ZnO:Al films deposited by in-line reactive AC magnetron sputtering for a-Si:H thin film solar cells

Throughout the last years strong efforts have been made to use aluminium doped zinc oxide (ZnO:Al) films on glass as substrates for amorphous or amorphous/microcrystalline silicon solar cells. The material promises better performance at low cost especially because ZnO:Al can be roughened in order to enhance the light scattering into the cell. Best optical and electrical properties are usually achieved by RF sputtering of ceramic targets. For this process deposition rates are low and the costs are comparatively high. Reactive sputtering from metallic Zn/Al compound targets offers higher rates and a comparable high film quality in respect to transmission and conductivity. In the presented work the process has been optimised to lead to high quality films as shown by reproducible cell efficiencies of around 9% initial for single junction amorphous silicon solar cells on commercial glass substrates. The crucial point for achieving high efficiencies is to know the dependency of the surface structure after the roughening step, which is usually performed in a wet etch, on the deposition parameters like oxygen partial pressure, aluminium content of the targets and temperature. The most important insights are discussed and the process of optimisation is presented.     

Ge/SiO2和Ge/ZnO/SiO2薄膜的磁控溅射制备及电学性能

采用射频磁控溅射方法以石英玻璃为衬底分别沉积制备出了Ge/SiO2和Ge/ZnO/SiO2薄膜。X射线衍射表明薄膜展示了明显的ZnO衍射峰和较弱的Ge衍射峰;傅里叶变换红外光谱曲线证明薄膜均具有各自的特征吸收峰;扫描电镜结果显示薄膜为颗粒状团簇结构,并且加入ZnO中间层可以有效的改善Ge层的质量。同时,对所得薄膜材料的电流-电压性能进行了研究,结果发现,Ge/SiO2薄膜的I-V曲线拟合后为斜线,相当于电阻;ZnO/SiO2薄膜为直线,可以认为是绝缘体;Ge/ZnO/SiO2薄膜在-10～10V之间电流电压呈线性关系,其电阻比Ge/SiO2薄膜小,当电压值超过15V之后,电流急剧增加而迅速使薄膜击穿,薄膜导通。     

Growth of CNx/BN:C multilayer films by magnetron sputtering

Symmetric CN_x/BN:C multilayer thin films, with nominal compositional modulation periods of Λ=2.5, 5, and 9 nm were deposited by unbalanced dual cathode magnetron sputtering from C (graphite) and B₄C targets in an Ar/N₂ (60/40) discharge. The multilayers and single-layer of the constituent CN_x and BN:C compounds were grown to a total thickness of 0.5 μm onto Si(001) substrates held at 225°C and a negative floating potential of 30 V (E_i≈24 eV). Layer characterizations were performed by TEM, X-ray reflectivity, RBS, and nanoindentation measurements. Results show that CN_0.33 and BN:C (35, 50, and 15 at.% of B, N, and C, respectively) layers were prepared at the above conditions. It is suggested that all films exhibit a three-dimensional interlocked structure with a cylindrical texture in the film growth direction. The structure was continuous over relatively well defined and smooth CN_x/BN:C interfaces. All coatings exhibit extreme elasticity with elastic recoveries as high as 85–90% (10 mN maximum load) attributed to the observed structure. However, the multilayers were stiffer and more elastic compared to that of the single-layers and thus shows promise for improved protective properties.     

Deposition of low-resistivity gallium-doped zinc oxide films by low-temperature radio-frequency magnetron sputtering

The transparent and conductive gallium-doped zinc oxide (GZO) film was deposited on 1737F Corning glass using the radio-frequency (RF) magnetron sputtering system with a GZO ceramic target. (The Ga₂O₃ contents are approximately 5 wt. %). In this study, the effect of the sputtering pressure on the structural, optical and electrical properties of GZO films upon the glass or polyester film (PET) substrate was investigated and discussed in detail. The GZO film was grown under a steady RF power of 400 W and a lower substrate temperature from room temperature up to 200 °C. The crystal structure and orientation of GZO thin films were examined by X-ray diffraction. All of the GZO films under various sputtering pressures had strong c-axis (002)-preferred orientation. Optical transparency was high (> 80%) over a wide spectral range from 380 nm to 900 nm. According to the experimental data, the resistivity of a single-layered GZO film was optimized at  8.3 × 10^− 4 Ω cm and significantly influenced by the sputtering pressure. In further research, the sandwich structure of the GZO film/Au metal/GZO film was demonstrated to improve the electrical properties of the single-layered GZO film. The resistivity of the sandwich-structured GZO film was around 2.8 × 10^− 4 Ω cm.     

反应RF磁控溅射法制备非晶氧化硅薄膜及其特性研究

在氧气和氩气的混合气体中,在没有额外加热的条件下用反应射（RF）溅射硅靶制备了非晶氧化硅（a-SiO2)薄膜,并测试分析了薄膜的结构和电特性与O2／Ar流量比的关系。当固定氩气流量,改变氧气流量时,薄膜沉积速率先急剧减少,再增大,然后又减少。当O2／Ar≥0．075时,得到满足化学配比的氧化硅薄膜。并且,随着O2／Ar流量比的增大,薄膜的电阻,电场击穿强度都有所增大,而在HF缓冲溶液（BHF）中的腐蚀速率下降,所有的样品中无明显的H－OH水分子的红外吸收峰。比较发现反应射频（RF）磁控溅射法制备的a-SiO2薄膜具有良好的致密性和绝缘性。     

Mo/SiO2 nanocomposite films for optical coatings prepared by vacuum magnetron sputtering

The embedding of metallic nanoparticles in the traditional optical materials (e.g. SiO₂) gives us the possibility to create new optical materials. Metallic particles of nanometric dimensions can be transparent in wide spectral ranges of light. The incorporation of nanocrystal inclusions in such nanocomposites provides the benefit of targeted manipulations of their macroscopic optical response. In this paper we present the possibility to create, using vacuum deposition methods, the nanocomposite coatings with fairly small refractivity.     

Rugate filters fabricated by a radio frequency magnetron sputtering system by use of an optical in situ monitoring technique

We propose, for the first time to our knowledge, a new feedback fabrication technique for rugate filters with sinusoidal refractive index distribution. The technique uses an in situ optical monitoring system, in contrast to conventional techniques for rugate filters that are based on time control, which is generally unsuitable for accurate fabrication of a continuous index distribution. We employed a-SiOx:H thin film as the material for the rugate filters because its refractive index can be successively controlled. Using the proposed technique and material, we fabricated near-infrared rugate minus filters having multiple and continuous refractive index distributions. The experimental and calculated spectra were well correlated as a result of applying the proposed feedback fabrication technique.     

Crystallization of amorphous indium zinc oxide thin films produced by radio-frequency magnetron sputtering

In this work we studied indium zinc oxide (IZO) thin films deposited by r.f. magnetron sputtering at room temperature. The films were annealed at high temperature (1100 K) in vacuum, and the oxygen exodiffusion was monitored in-situ. The results showed three main peaks, one at approximately 600 K, other at approximately 850 K and the last one at 940 K, which are probably from oxygen bonded in the film surface and in the bulk, respectively. The initial amorphous structure becomes microcrystalline, according to the X-ray diffraction. The electrical conductivity of the films decreases (about 3 orders of magnitude), after the annealing treatment.This behavior could be explained by the crystallization of the structure, which affects the transport mechanism. Apart from the changes in the material structure, a small variation was observed on the absorption coefficient.     

The selective growth of rutile thin films using radio-frequency magnetron sputtering

Using unbalanced radio-frequency (RF) magnetron sputtering crystalline rutile films were synthesised on glass substrates at (combined Ar and O₂) pressures of 0.4 Pa or less, at RF powers of 500 and 600 W with substrate to magnetron distances of 40 mm or longer. Anatase films were deposited at the greater pressure of 1.2 Pa (substrate to magnetron distance of 40 mm) or shorter substrate to magnetron distance of 20 mm (at 0.4 Pa). A mixture of anatase and rutile was formed at 0.5 Pa with all other conditions being as for those required for rutile or the power was reduced along with the substrate to magnetron distance (500 W and 20 mm). The crystallite sizes of rutile obtained were 1 - 3 nm. It is proposed that the greater the energy imparted to the substrate surface by the impinging positive species the greater the activation energy to crystalline phase formation that can be overcome. Hence the formation of rutile over anatase is favoured at greater power, longer magnetron to substrate distances and decreased pressure. Moreover, not only is it possible to control the phase of TiO₂ formed it appears to be possible to control the degree of oxygen non-stoichiometry in the rutile films formed. Smaller O₂ partial pressures, shorter substrate to magnetron distances and greater RF power are believed to produce an environment of reduced reaction of sputtered Ti species with O₂ and to result in the formation of non-stoichiometric rutile structures resulting in increased band gap energies and decreased refractive indices.     

Atomic scale microstructures of high-k HfSiO thin films fabricated by magnetron sputtering

High-k hafnium-silicate films were deposited by RF magnetron sputtering approach on silicon wafer. The microstructure has been investigated using the combination of transmission electron microscopy and atom probe tomography. It was evidenced that the elaborated HfSiO thin films subsequently annealed at 950 °C during 15 min leads to a complex phase separated nanostructure where silica, hafnia and silicon nanoclusters coexist. The formation of silicon nanoclusters in hafnia-based host was never reported before. The results demonstrate the capability of RF magnetron sputtering to pave the way for realization of nanomemory devices based on silicon clusters embedded in high-k matrix.     

High-index low-loss gallium phosphide thin films fabricated by radio frequency magnetron sputtering

High-index low-loss Gallium Phosphide thin films for visible light have been produced by radio frequency magnetron sputtering in an argon environment. This broadens the high refractive index limit of transparent optical materials using a physical deposition process. Energy-dispersive x-ray analysis and spectroscopic ellipsometry were used to characterize the stoichiometry and optical properties. A post-deposition high-temperature anneal was found to be necessary to restore the proper stoichiometric ratio and to reduce the absorption. The annealing conditions were optimized by an in-situ fiber-optic transmission spectrum monitoring system. The films exhibit a high refractive index (N = 3.23) and a low extinction coefficient (K = 0.029) at 633 nm. Such high index GaP films have broad applications in nanophotonic device designs.     

Growth of lithium tantalate thin films by radio-frequency magnetron sputtering with lithium enriched target

LiTaO₃ thin films were deposited by radio-frequency magnetron sputtering with a Li enriched target composed of Li₂O₂/Ta₂O₅ (55:45 at.%). Morphology, crystallinity, dielectric and pyrolectric properties of thin films of LiTaO₃ are studied according to the temperature of deposition and the nature of the back electrode (Ru/RuO₂ and RuO₂). In order to develop thermal microsensors containing pyrolectric thin layers deposited on membranes of SiN_x ensuring the thermal isolation of the device, the final aim is to improve the pyroelectric coefficient for infrared pyroelectric detectors applications. The best pyroelectric coefficient of LiTaO₃ thin films (400 nm), obtained for a growth temperature of 620 °C and a pressure of 0.67 Pa, is equal to 40 µC/m² K.     

High quality ZnO films deposited by radio-frequency magnetron sputtering using layer by layer growth method

Three-layered ZnO films were deposited on Si substrates by radio-frequency magnetron sputtering using layer by layer growth method. The Raman scattering confocal analysis confirms that ZnO film quality is improving at increasing the number of ZnO layers at film deposition.Applied method of deposition was used to realize homoepitaxial growth of ZnO films on c-Al₂O₃, Si, SiN_x/Si, glass and ITO/glass substrates. In order to improve the film quality we increased the number of deposition stages up to 5. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmittance measurements were used to testify the quality of grown five-layered ZnO films. XRD results showed that all five-layered ZnO films have (002) texture. The second order diffraction peak (004) on XRD spectra additionally testifies to the high quality of all five-layered ZnO films. SEM results demonstrated that no defects such as cracks and dislocations caused by interruption of deposition ZnO films were observed. Transmittance measurement results showed that ZnO films deposited on transparent substrates have abrupt absorption edge and high optical transmission in the visible region of the spectrum.     

磁控溅射法制备NiZnCo铁氧体磁性薄膜的后退火处理研究

研究了后退火处理对磁控溅射法制备NiZnCo铁氧体磁性薄膜的成分、组织及性能影响.用EPMA、XRD和AFM分别表征后退火处理前后薄膜的成分、物相和微观结构,用VSM测试后退火处理前后的薄膜磁性能.结果表明经后退火处理后,薄膜中氧含量增加,结构更为稳定,薄膜由非晶态彻底转变为晶态;晶粒尺寸细小,排列均匀致密;磁滞回线更为狭长,饱和磁化强度明显增大.     

Dependence of the MgO sputtering power on the characteristics of MgZnO thin films grown by radio-frequency magnetron sputtering

The dependence of the MgO sputtering power on the structural and optical properties of epitaxially grown MgZnO thin films on GaN/sapphire substrates by radio-frequency magnetron sputtering was investigated. The photoluminescence investigation showed blue shift of 170 meV in MgZnO film grown at the MgO power of 300 W, compared with the ZnO films grown at the MgO power of 0 W, which was attributed to the enhancement of the Mg incorporation at higher power. In addition, increase in Mg mole fraction with increase in sputtering power of MgO was observed from the PL results, and a maximum of 6.6 at.% Mg was obtained at the MgO power of 300 W. The high-resolution X-ray diffraction and transmission electron microscopy (TEM) investigations revealed that the threading dislocation density in the MgZnO thin films increased with increase in sputtering power. Furthermore, microstructural analysis performed by TEM revealed formation of a thin cubic-like phase in the interface between GaN template and MgZnO thin film, together with increased thickness of the interfacial layer with sputtering power.     

Tribological and mechanical behaviors of TiN/CNx multilayer films deposited by magnetron sputtering

TiN/CN_x multilayer films with bilayer periods of 4.5-40.3 nm were deposited by direct-current magnetron sputtering. Layer morphology and structure of the multilayered films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. The TiN/CN_x multilayers exhibited coherent epitaxial growth due to the mutual growth-promoting effect at small bilayer period and some crystalline regions going through the interface of TiN/CN_x. Nanoindentation tests showed that the hardness of the multilayers varied from 12.5 to 31 GPa, with the highest hardness being obtained with a bilayer period of 4.5 nm. The tribological properties of the films were investigated using a ball-on-disk tribometer in humid air, and the TiN/CN_x multilayer with a bilayer period of 4.5 nm also exhibited the lowest friction coefficient and the highest wear resistance.     

Effects of process parameters on the LaNiO3 thin films deposited by radio-frequency magnetron sputtering

LaNiO₃ thin films were deposited by radio-frequency magnetron sputtering on both (100) Si and platinized Si substrates. The effects of relative oxygen ratio, substrate and annealing temperatures on the microstructure and the electrical properties of the films were investigated. The La/Ni ratio was found to be influenced by the relative oxygen ratio. On the other hand, the orientation of LaNiO₃ was significantly influenced by the substrate temperature. Highly (100)-oriented LaNiO₃ thin films were obtained on SiO₂/Si(100) and Pt/Ti/SiO₂/Si substrates when the substrates temperature was 300 °C with the relative oxygen ratio below 33%. In addition, the (100)-oriented LaNiO₃ showed the lower resistivity than that of random-oriented LaNiO₃.     

Growth of FeSb2 thin films by magnetron sputtering

The detailed growth of FeSb₂ films formed on quartz (0001) substrates by magnetron sputtering is reported. FeSb₂ films with different orientations and compositions can be produced by adjusting the Ar working gas pressure and the substrate temperature. By employing FeSb₂ thin layers produced at different substrate temperatures as templates, < 101>-, < 120>- and < 002>-textured FeSb₂ films were produced under identical growth conditions. The thermoelectric properties of film samples grown at different temperatures were measured and the effects of Sb and FeSb impurities were investigated.