We performed a thermodynamic analysis of GaN metalorganic vapor phase epitaxy considering the (0001) and surface states. Surface reconstruction, which depends on growth conditions such as temperature and partial pressure, affects growth processes. To discuss the effects of surface states on growth processes, we investigated the driving force of precursor deposition to form the surface phase defined stoichiometrically. In both N ₂ and H ₂ carrier gas cases, we showed surface phase diagrams, calculated driving forces, and discussed the difference in growth orientation.

The carbon incorporation mechanism in GaN(0001) and GaN(000$\overline{1})$ during MOVPE was investigated using density functional theory (DFT) calculations. The results confirm that the crucial factors for carbon incorporation are Fermi level pinning and accompanying surface band bending. In addition, the lattice symmetry has a strong dependence on the stability of carbon in a few subsurface layers, which results from interactions between the impurities and surface states. It was shown that these effects are responsible for facilitating or hindering the incorporation of impurities and dopants. The influence of diluent gas species (hydrogen or nitrogen) on carbon incorporation was discussed.

GaN(0001) surfaces with Ga- and H-adsorbates are fundamental stages for epitaxial growth of semiconductor thin films. We explore stable surface structures with a nanometer scale by the density-functional calculations combined with Bayesian optimization and reach a single structure with satisfactorily low mixing enthalpy among hundreds of thousand possible candidate structures. We find that the obtained structure is free from any postulated high symmetry previously introduced by human intuition, satisfies an electron counting rule locally, and shows a complex adsorbate arrangement, reflecting characteristics of nitride semiconductors. The proposed scheme toward a high-resolution surface phase diagram contributes to a more precise design of GaN epitaxial growth conditions, especially the ratio of Ga and H partial pressures.

Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and N_ad-H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium where the state evolution is a combination of reversible and irreversible dynamics. SEAQT is an ideal choice to handle this problem on a first-principles basis since the chemical adsorption process starts from a highly non-equilibrium state. A result of the analysis shows that the probability of adsorption on 3Ga-H is significantly higher than that on N_ad-H + Ga-H. Additionally, the growth temperature dependence of these adsorption probabilities and the temperature increase due to the heat of reaction is determined. The non-equilibrium thermodynamic modeling applied can lead to better control of the MOVPE process through the selection of preferable reconstructed surfaces. The modeling also demonstrates the efficacy of DFT-SEAQT coupling for determining detailed non-equilibrium process characteristics with a much smaller computational burden than would be entailed with mechanics-based, microscopic-mesoscopic approaches.

Suppression of carbon contamination in GaN films grown using metalorganic vapor phase epitaxy (MOVPE) is a crucial issue in its application to high power and high frequency electronic devices. To know how to reduce the C concentration in the films, a sequential analysis based on first principles calculations is performed. Thus, surface reconstruction and the adsorption of the CH₄ produced by the decomposition of the Ga source, Ga(CH₃)₃, and its incorporation into the GaN sub-surface layers are investigated. In this sequential analysis, the dataset of the adsorption probability of CH₄ on reconstructed surfaces is indispensable, as is the energy of the C impurity in the GaN sub-surface layers. The C adsorption probability is obtained based on steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic ensemble-based, non-phenomenological framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium. This framework is suitable especially when one studies the adsorption behavior of an impurity molecule because the conventional approach, the chemical potential control method, cannot be applied to a quantitative analysis for such a system. The proposed sequential model successfully explains the influence of the growth orientation, GaN(0001) and (000−1), on the incorporation of C into the film. This model can contribute to the suppression of the C contamination in GaN MOVPE.

We propose a newly improved thermodynamic analysis method that incorporates surface energies. The new theoretical approach enables us to investigate the effects of the growth orientation and surface reconstruction. The obtained knowledge would be indispensable for examining the preferred growth conditions in terms of the contribution of the surface state. We applied the theoretical approach to study the growth processes of InN(0001) and by metalorganic vapor phase epitaxy. Calculation results reproduced the difference in optimum growth temperature. That is, we successfully developed a new theoretical approach that can predict growth processes on various growth surfaces.