Theoretical Analysis of Si 2 H 6 Adsorption on Hydrogenated Silicon Surfaces for Fast Deposition Using Intermediate Pressure SiH 4 Capacitively Coupled Plasma

: The rapid and uniform growth of hydrogenated silicon (Si:H) ﬁlms is essential for the manufacturing of future semiconductor devices; therefore, Si:H ﬁlms are mainly deposited using SiH 4 -based plasmas. An increase in the pressure of the mixture gas has been demonstrated to increase the deposition rate in the SiH 4 -based plasmas. The fact that SiH 4 more efﬁciently generates Si 2 H 6 at higher gas pressures requires a theoretical investigation of the reactivity of Si 2 H 6 on various surfaces. Therefore, we conducted ﬁrst-principles density functional theory (DFT) calculations to understand the surface reactivity of Si 2 H 6 on both hydrogenated (H-covered) Si(001) and Si(111) surfaces. The reactivity of Si 2 H 6 molecules on hydrogenated Si surfaces was more energetically favorable than on clean Si surfaces. We also found that the hydrogenated Si(111) surface is the most efﬁcient surface because the dissociation of Si 2 H 6 on the hydrogenated Si(111) surface are thermodynamically and kinetically more favorable than those on the hydrogenated Si(001) surface. Finally, we simulated the SiH 4 /He capacitively coupled plasma (CCP) discharges for Si:H ﬁlms deposition.


Introduction
The most advanced production facilities in the semiconductor industry require technically complex and expensive reactors for the manufacturing of future semiconductor devices [1][2][3]. However, the acquisition of state-of-the-art reactors has had serious financial consequences for chip manufacturers when the production capacity needs to be expanded. Therefore, manufacturers have continuously targeted ways to enhance the efficiency of the production process. The thin film deposition process often meets various technical challenges related to coatings of functional layers [4]. Due to the ability to grow uniform films fast, plasma-enhanced chemical vapor deposition (PECVD) has been considered a mainstream production tool [5].
Hydrogenated silicon thin films (Si:H) are often deposited on Si substrates by PECVD [6]. Despite its long history of development, the PECVD of hydrogenated silicon is still considered a challenging area of research. In industrial applications, Si:H thin films are mainly deposited using the SiH 4 -based plasmas [7,8]. It is worthy to note that, in the plasma deposition process, optimization of the process window is often achieved under conditions of higher gas pressures (p g ) [9,10]. For example, Isomura et al. [9] experimentally explored the feasibility of the high-pressure regime in the plasma silicon deposition. In the meantime, at higher gas pressure, SiH 4 -based plasma generates Si 2 H 6 to a non-negligible degree. Si 2 H 6 can be directly adsorbed onto Si surfaces to form SiH x species. This leads to the growth of a Si:H thin film with the release of H 2 gas. Based thereupon, in several previous reports,  The calculated lattice parameter of bulk Si was a0 = 2.368 Å, which corresponds well with the experimental value (a0 = 2.351 Å) [25]. For the surfaces we considered, namely the H-50% covered Si(001) and Si(111) surfaces, vacuum gaps with sizes of 18.8 Å and 19.3 Å were inserted in the z-direction to avoid interactions between adjacent slabs. The dangling bonds of the bottom layer of all the surfaces were terminated by hydrogen atoms to avoid reconstruction of the structure. The three bottom layers of all surfaces containing generalized gradient approximation (GGA) [23,24]. Details of DFT calculations were provided in our previous report [14]. We searched for the most probable hydrogen configurations (see Figures 1 and 2) in the top layer of the H-50% covered Si(001) and H-50% covered Si(111) surfaces. Thus, the H-50% covered Si(001)-(4 × 4) and H-50% covered Si(111)-(4 × 4) surfaces were employed (see Figures 3 and 4) to reduce the molecular interactions between the inter-unit cells by using a cell size twice as large as that of (4 × 2). Each slab consists of six atomic layers for all Si surfaces. As shown in Figures 3 and 4, we considered two geometries and 10 positions for the Si2H6 on the H-50% covered Si(001) surface, whereas for the H-50% covered Si(111) surface, we used two geometries for Si2H6 together with six positions. The complete details of these cases are available in Electronic Supplementary Information (ESI).  The calculated lattice parameter of bulk Si was a0 = 2.368 Å, which corresponds well with the experimental value (a0 = 2.351 Å) [25]. For the surfaces we considered, namely the H-50% covered Si(001) and Si(111) surfaces, vacuum gaps with sizes of 18.8 Å and 19.3 Å were inserted in the z-direction to avoid interactions between adjacent slabs. The dangling bonds of the bottom layer of all the surfaces were terminated by hydrogen atoms to avoid reconstruction of the structure. The three bottom layers of all surfaces containing         The calculated lattice parameter of bulk Si was a 0 = 2.368 Å, which corresponds well with the experimental value (a 0 = 2.351 Å) [25]. For the surfaces we considered, namely the H-50% covered Si(001) and Si(111) surfaces, vacuum gaps with sizes of 18.8 Å and 19.3 Å were inserted in the z-direction to avoid interactions between adjacent slabs. The dangling bonds of the bottom layer of all the surfaces were terminated by hydrogen atoms to avoid reconstruction of the structure. The three bottom layers of all surfaces containing the terminated hydrogen atoms were kept fixed during structural relaxation in all DFT calculations.

Plasma Discharge Simulations
Particulars of the plasma discharge model were presented in our previous reports [26][27][28][29][30]; therefore, details are omitted here. Only equations about the electron density and flux balances are shown below: J e = −D e ∇n e + µ e n e ∇φ (2) Here, n e , t, J e , S e , D e , µ e and φ represent the electron density, time, electron flux, source of the electrons, electron diffusion coefficient, electron mobility and electric potential, respectively.
In this study, we used CFD-ACE+ software [31]. The Scharfetter-Gummel exponential scheme was adopted in both the electron and electron energy conservation equations. We calculated both the electron transport coefficients and the electron impact reaction rates, by solving the 0D Boltzmann equation.

Experimental Details
The experimental setup and methodology were described in detail in our previous studies [28][29][30]. By using an ellipsometer and an X-ray diffractometer, we measured the properties of the Si:H layer experimentally. We measured the film densities of the Si:H layer (ρ Si ), and the film densities were used to numerically estimate the deposition rates in the simulations: at the heater temperature of 673 K, ρ Si was 2.32 g cm −3 . By using an ellipsometer, film thicknesses were measured. To simulate surface depositions, by referring to the surface fluxes of silicon-containing radicals (Si x H y ), a sticking model was applied as similarly performed in previous studies [28][29][30]. Sticking coefficients of radicals were adopted from other groups' experimental data [32,33].

Results
In Figure 5, due to the cylindrical shape of our reactor, computational domain was set in the r-z plane, where r represents the radial coordinate and z represents the axial coordinate. The left boundary denotes the axis, whereas the right boundary denotes the sidewall. The showerhead acts as a radio frequency (RF; 13.56 MHz)-powered electrode. The thin film is deposited on the heater (a grounded electrode). The gas mixture is fed through the showerhead inlet. Note that, in this study, due to the high computational cost, CCP discharge simulations were performed in a two-dimensional simplified geometry. In fact, since the showerhead has many very small holes to disperse the gas mixture uniformly into the discharge volume, the showerhead has a complex structure, which should be considered in a three-dimensional geometry. However, the gas mixture fed through the showerhead was assumed to have radially uniform density and temperature distributions in the showerhead inlet, as similarly assumed in other groups' previous reports about CCP simulations [34][35][36].

DFT Results: Si2H6 Adsorption
The optimized atomic structures of the initial, transition and final states for the first dissociative reaction step of the Si2H6 molecule on the H-50% covered Si(001) surface are shown in Figure 6. The calculated energy diagram representing the overall reaction for the decomposition of Si2H6 on the surface is presented in Figure 7. As depicted in Figure  7, on the H-50% covered Si(001) surface, the most stable of the various adsorbates is Si2H2 (Figure 7, circled adsorbate). The detailed atomic configurations of the transition states for the overall decomposition reaction of Si2H6 (i.e., along paths a and b) are included as ESI (Figures S1 and S2; Tables S3 and S4). The following input conditions were specified for all cases: the SiH 4 flow rate was set to 50 sccm, the He flow rate was set to 5000 sccm, the input power was set to 100 W, the electrode spacing (d) was set to 15 mm and the temperatures of the showerhead (T sh ), sidewall (T sw ) and heater (T s ) were set to 473 K, 423 K and 673 K, respectively. The spatial variation in the gas temperature (T g ) is depicted in Figure 5a. Finally, Figure 5b,c show that H 2 and H densities are spatially altered, respectively.

DFT Results: Si 2 H 6 Adsorption
The optimized atomic structures of the initial, transition and final states for the first dissociative reaction step of the Si 2 H 6 molecule on the H-50% covered Si(001) surface are shown in Figure 6. The calculated energy diagram representing the overall reaction for the decomposition of Si 2 H 6 on the surface is presented in Figure 7. As depicted in Figure 7, on the H-50% covered Si(001) surface, the most stable of the various adsorbates is Si 2 H 2 ( Figure 7, circled adsorbate). The detailed atomic configurations of the transition states for the overall decomposition reaction of Si 2 H 6 (i.e., along paths a and b) are included as ESI (Figures S1 and S2 ; Tables S3 and S4).  The dissociative reaction mechanism of Si2H6 was also investigated on the H-50% covered Si(111) surface, as illustrated in Figures 8 and 9. As depicted in Figure 9, also on the H-50% covered Si(111) surface, the most stable of the various adsorbates is still Si2H2 (Figure 9, circled adsorbate). The detailed atomic configurations of the transition states of Si2H6 that were calculated to form on the surface during the overall reaction (i.e., along   The dissociative reaction mechanism of Si2H6 was also investigated on the H-50% covered Si(111) surface, as illustrated in Figures 8 and 9. As depicted in Figure 9, also on the H-50% covered Si(111) surface, the most stable of the various adsorbates is still Si2H2 (Figure 9, circled adsorbate). The detailed atomic configurations of the transition states of Si2H6 that were calculated to form on the surface during the overall reaction (i.e., along paths a and b) are also included as ESI (Figures S3 and S4; Tables S5 and S6).  The dissociative reaction mechanism of Si 2 H 6 was also investigated on the H-50% covered Si(111) surface, as illustrated in Figures 8 and 9. As depicted in Figure 9, also on the H-50% covered Si(111) surface, the most stable of the various adsorbates is still Si 2 H 2 ( Figure 9, circled adsorbate). The detailed atomic configurations of the transition states of Si 2 H 6 that were calculated to form on the surface during the overall reaction (i.e., along paths a and b) are also included as ESI (Figures S3 and S4; Tables S5 and S6).

Plasma Modeling Results: SiH 4 /He Discharges
In this section, the effects of the gas pressure (p g ) on the spatial distributions of the plasma variables are discussed. Note that Si 2 H 6 production mainly occurs, as shown below: Here k r is the reaction rate coefficient. Thus, higher gas pressure accelerates the SiH 2 insertion reaction. The results in Figures 10 and 11 were obtained by varying the gas pressure between 400 Pa and 1200 Pa.

Plasma Modeling Results: SiH4/He Discharges
In this section, the effects of the gas pressure (pg) on the spatial distributions of the plasma variables are discussed. Note that Si2H6 production mainly occurs, as shown below: SiH4 + SiH2 → Si2H6 kr = 2.0 × 10 −16 [1 − (1 + 0.0032 pg (Pa)) −1 ] (m 3 ·s −1 ) [32] ( Here kr is the reaction rate coefficient. Thus, higher gas pressure accelerates the SiH2 insertion reaction. The results in Figures 10 and 11 were obtained by varying the gas pressure between 400 Pa and 1200 Pa. In Figure 10a, the ionization reaction [the production of SiH2 + : e − + SiH4 → SiH2 + + H + H + e − + e − ] rate profiles for the cases of pg = 400 Pa, pg = 800 Pa and pg = 1200 Pa are depicted. For the cases of pg = 400 Pa and pg = 800 Pa, the ionization rates are significantly enhanced near the respective edges of both the showerhead and the heater. However, the ionization rate profile obtained by further increasing the gas pressure to pg = 1200 Pa clearly shows that the peak ionization rates are noticeably lower near the electrode edges, and its radial distribution becomes relatively more uniform in both the radial and axial directions. In Figure 10b, the electron density contours for the cases of pg = 400 Pa, pg = 800 Pa and pg = 1200 Pa are depicted. Even though an increase in the pressure leads to an increase in the density of the source gas inside the reactor, the ionization rates decrease as shown in Figure 10a. However, the higher gas pressure can induce an increase in the electron density. These contradictory phenomena can be explained by the fact that higher pressure reduces the diffusion fluxes of the charged species, thus the wall losses of the charged species decrease. In addition, at higher pressure, the decrease in the electron mean free path lowers the mean energy of the electrons. Since the plasma potential also decreases Figure 10. Effects of the gas pressure on the spatial distributions of plasma variables. Contour plots for the spatial profiles of the time-averaged (a) direct impact ionization rate (kmol m −3 s −1 ) for p g = 400, 800 and 1200 Pa, (b) electron density (N e ; m −3 ) for p g = 400, 800 and 1200 Pa, and (c) electron power density (P e ; W m −3 ) for p g = 400, 800 and 1200 Pa for r ≥ 120 mm.
in the gas phase, the SiH3 radical is eliminated fast, as shown below: SiH3 + SiH3 → SiH2 + SiH4 kr = 1.5 × 10 −16 (m 3 s −1 ) [32] (4) In addition, due to the reduced diffusion coefficients of SiH3 (based on the Chapman-Enskog theory [37]), since a higher pressure can induce the "local accumulation" of SiH3, the loss of SiH3 occurs rapidly with concomitant lowering of the density near the bottom surface.  In Figure 10a, the ionization reaction [the production of SiH 2 + : e − + SiH 4 → SiH 2 + + H + H + e − + e − ] rate profiles for the cases of p g = 400 Pa, p g = 800 Pa and p g = 1200 Pa are depicted. For the cases of p g = 400 Pa and p g = 800 Pa, the ionization rates are significantly enhanced near the respective edges of both the showerhead and the heater. However, the ionization rate profile obtained by further increasing the gas pressure to p g = 1200 Pa clearly shows that the peak ionization rates are noticeably lower near the electrode edges, and its radial distribution becomes relatively more uniform in both the radial and axial directions.
In Figure 10b, the electron density contours for the cases of p g = 400 Pa, p g = 800 Pa and p g = 1200 Pa are depicted. Even though an increase in the pressure leads to an increase in the density of the source gas inside the reactor, the ionization rates decrease as shown in Figure 10a. However, the higher gas pressure can induce an increase in the electron density. These contradictory phenomena can be explained by the fact that higher pressure reduces the diffusion fluxes of the charged species, thus the wall losses of the charged species decrease. In addition, at higher pressure, the decrease in the electron mean free path lowers the mean energy of the electrons. Since the plasma potential also decreases with higher pressure, the edge effects are suppressed. Due to the suppressed edge effects, with higher pressure, although the off-axis maximum of the electron density decreases, the overall electron density increases in the bulk.
In Figure 10c, the increase in the gas pressure also results in a more uniform spatial distribution of the electron power density. In particular, the maxima of the spatial timeaveraged profile of the power coupled to the electrons intensify and shift toward the electrodes. The positions of these maxima correlate with the position of the plasma-sheath boundary. We can therefore conclude that the shift of the maxima toward the electrodes is evidence of plasma bulk expansion. As a result, an increase in the pressure at constant frequency has the effect of enabling a larger amount of power to be transferred to electrons. This leads to higher dissociation/production of active radicals. Figure 11 shows the spatial variations in the densities (m −3 ) of SiH 3 , SiH 2 and Si 2 H 6 when the gas pressure is increased from 400 Pa to 1200 Pa. In Figure 11a, since at higher pressure, more electrons are generated (Figure 10b), and a larger amount of power is transferred to electrons (Figure 10c). As a result, more radicals are generated: the SiH 3 density increases in the bulk and its off-axis maximum is also enhanced. However, despite the pressure increasing threefold (i.e., p g increases from 400 Pa to 1200 Pa), the SiH 3 density does not increase as much as expected. This saturation can be explained by the fact that, in the gas phase, the SiH 3 radical is eliminated fast, as shown below: In addition, due to the reduced diffusion coefficients of SiH 3 (based on the Chapman-Enskog theory [37]), since a higher pressure can induce the "local accumulation" of SiH 3 , the loss of SiH 3 occurs rapidly with concomitant lowering of the density near the bottom surface. At the same time, as shown in Figure 11b, the SiH 2 densities even decrease as the pressure increases. This is mainly because the rate of the SiH 2 insertion reaction is a function of the pressure (see Equation 3). Thus, the pressure dependence of the SiH 2 density distribution can be attributed to the fact that higher pressure promotes both its rate of generation and depletion in the gas phase, as the secondary gas phase reaction with SiH 4 is accelerated. For the case with 1200 Pa, as the higher production rate does not compensate for the loss in the bulk, the axial density distribution develops a doublehumped shape. Consequently, more extensive depletion of SiH 2 promotes the generation of Si 2 H 6 with higher pressure (Figure 11c): the density distribution of Si 2 H 6 is nearly zero at the showerhead inlet and rapidly increases as it approaches the bulk plasma region. Finally, at higher pressure, the boundary layers of both SiH 3 and SiH 2 become thinner near the edge. Table 1 summarizes the reactivities of the Si 2 H 6 molecules on the H-50% covered Si(001) and Si(111) surfaces. This table compares the energies of the initial and most stable adsorbates (E initial adsorbate , E most stable adsorbate , eV), the reaction energies of the initial to the most stable adsorbates (E rxn , eV) and the minimum and maximum activation energies of the initial to the most stable adsorbates (E a, min , E a, max , eV) on the two different Si surfaces. The energies in Table 1 were calculated following Appendix A. In Table 1, one can find that the dissociative reactions of Si 2 H 6 on the H-50% covered Si(111) surface from the initial adsorbate to the most stable adsorbate are more favorable than those on the H-50% covered Si(001) surface because the reaction and activation energies on the former surface are lower than those on the latter of these two surfaces. Regardless of the hydrogenated state of the Si surface, the reactivity of the Si 2 H 6 is highly dependent on the orientation of Si surfaces.

Comparisons of Si 2 H 6 Surface Reactivities
Important to note is that the reactivity of Si 2 H 6 molecules on H-covered Si surfaces is more energetically favorable than on clean Si surfaces (for the reactivities on the clean Si (001) and Si(111) surfaces, see Park et al. [14]). The H atoms covering the surface interact with the Si and H atoms attached to the Si 2 H 6 molecules. Therefore, the H atoms lower the total energy of the system. The reason why the H atoms on the surface readily interact with the Si atoms is the strength of the Si-H bond. In addition, the H atoms on the surface easily interact with the H atoms of Si 2 H 6 molecules because the H atoms tend to combine to form H 2 . That is, H atoms in close proximity to each other appear to interact to become energetically stable. This phenomenon is evident from the DFT results, as shown in Figures 1 and 2. In Figures 1 and 2, the H-covered Si surface is the most stable when the H atoms gather together. In fact, according to Le et al. [22], the mechanism for a partially H-covered Si (100) surface was similar but was characterized by higher adsorption energies in most cases. This implies that the presence of hydrogen atoms on the surface stabilizes the surface species.
At the same time, with respect to the H-covered Si surfaces, Si 2 H 6 molecules are more reactive on the Si(111) surfaces. This comparison is against the results on the clean Si surfaces [14] and can be explained as follows. On the H-covered Si(111) surface, the H atoms are tilted slightly in the direction perpendicular to the xy-plane with a tetrahedral structure to form a crystallographically stable structure, because the H atoms form Si-H bonds. Therefore, the Si 2 H 6 molecules are more reactive on the H-covered Si(111) surface on which the tilted H atoms are closer to each other on the surface.
The dependence of the surface reactivity on Si on the molecular size of Si x H y molecules is understood as follows. As reported in our previous study [14], the surface reactivity of Si 2 H 6 is superior to that of SiH 4 . The higher surface reactivity is because the Si-H bonds in Si 2 H 6 are weaker than those in SiH 4 . This was clear from our previous study [14], which showed that strong Si-Si bonding weakens Si-H bonding, thereby ensuring that the surface reactivity of Si 2 H 6 molecules is excellent. Similar results were obtained in other studies [38]. Similarly, the larger the size of the molecules of the Si x H y species, the weaker the Si-H bond strength and the higher the surface reactivity becomes. As observed in previous studies, understanding the surface reactivity is important to improve the deposition rate and, consequently, the throughput of Si thin films [39,40]. Therefore, considering the high bonding nature and reactivity of Si 2 H 6 , the deposition rate of the Si films can be enhanced when Si 2 H 6 adsorption occurs to a sufficient degree. Figure 12a,b show the deposition rate profiles for p g = 400, 800 and 1200 Pa. Due to the non-uniformities of the deposition rate profiles less than 10%, to compare the profiles keeping their shapes, the profiles were normalized using their own average values. However, the profiles of cases without consideration of Si 2 H 6 adsorption were normalized to the average values of the corresponding numerical data with consideration of Si 2 H 6 adsorption to serve as a quantitative comparison of their deposition rate profiles. In fact, in cases with the gas pressure less than 100 Pa, adsorption of reactive radicals such as SiH, SiH 2 and SiH 3 were considered, but Si 2 H 6 adsorption was neglected due to its small amount produced in the gas phase under the given condition [7,41]. Due to the axi-symmetry of our reactor, we could compare the deposition rate profiles along the radial direction. Regardless of changes in the gas pressure, the experimental data were in good agreement with the simulated data. At p g = 400 Pa, the average value of the simulated data was 7.18 Å s −1 , while that of the experimental data was 7.25 Å s −1 . At p g = 800 Pa, the average value of the simulated data was 9.1 Å s −1 , while that of the experimental data was 9.19 Å s −1 . At p g = 1200 Pa, the average value of the simulated data was 10.18 Å s −1 , while that of the experimental data was 10.32 Å s −1 . In fact, in the experiment with p g higher than 1500 Pa, particle contamination was too serious due to the enhanced gas phase reaction, and also azimuthal non-uniformities were too high. In Figure 12a, at p g = 400 Pa and p g = 800 Pa, relative discrepancies of 4% and 8.4% can be seen between the deposition rates of cases with and without consideration of Si 2 H 6 adsorption. Noteworthy is that, in Figure 12b, at p g = 1200 Pa, the relative discrepancy reaches 15% although a small amount of SiH 4 (50 sccm) is used. The higher discrepancy is originated from the more efficient Si 2 H 6 production ( Figure 11c). One should also note that as depicted in Figure 10c, regardless of changes in the gas pressure, the maximum electron power densities were observed radially outward from the heater edge (i.e., outside the discharge volume between the showerhead and the heater). Even though these observations about the electron power densities were not experimentally validated, one can be sure about these observations by the fact that the deposition rate profiles are all concave: the deposition rates decrease along the radially outward direction. If the maximum electron power densities locate inside the discharge volume, enhanced ion and radical fluxes can induce high deposition rates near the heater edge, forming convex deposition rate profiles, as demonstrated in Kim and Lee [27].   Figure 12. Deposition rates are plotted along the radial direction for p g = 400 Pa (squares), 800 Pa (triangles) and 1200 Pa (diamonds). (a) Deposition rate profiles for p g = 400 and 800 Pa superimposed with the corresponding experimental data. (b) Relative discrepancy of approximately 15% at p g = 1200 Pa between the deposition rates with and without consideration of Si 2 H 6 adsorption.

Conclusions
We investigated the decomposition of Si 2 H 6 on H-covered Si surfaces to allow us to fundamentally comprehend the reaction mechanisms of Si:H thin films in detail on the basis of DFT calculations. We found the reactivities of Si 2 H 6 molecules on H-covered Si surfaces to be more energetically favorable than those on the clean Si surfaces. Furthermore, our theoretical results also showed that, upon exposure to Si 2 H 6 , the H-50% covered Si(111) surface enables efficient and rapid deposition of Si:H thin films. This finding is justified because, on the H-50% covered Si(111) surface, the dissociative reactions of Si 2 H 6 are thermodynamically and kinetically more favorable than on the H-50% covered Si(001) surface. Using PECVD as an example, we investigated the deposition of a hydrogenated silicon (Si:H) film using SiH 4 /He CCP discharges. In the range of 400 Pa ≤ p g ≤ 1200 Pa, an increase in the gas pressure promoted the production of Si 2 H 6 . The experimental data (deposition rates) were in good correspondence with the simulated data. When the gas pressure was increased to 1200 Pa, a relative discrepancy of approximately 15% was observed between the deposition rates of cases with and without consideration of Si 2 H 6 adsorption. The large relative discrepancy was attributed to an increase in the Si 2 H 6 density difference. Based on our findings, since the larger the size of the molecules of the Si x H y species, the weaker the Si-H bond strength and the higher the surface reactivity becomes, insertion of larger sized Si x H y species will enhance productivity in plasma deposition of the Si:H layer.

Supplementary Materials:
The following are available online at https://www.mdpi.com/article/10 .3390/coatings11091041/s1, Table S1: Adsorption energies of Si 2 H 6 on the H-50% covered Si(001)-(4 × 4) surface, calculated for each geometry and position. Table S2: Adsorption energies of Si 2 H 6 on the H-50% covered Si(111)-(4 × 4) surface, calculated for each geometry and position. Figure S1: Initial (IS), transition (TS), and final (FS) states of intermediate reactions of Si 2 H 6 from the 2 nd reaction step to the 8 th reaction step for path a on the H-50% covered Si(001) surface. Table S3: Activation energies (E a , eV) and reaction energies (E rxn , eV) of Si 2 H 6 dissociation for path a on the H-50% covered Si(001) surface. Figure S2: Initial (IS), transition (TS), and final (FS) states of intermediate reactions of Si 2 H 6 from the 3 rd reaction step to the 6 th reaction step for path b on the H-50% covered Si(001) surface. Table S4: Activation energies (E a , eV) and reaction energies (E rxn , eV) of Si 2 H 6 dissociation for path b on the H-50% covered Si(001) surface. Figure S3: Initial (IS), transition (TS), and final (FS) states of intermediate reactions of Si 2 H 6 from the 2 nd reaction step to the 8 th reaction step for path a on the H-50% covered Si(111) surface. Table S5: Activation energies (E a , eV) and reaction energies (E rxn , eV) of Si 2 H 6 dissociation for path a on the H-50% covered Si(111) surface. Figure S4: Initial (IS), transition (TS), and final (FS) states of intermediate reactions of Si 2 H 6 from the 3 rd reaction step to the 6 th reaction step for path b on the H-50% covered Si(111) surface. Table S6: Activation energies (E a , eV) and reaction energies (E rxn , eV) of Si 2 H 6 dissociation for path b on the H-50% covered Si(111) surface.

Conflicts of Interest:
The authors declare no conflict of interest.

Appendix A.
Appendix A. 1

. Adsorption Energy, Activation Energy and Reaction Energy
The adsorption energy (E ads ) was calculated using: E ads = E tot, ads − (E surf + E pre ) where E tot,ads , E surf and E pre are the total energy of the system after adsorption, the energy of the surface only and the energy of the precursor only, respectively. The activation energy (E a ) was calculated using: E a = E tot, tran − E tot, b.tr where E tot, tran and E tot, b.tr are the total energy of the transition state and the total energy before transition, respectively. The reaction energy (E rxn ) was calculated using: E rxn = E tot, a.tr − E tot, b.tr where E tot, a.tr is the total energies of the system after transition.