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Metal Oxide-Based Thin Film Structures: Formation, Characterization and Application of Interface-Based Phenomena

Metal Oxide-Based Thin Film Structures: Formation, Characterization and Application of Interface-Based Phenomena

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Metal Oxide-Based Thin Film Structures: Formation, Characterization and Application of Interface-Based Phenomena

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Sep 7, 2017


Metal Oxide-Based Thin Film Structures: Formation, Characterization and Application of Interface-Based Phenomena bridges the gap between thin film deposition and device development by exploring the synthesis, properties and applications of thin film interfaces.

Part I deals with theoretical and experimental aspects of epitaxial growth, the structure and morphology of oxide-metal interfaces deposited with different deposition techniques and new developments in growth methods. Part II concerns analysis techniques for the electrical, optical, magnetic and structural properties of thin film interfaces. In Part III, the emphasis is on ionic and electronic transport at the interfaces of Metal-oxide thin films.

Part IV discusses methods for tailoring metal oxide thin film interfaces for specific applications, including microelectronics, communication, optical electronics, catalysis, and energy generation and conservation.

This book is an essential resource for anyone seeking to further their knowledge of metal oxide thin films and interfaces, including scientists and engineers working on electronic devices and energy systems and those engaged in research into electronic materials.

  • Introduces the theoretical and experimental aspects of epitaxial growth for the benefit of readers new to the field
  • Explores state-of-the-art analysis techniques and their application to interface properties in order to give a fuller understanding of the relationship between macroscopic properties and atomic-scale manipulation
  • Discusses techniques for tailoring thin film interfaces for specific applications, including information, electronics and energy technologies, making this book essential reading for materials scientists and engineers alike
Lançado em:
Sep 7, 2017

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Metal Oxide-Based Thin Film Structures - Elsevier Science

Metal Oxide-Based Thin Film Structures

Formation, Characterization and Application of Interface-Based Phenomena

First Edition

Nini Pryds

Vincenzo Esposito

Series Editor

Ghenadii Korotcenkov

Table of Contents

Cover image

Title page



Editors’ biographies

Series editor’s biography

Preface to the series


Section A: Interface formation: Theoretical aspect in epitaxial growth mechanisms, structural features and defects formation

1: Epitaxy of 5d transition metal oxide thin films and heterostructures



1.1 Introduction

1.2 Challenges and opportunities in thin film synthesis

1.3 Single-phase films

1.4 5d heterostructures and superlattices

1.5 Conclusions and future direction

2: Oxide superlattices by PLD: A practical guide


2.1 Introduction

2.2 Growth templates

2.3 Growth of superlattices (diagnostics); examples

2.4 Conclusions

3: Oxide molecular beam epitaxy of complex oxide heterointerfaces


3.1 Introduction

3.2 Oxide MBE system

3.3 MBE synthesis schemes

3.4 MBE growth control of oxide heterostructures

3.5 Cases of heterointerface study

3.6 Conclusions

3.7 Final remarks

4: Electrochemical ionic interfaces



4.1 Introduction

4.2 Defects and transport in ionic conductors

4.3 Interfacial transport

4.4 Outlook

Section B: Experimental: Structural and compositional characterization techniques of metal oxides interfaces

5: In situ stress measurements of metal oxide thin films


5.1 Materials engineering in heteroepitaxial thin films

5.2 Strain relaxation in epitaxial films: An overview of established principles and models

5.3 In situ strain or stress observation techniques

5.4 Application of in situ strain/stress monitoring techniques

5.5 Summary and outlook

6: Plume characterization in pulsed laser deposition of metal oxide thin films


6.1 Introduction

6.2 Experimental diagnostic techniques of the laser ablation plume

6.3 Plume dynamics of metal oxides in a background gas

6.4 Deposition rate of metal oxides in a background gas

6.5 Ion probe investigations of metal oxides in a background gas

6.6 Influence of the background gas on metal oxide thin films stoichiometry

6.7 Summary

7: Photoemission of buried metal oxide interfaces



7.1 Introduction

7.2 Basics of photoemission spectroscopy

7.3 Photoemission of core levels

7.4 Photoemission of valence band

7.5 Conclusions and outlook

8: Functional material properties of oxide thin films probed by atomic force microscopy on the nanoscale


8.1 Introduction to dynamic contact mode atomic force microscopy

8.2 Electrostatic forces in contact mode

8.3 Piezoelectric coefficients of ferroelectric materials

8.4 Dielectric tunability

8.5 Ionic motion in Li-ion conducting materials

8.6 Outlook

9: Controlled atmosphere high-temperature scanning probe microscopy (CAHT-SPM)


9.1 Introduction to high-temperature SPM

9.2 Importance of in situ and in operando local probing measurements

9.3 The CAHT-SPMs

9.4 In situ surface reduction of NiO by hydrogen between 312°C and 523°C

9.5 Local electrochemical measurements at 650°C to 850°C

9.6 Conductance mapping of LSM microelectrodes and correlation with complementary techniques

9.7 Strong cathodic polarization of PtIr-YSZ microcontacts at 650°C

9.8 High-temperature Kelvin probe force microscopy at 300–600°C

9.9 Outlook

10: Scanning SQUID measurements of oxide interfaces



10.1 Introduction to scanning superconducting quantum interference device (SQUID)

10.2 Introduction to scanning SQUID measurements of oxides

10.3 Superconductivity

10.4 Magnetism

10.5 LaMnO3/SrTiO3

10.6 Current flow

Section C: Modeling and properties at the metal oxide interfaces

11: First-principle study of metal oxide thin films: Electronic and magnetic properties of confined d electrons


11.1 Transition metal oxides: d electron

11.2 Perovskite TM oxides: Symmetry and correlation

11.3 DFT and simplified TB model for bulk SrVO3

11.4 DFT results of thin films

11.5 Difference between bulk and thin films

11.6 The first change: Cutting the hopping term and intrinsic confinement effect

11.7 Additional effects from the surface/interface and spin-orbit coupling

11.8 Correlation effects on confined d electrons

11.9 Discussion of SrRuO3 (001) and (111) thin films

11.10 Summary

12: Computational study of energy materials


12.1 Introduction

12.2 Atomic simulation methodology

12.3 The role of point defects in MO

12.4 Intrinsic defects in MoO3

12.5 Hydrogen defects in WO3

12.6 Oxygen diffusion in doped CeO2

12.7 Summary and future perspectives

13: High-mobility two-dimensional electron gases at complex oxide interfaces


13.1 Introduction

13.2 2DEGs at SrTiO3-based oxide interfaces

13.3 Modulation-doping of oxide 2DEGs

13.4 Conclusions and remarks

14: Strain and interfaces for metal oxide-based memristive devices


14.1 Introduction

14.2 Fabrication of strained interfaces for mixed ionic-electronic multilayer conductors

14.3 Structural characterization of strained multilayer interfaces—A critical discussion of tools

14.4 Integration of strained multilayer oxides to ionotronic devices: Modulation of memristance through interfacial strain in multilayers

14.5 A case study on the system Gd0.1Ce0.9O2−δ/Er2O3

14.6 Summary and outlook

Section D: Applications of metal oxide interfaces

15: Metal oxide thin film-based low-temperature-operating solid oxide fuel cell by interface structure control



15.1 What is solid oxide fuel cell (SOFC)?

15.2 Why low-temperature-operating SOFC (LT-SOFC) is interesting?

15.3 Operating temperature range of LT-SOFC

15.4 Approaches for lowering the operating temperature of SOFCs

15.5 Challenges in realizing proper metal oxide thin film structure in LT-SOFCs

15.6 Free-standing-membrane-based LT-SOFCs: Micro-SOFCs

15.7 LT-SOFCs fabricated over porous supports

15.8 Concluding remarks

16: Ionic conductivity of metal oxides: An essential property for all-solid-state lithium-ion batteries


16.1 MeO-based materials for all-solid-state LIBs

16.2 Thin film deposition for all-solid-state Li-ion micro-batteries

16.3 3D thin film deposition for all-solid-state Li-ion batteries

16.4 Mobility of Li-ions in all-solid-state batteries

16.5 Conclusions

17: Nanoionics and interfaces for energy and information technologies


17.1 Introduction to nanoionics: Beyond bulk properties

17.2 Origin of nanoionics effects: Local defects and interfaces

17.3 Strategies for the implementation of nanoionics in functional oxide thin films

17.4 Prospects for applications of nanoionics in metal oxide thin film-based devices for energy and information applications

18: Thermoelectrics based on metal oxide thin films


18.1 Introduction

18.2 Epitaxial films of oxide thermoelectrics

18.3 Two-dimensional electron system for oxide thermoelectrics

18.4 Summary and future prospect

19: Ferroelectric and piezoelectric oxide nanostructured films for energy harvesting applications


19.1 Introduction

19.2 Ferroelectric oxide nanostructures with enhanced properties

19.3 Piezoelectric oxide nanostructures for energy harvesting

19.4 Outlook

20: Redox-based memristive metal-oxide devices


20.1 Introduction

20.2 Basic mechanisms of redox-based memristive switching

20.3 Filamentary switching

20.4 Area-dependent switching

20.5 Switching kinetics

20.6 Fields of application




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S. Amoruso     Università di Napoli Federico II, Complesso Universitario di Monte S. Angelo, Naples, Italy

F. Baiutti     Max Planck Institute for Solid State Research, Stuttgart, Germany

N. Balke     Oak Ridge National Laboratory, Oak Ridge, TN, United States

C. Bäumer     Peter Grünberg Institute (PGI-7) and JARA-FIT, Jülich, Germany

Y.Z. Chen     Technical University of Denmark, Roskilde, Denmark

C. Chen

Eindhoven University of Technology, Eindhoven, The Netherlands

Forschungszentrum Jülich (IEK-9), Jülich, Germany

F. Chiabrera     Catalonia Institute for Energy Research (IREC), Barcelona, Spain

G. Christiani     Max Planck Institute for Solid State Research, Stuttgart, Germany

A. Chroneos

Coventry University, Coventry, United Kingdom

Imperial College London, London, United Kingdom

A. Datta     University of Cambridge, Cambridge, United Kingdom

R. Dittmann     Peter Grünberg Institute (PGI-7) and JARA-FIT, Jülich, Germany

R.-A. Eichel

Eindhoven University of Technology, Eindhoven, The Netherlands

RWTH Aachen University, Aachen, Germany

A. Fluri     Paul Scherrer Institut, Villigen, Switzerland

Y. Frenkel     Bar-Ilan University, Ramat-Gan, Israel

I. Garbayo     Catalonia Institute for Energy Research (IREC), Barcelona, Spain

K.V. Hansen     Technical University of Denmark, Lyngby, Denmark

G.F. Harrington

Massachusetts Institute of Technology, Cambridge, MA, United States

Kyushu University, Fukuoka, Japan

M. Huijben     University of Twente, Enschede, Netherlands

B. Kalisky     Bar-Ilan University, Ramat-Gan, Israel

S. Kar-Narayan     University of Cambridge, Cambridge, United Kingdom

G. Koster     University of Twente, Enschede, Netherlands

H.N. Lee     Oak Ridge National Laboratory, Oak Ridge, TN, United States

G. Logvenov     Max Planck Institute for Solid State Research, Stuttgart, Germany

Y. Lu     Max Planck Institute for Solid State Physics, Stuttgart, Germany

D. Mukherjee     Technical Research Center, Indian Association for the Cultivation of Science, Kolkata, India

J. Nichols     Oak Ridge National Laboratory, Oak Ridge, TN, United States

P.H.L. Notten

Eindhoven University of Technology, Eindhoven, The Netherlands

Forschungszentrum Jülich (IEK-9), Jülich, Germany

H. Ohta     Hokkaido University, Sapporo, Japan

D. Pergolesi     Paul Scherrer Institut, Villigen, Switzerland

N.H. Perry

Massachusetts Institute of Technology, Cambridge, MA, United States

Kyushu University, Fukuoka, Japan

G. Rijnders     University of Twente, Enschede, Netherlands

J.L.M. Rupp     Massachusetts Institute of Technologies (MIT), Cambridge, MA, United States

C.W. Schneider     Paul Scherrer Institut, Villigen, Switzerland

S. Schweiger     ETH Zurich, Zurich, Switzerland

M. Sing     University of Würzburg, Würzburg, Germany

J.-W. Son

Korea Institute of Science and Technology (KIST), Seoul, Republic of Korea

Korea University of Science and Technology, Daejeon, Republic of Korea

A. Tarancón     Catalonia Institute for Energy Research (IREC), Barcelona, Spain

A. Tselev     University of Aveiro, Aveiro, Portugal

H.L. Tuller     Massachusetts Institute of Technology, Cambridge, MA, United States

F. Wrobel     Max Planck Institute for Solid State Research, Stuttgart, Germany

Z. Zhong     Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, China

Editors’ biographies

Nini Pryds is professor and head of the research section Electrofunctional Materials at the Department of Energy Conversion and Storage, The Technical University of Denmark (DTU), where he leads a group of about 35 researchers working in the field of magnetic refrigeration, thermoelectricity, and functional oxide thin films. During the last 15 years, he has played a leading role in new cross-disciplinary research fields in the area of functional materials for energy application. In Denmark, he has started and matured an area now known as magnetic refrigeration, which is based on the magnetocaloric effect. His group is recognized internationally as one of the leading group worldwide in this area. At DTU, he also started the work on high-temperature thermoelectric materials and his group succeeded to develop the highest zT p-type oxide materials reported so far. His group has developed a thermoelectric oxide module, which currently holds the highest efficiency oxide module. His interest also includes the area of epitaxial growth of complex oxides, which include materials physics of complex oxides. The most exciting result of his group is the creation of a metallic interface between amorphous oxide films and crystalline SrTiO3 (STO) controlled by chemical redox reactions at oxide interfaces. His group has also shown for the first time a new interface system, which exhibits electron mobilities of greater than 100,000 cm² V−1 s−1 at 2K. An original concept of modulation-doped complex oxide interfaces by charge transfer, which leads to the observation that the quantum Hall effect at these oxide interfaces was developed by his group.

Vincenzo Esposito is a professor in Ceramic Science and Engineering and a technology coordinator at the Department of Energy Conversion and Storage, Technical University of Denmark. He developed his career at Risø DTU National Laboratory for Sustainable Energy, University of Rome Tor Vergata, University of Florida, and at the Instituto de Pesquisas Energéticas e Nucleares (IPEN)—Brazil. His research interest is primarily on functional inorganic nanomaterials and on processing for emerging technologies in energy, catalysis, electromechanical, electronics, and electrochemical systems. His research profile lies at the frontiers between nanoionics, solid-state chemistry, and advanced materials processing. Highlights of his recent work are on nanoconfinement of highly defective metal-oxide interfaces to achieve new metastability domains, designing new thermochemical methods to manipulate interfaces in ionotronic composites, and disclosing fast mass diffusion mechanisms in highly defective metal oxides.

Series editor’s biography

Ghenadii Korotcenkov received his PhD in material sciences from the Technical University of 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 the manager of various national and international projects carried out in the Laboratory of Micro- and Optoelectronics in the Technical University of Moldova. His research had financial support from international foundations and programs such as CRDF, MRDA, ICTP, INTAS, INCO-COPERNICUS, COST, and NATO. From 2007 to 2008, he was an invited scientist in the Korea Institute of Energy Research (Daejeon). After which, and until now, Dr. G. Korotcenkov is a research professor at the School of Materials Science and Engineering at the Gwangju Institute of Science and Technology in Korea.

Scientific interests of G. Korotcenkov, starting from 1995, include material sciences, focusing on metal oxide film deposition and characterization; surface science; and the design of thin-film gas sensors and thermoelectric convertors. G. Korotcenkov is the author or editor of 35 books, including the 11-volume Chemical Sensors series published by Momentum Press (the 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 (the United States), and 2-volume Handbook of Gas Sensor Materials published by Springer (the United States). G. Korotcenkov is the author and coauthor of more than 550 scientific publications, including 20 review papers, 35 book chapters, and more than 250 articles published in peer-reviewed scientific journals (h-factor=38 (Scopus) and h=44 (Google Scholar citation)). He is a holder of 17 patents. He has presented more than 200 reports at national and international conferences, including 15 invited talks. G. Korotcenkov was the coorganizer of several international conferences. His research activities are honored by an award of the Supreme Council of Science and Advanced Technology of the Republic of Moldova (2004); the Prize of the Presidents of the Ukrainian, Belarus, and Moldovan Academies of Sciences (2003); and the 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 & Exchanges Board (IREX, the United States, 1998), Brain Korea 21 Program (2008–12), and Brain Pool Program (Korea, 2015–17).

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 have a 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 to other solid materials. In particular, metal oxides represent an assorted and appealing class of materials, the properties of which exhibit a full spectrum of electronic properties—from insulating to semiconducting, metallic, and superconducting. Moreover, almost all the known effects such as 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 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, i.e., they can be used as active and passive components.

Among the 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 as thin films. For thin-film deposition, deposition techniques that are compatible with standard microelectronic technology can be used. The 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-oxide 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 a spectacular variation in properties and behavior of metal oxides. Even now, advances in synthesizing and characterizing techniques are showing 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 books are collections of various original works without any generalizations, and the other ones were published many years ago. However, during the past decade 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 study of metal oxides and their 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 the proposed book series Metal Oxides is the first one, devoted to the consideration of metal oxides only. We believe that combining books on metal oxides in a series could help readers in searching the required information on the subject. In particular, we plan 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 to use. I also hope that the readers will consider this Metal Oxides book series like an encyclopedia of metal oxides that enables one to understand the present status of metal oxides, to estimate the role of multifunctional metal oxides in the design of advanced devices, and then based on observed knowledge to formulate new goals for further research.

The intended audience of the present book series is scientists and researchers, working or planning to work in the field of materials related to metal oxides, i.e., scientists and researchers whose activities are related to electronics, optoelectronics, energy, catalysis, sensors, electrical engineering, ceramics, biomedical designs, etc. I believe that this Metal Oxides book series will also be interesting for practicing engineers or project managers in industries and national laboratories, which would like to design metal-oxide–based devices, but do not know how to do it, and how to select the 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 the existing metal-oxide–based devices and for designing new metal-oxide–based materials with new and unexpected properties.

I believe that this 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 the features of metal-oxide 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.


N. Pryds; V. Esposito, Copenhagen 2017

Solid-state oxides are widely and abundantly distributed in nature with different degrees of structural complexity, from the simplest rock salt to the more complex silicate structures. Functional oxides have specific structural characteristics: cations with possible mixed valance states and oxygen anions with deficiencies (e.g., vacancies). By tuning these constituents, the oxide materials exhibit a wide range of unusual and valuable properties such as electrical, optical, magnetic, and chemical properties.

Among the different type of oxides, transition metal oxides (TMOs) are probably one of the most interesting classes of solid materials, exhibiting a wide range of structures and physical properties such as superconductivity, semiconductivity, metallic, ferromagneticity, ferroelectricity, or can undergo semiconductor-metal transitions just to name a few. They are also used as electrodes in electrochemical processes, in selective oxidation, selective reduction, and in dehydrogenation. The properties of TMOs are the result of a unique nature of the outer d-electrons and the strong electronic correlations, enhanced by the interplay of spin, orbital, charge, and lattice degrees of freedom. In transition-metal ions, d-electrons experience competing forces: Coulombic repulsion tends to localize individual electrons at atomic lattice sites (ionic), while hybridization with the oxygen p electron states tends to delocalize the electrons (covalent).

Among the different TMOs, perovskite oxides having the structural formula ABO3 or A2BO4 building block, where A and B are metallic cations, constitute a very important family with a rather simple structure but with a large variety of possible substitutional cations and dopants. These perovskite oxides form an interesting class of materials with a wide range of physical and chemical properties, where the thin-film properties of these oxides usually differ from the bulk material. The study of surfaces and interfaces of thin films has driven the development of several advanced film fabrication and characterization techniques that are required to probe such heterostructures down to the scale of single atoms. Great progress has been therefore made over the years in terminating oxide substrates at well-defined atomic planes, followed by deposition using a variety of growth techniques such as pulsed laser deposition (PLD) and/or oxide molecular beam epitaxy (oxide-MBE) equipped with high-pressure reflection high-energy electron diffraction (RHEED) to monitor the deposition of single atomic layers.

Semiconductors and their interfaces have transformed our society and provided a continued stream of ground-breaking fundamental discoveries for the past half century. Oxide interfaces share key properties with semiconductors and, in addition, provide new intrinsic functionality to the world of electronics. Oxide interfaces, known also as oxide electronics, are still in their infancy. However, just as the development in semiconductor technology always has gone hand in hand with developments and refinements of the underlying crystal hosts, understanding the properties of oxide interfaces is essential in order to exploit the full potential of their remarkable functionalities. This book is focused mainly on the study of metal oxide surfaces, interfaces, and thin films often grown epitaxial on an oxide substrate. A multitude of important chemical and physical processes that occur at surfaces and interfaces of these oxides have proved to be significant for many fields including heterogeneous catalysis, chemical sensors, electrical, and magnetic devices, which is illustrated and discussed in this book.

The overall aim of this book is to give an overview of some aspects of advanced topics in TMOs, i.e., the fundamentals of film growth, synthesis, characterization, and applications. This book is primarily intended for two audiences: (1) those who are experts in the area, finding a multidisciplinary approach covering current knowledge and advanced characterization tools and (2) those who want to enter this area with a solid base of fundamental knowledge and practical applications.

The structure of the book is organized as follows:

Section A provides an introduction to the interface formation: the theoretical aspect of the epitaxial growth mechanisms, structural features, and formation of defects.

Section B describes the structural and compositional characterization techniques of metal-oxide interfaces.

Section C describes the stat-of-the-art modeling methods and properties at the metal-oxide interfaces.

Section D describes and illustrates selected possible applications of metal-oxide interfaces

Section A

Interface formation: Theoretical aspect in epitaxial growth mechanisms, structural features and defects formation


Epitaxy of 5d transition metal oxide thin films and heterostructures

J. Nichols; H.N. Lee    Oak Ridge National Laboratory, Oak Ridge, TN, United States


The epitaxy of complex-oxide thin films and heterostructures provides an immense challenge in designing novel functional oxides, enabling us to explore previously unavailable phase space regions. It has been recently shown that strong spin-orbit coupling offered in 5d transition metal oxides can be used to create or manipulate many interesting quantum mechanical behaviors. This perfect marriage between exotic materials and thin film synthesis has inspired many researchers to overcome the technical challenges associated with growing thin films and artificial heterostructures that include these 5d oxides to manipulate their novel properties. Here, we chronicle the motivation and results of these recent studies, which include details of thin film synthesis along with results for both phase pure and multilayer systems. In addition, we also provide some insight for the future direction of this community.


5d transition metal oxides; Thin film; Spin-orbit coupling; Iridate


This work was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

1.1 Introduction

Although experimental investigations of 5d transition metal oxides (TMOs), in particular bulk iridates, began over half a century ago [1], there was limited progress until the origin of the insulating ground state was experimentally observed in the single-layered perovskite Sr2IrO4 [2]. Unlike 3d TMOs, in which strong on-site Coulomb interactions (U) give rise to exotic physical phenomena [3–6], electrons in 5d TMOs are much more spatially extended than 3d electrons; thereby, the effect of U is strongly suppressed. Therefore, 5d TMOs were naively anticipated to be governed by simple paramagnetic metallic ground states. Nevertheless, it turns out that many of these materials have rich electronic and magnetic ground states, as is evident from the canted antiferromagnetic insulating ground state as observed in the prototypical example, Sr2IrO4 [7]. It was shown that although U is reduced there, the spin-orbit interaction strength (ξ)—which typically scales as Z⁴—where Z is the atomic number, is of a comparable energy scale to both the crystal fields and U, where all three are responsible for removing degeneracy within the 5d manifold, resulting in a novel Jeff=1/2 ground state [2]. Since this discovery, the field has exploded with both experimental and theoretical efforts to harness spin-orbit coupling (SOC) to discover intriguing physical properties or behaviors. These desired states include unconventional superconductivity, which is found to coexist with magnetism in Ruddlesden-Popper phases [8], Weyl semimetallicity in pyrochlore phases [9], the quantum spin Hall effect in honeycomb phases [10], and the quantum anomalous Hall effect in artificial heterostructures [11]. All of these collectively have created much interest in 5d TMOs, with particular interest given to the iridates.

Synthesis of iridate thin films was initially motivated by the need to create epitaxially stabilized metastable phases of the orthorhombic perovskite SrIrO3 by metal organic chemical vapor deposition (MOCVD) when no bulk crystals were available [12]. Since this initial investigation, experimentalists have successfully synthesized films via techniques that have extended to pulsed laser deposition (PLD) [13], molecular beam epitaxy (MBE) [14], and magnetron sputtering [15] in order to experimentally probe the strong interplay between SOC and other fundamental interactions, including electron-electron coupling, and crystal fields. Thin film samples are advantageous in that they provide large surface areas that are ideal for many spectroscopic techniques; and many parameters, such as strain, dimensionality, and stoichiometry can readily be manipulated. This has inspired the field of 5d oxide films and has led to a number of experimental investigations of Ruddlesden-Popper [16,17], honeycomb [18], pyrochlore [19,20], and multilayer systems [21–23], in addition to the perovskites discussed earlier. Current progress in the field is discussed in the following sections.

1.2 Challenges and opportunities in thin film synthesis

Early experimental efforts to synthesize high-quality phase-pure epitaxial iridate films proved to be much more challenging than the synthesis of many 3d analogs. Even though numerous deposition techniques have proved to be successful in synthesizing 5d oxide films, to date, the vast majority of experimental effort has been with PLD, and it will be the focus here. Although it was empirically discovered that the optimal growth window is narrow and synthesis is highly sensitive to growth parameters-including oxygen partial pressure (PO2), substrate temperature (Tsub), laser fluence, and deposition rate-it was not until sometime later that a detailed understanding of the growth mechanism of Ruddlesden-Popper strontium iridate films (Srn+1IrnO3n+1) was determined [24,25]. In both of these studies, it was shown that the Sr:Ir ratio is quite volatile. In the former Nishio et al. [24] used a SrIrO3 (n=∞ member of Ruddlesden-Popper series) target to synthesize both Sr2IrO4 and Sr3Ir2O7 films, which have a larger Sr:Ir ratio than the target. This may not be so surprising considering that Ir in a small PO2 is known to be somewhat volatile [26]. However in Seo et al. [25] a Sr2IrO4 target was used to stabilize all three phases, indicating that different Sr:Ir ratios can be transferred to a film. This result indicates that the stabilization of a particular phase is not due to cation volatility but rather due to the thermodynamic equilibrium, which can be modified during PLD, that is intrinsic to each compound. This is quite evident in Fig. 1.1 where the phase diagram, which illustrates the energetically favorable crystallographic phase for a given PO2 and Tsub for two different laser fluences is shown. Note that there are many conditions in which multiple phases are energetically favorable, resulting in samples with secondary impurity phases. It was also shown that the target surface rapidly changed after a single spot was ablated a few hundred times, demonstrating that to grow high-quality films, targets need to be perpetually refreshed and the area of the target used for synthesis should be maximized [27]. Similar challenges were observed in the synthesis of the honeycomb iridates (i.e., Na2IrO3), in that small deviations from the optimal PO2 result in secondary phases [18]. In addition, the pyrochlore iridates (R2Ir2O7, in which R is a rare earth ion), have emerged as the most challenging iridate phase to synthesize thus far. In fact, growth requires deposition of an amorphous film that is followed by an ex-situ high-temperature baking in an Ir-rich environment, which greatly limits the sample quality [20]. Despite the many challenges associated with creating 5d films, many of them have already been overcome to develop the perpetually growing field of functional 5d oxide films and nanostructures, ultimately creating great potential for fundamental breakthroughs in materials research.

Fig. 1.1 Phase diagram of strontium iridate films grown by PLD utilizing a SrIrO 3 target with a laser fluence of (A) 3.75 J cm −2 and (B) 0.78 J cm −2 . Used with permission from K. Nishio, H.Y. Hwang, Y. Hikita, Thermodynamic guiding principles in selective synthesis of strontium iridate Ruddlesden-Popper epitaxial films, APL Mater. 4 (2016) 036102.

1.3 Single-phase films

Although experimental studies of bulk crystals of many of these iridates predate much of the work on thin film samples, there still exists great potential to tune thin films in ways inaccessible in their bulk counterparts. Examples include manipulating biaxial epitaxial strain and dimensionality along with providing large-area samples that are advantageous for numerous spectroscopic techniques and catalytic measurements. In addition, for several of these materials, it is quite challenging to create bulk crystals; thus, many of their known properties originate from work on pure-phase films in lieu of bulk crystals. Therefore, many research groups have been inspired to synthesize thin film samples of various iridate phases, including perovskite, Ruddlesden-Popper, honeycomb, and pyrochlore, by several different deposition techniques in order to investigate their intriguing physical properties. A brief summary of this recent work on single-phase iridate films is provided below.

1.3.1 Perovskite

Following the initial realization of epitaxial SrIrO3 films by MOCVD [28], an early experimental investigation of iridate films was to provide an orthorhombic perovskite sample for comparison with bulk Ruddlesden-Popper Sr2IrO4 and Sr3Ir2O7 crystals [29]. For this study, the perovskite structure was epitaxially stabilized on an MgO substrate to realize single-crystalline samples when no bulk samples existed. In fact, polycrystalline samples can be created only under high pressure [30] and to the best of our knowledge, no single-crystalline samples other than epitaxial thin films currently exist. In this study, it was shown that although SrIrO3 is a paramagnetic metal, isolating the IrO2 layers, as is the case for the layered perovskites, results in an antiferromagnetic insulating ground state.

This initial work motived many research groups to investigate SrIrO3 in greater detail, studying its properties as a function of both thickness and strain. Although subtle inconsistencies exist among these studies, such as different phenomenological electronic conduction mechanisms and significantly different lattice parameters for films grown on identical substrates [15,31–37], consistent patterns have emerged. These include SrIrO3 having a robust paramagnetic ground state, a metal-insulator transition (MIT) induced by biaxial compression, and electronic transport properties that are governed by both strong correlations and disorder. Although SrIrO3 under strong compressive strain (i.e., on LaAlO3) is insulating by the definition (dρ/dT<0), optical conductivity measurements indicate that the Drude peak persists without a gap opening (see Fig. 1.2). This result indicates that weak localization is responsible for the increase in resistivity with compressive strain [13].

Fig. 1.2 Optical absorption spectra of SrIrO 3 films grown on MgO, SrTiO 3 , and (LaAlO 3 ) 0.3 -(Sr 2 AlTaO 6 ) 0.7 substrates, where the dashed lines represent fits using a two oscillator Drude-Lorentz model. Used with permission from J.H. Gruenewald, J. Nichols, J. Terzic, G. Cao, J.W. Brill, S.S.A. Seo, Compressive strain-induced metal-insulator transition in orthorhombic SrIrO3 thin films, J. Mater. Res. 29 (2014) 2491–2496.

There have also been attempts at synthesizing thin films of the double perovskites, Sr0.5Ca0.5IrO3 [38] and SrRu0.5Ir0.5O3 [39]. However, in both cases, their properties were quite similar to what one would expect from interpolating the properties from those of the two constituent materials of each solid solution sample.

Since the realization of topologically protected insulating ground states in binary sulfides and selenides that require the relativistic SOC to be quite strong-5d oxides like SrIrO3, in which SOC has been shown to be quite strong and influential in defining their unique ground states-SrIrO3 has emerged as a candidate in which to discover such a state in a complex oxide [40,41]. In fact, experimental evidence of this potential has been observed in the lifting of the Dirac nodes in SrIrO3 films [42,43].

In addition, in light of the catalytic properties of both Ir metal and binary IrO2, SrIrO3 has inspired researchers to investigate these properties in SrIrO3-based systems [44,45]. Oxygen evolution reaction (OER) measurements were performed on both stoichiometric SrIrO3 [45] and Sr-leached IrOx-SrIrO3 [44] thin film samples. As illustrated in Fig. 1.3, SrIrO3 significantly outperformed the binary oxides IrO2 and RuOx, which were previously shown to have the strongest OER properties in acidic electrolytes [44]. Thus, these preliminary studies clearly demonstrate the strong potential for complex iridium oxide films for electrochemical and catalytic device applications.

Fig. 1.3 Tafel plot comparing the catalytic activity of IrO 2 and SrIrO 3 films, while the shaded region represents the standard deviation obtained from multiple measurements. Used with permission from R. Tang, Y. Nie, J.K. Kawasaki, D.-Y. Kuo, G. Petretto, G. Hautier, G.-M. Rignanese, K.M. Shen, D.G. Schlom, J. Suntivich, Oxygen evolution reaction electrocatalysis on SrIrO3 grown using molecular beam epitaxy, J. Mater. Chem. A 4 (2016) 6831–6836.

1.3.2 Ruddlesden-popper

The initial motivation for investigating Sr2IrO4 arises from its structural similarities to La2CuO4, the parent compound for high-temperature superconductivity. Both materials are isostructural and antiferromagnetic insulators well described by Mott physics. These similarities have led to the prediction that Sr2IrO4 may become superconducting upon carrier doping [8,46–48]. Although both electron and hole-doped bulk crystals have been driven to a metallic state [49,50], and there is indirect experimental evidence of superconductivity in potassium-doped Sr2IrO4 [51–53], direct evidence of superconductivity is yet to be discovered. The numerous tuning parameters intrinsic to thin film synthesis make Sr2IrO4 thin films an ideal platform on which to potentially realize this exotic ground state.

Initial experimental investigations of Sr2IrO4 films began with both a thickness [17] and strain [16] dependence. For the former, films ranging in thickness from 5 to 60 nm were deposited on SrTiO3 (STO) substrates by PLD. It was observed that, in thin epitaxially strained films, the activation energy is suppressed; whereas thicker films exhibit an activation energy and lattice constants more consistent with those of bulk crystals (see Fig. 1.4). In the latter case, coherently strained films were grown on various substrates, also by PLD, to investigate the dependence of their electronic properties on biaxial strain. As demonstrated by optical conductivity measurements presented in Fig. 1.5, even though increasing the in-plane strain does increase the electronic bandwidth (W), the effective electronic correlation energy also increases monotonically, with strain resulting in an approximately strain-independent gap energy of ~300 meV.

Fig. 1.4 Temperature dependence of the activation energy ( Δ ) obtained from applying an Arrhenius activation model to the resistivity data of Sr 2 IrO 4 films of various thicknesses grown on SrTiO 3 substrates. Used with permission from C. Rayan Serrao, J. Liu, J.T. Heron, G. Singh-Bhalla, A. Yadav, S.J. Suresha, R.J. Paull, D. Yi, J.H. Chu, M. Trassin, A. Vishwanath, E. Arenholz, C. Frontera, J. Železný, T. Jungwirth, X. Marti, R. Ramesh, Epitaxy-distorted spin-orbit Mott insulator in Sr2IrO4 thin films, Phys. Rev. B 87 (2013) 085121.

Fig. 1.5 Optical absorption spectra of Sr 2 IrO 4 films grown on GdScO 3 , SrTiO 3 , (LaAlO 3 ) 0.3 -(SrAl 0.5 Ta 0.5 O 3 ) 0.7 , and LaAlO 3 substrates, where the peaks α and β represent d - d optical transitions, the solid black lines are fits using two Lorentz oscillators, and the black dashed lines represent an estimate of the gap energy where there is a vertical offset for clarity. Used with permission from J. Nichols, J. Terzic, E.G. Bittle, O.B. Korneta, L.E. de Long, J.W. Brill, G. Cao, S.S.A. Seo, Tuning electronic structure via epitaxial strain in Sr2IrO4 thin films, Appl. Phys. Lett. 102 (2013) 141908.

These initial studies were followed by more through investigations of the electronic and magnetic properties through resistivity, magneto-transport, and x-ray magnetic scattering measurements. C. Lu et al. showed that the electronic conduction mechanism in Sr2IrO4 films depend strongly on both temperature and sample thickness [54]. As shown in Fig. 1.6, conduction in thin films is well described with a Mott variable range hopping model over a wide temperature range, whereas this range is suppressed in thicker films, with Efros-Shklovskii variable range hopping (thermal activation) being dominant at low (high) temperature. This crossover in conduction mechanism is consistent with the robust sign change in magnetoresistance at roughly 90 K observed in both ionic liquid gated Sr2IrO4 films and pristine (Sr1−xLaxO bond length, rather than through rotations of the IrO6 octahedra (as in bulk Sr2IrO4), and that tensile (compressive) strain enhances (reduces) the magnetic ordering temperature.

Fig. 1.6 Phase diagram demonstrating the dependence of the electronic conduction mechanism of Sr 2 IrO 4 films grown on SrTiO 3 on temperature and film thickness. Used with permission from C.L. Lu, A. Quindeau, H. Deniz, D. Preziosi, D. Hesse, M. Alexe, Crossover of conduction mechanism in Sr2IrO4 epitaxial thin films, Appl. Phys. Lett. 105 (2014) 082407.

Fig. 1.7 Temperature-dependent resistance of (A) Sr 2 IrO 4 /La 2/3 Sr 1/3 MnO 3 and (C) Sr 2 IrO 4 /LaNiO 3 /La 2/3 Sr 1/3 MnO 3 heterostructures grown on SrTiO 3 substrates with the excitation current applied both in-plane (CIP) and out-of-plane (CPP). (B) Anisotropic magnetoresistance and (D) X-ray diffraction of two samples. Used with permission from I. Fina, X. Marti, D. Yi, J. Liu, J.H. Chu, C. Rayan-Serrao, S. Suresha, A.B. Shick, J. Železný, T. Jungwirth, J. Fontcuberta, R. Ramesh, Anisotropic magnetoresistance in an antiferromagnetic semiconductor, Nat. Commun., 5 (2014) 4671.

This compound was also investigated by replacing the Sr ions in A2IrO4 with other isovalent cations (A=Ba or Ca), thereby applying chemical pressure to the lattice [59,60]. This again highlights the advantage of thin film approaches for metastable materials, in which limited or no studies are performed on bulk samples. It can be seen in Fig. 1.8 that even though only subtle changes are observed in the resistivity data, the electronic structure is significantly modified when chemical pressure is applied. The most pronounced effects are the smaller (larger) gap energy in Ba2IrO4 (Ca2IrO4), with all the optical transitions being influenced by the Ir 5d manifold, and depend strongly on the size of the A-site ions. However, a complete microscopic understanding of this behavior remains an open issue.

Fig. 1.8 (A) Resistivity and (B) optical absorption spectra of A 2 IrO 4 (A=Ca, Sr, or Ba) films. (C) Magnification of the low-energy data from panel (B) highlighting the gap energy (dashed lines) . Used with permission from M. Souri, J.H. Gruenewald, J. Terzic, J.W. Brill, G. Cao, S.S.A. Seo, Investigations of metastable Ca2IrO4 epitaxial thin-films: systematic comparison with Sr2IrO4 and Ba2IrO4, Sci. Rep. 6 (2016) 25967.

Although the majority of commercially available single-crystalline oxide substrates are cubic (or pseudocubic) perovskites, there are a limited number available that are isostructural to Sr2IrO4, such as LaSrAlO4 and LaSrGaO4 (LSGO), which enable films to be grown with many different facets of the material normal to the substrate surface. In particular, a-axis oriented Sr2IrO4 has been grown on LSGO (100), enabling the anisotropic electronic properties of this layered compound to be readily investigated [61]. As shown in Fig. 1.9, although the resistivities in these two directions differing by only an order of magnitude, their electronic structures differ significantly in that the intra d optical transitions are forbidden for E//c and the gap energy is significantly larger here, indicating that defects are likely dominating the electronic conduction in this direction. Greunewald et al. have taken advantage of this fact to further isolate the IrO2 conducting channels in [LSGO]5/[Sr2IrO4]m (m=1–4) on LSGO (100) substrates; this results in a quantum one-dimensional behavior as m is reduced, as shown by the enhanced excitation energy and emergence of a spin-orbit exciton, as determined from the resonant inelastic x-ray scattering data [62].

Fig. 1.9 (A) Optical absorption spectra of a -axis oriented Sr 2 IrO 4 films grown on LaSrGaO 4 (100) substrates, demonstrating the strongly anisotropic electronic properties. (B) and (C) Schematic diagram of the electronic structure along the two crystallographic directions. Used with permission from J. Nichols, O.B. Korneta, J. Terzic, L.E. de Long, G. Cao, J. W. Brill, S.S.A. Seo, Anisotropic electronic properties of a-axis-oriented Sr2IrO4 epitaxial thin-films, Appl. Phys. Lett. 103 (2013) 131910.

1.3.3 Honeycomb

Another class of materials that is receiving considerable attention from researchers is the Mott-insulating [63] honeycomb iridates A2IrO3 (A=Na or Li). Novel physical properties such as the quantum spin Hall effect [10], spin-liquid behavior [64], topological superconductivity [65], and topological order [66] are expected in this system. Thin film samples are of particular importance due to the fact that manipulating the dimensionality and strain states of these compounds shows great promise for the ultimate realization of these exciting physical ground states [67,68]. This is quite evident in Fig. 1.10, where the phase diagram clearly demonstrates that a topologically insulating ground state is expected for small U.

Fig. 1.10 Phase diagram of Na 2 IrO 3 that demonstrates that manipulating the relative strengths of Coulomb interactions ( U ) and spin-orbit coupling ( t ′) exotic properties such as the anisotropic quantum spin Hall effect are expected to emerge. Used with permission from T. Liu, B. Douçot, K. Le Hur, Anisotropic quantum spin Hall effect, spin-orbital textures, and the Mott transition, Phys. Rev. B 88 (2013) 245119.

In fact, films of both Na2IrO3 [18] and Li2IrO3 [69] have recently been synthesized; and it has been shown that they have optical gaps of 200 meV and 300 meV, respectively, which are both smaller than that of bulk Na2IrO3 [70]. In addition, the transport properties of both systems are dominated by three-dimensional variable range hopping, while the positive magnetoresistance observed in Na2IrO3 is consistent with the presence of weak antilocalization (see Fig. 1.11). Also, Li2IrO3 provides another example in which epitaxial films provide large single-crystalline samples of a system where the availability of bulk samples is quite limited.

Fig. 1.11 Transport properties of Na 2 IrO 3 films grown on YAlO 3 . (A) and (B) Temperature-dependent resistivity (log  ρ vs. T −1/4 ) indicating a three-dimensional Mott-variable range-hopping conduction mechanism. Magnetic field-dependent (C) magnetoresistance where the dashed lines are parabolic fits to the high field data and (D) magnetoconductance where the lines are fits to the Hikami-Larkin-Nagaoka equation. Used with permission from M. Jenderka, J. Barzola-Quiquia, Z. Zhang, H. Frenzel, M. Grundmann, M. Lorenz, Mott variable-range hopping and weak antilocalization effect in heteroepitaxial Na2IrO3 thin films, Phys. Rev. B 88 (2013) 045111.

1.3.4 Pyrochlore

Pyrochlore iridates have received appreciable attention owing to the sensitivity of their physical properties to external stimuli. For example, as illustrated in Fig. 1.12, the rare earth pyrochlore iridates A2Ir2O7 (A=Pr-Yb) are highly sensitive to chemical pressure in their properties, ranging from a nonmagnetic metal (Pr), to an MIT (Nd or Sm), to a magnetic insulating ground state (Gd-Yb) [71]. In addition, a phase diagram of anticipated properties can be found in Fig. 1.13, where it is demonstrated that although ferromagnetism dominates in larger magnetic fields, there is a rich dependence of the ground state on the correlation strength for small fields. In addition, films and artificial structures are expected to make various exotic physical ground states more accessible by tuning properties with parameters intrinsic to thin film synthesis, such as strain and reduced dimensionality. Examples include a large anomalous Hall response [72,73], Weyl semi-metals [73], and various topological insulating phases [74,75].

Fig. 1.12 Phase diagram of the rare earth pyrochlore iridates Ln 2 Ir 2 O 7 ( Ln =Pr-Ho) illustrating its dependence on temperature and chemical pressure. Used with permission from K. Matsuhira, M. Wakeshima, Y. Hinatsu, S. Takagi, Metal-insulator transitions in pyrochlore oxides Ln2Ir2O7, J. Phys. Soc. Jpn. 80 (2011) 094701.

Fig. 1.13 Phase diagram of pyrochlore iridates R 2 Ir 2 O 7 , showing how the ground state depends strongly on correlations ( U ) and the applied magnetic field ( B ). Used with permission from X. Wan, A.M. Turner, A. Vishwanath, S.Y. Savrasov, Topological semimetal and Fermi-arc surface states in the electronic structure of pyrochlore iridates, Phys. Rev. B 83 (2011) 205101.

The first successful example of pyrochlore iridate films was reported by Fujita et al. [20] with their synthesis of Eu2Ir2O7 films. Although the sample quality was somewhat limited by ex situ annealing, they were still able to observe the all-in-all-out spin structure through magnetotransport measurements. Since this initial work, it has been determined that the average magnetic domain size in Eu2Ir2O7 is 1–2 μm [76]. In addition, conductivity across the domain wall between Eu2Ir2O7 and Tb2Ir2O7 is highly sensitive to external magnetic fields [77]. It has also been shown that Nd2Ir2O7 films can be grown by magnetron sputtering of amorphous films followed by postannealing. During this annealing process, small single-crystalline domains form near the substrate in just a few minutes. However, they claim it takes at least 6 hours to obtain an epitaxial phase-pure film [78].

1.4 5d heterostructures and superlattices

Recent trends within the oxide community have strongly focused on interfaces between dissimilar 3d oxides with properties that greatly contrast with those of their constituent materials. Examples of such phenomena include the formation of a two-dimensional electron gas between two large-bandgap insulators [79], enhanced superconducting Tc in lanthanum strontium cuprate bilayers [80], the quantum Hall effect [81], conducting interfaces between optically transparent insulators [82], and improved electronic and thermal properties at fractionally doped interfaces [83,84]. Although these include a diverse variety of physical properties, they all collectively require a strong U to be realized. Since, as discussed earlier 5d oxides have modest U values and strong SOCs, interfaces between 5d and 3d oxides can potentially have both U and SOC that are collectively much larger than what occurs naturally in bulk systems, thus creating the potential for unprecedented discoveries of novel physical properties. Thus far, this field of investigating 3d-5d interfaces is relatively new and is limited to a few studies that are discussed below.

1.4.1 Iridate-titanate

Interfacial coupling of two dissimilar materials has proved to be a very powerful technique to manipulate and induce intriguing physical properties, such as superconductivity, magnetism, ferroelectricity, and thermal transport in 3d complex oxides. However, until recently, such efforts including 5d materials were largely ignored until Matsuno et al. demonstrated the successful growth of [(SrTiO3)1/(SrIrO3)m] superlattices on STO (001) [21]. Their properties were quite analogous to those of bulk Ruddlesden-Popper crystals (see Fig. 1.14). For example, both m=1 and Sr2IrO4 are canted antiferromagnetic insulators, and this behavior is suppressed by increasing the dimensionality (i.e., increasing the number of nearest neighbor IrO2 planes). In fact, all samples with m>3 are governed by a paramagnetic metallic ground state similar to that of homogeneous SrIrO3. This study motivated theoretical work to better understand this system. Conclusions from these studies include verification of the Jeff=1/2 ground state [85], along with verification of a band gap that increases with decreasing SrIrO3 layer thickness [85] and an in-plane canted antiferromagnetic magnetic moment that decreases [86] with the application of tensile strain. In addition, a second experimental study of this system has emerged. In a (SrTiO3)n/(SrIrO3)m bilayer, STO largely serves as a capping layer to preserve the integrity of their ultrathin SrIrO3 layers. This system, however, does not demonstrate strong coupling between the two materials [87].

Fig. 1.14 Temperature dependence of the (A) resistivity, (B) first derivative of the resistivity with respect to temperature, (C) the Hall coefficient, and (D) the magnetization of a series of (SrTiO 3 ) 1 /(SrIrO 3 ) m superlattices grown on SrTiO 3 . Used with permission from J. Matsuno, K. Ihara, S. Yamamura, H. Wadati, K. Ishii, V.V. Shankar, H.-Y. Kee, H. Takagi, Engineering a spin-orbital magnetic insulator by tailoring superlattices, Phys. Rev. Lett. 114 (2015) 247209.

A strong motivation for investigating artificial superstructures, including 5d oxides, is the expectation of topologically protected states in many of these systems [11]. Consider, for example, the specific case of a (111)-oriented heterostructure involving a perovskite, such as SrIrO3, that is sandwiched between a substrate and a capping layer that are both large bandgap insulators such as SrTiO3. For this geometry, if the iridate is a few monolayers thick, it will have hexagonal symmetry quite analogous to that of two-dimensional systems such as graphene [88]. Although one of the initial studies of SrIrO3 with (111)-oriented films grown via MOCVD, synthesis through PLD has proved to be more formidable. Nevertheless, two research groups have independently mitigated these challenges to grow (111) perovskite iridates with STO. One group stabilized phase-pure samples with chemical pressure to grow [(SrTiO3)2/(Sr0.5Ca0.5IrO3)2m] superlattices [89] while the second kept the SrIrO3 thinner than the critical thickness of 6–7 bilayers in the bilayer system (SrTiO3)2n/(SrIrO3)2m [90]. Although both studies are impressive feats of extreme sample synthesis, neither report provides evidence of strong interfacial coupling between constituent materials or the presence of exotic topological ground states.

1.4.2 Iridate-manganite

In light of the synthesis of iridate-titanate superlattices discussed earlier, two groups independently began working on systems including SrIrO3 and perovskite manganites [22,23]. For one case, [(SrMnO3)m/(SrIrO3)m] superlattices exhibited ferromagnetism at both Mn and Ir sites, which drove a strong anomalous Hall response (see Fig. 1.15). This behavior originated from interfacial charge transfer and demonstrated strong interfacial coupling between 5d and 3d oxides. In the other study, [(La2/3Sr1/3MnO3)m/(SrIrO3)n] superlattices were investigated. Although La2/3Sr1/3MnO3 is known to be ferromagnetic (as shown in Fig. 1.16), this study demonstrated that SrIrO3 could be effectively utilized to manipulate the magnetic structure of the superlattice in that the magnetic easy axis could be flipped from the (110) direction in pure La2/3Sr1/3MnO3 to the (100) axis for superlattices with atomically thin SrIrO3 layers (i.e., small n) [23]. These studies provide direct evidence that 5d-3d interfaces that conceptually have both SOC and U that are stronger than for the constituent materials can have novel physical properties that strongly contrast with those of the parent compounds.

Fig. 1.15 (A) X-ray absorption and x-ray magnetic circular dichroism spectra obtained near the L 3 and L 2 edges of both Ir and Mn for a series of (SrMnO 3 ) n /(SrIrO 3 ) n superlattices where the inset shows the change in oxidation state. (B) Temperature-dependent sheet resistance and (C) field-dependent transverse resistivity. Used with permission from J. Nichols, X. Gao, S. Lee, T.L. Meyer, J.W. Freeland, V. Lauter, D. Yi, J. Liu, D. Haskel, J.R. Petrie, E.-J. Guo, A. Herklotz, D. Lee, T.Z. Ward, G. Eres, M.R. Fitzsimmons, H.N. Lee, Emerging magnetism and anomalous Hall effect in iridate-manganite heterostructures, Nat. Commun. 7 (2016) 12721.

Fig. 1.16 (A) Phase diagram of a series of (SrIrO 3 ) n /(La 2/3 Sr 1/3 MnO 3 ) m superlattices showing the change in magnetic easy axis with iridate layer thickness. (B) M ( H ) for ( n , m )=(3, 1) superlattice at T =10 K. (C) Anisotropic magnetoresistance for (3, 3) and (3, 10) superlattices at T =10 K. Used with permission from D. Yi, J. Liu, S.-L. Hsu, L. Zhang, Y. Choi, J.-W. Kim, Z. Chen, J.D. Clarkson, C.R. Serrao, E. Arenholz, P.J. Ryan, H. Xu, R.J. Birgeneau, R. Ramesh, Atomic-scale control of magnetic anisotropy via novel spin-orbit coupling effect in La2/3Sr1/3MnO3/SrIrO3 superlattices, Proc. Natl. Acad. Sci. 113 (2016) 6397–6402.

1.4.3 Iridate-ruthenate

Another interesting behavior that has been observed in artificial iridate superstructures is observed in the transverse resistivity measurements of bilayers of SrIrO3 and the itinerant ferromagnet SrRuO3. This Hall resistivity is traditionally described by the sum of a term that is proportional to the magnetic field, known as the ordinary Hall effect, and deviations from this linear behavior are almost exclusively attributed to the anomalous Hall effect (AHE) due to either magnetic order or a multiple carriers present within the material. As shown in Fig. 1.17, Matsuno et al. [91] discovered that this description alone is insufficient to describe their data, and they attribute this deviation from this conventional formulism to an additional topological Hall effect due to the onset of a Neel-type skyrmion lattice. Although there are a few examples of this type of behavior in metal and alloy systems, this is the first example of such a state in an all-oxide system.

Fig. 1.17 Hall resistivity of a (SrRuO 3 ) 5 /(SrIrO 2 ) bilayer showing the measured transverse resistivity (red line) , the normalized magnetization (orange circles) , and the difference which represents the topological Hall effect (THE). Used with permission from J. Matsuno, N. Ogawa, K. Yasuda, F. Kagawa, W. Koshibae, N. Nagaosa, Y. Tokura, M. Kawasaki, Interface-driven topological Hall effect in SrRuO3-SrIrO3 bilayer, Sci. Adv. 2 (2016) e1600304.

1.5 Conclusions and future direction

5d TMOs are an interesting class of materials, in which the strong spin orbit coupling provides a unique playground to explore many novel properties and behaviors. As we summarized in this chapter, now we have a good understanding on the synthesis of 5d TMO thin films. Thus, it is now time for the thin

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