Evaluation of CF4 plasma chemistry by power modulation

The dominant chemical reaction kinetics occurring in the plasma environment are studied by small periodic power modulation and analyzed using transfer functions. A CF₄/Ar rf plasma at 500 mTorr was chosen to validate this experimental methodology because the kinetics of the CF, system have been well studied previously.(1) The experimental results demonstrated that the modulation technique can determine dominant reactions in the plasma. The experimental results also confirmed the importance of surface recombination reactions and provided quantitative total sticking coefficients for F, CF₂ and CF: _F=0.02, _CF2=0.05, and CF0.20. The results also indicated that an activated intermediate may be a precursor to the formation of both CF₂ and CF from CF₄. Energetic considerations and excited-.state lifetime calculations suggest that this activated intermediate may be an internally excited CF₃* radical.     

A comparative study of CH4 and CF4 rf discharges using a consistent plasma physics and chemistry simulator

A self-consistent, one-dimensional simulator for the physics and chemistry of radio frequency (rf) plasmas was developed and applied for CH₄ and CF₄. The simulator consists of a fluid model for the discharge physics, a commercial Boltzmann equation solver for calculations of electron energy distribution fuction (EEDF), a generalized plasma chemistry code, and an interface module among the three models. The CH₄ and CF₄ discharges are compared and contrasted: CH₄ plasmas are electropositive, with negative ion densities one order of magnitude less than those of electrons, whereas CF₄ plasmas are electronegative, with ten times more negative ions than electrons. The high-energy tail of tire EEDF in CH₄, lies below both the Druyvensteyn and Maxwell distributions, whereas tire EEDF high-energy tail in CF₄ lies between the two. For CH₄, the chemistry model was applied for four species, namely, CH₄ CH₃ CH₂, and H, whereas for CF₄, five species were examined namely CF₄, CF₃, CF₂, CF, and F The predicted densities and profiles compare favorably with experimental data. Finally, the chemistry results were fedback into the physics model until convergence was obtained.     

Gas-phase reactions of CF3 and CF2 with atomic and molecular fluorine: Their significance in plasma etching

Reaction rate coefficients have been measured at 295 K for both CF₃ and CF₂ with atomic and molecular fluorine. The reaction between CF₃ and F was studied over a gas number density range of (2.4–23)×10¹⁶ cm^–3 with helium as the bath gas. The measured rate coefficient increased from (1.1–1.7)×10^–11 cm³ s^–1 as the gas number density increased over this range. In contrast to this relatively small change in rate coefficient with gas number density, the rate coefficient for CF₂+F increased from (0.4–2.3)×10^–12 cm³ s^–1 as the helium gas number density increased from (3.4–28.4)×10¹⁶ cm^–3. Even for the highest bath gas number density employed, the rate coefficient was still more than an order of magnitude lower than earlier measurements of this coefficient performed at comparable gas number densities.Both these association reactions are examined from the standpoint of the Gorin model for association of radicals and use is made of unimolecular dissociation theory to examine the expected dependence on gas number density. The calculations reveal that CF₃+F can be explained satisfactorily in these terms but CF₂+F is not well described by the simple Gorin model for association.CF₃ was found to react with molecular fluorine with a rate coefficient of (7±2)×10^–14 cm³ s^–1 whereas only an upper limit of 2×10^–15 cm³ s^–1 could be placed on the rate coefficient for the reaction between CF₂ and F₂. The values obtained for this set of reactions mean that the reaction between CF₃ and F will play an important role in plasmas containing CF₄. The high rate coefficient will mean that, under certain conditions, this particular reaction will control the amount of CF₄ consumed. On the other hand, the much lower rate coefficient for reactions between CF₂ and F means that CF₂ will attain much higher concentrations than CF₃ in plasmas where these combination reactions are dominant.     

Rate Coefficient for Self-Association Reaction of CF2 Radicals Determined in the Afterglowof Low-Pressure C4F8 Plasmas

We have analyzed decay kinetics of CF₂ radicals in the afterglow of low-pressure, high-density C₄F₈ plasmas. The decay curve of CF₂ density has been approximated by the combination of first- and second-order kinetics. The surface loss probability evaluated from the frequency of the first-order decay process has been on the order of 10^–4. This small surface loss probability has enabled us to observe the second-order decay process. The mechanism of the second-order decay is self-association reaction between CF₂ radicals (CF₂+CF₂C₂F₄). The rate coefficient for this reaction has been evaluated as (2.6–5.3)×10^–14 cm³/s under gas pressures of 2 to 100 mTorr. The rate coefficient was found to be almost independent of the gas pressure and has been in close agreement with known values, which are determined in high gas pressures above 1 Torr.     

Experimental and Theoretical Studies of a Pulsed Microwave Excited Ar/CF4 Plasma

The present work deals with a pulsed microwave discharge in an Ar/CF ₄ gas mixture under a low pressure (1–10 mbar). The discharge chamber developed has a cylindrical geometry with a coupling window alternatively made of quartz or alumina. The setup allows one to investigate the plasma–wall interactions (here etching of the quartz window) and the ignition process of the pulsed microwave plasma. Microwave pulses with a duration of 50–200 s and repetition rate between 1 and 10 kHz are typical for the experiments. The space-time behavior of the fluorine number density in the discharge has been investigated experimentally by optical actinometry. The discharge kinetics is modeled using electron-transport parameters and rate coefficients derived from solutions of the Boltzmann equation. Together with the solution of the continuity and electron balance equations and the rate equations describing the production of CF _x (x=2, 3, 4) radicals and F atoms, a good agreement between experimental and theoretical data can be achieved.     

A model for the etching of Si in CF4 plasmas: Comparison with experimental measurements

A model has been developed to describe the chemistry which occurs in CF₄ plasmas and the etching of Si both in the plasma and downstream. One very important feature of this model is that for discharge residence times which vary by more than an order of magnitude, the amount of CF₄ consumed is low and relatively constant. This is because the gas-phase combination reactions between F and both CF₃ and CF₂ lead to the rapid reforming of CF₄. The model predicts that CF₂ is a major species in the gas phase and that the [F] detected as a sample point downstream is a very sensitive function of [CF₂]/[F] in the discharge. Even though the calculations show that [F] in the discharge varies only slightly over the wide range of experimental conditions considered, large variations in [F] at the sample point occur because the [CF₂]/[F] ratio in the discharge changes. The concentrations of C₂F₆ and SiF₄ are predicted to within a factor of 2 over a very wide range of experimental conditions. This confirms the importance of gas-phase free radical reactions in the etching of Si.     

Quartz crystal microbalance simulation of the directionality of Si etching in CF4 glow discharges

Two quartz crystal microbalances have been mounted in a planar rf discharge system in such a way that the potential of the microbalances with respect to the glow discharge can be varied. This apparatus allows a rapid simulation of the etching directionality that can be expected in real pattern transfer situations in that operating one microbalance at ground and one at a negative potential gives a measure of the sidewall and vertical etch rates, respectively. The voltage threshold for ion-assisted etching has been determined to be 20 V which is the approximate value of the plasma potential in this asymmetric system.     

Surface modification of carbon anodes for secondary lithium battery by fluorination

Recent results on the surface modification of petroleum cokes and their electrochemical properties as anodes of secondary lithium batteries are summarized. The surface of petroleum coke and those heat-treated at 1860-2800 °C were fluorinated by elemental fluorine (F₂), chlorine trifluoride (ClF₃) and nitrogen trifluoride (NF₃). No surface fluorine was found except only one sample when ClF₃ and NF₃ were used as fluorinating agents while surface region of petroleum coke was fluorinated when F₂ was used. Transmission electron microscopic (TEM) observation revealed that closed edge of graphitized petroleum coke was destroyed and opened by surface fluorination. Raman spectra showed that surface fluorination increased the surface disorder of petroleum cokes. Main effect of surface fluorination with F₂ is the increase in the first coulombic efficiencies of petroleum cokes graphitized at 2300-2800 °C by 12.1-18.2% at 60 mA/g and by 13.3-25.8% at 150 mA/g in 1 mol/dm³ LiClO₄-ethylene carbonate (EC)/diethyl carbonate (DEC) (1:1, v/v). On the other hand, main effect of the fluorination with ClF₃ and NF₃ is the increase in the first discharge capacities of graphitized petroleum cokes by ∼63 mAh/g (∼29.5%) at 150 mA/g in 1 mol/dm³ LiClO₄-EC/DEC.     

Surface modification of clay-coated paper by atmospheric-pressure plasma in air

The aim of this work was the wettability improvement of clay-coated paper by ambient air plasma exposure. Industrial corona with a volume dielectric barrier discharge in cylindrical configuration was used as a plasma source; the exposure times varied from 0.25 up to 5 s. Water contact angle (WCA) measurement and surface free energy (SFE) evaluation were carried out for the estimation of wettability changes. Plasma treatment in the duration of 0.25 s was sufficient to decrease the WCA almost to the half of the original value, which was 76°. SFE of paper has increased by 40%–50% after plasma treatment. Long-term ageing effect study of treated samples was carried out up to 3 months after the treatment. WCA did not reach the original value even after 3 months, and it was still 20%–30% lower. O/C ratio increased from 0.7 to 1.8 in case of 5-s plasma treatment, and the new chemical bonds (C=O, O–C=O) were created on the surface.     

Surface fluorination of the cathode active materials for lithium secondary battery

LiMn₂O₄ was treated with F₂ at room temperature (RT), 373 and 473 K under 1.3, 6.6 and 13.2 kPa-F₂. XPS data indicate that two kinds of fluorine species may exist on the sample surface and the ratio of these fluorines is affected by choosing the reaction condition. The peak indicating Mnⁿ⁺ bonded to fluorine appeared in the XPS spectra of Mn2p3/2 electron. From the results of the charge/discharge measurements, the efficiency of charge/discharge process for the sample fluorinated under 1.3, 6.6 and 13.2 kPa-F₂ below 373 K was larger than that of untreated one. The discharge capacity of the fluorinated sample was also larger than that of untreated one. The discharge capacity, the loss of discharge capacity during 50 charge/discharge cycles, F/O ratio measured from XPS data and the intensity of the peak indicating Mnⁿ⁺ bonded to fluorine in the XPS spectra were closely related to each other. The optimal fluorination condition was under 1.3 kPa-F₂ at RT for 1 h.     

Mechanisms of hydrophobization of polymeric composites etched in CF4 plasma

Achieving optimal hydrophobicity of polymer materials especially polymer–matrix composites is important for many material applications. Herein the interplay of factors determining hydrophobic surface is presented during CF₄ plasma treatments which lead to functionalization as well as selective polymer–matrix etching. The continuous exposure to plasma reactive species induces functionalization and etching on the surface, which decides the surface morphology and surface chemistry. Consequently, exothermic processes during the plasma–surface interactions are another important factor which influences the surface chemistry and etching rate of the material. The results demonstrate that despite etching and increasing surface roughness, the major contribution to hydrophobic character is dependent on the number of carbon atoms populated with fluorine, whereas the temperature is a deciding factor for type of created bonds. Copyright © 2016 John Wiley & Sons, Ltd.     

Etching Efficiency for Si and SiO2 by CF+x,F+, and C+ Ion Beams Extracted from CF4 Plasmas

Fluorocarbon (CF⁺ _x), fluorine (F⁺), and carbon (C⁺) ion beams with highcurrent density (50i<800 A/cm²) were irradiated to Si and SiO₂surfaces to investigate the influence of the ion species on the etchingefficiency. The ion beams were extracted from magnetized helicon-wave CF₄plasmas operated in pulsed modes. The CF⁺ ₃ beam had the largest etchingefficiency for Si at the same beam energy. When the same data weresummarized as a function of the momentum of the incident ion beam, thedifference in the etching efficiency became small, although the CF⁺ ₃ beamstill had a slightly larger etching efficiency. On the other hand, theetching efficiency for SiO₂ by the CF⁺ ₃ beam was larger than that by theother ion beams in the low-momentum region. In addition, in the low-momentumregion, the etching efficiency for SiO₂ by CF⁺ ₃ was larger than that forSi. These results suggest the high chemical reactivity of CF⁺ ₃ with SiO₂,leading to the high etching selectivity of SiO₂ over underlying Si in thefabrication of semiconductor devices.     

Synthesis Of CF3-Heterocycles Based on 4-Dimethylamino-1,1,1-trifluoro-3-buten-2-one

Novel heterocyclizations have been investigated based on the reaction of the complex between trifluoromethanesulfonic anhydride and 4-dimethylamino-1,1,1-trifluoro-3-buten-2-one with 2,2'-biindolyl and N,N'-dipyrrolylmethane leading to closure of 6- or 7-membered rings.     

Reactions of Diazoalkanes with Unsaturated CF3-Ketones

The cycloaddition reactions of various diazoalkanes with unsaturated trifluoromethyl-containing ketones have been investigated. The reactions proceed regiospecifically and stereoselectively to the formation of trifluoroacetyl derivatives of 1H-pyrazolines.     

Semiempirical method for extracting electron molecule cross sections from experimental data: CF4 as an example

A semiempirical method is described for calculating electron-molecule interaction potential, electron density, and elastic and vibrational inelastic cross sections using experimental data.CF ₄ was considered as un example. Experimental data from IR and Raman spectra, molecular property calculations (dipole matrix elements, polarizability, distance between atoms in molecule), beam measurements of total, momentum transfer, and differential cross sections, and swarm data (diffusion and drift veolcity) are used for extracting the interaction potential, the molecule electron density, avid the differential cross sections. Electron energy distribution functions, drift velocity, and characteristic energy are calculated with the obtained differential e-CF ₄ cross sections lierAr/CF ₄ mixtures.     

Excited states of CF4 plasma for polymerization of TMPTA monomer

The F and CF₂–CF₂⁺ excited states have been detected by emission spectroscopy in CF₄RF plasmas used for TMPTA polymerization. These excited states are related through electron collision to F and CF₂ ground states. The temporal variation of the F and CF₂–CF₂⁺ radiative states near the substrate reveals that the F atoms disappear first by incorporation in the monomer during the polymerization phase and, then, by a third body recombination process enhanced by the polymer surface. The CF₂–CF₂⁺ radiative states are varying as the inverse of the F states indicating a strong destruction mechanism of CF₂ radicals by F atoms.     

Decomposition of SiCl4 and deposition of Si in inductively coupled plasmas of H2+SiCl4

The mechanism of homogeneous reactions in plasmas of H₂+5%SiCl₄ was studied by mass spectrometry and was compared to the mechanism observed in plasmas of Ar+H₂+SiCl₄. Contrary to the behavior with Ar, the results indicate that without argon the SiCl₄ molecule undergoes only fragmentation and the deposition proceeds through SiCl₂. No polymerization was observed. The deposition rates of c-Si were lower and the amounts of chlorine incorporated in the films were higher in the plasma of SiCl₄+H₂ than in the argon-containing plasma.     

Surface chemistry and optical property of TiO2 thin films treated by low-pressure plasma

The low temperature RF plasma treatment was used to control the surface chemistry and optical property of TiO₂ thin films deposited by RF magnetron sputtering with a very good uniformity at 300 °C substrate heating temperature. The XRD pattern indicates the crystalline structure of the film could be associated to amorphous structure of TiO₂ in thin film. The plasma treatment of TiO₂ film can increase the proportion of Ti³⁺ in Ti2p and decrease in carbon atoms as alcohol/ether group in C1s at the surface. The optical transmittance of the film was enhanced by 50% after the plasma treatment. The surface structure and morphology remain the same for untreated and low-pressure plasma-treated films. Therefore, increase in the optical transmission could be due to change in surface chemistry and surface cleaning by plasma treatment.     

Study of reactive ion etching of Si and SiO2 for CFxCl4−x gases

A parametric study of the etching of Si and SiO₂ by reactive ion etching (RIE) was carried out to gain a better understanding of the etching mechanisms. The following fluorocarbons (FCs) were used in order to study the effect of the F-to-Cl atom ratio in the parent molecule to the plasma and the etching properties: CF₄, CF₃Cl, CF₂Cl₂, and CFCl₃ (FC-14, FC-13, FC-12, and FC-11 respectively). The Si etch rate uniformity across the wafer as a function of the temperature of the wafer and the Si load, the optical emission as a function of the temperature of the load, the etch rate of SiO₂ as a function of the sheath voltage, and the mass spectra for each of the FCs were measured. The temperature of the wafer and that of the surrounding Si load strongly influence the etch rate of Si, the uniformity of etching, and the optical emission of F, Cl, and CF₂. The activation energy for the etching reaction of Si during CF₄ RIE was measured. The etch rate of Si depends more strongly on the gas composition than on the sheath voltage; it seems to be dominated by ion-assisted chemical etching. The etching of photoresist shifted from chemical etching to ion-assisted chemical etching as a function of the F-to-Cl ratio and the sheath voltage. The etch rate of SiO₂ depended more strongly on the sheath voltage than on the F-to-Cl ratio.     

Oxidative Conversion of PFC via Plasma Processing with Dielectric Barrier Discharges

Perfluorocompounds (PFCs) have been extensively used as plasma etching andchemical vapor deposition (CVD) gases for semiconductor manufacturingprocesses. PFCs have significant effects on the global warming and havevery long atmospheric lifetimes. Laboratory-scale experiments were performedto evaluate the effectiveness of CF4 conversion by using dielectric barrierdischarges (DBD). The results of this study revealed that the removalefficiency of CF₄ increased with application of higher voltage, gas residence time, oxygen content, and frequency. Combined plasma catalysis(CPC) is an innovative way for abatement of PFC and experimental results indicated that combining plasma with catalysts could effectively remove CF4. Products were analyzed by Fourier transform–infrared spectroscopy (FT–IR) and the major products of the CF4 processing with DBD were CO2, COF2, and CO, when O was included in the discharge process. Preliminary results indicated that as high as 65.9% of CF4 was decomposed with CPC operated at 15 kV, 240 Hz for the gas stream containing 300 ppmv CF₄,20% by volume O₂, and 40% by volume Ar, with N₂ as thecarrier gas.