Cuprite, paramelaconite and tenorite films deposited by reactive magnetron sputtering

Copper oxides films (Cu₂O, Cu₄O₃ and CuO) have been deposited by magnetron sputtering of a copper target in various Ar–O₂ reactive mixtures. The films are characterized by X-ray diffraction, scanning electron microscopy, four-point probe method and UV-Vis spectrometry. The three defined compounds in the Cu---O binary system can be deposited by varying the oxygen flow rate introduced into the reactor. All the films are crystallized with a mean crystal size ranging from 10 to about 35 nm. They are highly resistive and present a direct optical band gap higher than 2 eV. The application of a bias voltage during the deposition phase modifies the texture of the Cu₂O films and also induces a preferential resputtering of oxygen from the Cu₄O₃ ones. This resputtering phenomenon leads firstly to the occurrence of the cuprite phase mixed with the paramelaconite one and secondly to the amorphisation of the films. Finally, the thermal stability in air of cuprite, paramelaconite and tenorite films has been investigated. The results show that the stability of Cu₂O and Cu₄O₃ films in air is influenced by the thickness and/or the texture of the films. Tenorite films with a low optical band gap (1.71 eV) can be formed after air annealing at 350 °C of an unbiased cuprite film.     

工作气压对磁控溅射ZnO薄膜结晶特性及生长行为的影响

采用射频反应磁控溅射方法，在Si(001)基片上制备了具有高c轴择优取向的ZnO薄膜.利用原子力显微镜、X射线衍射、透射电子显微镜和透射光谱分析技术，对不同工作气压下合成的ZnO薄膜的表面形貌、微观结构和光学性能进行表征，研究了工作气压对ZnO薄膜的结晶性能以及生长行为的影响.研究结果显示：对于Ar/O₂流量比例接近1∶1的固定比值下，ZnO薄膜的生长行为主要取决于成膜空间中氧的密度，临界工作气压介于0.5—1.0 Pa之间.当工作气压小于临界值时，ZnO薄膜的成核密度较高，且随工作气压的变化明显，ZnO的生长行为受控于氧的密度，属于氧支配的薄膜生长；当工作气压大于临界值以后，ZnO薄膜的成核密度基本保持不变，Zn原子的数量决定薄膜的生长速率；在0.1—5.0 Pa的工作气压范围内，均可获得高度c轴取向的ZnO薄膜，但工作气压的变化改变着ZnO晶粒之间的界面特征和取向关系.随着工作气压的增加，ZnO晶粒之间的界面失配缺陷减少，但平面织构特征逐渐消失，三叉晶界的空洞逐渐扩大，薄膜的密度下降，折射率减小. 关键词： ZnO薄膜 磁控溅射 表面形貌 微观结构 光学性能     

Cu-In-O composite thin films deposited by reactive DC magnetron sputtering

Cu-In-O composite thin films were deposited by reactive DC magnetron sputtering at room temperature. The samples were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), UV/vis spectrophotometer, four-probe measurement and Seebeck effect measurement, etc. The samples contain Cu, In and O. The ratios of Cu to In and O to In increase with increase in O₂ flow rates. The ratio of Cu to In is over 1 and this suggests that Cu is in excess. The obtained Cu-In-O thin films are very possibly made of rhombohedral In₂O₃ and monoclinic CuO. Transmittance of the films decreases with increase in O₂ flow rate. The decrease in transmittance results from increase in Cu content in the films. The optical band gap of all the samples is estimated to be 4.1-4.4 eV, which is larger than those of In₂O₃ and CuO. The sheet resistance of the films decreases with increase in O₂ flow rate. Conductivity of the films is a little low, due to the addition of Cu and the poor crystalline quality of the film. The conduction behavior of the films is similar to that of In₂O₃ and the conduction mechanism of Cu-In-O thin films is through O vacancy.     

Structures and optical properties of tungsten oxide thin films deposited by magnetron sputtering of WO_3 bulk:Effects of annealing temperatures

Tungsten oxide thin films were deposited on glass substrates by the magnetron sputtering of WO3 bulk at room temperature. The deposited films were annealed at different temperatures in air. The structural measurements indicate that the films annealed below 300℃ were amorphous, while the films annealed at 400℃ were mixed crystalline with hexagonal and triclinic phases of WO3. It was observed that the crystallization of the annealed films becomes more and more distinct with an increase in the annealing temperature. At 400℃, nanorod-like structures were observed on the film surface when the annealing time was increased from 60 min to 180 min. The presence of W=O stretching, W–O–W stretching, W–O–W bending and various lattice vibration modes were observed in Raman measurements. The optical absorption behaviors of the films in the range of 450–800 nm are very different with changing annealing temperatures from the room temperature to 400℃. After annealing at 400℃, the film becomes almost transparent. Increasing annealing time at 400℃ can lead to a small blue shift of the optical gap of the film.     

Microstructure, optical and electrical properties of nitrogen doped sp-rich a-C thin films grown by facing-target magnetron sputtering

N atoms were incorporated into sp²-rich a-C networks using DC facing-target reactive sputtering at various N₂ fraction (P_N2) and their structure and opto-electrical properties were investigated systematically. As P_N2 increases, the fraction of CN bonded carbons (or the N content) increases primarily at the expense of the CC bonded carbons and then reaches its saturated value at P_N2 > 40%. The incorporated N preferentially forms different kinds of non-aromatic CN phase, leading to more localization of π electrons and the loss of the connectivity of nanographite fragments in the films, which is different from the case in N-doped sp³-rich a-CN_x films. Hence, with increasing P_N2, the a-C(:N) film converts from a semiconductor with a narrower optical band gap to an insulator-like material with a wider gap. Additionally, the variation of optical constants (n and k) and spin defects are related to the enhancement of the non-aromatic CN phase.     

Influence of sputter-etching of substrate on the microstructural and optical properties of ZnO films deposited by RF magnetron sputtering

ZnO films were prepared using radio frequency magnetron sputtering on Si(1 1 1) substrates that were sputter-etched for different times ranging from 10 to 30 min. As the sputter-etching time of the substrate increases, both the size of ZnO grains and the root-mean-square (RMS) roughness decrease while the thickness of the ZnO films shows no obvious change. Meanwhile, the crystallinity and c-axis orientation are improved by increasing the sputter-etching time of the substrate. The major peaks at 99 and 438 cm⁻¹ are observed in Raman spectra of all prepared films and are identified as E₂(low) and E₂(high) modes, respectively. The Raman peak at 583 cm⁻¹ appears only in the films whose substrates were sputter-etched for 20 min and is assigned to E₁(LO) mode. Typical ZnO infrared vibration peak located at 410 cm⁻¹ is found in all FTIR spectra and is attributed to E₁(TO) phonon mode. The shoulder at about 382 cm⁻¹ appearing in the films whose substrates were sputter-etched for shorter time (10-20 min) originates from A₁(TO) phonon mode. The results of photoluminescence (PL) spectra reveal that the optical band gap (Eg) of the ZnO films increases from 3.10 eV to 3.23 eV with the increase of the sputter-etching time of the substrate.     

GaN films deposited by middle-frequency magnetron sputtering

GaN films were deposited on Si (111) substrates by middle-frequency magnetron sputtering. X-ray diffraction revealed preferential GaN (0 0 0 2) orientation normal to the substrate surface for all the films deposited. The diffraction intensity and N contents were found to depend strongly on the total gas pressure. Good quality films were only obtained at pressures in the range of 0.4-1.0 Pa. Little diffraction of GaN (0 0 0 2) could be observed either at total pressures below 0.4 Pa or above 1.0 Pa. The GaN films produced under the optimized conditions have an N:Ga ratio of 1:1 as determined by energy-dispersive X-ray spectroscopy.     

生长温度对磁控溅射ZnO薄膜的结晶特性和光学性能的影响

采用反应射频磁控溅射方法，在Si (100) 基片上制备了具有高c轴择优取向的ZnO薄膜.利用 原子力显微镜、透射电子显微镜、X射线衍射分析、拉曼光谱等表征技术，研究了沉积温度 对ZnO薄膜的表面形貌、晶粒尺度、应力状态等结晶性能的影响；通过沉积温度对透射光谱 和光致荧光光谱的影响，探讨了ZnO薄膜的结晶特性与光学性能之间的关系.研究结果显示， 在室温至500℃的范围内，ZnO薄膜的晶粒尺寸随沉积温度的增加而增加，在沉积温度为500 ℃时达到最大；当沉积温度为750℃时，ZnO薄膜的晶粒尺度有所减小；在室温至750℃的范 围内，薄膜中ZnO晶粒与Si基体之间均存在着相对固定的外延关系；在沉积温度低于500℃时 ，制备的ZnO薄膜处于压应变状态，而750℃时沉积的薄膜表现为张应变状态.沉积温度的不 同导致ZnO薄膜的折射率、消光系数、光学禁带宽度以及光致荧光特性的变化，沉积温度对 紫外光致荧光特性起着决定性的作用.此外，探讨了影响薄膜近紫外光致荧光发射的可能因 素. 关键词： ZnO薄膜 表面形貌 微观结构 光学常数     

溅射功率对直流磁控溅射Ti膜结构的影响

 采用直流磁控溅射方法制备了纯Ti膜,研究了不同功率下Ti膜的沉积速率、表面形貌及晶型结构,并对其应力进行了研究。研究表明：薄膜的沉积速率随溅射功率的增加而增加,当溅射功率为20 W时,原子力显微镜(AFM)图像显示Ti膜光洁、致密,均方根粗糙度最小可达0.9 nm。X射线衍射(XRD)分析表明薄膜的晶体结构为六方晶型,Ti膜应力先随溅射功率增大而增大,在60 W时达到最大值（为945.1 MPa）,之后随溅射功率的增大有所减小。     

溅射功率对直流磁控溅射Ti膜结构的影响

采用直流磁控溅射方法制备了纯Ti膜,研究了不同功率下Ti膜的沉积速率、表面形貌及晶型结构,并对其应力进行了研究。研究表明：薄膜的沉积速率随溅射功率的增加而增加,当溅射功率为20 W时,原子力显微镜(AFM)图像显示Ti膜光洁、致密,均方根粗糙度最小可达0.9 nm。X射线衍射(XRD)分析表明薄膜的晶体结构为六方晶型,Ti膜应力先随溅射功率增大而增大,在60 W时达到最大值（为945.1 MPa）,之后随溅射功率的增大有所减小。     

溅射功率对Mo薄膜微结构和性能的影响

实验采用直流磁控溅射沉积技术在不同溅射功率下制备Mo膜,研究了不同溅射功率下Mo膜的沉积速率、表面形貌及晶型结构,并对其晶粒尺寸和应力进行了研究。利用原子力显微镜观察样品的表面形貌发现随着溅射功率的增加,薄膜表面粗糙度逐渐增大。X射线衍射分析表明薄膜呈立方多晶结构,晶粒尺寸为14.1～17.9 nm;应力先随溅射功率的增大而增大,在40 W时达到最大值(2.383 GPa),后随溅射功率的增大有所减小。     

溅射功率对Mo薄膜微结构和性能的影响

 实验采用直流磁控溅射沉积技术在不同溅射功率下制备Mo膜,研究了不同溅射功率下Mo膜的沉积速率、表面形貌及晶型结构,并对其晶粒尺寸和应力进行了研究。利用原子力显微镜观察样品的表面形貌发现随着溅射功率的增加,薄膜表面粗糙度逐渐增大。X射线衍射分析表明薄膜呈立方多晶结构,晶粒尺寸为14.1～17.9 nm;应力先随溅射功率的增大而增大,在40 W时达到最大值(2.383 GPa),后随溅射功率的增大有所减小。     

Violet and blue-green luminescence from Ti-doped ZnO films deposited by RF reactive magnetron sputtering

Pure and Ti-doped zinc oxide (TZO) films are deposited using radio frequency (RF) reactive magnetron sputtering at different RF powers. Micro-structural and optical properties in doped ZnO films are systematically investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electronic microscopy (SEM), and a fluorescence spectrophotometer. The results indicate that ZnO films show stronger preferred orientation toward the c$c$-axis and smoother surface roughness after Ti doping. As for TZO films, the full width at half maxima (FWHM) of (002) diffraction peaks decreased first and then increased, reaching a minimum of about 0.92° at 150 W, while the residual compressive stress of the TZO film prepared at 150 W became the largest. The photoluminescent (PL) spectra measured at room temperature reveal a violet, a blue and two green emissions. Intense violet and blue-green luminescence is obtained for the sample deposited at higher RF power. The origin of these emissions is discussed.     

Transparent conductive and near-infrared reflective Cu-based Al-doped ZnO multilayer films grown by magnetron sputtering at room temperature

Cu-based Al-doped ZnO multilayer films were deposited on glass substrates by DC magnetron sputtering at room temperature. Three kinds of multilayer structures (AZO/Cu, AZO/Cu/AZO, and Cu/AZO) were designed for comparison, and the effects of the Cu layer thickness on photoelectrical properties of the multilayer films were investigated. The results revealed that the transparent-conductive property and near-infrared reflectance of the films are closely correlated with the Cu layer thickness, and among the three structures, AZO/Cu bi-layer films exhibited preferable photoelectrical properties. The AZO/Cu bi-layer film with a Cu layer thickness of 7 nm displayed the highest figure of merit of 4.82 × 10⁻³ Ω⁻¹, with a low sheet resistance of 21.7 Ω/sq and an acceptable visible transmittance of 80%. The near infrared reflectance above 50% can be simultaneously obtained. The good performance of the coatings indicates that they are promising for coated glasses, thin film solar cells and heat-reflectors.     

Optical properties of aluminum-doped zinc oxide films deposited by direct-current pulse magnetron reactive sputtering

A series of （103）-oriented aluminum-doped zinc oxide （AZO） films were deposited on glass substrates via direct- current pulse magnetron reactive sputtering at different O2-to-Ar gas flow ratios （GFRs）. The optical properties of the films were characterized using the fitted optical constants in the general oscillator model （which contains two Psemi-Tri oscillators） through the use of measured ellipsometric parameters. The refractive index dispersion data below the interband absorption edge were analyzed using a single-oscillator model. The fitted optical energy gap obtained using the single- oscillator model clearly shows a blue shift, followed by a red shift, as the GFR increases from 0.9/18 to 2.1/18. This shift can be attributed to the change in the free electron concentration of the film, which is closely related to the film stress. In addition, the fitted β value indicates that the AZO film falls under the ionic class. The pbotoluminescence spectrum indicates a photoluminescence mechanism of the direct and wide energy gap semiconductor.     

Magnetic anisotropy properties of CoZrNb thin films deposited on PET substrate by magnetron sputtering

Soft magnetism and magnetic anisotropy properties of CoZrNb thin films deposited on polyethylene terephthalate (PET) substrate by magnetron sputtering were investigated. As the film thickness increases, the coercivity of films decreases from 7 to 4 Oe. It exhibits an in-plane uniaxial magnetic anisotropy as the thickness of CoZrNb thin films increases. An easy axis is observed in CoZrNb films along the direction transverse to the rolling direction of the polymer web.     

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.     

Transmission characteristics of multilayer films composed of electro-optic and dielectric materials

We describe the theoretical evaluation for the transmission characteristics of multilayer films composed of periodic electro-optic and dielectric materials in a variable electric field. The films are assumed to have cavity-type layer stacking structures, which work as a narrow bandpass filter, and their electro-optic material is uni-axial BaTiO₃, whose electro-optic coefficient r₅₁ is larger than 1300 pm/V. The evaluation indicates that films composed of BaTiO₃ and SiO₂ or MgO function as tunable optical bandpass filters, with a tunable range larger than 6 nm for an electric field of less than 4 V/μm.     

Growth, structural, and magnetic properties of iron nitride thin films deposited by dc magnetron sputtering

FeN thin films were deposited on glass substrates by dc magnetron sputtering at different Ar/N₂ discharges. The composition, structure and the surface morphology of the films were characterized using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and atomic force microscopy (AFM). Films deposited at different nitrogen pressures exhibited different structures with different nitrogen contents, and the surface roughness depended on the mechanism of the film growth. Saturation magnetization and coercivity of all films were determined using superconducting quantum interference device, which showed that if N₂/(Ar+N₂) flow ratio was equal to or larger than 30% the nonmagnetic single-phase γ″-FeN appeared. If N₂/(Ar+N₂) flow ratio was less than 10%, the films consisted of the mixed phases of FeN_0.056 and γ′-Fe₁₆N₂, whose saturation magnetizations were larger than that of -Fe. If N₂/(Ar+N₂) flow ratio was 10%, the phases of γ′-Fe₄N and -Fe₃N appeared, whose saturation magnetizations were lower than that of -Fe.     

Evolution of the structural and optical properties of silver oxide films with different stoichiometries deposited by direct-current magnetron reactive sputtering

Nitrogen doping of silver oxide(AgxO) film is necessary for its application in transparent conductive film and diodes because intrinsic AgxO film is a p-type semiconductor with poor conductivity.In this work,a series of AgxO films is deposited on glass substrates by direct-current magnetron reactive sputtering at different flow ratios(FRs) of nitrogen to O2.Evolutions of the structure,the reflectivity,and the transmissivity of the film are studied by X-ray diffractometry and sphectrophotometry,respectively.The specular transmissivity and the specular reflectivity of the film decreasing with FR increasing can be attributed to the evolution of the phase structure of the film.The nitrogen does not play the role of an acceptor dopant in the film deposition.