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Gallium Oxide: Technology, Devices and Applications

Gallium Oxide: Technology, Devices and Applications

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Gallium Oxide: Technology, Devices and Applications

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Lançado em:
Oct 15, 2018


Gallium Oxide: Technology, Devices and Applications discusses the wide bandgap semiconductor and its promising applications in power electronics, solar blind UV detectors, and in extreme environment electronics. It also covers the fundamental science of gallium oxide, providing an in-depth look at the most relevant properties of this materials system. High quality bulk Ga2O3 is now commercially available from several sources and n-type epi structures are also coming onto the market. As researchers are focused on creating new complex structures, the book addresses the latest processing and synthesis methods.

Chapters are designed to give readers a complete picture of the Ga2O3 field and the area of devices based on Ga2O3, from their theoretical simulation, to fabrication and application.

  • Provides an overview of the advantages of the gallium oxide materials system, the advances in in bulk and epitaxial crystal growth, device design and processing
  • Reviews the most relevant applications, including photodetectors, FETs, FINFETs, MOSFETs, sensors, catalytic applications, and more
  • Addresses materials properties, including structural, mechanical, electrical, optical, surface and contact
Lançado em:
Oct 15, 2018

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Gallium Oxide - Elsevier Science

Gallium Oxide

Technology, Devices and Applications

First Edition

Stephen Pearton

Fan Ren

Michael Mastro

Series Editor

Ghenadii Korotcenkov

Table of Contents

Cover image

Title page


List of contributors

Series editor's biography

Editors biography

Preface to the series


Part One: Growth technology of Ga2O3

1: Progress in MOVPE growth of Ga2O3


1.1 Introduction

1.2 Homoepitaxial deposition of β-Ga2O3

1.3 Heteroepitaxial deposition of β-Ga2O3

1.4 Heteroepitaxial deposition of ɛ-Ga2O3

2: MBE growth and characterization of gallium oxide



2.1 Introduction

2.2 MBE growth of Ga2O3 and materials characterization

2.3 Current status and future prospects

2.4 Summary

3: Properties of sputter-deposited gallium oxide



3.1 Introduction

3.2 Experimental

3.3 Results and discussion

3.4 Summary and conclusions

4: Synthesis, optical characterization, and environmental applications of β-Ga2O3 nanowires


4.1 Introduction

4.2 Ambient controlled synthesis of β-Ga2O3 nanowires

4.3 Optical characterization of β-Ga2O3 nanowires

4.4 Photocatalytic property of β-Ga2O3 nanowires

4.5 Summary

5: Growth, properties, and applications of β-Ga2O3 nanostructures



5.1 Introduction

5.2 Study of β-Ga2O3 nanostructures

5.3 Functional nanowires based on β-Ga2O3

5.4 Conclusions and future perspective

Part Two: Properties and Processing

6: Properties of (In,Ga)2O3 alloys


6.1 Introduction

6.2 Overview on crystal structures observed in (In,Ga)2O3

6.3 Lattice parameters of bulk material

6.4 Thin film growth

6.5 Deep-UV absorption and band gap engineering

6.6 Phonon modes

6.7 Dielectric function and index of refraction

6.8 Schottky barrier diodes

6.9 Photodetectors

6.10 Summary and outlook

7: Low-field and high-field transport in β-Ga2O3



7.1 Introduction

7.2 Electron-phonon interaction in β-Ga2O3

7.3 Electron mobility in β-Ga2O3

7.4 Velocity-field curves in β-Ga2O3

7.5 Summary

8: Electron paramagnetic resonance (EPR) from β-Ga2O3 crystals



8.1 Introduction

8.2 Crystal structure of β-Ga2O3

8.3 Shallow donors and conduction electrons

8.4 Acceptors and self-trapped holes

8.5 Transition-metal and rare-earth ions

8.6 Oxygen vacancies

9: Hydrogen in Ga2O3


9.1 Introduction

9.2 Hydrogen in the transparent conducting oxides ZnO, SnO2, and In2O3

9.3 Hydrogen in β-Ga2O3

9.4 Conclusion


10: Ohmic contacts to gallium oxide



10.1 Introduction

10.2 Ohmic contacts and contact resistance

10.3 Ohmic contacts to gallium oxide

10.4 Development of Ohmic contacts for Ga2O3 microelectronics

10.5 Research opportunities for Ohmic contacts to Ga2O3

11: Schottky contacts to β-Ga2O3



11.1 Introduction

11.2 Physics of Schottky contacts and SBH measurements

11.3 Properties of Ga2O3 for SBDs

11.4 Schottky contacts on β-Ga2O3: Materials and processing

11.5 Defects relevant to β-Ga2O3 Schottky contacts

11.6 Nonideal and inhomogeneous Schottky barriers

11.7 β-Ga2O3 Schottky devices

11.8 Summary

12: Dry etching of Ga2O3



12.1 Introduction

12.2 Dry etching

12.3 Dry etching techniques

12.4 Etch results for Ga2O3

12.5 Summary

13: Band alignments of dielectrics on (− 201) β-Ga2O3


13.1 Introduction

13.2 Methods

13.3 Band offsets

13.4 Conclusion

14: Radiation damage in Ga2O3



14.1 Introduction

14.2 Radiation damage in wide bandgap semiconductors

14.3 Properties of Ga2O3

14.4 Radiation damage effects in Ga2O3

14.5 Summary and conclusion

Part Three: Applications

15: Ga2O3 nanobelt devices


15.1 Introduction

15.2 β-Ga2O3-based optoelectronic nanodevice

15.3 β-Ga2O3-based nanoelectronic devices

15.4 Summary

16: Advances in Ga2O3 solar-blind UV photodetectors


16.1 Introduction

16.2 Figures of merit for photodetectors

16.3 β-Ga2O3 UV photodetectors: Types, operational principles, and status

16.4 Gain mechanism and barrier height calculation

16.5 Comparison with AlGaN deep-UV photodetectors

16.6 Design consideration, possible geometries, and arrays of detectors for deep UV detection

16.7 Summary, conclusion/future work

17: Power MOSFETs and diodes


17.1 Introduction

17.2 Properties

17.3 Schottky diodes

17.4 Power MOSFETs

17.5 Application space and competing technologies

17.6 Future

18: Ga2O3-photoassisted decomposition of insecticides



18.1 Introduction

18.2 Photochemical and photocatalytic degradation reactions

18.3 Toxicity test of photodegraded intermediate products

18.4 Photocatalytic mineralization of chemical substances

18.5 Concluding remarks

19: Ga2O3-based gas sensors


19.1 Introduction

19.2 Ga2O3-based gas sensors

19.3 Conclusions




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List of contributors

Kwang Hyeon Baik       Department of Materials Science and Engineering, Hongik University, Jochiwon, South Korea

Kristen Bevlin       Plasma-Therm, St. Petersburg, FL, United States

Patrick H. Carey , IV

Department of Chemical Engineering

Department of Materials Science and Engineering, University of Florida, Gainesville, FL, United States

Kalyan K. Das       Materials Science & Engineering, North Carolina State University, Raleigh, NC, United States

Roberto Fornari

Department of Mathematical, Physical and Computer Sciences, University of Parma

IMEM-CNR Institute, Parma, Italy

W. Beall Fowler       Department of Physics, Lehigh University, Bethlehem, PA, United States

Dwarakanath Geerpuram       Plasma-Therm, St. Petersburg, FL, United States

Krishnendu Ghosh       Electrical Engineering Department, University at Buffalo, Buffalo, NY, United States

B.P. Gila       Department of Materials Science and Engineering, University of Florida, Gainesville, FL, United States

N.C. Giles       Department of Engineering Physics, Air Force Institute of Technology, Wright-Patterson Air Force Base, Dayton, OH, United States

L.E. Halliburton       Department of Physics and Astronomy, West Virginia University, Morgantown, WV, United States

D. Hays       Department of Materials Science and Engineering, University of Florida, Gainesville, FL, United States

Hisao Hidaka       Department of Chemistry, Meisei University, Hodokubo, Hino-shi, Tokyo, Japan

Ching-Hwa Ho       Graduate Institite of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei, Taiwan

Soohwan Jang       Department of Chemical Engineering, Dankook University, Yongin, South Korea

Lai Jiang       Materials Science & Engineering, Carnegie Mellon University, Pittsburgh, PA, United States

Sunwoo Jung       Department of Chemical Engineering, Dankook University, Yongin, South Korea

Rohit Khanna       Plasma-Therm, St. Petersburg, FL, United States

Jihyun Kim       Department of Chemical and Biological Engineering, Korea University, Seoul, South Korea

Janghyuk Kim       Department of Chemical and Biological Engineering, Korea University, Seoul, South Korea

Suhyun Kim       Department of Chemical and Biological Engineering, Korea University, Seoul, South Korea

Sriram Krishnamoorthy       Electrical and Computer Engineering, The University of Utah, Salt Lake City, UT, United States

Mukesh Kumar

Department of Physics

Nanoscale Research Facility, Indian Institute of Technology Delhi, New Delhi, India

Sudheer Kumar       Department of Physics, Indian Institute of Technology Delhi, New Delhi, India

Vikram Kumar

Nanoscale Research Facility, Indian Institute of Technology Delhi

Solid State Physical Laboratory, New Delhi, India

Luke A.M. Lyle       Materials Science & Engineering, Carnegie Mellon University, Pittsburgh, PA, United States

M.A. Mastro       U.S. Naval Research Laboratory, Washington, DC, United States

David J. Meyer       U.S. Naval Research Laboratory, Washington, DC, United States

Rangarajan Muralidharan       Centre for Nano Science and Engineering (CeNSE), Indian Institute of Science (IISc), Bangalore, India

Digbijoy N. Nath       Centre for Nano Science and Engineering (CeNSE), Indian Institute of Science (IISc), Bangalore, India

Neeraj Nepal       U.S. Naval Research Laboratory, Washington, DC, United States

Sooyeoun Oh       Department of Chemical and Biological Engineering, Korea University, Seoul, South Korea

Stephen Pearton       Department of Materials Science and Engineering, University of Florida, Gainesville, FL, United States

Lisa M. Porter       Materials Science & Engineering, Carnegie Mellon University, Pittsburgh, PA, United States

Anamika Singh Pratiyush       Centre for Nano Science and Engineering (CeNSE), Indian Institute of Science (IISc), Bangalore, India

Ying Qin       Department of Physics, Lehigh University, Bethlehem, PA, United States

Siddharth Rajan       Department of Electrical and Computer Engineering, The Ohio State University, Columbus, OH, United States

C.V. Ramana       Department of Mechanical Engineering, University of Texas at El Paso, El Paso, Texas, United States

F. Ren

Department of Chemical Engineering

Department of Materials Science and Engineering, University of Florida, Gainesville, FL, United States

D. Scott Katzer       U.S. Naval Research Laboratory, Washington, DC, United States

R. Singh

Department of Physics

Nanoscale Research Facility, Indian Institute of Technology Delhi, New Delhi, India

Uttam Singisetti       Electrical Engineering Department, University at Buffalo, Buffalo, NY, United States

Michael Stavola       Department of Physics, Lehigh University, Bethlehem, PA, United States

Marko J. Tadjer       U.S. Naval Research Laboratory, Washington, DC, United States

Li-Chia Tien       Department of Materials Science and Engineering, National Dong Hua University, Hualien, Taiwan

Tohru Tsukamoto       Department of Chemistry, Meisei University, Hodokubo, Hino-shi, Tokyo, Japan

Holger von Wenckstern       Universität Leipzig, Felix-Bloch-Institut für Festkörperphysik, Halbleiterphysik, Linnéstraße 5, Leipzig, Germany

Philip Weiser       Department of Physics, Lehigh University, Bethlehem, PA, United States

Jiancheng Yang

Department of Chemical Engineering

Department of Materials Science and Engineering, University of Florida, Gainesville, FL, United States

Series editor's biography

Ghenadii Korotcenkov earned his PhD in material sciences from the Technical University of Moldova, Chisinau, Moldova, in 1976 and his Doctor of Science degree in physics from the Academy of Science of Moldova in 1990 (Highest Qualification Committee of the USSR, Moscow). He has more than 40 years of experience as a scientific researcher. For a long time, he was the leader of the gas sensor group and manager of various national and international scientific and engineering projects carried out in the Laboratory of Micro- and Optoelectronics, Technical University of Moldova. His research had financial support from international foundations and programs such as the CRDF, the MRDA, the ICTP, the INTAS, the INCO-COPERNICUS, the COST, and the NATO. From 2007 to 2008, he was an invited scientist in the Korea Institute of Energy Research, Daejeon, South Korea. After which, until the end of 2017 G. Korotcenkov was a research professor at the School of Materials Science and Engineering at the Gwangju Institute of Science and Technology, Gwangju, South Korea. Currently G. Korotcenkov is the chief scientific researcher at the Department of Physics and Engineering at the Moldova State University, Chisinau, Rep. of Moldova.

Specialists from the former Soviet Union know G. Korotcenkov's research results in the field of study of Schottky barriers, MOS structures, native oxides, and photoreceivers on the basis of III–V compounds such as InP, GaP, AlGaAs, and InGaAs. His present scientific interests starting from 1995 include material sciences, focusing on the metal oxide film deposition and characterization, surface science, and the design of thin film gas sensors and thermoelectric convertors. These studies were carried out in cooperation with scientific teams from Ioffe Institute (St. Petersburg, Russia), University of Michigan (Ann Arbor, United States), Kiev State University (Kiev, Ukraine), Charles University (Prague, Czech Republic), St. Petersburg State University (St. Petersburg, Russia), Illinois Institute of Technology (Chicago, United States), University of Barcelona (Barcelona, Spain), Moscow State University (Moscow, Russia), University of Brescia (Brescia, Italy), Belarus State University (Minsk, Belarus), and South-Ukrainian University (Odessa, Ukraine).

G. Korotcenkov is the author or editor of 38 books, including the 11-volume Chemical Sensors series published by the Momentum Press (United States), 15-volume Chemical Sensors series published by Harbin Institute of Technology Press (China), 3-volume Porous Silicon: From Formation to Application published by CRC Press (United States), 2-volume Handbook of Gas Sensor Materials published by Springer (United States), and 3-volume Handbook of Humidity Measurement, which is being published by CRC Press (United States). In addition, at present, G. Korotcenkov is a series’ editor of Metal Oxides series, which is published by Elsevier.

G. Korotcenkov is author and coauthor of more than 600 scientific publications, including 30 review papers, 38 book chapters, and more than 250 articles published in peer-reviewed scientific journals (h-factor = 40 [Scopus] and h-factor = 47 [Google Scholar citation]). He is a holder of 17 patents. He has presented more than 200 reports at national and international conferences, including 17 invited talks. G. Korotcenkov was co-organizer of several international conferences. His name and activities have been listed by many biographical publications, including Who's Who. His research activities are honored by an Award of the Supreme Council of Science and Advanced Technology of the Republic of Moldova (2004); Prize of the Presidents of the Ukrainian, Belarus, and Moldovan Academies of Sciences (2003); and National Youth Prize of the Republic of Moldova in the field of science and technology (1980), among others. G. Korotcenkov also received a fellowship from the International Research Exchange Board (IREX, United States, 1998), Brain Korea 21 Program (2008–2012), and Brain Pool Program (Korea, 2007–2008 and 2015–2017).

Editors biography

Stephen Pearton is a distinguished professor and alumni chair of Materials Science and Engineering at the University of Florida, Gainesville, FL, United States. He has a PhD in Physics from the University of Tasmania and was a postdoc at UC Berkeley prior to working at AT&T Bell Laboratories in 1994–2004. His interests are in the electronic and optical properties of semiconductors. He is a Fellow of the IEEE, AVS, ECS, TMS, MRS, SPIE, and APS. He was the recipient of the J.J. Ebers Award from IEEE, Gordon Moore Award from ECS, John Thornton Award from AVS, Adler Award from APS, and the Bardeen Award from TMS.

Michael Mastro is a scientist at the US Naval Research Laboratory in Washington DC, United States. His research interests are in fabrication and modeling physics of high-power transistors as well as light emitting, photonic crystal, plasmonic, metamaterial, and photovoltaic devices, fabrication of nanostructured devices, development of numerical models, and neural network algorithms to describe nanoscale semiconductor physics. He has a PhD in Chemical Engineering from University of Florida and BS from John's Hopkins University. He is the co-editor of the very popular book III–V Compound Semiconductors: Integration with Silicon-Based Microelectronics and won an outstanding paper award from Japan Society of Applied Physics in 2014.

Fan Ren is a distinguished professor of Chemical Engineering at the University of Florida, Gainesville, FL, United States. He joined UF in 1997 after 12 years as a member of Technical Staff at AT&T Bell Laboratories, where he was responsible for high-speed compound semiconductor device development. He is a fellow of AIChE, ECS, IEEE, APS, MRS, and AVS. He was the recipient of the Gordon Moore Award from ECS and the Albert Nerken Award from AVS.

Preface to the series

Ghenadii Korotcenkov

The field of synthesis, study, and application of metal oxides is one of the most rapidly progressing areas of science and technology. Metal oxides are one of the most ubiquitous compound groups on earth, which has large variety of chemical compositions, atomic structures, and crystalline shapes. In addition, metal oxides are known to possess unique functionalities that are absent or inferior in other solid materials. In particular, metal oxides represent an assorted and appealing class of materials, properties of which exhibit a full spectrum of electronic properties—from insulating to semiconducting, metallic, and superconducting. Moreover, almost all the known effects including superconductivity, thermoelectric effects, photoelectrical effects, luminescence, and magnetism can be observed in metal oxides. Therefore, metal oxides have emerged as an important class of multifunctional materials with a rich collection of properties, which have great potential for numerous device applications. Specific properties of the metal oxides, such as the wide variety of materials with different electrophysical, optical, and chemical characteristics, their high thermal and temporal stability, and their ability to function in harsh environments, make metal oxides very suitable materials for designing transparent electrodes, high-mobility transistors, gas sensors, actuators, acoustical transducers, photovoltaic and photonic devices, photo- and heterogeneous catalysts, solid-state coolers, high-frequency and micromechanical devices, energy harvesting and storage devices, nonvolatile memories, and many others in the electronics, energy, and health sectors. In these devices metal oxides can be successfully used as sensing or active layers, substrates, electrodes, promoters, structure modifiers, membranes, and fibers, that is, can be used as active and passive components.

Among other advantages of metal oxides are the low fabrication cost and robustness in practical applications. Furthermore, the metal oxides can be prepared in various forms such as ceramics, thick films and thin film. In addition thin-film deposition can be used in deposition techniques that are compatible with standard microelectronic technology. Last factor is very important for large-scale production, because the microelectronic approach promotes low cost for mass production, offers the possibility of manufacturing devices on a chip, and guarantees good reproducibility. Various metal oxides nanostructures, including nanowires, nanotubes, nanofibers, core-shell structures, and hollow nanostructures can also be synthesized. As it is known, the field of metal-oxide nanostructured morphologies (e.g., nanowires, nanorods, nanotubes, etc.) has become one of the most active research areas within the nanoscience community.

The ability to create a variety of metal oxide-based composites and the ability to synthesize various multicomponent compounds significantly expand the range of properties that metal oxide-based materials can have, making metal oxides a truly versatile multifunctional material for widespread use. As it is known small changes in their chemical composition and atomic structure can be accompanied by the spectacular variation in properties and behavior of metal oxides. Even now, advances in synthesizing and characterizing techniques are revealing numerous new functions of metal oxides.

Taking into account the importance of metal oxides for progress in microelectronics, optoelectronics, photonics, energy conversion, sensor, and catalysis, a large number of various books devoted to this class of materials have been published. However, one should note that some books from this list are too general, some are collections of various original works without any generalizations, and other ones were published many years ago. But, during past decade a great progress has been made on the synthesis as well as on the structural, physical, chemical characterization and application of metal oxides in various devices, and a large number of papers have been published on metal oxides. In addition, till now many important topics related to metal oxides study and application have not been discussed. To remedy the situation in this area, we decided to generalize and systematize the results of research in this direction and to publish a series of books devoted to metal oxides.

One should note that proposed book series Metal Oxides is the first one, devoted to consideration of metal oxides only. We believe that combining books on metal oxides in a series could help readers in searching required information on the subject. In particular, we believe that the books from our series, which have a clear specialization by its content, will provide interdisciplinary discussion for various oxide materials with a wide range of topics, from material synthesis and deposition to characterizations, processing, and then to device fabrications and applications. This book series is prepared by a team of highly qualified experts, which guarantees it a high quality.

I hope that our books will be useful and comfortable in use. I also hope that readers will consider the Metal Oxides book series like an encyclopedia of metal oxides that enables to understand the present status of metal oxides, to estimate the role of multifunctional metal oxides in design of advanced devices, and then based on observed knowledge formulate new goals for the further research.

The intended audience of present book series is scientists and researchers, working or planning to work in the field of materials related to metal oxides, that is, scientists and researchers whose activities are related to electronics, optoelectronics, energy, catalysis, sensors, electrical engineering, ceramics, biomedical designs, etc. I believe that the Metal Oxides book series will also be interesting for practicing engineers or project managers in industries and national laboratories, who would like to design metal oxide-based devices, but don’t know how to do it, and how to select optimal metal oxide for specific applications. With many references to the vast resource of recently published literature on the subject, this book series will be serving as a significant and insightful source of valuable information, providing scientists and engineers with new insights for understanding and improving existing metal oxide-based devices and for designing new metal oxide-based materials with new and unexpected properties.

I believe that the Metal Oxides book series would be very helpful for university students, postdocs, and professors. The structure of these books offers a basis for courses in the field of material sciences, chemical engineering, electronics, electrical engineering, optoelectronics, energy technologies, environmental control, and many others. Graduate students could also find the book series to be very useful in their research and understanding features of metal oxides synthesis, study and application of this multifunctional material in various devices. We are sure that all of them will find information useful for their activity.

Finally, I thank all contributing authors and book editors who have been involved in the creation of these books. I am thankful that they agreed to participate in this project and for their efforts in the preparation of these books. Without their participation, this project would have not been possible. I also express my gratitude to Elsevier for giving us the opportunity to publish this series. I especially thank all team of editorial office at Elsevier for their patience during the development of this project and for encouraging us during the various stages of preparation.


Stephen Pearton, Department of Materials Science and Engineering, University of Florida, Gainesville, FL, United States

Fan Ren, Department of Chemical Engineering, University of Florida, Gainesville, FL, United States

Michael Mastro, Electronics and Science Technology Division, US Naval Research Laboratory, Washington DC, United States

The properties of Ga2O3 have been investigated over a long period. For example, the phase equilibria of the Al2O3-Ga2O3-H2O system was first reported in 1952, just 5 years after the first demonstration of transistors in the Ge system. That initial work also identified the different polymorphs (i.e., different forms or crystal structures) of Ga2O3 and established their regions of stability. There are five commonly identified polymorphs of Ga2O3, labeled as α, β, γ, δ, and ɛ. These are known, respectively, as corundum (α), monoclinic (β), defective spinel (γ), and orthorhombic (ɛ), with the δ-phase commonly accepted as being a form of the orthorhombic phase. Among these different phases of Ga2O3, the orthorhombic β-gallia structure (β-phase or β-Ga2O3) is the most stable crystal structure and has attracted most of the recent attention. It is also the subject of this book. The melting point of Ga2O3 is about 1800°C and at such temperature only β-phase is stable among the five polymorphs. The different polymorphs can be either insulators or conductors, depending on the growth conditions. The resulting crystals are layered materials, similar to the behavior of GaSe and GaTe. The original studies in the 1950s and 1960s indicated that the other polymorphs of Ga2O3 convert to the stable β-form with heat treatment.

β-Gallium oxide (Ga2O3) is emerging as a viable candidate for certain classes of power electronics, solar blind UV photodetectors, solar cells, and sensors with capabilities beyond existing technologies due to its large bandgap. Research on β-Ga2O3 and to a lesser extent some of the other polymorphs, has been accelerating worldwide, especially since 2010. This is because its ultrawide-band-gap (~ 5 eV) has attracted considerable attention from the field of power electronics and ultraviolet optical device engineering, and 6-in. high-quality single crystals are now available owing to the development of liquid-solution technologies. Fig. 1 shows the exponential growth in the number of publications on Ga2O3 as a function of time on logarithmic scale. The observed exponential growth is evidence of constantly increasing interest in the topic. It is expected this trend will continue for the foreseeable future as research funding for power device development increases, which in turn will be driven by funding for development of bulk and epitaxial growth.

Fig. 1 Number of publications Ga 2 O 3 as a function of time. Data from the ISI Web of Knowledge search engine and was collated by Dr. Marko Tadjer of Naval Research Laboratory. The data were then plotted and supplied by courtesy of Dr. Lucas Lacasa, EPSRC Early Career Fellow and Senior Lecturer in Applied Mathematics, Queen Mary University of London (http://www.maths.qmul.ac.uk/~lacasa/main.html).

Since melt growth techniques can be used to grow bulk crystals of β-GaO3, the cost of producing larger area, uniform substrates is potentially lower compared with the vapor growth techniques used to manufacture bulk crystals of GaN and SiC, or more exotic wide-band-gap semiconductors like diamond. The main melt growth methods reported to date have included Czochralski (CZ), float zone (FZ), vertical Bridgman (VB)/vertical gradient freeze (VGF), and edge-defined film-fed growth (EFG) methods. An illustration of the relative cost of β-Ga2O3 grown by the EFG technique to a large diamond crystal of comparable value is shown in Fig. 2, where the Ga2O3 is already a thousand times less expensive than diamond. There are aggressive moves worldwide to lower the cost of bulk Ga2O3 substrates in order to accelerate the competitiveness of power electronics based on this material with that of SiC and GaN.

Fig. 2 Approximate cost of two representative ultrawide large bulk crystals of diamond (left) or Ga 2 O 3 (right). Courtesy of Dr. Marko Tadjer and Michael Mastro (Naval Research Laboratory, Washington DC, United States).

The performance of technologically important high-voltage rectifiers and enhancement-mode metal-oxide field effect transistors benefit from the larger critical electric field of β-Ga2O3 relative to either SiC or GaN. The estimated electric field breakdown field strength (EB) is in the range of 5–9 MV.cm and is commonly quoted as ~ 8 MV cm− 1 for β-Ga2O3. This value is roughly a factor of two larger than the theoretical limits of SiC and GaN. In terms of power switching device figures-of-merit, the large EB for Ga2O3 leads to a Baliga figure of merit almost three times larger than for GaN and SiC. Of course, this is a rule-of-thumb comparison only and it does not take into account limiting factors such as the low thermal conductivity of Ga2O3 and the need to develop the epitaxial growth, contacting, and gate dielectrics needed for a complete device technology. Similarly, the absence of facile p-type doping in Ga2O3, which may be a fundamental issue resulting from the band structure, makes it very difficult to simultaneously achieve low turn-on voltages on power switching devices. For simple switching devices like Schottky rectifiers, the ability to reduce DC conduction losses in by minimizing on-resistance (Ron) and maximizing breakdown voltage (VB) is attractive for high-power and high-voltage applications and, when combined with advanced scaling techniques, high-speed switches for low/medium-power applications.

The purpose of this book is to provide an update on recent advances in all areas of Ga2O3 materials, processing, and device development. These include epitaxial growth using advanced methods like metal organic chemical vapor deposition and molecular beam epitaxy, which are the workhorse thin film growth techniques for other compound semiconductors and because of their large installed base, will need to perform the same function for Ga2O3 transistor technologies. Recent work has shown the ability to control the electron densities in epitaxial layers from 10¹⁵ to 10²⁰ cm− 3 using Sn, Si, or Ge as the donor dopants. In terms of p-type doping, theory indicates that that all the expected acceptor dopants occupying Ga substitutional sites, a list that includes Li, Na, K, Be, Mg, Ca, Cu, Au, and Zn, result in deep acceptor levels and do not produce p-type conductivity in β-Ga2O3. These dopants are found to introduce deep acceptor levels with ionization energies of more than 1 eV. The prediction that holes are self-trapped to form polarons limits the current range of possible devices to unipolar conductivity. There has been observation of p-type conductivity, due most likely to ionized Ga vacancies at elevated temperature. The ionization energy of the acceptor level was measured to be 1.1 eV above the valence band edge. At elevated temperatures, up to 650 k, the measured hole mobility was 4.2 cm² V s− 1, much larger than predicted from the self-trapped (bound polaron) hole assumption.

The availability of high-quality, large-area native substrates offer a complete platform for various applications such as high-performance power switching, radio frequency (RF) amplifiers, and harsh environment signal processing. In this book, we did not cover bulk crystal growth and single crystals, because this has been the subject of a series of recent reviews in the special issues of Japanese Journal of Applied Physics, Vol. 55, Issue 12 (2016), entitled Gallium Oxide and Related Semiconductors, and the Electrochemical Society Journal of Solid State Science and Technology Focus Issue on Ultrawide Bandgap Materials and Devices, Vol. 6, Issue 2 (2017), as well as in a recent review on the progress in the growth of β-Ga2O3 for power electronics applications (Materials Science in Semiconductor Processing, Vol. 78, May 2018, pages 132–146, authored by Michele Baldini, Zbigniew Galazka, Günter Wagner). Examples of bulk crystals grown by various solution growth methods are shown in Fig. 3 and for more details, the reader is referred to the special journal issues listed above. In the materials synthesis area, we have instead focused on the topics of epitaxy and thin film deposition, as well as progress in nanostructures of β-Ga2O. We then explore the state-of-the-art in doping and structural properties, currently dominated by extended and point defects, look at the properties of (In,Ga)2O3 alloys, which will be critical for heterostructure devices based on Ga2O3 and examine the theory and mechanisms for high and low-field transport properties as well as the study and identification of electronic states using electron paramagnetic resonance.

Fig. 3 Bulk β-Ga 2 O 3 crystals grown from the melt by: (A) float zone (FZ), (B) EFG, (C) Czochralski (CZ), and (D) vertical Bridgman (VB). Reprinted with permission from Elsevier, Copyright 2016, Michele Baldini, Zbigniew Galazka, Günter Wagner, Recent progress in the growth of β-Ga2O3 for power electronics applications, Mater. Sci. Semicond. Process. 78 (2018) 132–146.

Hydrogen has a strong influence on the electrical properties of transparent conducting oxides where it can give rise to shallow donors and can passivate deep compensating defects. A lot of new information is now being reported about the nature of the dominant hydrogen-related defects in Ga2O3. This is followed by the crucial device processing technologies, namely, fabrication of Ohmic contacts and Schottky barriers and plasma and wet etching. Wide-band-gap devices are normally assumed to be radiation hard, allowing their use in environments like space. We include a chapter discussing the relative radiation hardness of Ga2O3 in comparison with GaN. There is a critical need to understand band alignments of common dielectrics on Ga2O3 and this is covered in one of the chapters. Finally, we have chapters on key device technologies, including solar-blind UV detectors using both thin films and exfoliated flakes, power MOSFETs and diodes, photo-assisted degradation of environmentally aggressive chemicals using Ga2O3 and finally, gas sensors capable of operation under elevated temperature conditions.

In summary, it is clear that Ga2O3 has an excellent combination of materials properties with the exception of thermal conductivity. The availability of large, high-quality bulk substrates, makes it an attractive option for power switching devices and solar-blind UV photodetection. There are still numerous areas that need additional work, including

(i)Improved Ohmic contacts through optimized surface cleaning, interface tailoring, and increased doping capabilities.

(ii)Better understanding of radiation damage in Ga2O3 and related heterostructures.

(iii)Interface state density mitigation processes for dielectrics for MOS devices, as well as how these are affected by process/patterning and contacting conditions.

(iv)Experimental clarification of energy levels of native defects such as oxygen vacancies and their role in residual conductivity relative to extrinsic impurities.

(v)Doping studies to obtain p-type conductivity.

(vi)Epi growth of β-(AlxGa1 − x)2O3/Ga2O3 and β-(InxGa1 − x)2O3 heterostructures growth to establish the stability regimes and compositional limits.

(vii)Novel thermal management approaches for power devices to exploit the much higher thermal conductivities available with heat-sink materials like Cu, SiC, or diamond.

This book provides a framework for understanding the current state-of-the-art and how advances might be made in the areas listed above.

Part One

Growth technology of Ga2O3


Progress in MOVPE growth of Ga2O3

Roberto Fornari⁎,†    ⁎ Department of Mathematical, Physical and Computer Sciences, University of Parma, Parma, Italy

† IMEM-CNR Institute, Parma, Italy


The metalorganic vapor-phase epitaxy (MOVPE) of gallium oxide is reviewed. It is shown that different Ga2O3 phases can be prepared by tuning the epitaxial growth parameters. The deposition temperature, partial pressure of the precursors, and crystallographic structure of the starting substrate/template are crucial in providing β, α, γ, and ɛ polymorph. At high deposition temperature (> 700°C), only the β-phase can be obtained, while at lower temperatures, the growth of the other metastable phases becomes possible. This chapter reviews the status of homoepitaxial and heteroepitaxial β-Ga2O3 as well as the heteroepitaxial growth of the orthorhombic pseudo-hexagonal ɛ-phase. It is shown that although metastable, ɛ-Ga2O3 may be grown with very good crystallographic properties on different hexagonal substrates.


Semiconducting gallium oxide; Metalorganic chemical vapor deposition; Polymorphism; Heterostructures

Chapter Outline


1.2Homoepitaxial deposition of β-Ga2O3

1.3Heteroepitaxial deposition of β-Ga2O3

1.4Heteroepitaxial deposition of ɛ-Ga2O3


1.1 Introduction

Semiconducting sesquioxides, especially Ga2O3, are known since decades [1–3]; however, it is only in the past few years that they are massively investigated. This is essentially due to the development of suitable technologies for growth of large single crystals [4–9] and homo- and heteroepitaxial layers [10–15]. The possibility of growing single crystals and films with relatively low defect density, opened the way to new application areas, in addition to the well-known transparent conducting oxides (TCO) electrodes, namely, (i) substrates for GaN epilayers and (ii) high-power transistors, and (iii) UV detectors.

Although the homoepitaxial growth is supposed to provide layers of higher crystallographic perfection, the deposition of gallium oxide on hetero-substrates such as α-Al2O3 (sapphire) is still very popular. It has the advantage of directly providing electrical isolation of the film, which may turn out useful in view of the application of β-Ga2O3 to power field effect transistors (FETs). Furthermore, sapphire wafers are commercially available with diameters of up to 6″ and very cheap compared with the still expensive Ga2O3 substrates.

This chapter provides a survey of the recent advances in homo- and heteroepitaxial deposition of Ga2O3 by metal-organic vapor-phase epitaxy (MOVPE). This includes (i) MOVPE deposition of β-Ga2O3 on differently oriented β-Ga2O3 homo-substrates; (ii) MOVPE deposition of β-Ga2O3 on hetero-substrates, with special emphasis on sapphire; and (iii) MOVPE deposition of metastable crystalline phases of gallium oxide.

1.2 Homoepitaxial deposition of β-Ga2O3

Most investigations on homoepitaxial β-Ga2O3 have been carried out by molecular beam epitaxy (MBE) and more rarely by MOVPE. The reason for this lies in the gap that for a long time existed between the relatively poor structural quality of β-Ga2O3 layers grown by MOVPE in comparison to MBE materials. Indeed, the maximum electron mobilities of MOVPE layers were limited to about 40 cm²/Vs, while in layers grown by MBE on (010)-oriented homosubstrates were > 100 cm²/Vs.

However, as the MOVPE technology is more suitable for large-scale production of semiconductors, in the last times great efforts were made in order to improve the quality of homoepitaxial β-Ga2O3 by MOVPE. Different types of β-Ga2O3 wafers were tested as substrates and two orientations were generally used: (100) and (010). Of greatest importance is the wafer surface preparation before initiating the epitaxial growth: the (100) β-Ga2O3 substrates were first cleaned with acetone and isopropylic alcohol and then annealed in oxygen ambient at 1000°C for at least 1 h. This was sufficient to remove the subsurface polishing damage and get a regular step-and-terrace surface as shown in Fig. 1.1. Of course, the terrace width is a function of the substrate disorientation. In the example of Fig. 1.1, the surface deviated by about 0.2 degrees from the perfect (100) and the corresponding width was about 70–100 nm.

Fig. 1.1 (A) AFM image of (100)-oriented β-Ga 2 O 3 after thermal annealing at 1000°C in oxygen ambient; (B) Corresponding surface scan. Note the formation of regular steps (0.6 nm high) and terraces (70–90 nm wide). From G. Wagner et al., Homoepitaxial growth of β-Ga2O3 layers by metal-organic vapor phase epitaxy, Phys. Status Solidi Appl. Mater. Sci. 211 (2014) 27–33.

Trimethylgallium (TMGa) is normally taken as Ga precursor while oxygen is supplied either as a pure gas (O2) or via water dissociation in the growth reactor. Surprisingly, the initial MOVPE deposition on (100) substrates did not result in coherent layers, but rather in nanowire and nanoparticles deposition, when using oxygen gas as oxidation source H bonds and thus reduce the surface state density. Therefore, this would change the surface potential and the kinetics at the substrate surface, promoting the layer-by-layer growth. The initial decomposition of the substrate, with the formation of tiny Ga clusters, that catalyzes the nucleation and growth of nanostructures cannot however be ruled out. If that is the actual case, one is therefore led to conclude that atomic oxygen from water dissociation in the high-temperature reactor chamber is more effective in preventing dissociation of the (100) surface of β-Ga2O3. What is sure is that taking H2O as atomic oxygen source leads to layer-by-layer growth and smooth layers as reported in Refs. [11, 13, 16].

The growth of homoepitaxial single-phase β-Ga2O3 on (010) substrates by low-pressure CVD was reported in Ref. [17]. Authors investigated the surface morphology and crystal quality as a function of growth temperature dependences. The growth studies were carried out in a custom-designed CVD system on commercial (010) β-Ga2O3 substrates synthesized by the EFG growth method. The dislocation density of the substrate was estimated to be < 10⁷ cm− 2. High-purity gallium pellets and oxygen were used as the source materials and argon (Ar) was used as the carrier gas. A maximum growth rate of 1.3 μm/h was obtained at 850°C while the best morphology was obtained at 950°C, at the expenses of a lower growth rate. The smallest root-mean-square surface roughness was ~ 7 nm, as shown in Fig. 1.2. The general trend indicates that the layers become more homogeneous with the increase of growth temperature. All the layers exhibited multistep arrays resembling terrace-like morphology (reproducing that of the substrate). The feature size became smaller with the increase of the growth temperature.

Fig. 1.2 Surface AFM images (5 μm × 5 μm) of β-Ga 2 O 3 homoepitaxial layers grown by low-pressure CVD at different temperatures. From S. Rafique, L. Han, M.J. Tadjer, J.A. Freitas, N.A. Mahadik, H. Zhao, Homoepitaxial growth of β-Ga2O3 thin films by low pressure chemical vapor deposition, Appl. Phys. Lett. 108 (18) (2016) 182105.

The crystal quality and interfacial structure of the β-Ga2O3 homoepitaxial layer grown at 850°C were investigated with cross sectional TEM and HRTEM as well as selected area electron diffraction (SAED) pattern [17]. The HRTEM study (see Fig. 1.3) confirmed that the deposited crystal is monoclinic β-Ga2O3 and that the interface between the grown layer and the substrate is undifferentiable along the cross section, indicating that the layer is coherently grown on the substrate (Fig. 1.3A). The SAED pattern of the layer taken along the [− 20 − 1] zone axis confirms that the synthesized thin film is just composed of monoclinic β-Ga2O3, and so does the HRTEM image of Fig. 1.3C, where the lattice fringes with marked interplane distances of 0.15 nm and 0.21 nm are shown. Such distances indeed correspond to interplane spacings of monoclinic β-Ga2O3 (020) and (− 112) planes, respectively.

Fig. 1.3 (A) Cross-sectional TEM image of β-Ga 2 O 3 homoepitaxial layer grown on β-Ga 2 O 3 (010) substrate at 850°C. (B) SAED pattern of β-Ga 2 O 3 homoepitaxial layer taken along [− 20 − 1] zone axis. (C) HRTEM image of β-Ga 2 O 3 homoepitaxial layer showing the lattice interplane distances. From S. Rafique, L. Han, M.J. Tadjer, J.A. Freitas, N.A. Mahadik, H. Zhao, Homoepitaxial growth of β-Ga2O3 thin films by low pressure chemical vapor deposition, Appl. Phys. Lett. 108 (18) (2016) 182105.

The HR-XRD characterization of the epilayers again showed that the substrate temperature has a great influence on the final crystalline quality of the layers. At 950°C, the X-ray diffraction (XRD) pattern of substrate and films were practically overlapping but the film grown and 900°C was found to be under slight compressive strain, estimated to be of about 0.11%. The reason for built-in strain at lower temperature however was not discussed.

The growth on (010) β-Ga2O3 substrates seems to be more favorable in terms of higher crystalline perfection than the growth on (100) substrates. Furthermore, if one considers that the thermal conductivity of bulk β-Ga2O3 is anisotropic [18], being higher along the [010] direction (27.0 W/mK at RT) and substantially lower along the [100] direction (10.9 W/mK at RT), the (010)-oriented substrates become advantageous from the point of view of heat dissipation. Actually, in power devices fabricated on (010) substrates, the heat transfer is predicted to be almost three times more efficient than in other directions. This is an interesting finding, although the overall thermal conductivity of bulk β-Ga2O3 remains lower than the one of the competing materials SiC and GaN.

Further experiments on the homoepitaxial growth of β-Ga2O3 on (010) substrates by MOVOP were recently reported in Refs. [13, 19]. The authors clearly stated that (010)-oriented films generally possess higher structural quality and are easier to grow with respect to (100) orientation. They used triethylgallium (TEGa) and O2 as precursors under standard temperature and pressure conditions of 850°C and 5 mbar. The layers exhibited a flat surface with a mean roughness (RMS) of ∼ 600 pm. The morphology being dominated by elongated islands oriented along the [001] direction. The growth rate, estimated from the resulting layer thickness and the growth time, was 2 nm/min, which was about 20% higher than that of layers grown on (100) substrates by the same group [11]. This result contrasted published data for MBE growth reporting that growth rates on (010) surfaces are > 10 times higher than those on (100) substrates because of a higher reevaporation rate of the highly volatile Ga2O species from the (100) plane [20]. Attempts to increase the growth rate by applying higher TEGa and O2 flow rates, while keeping a constant molar ratio between the two precursors, resulted in progressively increasing roughness up to a RMS value around 11 nm. The epitaxial growth on (010) Fe-doped semiinsulating β-Ga2O3 substrates proved to be very suitable from the point of view of n-type doping. Actually, by using tetraethylorthosilicate (TEOS) and tetraethyltin (TESn) as metallorganic precursors for Si and Sn, it was possible to achieve very high carrier concentrations. When the flow rates of TEOS and TESn were varied in the range ∼ 1 × 10− 11–1 × 10− 8 mol/min, the free carrier concentrations could be adjusted in the doping range 1 × 10¹⁷ and 8 × 10¹⁹ cm− 3 [19]. It seems however that Si has to be preferred as donor, because of its higher incorporation rate and no memory effects in the MOVPE reactor.

In a series of recent papers, the group at IKZ Berlin explained why the doping is more successful for epitaxial growth on (010) substrates and also provided some hints on elimination of structural defects in (100)-oriented films as a method to improve the doping efficiency in these epilayers [21, 22]. In Ref. [21], the electrical transport properties of Si-doped β-Ga2O3 (100) homoepitaxial layers were studied as a function of substrate misorientation: the layers perfectly (100) oriented, or with small off-orientation, exhibited low mobility values as well as low doping efficiency. Furthermore, the Hall mobility collapsed below a threshold electron concentration (about 10¹⁸ cm− 3), in that reproducing the behavior already observed for Sn-doped layers [13]. By using transmission electron microscopy (TEM), authors showed that these homoepitaxial layers contained a very high density of twin lamellae with two different atomic structures, namely, coherent boundaries parallel to (100) and incoherent ones parallel to (001). While the former type of twins preserves the atomic coordination, in case of the incoherent twin boundaries (ITBs) one dangling bond per unit cell is present. The dangling bonds are arranged along the ITBs of thin twin lamellae and may act as acceptors. This model of electrically active dislocations is similar to the one first suggested by Read [23] and applied more recently in order to explain unusual carrier mobilities in GaN with high dislocation density [24, 25]. Based on the density and geometry of the ITBs, estimated by TEM measurements, authors could quantitatively confirm that mobility reduction and collapse, as well as part of the compensation, are due to the presence of twin lamellae. Fig. 1.4 shows the presence and distribution of such defects in layers homoepitaxially grown on substrates with different mis-cuts between 0.1 degrees and 4 degrees. It is apparent that only substrates with relatively large misorientation yield layers free of laminar twins. On the other hand, one should remember that the terrace width changes with the misorientation, that is, it is larger for small angles, which enhances the probability of two-dimensional (2D) island nucleation, as schematically reported in Fig. 1.5. The way Ga atoms may stick to the surface is clearly twofold; therefore, if they do not reach the step, due to large terraces or reduced diffusivity, the chance of laminar twinning becomes high. Based on this model, the authors concluded that homoepitaxial growth by MOVPE on (100) β-Ga2O3 is very challenging. The stacking faults, in form of laminar twins, are characterized by a c/2 glide reflection as twin relation. Coalescence of twinned and epitaxial 2D islands results in the formation of ITBs that actually present electrically active dangling bonds, and thus compensate and reduce the mobility of charge carriers. The limited surface diffusion of the Ga-adatoms and the small substrate miscut-angle are responsible for the high density of stacking-faults experimentally observed in homoepitaxial films. Therefore, one should look for growth conditions that yield step-flow. Possible approaches toward twin-free epilayers include higher growth temperatures, application of surfactants in order to enhance the species diffusion on the surface or reduction of terrace width by adopting substrates with high miscut-angles of about 6 degrees. The diffusion coefficient of Ga at the gas–solid interface at the growth temperature of 850°C was estimated to be 7 × 10− 9 cm− 2 s− 1, that is, two orders of magnitude lower than the one experimentally found in GaAs but 6 orders of magnitude higher than for cubic GaN.

Fig. 1.4 TEM study of twin lamellae in homoepitaxial (100) β-Ga 2 O 3 : (A) substrate with off-orientation of 0.1 degrees; (B) of 0.2 degrees; (C) of 2.0 degrees; and (D) of 4.0 degrees. From R. Schewski et al., Evolution of planar defects during homoepitaxial growth of β-Ga2O3 layers on (100) substrates—a quantitative model, J. Appl. Phys. 120 (2016) 225308.

Fig. 1.5 Schematic of monolayer growth on a terraced (100) surface of β-Ga 2 O 3. (A) Stick-and-ball model illustrating two possible positions of Ga on the (100); dark green and light green balls correspond to tetrahedral (Ga I) and octahedral (Ga II) bound Gallium atoms, respectively. The little red, orange, and yellow balls correspond to different oxygen sites OI, OII, and OIII. (B) Schematic diffusion model showing step-flow growth or island nucleation in dependence of terrace width and/or atom surface diffusion coefficient. From R. Schewski et al., Evolution of planar defects during homoepitaxial growth of β-Ga2O3 layers on (100) substrates—a quantitative model, J. Appl. Phys. 120 (2016) 225308.

In another study on homo- and heteroepitaxial β-Ga2O3, it was pointed out that in spite of an heavy Si-doping the films were found to be electrically insulating [26]. The positron annihilation study of these samples evidenced a relatively high Ga vacancy concentration (> 5 × 10¹⁷ cm− 3), higher than the silicon concentration of 10¹⁷ cm− 3. Theoretical calculations predict that the VGa should be in a negative charge state when Fermi levels is located in the upper half of the band gap, hence compensating for n-type doping [27]. The high resistivity of those Si-doped β-Ga2O3 epilayers was therefore attributed to the experimentally observed Ga vacancy concentrations in films.

1.3 Heteroepitaxial deposition of β-Ga2O3

As for homoepitaxial Ga2O3, also in the case of heteroepitaxy, most work has till now been done with plasma-assisted MBE and relatively little with MOVPE. (0001)-Oriented sapphire wafers were by far the most used hetero-substrates [10, 14, 28–31], although attempts were made also on GaAs [15], MgAl2O4 [12], and MgO [32] substrates.

In Ref. [14], MOVPE heteroepitaxy of β-Ga2O3 was performed on both a-plane and c-plane sapphire substrates using a TMGa precursor (22.5 Lmol/min) and approximately 5:1 O2/TMGa flow rate ratio. A pressure level of 6.67 kPa (0.066 atm, 50 Torr) at a temperature range of 600–800°C was used to obtain crystalline films in the preferred phase. The as-grown films were characterized by high-resolution XRD and Raman spectroscopy. According to Raman investigation, the films were not phase pure but probably contained some α-Ga2O3 inclusions as well as other Ga-related phases. It is to be recalled here that small α-phase inclusions were usually detected in heteroepitaxial Ga2O3 by high-resolution

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