HIECAP 23(2) 79-150 (1989) ISSN 0018-1439 Russian Original Vol. 23 March-April, 1989 September, 1989 HIGH ENERGY CHEMISTRY XMMMA BbICOKMX SHEPIMA (KHIMIYA VYSOKIKH ENERGII) TRANSLATED FROM RUSSIAN CONSULTANTS BUREAU, NEW YORKREACTION OF TETANIUM AND A TUNGSTEN-TITANIUM ALLOY WITH THE PRODUCTS OF DECOMPOSITION OF SULFUR HEXAFLUORIDE IN A HIGH-FREQUENCY CAPACITANCE GLOW DISCHARGE A. I. Azarov, I. I. Amirov, upc 537.924 G. K. Vinogradov, D. I. Slovetskii, and Yu, B. Makarychev The process of gasification of films of titanium and a tungsten-titanium alloy (82 W-122 Ti) in a high-frequency capacitance glow discharge in sulfur hexa~ fluoride with controlled flows of neutral and charged particles to the surface was investigated. It was shown that: The reaction rate is determined by the reaction vith SF, radicals (n = 1-5); the activation energies of the gasifica~ tion reactions of Ti and WTi films are the sane, within limits of error; pro- cosses of gasification of Ti and WTi differ when there is high intensity bon- barénent of the surface by charged particles. The composition of the surface was analyzed by x-ray electron spectroscopy. ‘The reactions of halogens with the surface of refractory metals, which lead to gasifi cation of the latter, have long attracted the attention of researchers [1, 2]. The first studies were concerned with the reactions with molecules and atoms of halogens, and later interest appeared in the reactions directly in a discharge [3]. In a discharge the gasifi- cation process is complicated by the simultaneous action on the surface not only from atoms and molecules of halogens, but also from halogen-containing radicals, ions, electrons, and excited particles. Nevertheless, up to now little attention has been given to the role of surface bombardment by these particles in the chemical reactions that occur in it. Studies of ion-stimulated processes demonstrate the importance of this bombardment [4]. The effect of ion bombardment can be especially great when the resulting metal halides have low fugacity (for example, TiF,); for this reason the goal of the present work was a study of the basic laws of interaction of the products of the decomposition of SF, in a high-frequency capaci~ tance glow discharge with the surface of titanium and a WTi alloy with controlled flows of atomic Fluorine and charged particles onto the surface. Varying the flows of particles of a specific species while keeping the other unchanged can serve as a basis for investigating the role of the individual components in chemical conversions. ‘The rectangular discharge chanber (8 * 2 cm) 14 cm long with side walls of fluoroplas- tic had cooled aluninun electrodes. Distributed input of gas vas accomplished from one end of the channel, and renoval was accomplished from the opposite end. The discharge chanber twas placed under the hood of a VUP-4 vacuum station. The chamber was evacuated with a pre~ vacuum pump with freeze trap (residual pressure ~3 Pa). The working gas was a mixture of purified sulfur hexafluoride and argon (96% SF, + 4% Ar). The argon vas added in order to realize the spectroscopic method of measuring the parameters of the discharge and the con- centration of atomic fluorine. The gas pressure was measured with a U-shaped manoneter with 25 Pa error, and the gas flow rate was measured with a float floweter with maximum 5% er~ ror. The HF power input to the discharge was determined with a feedthrough poxerneter that had been calibrated on the active load. The absolute error in measuring power did not ex- ceed 30% and the relative error did not exceed 10%. The specinens were filns of titanium land WTi alloy (88% W-12% Ti) deposited by magnetron sputtering onto the oxidized surface Of single-crystal silicon (111). The thickness of the layer of metal varied (20-300 nm), the thickness of the silicon oxide layer was 200 nn, and the thickness of the silicon plate B. V, Topchiev Inatitute of Petrochemical Synthesis, Academy of Sciences of the USSR. ‘Translated from Khimiya Vysokikh Energii, Vol. 23, No. 2, pp. 161-165, March-April, 1989. Original article submitted June 5, 1987. 132 (0018-1439/89/2302-0132$12.50 © 1989 Plenum Publishing Corporationwas 400 ym. The specimen was placed on an electrically insulated heater installed in the Genter of the lover grounded electrode. Thermal contact between the specimen and the heater was accomplished via an indiun-gallium eutectic. The heater temperature was measured with 2 copper-constantan thermocouple. This design made it possible to alter the surface tenper- ature of the specimens while keeping the temperature and parameters of the discharge the Same. The area of the exposed surface of the metal was determined by the size of a mica mask 70 um thick and was 3 mmé. From above the sample was covered with a gate of silicon plate with aluminized outer surface. Reaction between the products of sulfur hexafluoride decomposition and the metals began fron the moment the gate was opened after steady-state discharge parameters had been established (5-10 sec after igniting the discharge). ‘The specimens in the plasma served as wall probes, which made it possible to specify the flows of charged particles onte their surface. The rate of gasification of the metal was determined from the time for removal of a layer of metal of known thickness. It was not de~ pendent on thickness (20, 40, and 100 nm for Ti, and 60, 150, and 300 nm for WTi), ive., it was a steady-state rate. In'(5, 6] it was found that the rate of removal of films of nio~ bium and titanium was dependent on the thickness of the film, which was attributed to induc- tion heating of the metal films by the HF field. Evidently, this effect develops at the high powers that were put into the discharge (W > 0.4 W/em*), and when there is insufficient thermal contact between the sample and the electrode. ‘The discharge emission spectrum was monitored with the aid of the KSVU-4 spectral com- plex. The ratio of the intensities of the lines of fluorine (A = 685.6 nm) and argon (A 675.2 nm) was used to find the concentrations of atomic fluorine (7]. The surface composi- tion of the titanium and WTi films was analyzed on the ESCALab-5 apparatus. ‘The methods that were used made it possible to investigate the dependences of the rate of reaction of the metal with the products of SF, decomposition in the discharge on the tem perature of the specimen for controlled flows of charged and neutral particles onto the sur~ face. Because of the low fugacity of titaniun tetrafluoride, renoval of the titanium film could be expected only when there was high intensity ionic bombardment of the surface (3). Indeed, after a specimen 1 cn? in area had been exposed for 5 min at 300 K near the floating potential a film formed on its surface. Its color changed after it was brought out into the air. Analysis of the composition of the film by x-ray electron spectroscopy showed that it evidently consisted of titanium oxyfluoride. Investigation of the film by depth shows that the maximum change occurred in the peaks that corresponded to titaniun; from the oxidized state of titanium to free titaniun. The concentration of oxygen and fluorine was unchanged ata depth to 20 nm, ‘The oxyfluoride film on the titanium surface did not form when there was high intensity ion donbardnent of it (U > ~20 V) and the sample temperature was above 323 K. Examination of the surface of the WTi alloy exposed in the discharge shoved that the thickness of the fluorinated film of metal was significantly less. Fluorine was observed only on the surface in bound state corresponding to the compound CyOnFk- Only traces of fluorine could be detected at a depth of 2.5 nm. Sulfur was not found on the surface of the WTi alloy or titanium, just as on the surface of tungsten [8]. One method of altering the concentration of radicals in a discharge is varying its power, i.e., changing the rate of production of radicals. Another method is selective re~ moval of certain radicals by increasing the rate of the elimination of them, for example, owing to heterogeneous processes. Both methods were used in our work. If the discharge power was increased, there vas an increase of the controlled concentration of fluorine atoms and other radicals of the type SF, (n= 1-5). The insertion of plates of silicon into the reactor made it possible to remove atomic fluorine selectively from the gas phase owing to the consumption of it in the process of gasification of Si. Figure 1 shows dependences of the rate of removal of the alloy on the concentration of atomic fluorine, which was al~ tered by various means. It can be seen that the rate of removal of the alloy does not cor~ relate with the concentration of fluorine in the discharge when silicon plates are inserted inte the discharge. At the samo time, a decrease of the power of the discharge, which leads to a change of concentration not only of atomic fluorine, but also of Sf, radicals, changes the rate of removal of the alloy with the constant flow of charged particles to the surface. Analogous data were obtained in the gasification of titanium (Fig. 2). It can be asserted, therefore, that it is mainly not fluorine atoms, but rather SF, radicals, that participate in the reactions with titanium and WTi alloy. This is also supported by experiments involv- 133