Research Article  Open Access
Influence of Vacancy Defect on Surface Feature and Adsorption of Cs on GaN(0001) Surface
Abstract
The effects of Ga and N vacancy defect on the change in surface feature, work function, and characteristic of Cs adsorption on a GaN(0001) surface have been investigated using density functional theory with a planewave ultrasoft pseudopotential method based on firstprinciples calculations. The covalent bonds gain strength for Ga vacancy defect, whereas they grow weak for N vacancy defect. The lower work function is achieved for Ga and N vacancy defect surfaces than intact surface. The most stable position of Cs adatom on Ga vacancy defect surface is at T_{1} site, whereas it is at site on N vacancy defect surface. The of Cs on GaN(0001) vacancy defect surface increases compared with that of intact surface; this illustrates that the adsorption of Cs on intact surface is more stable.
1. Introduction
Due to its important characteristics such as wide band gap, high thermal conductivity, high breakdown voltage, high melting point, and chemical stability, among others, GaN and its compounds such as [1–3] have emerged as a new type material for the fabrication of optoelectronic devices in the blue and ultraviolet spectral region [4–10]. Most research has focused on its physical properties, growth mechanisms, and surface structures [11–15]. The (0001) surface of Wurtzite GaN has good surface state and simple production process [16], the surface size of GaN(0001) is different, and the reconstruction is different in atomic structure [17, 18]. The surface is considered the most stable surface [19], while a Ga adatom model is thermodynamically favored under moderately Garich conditions [20]. The surface stability and conductivity properties of GaN(0001) are superior to that of (000) [13, 21]. GaN(0001) surface becomes the focus of attention of optoelectronics community. The effective negative electron affinity has been demonstrated for GaN(0001) surfaces after Cs adsorption or Cs and O activating [22–27]; this is important for vacuumtype optoelectronic devices.
Defects may be produced in GaN materials growth process and interact with carriers. The existence of defects will affect the adsorption of Cs on GaN surface and then affect the performances of photoelectric devices. Theoretical studies of the eigen defects of GaN have been reported [28–30]; however, the influence of such defects on the adsorption of Cs on GaN surface has not been determined. In this paper, we employ planewave with ultrasoft pseudopotential method to study the influence of Ga and N vacancy defects on the surface feature and adsorption of Cs on GaN(0001) surface based on the firstprinciple density functional theory (DFT).
2. Computational Methods
The parameters for the optimized bulk wurtzite GaN structures are nm and nm [31]. All calculations were performed with the quantum mechanics program Cambridge Serial Total Energy Package [32] based on density functional theory (DFT). The BroydenFletcherGoldfarbShanno algorithm was used to relax the structure of the crystal model. The convergence precision was set to an energy change < eV/atom, force < 0.005 eV/nm, convergence tolerance of a single atomic energy < eV/atom, stress < 0.05 GPa, and change in displacement < 0.0001 nm in an iterative process. The surface slab was modeled with six GaN(0001) bilayers of which the lower three bilayers were fixed in the bulk configurations and a vacuum region equivalent to six GaN bilayers with overall approximate length of 1.3 nm was required. The bottom side of the slab was saturated with pseudohydrogen atoms to prevent transfer of surface charges (shown in Figure 1). Wave functions were expanded in a planewave basis set up to an energy cutoff of 400 eV and integrations over the Brillouin zone were performed using a MonkhorstPack set samplingpoint scheme for the surface supercell. The electron exchange and correlation were treated by using the PerdewBurkeErnzerhof (PBE) formulation of the generalized gradient approximation (GGA) [33].
(a)
(b)
(c)
(d)
One Ga atom or one N atom on the outmost layer of GaN(0001) surface was removed in researching vacancy defect surface, respectively (shown in Figure 1). Figure 1(a) shows the side view of Ga vacancy defect surface and (c) is the top view. Figure 1(b) shows the side view of N vacancy defect surface and (d) is the top view. For a Cs adsorption on GaN(0001) surface, five typical adsorption models including sites of T_{1} (Ga top), H_{3} (hollow site), T_{4} (N top), B_{Ga} (Ga bridge), and B_{N} (N bridge) were chosen [34, 35]. In this paper, these five typical adsorption sites are adopted to study the influence of Ga and N vacancy defects on the adsorption of Cs on GaN(0001) surface. Figure 2 shows the top view of Cs at T_{1}, H_{3}, T_{4}, B_{Ga}, and B_{N} sites on GaN(0001) defect surface. Figure 2(a) shows the top view of Cs on Ga vacancy defect surface and Figure 2(b) is Cs on N vacancy defect surface.
(a)
(b)
3. Deficient Surface
Based on the mean of atoms coordinates, the thickness of the first bilayer is calculated; it is 0.0272 nm for Ga vacancy defect surface, whereas it is 0.0436 nm for N vacancy defect surface and 0.0653 nm for intact surface, compared with an ideal value 0.0647 nm. It has the biggest change in surface feature for Ga vacancy defect surface after relaxation. To study the reason for the change of surface feature, the charges of atoms in the outmost layer are shown in Table 1; the overlap populations and bond lengths between Ga and N atoms in the outmost layer of intact, Ga vacancy defect, and N vacancy defect surfaces are shown in Table 2.


The overlap population increases, the bond length decreases, and the covalent bond between Ga and N gains strength for Ga vacancy defect surface as shown in Table 2 caused mainly by the increase of charges of every Ga atom (see Table 1) compared with that of intact surface.
The overlap population decreases, covalent bond is weakened, and bond length between Ga and N increases for N vacancy defect surface as shown in Table 2 caused mainly by the decrease of charges of N and Ga atoms (see Table 1) compared with that of intact surface.
The main reason for the change of surface feature is the break of atoms bonds in the outmost surface layer, there are uncompensated electrons, and dipole moment directing to outside is formed. Compared with the intact surface, the charges of every Ga atom in Ga vacancy defect surface increases, while the total charges of Ga atoms in the outmost layer decrease, so the dipole moment increases. The thickness of the first bilayer is compacted by means of strong dipole moment and covalent bond. There is a preponderance of uncompensated electrons for N vacancy defect surface; the dipole moment is the max, but the change in the first layer thickness is less than that of Ga vacancy defect surface by means of the weak covalent bond.
For semiconductors, the work function is the minimum energy needed by electrons at the bottom of the semiconductor to escape externally. The easier the escape is, the larger dipole moment directing to outside is formed, the lower work function is. The size of the dipole moment among three surfaces is intact surface < Ga vacancy defect surface < N vacancy defect surface. Work functions of three surfaces are 4.20 eV (in agreement with Re.18), 4.054 eV, and 4.052 eV, respectively (shown in Table 3). Calculations show that the defect favors the escape of electrons but can induce bigger change in surface feature.

The charge density difference in the (0001) plane of the surface atoms is shown in Figure 3 to indicate the influence of Ga, N defect on the interaction between atoms visually, in which the bond length is also given. The electron cloud of the N atoms is uniformly distributed in three directions, joining to Ga atoms in the (0001) plane for intact surface, as shown in Figure 3(a). The degree of electron aggregation enlarges after Ga defect (Figure 3(b)), the overlap population increases, the covalent bond of GaN is stronger and the bond length of GaN is shorter than that of intact surface. The overlap population between the Ga and N atoms gets its minimum after N defect (Figure 3(b)); the bond length of GaN increases.
(a)
(b)
(c)
4. Cs Adsorption on GaN(0001) Deficient Surface
To study the effect of defect on the adsorption of Cs on GaN(0001) surface, first, a Cs was placed at H_{3} site on Ga and N vacancy defect surfaces above surface 0.1 nm moving freely in relaxation process and, then, was fixed at five high symmetry sites moving only in direction.
Adsorption energy was calculated as the difference between the total energy of the GaN(0001) slab with adsorbed Cs and the sum of the total energies of the clean surface and isolated Cs atom [25]. The of a Cs at these six sites on Ga vacancy defect surface is shown in Table 3. The results show that is negative no matter Cs is at the five high symmetry sites or moves freely; it means that the absorption process is an exothermic chemical process and is stable. The final convergence position of Cs is above the Ga vacancy when it moves freely on Ga vacancy defect surface. The of every symmetry site decreases compared with that of Cs on intact surface. The most stable adsorption site is T_{1} site (top of Ga vacancy), no longer the B_{N} and H_{3} sites for intact surface [26]; the most unstable adsorption site is T_{4} site. The lack of Ga atom makes the repulsive interaction of Ga to Cs nonexistent and Cs be attracted only by three N atoms, so the stable adsorption site changes compared with that of intact surface. Since the increase of uncomplexed electrons after Ga absence leads to the increasing of dipole moment; work functions of Ga vacancy defect surface with Cs at different high symmetry sites decline slightly compared with that of intact surface.
The is negative no matter a Cs is at the five high symmetry sites or moves freely on N vacancy defect surface (shown in Table 3); it means that the absorption process is also stable. The results show that of every symmetry site decreases compared with that of Cs on intact surface, while it is bigger than that of Cs on Ga vacancy defect surface. B_{Ga} is the most stable adsorption site in agreement with the case when Cs moves freely on N vacancy defect surface; H_{3} is not convergence different from the case of intact surface. Since the increase of uncomplexed electrons after N absence leads to the increasing of dipole moment, work functions of N vacancy defect surface in different high symmetry sites decline slightly compared with that of intact surface.
Comparing the of Cs on Ga and N vacancy defect surfaces, it can be seen that the adsorption of Cs on N vacancy defect surface is more stable than on Ga vacancy defect surface. The lower work function is achieved for Ga and N vacancy defects surfaces than intact surface in agreement with the analysis of dipole moments before.
5. Discussion and Conclusions
The change of surface feature has been compared between GaN(0001) vacancy defect and intact surfaces. Adsorption characteristic and change in work function of a Cs atom on GaN(0001) () vacancy defect surface have been investigated using DFT with a planewave ultrasoft pseudopotential method based on firstprinciples calculations, compared with that of intact surface. Results show that Ga and N vacancy defects may cause contraction of the first bilayer and decrease of surface work function for the increase of dipole moment. The most stable adsorption site is T_{1} site (top of Ga vacancy) for Ga vacancy defect surface, while it is B_{Ga} site for N vacancy defect surface. When the Cs was adsorbed on the vacancy defect surfaces, work functions for different high symmetry sites decline slightly compared with that of intact surface, but increases, this illustrates that the adsorption of Cs on intact surface is more stable.
Conflict of Interests
The authors declare that there is no conflict of interests regarding the publication of this paper.
Acknowledgments
The authors acknowledge supports from the National Natural Science Foundation of China (Grant no. 61171042), the Postdoctoral Research Assistance program of Jiangsu (Grant no. 1301008B), the Shandong Natural Science Foundation (Grant no. ZR2013FM003), the Shandong University Science and Technology Project (J14LJ52) and the Binzhou Science and Technology Development Planning (Grant no. 2013ZC0107).
References
 A. H. Reshak, “Dispersion of the second harmonic generation in GaN_{x} As_{1x}(x = 0.25, 0.5, 0.75) alloys,” Journal of Alloys and Compounds, vol. 589, pp. 213–217, 2014. View at: Google Scholar
 A. H. Reshak, Z. Charifi, and H. Baaziz, “The influence of the lattice relaxation on the optical properties of GaN_{x}As_{1x} alloys,” Solar Energy, vol. 90, pp. 134–143, 2013. View at: Publisher Site  Google Scholar
 H. Baaziz, Z. Charifi, A. H. Reshak, B. Hamad, and Y. AlDouri, “Structural and electronic properties of GaN_{x} As_{1x} alloys,” Applied Physics A, vol. 106, no. 3, pp. 687–696, 2012. View at: Publisher Site  Google Scholar
 A. Hass BarIlan, S. Zamir, O. Katz, B. Meyler, and J. Salzman, “GaN layer growth optimization for high power devices,” Materials Science and Engineering A, vol. 302, no. 1, pp. 14–17, 2001. View at: Publisher Site  Google Scholar
 H. Zhao, G. Liu, and N. Tansu, “Analysis of InGaNdeltaInN quantum wells for lightemitting diodes,” Applied Physics Letters, vol. 97, no. 13, Article ID 131114, 2010. View at: Publisher Site  Google Scholar
 W. W. Chow, “Modeling excitationdependent bandstructure effects on InGaN lightemitting diode efficiency,” Optics Express, vol. 19, no. 22, pp. 21818–21831, 2011. View at: Publisher Site  Google Scholar
 R. M. Farrell, P. S. Hsu, D. A. Haeger et al., “Lowthresholdcurrentdensity AlGaNcladdingfree m plane InGaN/GaN laser diodes,” Applied Physics Letters, vol. 96, no. 23, Article ID 231113, 2010. View at: Publisher Site  Google Scholar
 J. Zhang, H.P. Zhao, and N. Tansu, “Large optical gain AlGaNdeltaGaN quantum wells laser active regions in mid and deepultraviolet spectral regimes,” Applied Physics Letters, vol. 98, no. 17, Article ID 171111, 2011. View at: Publisher Site  Google Scholar
 X. H. Wang, B. K. Chang, Y. J. Du, and J. L. Qiao, “Quantum efficiency of GaN photocathode under different illumination,” Applied Physics Letters, vol. 99, no. 4, Article ID 042102, 2011. View at: Publisher Site  Google Scholar
 X. H. Wang, B. K. Chang, L. Ren, and P. Gao, “Influence of the ptype doping concentration on reflectionmode GaN photocathode,” Applied Physics Letters, vol. 98, no. 8, Article ID 082109, 2011. View at: Publisher Site  Google Scholar
 D. Kapolnek, S. Keller, R. Vetury et al., “Anisotropic epitaxial lateral growth in GaN selective area epitaxy,” Applied Physics Letters, vol. 71, no. 9, pp. 1204–1206, 1997. View at: Publisher Site  Google Scholar
 M. S. Brandt, P. Herbst, H. Angerer, O. Ambacher, and M. Stutzmann, “Thermopower investigation of n and ptype GaN,” Physical Review B, vol. 58, no. 12, pp. 7786–7791, 1998. View at: Publisher Site  Google Scholar
 K. Motohashi, K. Hosoya, M. Imano, S. Tsurubuchi, and A. Koukitu, “Analyses of GaN (0 0 0 1) and $(\text{000}\stackrel{}{1})$ surfaces by highlycharged ions,” Surface Science, vol. 601, no. 22, pp. 5304–5308, 2007. View at: Publisher Site  Google Scholar
 Y. Du, B. Chang, X. Fu, X. Wang, and M. Wang, “Electronic structure and optical properties of zincblende GaN,” Optik, vol. 123, no. 24, pp. 2208–2212, 2012. View at: Publisher Site  Google Scholar
 V. Timon, S. Brand, S. J. Clark, M. C. Gibson, and R. A. Abram, “Firstprinciples calculations of $2\times 2$ reconstructions of GaN(0001) surfaces involving N, Al, Ga, In, and As atoms,” Physical Review B: Condensed Matter and Materials Physics, vol. 72, no. 3, Article ID 035327, 2005. View at: Publisher Site  Google Scholar
 S. Nakamura and G. Fasol, The Blue Laser Diode, Springer, Berlin, Germany, 1997.
 A. L. Rosa and J. Neugebauer, “Firstprinciples calculations of the structural and electronic properties of clean GaN (0001) surfaces,” Physical Review B. Condensed Matter and Materials Physics, vol. 73, no. 20, Article ID 205346, 2006. View at: Publisher Site  Google Scholar
 A. N. Hattori, K. Endo, K. Hattori, and H. Daimon, “Surface treatments toward obtaining clean GaN(0 0 0 1) from commercial hydride vapor phase epitaxy and metalorganic chemical vapor deposition substrates in ultrahigh vacuum,” Applied Surface Science, vol. 256, no. 14, pp. 4745–4756, 2010. View at: Publisher Site  Google Scholar
 K. Rapcewicz, M. B. Nardelli, and J. Bernholc, “Theory of surface morphology of wurtzite GaN (0001) surfaces,” Physical Review B. Condensed Matter and Materials Physics, vol. 56, no. 20, Article ID R12725, 1997. View at: Publisher Site  Google Scholar
 R. M. Feenstra, J. E. Northrup, and J. Neugebauer, “Review of structure of bare and adsorbatecovered GaN(0001) surfaces,” MRS Internet Journal of Nitride Semiconductor Research, vol. 7, pp. 1–27, 2002. View at: Google Scholar
 Y. Du, B. Chang, J. Zhang, B. Li, and X. Wang, “Firstprinciples study of the electronic structure and optical properties of GaN(0001) surface,” Acta Physica Sinica, vol. 61, no. 6, Article ID 067101, 2012 (Chinese). View at: Google Scholar
 A. A. Pakhnevich, V. V. Bakin, A. V. Yaz'kov et al., “Energy distributions of photoelectrons emitted from pGaN(Cs, O) with effective negative electron affinity,” JETP Letters, vol. 79, no. 10, pp. 479–483, 2004. View at: Publisher Site  Google Scholar
 F. Machuca, Z. Liu, J. R. Maldonado, S. T. Coyle, P. Pianetta, and R. F. W. Pease, “Negative electron affinity group IIInitride photocathode demonstrated as a high performance electron source,” Journal of Vacuum Science and Technology B: Microelectronics and Nanometer Structures, vol. 22, no. 6, pp. 3565–3569, 2004. View at: Publisher Site  Google Scholar
 J. Qiao, S. Tian, B. K. Chang, X. Du, and P. Gao, “Progress in study of negative electron affinity GaN vacuum surface electron source,” Chinese Physical Society, vol. 58, article 5847, 2009 (Chinese). View at: Google Scholar
 X. Du, B. Chang, Y. Qian, R. Fu, P. Gao, and J. Qiao, “Activation technique of GaN negative electron affinity photocathode,” Chinese Journal of Lasers, vol. 37, no. 2, pp. 385–388, 2010. View at: Publisher Site  Google Scholar
 Y. Du, B. Chang, X. Wang, J. Zhang, B. Li, and M. Wang, “Theoretical study of Cs adsorption on GaN(0 0 0 1) surface,” Applied Surface Science, vol. 258, no. 19, pp. 7425–7429, 2012. View at: Publisher Site  Google Scholar
 Y. Shen and J. Kang, “Ab initio calculation of the electronic structure of carbon and oxygen impurities in GaN,” Acta Physica Sinica, vol. 51, no. 3, article 645, 2002 (Chinese). View at: Google Scholar
 C. Pang, J. Shi, Y. Zhang et al., “Electronic structures of wurtzite GaN with Ga and N vacancies,” Chinese Physics Letters, vol. 24, no. 7, pp. 2048–2051, 2007. View at: Publisher Site  Google Scholar
 W. W. Jie and C. Yang, “The electronic structures of vacancy defects in hexagonal GaN,” Journal of Sichuan Normal University (Natural Science), vol. 33, article 803, 2010 (Chinese). View at: Google Scholar
 Y. Du, B. Chang, H. Wang, J. Zhang, and M. Wang, “First principle study of the influence of vacancy defects on optical properties of GaN,” Chinese Optics Letters, vol. 10, no. 5, Article ID 051601, 2012. View at: Publisher Site  Google Scholar
 P. Perlin, C. JauberthieCarillon, J. P. Itie, A. San Miguel, I. Grzegory, and A. Polian, “Raman scattering and xrayabsorption spectroscopy in gallium nitride under high pressure,” Physical Review B, vol. 45, no. 1, pp. 83–89, 1992. View at: Publisher Site  Google Scholar
 M. D. Segall, P. J. D. Lindan, M. J. Probert et al., “Firstprinciples simulation: ideas, illustrations and the CASTEP code,” Journal of Physics Condensed Matter, vol. 14, no. 11, pp. 2717–2744, 2002. View at: Publisher Site  Google Scholar
 J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized gradient approximation made simple,” Physical Review Letters, vol. 77, no. 18, pp. 3865–3868, 1996. View at: Publisher Site  Google Scholar
 C. Hu, Y. Chen, J. Li, and Y. Zhang, “Firstprinciples calculations of ethanethiol adsorption and decomposition on GaN (0 0 0 1) surface,” Applied Surface Science, vol. 254, no. 20, pp. 6514–6520, 2008. View at: Publisher Site  Google Scholar
 Q. Sun, A. Selloni, T. H. Myers, and W. A. Doolittle, “Oxygen adsorption and incorporation at irradiated GaN(0001) and GaN(000 1̄) surfaces: firstprinciples densityfunctional calculations,” Physical Review B. Condensed Matter and Materials Physics, vol. 74, no. 19, Article ID 195317, 2006. View at: Publisher Site  Google Scholar
Copyright
Copyright © 2014 Yanjun Ji et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.