Low temperature sputter deposition of SnOx:Sb films for transparent conducting oxide applications

SnO_x:Sb films have been prepared by reactive dc magnetron sputtering from a metallic target, with the aim of evaluating the potential of SnO_x:Sb as an attractive low-cost alternative to In₂O₃:Sn (ITO) for TCO applications. The deposition was performed without any additional heating of the substrates. The films were subsequently analysed regarding their optical, electrical and structural properties. Our results show that there is only a narrow process window for the sputter deposition of transparent and conducting tin oxide films at low temperature. A sharp minimum in resistivity of 4.9 mΩ cm is observed at an oxygen content of approximately 17% in the sputtering gas. Under these deposition conditions, the SnO₂:Sb films turn out to be both highly transparent and crystalline. At lower oxygen content (10-15%) the SnO_x:Sb films are substoichiometric, as revealed by Rutherford backscattering, and show a low transmission and high resistivity due to numerous defects and the presence of the SnO phase. At higher oxygen content (> 17%) excess oxygen is incorporated into the films, which is attributed to an increase of oxygen ion bombardment. This leads to a degradation of the electrical properties and a decrease of the density of the films, whilst the optical transmittance slightly improves.     

玻璃衬底温度对溅射制备SnO2-Al2O3双金属元素薄膜电学及光学特性的影响研究

采用射频(RF)磁控溅射法在玻璃衬底上制备了SnO₂-Al₂O₃ (SAO) 双金属元素薄膜. 通过扫描电镜(SEM)图像,X射线衍射(XRD)图谱,四探针测量,UV-IR及光致发光(PL)谱研究了衬底温度对薄膜表面形貌,晶体微结构,电学及光学特性的影响. 当衬底温度增加时,SAO薄膜的晶粒尺寸增大. SEM图像及XRD图谱所显示的均质表面结构及大晶粒尺寸表明薄膜具有良好的表面形貌和结晶度. 在400-800nm的可见光范围,薄膜的透射率可达~80%-90%, 计算得到薄膜的带隙约4.11-4.14eV, 表面电阻约7.0 -9.4 . 通过合理选择溅射温度, 薄膜的带隙可得到增宽, 表面电阻可被降低. 测量还发现所制备SAO薄膜的PL谱在UV及红光带发光. 这种多晶SAO薄膜可用于透明导电氧化物(TCO)薄膜, 太阳能电池窗, 传感器及光发射器.     

Preparation and Properties Of ZnO:Al (ZAO) Thin Films Eposited by DC Reactive Magnetron Sputtering

采用磁控溅射技术制备了ZnO:Al(ZAO)薄膜。研究了不同的工艺参数对薄膜的组织结构和光电特性的影响.实验结果表明，多晶ZAO薄膜具有（001）择优取向且呈柱状生长，能量机制决定其微观生长状态。讨论了薄膜的内应力，高的沉积温度和低的溅射功率可有效减小薄膜的内应力。优化的ZAO薄膜电阻率和在可见光区的平均透射率可分别达到310-4-410-4cm和80%以上。     

Nanocrystalline p-type-cuprous oxide thin films by room temperature chemical bath deposition method

Nanocrystalline cuprous oxide (Cu₂O) thin films were synthesized on amorphous glass substrate by using simple room temperature chemical route namely, chemical bath deposition (CBD) method. The deposition kinetics played important role to get good quality nanocrystalline films with uniform thickness. The structural, surface morphological, optical and electrical properties of the films were investigated. Crystallization and growth processes obtained micro-spherical shaped grains of Cu₂O due to agglomeration of smaller nanoparticles. An optical and electrical characterization was performed to study the optical band gap and type of electrical conductivity of the film.     

P-type transparent conducting SnO2:Zn film derived from thermal diffusion of Zn/SnO2/Zn multilayer thin films

Highly transparent, p-type conducting SnO₂:Zn thin films are prepared from the thermal diffusion of a sandwich structure of Zn/SnO₂/Zn multilayer thin films deposited on quartz glass substrate by direct current (DC) and radio frequency (RF) magnetron sputtering using Zn and SnO₂ targets. The deposited films were annealed at various temperatures for thermal diffusion. The effect of annealing temperature and time on the structural, electrical and optical performances of SnO₂:Zn films was studied. XRD results show that all p-type conducting films possessed polycrystalline SnO₂ with tetragonal rutile structure. Hall effect results indicate that the treatment at 400 °C for 6 h was the optimum annealing parameters for p-type SnO₂:Zn films which have relatively high hole concentration and low resistivity of 2.389 × 10¹⁷ cm^− 3 and 7.436 Ω cm, respectively. The average transmission of the p-type SnO₂:Zn films was above 80% in the visible light range.     

Structural,electrical and optical properties of p-type transparent conducting SnO2:Al film derived from thermal diffusion of Al/SnO2/Al multilayer thin films

Highly transparent, p-type conducting SnO₂:Al films derived from thermal diffusion of a sandwich structure Al/SnO₂/Al multilayer thin films deposited on quartz substrate have been prepared by direct current and radio-frequency magnetron sputtering using Al and SnO₂ targets. The deposited films were annealed at various temperatures for different durations. The effect of thermal diffusing temperature and time on the structural, electrical and optical performances of SnO₂:Al films has been studied. X-ray diffraction results show that all p-type conducting films possessed polycrystalline SnO₂ with tetragonal rutile structure. Hall-effect results indicate that 450 °C for 4 h were the optimum annealing parameters for p-type SnO₂:Al films, resulting in a relatively high hole concentration of 7.2 × 10¹⁸ cm^?3 and a low resistivity of 0.81 Ω cm. The transmission of the p-type SnO₂:Al films was above 80%.     

Effect of annealing temperature on optical band-gap of amorphous indium zinc oxide film

The effect of annealing temperature on the electrical and optical properties of indium zinc oxide (IZO) (In₂O₃:ZnO = 90:10 wt.%) thin films has been investigated. The IZO thin films were deposited on glass substrates by radio frequency magnetron sputtering and then subjected to annealing in a mixed ambient of air and oxygen at 100, 200 and 300 °C. All the IZO films were found to have amorphous structure. With the increase of the annealing temperature, the carrier concentration decreased and the resistivity increased. The average transmittance of IZO thin films decreased slightly with annealing temperature. Interestingly, a systematic reduction of the optical band-gap from 3.79 eV to 3.67 eV was observed with annealing temperature. The change in optical band-gap was observed to be caused predominantly by Burstein-Moss band-gap widening effect suggesting unusual absence of band narrowing effect. The effects on optical and electrical properties of IZO films have been discussed in detail.     

Annealing time dependent structural,morphological, optical and electrical properties of RF sputtered p-type transparent conducting SnO2/Al/SnO2 thin films

Transparent p-type conducting SnO₂/Al/SnO₂ multilayer films were fabricated on quartz substrates by radio frequency (RF) sputtering using SnO₂ and Al targets. The deposited films were annealed at a fix temperature of 500 °C for different time durations (1–8 h). The effect of annealing time on the structural, morphological, optical and electrical performances of SnO₂/Al/SnO₂ multilayer films was studied. X-ray diffraction (XRD) results show that all the p-type conducting films possess polycrystalline SnO₂ with tetragonal rutile structure. Hall-effect results indicate that 500 °C for 1 h is the optimum annealing condition for p-type SnO₂/Al/SnO₂ multilayer films, resulting in a hole concentration of 1.14×10¹⁸ cm^–3 and a low resistivity of 1.38 Ω·cm, respectively. The optical transmittance of the p-type SnO₂/Al/SnO₂ multilayer films is above 80% within annealing time range of 1–8 h, showing maximum for the films annealed for 1 h.     

磁控溅射制备Mo薄膜的优化工艺和组织及性能研究

基于正交试验设计,采用射频磁控溅射技术在不同工艺条件下制备了一系列纯金属Mo薄膜。以薄膜的纳米硬度和结合强度为评价指标,考察分析了溅射靶功率、基片温度、氩气流量和真空度4个工艺参数对溅射Mo薄膜综合力学性能和组织结构的影响规律及机理。结果表明,所制备的多种Mo薄膜均为立方多晶结构,并在(110)和(220)晶面择优生长。薄膜由细小的"树枝"状颗粒随机堆叠而成,表面呈压应力状态。综合考虑薄膜的沉积质量和沉积效率,提出磁控溅射制备Mo薄膜的较佳工艺参数为Mo靶功率100 W,沉积温度120℃,氩气流量90 cm3/min,真空度0.2 Pa。采用优化工艺制备的Mo薄膜具有良好的结晶状态和均匀致密的组织结构,纳米硬度为7.269 GPa,结合强度高达33.8 N。     

Annealing driven performance and optical effects in nanocrystalline SnO2 thin films induced by pulsed delivery

Tin dioxide thin films were prepared successfully by pulsed laser deposition techniques on glass substrates. The thin films were then annealed for 30 min from 50 °C to 550 °C at 50 °C intervals. The influence of the annealing temperature on the microstructure and optical properties of SnO₂ thin films was investigated using X-ray diffraction, optical transmittance and reflectance measurements. Various optical parameters, such as optical band gas energy, refractive index and optical conductivity were calculated from the optical transmittance and reflectance data recorded in the wavelength range 300-2500 nm. We found that the SnO₂ thin film annealed at temperatures up to 400 °C is a good window material for solar cell application. Our experimental results indicated that SnO₂ thin films with the high optical quality could be synthesized by pulsed laser deposition techniques.     

Microstructure and Optical Properties of SS/Mo/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Spectrally Selective Solar Absorber Coating

Surface-textured Mo thin film is fabricated by magnetron sputtering through the adjustment of deposition parameters, which exhibits a high absorptance of 0.80 and a low emittance of 0.09. The single-layer Mo deposited on stainless steel (SS) is characterized by x-ray diffraction (XRD), ultra-high resolution scanning electron microscope, atomic force microscope and optical measurement. The controlled surface roughness combined with larger aspect ratio contributes much to the high absorptance and low emittance. Based on the SS/Mo coating, a spectrally selective coating (SS/Mo/Al₂O₃) is designed and fabricated. The coating shows an amorphous structure and exhibits an absorptance of 0.90 and an emittance of 0.08. Tauc-Lorentz and Drude free-electron models are used to modeling the optical properties of Al₂O₃ and Mo layers by phase-modulated spectroscopic ellipsometry.     

Structural, optical and hydrophilic properties of nanocrystalline TiO2 ultra-thin films prepared by pulsed dc reactive magnetron sputtering

TiO₂ ultra-thin (15 nm) films were deposited on silicon wafers (100) and glass slides by pulsed dc reactive magnetron sputtering in an ultra-high vacuum (UHV) system. The effects of substrate temperature, from room temperature to 400 °C, on structural, optical, and hydrophilic properties of the obtained films have been investigated. The structure of the films was characterized by grazing-incidence X-ray diffraction, high-resolution transmission electron microscopy, and atomic force microscopy. The optical properties were determined by UV-vis spectrophotometer and spectroscopic ellipsometry. The hydrophilic properties of the films, after exposed to ultraviolet illumination, were analyzed from contact angle measurements. The results suggested that the substrate temperature at 300 °C was critical in the crystalline phase transformation from amorphous to anatase in the TiO₂ films. The obtained films exhibited good qualities in the optical properties, in addition to excellent photo-induced hydrophilic activities.     

Structure, composition, and physicomechanical characteristics of HfB2 and Hf-B-N films

The paper deals with the study of the effect of the deposition conditions (the bias potential and substrate temperature) on the structure, composition, and physicomechanical characteristics of nanocrystalline films of hafnium diboride and boridonitride formed by the method of nonreactive (in Ar) and reactive (in Ar + N₂) HF magnetron sputtering, respectively. The optimal conditions for the deposition of the hafnium diboride coatings with growth texture in plane (00.1) and the best physicomechanical characteristics are deter-mined. It is shown that at a bias potential of ±50 V and a substrate temperature of ～500°C superstoichiometric highly textured films are formed with a nanohardness of 44 GPa and an elastic modulus of 396 ± 11 GPa. A relation between the composition, structure, and physicomechanical characteristics of the films is found. Reactive sputtering in (Ar + N₂) makes it possible to produce amorphous-crystalline films of the composite (HfB₂ + BN) that consists of grains of the HfB₂ nanocrystalline phase, the spaces between which are filled with the amorphous phase of graphite-like BN.     

Fabrication and characterization of ITO thin films on heat-resistant transparent flexible clay films

Transparent conductive indium tin oxide (ITO) thin films were deposited on transparent flexible clay films with heat resistant and high gas barrier properties by rf magnetron sputtering. The electrical, structural, and optical properties of these films were examined as a function of deposition temperature. A lowest resistivity of 4.2 × 10^− 4 Ωcm and an average transmittance more than 90% in the visible region were obtained for the ITO thin films fabricated at deposition temperatures more than 300 °C. It was found that ITO thin films with low resistivity and high transparency can be achieved on transparent flexible clay film using conventional rf magnetron sputtering at high temperature, those characteristics are comparable to those of ITO thin films deposited on a glass substrate.     

Influence of deposition parameters on the structure and optical property of Zn(S,O) films

This paper presents the influence of process parameters, including sputtering power, oxygen partial pressure (R _O), and substrate temperature on the optical property of Zn(S,O) thin films fabricated by radio frequency magnetron sputtering technology and deposited on glass substrates. The chemical composition, structural and optical properties of the samples were investigated by electron spectroscopy for chemical analysis, X-ray diffraction, and spectrophotometer. All the films mainly exhibited β-ZnS phase with (111) preferred orientation. [S]/([S]+[O]) ratio increased at high sputtering power, low RO, and low substrate temperature. Moderate ranges in sputtering power and substrate temperature and low RO resulted in large grain size. Adatoms are expected to exhibit increased mobility under these conditions. Average transmittance exceeded 75% in the visible wavelength region. Bandgap under these conditions was dominated strongly by the change in grain size and [S]/([S]+[O]) ratio. Optical properties of Zn(S,O) thin films could be modified, which is promising for optoelectronic applications.     

SnO<Subscript>2</Subscript>-core/SiO<Subscript>x</Subscript>-shell coaxial whiskers with a needle-like morphology

Needle-shaped structures of tin oxide (SnO₂) were coated with a shell layer of SiO_x via a sputtering method. The diameters of the SiO_x-coated structures gradually became thinner, leading to the formation of sharp tips. The whiskers consisted of a crystalline SnO₂ core surrounded by an amorphous SiO_x shell. The photoluminescence (PL) spectrum with a Gaussian fitting exhibited yellow-green and orange light emission bands, and the overall shape and intensity of the PL spectrum were not changed by the SiO_xcoating. The results of this study suggest that sputtering can be employed to achieve the layered growth of shell layers on a variety of nanostructures.     

沉积温度对Ge2Sb2Te5溅射薄膜结构、电/光性质的影响

在衬底加热条件下利用磁控溅射法制备Ge2Sb2Te5薄膜,利用X射线衍射仪表征各种沉积温度下薄膜的结构,差示扫描量热法(DSC)确定的薄膜晶化温度为168℃(加热升温速率为5℃/min)。用四探针法测试薄膜的方块电阻,分光光度计测试薄膜的反射率谱,并根据反射率数据讨论在波长为405和650nm时薄膜的反射率对比度同沉积温度关系。结果表明:室温沉积的薄膜为非晶态;在衬底温度为140℃条件下薄膜已完全转变为晶态Ge2Sb2Te5,在300℃时出现少量的六方相;低于140℃时易形成非Ge2Sb2Te5组分的其它晶相,它们对薄膜的电/光性质有很大的影响,可能是导致此类相变光存储薄膜使用过程中反射率对比度下降的原因。     

Nanomechanical Properties of Amorphous and Polycrystalline SrTiO3 Transparent Thin Films Prepared by Ion Beam Sputtering

Transparent SrTiO₃ thin films were deposited on glass substrates by ion beam sputtering at various substrate temperatures. The structural characteristic of the deposited films shows the transition from amorphous phase to polycrystalline phase at 600 °C. The films exhibit a good transparency in the visible region (~80-85%) and a relatively smooth surface. The calculated band gaps for amorphous and polycrystalline films were ~4.20 and ~3.84 eV, respectively. The refractive index of the films increases with increasing the substrate temperature, and the extinction coefficient of the films in the visible region is in the order of 10^?3, indicating low optical loss. The nanomechanical properties of the films were investigated using nanoindentation technique. Young’s modulus and hardness for all films are found to be increased with the increase of substrate temperature.     

Sputter deposition and computational study of M-TiO2 (M = Nb, Ta) transparent conducting oxide films

Titanium dioxide (TiO₂) of the anatase phase has recently attracted much attention as a novel transparent conducting oxide (TCO) due to its rich availability, high refractive index with low absorption in the solar spectrum. While it has been found that Nb is a dopant to obtain low resistivity (~ 10^− 4 Ωcm), other metals such as Ta, W etc., are also considered as potential effective dopants. In this paper, we carried out a parallel study on Nb- and Ta-doped TiO₂ anatase films both theoretically by first principles calculation and experimentally by sputtering deposition and optical/electrical characterizations. The Nb-TiO₂ films deposited on glass by co-sputtering at room temperature were amorphous, and the films crystallized into an anatase structure after vacuum-annealing, with the measured resistivity values comparative to the reported. The Ta-TiO₂ films were deposited similarly, and the structure and properties were compared with the Nb-doped ones. Results showed that better performance was found in Nb-TiO₂ films than that in Ta-TiO₂ films. Theoretical calculations indicate that the larger lattice distortion by substitution of Ta for Ti is the dominating factor to suppress crystal growth and weaken the ability of electron mobility.     

Filtered vacuum arc deposition of undoped and doped ZnO thin films: Electrical, optical, and structural properties

Filtered vacuum (cathodic) arc deposition (FVAD, FCVD) of metallic and ceramic thin films at low substrate temperature (50-400 °C) is realized by magnetically directing vacuum arc produced, highly ionized, and energetic plasma beam onto substrates, obtaining high quality coatings at high deposition rates. The plasma beam is magnetically filtered to remove macroparticles that are also produced by the arc. The deposited films are usually characterized by their good optical quality and high adhesion to the substrate. Transparent and electrically conducting (TCO) thin films of ZnO, SnO₂, In₂O₃:Sn (ITO), ZnO:Al (AZO), ZnO:Ga, ZnO:Sb, ZnO:Mg and several types of zinc-stannate oxides (ZnSnO₃, Zn₂SnO₄), which could be used in solar cells, optoelectronic devices, and as gas sensors, have been successfully deposited by FVAD using pure or alloyed zinc cathodes. The oxides are obtained by operating the system with oxygen background at low pressure. Post-deposition treatment has also been applied to improve the properties of TCO films.The deposition rate of FVAD ZnO and ZnO:M thin films, where M is a doping or alloying metal, is in the range of 0.2-15 nm/s. The films are generally nonstoichiometric, polycrystalline n-type semiconductors. In most cases, ZnO films have a wurtzite structure. FVAD of p-type ZnO has also been achieved by Sb doping. The electrical conductivity of as-deposited n-type thin ZnO film is in the range 0.2-6 × 10^− 5 Ω m, carrier electron density is 10²³-2 × 10²⁶ m^− 3, and electron mobility is in the range 10-40 cm²/V s, depending on the deposition parameters: arc current, oxygen pressure, substrate bias, and substrate temperature. As the energy band gap of FVAD ZnO films is ∼ 3.3 eV and its extinction coefficient (k) in the visible and near-IR range is smaller than 0.02, the optical transmission of 500 nm thick ZnO film is ∼ 0.90.