Deposition of SiO2-Like Films by HMDSN/O2 Plasmas at Low Pressure in a MMP-DECR Reactor

The effects of process parameters such as O₂/HMDSN (hexamethyldisilazane) ratio, microwave discharge power and deposition pressure on the growth rate, chemical bonding nature, and refractive index of thin films deposited by microwave plasma from HMDSN with oxygen, have been investigated. The plasma was created in a Microwave Multipolar reactor excited by Distributed Electron Cyclotron Resonance. The films were deposited at room temperature and characterized by Fourier Transform Infrared spectroscopy and ellipsometry. Growth rate increased with the discharge power P or the deposition pressure but decreased significantly with increasing O₂/HMDSN ratio. A large change in the film composition was observed when the O₂/HMDSN ratio was varied: films deposited with only HMDSN precursor are polymer-like but as the O₂/HMDSN ratio increased, organic groups decreased. For relative pressure values over 70%, deposited films are SiO₂-like with refractive index values close to those found for thermal silicon dioxide.     

Plasma polymerization of styrene with controlled particle energy

A new type of reactor for plasma polymerization was developed in order to achieve an effective control of styrene polymerization process. Electrons and ions were extracted from the radio frequency (rf) glow discharge region to the downstream region to generate plasma polymerization. The energy of extracted ionized particles was controlled by the bias voltage of a screen grid unit. Deposited polymer thin films were analyzed by X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy. The result showed that the polarity and energy of the extracted particles had considerable effect on the deposition rate and structure of the deposited films. At each bias polarity there was a maximum deposition rate vs. voltage magnitude, and the maximum at the positive voltage was higher. In addition, the bulk aromaticity of the film deposited at the negative bias was lower than at the positive bias; the surface aromaticity of the films was much higher than that of the films prepared by usual rf discharge. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1265–1270, 1998     

Precise Control of Metal Oxide Thin Films Deposition in Magnetron Sputtering Plasmas for High Performance Sensing Devices Fabrication

Magnetron sputtering deposition is a widely used technique to deposit thin film precisely at nanoscale level. During the deposition of metal oxide thin films, reactive oxygen gas is introduced into the deposition chamber. Pure metal and metal oxide materials can be used as sputter target, although the simplest way is by using a pure metal target. In such reactive process, the effect of target poisoning significantly influence the deposition process and the growth mechanisms of metal oxide thin films became very complex. In general, external parameters such as discharge power, working pressure, reactive gases ratio and substrate temperature are used to optimize the properties of deposited thin films. Then, ex-situ analyses such as scanning electron microscope and X-ray diffraction analysis are performed to obtain the optimized parameter. Sample depositions and ex-situ analyses consume time to achieve the goal through try and error. In this article, in-situ plasma diagnostics are reviewed focusing on an optical emission spectroscopy to precisely control and investigate the sputter target poisoning effect during the deposition of metal oxide thin films. The emission of atomic lines from several metal and oxygen atoms were used to discuss the deposition mechanisms and their correlation with the deposited thin films was observed. Finally, the deposited metal oxide thin films were proposed and tested for several applications such as gas sensor and frequency selective surface glass.     

Deposition of Gallium Nitride Thin Films by MOCVD in Microwave Plasma

The deposition of GaN thin films in a nitrogen–hydrogen microwave plasma using Ga(CH ₃ ) ₃ as a gallium precursor was investigated. The deposit was identified as stoichiometric GaN by XPS and XRD. The substrate was dielectrically heated in the microwave discharge and the substrate temperature was lower than that in usual thermal MOCVD. The NH radicals, which were the primary N-atoms precursors, and fragments of Ga(CH ₃ ) ₃ were identified in the plasma by OES. The NH radical formation and the decomposition of Ga(CH ₃ ) ₃ in the plasma may be one of the reasons for the lower deposition temperature of GaN. The position dependence of the substrate temperature showed similar tendency as the position dependence of the electron temperature. The plasma state contributes to the deposition of GaN thin films. The deposited GaN exhibited a wide optical band gap of 3.4eV. Material highly oriented along the c axis was detected in the deposit, and a PL spectrum which has the band head at about 450 mm was obtained.     

DC plasma polymerization of hexamethyldisiloxane

Hexamethyldisiloxane (HMDS) was polymerized onto metallic and insulating substrates in a parallel-plate DC reactor. The limits of the DC reactor with respect to pressure and power were determined for deposition of PP-HMDS films. In all conditions ranging from 5 Pa/0.3 W to 100 Pa/50 W, solid films were deposited. No powders or oily films were obtained under any condition in this operating range. The films were polymeric in nature,i.e., they were neither carbon-like nor SiO _x -like films. The structures and crosslink densities of the plasma films dependend strongly on the deposition conditions. The highest deposition rates, up to 2 μm per minute (or0.3 mg/cm² min), were obtained at high power, pressure, and flow rate conditions. An efficiency ɛ is introduced, defined as the fraction of the monomer that is retained in the form of a polymer deposited on the substrate. Efficiencies as high as 25% could be obtained in certain conditions. Pulsing the discharge power increased the conversion efficiency markedly, but the effect depended strongly on the monomer used. In addition to HMDS, plasma polymers were also deposited from pyrrole in pulsed conditions for comparison. A method is described for depositing films on insulators from a DC glow discharge using two wire meshes held at a negative potential.     

Plasma pretreatment of polycarbonate substrates for indium zinc oxide film deposition

The influence of plasma treatment of polycarbonate (PC) substrates on the morphological, electrical, and adhesion properties of deposited amorphous transparent indium zinc oxide (IZO) by direct current magnetron sputtering was investigated by analyzing atomic force microscopy, contact angles, Hall, and nano‐scratch measurements. The surfaces of PC substrates were performed by plasma treatment at various processing times in Ar/O₂ mix atmosphere. The atomic force microscopy images indicated that the microstructure of the substrates considerably influenced the surface morphology of deposited IZO films, and the least surface roughness of IZO was obtained after 5‐s plasma treatment. The IZO film deposited on PC with 5‐s plasma treatment presented an improved electrical conductivity and thermal stability after annealing at 120 °C in air, whereas the significant decrease in carrier concentration and increase in resistivity with extending plasma treatment time were observed, which was attributed to the elevated oxygen adsorption during annealing for a loosely packed structure. Moreover, the adhesion properties of IZO films with PC substrates decreased after 30‐s plasma treatment because of the significant difference on the surface polarity between the PC and thin films and the increased roughness caused by plasma etching. Copyright © 2016 John Wiley & Sons, Ltd.     

Zone-resolved mass spectroscopic study on RF plasma polymerization of styrene

The radiofrequency (rf) glow discharge plasma of styrene was investigated by direct sampling mass spectroscopy. Measurements were taken in three regions of the discharge: the plasma column and two dark zones before the electrodes. The plasma-polymerized styrene (PPS) thin films were analyzed by infrared spectroscopy (IR). The effects of monomer pressure and rf power on the ratios of mass peak heights C₄H/C₄H, C₆H/C₆H₅()CH in the three discharge regions, the polymer deposition rate, and the polymeric structure of the PPS films were studied. It was found that in the different discharge regions and under various discharge conditions, a variety of reactive species were formed by electron impact on monomer molecules. The polymer deposition rate was mainly dependent on the total number of the reactive species produced in the discharge. The concentration of phenyl groups in PPS films was proportional to the relative concentration of phenyl ring-containing reactive species in the gas phase plasma. © 1996 John Wiley & Sons, Inc.     

TiOx Films Deposited by Plasma Enhanced Chemical Vapour Deposition Method in Atmospheric Dielectric Barrier Discharge Plasma

The plasma enhanced chemical vapour deposition method applying atmospheric dielectric barrier discharge (ADBD) plasma was used for TiO_x thin films deposition employing titanium (IV) isopropoxide and oxygen as reactants, and argon as a working gas. ADBD was operated in the filamentary mode. The films were deposited on glass. The films?? chemical composition, surface topography, wettability and aging were analysed, particularly the dependence between precursor and reactant concentration in the discharge atmosphere and its impact on TiO_x films properties. Titanium in films near the surface area was oxidized, the dominating species being TiO₂ and substoichiometric titanium oxides. The films exhibited contamination with carbon, as a result of atmospheric oxygen and carbon dioxide reactions with radicals in films. No relevant difference of the film surface due to oxygen concentration inside the reactor was determined. The films were hydrophilic immediately after deposition, afterwards their wettability diminished, due to chemical reactions of the film surface and chemical groups involved in the atmosphere.     

Growth rate studies of CVD diamond in an RF plasma torch

This paper addresses the complex chemistry in the boundary later over a substrate in a chemical vapor deposition rector at atmospheric pressure. In this study, a highspeed plasma (140m/s) was created using a radio-frequency inductively coupled plasma torch for the deposition of diamond thin films. Growth rates on the order of 50 m/ h were obtained for well-faceted continuous films grown on molybdenum substrates positioned normal to the plasma flow. The highest growth rates were obtained at substrate temperatures of 1370 K and a feed gas ratio of 2.5% CH₄ in H₂. Growth rates are compared to predicted results obtained from numerical simulations, based on a one-dimensional stagnation-point flow, and are/mend to be in good agreement. Several other surface analysis techniques were used to characterize the deposited films, inchaling SEA/, Raman spectroscopy, transmission electron microscopy. Rutherfard backscattering spectroscopy, and hydrogen-forward recoil spectroscopy. Optical emission spectroscopy was used to characterize the RF plasma during the deposition process. Results from these studies form an important database for the validation and improvement of current models of the atmospheric-pressure diamond CVD environment.     

Atmospheric Pressure Plasma Deposition of Polyfuran

The atmospheric pressure radiofrequency (RF) plasma polymerization of furan was carried out with the objective of synthesizing polyfuran thin film. The structure, compositions and morphology of the plasma deposited polyfuran film were investigated by Fourier transform infrared (FTIR), atomic force microscopy (AFM), ultraviolet‐visible absorption spectroscopy (UV‐vis) and thermogravimetric analysis (TGA). The formation of polyfuran was confirmed using FTIR and UV‐visible analysis. The properties of plasma‐deposited polyfuran were compared with those of chemically synthesized polyfuran. Although the plasma deposited thin film polyfuran shows lower thermal stability than that of chemically synthesized polyfuran. It has better solubility in CHCl₃, also. Thin uniform polyfuran films are obtained in plasma assisted polyfuran deposition, while particles are obtained in chemical polyfuran polymerization.     

Substrate temperature effects on film chemistry in plasma depositions of organics. II. Polymerizable precursors

The influence of substrate temperature during plasma deposition on the chemistry of the organic films formed was examined. Plasma ionization of precursor gases that are polymerizable by conventional mechanisms was studied. Film chemistry was analyzed by x-ray photoelectron spectroscopy (XPS). Monomers that polymerize by a free radical mechanism [2-hydroxyethyl methacrylate (HEMA) and hexafluorobutadiene (HFB)] form more regular polymers (i.e. with less molecular rearrangement) by plasma deposition at low substrate temperatures than monomers that polymerize by ionic mechanisms [ethylene oxide (EO) and tetrahydrofuran (THF)]. In all cases, lowering the substrate temperature during deposition produces films with elemental composition virtually identical to that of the precursor gas. Comparison of high-resolution XPS spectra of the deposited films with those for model polymers suggests that functional groups in the monomers used to generate the plasma are incorporated to a greater extent at low substrate temperatures. The effect of plasma power on the degree of precursor structure retention obtained when reduced substrate temperatures are employed was also examined. Plasma deposition of HEMA at low substrate temperatures and low plasma power produces thin films which are, by core level XPS, indistinguishable from HEMA polymerized by conventional methods. EO and THF films coated at low substrate temperatures on glass, polyethylene, or polytetrafluoroethylene varied widely in surface chemistry due to differences in film uniformity. Film quality (uniformity) is enhanced for these low reactivity precursors by pretreating substrates with an argon plasma. © 1992 John Wiley & Sons, Inc.     

Plasma polymerization of fluoromethanes

Methane and fluoromethanes (CH_nF_4−n, 1 ≤ n ≤ 3) were subjected to an rf glow discharge plasma. All the fluoromethanes (including methane) polymerized in the plasma and formed thin films. The deposition rate of the fluoromethanes depended on their monomer structure: CH₂F₂, of which the F/H ratio is unity, showed the greatest deposition rate. The elimination of H and F atoms as H—F was found to be a key factor for the polymerization of fluoromethanes. The chemical composition of the polymerized film, measured with X-ray photoelectron spectroscopy and glow discharge emission spectroscopy, was also found to be strongly dependent on monomer structure. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2043–2050, 1998     

Structure,Composition, Mechanical,and Tribological Properties of BCN Films Deposited by Plasma Enhanced Chemical Vapor Deposition

In this work thin BCN films were deposited by plasma enhanced chemical vapor deposition (PECVD) using chloridic precursors. Through adjusting the BCl₃ content in the inlet gas mixture the chemical composition of the deposited films was changed from carbon rich to boron rich. Based on optical emission spectroscopy (OES) measurements, a correlation between film composition and precursor species concentration in the plasma was established. The films were amorphous as detected by grazing incidence X-ray diffraction (GIXRD). The hardness and the elastic modulus have maximal values of 25.5±1.2 and 191±6 GPa, respectively, for the films with a boron concentration of 45.2 at.%. GIXRD data suggest that a depletion in boron content may initiate the formation of graphitic domains in the amorphous matrix. The observed degradation of the mechanical properties is associated with the graphitization. The tribological behavior was studied with a tribometer operated in pin-on-plate configuration at the temperatures 25 and 400°C. The wear mechanisms were discussed with respect to the formation of a boric acid surface layer which was detected by reflection electron energy loss spectroscopy (REELS) analysis.     

Preparation of Silicon Thin Films of Different Phase Composition from Monochlorosilane as a Precursor by RF Capacitive Plasma Discharge

Monochlorosilane/argon/hydrogen (SiH₃Cl-Ar-H₂) mixture of different ratios was investigated from the point of PECVD application. RF capacitive plasma discharge of 40.68 MHz frequency was used. The process of deposition was studied by optical emission spectroscopy. The silicon thin films of different phase composition were obtained. The thin films were characterized by Raman-spectroscopy, atomic force microscopy, and secondary ion mass spectrometry. The exhaust gas mixture was analyzed by IR-spectroscopy in outlet of the reactor during PECVD process. The chemical mechanism for the deposition process was also proposed.     

Surface characterization of the SiOx films prepared by a remote atmospheric pressure plasma jet

The deposition rate and surface properties of SiO_x films were prepared and investigated using remote atmospheric pressure plasma (APP) jet. The APP, generated with low frequency power at 16 kHz, was fed with tetraethoxysilane (TEOS)/air gas mixture. After deposition, the SiO_x films were analyzed for chemical characteristics, elemental composition, surface morphology, and hardness. It was found that the deposition substrate temperature is the key factor to affect the deposition rate of remote APP chemical vapor deposition process. Fourier transform infrared (FTIR) spectra indicated that APP deposited SiO_x films are an inorganic feature. XPS examination revealed that the SiO_x films contained approximately 30% silicon, 58% oxygen and 12% carbon. Atomic forced microscopy (AFM) analysis results indicated a smooth surface of SiO_x films in deposition under higher substrate temperature. Also, pencil hardness tests indicated that the hardness of APP deposited SiO_x films was greatly improved with increasing substrate temperatures. Copyright © 2008 John Wiley & Sons, Ltd.     

Deposition of polyacrylic acid films on PDMS substrate in dielectric barrier corona discharge at atmospheric pressure

This paper reports on deposition of acrylic acid films polymerized by an efficient and cost‐effective technique of dielectric barrier corona discharge at atmospheric pressure. The liquid acrylic acid was vaporized and carried by argon gas into plasma to deposit polyacrylic acid films on polydimethylsiloxane substrate. A nonthermal corona discharge was generated in a pyrex flask using a steel tube‐to‐plate asymmetric electrode configuration. The plasma was excited using an in‐house developed power supply operating with continuous wave signals of 10‐kHz frequency. The emission spectra of plasma species were recorded to know their contribution during deposition process. The deposited surfaces were characterized using contact angle measurements, atomic force microscopy, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy and film thickness measurements. A maximum film growth rate of 363 nm/min was achieved under optimal condition of discharge. The results suggest that this plasma technique is capable of depositing organic coatings with a high concentration of carboxylic functional groups that could be potentially used for biomedical and microfluidic applications.     

Deposition of Diamond-Like Carbon Film in a Closed-Space CH4 RF Plasma

Deposition of diamond-like carbon (DLC) film and mass spectrometry measurements were carried out in a closed-space CH₄ rf (13.56 MHz) plasma (without both gas injection and vacuum pumping during the process). At pressures less than 0.6 Torr, the thickness of the DLC film deposited increased with increasing elapsed deposition time, and reached a maximum value, but after this the film thickness started to decrease, which was considered to be caused predominantly by ion-induced sputter etching. The maximum film thickness appeared at larger elapsed time for higher deposition pressure. The mass concentrations of hydrocarbon ions indicated anomalous behavior at early deposition times, but those of higher hydrocarbon ions are clearly increased at the point where the film thickness started to decrease. These results suggested that the ratio of precursor CH₃al density to the total hydrocarbon ion density (_CH3/_ion in the CH₄a was an important factor for the carbon film formation, and when this ratio reduced to a certain critical value with increasing elapsed deposition time, the deposited film was then re-etched predominately by the secondary higher hydrocarbon ions. At 1.0 Torr where a polymer-like soft carbon film was deposited, such re-etching of the deposited film was not observed.     

Molecular adsorption and the chemistry of plasma-deposited thin organic films: Deposition of oligomers of ethylene glycol

Weakly ionized, radio-frequency, glow-discharge plasmas formed from methyl ether or the vapors of a series of dimethyl oligo(ethylene glycol) precursors (general formula: H-(CH₂OCH₂)_n-H;n=1 to 4) were used to deposit organic thin films on polytetrafluoroethylene. X-ray photoelecton spectroscopy (XPS) and static secondary ion mass spectrometry (SIMS) of the thin films were used to infer the importance of adsorption of molecular species from the plasma onto the surface of the growing, organic film during deposition. Films were prepared by plasma deposition of each precursor at similar deposition conditions (i.e., equal plasma power (W), precursor flow rate (F), and deposition duration), and at conditions such that the specific energy (energy/mass) of the discharge (assumed to be constrained byW/FM, whereM=molecular weight of the precursor) was constant. At constantW/FM conditions, two levels of plasma power (and, hence, twoFM levels) and three substrate temperatures were examined. By controlling the energy of the discharge (W/FM) and the substrate temperature, these experiments enabled the study of effects of the size and the vapor pressure of the precursor on the film chemistry. The atomic % of oxygen in the film surface, estimated by XPS, and the intensity of theC-O peak in the XPS C_ls spectra of the films, were used as indicators of the degree of incorporation of precursor moieties into the plasma-deposited films. Analysis of films by SIMS suggested that these two measures obtained from XPS were good indicators of the degree of retention in the deposited films of functional groups from the precursors. The XPS and SIMS data suggest that adsorption of intact precursor molecules or fragments of precursor molecules during deposition can have a significant effect on film chemistry. Plasma deposition of low vapor pressure precursors provides a convenient way of producing thin films with predictable chemistry and a high level of retention of functional groups from the precursor.     

Plasma-induced deposition of thin films of aluminum oxide

Plasma-induced deposition of wear-protecting A1₂O₃ films has been investigated for two different gas mixtures, one of which is ususally used in thermal CVD. It is shown that, contrary to thermal CVO, the properties of thin films deposited from an AlCl₃/O₂/Ar mixture are superior to those prepared from AICl₃/CO₂/H₂. High Vickers hardness of 1800-2500 and a low chlorine content of 0.7 at. % have been obtained in films deposited from an AICl₃/O₂/Ar mixture at a substrate temperature of 500°C.     

Understanding the synthesis of DEGVE pulsed plasmas for application to ultra thin biocompatible interfaces

There is interest in the development of novel surface treatments for biocompatibility and non-fouling behaviors on various surfaces of in vivo devices. Polyethylene glycol thin films have shown promise as non-fouling passivation layers for such devices. Studies of the surface chemistry and non-fouling effectiveness of plasma deposited di(ethylene glycol) vinyl ether (DEGVE) films have observed that non-fouling performance is maximized when plasma deposition occurs at low values of average power, (<5 W). [Y.J. Wu, R.B. Timmons, J.S. Jen, Frank E. Molock, Non-fouling surfaces produced by gas phase pulsed plasma polymerization of an ultra low molecular weight ethylene oxide containing monomer, Colloids and Surfaces B: Biointerfaces 18 (2000) 235–248.] Chemical properties of plasma deposited films were directly attributed to the complex interactions occurring within the gas phase. In order to better understand the deposition process, as well as the significance of the conclusions drawn by Wu et al. [Y.J. Wu, R.B. Timmons, J.S. Jen, Frank E. Molock, Non-fouling surfaces produced by gas phase pulsed plasma polymerization of an ultra low molecular weight ethylene oxide containing monomer, Colloids and Surfaces B: Biointerfaces 18 (2000) 235–248.] an investigation of the gas phase behavior in DEGVE pulsed plasma discharges was performed. Infrared spectra were used to characterize the chemical composition and dissociative behavior of DEGVE plasmas across a range of average powers. This allowed for the construction of a dissociative model of the DEGVE monomer in the plasma discharge. Analysis of the observed dissociative pattern demonstrates the presence of key daughter species which would account for the observations made on deposited DEGVE films by Wu et al. [Y.J. Wu, R.B. Timmons, J.S. Jen, Frank E. Molock, Non-fouling surfaces produced by gas phase pulsed plasma polymerization of an ultra low molecular weight ethylene oxide containing monomer, Colloids and Surfaces B: Biointerfaces 18 (2000) 235–248.].