TEOS-based PECVD of silicon dioxide for VLSI applications

Silicon dioxide films deposited from tetraethylorthosilicate (TEOS) using plasma-enhanced chemical vapour deposition (PECVD) are reviewed. The effect of the presence of oxygen on the film deposition rate and mechanism and the physical properties of the films, particularly the step coverage properties (conformality), are discussed in detail. Structural characterisation of the films has been carried out via etch rate measurements, infrared transmission spectroscopy, X-ray photoelectron spectroscopy (XPS) and Auger and secondary ion mass spectroscopy (SIMS) analysis. Electrical properties, i.e. resistivity, breakdown strength, fixed oxide charge density, interface state density and trapping behaviour, have been evaluated using metal-oxide-semiconductor (MOS) structures fabricated using the deposited oxides. Films deposited by microwave plasma-enhanced decomposition of TEOS in the presence of oxygen have been found to be comparable with standard silane-based low-pressure chemical vapour deposition (LPCVD) and PECVD oxides. It has been shown that films deposited on thin native oxides grown by either in situ plasma oxidation or low-temperature thermal oxidation exhibit excellent electrical properties.     

Effects of the substrate temperature and solution molarity on the structural opto-electric properties of ZnO thin films deposited by spray pyrolysis

Zinc oxide (ZnO) was largely studied in various applications such as photovoltaic conversion, optoelectronics and piezoelectric, because of its interesting physical properties (morphological, structural, optical and electrical). The present work deals with the preparation of zinc oxide thin films (ZnO) deposited by the spray pyrolysis method. The starting solution was zinc chloride (ZnCl₂). Effects of solution molarity and substrate temperature on films properties were investigated. All films deposited were characterized by various techniques such as X-ray diffraction for structural characterizations, profilometry for thickness measurements, UV–vis transmission spectrophotometry for optical properties and the four probes conductivity measurements for electrical characterization. The X-ray diffraction (XRD) patterns show that the films deposited are polycrystalline with (0 0 2) plan as preferential orientation. The UV–vis spectroscopy confirms the possibility of good transparent ZnO thin films deposition with an average transmission of about ∼85% in the visible region. However, the measured electrical resistivities of the deposited films were in the order of 10⁴ Ω cm     

A study of atypical grain growth properties for SnO2 thin films

SnO₂ thin films were grown on Si substrate using the chemical vapor deposition(CVD) method. The surface of the thin film was examined using a transmission electron microscope (TEM) and a scanning electron microscope (SEM). Atypical shaped grains and atypical columnar structures were observed on the SnO₂ thin films that were exposed to air after first deposition and during re-deposition in anaerobic conditions in the CVD. The electrical properties of SnO₂ thin films feature a lower range of resistance in single mode, but after the atypical particles appear, the electrical resistance decreased.     

Fabrication of Microstructured thermoelectric Bi2Te3 thin films by seed layer assisted electrodeposition

In this work, bismuth telluride (Bi₂Te₃) thin films have been fabricated on Bi₂Te₃/ITO substrates by constant potential electrochemical deposition at room temperature. Bi₂Te₃ seed layers with different thicknesses (2 nm, 4 nm and 6 nm) were deposited onto ITO substrates using molecular beam epitaxy (MBE) method. The SEM images show that the morphology of Bi₂Te₃ thin films can be controlled not only by the deposition potential, but also the thickness of seed layer. Moreover, the morphologies of Bi₂Te₃ thin films with different thickness of seed layers tend to be similar and contain two-layer structure along the vertical direction after prolonged deposition time. Due to the two layers structure, Bi₂Te₃ thin films have shown different electrical conductivity performances. At room temperature, Bi₂Te₃ thin films with 4 nm-thick seed layer possess the maximum electrical conductivity value of 617.9 s cm^-1.     

Microstructures and electrical properties of SrRuO3 thin films on LaAIO3 substrates

Conductive SrRuO₃ thin films have been deposited using pulsed laser deposition on LaA10₃ substrates at different substrate temperatures. Structural and microstructural properties of the SrRuO₃/LaAlO₃ system have been studied using x-ray diffraction, scanning electron microscopy, and scanning tunneling microscopy. Electrical properties of SrRuO₃ thin films have been measured. It was found that the film deposited at 250°C is amorphous, showing semiconductor-like temperature dependence of electrical conductivity. The film deposited at 425°C is crystalline with very fine grain size (100∼200?), showing both metallic and semiconductor-like temperature dependence of electrical conductivity in different temperature regions. The film deposited at 775°C shows a resistivity of 280 μΩ.cm at room temperature and a residual resistivity ratio of 8.4. Optimized deposition conditions to grow SrRuO₃ thin films on LaA10₃ substrates have been found. Possible engineering applications of SrRuO₃ thin films deposited at different temperatures are discussed. Bulk and surface electronic structures of SrRuO₃ are calculated using a semi-empirical valence electron linear combination of atomic orbitals approach. The theoretical calculation results are employed to understand the electrical properties of SrRuO₃ thin films.     

Role and Optimization of the Active Oxide Layer in TiO2‐Based RRAM

TiO₂ is commonly used as the active switching layer in resistive random access memory. The electrical characteristics of these devices are directly related to the fundamental conditions inside the TiO₂ layer and at the interfaces between it and the surrounding electrodes. However, it is complex to disentangle the effects of film “bulk” properties and interface phenomena. The present work uses hard X‐ray photoemission spectroscopy (HAXPES) at different excitation energies to distinguish between these regimes. Changes are found to affect the entire thin film, but the most dramatic effects are confined to an interface. These changes are connected to oxygen ions moving and redistributing within the film. Based on the HAXPES results, post‐deposition annealing of the TiO₂ thin film was investigated as an optimisation pathway in order to reach an ideal compromise between device resistivity and lifetime. The structural and chemical changes upon annealing are investigated using X‐ray absorption spectroscopy and are further supported by a range of bulk and surface sensitive characterisation methods. In summary, it is shown that the management of oxygen content and interface quality is intrinsically important to device behavior and that careful annealing procedures are a powerful device optimisation technique.     

Post deposition UV-induced O2 annealing of HfO2 thin films

UV-assisted annealing processes for thin oxide films is an alternative to conventional thermal annealing and has shown many advantages such as low annealing temperature, reducing annealing time and easy to control. We report in this work the deposition of ultra-thin HfO₂ films on silicon substrate by two CVD techniques, namely thermal CVD and photo-induced CVD using 222 nm excimer lamps at 400 °C. As-deposited films of around 10 nm in thickness with refractive indices from 1.72 to 1.80 were grown. The deposition rate measured by ellipsometry was found to be about 2 nm/min by UV-CVD, while the deposition rate by thermal CVD is 20% less than that by UV-CVD. XRD showed that the as-deposited HfO₂ films were amorphous. This work focuses on the effect of post deposition UV annealing in oxygen on the structural, optical and electrical properties of the HfO₂ films at low temperature (400 °C). Investigation of the interfacial layer by FTIR revealed that thickness of the interfacial SiO₂ layer slightly increases with the UV-annealing time and UV annealing can convert sub-oxides at the interface into stoichiometric SiO₂, leading to improved interfacial qualities. The permittivity ranges in 8–16, are lower than theoretical values. However, the post deposition UV O₂ annealing results in an improvement in effective breakdown field and calculated permittivity, and a reduction in leakage current density for the HfO₂ films.     

基于PECVD的SiO2薄膜制备研究进展

二氧化硅(SiO₂)薄膜因其卓越的光学性能,在半导体器件、集成电路、光学涂层等领域具有巨大的应用潜力。然而,SiO₂薄膜制备过程中面临表面粗糙度、杂质控制和致密性等问题。为解决这些问题,研究者们通过工艺改进和表面修饰等手段来提高SiO₂薄膜的性能。在众多SiO₂薄膜制备技术中,等离子体增强化学气相沉积(Plasma-Enhanced Chemical Vapor Deposition, PECVD)技术由于沉积SiO₂薄膜所需温度低、原位生长等优势,成为制备SiO₂薄膜最常用的方法。综述了用PECVD技术制备SiO₂薄膜的发展历程,并探讨了关键工艺参数和后处理工艺对薄膜质量的影响。对PECVD技术的深入研究,有助于实现对SiO₂薄膜生长的更精准控制,进一步拓展其广泛的应用前景。     

Effect of the deposition rate on the phase transition in silver telluride thin films

Silver telluride thin films of thickness 50 nm have been deposited at different deposition rates on glass substrates at room temperature and at a pressure of 2×10⁻⁵ mbar. The electrical resistivity was measured in the temperature range 300–430 K. The temperature dependence of the electrical resistance of Ag₂Te thin films shows structural phase transition and coexistence of low temperature monoclinic phase and high temperature cubic phase. The effect of deposition rate on the phase transition and the electrical resistivity of silver telluride thin films in relation to carrier concentration and mobility are discussed.     

Electrospray deposition and characterization of cobalt oxide thin films

Cobalt oxide thin films were fabricated by means of electrospray deposition. The obtained films were characterized by Raman spectroscopy, X-ray diffraction and Scanning electron microscopy. The solution that was used gave the Co₃O₄ phase at different growth temperatures. The best granular surfaces were obtained at 250 °C as verified by all characterization techniques, while flaky surfaces were obtained at higher temperatures. The surface morphology is mostly granular except for high temperatures where the cobalt oxide is formed as flakes instead of grains.     

Nanoscale structural characteristics and electron field emission properties of transition metal–fullerene compound TiC60 films

Transition-metal compound TiC₆₀ thin films were grown by co-deposition from two separated sources of fullerene C₆₀ powder and titanium. Study of structural properties of the films, by Raman spectroscopy, atomic force microscopy, and scanning tunneling spectroscopy reveals that the films have a deformed C₆₀ structure with certain amount of sp³ bonds and a rough surface with a large number of nanoclusters. z–V tunnelling spectroscopic measurements suggest that several charge transport mechanisms are involved in as the tip penetrates into the thin film. Conventional field electron emission (FEE) measurements show a high emission current density of 10 mA/cm² and a low turn-on field less than 8 V/μm, with the field enhancement factors being 659 and 1947 for low-field region and high-field region, respectively. By exploiting STM tunneling spectroscopy, local FEE on nanometer scale has also been characterized in comparison with the conventional FEE. The respective field enhancement factors are estimated to be 99–355 for a gap varying from 36 to 6 nm. The enhanced FEE of TiC₆₀ thin films can be ascribed to structural variation of C₆₀ in the films and the electrical conducting paths formed by titanium nanocrystallites embedded in C₆₀ matrix.     

A Solution‐Processed MoOx Anode Interlayer for Use within Organic Photovoltaic Devices

A simple, solution‐processed route to the development of MoO_x thin‐films using oxomolybdate precursors is presented. The chemical, structural, and electronic properties of these species are characterized in detail, within solution and thin‐films, using electrospray ionization mass spectrometry, grazing angle Fourier transform infrared spectroscopy, thermogravimetric analysis, atomic force microscopy, X‐ray photoelectron spectroscopy, and ultraviolet photoelectron spectroscopy. These analyses show that under suitable deposition conditions the resulting solution processed MoO_x thin‐films possess the appropriate morphological and electronic properties to be suitable for use in organic electronics. This is exemplified through the fabrication of poly(3‐hexylthiophene):[6,6]‐phenyl C₆₁ butyric acid methyl ester (P3HT:PC₆₁BM) bulk heterojunction (BHJ) solar cells and comparisons to the traditionally used poly(3,4‐ethyldioxythiophene)/poly(styrenesulfonate) anode modifying layer.     

Properties of Flame Sprayed Ce0.8Gd0.2O1.9‐δ Electrolyte Thin Films

Thin films of Ce_0.8Gd_0.2O_1.9‐δ (CGO) are deposited by flame spray deposition with a deposition rate of about 30 nm min^?1. The films (deposited at 200 °C) are dense, smooth, and particle‐free and show a biphasic amorphous/nanocrystalline microstructure. Isothermal grain growth and microstrain are determined as a function of dwell time and temperature and correlated to the electrical conductivity. CGO films annealed for 10 h at 600 °C present the best electrical conductivity of 0.46 S m^?1 measured at 550 °C. Reasons for the superior performance of films annealed at low temperature over higher‐temperature‐treated samples are discussed and include grain‐size evolution, microstrain relaxation, and chemical decomposition. Nanoindentation measurements are conducted on the CGO thin films as a function of annealing temperature to determine the hardness and elastic modulus of the films for potential application as free‐standing electrolyte membranes in low‐temperature micro‐SOFCs (solid oxide fuel cells).     

Investigation of Cu(In,Ga)Se2 thin‐film formation during the multi‐stage co‐evaporation process

In order to transfer the potential for the high efficiencies seen for Cu(In,Ga)Se₂ (CIGSe) thin films from co‐evaporation processes to cheaper large‐scale deposition techniques, a more intricate understanding of the CIGSe growth process for high‐quality material is required. Hence, the growth mechanism for chalcopyrite‐type thin films when varying the Cu content during a multi‐stage deposition process is studied. Break‐off experiments help to understand the intermediate growth stages of the thin‐film formation. The film structure and morphology are studied by X‐ray diffraction and scanning electron microscopy. The different phases at the film surface are identified by Raman spectroscopy. Depth‐resolved compositional analysis is carried out via glow discharge optical emission spectrometry. The experimental results imply an affinity of Na for material phases with a Cu‐poor composition, affirming a possible interaction of sodium with Cu vacancies mainly via In(Ga)_Cu antisite defects. An efficiency of 12.7% for vacancy compound‐based devices is obtained. Copyright © 2011 John Wiley & Sons, Ltd.     

Influence of substrate temperature on the deposition and structural properties of μc-Si: H thin films fabricated with VHF-PECVD

With in situ optical emission spectroscopy (OES) diagnosis on VHF-generated H₂+SiH₄ plasmas, and with the measurements of deposition rate and structure of μc-Si: H thin films fabricated with VHF-PECVD technique at different substracte temperature, influence of substrate temperature on the deposition of μc-Si: H thin film and on its structural properties have been investigated. The results show that with the increase of substrate temperature, the crystalline volume fraction Xc and average grain size d are enhanced monotonously, but the deposition rate increases firstly and then decreases. The optimized substrate temperature for (μc-Si: H thin films deposition under our current growth system is about 210 °C, at which deposition rate 0.8 nm/s of μc-Si: H thin film with Xc?60% and d?9 nm can be obtained.     

Fabrication of 128×128 element optical switch array by micromachining technology

Polycrystalline VO₂ thin films were obtained on Si substrates by ion beam sputtering deposition and annealing in flowing Ar gas. SEM images indicate that VO₂ thin films were grown into compact surfaces. Four-probe measurements indicated that the VO₂ thin films own good electrical homogeneity. After the films' production, micromachining technology including lithography, reaction ion etching and metallization connection processes was used to produce the optical switch array. As a result, the 128×128 element optical switch array was achieved.     

Thermal stability of sputter-deposited ZnO thin films

This paper describes our investigation on the thermal stability of sputterdeposited, piezoelectric, ZnO thin films, using x-ray photoelectron spectroscopy (XPS), capacitance-voltage (C-V) measurements of metal-insulator-semiconductor structures, and electron microprobe. We focus on out-diffusion of Zn from ZnO thin films at a high temperature (450°C) and the composition change of zinc and oxygen after high temperature annealing (up to 700°C), since these factors are related to reliability and integrated circuits-process-compatibility of the ZnO films which are being used increasingly more in microtransducers and acoustic devices. Our experiments with electron microprobe show that ZnO thin films sputter-deposited from a ZnO target in a reactive environment (i.e., with O₂) are thermally stable (up to 700°C). Additionally, the out-diffusion of zinc atoms from the ZnO films at a high temperature (450°C) is verified to be negligible using the XPS and C-V measurement techniques. The usage of a compound ZnO target, reactive environment with O₂ and optimized deposition parameters (including gas ratio and pressure, substrate temperature, target-substrate distance and rf power, etc.) is critical to deposit thermally stable, high quality ZnO films.     

XPS analysis and characterization of thin films Cu2ZnSnS4 grown using a novel solution based route

A new technique to grow single phase Cu₂ZnSnS₄ (CZTS) thin films for solar cells applications using a chemical route is presented; this consist in sequential deposition of Cu₂SnS₃ (CTS) and ZnS thin films followed by annealing at 550 °C in nitrogen atmosphere, where the CTS compound is prepared in one step process by simultaneous precipitation of Cu₂S and SnS₂ performed by diffusion membranes assisted CBD (chemical bath deposition) technique and ZnS by conventional CBD technique.Measurements of X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM) were used to identify the phases present in the CTS and CZTS films as well as to study their structural and morphological properties. Further, the oxidation states and the chemical composition homogeneity in the volume were studied by X-ray photoelectron spectroscopy (XPS) analysis. Oxidation states and results regarding structural and morphological characterization of CZTS films prepared using the novel technique are compared with those results obtained from single phase CZTS films prepared by sequential evaporation of metallic precursors in presence of elemental sulfur. XRD and Raman spectroscopy studies were used to verify that the CZTS films prepared by the novel method do not present secondary phases.     

Influence of substrate on the growth of microcrystalline silicon thin films deposited by plasma enhanced chemical vapor deposition

Microcrystalline silicon (μc-Si) thin films are widely used for silicon thin film solar cells, especially in the high performance tandem solar cells which comprise an amorphous silicon junction at the top and a μc-Si junction at the bottom. One of the major factors affecting the photovoltaic properties of μc-Si thin film solar cells of thin films is the quality of the μc-Si thin films. In this work, we investigated the effect of substrates on the crystallization characteristics and growth behaviors of μc-Si thin films grown by the plasma enhanced chemical vapor deposition method (PECVD), and found that substrates have a strong effect on the crystallization characteristics of μc-Si thin films. In addition, the growth rate of μc-Si thin films was also highly influenced by the substrates. Three types of substrates, quartz glass, single crystalline silicon and thermally oxidized single crystalline silicon, were used for growing μc-Si thin films from SiH₄/H₂ with a flow rate ratio 2:98 at different temperatures. Crystallization characteristics of these μc-Si thin films were studied by Raman scattering and X-ray diffraction techniques.