带隙可调的Al，Mg掺杂ZnO薄膜的制备

利用射频磁控溅射（RF-MS）方法,固定Al₂O₃掺杂量2 wt%,Mg掺杂量分别为1 wt%,3 wt%和5 wt%,在玻璃基底上制备了Al掺杂和Al,Mg共掺杂的ZnO薄膜,在500 ℃空气中退火2 h后,测量并比较了它们的光学和电学性质．结果表明,Al,Mg共掺杂的ZnO薄膜结晶质量良好,具有ZnO纤锌矿结构,具有较强的（002）面衍射峰,表明薄膜晶体沿c轴优先生长;与Al掺杂ZnO薄膜相比蓝端光透射率增加,1 wt%和3 wt% Mg掺杂薄 关键词： 射频磁控溅射 ZnO薄膜 Al Mg共掺杂     

反应磁控溅射ZrN/AlON纳米多层膜的晶体生长和超硬效应

采用Zr靶和Al₂O₃靶通过在Ar，N₂混合气氛中进行反应磁控溅射的方法制备了不同AlON调制层厚和不同ZrN调制层厚的两个系列的ZrN/AlON纳米多层膜.利用X射线能量色散谱仪、X射线衍射仪、高分辨透射电子显微镜和微力学探针研究了多层膜的成分、微结构和力学性能.结果表明，在Ar，N₂混合气氛中对Al₂O₃进行溅射的过程中，N原子会部分取代Al₂O₃中的氧原子，形成AlON化合物.在ZrN/AlON纳米多层膜中，由于受到ZrN晶体调制层的模板作用，溅射条件下以非晶态存在的AlON层在其厚度小于0.9nm时被强制晶化并与ZrN层形成共格外延生长；相应地，多层膜的硬度明显提高，最高硬度达到33.0GPa.进一步增加多层膜中AlON调制层的厚度，AlON层形成非晶结构，破坏了多层膜的共格外延生长，导致其硬度逐步降低. 关键词： ZrN/AlON纳米多层膜 外延生长 非晶晶化 力学性能     

The film thickness dependent thermal stability of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>:Ag thin films as high-temperature solar selective absorbers

The monolayer Al₂O₃:Ag thin films were prepared by magnetron sputtering. The microstructure and optical properties of thin film after annealing at 700 °C in air were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and spectrophotometer. It revealed that the particle shape, size, and distribution across the film were greatly changed before and after annealing. The surface plasmon resonance absorption and thermal stability of the film were found to be strongly dependent on the film thickness, which was believed to be associated with the evolution process of particle diffusion, agglomeration, and evaporation during annealing at high temperature. When the film thickness was smaller than 90 nm, the film SPR absorption can be attenuated until extinct with increasing annealing time due to the evaporation of Ag particles. While the film thickness was larger than 120 nm, the absorption can keep constant even after annealing for 64 h due to the agglomeration of Ag particles. On the base of film thickness results, the multilayer Al₂O₃:Ag solar selective thin films were prepared and the thermal stability test illustrated that the solar selectivity of multilayer films with absorbing layer thickness larger than 120 nm did not degrade after annealing at 500 °C for 70 h in air. It can be concluded that film thickness is an important factor to control the thermal stability of Al₂O₃:Ag thin films as high-temperature solar selective absorbers.     

First nucleation steps of vanadium oxide thin films studied by XPS inelastic peak shape analysis

The initial states of deposition of vanadium oxide thin films have been studied by analysis of the peak shape (both inelastic background and elastic contributions) of X-ray photoemission spectra (XPS) after successive deposition experiments. This study has permitted to assess the type of nucleation and growth mechanisms of the films. The experiments have been carried out in situ in the preparation chamber of a XPS spectrometer. Thin films of vanadium oxide have been prepared on Al₂O₃ and TiO₂ by means of thermal evaporation, ion beam assisted deposition and plasma enhanced chemical vapour deposition. The thin films prepared by the first two procedures consisted of V₂O₄, while those prepared by the latter had a V₂O₅ stoichiometry. The analysis of the inelastic background of the photoemission spectra has shown that the films prepared by thermal evaporation on Al₂O₃ are formed by big particles that only cover completely the surface of the substrate when their height reaches 16 nm. By contrast, the thin films prepared with assistance of ions on Al₂O₃ or with plasma on TiO₂ consist of smaller particles that succeed in covering the substrate surface already for a height of approximately 4 nm. Thin films prepared by plasma-assisted deposition on Al₂O₃ depict an intermediate situation where the substrate is completely covered when the particles have a height of approximately 6 nm. The type of substrates, differences in the deposition procedure or the activation of the adatoms by ion bombardment are some of the factors that are accounted for by to explain the different observed behaviours.     

Monitoring structural defects and crystallinity of carbon nanotubes in thin films

We report the influence of catalyst formulation and reaction temperature on the formation of carbon nanotube (CNT) thin films by the chemical vapour deposition (CVD) method. Thin films of CNTs were grown on Fe-Mo/Al₂O₃-coated silicon wafer by thermal decomposition of methane at different temperatures ranging from 800 to 1000°C. The electron microscopic investigations, SEM as well as HRTEM, of the as-grown CNT thin films revealed the growth of uniform multi-walled CNTs in abundance. The intensity ratio of D-band to G-band and FWHM of G-band through Raman measurements clearly indicated the dependency of structural defects and crystallinity of CNTs in thin films on the catalyst formulation and CVD growth temperature. The results suggest that thin films of multi-walled CNTs with negligible amount of defects in the nanotube structure and very high crystallinity can be obtained by thermal CVD process at 925°C.     

Characterization of CuAlO2 thin film prepared by rapid thermal annealing of an Al2O3/Cu2O/sapphire structure

CuAlO₂ thin film was successfully prepared by rapid thermal annealing of an Al₂O₃/Cu₂O/sapphire structure in air above 1000 °C. The film was mostly with single crystalline structure as verified by X-ray diffraction methods. We found that crystal quality and electrical conductivity of the films were affected by the cooling rate after annealing. The highest conductivity obtained in this work was 0.57 S/cm. Optical gap of this film was determined to be 3.75 eV.     

Study of Sm-doped ZnO samples sintered in a nitrogen atmosphere and deposited on n-Si(1 0 0) by evaporation technique

The samarium doping zinc oxide (Zn_1-xSm_xO) with (x=0.0, 0.04, 0.05 and 0.17) polycrystalline thin films have been deposited on n-Si(1 0 0) substrate using thermal evaporation technique. Ceramic targets for deposition were prepared by the standard solid-state reaction method and sintered in nitrogen atmospheres. X-ray diffraction and scanning electron microscopy analyses show that the bulk and films features reveal wurtzite crystal structure with a preferential (1 0 1) crystallographic orientation and grows as hexagonal shape grains. According to the results of the Hall effect measurements, all the films show p-type conductivity, possibly a result of nitrogen incorporation into the Sm-doped ZnO samples. Magnetic measurements show that ferromagnetic behavior depends on the Sm³⁺ concentration. For a film with lower Sm₂O₃ contents (x=0.04), a phenomenon of paramagnetism has been observed. While, with further increase of Sm³⁺ contents (x=0.05) the ferromagnetic behavior has been observed at room temperature. However, at higher doping content of Sm³⁺, the ferromagnetic behavior was suppressed. The decrease of ferromagnetism with increasing doping concentration demonstrates that ferromagnetism observed at room temperature is an intrinsic property of Zn_1-xSm_xO films.     

Effect of 60Co γ-irradiation on structural and optical properties of thin films of Ga10Se80Hg10

Thin films of Ga₁₀Se₈₀Hg₁₀ have been deposited onto a chemically cleaned Al₂O₃ substrates by thermal evaporation technique under vacuum. The investigated thin films are irradiated by ⁶⁰Co γ-rays in the dose range of 50–150 kGy. X-ray diffraction patterns of the investigated thin films confirm the preferred crystallite growth occurs in the tetragonal phase structure. It also shows, the average crystallite size increases after γ-exposure, which indicates the crystallinity of the material increases after γ-irradiation. These results were further supported by surface morphological analysis carried out by scanning electron microscope and atomic force microscope which also shows the crystallinity of the material increases with increasing the γ-irradiation dose. The optical transmission spectra of the thin films at normal incidence were investigated in the spectral range from 190 to 1100 nm. Using the transmission spectra, the optical constants like refractive index (n) and extinction coefficient (k) were calculated based on Swanepoel’s method. The optical band gap (E_g) was also estimated using Tauc’s extrapolation procedure. The optical analysis shows: the value of optical band gap of investigated thin films decreases and the corresponding absorption coefficient increases continuously with increasing dose of γ-irradiation.     

Crystallinity and morphology dependent luminescence of Li-doped Y2−xGdxO3:Eu thin film phosphors

The influence of lithium doping on the crystallization, the surface morphology, and the luminescent properties of pulsed laser deposited Y_2−xGd_xO₃:Eu³⁺ thin film phosphors was investigated. The crystallinity, the surface morphology, and the photoluminescence (PL) of films depended highly on the Li-doping and the Gd content. The relationship between the crystalline and morphological structures and the luminescent properties was studied, and Li⁺ doping was found to effectively enhance not only the crystallinity but also the luminescent brightness of Y_2−xGd_xO₃:Eu³⁺ thin films. In particular, the incorporation of Li and Gd into the Y₂O₃ lattice could induce remarkable increase in the PL. The highest emission intensity was observed Li-doped Y_1.35Gd_0.6O₃:Eu³⁺ thin films whose brightness was increased by a factor of 4.6 in comparison with that of Li-doped Y₂O₃:Eu³⁺ thin films.     

Effect of nitrogen doping on the thermal conductivity of GeTe thin films

The 3ω method was employed to determine the effect of nitrogen doping (5 at.%) on the thermal conductivity of sputtered thin films of stoichiometric GeTe (a material of interest for phase change memories). It was found that nitrogen doping has a detrimental effect on the thermal conductivity of GeTe in both phases, but less markedly in the amorphous (–25%) than in the crystalline one (–40%). On the opposite, no effect could be detected on the measured thermal boundary resistance between these films and SiO₂, within the experimental error. Our results agree with those obtained by molecular dynamic simulation of amorphous GeTe. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

新型混合离子-电子导体Sm0.9Ca0.1Al1-xMnxO3-δ的制备及其电性能研究

采用有机凝胶法结合固相烧结技术制备了单相的Sm_0.9Ca_0.1Al_1-xMn_xO_3-δ（SCAM, x=0.1—0.5）新型混合离子-电子导体.通过TG-DTA,XRD和直流四引线法研究了凝胶前驱体的热分解和相转化过程、烧结体的结构、相稳定性、导电性能及其电输运机理.结果表明,凝胶前驱体在900℃焙烧5h可以形成完全晶化的四方钙钛矿相纳米粉体 关键词： 混合离子-电子导体 3')" href="#">SmAlO₃ 有机凝胶法 电导率     

Effect of chloride doping concentration on enhancement of protonic conductivity of mesoporous Al2O3

Mesoporous Al₂O₃ was prepared by a sol-gel method with doping different amount of LaCl₃. The proton conductivity of mesoporous Al₂O₃ increased with increasing the doping concentration up to the optimum doping, 0.1 Cl/Al mole ratio. The surface acidities of different samples were investigated by NH₃-TPD method. The change trends of surface acidity are consistent with that of proton conductivity. It indicates that the proton conductivity of mesoporous Al₂O₃ can be increased by enhancing its surface acidity via the chloride doping.     

Effects of substrate on surface morphology, crystallinity, and photoluminescence properties of sputtered ZnO nano films

Effects of substrate on crystallinity, surface morphology, and luminescence properties of radio frequency sputtered zinc oxide (ZnO) thin films were investigated. A variety of materials such as Si (100), Si (111), Al₂O₃, quartz, and silicon carbide (SiC) wafers were examined as substrates for deposition of ZnO thin films. The results showed smooth and uniform growth of c-axis orientation films. The thickness of the layers was about 50 nm. The average grain sizes of films were about 10, 13, and 12 nm for Si (111), quartz, and SiC samples, respectively. The deposited film on Al₂O₃ showed the largest grain size, about 500 nm. Grazing incidence x-ray diffraction patterns of the samples revealed that sputtered layers on Al₂O₃ and quartz had better crystallinity with higher peak at (002) orientation compared to Si and SiC substrates. Moreover, the Al₂O₃ sample exhibited a weak peak at position of (100) planes of ZnO too. The photoluminescence spectra of the samples showed a typical luminescence behavior with a broad UV band, including a main peak at around 388 nm and a weak shoulder peak at around 381 nm, corresponding with bound excitonic recombination and free excitonic recombination, respectively. The luminescence peak revealed that the intensity of UV emission is not necessarily dependent on the grain sizes and the micro-structural quality of ZnO films.     

Photoluminescence behavior of pulsed laser deposited ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript> thin-film phosphors grown on various substrates

ZnGa₂O₄ thin-film phosphors have been grown on Si(100), Al₂O₃(0001) and MgO(100) substrates using pulsed laser deposition. The structural characterization was carried out on a series of ZnGa₂O₄ films grown on various substrates under various substrate temperatures and oxygen pressures. The films grown on these substrates not only have different crystallinity and surface morphology, but also different Zn/Ga composition ratio. The crystallinity and photoluminescence (PL) of the ZnGa₂O₄ films are highly dependent on the deposition conditions, in particular the stoichiometry ratio of Zn/Ga and the kind of substrate. The variation of Zn/Ga in the films also depends on not only the oxygen pressure but also the substrate temperature during deposition. The PL properties of pulsed laser deposited ZnGa₂O₄ thin films have indicated that Al₂O₃(0001) and MgO(100) are promising substrates for the growth of high-quality ZnGa₂O₄ thin films and that the luminescence brightness depends on the substrate. The luminescence spectra show a broad band extending from 350 to 600 nm and peaking at 460 nm. Received: 11 July 2002 / Accepted: 31 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +82-51-6206356, E-mail: jhjeong@pknu.ac.kr     

A comparative study of the physical properties of Sb2S3 thin films treated with N2 AC plasma and thermal annealing in N2

As-deposited antimony sulfide thin films prepared by chemical bath deposition were treated with nitrogen AC plasma and thermal annealing in nitrogen atmosphere. The as-deposited, plasma treated, and thermally annealed antimony sulfide thin films have been characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy, scanning electron microscopy, atomic force microscopy, UV-vis spectroscopy, and electrical measurements. The results have shown that post-deposition treatments modify the crystalline structure, the morphology, and the optoelectronic properties of Sb₂S₃ thin films. X-ray diffraction studies showed that the crystallinity of the films was improved in both cases. Atomic force microscopy studies showed that the change in the film morphology depends on the post-deposition treatment used. Optical emission spectroscopy (OES) analysis revealed the plasma etching on the surface of the film, this fact was corroborated by the energy dispersive X-ray spectroscopy analysis. The optical band gap of the films (E_g) decreased after post-deposition treatments (from 2.36 to 1.75 eV) due to the improvement in the grain sizes. The electrical resistivity of the Sb₂S₃ thin films decreased from 10⁸ to 10⁶ Ω-cm after plasma treatments.     

Effect of Annealing Temperature on Structural and Optical Properties of N-Doped ZnO Films

Nitrogen-doped ZnO （ZnO：N） films are prepared by thermal oxidation of sputtered Zn3N2 layers on A1203 substrates. The correlation between the structural and optical properties of ZnO：N films and annealing temperatures is investigated. X-ray diffraction result demonstrates that the as-sputtered Zn3N2 films are transformed into ZnO：N films after annealing above 600℃. X-ray photoelectron spectroscopy reveals that nitrogen has two chemical states in the ZnO：N films： the No acceptor and the double donor （N2）o. Due to the No acceptor, the hole concentration in the film annealed at 700℃ is predicted to be highest, which is also confirmed by Hall effect measurement. In addition, the temperature dependent photoluminescence spectra allow to calculate the nitrogen acceptor binding energy.     

Structural, optical and electrical properties of ZnO and ZnO-Al2O3 films prepared by dc magnetron sputtering

ZnO and ZnO-Al₂O₃ thin films were prepared by dc magnetron sputtering and their structural, optical and electrical properties were studied comparatively. It is discovered that the ZnO-Al₂O₃ thin films remain transparent in a shorter wavelength range than the ZnO films, resulting from the increase of their band gap. Their resistivity decreases by seven orders of magnitude, which is caused by doping of Al to ZnO grains in the film. Preferential orientation of ZnO grains in the ZnO-Al₂O₃ thin films deteriorates because of the existence of Al₂O₃ impurity phase in the film. Received: 5 January 1999 / Accepted: 11 October 1999 / Published online: 8 March 2000     

Pulsed laser deposition of high temperature protonic films

Pulsed laser deposition has been used to fabricate nanostructured BaCe_0.85Y_0.15O_3−δ films. Protonic conduction of the fabricated BaCe_0.85Y_0.15O_3−δ films was compared to the sintered BaCe_0.85Y_0.15O_3−δ. Sintered samples and laser targets were prepared by sintering BaCe_0.85Y_0.15O_3−δ powders derived by solid state synthesis. Films 1 to 8 μm thick were deposited by KrF excimer laser on porous Al₂O₃ substrates. Thin films were fabricated at deposition temperatures of 700 to 950 °C at O₂ pressures up to 200 mTorr using laser pulse energy densities of 1.4–3 J/cm². Fabricated films were characterized by X-ray diffraction, electron microscopy and electrical impedance spectroscopy. Single phase BaCe_0.85Y_0.15O_3−δ films with a columnar growth morphology are observed with preferred crystal growth along the [100] or [001] direction. Results indicate [100] growth dependence upon laser pulse energy. Electrical conductivity of bulk samples produced by solid state sintering and thin film samples were measured over a temperature range of 100 to 900 °C. Electrical conduction behavior was dependent upon film deposition temperature. Maximum conductivity occurs at deposition temperature of 900 °C; the electrical conductivity exceeds the sintered specimen. All other deposited films exhibit a lower electrical conductivity than the sintered specimen. Activation energy for electrical conduction showed dependence upon deposition temperature, it varied from 115 to 54 kJ. Film microstructure was attributed to the difference in electrical conductivity of the BaCe_0.85Y_0.15O_3−δ films.     

Effect of crystallinity of ZnO buffer layer on the properties of epitaxial (ZnO:Al)/(ZnO:Ga) bi-layer films deposited on c-sapphire substrate

Bi-layer ZnO films with 2 wt.% Al (AZO; ZnO:Al) and 4 wt.% Ga-doped (GZO; ZnO:Ga) were deposited on the ZnO buffered and annealed ZnO buffered c(0 0 0 1)-sapphire(Al₂O₃) substrates respectively by Pulsed Laser Deposition (PLD). The effect of crystallinity of ZnO buffer layer on the crystallinity and electrical properties of the AZO/GZO bi-layer thin films was investigated. It was seen that the crystallinity of ZnO buffer layer had a great influence on the orientation and defect density of AZO/GZO bi-layer thin films from X-ray Diffraction (XRD) peaks and High Resolution Transmission Electron Microscopy (HRTEM) images. In a word, it was found in the films that more preferred c-axis orientation texture and reduction of the defects such as stacking faults and dislocations, with increasing of the crystallinity of ZnO buffer layer.     

Influences of the iron ion (Fe)-doping on structural and optical properties of nanocrystalline TiO2 thin films prepared by sol-gel spin coating

Titanium dioxide (TiO₂) thin films doping of various iron ion (Fe³⁺) concentrations were deposited on silicon (Si) (100) and quartz substrates by sol-gel Spin Coating technique followed by a thermal treatment at 600 °C. The structure, surface morphology and optical properties, as a function of the doping, have been studied by X-ray diffractometer (XRD), Raman, ultraviolet-visible (UV-vis) and Spectroscopic Ellipsometry (SE). XRD and Raman analyzes of our thin films show that the crystalline phase of TiO₂ thin films comprised only the anatase TiO₂, but the crystallinity decreased when the Fe³⁺ content increased from 0% to 20%. During the Fe³⁺ addition to 20%, the phase of TiO₂ thin film still maintained the amorphous state. The grain size calculated from XRD patterns varies from 29.3 to 22.6 nm. The complex index and the optical band gap (E_g) of the films were determined by the spectroscopic ellipsometry analysis. We have found that the optical band gap decreased with an increasing Fe³⁺ content.