumed, the atomic ratio H/Gd could be determined and correlated with ΔΦ and P at every step of the process. Parallel experiments were performed measuring the resistance and optical transparency of thin gadolinium films deposited under identical conditions during their transition into GdH_x (0.01 < x < 3). It was found that in the process of GdH_x formation, light-reflecting metallic thin Gd film is transferred into transparent trihydride while its resistance increases by several orders of magnitude. At low coverage, positively polarized hydrogen adspecies arise, penetrating quickly into the bulk. When the average H/Gd concentration approaches 1, negatively charged hydrogen adspecies appear directly on the surface, slowly penetrating into the bulk.