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Extreme Electron Density Perovskite Oxide Heterostructures for Field Effect Transistors THESIS Presented in Partial Fulfillment of the Requirements for the Degree Master of Science in the Graduate School of The Ohio State University By Omor Faruk Shoron Graduate Program in Electrical and Computer Science The Ohio State University 2015 Dissertation Committee: Prof. Siddharth Rajan, Advisor Prof. Betty L. Anderson Copyright by Omor Faruk Shoron 2015 Abstract Perovskite oxides are an interesting group of materials with diverse and unique electronic, photonic, optical and magnetic properties. One of the recent discoveries in perovskite oxide is the extreme high electron density at polar and non-polar oxide heterojunction interfaces. GdTiO3/SrTiO3 heterostructure shows an electron density of 3x1014 cm-2 at the interface that is around one order higher than any conventional semiconductor heterostructures. In this work, GdTiO3/SrTiO3 heterostructures were used to demonstrate field effect transistors. This is the first demonstration of transistor with such high charge density. We also investigated the factors that limit the charge modulation in this heterostructure, and developed an analytical model that can predict charge control characteristics of this heterostructure. Three methods were proposed and demonstrated to improve the modulation, leading to record charge modulation of 1.5x1014 cm-2, which is the highest to date for any semiconductor system using electronic gating. ii Dedication This work is dedicated to my family iii Acknowledgments I would like to thank my advisor and mentor Prof. Siddharth Rajan for guiding me for this project. This work is done as a part of Multi University Research Initiative project and this work is funded by Office of Naval research. I would like to thank all of the members of this project for their collaboration. Specially, I would like to thank Prof. Susanne Stemmer, Clayton Jackson, Santosh Raghavan, and MC Buffon for providing great samples for this work. I would like to acknowledge the help of Dr. MC Boucherit, who also worked in this project in the beginning. I would like to thank my group mates β Dr. DN Nath, Dr. PS Park, Dr. S Krishnamoorthy, TS Hung, S Bajaj, E Lee, F Akyol, Z Yang, Y Zhang and CH Lee for their help, suggestion and academic discussion. I was at OSU without my family and this journey was not an easy one. I would like to thank all of my Bangladeshi friends here, especially Dr. S Arafat, Dr. NF Laboni, Saady Amin, Dr. Sajedur Akand, Dr. Rubab Khan, ATM Sarwar, Sadia Nasrin, Faiza Faria, iv Rashedul Alam Zuboraj, Syed Ashraf, Syed Saqueb, Pran Paul, Shariq B Shafi, Rubayet Ratul who are always beside me even in my bad time. I can never forget their help. Finally, I would like to thank my parents β Mr. Shafiqul Islam and Mrs. Suriaya Islam. They are the sole reason I am here today. They sacrificed their dreams to build my future. My two younger brothers β Shovon and Sudeep, are the best brothers in this world. I am very happy to have such loving brothers. I would like to thank them for their encouragement. I thank my family for believing me. v Vita 2003................................................................ Secondary School Certificate 2005................................................................Higher Secondary School Certificate 2011 ...............................................................B.Sc. Electrical and Electronic Engineering Bangladesh University of Engineering and Technology 2012 to present ..............................................Graduate Research Associate, ECE Department, The Ohio State University Publications Journals: 1. M Boucherit, O Shoron, CA Jackson, TA Cain, MLC Buffon, C Polchinski, S Stemmer, S Rajan, βModulation of over 10 14 cmβ 2 electrons at the SrTiO3/GdTiO3 heterojunctionβ Applied Physics Letters, Vol. 104, Issue 18 (2014). 2. M Boucherit, OF Shoron, TA Cain, CA Jackson, S Stemmer, S Rajan, βExtreme charge density SrTiO3/GdTiO3 heterostructure field effect transistorsβ Applied Physics Letters, Vol. 102, Issue 24 (2013). 3. SA Siddiqui, OF Shoron, A Zubair, QD Khosru, βBand to Band Tunneling vi Current of Surface Channel Strained InxGa1-xAs (x= 0.47, 0.65, 0.75) Double Gate Planner TFETβ ECS Transactions, Vol. 35, Issue 3 (2011). 4. Subramaniam Arulkumaran , Geok Ing Ng , C. M. Manoj Kumar , Kumud Ranjan , Khoon Leng Teo , Omor Faruk Shoron , Siddharth Rajan , Surani Bin Dolmanan , Sudhiranjan Tripathy, βElectron Velocity of 6×107 cm/s at 300 K in Stress Engineered InAlN/GaN nano-channel High-Electron-Mobility Transistorsβ, Accepted to Applied Physics Letters 5. OF Shoron, Pil Sung Park, S Bajaj, S Krishnamoorthy, S Rajan, βEffect of charge dependent velocity on device characteristic of AlGaN/GaN HEMTsβ (in preparation for EDL) 6. OF Shoron, M Boucherit, CA Jackson, TA Cain, MLC Buffon, C Polchinski, S Stemmer, S Rajan, βEffect of high-k BaSrTiO3 gate dielectric layer on GdTiO3/SrTiO3 HFETsβ (in preparation for APL) 7. M Boucherit, OF Shoron, CA Jackson, TA Cain, MLC Buffon, C Polchinski, S Stemmer, S Rajan, βHigh Electric breakdown field of 5.7 MV/cm in SrTiO3/GdTiO3 Heterostructureβ (in preparation for APL) Selected Conferences Presentations: 1. O Shoron, M Boucherit, CA Jackson, TA Cain, MLC Buffon, C Polchinski, S Stemmer, S Rajan, βModulation of over 10 14 cmβ 2 electrons at the SrTiO3/GdTiO3 heterojunctionβ 72nd Annual Device Research Conference (DRC), 2014, Santa Barbara, USA vii 2. Omor F Shoron ,M. Boucherit ,C. A. Jackson ,S. Raghavan ,C. Polchinski ,S. Stemmer ,S. Rajan, βImprovement of Charge Modulation in SrTiO3/GdTiO3 HFETβ MRS Spring Meeting, 2014, San Francisco, USA. 3. OF Shoron, M Boucherit, CA Jackson, P Moetakef, S Stemmer, S Rajan, βSrTiO 3/GdTiO 3 heterostructure field effect transistorsβ 71st Annual Device Research Conference (DRC), 2013, South Bend, USA 4. O. F. Shoron, S. A. Siddiqui, A. Zubair, Q. D. M.Khosru βA simple physically based model of temperature effect on drain current for nanoscale Si and GaAs TFETβ IEEE International Conference of Electron Devices and Solid-State Circuits, 2010, Hong Kong. 5. S. Arulkumaran, N. G. Ing, C. M. M. Kumar, K. Ranjan, K.L. Teo, O. F. Shoron, S. Rajan, S. B. Dolmanan and S. Tripathy βIn0.17Al0.83N/AlN/GaN Triple T-shape FinHEMT with gm=646 mS/mm, Ion=1030 mA/mm, Ioff=1.13 ΞΌA/mm, SS=82 mV/dec and DIBL=28 mV/V at VD=0.5 V β International Electron Device Meeting (IEDM) 2014 Fields of Study Major Field: Electrical and Computer Engineering viii Table of Contents Abstract ............................................................................................................................... ii Dedication ......................................................................................................................... iiii Acknowledgments.............................................................................................................. iv Vita..................................................................................................................................... vi List of Tables ..................................................................................................................... xi List of Figures ................................................................................................................... xii Chapter 1: Introduction ...................................................................................................... 1 1.1 Research on perovskite oxidesβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...2 1.2 Motivation and research objectiveβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦.....8 1.3 Thesis Organizationβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...9 Chapter 2: GdTiO3/SrTiO3 Heterojunction Field Effect Transistors (HFETs) ................. 10 2.1 GdTiO3/SrTiO3 Heterostructureβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...10 2.2 Inverted transistor Structureβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦.16 2.3 Fabricationβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...β¦18 2.4 Transistor characteristicsβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦.26 Chapter 3: Improvement of modulation in GdTiO3/SrTiO3 HFETβ¦β¦β¦β¦β¦β¦β¦β¦..33 3.1 Interfacial Layerβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦..33 ix 3.2 Effect of SrTiO3 Thicknessβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦.38 3.3 Surface treatmentβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦.49 3.4 High k dielectricβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦..60 Chapter 4: Perovskite oxide MESFET and FerroFETβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...74 4.1 SrTiO3 MESFETβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦..74 4.2 Ferroeletric FETβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...83 Chapter 5: Summary and Future Workβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦..90 Referencesβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦..91 x List of Tables Table 1: ICP-RIE etching test ......................................................................................... 25 Table 2: Calculated and experimental breakdown field of different materialsβ¦β¦β¦.β¦59 Table 3: Constants of field dependent permittivityβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦78 Table 4: Baliga Figure of Merits (BFOM) for different materialsβ¦β¦β¦β¦β¦β¦β¦β¦β¦81 xi List of Figures Figure 1.1: Crystal structure of perovskite oxide................................................................ 1 Figure 1.2: Mott Materialβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...5 Figure 2.1: Origin of free electron (2DEG) at polar non-polar oxide interfacesβ¦β¦β¦..11 Figure 2.2: (a) Sheet Carrier concentration versus number of interfaces (b) TEM image of GdTiO3/SrTiO3 interfaceβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦.13 Figure 2.3: (a) Sheet resistance versus temperature for different GdTiO3 and SrTiO3 thicknesses (b) Mobility of 2DEG for different SrTiO3 thicknessβ¦β¦β¦15 Figure 2.4: (a) Inverted transistor structure (b) Band diagram and electron profileβ¦β¦..17 Figure 2.5: Ohmic contact resistance for Al/Ni Au, without any surface processingβ¦...19 Figure 2.6: (a) AFM image of sample after 10s of BOE dip (b) Cross section height..β¦20 Figure 2.7: Ohmic contact resistance for Al/Ni/Au metal stackβ¦β¦β¦β¦β¦β¦β¦β¦β¦....21 Figure 2.8: Ohmic Contact resistance of Nb/Au metal stackβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦.22 Figure 2.9: Schottcky contact behavior of different metalsβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...23 Figure 2.10: Gate leakage for different gate lengthβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...24 Figure 2.11: Effect of oxygen plasma treatmentβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦24 Figure 2.12: Etching profiles after 4 minutes for different etching recipeβ¦β¦β¦β¦β¦β¦27 Figure 2.13: Thickness of (a) SPR 950 and (b) SPR 220 after spin coatingβ¦β¦β¦β¦β¦.28 Figure 2.14: Fabrication process flowβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...29 xii Figure 2.15: Capacitance-Voltage (C-V) profile of GdTiO3/SrTiO3 HFETsβ¦β¦β¦β¦β¦31 Figure 2.16: ID-VD characteristic for different drain gate biasβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦.32 Figure 3.1: (a) Band diagram with interfacial layer (b) Capacitance modelβ¦β¦β¦β¦β¦.34 Figure 3.2: (a) Band diagram at equilibrium and (b) Band diagram at breakdownβ¦β¦..35 Figure 3.3: Device structure for SrTiO3 thickness studyβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...39 Figure 3.4: Band diagram and electron profile for different SrTiO3 thicknessβ¦β¦β¦β¦39 Figure 3.5: Capacitance-Voltage study for different SrTiO3 thicknessβ¦β¦β¦β¦β¦β¦β¦40 Figure 3.6: ID-VD characteristics for 28nm SrTiO3/5nm GdTiO3 HFETβ¦β¦β¦β¦β¦β¦...41 Figure 3.7: ID-VD characteristics for 40nm SrTiO3/5nm GdTiO3 HFETβ¦β¦β¦β¦β¦β¦...42 Figure 3.8: ID-VD characteristics for 96nm SrTiO3/5nm GdTiO3 HFETβ¦β¦β¦β¦β¦β¦...43 Figure 3.9: Improvement in charge modulation with increasing SrTiO3 thicknessβ¦β¦..44 Figure 3.10: Effective low field SrTiO3 permittivity for different SrTiO3 thicknessβ¦...45 Figure 3.11: Charge modulation versus gate bias for different SrTiO3 thicknessesβ¦β¦..48 Figure 3.12: Charge modulation versus electric field in interfacial layerβ¦β¦β¦β¦β¦β¦..48 Figure 3.13: (a) Device structure for surface treatment (b) Band diagram and electron profile of the sampleβ¦β¦β¦β¦β¦β¦β¦β¦51 Figure 3.14: Gate leakage characteristicβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...β¦.52 Figure 3.15: Capacitance-voltage characteristic with and without surface treatmentβ¦...53 Figure 3.16: Simulation of the charge modulation as a function of the gate biasβ¦β¦β¦..54 Figure 3.17: ID-VD characteristics for 40nm SrTiO3/5nm GdTiO3 HFETβ¦β¦β¦β¦β¦β¦.55 Figure 3.18: Transconductance characteristics for 40nm SrTiO3/5nm GdTiO3 HFETβ¦.56 Figure 3.19: Triangular barrier at the gateβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦.57 xiii Figure 3.20: Breakdown field calculation for different materialβ¦β¦β¦β¦β¦β¦β¦β¦β¦...59 Figure 3.21: Comparison of breakdown field of different materialsβ¦β¦β¦β¦β¦β¦β¦β¦.60 Figure 3.22: Device structure with high-k dielectric (Ba0.5Sr0.5TiO3)β¦β¦β¦β¦β¦β¦β¦...61 Figure 3.23: Transfer length measurement (TLM) I-V characteristic for Al/Ni/Au ohmic contact. No etching and BOE dip before metal depositionβ¦β¦β¦β¦β¦β¦.62 Figure 3.24: Transfer length measurement (TLM) I-V characteristic for Al/Ni/Au ohmic contact. 8 min etch etching and no BOE dip before metal depositionβ¦β¦63 Figure 3.25: Transfer length measurement (TLM) I-V characteristic for Al/Ni/Au ohmic contact. 10 min etching and 10s BOE dip before metal depositionβ¦β¦β¦64 Figure 3.26: Process flow for sample with high-k barrier layerβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦65 Figure 3.27: Gate barrier for (a) SrTiO3/GdTiO3 and (b) BaSrTiO3/ SrTiO3/GdTiO3 structuresβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦.66 Figure 3.28: Tunneling probability of electron at gate barrier at different applied electric fieldβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦..68 Figure 3.29: Gate leakage characteristics for sample with and without BaSrTiO3 layer. 69 Figure 3.30: Capacitance voltage characteristicsβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...β¦70 Figure 3.31: Charge modulation for different barrier thicknessβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦71 Figure 3.32: ID-VD profile of BaSrTiO3/SrTiO3/GdTiO3 transistorβ¦β¦β¦β¦β¦β¦β¦β¦.72 Figure 3.33: gm profile of BaSrTiO3/SrTiO3/GdTiO3 transistorβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦73 Figure 4.1: MESFET device structureβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...75 Figure 4.2: Gate leakage characteristic of HFET and MESFET with similar SrTiO3 thicknessβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦75 xiv Figure 4.3: ID-VD profile of SrTiO3 MESFETβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦.76 Figure 4.4: gm profile of SrTiO3 MESFET and SrTiO3/GdTiO3 HFET with same SrTiO3 thicknessβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦77 Figure 4.5: Capacitance-Voltage characteristics of SrTiO3 MESFETβ¦β¦β¦β¦β¦β¦β¦...79 Figure 4.6: 1/C2 versus gate voltageβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦..80 Figure 4.7: Field dependent dielectric constant of SrTiO3β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦80 Figure 4.8: BFOM and BHFFM of different materialsβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦..82 Figure 4.9: Hysteresis loop of ferroelectric materialsβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦83 Figure 4.10: (a) Simulated device structure (b) ID-VG characteristicsβ¦β¦β¦β¦β¦.........84 Figure 4.11: (a) Device structure of FerroFET (b) Effect of ferroelectricity on band diagramβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦.....85 Figure 4.12: Schottky diode characteristic of FerroFETβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...86 Figure 4.13: Capacitance-Voltage profileβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦..87 Figure 4.14: ID-VD profile of FerroFETβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦...88 Figure 4.15: ID-Vg and Gm profile of FerroFETβ¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦..88 Figure 4.16: (a) Hysteresis in C-V profile (b) Hysteresis in ID-VG profileβ¦β¦β¦β¦β¦β¦89 xv Chapter 1: Introduction After discovering mineral CaTiO3, geologist Gustave Rose named it perovskite. The βPerovskiteβ term was coined honoring renowned mineralogist Count Lev Alexevich von Perovski. But now, perovskite represents a large group of compound that has the chemical formula ABC3. Perovskite oxide is a subclass of this group with common chemical formula ABO3. In these compounds, transition metal ion B is bonded with eight oxygen ions, forming an octahedron. The crystal structure of perovskite oxide is shown in figure 1.1. Figure 1.1: Crystal structure of perovskite oxide. Here, B is transition metal surrounded by 6 oxygen atoms (O). [1] 1 Because of interesting electronic, magnetic and optical properties, currently perovskite oxides are one of the central attractions of research in the field of physics, chemistry, material science and electronics. Perovskite oxide covers all aspects of solid state phenomena β metallic (LaTiO3, NaWO3 etc.), insulating (BaTiO3, SrTiO3 etc.), semiconducting (doped SrTiO3), magnetic (PbCrO3, LaFeO3 etc.), superconducting (NaWO3, LiWO3 etc.), ferroelectric (BaTiO3), Mott transition material (GdTiO3, VO2). Because of wide varieties of material properties and similar chemical formula, integration between different typed of perovskite materials can lead to new phenomena that could be interesting for both physics and engineering. For example, polar and non-polar heterostructures can produce high electron density two dimensional electron gases, a heterojunction of Mott and band insulators can lead to insulator to metal transition. In this chapter, I will summarize present status of perovskite oxide research, motivation of my research and a brief overview of this dissertation. 1.1 Research on perovskite oxides One of the most interesting properties that many perovskite oxides have is ferroelectricity. In ferroelectric material, we can switch macroscopic polarization. A large number of ferroelectric materials with technological significance are perovskites. The first ferroelectric material was discovered in 1941 by Thurnaurer and Deaderick [2]. BaTiO3 ceramic was the first discovered ferroelectric perovskite oxide. BaTiO3 exhibited very unique dielectric properties with very high relative permittivity β exceeding 1000 [3- 2 5]. Von Hippel [6] and Wul and Goldman [7] demonstrated ferroelectric behavior of BaTiO3 for the first time. To understand the origin of ferroelectricity in perovskite oxides, lot of experimental and theoretical works have been done. Ronald E. Cohen [8] showed electronic calculation of two very common ferroelectric perovskite oxides β BaTiO3 and PbTiO3 and suggested that hybridization between 3d orbital of titanium atoms and 2p orbital of oxygen atoms is necessary for ferroelectricity in perovskite titanates. In another study, Helen D. Megaw [9] showed that perovskites that have bonds allowsing parallel dipoles with small displacement and small barrier at potential maxima show ferroelectricity. Because of ferroelectric behavior, perovskite oxide is a potential candidate for volatile and non-volatile memory applications. Solid-state dynamic and static random access memory (DRAM and SRAM) allow faster data storage for computers. But one of the major drawbacks of conventional solid-state RAM is that when power is disconnected, stored data is lost. In ferroelectric RAM (FRAM), the polarization state stores the data. So, these devices can store data even without any power. So, in principle FRAM can be operated in low power. In 1989, Gnadinger and Bondurant [10] showed how a metalferroelectric-metal (MFM) sandwich capacitor can be used as a memory device. But one of the major problems with tradition ferroelectric materials is degradation over time or fatigue [10-12]. Araujo et al. [13] showed ferroelectric capacitors using 3 perovskite oxides such as SrBi2Ta2O9, SrBiNbTaO9 and SrBi4Ta4O15 can overcome fatigue problem. They found no sign of degradation even after 1012 switching cycles. B. H. Park et al. [14] showed that lanthinum substituted bismuth titanate ferroelectric capacitors could be a viable alternative for fatigue free FRAM. Uong Chon et al. [15] showed that Bi4-xNdxTi3O12 could be an excellent material for FRAM because of its giant spontaneous polarization. By switching the polarity of polarization, it is possible to use ferroelectric insulators as voltage step up transformers. By replacing dielectric insulators with ferroelectric insulators in a MOSFET, it is possible to get negative differential capacitance and by choosing appropriate thickness, theoretically it is possible to get subthreshold swing below 60mV/dec at room temperature. This concept was first proposed by Salahuddin and Datta [16]. In 2011, A.I Khan et al. [17] demonstrated the first experimental evidence of negative differential capacitance using Pb(Zr0.2Ti0.8)O3 (PZT), a ferroelectric perovskite. But in that work they used a ferroelectric and band insulator bilayer. In 2015 they demonstrated direct evidence of differential negative capacitance from pure ferroelectric capacitor [18]. Another important property that some perovskite oxides have is Hubbard-Mott transition or metal to Insulator transition (MIT). In late 1920βs, Beth, Bloch and Sommerfeld developed a model that can describe metallic and insulating properties of material. This model is the band-theory of materials. In this theory, electrons are considered 4 independent and if there is any partially filled band, that material is considered as metal. On the other hand if the band is completely filled or empty, that material is an insulator. But later, it was found that many transition metal oxides (perovskites) exhibit poor conductivity, though those materials have partially filled d-orbital. According to band theory, those materials should be metal, but in reality they are not. Later N. Mott came up with a theory that can exhibit this unusual behavior [19,20]. In band theory, electronelectron interaction was not considered. But in some perovskite oxide, electron-electron interaction is very strong and that can split the partially filled band into two bands β upper Hubbard band and lower Hubbard band. If one of those bands is completely filled, it makes the material insulating. This class of material is called Mott insulator in the honor of N. Mott. The origin of insulating behavior in Mott material is shown in figure 1.2. Figure 1.2: In the left, band is shown predicted by band theory. It shows half-filled band that is a characteristic of metal. But strong electron-electron interaction splits the band into two β upper Hubbard band (UHB) and lower Hubbard band (LHB). Now one band is completely filled and another one is completely empty. So it shows insulating behavior. 5 But if we can change the electron configuration in the Hubbard band, we can make a transition from insulator to metal. We can perturb the system by injecting electrons, changing temperature, photoluminescence and electric field. M. M. Qazilbash et al. [21] induced metallic state in insulating vanadium dioxide by increasing the temperature. The result was confirmed by infrared spectroscopy. S. Lupi et al. [22] showed that by lowering temperature Mott-Hubbard transition is possible in Cr-doped V2O3 and this induced metallic state can coexist with insulating background. G Stefanovich et al. [23] demonstrated electric field induced MIT. By electric field they injected electrons and that induced MIT in VO2. They also found that critical electron density for MIT is in the order of 1018-1019 cm-3. D. M. Newns et al. [24] demonstrated a field effect transistor based on metal to insulator transition. They used back-gated transistor structure. A Mott insulator cuprate layer, Y1-xPrxBa2Cu3O7-Ξ΄ (YPBCO), was used as channel material. Perovskite oxides have taken the superconductor research to the next level by introducing high-Tc superconductor. Bednorz and Muller demonstrated [25] high-Tc superconductor for the first time in 1986. They reported super conductance with onset temperature 90K. This finding drew a lot of attention and made it possible to use the superconductor for practical application such as electric motor, generator, magnet, transmission line, connecting wires etc. 6 D. Mateika et al. [26] reported mixed perovskite (cations of Al based perovskites are replaced by Sr2+, Ca2+, Ta5+, Nb5+ ions) for high-Tc superconductor. S. Takekawa et al. [27] reported high temperature superconductivity in Nd1+xBa2-xCu3Oy. They also demonstrated that they can vary onset of superconductivity from 93.5K to 40K by changing mole fraction, x. Z. Ren et al. [28] demonstrated superconductivity in rare-earth perovskite, ReFeAsO1-Ξ΄ (Re = rare-earth metal, Sm, Nd, Pr, Ce, La). They showed that Perovskite with Sm has highest Tc (55K) and Perovskite with La has the lowest Tc (25K). A. Schilling et al. [29] demonstrated superconductor with highest Tc. They reported that HgBa2Ca2Cu3O1+x is the superconductor with highest Tc (133K). Another application of perovskite oxide is Resistance change Random Access Memory (RRAM). This device has two different resistance states or bistable resistivity. Resistivity changes because of the drift of anions (usually oxygen ions) by applied electric field. This device is usually metal-insulator-metal (MIM) capacitor structure. First reported RRAM was Al/Al2O3/Al MIM structure [30]. Later same characteristics are demonstrated using NiO [31] and SiO2 [32]. All of these devices were unipolar or nonpolar devices. First bipolar structure was demonstrated using perovskite oxide β Nb2O5 [33]. In this case asymmetric electrodes of Nb and Bi were used. SrZrO3 was first used to demonstrate reproducible resistive switching devices at +/- 0.5 V [34]. Pr0.7Ca0.3MnO3 (PCMO) shows reversible resistance change effect in epitaxial grown structures [35]. 7 Perovskite oxides are also used for high efficient and low temperature Solid Oxide Fuel Cells (SOFC). In 1994, Ishihara first demonstrated SOFC using lanthanum strontium gallium magnesium oxides (LSGM) [36, 37]. Then a lot of works have been done to make it more efficient and lower the operating temperature [38-42]. In 2007, SOFC system was demonstrated for residential application for the first time [43]. Because of unique dielectric properties of perovskite oxides (i.e. high permittivity and field dependent permittivity), these materials are used for reconfigurable high frequency (> 1GHz) microwave capacitors [44-45]. One of the major advancements in perovskite oxide material is two dimensional electron gases (2DEG) at polar non-polar oxide interface [46]. There are lot of perovskite oxide heterostructures that exhibit 2DEG at the interface, such as - LaTiO3/SrTiO3, [47] LaAlO3/SrTiO3, [48-49] LaVO3/SrTiO3, [50] SrTiO3/GdTiO3, [51] and NdTiO3/SrTiO3 [52]. This 2DEG could be used for electronic applications [53-55]. 1.2 Motivation and research objective The main motivation of my research was to use perovskite oxide for electronic applications. In 2011, J. Son et al. demonstrated a very high 2DEG density (3x1014 cm-2) at GdTiO3/ SrTiO3 interface [51]. In this work, my motivation was to use this extreme electron density for electronic applications. We demonstrated the first heterojunction field effect transistor (HFET) in the GdTiO3/SrTiO3 material system. We also analyzed, 8 proposed and demonstrated different mechanisms that can improve charge modulation in this heterostructure. We also analyzed the prospect of SrTiO3 for high power application. We also investigated the effect of ferroelectric gate in GdTiO3/SrTiO3 HFETs. This work could be very important for high power electronics and tunable plasmonic applications. 1.3 Thesis Organization In Chapter 2, I will discuss the origin of 2DEG at GdTiO3/SrTiO3 interface. Then I will describe the transistor structure I used. Then I will summarize the fabrication technique that we developed. Finally, I will show the electrical characterization of the HFET. In Chapter 3, I will discuss the factors that are responsible for limiting charge modulation in GdTiO3/SrTiO3 HFETs. Then I will discuss three mechanisms that can improve charge modulation. I will also show an analytical model that can predict device performance. In Chapter 4, I will discuss two other device structures β MESFET and Ferroelectric gated FET (FerroFET). I will also analyze the prospect of SrTiO3 for high power application. Finally, in Chapter 5, I will summarize my results and discuss possible future works. 9 Chapter 2: GdTiO3/SrTiO3 Heterojunction Field Effect Transistors (HFETs) GdTiO3/SrTiO3 heterostructure exhibits extreme two dimensional electron gases (2DEG) at the interface. In this chapter, at first I will discuss the origin of 2DEG at the interface. Then I will discuss growth mechanism and electrical characteristic of the heterostructure. Then I will describe fabrication steps to fabricate transistors in this material system. Finally, I will show the electrical characterization of the HEFTs. 2.1 GdTiO3/SrTiO3 Heterostructure Recently, 2-dimensional electron gas (2DEG) at polar and non-polar perovskite oxide interfaces has become one of the center foci of condensed matter physics research. Because of unique properties, such as extreme high charge density [47-52], superconductivity, magnetism, metal-insulator transition (MIT), strong electron correlation etc., researchers from different communities are working on understanding and development of this unique material system [56-61]. The pioneer discovery of 2DEG at LaTiO3/SrTiO3 interface [47] led to discover many more oxide combinations that exhibit 2DEG such as LaAlO3/SrTiO3 [48,49] LaVO3/SrTiO3, [50] SrTiO3/GdTiO3, [51,62] and NdTiO3/SrTiO3 [52]. 10 The origin of this 2DEG is the polar discontinuity at the interface [46]. In polar material, there is an alternating layer of positive and negatively charged sheets. Positively charged sheet shares give their electrons to the adjacent negatively charged layers. But at the interface, if the other material is non polar, the electron released by the positively charged layer are not captured by any atoms. These free mobile electrons are the origin of 2DEG at oxide interfaces. As every unit cell releases on electron and electrons are shared by two layers (top and bottom), electron density at 2DEG should be half of the density of unit cell at the interface, around 3x1014 cm-2. This phenomenon is clearly shown in figure 2.1. Figure 2.1: Origin of free electron (2DEG) at polar non-polar oxide interfaces [63] 11 Though theory predicts a very high electron density at polar/non-polar oxide interfaces, different issues, such as macroscopic fields, traps, non-stoichiometry, intermixing at the interfaces etc., can lower the electron density by one order of magnitude. So we need a very controlled growth mechanism where the interface is very sharp, defect and trap free. So far most of the works done in oxide interfaces were focused on LaAlO3/SrTiO3 and LaTiO3/SrTiO3 interfaces. These materials are mainly grown by pulsed laser deposition (PLD) that requires high energy. Electron density at LaAlO3/SrTiO3 interface is around 1013 cm-3, that is, at least one order lower than the predicted by interface reconstruction theory [64-66]. LaTiO3/SrTiO3 shows electron density that is close to the predicted value [67,68], but the origin of free electron is still not clear [67,69]. Recently, Pouya Moetakef et al. developed a technique to grow a heterostructure between Mott insulator GdTiO3 and band insulator SrTiO3 by Molecular Beam Epitaxy (MBE) on LSAT substrate [62]. Because of controlled growth mechanism, the interface between GdTiO3 and SrTiO3 is very smooth that can be seen in TEM image 2.2 (b). Because of very sharp interface and 50:50 mixture of Ti3+ and Ti4+ at the interface, this heterostructure exhibits a 2DEG of electron density 3x1014 cm-2, exactly same as predicted by interface reconstruction theory. To verify the origin of this 2DEG, they grew supper lattices of GdTiO3/SrTiO3 with different number of interfaces and they found that 2DEG electron density increases linearly with number of interfaces [62]. This confirms 12 that the origin of 2DEG at GdTiO3/SrTiO3 is the electronic reconstruction of the interface, not artifacts due to growth issues or traps. This fact is shown in figure 2.3 (a). Figure 2.2: (a) Sheet Carrier concentration versus number of interfaces (b) TEM image of GdTiO3/SrTiO3 interface [62] 13 The electrical transport properties of SrTiO3/GdTiO3 heterostructures are shown in figure 2.3. In figure 2.3 (a), sheet resistance is shown for different GdTiO3 and SrTiO3 thickness. In figure 2.3 (b), mobility, electron density are shown. From these figures it is evident that even a 1nm SrTiO3 layer can exhibit 2DEG electron at the interface and the electron density is independent of SrTiO3 thickness, which is another proof of electronic reconstruction of the interface. Above 20 nm SrTiO3 thickness mobility of 2DEG is independent of SrTiO3 thickness. Room temperature mobility of 2DEG is 8 cm2/V-s and at low temperature it becomes 400 cm2/V-s [62]. The mobility of a 2DEG is Optical Phonon (OP) limited at room temperature and impurity scattering limited at low temperature [70]. 14 Figure 2.3: (a) Sheet resistance versus temperature for different GdTiO3 and SrTiO3 thicknesses (b) Mobility of 2DEG for different SrTiO3 thickness [62] 15 2.2 Inverted transistor Structure: As there is a huge mobile 2DEG at GdTiO3/SrTiO3 interface, it could be an interesting material to explore from device engineering point of view. To make a transistor out of this material system, our first concern was what should be the preferable device structure for electronic application. Because of staggered band line-up between SrTiO3 and GdTiO3, 2DEG electrons are confined in SrTiO3 layer [71]. The bandgaps of GdTiO3 and SrTiO3 are 3.25eV and 1.8 eV respectively [72,62]. The dielectric constant of SrTiO3 is 300Ξ΅0 at low field and it varies with electric field [73]. GdTiO3 has a lower dielectric constant - 30Ξ΅0 [62]. The conduction band offset between GdTiO3 and SrTiO3 is 0.7eV measured by Hard X-ray Photoelectron Spectroscopy (HXPS) [71]. As the 2DEG density is very high, electrons occupy multiple sub-bands with different effective masses. The effective mass of this 2DEG electron is 1-2m0. As these electrons are d-orbital electrons, these electrons have very high effective mass. Based on this information we calculate the band and charge profile using 1D Poisson, a self-consistent Schrodinger-Poisson solver [74]. The band diagram and 2DEG profile for GdTiO3/SrTiO3 are shown in figure 2.4 (b). From this figure, it is clear that the 2DEG is highly confined because of high effective mass. 16 (a) (b) Figure 2.4: (a) Inverted transistor structure (b) Band diagram and electron profile 17 Based on our study of material properties and band diagrams, we found that the inverted structure will be good for Heterojunction Field Effect Transistors (HFETs). Inverted structure means SrTiO3 will be the top layer and 2DEG channel will be just below the gate contact as shown in figure 2.4 (a). Inverted structure has some benefits over normal structure where GdTiO3 is on top. Advantages of inverted structure are: ο± Higher Breakdown strength for SrTiO3 ο± Better short channel scaling ο± Simple contacts (no barrier) ο± Reduced CGS degradation due to wavefunction spread 2.3 Fabrication As GdTiO3/SrTiO3 is a very new material system, we had to optimize each fabrication step. We started our processing with the ohmic contact. As SrTiO3 has an electron affinity of 4.1 eV and oxygen deficient growth condition makes the SrTiO3 layer slightly n-type, a low workfunction metal would be a good choice for an ohmic contact. At first we used Aluminum (Al) that has a workfunction 4.09 eV. It gives a contact resistance 3.6 Ξ©-mm that is shown in figure 2.5. As there is a barrier of SrTiO3 thin film between 2DEG and ohmic metal, it causes higher contact resistance. As GdTiO3 can decompose at high temperature, we could not use rapid thermal annealing (RTA) to reduce contact resistance. Later we found out that if we dip our sample in Buffer Oxide Etchant (BOE) (HF:H2O=1:10) for several seconds, it creates some holes in the epitaxial layer, shown in figure 2.6. These holes may help to create contact between the metal and the 2DEG. So 18 we repeated the experiment with same metal stack (Al/Ni/Au), but this time we dipped our sample in BOE for 10s just before depositing the metal. This time we got a contact resistance of 0.5 Ξ©-mm that is shown in figure 2.7. High electron density at 2DEG is the reason for this low contact resistance [75]. Figure 2.5: Ohmic contact resistance for Al/Ni Au, without any surface processing 19 (a) (b) Figure 2.6: (a) AFM image of sample after 10s of BOE dip (b) Cross section height analysis shows holes with depth 40~80 nm 20 Figure 2.7: Ohmic contact resistance for Al/Ni/Au metal stack. Contact resistance after 10s BOE dip is 0.5 Ξ©-mm 21 We tried other metals for ohmic contacts, too. Niobium (Nb) is another low workfunction (4.3eV) material. We deposited Nb/Au metal stack with BOE dip, and transfer length measurement (TLM) gives a contact resistance 0.3 Ξ©-mm (figure 2.8). But the sticking coefficient between Nb and SrTiO3 is very low. So we used Al/Ni/Au metal stack as ohmic contact for all of our device fabrication. Figure 2.8: Ohmic Contact resistance of Nb/Au metal stack. Contact resistance after 10s BOE dip is 0.3Ξ©-mm 22 After the ohmic contact, we optimized Schottky contact. For Schottky, we tried different high workfunction materials β Platinum (Pt), Nickel (Ni) and Silver (Ag). Schottky diode characteristics are shown in figure 2.9. From the figure, it is clear that Pt gives the best Schottky behavior. Gate leakage current also depends on the area of the gate contact. For higher contact area leakage current density is higher (figure 2.10) and it is because of non-uniformity of the sample. We can also improve gate leakage characteristics by O2 treatment just before depositing gate metal. It is shown in figure 2.11. O2 plasma helps to clean the surface. Moreover, there are oxygen vacancies in SrTiO3 and O2 plasma helps to fill up O2 vacancies and make it more insulating. All these help to reduce gate leakage. Figure 2.9: Schottky contact behavior of different metals. Pt shows best rectification behavior 23 Figure 2.10: Gate leakage for different gate length. Larger gate causes higher leakage Figure 2.11: Effect of oxygen plasma treatment. Oxygen plasma improves gate leakage. 24 Perovskite oxides are very hard materials to etch. So we used Reactive Ion Etching (RIE) to etch SrTiO3 and GdTiO3. We used Chlorine based etching recipe (Cl2/BCl3). We used 100W RIE power with different Cl2/BCl3 ratio. Chamber pressure was fixed at 5mT. We used three different conditions to run the etching test β 5 sccm BCl3 & 50 sccm Cl2, 35 sccm BCl3 & 5 sccm Cl2 and 50 sccm BCl3 & 5 sccm Cl2. Samples were etched for 5min under each condition. Etching profiles are shown in figure 2.12 and the results are summarized in the table below: RIE Power: 100W, Base Pressure: 5mT, Etch Time: 5min Condition Etch Depth Etch rate (nm/min) 5 sccm BCl3 & 50 sccm Cl2 20nm 4 nm/min 35 sccm BCl3 & 5 sccm Cl2 12nm 2.4 nm/min 50 sccm BCl3 & 5 sccm Cl2 13nm 2.6 nm/min Table 1: ICP-RIE etching test From our result we found that 5sccm BCl3 and 50sccm Cl2 with 100W RIE power gives best etch rate. As we used very high power etching, it created burnt photoresist residue on the sample that contaminates the surface and increases the gate leakage. So instead of etching continuously for long period, we divided our etch time into 2 minute segments, so that the sample can cool down and prevent the burnt photoresist issue. We used GCA i-line stepper for optical photolithography and for that we use SPR 950 photoresist. This photoresist has a thickness of 750 nm (figure 2.13 (a)) and the etch rate 25 of photoresist under our selected RIE condition is around 100nm/min. So we cannot etch more than 25 nm at a time using SPR 950. So we used SPR 220 that is denser and gives thicker coverage (around 7 ΞΌm) (figure 2.13 (b)). We can etch more than 100nm at a time using this process recipe. A complete process flow of transistor fabrication is shown in figure 2.14. 2.4 Transistor characteristics Using the process flow described above, we fabricated GdTiO3/SrTiO3 HFETs. We are the first to demonstrate HFET characteristics in GdTiO3/SrTiO3 material system. We observed modulation from capacitance-voltage (C-V) characteristics. We also observed drain current modulation with gate bias that also confirms 2DEG electron modulation. 26 (a) (b) (c) Figure 2.12: Etching profiles after 4 minutes for different etching recipe (a) 50sccm Cl2/5sccm BCl3 (b) 5sccm Cl2/50sccm BCl3 (c) 5sccm Cl2/35sccm BCl3 27 (a) (b) Figure 2.13: Thickness of (a) SPR 950 and (b) SPR 220 after spin coating 28 Figure 2.14: Fabrication process flow 29 The C-V characteristic is shown in figure 2.15. From the C-V profile we found that the charge modulation is 6x1013 cm-2, which was the highest charge modulation for any material system. The zero bias capacitance is very high (1.45 ΞΌF/cm2) compared to conventional materials and it corresponds to a relative dielectric constant of 40 that is very low compared to the bulk relative dielectric constant of SrTiO3 (350). This low relative dielectric constant is due to the interfacial layer just below the gate. We will discuss more about this interfacial layer and mechanisms to reduce the effect of interfacial layer in next chapter. The I-V characteristic is shown in figure 2.16. The I-V characteristic shows 20% modulation in current. As the total 2DEG density is 3x1014 cm-2, 20% current modulation corresponds to charge modulation of 6x1013 cm-2 that is consistent with our C-V result. Though 6x1013 cm-2 electron modulation is the highest for any material system, still it is only 20% of the total charge. In the next chapters we will discuss three mechanisms to improve charge modulation. 30 Figure 2.15: Capacitance-Voltage (C-V) profile of GdTiO3/SrTiO3 HFETs. From C-V profile, total modulated charge is 6x1013 cm-2 31 Figure 2.16: ID-VD characteristic for different drain gate bias. Gate voltage is varied from 0V to -10V. The source to drain spacing of the transistor is 3.5 ΞΌm, the source to gate spacing is 0.5 ΞΌm and the gate length is 1 ΞΌm 32 Chapter 3: Improvement of modulation in GdTiO3/SrTiO3 HFET In the previous chapter we described GdTiO3/SrTiO3 HFET and concluded that modulation in these HFETs are mainly limited by the interfacial layer. In this chapter I will investigate the effect of the interfacial layers more qualitatively and develop a model to explain charge modulation in GdTiO3/SrTiO3 HFETs including interfacial layers. Then I will discuss three techniques to improve charge modulation. The first technique is increasing the thickness of SrTiO3 layer. The second technique is surface treatment and the final method is using high-k gate dielectric. I will discuss the high breakdown field of SrTiO3, too. 3.1 Interfacial Layer As mentioned in last chapter, an interfacial dead layer is one of the major factors that limit the charge modulation of GdTiO3/SrTiO3 HFETs. There is always a thin dead interfacial layer with low dielectric constant on SrTiO3 surface [76]. So the gate capacitance consists of two series capacitors β the interfacial layer capacitance and the SrTiO3 thin film capacitance. This is shown in figure 3.1. 33 If there is no charge at the interface, perpendicular electric fields of interfacial layer and SrTiO3 layer can be related using the boundary condition: ππππ πΈπππ = ππππ‘ πΈπππ‘ β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦β¦ (1) Here, Ξ΅STO and Ξ΅int are the dielectric constants of SrTiO3 and interfacial layers respectively and ESTO and Eint are the perpendicular electric fields of SrTiO3 and interfacial layers respectively. As the interfacial layer has a very low dielectric constant compared to SrTiO3 [76], the field at the interfacial layer is very high, causing early breakdown at the interfacial layer that is shown in figure 3.2. This early breakdown at the interfacial layer limits the gate bias that can be applied to modulate 2DEG electrons and hence limit charge modulation. Figure 3.1: (a) Band diagram with interfacial layer (b) Capacitance model 34 1 At Equilibrium Energy (eV) 0 -1 -2 -3 -4 -5 -20 0 20 40 60 80 100 120 Thickness (nm) (a) Energy (eV) 20 At Breakdown Voltage 10 0 -20 0 20 40 60 80 100 120 Thickness (nm) (b) Figure 3.2: (a) Band diagram at equilibrium and (b) Band diagram at breakdown 35 Now we will use a very simple parallel plate capacitor model to analyze the effect of the interfacial layer. The calculation is based on the model shown in figure 3.1. This is a very simple model and we assumed 2DEG is highly confined so that we can consider it as sheet charge. Moreover we will not consider field dependent dielectric constant of SrTiO3 in this calculation. We will show more accurate and modified capacitance model using a field dependent dielectric constant later in this chapter. As mentioned earlier, the gate capacitance, CG, has two components β capacitance due to interfacial layer (Cint) and capacitance due to SrTiO3 layer (CSTO). Let the thickness of SrTiO3 and interfacial layers be tSTO and tint respectively. If the dielectric constant of SrTiO3 and interfacial layer are Ξ΅STO and Ξ΅int respectively, we can define CSTO and Cint as below: πΆπππ = πΆπππ‘ = ππππ π‘π π‘π ππππ‘ π‘πππ‘ β¦β¦β¦β¦β¦.. (2) β¦β¦β¦β¦β¦β¦β¦β¦ (3) So, total gate capacitance, CG can be written as β 1 πΆπΊ = => 1 πΆπππ 1 πΆπΊ = => πΆπΊ = + 1 πΆπππ‘ π‘πππ ππππ + π‘πππ‘ ππππ‘ ππππ ππππ‘ ππππ π‘πππ‘ +π‘πππ ππππ‘ β¦β¦β¦β¦β¦β¦β¦β¦. (4) 36 So the total charge modulation can be described as π = πΆπΊ ππΊ,πππ₯ β¦β¦β¦β¦β¦β¦β¦. (5) Now, VG,max can be related to the electric field at SrTiO3 at the breakdown of interfacial layer (EBR). As the interfacial layer is very thin compared to the SrTiO3 barrier thickness, we can assume all of the gate voltage drops at SrTiO3 barrier layer and in that case we can write β ππΊ.πππ₯ = πΈπ΅π π‘πππ β¦β¦β¦β¦β¦β¦β¦β¦ (6) Combining (4), (5) and (6) we can write β π= ππππ ππππ‘ πΈπ΅π π‘πππ ππππ π‘πππ‘ +π‘πππ ππππ‘ β¦β¦β¦β¦β¦β¦β¦β¦ (7) If we rewrite (7) we can find that β π π πππ πππ‘ π = ππππ π‘πππ‘ π‘πππ πΈπ΅π +ππππ‘ β¦β¦β¦β¦β¦β¦β¦β¦ (8) From (8), it is evident that if we can increase the SrTiO3 layer thickness, it will reduce the effect of the interfacial layer and improve charge modulation. We can rewrite (7) in a different way, too π= ππππ‘ πΈπ΅π π‘πππ π‘ ππππ‘ π‘πππ‘ + πππ π β¦β¦β¦β¦β¦β¦β¦β¦ (9) πππ From (9), it is clear that if we can increase effective SrTiO3 dielectric constant, we can improve charge modulation. Based on the discussion above, we find couple of ways that can improve charge modulation. In next three section, three different mechanisms will be discussed that cam 37 improve charge modulation in GdTiO3/SrTiO3 HFETs. At first, I will discuss how SrTiO3 thickness improves charge modulation. Then I will explain a surface treatment mechanism that can reduce interfacial layer effect and hence improve charge modulation. And finally I will describe the effect of high-k gate dielectric layer that increases effective capacitance and thus increases charge modulation. 3.2 Effect of SrTiO3 Thickness As discussed in previous section, thickness of SrTiO3 layer can reduce the effect of interfacial layer and hence increase charge modulation. To verify this idea we run an experiment, where we varied SrTiO3 thickness in SrTiO3/GdTiO3 heterostructures. We used three samples where SrTiO3 thicknesses are 28 nm, 40 nm and 96 nm. In all cases, GdTiO3 thickness is 5nm. Hall measurement shows 2DEG electron density 3x1014 cm-2 in each sample. So in this experiment all heterostructures are identical except SrTiO3 thickness. Device structure is shown in figure 3.3. Band diagram is shown in figure 3.4. After preparing the samples, we fabricated these samples using the process flow described in previous chapter. Ohmic contact was good in all samples and we also got very good Schottky behavior. Schottky breakdown increased with increasing SrTiO3 thickness. After Ohmic contact deposition, mesa isolation and gate contact deposition, electrictical characterization was carried out. 38 Figure 3.3: Device structure for SrTiO3 thickness study. Gate length is 1ΞΌm, Source to drain spacing is 3.5ΞΌm and source to gate separation is 0.5ΞΌm Figure 3.4: Band diagram and electron profile for different SrTiO3 thickness 39 Capacitance voltage characteristic of all three device structures are shown in figure 3.5. By integrating the area of C-V curve, we can get the total charge modulation. From C-V profile, charge modulations are 5.5x1013 cm-2, 8.5x1013 cm-2 and 1.05x1014 cm-2 for 26nm, 40nm and 96nm device structure respectively. From, C-V profile, it is evident that charge modulation increases with SrTiO3 barrier thickness. So this result undoubtedly verifies our idea described in previous section. Figure 3.5: Capacitance-Voltage study for different SrTiO3 thickness. From C-V profile, charge modulations are 6x1013, 8.5x1013 and 1.05x1014 cm-2 for 28nm, 40nm and 96nm SrTiO3 layer respectively 40 In figure 3.6, ID-VD characteristic for different gate bias is shown for 26nm SrTiO3/ 5nm GdTiO3 HFETs. From ID-VD characteristic, we can observe 20% of current modulation. From C-V profile, we observed charge modulation of 5.5x1013 cm-2 that is around 20% of total charge in 2DEG. So ID-VD and C-V results are consistent. Figure 3.6: ID-VD characteristics for 28nm SrTiO3/5nm GdTiO3 HFET. Gate voltage is varied from 0V to -5V. Total current modulation is 20%. Gate length is 1ΞΌm, Source to drain spacing is 3.5ΞΌm and source to gate separation is 0.5ΞΌm 41 In figure 3.7, ID-VD characteristic for different gate bias is shown for 40nm SrTiO3/ 5nm GdTiO3 HFETs. From ID-VD characteristic, we can observe 30% of current modulation. From C-V profile, we observed charge modulation of 8.5x1013 cm-2 that is around 30% of total charge in 2DEG. So ID-VD and C-V results are consistent. Figure 3.7: ID-VD characteristics for 40nm SrTiO3/5nm GdTiO3 HFET. Gate voltage is varied from 0V to -10V. Total current modulation is 30%. Gate length is 1ΞΌm, Source to drain spacing is 3.5ΞΌm and source to gate separation is 0.5ΞΌm 42 In figure 3.8, ID-VD characteristic for different gate bias is shown for 96nm SrTiO3/ 5nm GdTiO3 HFETs. From ID-VD characteristic, we can observe 35% of current modulation. From C-V profile, we observed charge modulation of 1.05x1014 cm-2 that is around 35% of total charge in 2DEG. So ID-VD and C-V results are consistent. Figure 3.8: ID-VD characteristics for 96nm SrTiO3/5nm GdTiO3 HFET. Gate voltage is varied from 0V to -20V. Total current modulation is 35%. Gate length is 1ΞΌm, Source to drain spacing is 3.5ΞΌm and source to gate separation is 0.5ΞΌm 43 As ID-VD and C-V profiles are giving same amount of charge modulation, it indicates that the charge modulated by gate bias is mobile charge. So it is an indication of modulation 2DEG, not the effect of traps or other artifacts. The charge and percentage of current modulation is shown in figure 3.9. This figure clearly shows the trend of increasing modulation with increasing SrTiO3 thickness. This is a clear verification of our model described in previous chapter. We also measured zero bias relative dielectric constant of SrTiO3 from C-V profile. Here capacitance is the combination of the contribution of both SrTiO3 and interfacial layer. So, calculated relative dielectric constant is the effective relative dielectric constant of the barrier layer. In figure 3.10, effective dielectric constant of barrier is plotted for different SrTiO3 thickness and it can be seen that effective dielectric constant increases with barrier thickness. This result suggests that effect of interfacial layer reduces when SrTiO3 thickness is increased, as suggested by our theory. Figure 3.9: Improvement in charge modulation with increasing SrTiO3 thickness 44 Figure 3.10: Improvement in effective low field SrTiO3 permittivity with increasing SrTiO3 thickness. This trend suggests that effect of interfacial layer is reduced with increasing SrTiO3 thickness To understand how SrTiO3 thickness affects change modulation, previous simple capacitance model is modified incorporating field dependent dielectric constant of SrTiO3 in calculation. In this modified model, we still considered two serial capacitors β CSTO and Cint. As electron of 2DEG is highly confined due to high effective mass of electron in SrTiO3, we ignored 2DEG spreading. Electric Field dependent dielectric constant of SrTiO3 can be given by [77], - 45 ππππ = π΄ βπ΅+πΈπππ 2 β¦ β¦ β¦ β¦ β¦ β¦ β¦ .. (10) We know, capacitance is defined by β πΆπππ = ππ πππππ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦. (11) For 2-dimension sheet charge, electric field and sheet charge density can be related by the following relation β π = ππππ Eπππ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦. (12) So, from (11) and (12) we get, πΆπππ = π(ππππ πΈπππ ) πππΊ = ππππ ππΈπππ πππΊ πππππ + πΈπππ πππΊ β¦ β¦ β¦ β¦ β¦ β¦.(13) But, field in SrTiO3 depends on the voltage drop in SrTiO3 (VSTO) and SrTiO3 layer thickness (tSTO) and the relation between these terms are β ππππ = πΈπππ π‘πππ β¦ β¦ β¦ β¦ β¦ β¦ β¦. (14) Using this relation in (10) we get β ππππ = π΄ π βπ΅+( π‘ πππ )2 β¦ β¦ β¦ β¦ β¦ β¦ β¦ .. (15) πππ So, πππππ πππΊ =β π΄ππππ 2 3 π 2 π‘πππ (π΅+( π‘ πππ ) )2 πππ β¦ β¦ β¦ β¦ β¦ β¦ (16) So, from (10)-(16) we can get capacitance due to SrTiO3 barrier, and that is πΆπππ (ππππ ) = π΄ π‘πππ βπ΅+πΈπππ 2 β π΄ππππ 2 π 2 3 π‘πππ 3 (π΅+( π‘ πππ ) )2 β¦ β¦ β¦ β¦ β¦ β¦.(17) πππ On the other hand, capacitance for interfacial layer is given by β πΆπππ‘ = ππππ‘ π‘πππ‘ β¦ β¦ β¦ β¦ β¦ β¦ β¦ .. (18) 46 From (17) and (18), we can get total gate capacitance using the relation 1 πΆπΊ = 1 πΆπππ + 1 πΆπππ‘ β¦ β¦ β¦ β¦ β¦ β¦ .. (19) We can also calculate the total gate bias using following equation β ππΊ = ππππ + ππππ‘ = π‘πππ πΈπππ + π‘πππ‘ πΈπππ‘ = π‘πππ πΈπππ + π‘πππ‘ π‘πππ‘ ππππ π΄ π‘πππ ππππ‘ βπ΅+πΈπππ 2 ππππ πΈπππ ππππ‘ = ππππ + β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ (20) So, if we vary VSTO, we can get the CG-VG relation for GdTiO3/SrTiO3 heterostructure including interfacial layer effect using equations (17)-(20). To verify our model, we compare our experimental results with this model. We calculate charge modulation for different field and gate bias and then compared it with our results. For our calculation, we assumed the dielectric constant of interfacial layer is 10Ξ΅0 and thickness is 1nm. Modulation for different gate bias and field are shown in figure 3.11 and figure 3.12, respectively. The comparison between model and experimental results is shown in figure 3.12. This figure clearly shows that our model matches quite accurately with experimental data. This result not only verifies our model, but also confirms that charge modulation is limited by interfacial layer. 47 Figure 3.11: Charge modulation versus gate bias for different SrTiO3 thicknesses Figure 3.12: Charge modulation versus electric field in interfacial layer (left). Proposed model is compared with experimental data (right) and it shows good agreement with experimental data 48 3.3 Surface treatment From our previous discussion, it is clear that interfacial layer is one of the main reasons that limit charge modulation in GdTiO3/SrTiO3 FETs. Increasing SrTiO3 layer thickness we can increase charge modulation. But we cannot modulate huge 2DEG electron at GdTiO3/SrTiO3 heterostructure completely just by increasing SrTiO3 thickness. There are three problems with this approach: Firstly, to grow good quality SrTiO3 on top of GdTiO3 by MBE technique, it needs to grow in oxygen deficient condition. It creates oxygen vacancies in SrTiO3 layer and make it n-type doped. Doping is in the order of 1019 cm-3 (will be discussed in next chapter). So if we increase SrTiO3 thickness, it will increase the charge, too. So it will be more difficult to pinch off the device. Moreover, if SrTiO3 is not insulating, then the layer between 2DEG and gate metal will be depleted that will increase the electric field and may cause early breakdown. Secondly, if we can fix the growth issue and make the SrTiO3 layer insulating, in that case it will be difficult to make a good ohmic contact through insulating layer. Finally, from figure 3.12, it is clear that charge modulation trends to be saturated with SrTiO3 thickness. So, even if we increase the SrTiO3 thickness indefinitely, we might not be able to deplete the whole channel. 49 So we need to apply different approach to solve this problem. To minimize the effect of interfacial layer we did a surface treatment that improves charge modulation. For this experiment, we used SrTiO3/GdTiO3 heterostructure with thickness 40 nm and 5nm respectively. Hall measurement shows 2DEG density 3x1014 cm-2. Device structure and Band diagram is shown in figure 3.13. We start our fabrication with usual recipe of ohmic contact deposition and mesa isolation. We used Al/Ni/Au metal stack as ohmic contact that gives ohmic resistance 0.5 Ξ©-mm. After mesa isolation an extensive O2 plasma treatment was done. We used ICP/RIE technique for this treatment. We used 50 sccm O2 with ICP power 300 W and RIE power 100 W. Chamber base pressure was 5 mTorr. We run ran this treatment for 30 min. This extensive treatment cleaned the surface and removed all burnt resist residue created by high power RIE etching for mesa isolation. Moreover, O2 diffusion helped to fill O2 vacancies in SrTiO3 layer that makes the layer more insulating and increased breakdown field. After O2 treatment, we deposited Pt/Au metal stack as gate contact. We also co-processed a same type of sample as reference without O2 surface treatment to compare our results. 50 (a) (b) Figure 3.13: (a) Device structure for surface treatment (b) Band diagram and electron profile of the sample 51 Schottky behavior of these two samples is shown in figure 3.14. From figure it is clear that, Schottky reverse breakdown increases from 10V to around 25V after O2 treatment. So, O2 plasma definitely improving breakdown field β either breakdown field of SrTiO3 or breakdown field of interfacial layer. In either case, it should improve charge modulation. Figure 3.14: Gate leakage characteristic. Gate breakdown voltage increases after surface treatment 52 We measured capacitance-voltage (C-V) characteristics of these two samples and that is shown in figure 3.15. By integrating C-V profile, we calculated charge modulation with and without O2 plasma treatment. Without surface treatment charge modulation is 8.5x1013 cm-2. After surface treatment, it became 1.5x1014 cm-2, almost double. This is the highest charge modulation in any semiconductor system using electronic gating found in literature. Figure 3.15: Capacitance-voltage characteristic with and without surface treatment. Charge modulation increases by around 75% 53 In C-V profile, one interesting point is both C-V curves coincide. It suggests that O2 plasma treatment is not changing the dielectric constant of the interfacial layer, but increasing the breakdown field of either interfacial layer or SrTiO3 layer. We used our model described in previous section to calculate the effect of interfacial layer and we found that dielectric constant of interfacial layer is 10Ξ΅0 (figure 3.16) that is exactly same of that we found previously. So O2 plasma treatment is not changing dielectric constant, but just improving breakdown field. 14 ο₯i ο½ο ο΅ο ο₯ο° -2 Charge modulation (cm ) 2.0x10 ο₯i ο½ο ο±ο°ο ο₯ο° 14 1.5x10 ο₯i ο½ο ο±ο΅ο ο₯ο° 14 1.0x10 Breakdown 13 5.0x10 0.0 0 1 2 3 4 5 6 Average Field (MV/cm) Figure 3.16: Simulation of the charge modulation as a function of the gate bias. Star mark shows the modulation in this experiment. 54 ID-VD profile of both devices is shown in figure 3.17. Current levels of both devices are same, but we achieved more current modulation (50%) in device with surface treatment. The reason of this high modulation is the high breakdown field of gate that allows us to apply more gate bias. 50% current modulation is consistent with our C-V measurement (1.5x1014 cm-2 electron modulation). In figure 3.18, transconductance (Gm) profile is shown for device with O2 plasma treatment. We measured peak gm 5mS/mm that is highest for GdTiO3/SrTiO3 HFETs. (a) (b) Figure 3.17: ID-VD characteristics for 40nm SrTiO3/5nm GdTiO3 HFET: (a) with and (b) without surface treatment. Gate length is 1ΞΌm, Source to drain spacing is 3.5ΞΌm and source to gate separation is 0.5ΞΌm. 55 Figure 3.18: Transconductance characteristics for 40nm SrTiO3/5nm GdTiO3 HFET. Drain voltage was 5V. Highest transconductance is 5mS/mm. Gate length is 1ΞΌm, Source to drain spacing is 3.5ΞΌm and source to gate separation is 0.5ΞΌm One of the interesting facts of figure 3.14 and 3.15 is the gate breakdown voltage β that is around 23V. This voltage drops in between gate contact and 2DEG, and this distance is around 40nm. So from this result it is clear that average field in SrTiO3 layer is 5.6MV/cm that is much higher than expected value. We know traditional semiconductor follows βsquare lawβ for breakdown field. According to βsquare lawβ, breakdown field is proportional to the square of bandgap (EBR β Eg2). As bandgap of SrTiO3 is 3.25eV, 56 close to bandgaps of SiC and GaN, we expect similar breakdown field for SrTiO3 that is around 2MV/cm. But as average field in SrTiO3 is 5.6MV/cm, SrTiO3 should have breakdown field at least 5.6MV/cm. But we are still not sure about the reason of breakdown of gate. It could be due to SrTiO3 breakdown or interfacial layer breakdown. If it is because of interfacial layer, in that case breakdown could be higher. Figure 3.19: Triangular barrier at the gate To understand the reason of high breakdown field of SrTiO3, we did simple calculation. We did our calculation assuming band-to-band tunneling for Zener breakdown. For bandto-band tunneling, tunneling barrier is triangular (shown in figure 3.19) and we can use Fowler-Nordheim tunneling approximation: 3 4β2πβ πΈ2 π π = πβ 3ππΈΔ§ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ .. (21) 57 Here, m* is the effective mass of electron, Eg is the bandgap, E is the applied electric field, e is the charge of an electron and Δ§ is Planck constant. If we compare two materials assuming that breakdown happens at same tunneling probability, we can relate the breakdown field of those two materials using following equation: πΈπ΅π 1 = πΈπ΅π 2 β π1β πΈπ1 β π12 (πΈ ) 3/2 π2 β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ .. (22) In most of the semiconductor m*βEg1/2, so EBRβEg2 and this is the origin of square law. But because of the presence of transition metal (Ti), SrTiO3 has mobile electron contributed by d-orbital. So SrTiO3 has a very high effective mass of electron. For GaN, bandgap is 3.4 eV with electron effective mass 0.2m0. On the other hand, SrTiO3 has effective mass around 2m0 with bandgap 3.25eV. If we plug these values in (22) and assume GaN breakdown field 2MV/cm, we found breakdown field 5.8MV/cm for SrTiO3 that is consistent with our experimental finding. We calculated band to band tunneling for different materials (Si, GaN, SiC, SrTiO3) and that is shown in figure 3.20. Taking Si breakdown field as reference we calculated the breakdown field of these materials. Calculation confirms that breakdown field of SrTiO3 does not follow βsquare lawβ (shown in figure 3.21). Our calculated result is very consistent with experimental result that is shown in following table: 58 Calculation Experimental value [78] Si 0.3 MV/cm 0.3 MV/cm GaN 2.2 MV/cm 2 MV/cm SiC 2.4 MV/cm 2.2 MV/cm SrTiO3 5.9 MV/cm 5.6 MV/cm Table 2: Calculated and experimental breakdown field of different materials So, from the discussion above, it is clear that SrTiO3 has a very high breakdown field because of high effective mass of electron. This could be a very important feature for power electronics. We will discuss this later in next chapter. 10 Tunneling Probability 10 STO Si GaN SiC Breakdown 0 10 -10 10 2.2MV/cm -20 0.4MV/cm 5.9MV/cm 2.4MV/cm 10 0 1 2 3 4 Field (MV/cm) 5 6 Figure 3.20: Breakdown field calculation for different material 59 7 Figure 3.21: Comparison of breakdown field of different materials. 3.4 High k dielectric As we discussed earlier, another approach to improve charge modulation is to improve effective dielectric constant of SrTiO3 barrier layer. But SrTiO3 itself has a very high dielectric constant - 350Ξ΅0 at low electric field and 25Ξ΅0 at very high electric field (6MV/cm). So traditional gate dielectric material will not be a good choice for gate dielectric material here. For example, Al2O3 has dielectric constant of 9Ξ΅0 and HfO2 has dielectric constant of 24Ξ΅0. Moreover, these materials are deposited using Atomic Layer Deposition (ALD), Low Pressure Chemical Vapor Deposition (LPCVD) or sputtering 60 method. These processes may create fixed charge or traps at the interface. So we need a material that has a very high dielectric constant and can be grown by MBE. Ba0.5Sr0.5TiO3 (BST) is such a material that has dielectric constant over 1000Ξ΅0 and lattice parameter is close to that of SrTiO3. So it can be grown in MBE. For this experiment, we used BaSrTiO3/SrTiO3/GdTiO3 sample with thickness 15nm, 20nm and 5nm respectively. Hall measurement shows 2DEG density 2x1014 cm-2. The device structure is shown in figure 3.22. Figure 3.22: Device structure with high-k dielectric (Ba0.5Sr0.5TiO3) 61 As there is an insulating layer on top of SrTiO3 layer (BaSrTiO3 layer), we need to optimize the ohmic contact. At first, we deposited ohmic metal (Al/Ni/Au) without etching BaSrTiO3 layer away. As BaSrTiO3 is insulating, it did not give good ohmic contact and there is little nonlinearity in the I-V characteristics. I-V characteristic is shown in figure 3.23. Figure 3.23: Transfer length measurement (TLM) I-V characteristic for Al/Ni/Au ohmic contact. No etching and BOE dip before metal deposition 62 Then, we etched the sample for 8min using Chlorine based recipe discussed in previous chapter, before depositing ohmic contact. Still there is nonlinearity as seen in figure 3.24. Surface roughness due to high power etching could be a reason of this non linearity in IV characteristics. Figure 3.24: Transfer length measurement (TLM) I-V characteristic for Al/Ni/Au ohmic contact. 8 min etch etching and no BOE dip before metal deposition 63 Finally, we etched the sample for 10min and dipped the sample for 10s in Buffer Oxide Etchant (BOE) just before depositing ohmic metal. Finally we got good ohmic behavior in I-V characteristic that is shown in figure 3.25. Then we continued our usual processing steps. Process flow diagram of complete fabrication is shown in figure 3.26. Figure 3.25: Transfer length measurement (TLM) I-V characteristic for Al/Ni/Au ohmic contact. 10 min etching and 10s BOE dip before metal deposition 64 Figure 3.26: Process flow for sample with high-k barrier layer 65 BaSrTiO3 is helping this modulation in two ways β Firstly, it is increasing capacitance. So we can get higher charge modulation. Secondly, Because of the low field in the BaSrTiO3, high-k layer helps to reduce gate leakage. So we can apply high gate bias and get high charge modulation. Schematic diagrams of conduction band are shown in figure 3.27. Without BaSrTiO3 layer, gate barrier is triangular. When there is BaSrTiO3 layer, because of high dielectric constant of BaSrTiO3, field is lower in this layer to satisfy boundary condition. So, in this case barrier is combination of trapezoidal barrier followed by triangular barrier. By simple calculation, we can compute the gate leakage probability for both cases. Figure 3.27: Gate barrier for (a) SrTiO3/GdTiO3 and (b) BaSrTiO3/ SrTiO3/GdTiO3 structures 66 When there is no high-k layer, tunneling probability can be calculated by FowlerNordheim tunneling approximation: ππΉπ = π 3 4β2πβ π2 π β 3ππΈ πππ Δ§ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ .. (23) Here, ΟB = barrier height of Schottky contact and ESTO is the field in the SrTiO3 layer. When there is a high-k layer, tunneling happens in two steps. First there is a direct tunneling through trapezoidal barrier and that can be expressed as: 3 3 2) 4β2πβ (π2 βπ 1 2 ππ· = π β 3ππΈπ΅ππ Δ§ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ .. (24) Then there is a Fowler-Nordheim tunneling through triangular barrier that can be expressed as: ππΉπ = π 3 4β2πβ π2 2 β 3ππΈπππ Δ§ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ .. (25) Here, ESTO and EBST are the electric field in SrTiO3 and BaSrTiO3 layer respectively. Here Ο1= ΟB = barrier height of Schottky contact and Ο2= ΟB-q x EBST x tBST , where tBST is the thickness of the BaSrTiO3 layer. 67 So we can calculate total tunneling probability combining Fowler-Nordheim and Direct tunneling. The result is shown in figure 3.28, where we compared tunneling probability for different BaSrTiO3 thickness. It is obvious that BaSrTiO3 layer improves gate leakage and device with thick cap layer has lower gate leakage. Figure 3.28: Tunneling probability of electron at gate barrier at different applied electric field. Gate leakage can be reduced by using thicker BaSrTiO3 layer 68 This observation can also be verified from experimental results. In figure 3.29, we compared the gate leakage of two device β device with high-k layer and device without any high-k layer. For both devices cap thickness is 35nm, but in one device complete cap is SrTiO3 and in another one there is 15nm of BaSrTiO3. But from figure it is clear that, sample with BaSrTiO3 shows low gate leakage. BaSrTiO3 is reducing gate leakage as we expected from our simple calculation. Figure 3.29: Gate leakage characteristics for sample with and without BaSrTiO3 layer 69 Capacitance-Voltage (C-V) characteristics are shown for these two devices in figure 3.30. BaSrTiO3 layer boosts the capacitance. Zero bias capacitance is almost double for high-k device compared to GdTiO3/SrTiO3 HFET, though both devices have same cap thickness. This high capacitance is due to high dielectric constant of BaSrTiO3. From C-V profile, total charge modulation is 1.4x1014 cm-2. If we compare this results with our thickness series study described earlier, this modulation is almost 40% higher than conventional GdTiO3/SrTiO3 structure. The comparison is shown in figure 3.31. Figure 3.30: Capacitance voltage characteristics. Charge modulation increased from 7.5x1013 cm-2 to 1.4x1014 cm-2 after using BaSrTiO3 layer 70 Figure 3.31: Charge modulation for different barrier thickness. BaSrTiO3 layer shows a boost in charge modulation. ID-VD characteristic is shown in figure 3.32. From figure we can see 65% modulation in current that corresponds to 1.4x1014 cm-2 charge modulation. In figure 3.33, gm profile is shown. 71 Figure 3.32: ID-VD profile of BaSrTiO3/SrTiO3/GdTiO3 transistor. Gate voltage is varied from 0V to -10V. Total current modulation is 65%. Gate length is 1ΞΌm, Source to drain spacing is 3.5ΞΌm and source to gate separation is 0.5ΞΌm 72 Figure 3.33: gm profile of BaSrTiO3/SrTiO3/GdTiO3 transistor. Drain bias is 5V. Gate length is 1ΞΌm, Source to drain spacing is 3.5ΞΌm and source to gate separation is 0.5ΞΌm 73 Chapter 4: Perovskite oxide MESFET and FerroFET In last two chapters, I discussed GdTiO3/SrTiO3 HFETs. In this chapter, I will introduce two new device structures β MESFETs and FerroFETs. Because of very high 2DEG density, it was difficult to pinch off transistor. So it was not possible to evaluate device and material performance. But it is possible to pinch off MESFET easily. So, it is possible to compare SrTiO3 with other materials for high power applications. Moreover Ferroelectric gate material acts both as high-k gate dielectric and polarization switched material. So we can observe higher modulation with hysteresis. 4.1 SrTiO3 MESFET As we discussed in previous chapter, SrTiO3 has a very high breakdown field. This huge breakdown field can be exploited for power electronics. But in traditional GdTiO3/SrTiO3 FET, it is very difficult to pinch off the device. As the origin of this 2DEG is electronic reconstruction of the interface, it is very difficult to lower 2DEG charge density. So in this chapter we will discuss about SrTiO3 Metal Semiconductor Field Effect Transistor (MESFET). For our study, we used sample of 100nm SrTiO3 grown on LSAT by MBE method (figure 4.1). This sample was grown in oxygen deficient condition that creates oxygen 74 vacancies and made the SrTiO3 layer n-type. Doping density of the sample was in the order of 1019 cm-3. We processed this sample following the procedure described in chapter 2. Gate leakage characteristic of MESFET is shown in figure 4.2. Gate current of MESFET is also compared with conventional HFET with same SrTiO3 thickness. From this figure it is very clear that gate leakage in MESFET is very low. Internal field due to 2DEG might increase gate leakage in HFETs. Figure 4.1: MESFET device structure 75 Figure 4.2: Gate leakage characteristic of HFET and MESFET with similar SrTiO3 thickness Current reduces significantly after depositing gate. It is because of the depletion of SrTiO3 layer by barrier height potential. ID-VD characteristic of transistor is shown in figure 4.3. This figure shows clear pinch off in the device. Pinch off voltage is -3.5V. In figure 4.4, ID-VG and Gm profiles are shown. 76 Figure 4.3: ID-VD profile of SrTiO3 MESFET. Gate voltage is varied from 0V to -4V. Gate length is 1ΞΌm, Source to drain spacing is 3.5ΞΌm and source to gate separation is 0.5ΞΌm 77 Figure 4.4: gm profile of SrTiO3 MESFET and SrTiO3/GdTiO3 HFET with same SrTiO3 thickness. Drain voltage is 5V. Gate length is 1ΞΌm, Source to drain spacing is 3.5ΞΌm and source to gate separation is 0.5ΞΌm Capacitance voltage characteristic is shown in figure 4.5. SrTiO3 has field dependent dielectric constant of form [77]: π(πΈ) = π΄π0 βπ΅+πΈ 2 β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦. (1) 78 For this type of material, capacitance can be expressed as [77]: 1 πΆ2 = 2βπ΅ (πππ π΄π0 πππ· β π) + 1 π΄2 π02 (πππ β π)2 β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ .. (2) In figure 4.6, 1/C2 vs. VG is plotted. From the fitting of this curve we can get Vbi, ND, A and B. From fitting we got ND=1019 cm-3, Vbi = 1.5V, A = 7.7938x107 and B = 1.4594x1011. In the following table these value are compared with literature. This work Literature [77] A 7.7938x107 1.42x108 B 1.4594x1011 1.64x1011 Table 3: Constants of field dependent permittivity As we know A and B from our experiment, we can plot field dependent dielectric constant for SrTiO3. The profile is shown in figure 4.7 and we also compared it with literature. Our result is lower than that of described in literature. This could be due to low dielectric constant interfacial layer. 79 Figure 4.5: Capacitance-Voltage characteristics of SrTiO3 MESFET 80 Figure 4.6: 1/C2 versus gate voltage Figure 4.7: Field dependent dielectric constant of SrTiO3. Red line (this work) and black line [77] 81 To evaluate the prospect of SrTiO3 for high power application, we calculated Baliga Figure of Merits (BFM) and Baliga High Frequency Figure of Merits (BHFFM). BFM describes the resistive loss of the device and BHFFM describes switching loss. BFM and BHFFM can be given by [79] β 3 π΅πΉπ = πππΈπ΅π β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ (3) 3 π΅π»πΉπΉπ = ππΈπ΅π β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ β¦ (4) To compare SrTiO3 as power electronics material, basic parameters of other conventional materials are tabulated in the following table. Si Eg (eV) 1.12 GaN (Bulk) [78] 3.4 GaN [78] 3.4 (epi) 4H-SiC [78] SrTiO3 (this work) 3.26 3.25 Eps_r 11.9 9 9 10.1 24 (at 5.6 MV/cm) Kth (W/K.m) 150 230 130 490 11 FBR (MV/cm) 0.3 3.3 2 2.2 5.6 Vsat (107 1 cm/s) Mobility 1350 (cm2/V-s) 3 3 2 0.03 1150 1150 900 10 BFM 1 850 190 223 97 BHFFM 1 98 36 45 48 Table 4: Baliga Figure of Merits (BFOM) for different materials 82 Based on the parameters we calculated BFM and BHFFM and those are shown in figure 4.8. This figure shows that figure of merits of SrTiO3 is already comparable to traditional material. Moreover, we underestimate the parameters to calculate figure of merits of SrTiO3. For example, we used break down field 5.6MV/cm. But it could be higher as we discussed before. Moreover we used dielectric constant 25Ξ΅0. This value is for very high field. For Ron, gate bias is zero and drain bias is also low, so dielectric constant is very high during Ron. So we need better theory that can describe BFM for field dependent dielectric constant materials and BFM will of course increase in that case. Figure 4.8: BFOM and BHFFM of different materials 4.2 Ferroeletric FET In ferroelectric material spontaneous polarization can be switched using a critical field. Electric field versus polarization shows hysteresis loop below Curie temperature (fig. 83 4.9). Single crystal material shows higher hysteresis. This material could be used for many applications, such as ferroelectric memory devices, Electro optic devices, ferroelectric waveguides etc. S. Salahuddin et al. [16] predicted that ferroelectric material could be used as gate dielectric material in FET to get differential negative capacitance. This negative differential capacitance can be used to lower subthreshold swing below 60mV/decade. Recently A.I. Khan et al. [17] demonstrated first experimental evidence of negative differential capacitance. Figure 4.9: Hysteresis loop of ferroelectric materials [80] To understand the effect of ferroelectric gate material, we simulated a HFET structure in Silvaco. For simulation we used frictions material as channel, as field dependent 84 dielectric constant of SrTiO3 cannot be incorporated in Silvaco. The device structure of simulation is shown in figure 4.10 (a). ID-VG profile of this device is shown in figure 4.10 (b). From this figure, we can see that threshold voltage is shifted while sweeping gate bias in reverse direction. This shift in threshold voltage is because of polarization switch in ferroelectric material due to gate bias. Figure 4.10: (a) Simulated device structure (b) ID-VG characteristics of simulated transistors. There is a shift in threshold voltage because of polarization inversion To study the effect of ferroelectric gate, we use BaTiO3 as gate dielectric material. BaTiO3 has a very high dielectric constant (over 1000Ξ΅0). It has critical field of 150 kV/cm and spontaneous polarization of 15ΞΌC/cm2 [81]. But it can vary for thin film. 85 Device structure of this experiment is shown in figure 4.11 (a). We used 15nm BaTiO3/5nm SrTiO3/5nm SmTiO3 grown on LSAT substrate for this experiment. SmTiO3 and GdTiO3 are electrically similar material and for this case we can consider these two materials equal. Hall measurement shows 2DEG charge density of 2.2x1014 cm2 . Band diagram of the device is shown in figure 4.11 (b). In this figure, effect of ferroelectricity on band diagram is also shown. Figure 4.11: (a) Device structure of FerroFET (b) Effect of ferroelectricity on band diagram We used the process flow for device fabrication as described in figure 3.26. We used Al/Ni/Au as ohmic contact and contact resistance is 8.1 Ξ©-mm. Contact resistance is much higher as the surface is rough because of high power etching just before ohmic metal deposition. Figure 4.12 is showing the Schottky behavior of the device. It shows around 4 order rectification up to -7V. 86 Figure 4.12: Schottky diode characteristic of FerroFET In figure 4.13, capacitance-voltage characteristic is shown. Zero bias capacitance is very high ~ 9 ΞΌF/cm2. From C-V profile, Total charge modulation is 1.8x1014 cm-2 that is highest for any material system till reported. 87 Figure 4.13: Capacitance-Voltage profile. Charge modulation in 1.8x1014 cm-2 In figure 4.14, ID-VD characteristic is shown. This figure shows 70% modulation in current. ID-VG and gm profile is shown in figure 4.15. 88 Figure 4.14: ID-VD profile of SrTiO3 MESFET. Gate voltage is varied from 0V to -5V. Gate length is 1ΞΌm, Source to drain spacing is 3.5ΞΌm and source to gate separation is Figure 4.15: ID-VG and Gm profile of SrTiO3 MESFET. Drain voltage is 5V. Gate length is 1ΞΌm, Source to drain spacing is 3.5ΞΌm. 89 As we are using ferroelectric gate, we are expecting hysteresis in C-V or ID-VG profile. We observed a hysteresis when we measured C-V in both directions. It is shown in figure 4.16 (a). We also observed hysteresis in ID-VG profile. It is shown in figure 4.16 (b). As we could not pinch off the device, we could not observe the effect of ferroelectric gate on threshold voltage and subthreshold swing. Figure 4.16: (a) Hysteresis in C-V profile (b) Hysteresis in ID-VG profile 90 Chapter 5: Summary and Future Work In this work, for the first time GdTiO3/SrTiO3 HFET is demonstrated. A whole process recipe is developed to fabricate this transistor. In this work, we found that interfacial layer limits the charge modulation in such type of high electron density heterostructure. We developed an analytical model to understand the effect of interfacial layer. We demonstrated three mechanisms that can improve charge modulation. We observed charge modulation up to 1.3x1014 cm-2 that is highest for any material system. We also found that high breakdown field of SrTiO3 makes it a suitable candidate for power electronics. We also reported the effect of ferroelectric gate on GdTiO3/SrTiO3 HFET. We observed hysteresis in C-V and I-V profiles because of ferroelectric gate. This work could be interesting for oxide based high power electronics. Moreover, this high charge modulation technique could be used for Mott transition based transistors that can allow subthreshold swing below 60mV/dec. Moreover, ferroelectric gate can introduce negative differential capacitance that can be useful for low power electronics. This high modulation could be integrated with microwave circuit for tunable plasmonic waveguide. 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