Thin film growth of TiO2 and Ti2O3 by the new method of liquid injection CVD investigated using optical interferometry,XRD and AFM

The method of liquid injection chemical vapour deposition (LICVD) is a new technique, which is being developed for its potential to allow new material compositions and simpler and more flexible deposition schemes. The potential advantage of this technique is that it is possible to fix the precursor composition(s) in the injection solvent, permitting a simpler injection scheme compared to the current need for bubblers or gaseous precursors in CVD. In our system the precursor solution is rapidly volatilised into a carrier gas stream, which is then passed over the heated substrate. In this initial study we use the single component titanium tetraisopropoxide (TTIP) dissolved in THF for the injection solution, and investigate the behaviour of the deposition with in situ optical reflectometry and ex situ XRD and AFM. The data gained gives information on the growth rate, morphology and crystalline properties of the films. The characteristics of our deposition system are that we find a flux controlled growth mode, changes in the rate of deposition as a function of thickness, which are related to the surface morphology and the growth of Ti₂O₃ at temperatures above 450 °C. Copyright © 2006 John Wiley & Sons, Ltd.     

Critical evaluation of conditions of plasma polymerization

Under conditions of plasma polymerization, we are dealing with the “reactive” or “self-exhausting” rather than the “nonreactive” or “non-self-exhausting” gas phase (plasma). Therefore, many parameters that define the gas phase, such as system pressure and monomer flow rate, which are measured in the nonplasma state (before glow discharge is initiated), do not apply to a steady state of plasma, the conditions under which most of the studies on plasma polymerization are carried out. Consequently, information based on: (1) the polymer deposition rate measured at a fixed flow rate and discharge power, (2) the dependence of deposition rate on flow rate at fixed discharge power, or (3) the dependence of deposition rate on discharge power at fixed flow rate, does not provide meaningful data that can be used to compare the characteristic nature of various organic compounds in plasma polymerization. The significance and true meaning of experimental parameters applicable to conditions of plasma polymerization are discussed. The most important feature is that plasma polymerizations of various organic compounds should be compared at comparable levels of composite discharge power parameter W/FM, where W is discharge power, F is the monomer flow rate (given in moles), and M is the molecular weight of a monomer.     

Diamond Deposition on Substrates with Different Geometries in a Thermal Plasma Reactor

The effects of process parameters on diamond film deposition have been considered in an atmospheric-pressure dc thermal plasma jet reactor. Two different precursor injection systems have been evaluated, counterflow and side injection. The precursor flow rate using ethanol has been found to strongly affect crystal size as well as orientation of crystal growth planes. Further, crystal size on sharp edges has been found to be up to five times larger than on planar surfaces. The effects of substrate geometry on the morphology and area of deposited diamond have been investigated as well. The results of this study show that dc thermal plasma jets can provide high diamond deposition rates, for example on wires and drills, although crystal size and film thickness show substantial variation.     

Use of Liquid Precursors for Diamond Chemical Vapor Deposition--The Effects of Mass Transport and Oxygen

Thermal plasma chemical vapor deposition of diamond-utilizing liquidfeedstock injection has been shown to yield higher mass deposition rates,larger crystal size, and thicker films when compared to the use of gaseousfeedstock for equivalent operating conditions. Increased mass transport ofthe activated precursor species across the substrate diffusion boundarylayer and the presence of oxygen in liquid precursors are investigated aspotential reasons for the observed results. Comparisons of the variousprecursor systems investigated in this study are based on crystal size andfilm thickness as a function of radial postion, area of deposit, totalmass deposition rate, and the observed liquid precursor droplet trajectorieswithin the deposition chamber using a laser strobe video system. The resultsindicate that the mass transport in both the liquid and gaseous precursorsystems is greatly improved by the use of an inert carrier gas. Further, theuse of a liquid versus a gaseous precursor does not seem toresult in higher total deposition rates when the operating conditions forboth have been optimized. Finally, the presence of oxygen in the liquidfeedstock system is found to be at least partly responsible for theincreased growth rate, which is observed when comparing the plainhydrocarbon precursor cases with the oxygenated liquid precursorcase.     

Preparation and in vitro/in vivo evaluation of anastrozole reservoir‐type intravaginal ring

This report details the preparation of anastrozole (ATZ) reservoir‐type intravaginal ring (IVR) and the detection of the concentration of ATZ in beagle dog plasma by liquid chromatography–tandem mass spectrometry (LC–MS/MS). An ATZ reservoir‐type IVR which included ATZ silicone elastomer core and a nonactive silicone layer was manufactured by reaction injection moulding at 80°C for 20 min. An in vitro release experiment was performed under sink conditions and the samples were determined by high‐performance liquid chromatography. A bioanalytical method was developed and validated for determination of ATZ in beagle dog plasma for IVR development. The analytical method consisted of the extraction of plasma samples and determination of ATZ by LC–MS/MS using buspirone as the internal standard. Separation was achieved on a Kinetex‐C₁₈ 110A column (3 × 30 mm, 2.6 μm, Phenomenex) using step‐gradient mobile phase and an isocratic flow rate consisting of formic acid. Protonated ions formed by a turboion spray in the positive mode was used to detect the analyte (ATZ) and internal standard. The MS–MS detection was performed on a triple quadrupole mass spectrometer equipped with electrospray ionization source. The mass spectrometer was operated in the multiple reaction monitoring mode. The mass transition ion‐pair was followed as m/z from 294.10 to 225.08 for anastrozole and m/z from 386.23 to 122.11 for buspirone. The results proved that the correlation between in vitro and in vivo analyses was relatively good.     

On the Correlation Between Deposition Rate and Process Parameters in Remote Plasma-Enhanced Chemical Vapor Deposition

Plasma-enhanced chemical vapor deposition has become one of the most important thin film deposition technologies. To avoid direct plasma exposure the substrates may be placed in the remote region. A carrier gas conveys the plasma energy to the deposition area where the reactions with the monomer molecules take place. For the engineering of such a process the modeling of the achievable deposition rate is of great interest. Among different possibilities semiempirical models provide a fast and easily utilizable tool without intensive computer simulations or the necessity of detailed knowledge about the chemistry involved. From deposition experiments with oxygen and an organosilicon monomer (hexamethyldisiloxane, HMDSO) the remote composite parameter is suggested. It combines microwave power, monomer and carrier gas flow rate, and the distance of the substrate from the plasma source. This parameter was derived from the ratio between atomic oxygen and monomer flow rate. In the parameter range considered the deposition rate is described as well ordered and the energy- and monomer-deficient regions are clearly separated.     

Density oscillations in a model of water and other similar liquids

It is suggested that the dynamics of liquid water have a component consisting of O^?2z (oxygen) anions and H^+z (hydrogen) cations, where z is a (small) reduced effective electron charge. Such a model may apply to other similar liquids. The eigenmodes of density oscillations are derived for such a two-species ionic plasma, included the sound waves, and the dielectric function is calculated. The plasmons may contribute to the elementary excitations in a model introduced recently for the thermodynamics of liquids. It is shown that the sound anomaly in water can be understood on the basis of this model. The results are generalised to an asymmetric short-range interaction between the ionic species as well as to a multi-component plasma, and the structure factor is calculated.     

Plasma homo- and copolymerizations of tetrafluoroethylene and chlorotrifluoroethylene

The plasma homo- and copolymerizations of tetrafluoroethylene (TFE) and chlorotrifluoroethylene (CTFE) in a capacitively coupled tubular reactor (TR) with external electrodes were studied by means of microgravimetry and FT-IR and XPS analyses. The deposition rates for CTFE/TFE plasma copolymers, as well as the ratios of IR absorbances at 1180 and 1225 cm⁻¹, and the XPS-derived Cl/C and F/C ratios, varied regularly with mol % CTFE in the feed, all of which results were dependent upon the rf power at which the plasma copolymerizations were conducted. The deposition rates for the plasma homopolymers of TFE (PPTFE) and CTFE (PPTCFE) depended markedly on rf power (W) and monomer molar flow rate (F). The F/C ratio for PPTFE was nearly independent of the composite parameter,W/FM (whereM is the monomer molecular weight), while for PPCTFE, the F/C ratio decreased significantly and the Cl/C ratio increased slightly with increase inW/FM. The percentage of carbon as CF₃ was 20–24% in PPTFE and 7–14% in PPCTFE. Plots of deposition rate versusW/FM for PPTFE and PPCTFE obtained in a TR differed considerably from corresponding plots in the literature for the same homopolymers prepared in a glass-cross or bell-jar reactor.     

A spectroscopic investigation of growth regimes in silane-ammonia discharges used for plasma nitride deposition

Using optical emission spectroscopy (OES) we have been able to distinguish three operating regimes for the ammonia-silane glow discharge used in plasma nitride deposition. By monitoring the deposition rate and analyzing the structure and composition of thea-SiN: H films it has been possible to correlate these three plasma regimes with three distinct deposition mechanisms. The growth plasma may be tuned to each of these regimes by varying one or more of the following three external parameters: ammonia mole fraction, r .f. power, and gas flow rate. Choice of these parameters allows control of the NH _n radical concentration and the residence time in the reactor, and hence control over the number of gas-phase SiH _n -NH _n radical-radical reactions. Thus OES makes control of the film deposition mechanism possible.     

Development and validation of a liquid chromatography with tandem mass spectrometry method for the quantification of vitisin B in rat plasma and urine

A new, rapid, and sensitive liquid chromatography with tandem mass spectrometry method was developed for the determination of vitisin B and validated in rat plasma and urine using carbamazepine as an internal standard. The plasma (0.05 mL) or urine (0.2 mL) samples were extracted by liquid–liquid extraction with ethyl acetate and separated on an Eclipse Plus C₁₈ column (100 × 4.6 mm, 3.5 μm) with a mobile phase consisting of acetonitrile and 0.1% formic acid water (60:40, v/v) at a flow rate of 0.7 mL/min. Detection and quantification were performed by mass spectrometry in selected reaction‐monitoring mode with positive electrospray ionization. The calibration curves were recovered over the concentration ranges of 10?5000 ng/mL (correlation coefficients, r≥0.9833) in plasma and 5?2500 ng/mL (r≥0.9977) in urine, respectively. All validation data, including the specificity, precision, accuracy, recovery, and stability, conformed to the acceptance requirements. No matrix effects were observed. The developed method was successfully applied to pharmacokinetic studies of vitisin B following intravenous administration of 0.5 and 1 mg/kg and intraperitoneal injection of 5, 10, and 25 mg/kg to rats. This is the first report on the pharmacokinetic properties of vitisin B. The results provide a meaningful basis to evaluate preclinical or clinical applications of vitisin B.     

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.     

A sensitive LC–MS/MS‐based bioanalytical method for quantification of salviaflaside and rosmarinic acid in rat plasma and its application in a pharmacokinetic study

A selective and sensitive liquid chromatography tandem mass spectrometry method was developed for the simultaneous determination of salviaflaside and rosmarinic acid in rat plasma. Sample preparation was carried out through liquid–liquid extraction with ethyl acetate using curculigoside as internal standard (IS). The analytes were determined by selected reaction monitoring operated in the positive ESI mode. Chromatographic separation was performed on an Agilent Eclipse Plus C₁₈ column (100 × 4.6 mm, 1.8 μm) with a mobile phase consisting of methanol–water–formic acid (50:50:0.1, v/v/v) at a flow rate of 0.3 mL/min. The run time was 1.9 min per sample and the injection volume was 5 μL. The method had an LLOQ of 1.6 ng/mL for salviaflaside and 0.94 ng/mL for rosmarinic acid in plasma. The linear calibration curves were fitted over the range of 1.6–320 ng/mL for salviaflaside and 0.94–188 ng/mL for rosmarinic acid in plasma with correlation coefficients (r²) >0.99. Intra‐ and inter‐day precisions (relative standard deviation) were < 13.5%, and accuracies (relative error) were between −8.6% and 14.5% for all quality control samples. The method was validated and applied to the pharmacokinetics of salviaflaside and rosmarinic acid in plasma after oral administration of Prunella vulgaris extract to rats.     

Preparation and characterization of plasma-polymerized N-vinyl-2-pyrrolidone films

Thin films (< 1 μm) of plasma polymerized N-vinyl-2-pyrrolidone (PPNVP) have been prepared, using an inductively coupled RF glow discharge in a flow-through reactor system. PPNVP films were hydrophilic, smooth, and appeared morphologically homogeneous. The polymer deposition rate was found to increase linearly with NVP flow rate, and to decrease with the distance from the induction coil. ATR–FT–IR spectral studies suggested a highly branched polymer structure and included absorptions at 2150 and 1540 cm^?1 which were unique to the plasma polymer and derived from lactam ring opening/breaking reactions. ESCA studies demonstrated that, under a given set of plasma reaction conditions, the surface composition was consistent throughout the reactor. However, polymer composition was influenced by larger changes in the plasma energy, since the nitrogen content was found to decrease with increasing W/FM. This corresponded to concomitant increases in the advancing water contact angles and to small but reproducible changes in the IR spectrum.     

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     

Comparisons Between Numerical Model and Experiments for a Direct Current Plasma Flow

The governing equations describing a flowing stream of a hydrogen plasma encountered in applications, such as diamond deposition, and in devices, such as arcjet thrusters, are solved numerically using the linearized implicit (LBI) Method of Briley and McDonald. The results of simulations under the assumption that the plasma can be described by a single temperature are compared with detailed experimental measurements of flow characteristics and species concentrations in a 1 kW arcjet. These comparisons show that by formulating the problem in terms of known experimental operating conditions, such as mass flow rate, power, and current levels, it is possible to predict many of the characteristics of the flowing plasma. As expected, predictions from this one-temperature model show that some deviations from the experimental results occur near the exit plane of the channel, where unequal electron and heavy particle temperatures are encountered because of lower pressures.     

Plasma polymerization of tetrafluoroethylene. III. Reproducibility and effects of substrate and reactor materials

Plasma polylmerization occurs in plasmas surrounded by surfaces and polymer formation is one of the complicated interactions that take place between active species and molecules which constitute surfaces and gas phases. Effects of reactor wall, substrate materials, flow rate, and discharge power on polymer formation, and properties of polymer deposits were investigated by ESCA, IR (infrared) spectroscopy, and the measurement of system pressure. The effect of surface is important at the initial stage of plasma polymerization which can be easily detected by the system pressure change; however, integrated properties such as IR spectroscopy and the deposition rate show the effect in a less pronounced manner. ESCA, which reflects the properties of surface (approximately 20 A? in depth), showed the effect of surface in an even less sensitive manner. The amount and properties (including the effects of surfaces) are dependent on plasma polymerization parameter W/FM(W, wattage; F, volume flow rate; and M, molecualar weight of monomer) and the location of deposition within a reactor. IR and ESCA data clearly showed the dependence of polymer properties on W/FM; i.e., increase of W and decrease of M to be equivalent. When all these factors were kept under control, the reproducibility of plasma polymerization was found to be excellent.     

Field‐assisted paper spray mass spectrometry for therapeutic drug monitoring: 1. the case of imatinib in plasma

The field‐assisted paper spray (FAPS) – mass spectrometric method has been employed to quantify the imatinib (IMT) plasma levels in treated patients. The quantitative measurements have been performed on the collisionally generated fragment at m/z 394 of the protonated molecules of IMT and deuterated IMT (d₃‐IMT), used as internal standard. The FAPS‐tandem mass spectrometry (MS/MS) method exhibits some limitations, because of the high number of operative parameters that need to be carefully controlled. For this aim, papers of different geometry, thickness, and porosity were tested. To obtain a more focalized and intense electrical field, a stainless steel needle was mounted axially and placed at 4 kV voltage. The variability observed in the measurements was ascribed either to the inter‐individual variability (e.g. the concomitant presence of other compounds such as proteins, lipids, drugs and/or salts in the plasma of different patients) or to the uncontrollable variables in the instrumental set‐up (e.g. sample deposition, changes in paper spray conditions). Furthermore, the manual sample deposition and solvent dripping strongly affects the measure reproducibility. Despite this, it is interesting to observe that, once applied in blind on 24 real plasma samples, FAPS‐MS/MS led to results analogous to those obtained by the well‐consolidated liquid chromatography‐MS/MS, even if the mean coefficient of variation % (CV%) values of 20.4% and 2.6% were observed for the two methods, respectively. In conclusion, despite CV values are relatively high, it is worth noting that the FAPS‐MS/MS method is much more straightforward, rapid and economical than the liquid chromatography‐MS/MS one, and it appears therefore very promising for applications where a high precision is not always a required task, as e.g. in some cases of therapeutic drug monitoring. Copyright © 2017 John Wiley & Sons, Ltd.     

Deposition behavior in a low‐temperature cascade arc torch (CAT) polymerization process

Two kinds of hydrocarbon type monomers and three kinds of organosilicons were polymerized by a low‐temperature cascade arc argon plasma torch. Their deposition behaviors were studied as a function of experimental parameters and monomer elemental compositions. It was found that the normalized deposition rate (DR), expressed as deposition yield of DR/(FM)_m, was determined by a composite operational parameter, W*(FM)_c/(FM)_m, where W is the power input, and (FM)_c and (FM)_m are the mass flow rates of carrier gases and monomers, respectively. Experimental results indicated that the deposition yield is highly dependent on the elementary compositions of monomers. Optical emission spectroscopy study on the argon plasma torch showed that the emission intensity of excited argon neutrals was proportional to the value of the parameter W*(FM)_c. These results further certified that excited argon neutrals are the main energy carriers from the cascade arc column to activate monomers in the argon plasma torch. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 967–982, 1999     

Room-Temperature Silicon Nitrides Prepared with Very High Rates (>50 nm/s) in Atmospheric-Pressure Very High-Frequency Plasma

We have investigated the structure and stability of SiN _x films deposited with very high rates (>50 nm/s) in atmospheric-pressure (AP) He-based plasma excited by a 150 MHz very high-frequency (VHF) power using a cylindrical rotary electrode at room temperature. The SiN _x films are prepared on Si(001) substrates with varying VHF power density (P _VHF), H₂ concentration and source ratio (NH₃/SiH₄). Infrared absorption spectroscopy is used to analyze the bonding configurations in the films. The results show that increasing H₂ concentration under the supply of a moderately large P _VHF, together with the adjustment of NH₃/SiH₄ ratio, enables us to prepare SiN _x showing reasonable stability against a buffered hydrofluoric acid solution in spite of the very high deposition rate of 130 nm/s. The achievement of such a high-rate deposition at room temperature is primarily due to the significant enhancement of both gas-phase and surface-phase reactions in AP-VHF plasma.     

Quantitative determination of sauchinone in rat plasma by liquid chromatography-mass spectrometry

A rapid, sensitive and specific method using liquid chromatography with tandem mass spectrometric detection (LC‐MS) was developed for the analysis of sauchinone in rat plasma. Di‐O‐methyltetrahydrofuriguaiacin B was used as internal standard (IS). Analytes were extracted from rat plasma by liquid–liquid extraction using ethyl acetate. A 2.1 mm i.d. × 150 mm, 5 µm, Agilent Zorbax SB‐C₁₈ column was used to perform the chromatographic analysis. The mobile phase was methanol–deionized water (80:20, v/v). The chromatographic run time was 7 min per injection and the flow‐rate was 0.2 mL/min. The tandem mass spectrometric detection mode was achieved with electrospray ionization interface in positive‐ion mode (ESI⁺). The m/z ratios [M + Na]⁺, m/z 379.4 for sauchinone and m/z 395.4 for IS were recorded simultaneously. Calibration curve were linear over the range of 0.01–5 µg/mL. The lowest limit of quantification was 0.01 µg/mL. The intra‐day and inter‐day precision and accuracy of the quality control samples were 2.94–9.42% and 95.79–108.05%, respectively. The matrix effect was 64.20–67.34% and the extraction recovery was 93.28–95.98%. This method was simple and sensitive enough to be used in pharmacokinetic research for determination of sauchinone in rat plasma. Copyright © 2011 John Wiley & Sons, Ltd.