A Reaction Pathway of Surface-Catalyzed Ammonia Decomposition and Nitrogen Incorporation in Epitaxial Growth of Gallium Nitride

The Journal of Physical Chemistry
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A Reaction Pathway of Surface-Catalyzed Ammonia

Decomposition and Nitrogen Incorporation in Epitaxial
Growth of Gallium Nitride
Journal: The Journal of Physical Chemistry
Manuscript ID Draft
Manuscript Type: Article
Date Submitted by the Author: n/a
Complete List of Authors: Bui, Kieu My; Nagoya University, Institute of Materials and Systems for
Sustainability
Iwata, Jun-ichi; AdvanceSoft Corporation
Kangawa, Yoshihiro; Kyushu Univ., RIAM
Shiraishi, Kenji; Univeristy of Tsukuba, Graduate School of Pure and
Applied Sciences; Nagoya University, Institute of Materials and Systems for
Sustainability
Shigeta, Yasuteru; Graduate School of Pure and Applied Sciences,
University of Tsukuba, Center for Computational Sciences
Oshiyama, Atsushi; The University of Tokyo, 7-3-1 Hongo; Nagoya
University, Institute of Materials and Systems for Sustainability
ACS Paragon Plus Environment

Page 1 of 22 The Journal of Physical Chemistry
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8 A Reaction Pathway of Surface-Catalyzed
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11 Ammonia Decomposition and Nitrogen
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15 Incorporation in Epitaxial Growth of Gallium
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18 Nitride
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†,‡ ¶,§ †,∥ †
22 Kieu My Bui, Jun-Ichi Iwata, Yoshihiro Kangawa, Kenji Shiraishi, Yasuteru
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24 ‡ ∗,†,¶
Shigeta, and Atsushi Oshiyama
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Institute of Materials and Systems for Sustainability, Nagoya University, Nagoya 464-8603,
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Japan, Center for Computational Science, University of Tsukuba, Tsukuba 305-8577,
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Japan, Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan,
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AdvanceSoft Corporation, Tokyo 101-0062, Japan, and Research Institute for Applied
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Mechanics, Kyushu University, Fukuoka 816-8580, Japan
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38 E-mail: oshiyama@imass.nagoya-u.ac.jp
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51 ∗
To whom correspondence should be addressed
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Institute of Materials and Systems for Sustainability, Nagoya University, Nagoya 464-8603, Japan
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Center for Computational Science, University of Tsukuba, Tsukuba 305-8577, Japan
54 ¶
Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan
55 §
AdvanceSoft Corporation, Tokyo 101-0062, Japan
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Research Institute for Applied Mechanics, Kyushu University, Fukuoka 816-8580, Japan
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60 ACS Paragon Plus Environment
The Journal of Physical Chemistry Page 2 of 22
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Abstract
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6 We report density-functional calculations that clarify atom-scale mechanisms of
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8 vapor-phase epitaxial growth of GaN with gas sources of trimethylgallium and ammo-
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10 nia. We identify various stable adsorption structures of a Ga atom and NHx molecules
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(x = 0 - 3) on GaN(0001) surfaces and nd that NH2 and NH units spontaneously
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13 intervene in Ga-Ga surface bonds on Ga-rich GaN (0001) surface. We then explore the
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15 reaction in which NH3 on the surface is decomposed and become an N-incorporated
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17 structure, - Ga - (NH) - Ga -, on the Ga-rich GaN (0001) and nd that the reaction
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19 occurs with the energy barrier of 0.63 eV. We next explore a reaction in which two -
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21 Ga - (NH) - Ga - structures are converted to the GaN network with an H2 molecule
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23 being desorbed, identify the reaction pathway and obtain the energy barrier less than
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1.5 eV. This barrier is easily overcome when we consider the chemical potential of an
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H2 molecule in the gas phase at the growth temperature. This NH3 decomposition and
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28 the subsequent N incorporation on GaN is a new growth mechanism catalyzed by the
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30 growing surface.
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35 1 Introduction
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38 The nitride semiconductor with group IIIb elements (Al, Ga, and In) is one of the most
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40 important semiconductors due to its wide range of direct band gaps, becoming a princi-
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42 pal material in optoelectronic devices. 13 This premier status of the nitride semiconductor
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44 was triggered and established by a pioneering work on crystal growth of GaN: 4,5 i.e., the
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46 introduction of the buer AlN layer and the hydrogen removal by the electron-beam irradi-
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48 ation and later by thermal treatment 6 in improving the thin-lm quality in Metal-Organic
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50 Vapor-Phase Epitaxy (MOVPE). 7
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52 In addition to the optoelectronics applications, GaN has emerged as a key material in
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54 power electronics. 8 This is obviously due to its wide band gap and robustness under harsh
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56 environment. In the power devices, interfaces between semiconductors and insulators in-
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59 2
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evitably include several interface alignments, thus demanding the higher quality of epitaxial
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GaN lms.
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Epitaxial growth is an atom-scale scrap-and-build process: The growing surface, though
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9 at high temperature, still keeps stable bond congurations, then the bonds are destructed,
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11 and nally a new bond conguration emerges in the growth process. Knowledge of the atom-
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13 scale mechanism for this bond destruction and creation is lacking so far but inevitable in
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15 future to advance science and technology of epitaxial growth.
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17 The MOVPE with trimethylgallium (TMG) and ammonia (NH3 ) as gas sources is re-
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19 garded as the most suitable technique of growing GaN lms. 1,2 Many experimental and
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21 theoretical eorts have revealed that TMG is decomposed in the gas phase and the growing
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23 surface is generally Ga rich. 911 On the other hand, the mechanism of the decomposition of
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25 NH3 is unclear though it is postulated without rm evidence to be decomposed in the gas
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27 phase and forms several NHx unit, i.e., adduct formation. 12 Then some empirical parameters
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29 for the decomposition are used to analyze the growth rate of GaN. 13,14
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31 In this paper, we report rst-principle total-energy electronic-structure calculations that
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33 clarify reaction pathways and corresponding energy barriers for the decomposition of NH3
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35 and the subsequent N incorporation on GaN lms with the formation of -Ga-N-Ga- bond
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37 network. We concentrate on the growing GaN(0001) surface which is mostly used in typical
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39 MOVPE of GaN. The calculated energy barriers indicate that the whole reaction we have
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41 found occurs under usual growth conditions. This is the rst proposal based on the quantum
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43 theory of the surface-catalyzed atom incorporation during the epitaxial growth.
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45 The organization of this paper is as follows. Section 2 describes the present density-
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47 functional calculations. Adsorption of a Ga atom and NHx molecules and their reactions
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49 on GaN(0001) bare surfaces are described in Section 3.1. Identication of the Ga-rich
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51 GaN(0001) surface and adsorbed structures of NHx are presented in Section 3.2. Reac-
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53 tion pathways of N incorporation from the adsorbed NH3 and corresponding energy barriers
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55 are also revealed in Section 3.2. Section 4 summarizes our ndings.
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59 3
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2 Methodology
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6 All the calculations have been performed in the density functional theory (DFT) 15,16 with
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8 the generalized gradient approximation 17 to the many-body exchange-correlation energy
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10 functional. Nuclei and core electrons are described by norm-conserving pseudo-potentials. 18
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12 The Ga 3d states are treated as core-electron states. Computations have been done using
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14 our real-space-scheme code called RSDFT 19 which has been developed so as to achieve the
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16 state-of-the-art high-performance computing. 20 The GaN (0001) surface is simulated by a
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18 repeating slab model in which each slab consisting of six GaN double layers are separated
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20 from its images by the 15-Å thick vacuum regions. The bottom N surface is passivated by
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22 fractionally charged (0.75 e) hydrogen to annihilate the dangling bonds and mimic the semi-
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24 innite GaN substrate. In the lateral planes, we use 2 × 2 supercell periodicity. The spacing
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26 of the real-space grid points in RSDFT scheme is taken as 0.18 Å which corresponds to the
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28 73-Ryd cuto energy in the conventional plane-wave-basis calculations. The Brillouin-zone
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30 (BZ) integration has been done with the Monkhorst-Pack k -point sampling scheme and the
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32 5 × 5 × 3 sampling points are found to suce for the BZ of wurtzite GaN. In the 2 × 2
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34 slab calculations, this sampling corresponds to the 3 × 3 × 1 sampling. These calculational
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36 parameters for the grid spacing and the k -point sampling lead to the lattice constants of
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38 3.20 Å and 5.20 Å for wurtzite GaN, which are larger than the experimental values 21 by 0.3
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40 % and 0.2 %, respectively. In the geometry optimization, all the atoms in the slab except
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42 for the bottom two double layers and H atoms are fully relaxed until the remaining forces
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44 become less than 25 meV/Å.
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46 Reaction pathways and corresponding energy barriers are calculated by using the hyper-
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48 plane constraint method (HPC). 22,23 In this method, we rst determine lines in the 3Natom
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50 dimensional space (Natom : the number of atoms in the simulation cell) which connect the
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52 initial {Ri } and the nal or the intermediate metastable structures {Rf } for a selected reac-
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54 tion pathway. Here, we use the notation {R} for a 3Natom dimensional vector which denotes
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56 the atomic geometry. Next, for each line in the selected pathway, the (M − 1) vectors {Pm }
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(m = 1, · · · , M − 1) along the line are selected as {Pm } ≡ {Ri } + m({Rf } − {Ri })/M and
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then a hyperplane perpendicular to the line at each {Pm } is dened. On each hyperplane,
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we perform geometry optimizations to nd the most probable reaction pathways.
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12 3 Results and Discussion
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23 H3
24 BR
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27 T4
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29 T1
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32 Figure 1: Top view of the GaN(0001) surface and its several atomic sites: T1, T4, H3 and
33 BR (see text). Green (large) and blue (small) balls depict the Ga and N atoms, respectively,
34 at the top several leyer.
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41 3.1 Adsorption and reaction on Ga-faced GaN (0001) surface
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43 We start with the GaN(0001) bare surface terminated with Ga atoms where the stoichiometry
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45 is the same as that in the bulk. The geometry optimization leads to a relaxed surface in
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47 which the top-layer Ga atoms are buckled alternately, as is already reported in the previous
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49 density-functional calculation. 24 We have found that this surface relaxation hardly aects
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51 the stable structures of adsorbed species and their energetics explained below. Figure 1
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53 depict representative atomic sites on such surface: T1 (on-top) site above the top-layer Ga
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55 atom, T4 (hcp) site above the top-layer N atom, BR (bridge) site between the two top-layer
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Ga atoms and H3 (fcc) site above the hollow of the hexagonal network. We have placed a
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Ga atom or NHx species on those sites and examined their stability. It is noteworthy that
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not only the surface atoms but also the ad-species are allowed to be relaxed toward the
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9 total-energy minimized structures. The binding energy Ebind dened below is the measure
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11 of the stability of each adsorbed structure:
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15 Ebind = −(Esur−ad − Esur − Ead ),
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19 where Esur−ad , Esur and Ead are the total energies of the GaN surface plus the ad-species,
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21 the GaN surface, and the adsorbed species in the gas phase, respectively.
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23 Table 1: Calculated binding energies in eV for Ga adatom and NHx molecule at
24 the atomic sites, T1, T4, H3 and BR (see text), on the bare GaN(0001) surface.
25 The sites at which the adsorbed species is unstable are depicted by hyphens.
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adsorbed species T1 T4 H3 Br
29 Ga 2.48 3.77 3.49
30 NH3 1.30
31 NH2 4.70 4.81
32 NH 6.67 7.39
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34 N 8.19 8.94
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For the Ga adatom, we have found that T4, H3 and T1 sites show positive binding
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energies (Table 1), meaning the exothermic adsorption, whereas BR site is unstable for
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the Ga adsorption. The most stable adsorption site is T4 where the Ga adatom form a
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bond with each of the three top-layer Ga atoms (Fig. 2). The H3 site provides smaller but
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47 comparable binding energy while the T1 site does much smaller binding energy. Previous
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49 density-functional calculations have also shown that the T4 site is most energetically fa-
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51 vorable for a Ga adatom. 25,26 When we count the number of Ga dangling bonds in the 2
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53 × 2 lateral cell, it is four on the bare surface. When a Ga adatom is adsorbed on either
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55 T4 or H3 site, the number of the Ga dangling bond becomes two, while it remains three
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20 Figure 2: Most stable adsorption structure for a Ga adatom (burgandy ball) at T4 site
21 on the GaN(0001) surface. Green (large) and blue (small) balls depict Ga and N atoms,
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respectively.
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27 at T1 site. At T4 and H3 sites, 3 electrons of the additional Ga atom plus 0.75 electrons
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29 nominally accommodated in the other Ga dangling bond is used to form the three Ga-Ga
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31 back-bonds. Hence the 2 cation (Ga) dangling bonds, which have higher orbital energy, in
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33 the 2 × 2 lateral cell becomes empty. This electron counting, which has been recognized
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35 as the electron counting rule (ECR), 27,28 explains the stability at T4 and H3 sites. The T4
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37 site is more favorable than the H3 site. This is due to the attractive interaction between the
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39 Ga adatom and the N atom located beneath the Ga adatom. In the most stable T4 site,
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41 the bond length between the Ga adatom and one of the top Ga atoms is 2.48 Å which is
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comparable with the Ga-Ga distance (2.7 Å) in the bulk Ga metal.
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Ammonia is the source of nitrogen in MOVPE. Hence the identication of the adsorption
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sites of NH3 and its possible adsorbates, NH2 , NH and N on the GaN (0001) bare surface is
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important to identify typical forms of the nitrogen-related species on the GaN (0001). Figure
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3 shows obtained stable adsorbed structures for the NH3 , NH2 , NH and N on the GaN (0001)
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bare surface. We have found that NH3 is stable only at the T1 site in which all the N and
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Ga atoms are four-fold coordinated as shown in Fig. 3(a). At other sites, such coordination
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22 Figure 3: Most stable adsorption structure for (a) NH3 at T1, (b) NH2 at Br, (c) NH at H3
23 and (d) N at H3 sites on the GaN(0001) surface. Color code is the same with Fig. 2. Salmon
24 pink balls depict H atoms in NHx units.
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27 number energetically favorable is impossible. The adsorption energy is calculated as 1.30
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29 eV (Table 1). The resulting Ga-N and average N-H bond lengths on the surface are 2.07 Å
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31 and 1.02 Å, respectively, whereas the H-N-H angles are 111.3◦ , 111.0◦ , and 106.8◦ . These
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33 structural parameters are close to those of an isolated ammonia.
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35 The rst two possible adsorbate, NH2 and NH, show bistability in their adsorption forms.
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37 The stable forms are well interpreted in terms of the coordination number. For NH2 , the
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39 BR and T1 sites are energetically favorable with the binding energies of 4.81 eV and 4.70
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41 eV, respectively (Table 1). In both adsorption forms, the NH2 attached Ga is four-fold
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43 coordinated whereas the N is either four-fold or three-fold coordinated [Fig. 3(b)]. For
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45 NH, the H3 and T4 sites are favorable with the binding energies of 7.39 eV and 6.67 eV,
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47 respectively (Table 1). In those adsorption forms, N in the NH unit becomes four-fold
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49 coordinated which assures the stability [Fig. 3(c)].
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51 The nal possible adsorbate is the N atom itself. We have found that the energetically
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53 favorable adsorption sites for N are the H3 and T4 sites with the binding energies of 8.94
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55 eV and 8.19 eV, respectively. Upon the adsorption on these sites, there remain a single
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Ga dangling bond and a single N dangling bond in the 2 × 2 lateral cell. At other sites,
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the N adatom is not eective to erase the surface Ga dangling bonds. In addition to that,
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the H3- and the T4-site congurations satisfy ECR: the electron accommodated in the Ga
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9 dangling bond (nominally 3/4 electrons) is transferred to the N dangling bond (nominally
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11 5/4 electrons accommodated), thus resulting in an N lone pair and an empty Ga dangling
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13 bond. The T4 site is less favorable than the H3 site. This is due to the repulsion between
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15 the N adatom and the N atom beneath.
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21 side view top view
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41 Figure 4: Calculated energy prole for the reaction of NH3 decomposition to NH plus an
42 desorbed H2 molecule on the bare GaN(0001) surface (see text). The inset is the transition-
43 state geometry.
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48 We have now identied stable adsorbed structures for NHx . Then we explore a decom-
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50 position reaction of ammonia on the surface: i.e., NH3 at T1 [Fig. 3(a)] becomes NH at
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52 H3 [Fig. 3(c)] with an H2 molecule being desorbed. We have identied the transition-state
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54 geometry in which N in NH3 moves from T1 to H3, elongating its bond with surface Ga
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56 from 2.0 Å to 2.7 Å (Fig. 4). In the geometry, two H atoms in NH3 move upward whereas
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the third H keeps its original position. This transition state leads to the activation barrier
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of 0.7 eV in this reaction as shown in Fig. 4. This reaction may be a possible process of the
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ammonia decomposition on the bare GaN(0001) surface. Yet as will be shown below, the
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9 Ga-rich surface catalyze more important reactions in MOVPE.
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13 3.2 Decomposition of NH3 and incorporation of N on Ga-rich GaN(0001)
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16 surface
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18 Thermodynamical analyses 10 have shown that the growing surface in GaN MOVPE at the
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20 typical range of temperature and pressure of gas sources is Ga rich. Calculated results in the
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22 previous subsection have claried that the T4 site is the most favorable for the adsorption
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24 of the Ga adatom (Fig. 2). We therefore consider the Ga-faced GaN(0001) surface with an
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26 additional Ga atom at the T4 site in the 2 × 2 lateral cell as a representative of the Ga-rich
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28 GaN(0001). The corresponding coverage of the Ga adatom is θ = 0.25. It is noteworthy that
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30 this coverage, i.e., n2 Ga adatoms in a 2n×2n lateral cell satises the ECR. In this subsection,
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32 we explore reaction pathways and corresponding energy barriers for the decomposition of
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34 ammonia and incorporation of nitrogen on the growing Ga-rich GaN surface.
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Table 2: Calculated binding energies in eV for NHx molecule at the atomic sites,
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38 T1, H3, BR and Tad (see text), on the Ga-rich GaN(0001) surface. The sites at
39 which the adsorbed species is unstable are depicted by hyphens.
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41 adsorbed species T1 H3 Br Tad
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NH3 1.27 0.33
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44 NH2 3.96 3.25 3.07
45 NH 6.36 5.14 6.19 3.50
46 N 8.34
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52 For the purpose, we rst identify the stable adsorption structures of NH3 on the Ga-rich
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54 surface. As shown in the previous section, NH3 is adsorbed only at T1 site on the bare GaN
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56 (0001) surface. This is due to the strong bond formation between the N atom in NH3 and the
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Figure 5: Stable adsorption structure and corresponding electron density of NH3 at Tad site
42 [(a) and (c)] and at T1 site [(b) and (d)] on the Ga-rich 2 × 2 GaN (0001) surface. Color
43 code in (a) and (b) is the same with Fig. 2 and Fig. 3. Electron density is represented by
44 yellow equivalue surfaces and by contour color plots at the cross-sections.
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top Ga atom. Hence on the Ga-rich surface, the site on the Ga adatom (Tad site hereafter)
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in addition to the T1 site is a candidate for the NH3 adsorption. We have indeed found
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that the Tad and T1 are the stable adsorption sites with the binding energies of 0.33 eV and
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9 1.27 eV, respectively (Table 2). The optimized geometries of adsorbed NH3 are shown in
10
11 Fig. 5. The structures of the NH3 unit at the Tad and T1 sites are almost identical: The
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13 N-Ga bond length and the averaged N-H bond length are 2.18 Å (2.08 Å) and 1.01 Å (1.02
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15 Å), respectively, at Tad (T1) site; the H-N-H bond angles are 111.1◦ ± 1.2◦ for both sites.
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17 It is of interest that both the Tad and the T1 congurations satisfy the ECR with the Ga
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19 dangling bond unoccupied. Calculated electron densities for the adsorbed NH3 at these sites
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21 are shown in Figs.5 (c) and (d). Formation of the covalent bond between N of NH3 and
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23 top Ga is evident. Furthermore, we have found that the Ga-Ga bonds in the structures
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25 are rather weak, as is shown by the smaller equivalue surfaces. This weak spots may be a
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27 candidate place for the N incorporation (see below).
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39 Figure 6: Stable adsorption structures of NHx units on the Ga-rich GaN (0001) surface. (a)
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NH2 on the T1 site, (b) NH on the T1 site, and (c) NH on the BR site, The color code is
42 the same as in Fig. 5.
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46 For the possible adsorbates, NH2 , NH, and N, we have found that in the stable adsorption
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48 structures the number of accommodated electrons at the Ga dangling bonds are minimized.
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50 For NH2 , we have found that the most stable site is the T1 site (Ebind = 3.96 eV) followed
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52 by the BR site (Ebind = 3.25 eV) and then the Tad site (Ebind = 3.07 eV) (Table 2). It is of
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54 note that the NH2 unit intervenes in the Ga-Ga bond after the geometry optimization for
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56 the NH2 at T1 site [Fig. 6 (a)]. The NH unit is adsorbed at any site, presumably due to the
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59 12
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unstable form of an isolated NH, with the binding energies of 6.36 eV (T1), 6.19 eV (BR),
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5.14 eV (H3), and 3.5 eV (Tad ). On the other hand, N is adsorbed only at H3 site with Ebind
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= 8.34 eV. This is obviously due to the limitation of the bonding ability of a single N atom
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9 (Table 2). We have found that in the most and the next stable NH geometries the NH unit
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11 intervenes in the Ga-Ga bond [Fig. 6 (b) and(c)].
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side view top view
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37 Figure 7: Calculated energy prole for the reaction of the NH3 decomposition and the NH
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incorporation (see text) on the Ga-rich GaN(0001) growing surface. The transition-state
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40 geometry is also shown. .
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44 Our geometry optimization has unequivocally claried that NH2 at the T1 site [Fig. 6
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46 (a)] and NH at the T1 site (most stable) and BR (next stable) sites [Figs. 6 (b) and (c)]
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48 spontaneously (or with a small energy barrier) intervene in the weak Ga-Ga bond. Then it
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50 is likely that the Ga-Ga weak bond is the reaction site for the N incorporation. We thus
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52 explore a pathway and a corresponding energy barrier for the reaction,
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56 [ NH3 on Tad ] → [ NH at T1 ] + H2 ,
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59 13
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using the HPC method. Figure 7 shows the obtained energy prole of the reaction from NH3
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at the Tad [Fig. 5(a)] toward NH near the T1 [Fig. 6(b)] with the H2 molecule being desorbed.
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7
It is noteworthy that the nal conguration satises ECR with the N dangling bond being
8
9 occupied by 2 electrons and the two Ga dangling bonds being unoccupied. The energy barrier
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11 for this reaction of the NH3 decomposition and the subsequent NH incorporation in the GaN
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13 bond network is calculated to be 0.63 eV. This value is surprisingly small in spite that the
14
15 reaction involves the destruction of a Ga-Ga bond. The transition-state geometry is shown
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17 in Fig. 7. In the geometry, the Ga adatom is moved from the Tad site to the H3 site, thus
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19 providing room for the NH unit to intervene in the Ga-Ga backbond. The distance from the
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21 incorporated N of the NH unit to the two Ga atoms are 1.90 Å and 1.92 Å, indicating that
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23 Ga-N bonds are already formed. In this sense the reaction is certainly concerted.
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48 Figure 8: Electron density of the incorporated NH near the Tad site after the decomposi-
49 tion and the subsequent incorporation reaction on the Ga-rich surface. Electron density is
50 presented by yellow equivalue surfaces and by contour color plot at the cross-sections.
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Figure 8 shows calculated valence electron density at the nal structures of the decompo-
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sition and the subsequent incorporation reaction. The relative weakness of the Ga-Ga bond
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59 14
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in the initial geometry of the NH3 at Tad site is demonstrated by the small equivalue surfaces
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in the region [Fig. 5 (c)]. In the nal geometry of the incorporated NH, we have found that
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two strong Ga-N bonds are formed, as shown by the larger equivalue surfaces in Fig. 8. The
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9 relatively weak Ga-Ga bond on the Ga-rich (0001) surface works as a catalyst for the NH3
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11 decomposition and the NH incorporation on the growing surface.
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29 Figure 9: Reaction pathway for the N incorporation on the Ga-rich GaN(0001) surface. The
30 two NH units intervening in the Ga-Ga backbonds (a) are incorporated in the GaN network
31 with the H2 molecule being desorbed (c) via the transition-state geometry (c). The color
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code is same as in Fig. 5.
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Since the energy barrier of the decomposition reaction we have found is relatively low,
38
it is expected that the nal conguration in which the NH unit intervenes in the Ga-Ga
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bond is ubiquitous on the growing surface. Even the situation in which the two NH units
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intervenes in the weak Ga-Ga bonds at the same Tad site is likely. The electron density
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shown in Fig. 8 indeed indicates such possibility as is corroborated by the small equivalue
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surface near the remaining Ga-Ga bonds. We then explore a possibility of the reaction in
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which the two NH units formed near the Tad site [Fig. 9 (a)] are incorporated in GaN network
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with the two H atoms being desorbed as a molecule. For the nal geometry in the reaction,
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we consider the two N atoms being incorporated into the GaN network near the T4 site and
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the H3 site [Fig. 9 (c)]. Our HPC calculation has revealed that this reaction takes place via
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a transition-state geometry shown in [Fig. 9 (b)].
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59 15
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20 side view top view
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40 Figure 10: Calculated energy prole for the reaction of the nitrogen incorporation from the
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two NH units which is shown in Fig. 9. The transition-state geometry is also shown.
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In the nal geometry, one of the two N atoms becomes four-fold coordinated with neigh-
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boring Ga atoms, thus forming a new basic unit constituting the GaN lm. The energy
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prole for this reaction involves a metastable conguration, indicative of the two-step reac-
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9 tion (Fig. 10). The energy barrier for each step is lower than 1.5 eV from our HPC calculation
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11 at zero temperature. The hydrogen chemical potential at 1300 K in the gas phase is eval-
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13 uated to be - 2.1 eV, considering translation, vibration and rotation motions of H2 . This
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15 value of the chemical potential compensates the zero-temperature energy barrier. Then the
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17 whole reaction of the formation of GaN unit and the H2 desorption that we have found is
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19 highly plausible in GaN MOVPE.
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24 4 Conclusions
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26
27 We have performed density-functional calculations that clarify an atom-scale mechanism for
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29 the growth of GaN using the Metal-Organic Vapor-Phase Epitaxy (MOVPE) with the gas
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31 sources of TMG and NH3 . First, we have determined stable adsorption structures for Ga,
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33 NH3 , NH2 , NH and N on the bare Ga (0001) surface and obtained the binding energy for each
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35 adsorption structure. We have identied a possible reaction pathway for the decomposition
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37 of NH3 on the GaN (0001) surface and obtained the reaction barrier of 0.7 eV. Based on the
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39 obtained adsorption structure of Ga atoms, we have identied Ga-rich GaN (0001) surface in
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41 which Ga-Ga bonds exist. This surface is regarded to appear in usual growth conditions. We
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43 have explored various adsorption structures of NH3 , NH2 , NH and N on this Ga-rich GaN
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45 (0001) and found that NH2 and NH units spontaneously intervene in the relatively weak
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47 Ga-Ga bond, forming a - Ga - (NHx ) - Ga - bond network. We have then explored a reaction
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49 in which NH3 on the surface is decomposed toward the - Ga - NH - Ga - conguration with
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51 an H2 molecule being desorbed. We have determined the reaction pathway and obtained the
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53 rather small energy barrier of 0.63 eV. We have then considered the reaction in which two -
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55 Ga - NH - Ga - congurations are converted to GaN network plus a desorbed H2 molecule.
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59 17
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We have identied such reaction pathway and obtained the energy barrier less than 1.5 eV.
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When we take into account the chemical potential of an H2 molecule in the gas phase at 1300
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K, this energy barrier at 0 K is found to be easily overcome. The reaction process for the
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9 NH3 decomposition and the N incorporation that we have found based on the rst-principle
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11 calculations is a new growth mechanism catalyzed by the growing surface.
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15 Acknowledgement
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18 This work was supported by the Ministry of Education, Culture, Sports, Science and Technol-
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20 ogy (MEXT) Japan under the research project, Social and Scientic Priority Issue (Creation
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22 of New Functional Devices and High-Performance Materials to Support Next-Generation
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24 Industries) to be Tackled by Using Post-K Computer. Computations were performed by K
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26 computer and other supercomputers at the Institute for Solid State Physics of The University
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28 of Tokyo, The Research Center for Computational Science of National Institutes of Natural
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30 Sciences, and the Center for Computational Science of University of Tsukuba.
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A Reaction Pathway of Surface-Catalyzed Ammonia Decomposition and Nitrogen Incorporation in Epitaxial Growth of Gallium Nitride

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A Reaction Pathway of Surface-Catalyzed Ammonia Decomposition and Nitrogen Incorporation in Epitaxial Growth of Gallium Nitride

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A Reaction Pathway of Surface-Catalyzed Ammonia

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