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A Comprehensive Review of Zno Materials and Devices Ü Virginia Commonwealth University VCU Scholars Compass Electrical and Computer Engineering Publications Dept. of Electrical and Computer Engineering 2005 A comprehensive review of ZnO materials and devices Ü. Özgür Virginia Commonwealth University, [email protected] Ya. I. Alivov Virginia Commonwealth University C. Liu Virginia Commonwealth University See next page for additional authors Follow this and additional works at: http://scholarscompass.vcu.edu/egre_pubs Part of the Electrical and Computer Engineering Commons Ozgur, U., Alivov, Y. I., Liu, C., et al. A comprehensive review of ZnO materials and devices. Journal of Applied Physics 98, 041301 (2005). Copyright © 2005 AIP Publishing LLC. Downloaded from http://scholarscompass.vcu.edu/egre_pubs/174 This Article is brought to you for free and open access by the Dept. of Electrical and Computer Engineering at VCU Scholars Compass. It has been accepted for inclusion in Electrical and Computer Engineering Publications by an authorized administrator of VCU Scholars Compass. For more information, please contact [email protected]. Authors Ü. Özgür, Ya. I. Alivov, C. Liu, A. Teke, M. A. Reshchikov, S. Doğan, Vitaliy Avrutin, S.-J. Cho, and H. Morkoç This article is available at VCU Scholars Compass: http://scholarscompass.vcu.edu/egre_pubs/174 JOURNAL OF APPLIED PHYSICS 98, 041301 ͑2005͒ APPLIED PHYSICS REVIEWS A comprehensive review of ZnO materials and devices ͒ ͒ ͒ Ü. Özgür,a Ya. I. Alivov, C. Liu, A. Teke,b M. A. Reshchikov, S. Doğan,c V. Avrutin, ͒ S.-J. Cho, and H. Morkoçd Department of Electrical Engineering and Physics Department, Virginia Commonwealth University, Richmond, Virginia 23284-3072 ͑Received 2 February 2005; accepted 13 June 2005; published online 30 August 2005͒ The semiconductor ZnO has gained substantial interest in the research community in part because of its large exciton binding energy ͑60 meV͒ which could lead to lasing action based on exciton recombination even above room temperature. Even though research focusing on ZnO goes back many decades, the renewed interest is fueled by availability of high-quality substrates and reports of p-type conduction and ferromagnetic behavior when doped with transitions metals, both of which remain controversial. It is this renewed interest in ZnO which forms the basis of this review. As mentioned already, ZnO is not new to the semiconductor field, with studies of its lattice parameter dating back to 1935 by Bunn ͓Proc. Phys. Soc. London 47, 836 ͑1935͔͒, studies of its vibrational properties with Raman scattering in 1966 by Damen et al. ͓Phys. Rev. 142, 570 ͑1966͔͒, detailed optical studies in 1954 by Mollwo ͓Z. Angew. Phys. 6, 257 ͑1954͔͒, and its growth by chemical-vapor transport in 1970 by Galli and Coker ͓Appl. Phys. Lett. 16, 439 ͑1970͔͒. In terms of devices, Au Schottky barriers in 1965 by Mead ͓Phys. Lett. 18, 218 ͑1965͔͒, demonstration of ͑ ͒ ͓ ͑ ͔͒ light-emitting diodes 1967 by Drapak Semiconductors 2, 624 1968 , in which Cu2O was used as the p-type material, metal-insulator-semiconductor structures ͑1974͒ by Minami et al. ͓Jpn. J. Appl. Phys. 13, 1475 ͑1974͔͒, ZnO/ZnSe n-p junctions ͑1975͒ by Tsurkan et al. ͓Semiconductors 6, 1183 ͑1975͔͒, and Al/Au Ohmic contacts by Brillson ͓J. Vac. Sci. Technol. 15, 1378 ͑1978͔͒ were attained. The main obstacle to the development of ZnO has been the lack of reproducible and low-resistivity p-type ZnO, as recently discussed by Look and Claflin ͓Phys. Status Solidi B 241, 624 ͑2004͔͒. While ZnO already has many industrial applications owing to its piezoelectric properties and band gap in the near ultraviolet, its applications to optoelectronic devices has not yet materialized due chiefly to the lack of p-type epitaxial layers. Very high quality what used to be called whiskers and platelets, the nomenclature for which gave way to nanostructures of late, have been prepared early on and used to deduce much of the principal properties of this material, particularly in terms of optical processes. The suggestion of attainment of p-type conductivity in the last few years has rekindled the long-time, albeit dormant, fervor of exploiting this material for optoelectronic applications. The attraction can simply be attributed to the large exciton binding energy of 60 meV of ZnO potentially paving the way for efficient room-temperature exciton-based emitters, and sharp transitions facilitating very low threshold semiconductor lasers. The field is also fueled by theoretical predictions and perhaps experimental confirmation of ferromagnetism at room temperature for potential spintronics applications. This review gives an in-depth discussion of the mechanical, chemical, electrical, and optical properties of ZnO in addition to the technological issues such as growth, defects, p-type doping, band-gap engineering, devices, and nanostructures. © 2005 American Institute of Physics. ͓DOI: 10.1063/1.1992666͔ TABLE OF CONTENTS A. Crystal structures....................... 3 B. Lattice parameters....................... 6 C. Electronic band structure................. 7 I. INTRODUCTION............................ 2 D. Mechanical properties.................... 12 II. PROPERTIES OF ZnO....................... 3 E. Lattice dynamics........................ 15 F. Thermal properties...................... 18 ͒ a Electronic mail: [email protected] 1. Thermal-expansion coefficients.......... 18 ͒ b Present address: Balikesir University, Faculty of Art and Science, Depart- 2. Thermal conductivity.................. 19 ment of Physics, 10100 Balikesir, Turkey. c͒ 3. Specific heat......................... 21 Present address: Atatürk University, Faculty of Art and Science, Depart- ....... ment of Physics, 25240 Erzurum, Turkey. G. Electrical properties of undoped ZnO 22 ͒ d Electronic mail: [email protected] 1. Low-field transport................... 23 0021-8979/2005/98͑4͒/041301/103/$22.5098, 041301-1 © 2005 American Institute of Physics [This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP: 128.172.48.58 On: Mon, 19 Oct 2015 20:45:44 041301-2 Ozgur et al. J. Appl. Phys. 98, 041301 ͑2005͒ 2. High-field transport................... 25 I. INTRODUCTION III. ZnO GROWTH............................. 26 There has been a great deal of interest in zinc oxide ........................... A. Bulk growth 26 ͑ZnO͒ semiconductor materials lately, as seen from a surge ............................. B. Substrates 28 of a relevant number of publications. The interest in ZnO is .................. C. rf magnetron sputtering 29 fueled and fanned by its prospects in optoelectronics appli- .................. D. Molecular-beam epitaxy 30 cations owing to its direct wide band gap ͑E ϳ3.3 eV at ................... g E. Pulsed-laser deposition 34 300 K͒. Some optoelectronic applications of ZnO overlap F. Chemical-vapor deposition................ 36 ͑ with that of GaN, another wide-gap semiconductor Eg IV. OPTICAL PROPERTIES OF ZnO.............. 39 ϳ3.4 eV at 300 K͒ which is widely used for production of ............................... A. Prelude 39 green, blue-ultraviolet, and white light-emitting devices. ................ B. Optical transitions in ZnO 39 However, ZnO has some advantages over GaN among which ............ 1. Free excitons and polaritons 39 are the availability of fairly high-quality ZnO bulk single ...................... 2. Bound excitons 42 crystals and a large exciton binding energy ͑ϳ60 meV͒. ZnO 3. Two-electron satellites in PL............ 44 also has much simpler crystal-growth technology, resulting 4. DAP and LO-phonon replicas in PL...... 45 in a potentially lower cost for ZnO-based devices. 5. Temperature-dependent PL measurements. 45 As indicated in the abstract, ZnO is not really a newly C. Time-resolved PL on ZnO................ 47 discovered material. Research on ZnO has continued for D. Refractive index of ZnO................. 48 many decades with interest following a roller-coaster pattern. E. Stimulated emission in ZnO............... 51 Interest in this material at the time of this writing is again at 1. Thin films........................... 51 a high point. In terms of its characterization, reports go back 2. Polycrystalline ZnO films and “random to 1935 or even earlier. For example, lattice parameters of lasers”.............................. 54 1–9 ZnO were investigated for many decades. Similarly, opti- 3. Multiple-quantum wells................ 56 cal properties and processes in ZnO as well as its refractive 4. Stimulated-emission dynamics.......... 56 10–25 index were extensively studied many decades ago. Vi- V. DEFECTS IN ZnO........................... 57 brational properties by techniques such as Raman scattering A. Predictions from first principles............ 57 26–32 were also determined early on. Investigations of ZnO B. Experimental studies of native and properties presumes that ZnO samples were available. unintentionally introduced defects.......... 58 Growth methods not much different from what is employed 1. Shallow acceptor in ZnO............... 58 lately have been explored, among which are chemical-vapor 2. Green luminescence band.............. 59 33 34 35 transport, vapor-phase growth, hydrothermal growth 3. Yellow luminescence band............. 61 which also had the additional motivation of doping with Li 4. Red luminescence band................ 62 36 in an effort to obtain p-type material, high-quality platelets, VI. DOPING OF ZnO.......................... 62 37 and so on. A. n-type doping.........................
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