Manipulating Bonding at a Cu/(0001)Al2O3 Interface by Different Substrate Cleaning Processes

Growth of Cu films on (0001)Al₂O₃ substrates can result in metallic Cu—Al or ionic-covalent Cu—O bonds at atomically abrupt interfaces. The type of bonding depends on the substrate cleaning procedure prior to film growth. Cu films deposited on Ar⁺-ion sputter-cleaned substrates exhibit interfacial Cu-L_2,3, Al-L_2,3 and O-K energy-loss near-edge structures that indicate the formation of metallic Cu—Al bonds at the Cu/Al₂O₃ interface. In contrast, growth on chemically cleaned -Al₂O₃ substrates results in interfacial energy-loss near-edge structures that suggest Cu—O bonding at the interface. The experimental electron energy-loss spectroscopic results are compared to calculated spectra, and the mechanisms causing the changes in the atomic and electronic structure are addressed.     

Effect of annealing temperature on the microstructure and optical–electrical properties of Cu–Al–O thin films

We have successfully prepared Cu–Al–O thin films on silicon (100) and quartz substrates by radio frequency (RF) magnetron sputtering method. The as-deposited Cu–Al–O film is amorphous in nature and post-annealing treatment in argon ambience results in crystallization of the films and the formation of CuAlO₂. The annealing temperature plays an important role in the surface morphology, phase constitution and preferred growth orientation of CuAlO₂ phase, thus affecting the properties of the film. The film annealed at 900 °C is mainly composed of CuAlO₂ phase and shows smooth surface morphology with well-defined grain boundaries, thus exhibiting the optimum optical–electrical properties with electrical resistivity being 79.7 Ω·cm at room temperature and optical transmittance being 80% in visible region. The direct optical band gaps of the films are found in the range of 3.3–3.8 eV depending on the annealing temperature.     

Growth and properties of YAlO film synthesized by RF magnetron sputtering

YAlO films are synthesized on (1 0 0)-oriented Si substrates by RF magnetron sputtering method. Al₂O₃ wafer is used as a target material, and some small pieces of Y bulk material are put on the Al₂O₃ target to synthesize YAlO films. Y composition ratio is varied from 0 to 34%. Amorphous YAlO films are characterized. An electrical resistivity as high as 3.4 × 10¹⁴ Ω-cm is achieved for the YAlO film with Y composition ratio of 10%. The dielectric constant increases with increasing Y composition ratio, and the YAlO film with Y composition ratio of 34% has a dielectric constant of 10.2. The bandgap energy of the YAlO film is suggested to be wider than 6.5 eV. YAlO films with a surface roughness of 0.4-1.3 nm are obtained irrespective of the Y composition ratio.     

Nanoscale Analysis of Multilayer Interfaces of W/Al2O3/Ti/Cu

W, Al₂O₃ and Ti films were deposited onto a Cu substrate by means of the rf magnetron sputtering method. After deposition, the foils were annealed at various temperatures in vacuum and the interfaces of the films were observed by a field-emission transmission electron microscopy (FE-TEM), after preparing a cross-sectional thin foil using a focused ion beam (FIB) machine. After annealing the foil at 473 and 623 K, no reaction phases were identified at each interface of W/Al₂O₃, Al₂O₃/Ti and Ti/Cu-substrate. However, from the results of compositional analysis at the interface of Al₂O₃/Ti bilayer, after heat-treatment at 623 K, the formation of an oxide layer was suggested even though it was not clearly observed. On the other hand, after heat-treatment at 823 K, the formation of CuTi₂, Cu₃Ti₂ and Cu₄Ti phases were identified at the interface of Ti/Cu bilayers from the compositional analysis of reaction layers after heat-treatment at different temperatures, and the diffusion coefficients and activation energies in the phases were evaluated. In this paper, the influence of heat-treatment on the interfacial behavior of multilayer are discussed on the basis of nanoscale analysis by EDS and HRTEM images.     

Interfacial reactions and oxidation behavior of Al2O3 and Al2O3/Al coatings on an orthorhombic Ti2AlNb alloy

The uniform and dense Al₂O₃ and Al₂O₃/Al coatings were deposited on an orthorhombic Ti₂AlNb alloy by filtered arc ion plating. The interfacial reactions of the Al₂O₃/Ti₂AlNb and Al₂O₃/Al/Ti₂AlNb specimens after vacuum annealing at 750 °C were studied. In the Al₂O₃/Ti₂AlNb specimens, the Al₂O₃ coating decomposed significantly due to reaction between the Al₂O₃ coating and the O-Ti₂AlNb substrate. In the Al₂O₃/Al/Ti₂AlNb specimens, a γ-TiAl layer and an Nb-rich zone came into being by interdiffusion between the Al layer and the O-Ti₂AlNb substrate. The γ-TiAl layer is chemically compatible with Al₂O₃, with no decomposition of Al₂O₃ being detected. No internal oxidation or oxygen and nitrogen dissolution zone was observed in the O-Ti₂AlNb alloy. The Al₂O₃/Al/Ti₂AlNb specimens exhibited excellent oxidation resistance at 750 °C.     

Transparent nano composite PVA–TiO2 and PMMA–TiO2 thin films: Optical and dielectric properties

Transparent nano composite PVA–TiO₂ and PMMA–TiO₂ thin films were prepared by an easy and cost effective dip coating method. Al/PVA–TiO₂/Al and Al/PMMA–TiO₂/Al sandwich structures were prepared to study the dielectric behavior. The presence of metal–oxide (Ti–O) bond in the prepared films was confirmed by Fourier transform infrared spectroscopy. X-ray diffraction pattern indicated that the prepared films were predominantly amorphous in nature. Scanning electron micrographs showed cluster of TiO₂ nanoparticles distributed over the film surface and also there were no cracks and pin holes on the surface. The transmittance of the films was above 80% in the visible region and the optical band gap was estimated to be about 3.77 eV and 3.78 eV respectively for PVA–TiO₂ and PMMA–TiO₂ films by using Tauc's plot. The determined refractive index (n) values were between 1.6 and 2.3. High value of dielectric constant (?′ = 24.6 and ?′ = 26.8) was obtained for the prepared composite films. The conduction in the composite films was found to be due to electrons. The observed amorphous structure, good optical properties and dielectric behavior of the prepared nano composite thin films indicated that these films could be used in opto-electronic devices and in thin film transistors.     

Structural properties of Al2O3 dielectrics grown on TiN metal substrates by atomic layer deposition

We investigated on the structural properties of Al₂O₃ dielectrics grown on TiN metal substrates using an atomic layer deposition technique with tri-methyl-aluminum and either O₃ or H₂O as the precursor and oxidant, respectively. The structural and morphological features of these films were examined by atomic force microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy measurements. We find that Al₂O₃ dielectric films with the O₃ oxidant exhibit a rough morphology, a thick TiO₂ film, and a small amount of contaminants such as carbon and hydrogen. The reason for the rapid diffusion of oxygen atoms into the TiN lattice leads to the formation of TiO₂ layer on the TiN substrate. This is due to the higher oxidation potential of the O₃ compared to the H₂O.     

Comparison of O adsorption on Ni3Al (0 0 1), (0 1 1), and (1 1 1) surfaces through first-principles calculations

First-principles calculations were performed to study the properties of O adsorption on Ni₃Al (0 0 1), (0 1 1), and (1 1 1) surfaces using the Cambridge serial total package (CASTEP) code. Stable adsorption sites are identified. The atomic and electronic structures and adsorption energies are predicted. The adsorption sites for O on the Ni₃Al (0 0 1) surface are at the 2Ni–2Al fourfold hollow site, whereas O prefers to adsorb at the Ni–Al bridge site on (0 1 1) surface and 2Ni–Al threefold hollow site on (1 1 1) surface. It is found that O shows the strongest affinity for Al and the state of O is the most stabilized when O adsorbs on (0 0 1) surface, while the affinity of O for Al on (0 1 1) surface is weaker than (0 0 1) surface, and (1 1 1) surface is the weakest. The stronger O and Al affinity indicates more stable Al₂O₃ when oxidized. The experiment has shown that the oxidation resistance of single crystal superalloy in different orientations improves in the order of (1 1 1), (0 1 1), and (0 0 1) surface, suggesting that the oxidation in different crystallographic orientations may be related to the affinity of O for Al in the surface.     

蓝宝石衬底上Gd2O3掺杂CeO2氧离子导体电解质薄膜的生长及电学性能

采用反应磁控溅射方法,在(0001)蓝宝石单晶衬底上,制备了纳米多晶Gd₂O₃掺杂CeO₂(GDC)氧离子导体电解质薄膜,采用X射线衍射仪(XRD)、原子力显微镜(AFM)对薄膜物相、结构、粗糙度、表面形貌等生长特性进行了表征,利用交流阻抗谱仪测试了GDC薄膜不同温度下的电学性能;实验结果表明,GDC薄膜为面心立方结构,在所研究的衬底温度范围内,均呈强(111)织构生长;薄膜表面形貌随衬底温度发生阶段性变化：衬底温度由室温升高到300℃时, 关键词： 2O₃掺杂CeO₂电解质薄膜')" href="#">Gd₂O₃掺杂CeO₂电解质薄膜 反应磁控溅射 生长特性 电学性能     

Optical properties of In2O3 oxidized from InN deposited by reactive magnetron sputtering

Unintentionally doped and zinc-doped indium nitride (U-InN and InN:Zn) films were deposited on (0 0 0 1) sapphire substrates by radio-frequency reactive magnetron sputtering, and all samples were then treated by annealing to form In₂O₃ films. U-InN and InN:Zn films have similar photon absorption characteristics. The as-deposited U-InN and InN:Zn film show the absorption edge, ∼1.8-1.9 eV. After the annealing process at 500 °C for 20 min, the absorption coefficient at the visible range apparently decreases, and the absorption edge is about 3.5 eV. Two emission peaks at 3.342 eV (371 nm) and 3.238 eV (383 nm) in the 20 K photoluminescence (PL) spectrum of In₂O₃:Zn films were identified as the free-exciton (FE) or the near band-to-band (B-B) and conduction-band-to-acceptor (C-A) recombination, respectively.     

镱铒共掺Al2O3薄膜上转换机理及其温度特性

采用中频磁控溅射法制备了镱铒共掺Al₂O₃薄膜,铒镱掺杂浓度分别为0.3%,3.6%(摩尔分数,全文同).讨论了三价铒离子529nm和549nm光致发光的上转换机理.在291.8—573.3K温度区间测量了两绿上转换光谱荧光强度比的温度特性,拟合表达式为R=5.37exp(-738/T).366 K温度时灵敏度最大,为0.0039 K^-1.结果表明镱铒共掺Al₂O₃薄膜适合作为小型、高温和高灵敏的光学温度传感材料. 关键词： 2O₃薄膜')" href="#">镱铒共掺Al₂O₃薄膜 中频磁控溅射 上转换 荧光强度比     

Oxygen flux influence on the morphological, structural and optical properties of Zn1−xMgxO thin films grown by plasma-assisted molecular beam epitaxy

The Zn_1−xMg_xO thin films were grown on Al₂O₃ substrate with various O₂ flow rates by plasma-assisted molecular beam epitaxy (P-MBE). The growth conditions were optimized by the characterizations of morphology, structural and optical properties. The Mg content of the Zn_1−xMg_xO thin film increases monotonously with decreasing the oxygen flux. X-ray diffractometer (XRD) measurements show that all the thin films are preferred (0 0 2) orientated. By transmittance and absorption measurements, it was found that the band gap of the film decreases gradually with increasing oxygen flow rate. The surface morphology dependent on the oxygen flow rate was also studied by field emission scanning electron microscopy (FE-SEM). The surface roughness became significant with increasing oxygen flow rate, and the nanostructures were formed at the larger flow rate. The relationship between the morphology and the oxygen flow rate of Zn_1−xMg_xO films was discussed.     

Development of rf plasma sputtered Al2O3-TiO2 multilayer broad band antireflecting coatings and its correlation with plasma parameters

TiO₂/Al₂O₃/TiO₂/Al₂O₃ multilayer structures were obtained at different oxygen:argon gas ratios of 20:80, 30:70, 50:50 and 60:40 sccm and constant rf power of 200 W using reactive magnetron sputtering. Grain size and elemental distribution in the films were studied from AFM image and XPS spectra respectively. The deposited grain size increased with increasing oxygen:argon gas ratio. The optical band gap, refractive index, extinction coefficient were calculated from UV-vis transmittance and reflectance spectra. It was observed that the value of refractive index, extinction coefficient and band gap increased with increasing oxygen. These variations are due to the defects levels generated by the heterostructure and explained by the PL spectrum. The antireflecting (AR) efficiency of the films was estimated from the reflectance spectra of the films. Broad band antireflecting coating for the visible range was achieved by varying oxygen content in the film. The plasma chemistry controlled the antireflecting property by the interface interdiffusion of atoms during layer transition in multilayer deposition. The in situ investigation of the plasma chemistry was performed using optical emission spectroscopy. The plasma parameters were estimated and correlated with the characteristics of the films.     

Combinatorial thin film synthesis of Gd-doped Y3Al5O12 ultraviolet emitting materials

Multi-layer Y₃Al₅O₁₂:Gd thin films were deposited in a combinatorial fashion using radio-frequency magnetron sputtering. Initially, Y₃Al₅O₁₂ (yttrium aluminum garnet or YAG) films were deposited in a combinatorial fashion to optimize the Y and Al sputtering conditions. Subsequently, alternating layers of uniform Y₃Al₅O₁₂ and graded Gd were deposited and the film composition was homogenized by post-deposition 1000 °C 10-h thermal treatment. A composition range of 1–12 at% Gd was produced in two films. Ultraviolet emission with a peak wavelength at 312 nm was observed from the gadolinium ⁸S_7/2-⁶P_7/2 transition via cathodoluminescence (CL) excitation. The CL-induced intensity was found to be maximum at 5.5 at% Gd. PACS 81.15.Cd, 78.60.Hf, 02.10.Ox, 78.66.-w, 81.15.-z, 78.67.Pt     

Annealing effects on the optical and structural properties of Al2O3/SiO2 films as UV antireflection coatings on 4H-SiC substrates

Al₂O₃/SiO₂ films have been prepared by electron-beam evaporation as ultraviolet (UV) antireflection coatings on 4H-SiC substrates and annealed at different temperatures. The films were characterized by reflection spectra, ellipsometer system, atomic force microscopy (AFM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. As the annealing temperature increased, the minimum reflectance of the films moved to the shorter wavelength for the variation of refractive indices and the reduction of film thicknesses. The surface grains appeared to get larger in size and the root mean square (RMS) roughness of the annealed films increased with the annealing temperature but was less than that of the as-deposited. The Al₂O₃/SiO₂ films maintained amorphous in microstructure with the increase of the temperature. Meanwhile, the transition and diffusion in film component were found in XPS measurement. These results provided the important references for Al₂O₃/SiO₂ films annealed at reasonable temperatures and prepared as fine antireflection coatings on 4H-SiC-based UV optoelectronic devices.     

Y掺杂Al2O3高k栅介质薄膜的制备及性能研究

利用射频反应共溅射方法制备了Y掺杂Al₂O₃电介质薄膜，用掠入射x射线衍射检测了薄膜的结构，用高分辨率扫描电子显微镜(HRSEM)、原子力显微镜(AFM)观察了薄膜断面和表面形貌，用高频C-V和变频C-V及J-V测量了样品的电学特性. 结果表明，Y的掺入使电介质薄膜的介电常数k有了很大提高(8.14—11.8)，并体现出了较好的介电特性. 分析认为：与氧具有较大电负性差的Y离子的加入，增大了薄膜中的金属—氧键(M—O)的强度；同时，Y的加入使Al₂O₃的结构和原子配位发生了改变，从而提高了离子极化对薄膜介电常数的贡献. 退火前后的XRD谱均显示薄膜为非晶态；HRSEM断面和AFM形貌像显示所制备的薄膜非常平整，能够满足器件要求. 关键词： 高k栅介质 掺杂氧化铝 射频反应溅射     

Anodization of aluminium thin films on pSi and annihilation of strong luminescence from Al2O3

Photoluminescence (PL) of Al₂O₃ films obtained by anodization of thermally evaporated and annealed thin Al films on p⁺⁺Si in 0.3 M oxalic acid has been investigated. Thermal annealing at 200–950 °C under the dry nitrogen atmosphere was used for deactivation of luminescence centres. Luminescence from as grown films was broad and located at 425 nm. This luminescence reached to highest level after annealing at 600 °C. Maximum 10 min was required for full optical activation and prolonged annealing up to 4 h did not change the luminescence intensity. Because of deep levels, absorption band edge of as grown films was shifted to the lower energy which is 3.25 eV. Annealing above 800 °C reduced the PL intensity and this observation was correlated with the blue shift of band edge as the defects annealed out. Disappearing PL intensity and blue shift of band edge absorption after annealing at 950 °C was mainly attributed to the oxygen-related defects and partly to impurities that may be originated from oxalic acid. AFM results did not show any hexagonally ordered holes but uniformly distributed nanosized Al₂O₃ clusters that were clearly seen. XRD measurements on as grown Al₂O₃ showed only [1 1 0] direction of α phase. Debye–Scherer calculation for this line indicates that cluster size is 35.7 nm. XRD and AFM pictures suggest that nanocrystalline Al₂O₃ are embedded in amorphous Al₂O₃.     

Nanostructure of photocatalytic TiO2 films sputtered at temperatures below 200 °C

The article reports on correlations between the process parameters of reactive pulsed dc magnetron sputtering, physical properties and the photocatalytic activity (PCA) of TiO₂ films sputtered at substrate surface temperature T_surf ≤ 180 °C. Films were deposited using a dual magnetron system equipped with Ti (Ø50 mm) targets in Ar + O₂ atmosphere in oxide mode of sputtering. The TiO₂ films with highly photoactive anatase phase were prepared without a post-deposition thermal annealing. The decomposition rate of the acid orange 7 (AO7) solution during the photoactivation of the TiO₂ film with UV light was used for characterization of the film PCA. It was found that (i) the partial pressure of oxygen pO₂ and the total sputtering gas pressure p_T are the key deposition parameters influencing the TiO₂ film phase composition that directly affects its PCA, (ii) the structure of sputtered TiO₂ films varies along the growth direction from the film/substrate interface to the film surface, (iii) ∼500 nm thick anatase TiO₂ films with high PCA were prepared and (iv) the structure of sputtered TiO₂ films is not affected by the substrate surface temperature T_surf when T_surf < 180 °C. The interruption of the sputtering process and deposition in long (tens of minutes) pulses alternating with cooling pauses has no effect on the structure and the PCA of TiO₂ films and results in a decrease of maximum value of T_surf necessary for the creation of nanocrystalline nc-TiO₂ film. It was demonstrated that crystalline TiO₂ films with high PCA can be sputtered at T_surf ≤ 130 °C. Based on obtained results a phase zone model of TiO₂ films was developed.     

Interface interaction and wetting of Sc<Subscript>2</Subscript>O<Subscript>3</Subscript> exposed to Cu–Al and Cu–Ti melts

Scandia is a thermodynamically stable oxide and could be used as a structural material for a crucible in order to avoid a melt contamination. In the present study wetting experiments of Cu–Al and Cu–Ti melts on Scandia substrate were preformed at 1423 K by a sessile drop method. It was established that Al and Ti additions lead to the improved wetting and that the final contact angle decreases with increasing the additives concentration. For Al containing melts, the contact angle changes gradually with time, and a relatively thick interaction layer, which consists of Al₂O₃, Sc₂O₃, and metallic channels, was formed at the Sc₂O₃/Cu–Al interface. For Ti containing melts, the final contact angle is achieved already during heating, and an extremely thin layer based on a Ti–Sc–O compound was detected by AES at the Sc₂O₃/Cu–Ti interface. The results of a thermodynamic analysis, which takes into account the formation free energy of the oxides, involved in the systems, and the thermodynamic properties of the liquid solutions are in a good agreement with the experimental observations.     

Zn掺杂β-Ga2O3薄膜的制备和特性研究

β-Ga₂O₃是一种宽带隙半导体材料,能带宽度E_g≈5.0eV,在光学和光电子学领域有广泛的应用。用射频磁控溅射方法在Si衬底和远紫外光学石英玻璃衬底制备了本征β-Ga₂O₃薄膜及Zn掺杂β-Ga₂O₃薄膜,用紫外 可见分光光度计、X射线衍射仪、荧光分光光度计对本征β-Ga₂O₃薄膜及Zn掺杂β-Ga₂O₃薄膜的光学透过、光学吸收、结构和光致发光进行了测量,研究了Zn掺杂和热退火对薄膜结构和光学性质的影响。退火后的β-Ga₂O₃薄膜为多晶结构,与本征β-Ga₂O₃薄膜相比,Zn掺杂β-Ga₂O₃薄膜的β-Ga₂O₃(111)衍射峰强度变小,结晶性变差,衍射峰位从35.69°减小至35.66°。退火后的Zn掺杂β-Ga₂O₃薄膜的光学带隙变窄,光学透过降低,光学吸收增强,出现了近边吸收,薄膜的紫外、蓝光及绿光发射增强。表明退火后Zn掺杂β-Ga₂O₃薄膜中的Zn原子被激活充当受主。