Oxidation Kinetics of Silicon Surfaces: Reactive Sticking Coefficient, Apparent Saturation Coverage and Effect of Surface Hydrogen

1988 ◽  
Vol 131 ◽  
Author(s):  
S. M. George ◽  
P. Gupta ◽  
C. H. Mak ◽  
P. A. Coon

ABSTRACTThe kinetics of the initial oxidation of silicon surfaces by O2 were studied using laser-induced thermal desorption (LITD), temperature programmed desorption (TPD) and Fourier Transform Infrared (FTIR) spectroscopy. The LITD results showed that the oxidation of Si(111)7×7 by O2 was characterized by two kinetic processes: an initial rapid oxygen uptake followed by a slower growth that asymptotically approached an apparent saturation oxygen coverage. The initial reactive sticking coefficient of O2 on Si(111)7×7 decreased with surface temperature. In contrast, TPD experiments on Si(111)7×7 and FTIR studies on porous silicon demonstrated that the apparent saturation oxygen coverage increased as a function of surface temperature. Experiments with preadsorbed hydrogen also revealed that silicon oxidation was inhibited as a function of increasing hydrogen coverage on the Si(111)7×7 surface.

1988 ◽  
Vol 131 ◽  
Author(s):  
P. Gupta ◽  
P. A. Coon ◽  
B. G. Koehler ◽  
S. M. George

ABSTRACTThe kinetics of SiCl4 adsorption on Si(lll) 7×7 were studied using laser induced thermal desorption (LITD) and temperature programmed desorption (TPD) techniques. The initial reactive sticking coefficient of SiCl4 on Si(lll) 7×7 was observed to decrease with increasing surface temperature. This decrease was consistent with a precursor-mediated adsorption model. Both LITD and TPD experiments monitored SiCl2 as the main desorption product. These results suggest that SiC12 may be the stable chlorine species on the Si(lll) 7×7 surface.


1999 ◽  
Vol 564 ◽  
Author(s):  
L. Chen ◽  
B. Ekstrom ◽  
J. Kelber

AbstractWe report results of Auger electron spectroscopy (AES) and temperature programmed desorption (TPD) studies under ultra high vacuum (UHV) conditions which demonstrate that even submonolayer coverages of oxygen on Ta significantly degrade the strength of Cu/Ta chemical interactions, and affect the kinetics of Cu diffusion into bulk Ta. On clean Ta, monolayer coverages of Cu will de-wet only above 600 K. A partial monolayer of adsorbed oxygen (3L O2 at 300 K) results in a reduction of the de-wetting temperature to 500 K, while saturation oxygen coverage (10 L O2, 300 K) results in de-wetting at 400 K. Diffusion of Cu into the Ta substrate at 1100 K occurs only after a 300-second induction period at this temperature. The induction period increases to 600 sec for partially oxidized Ta and to 1200 sec for saturation oxygen coverage. TPD studies indicate no desorption of Cu for temperatures below 1300 K. The higher desorption temperature of Cu (compared to the 1150 K sublimation temperature) indicates that all the Cu originally deposited is now chemically bound to Ta.


1999 ◽  
Vol 567 ◽  
Author(s):  
Heiji Watanabe ◽  
Noriyuki Miyata ◽  
Masakazu Ichikawa

ABSTRACTLayer-by-layer oxidation of Si(111) and (001) surfaces has been studied by using scanning reflection electron microscopy (SREM). We found that SREM images reveal interfacial structures of the SiO2/Si system. Our results showed that the initial step structure of Si substrates was preserved at SiO2/Si interfaces and that interfacial steps did not move laterally during oxidation. We also observed a periodic reversal of terrace contrast in SREM images during the initial oxidation of Si(001) surfaces. These results indicate layer-by-layer oxidation of Si surfaces, which is promoted by the nucleation of nanometer-scale oxide islands at SiO2/Si interfaces. In addition, we investigated the kinetics of initial layer-by-layer oxidation of Si(001) surfaces. We found that a barrierless oxidation of the first subsurface layer, as well as oxygen chemisorption onto the top layer, occur at room temperature. The energy barrier of the second-layer oxidation was found to be 0.3 eV. The initial oxidation kinetics are discussed based on first-principles calculations. Moreover, we confirmed that the layer-by-layer oxidation of Si surfaces holds true for conventional furnace oxidation.


1992 ◽  
Vol 282 ◽  
Author(s):  
Michael L. Wise ◽  
Lynne A. Okada ◽  
Peter A. Coon ◽  
Steven M. George

ABSTRACTThe controlled atomic layer growth of SiO2 insulating layers on silicon surfaces might be achieved through the sequential reaction of SiCl4 and H2O:(A) Si-Cl + H2O → Si-OH + HCl(B) Si-OH + SiCl4 → Si-O-SiCl3 + HCl.To explore this ABAB… binary reaction scheme, laser-induced thermal desorption, temperature-programmed desorption, and Auger electron spectroscopy techniques were utilized to measure the kinetics of H2O oxidation of a Si(111)7×7 surface that had been previously subjected to a saturation SiCl4 exposure. Reaction kinetics studies for the oxidation of the chlorinated surface revealed that the rate of oxygen gain and the rate of chlorine loss were equal at reaction temperatures between 200 K and 700 K. These results were consistent with a direct substitution reaction according to:(A) Si-Cl + H2O → Si-OH + HCl.Above 700 K, the amount of oxygen gain became progressively greater than the amount of chlorine loss. This behavior was associated with the thermal desorption of H2 and the resultant formation of new dangling bond sites for H2O adsorption. For all temperatures, the oxidation kinetics of the chlorinated surface were nearly equivalent to the kinetics for the oxidation of clean silicon. This surprising result indicates that chlorine sites and free dangling bond sites react with equal probability to H2O. The kinetics of SiCl4 deposition were also measured on a Si(111)7×7 surface previously exposed to a saturation H2O dose. This chlorination reaction occurred at a much slower rate and was not as amenable to UHV studies.


1990 ◽  
Vol 204 ◽  
Author(s):  
P.A. Coon ◽  
M.L. Wise ◽  
A.C. Dillon ◽  
M.B. Robinson ◽  
S.M. George

ABSTRACTDiethylsilane (DES), Si(C2H5)2H2, is a promising candidate for the atomic layer epitaxy of silicon. The adsorption and decomposition kinetics of DES on silicon surfaces were studied using laser-induced thermal desorption (LITD), temperature programmed desorption (TPD), and Fourier transform infrared (FTIR) spectroscopy. FTIR studies on porous silicon surfaces indicated that DES dissociatively adsorbs below 600 K and produces Si-H and Si-C2H5 surface species. The desorption products following DES adsorption on Si(111) 7×7 were C2H4 and H2 for all surface coverages using both LITD and TPD techniques. Ethylene and H2 desorption occurred at 700 and 810 K, respectively, during TPD experiments with a heating rate of β = 9 K/s. Ethylene desorption was consistent with a β-hydrogen elimination mechanism from the Si-C2H2 surface species. Isothermal LITD studies monitored the desorption kinetics of C2 H4 from Sl (111) 7×7 as a function of time following DES exposures. The first-order ethylene desorption kinetics were Ed = 36 kcal/mol and vd = 2.7 × 109 s−1. Additional LITD measurements determined that le initial reactive sticking coefficient of DES on Si(111) 7×7 decreased versus surface temperature. The temperature-dependent sticking coefficients suggested a precursormediated adsorption mechanism.


1983 ◽  
Vol 48 (12) ◽  
pp. 3340-3355 ◽  
Author(s):  
Pavel Fott ◽  
Pavel Šebesta

The kinetic parameters of reactivation of a carbonized hydrodesulphurization (HDS) catalyst by air were evaluated from combined thermogravimetric (TG) and differential thermal analysis (DTA) data. In addition, the gaseous products leaving a temperature-programmed reactor with a thin layer of catalyst were analyzed chromatographically. Two exothermic processes were found to take part in the reactivation, and their kinetics were described by 1st order equations. In the first process (180-400 °C), sulphur in Co and Mo sulphides is oxidized to sulphur dioxide; in the second process (300-540 °C), in which the essential portion of heat is produced, the deposited carbon is oxidized to give predominantly carbon dioxide. If the reaction heat is not removed efficiently enough, ignition of the catalyst takes place, which is associated with a transition to the diffusion region. The application of the obtained kinetic parameters to modelling a temperature-programmed reactivation is illustrated on the case of a single particle.


Author(s):  
Huilin Lun ◽  
Yi Zeng ◽  
Xiang Xiong ◽  
Ziming Ye ◽  
Zhongwei Zhang ◽  
...  

AbstractMulti-component solid solutions with non-stoichiometric compositions are characteristics of ultra-high temperature carbides as promising materials for hypersonic vehicles. However, for group IV transition-metal carbides, the oxidation behavior of multi-component non-stoichiometric (Zr,Hf,Ti)Cx carbide solid solution has not been clarified yet. The present work fabricated four kinds of (Zr,Hf,Ti)Cx carbide solid solution powders by free-pressureless spark plasma sintering to investigate the oxidation behavior of (Zr,Hf,Ti)Cx in air. The effects of metallic atom composition on oxidation resistance were examined. The results indicate that the oxidation kinetics of (Zr,Hf,Ti)Cx are composition dependent. A high Hf content in (Zr,Hf,Ti)Cx was beneficial to form an amorphous Zr-Hf-Ti-C-O oxycarbide layer as an oxygen barrier to enhance the initial oxidation resistance. Meanwhile, an equiatomic ratio of metallic atoms reduced the growth rate of (Zr,Hf,Ti)O2 oxide, increasing its phase stability at high temperatures, which improved the oxidation activation energy of (Zr, Hf, Ti)Cx.


1992 ◽  
Vol 280 ◽  
Author(s):  
J. F. Egler ◽  
N. Otsuka ◽  
K. Mahalingam

ABSTRACTGrowth kinetics on non-singular surfaces were studied by Monte Carlo simulations. In contrast to the growth on singular and vicinal surfaces, the sticking coefficient on the non-singular surfaces was found to decrease with increase of the surface roughness. Simulations of annealing processes showed that surface diffusion of atoms leads to a stationary surface roughness, which is explained by multiple configurations having the lowest energy in the non-singular surface.


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