Rekha Rajaram March 2007

STUDY OF MAGNETISM IN DILUTE MAGNETIC SEMICONDUCTORS BASED ON III-V NITRIDES
A DISSERTATION SUBMITTED TO THE DEPARTMENT OF MATERIALS SCIENCE AND ENGINEERING AND THE COMMITTEE ON GRADUATE STUDIES OF STANFORD UNIVERSITY IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
Rekha Rajaram March 2007
c Copyright by Rekha Rajaram 2007 All Rights Reserved
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I certify that I have read this dissertation and that, in my opinion, it is fully adequate in scope and quality as a dissertation for the degree of Doctor of Philosophy.
James S. Harris, Jr. Electrical Engineering Principal Co-Advisor I certify that I have read this dissertation and that, in my opinion, it is fully adequate in scope and quality as a dissertation for the degree of Doctor of Philosophy.
Stuart S. P. Parkin Applied Physics Principal Co-Advisor I certify that I have read this dissertation and that, in my opinion, it is fully adequate in scope and quality as a dissertation for the degree of Doctor of Philosophy.
Bruce Clemens Materials Science and Engineering Approved for the University Committee on Graduate Studies.
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Abstract
Spin based electronics, commonly referred to as spintronics, seeks to expand the functionalities of microelectronic devices by introducing the ability to manipulate the carriers spin, in addition to or instead of its charge. Key steps in spintronic devices include the injection, manipulation and detection of the carriers spin. Metal-based spintronic devices such as spin valves have already found applications in high capacity hard disk drive read heads and have potential in non-volatile solid state memories. However, in order to realize the full potential of spintronics, spin manipulation must be introduced into semiconductor devices. This in turn, requires the development of magnetic semiconductors. Dilute magnetic semiconductors (DMS) are a class of magnetic semiconductors in which a fraction of the cations are substitutionally replaced by magnetic ions. The exchange interaction between the spin of the dopant atoms and the carriers in the semiconductor host is expected to bring about global ferromagnetic order in the entire lattice in these materials. The search for novel DMS candidates has been driven by two cardinal requirements - a material system with well-developed growth technology, and a high Curie temperature. In this work, we have investigated the growth and characteristics of one such promising candidate, transition-metal doped InN. InN lms were deposited on csapphire substrates by molecular beam epitaxy, employing GaN underlayers to reduce the lattice mismatch between the lm and substrate. The lms were doped from v
0.1-6% Cr with no noticeable trace of crystalline secondary phases detected by Xray diraction. However, Mn-doping led to segregation of manganese nitride. Hall eect measurements revealed n-type behavior in both undoped as well as Cr-doped lms. A magnetic hysteresis, with a small remanence and coercivity was observed in Cr:InN up to room temperature, conrming long-range magnetic order in this material. X-ray magnetic circular dichroism experiments revealed dichroism at the Cr L-edge, indicating that the Cr in the matrix was magnetically active. However, deeper probing of the magnetic behavior revealed some metastable characteristics. The origin of magnetic behavior in Cr:InN is discussed in the context the role of impurity bands in mediating magnetic order.
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Acknowledgements
Much of the work presented in this thesis would never have materialized but for the support, advice and companionship that I got from so many people, both in my professional, as well as my personal life. This thesis is incomplete without a mention of all those who have aected my graduate life in so many ways. First and foremost, I thank my adviser, Professor James Harris whom we all have come to know as Coach! True to his name, he has always been encouraging, providing me with all the guidance that I needed, while at the same time allowing me enough leeway to pursue my research interests. I am just as grateful to my co-adviser, Dr. Stuart Parkin, who despite his busy schedule, always found the time to guide me through dicult stints during my research career. I thank my oral thesis committee members, professors Bruce Clemens, Anders Nilsson and Paul McIntyre. In addition, I thank Professor Clemens for serving on my reading committee as well. The role played by Andreas Ney in shaping this project is invaluable, and I am grateful for all that I learnt from him about magnetism. I thank Robin Farrow and Ron Marks at IBM Almaden Research Center for their help with getting me oriented with the MBE system. Valuable contributions were made by Andrew Kellock and Vaughn Deline at IBM, who helped with RBS and SIMS measurements respectively. I am also grateful to Elke Arenholz at the Advanced Light Source in Lawrence Berkeley lab as well as Mahesh Samant at IBM for their help with the X-Ray magnetic vii
dichroism experiments. Glenn Solomon and David Miller made an instrumental contribution by providing the GaN templates used in this work. I would also like to recognize the contributions of fellow Harris group members Hyunsoo-Yang and Hopil Bae with Hall measurements, and Photoluminescence measurements respectively. Several people made my graduate life at Stanford a great experience. I thank my co-workers at IBM - Brian, Kevin, Guenole, Roger, Rai, Bob, Victor and others who were a pleasure to work with. I also enjoyed the companionship of other current and ex Parkin group members at IBM, including Masa, Xin, Bastiaan, Nicolas, See-Hun, Christian and Alex. I wish the newer students in the group, Cheng-Han, Li and Justin the very best in their graduate careers. I am also thankful to all the Harris group members for all the help and companionship that I received from them. I learnt a lot about MBE from several students in the group including Homan, Seth, Mark and Xiao-Jun, to name a few. On a more personal note, the support that I have received from my friends and family over the years is of immense value to me, and has helped me get this far. I thank my parents and sisters for always standing by me. I am also grateful to my in-laws for their support and acceptance of me. Finally, I thank my husband for always believing in me.
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Contents
Abstract Acknowledgements 1 Introduction 2 Dilute Magnetic Semiconductors 2.1 2.2 2.3 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Magnetic interactions in solids . . . . . . . . . . . . . . . . . . . . . . Models describing magnetism in DMS . . . . . . . . . . . . . . . . . . 2.3.1 2.3.2 2.4 2.5 Mean Field Theory . . . . . . . . . . . . . . . . . . . . . . . . Bound Magnetic Polaron . . . . . . . . . . . . . . . . . . . . . v vii 1 6 6 8 10 11 12 15 17 20 21 23 25 26 28
Spin glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Promising DMS candidates . . . . . . . . . . . . . . . . . . . . . . . .
3 Growth of InN and doped InN by MBE 3.1 3.2 Growth of III-Nitrides . . . . . . . . . . . . . . . . . . . . . . . . . . Molecular Beam epitaxy . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.1 3.2.2 3.3 Growth of InN by MBE . . . . . . . . . . . . . . . . . . . . . Reection High Energy Electron Diraction (RHEED) . . . .
Growth of Cr and Mn-doped InN . . . . . . . . . . . . . . . . . . . . ix
3.3.1 3.3.2
Nitridization of Sapphire . . . . . . . . . . . . . . . . . . . . . Growth of InN and Cr, Mn-doped InN over GaN templates . .
30 32 36 37 37 42 47 50 51 54 54 57 61 66 66 67 67 73 78 79 79 81 85 88 96
4 Structural Characterization 4.1 4.2 4.3 4.4 4.5 Transmission Electron Microscopy . . . . . . . . . . . . . . . . . . . . X-Ray Diraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . d-spacing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Photoluminescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . Hall Eect Measurement . . . . . . . . . . . . . . . . . . . . . . . . . 4.5.1 Hall Eect measurements on InN and Cr:InN . . . . . . . . .
5 Magnetic and Electrical Characterization 5.1 5.2 5.3 5.4 Magnetic Characterization . . . . . . . . . . . . . . . . . . . . . . . . Magnetic behavior of Cr and Mn-doped InN . . . . . . . . . . . . . . Normalized saturation magnetization moment . . . . . . . . . . . . . Spin-Glass like Behavior . . . . . . . . . . . . . . . . . . . . . . . . . 5.4.1 5.4.2 5.5 5.6 Measurement Procedure . . . . . . . . . . . . . . . . . . . . . FC/ZFC measurements in Cr-doped InN . . . . . . . . . . . .
Metastable behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . Evidence of spin polarized carriers . . . . . . . . . . . . . . . . . . . .
6 Secondary Phases and Cr L-Edge Spectroscopy 6.1 Potential secondary phase - CrN . . . . . . . . . . . . . . . . . . . . . 6.1.1 6.1.2 6.2 6.3 Growth and structure . . . . . . . . . . . . . . . . . . . . . . . Magnetic properties of CrN . . . . . . . . . . . . . . . . . . .
X-Ray Absorption Spectroscopy . . . . . . . . . . . . . . . . . . . . . X-Ray Magnetic Circular Dichroism . . . . . . . . . . . . . . . . . . .
7 Conclusions x
Bibliography
99
xi
List of Tables
2.1 3.1 3.2 4.1 High temperature ferromagnetism in n-type DMS [19] . . . . . . . . . lattice mismatch between sapphire and III-V nitrides . . . . . . . . . SIMS prole of Cr:InN lms used to determine composition . . . . . . Hall eect measurement on InN and Cr:InN lms . . . . . . . . . . . 18 21 35 52
xii
List of Figures
1.1 1.2 2.1 2.2 2.3 2.4 Schematic of Datta-Das transistor . . . . . . . . . . . . . . . . . . . . Curie temperatures of various DMS candidates [9] . . . . . . . . . . . Semiconductor host doped with magnetic ions . . . . . . . . . . . . . Representation of Polaron pair model indicating an interstitial region Representation of Magnetic Polarons in a semiconductor lattice [19] . Cusp observed in the magnetic susceptibility vs. temperature plot in Au:Fe alloys with 1-2% Fe [20]. Data for 1 % Fe from Lutes and Schmit (1964) are also included. . . . . . . . . . . . . . . . . . . . . . . . . . 2.5 Important characteristics of spin glasses include frustration and quenched disorder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 3.2 3.3 3.4 3.5 The preferred orientation of deposition of GaN over sapphire [44] Schematic of Nitride MBE system . . 17 22 24 27 30 16 3 4 7 14 15
. . . . . . . . . . . . . . . . . . .
Schematic of RHEED measurement geometry . . . . . . . . . . . . . Chemistry of nitridization of sapphire [46] . . . . . . . . . . . . . . . RHEED construction during sapphire nitridization (a) [1120] direction of Sapphire (b) Polycrystalline InN deposited over the substrate . . .
31
3.6
RHEED construction during deposition (a) InN buer layer (b) Buer annealed at 450 C under N ux (c) Cr-doped InN . . . . . . . . . . . 33 34
3.7
SIMS prole of a 5.25% Cr-doped InN lm . . . . . . . . . . . . . . . xiii
4.1
TEM of a 100 nm thick InN buer layer. (a) Shows the bright eld image (b) shows the CBED pattern obtained along the InN lm . . . 37 39 40 41 43 44
4.2 4.3 4.4 4.5 4.6 4.7
X-Ray Diraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . High Resolution X-Ray Diraction of Cr- and Mn-doped InN . . . . . X-Ray Diraction of Asymmetric peaks of InN . . . . . . . . . . . . . X-Ray Diraction using an area detector . . . . . . . . . . . . . . . . Out-of-plane d-spacing dependence on concentration . . . . . . . . . . Variation of in-plane lattice parameter (open squares) and out-of-plane lattice parameter (circles) with Cr-doping . . . . . . . . . . . . . . .
45 46 49 51 55 56
4.8 4.9
Schematic of Photoluminescence in a direct band gap material . . . . Photoluminescence observed in Cr-doped InN . . . . . . . . . . . . .
4.10 Hall Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1 5.2 5.3 Schematic of the Josephson junction . . . . . . . . . . . . . . . . . . Typical magnetic hysteresis of ferromagnetic materials . . . . . . . . Magnetic behavior of 0.9% Cr-doped InN. (a)Shows magnetic hysteresis observed at various temperatures. (b) Shows the low eld behavior 5.4 Magnetic remanence of doped InN. (a) Cr:InN shows steady decrease in MR with temperature. (b) Mn:InN shows paramagnetic remanence behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.5 Small anisotropy observed in 1.8% Cr-doped InN. In-plane easy axis (open squares) and out of plane hard axis (circles) 5.6 . . . . . . . . . .
58
60
61
Doping level dependence of normalized saturation magnetization in Cr:InN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.7
Doping level dependence of normalized saturation magnetization in Cr:InN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiv 64
5.8
A comparison of the magnetic hysteresis obtained at 20 K from a 0.9% Cr:InN(open circles) lm with that of a 5.5% Cr:InN (squares) lm . 65 66
5.9
Field cooled vs. Zero eld cooled measurements. . . . . . . . . . . . .
5.10 Field cooled vs. Zero eld cooled measurements in a 0.9% Cr-doped InN. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.11 Remanence dependence on temperature in 0.9% Cr-doped InN. Increase in remanence due to application of magnetic eld observed. . . 5.12 Temperature dependence of MR in 0.9% Cr:InN . . . . . . . . . . . 5.13 Remanence stays constant with time in 0.9% Cr-doped InN. . . . . . 5.14 Schematic of the Physical Property Measurement System (PPMS) : Courtesy Quantum Design . . . . . . . . . . . . . . . . . . . . . . . 74 69 71 72 68
5.15 Small anomalous Hall contribution observed in a 1.8% Cr-doped InN lm, in addition to a normal Hall eect and a positive magnetoresistance. 76 5.16 Comparison between anomalous Hall contribution (open squares) of a 1.8 % Cr-doped InN lm and its in plane (triangles) and out of plane (circles) magnetization measurement. . . . . . . . . . . . . . . . . . . 6.1 XRD 2- patterns obtained from CrN lms grown over (a) sapphire and (b)(001) MgO. The insets show the RHEED patterns recorded during the deposition. . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2 Magnetic behavior of CrN lms. (a) CrN deposited over sapphire shows a small hysteresis (b) CrN deposited over MgO shows no hysteresis. . 6.3 Comparison of the hysteretic behavior of CrN/sapphire with that of CrN/MgO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xv 84 83 80 77
6.4
Field cooled vs. Zero eld cooled behavior of CrN lms. FC measurement was made by cooling under 50 kOe, followed by a warm up at 100 Oe, and ZFC measurement involved cool down under zero eld followed by warm up at 100 Oe. (a) CrN deposited over sapphire shows spin glass like behavior (b) CrN deposited over MgO shows paramagnetic behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86 87 88 89 91 92
6.5 6.6 6.7 6.8 6.9
Schematic of X-Ray Absorption process
. . . . . . . . . . . . . . . .
Cr L-edge observed in Cr:InN and in CrN . . . . . . . . . . . . . . . Schematic of the physics behind the XMCD eect . . . . . . . . . . . XMCD measurement setup . . . . . . . . . . . . . . . . . . . . . . . . Dichroism at the Cr L-edge in Cr-doped InN . . . . . . . . . . . . . .
6.10 Temperature dependence of dichroism observed at the Cr L-edge in Cr-doped InN. The spectrum taken at 100 K has been smoothed out. 94
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Chapter 1 Introduction
Over the past few decades, the microelectronics industry has made tremendous progress, with its basic unit, the integrated circuit chip inltrating down to a large number of everyday applications. The smallest electronic component of such a chip is the transistor, which was developed in the late 1940s by scientists at Bell labs. Over time, the metal oxide semiconductor eld eect transistor (MOSFET) evolved as the most widely used transistor structure. In 1965 Gordon Moore, then at Fairchild Semiconductor, proposed what has now come to be known as Moores law [1]. The essence of the law was that the number of transistors built on a wafer would double every two years, and that this scaling would be the key improving performance and protability in the microelectronic industry. However, with scaling come problems such as the need for very thin gate oxide layers, that could be leaky and require constant refreshing. This would call for unacceptably high power consumption, which could act as an impediment to further scaling down. Thus newer approaches have constantly been explored in order to further the miniaturization of microelectronics. One such possibility is to utilize the spin of the charge carriers in addition to their charge in devices. There are two potential advantages of doing this, the rst being the ability of magnetic materials to remember their spin state, without any refresh. This could 1
CHAPTER 1. INTRODUCTION
allow us to integrate logic and storage processes and potentially lead to instant-on computers, where no boot up is required. The other advantage is that relatively low energy is required to manipulate the orientation of spin of a carrier, which could allow development of low power spintronic devices. Metal-based spintronics already has several applications such as hard disk drives and read-write heads. However, new functionalities can be derived from semiconductor spintronic devices. The Datta-Das spin modulator [2] demonstrates an example of such a functionality. Shown in gure 1.1is a schematic of this device. A ferromagnetic source and drain is used in this structure, which is operated under external magnetic eld. The carriers injected into the channel are spin polarized, and readily accepted by the drain, leading to the on state. If, however, a small gate bias is applied, the spins start to precess or rotate, due to interaction with the semiconductor lattice under a bias. By the time they reach the gate, their spin is no longer aligned in the original conguration, and the drain no longer accepts them (the ostate). The utility of this device lies in the fact that a very small energy is needed to precess spins compared to that required in a MOSFET, where the channel needs to be under inversion. The key elements of spintronics are injection, manipulation, transfer and detection of spin-polarized carriers across a semiconductor device. A ferromagnetic source material is required to produce such spin-polarized carriers. Ferromagnetic materials have an unequal density of states (DOS) of spin-up and spin-down states at the Fermi level. The degree of polarization, P can be dened as :
P=
(nn) (n+n)
(1.1)
Figure 1.1: Schematic of Datta-Das transistor
Where, n and n represent the DOS of electrons polarized in opposite directions. Although ferromagnetic metals oer a high degree of polarization, they are inecient sources of spin-polarized carriers into a device. This is a result of the mismatch in conductivity between a metal and a semiconductor [3]. This problem can be circumvented with the use of a magnetic semiconductor source instead. Several magnetic semiconductors such as Europium and Chromium chalcogenides (EuS, EuO, CdCr2 S4 , CdCr2 Se4 ) [4] have been studied in the past for the interplay between semiconducting and magnetic properties. However, these compounds are not useful technologically due to dicult growth processes and incompatibility with systems currently in use, such as Si or GaAs. A class of materials known as dilute magnetic semiconductors (DMS)was developed and studied in the 1980s. The underlying principle behind ferromagnetism in these materials was the interaction between the itinerant electrons in the semiconductor and the atomic magnetic moments of the dopants via an exchange bias mechanism which resulted in spin-polarized carriers in the semiconductor. Thus one
CHAPTER 1. INTRODUCTION
Figure 1.2: Curie temperatures of various DMS candidates [9] could develop an all-semiconductor spintronic device with minimal losses during spin injection. Another important aspect of DMS is that since ferromagnetism is related to the carriers in the semiconductor, one can, in principle, deplete the semiconductor of carriers and thus disturb ferromagnetic order. This gives rise to new possibilities such as optical manipulation of magnetic behavior of DMS [6] or gate-controlled ferromagnetism [5]. The behavior of spins in a semiconductor lattice was studied as early as the 1960s in chalcogenides such as EuO and EuSe [7]. However, it was not until the 1980s, when II-VI compounds such as ZnS were doped with transition metals, that the early work on DMS started. Tremendous progress was made in the understanding of exchange interactions between magnetic moments of the dopants and the charge carriers in the host. However, problems with controlling the n or p-type doping of these materials, as well as a low Curie temperature served as impediments in the development of II-VI DMS. Nevertheless, this was a precedent to research into III-V materials as potential DMS candidates. Initial work by Ohno and Munekata [8] on Mn doped InAs opened
up the technologically signicant III-V semiconductors as potential hosts for DMS applications. This eld has been advancing rapidly ever since. However, the search for better materials and an understanding of the physical mechanisms underlying the magnetism is an ongoing process. Figure 1.2 shows the Curie temperatures of various DMS candidates, as predicted by Mean eld theory [9]. The Curie temperatures were calculated based on Mn doping with a high p-type doping level. The candidates that result in the highest Tc include III-V Nitrides such as GaN and InN, as well as oxides such as ZnO. Following these predictions, a lot of DMS research has been focussed upon nitrides and oxides. In this work, we have studied one such potential candidate, InN. The thesis is organized to rst discuss basic underlying principles of magnetism. This is followed by a review of models describing magnetism in DMS materials, which leads to a discussion of promising DMS candidates. The experimental results obtained from the investigation of the growth and characterization of one such set of interesting DMS candidates, Cr and Mn-doped InN are then described. Finally, the origin of magnetic behavior in these material is analyzed and discussed.
Chapter 2 Dilute Magnetic Semiconductors

2.1 Introduction
Dilute magnetic semiconductors (DMS) are semiconductors where a fraction of the cations in the lattice are replaced substitutionally by magnetic ions (g 2.1). The atomic spin on these magnetic dopants is expected to interact with the carriers in the lattice to bring about global ferromagnetic order in the material. They have unusual magnetic characteristics due to the presence of isolated magnetic ions in semiconducting lattice. Signicant eort was made in trying to develop various DMS candidates as well as in understanding the origin of magnetism in these materials starting from the 1980s. Initial studies focused on II-VI compounds such as CdSe doped with transition metals [12]. DMS were interesting from both a theoretical, as well as a technological standpoint. Unlike metals, semiconductors allow properties such as band gap and carrier concentration to be tailored to t the application. Further, if the magnetism in the material is related to the carrier concentration, then it might be possible to electrically tune the magnetism. This could lead to a new functionality of gate-controlled ferromagnetism. Although physics of the magnetism was thoroughly investigated in 6
2.1. INTRODUCTION
II-VI DMS, they were not suitable for technological applications. One of the reasons for this was that they did not have a mature growth technology. Furthermore, ferromagnetic order could not be achieved at high temperatures in these materials. In fact, the magnetism observed was attributed to spin-glass like frustrated behavior, with very low spin glass transition temperatures.
Figure 2.1: Semiconductor host doped with magnetic ions
The area of DMS caught the attention of a much larger research community with the demonstration of magnetic order in Mn-doped InAs [8] and GaAs [13]. Moreover, several curious eects arise from combining magnetism with semiconductors. For instance, in certain systems such as Co-doped TiO2 [15] or SnO2 [16] as well as in the case of Gd-doped GaN [14], unusually large magnetic moments per dopant ion have been observed. In order to utilize DMS for technological applications, a sound understanding of the origin of magnetism in these materials is required. Magnetic interactions in solids are discussed in this chapter, as well as the important models used to predict Curie temperatures in prospective DMS candidates.
CHAPTER 2. DILUTE MAGNETIC SEMICONDUCTORS
2.2
Magnetic interactions in solids
The fundamental property of an electron which gives rise to its magnetic properties is its spin. No two electrons with the same spin can occupy the same energy state. This determines the orientation of spins of electrons in the various energy states, and is also responsible for properties such as polarization-dependent optical selection rules. Although spin is a quantum-mechanical property, it can be understood via a semiclassical approach in terms of an electron orbiting along a circular orbit. With charge e, and an angular momentum L the electron would classically induce a magnetic dipole given by
M = current x area =
Le 2m0
(2.1) If the angular momentum is presumed to be quantized in units of h then the unit of magnetic moment is
B =
e h 2m0
(2.2) Electronic spin angular momentum only contributes in part to the total magnetic moment of an atom. In addition, electrons around the atom also have orbital angular momentum associated with them. The interaction of the spins on the dierent electrons as well as their coupling with the angular momentum plays an important role in determining whether the spins on individual electrons have any form of collective order. Furthermore, application of an external magnetic eld also contributes to the magnetic moment of the atom by changing the orbital momentum [17] and resulting in a diamagnetic moment.
2.2. MAGNETIC INTERACTIONS IN SOLIDS
Diamagnetic behavior is exhibited by all materials to some extent. When an external magnetic eld is applied on an electron orbiting an atom, it travels in a direction that induces an orbital magnetic moment, opposing the external eld. The moment associated with such an electron is the diamagnetic moment. In addition, most materials exhibit a paramagnetic or a ferromagnetic contribution which far exceeds that of the diamagnetism. Paramagnetism is seen in materials with an unpaired number of electrons. This includes transition metals with incomplete inner shells, lattice defects, atoms or molecules with an uneven number of electrons as well as metals. Although orbital moment of the electrons changes to oppose the external eld, the unpaired electrons have a spin moment, which points in a direction parallel to that of the applied eld. This results in a net positive paramagnetic moment, when a eld is applied. There is no collective order in paramagnetic materials, which means that while the spins on the individual electrons are dependent on the external magnetic eld, they do not interact strongly with each other. Any collective magnetic order in a material is brought about by energy considerations. In other words, if there exists a spin conguration that would allow the entire system to lower its energy by aligning the spins in a specic orientation with respect to each other in the absence of an external eld, then some kind of ferromagnetic order will persist. The dominant interaction between two spins is the exchange interaction. This interaction is given by :
H = -J S1 .S2 (2.3) Here, J is the exchange coupling constant, that is positive if the interaction is ferromagnetic, and negative if it is antiferromagnetic. Exchange interaction is the balance
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between magnetostatic and electrostatic energies. It can be understood by Paulis exclusion principle, which states that no two fermions (electrons, in this case) can have the exact same quantum state. Consequently, two electrons with the same spin are spatially separated, thereby decreasing their electrostatic energy. This makes up for the increase in their magnetostatic energy, which is caused by the magnetic repulsion of the like spins. The orientation of a small enough magnetic particles is governed predominantly by this exchange interaction. However, in a crystal lattice, other longer range interactions such as dipole interactions or anisotropy also begin to aect the magnetization direction. Dipole energy causes the moments at the surface of a magnetic material to get oriented along antiferromagnetic directions. On the other hand, anisotropy tends to orient the magnetic moment along certain crystallographic axes, known as easy axes. This comes about as a result of spin orbit coupling that results in dierent coupling energies along dierent crystallographic axes. The magnetic behavior of a material is a result of the sum total of all these interaction energies. In a ferromagnet, the energy bands are spin-split at the fermi level even when there is no external magnetic eld present. The exchange interactions in dilute alloys of magnetic elements are somewhat complex, and are usually understood in terms of hybridization between the localized spin-split atomic orbitals of the element with the energy bands of the rest of the lattice. The next section reviews the underlying mechanisms of magnetism in dilute magnetic semiconductors.
2.3
Models describing magnetism in DMS
The basic model for DMS is of a magnetically inert host semiconductor doped with localized spins, which may then be doped with electrons or holes. In some cases such as that of Mn-doped III-V materials, the magnetic ion itself is an acceptor and
2.3. MODELS DESCRIBING MAGNETISM IN DMS
11
acts as a source of holes. The magnetic spins are localized on much smaller scales than the carriers. The magnetic interactions seen in DMS are governed by an sp-d exchange, which allows carrier mediated magnetic order and leads to such eects as a giant Faraday rotation and the formation of bound magnetic polarons. Several mechanisms have been suggested that explain the origin of magnetism in DMS. Most theories attempt to identify the various spin coupling energetic concurrent in a system, and by plugging in the material parameters, attempt to estimate if the energetics lead to ferromagnetic, antiferromagnetic or spin-glass like interactions between individual atomic spins.
2.3.1
Mean Field Theory
Zener originally proposed a model for ferromagnetism in dilute alloys of transition metals, driven by the exchange interaction between carriers and localized spins [11]. The three important ideas behind the model are: 1. In an isolated atom, the lowest energy state is given by the electronic state where an incomplete d-shell has the highest spin - meaning that all the spins are aligned. 2. The exchange integral between d-shells of adjacent atoms always leads to antiferromagnetic order 3. The spin of an incomplete shell is strongly coupled to the conduction electrons. When this coupling dominates over the direct exchange, ferromagnetism is made possible. The net spin coupling energy in such a system is a combination of three terms. The rst one is the direct exchange between incomplete d-shell electrons while the second is the exchange between the d-shell electrons and the conduction electrons. The
12
third interaction is the Fermi kinetic energy of the conduction electrons. This is at a minimum (0) when there is an even number of spin up and spin down electrons, since the spin distribution at the Fermi level is balanced. A combination of these three terms are given by :
2 2 - Sd Sc + 1 Espin = 1 Sd Sc 2 2
(2.4) Here, Sc and Sd are the net spin polarizations of the conduction electrons and the d-shell electrons respectively. The sign of Espin determines the nature of magnetic order. While a positive value is indicative of antiferromagnetic order, a negative sign implies ferromagnetism. This model was later modied by Dietl et al [9] to understand ferromagnetism in p-type DMS materials such as GaMnAs. The theory considers ferromagnetic correlation mediated by holes originating from shallow acceptors in the ensemble of the localized spins in doped magnetic semiconductors. For instance, in GaMnAs, Mn, which occupies the cation (Ga) sublattice in zinc-blende GaAs provides a localized spin and at the same time acts as an acceptor. Dietls theory can be extended to several such p-type DMS, and has been used to estimate Curie temperatures of various candidates.
2.3.2
Bound Magnetic Polaron
An important attribute of diluted magnetic semiconductors is the sp-d exchange coupling between spins of magnetic ions and those of the impurity electrons in the semiconductor band. This results in phenomena such as valence band splitting under magnetic eld and polaron eects. A bound magnetic polaron (BMP) is a collection of electrons (or holes) bound to impurity atoms through exchange interactions within
2.3. MODELS DESCRIBING MAGNETISM IN DMS
13
an orbit [10]. These interactions can render carriers parallel or anti-parallel to the magnetic impurity, depending upon the system. These two congurations dier in energy, and this results in a non-zero spin ip energy that is a characteristic of BMPs. The net energy of the system can be lowered if the ions are aligned parallel to each other, since they all interact with carriers the same way. At low temperatures, where the s-d exchange energy exceeds KB T, mutual alignment of the ions and carriers results in a ferromagnetic bubble. At higher temperatures however, the spins of the magnetic ions are not constant anymore. A nonzero magnetization results from the spin uctuations within any carrier orbit. While the former instance comprises the collective regime, the latter is a characteristic of the uctuation regime. The temperature up to which a BMP can facilitate magnetic order depends upon the nature of the interactions between the atomic spins and the charge carriers. The net exchange has been computed by Durst et al [18] based on the polaron-pair model. This model considers the interaction between a pair of BMPs via a shared interstitial area, where the magnetic ions interact with carriers belonging to both the polarons. Such an area is crucial for carrier mediated ordering of the individual polarons. Fig. 2.2 shows a schematic of the polaron-pair model. The Hamiltonian that results from this model is given by :
Hm =[(s1 .S1 )+(s2 .S2 )]+K(s1 +s2 ).S3 +Js1 .s2 (2.5) where K is the intrapolaron ion-carrier exchange constant,K is the interstitial ioncarrier exchange constant, J is the direct carrier-carrier exchange constant, s1 and s2 are the carrier spins, S1 and S2 are the net polaron spins, and S3 is the collective spin of the interstitial region.
14
Figure 2.2: Representation of Polaron pair model indicating an interstitial region
Donor bands are relatively large and s-d interactions, weak. Therefore, in cases where these are involved in the formation of BMPs, the collective phase is observed only at low temperatures. On the other hand, when the more localized valence bands are involved, the p-d interaction is strong enough to sustain collective order even at higher temperatures. Coey et al [19] have proposed a model for n-type DMS materials based on exchange interaction between highly correlated narrow impurity bands and the atomic spin moment on the dopant ions. Figure 2.3 shows a schematic of the interaction in oxides, where defects such as oxygen vacancies act as a source of electrons. These electrons lie in hydrogenic orbitals with characteristic Bohr radii. As their concentration increases, their individual orbits extend out into narrow impurity bands. The electrons interact with all the magnetic ions that lie within their orbit. Each electron has an exchange interaction with all the magnetic ions lying within its orbital or sphere of inuence. If there are a large enough number of magnetic spins within the orbital, the electron is completely spin polarized. Furthermore, the atomic magnetic moments have an indirect exchange interaction mediated by the carriers, that results in their ferromagnetic ordering.
2.4. SPIN GLASSES
15
Figure 2.3: Representation of Magnetic Polarons in a semiconductor lattice [19]
2.4
Spin glasses
Spin glasses are complex magnetic systems that never equilibrate given any amount of time. They are comprised of numerous magnetic moments that are constantly in a state of cooperative relaxation, which can typically only be modeled phenomenologically. Glassy behavior was rst observed at low temperatures in dilute magnetic alloys Au:Fe, Ag:Mn and Cu:Mn with Mn concentrations in the range 1-3% was rst observed by De Nobel and Du Chantenier (1959) and Zimmermann and Hoare (1960). They observed an unexplained linear term in the specic heat of these materials which was independent the Mn concentration. Another curious eect discovered in similar
16
Figure 2.4: Cusp observed in the magnetic susceptibility vs. temperature plot in Au:Fe alloys with 1-2% Fe [20]. Data for 1 % Fe from Lutes and Schmit (1964) are also included. dilute alloys by Cannella et al. [20], was a cusp in the magnetic susceptibility (g. 2.4). This was later understood as the spin glass freezing temperature. Key ingredients that contribute to glassy behavior in materials are frustration and quenched disorder. Fig. 2.5 represents these characteristics diagrammatically. The concept of frustration is understood through the canonical example of antiferromagnetically interacting Ising spins on a triangular lattice. For antiferromagnetic interactions, the lowest energy state for two spins is one in which they point in opposite directions. It is not possible to satisfy all three bonds simultaneously, as having two spins aligned anti-parallel leads to a conict for the third spin. More generally, frustration refers to a situation in which there are competing interactions that cannot all be satised simultaneously. Frustration alone is not sucient for spin glass behavior. At low temperatures,
2.5. PROMISING DMS CANDIDATES
17
Figure 2.5: Important characteristics of spin glasses include frustration and quenched disorder the magnetic moments in these materials get frozen in an arbitrary state, with no long range order. Such an ensemble of disordered spins represents a system with quenched randomness. This can be brought about by disorder of any kind - bond,chemical or topological. If the single ion anisotropy of the individual spin clusters exceeds long range order, frustration and quenched disorder can result in spin glass behavior.
2.5
Promising DMS candidates
Regardless of the reason behind the magnetic behavior, the characteristics that are sought after in novel DMS materials are a high Curie temperature, and a well established growth technology. Dietl proposed several suitable candidates as hosts for DMS based on the mean eld theory. All these materials were assumed to be exhibit p-type conductivity, and the carrier-mediated magnetism was expected to come about due to sp-d hybridization. However, most of the work published on high temperature magnetic order DMS materials has involved n-type materials such as Co-doped ZnO
18
Material GaN
Eg (eV) 3.5
Doping 0.9% Mn Cr 7% Cr 5% V 1-2% Co 7% Co 2% Fe 5% Fe 5% Co 15% V 5% Fe, 1% Cu 10% Co 0.9% Ni 5% Co, 0.5% Al 5% Mn
B 0.9 1.2 4.2 0.3 1.4 2.4 1.8 7.5 0.5 0.75 2.0 0.06 0.2 0.8
TC (K) 940 > 400 > 600 > 400 > 300 650-700 > 300 610 650 > 350 550 280-330 > 300 > 300 > 300
Ref [21] [22] [23] [15] [24] [25] [26] [27] [16] [28] [29] [30] [31] [32] [33]
AlN
4.3
TiO2
3.2
SnO2
3.5
ZnO
3.3
Cu2 O In1.8 Sn0.2 O3
2.0 3.8
Table 2.1: High temperature ferromagnetism in n-type DMS [19] or Mn-doped GaN. Shown in table 2.5 are the reported Curie temperatures of some of these candidates. Theoretical models based on the formation of impurity bands have been proposed in order to explain some of these results. Nevertheless, a thorough understanding of the mechanism behind the magnetic behavior of such n-type DMS is yet to be rmly established. The DMS candidate that we have explored in this work, InN is also an n-type material. The lms were deposited over c-sapphire using Molecular beam epitaxy. GaN buer layers were employed to accommodate the lattice mismatch between the lm and the substrate. The lms were doped with Cr in the range of 0.1-6%, and up to about 1% Mn. The next few chapters discuss a thorough structural, magnetic and
2.5. PROMISING DMS CANDIDATES
19
electrical investigation of this material. Techniques such as X-ray diraction (XRD) and reection high energy electron diraction (RHEED) were used for structural characterization and Hall eect measurements for electrical characterization of doped InN lms. Superconducting quantum interference device (SQUID) magnetometry as well as X-ray magnetic circular dichroism (XMCD) were employed in the investigation of the magnetic properties. An attempt was made to understand the magnetic behavior of this novel DMS candidate.
Chapter 3
Growth of InN and doped InN by MBE
The quest for better DMS candidates has predominantly been dictated by a high Curie temperature. The more promising candidates turn out to belong to III-V nitride and II-VI oxide families. A lot of attention has been paid to oxides such as TiO2 and ZnO as well as nitrides such as GaN and AlN. However, there have been relatively few reports of diluted magnetic InN alloys [34, 35, 36, 37, 38], despite its attractive attributes. InN has a low spin orbit coupling of 0.003 eV, as compared to a value of 0.34 eV in GaAs [39]. This translates to a long spin lifetime due to lower spin-orbit scattering. Furthermore, it also has a high Hall mobility [40] and carrier drift velocity [41], which could be attractive properties for device applications. The chief issue with InN is that growth of high quality lms is not straightforward. The following section discusses the chief growth issues and the procedure used for growth of doped InN. 20
3.1. GROWTH OF III-NITRIDES
21
3.1
Growth of III-Nitrides
One of the major challenges in growing epitaxial III-nitrides is the lack of appropriately lattice-matched substrate [42]. Like other III-nitrides, InN has a Wurtzite structure, and ideally requires a substrate with a crystal structure that has three-fold symmetry. Sapphire is one such substrate with a trigonal lattice structure that is routinely used for growth of nitrides. However, this is far from ideal, since the lattice mismatch between sapphire and any of the nitrides is so large that mist dislocations are expected at the interface to accommodate the strain [43]. [1120]III N [1120]Sapphire -34.6% -33.0% -25.4% [1010]III N [1120]Sapphire +13.3% +16.0% +29.2%
AlN GaN InN
Table 3.1: lattice mismatch between sapphire and III-V nitrides
Table 3.1 shows the lattice mismatch values of the nitrides along two dierent orientation relationships. The rst column shows the mismatch when the [1120]III N [1120]Sapphire . In other words, the in-plane axes of the III-N are oriented parallel to the corresponding axes in the substrate. The second column lists the lattice mismatch values under the orientation relationship : [1010]III N [1120]Sapphire , which corresponds to the III-N in-plane axes oriented at 30 with respect to those of the substrate. The mismatch values along the second orientation relationship are much lower in both AlN and GaN compared to that of the rst relationship, as depicted for the case of GaN in g 3.1. However, InN has comparable mismatch along both these orientations. Thus, while GaN and AlN have a preferred orientation of deposition over sapphire, corresponding to that with lower mismatch, InN does not. This results in yet another challenge in the growth of epitaxial InN lms, namely, multi-domain
22
CHAPTER 3. GROWTH OF INN AND DOPED INN BY MBE
Figure 3.1: The preferred orientation of deposition of GaN over sapphire [44] deposition. InN lms grown directly on bare sapphire substrates are not single crystal, but end up with multiple domains including the two mentioned as well as a third domain corresponding to [1450]InN [1120]Sapphire [45].
One way to get around this problem is to nitridize the sapphire substrate. This results in formation of a combination of AlN and AlNOx , depending upon the nitridization temperature [46]. The AlN layer acts as a suitable template for deposition of InN, and results in the orientation relationship [1010]InN [1010]AlN InN deposition, which has the same eect as the nitridized sapphire. We have used this second approach in this work in order to grow crystalline InN lms. Thin GaN buer layers grown by CVD were used to accommodate the high lattice mismatch between InN and Sapphire. In-situ RHEED was used to analyze the eect of growth temperature and plasma power on the crystalline quality of the [1120]Sapphire .
Alternately, one can deposit thin buer layers of AlN or GaN over sapphire, prior to
3.2. MOLECULAR BEAM EPITAXY
23
lms. X-ray diraction (XRD) conrmed crystalline lms with InN (0001) oriented parallel to Al2 O3 (0001). The following section discusses the growth of InN-based DMS materials by molecular beam epitaxy.
3.2
Molecular Beam epitaxy
Molecular Beam Epitaxy or MBE was developed in the 1970s as an alternative to existing crystalline thin lm deposition techniques such as metal-organic chemical vapor deposition (MOCVD). The key advantage of MBE that distinguished it from other techniques was the precise control over elemental uxes in an ultra high vacuum (UHV) conditions, which allowed deposition of very high quality crystalline lms, as well as atomically abrupt interfaces. MBE systems are operated in a UHV environment, which corresponds to a pressure range in the order of 1.1010 Torr. At such low pressures, the level of oxygen or other contaminants in the chamber is suciently low, so that there is minimal incorporation of impurities in the lms. Furthermore, since the evaporated molecules have a free path till they hit the substrate, gas phase reactions are also avoided. Deposition rates in MBE are relatively low, usually lower than 1 A/s. This allows precise control of layer thicknesses, which is useful for deposition of multi layer device structures. Figure 3.2 shows a schematic of a typical MBE system similar to the one used used in this work for growth of InN. Films are deposited by evaporating various sources, which are pointed in a direction facing the substrate. The sources are usually in solid form and placed in shuttered ovens known as eusion or Knudsen-cells (Kcells), where they are resistively heated. When the shutters are opened, the elements evaporate into gaseous molecules, which move unidirectionally due to the geometry of the k-cells. Thus formed molecular beams strike the substrate. Depending on how much energy a molecule has, it either bounces o the substrate or moves around on
24
Figure 3.2: Schematic of Nitride MBE system the surface until it bonds with another adatom. The UHV environment allows control over the uxes of each individual species in order to precisely tailor the composition of thin lm alloys and to vary doping levels in semiconductors. One important characteristic of MBE is that the substrate temperature used is much lower than that in other growth techniques such as CVD. This is because the growth does not depend upon any chemical reactions occurring under equilibrium conditions. Instead, it relies on providing the individual components at the right ux ratio, so that they can recombine at the substrate. The bulk diusion coecients of the constituent elements is not large enough at the low growth temperatures. This is the reason why it is possible to deposit abrupt interfaces by MBE. The substrate temperature plays a crucial role in the quality of the deposited lms.
25
If it is too high, a large amount of energy is imparted on the incident molecules, making them bounce o, thereby leading to a low sticking coecient. On the other hand, if the substrate temperature is too low, the adatoms are left with insucient mobility to move about on the surface and nd an appropriate atom on the previous monolayer to attach themselves to. As a result, the lms deposited are in the form of rough 3-dimensional islands, and not smooth layers. However, using low growth temperatures results in deposition under non-equilibrium conditions, which can be a powerful way to grow alloys even with dissimilar constituents. If the energy barrier that must be overcome in order to transform from a local energy minimum corresponding to a metastable state into an equilibrium state such as that corresponding to a secondary precipitate, is larger than the thermal energy of the adatoms, then one can eectively avoid such phases. Thus there is a tradeo between structural quality and the ability to synthesize exotic compounds far from equilibrium conditions.
3.2.1
Growth of InN by MBE
For growth of InN by MBE, while the group III source is solid, a gas source is used for nitrogen. The gas sources commonly used include NH3 and N2 . The dissociation pressure of InN is relatively low, because of which, its optimum growth temperature is low compared to that of GaN. This could be a disadvantage while using NH3 as a nitrogen source, since the temperature may not be high enough for eective decomposition of NH3 . This could lead to nitrogen vacancies in the resulting lms. On the other hand, the dissociation energy of N2 molecules is as high as 9.5 eV [42]. Therefore supplying N2 molecules at the substrate surface is not sucient for any reaction. Radio frequency (RF) or electron cyclotron resonance (ECR) plasma sources have been used to supply the much more reactive atomic nitrogen for the growth of IIInitrides. One key issue with using plasma sources is that they could produce high
26
energy ions that can cause damage during epitaxy [47]. The other problem that they cause is contamination due to oxygen or carbon dioxide. To prevent this, pyrolytic boron nitride (PBN) aperture plates are typically used with plasma sources. The growth temperature is very crucial in determining the quality of lms obtained. High growth temperatures above about 550 C result in dissociation of InN. On the other hand, very low temperatures lead to poor morphology of the lms deposited. Therefore most groups have reported growth temperatures between 400 and 550 C. Another important parameter that should be controlled in order to obtain high quality InN is the III/V ratio. A high ux of In leads to the formation of In droplets, and In-rich lms. This is largely because the excess In cannot desorb from the surface at the typical low growth temperatures. A higher ux of N can be used to avoid this. However, this again, can increase surface roughening since the migration of In atoms on the surface is inhibited. Thus the ideal III/V ratio is close to stoichiometry, on the N-rich side [48].
3.2.2
Reection High Energy Electron Diraction (RHEED)
RHEED is an in situ electron diraction technique which can reveal a lot of information about a surface such as roughness, coverage or the coordination and bonding of the atoms. The RHEED gun emits electron beams with energies in the range of 10 20 KeV. The beams are incident at a grazing angle, which is typically well under 5 . Due to the grazing angle of incidence, very little momentum gets transferred normal to the lm, and a large area of the surface is probed. This makes RHEED is a surface sensitive technique.
27
Figure 3.3: Schematic of RHEED measurement geometry
Figure 3.3 depicts the typical RHEED set up in an MBE chamber. The incident electron beam gets diracted o lattice planes parallel the surface, with the diraction condition given by :
K= G (3.1) Where K, the wave vector is given by 2 ,K is the dierence between the incident and diracted beams and G is the reciprocal lattice vector. The relative intensities of the diracted beams depends upon the morphology of the surface. Planar 2-dimensional surfaces lead to smooth RHEED patterns, whereas surface roughness or 3-dimensional features such as islands result in spotty streaks. One of the applications of RHEED is to measure the in-plane lattice parameter in cases where there is lattice relaxation. Since RHEED is sensitive only to a few monolayers, the interplanar distance of the top few layers alone can be measured, without averaging out over the entire lm thickness [49, 50]. The spacing between consecutive streaks, t, obtained along any direction depends inversely upon the interplanar spacing of the planes, and
28
is given by :
t=
dparallel
(3.2) L is the distance of separation between the lm and the screen, is the wavelength of the electron beam and dparallel is the interplanar distance between planes parallel to the electron beam. This can be used to determine the lattice parameters of planes parallel to the surface. RHEED measurements were used in this work to monitor the growth process and to determine optimum deposition conditions. They were also used to examine the in-plane lattice constant of the Cr-doped lms. The following section elaborates the procedure adopted for growth of InN.
3.3
Growth of Cr and Mn-doped InN
Growth of Cr and Mn-doped InN was carried out in an MBE system that was built by VG. The pumping on the system included a diusion pump and a cryopanel, which was constantly relled with liquid nitrogen. A phase separator was used to maintain a closed loop of nitrogen. The pumping geometry allowed a pumping speed of 500 l/s, and the base pressure of the system was typically in the range of 5.1010 to 1.109 mbar. The system had previously been used for deposition of metal lms, and therefore included three electron-beam gun (e-gun) sources in addition to ports for four eusion-cells. However, for this work, the e-gun sources were not utilized. Instead eusion cells were used for In, Mn and Cr. A high temperature cell was needed for Cr, since it has a low vapor pressure at lower temperatures. An RF-plasma nitrogen
3.3. GROWTH OF CR AND MN-DOPED INN
29
atom source was used as the source of atomic nitrogen. The model used was the HD25 made by Oxford Applied Research. Puried nitrogen was allowed into the system through a leak valve, and the pressure of the chamber was maintained at around 2.105 mbar during InN deposition. A PBN aperture plate with 10 holes of 0.3 mm diameter was used at the opening of the source to the chamber. The number of holes on the aperture plate was relatively small to that used ordinarily in the growth of III-V nitrides. This small number of holes proved to be a limitation on the amount of nitrogen available during growth, and hence the growth rate. However, a higher conductance under the pumping speed would have resulted in the chamber pressure exceeding the operating limits of the diusion pump.
The system was equipped with a quartz crystal monitor to measure growth rates of lms deposited. However, this was not adequately sensitive to measure the uxes of In, Cr or Mn being used. Therefore, several of the growth runs were monitored by controlling the temperature of the sources. This gave fairly repeatable growth rates on a day to day basis. Several calibration runs were made in order to determine growth rates corresponding to various source temperatures. Typical operating temperatures were around 750 C for In, 1100 C for Cr and 620 C for Mn. A beam ux monitor was later built for better control over the ux of incident In atoms prior to deposition. This monitor was comprised of an ionization gauge mounted at the end of a shaft, which could be translated in and out of the chamber using a bellowed ange. The substrates were mounted on a sample stage which rotated in order to maintain the lateral uniformity of the composition across the wafer. The samples were heated resistively by a Tantalum heater placed on the back of the stage. The heater could reach temperatures up to about 550 C. This was sucient for most steps involved in the growth of InN as well as Cr or Mn-doped InN.
30
3.3.1
Nitridization of Sapphire
Figure 3.4: Chemistry of nitridization of sapphire [46] Nitridization of sapphire refers to the surface treatment of the bare substrate at an elevated temperature under the presence of a reactive nitrogen species, prior to deposition of III-V nitrides. This step has been shown to result in the formation AlN or AlNOx) [46, 51]. It has been suggested that active nitrogen reacts with the Al in sapphire to form AlN, and with the O to form NO. Fig 3.4 shows the possible chemical reactions that comprise the nitridization process. Depending upon the bonding of NO, it can either readily desorb or get adsorbed to the Al sites, preventing the formation of AlN. The latter bonding is favored at higher temperatures, implying that nitridization at higher temperatures leads to a mixture of AlN and NO, whereas nitridizing at lower temperatures is more ideally suited to the formation of AlN alone. The authors of ref. [51] observed this in the RHEED construction obtained at the end of the nitridization step. A RHEED construction corresponding only to AlN was observed upon nitridization at 200 C. Upon increasing the nitridization temperature to 700 C, some of the sapphire streaks were still visible in the RHEED construction, indicating the process remained incomplete. A similar attempt was made to nitridize a sapphire substrate at a wide range of temperatures from 100 C-550 C. The nitrogen pressure used was 2.105 mbar, at a
31
plasma power of 350 W. Within the temperature range, at every 100 C, the substrate was exposed to the nitrogen plasma for about an hour. The RHEED construction obtained was monitored for any changes. Fig. 3.5(a) shows the RHEED construction obtained during the process. No change was observed from the sapphire [1120] RHEED pattern. Nevertheless an InN lm was deposited on this substrate.
Figure 3.5: RHEED construction during sapphire nitridization (a) [1120] direction of Sapphire (b) Polycrystalline InN deposited over the substrate However, this lm was observed to be polycrystalline from the RHEED construction (g. 3.5 (b)). Thus nitridization of sapphire was unsuccessful within the temperature range accessible by the substrate heater. A potential explanation for this could
32
be relatively small nitrogen ux that was available at the sapphire surface. Following this experiment, further growth of InN was carried out employing a GaN buer layer. The details of the growth procedure follow.
3.3.2
Growth of InN and Cr, Mn-doped InN over GaN templates
The GaN templates employed in the deposition of InN were deposited by MOVPE at CBL Technologies. The procedure adopted was started with degreasing of the c-plane sapphire substrates were rst degreased and thermally cleaned at 1050 C for 30 min. The next step was the deposition of low temperature GaN buer layers at 500 C, followed by recrystallization at 1050 C. various thicknesses of GaN were used in dierent growth runs. The quality of the InN layers, which were typically under 1000 A in thickness, was not seen to depend upon the thickness of the GaN buer layers used. Following the GaN deposition step, InN buer and doped layers were grown in the MBE chamber. Growth proceeded with thermal cleaning of the templates at 500 C, following which 200-1000 A thick InN buer layers were deposited at 450 C. Thereafter, 200-500 A thick Cr- and Mn-doped InN layers were grown at 350 C. The substrate temperature was reduced prior to deposition of the doped layers in order to prevent formation of secondary precipitates. The nitrogen source was operated at 350W plasma power with a N2 partial pressure of 2.105 mbar. With the In cell at 750 C, Cr at 1100 C and Mn at 620 C growth rates of the various layers were low, typically around 90 A/min. Calibration runs were used to keep the growth rates constant. The Cr doping levels were varied from 0.5% to 6% and Mn from 1% to 2%. RHEED was used to monitor the depositions. The energy of the electron beam used was 18.8 keV. Fig. 3.6 shows the RHEED pattern recorded during the deposition
33
of a 3% Cr-doped lm, with the beam parallel to the <1010> direction of InN. Part (a) shows the RHEED construction that was exhibited by the buer layer.
Figure 3.6: RHEED construction during deposition (a) InN buer layer (b) Buer annealed at 450 C under N ux (c) Cr-doped InN
34
Figure 3.7: SIMS prole of a 5.25% Cr-doped InN lm The spotty-streaks were indicative of roughness in the lm. Upon annealing the lm at 450 C for about 30 min, under a nitrogen ux, the surface roughness, as observed by RHEED appeared to improve (part (b)). This was followed by deposition of the Cr-doped InN layer (g. 3.6(c)). The lms were analyzed by Rutherford backscattering spectroscopy (RBS) and secondary ion mass spectroscopy (SIMS) for thickness and concentration measurements. The RBS and SIMS data were obtained at IBM Almaden Research Center, courtesy of Andrew Kellock and Vaughn Deline respectively. Fig. 3.7 shows the SIMS prole of a 5.525% Cr-doped lm. The Cr was seen to form a Gaussian prole near the surface, in the Cr:InN layer. The total thickness of the lm and the concentration of Cr relative to In were measured by RBS. This information, together with the SIMS prole was used to determine the thickness of the doped layer, as well as its doping concentration. Note that the intensities of the various elements were not normalized by their cross sections, and therefore their relative intensities are not representative of the sample composition. Instead, RBS was used to conrm stoichiometric In:N
35
ratio, as well as to determine the Cr doping concentration. Table 3.3.2 shows data from several lms, indicating the fraction of the total sputtering time that was taken up by the Cr:InN layer. Sample 1641 1643 1685 1635 1681 Time (InCrN : Total) (sec:sec) 490:1140 360:1600 167:381 360:640 103:344 Average % Cr (RBS) 0.4 0.4 0.8 2.8 1.7 %Cr in doped layer 0.93 1.77 1.81 5.0 5.53
Table 3.2: SIMS prole of Cr:InN lms used to determine composition Thus Cr and Mn doped InN lms were deposited by MBE using GaN templates. The growth rates were maintained constant by controlling the solid source temperatures and the nitrogen pressure. RHEED was used to monitor the growths. The thicknesses and doping concentrations obtained were measured by using RBS and SIMS. The next chapters discuss structural, electrical and magnetic characterization of these lms.
Chapter 4 Structural Characterization

One of the main issues with the development of InN based DMS materials is the ability to grow single crystalline lms of reasonable structural quality. The large lattice mismatch of InN with sapphire, coupled with its tendency to form multiple crystallographically misoriented domains over this substrate, presents diculties in the epitaxy of this material. Growth of high quality lms is further deterred by the low dissociation temperature of InN. This sets a limit on the growth temperature, which, in turn, leads to roughening and poor quality lms. In order to control the magnetic behavior of InN based DMS, it is important to study the structural properties of this material. In this chapter the results of the structural characterization of InN by techniques such as X-Ray diraction and transmission electron microscopy are presented. The eect of doping of the lms with Cr and Mn is also studied in detail. A study of the electrical transport properties made by Hall eect measurements is also presented. Finally, an investigation of the band gap by photoluminescence measurements are discussed. The set up and measurement procedures used have been explained before the data are presented. 36
4.1. TRANSMISSION ELECTRON MICROSCOPY
37
Figure 4.1: TEM of a 100 nm thick InN buer layer. (a) Shows the bright eld image (b) shows the CBED pattern obtained along the InN lm
4.1
Transmission Electron Microscopy
Initial structural characterization of a 100 nm thick InN buer layer deposited over nitridized sapphire was carried out by cross-sectional transmission electron microscopy (TEM). Figure 4.1(a) shows the TEM bright eld image the lm. The InN lm appeared to nucleate with a granular structure on the substrate, with the grains coalescing at higher thicknesses. However, these grains were crystallographically ordered, as observed by the consistent convergent beam electron diraction (CBED) pattern obtained at various grains (g. 4.1(b)). Within the grains, several line defects were observed. Thus the InN buer had several defects, likely due to the large lattice mismatch between the nitridized sapphire and the lm. Further structural characterization was carried out by X-Ray diraction.
4.2
X-Ray Diraction
X-Ray Diraction (XRD) is a widely used method for characterization of crystalline materials. It is commonly used as a means for determining crystalline phases present
38
CHAPTER 4. STRUCTURAL CHARACTERIZATION
in a polycrystalline sample, or to determine the crystalline orientation of single-crystal lms. The setup involves an anode, often made of copper, which emits radiation at a specic wavelength due to electronic transitions. This incident X-Ray is then monochromated using a crystal monochromator before it is incident on the sample. Figure 4.2 shows a schematic of the XRD geometry. The incident X-Ray gets reected o successive crystalline planes. If the angle of incidence is such that waves diracted o successive planes interfere constructively, then an intensity is observed at that angle by the detector. This relationship is given quantitatively by Braggs law (4.1). An area detector can be used to determine the degree of mosaicity or disorder in the epitaxial lm, since it detects diracted beams in their o-Bragg condition as well.
n. = 2d.sin (4.1) Where is the wavelength of the incident X-Ray, d is the out-of-plane d-spacing and is the angle of incidence, which is equal to the angle of reection. If the crystal is perfect, the peaks obtained at their respective Bragg angles have a full width at half maximum (FWHM) tending to zero. However, most crystals have structural imperfections that give them a nite FWHM. Thus the FWHM can be used to gauge the structural quality of single crystal lms. XRD was used as a tool for structural characterization of epitaxial InN as well as Cr and Mn-doped InN. The type of measurement made was the 2- scan. In order to make this measurement, the angle of the sample stage with respect to the source, (which is numerically equal to ), is increased in small increments, and the detector is maintained at an angle of 2 with respect to the source. Figure 4.3 shows
4.2. X-RAY DIFFRACTION
39
Figure 4.2: X-Ray Diraction
40
GaN InN:Mn (2%) (0002) (0002)
Sapphire (0006)
Mn N
3
(103)
InN:Cr (0.9%) (0002) CrN (111)
30
32
34
36
2
38
40
42
Figure 4.3: High Resolution X-Ray Diraction of Cr- and Mn-doped InN the typical XRD pattern exhibited by doped InN. The FWHM of the 2- rocking curve in most cases was found to be of the order of 0.1deg, with the (0002) peak of the InN and GaN lined up with the (0006) peak of sapphire. This is indicative of relatively good crystalline growth. While Cr-doped InN doped with Cr over a wide range showed no signs of segregation, a clear peak corresponding to the (103) Mn3 N2 peak was observed in several Mn-doped InN lms. In order to gain information about the in-plane orientation of the lms, asymmetric peaks were scanned using XRD. These are peaks corresponding to planes whose axes are not normal to the substrate, but have a component parallel to it. The peaks that were investigated were those corresponding to the (119) sapphire planes and (114) InN and GaN planes. The samples were rotated along the Phi direction in order to observe the relative orientations of the InN, GaN and sapphire layers. Figure 4.4 shows the pattern obtained from a typical InN lm. The (114) GaN was observed
4.2. X-RAY DIFFRACTION
41
Sapphire (119)
InN (114)
GaN (114)
-10
10
20
Phi
30
40
50
60
Figure 4.4: X-Ray Diraction of Asymmetric peaks of InN
42
at an angle 30 rotated with respect to the (119) Sapphire peak. The InN (114) peak lined up with the (114) GaN peak. This is an expected result, and is evidence that the GaN layer did in fact act as a crystallographic template fr InN deposition. An area detector was also used in order to qualitatively estimate the degree of disorder in the lms. Since an area detector can detect reections that are o their Bragg condition, it can be used to observe reections coming from planes which have some degree of misorientation or a dierent lattice constant (gure 4.2(b)). Figure 4.5 shows a comparison between the InN (0002) reections obtained for lms grown under various growth conditions. Also shown, is the sapphire (0006) peak for reference. The lm deposited on bare sapphire clearly showed the maximum mosaicity, followed by the lm grown over nitridized sapphire. As expected, the lm deposited over GaN showed the smallest width of the InN reection, indicating the most ordered lm. Another advantage of the area detector is that it can pick up small traces of secondary elements which do not have any specic crystalline orientation. A peak corresponding to metal In (101) was seen in some of the In-rich lms (not shown), however, no CrN was observed in any of the lms.
4.3
d-spacing
High resolution XRD was used to compute the out-of-plane lattice spacing in several of the Cr-doped InN lms using Braggs law. The Cr3+ ion is smaller than In3+ , and the bond length of In-N in the Wurtzite structure is about 2.15 A [52], whereas that of Cr-N is 2.07 A [53]. Therefore, if all the Cr in Cr:InN went into substitutional positions, the lattice parameter of the alloy would decrease with increase in doping. Separate diracted peaks corresponding to the InN and Cr:InN layers were not observed in any of the Cr-doped lms characterized by XRD. Given the structural disorder in the lms, the width of the peaks was not narrow enough in order for
4.3. D-SPACING
43
Figure 4.5: X-Ray Diraction using an area detector
distinct reections corresponding to both layers. The lattice parameter was however, seen to drop with increase in Cr at lower concentrations (gure 4.6) up to about 1.5% Cr doping. However, at higher concentrations, the lattice parameter started to increase again. This could likely be a result of increasing concentration of substitutional Cr at lower doping concentrations, up to 1.5 - 2 % Cr, beyond which a large fraction of Cr either went into interstitial positions or segregated out into Cr clusters. The caveat with this analysis is that these lms is that the lattice parameter is also aected by several factors in addition to the Cr doping level. The InN buer was observed to have several defects such as dislocations, and even formation of islands or domains, as observed by TEM. These could aect the observed out-of-plane lattice parameter. The dierent lms had dierent buer layers of varying thicknesses. Since it was not possible to distinguish between the doped layer and the buer layer peaks, the eect of the buer on the change in the out-of-plane lattice parameter
44
Figure 4.6: Out-of-plane d-spacing dependence on concentration
4.3. D-SPACING
45
was indeterminate. On the other hand, RHEED could be used to independently determine the in-plane lattice parameters of the buer and doped layers. This could eliminate spurious eects created by defective buer layers. However, RHEED is a surface sensitive technique and could mask bulk eects. In order to gauge the eect of Cr-doping on the lattice parameter using the RHEED data, the lattice parameter of undoped buer layers was rst computed by measuring the spacing between the streaks observed along the [1010] direction.
Figure 4.7: Variation of in-plane lattice parameter (open squares) and out-of-plane lattice parameter (circles) with Cr-doping Thereafter, the same calculation was made for the Cr-doped layers, in order to calculate their in-plane lattice parameters. The dierence between the lattice constants of the buer and doped layers was then computed for all the samples. Assuming a d-spacing of 3.07 A [54] for nominally undoped InN along this direction, the lattice parameters for the various Cr-doped lms were estimated. The results observed are summarized in g 4.7. The open squares represent data from the RHEED analysis,
46
Figure 4.8: Schematic of Photoluminescence in a direct band gap material
whereas the circles show the out-of-plane lattice parameter measured by XRD, for reference. Schematically, the in-plane lattice parameter showed similar behavior to that of the out of plane lattice constant, dropping in value at lower values of Cr-doping and increasing beyond a doping level of about 2%.
Once again, this was only a qualitative observation, and the actual amount of Cr incorporated in the lattice could not be quantitatively calculated. This is because the lattice parameter also varies depending upon other factors such as antisite defects. Nevertheless, the structural data was taken as evidence that Cr doping led to substitutional Cr only at lower doping levels, following which, it probably dissolved as interstitial Cr or segregated into metal rich clusters. This had an eect on the magnetic behavior of these lms as well. This is discussed in greater detail in the next chapter.
4.4. PHOTOLUMINESCENCE
47
4.4
Photoluminescence
Certain materials can release the energy they absorb from an external source in the form of radiation. This process is known as luminescence. In order to produce luminescence, electron-hole pairs must rst be created, which subsequently recombine to produce the radiation. For this purpose, excitation energy can be provided in several ways such as by using a light source or by applying an electric eld. Photoluminescence (PL) occurs as a result of photon absorption, when a radiative source such as a laser is used for excitation (g 4.8). The incident photons must have an energy that exceeds the band gap value of the material, sucient to excite electrons from the valence band to the conduction band, leaving behind excited holes. These electrons and holes quickly relax by losing their energy non-radiatively to phonons. While electrons settle at the bottom of the conduction band, holes move to the top of the valence band. The electrons and holes can relax further by recombining either radiatively or non-radiatively. The total relaxation time, t, is given by the following expression:
1 t
1 tr
1 tnr
(4.2) Here, tr and tnr are the radiative and non-radiative lifetimes respectively. In direct band gap semiconductors such as the III-Vs, the top of the valence band is lined up with the bottom of the conduction band in momentum or k-space. This allows direct recombination without an intermediate phonon interaction, unlike in the case of indirect band gap semiconductors, where momentum conservation requires that the recombination is phonon assisted. Therefore, the eciency of radiative recombination is much higher for these materials than in indirect semiconductors such as
48
Si. This property is utilized in order to measure the band gap of direct band gap semiconductors. A pump laser emits photons with an energy exceeding the band gap, which results in the semiconductor luminescing at its band gap energy. The most commonly quoted band gap value for InN, which is also a direct band gap semiconductor, is 1.89 eV at room temperature [55]. Most of the earlier band gap studies on InN lms were done by measuring optical absorption, and not photoluminescence since the material quality was not good enough for photon emission. Photoluminescence (PL) in InN lms was rst reported in 2001. With the realization of high quality InN lm several groups studied the PL measurement in the single crystalline InN lms. These lms were grown by modern deposition techniques such as MOVPE or MBE. The band gap energy of InN was discovered to be much smaller than earlier reported 1.89 eV [56, 57, 58]. In fact, it was found to lie around 0.90 eV. This created a controversy about the exact band gap energy, especially because the newly reported small band gap values were compatible with the wavelength of the optical ber. Therefore, if high quality InN lms with a direct band gap of 0.65 0.90 eV can be grown, could have potential applications in high speed LEDs and photodiodes (PDs). With progress in the growth procedure of InN, it has been fairly well established that the band gap is around 0.65 - 0.9 eV. PL measurements were used to measure the band gap of the InN as well as Cr:InN in this work. An Ar ion laser with a wavelength of 514.5 nm was used as a pump source with a constant incident pump power of 250 mW. An InGaAs photodiode measured the optical spectrum. Fig 4.9 shows the PL data taken at room temperature. The intensities are presented on a log scale. Luminescence was observed at 0.84 eV, which is quite consistent with values reported in the literature. The peak was not signicantly shifted in the Cr-doped lms. However, the intensities on the PL peaks was much lower in Cr-doped lms than in nominally undoped InN. This was likely due to poorer quality of Cr-doped lms owing to their lower deposition temperatures.
4.4. PHOTOLUMINESCENCE
49
Figure 4.9: Photoluminescence observed in Cr-doped InN
50
4.5
Hall Eect Measurement
The electrical behavior of the InN and Cr:InN lms was studied using Hall eect measurements. The Hall eect arises from the interaction of charge carriers in a semiconductor with an applied electric eld in the presence of a magnetic eld. Figure 4.10 shows a schematic representation of the setup, where a potential (Vapp ) and a magnetic eld (B) are applied across a semiconducting samples along orthogonal directions. An electron moving with a velocity v , in the potential applied feels a Lorentz force given by :
F = e v xB (4.3) Holes in the semiconductor experience a similar force along the opposite direction, leading to an accumulation of charge carriers along opposite edges of the semiconductor. This, in turn, gives rise to electrostatic forces, which, at equilibrium, are equal and opposite the Lorentz force. Thus a potential develops along this direction, perpendicular to the applied voltage. This potential is known as the Hall voltage, and is give by :
VH = IB/ned (4.4) Where, n is the density of charge carriers, e is the electron charge and d is the thickness of the lm. The sign of VH gives information whether the material is n-type or ptype. The sheet resistance of the lm can also be measured using the standard Van Der Pauw technique. This can be used together with VH to calculate the mobility,
4.5. HALL EFFECT MEASUREMENT
51
Figure 4.10: Hall Setup . This is given by :
= V H /RS IB = 1/enS rS (4.5)
4.5.1
Hall Eect measurements on InN and Cr:InN
The high n-type carrier concentration in III-Nitrides has been attributed to both nitrogen vacancies as well as oxygen [59] incorporation in the lms. There are several sources of oxygen in the growth process. For instance, in MOCVD, the ammonia precursor could contain oxygen, and in MBE the background water pressure in the chamber, oxygen from the sapphire substrate or from the quartz cavity on some plasma sources could all lead to oxygen incorporation.
52
Hall eect measurements were used in order to get an idea of the type of conduction, as well as the mobility. Indium contacts were used in the four point probe conguration. The Hall setup described above was used, with sheet resistance calculated by the Van Der Pauw method. The Hall set up was used to determine the sheet carrier concentration and mobility. As expected the lms were observed to exhibit n-type conduction. Table 4.5.1 sums up the data obtained for some InN and Cr:InN lms. The sheet concentration obtained varied from about 3.1014 to 1.1015 cm2 . Based on the assumption that all the conduction occurred through the InN (and InN:Cr) layers, and not the buer GaN layers, this yielded a carrier concentration between 1.1019 and 1.1020 cm3 . Cr-doping did not seem to have an eect on the carrier concentration. This is reasonable since Cr has the same valence as In, and neither acts as a donor, nor an acceptor in InN. Polycrystalline (sample 1591) as well as crystalline InN (sample 1625) lms grown directly over sapphire also exhibited n-type behavior. The mobility of the lms was relatively low, in the range of 25 - 100 cm2 V1 s1 . High mobility of over 3000 cm2 V1 s1 has been observed in high quality InN lms [60]. The lms in question were much thicker than our InN lms, at about 7500 nm. Thus they were presumably relatively more defect-free than the ones discussed in this work, which explains the better electrical properties. Sample No. 1591 1593 1625 1639 1642 Description 90nm Polycrystalline InN 105nm InN/GaN 45nm InCrN/100nm InN/Sapphire 35nm InCrN/90nm InN/GaN 30nm InCrN/140nm InN/GaN n (cm3 ) 5.69E+19 1.46E+20 6.46E+19 8.74E+19 1.84E+19 Mobility (cm2 V1 s1 ) 25.3 40.2 25.8 97.3 76.6
Table 4.1: Hall eect measurement on InN and Cr:InN lms The structural properties of InN as well as Mn and Cr:InN were thus examined
4.5. HALL EFFECT MEASUREMENT
53
by a variety of characterization tools. The lms were seen to have relatively good crystalline quality, with the [0001] direction of InN and GaN pointing parallel to the c-axis of the substrate. The FWHM of the 2- XRD curve was 0.1 . While secondary phase formation was observed in Mn:InN, Cr:InN did not appear to have any other phases. However, an examination of the lattice constant of Cr-doped lms revealed that large fractions of the dopant likely went into interstitial positions, or somehow precipitated out above a doping level of about 1 - 2%. PL measurements revealed a band gap around 0.84 eV in InN and Cr:InN, which is consistent with values reported in the literature. Hall eect measurements revealed n-type behavior in these materials with very high carrier concentrations between 1.1019 and 1.1020 cm3 . The mobilities were not very high, since the lm thicknesses were relatively low compared to that of high quality InN lms. The magnetic properties, and the eect of the structure of the Cr:InN lms on them is discussed in the next couple of chapters.
Chapter 5 Magnetic and Electrical Characterization

5.1 Magnetic Characterization
The magnetic behavior of doped InN was measured by Superconducting Quantum Interference Device (SQUID) magnetometry. The magnetometer used in this work was designed by Quantum Design, and uses a radio-frequency (RF) SQUID. An RF SQUID is based on a superconducting coil with a thin insulator sandwiched in-between, which leads to the formation of a Josephson junction (g 5.1). The electron pairs that are responsible for zero resistance conduction in a superconductor are phase-coherent over long distances. Thus the electrons carrying current in the superconducting coil travel as waves, with a constant phase at any point on the coil. A small change in magnetic ux through the superconducting coil changes the momentum of the electrons, thereby changing their phase. Quantum mechanical boundary conditions due to which the phase change through the entire coil must be an integral multiple of 2 , determine the allowed quantized values of change in magnetic ux through the coil. Any excess change in ux is balanced out by a small current that is 54
5.1. MAGNETIC CHARACTERIZATION
55
Figure 5.1: Schematic of the Josephson junction
induced in the coil. Measuring the voltage across the Josephson junction in the loop, which arises from this balancing current allows the detection of very small changes in the magnetic ux through the coil. In an RF SQUID, a superconducting coil similar to the one described, is coupled with an inductor in an LC-tank circuit. The LC-tank, also known as a ux transformer, is excited at its resonant frequency using an RF current. The sample is mounted in a holder that can be as simple as a plastic straw and is oscillated back and forth through the transformer. Through the mutual induction between the transformer and the coil, a change is induced in the magnetic ux across the superconducting coil. The resulting voltage change across the Josephson junction is used to determine the magnetic induction of the sample. In the setup used, the sample could be cooled down to below 2 K using liquid Helium. The upper temperature limit was about 350 K. The Helium-cooled magnet could operate in the range of -70 to +70 kOe. SQUID magnetometry is an extremely sensitive measurement technique, with a measurement limit of 107 emu. Therefore, the magnetic signal measured by it could include several spurious eects arising from
56
CHAPTER 5. MAGNETIC AND ELECTRICAL CHARACTERIZATION
Figure 5.2: Typical magnetic hysteresis of ferromagnetic materials magnetic inclusions or precipitates in the lms, or contamination introduced during sample handling. Nevertheless, this was the primary magnetic characterization tool that was employed to study the temperature and eld dependent behavior of the Cr and Mn-doped samples. All ferromagnetic materials exhibit magnetic hysteresis, when subjected to an external magnetic eld. Fig 5.2 shows the typical hysteresis obtained by a ferromagnet. As the external eld is increased, the magnetization of the sample also increases till its magnetization reaches a saturation value, given by Ms . Thereafter, even if the eld is completely removed, the sample still retains some of its magnetization, known as remanence or MR . If the external eld is now reversed, the magnetization slowly drops, until it is completely demagnetized, at a value for the external eld corresponding to the coercive eld, or HC . Thus the sample absorbs energy from the externally applied magnetic eld.
5.2. MAGNETIC BEHAVIOR OF CR AND MN-DOPED INN
57
The shape of the hysteresis curve is also indicative of whether the sample is magnetized along its easy or hard axis. The dierence between these two axes is that the magnetization of a sample can be saturated along its easy axis with a much lower external applied eld, than what is required to saturate the sample along its hard axis. The anisotropy of a sample is the energy required to ip its magnetization from the easy to the hard axis. The reason for anisotropy is the coupling between the spin magnetic moment and the crystal lattice. Anisotropy can come about from various sources such as shape of the sample, or crystalline orientation, stress etc.
5.2
Magnetic behavior of Cr and Mn-doped InN
Most Cr-doped lms exhibited magnetic hysteresis from 5 K up to room temperature. Fig 5.3(a) shows the magnetic hysteresis of a 0.9% Cr-doped InN sample, with the low eld behavior shown in 5.3(b). A small coercivity of about 100 Oe was observed in this as well as several other samples. The hysteresis was rounded in shape, which could indicate partial demagnetization at low elds. This behavior has been observed in several nitride DMS materials [61, 62]. The hysteresis was corrected for a diamagnetic background, measured at 300 K from 30 to 70 kOe. This background was attributed to the sapphire substrate and buer layers. The background was measured from the hysteresis at 300 K since the paramagnetic background is negligible at higher temperatures. The additional paramagnetic background seen at 5 K under high elds was attributed to imperfections in the InN buer layers resulting from the large lattice mismatch of 10% between GaN and InN and was also observed in undoped InN lms (not shown). Mn-doped samples, however, showed very weak hysteresis at low temperatures and none at room temperature. This is consistent with XRD that suggested a lack of solubility of Mn in InN.
58
Figure 5.3: Magnetic behavior of 0.9% Cr-doped InN. (a)Shows magnetic hysteresis observed at various temperatures. (b) Shows the low eld behavior
5.2. MAGNETIC BEHAVIOR OF CR AND MN-DOPED INN
59
Temperature dependence of remanent magnetization was measured from 5 to 350 K. The moment of the samples was saturated by applying a eld of 50 kOe prior to each measurement. While Cr-doped lms exhibited a steady drop in remanence with increase in temperature, indicating magnetic order (Fig 5.4(a)), Mn-doped samples showed paramagnetic behavior (Fig 5.4(b)), with a
1 -like T
temperature dependence.
Cr-doped samples exhibited a signal arising from two distinct contributions. The high remanence seen at low temperatures was attributed to the paramagnetic background from the InN and GaN buer layers and was observed in undoped lms as well (not shown). At higher temperatures, Cr-doped lms exhibited a smooth drop in remanence with temperature, indicating magnetic order. The shape of the remanence was dierent from that observed in conventional ferromagnets, however was quite similar to that observed in several n-type DMS such as Mn:GaN. In contrast, Mndoped and undoped lms showed no temperature dependence of remanence in this region. The dierence in magnetic behavior between Cr- and Mn-doped InN can, once again, be ascribed to secondary phases. Mn forms several compounds with N, most of which, including Mn3 N2 , are antiferromagnetic with high N eel temperatures [14, 63] The small magnetic moment observed in InN:Mn is likely due to uncompensated spins resulting from clusters of Mn3 N2 randomly distributed in the InN matrix, whose presence was conrmed by X-Ray diraction. On the other hand, Cr essentially forms only one compound, CrN, with N. Although it can purportedly react with N to form Cr2 N, there are no experimental accounts of this compound. CrN is an antiferromagnet with a N eel temperature of 273 K [64]. Although this compound was not observed by high resolution X-Ray diraction, this was insucient proof of its absence in Cr:InN. Instead, other indirect tools such as the magnetic signature of this phase, and spectroscopy at the Cr L-edge were used to probe deeper into the possibility of potential precipitation of CrN. For this purpose, CrN lms were deposited on two dierent substrates.
60
Figure 5.4: Magnetic remanence of doped InN. (a) Cr:InN shows steady decrease in MR with temperature. (b) Mn:InN shows paramagnetic remanence behavior
5.3. NORMALIZED SATURATION MAGNETIZATION MOMENT
61
Figure 5.5: Small anisotropy observed in 1.8% Cr-doped InN. In-plane easy axis (open squares) and out of plane hard axis (circles) A small anisotropy was also observed in Cr:InN, as depicted in g 5.5. The easy axis was observed to be in the plane of the lm, while the out of plane axis was the hard axis.
5.3
Normalized saturation magnetization moment
The saturated magnetic moment of Cr-doped InN at 300 K was normalized per unit Cr atom for a wide range of Cr-doped lms. In order to make this calculation, the saturation moment observed at 300 K was divided by the volume of the Cr-doped lm and the doping level. Fig 5.6 shows the summary of the observed normalized
62
% Cr
Figure 5.6: Doping level dependence of normalized saturation magnetization in Cr:InN
63
moment. The moment had a peculiar dependence upon doping concentration. At lower concentration levels, below about 1% Cr, it tended to rise with increase in doping, dropping o thereafter. Some of the behavior could be explained by correlating the magnetism with the structural behavior. Both XRD and RHEED indicated suggested that an Cr increasingly dissolved in the InN matrix up to about 1-2% doping, as suggested by the in-plane as well as out-of-plane d-spacing reducing in this range. This would suggest that more and more Cr went into substitutional positions as the nominal Cr doping was increased, thereby causing a rise in the moment per Cr. The mechanism by which this would happen is not obvious. One could potentially model this system in a manner similar to that of Gd:GaN [14], where the magnetic ions have a region of inuence in their vicinity that they magnetically polarize. Such a theory could explain the relatively large moment obtained per Cr atom, which was as high as 5 B in the case of the 0.9% Cr-doped lm. At higher Cr doping levels, the normalized magnetic moment was observed to fall o as the doping level increased. This observation was consistent with the the structural analysis, which suggested that large fractions of Cr were likely present in the form of precipitates or went into interstitial positions, rendering them magnetically inactive. This was also corroborated by the higher paramagnetic moment exhibited at lower temperatures by lms with higher Cr doping than that shown by comparable lms with a lower Cr doping level. Fig 5.8 shows this behavior in two lms - one with 5.5% Cr and the other with 0.9% Cr. The magnetic moment measured has been normalized per Cr atom in both cases. As observed, the lm with higher Cr concentration exhibits a larger slope at higher elds, indicating greater paramagnetic contribution. Furthermore, signs of low temperature paramagnetic blocking were observed in some of the lms with a higher Cr concentration, pointing towards the formation of paramagnetic clusters. This is discussed in more detail in the following sections.
64
Figure 5.7: Doping level dependence of normalized saturation magnetization in Cr:InN
65
Figure 5.8: A comparison of the magnetic hysteresis obtained at 20 K from a 0.9% Cr:InN(open circles) lm with that of a 5.5% Cr:InN (squares) lm
66
Figure 5.9: Field cooled vs. Zero eld cooled measurements.
5.4
5.4.1
Spin-Glass like Behavior

Measurement Procedure
Field-cooled vs zero-eld cooled (FC/ZFC) measurements are used to study the inuence of the sample history on its temperature dependent magnetization. The technique attempts to determine if it is possible to freeze any spin clusters by applying a magnetic eld at lower temperatures. Figure 5.9 shows a schematic of the how the measurement is made. During the eld cooled measurement, a high eld, typically 50 kOe is applied in order to saturate the lm following which, it is cooled down. The sample is subsequently warmed up under a much smaller eld, of the order of 100 Oe. If the lm is comprised of clusters, their moments get saturated. When the sample is heated up under a much smaller eld, domain formation reduces the moment. The zero eld cooled measurement involves cooling the sample under 0 magnetic eld.
5.5. METASTABLE BEHAVIOR
67
The clusters, which have random spin orientations, get frozen in their orientation. Now during the warm up step, the domains orient themselves with the external eld. This causes an increase in the magnetization as temperature is increased up to a point, beyond which it drops again. While a separation of the FC and ZFC curves is indicative of hysteretic behavior, a cusp in the ZFC trace is a clear indicator of spin-glass or cluster-glass behavior.
5.4.2
FC/ZFC measurements in Cr-doped InN
The magnetic behavior of Cr-doped InN was probed deeper by means of FC vs. ZFC measurements. Fig 5.10 shows the FC vs.ZFC traces observed in a 2.5% Crdoped InN lm. A clear separation was observed between the two traces for the entire temperature range, indicating hysteretic behavior above room temperature. However, this measurement did not indicate conventional ferromagnetism, since the tendency to form a broad cusp-like feature was observed at relatively high temperatures. All Cr-doped lms in the Cr-doping range from 0.5-6% Cr exhibited this behavior, where a cusp could not be observed since the samples could only be measured up to about 350 K. Thus the Cr:InN exhibited spin-glass like behavior.
5.5
Metastable behavior
In addition to the FC/ZFC behavior which indicated a deviation from traditional ferromagnetism, Cr:InN also exhibited metastability in its temperature dependence of remanent magnetization. Figure 5.11 shows the typical measurements made that revealed this behavior. A 0.9% Cr:InN lm was rst cooled down to 5 K and a eld of 50 kOe was applied to saturate the sample. The eld was then set to zero again followed by the measurement of the remanence while warming up the sample to 300 K. The remanence was seen to smoothly decrease with temperature. Subsequently,
68
6.3x10
-6
FC (warmed under 100Oe)
M (emu)
5.4x10
-6
4.5x10
-6
ZFC (warmed under 100 Oe)

-6
3.6x10
100
200
300
400
Temperature (K)
Figure 5.10: Field cooled vs. Zero eld cooled measurements in a 0.9% Cr-doped InN.
69
Figure 5.11: Remanence dependence on temperature in 0.9% Cr-doped InN. Increase in remanence due to application of magnetic eld observed. the sample was again saturated at 300 K in a eld of 50 kOe, the eld is switched o, and the remanence was now measured while cooling the sample down to 5 K. Two surprising observations were noted which are atypical for common ferromagnets. First of all, after applying the external eld, the remanence increased by about 10% as compared to its value at the end of the warm-up. We referred to this eect as MR . Secondly, the remanence did not increase with decreasing temperature but stayed constant. Fig. 5.12 shows the dependence of MR on the warm up temperature. This data was obtained by warming up to dierent end temperatures, followed by applying a eld of 50 kOe before the subsequent cool down. The increase in remanence was observed only down to 200 K, below which, no such eect was observed. Below
70
200 K, the remanence previously measured while warming could be re-established by applying 50 kOe, while at higher temperatures from about 250 K up to 400 K a MR as high as 13% was obtained, with a 2-3% uncertainty. An explanation of these ndings is not obvious. The reduction in remanence with warming could potentially arise from magnetic domain formation, which are removed upon application of external eld, thereby leading to an increase in remanence. However, this is not a plausible explanation as it assumes that either this domain formation occurs only above 200 K. This would imply that below this temperature, relaxation originates from other mechanisms such as spin waves or magnetic uctuations, which are typically reversible with temperature. However, this is in contradiction with the remanence staying constant with cool down. The other possibility is that magnetic domains do exist below 200 K, but 50 kOe is insucient to remove them. However this is not likely, since 50 kOe is sucient to reestablish the remanence at lower temperatures. Thus the MR and its temperature dependence do not seem to have an explanation which point in the direction of traditional ferromagnetism, and suggest spin glass like behavior. Comparable observations were also made in a Gd:GaN sample with a Gd concentration of about 2.1019 cm3 [65]. Since the remanence exhibited metastable behavior, its relaxation behavior with time was also looked into. The 0.9% Cr:InN lms was subjected to a magnetic eld of 50 kOe to saturate it. The eld was then removed, and the remanence was measured as a function of time. Fig. 5.13 shows the summary of the results obtained. The measurement was made at 300 K and 350 K. As observed, the remanence stayed constant over a timescale of hours, showing no tendency to relax. Thus the metastable behavior was temperature dependent, but not time dependent. This could indicate that the spin glass freezing or ordering temperature for this material is well above 350 K.
71
Figure 5.12: Temperature dependence of MR in 0.9% Cr:InN
72
Figure 5.13: Remanence stays constant with time in 0.9% Cr-doped InN.
5.6. EVIDENCE OF SPIN POLARIZED CARRIERS
73
5.6
Evidence of spin polarized carriers
Hall eect measurements suggested n-type conductivity in Cr:InN, as discussed in chapter 4. Ferromagnetic materials exhibit a Hall resistance, which carries an additional term, proportional to their magnetization. This phenomenon is known as the anomalous Hall eect. It occurs as a result of spin orbit coupling between spin polarized carriers in a spin-split band, that leads to asymmetry in orbital momentum. The anomalous Hall coecient is much larger than the normal coecient, and it tends to saturate at high elds. Thus the net Hall resistivity of a ferromagnet can be given by the relation :
H = R0 0 H + Rs M (5.1)
Here, H is the net resistance, 0 H is the magnetic induction, Rs is the anomalous Hall coecient, and M is the magnetization of the material. A description of this eect in III-V DMS is based on the mean eld theory, whereby, the valence band is spin-split due to exchange interaction with transition metal moment. This interaction leads to an additional term in the Hamiltonian [66], given by :
Hsplit = hm . s (5.2) Where, m corresponds to the localized moment of Mn atoms, s is the spin of an electron and h is proportional to the average magnetization eld, and is non-zero only
74
in the ferromagnetic state. If the Mn is fully polarized, then
H = NM n Jpd S (5.3) where S is the spin of the polarized Mn (5/2), NM n is the density of Mn atoms and Jpd is the exchange interaction between the local moments and the valence band electrons. This leads to an eective magnetic eld within the crystal, which, alongside spin orbit coupling is responsible for giving rise to the anomalous hall eect (AHE).
Figure 5.14: Schematic of the Physical Property Measurement System (PPMS) : Courtesy Quantum Design The geometry used for measurement of anomalous Hall eect (AHE) in Cr:InN was the same as that for the Hall eect. A four point probe method was used, via Indium contacts on the lms. The magnetic eld applied out of plane was varied in magnitude, in order to measure any hysteretic behavior of the carriers. The measurements were
75
made on a physical property measurement system (PPMS) built by Quantum Design (g. 5.14). The system is designed to make measurements over a temperature range of 2 K - 400 K. The applied magnetic eld could be varied from -70 kOe to 70 kOe. The Hall voltage of several Cr-doped InN lms was measured using this setup using an AC excitation voltage, whose magnitude was varied. While most lms only showed a magnetoresistance (MR) and linear Hall background, a small anomalous contribution was measured in one of the lms doped with 1.8 % Cr. Figure 5.15 shows the raw signal from this lm including the linear, MR and anomalous signal. Also shown is the anomalous part alone, obtained by subtracting the other contributions. It shows a hysteretic behavior, giving rst evidence of spin polarized transport in this material. The anomalous part was compared to the magnetization measurement in this material. Figure 5.16 shows this comparative plot. The Hall voltage follows the out-of-plane magnetization quite closely. This is reasonable since the Hall voltage is measured under a magnetic eld pointing out of plane. In summary of the magnetic behavior of InN based DMS, Mn:InN behaved like a paramagnet, presumably due to precipitation of Mn3 N2 , while Cr:InN exhibited long range magnetic order up to room temperature. Behavior that supported long range magnetic order included demonstration of a magnetic hysteresis, remanence that decreased with increase in temperature and rst evidence of spin polarized transport in this material. However the magnetic order in Cr:InN was far from traditional ferromagnetism. The FC/ZFC behavior was indicative of spin-glass like behavior. Furthermore, the remanence exhibited a metastability with temperature, although it did not show signs of relaxation with time. These results could point towards secondary phase formation, although no structural evidence of any such phase was seen by XRD. The next chapter deals with one such potential secondary phase - CrN. The magnetic properties of this compound are studied. Further, spectroscopic techniques are used in order to understand the origin of magnetism in Cr:InN.
76
Figure 5.15: Small anomalous Hall contribution observed in a 1.8% Cr-doped InN lm, in addition to a normal Hall eect and a positive magnetoresistance.
77
Normalized Signal (a.u.)
Anomalous Hall Contribution Hysteresis (Out of Plane) Hysteresis (In Plane)
300K
-20
20
H (KOe)
Figure 5.16: Comparison between anomalous Hall contribution (open squares) of a 1.8 % Cr-doped InN lm and its in plane (triangles) and out of plane (circles) magnetization measurement.
Chapter 6 Secondary Phases and Cr L-Edge Spectroscopy

The bulk of the evidence of magnetic order in Cr:InN that has been discussed so far is based on measurements made by SQUID magnetometry. However, as mentioned in chapter 5, the SQUID magnetometer is extremely sensitive to small magnetic signals obtained from contamination, secondary phases and precipitates. Moreover, such phases often cannot be detected by techniques such as XRD. Therefore, other methods are required to probe deeper into the origin of magnetic behavior of these lms. These could include spectroscopic methods such as X-ray absorption spectroscopy (XAS) or X-ray magnetic dichroism (XMCD), which can be used to probe the element specicity of the magnetism. Also, the magnetic signature of potential secondary phases can be compared with that of the Cr-doped InN, in order to assess whether they play any role in the magnetic behavior of the lms. In this chapter, these techniques are used to determine whether the magnetic order observed in Cr:InN comes about from an intrinsic source or if it is a result of contamination and impurities. 78
6.1. POTENTIAL SECONDARY PHASE - CRN
79
6.1
Potential secondary phase - CrN
Although no trace of CrN observed by X-Ray diraction in the Cr-doped InN lms, the possibility of the presence of this secondary phase could not be eliminated altogether. Therefore, the magnetic properties of CrN were examined in some detail. Two lms of CrN were grown, one over a (001) MgO substrate and the other over c-sapphire. CrN, in the bulk form is an antiferromagnet with a Ne el temperature around 280 K. This is accompanied by a structural transformation from the NaCl structure to an orthorhombic structure [64]. Although it is antiferromagnetic in the bulk form, CrN inclusions could lead to uncompensated moments that give rise to a magnetic signal.
6.1.1
Growth and structure
The CrN lms were grown on thermally precleaned (001) MgO as well as c-plane sapphire substrates by RF plasma-assisted MBE. Thus it has cubic symmetry. When grown over the trigonal sapphire substrate, it is expected to get deposited in the (111) orientation, which also has a three fold symmetry of the substrate. This lm deposited over sapphire was grown in order to gauge the magnetic signature of CrN clusters that could potentially have been the source of magnetism in Cr:InN. On the other hand, the lm deposited over MgO was expected to have better crystalline quality, and was used as a reference lm. The lm over MgO was deposited at a substrate temperature of 400 C, while the growth temperature over sapphire was 350 C. the thickness of CrN over sapphire was 40 A while that over MgO was 330 A. In both cases, a plasma power of 345 W was used, with a nitrogen partial pressure of 2.105 mbar. The growths were monitored in situ by RHEED. RBS, with an experimental accuracy of under 1% was used to conrm the stoichiometry of the CrN lms and to determine the lm thickness. The
80
CHAPTER 6. SECONDARY PHASES AND CR L-EDGE SPECTROSCOPY
Figure 6.1: XRD 2- patterns obtained from CrN lms grown over (a) sapphire and (b)(001) MgO. The insets show the RHEED patterns recorded during the deposition.
81
structural properties of these lms were investigated by XRD. Figure 6.1 shows the XRD pattern obtained from the two lms. The XRD 2- measurement made on the CrN lm grown over sapphire revealed that the CrN was oriented with its (111) plane oriented parallel to the [0001] direction of the sapphire (g. 6.1 (a)). This was expected since sapphire has 3-fold symmetry. The (111) CrN peak was very broad, with a FWHM of about 2.5 indicating poor crystalline quality. The CrN deposited over MgO had its (001) plane oriented along the [001] direction of MgO. This lm had a FWHM of about 0.6 , which indicated better crystalline quality.
6.1.2
Magnetic properties of CrN
The magnetic behavior of the two lms was measured using SQUID magnetometry. Figure 6.2 shows the hysteresis measurement made on the CrN lms. The CrN deposited over sapphire was seen to qualitatively behave in a manner very similar to the Cr-doped InN lms (g. 6.2(a)). Clear magnetic hysteresis was observed up to room temperature, with a small coercive eld of about 150 Oe. This was a surprising result given that CrN is expected to behave antiferromagnetically. The poor crystalline quality of the lm, which was in the form of weakly ordered grains, could explain the hysteretic behavior, which could come about from uncompensated Cr moments along grain boundaries. The saturation moment per Cr atom was estimated for this lm, and was found to be about 0.47 B . This is only about an order of magnitude lower than the highest moment obtained in Cr-doped InN lms. On the other hand, CrN deposited over MgO did not exhibit any ferromagnetic-like behavior (g. 6.2(b)). This lm behaved in a paramagnetic manner. The dierence between the hysteretic behavior of the CrN/Sapphire and the CrN/MgO lms is more apparent in g. 6.3. It reveals schematically, the paramagnetic signal obtained from the lm grown over MgO at low temperatures, as opposed to the additional saturation
82
observed in the CrN/sapphire sample. Since the MgO substrate has paramagnetic impurities, it could contribute largely to the paramagnetic moment. Therefore, the contribution of the bare substrate was measured separately and subtracted from the total magnetic signal. It was observed that the CrN alone exhibited a large paramagnetic moment of 2.17 B at low temperatures, which is very close to the bulk antiferromagnetic moment of 2.36 B [64], implying that most of the Cr atoms were not antiferromagnetically aligned. The reason for this behavior was attributed to the epitaxial constraints imposed by the substrate on the crystal structure of the CrN lm, which did not allow the transformation into the antiferromagnetic orthorhombic structure [67]. This was evident from the measured values of the in-plane and out-of-plane lattice parameters in this lm. The value of the in-plane parameter was estimated by comparing the RHEED streak spacing obtained from the MgO substrate with that of the CrN lm, using the technique described in section 3.2.2. On the other hand, the out-of-plane parameter was measured by high resolution XRD measurements. Using these techniques, the inplane lattice constant was estimated at 4.139 A and the out-of-plane lattice constant, 4.132 A, indicating a nearly cubic crystalline structure. Thus epitaxial constraint resulted in paramagnetic behavior in the CrN lm deposited over MgO. Further magnetic characterization included eld-cooled vs. zero eld-cooled measurements, which have been summarized in g. 6.4. The measurement procedure used was the same as that used for Cr:InN, where the FC measurement involved cool-down under 50 kOe, and warm up under 100 Oe, and the ZFC measurement involved cool down under zero eld, and warm up at 100 Oe. The CrN deposited over sapphire exhibited a separation between the FC and ZFC traces, indicating hysteretic behavior (g. 6.4 (a)). It behaved in a manner similar to that of Cr-doped InN, exhibiting dierent slopes in the two traces, and showing some evidence of a high temperature blocking-like behavior. On the other hand, the CrN over MgO behaved much like
83
Figure 6.2: Magnetic behavior of CrN lms. (a) CrN deposited over sapphire shows a small hysteresis (b) CrN deposited over MgO shows no hysteresis.
84
Figure 6.3: Comparison of the hysteretic behavior of CrN/sapphire with that of CrN/MgO
6.2. X-RAY ABSORPTION SPECTROSCOPY
85
a paramagnet (g. 6.4(b)) with no separation between the two traces, implying the absence of hysteresis. The paramagnetism. Thus it is clear that the magnetic behavior of the two lms diered vastly, and that this could be attributed to their structure. The CrN deposited over MgO had much better crystalline quality than that deposited over sapphire. This lm behaved like a paramagnet down to low temperatures, presumably because the cubic to orthorhombic distortion accompanying the paramagnetic to antiferromagnetic phase transformation was suppressed by epitaxial constraints. On the other hand, the CrN over sapphire was likely granular in structure. The uncompensated moments at the grain boundaries could potentially result in the hysteretic behavior observed. The FC/ZFC behavior in this lm suggests that similar CrN clusters in InN could lead to the spin-glass like behavior in Cr:InN as well, although no CrN was observed by XRD. Somewhat similar behavior has been observed in Mn:GaN as well [68, 69], with a cusp observed in the ZFC trace. In neither case was any evidence of secondary precipitates observed by XRD or TEM. The behavior was attributed to the spin glass character of Mn:GaN [68]. Further experiments observing the Cr Ledge using spectroscopic techniques were performed in order to understand whether all the magnetic behavior of Cr:InN could be explained by the formation of CrN clusters.
1 -like T
dependence over temperature also pointed towards
6.2
X-Ray Absorption Spectroscopy
X-Ray absorption is a technique used to probe the core electronic levels of elements in order to determine their local environment. g.6.5 shows a schematic of the absorption process. An X-Ray beam is used to excite a core electron. When the energy of the incident photon exceeds the binding energy of the electron, it is absorbed by the
86
Figure 6.4: Field cooled vs. Zero eld cooled behavior of CrN lms. FC measurement was made by cooling under 50 kOe, followed by a warm up at 100 Oe, and ZFC measurement involved cool down under zero eld followed by warm up at 100 Oe. (a) CrN deposited over sapphire shows spin glass like behavior (b) CrN deposited over MgO shows paramagnetic behavior
6.2. X-RAY ABSORPTION SPECTROSCOPY
87
Figure 6.5: Schematic of X-Ray Absorption process
electron, promoting it to a higher energy level. This is accompanied by a sharp increase in the absorption, resulting in an absorption edge. Since the binding energy of electrons in a certain atomic orbital is xed, the corresponding absorption edge is abrupt.The absorption can be measured in several ways. The excited photoelectron yield can be measured as a current, or alternately, X-Ray uorescence can also be measured. Fluorescence occurs when the hole left behind by the excited core electron is lled by an electron from a higher level. The energy thus lost by the electron is emitted in the form of a uorescent photon of the characteristic energy of the transition. Another interaction that can come about by such photon absorption is the generation of Auger electrons. This happens when the uorescent photon produced is reabsorbed by third electron, which is then promoted to a higher energy state. XAS is typically used to study L-edge absorption, which involves transitions from 2p to 3d levels. The excited core electrons are promoted to empty valence band levels. Therefore, the absorption spectrum reveals information about these empty levels. This is the reason why elements in compounds, which have localized electrons exhibit several multiplet features, whereas metals with delocalized electrons do not. The X-ray measurements on Cr:InN were carried out at Beamline 4 at the Advanced Light Source (ALS) at Lawrence Berkeley National Lab. Measurements were carried out in the soft X-ray regime, with the X-ray beam at normal incidence with
88
the sample. The total electron yield was measured in order to obtain the spectra. Fig. 6.6 shows the absorption spectra obtained at the Cr L2,3 edge of Cr:InN lms as well as CrN lms grown over sapphire and MgO. The L3 peaks of the spectra were normalized for comparison. The spectra from the dierent lms looked quite similar. While the spectra for the 0.9% and the 1.8% Cr-doped lms seemed to line up well, the spectral weights appeared to be shifted more toward the L2 peak in the case of CrN. This could indicate a dierence between the Cr chemical environment in CrN and that in Cr:InN. However, such a small dierence could also be an artifact of the normalization procedure.
6.3
X-Ray Magnetic Circular Dichroism
In order to extend the utility of XAS to understand the magnetic behavior of the element, the absorption process must be made spin-dependent. This is done by
Figure 6.6: Cr L-edge observed in Cr:InN and in CrN
6.3. X-RAY MAGNETIC CIRCULAR DICHROISM
89
Figure 6.7: Schematic of the physics behind the XMCD eect
using circularly polarized light, which leads to the demonstration of X-ray magnetic circular dichroism (XMCD) in magnetic materials. The XMCD eect is the dierence in absorption cross sections for photons circularly polarized along opposite directions at the absorption edge of a spin-polarized band in a material. It is a unique technique to study magnetism, that oers element-specicity, and thus allows us to identify the origin of magnetic signal in an alloy. Fig. 6.7 schematically depicts the underlying mechanism behind this eect. A circularly polarized photon is used to excite a photoelectron. In the process, the
90
photon transfers its angular moment to the photoelectron. This results in a change in the spin polarization or the angular momentum of the electron. If the electron lies in a spin-orbit split band, such as the L2 or the L3 edge, then some of the momentum can be transferred to the spin of the electron via spin-orbit coupling. Right circular polarized photons transfer angular momentum of the opposite sense as left circular polarized photons. Thus the relative population of spin-up to spindown photoelectrons depends upon the sense of the incident light. In order to make an XMCD measurement, a magnetic eld is applied in addition to producing spin polarized photoelectrons. If the element is magnetically ordered it has a spin split band, such as the d-shell in transition metals. Such a spin-split valence band acts as a detector for the spin of the photoelectron, since an electron can only recombine with a hole of the same spin. Therefore, the resultant absorption coecient of electrons of opposite spins is dierent. This dierence in absorption coecient is considered evidence of magnetic order of the element. Fig. 6.8 shows a schematic of the setup used for the measurement. The X-ray was incident on the sample at either 30 or at normal incidence. In both cases, the external magnetic eld was applied parallel to the incident light, as this maximizes the dichroic signal. The incident X-ray was circularly polarized 81%. The degree of circular polarization was chosen to maximize the dichroic signal obtained. A higher degree of circular polarization could result in a higher percentage of asymmetry at the L-edge. However, it was detrimental to the intensity of the beam and thus, to the net dichroic signal obtained. The measurements were made at 15 K and 100 K. The procedure adopted involved measuring the absorption of light circularly polarized with a constant sense, by the electron yield technique. The energy range probed was around the Cr L-edge, under a magnetic eld of 0.5 Tesla. The eld was reversed at each photon energy and the absorption was measured. The asymmetry at the L-edge was calculated by (I+ (E) - I (E))/ (I+ (E) + I (E)). Where I+ (E) was the absorption
91
Figure 6.8: XMCD measurement setup with the photon helicity parallel to the magnetic eld at photon energy E, while I (E) was that with the helicity antiparallel to the eld. Similar measurements were made with the incident photons circularly polarized along the opposite sense. This was done in order to check if the dichroic signal changed sign, thereby conrming that the observed asymmetry was in fact real, and not a measurement artifact. Figure 6.9 shows the dichroism observed at the Cr L-edge in the 0.9% Cr-doped InN at 15K, under normal incidence. A small but clear dichroism was observed at the L-edge, and the sign of the signal reversed upon changing the sense of the circular polarization of the incident X-ray. This was evidence that the Cr in Cr:InN did exhibit long range magnetic order. One point to note was the magnitude of the dichroic signal. The asymmetry was only 0.15% of the edge jump, which was very small given that the normalized moment per Cr in this sample was computed to be about 5 B . Sum rules normally relate the spin and orbital momentum quantitatively to a linear combination
92
Figure 6.9: Dichroism at the Cr L-edge in Cr-doped InN of the L2 and L3 branches of the dichroic signals [70]. These however, are less eective in the case of early 3d elements [71] such as Cr, mainly because of mixing of the L3,2 branches which makes deconvolution of the two branches dicult. Therefore the spin moment per Cr was not computed from the dichroic signal. Nevertheless, it could be concluded qualitatively, that the Cr moment suggested by XMCD was signicantly lower than that observed by SQUID. This discrepancy suggests that some of the magnetic signal observed could probably be attributed to polarization of the In or N. However, no XMCD signal was observed at the In L-edge. Similar observation has been made with Co-doped ZnO [19], and has been attributed to the magnetic polarization of the semiconductor lattice. The caveat is that while, XMCD is sensitive only to the top 2 nm of the lm, SIMS data for this lm suggested that it was terminated with a 1 nm layer of Nitrogen. This could be the reason for the small dichroic signal observed.
93
Dichroism was observed as high as 100 K. Fig. 6.10 shows the spectrum taken at 100 K, with the data smoothed out for improved clarity. The signal was signicantly smaller due to the temperature dependence of the magnetization. The observation dichroism under an applied eld of 5 kOe at 100 K ruled out paramagnetic behavior, indicating either ferromagnetic order or spin-glass behavior that was robust up to high temperatures. While dichroism was observed at the Cr L-edge in several Cr-doped InN lms, neither of the CrN lms showed any dichroism. This, in addition to the XAS spectra was taken to be evidence that CrN inclusions were probably not responsible for the magnetic behavior of Cr:InN. To compare the behavior of Cr-doped InN to reports in the literature, the absorption spectrum appears similar to that exhibited by CrO2 [72]. However, the dichroic signal is dierent, with CrO2 exhibiting a stronger multiplet structure. Furthermore, a large fraction of the negative weight of the asymmetry is observed at the low energy side of the L3 edge in Cr-doped InN, whereas it is right at the L3 edge in CrO2 . The dichroism is more similar to that exhibited by chalcogenides CuCr2 Se4 [73]. Earlier work on CoCrTa and CoCrPt indicate that the two features with opposite sign in the asymmetry for the Cr L3 edge are not observed in metallic Cr [74]. Thus the electronic and magnetic conguration of Cr in Cr:InN is most not metallic in nature either, but similar to that in chalcogenides. In summary, the role of secondary phases and the origin of the magnetic behavior of Cr-doped InN was probed in greater detail using both SQUID magnetometry and spectroscopic techniques. CrN deposited over MgO had relatively good crystalline quality and behaved like a paramagnet. On the other hand, CrN grown on sapphire was deposited in the form of grains and exhibited similar magnetic behavior to that of Cr:InN. While there was a dierence between the shape of the Cr L-edge absorption spectrum of Cr:InN and that of CrN, this could not conclusively be considered evidence that the chemical environment of Cr was dierent in the two compounds.
94
Figure 6.10: Temperature dependence of dichroism observed at the Cr L-edge in Cr-doped InN. The spectrum taken at 100 K has been smoothed out.
95
However, a dichroism was observed at the Cr L-edge in Cr:InN up to 100 K, indicating long range magnetic order, which was not observed in CrN. The magnitude of the signal was very small compared to the large moment observed by SQUID. This led us to conclude that it was possible that the InN matrix was partially polarized, and that it contributed to the net magnetization.
Chapter 7 Conclusions
While dilute magnetic semiconductors could be a useful class of materials and assume a crucial role in enabling the semiconductor spintronic devices, much remains unanswered with regards to the mechanism of magnetism in these materials. Traditional III-V candidates such as GaMnAs and InMnAs, which are typically p-type, have been studied in great detail. Optical as well as electrical measurements have established carrier-mediated ferromagnetism in these materials. However, the highest Tc obtained in these materials still remains under 200 K, making them undesirable for technological applications. On the other hand, up and coming n-type candidates such as doped GaN and ZnO seem to exhibit magnetic order at much higher temperatures. However, with no solid theories explaining the observed properties such as magnetic hysteresis in n-type materials, the origin of magnetism is still under debate. In this work we have studied one such candidate - Cr and Mn doped InN. The growth, structure and magnetism in Cr-doped InN was examined in detail. The lms were deposited by MBE, which is an ideal technique for growth of these materials that need to be deposited under non-equilibrium conditions. C-plane sapphire substrates were used, and thin GaN buer layers, whose thickness was typically around 1000 A. Thereafter, InN lms of thickness varying between 250 A and 1500 A were 96
97
deposited, followed by the Cr or Mn-doped layers, whose thickness was in the range of 100-700 A. The growths were monitored in situ by reection high energy electron diraction, which indicated a smooth 2-dimensional deposition. The lms were of reasonably good structural quality, as observed by a full width at half maximum of 0.1 rocking curve X-Ray Diraction. Cr-doped lms showed no signs of secondary phase segregation, whereas Mn-doped lms clearly exhibited segregation of Mn3 N2 . Both Cr-doped lms and nominally undoped lms exhibited a very high n-type carrier concentration, around 5.1019 - 1.1020 cm3 . The high carrier concentration is expected to arise from defects in the crystal such as nitrogen vacancies and oxygen inclusions. Cr-doped lms showed n-type behavior as well. The lms showed poor mobility, under 100 cm2 V1 s1 . This could be a result of the small thickness of the lms, which would lead to lms with a high defect concentration. Further, since the Cr-doped layers were deposited at low temperatures, they had poorer structural quality, leading to the low mobilities. Photoluminescence revealed a band gap of 0.84 eV in both InN and Cr:InN. Magnetic characterization of Cr:InN revealed a hysteresis up to room temperature, with a rounded shape, and small coercivity. The remanence showed a steady drop with increase in temperature. All this indicated long range magnetic order up to room temperature. On the other hand, Mn:InN exhibited paramagnetic behavior, showing a very weak hysteresis behavior, and a 1/T-like temperature dependence of magnetism. This was attributed to secondary phase formation in this material. The moment obtained per Cr atom was relatively large in Cr:InN, with one of the 0.9% doped lms exhibiting a moment as large as 5B . Further, rst evidence of spin polarized transport was also seen in one of the Cr:InN samples doped with 1.8% Cr, as a small anomalous Hall contribution. Despite all this evidence indicating ferromagnetism, there were aspects of the magnetic behavior that pointed towards frustrated or spin-glass like behavior. Field
98
CHAPTER 7. CONCLUSIONS
cooled vs.zero eld cooled measurements showed dierent slopes for the FC and ZFC traces. Further, the remanence showed irreversibility in it temperature dependence, although it did not show any signs of relaxation with time. One potential secondary phase that could produce this behavior, CrN was also studied. Although this material exhibited magnetic behavior similar qualitatively to that of Cr:InN, X-ray absorption spectroscopy showed a dierence in the Cr L-edge between CrN and Cr:InN. Moreover, a small dichroism was observed at the Cr L-edge up to 100 K, indicating magnetic order of the Cr. This was not observed in CrN. One interesting point about the magnetic behavior was the magnitude of the saturated moment per Cr. While the moment obtained by SQUID in the 0.9% Crdoped InN lm was relatively large (5 B ), the asymmetry relative to the edge jump at the L-edge in this sample was only 0.15%. This would indicate a much smaller atomic spin moment on the Cr than that measured by SQUID. This discrepancy in the magnitudes of the moment on the Cr could be explained in part from an ination in the signal measured due to impurities, or reduction in the XMCD signal due to surface contamination. However, this behavior was consistently observed in several samples, and has also been seen in Gd:GaN [65]. Therefore, it is possible that polarization of the lattice by the magnetic ions results contributes to the magnetic signal observed. In summary, Cr:InN appears to be a frustrated system, exhibiting such properties as thermomagnetic irreversibility. However, it shows magnetic order that is robust with time, and is observed well above room temperature. Further, the high saturation moment exhibited as well as rst evidence seen of spin-polarized transport make this and other similar n-type DMS materials potentially signicant materials, both from the point of view of understanding the magnetism, as well as for device applications.
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STUDY OF MAGNETISM IN DILUTE MAGNETIC SEMICONDUCTORS BASED ON III-V NITRIDES

Rekha Rajaram March 2007

c Copyright by Rekha Rajaram 2007 All Rights Reserved

Spin glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Promising DMS candidates . . . . . . . . . . . . . . . . . . . . . . . .

Growth of Cr and Mn-doped InN . . . . . . . . . . . . . . . . . . . . ix

Metastable behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . Evidence of spin polarized carriers . . . . . . . . . . . . . . . . . . . .

X-Ray Absorption Spectroscopy . . . . . . . . . . . . . . . . . . . . . X-Ray Magnetic Circular Dichroism . . . . . . . . . . . . . . . . . . .

SIMS prole of a 5.25% Cr-doped InN lm . . . . . . . . . . . . . . . xiii

4.2 4.3 4.4 4.5 4.6 4.7

Doping level dependence of normalized saturation magnetization in Cr:InN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

Doping level dependence of normalized saturation magnetization in Cr:InN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiv 64

Field cooled vs. Zero eld cooled measurements. . . . . . . . . . . . .

6.5 6.6 6.7 6.8 6.9

Schematic of X-Ray Absorption process

Figure 1.1: Schematic of Datta-Das transistor

Chapter 2 Dilute Magnetic Semiconductors

Figure 2.1: Semiconductor host doped with magnetic ions

CHAPTER 2. DILUTE MAGNETIC SEMICONDUCTORS

Magnetic interactions in solids

2.2. MAGNETIC INTERACTIONS IN SOLIDS

CHAPTER 2. DILUTE MAGNETIC SEMICONDUCTORS

Models describing magnetism in DMS

2.3. MODELS DESCRIBING MAGNETISM IN DMS

Mean Field Theory

CHAPTER 2. DILUTE MAGNETIC SEMICONDUCTORS

Bound Magnetic Polaron

2.3. MODELS DESCRIBING MAGNETISM IN DMS

CHAPTER 2. DILUTE MAGNETIC SEMICONDUCTORS

Figure 2.2: Representation of Polaron pair model indicating an interstitial region

2.4. SPIN GLASSES

Figure 2.3: Representation of Magnetic Polarons in a semiconductor lattice [19]

CHAPTER 2. DILUTE MAGNETIC SEMICONDUCTORS

2.5. PROMISING DMS CANDIDATES

Promising DMS candidates

CHAPTER 2. DILUTE MAGNETIC SEMICONDUCTORS

Doping 0.9% Mn Cr 7% Cr 5% V 1-2% Co 7% Co 2% Fe 5% Fe 5% Co 15% V 5% Fe, 1% Cu 10% Co 0.9% Ni 5% Co, 0.5% Al 5% Mn

Cu2 O In1.8 Sn0.2 O3

2.5. PROMISING DMS CANDIDATES

Growth of InN and doped InN by MBE

3.1. GROWTH OF III-NITRIDES

AlN GaN InN

Table 3.1: lattice mismatch between sapphire and III-V nitrides

CHAPTER 3. GROWTH OF INN AND DOPED INN BY MBE

3.2. MOLECULAR BEAM EPITAXY

Molecular Beam epitaxy

CHAPTER 3. GROWTH OF INN AND DOPED INN BY MBE

3.2. MOLECULAR BEAM EPITAXY

Growth of InN by MBE

CHAPTER 3. GROWTH OF INN AND DOPED INN BY MBE

Reection High Energy Electron Diraction (RHEED)

3.2. MOLECULAR BEAM EPITAXY

Figure 3.3: Schematic of RHEED measurement geometry

CHAPTER 3. GROWTH OF INN AND DOPED INN BY MBE

Growth of Cr and Mn-doped InN

3.3. GROWTH OF CR AND MN-DOPED INN

CHAPTER 3. GROWTH OF INN AND DOPED INN BY MBE

3.3. GROWTH OF CR AND MN-DOPED INN

CHAPTER 3. GROWTH OF INN AND DOPED INN BY MBE

Growth of InN and Cr, Mn-doped InN over GaN templates

3.3. GROWTH OF CR AND MN-DOPED INN

CHAPTER 3. GROWTH OF INN AND DOPED INN BY MBE

3.3. GROWTH OF CR AND MN-DOPED INN

Chapter 4 Structural Characterization