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18 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1999

CF2 Detection in Radio-Frequency Ar/CHF3 Plasmas by Fourier Transform Infrared Spectroscopy

CFx radicals, in particular CF2, are instrumental in anisotropic etching of SiO2. In order to optimize the CFx radical population in a given process environment, it is imperative that we understand their production mechanism. Towards this goal, we have conducted a series of quantitative measurements of CF2 radicals in low pressure RF plasmas similar to those used in SiO2 etching. In this study, we present preliminary results for Ar/CHF3 plasmas operating at pressures ranging from 10-50 mTorr and powers ranging from 100-500 W in the GEC reference cell, modified for inductive (transformer) coupling. Fourier transform infrared (FTIR) spectroscop) is used to observe the absorption features of the CF2 radical in the 1114 cm-1 and 1096 cm-1 spectral regions. The FTIR spectrometer is equipped with a high-sensitivity mercury cadmium telluride (MCT) detector and has afixed resolution of 0.125 cm- 1. The CF2 concentrations are measured for a range of operating pressures and discharge power levels, and are compared to measurements of the relative CF2 concentrations made by mass spectrometry using the method of appearance potential for radical selectivity.

Kim, J. S.↗
NASA NTRS2004

A Monte Carlo Sensitivity Analysis of CF2 and CF Radical Densities in a c-C4F8 Plasma

A Monte Carlo sensitivity analysis is used to build a plasma chemistry model for octacyclofluorobutane (c-C4F8) which is commonly used in dielectric etch. Experimental data are used both quantitatively and quantitatively to analyze the gas phase and gas surface reactions for neutral radical chemistry. The sensitivity data of the resulting model identifies a few critical gas phase and surface aided reactions that account for most of the uncertainty in the CF2 and CF radical densities. Electron impact dissociation of small radicals (CF2 and CF) and their surface recombination reactions are found to be the rate-limiting steps in the neutral radical chemistry. The relative rates for these electron impact dissociation and surface recombination reactions are also suggested. The resulting mechanism is able to explain the measurements of CF2 and CF densities available in the literature and also their hollow spatial density profiles.

Bose, Deepak↗
NASA NTRS1986

CF2 and CFCl fluorescence from VUV excitation of C2F3Cl

The photoexcitation process of C2F3Cl molecule was investigated in the 106 to 230 nm region using synchrotron radiation as a light source. Photoabsorption and fluorescence cross sections were measured and used to determine the fluorescence quantum yield. Fluorescence yield starts to appear at 170 nm and increases to about 2% at 155 nm. The fluorescence spectra were dispersed to identify the emitting species. At the excitation wavelength of 155 nm, the emission system is CFCl (Hermitian conjugate of A - Hermitian conjugate of X), and at 123.9 nm, both the CF2 (Hermitian conjugate of A - Hermitian conjugate of X) and CFCl (Hermitian conjugate of A - Hermitian conjugate of X) systems are observed. The dissociation processes that produced these excited species are discussed.

Nee, J. B.↗
NASA NTRS1987

CF2 and CFCl fluorescence from VUV excitation of C2F3Cl

The photoexcitation process of the C2F3Cl molecule was investigated in the 106-230-nm region using synchrotron radiation as a light source. Photoabsorption and fluorescence cross sections were measured and used to determine the fluorescence quantum yield. Fluorescence yield starts to appear at 170 nm and increases to about 2 percent at 155 nm. The fluorescence spectra were dispersed to identify the emitting species. The (A-X) systems of CFCl (at excitation wavelengths 155 and 123.9 nm) and CF2 (at 123.9 nm) are observed. The dissociation processes that produced these excited species are discussed.

Nee, J. B.↗
NASA NTRS1968

Fluorine-containing polyformals

A fluorine-containing polymeric polyformals is described which has the repeating unit O CH2 O CH2 (CF2) sub n CH2 wherein n is an integer of from about 3 to about 6 prepared by reacting trioxane with a diol having the formula HO CH2 (CF2) sub n CH2 OH. These polymeric polyformals are useful directly for impervious coatings on metals and the like.

Trischler, F. D.↗
NASA NTRS2001

Langmuir Probe and Mass Spectroscopic Measurements in Inductively Coupled CF4 Plasmas

Abstract Electron and ion energy distribution functions and other plasma parameters such as plasma potential (V(sub p)) , electron temperature (T(sub e)), and electron and ion number densities (n (sub e) and n(sub i)) in low pressure CF4 plasmas have been measured. The experiments were conducted in a GEC cell using an inductively coupled plasma (ICP) device powered by a 13.56 MHz radio-frequency (rf) power source. The measurements were made at 300 W of input rf power at 10, 30 and 50 mTorr gas pressures. Langmuir probe measurements suggest that n(sub e), n(sub i) and V(sub p) remain constant over 60% of the central electrode area, beyond which they decrease. Within the limits of experimental error (+/- 0.25 eV), T(sub e) remains nearly constant over the electrode area. T(sub e) and V(sub p) increase with a decrease in pressure. n(sub e) and n(sub i) are not affected as significantly as T(sub e) or V(sub p) by variation in the gas pressure. The electron energy distribution function (EEDF) measurements indicate a highly non-Maxwellian plasma. CF3+ is the most dominant ion product of the plasma, followed by CF2+ and CF+. The concentrations of CF2+ and CF+ are much larger than that is possible from direct electron impact ionization of the parent gas. The cross-section data suggest that the direct electron impact ionization of fragment neutrals and negative ion production by electron attachment may be responsible for increase of the minor ions.

Rao, M. V. V. S.↗
NASA NTRS1988

Mixing ratios of trace gases in the austral polar atmosphere during August and September of 1987

Mixing ratios are presented for a number of long-lived trace gases in the austral polar atmosphere during August and September of 1987. The recent discovery of a 12-year trend of increasing depletion of ozone over the Antarctic Continent in the spring of each year led to numerous theoretical interpretations and several scientific expeditions to the region. The results herein were obtained as part of a major effort involving penetration of the region of ozone depletion by NASA's multi-instrumented aircraft. One of the 14 instruments on the high-altitude ER-2 aircraft collected pressurized air samples between latitudes of 53 degrees and 72 degrees south at pressure altitudes up to 21 km in a series of 12 flights from Punta Arenas, Chile, over the Palmer Peninsula. The sampling system, located in the nose section of ER-2, has an inlet tube in the free airstream, a metal-bellows air pump, and 14 specially treated 1.6 l stainless-steel canisters for containing the pressurized air at 350 kPa. A typical flight profile consisted of a southbound path on the 428 K potential temperature surface, a descent to a pressure altitude of 13.7 km, a climb to the 460 K surface, and return on this surface. Mixing ratios for the trace gases were obtained from gas chromatographic analyses of the pressurized air samples. Of the species measured, the mixing ratios for CH4, CO, N2O, CF2 Cl2, CFCl3, CH3, CCl3, CCl4, and C2F3Cl3 are reported here.

Vedder, James F.↗
NASA NTRS1993

A study of the UV and VUV degradation of FEP

UV and VUV degradation of fluorinated ethylene propylene (FEP) copolymer was studied using electron spin resonance (ESR) spectroscopy, x-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The ESR study revealed the formation of a terminal polymer radical. The stability of this radical was investigated under different environments. An XPS study of FEP film exposed to VUV and atomic oxygen showed that oxidation takes place on the polymer surface. The study revealed also that the percentage of CF2 in the polymer surface decreased with exposure time and the percentage of CF, CF3, and carbon attached to oxygen increased. SEM micrographs of FEP film exposed to VUV and atomic oxygen identified a rough surface with undulations similar to sand dunes.

George, Graeme A.↗
NASA NTRS1996

Phospa-s-Triazines and Related Compositions of Improved Hydrolytic and Thermal Stability

The objective of the Program was to synthesize novel degradation inhibitors for perfluoropolyalkylether fluids and to evaluate their performance as well as that of other available inhibitors. Four novel additives: (C3F7OCF(CF3)CF2OC(CF3)2CN)((C6H5)2PN)2, (C3F7O(CF(CF3)CF2O)2C(CF3)2CN)((C6H5)2PN)2, u-(C3F7OCF(CF3)CF2OC(CF3)2CN)2((C6H5)2PN)2 and C3F7(OCF(CF3)CF2)6C6H4OP(O)(OC6H5)2 were prepared, characterized and their thermal stabilities established. The alloys studied were: 440C steel, M-50 steel, Pyrowear 675, Cronidur 30, Ti (4Al, 4Mn), and Ti (6Al, 4V). The additives and metals were evaluated in two different lots of Fomblin Z25, in Krytox 143AC and in Krytox 16256. Phosphate esters were found to be fully effective in arresting perfluoropolyaucylether fluid's degradation at temperatures up to 300 C over 24 h in the presence of alloys in oxygen. The overall rating of additives was: phosphates greater than phosphate/diester mixture greater than phosphine grater vthan or equal to phpospha-s-triazines.

Paciorek, K. J. L.↗
NASA NTRS1994

X-ray Photoelectron Spectroscopy Study of Argon-Plasma-Treated Fluoropolymers

Films of poly(tetrafluoroethylene) (PTFE) and of a tetrafluoroethylene-perfluoroalkyl vinyl ether (approximately 49:1) copolymer (PFA) were exposed to a radio-frequency argon plasma and then examined by X-ray photoelectron spectroscopy (XPS). The use of fluoropolymer films nearly free of surface hydrocarbon contamination as well as the use of a monochromatized X-ray source for XPS removed two factors contributing to conflicting reports on the effect of exposure time on the fluorine-to-carbon (F/C) and oxygen-to-carbon (O/C) ratios for several Ar-plasma-treated fluoropolymers. Contrary to literature indications, a common pattern was found for PTFE and PFA: a moderate decrease in F/C ratio (from 1.99 to 1.40, and from 1.97 to 1.57, respectively), together with a moderate increase in O/C ratio (from negligible to about 0.10, and from 0.012 to about O.10, respectively) at very short exposures, after which the F/C ratios remained essentially constant on prolonged exposures, while the O/C ratios for PTFE and PFA leveled off at 0.11 and 0.15, respectively. The XPS C(sub 1s), spectra for these polymers exposed to the Ar plasma for 20 min were similar and presented, besides a prominent peak at 292.0 eV (CF2,) and a minor peak at 294.0 or 294.1 eV (CF3), a composite band of four curve-resolved peaks (approximately 285-290 eV) representing various CH, CC, CO, CN, and CF functionalities.

Golub, Morton A.↗
NASA NTRS1997

Effect of Metal Alloys, Degradation Inhibitors, Temperatures on Thermal Oxidative Stability of CF3O(CF2O)(sub x)(CF2O)(sub y)CF3 Fluids

Degradation-promoting action of a series of ferrous and titanium alloys on CF3O(CF2O)(sub x)(CF2-CF2O)(sub y)CF3-based Z25 fluids and the inhibition effectiveness of several classes of additives were investigated. Four types of additives-phosphines, phosphates, phospha-s-triazines, and diphosphatetraazacyclooctatetraene-were studied in two batches of Z25 fluid, P28 and P151. In the absence of inhibitors, titanium alloys were more detrimental than the ferrous metals, but the additives were more effective in the presence of titanium alloys. Phosphate esters totally inhibited the decomposition of P151 at 330 C over 24 h in both types of alloys. The other additives were effective at lower temperatures. The responsiveness of fluid to an additive was found to be batch dependent.

Jones, William R., Jr.↗
NASA NTRS1999

Measurements of Ion Energy and Ion Flux Distributions in Inductively Coupled Plasmas in CF4/O2/Ar Mixtures

We report mass spectrometric studies of energy distributions and absolute concentrations of ions generated in CF4/O2/Ar inductively coupled rf plasmas. The ions were collected through a 100 mm orifice in the grounded and water cooled lower electrode in a GEC cell configuration. The measurements were made at gas pressures in the 10-50 mTorr range and rf coil power in the 100-300 W range. The observed ions are CF3(+), CF2(+), CF(+), C(+), F(+), COF(+), CO(+), O2(+), and O(+). The relative abundance of these ions varies with pressure and rf power. The energy distribution and absolute concentrations are correlated with electron number density and floating plasma potential measured by a compensated Langmuir probe.

Rao, M. V. V. S.↗
NASA NTRS1998

Fluoropolymer Films Deposited by Argon Ion-Beam Sputtering of Polytetrafluoroethylene

The FT-IR, XPS and UV spectra of fluoropolymer films (SPTFE-I) deposited by argon ion-beam sputtering of polytetrafluoroethylene (PTFE) were obtained and compared with prior corresponding spectra of fluoropolymer films (SPTFE-P) deposited by argon rf plasma sputtering of PTFE. Although the F/C ratios for SPTFE-I and -P (1.63 and 1.51) were similar, their structures were quite different in that there was a much higher concentration of CF2 groups in SPTFE-I than in SPTFE-P, ca. 61 and 33% of the total carbon contents, respectively. The FT-IR spectra reflect that difference, that for SPTFE-I showing a distinct doublet at 1210 and 1150 per centimeter while that for SPTFE-P presents a broad, featureless band at ca. 1250 per centimeter. The absorbance of the 1210-per centimeter band in SPTFE-I was proportional to the thickness of the film, in the range of 50-400 nanometers. The SPTFE-I was more transparent in the UV than SPTFE-P at comparable thickness. The mechanism for SPTFE-I formation likely involves "chopping off" of oligomeric segments of PTFE as an accompaniment to "plasma" polymerization of TFE monomer or other fluorocarbon fragments generated in situ from PTFE on impact with energetic Ar ions. Data are presented for SPTFE-I deposits and the associated Ar(+) bombarded PTFE targets where a fresh target was used for each run or a single target was used for a sequence of runs.

Golub, Morton A.↗
NASA NTRS1997

XPS Study of Plasma- and Argon Ion-Sputtered Polytetrafluoroethylene

The similarity of plasma-polymerized tetrafluoroethylene (PPTFE) and the fluoropolymer film deposited by rf (radio frequency) plasma sputtering (SPTFE) of polytetrafluoroethylene (PTFE), noted earlier in the literature, has been reconfirmed. FT-IR (Fourier Transform Infrared), XPS (X ray Photoelectron Spectroscopy) and UV (ultraviolet) spectroscopy has been employed in apparently the first study to involve preparation of PPTFE and SPTFE in the same reactor and under comparable low-power plasma conditions. Most of the work concerned the use of He or Ar as sputtering gas, but some runs were also carried out with the other rare gases Ne, Kr and Xe. The C1s XPS spectra of SPTFE films displayed a relatively higher content of CF2 groups, and yielded higher F/C (fluorine / carbon) ratios, than PPTFE films, while the SPTFE films were somewhat more transparent in the UV than PPTFE. The F/C ratios for SPTFE were essentially independent of the rare gas used for sputtering. Increasing rf power from 10 to 50 W for Xe plasma-sputtering of PTFE resulted in successively lower F/C ratios (1.55 to 1.21), accompanied by sputtering of the glass reactor occurring at 40 W and above. Some limited XPS, FT-IR and UV data are presented on Ar ion-sputtered PTFE.

Golub, Morton A.↗
NASA NTRS2020

Chandra and XMM-Newton Observations of A2256: Cold Fronts, Merger Shocks, and Constraint on the IC Emission

We present the results of deep Chandra and XMM-Newton observations of a complex merging galaxy cluster Abell 2256 (A2256) that hosts a spectacular radio relic (RR). The temperature and metallicity maps show clear evidence of a merger between the western subcluster (SC) and the primary cluster (PC). We detect five X-ray surface brightness edges. Three of them near the cluster center are cold fronts (CFs): CF1 is associated with the infalling SC; CF2 is located in the east of the PC; and CF3 is to the west of the PC core. The other two edges at cluster outskirts are shock fronts(SFs): SF1 near the RR in the NW has Mach numbers derived from the temperature and the density jumps, respectively, of MT=1.62±0.12 and Mρ=1.23±0.06; SF2 in the SE has MT=1.54±0.05 and Mρ=1.16±0.13. In the region of the RR, there is no evidence for the correlation between X-ray and radio substructures, from which we estimate an upper limit for the inverse-Compton emission, and therefore set a lower limit on the magnetic field (∼450 kpc from PC center) of B>1.0μG for a single power-law electron spectrum or B>0.4μG for a broken power-law electron spectrum. We propose a merger scenario including a PC, an SC, and a group. Our merger scenario accounts for the X-ray edges, diffuse radio features, and galaxy kinematics, as well as projection effects.

Chong Ge↗
NASA NTRS2020

Chandra and XMM-Newton Observations of A2256: Cold Fronts, Merger Shocks, and Constraint on the IC Emission

We present the results of deep Chandra and XMM-Newton observations of a complex merging galaxy cluster Abell 2256 (A2256) that hosts a spectacular radio relic (RR).The temperature and metallicity maps show clear evidence of a merger between the western subcluster (SC) and the primary cluster (PC). We detect five X-ray surface brightness edges. Three of them near the cluster center are cold fronts (CFs): CF1is associated with the infalling SC; CF2 is located in the east of the PC; and CF3 is to the west of the PC core. The other two edges at cluster outskirts are shock fronts(SFs): SF1 near the RR in the NW has Mach numbers derived from the temperature and the density jumps, respectively, of MT=1.62±0.12andMρ=1.23±0.06; SF2 in the SE has MT=1.54±0.05andMρ=1.16±0.13. In the region of the RR, there is no evidence for the correlation between X-ray and radio substructures, from which we estimate an upper limit for the inverse-Compton emission, and therefore set a lower limit on the magnetic field (∼450 kpc from PC center) of B>1.0μG for a single power-law electron spectrum or B>0.4μG for a broken power-law electron spectrum. We propose a merger scenario including a PC, an SC, and a group. Our merger scenario accounts for the X-ray edges, diffuse radio features, and galaxy kinematics, as well as projection effects.

Chong Ge↗