Effect of the substrate temperature and deposition rate on the initial growth of thin lithium niobate-tantalate films deposited from a thermal plasma

Thin lithium niobate-tantalate (LiNb_0.5Ta_0.5O₃) films are studied at the initial stage of deposition from a thermal plasma. The effect of two deposition parameters (the substrate temperature and the deposition rate) on the film morphology, the film crystallinity, and the density of nuclei growing on a (0001) sapphire substrate are investigated. It is shown that the crystalline structure and roughness of a film are determined, for the most part, in the initial growth stage and therefore depend directly on both parameters. At the optimum temperatures and growth rates for obtaining good characteristics of (0006) texture, crystallinity, and surface roughness of the films, the film nuclei on the substrate have a high density and good epitaxial orientation to it. If the growth conditions are not optimum, the islands are either amorphous or have a low density on the substrate surface. The nucleation activation energy is observed to decrease as the deposition rate increases, which supports the assumption that the species that are active in film deposition are “hot” clusters forming in an oxygen-argon plasma in the immediate vicinity of the substrate.     

Study on SiN and SiCN film production using PE-ALD process with high-density multi-ICP source at low temperature

SiN and SiCN film production using plasma-enhanced atomic layer deposition (PE-ALD) is investigated in this study. A developed high-power and high-density multiple inductively coupled plasma (multi-ICP) source is used for a low temperature PE-ALD process. High plasma density and good uniformity are obtained by high power N₂ plasma discharge. Silicon nitride films are deposited on a 300-mm wafer using the PE-ALD method at low temperature. To analyze the quality of the SiN and SiCN films, the wet etch rate, refractive index, and growth rate of the thin films are measured. Experiments are performed by changing the applied power and the process temperature (300–500 °C).     

Present status of thin oxide films creation in a microwave plasma

This paper summarizes present knowledge of the creation of thin films in isotropic and magnetoactive plasma. It analyses conditions under which films in the microwave plasma can be created and shows how the growth rate and properties of films depend on microparameters of plasma. On the basis of plasma floating potential measurements it is shown why the creation of thin films in microwave discharges takes place at high electron plasma densities (N 10¹² cm^–3) only. Besides this it describes properties of created films, underlies negative role of fast electrons in forming of good quality films and gives recommendation how to avoid their generation. Considerable attention is devoted also to a comparison of films creation in pulse and continuous plasma. At the end possibility of films creation at low temperatures by a deposition technique utilizing a microwave excitation of molecular gases is given.The authors gratefully acknowledge many stimulating and fruitful discussions with Dr. F. áek of Institute of Plasma Physics of Czechoslovak Academy of Sciences. We also thank Dr. V. Malina of Institute of Radioelectronics of Czechoslovak Academy of Sciences for measurements of C—V curves of SiO₂ films.     

Precise control over oxygen impurities in nano-crystalline silicon thin film processed with a low hydrogen dilution gas system at near room temperature

An atmosphere highly diluted with hydrogen is essential to increase the crystal fraction during formation of hydrogenated nano-crystalline (nc) or micro-crystalline (μc) silicon thin films via chemical vapor deposition (CVD). This hydrogen-rich process, however, hinders the ability for the material to find adequate use in micro-electronic devices due to contamination that results in oxygen-related problems such as donor-like doping, defect creation, or passivation. The use of neutral beam assisted chemical vapor deposition (NBaCVD), with a low hydrogen ratio (R = H₂/SiH₄) of 4, successfully deposits a highly-crystallized nc-silicon (HC nc-Si) thin film (TF) at near room temperature (<80 °C) and effectively reduces oxygen contamination by as much as 100 times when compared to conventional plasma enhanced CVD. During the formation of HC nc-Si TF via NBaCVD, energetic hydrogen atoms directly react with oxygen atoms near the surface of the nc-Si TF and remove the oxygen impurities. This is a completely different mechanism from the hydrogen-enhanced oxygen diffusion model. This technology meets the recent requirements of a high deposition rate and low temperature necessary for flexible electronics.     

Yttrium oxide thin films prepared under different oxygen-content atmospheres: microstructure and optical properties

Yttrium oxide films were prepared on silicon wafers by reactive magnetron sputtering at different oxygen flow rates to investigate the microstructure and optical properties for desirable planar optical waveguiding applications. Under the different conditions of target surface, the deposition rate, structure, and optical properties have great changes. The deposition rate increases to the maximum, and then monotonically decreases. Oxygen content in films increases and the composition of films transforms from stoichiometry to an oxygen-rich state. Y₂O₃ films grow with the (222) preferred growth orientation at low oxygen flow rate, and then turn into the (622) orientation; the microstructure evolves from crystal structure to amorphous state as oxygen flow rate increases from 2 to 12 sccm. Sufficient oxygen makes films low-order structure and oxygen-rich films have poor crystallinity. Very smooth film has been obtained at oxygen flow rate of 12 sccm. The refractive index can be greatly modulated by the oxygen-content factor. It is convincing that the controllable structure and optical properties of Y₂O₃ films can be achieved by adjustment the oxygen flow rate for desired optical design and applications.     

SiH4/H2等离子体气相生长硅薄膜的动力学模型

在化学气相沉积微晶硅薄膜过程中,为了降低成本,必须提高生长速率,但薄膜的微观结构和光电性能则随之降低,原因是成膜先驱物在薄膜表面上的扩散长度降低了. 本文利用量子化学的反应动力学理论建立有关成膜先驱物SiH₃和H的反应平衡方程,求解薄膜生长速率和成膜先驱物的扩散长度,并找出影响生长速率与扩散长度的微观参数,发现生长速率不仅与流向衬底的SiH₃的通量密度有关,而且与H的通量密度有关;SiH₃的扩散长度与衬底温度和薄膜表面的硅氢键的形态有关,当     

Preferential growth of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> films with a nanolayer structure: enhancement of thermoelectric properties induced by nanocrystal boundaries

Preferential growth of different crystal planes in layered Bi₂Te₃ thin films with each layer <40 nm has been achieved by a simple magnetron co-sputtering method. The preferential growth of (015) plane or (001) was achieved at special depositing conditions due to the more sufficient growth along the in-plane direction induced by the enhanced diffusion of atoms and lower deposition rate. The Bi₂Te₃ film with preferential growth of (001) plane possesses about two times higher electrical conductivity and Seebeck coefficient as compared to the film with preferential growth of (015) plane, due to the greatly enhanced carrier mobility. Furthermore, the thermal conductivity has been suppressed due to more phonon scattering at grain boundaries, compared with ordinary Bi₂Te₃ alloys and films.     

Effect of process parameters on the mechanical properties of carbon nitride thin films synthesized by plasma assisted pulsed laser deposition

We present an investigation of the effect of the process parameters, namely deposition pressure and laser intensity, on the growth and mechanical properties of carbon nitride (CN_x) thin films synthesized by plasma assisted pulsed laser deposition. Deposition at high remote plasma pressure (200 mTorr) enhances both growth rate and nitrogen incorporation (up to 40 at.%), but nano-indentation measurements indicate that these films are very soft and have poor mechanical properties. At low remote plasma pressure (0.5 mTorr), the nitrogen content varies from 24 to 16 at.% with increasing laser intensity as the films become much harder and more elastic, with hardness and Youngs modulus values reaching 24 GPa and 230 GPa, respectively. These effects are explained in terms of a thermalization of the laser plasma at 200 mTorr and indicate that plasma activation of nitrogen does not provide any particular benefit to the film properties when deposition is performed at high pressure. However, at low pressure, the benefit of plasma activation is evidenced through enhanced nitrogen incorporation in the films while preserving the highly energetic species in the ablation plume. Such conditions lead to the synthesis, at room temperature, of hard and elastic films having properties close to those of fullerene-like CN_x. PACS 81.15.Fg; 81.05.Gc; 68.60.Bs     

PECVD制备AZO（ZnO:Al）透明导电薄膜

采用PECVD（等离子体增强化学气相沉积）工艺在普通玻璃和Si基上制备出了方块电阻低至89 Ω,可见光透过率高达79%,对基体附着力强的多晶态的AZO（ZnO:Al）薄膜.采用PECVD法制备AZO薄膜是一种有益的尝试,AZO透明导电薄膜不仅具有与ITO（透明导电薄膜,如In₂O₃:Sn）可比拟的光电特性,而且价格低廉、无毒,在氢等离子体环境中更稳定,所获结果对实际工艺条件的选择具有一定借鉴作用和参考价值. 关键词： AZO（ZnO:Al） 等离子体增强化学气相沉积 透明导电薄膜     

Laser-produced plasma ion characteristics in laser ablation of lithium manganate

Laser ablation is widely used to assist in the fabrication of prototype lithium manganate (LiMn₂O₄) thin film structures for Li-ion battery electrodes via the pulsed laser deposition technique. However, films can be considerably Li and/or O deficient, depending the deposition conditions used. Here we present data on the ionic component of laser-produced plasma in laser ablation of lithium manganate with ns excimer laser. Plasma was monitored using an electrical Langmuir ion probe, in time-of-flight mode in conjunction with mass spectrometry to identify the dominant ionic species. Ablation in vacuum at ∼2.5 J cm⁻² revealed the plasma's ionic component was composed primarily of singly charged Li and Mn ions. The time-of-flight data indicates significant deceleration of the plasma when ablation is carried out in an oxygen background gas pressure of the order of 10 Pa. The implications for thin film growth are considered in terms of the possible gas phase interactions and/or thin film re-sputtering yield.     

Defect-free growth of epitaxial silicon at low temperatures (500–800 °C) by atmospheric pressure plasma chemical vapor deposition

Epitaxial Si growth at low temperatures (500–800 °C) by atmospheric pressure plasma chemical vapor deposition has been investigated. Silicon films are deposited on (001) Si wafers using gas mixtures containing He, H₂, and SiH₄. The effects of deposition parameters (composition of reactive gases, very high frequency (VHF) power, and substrate temperature) on film properties are investigated by reflection high-energy electron diffraction, atomic force microscopy, cross-sectional transmission electron microscopy, and plasma emission spectroscopy. It is found that epitaxial temperature can be reduced by increasing VHF power, and that an optimum range of VHF power exists for Si epitaxy, depending on the substrate temperature and the composition of the reactive gases. The result of the H₂ concentration dependence of H_α emission intensity, shows that hydrogen atoms generated in the atmospheric pressure plasma play an important role in Si epitaxial growth. Under the optimized growth conditions, defect-free epitaxial Si films (as observed by transmission electron microscopy) with excellent surface flatness are grown at 500 °C with an average growth rate of approximately 0.25 μm/min. PACS 81.05.Cy; 81.15.Gh; 68.55.Jk     

Low temperature plasma production of hydrogenated nanocrystalline silicon thin films

The hydrogenated nanocrystalline silicon (nc-Si:H) thin films were produced by capacitively-coupled plasma enhanced chemical vapor deposition (PECVD) technique at low substrate temperatures (T_s ≈ 40–200 °C). Firstly, for particular growth parameters, the lowest stable T_s was determined to avoid temperature fluctuations during the film deposition. The influence of the T_s on the structural and optical properties of the films was investigated by the Fourier transform infrared (FTIR), UV–visible transmittance/reflectance and X-ray diffraction (XRD) spectroscopies. Also, the films deposited at the center of the PECVD electrode and those around the edge of the PECVD electrode were compared within each deposition cycle. The XRD and UV–visible reflectance analyses reveal the nanocrystalline phase for the films grown at the edge at all T_s and for the center films only at 200 °C. The crystallinity fraction and lateral dark conductivity decrease with lowered T_s. FTIR analyses were used to track the hydrogen content, void fraction and amorphous matrix volume fraction within the films. The optical constants obtained from the UV–visible transmittance spectroscopy were correlated well with the FTIR results. Finally, the optimal T_s was concluded for the application of the produced nc-Si:H in silicon-based thin film devices on plastic substrates.     

Effect of H2 and O2 plasma etching treatment on the surface of diamond-like carbon thin film

In this study, we investigated the surface properties of diamond-like carbon (DLC) films for biomedical applications through plasma etching treatment using oxygen (O₂) and hydrogen (H₂) gas. The synthesis and post-plasma etching treatment of DLC films were carried out by 13.56 MHz RF plasma enhanced chemical vapor deposition (PECVD) system. In order to characterize the surface of DLC films, they were etched to a thickness of approximately 100 nm and were compared with an as-deposited DLC film. We obtained the optimum condition through power variation, at which the etching rate by H₂ and O₂ was 30 and 80 nm/min, respectively. The structural and chemical properties of these thin films after the plasma etching treatment were evaluated by Raman and Fourier transform infrared (FT-IR) spectroscopy. In the case of as-deposited and H₂ plasma etching-treated DLC film, the contact angle was 86.4° and 83.7°, respectively, whereas it was reduced to 35.5° in the etching-treated DLC film in O₂ plasma. The surface roughness of plasma etching-treated DLC with H₂ or O₂ was maintained smooth at 0.1 nm. These results indicated that the surface of the etching-treated DLC film in O₂ plasma was hydrophilic as well as smooth.     

Preparation and characterization of alkyl sulfate and alkylbenzene sulfonate surfactants/TiO2 hybrid thin films by the liquid phase deposition (LPD) method

Hybrid titanium oxide thin films containing surfactants, sodium dodecyl benzylsulfonate and sodium dodecyl sulfate, have been prepared by a novel liquid-phase deposition method. It is a new attempt to prepare organic–inorganic hybrid thin film by this method which usually be applied in preparing metal oxide thin film before. The two kinds of surfactants/TiO₂ hybrid thin films were characterized by means of FT-IR, SEM, XRD, fluorescence X-ray, ICP–AES and Raman spectroscopy, and showed noticeable differences in surface top view and particle diameter, cross-section image and thickness, deposited amount of Ti, XRD patterns and Raman shift. The reasons giving rise to above differences of the two kinds composite thin films has been discussed. The deposition mechanism of organic–inorganic hybrid thin film has been also presumed. The use of this processing parameter may open up a new way to the preparing of the organic–inorganic hybrid thin film.     

Thin film solid oxide fuel cells

We have investigated the deposition of 91% ZrO₂ − 9% Y₂O₃ thin films by a variety of sputtering techniques for the application as electrolytes in thin film solid oxide fuel cells. The deposition by RF sputtering was accomplished by using an oxide target of the desired composition. The deposition rate in these initial tests was limited to 0.5 μm/hr and the morphology of the film was substantially modified by deposition rate and substrate temperature. Using DC magnetron sputtering we deposited metallic films from a metallic target with the desired chemical composition. We introduced oxygen into the sputtering chamber to reactively deposit the desired 91% ZrO₂ − 9% Y₂O₃ thin films; however, we encountered problems with target oxidation and growth rate reproducibility. We subsequently demonstrated that controlled oxidation of the metallic films could result in adhering, non porous yttria stabilized zirconia films. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Characteristics of N-doped TiO2 thin films grown on unheated glass substrate by inductively coupled plasma assisted dc reactive magnetron sputtering

N-doped TiO₂ thin films have been deposited on unheated glass substrates by an inductively coupled plasma (ICP) assisted direct current (dc) reactive magnetron sputtering. All films were produced in the metallic mode of sputtering in order to achieve a high deposition rate. The structures and properties of the N-doped TiO₂ films were studied by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, field emission scanning electron microscopy and UV–Vis spectrophotometer. Experimental results show that we can obtain well crystallized N-doped anatase phase TiO₂ thin films at low deposition temperature and at high deposition rate by using the ICP assisted dc reactive magnetron sputtering process. The doping of nitrogen into TiO₂ lattices leads to a smooth shift of the absorption band toward visible light regions.     

Characteristics of nitrogen-incorporated silicon oxycarbide films and plasmas for plasma enhanced chemical vapor deposition with TMOS/N2/NH3

Plasma enhanced chemical vapor deposition of nitrogen-incorporated silicon oxycarbide thin films obtained from the gas mixture of TMOS (tetramethoxysilane), N₂, and NH₃ is studied. The effects of the TMOS to N₂ pressure ratio on the properties of the film and the plasma are investigated. The deposited films are analyzed by in situ ellipsometry, ex situ Fourier transform infrared spectroscopy (FTIR), and by X-ray photoelectron spectroscopy (XPS). The plasma is characterized by using optical emission spectroscopy (OES). The mass spectra of the constituents in the plasma are obtained by quadrupole mass spectroscopy. The correlation between the film properties and the plasma characteristics is explained wherever possible. As the partial pressure of N₂ is decreased, the refractive index begins to decrease, reaches a minimum, and then saturates. The FTIR absorption bands are observed from about 850 to 1000 cm⁻¹ and from 1000 to 1250 cm⁻¹, and can be attributed to the formation of a nitrogen-incorporated silicon oxycarbide thin film. The variation of the refractive index is discussed in relationship with the deposition rate, the OES spectra, the mass spectra of the plasma, the film composition obtained by XPS, and FTIR spectra.     

Radio frequency plasma enhanced chemical vapor based ZnO thin film deposition on glass substrate: A novel approach towards antibacterial agent

In the present study, the structural, optical and antibacterial properties of ZnO thin films are reported. ZnO thin films are deposited on borosilicate glass substrates by radio frequency plasma enhanced chemical vapor deposition (PECVD) using oxygen as process gas. The crystallinity of the deposited films is improved upon annealing at 450 °C in air for 1.5 h and the polycrystalline nature of the films is further confirmed by selected area electron diffraction. The particle size of the annealed film (thickness 476 nm) is found to be ∼34 nm from the transmission electron microscopic observation. Energy dispersive X-ray spectrum indicates the stoichiometric deposition of ZnO films. The films are highly transparent (transmittance >85%) in the visible region of electromagnetic spectrum. The films exhibit excellent antibacterial effect towards the growth of Escherichia coli and Pseudomonas aeruginosa.     

Miniature plasma focus as a novel device for synthesis of soft magnetic FeCo thin films

The Letter reports the first ever application of low energy miniature plasma focus device as a deposition facility for nanostructured thin films. We demonstrate successful utilization of a 120 J fast miniature plasma focus device as a novel facility for the deposition of magnetically soft FeCo thin films. Different gas types and the substrate materials were used to investigate their effects on magnetic properties of the films. The FeCo films deposited on Si₍₁₀₀₎ with hydrogen as the filling gas were found to have an average grain size of 10.8±1.2 nm with narrow size distribution and soft magnetic properties with coercivity of about 6.3 Oe. The experimental coercivity value matched reasonably well with the theoretical calculation done using ripple theory.     

Preparation of thin Si:H films in an inductively coupled plasma reactor and analysis of their surface roughness

An important concern in the deposition of Si:H films is to obtain smooth surfaces. Herein, we deposit the thin Si:H films using Ar-diluted SiH₄ as feedstock gas in an inductively coupled plasma reactor. And we carry a real-time monitor on the deposition process by using optical emission spectrum technology in the vicinity of substrate and diagnose the Ar plasma radial distribution by Langmuir probe. Surface detecting by AFM and surface profilometry in large scale shows that the thin Si:H films have small surface roughness. Distributions of both the ion density and the electron temperature are homogeneous at h = 0.5 cm. Based on these experimental results, it can be proposed inductively coupled plasma reactor is fit to deposit the thin film in large scale. Also, Ar can affect the reaction process and improve the thin Si:H films characteristics.