Deposition conditions

The residence times presented in Table 7.1 are relative values, but they provide a feeling for the large differences in the surface dynamics of these metals under deposition conditions. While the differences in the bond energies are inconspicuous, the differences in the residence times cover several orders of magnitude. 

4 DENSITY OF KINK SITE POSITIONS 7.4.1 Equilibrium conditions 

In a first approximation it can be assumed that the density of kink site positions is in equilibrium with the ad-atom concentration. More generally, all partial reactions are in equilibrium at the Nemst potential. The following equation describes equilibrium between ions in the electrolyte and atoms in kink site positions  

This reaction expresses the repeating nature of the reaction of an ion with a kink site position A that forms a new kink site position AA. The equilibrium constant Kf is related to the rate constants and by the following equation  

The rate of the deposition reaction corresponds to the cathodic current density 

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The deposition of titanium oxide thin-films on Mo(l 10) represents a case where the stoichiometry of the film is sensitive to the deposition conditions [4T]. It was found that both Ti02 and Ti203 thin-films could be made. 

Ion implantation (qv) has a large (10 K/s) effective quench rate (64). This surface treatment technique allows a wide variety of atomic species to be introduced into the surface. Sputtering and evaporation methods are other very slow approaches to making amorphous films, atom by atom. The processes involve deposition of a vapor onto a cold substrate. The buildup rate (20 p.m/h) is also sensitive to deposition conditions, including the presence of impurity atoms which can faciUtate the formation of an amorphous stmcture. An approach used for metal—metalloid amorphous alloys is chemical deposition and electro deposition. 

The optoelectronic properties of the i -Si H films depend on many deposition parameters such as the pressure of the gas, flow rate, substrate temperature, power dissipation in the plasma, excitation frequency, anode—cathode distance, gas composition, and electrode configuration. Deposition conditions that are generally employed to produce device-quahty hydrogenated amorphous Si (i -SiH) are as follows gas composition = 100% SiH flow rate is high, --- dO cm pressure is low, 26—80 Pa (200—600 mtorr) deposition temperature = 250° C radio-frequency power is low, <25 mW/cm and the anode—cathode distance is 1-4 cm. 

Microcracked chromium topcoats Historically, microcracked chromium preceded the micro-porous chromium just described, but it is related to it in that the deposition conditions and thickness of the chromium topcoat are controlled to give porosity through a network of very fine cracks. 

In many cases, a more complete understanding of CVD reactions and a better prediction of the results are needed and a more thorough thermodynamic and kinetic investigation is necessary. This is accomplished by the calculation of the thermodynamic equilibrium of a CVD system, which will provide useful information on the characteristics and behavior of the reaction, including the optimum range of deposition conditions. 

The composition and amount of deposited material that is theoretically possible under any given set of deposition conditions, that is at a given temperature, a given pressure and given input concentration of reactants. 

In the previous sections, it was shown how thermodynamic and kinetic considerations govern a CVD reaction. In this section, the nature of the deposit, i.e., its microstructure and how it is controlled by the deposition conditions, is examined. 

The properties of a CVD material are directly related to the nature of its structure which is in turn controlled by the deposition conditions. In this section and the next, the relationship between properties, structure, and deposition conditions is examined. 

Most metals can be deposited by MOCVD and in some cases the process is an important industrial operation. The metals most readily deposited by MOCVD are the non-transition metals. The following is a summary of the metallo-organic precursors and deposition condition presently used in development or production. 

It was reported recently [216] that optical-quality PbTe thin films can be directly electrodeposited onto n-type Si(lOO) substrates, without an intermediate buffer layer, from an acidic (pH 1) lead acetate, tellurite, stirred solution at 20 °C. SEM, EDX, and XRD analyses showed that in optimal deposition conditions the films were uniform, compact, and stoichiometric, made of fine, 50-100 nm in size, crystallites of a polycrystalline cubic structure, with a composition of 51.2 at.% Pb and 48.8 at.% Te. According to optical measurements, the band gap of the films was 0.31 eV and of a direct transition. Cyclic voltammetry indicated that the electrodeposition occurred via an induced co-deposition mechanism. 

The deposition conditions should be optimized to obtain approximately equal amounts of matrix and spreader-bar molecules on the surface [18,21]. Analysis of monolayers by near-edge X-ray absorption fine-structure spectroscopy. 

Recently Butler et al. [4] reported the deposition of nanocrystalline diamond films with the conventional deposition conditions for micrometer-size polycrystalline diamond films. The substrate pretreatment by the deposition of a thin H-terminated a-C film, followed by the seeding of nanodiamond powder, increased the nucleation densities to more than 10 /cm on a Si substrate. The resultant films were grown to thicknesses ranging from 100 nm to 5 fim, and the thermal conductivity ranged from 2.5 to 12 W/cm K. 

Hydrogenated amorphous silicon is not a homogeneous material. Its structure is thought to consist of voids embedded in an amorphous matrix [62, 63]. The size and number density of the voids depend on the deposition conditions. Poor-quality material can have a void fraction around 20%, while device quality a-Si H has been shown to contain fewer voids, 1%. with a diameter of 10 A [64-66]. The surfaces of the voids may be partly covered with hydrogen atoms [62, 67],... 

The addition of an extra feedstock gas (GeH4 or CH4) in large quantities (compared to dopant gases) adds an extra degree of freedom to the already complex chemistry of the discharge. It is therefore even more complicated to relate material properties to deposition conditions [105]. 

Matsuda and Hata [287] have argued that the species that are detectable using OES only form a very small part (<0.1%) of the total amount of species present in typical silane deposition conditions. From the emission intensities of Si and SiH the number density of these excited states was estimated to be between 10 and 10 cm", on the basis of their optical transition probabilities. These values are much lower than radical densities. lO " cm . Hence, these species are not considered to partake in the deposition. However, a clear correlation between the emission intensity of Si and SiH and the deposition rate has been observed [288]. From this it can be concluded that the emission intensity of Si and SiH is proportional to the concentration of deposition precursors. As the Si and SiH excited species are generated via a one-electron impact process, the deposition precursors are also generated via that process [123]. Hence, for the characterization of deposition, discharge information from OES experiments can be used when these common generation mechanisms exist [286]. 

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