Share This Article:

First Principles Study of the Structural and Electronic Properties of the ZnO/Cu2O Heterojunction

Abstract Full-Text HTML XML Download Download as PDF (Size:2755KB) PP. 661-675
DOI: 10.4236/msa.2015.67068    3,371 Downloads   4,409 Views   Citations


Many materials have been used in nanostructured devices; the goal of attaining high-efficiency thin-film solar cells in such a way has yet to be achieved. Heterojunctions based on ZnO/Cu2O oxides have recently emerged as promising materials for high-efficiency nanostructured devices. In this work, we are interested in the characterization of the surface and interface through nano-scale modeling based on ab initio (Density Functional Theory (DFT), Local Density Approximation (LDA), Generalized Gradient Approximation (GGA-PBE), and Pseudopotential (PP)). This study aims also to build a supercell containing a ZnO/Cu2O heterojunction and study the structural properties and the discontinuity of the valence band (band offset) from a semiconductor to an-other. We investigate crystal terminations of ZnO (0001) and Cu2O (0001). We calculate the energies of the polar surfaces and the work function in the c-axis for both oxides. We built a zinc oxide layer in the wurtzite structure along the [0001] direction, on which we placed a copper oxide layer in the hexagonal structure (CdI2-type). We choose the method of Van de Walle and Martin to calcu-late the energy offset. This approach fits well with the DFT. Our calculations give us a value that corresponds to other experimental and theoretical values.

Conflicts of Interest

The authors declare no conflicts of interest.

Cite this paper

Zemzemi, M. and Alaya, S. (2015) First Principles Study of the Structural and Electronic Properties of the ZnO/Cu2O Heterojunction. Materials Sciences and Applications, 6, 661-675. doi: 10.4236/msa.2015.67068.


[1] O’Regan, B. and Grätzel, M. (1991) A Low-Cost, High-Efficiency Solar Cell Based on Dye-Sensitized Colloidal TiO2 Films. Nature, 353,737-740.
[2] Graetzel, M., Janssen, R.A., Mitzi, D.B. and Sargent, E.H. (2012) Materials Interface Engineering for Solution-Processed Photovoltaics. Nature, 488, 304-312.
[3] Parida, B., Iniyan, S. and Goic, R. (2011) A Review of Solar Photovoltaic Technologies. Renewable and Sustainable Energy Reviews, 15, 1625-1636.
[4] Shevaleevskiy, O. (2008) The Future of Solar Photovoltaics, a New Challenge for Chemical Physics. Pure and Applied Chemistry, 80, 2079-2089.
[5] Zunger, A., Wagner, S. and Petroff, P. (1993) New Materials and Structures for Photovoltaics. Journal of Electronic Materials, 22, 3-16.
[6] Surek, T. (2005) Crystal Growth and Materials Research in Photovoltaics, Progress and Challenges. Journal of Crystal Growth, 275, 292-304.
[7] Loferski, J.J. (1956) Theoretical Considerations Governing the Choice of the Optimum Semiconductor for Photovoltaic Solar Energy Conversion. Journal of Applied Physics, 27, 777-784.
[8] Nickel, N.H. and Terukov, E. (2005) Zinc Oxide—A Material for Micro- and Optoelectronic Applications. Springer, Berlin.
[9] Zemzemi, M. and Alaya, S. (2014) Structural, Electronic, and Fermi Surface Evolution in Zinc Oxide under High Pressure. Journal of Optoelectronics and Advanced Materials, 16, 471-475.
[10] Look, D.C. (2001) Recent Advances in ZnO Materials and Devices. Materials Science and Engineering: B, 80, 383-387.
[11] Özgür, ü., Alivov, Y.I., Liu, C., Teke, A., Reshchikov, M.A., Dogan, S., Avrutin, V., Cho, S.J. and Morkoç, H. (2005) A Comprehensive Review of ZnO Materials and Devices. Journal of Applied Physics, 98, Article ID: 041301.
[12] Rai, B.P. (1998) Cu2O Solar Cells: A Review. Solar Cells, 25, 265-272.
[13] Briskman, R.N. (1992) A Study of Electrodeposited Cuprous Oxide Photovoltaic Cells. Solar Energy Materials and Solar Cells, 27, 361-368.
[14] Herion, J., Niekisch, E.A. and Scharl, G. (1980) Investigation of Metal Oxide/Cuprous Oxide Heterojunction Solar Cells. Solar Energy Materials, 4, 101-112.
[15] Zemzemi, M., Alaya, S. and Ben Ayadi, Z. (2014) Ab Initio Study of Heterojunction Discontinuities in the ZnO/Cu2O System. Journal of Experimental and Theoretical Physics, 118, 945-950.
[16] Minami, T., Nishi, Y., Miyata, T. and Nomoto, J. (2011) High-Efficiency Oxide Solar Cells with ZnO/Cu2O Heterojunction Fabricated on Thermally Oxidized Cu2O Sheets. Applied Physics Express, 4, Article ID: 062301.
[17] Kramm, B., Laufer, A., Reppin, D., Kronenberger, A., Hering, P., Polity, A. and Meyer, B.K. (2012) The Band Alignment of Cu2O/ZnO and Cu2O/GaN Heterostructures. Applied Physics Letters, 100, Article ID: 094102.
[18] Jeong, S.S., Mittiga, A., Salza, E., Masci, A. and Passerini, S. (2008) Electrodeposited ZnO/Cu2O Heterojunction Solar Cells. Electrochimica Acta, 53, 2226-2231.
[19] Ichimura, M. and Song, Y. (2011) Band Alignment at the Cu2O/ZnO Heterojunction. Japanese Journal of Applied Physics, 50, Article ID: 051002.
[20] Noda, S., Shima, H. and Akinaga, H. (2013) Cu2O/ZnO Heterojunction Solar Cells Fabricated by Magnetron-Sputter Deposition Method Films Using Sintered Ceramics Targets. Journal of Physics: Conference Series, 433, Article ID: 012027.
[21] Akimoto, K., Ishizuka, S., Yanagita, M., Nawa, N., Paul, G.K. and Sakurai, T. (2006) Thin Film Deposition of Cu2O and Application for Solar Cells. Solar Energy, 80, 715-722.
[22] Ozawa, K., Oba, Y. and Adamoto, K. (2009) Formation and Characterization of the Cu2O Overlayer on Zn-Terminated ZnO (0001). Surface Science, 603, 2163-2170.
[23] Machon, D., Sinitsyn, V.V., Dmitriev, V.P., Bdikin, I.K., Dubrovinsky, L., Kuleshov, I.V., Ponyatovsky, G. and Weber, H.P. (2003) Structural Transitions in Cu2O at Pressures up to 11 GPa. Journal of Physics: Condensed Matter, 15, 7227-7235.
[24] Bechstedt, F. (2003) Principles of Surface Physics. Springer-Verlag, Berlin.
[25] Holec, D. and Mayrhofer, P.H. (2012) Surface Energies of AlN Allotropes from First Principles. Scripta Materialia, 67, 760-762.
[26] Meyer, B. and Marx, D. (2003) Density Functional Study of the Structure and Stability of ZnO Surfaces. Physical Review B, 67, Article ID: 035403.
[27] Soon, A., Sohnel, T. and Idriss, H. (2005) Plane-Wave Pseudopotential Density Functional Theory Periodic Slab Calculations of CO Adsorption on Cu2O (111) Surface. Surface Science, 579, 131-140.
[28] Duan, Y., Zhang, K.M. and Xie, X.D. (1994) Theoretical Studies of CO and NO on CuO and Cu2O (110) Surfaces. Surface Science, 321, 249-254.
[29] Bredow, T. and Pacchioni, G. (1997) Comparative Periodic and Cluster Ab Initio Study on Cu2O (111)/CO. Surface Science, 373, 21-32.
[30] Yang, Y., Schlepütz, C.M., Bellucci, F., Allen, M.W., Durbin, S.M. and Clarke, R. (2013) Structural Investigation of ZnO-Polar (000-1) Surfaces and Schottky Interfacs. Surface Science, 610, 22-26.
[31] Schulz, K.H. and Cox, D.F. (1991) Photoemission and Low-Energy-Electron-Diffraction Study of Clean and Oxygen-Dosed Cu2O (111) and (100) Surfaces. Physical Review B, 43, 1610-1621.
[32] Soltys, J., Piechota, J., Lopuszyński, M. and Krukowski, S. (2013) Density Functional Theory (DFT) Study of Zn, O2 and O Adsorption on Polar ZnO (0001) and ZnO (000-1) Surfaces. Journal of Crystal Growth, 374, 53-59.
[33] Islam, M.M., Diawara, B., Maurice, V. and Marcus, P. (2009) First Principles Investigation on the Stabilization Mechanisms of the Polar Copper Terminated Cu2O (1 1 1) Surface. Surface Science, 603, 2087-2095.
[34] Cortona, P. and Mebarki, M. (2011) Cu2O Behavior under Pressure, an Ab Initio Study. Journal of Physics: Condensed Matter, 23, Article ID: 045502.
[35] Bernardini, F. and Fiorentini, V. (1998) Macroscopic Polarization and Band Offsets at Nitride Heterojunctions. Physical Review B, 57, 9427-9430.
[36] Wei, S.-H. and Zunger, A. (1998) Calculated Natural Band Offsets of All II-VI and III-V Semiconductors, Chemical Trends and the Role of Cation d Orbitals. Applied Physics Letters, 72, 2011.
[37] Franciosi, A. and Van de Walle, C.G. (1996) Heterojunction Band Offset Engineering. Surface Science Reports, 25, 1-140.
[38] Wilk, G.D., Wallace, R.M. and Anthony, J.M. (2001) High-κ Gate Dielectrics, Current Status and Materials Properties Considerations. Journal of Applied Physics, 89, 5243.
[39] Morteani, A.C., Sreearunothai, P., Hertz, L.M., Friend, R.H. and Silva, C. (2004) Exciton Regeneration at Polymeric Semiconductor Heterojunctions. Physical Review Letters, 92, Article ID: 247402.
[40] Li, J. and Wang, L. (2004) Deformation Potentials of CdSe Quantum Dots. Applied Physics Letters, 85, 2929.
[41] Zhang, S.B., Wei, S.H. and Zunger, A. (2000) Microscopic Origin of the Phenomenological Equilibrium “Doping Limit Rule” in N-Type III-V Semiconductors. Physical Review Letters, 84, 1232.
[42] Kavan, L., Graetzel, M., Gilbert, S.E., Klemenz, C. and Scheel, H.J. (1996) Electrochemical and Photoelectrochemical Investigation of Single-Crystal Anatase. Journal of the American Chemical Society, 118, 6716-6723.
[43] Shaltaf, R., Rignanese, G.M., Gonze, X., Giustino, F. and Pasquarello, A. (2008) Band Offsets at the Si/SiO2 Interface from Many-Body Perturbation Theory. Physical Review Letters, 100, Article ID: 186401.
[44] Tersoff, J. (1984) Theory of Semiconductor Heterojunctions, The Role of Quantum Dipoles. Physical Review B, 30, 4874-4877.
[45] Cordona, M. and Christensen, N.E. (1987) Acoustic Deformation Potentials and Heterostructure Band Offsets in Semiconductors. Physical Review B, 35, 6182-6194.
[46] Hybertsen, M.S. (1990) Role of Interface Strain in a Lattice-Matched Heterostructure. Physical Review Letters, 64, 555-558.
[47] Van de Walle, C.G. and Martin, R.M. (1986) Theoretical Calculations of Heterojunction Discontinuities in the Si/Ge System. Physical Review B, 34, 5621-5634.
[48] Wong, L.M., Chiam, S.Y., Huang, J.Q., Wang, S.J., Pan, J.S. and Chim, W.K. (2010) Growth of Cu2O on Ga-Doped ZnO and Their Interface Energy Alignment for Thin Film Solar Cells. Journal of Applied Physics, 108, Article ID: 033702.
[49] Hohenberg, P. and Kohn, W. (1964) Inhomogeneous Electron Gas. Physical Review, 136, B864.
[50] Kohn, W. and Sham, L.J. (1965) Quantum Density Oscillations in an Inhomogeneous Electron Gas. Physical Review, 140, A1133-A1138.
[51] Sharia, O., Demkov, A.A., Bersuker, G. and Lee, B.H. (2007) Theoretical Study of the Insulator/Insulator Interface, Band Alignment at the SiO2/HfO2 Junction. Physical Review B, 75, Article ID: 035306.
[52] 52Gonze, X., Beuken, J.-M., Caracas, R., Detraux, F., Fuchs, M., Rignanese, G.-M., et al. (2002) First-Principles Computation of Material Properties: The ABINIT Software Project. Computational Materials Science, 25, 478-492. http,//
[53] Gonze, X., Amadon, B., Anglade, P.-M., Beuken, J.-M., Bottin, F., Boulanger, P., et al. (2009) ABINIT: First-Principles Approach to Material and Nanosystem Properties. Computer Physics Communications, 180, 2582-2615.
[54] Troullier, N. and Martins, J.L. (1991) Efficient Pseudopotentials for Plane-Wave Calculations. Physical Review B, 43, 1993-2006.
[55] Fuchs, M. and Scheffler, M. (1999) Ab Initio Pseudopotentials for Electronic Structure Calculations of Poly-Atomic Systems Using Density-Functional Theory. Computer Physics Communications, 119, 67-98.
[56] Perdew, J.P. and Wang, Y. (1992) Accurate and Simple Analytic Representation of the Electron-Gas Correlation Energy. Physical Review B, 45, 13244-13249.
[57] Ceperley, D.M. and Alder, B.J. (1980) Ground State of the Electron Gas by a Stochastic Method. Physical Review Letters, 45, 566-569.
[58] Perdew, J.P., Burke, K. and Ernzerhof, M. (1996) Generalized Gradient Approximation Made Simple. Physical Review Letters, 77, 3865-3868.
[59] Monkhorst, H.J. and Pack, J.D. (1976) Special Points for Brillouin-Zone Integrations. Physical Review B, 13, 5188-5192.
[60] Jeong, S.H. and Aydil, E.S. (2009) Heteroepitaxial Growth of Cu2O Thin Film on ZnO by Metal Organic Chemical Vapor Deposition. Journal of Crystal Growth, 311, 4188-4192.
[61] Fariza, B.M., Sasano, J., Shinagawa, T., Watase, S. and Izaki, M. (2012) Light-Assisted Electrochemical Construction of (111)Cu2O/(0001)ZnO Heterojunction. Thin Solid Films, 520, 2261-2264.
[62] Yang, M.J., Zhu, L.P., Li, Y.G., Cao, L. and Guo, Y.M. (2013) Asymmetric Interface Band Alignments of Cu2O/ZnO and ZnO/Cu2O Heterojunctions. Journal of Alloys and Compounds, 578, 143-147.
[63] Akimoto, K., Ishizuka, S., Yanagita, M., Nawa, N., Paul, G.K. and Sakurai, T. (2000) Thin Film Deposition of Cu2O and Application for Solar Cells. Solar Energy, 80, 715-722.
[64] Pearson, W.B. (1958) Handbook of Lattice Spacings and Structures of Metals and Alloys. Pergamon Press, Belfast.
[65] Zemzemi, M., ElGhoul, N., Khirouni, K. and Alaya, S. (2014) First-Principle Study of the Structural, Electronic, and Thermodynamic Properties of Cuprous Oxide under Pressure. Journal of Experimental and Theoretical Physics, 118, 235-241.
[66] Werner, A. and Hochheimer, H.D. (1982) High Pressure X-Ray Study of Cu2O and Ag2O. Physical Review B, 25, 5929-5934.
[67] Onsten, A., Mansson, M., Muro, T., Matsushita, T., Nakamura, T., Kinoshita, T., Karlsson, O.U. and Tjernberg, O. (2009) Probing the Valence Band Structure of Cu2O Using High-Energy Angle-Resolved Photoelectron Spectroscopy. Physical Review B, 76, 115-127.
[68] Cox, D. and Schulz, K.H. (1991) H2O Adsorption on Cu2O (100). Surface Science, 256, 67-76.
[69] Soon, A., Todorova, M., Delly, B. and Stampfl, C. (2006) Oxygen Adsorption and Stability of Surface Oxides on Cu (111): A First-Principles Investigation. Physical Review B, 73, Article ID: 165424.
[70] Altarawneh, M., Radney, M., Smith, P.V., Mackie, J.C., Kennedy, E.M., Dlugogorski, B.Z., Soon, A. and Stampfl, C. (2009) A First-Principles Density Functional Study of Chlorophenol Adsorption on Cu2O (110), CuO. The Journal of Chemical Physics, 130, Article ID: 184505.
[71] Kuo, F.L., Li, Y., Solomon, M., Du, J. and Shepherd, N.D. (2012) Workfunction Tuning of Zinc Oxide Films by Argon Sputtering and Oxygen Plasma: An Experimental and Computational Study. Journal of Physics D: Applied Physics, 45, Article ID: 065301.
[72] Kim, T., Yoshitake, M., Yagyu, S., Nemsák, S., Nagata, T. and Chikyow, T. (2010) XPS Study on Band Alignment at Pt-O-Terminated ZnO (000-1) Interface. Surface and Interface Analysis, 42, 1528-1531.
[73] Jacobi, K., Zwicker, G. and Gutmann, A. (1984) Work Function, Electron Affinity and Band Bending of Zinc Oxide Surfaces. Surface Science, 141, 109-125.
[74] Schlesinger, R., Xu, Y., Hofmann, O.T., Winkler, S., Frisch, J., Niederhausen, J., Vollmer, A., Blumstengel, S., Henneberger, F., Rinke, P., Scheffler, M. and Koch, N. (2013) Controlling the Work Function of ZnO and the Energy-Level Alignment at the Interface to Organic Semiconductors with a Molecular Electron Acceptor. Physical Review B, 87, Article ID: 155311.
[75] Marien, J. (1976) Field Emission Study of the Specificity of Zinc Oxide Polar Surfaces (0001) and (0001). Work Function and Hydrogen Adsorption. Physica Status Solidi (a), 38, 513-522.
[76] Wander, A., Schedin, F., Steadman, P., Norris, A., McGrath, R., Turner, T.S., Thornton, G. and Harrison, N.M. (2001) Stability of Polar Oxide Surfaces. Physical Review Letters, 86, 3811-3814.
[77] Na, S.-H. and Park, C.-H. (2010) First-Principles Study of the Surface Energy and Atom Cohesion of Wurtzite ZnO and ZnS-Implications for Nanostructure Formation. Journal of the Korean Physical Society, 56, 498-502.
[78] Soon, A., Todorova, M., Delly, B. and Stampfl, C. (2007) Thermodynamic Stability and Structure of Copper Oxide Surfaces: A First-Principles Investigation. Physical Review B, 75, Article ID: 125420.
[79] Yang, W.Y. and Rhee, S.W. (2007) Effect of Electrode Material on the Resistance Switching of Cu2O Film. Applied Physics Letters, 91, Article ID: 232907.
[80] Soon, A., Sohnel, T. and Idriss, H. (2005) Plane-Wave Pseudopotential Density Functional Theory Periodic Slab Calculations of CO Adsorption on Cu2O (111) Surface. Surface Science, 579, 131-140.
[81] Heimel, G., Romaner, L., Bredas, J.L. and Zojer, E. (2006) Interface Energetics and Level Alignment at Covalent Metal-Molecule Junctions: Π-Conjugated Thiols on Gold. Physical Review Letters, 96, Article ID: 196806.
[82] Lang, N.D. and Kohn, W. (1971) Theory of Metal Surfaces: Work Function. Physical Review B, 3, 1215-1223.
[83] Feibelman, P.J. and Hamann, D.R. (1984) Quantum-Size Effects in Work Functions of Free-Standing and Adsorbed Thin Metal Films. Physical Review B, 29, 6463-6467.
[84] Ciraci, S. and Batra, I.P. (1986) Theory of the Quantum Size Effect in Simple Metals. Physical Review B, 33, 4294-4297.
[85] Fall, C., Binggeli, N. and Baldereschi, A. (1999) Deriving Accurate Work Functions from Thin-Slab Calculations. Journal of Physics: Condensed Matter, 11, 2689-2696.
[86] Desgreniers, S. (1998) High-Density Phases of ZnO: Structural and Compressive Parameters. Physical Review B, 58, 14102-14105.
[87] Zhang, D.K., Liu, Y.C., Liu, Y.L. and Yang, H. (2004) The Electrical Properties and the Interfaces of Cu2O/ZnO/ITO p-i-n Heterojunction. Physica B, 351, 178-183.
[88] Murnaghan, F. (1944) The Compressibility of Media under Extreme Pressures. Proceedings of the National Academy of Sciences of the United States of America, 30, 244-247.
[89] Hebbache, M. and Zemzemi, M. (2004) Ab Initio Study of High-Pressure Behavior of a Low Compressibility Metal and a Hard Material, Osmium and Diamond. Physical Review B, 70, Article ID: 224107.
[90] Lee, H. and Martin, R.M. (1997) Applications of the Generalized-Gradient Approximation to Atoms, Clusters, and Solids. Physical Review B, 56, 7197-7205.
[91] Gillen, R. and Robertson, J. (2013) Accurate Screened Exchange Band Structures for the Transition Metal Monoxides MnO, FeO, CoO and NiO. Journal of Physics: Condensed Matter, 25, Article ID: 165502.
[92] Kümmel, S. and Kronik, L. (2008) Orbital-Dependent Density Functionals: Theory and Applications. Reviews of Modern Physics, 80, 3-60.

comments powered by Disqus

Copyright © 2019 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.