Chemically deposited copper oxide thin films: structural, optical and electrical characteristics

Thin films of copper oxide with thickness ranging from 0.05–0.45 μm were deposited on microscope glass slides by successively dipping them for 20 s each in a solution of 1 M NaOH and then in a solution of copper complex. Temperature of the NaOH solution was varied from 50–90°C, while that of the copper solution was maintained at room temperature. X-ray diffraction patterns showed that the films, as prepared, are of cuprite structure with composition Cu₂O. Annealing the films in air at 350°C converts these films to CuO. This conversion is accompanied by a shift in the optical band gap from 2.1 eV (direct) to 1.75 eV (direct). The films show p-type conductivity, 5×10⁻⁴ Ω⁻¹ cm⁻¹ for a film of thickness 0.15 μm. Electrical conductivity of this film increases by a factor of 3 when illuminated with 1 kW m⁻² tungsten halogen radiation. Annealing in a nitrogen atmosphere at temperatures up to 400°C does not change the composition of the films. However, the conductivity in the dark as well as the photoconductivity of the film increases by an order of magnitude. The electrical conductivity of the CuO thin films produced by air annealing at 400°C, is high, 7×10⁻³ Ω⁻¹ cm⁻¹. These films are also photoconductive.     

一种加载电阻膜吸波材料的新型频率选择表面

通常频率选择表面雷达罩借助其几何外形, 将带外信号反射到远离来波的方向, 从而实现隐身. 然而随着多基雷达反隐身技术的发展, 这种反射信号仍然可以被侦测到. 针对这一难题, 提出一种加载电阻膜吸波材料的新型频率选择表面. 该频率选择表面在低频工作带通内, 不仅对大入射角和不同极化电磁波具有稳定的带通特性, 而且在高频带外对电磁波表现出吸收特性, 可以将探测信号吸收掉, 从而大大降低被反隐身多基雷达探测的风险. 另外, 由于吸波材料的作用, 使得频率选择表面的栅瓣也得到了很好的压制, 降低了栅瓣对频率选择表面工作频带的干扰.     

Low frictional property of copper oxide thin films optimised using a combinatorial sputter coating system

A combinatorial sputter coating system has been developed that can optimize the crystal preferred orientation of coating films. With this system, it is possible to synthesize various kinds of coatings whilst precisely controlling conditions such as the sputter gas, the gas pressure, the gas partial pressure, the r.f. power, the substrate temperature, the distance between the substrate and target, etc. In this way, we successfully synthesized copper oxide coatings with different crystal preferred orientations, and low frictional property was obtained by optimizing the crystal preferred orientation.     

Gas sensor using gold doped copper oxide nanostructured thin films as modified cladding fiber

We investigate the spectral response of nanostructured copper oxides thin film. Gold was doped in two different concentrations (2% and 4%) using the spray method. A novel ammonia gas sensor at various concentrations (0-500 ppm) was fabricated by replacing CuO films with a clad region. In addition, the effect of gold doping on structural, optical, and morphological properties has been demonstrated. The study shows that the spectral intensity increases linearly with ammonia concentration. The 4% Au doped CuO presents higher sensitivity compared with 2% doped and pure copper oxides. Time response characteristics of the sensor are also reported.     

Chemical synthesis of p-type nanocrystalline copper selenide thin films for heterojunction solar cells

Nanocrystalline thin films of copper selenide have been grown on glass and tin doped-indium oxide substrates using chemical method. At ambient temperature, golden films have been synthesized and annealed at 200 °C for 1 h and were examined for their structural, surface morphological and optical properties by means of X-ray diffraction (XRD), scanning electron microscopy and UV-vis spectrophotometry techniques, respectively. Cu_2−xSe phase was confirmed by XRD pattern and spherical grains of 30 ± 4 - 40 ± 4 nm in size aggregated over about 130 ± 10 nm islands were seen by SEM images. Effect of annealing on crystallinity improvement, band edge shift and photoelectrochemical performance (under 80 mW/cm² light intensity and in lithium iodide electrolyte) has been studied and reported. Observed p-type electrical conductivity in copper selenide thin films make it a suitable candidate for heterojunction solar cells.     

Electrodeposition of zinc oxide/tetrasulfonated copper phthalocyanine hybrid thin film for dye-sensitized solar cell application

Hybrid film of zinc oxide (ZnO) and tetrasulfonated copper phthalocyanine (TSPcCu) was grown on an indium tin oxide (ITO) glass by one-step cathodic electrodeposition from aqueous mixtures of Zn(NO₃)₂, TSPcCu and KCl. The addition of TSPcCu strongly influences the morphology and crystallographic orientation of the ZnO. The nanosheets stack of ZnO leads to a porous surface structure which is advantageous to further adsorb organic dyes. The photovoltaic properties were investigated by assembling the DSSC device based on both the only ZnO film and the ZnO/TSPcCu hybrid films. Photoelectrochemical analysis revealed that the optimized DSSC device with TSPcCu represented a more than three-fold improvement in power conversion efficiency than the device without TSPcCu. The DSSC based on ZnO/TSPcCu hybrid films demonstrates an open circuit voltage of 0.308 V, a short circuit current of 90 μA cm⁻², a fill factor of 0.26, and a power conversion efficiency of 0.14%.     

A facile two-step preparation of compact and crystalline Sb2S3 thin film for efficient solar cells

The two-step preparation of compact and crystalline Sb₂S₃ thin films was firstly reported using the pyrolysis of the Sb-butyldithiocarbamate complex solution in DMF. The porous and amorphous Sb₂S₃ thin films were successfully prepared at 170 °C for 30 min, and then can be converted to compact and crystalline Sb₂S₃ thin films at 200 °C for 30 min or 300 °C for 2 min. The corresponding solar cells with the architecture of FTO/TiO₂ compact layer/Sb₂S₃/spiro-OMeTAD/Au achieved the photoelectric conversion efficiency of 4.16% at 200 °C and 5.05% at 300 °C. The two-step preparation of the compact and crystalline Sb₂S₃ thin films can provide the feasible approach for the fabrication of various microstructure thin film solar cells and the low preparation temperature of 200 °C was also attractive to assemble the flexible Sb₂S₃ thin film solar cells.     

快速热处理制备相变氧化钒薄膜及其特性研究

采用直流对靶磁控溅射在Si<100>基底上沉积金属V薄膜, 然后分别在纯氧气环境和纯氮气环境下进行快速热处理制备具有 金属-半导体相变特性的氧化钒(VO_X)薄膜, 热处理条件分别为纯氧气环境下430℃/40 s, 450℃/40 s, 470℃/40 s, 450℃/30 s, 450℃/50 s, 纯氮气环境下500℃/15 s. 用X射线衍射仪、X射线光电子能谱、原子力显微镜 和扫描电子显微镜对薄膜的结晶结构、钒的价态和组分以及微观形貌进行分析. 利用四探针薄膜电阻测量方法和THz时域频谱技术分析薄膜的电学特性和光学特性. 结果表明: 金属V薄膜经过纯氧气环境450℃/40 s快速热处理 后形成了具有低相变特性的VO_X薄膜, 升温前后薄膜方块电阻变化幅度达到两个数量级, THz透射强度变化幅度较小. 为了提高薄膜的相变特性, 对制备的VO_X薄膜采用纯氮气环境500℃/15 s快速热处理, 薄膜的相变特性有了明显提升, 相变前后方块电阻变化达到3个数量级, THz透射强度变化达到56.33%.     

Effect of tin-doped indium oxide film as capping layer on the agglomeration of copper film and the appearance of copper silicide

In this work, the effect of tin-doped indium oxide (ITO) film as capping layer on the agglomeration of copper film and the appearance of copper silicide was studied. Both samples of Cu 100 nm/ITO 10 nm/Si and ITO 20 nm/Cu 100 nm/ITO 10 nm/Si were prepared by sputtering deposition. After annealing in a rapid thermal annealing (RTA) furnace at various temperatures for 5 min in vacuum, the samples were characterized by four probe measurement for sheet resistance, X-ray diffraction (XRD) analysis for phase identification, scanning electron microscopy (SEM) for surface morphology and transmission electron microscopy (TEM) for microstructure.The results show that the sample with ITO capping layer is a good diffusion barrier between copper and silicon at least up to 750 °C, which is 100 °C higher than that of the sample without ITO capping layer. The failure temperature of the sample with ITO capping layer is about 800 °C, which is 100 °C higher than that of the sample without ITO capping layer. The ITO capping layer on Cu/ITO/Si can obstacle the agglomeration of copper film and the appearance of Cu₃Si phase.     

Post-annealing effect on the reactively sputter-grown CIGS thin films and its influence to solar cell performance

Using a reactive co-sputtering from Cu_0.6Ga_0.4 and Cu_0.4In_0.6 alloy targets, we prepared CuIn_1−xGa_xSe₂ (CIGS) thin films on Mo/soda-lime glass (SLG) in association with a thermal cracker for elemental atomic Se radicals. The film growth was performed at 500 °C for 90 min. To achieve the composition ratio of CIGS absorber layer, Cu_0.6Ga_0.4 target was set at RF power of 50 W, 60 W, 70 W, and 80 W while keeping at 100 W for Cu_0.4In_0.6 alloy target. Post-annealing was done for all the CIGS films at 550 °C for 30 min. The composition ratio of [Cu]/[In + Ga] and [Ga]/[In + Ga] was increased with RF power but showed no change after post-annealing. X-ray diffraction analysis revealed all the samples has grown dominantly in the [112] crystal orientation. We found the Cu_2−xSe and (InGa)_2−xSe₃ defect phase both at the surface and in the bulk, and developed with post-annealing. From the devices fabricated in the structure of grid/ITO/i-ZnO/CdS/CIGS/Mo/soda-lime glass (SLG), the external quantum efficiency (EQE) was observed to improve in the wavelength, λ ≥ 550 nm in the samples treated with annealing. In the current–voltage (J–V) measurements, the solar cell showed the best performance of FF = 54.1%, V_oc = 0.48 V, J_sc = 33.1 mA/cm² and η = 8.5% in the sample with [Cu]/[In + Ga] = 0.84 that improved largely from η = 4.6% for the solar cell with an as-grown CIGS films.     

Low-temperature synthesis of conducting boron-doped nanocrystalline silicon oxide thin films as the window layer of solar cells

Low-temperature synthesis of highly transparent conducting B-doped (p-type) nc-SiO_X:H films has been pursued by 13.56 MHz plasma-CVD, using a combination of SiH₄, CO₂ and B₂H₆, diluted by H₂ and He. Higher substrate temperature (T_S) encourages nanocrystallization in B-doped nc-SiO_X:H network by reducing bonded H-content, while bonded O-content also reduces simultaneously. At optimized T_S = 150 °C, p–nc-SiO_X:H film having an optical band gap ~1.98 eV, high conductivity ~0.18 S cm⁻¹, has been obtained via dopant-induced escalation of the electrically active carriers at a deposition rate ~5.3 nm/min. The p–nc-SiO_X:H film appears as a promising window layer for the top sub-cell of multi-junction silicon solar cells. A single-junction nc-Si:H based p-i-n solar cell of efficiency (η) ~7.14% with a current-density (J_SC) ~14.18 mA/cm², reasonable fill-factor (FF) ~66.2% and open-circuit voltage (V_OC) ~0.7606 V has been fabricated, using the optimum p-type nc-SiO_X:H as the window layer deposited at T_S = 150 °C.     

A scanning tunneling microscopy study on the effect of post-deposition annealing of copper phthalocyanine thin films

Using scanning tunneling microscopy, overlayer lattice structures and thin film morphology of copper phthalocyanine (CuPc) have been investigated while varying posterior, annealing temperatures. The room temperature deposition of CuPc on Ag(1 1 1) resulted in ordered domains, which were three molecular layers high and separated with disordered regions. The ordered surface also exhibited an oblique lattice with the lattice constants of 13.3 Å and 16.4 Å and the angle of 74° between the two. By annealing the thin films systematically to 580 K, the symmetry of overlayer lattice increased from the oblique to the square lattice, commonly observed on various substrates. Further annealing to 780 K desorbed much of the CuPc molecules. However, the remaining molecules reacted and formed dendrite-like chains, in which each CuPc molecule was linked through its isoindole rings. A possible model for the formation of dendritic chains through polymerization is discussed.     

Utilization of ultrasonic irradiation as a green and effective strategy to prepare poly(N-vinyl-2-pyrrolidone)/modified nano-copper (II) oxide nanocomposites

The present paper describes the result of investigations into preparation of novel nanocomposites (NCs) based on poly(N-vinyl-2-pyrrolidone) (PVP) as a biocompatible polymer and modified copper (II) oxide nanoparticles (NPs) as a nano-filler. To achieve optimum NCs properties, different ratios of modified copper (II) oxide NPs (3, 5, and 7 wt%) were used to fabricate PVP NCs and also the ultrasonic irradiation was utilized to perform these processes as a fast and effective method. Subsequently, the structure of the obtained nanohybrids was characterized by various techniques. The suitable incorporation between PVP matrix and modified CuO NPs can be seen from the FT-IR spectra. The obtained NCs indicated an efficient thermal improvement in comparison to the pristine polymer. Also, the uniform dispersion of modified CuO NPs in the PVP matrix was detected by FE-SEM and EDX. According to UV absorption spectra, it is clear that these NCs can be used in UV protecting applications.     

Preparation of Ga-doped ZnO films by pulsed dc magnetron sputtering with cylindrical rotating target for thin film solar cell applications

Applicability of Ga-doped ZnO (GZO) films for thin film solar cells (TFSCs) was investigated by preparing GZO films via pulsed dc magnetron sputtering (PDMS) with rotating target. The GZO films showed improved crystallinity and increasing degree of Ga doping with increasing thickness to a limit of 1000 nm. The films also fulfilled requirements for the transparent electrodes of TFSCs in terms of electrical and optical properties. Moreover, the films exhibited good texturing potential based on etching studies with diluted HCl, which yielded an improved light trapping capability without significant degradation in electrical propreties. It is therefore suggested that the surface-textured GZO films prepared via PDMS and etching are promising candidates for indium-free transparent electrodes for TFSCs.     

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.     

The effect of UV irradiation on nanocrysatlline zinc oxide thin films related to gas sensing characteristics

The effect of ultraviolet (UV) light irradiation on the nanocrystalline ZnO thin films was investigated. The degree of crystallinity, electrical conductivity, optical properties and surface properties of ZnO thin films were measured as a function of UV irradiation time. It was found that the degree of crystallinity and electrical properties of ZnO films were affected by UV irradiation, however, no noticeable change in the surface morphology was observed. The gas sensing properties of as-deposited and UV irradiated films were also measured. It was observed that the gas sensing properties were affected by the UV irradiation. The irradiation time less than 5 min has improved the sensor while the irradiation time more than 5 min degraded the sensor characteristics for a UV power density of 2.45 W cm⁻².     

高绒度掺硼氧化锌透明导电薄膜用作非晶硅太阳电池前电极的研究

将自行研制的具有优异陷光能力的掺硼氧化锌用作p-i-n型非晶硅太阳电池的前电极,并且将传统商业用U型掺氟二氧化锡作为对比电极.相比表面较为平滑的掺氟二氧化锡,掺硼氧化锌表面大类金字塔的绒面结构会在本征层生长过程中触发阴影效应,形成大量的高缺陷材料区和漏电沟道,进而恶化电池的开路电压和填充因子.在不修饰掺硼氧化锌表面形貌的情况下,通过调节非晶硅本征层的沉积温度来消弱高绒度表面形貌引起的这种不利影响,对应的电池开路电压和填充因子均出现提升.在仅有铝背电极的情况下,在本征层厚度为200 nm的情况下,以掺硼氧化锌为前电极的非晶硅太阳电池转换效率达7.34%(开路电压为0.9 V,填充因子为70.1%,短路电流密度11.7 mA/cm2).     

A study on the aluminum fire-through to a-SiNx:H thin film for crystalline solar cells

The relationship between aluminum fire-through and the properties of a-SiN_x:H thin films was investigated to aid their use as dielectric layers in rear side and front passivation layers in crystalline solar cells. Aluminum fire-through was shown to depend on the refractive index and the deposition rate of the films.Refractive index, density and deposition rate increased with increasing SiH₄/NH₃ ratio, while the etching rate decreased. Aluminum fire-through occurred in a sample of refractive index 2.0 during fast deposition but not when the deposition rate was slow. Aluminum fire-through occurred during extended firing, despite it not occurring during normal firing by RTP. The results of this work demonstrate that refractive index was the major determinant of aluminum fire-through, and that the aluminum and the a-SiN_x:H thin film reacted immediately at the beginning of firing at a rate determined by the deposition rate.     

A route to continuous ultra-thin cerium oxide films on Cu(1 1 1)

The growth and morphology of ultra-thin CeO₂(1 1 1) films on a Cu(1 1 1) substrate were investigated by means of low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). The films were grown by physical vapor deposition of cerium in an oxygen atmosphere at different sample temperatures. The preparation procedure is based on a modification of a previous method suggested by Matolin and co-workers [1], involving growth at elevated temperature (520 K). Here, LEED shows good long range ordering with a “(1.5 × 1.5)” superstructure, but STM reveals a three-dimensional growth mode (Vollmer-Weber) with formation of a closed film only at larger thickness. Using a kinetically limited growth process by reactive deposition at low sample temperatures (100 K) and subsequent annealing, we show that closed layers of ceria with atomically flat terraces can be prepared even in the regime of ultra-thin films (1.5 ML). Closed and atomically flat ceria films of larger thickness (3 ML) are obtained by applying a multistep preparation procedure, in which successive ceria layers are homoepitaxially grown on this initial film. The resulting overlayers show strong similarities with the morphology of CeO₂(1 1 1) single crystal surfaces, suggesting the possibility to model bulk ceria by thin film systems.