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Erbium Doped Silicon As an Optoelectronic Semiconductor Material by Yong-Gang Frank Ren B.S

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Erbium Doped Silicon As an Optoelectronic Semiconductor Material by Yong-Gang Frank Ren B.S ? Erbium Doped Silicon as an Optoelectronic Semiconductor Material by Yong-Gang Frank Ren B.S. Materials Science, Beijing University of Aeronautics, 1985 M.S. Physics, University of Nebraska-Lincoln, 1989 MBA, MIT Sloan School of Management, 1994 Submitted to the Department of Materials Science and Engineering in partial fulfillment of the requirements for the degree of DOCTOR of PHILOSOPHY in Electronic Materials at the Massachusetts Institute of Technology May 1994 © Massachusetts Institute of Technology 1994. All rights reserved. Signature of Author ...... .... ...... '..V. Department of Materials Science and Engineering April 29, 1994 Certified by..' 1 Lionel C. Kimerling Professor Thesis Supervisor Acceptedby... Carl V. Thompson II Professor of Electronic Materials Chair, Departmental Committee on Graduate Students A '1,"' .. .1.. '4 AU 18 1994 iSence Erbium Doped Silicon as an Optoelectronic Semiconductor Material by Yong-Gang Frank Ren Submitted to the Department of Materials Science and Engineering on April 29, 1994, in partial fulfillment of the requirements for the degree of DOCTOR of PHILOSOPHY in Electronic Materials Abstract In this thesis, the materials aspects of erbium-doped silicon (Si:Er) are studied to maximize Si:Er luminescence intensity and to improve Si:Er performance as an opto- electronic semiconductor material. Studies of erbium (Er) and silicon (Si) reactivity, erbium diffusion and solubility in silicon, Si:Er heat treatment processing with oxy- gen and fluorine co-implantation and the mechanism of Si:Er light emission have been carried out to define optimum processing conditions and to understand the nature of optically active centers in Si:Er. In the erbium and silicon reactivity studies, a ternary phase diagram of Er-Si-O was determined. ErSi 2_x(X = .3) was found to be the most stable erbium silicide formed on single crystal silicon, and it could be oxi- dized in the presence of oxygen (02). These findings confirm the results that erbium precipitates as ErSi2_(x = .3) in silicon and erbium clusters with oxygen to form complexes in Si:Er with oxygen co-implantation. Luminescence studies on various erbium compounds established a unique spectrum for Si:Er, which can be used to fingerprint products of Si:Er processing. The diffusivity and solubility of Er in Si are determined based on the analysis of changes in implanted Er SIMS profiles of Si:Er after high temperature annealing (1150 - 13000C). Er is a slow diffuser with moderate solubility in Si. The diffusivity of Er in Si D(Er) is 5 x 10- 11cm 2 /s at 1200°C with a migration energy of - 4.6eV, at a rate similar to Ge in Si. The equilibrium solid solubility of Er in Si [Er], is , 10l1 6atoms/cm 3 between 1150 - 13000C, similar to S in Si. The low Er diffusivity in Si enables metastable concentrations of Er to be incorporated into Si at levels far exceeding the equilibrium solid solubility of 10 16 atoms/cm 3. Furthermore, the low diffusivity and high oxidation tendency make Si:Er process compatible with existing Si fablines, since cross contamination during heat treatment is minimized. Post-implantation annealing and ligand enhancement are essential to achieve lu- minescence in Si:Er. The heat treatment process of Si:Er and the impact of oxygen (O) and fluorine (F) ligands have been studied. The Si:Er heat treatment process is determined by three internal processes in Si:Er: (1) implantation damage anneal; (2) ligand impurity outdiffusion; and (3) formation and dissociation of optically active Er-ligand complexes. Fluorine is found to be 100 times more effective than oxygen in enhancing luminescence intensity in Si:Er under the similar processing conditions. In Si:Er co-doped with F, Er-F associates, most likely ErF3 , are the optically active center, responsible for the light emission. A process model has been constructed to simulate the physical processes occurring in Si:Er during the heat treatment. The simulation includes the processes of the complexes formation and dissociation, and the ligand outdiffusion and exhibits their limiting role in determining the lumines- cence intensity. The optimum heat treatment condition to achieve maximum light emission in Si:Er is constrained by the process of implantation damage anneal. Light emission studies at different measurement temperatures show the presence of the thermal quenching of Si:Er luminescence: a sharp decrease of luminescence intensity at measurement temperatures above 200K. An energy back transfer process of non-radiative de-excitation of Er3 + excited states to Si lattice is proposed as the most likely mechanism in Si:Er. Si:Er is demonstrated as a potential optoelectronic semiconductor material, com- patible with current Si technology. The Si:Er light emission intensity can be increased by maximizing metastable Er-ligand complexes in Si:Er through optimizing process- ing conditions. The optimal process of high performance Si:Er photonic devices can be achieved by controlling the metastable kinetics of Si:Er. Thesis Supervisor: Lionel C. Kimerling Title: Professor Acknowledgments I would like to thank my advisor Professor L.C. Kimerling for his insights and guidance on directing my thesis research and as a personal role model for hardworking and effective communication. I feel very fortunate to have been his first Ph.D student at MIT. I would also like to thank other members of my thesis committee Professors Tuller and Bawendi for their advise and support. I am indebted to Dr. Jurgen Michel for many discussions about the project. His friendship and his help on photoluminescence measurements were most appreciated. I am also grateful to Visiting Professor Hajime Kitagawa from Fukuoka Institute of Technology, Japan, who worked with me at the early stage of this project when we were setting up the lab. A special thank to Professor Scott Dunham at Boston University, who had helped me to start on the Si:Er process simulation and generously provide free access to the PEPPER and PROFILE software. I want to acknowledge Dr. Dale Jacobson and Dr. John Poate at AT&T Bell Laboratory for supplying the implanted materials. Many other people at MIT had helped me throughout the course of this thesis research. In particular, I want to thank John Martin at the MIT Surface Analytical Lab, who helped me in performing SIMS measurements. I would also like to acknowl- edge the past and present members of our Silicon Microphotonics research group whom I have worked with over the years: Visiting Scientist Dr. Irene Yassievich, Dr. Qing Sun-Paduano, Bo Zheng, Lynn McDonough, Michael Morse, Jim Foresi, Laura Giovane, Debra Koker and Fanqi Gan. I wish Laura good luck in continuing the project. I dedicate this thesis to my father. The memory of him is a constant inspiration in my life. Contents 1 Motivation 13 1.1 Optoelectronic Technology. 15 ].2 Erbium-Doped Silicon .......................... 16 ].3 Materials Requirements for Si:Er Photonic Devices .......... 18 2 Literature Review 22 2.1 Fundamentals of Erbium-Doped Silicon 22 2.2 Erbium--Doped Silicon as an Optoelectronic Semiconductor Material 25 2.2.1 Metallurgical Properties ...... 25 2.2.2 Electrical Characteristics. 31 2.2.3 Optical Characteristics ....... 35 3 Erbium and Silicon Reactivity 39 3.1 Introduction. 39 3.2 Experiment ................. 39 3.3 Results and Discussion ........... 40 3.4 Conclusion. ................. 49 4 Er Diffusion and Solubility in Silicon 50 4.1 Introduction. 50 4.2 Experiment. 51 4.3 Results and Discussion ........... 52 4.4Conclusion .......... ... 59 5 5 Optical Activity of Erbium-Doped Silicon 60 5.1 Introduction . 60 5.2 Experiment ................. 62 5.3 Si:Er with Oxygen Co-implantation . 62 5.4 Si:Er with F Co-implantation ....... 67 5.5 Si:Er Process Simulation .......... 79 5.5.1 Si:Er Process Model ........ 80 5.5.2 Results and Discussion ....... .. 83 6 Light Emission Mechanism in Si:Er 89 6.1 Thermal Quenching in Si:Er ........ 90 6.2 Energy Back Transfer Mechanism ..... 93 7 Summary and Recommended Future Work 100 ,. 1 Summary. ........... .100 17.2 Recommendations for Future Work .... 103 A Computer Simulation Program for Erbium Diffusion and Precipita- tion in Silicon 106 EB Erbium-Doped Silicon Process Simulation 109 6 List of Figures 1-1 Schematic cross section of a Si:Er surface emitting LED. ....... 17 1-2 Schematic design of a Si:Er edge emitting LED integrated with a silicon waveguide on a silicon-on-insulator substrate. ............. 18 2-1 Er3 + 4f states splitting in a crystal field ................. 23 2-2 Er-Si binary phase diagram. The figure is taken from [21]. ...... 26 2-3 Annealing temperature dependence of the Er PL intensity for Fz and Cz Si. The annealing time was 30 min. The filled data points are from Fz samples with additional oxygen implantation (1 x 1018cm-3 ). The figure is taken from [6] .......................... 29 2-4 Schematic pictures of the first coordination shell surrounding Er in Fz-Si(a) and Cz-Si(b). The figure is reproduced from [51]. ...... 30 2-5 Excess mobile carrier concentration vs implanted Er concentration. All samples are Er doped Cz p-type silicon. The figure is taken from [38]. 32 2-6 SIMS profile of Er(-) in Si:Er. Er was implanted at 5 MeV. The spreading resistance electrical profiles of this Er implant in Fz Si(A), Cz Si(*) and O-doped Si(o) are also reported. The O SIMS profile in this last sample is also shown(-). The figure is taken from [7] ..... 33 2-7 Temperature dependence of the Er luminescence in Cz Si. The Er peak concentration was 1 x 1018 cm-3 . The filled cycles show the PL intensity of the surface passivated sample which showed RT PL. The figure is take from [6]. .......................... 37 7 3-1 X-ray diffraction phase identification of Er 3Si 5, Er 203 and ErN, formed by reacting Er/Si in vacuum, 02 and N2.
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