Zinc Oxide Materials for Electronic and Optoelectronic Device Applications E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 726

Veröffentlichungsjahr: 2011

Beschreibung

Zinc Oxide (ZnO) powder has been widely used as a white paint pigment and industrial processing chemical for nearly 150 years. However, following a rediscovery of ZnO and its potential applications in the 1950s, science and industry alike began to realize that ZnO had many interesting novel properties that were worthy of further investigation.

ZnO is a leading candidate for the next generation of electronics, and its biocompatibility makes it viable for medical devices. This book covers recent advances including crystal growth, processing and doping and also discusses the problems and issues that seem to be impeding the commercialization of devices.

Topics include:

• Energy band structure and spintronics
• Fundamental optical and electronic properties
• Electronic contacts of ZnO
• Growth of ZnO crystals and substrates
• Ultraviolet photodetectors
• ZnO quantum wells

Zinc Oxide Materials for Electronic and Optoelectronic Device Applications is ideal for university, government, and industrial research and development laboratories, particularly those engaged in ZnO and related materials research.

Leseprobe

Contents

Cover

Wiley Series in Materials for Electronic and Optoelectronic Applications

Title Page

Copyright

Dedication

In Memoriam: Cole Litton

Series Preface

Preface

List of Contributors

Chapter 1: Fundamental Properties of ZnO

1.1 Introduction

1.2 Band Structure

1.3 Optical Properties

1.4 Electrical Properties

1.5 Band Gap Engineering

1.6 Spintronics

1.7 Summary

References

Chapter 2: Optical Properties of ZnO

2.1 Introduction

2.2 Free Excitons

2.3 Strain Splitting of the Γ5 and Γ6 Free Excitons in ZnO

2.4 Photoluminescence from the Two Polar Faces of ZnO

2.5 Bound-Exciton Complexes in ZnO

2.6 Similarities in the Photoluminescence Mechanisms of ZnO and GaN

2.7 The Combined Effects of Screening and Band Gap Renormalization on the Energy of Optical Transitions in ZnO and GaN

2.8 Closely Spaced Donor–Acceptor Pairs in ZnO

2.9 Summary

References

Chapter 3: Electrical Transport Properties in Zinc Oxide

3.1 Introduction

3.2 Hall-Effect Analysis

3.3 Donor States and n-type Doping

3.4 Hydrogen

3.5 Acceptor States and p-type Doping

3.6 Photoconductivity

3.7 Summary

References

Chapter 4: ZnO Surface Properties and Schottky Contacts

4.1 Historical Background of Schottky Contacts on ZnO

4.2 Recent Schottky Barrier Studies

4.3 The Influence of Surface Preparation on Schottky Barriers

4.4 The Influence of Defects on Schottky Barriers

4.5 The Influence of ZnO Polarity on Schottky Barriers

4.6 The Influence of Chemistry

4.7 Charge Transport and Extended Metal–ZnO Schottky Barriers

4.8 Conclusion

Acknowledgements

References

Chapter 5: Native Point Defects and Doping in ZnO

5.1 Introduction

5.2 Theoretical Framework

5.3 Native Point Defects

5.4 Donor Impurities

5.5 Acceptor Impurities

5.6 Isoelectronic Impurities

Acknowledgements

References

Chapter 6: Spectral Identification of Impurities and Native Defects in ZnO

6.1 Introduction

6.2 Optical Spectroscopy

6.3 Magnetic Resonance Investigations

References

Chapter 7: Vapor Transport Growth of ZnO Substrates and Homoepitaxy of ZnO Device Layers

7.1 Introduction

7.2 Transport Theory and Comparison with Growth Data

7.3 Characterization

7.4 In-situ Doping

7.5 ZnO Homoepitaxy

7.6 Summary

7.7 Acknowledgement

References

Chapter 8: Growth Mechanisms and Properties of Hydrothermal ZnO

8.1 Introduction

8.2 Overview of Hydrothermal Solution Growth

8.3 Thermodynamics of Hydrothermal Growth of ZnO

8.4 Hydrothermal Growth Techniques

8.5 Growth Kinetics of Hydrothermal ZnO

8.6 Properties of Bulk Hydrothermal ZnO

8.7 Conclusion

Acknowledgements

References

Chapter 9: Growth and Characterization of GaN/ZnO Heteroepitaxy and ZnO-Based Hybrid Devices

9.1 Introduction

9.2 Growth of GaN/ZnO

9.3 Compositional Analysis

9.4 Structural Analysis

9.5 Surface Studies

9.6 Optical Properties

9.7 Electrical Properties

9.8 GaN/ZnO Hybrid Devices

9.9 Conclusions

Acknowledgements

References

Chapter 10: Room Temperature Stimulated Emission and ZnO-Based Lasers

10.1 Introduction

10.2 Emission Mechanisms

10.3 Stimulated Emission

10.4 Zinc Oxide Lasers

10.5 Conclusions

References

Chapter 11: ZnO-Based Ultraviolet Detectors

11.1 Introduction

11.2 Photoconductivity in ZnO

11.3 ZnO Film-Based UV Photodetectors

11.4 ZnO NW UV Photodetectors

11.5 Conclusions

Acknowledgements

References

Chapter 12: Room-Temperature Stimulated Emission from ZnO Multiple Quantum Wells Grown on Lattice-Matched Substrates

12.1 Introduction

12.2 Experimental Details

12.3 Quantum Confinement Effect of Excitons in QWs

12.4 Exciton–Phonon Interaction in QWs

12.5 The Localization Mechanism of the Exciton in a QW

12.6 Time-Resolved Luminescence in ZnO QWs

12.7 Stimulated Emission in MQWs

12.8 Summary

Acknowledgements

References

Index

Wiley Series in Materials for Electronic and Optoelectronic Applications

www.wiley.com/go/meoa

Series Editors

Dr Peter Capper, SELEX Galileo Infrared Ltd, Southampton, UK

Professor Safa Kasap, University of Saskatchewan, Canada

Professor Arthur Willoughby, University of Southampton, UK

Published Titles

Bulk Crystal Growth of Electronic, Optical and Optoelectronic Materials, Edited by P. Capper

Properties of Group–IV, III–V and II–VI Semiconductors, S. Adachi

Charge Transport in Disordered Solids with Applications in Electronics, Edited by S. Baranovski

Optical Properties of Condensed Matter and Applications, Edited by J. Singh

Thin Film Solar Cells: Fabrication, Characterization and Applications, Edited by J. Poortmans and V. Arkhipov

Dielectric Films for Advanced Microelectronics, Edited by M. R. Baklanov, M. Green and K. Maex

Liquid Phase Epitaxy of Electronic, Optical and Optoelectronic Materials, Edited by P. Capper and M. Mauk

Molecular Electronics: From Principles to Practice, M. Petty

Luminescent Materials and Applications, Edited by A. Kitai

CVD Diamond for Electronic Devices and Sensors, Edited by R. S. Sussmann

Properties of Semiconductor Alloys: Group–IV, III–V and II–VI Semiconductors, S. Adachi

Mercury Cadmium Telluride: Growth, Properties and Applications, Edited by P. Capper and J. Garland

Forthcoming Titles

Principles of Solar Cells, LEDs and Diodes: The Role of the PN Junction, A. Kitai

Silicon Photonics: Fundamentals and Devices, M. J. Deen and P. K. Basu

Photovoltaic Materials: From Crystalline Silicon to Third–Generation Approaches, Edited by G. J. Conibeer

Inorganic Glasses for Photonics: Fundamentals, Engineering and Applications, A. Jha, R. M. Almeida, M. C. Goncalves and P. G. Kazansky

Lead–Free Solders: Materials Reliability for Electronics, Edited by K.N. Subramanian

Wiley Series in Materials for Electronic and Optoelectronic Applications

www.wiley.com/go/meoa

Series Editors

Dr Peter Capper, SELEX Galileo Infrared Ltd, Southampton, UK

Professor Safa Kasap, University of Saskatchewan, Canada

Professor Arthur Willoughby, University of Southampton, UK

Published Titles

Bulk Crystal Growth of Electronic, Optical and Optoelectronic Materials, Edited by P. Capper

Properties of Group-IV, III–V and II–VI Semiconductors, S. Adachi

Charge Transport in Disordered Solids with Applications in Electronics, Edited by S. Baranovski

Optical Properties of Condensed Matter and Applications, Edited by J. Singh

Thin Film Solar Cells: Fabrication, Characterization and Applications, Edited by J. Poortmans and V. Arkhipov

Dielectric Films for Advanced Microelectronics, Edited by M. R. Baklanov, M. Green and K. Maex

Liquid Phase Epitaxy of Electronic, Optical and Optoelectronic Materials, Edited by P. Capper and M. Mauk

Molecular Electronics: From Principles to Practice, M. Petty

Luminescent Materials and Applications, Edited by A. Kitai

CVD Diamond for Electronic Devices and Sensors, Edited by R. S. Sussmann

Properties of Semiconductor Alloys: Group-IV, III–V and II–VI Semiconductors, S. Adachi

Mercury Cadmium Telluride: Growth, Properties and Applications, Edited by P. Capper and J. Garland

Forthcoming Titles

Principles of Solar Cells, LEDs and Diodes: The Role of the PN Junction, A. Kitai

Silicon Photonics: Fundamentals and Devices, M. J. Deen and P. K. Basu

Photovoltaic Materials: From Crystalline Silicon to Third-Generation Approaches, Edited by G. J. Conibeer

Inorganic Glasses for Photonics: Fundamentals, Engineering and Applications,

A. Jha, R. M. Almeida, M. C. Goncalves and P. G. Kazansky

Lead-Free Solders: Materials Reliability for Electronics, Edited by K.N. Subramanian

This book is dedicated to the memory of Cole W. Litton who was

the driving force behind it and the lead editor. Cole passed

away before its completion.

In Memoriam: Cole Litton

Cole W. Litton, the editor and compiler of Zinc Oxide Materials for Electronic and Optoelectronic Device Applications, died of a heart attack on Tuesday, January 26, 2010, while attending the SPIE Photonics West Conference in San Francisco.

Cole was a native of Memphis, Tennessee, born in 1930, and he attended the University of Tennessee graduating with a bachelor's degree. He served for four years as an officer in the US Air Force and then joined the Air Force Research Laboratory as a civilian scientist at Wright Patterson Air Force Base in Dayton, Ohio. There he worked on the solid-state physics team of Don Reynolds, Tom Collins, and later David Look, and was the principal designer of what became the world's highest resolution optical spectrometer. He spent 50 years with the Air Force during which time he studied at several other universities in the United States and Europe. Litton was acknowledged as a world leader in research in solid-state and semiconductor physics and crystal growth, particularly in the optical, electrical, and structural properties of compound semiconductor materials and devices. In 1971 Cole was elected a fellow of the American

Physical Society. He has been a long-time devoted member of SPIE, where he was a founder and current co-chair of the Gallium Nitride Materials and Devices Conference and also the Oxide-Based Materials and Devices Conference, two of the most successful conferences at Photonics West since their inception. In memory of Litton, the Gallium Nitride Materials and Devices Conference will now bear his name, recognizing his many contributions not only to SPIE but to advancing optics- and photonics-based research as well.

Cole Litton retired in 2006 as Senior Scientist from the Air Force Research Laboratory, but he continued to enjoy an active role in scientific workshops and symposia. At the time of his death, he had authored or co-authored about 200 scientific/technical research papers published in physics and engineering journals. He was committed to discovery and was passionate about the future of science and technology. Cole died fully engaged in the activity he most enjoyed: participating in scientific meetings. He was a unique individual with a great love of life, and he will be remembered by all who knew him.

David F. Bliss US Air Force Laboratory Hanscom Research Site MA, USA

Series Preface

WILEY SERIES IN MATERIALS FOR ELECTRONIC AND OPTOELECTRONIC APPLICATIONS

This book series is devoted to the rapidly developing class of materials used for electronic and optoelectronic applications. It is designed to provide much-needed information on the fundamental scientific principles of these materials, together with how these are employed in technological applications. The books are aimed at (postgraduate) students, researchers and technologists, engaged in research, development and the study of materials in electronics and photonics, and industrial scientists developing new materials, devices and circuits for the electronic, optoelectronic and communications industries.

The development of new electronic and optoelectronic materials depends not only on materials engineering at a practical level, but also on a clear understanding of the properties of materials, and the fundamental science behind these properties. It is the properties of a material that eventually determine its usefulness in an application. The series therefore also includes such titles as electrical conduction in solids, optical properties, thermal properties, and so on, all with applications and examples of materials in electronics and optoelectronics. The characterization of materials is also covered within the series in as much as it is impossible to develop new materials without the proper characterization of their structure and properties. Structure–property relationships have always been fundamentally and intrinsically important to materials science and engineering.

Materials science is well known for being one of the most interdisciplinary sciences. It is the interdisciplinary aspect of materials science that has led to many exciting discoveries, new materials and new applications. It is not unusual to find scientists with a chemical engineering background working on materials projects with applications in electronics. In selecting titles for the series, we have tried to maintain the interdisciplinary aspect of the field, and hence its excitement to researchers in this field.

Peter CapperSafa KasapArthur Willoughby

Preface

Zinc oxide (ZnO) powder has been widely used as a major white paint pigment and industrial processing chemical for nearly 150 years. Indeed, interest in this fascinating chemical compound dates back even to antiquity. ZnO, the first man-made zinc compound, originated many centuries ago as an impure by-product of copper smelting. The ancients discovered and put to use some of its unusual properties, which included production of the first brass metal, development of a purified ZnO for medical purposes, and the early alchemists even attempted to make gold with it. Beginning in the early 1900s, white, polycrystalline ZnO powder found extensive application in medical technology, in particular the cosmetics and pharmaceutical industries, where it is today used in facial and body powders, sun screen preparation, antibiotic lotions and salves and in dental technology for dental cements.

A modern rediscovery of ZnO and its potential applications began in the mid 1950s. At that time, science and industry alike, mostly in the US and Europe, began to realize that ZnO had many interesting novel properties that were worthy of further investigation and exploration. These novel properties included its semiconductor, piezoelectric, luminescent, ultraviolet (UV) absorption, catalytic, ferrite, photoconductive and photochemical properties. Although study of the photoluminescence and electroluminescence properties of ZnO began as early as the mid 1930s, extensive investigation of its semiconductor properties did not begin until the mid to late 1950s, once good single crystals became available, either from natural sources, or grown synthetically by vapor transport and various other techniques, for study of the optical, electrical and structural properties of semiconducting ZnO. These early ZnO single crystals, mostly needles, platelets and prisms, were, however, small and limited in size to a few millimeters. ZnO single crystals typically crystallize in the wurtzitic, hexagonal modification, are visibly transparent and have a wide, direct band gap in the near UV at 3.437 eV (at 2 K). During this same period, the late 1950s to early 1960s, it was also recognized that ZnO had very high piezoelectric coefficients which led to the development of ZnO-based piezoelectric transducers, such as sensitive strain gauges and pressure sensors, a technology which continues today. Throughout the 1960s, extensive investigations of the fundamental semiconductor properties of ZnO were made, including study of its energy band structure, band gaps, excitonic properties, electron and hole effective masses, phonon properties and the electrical transport properties of the intrinsic (undoped) material. At this time (the mid to late 1960s) it was also recognized that ZnO, like the other wide band gap II–VI materials, would be difficult to dope controllably with high concentrations of shallow donor and acceptor impurities in order to demonstrate n- and p-type conductivity and p-n junctions, which would be necessary in order to realize the full potential of ZnO in devices, such as UV diode emitters, detectors and transistors. At that time, modern epitaxial growth and doping techniques, such as molecular beam epitaxy (MBE) and metal organic chemical vapor deposition (MOCVD), had not yet been developed, and p-type doping of both epitaxial films and bulk substrates did not exist; moreover, lack of large, bulk single crystals of ZnO also hampered progress in the development of ZnO-based electronic and optoelectronic devices. Nevertheless, much progress has been made over the past four decades (1970 to present) on the development of ZnO-based transducers, varistors, white-light-emitting cathodoluminescent phosphors (in conjunction with ZnS), optically transparent electrically conducting films, optically pumped lasing, MSM-type UV detectors, based on both ZnO (near UV) and MgZnO/ZnO heterostructures (deeper UV), and surface acoustic wave devices, none of which require the use of p-type ZnO.

Demonstration of the first InGaN/GaN-based, long-lived, room-temperature, continuous wave (CW) blue light-emitting diodes (LEDs) and diode lasers in Japan in the mid 1990s, led several ZnO investigators to consider the possibility of using isomorphic, nearly lattice-matched, c-plane bulk ZnO as a substrate for GaN device epitaxy (∼2% mismatch to GaN), since bulk GaN substrates did not exist, and it was clear that the large threading dislocations resulting from growth of InGaN/GaN laser device structures on lattice mismatched c-plane sapphire (∼14% lattice mismatch) were degrading both the performance and lifetimes of the blue laser diodes, particularly in CW, single mode operation. Earlier a US nitride research group had already demonstrated that GaN device epitaxy could be grown by MBE on small, c-plane ZnO substrates with as much as two to three orders of magnitude reduction in threading dislocation densities within the GaN device epitaxy, in comparison with growth on highly lattice mismatched sapphire substrates. Over the past decade, this achievement led another group to successfully grow and market large (40 mm diameter), high-quality, single-crystal ZnO substrates by vapor transport techniques specifically for this purpose and more recently still another group has also developed large diameter, bulk ZnO substrates by the Pressure-Melt technique for this purpose. Work is presently underway to demonstrate the MBE growth of AlGaN/GaN-based microwave power field-effect transistor (FET) device structures, where the relatively cheap ZnO substrate will be etched away and a high thermal conductivity substrate substituted by wafer bonding techniques to improve heat dissipation from the device.

Over the past decade, a number of groups have proposed that ZnO might be a good optoelectronic device material in its own right, owing to the many similarities between the optical, electrical and structural properties of ZnO and GaN, including their band gaps (3.437 eV for ZnO and 3.50 eV for GaN at 2 K) and their lattice constants. In addition, still others have noted that ZnO has a free exciton binding energy of 60 meV, approximately twice that of GaN, which could lead to highly efficient, ZnO- and MgZnO-based, UV injection lasers (UV laser diodes and detectors) at room temperature, provided that efficient p-doping and good p-n junctions and heterojunctions can be demonstrated in these materials. p-type doping of hetero-epitaxial ZnO on sapphire has been reported by several Japanese and US groups, using N acceptor doping and several different growth techniques, with varying degrees of success, but a major breakthrough was achieved by a US group recently which reported the first MBE growth of homo-epitaxial, N-doped, p-type ZnO on high-resistivity, Li-diffused ZnO substrates. Although the temperature-dependent Hall conductivity of these p-type layers is not yet fully understood, this approach could lead rapidly to p-doping at higher hole mobilities and carrier concentration and to the formation of good p-n junctions, provided that we can achieve a better understanding of both the shallow and deep donor/acceptor compensation mechanisms in ZnO. It is important to address the questions of donor and acceptor impurity incorporation together with the likely formation of native point defect donors and acceptors in ZnO and their possible compensation mechanisms; and look into the question of possible hydrogen donor incorporation in ZnO which must be better understood if rapid progress is to be made in the p-doping of ZnO.

This book comprises some 12 chapters that are written by experts in various aspects of ZnO materials and device technology. The topics included and discussed in these chapters range from our latest understanding of the energy band structure and spintronics (Chapter 1) to our most recent understanding of the fundamental optical and electrical properties of ZnO (Chapters 2 and 3). With the generation of new devices, one has to understand and control the electronic contacts of ZnO. This is covered in Chapter 4. The latest advances in our understanding of the formation of native point defect donors and acceptors in ZnO are discussed and summarized in Chapter 5. The following chapter (Chapter 6) investigates both the intrinsic and extrinsic defects that are found in ZnO. The growth of the ZnO crystals and substrates are discussed in the next three chapters (Chapters 7, 8 and 9) along with hybrid devices, Chapter 10 reports on some recent advances in optically pumped lasing and room temperature stimulated emission from ZnO-based materials. Chapter 11 reviews the progress of UV photodetectors and points out the promise for unique applications such as single-photon detection. The final chapter (Chapter 12) presents a review of optical properties of ZnO quantum wells in which strong stimulation was observed in ZnO/ZnMgO multiple quantum wells from 5 °C to room temperature.

Cole W. LittonDonald C. ReynoldsThomas C. Collins

List of Contributors

M. N. Alexander, Air Force Research Laboratory, Hanscom AFB, MA, USA

D. M. Bagnall, University of Southampton, Southampton, UK

Leonard J. Brillson, The Ohio State University, Columbus, OH, USA

M. J. Callahan, Teleos Solar, Hanson, MA, USA and Air Force Research Laboratory, Hanscom AFB, MA, USA

Gene Cantwell, ZN Technology, Inc., Brea, CA, USA

B. Claflin, Wright State University, Dayton, OH, USA

T. C. Collins, Oklahoma State University, Stillwater, OK, USA

Dirk Ehrentraut, Tohoku University, Aoba-ku, Sendai, Japan

R. J. Hauenstein, Oklahoma State University, Stillwater, OK, USA

A. Hoffmann, Technical University Berlin, Berlin, Germany

D. M. Hofmann, Justus Liebig University Giessen, Giessen, Germany

Anderson Janotti, University of California, Santa Barbara, CA, USA

Masashi Kawasaki, Tohoku University, Sendai, Japan, Cross-Correlated Materials Research Group, Advanced Science Institute, RIKEN, Wako, Japan and CREST, Japan Science and Technology Agency, Tokyo, Japan

Hideomi Koinuma, The University of Tokyo, Kashiwa, Chiba, Japan

C. W. Litton, Air Force Research Laboratory, Wright-Patterson Air Force Base, OH, USA

D. C. Look, Wright State University, Dayton, OH, USA

Yicheng Lu, Rutgers University, Piscataway, NJ, USA

Takayuki Makino, Tohoku University, Sendai, Japan

B. K. Meyer, Justus Liebig University Giessen, Giessen, Germany

Hadis Morkoç, Virginia Commonwealth University, Richmond, VA, USA

D. C. Reynolds, Wright State University, Dayton, OH, USA and Air Force Research Laboratory, Wright-Patterson Air Force Base, OH, USA

Yusaburo Segawa, Advanced Science Institute, RIKEN, Wako, Japan

Ryoko Shimada, Virginia Commonwealth University, Richmond, VA, USA

J. J. Song, ZN Technology, Inc., Brea, CA, USA and University of California at San Diego, La Jolla, CA, USA

J. Stehr, Justus Liebig University Giessen, Giessen, Germany

Chris G. Van de Walle, University of California, Santa Barbara, CA, USA

Buguo Wang, Solid State Scientific Inc., Nashua, NH, USA

Jizhi Zhang, ZN Technology, Inc., Brea, CA, USA

Jian Zhong, Rutgers University, Piscataway, NJ, USA

Chapter 1

Fundamental Properties of ZnO

T. C.Collins and R. J.Hauenstein

Department of Physics, Oklahoma State, University, Stillwater, OK, USA

1.1 Introduction

1.1.1 Overview

Wurtzitic ZnO is a wide band gap semiconductor (Eg = 3.437 eV at 2 K) that has many applications, including piezoelectric transducers, varistors, phosphors, and transparent conduction films. Most of these applications only require polycrystalline materials; however, recent successes in producing large-area single crystals make possible the production of blue and UV light emitters and high temperature, high power transistors. The main advantage of ZnO as a light emitter is its large exciton binding energy (Eb = 60 meV). This binding energy is three times larger than that of the 20 meV exciton of GaN, which permits excitonic recombination to dominate in ZnO at room temperature (and even above). Excitonic recombination is preferable because the exciton, being an already bound system, radiatively recombines with high efficiency without requiring traps to localize carriers, as in the case in radiative recombination of electron–hole plasmas. Secondly, the deeper exciton of ZnO is more stable against field ionization due to piezoelectrically induced fields. Such piezoelectric effects are expected to increase with increasing dopant concentration for both ZnO and GaN.

For electronic applications, the attractiveness of ZnO lies in having high breakdown strength and high saturation velocity. ZnO also affords superior radiation hardness compared with other common semiconductor materials, such as Si, GaAs, CdS, and even GaN, enhancing the usefulness of ZnO for space applications. Optically pumped UV laser action in ZnO has already been demonstrated at both low and high temperatures although efficient electrically induced lasing awaits further improvements in the experimental ability to grow high quality p-type ZnO material. Nonetheless, over the past decade, researchers world-wide have made substantial theoretical and experimental progress concerning the p-type dopability of ZnO, with 1017 cm−3 range hole concentrations now plausibly achieved with material stability persisting for over 1 year, and with isolated (though often controversial) reports of hole concentrations as high as ∼1019 cm−3 even being reported from time to time. Finally, ZnO structures can be doped with transition metal (TM) ions to form dilute magnetic materials, denoted (Zn,TM)O, which can form a ferromagnetic state, an antiferromagnetic state as well as a general spin glass. The important point is that the Curie temperature (TC) can be above room temperature. Such above-room-temperature anti- and ferromagnetic states form the basis for novel charge-based, spin-based, or even mixed spin- and charge-based devices which, collectively, are known as “spintronic” devices.

1.1.2 Organization of Chapter

The remainder of this chapter is organized as follows. In Section 1.2, a theoretical overview of the fundamental band structure of ZnO near the zone center is presented. The discussion includes the long-standing controversy over the symmetry-ordering of the valence bands at the Γ point. Next, in Section 1.3, the optical properties of intrinsic ZnO are reviewed, with particular emphasis on the excitons. Also presented in this same section are a discussion of the interaction of light, magnetic field, and strain field, as three examples of the general types of calculations done for excitons in ZnO, as well as a discussion of spatial resonance dispersion (Section 1.3.4) in which the polariton, a combined state arising out of the mixing of an exciton and light, plays a particularly important role. The electrical properties of ZnO are considered next in Section 1.4, including a discussion of intrinsic along with n-type and p-type ZnO. In particular, the important question of p-type dopability is discussed in detail in Section 1.4.3. For the implementation of optoelectronic devices, one will need Schottky barriers and ohmic contracts; recent progress in these areas is presented in Section 1.4.4. For heterojunction-based devices, band gap engineering will be required and this is considered in Section 1.5. Finally, presented in Section 1.6 is the theoretical basis for the ZnO spintronic device. The different models are based on the Heisenberg Spin Hamiltonian to describe the dilute magnetic system (Zn,TM)O. One can investigate both the interaction of the carriers with the magnetic moment of the TM as well as the TM–TM interactions. It is found that the resulting Curie temperature can be above room temperature. Spintronic devices made of (Zn,TM)O are expected to be faster and to consume less power since flipping the spin requires 10–50 times less power, and occurs roughly an order of magnitude faster, than does transporting an electron through the channel of traditional field-effect transistors (FETs).

1.2 Band Structure

1.2.1 Valence and Conduction Bands

The general electronic structure of binary III–V and II–VI compounds form semiconductors with the valence band mostly derived from the covalent bonding orbitals (s and p). While the conduction band consists of antibonding orbitals, as one moves further outward from column IV of the periodic table, the binary compound semiconductors acquire a more ionic character. These compounds form cubic (zinc blende) and hexagonal (wurtzite) crystal structures, with ZnO crystallized in the wurtzite structure. The difference between the zinc blende and wurtzite structures is that the zinc blende is cubic while the wurtzite is a distortion of the cube in the [111] direction generally taken to be the z direction in the wurtzite.

The ionicity effect puts more electrons on the group V or group VI atoms giving the charge density more s and p characteristics of these elements in the valence band. It also causes gaps at the edge of the Brillouin zone compared with just covalent bonding materials. This translates into flatter bands across the Brillouin zone.

ZnO is a direct band gap semiconductor with valence-band maximum and conduction-band minimum occurring at the Γ point. The conduction band is s-like from Zn at Γ and is spin degenerate. The top three valence bands are p-like in character. They are split by the spin-orbit interaction in both the zinc blende and wurtzite symmetry, while wurtzite symmetry also has a crystal field splitting.

Figure 1.1 shows [1] the Quasi-cubic model [2–4] of the bottom of the con-duction band and the top of the valence band. Assuming that one has both zinc blende and wurtzite and that , one can write matrices of the form:

(1.1)

for zinc blende, using j = 3/2 and j = 1/2 eigenstates. For wurtzite the basis is rotated as stated above, so that one has S+α, S−β, −S−α, S+β, Szα, and Szβ. This basis gives matrices (including crystal field effects δ) of the form

(1.2)

Figure 1.1 Structure and symmetries of the lowest conduction band and upmost valence bands in ZnO compounds at the Γ point

Using the values obtained by Thomas, [5] a difficulty arises. As can be seen in Equation (1.3), there are values of energy difference which can give a complex number for δ:

(1.3)

where E1 is the energy difference between the Γ9 excitons and Γ7 exciton and E2 is the energy difference between the two Γ7 excitons. In fact, using Thomas [5] numbers, δ is a complex number with Γ9 being the top valence band. This difficulty can be surmounted by assuming a negative spin-orbit splitting, which is different from all the other II–VI compounds and GaN. The physical mechanism that could produce a negative spin-orbit splitting was investigated by Cardona [6] for CuCl. In this zinc blende material, it was postulated that the valence band was formed from Cl wave functions, with a large proportion of Cu wave functions (Cu 4s3d). The inverted nature of the CuCl indicates that the Cu contributes a negative term to the spin-orbit splitting, since for this material the anion splitting is small and negative. Cardona6 estimated the “fraction” of the metal wave function in the valence band states by writing the spin-orbit splitting of the compound as:

(1.4)

where α is the proportion of halogen in the wave function, Δhal is the one-electron atomic spin-orbit splitting parameter of the halogen and Δmet is one of the d-electrons of the metal. This gave α = 0.25 for CuCl. It was also presented that the energy interval between the ground state of the Cu+ ion (3d10) and the first excited state (3d9, 4s) is 2.75 eV.

Returning to ZnO, one finds the Zn d-bands below the uppermost p-like valence bands to be greater than 7 eV. [7–9] This makes it very unlikely that one has much mixing at all. Further, the d-band appeared to be relatively flat, noting again very little mixing. Also, the availability of ZnO crystals in which intrinsic exciton transitions [10] are observed in emission and their splitting in a magnetic field have led to a positive spin-orbit splitting of 16 meV. With this interpretation, the Quasi-cubic model [2–4] gives results in line with the other II–VI compounds.

In order to investigate the valence band ordering of ZnO further, Lambrecht et al. [11] calculated the band structure of ZnO using a linear muffin-tin potential and a Kohn–Sham local density approximation. The band gap at Γ was 1.8 eV compared with experiment of 3.4 eV and the Zn d-band was approximately 5 eV below the top of the valence band at Γ. To correct for the band gap Reynolds et al. [10] rigidly shifted the conduction band up to match the experimental Γ-point gap (a shift of 1.624 eV).

As is seen from above in the Quasi-cubic model, [2–4] the spin-orbit magnitude and sign are a function of the energy difference between the top of the valence and the 3d band of Zn. It is found to be greater than 7 eV. [7–9] In Reynolds et al., [10] the d-band was adjusted to where the spin-orbit gave the right energy difference with the Γ7 above the Γ9. The d band was put at 6.25 eV below the top of the valence band. This led to a negative g-value and of course a negative spin-orbit parameter. This in turn matched the experimental data given in Hong et al. [9] but with a different interpretation of the splitting of the exciton lines. Thus, there is no agreement of the spin-orbit value for ZnO. In first principle electron structure calculations, one has an accuracy only on the order of ∼100 meV whereas the splittings of the levels in the top valence band are on the order of ∼10 meV!

1.3 Optical Properties

1.3.1 Free and Bound Excitons

The optical absorption (emission) of electromagnetic radiation in a ZnO crystal is dependent on the matrix element

(1.5)

where

(1.6)

Here, A is the vector potential of the radiation field and has the form

e is the electronic charge, m is the electron mass, c is the velocity of light, is a unit vector in the direction of polarization, and q is the wave vector. Expanding the spatial part of A in a series gives

(1.7)

where

(1.8)

and the dipole term is then the first term (i = 0). The matrix element in Equation (1.5) transforms under rotation like the triple direct product

(1.9)

The selection rules are then determined by which of the triple-direct-product matrix elements in question do not vanish, where is the symmetry of the expansion term in Equation (1.8).

The dipole moment operator for electric dipole radiation transforms like x, y, or z dependent on the polarization. When the electric field vector E of the incident light is parallel to the crystal axis of ZnO, the operator corresponds to the Γ1 representation. When it is perpendicular to the crystal axis, the operator corresponds to the Γ5 representation. Since the crystal has a principal axis, the crystal field removes part of the degeneracy of the p-levels as seen in Figure 1.1. Including spin in the problem doubles the number of levels. Since the conduction band at k = 0 is the Zn (4s) level [4, 5] it transforms as Γ7 while the k = 0 at top of the valence band is made up of the O(2p) level and it splits into (px, py)Γ5 and (pz)Γ1. When crossed with the spin one has

(1.10)

(1.11)

as shown in Figure 1.1.

One of the light absorption (emission) intrinsic states is an exciton, which is made up of a hole from the top of the valence band and an electron from the bottom of the conduction band. These are excitations of the N-particle system whereas electron structure calculations are of the (N ± 1)-particle system. All solutions to the one-body calculations such as the one-particle Green's functions method do not contain the interaction of the excited “particle” with the other “particles.” The more localized the excitation the more important it is to include this interaction. The more localized the excitation is, the flatter the one-electron bands, leading to heavier effective masses. This is turn leads to increased binding energy of the electron–hole pair. In ZnO, the binding energy of the ground state exciton is 60 meV. Adding in the Coulomb term of the electron–hole pair gives a hydrogenically bound pair. For the Γ9 hole and Γ7 electron one has

(1.12)

and for the Γ7 hole and Γ7 electron one has

(1.13)

The Γ5 and Γ6 are doubly degenerate and the Γ1 and Γ2 are nondegenerate. The Hamiltonian for the exciton becomes:

(1.14)

where and are the Hamiltonian for the electron and the hole and is the interaction between the electron and hole including Coulomb, exchange and correlation. To first approximation one generally includes just the Coulomb term as noted above. Equation (1.14) gives what are referred to as the “free” excitons.

There are several extrinsic effects which modify the excitons. Most notable of these in ZnO are the bound complexes. One can have the exciton bound to an ionized donor or a neutral donor. In the case of the ionized donor, one has the molecular attraction of the exciton to the donor plus central cell corrections. For the neutral donor, one has again the molecular binding energy plus the ability of the neutral donor to be left in an excited state. Similar results are obtained with the ionized acceptor or neutral acceptor. The method of calculating these systems is to treat the system as a molecular system in the field of the crystal.

1.3.2 Effects of External Magnetic Field on ZnO Excitons

The case of an applied uniform magnetic field was developed by Wheeler and Dimmock [12] for the exciton in ZnO. It was assumed the electron bands are isotropic at least to second order in k with only double spin degeneracy. The exciton equation is a simple hydrogen Schrödinger equation including effective-mass and dielectric anisotropies. It is found that the mass anisotropy is small, allowing first-order perturbation calculations to be made for the energy states as well as for the magnetic-field effects.

Since the valence and conduction band extrema are at k = 0, the wave vector of the light that creates the exciton k will also represent the position of the exciton in k-space. Dividing the momentum and spaces coordinates into the center-of-mass coordinates and the internal coordinates, the exciton Hamiltonian can be divided into seven terms as follows:

(1.15)

(1.16)

(1.17)

(1.18)

(1.19)

(1.20)

(1.21)

(1.22)

where m is the free-electron mass and μx is the reduced effective mass of the exciton in the x direction at Γ (μx = μy). Also,

(1.23)

(1.24)

(1.25)

The first term is the Hamiltonian for a hydrogenic system in the absence of external fields. One could include the possibility of the mass and dielectric anisotropies. The second term is an A·p term which leads to the linear Zeeman magnetic field term. In this term, the momentum operator is pi − 2eAi/c where Ai = (1/2)H × ri is the vector potential, H is the magnetic field, and ri is the coordinate of the ith electron. The A2 term is the diamagnetic field term proportional to |H|2. The fourth term is the linear interaction of the magnetic field with the spin of the electron and hole. If one has small effective reduced mass for the electron and a large dielectric constant, the radii of the exciton states are much larger than the corresponding hydrogen-state radii. Hence, the spin-orbit coupling is proportional to r−3 and thus quite small, it is legitimate to write the magnetic field perturbations in the Paschen–Back limit as done above.

The last three terms are the K·P, K·A, and K2 terms; K is the center-of mass momentum. Treating the K·P to second order and adding the K2 term, one can obtain an energy term that appears like the center-of-mass kinetic energy. The K·A term has little effect upon the energy; however, it has very interesting properties. This term represents the quasi-electric field that an observer riding with the center-of-mass of the exciton would experience because of the magnetic field in the laboratory. This quasi-field would produce a Stark effect linear in H, and this would give rise to a maximum splitting interpretable as a “g” value.

1.3.3 Strain Field

The effective Hamiltonian formalism of Pikus [13, 14] is of the form

(1.26)

Using the angular momentum operators J(L = 1) gives

(1.27)

where Δ1 is the crystal field splitting of the Sx, Sy bands from the Sz band; Δ2 is the spin-orbit splitting of the j = 3/2 bands from the j = 1/2 band, and Δ3 is a trigonal splitting of the bands from the bands.

The operator , which describes the interaction between the valence bands due to strain, can be determined from symmetry considerations by combining the strain tensor εij with the angular momentum operators J and σ:

(1.28)

Here,

(1.29)

and [JiJj] = (JiJj + JjJi)/2. These operators then describe the mixing of the p-like valence bands due to crystalline strain in the terms of material-dependent parameters (the Ci's).

The operator represents the conduction-band energy. Because of the Γ1 symmetry of the conduction band, the operator has the form

(1.30)

is the Coulomb interaction plus the exchange term

(1.31)

where in Equation (1.31)j denotes the usual exchange integral (not to be confused with the usage of j as the angular momentum quantum number in the earlier equations). The exchange term has off-diagonal matrix elements, and for example, removes the Γ5 degeneracy. This leads to strain splittings, which are measured.

1.3.4 Spatial Resonance Dispersion

The excitons in ZnO interact with photons when the wave vector are essentially equal. The energy denominator for exciton–photon mixing is small and the mixing becomes large. These states are not to be considered as pure photon states or pure exciton states, but rather mixed states. Such a mixed state is called a polariton. When there is a dispersion of the dielectric constant, spatial dispersion has been invoked to explain certain optical effects of the crystal. This causes more than one energy transport mechanism. Spatial dispersion addresses the possibility that two different kinds of waves of the same energy and same polarization can exist in a crystal differing only in wave vector. The one with an anomalously large wave vector is an anomalous wave. In the treatment of dispersion by exciton theory, it was shown that if the normal modes of the system were allowed to depend on the wave vector, a much higher-order equation for the index of refraction would result. These new solutions occur whenever there is any curvature of the ordinary exciton band in the region of large exciton–photon coupling. These results apply to the Lorentz model as well as to quantum-mechanical models whenever there is a dependence of frequency on wave vector.

The specific dipole moment of polarization of a crystal and the electric field intensity are not in direct proportion. The two are related by a differential equation that resulted in giving Maxwell equations of higher order. This leads to the existence of several waves of the same frequency, polarization, and direction but with different indices of refraction. The index of refraction becomes

(1.32)

Here, the sum over j is to include the excitons in the frequency region of interest, and the contributions from other oscillators are included in a background dielectric constant . In Equation (1.32) the numerator and denominator have been expanded in powers of k, keeping terms to order of k2, m∗ is the sum of the effective masses of the hole and electron that comprise the exciton, and ω0j is the frequency of the j th oscillator at k = 0. Eliminating k2 from Equation (1.32) and neglecting the linewidth of the oscillators, the equation becomes

(1.33)

The sum is over excitons from the top two valence bands where the “allowed” excitons have been included with a0j ≠ 0, a2j = 0 while the “forbidden” (because excitons are included with a0j ≠ 0, a2j = 0). Equation (1.33) reduces to a polynomial in n2 whose roots give the wavelengths of the various “normal modes” for the transfer of energy within the crystal.

There is another structure seen in the spectra near the free exciton. This is the result of the mixing of the exciton and photon with non crossing effects of the photon dispersion. This creates a larger density of states where the mixing becomes strong enough to bind the photon curve.

1.4 Electrical Properties

Electrically, ZnO is a transparent-conducting-oxide semiconductor which at room temperature exhibits defect- or impurity-dominated n-type conductivity, even in nominally undoped materials. This defect- or impurity-dominated conductivity is a consequence of the large band gap [15, 16] (≈3.3 eV at room temperature) combined with the unavoidable presence of electrically active native defects and impurities with donor ionization energies typically [15] ∼10–100 meV at concentrations typically [15] ∼1015–1016 cm−3. Furthermore, while ZnO is readily doped n-type and carrier concentrations as high as ∼1021 cm−3 are achievable, [17] at present p-type doping remains challenging. Furthermore, for purposes of utilizing ZnO-based materials for extending semiconductor optoelectronics further into the UV, two of the biggest technological challenges will be to develop growth and device-processing techniques to achieve control over p-type doping as well over metal/semiconductor junction formation (including both Schottky and ohmic contacts) to both n-type and p-type materials.

Most of what is known experimentally about the electronic properties of “pure” ZnO is actually based on n-type specimens. The fundamental electronic transport properties of nominally undoped and intentionally doped ZnO will be presented in Section 1.4.1. Next, in Section 1.4.2, intentional n-type doping and dopants will be considered. Then, in Section 1.4.3 will be discussed recent progress, both experimental and theoretical, concerning the technologically important question of p-type dopability in ZnO. Finally, recent progress on the fabrication of Schottky contacts to n-type, and of ohmic contacts to both n-type and p-type ZnO, will be reviewed in Section 1.4.4.

1.4.1 Intrinsic Electronic Transport Properties

To date, available data concerning fundamental electronic properties of intrinsic, accurately stoichiometric ZnO remains largely unknown. [15] In part this is because of the historical unattainability of sufficiently high-quality materials, a consequence of the difficulty (especially through bulk crystal-growth methods) in achieving adequate O incorporation into the specimen. While such a circumstance may seem merely a technological rather than a fundamental limitation, recent theoretical work [18, 19] suggests that the n-type character resulting from electrically active stoichiometric native point defects such as vacancies, inter-stitials, and antisites, [18] as well as the unusually nonamphoteric and donor-like character of unintentional but ever-present hydrogen, [20] may be inherent to ZnO, at least, to materials produced through the use of near-equilibrium crystal growth methods. The question of p-type dopability shall be deferred to Section 1.4.3. For the remainder of the present section we will consider the basic electronic transport properties of nominally undoped ZnO which have been established experimentally, along with modifications due to intentional n-type doping.

In general, electrical transport properties of ZnO are directionally dependent due to the anisotropy of its wurtzite crystal structure. For the case of nominally undoped (i.e. residually n-type ∼1016 cm−3 carrier concentration) ZnO, Figure 1.2 shows temperature-dependent Hall mobility data for current transport both parallel and perpendicular to the crystallographic c axis of bulk ZnO. As seen in Figure 1.2, the electron mobility attains a peak value of ∼1000 cm2 V−1 s−1 at a temperature of 50–60 K, and drops off approximately as the power law, Tp for low temperatures and Tq for high temperatures where p ≈ 3 and q ≈ −2 in Figure 1.2(a). The drop off at low temperature falls off faster than that expected due to ionized-impurity scattering alone whereas that at high temperatures is at-tributable primarily to the combination of acoustic-deformation-potential with polar-optical-phonon scattering mechanisms. [21] The slight anisotropy observed in Hall mobility data [compare Figure 1.2(a) and (b)] has been attributed exclusively to piezoelectric scattering. [15]

Figure 1.2 Hall mobility vs temperature of nominally undoped ZnO. Current transport is parallel in (a) and perpendicular in (b) to the wurtzite c-axis. In each case, the magnetic field is perpendicular to the current flow. Superimposed are theoretical curves corresponding to separate scattering mechanisms. Reprinted from R. Helbig, P. Wagner, Halleffekt und anisotropie der beweglichkeit der elektronen in ZnO,. Phys. Chem. Solids 35, 327. Copyright (1974) with permission from Elsevier

Also of interest is the electric-field dependence of the mobility. Figure 1.3 compares theoretically obtained plots [22] of drift velocity (vd) vs electric field; results predicted for ZnO are contrasted with those for GaN, another direct-gap semiconductor having a closely comparable band gap ( ≈ 3.4 eV) to ZnO. A comparison of the GaN and ZnO curves at low field reveals that μZnO < μGaN while at the same time the saturated drift velocities obey the opposite relation: . For hot-electron devices, where fields are high and transport is nonohmic, it is υsat rather than μ that can be the more important parameter to device operation. [23]

Figure 1.3 Theoretical electron drift velocity vs electric field for ZnO (solid line) and GaN (dashed line). Though GaN exhibits higher mobility at low fields, ZnO is expected to have greater saturated drift velocity at high fields. Reprinted from J. D. Albrecht, et al., High field electron transport properties of bulk ZnO. J. Appl. Phys. 86, 6864. Copyright (1999) with permission from American Institute of Physics

1.4.2 n-type Doping and Donor Levels

Intentional n-type doping is readily achieved through the use of column-III elements such as Al, Ga, or In, or, column-VII elements such as Cl, F, or I. All of these sit substitutionally on the appropriate cation or anion site and form reasonably shallow levels. In a 2001 review article, Look discusses the presence of three predominant donor levels in ZnO appearing at approximately 30, 60, and 340 meV. [23] Among these, the 60 meV level is that corresponding to effective mass theory (≈65 meV), whereas the 30 meV level was at the time believed [18, 24] to be due to interstitial Zn (Zni) and no longer believed to be due to the O vacancy (VO), which instead was thought to be a deep donor. [18] The identity of the 340 meV level was not established. Interestingly, also presented by Look in this same review article [23] are some of his own temperature-dependent Hall mobility data which were at the time obtained on single crystals grown through the use of relatively modern bulk techniques such as the seeded vapor phase transport (SVPT) method. The SVPT-grown sample in this case was seen to exhibit a temperature-dependent mobility which compares very favorably to the best results from the older literature (shown in Figure 1.2), with peak mobility of ≈1900 cm2 V−1 s−1, once again occurring near 60 K. [23] Analysis of the temperature-dependent mobility data [23] indicates for this sample the presence of the two shallow donors mentioned above (31 and 61 meV at donor concentrations of 9 × 1015 and 1 × 1017 cm−3, respectively) along with a shallow acceptor level (NA = 2 × 1015 cm−3; EA not given). [23]

In addition to the list of above-mentioned substitutional n-type species may be added interstitial H which, while normally entering as an amphoteric species for most other semiconductors (either as H+ or H− as needed to effect passi-vation), for ZnO enters only in the positive charge state, and thus is able to contribute to doping rather than passivation through the formation of a O–H complex, according to a recent theoretical prediction by Van de Walle. [20] This atypical behavior of H when in ZnO is attributed to the strong O–H bond which forms and functions as an effective donor “atom” sitting on an O site. [20] As an aside, it is interesting to observe that the long-standing p-type-dopability problem in GaN was finally resolved once it was realized that, in that case, H acts as a passivating agent (through formation of complexes with the intended acceptor species). Evidently, though the roles played by H in ZnO and GaN appear to be entirely different, it would appear nonetheless important to minimize the H concentration for purposes of achieving p-type material.

1.4.3 p-type Doping and Dopability

For ZnO to be technologically successful as a UV-range optoelectronic device material, an important growth issue is the ability to reliably produce both n-type and p-type ZnO materials. As noted above, n-type doping is readily achieved (and occurs natively through Zni and possibly other defects in stoichiometry). However, like most wide-band-gap semiconductors, including other II–VI compounds25 as well as III–V refractory-nitride compounds AlN (presently) and GaN (previously), ZnO exhibits an asymmetric ease of dopability one way (n-type) but not the other way (p-type). The physical origins of such dopability asymmetries in the II–VIs generally have been reviewed recently by Desnica; [25] briefly, doping-limiting mechanisms common to II–VI semiconductors include self-compensation (via native defects, lattice relaxation, amphoteric incorporation), solubility limitations, activation-efficiency limitations, in addition to other mechanisms which do not apply to higher hardness materials such as ZnO. [25]

Prior to 1999 there was only one report [26] of p-ZnO and in that case both material quality and growth reproducibility were poor. Since that time have come a number of papers, at first mostly theoretical, and more recently experimental, seeking to elucidate or obviate the difficulties of ZnO p-type doping. Among the conclusions from the aforementioned body of theoretical work [18–20, 27, 28] –all since 1998 and all based on ab initio band calculations–are the following explanations and conclusions concerning the long-standing p-type-doping problem in ZnO and how it might be solved.

According to Yamamoto and Katayama-Yoshida, [27] the doping asymmetry of ZnO is the consequence of fundamentally opposing effects of doping type on Madelung energy [n-type (p-type) doping decreases (increases) the Madelung energy]. If this is the governing mechanism, then, the proper strategy to attain p-ZnO should be to co-dope with both donors and acceptors, for example, p-ZnO:(N,Ga).

An alternative explanation was put forth by Zhang et al. [18] who considered the case of intrinsic ZnO and examined through ab initio theory the energetics of formation of native point defects as well as the donor or acceptor level(s) that these defects introduce. For each type of native stoichiometric point defect (e.g. Zni, ZnO, VO, which are all the possible native donors in ZnO, and Oi and VZn which are all the acceptors) they systematically computed, for each defect, its formation enthalpy and any donor or acceptor level(s) which it intro-duced. They concluded that native ZnO should only be able to come out n-type but never p-type, assuming growth under quasi-equilibrium conditions. [18] The argument could be stated as follows: Under Zn-rich growth conditions, Zni, a shallow donor, should form readily due to favorable thermodynamics, and the only possible compensators (Oi, VZn) both have unfavorable thermodynamics for formation. Thus, the prediction is that nominally undoped ZnO grown under Zn-rich conditions (again through equilibrium techniques) should come out n-type due to the existence of uncompensated Zni donor defects. Equally, under either O-rich or Zn-rich conditions: natively p-type ZnO should not be possible because there always should be some native donor defect (VO, Zni, or ZnO) which–shallow or deep–would be favored to form thermodynamically (which one forms would depend upon the growth conditions), and hence should be available to compensate any possible native acceptor defects (Oi, VZn) which might have formed. [18] However, it is important to note that this theory specifically presupposes equilibrium (quasi-equilibrium) crystal growth; thus, it might be theoretically possible in principle through nonequilibrium techniques to “freeze in” a metastable p-ZnO film though, evidently, the origin of the acceptor would probably have to be an impurity species rather than a native point defect of ZnO.

In another ab initio study, this time for extrinsic ZnO, Yan et al. [28] considered the role of the impurity species chemical potential in addition to those of the host (Zn and O) species considered in the earlier work by Zhang et al. [18] just discussed. Yan et al.'s work predicts that through consideration together of both dopant (N) and host (O in particular) chemical potentials during equilibrium growth that the use of certain N-containing dopant species–either NO or NO2 in particular (as opposed to the N2 or N2O that had been actually attempted initially but with little success)–should enable p-type doping. It is noteworthy that both Yan et al.'s and Zhang et al.'s theories provide alternative explanations to the “co-doping” concept as proposed by Yamamoto and indeed show the latter to be incorrect. Finally, in a later theoretical overview, Zunger [29] summarized on general grounds the thermodynamics of dopant incorporation (“dopant” in this context referring either to an impurity or to a native defect often spontaneously formed) by way of the formation enthalpy ΔH(D,q) for an arbitrary dopant D in a host crystal wherein the dopant is formed in charge state q (q > 0 for donors and q < 0 for acceptors):

(1.34)

In this equation, εF is the Fermi energy, μD,H are the chemical potentials of dopant and host, respectively, and ΔUb denotes any excess energy associated with local chemical bonds around the dopant, relative to the otherwise undoped crystal. The qεF term of Equation (1.34) explains the thermodynamic origin of the spontaneous formation of so-called “killer defects”. For example, if one were to attempt to dope ZnO p-type via a near-equilibrium crystal-growth technique, the lowering of εF would make more negative the term, qεF (since q > 0 for any donor spontaneously formed), thereby enhancing the spontaneous formation through thermodynamics of compensating donor defects [by making more negative the heat of formation ΔH via Equation (1.34)], other things being equal. The terms involving μD,H show the further dependence on (quasi-equilibrium) growth conditions, with these terms affecting essentially the solubility of, e.g., a substituent such as N on the O site of a ZnO crystal (the solubility obviously being enhanced under oxygen-deficient growth conditions).

A couple of experimental results dating from around 1999 have been reported which shed additional light on the p-ZnO dopability question. First, there is the report by Joseph et al., [30] who sought to implement Yamamoto's co-doping idea using N and Ga as the p-type and n-type dopants, respectively. Some of the films obtained indeed appeared to be p-type, but only under specific conditions of growth and with an odd and excessive acceptor-concentration/hole-mobility trade-off. [30] In particular, the use as dopant of N2 proved unsuccessful and use of N2O conditionally successful, depending also on the use of plasma excitation of the N2 or N2O source gas {via an electron cyclotron resonance (ECR) source in this case]. [30] It should be noted from GaN MBE growth that the commercially available radio frequency (RF) sources in general have proved much more successful than the ECR sources in “cracking” the N2 source gas down to the desired neutral-atomic N species relative to the undesired ionized dimers. This dependence on the type of plasma source (ECR vs RF) might be critical for purposes of effecting p-type doping in ZnO with plasma-excited N2 gas.

Interestingly, another experimental paper from around the same time discusses Ga and N co-dopants in ZnO films grown using both O and N radicals produced with the aid of separate RF plasma sources on the same system. [31]

This last work, which nominally set out to effect the co-doping approach of Yamamoto and Katayama-Yoshida, [27] found instead direct experimental evidence that (i) the approach can be fraught with serious problems31 under certain circumstances; and (ii) worse, the layer nominally intended to be “p-ZnO” in fact turned out to be a layer of the spinel compound ZnGa2O4, which formed due to metallurgical reaction during growth between the ZnO and the high concentrations of Ga needed to effect the co-doping idea [27] as proposed.

Fortunately, in the years since, and especially most recently, numerous experimental groups now have reported the successful p-type doping of ZnO. [32–41] At the time of this writing, reported hole concentrations in the ∼1017 cm−3 range are becoming increasingly common, with occasional reports of (ostensible) holeconcentrations as high as ∼1019 cm−3 though the latter are often regarded with suspicion; for example, Zhao et al. [33] attribute such an anomalous 1019 cm−3-range hole concentration in their putative p-ZnO ultrasonic spray pyrolysis films grown on n-Si substrates to actually be a Hall-measurement misinterpretation due to the formation of a two-dimensional hole gas (2DHG) at the heterointer face between what they believe to be actually an n-ZnO film on the n-type Si substrate: band offsets and Fermi-level pinning they argue likely give rise to a 2DHG of high sheet concentration, and it is the latter which most likely is being reflected in their Hall measurements. [33]

Many of the recent p-type doping studies have embraced the co-doping Idea, [27] often involving N on an O site of ZnO as the acceptor with a column-III element such as Ga, Al, or In as the co-donor. [42–44] In a recent study, even Zr has been employed as co-donor: Pulsed-laser-deposited ZnO doped films on Al2O3 with hole concentrations as high as 5.49 × 1019 cm−3 along with low resistivity (0.026 Ω·cm) and not too poor mobility (4.38 cm−2 V−1 s−1) have been achieved in ZnO:(Zr,N) co-doped films. [36] Besides N, other column-V elements, putatively substituting for O in ZnO, have been attempted for p-type doping. For instance, a recent study based on RF magnetron-sputtered, P-doped ZnO films has shown that, by considering the effect of post-growth anneals in O2, N2, and Ar ambients, it can be inferred from the activation kinetics that the identity of the P-related acceptor in this case, giving hole concentrations ranging between ∼1016 and 1019 cm−3, is indeed substitutional PO, and not a PZn + 2VZn complex. [34]

The principal problems which remain include a generally low acceptor solubility, large (∼100 meV) hole binding energy (implying poor dopant activation efficiency at room temperature), a low hole mobility with accompanying excessive mobility vs concentration trade-off (though unlike the aforementioned issues this one may not be fundamental), and long-term material instability. Indeed, metastable phenomena such as persistent photoconductivity, often with accompanying type-conversion (p-type to n-type) upon illumination being observed, [37] are not uncommon. Often, due to the wide range of ZnO material fabrication techniques (many leading to decidedly nonepitaxial films) involved in the ZnO doping studies, combined with the apparent heightened significance of surface-, and grain-boundary-interfacial states in determining measured electrical properties in ZnO specimens in comparison with more traditional semiconductor materials such as Si, GaAs, or even GaN, it is challenging to sift through the vast and increasing pool of ZnO doping studies and then to reach any consensus as to a “best” method or “best” dopant species to use. At present, no such consensus exists.

Summarizing this section, theoretically it appears possible in principle to achieve at least some level of p-type doping in ZnO but such structures appear fundamentally to be: (i) probably metastable if achieved experimentally (unless current theories are wrong); (ii) evidently achievable experimentally (though by no means is there a universal consensus as to the best dopants or methods to use); and (iii) difficult to precisely reproduce and often challenging to interpret experimental results due to the wide variability of ZnO microstructural quality and character (often nonepitaxial in recent studies), as well as the apparently very important, and yet-to-be clarified, role of defect states at the typically high density of surfaces and interfaces between grain boundaries.

1.4.4 Schottky Barriers and Ohmic Contacts