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Investigation on InSb Epitaxial Growth and Surface Passivation to Improve Device Performances : 적외선 검출소자 특성향상을 위한 InSb 성장 및 표면 보호막에 대한 연구

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dc.contributor.advisor윤의준-
dc.contributor.author박세훈-
dc.date.accessioned2017-07-13T05:49:50Z-
dc.date.available2017-07-13T05:49:50Z-
dc.date.issued2016-02-
dc.identifier.other000000132464-
dc.identifier.urihttps://hdl.handle.net/10371/118054-
dc.description학위논문 (박사)-- 서울대학교 대학원 : 공과대학 재료공학부, 2016. 2. 윤의준.-
dc.description.abstractPhotodetectors (PDs) detecting mid-wavelength infrared (MWIR) region has been developed for the military applications for the first time by some developed countries, these days they have been widely used in the field of industry, medical and astronomy. Hence the market of IR PDs has been expanded significantly. However, the fabrication technology of IR PDs was selected as a key technology for military application, exportation to abroad or other countries are strictly restricted. On the other hand, the fabrication technology of IR PDs in Korea is positioned at low level to study fundamental technologies hence huge gap are existed.

Indium antimonide (InSb) is one of the suitable materials for MWIR detection due to the band gap of 0.23 eV at 77 K and its high electron mobility. To fabricate IR PDs, diffusion or ion-implantation of p-type dopant into n-type InSb substrate were generally adopted. However, these methods produced the surface defects, acting as the trap centers. Hence, device performances can be degraded due to the leakage current. In order to improve device performances, epitaxial growth of InSb was conducted. Unlike to other As, P and N related material growth, it has lots of difficulties in the epitaxial growth of InSb. Even though there are lots of difficulties, in this thesis, InSb epitaxial layers were grown by low pressure metalorganic chemical vapor deposition to obtain high quality of InSb epitaxial layers and its morphological, structural, electrical and optical properties was systematically investigated. For the device application, surface passivations for InSb were thoroughly investigated using ZnS films.

First prerequisites to growth high quality of InSb epitaxial layers was how to prepare the substrate for the epitaxial growth, called the preparation of epi-ready substrate. Although the preparation of well prepared substrate is very important process, it was not easy due to the low vapor pressure of Sb and no hydride precursors of Sb. Due to the these facts, thermal cleaning without Sb overpressure was reported. I noticed, however, that Sb overpressure during thermal cleaning process is necessary process in order to suppress undesirable byproducts. The thermal cleaning under H2 ambient produces the In droplets surrounded by rectangular etch pits on InSb surface due to the selectively evaporation of Sb. Because, Sb has a much higher vapor pressure than that of In. The formation of rectangular etch pits were reflected by the etching characteristics of zincblende structures. This preparation method of substrates found to influence on the crystal quality of InSb epitaxial layers.

In order to growth high quality of InSb epitaxial layers, growth parameters i.e., V/III ratio and growth temperature, were varied to find optimized growth conditions and its morphological, structural, electrical and optical properties were investigated. Optimized growth condition in this thesis found to be a growth temperature of 490 oC under V/III ratio of 8.8. With decreasing V/III ratio at low growth temperature such as 450 and 470 oC, In droplets were formed on the surface due to the insufficient supply of Sb. They were removed with increasing V/III ratio. At low V/III ratio at higher temperature of 490 or 510 oC, the formation of In droplets were prohibited due to the sufficient Sb supply, implying that TMSb was not fully decomposed in the investigated growth temperature ranges. Based on the growth behaviors of InSb, InSb growth rate was controlled by the surface reaction kinetics, called kinetically limited. It was dependent on the TMIn mole fraction but independent on the TMSb mole fraction. These growth behaviors represented that TMIn was also not fully decomposed in this growth temperature regions.
From the optical properties analysis, two dominant phenomena were observed. Growth parameters influenced on the optical quality of InSb epilayers. When the InSb were grown at non-stoichiometric growth condition, indium interstitial defects were incorporated into InSb epitaxial layers, affecting the reduction of band gap energy. Second, the origin of new PL emission, which has not been reported yet, was investigated. It was originated from the carbon due to the uncomplete decomposition of metaloranic precursors.

Properties of ZnS were studied for the InSb surface passivation material. Until now, SiO2 passivation material has been widely used but it showed degradation during the deposition or after deposition at the interface regions. In order to overcome these problems, new material was studied. After deposition of ZnS, interface properties showed the similar quality with interface trap density of 2 x 1011 cm-2eV-1 compared to SiO2. It was found that surface leakage currents were reduced by depositing slightly non-stoichiometric ZnS films due to the charge compensation effects. It produces the flat-band voltage conditions, restricting the formation of surface leakage current paths.

The effectiveness of ZnS passivation deposited under optimized condition was investigated. The dark current of the sample passivated ZnS films were more than one order of magnitude reduction compared to the unpassivated sample. By comparing the sample passivated SiO2, it was also much effective way to reduce surface leakage current. Differential resistance area product at zero bias (RoA) was extracted from the current-voltage measurement. It shows that 1.6 x 104 Ω cm2 was obtained from the ZnS passivated InSb devices. It was decreased to 2 x 103 Ω cm2 and 31 Ω cm2 when the SiO2 and unpassivated films were deposited, respectively. The reduction of surface leakage current also influence on the spectral response, responsivity and detectivity. All devices show the spectral response in the wavelength range between 1 to 5.5 m where maximum intensities were observed near 5.5 m. However, the strong intensity of spectral response when ZnS deposited was observed and it was decreased when SiO2 and unppassivated films were deposited. In case of ZnS deposition sample, spectral response was even observed near 220 K, implying that crystal quality was very high. From the responsivity and detectivity measurements at 77 K, maximum intensity of responsivity was observed near 5.18 m. The corresponding detectivity show the strong intensity when ZnS films were deposited but it was reduced when InSb surface were not passivated.
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dc.description.tableofcontentsChapter 1. Introduction 1
1.1. Infrared fundamentals 1
1.1.1. Infrared history 1
1.1.2. Infrared radiation 3
1.1.3. Infrared sources 4
1.1.4. Concept of blackbody radiation 4
1.1.5. Radiation transmission window at atmospheic ambient 8
1.1.6. Selection of IR wavelength 9
1.2. Photo-detection principle and materials for MWIR detection 12
1.2.1. Operating principle of photodiodes 12
1.2.2. Application fields of IR photodiodes 13
1.2.3. Materials for MWIR photodetection 17
1.3. A survey of previous researches for InSb MWIR photodiodes 23
1.3.1. Previous research of MWIR photodiodes fabricated by diffusion and ion implantation 23
1.3.2. Previous research of MWIR photodiodes fabricated by crystal growth techniques 24
1.4. Organization of this thesis 32
1.5. Bibliography 34

Chapter 2. Experimental methods: material growth, device fabrication and characterization tools 40
2.1. Material growth system: Low-Pressure Metalorganic Chemical Vapor Deposition (LP-MOCVD) 40
2.1.1. LP-MOCVD system @ SNU 40
2.1.2. Metalorganic (MO) source materials 44
2.1.3. InSb substrate preparation 45
2.1.4. Epitaxial growth procedures 46
2.2. Dielectric deposition systems 49
2.2.1. Plasma Enhanced Chemical Vapor Deposition (PECVD) 49
2.2.2. Electron Beam Evaporation 49
2.3. Device fabrication methods 50
2.3.1. Sample preparation 50
2.3.2. Mesa etching 50
2.3.3. Dielectric deposition 54
2.3.4. Metallization 54
2.4. Characterization tools 56
2.4.1. Atomic Force Microscopy 56
2.4.2. Ellipsometry 56
2.4.3. High resolution X-Ray Diffraction 57
2.4.4. Scanning Electron Microscopy 57
2.4.5. Transmission Electron Microscopy 58
2.4.6. Secondary Ion Mass Spectroscopy 58
2.4.7. Energy Dispersive X-ray Spectroscopy 58
2.4.8. X-ray Photoelectron Spectroscopy 58
2.4.9. Auger Electron Spectroscopy 59
2.4.10. Photoluminescence 59
2.4.11. Capacitance-Voltage measurement 60
2.4.12. Current-Voltage measurement 60
2.4.13. Hall measurement 61

Chapter 3. Surface treatement ambient on the quality of InSb epitaixal layers 63
3.1. Introduction 63
3.2. Motivation 67
3.3. Theoretical backgroud 70
3.4. Experimental procedures 73
3.5. ex-situ wet chemical etching of InSb substrate 74
3.6. in-situ thermal cleaning (TC) of InSb substrat 80
3.6.1. H2 ambient 80
3.6.1.1. Effects of TC temperatures on InSb substrate 80
3.6.1.2. Formation of indium droplets surrounded by rectangular etch pits 80
3.6.2. TMSb ambient 87
3.6.2.1. Effects of TC temperatures on InSb substrate 87
3.6.2.2. Effects of TMSb mole fraction on InSb surface morphology 88
3.7. Effects of thermal cleaning ambient on the quality of InSb epilayers 94
3.7.1. Influence on the crystallinity 94
3.7.2. Origin of the degraded quality of InSb epilayers 95
3.8. Summary 99
3.9. Bibliography 100

Chapter 4. Growth and characterization of InSb epitaxial layers 104
4.1. Introduction 104
4.2. Motivation 107
4.3. Experimental procedures 109
4.4. Epitaxial growth of unintentionally doped InSb 111
4.4.1. Effect of growth parameters on InSb surface morphologies 111
4.4.2. Effects of growth parameters on InSb crystallinity 112
4.4.3. Growth behavior of InSb grwon using TMIn and TMSb 113
4.5. Optical analysis of unintentionally doped InSb 121
4.5.1. Near band edge emission shift 121
4.5.2. Carbon impurity related PL emission 133
4.6. p-type doping in InSb 137
4.7. Summary 140
4.8. Bibliography 142

Chapter 5. ZnS surface passivation of InSb photodiodes and its device performances 148
5.1. Introduction 148
5.2. Motivation 151
5.3. Experimental procedures 154
5.4. Interfacial properties of Au/ZnS/InSb MIS structures 155
5.4.1. Effects of deposition rate on interface trap density (Dit) 155
5.4.2. Effects of deposition rate on fixed charge density (Nf) 158
5.4.3. Chemical composition analysis of ZnS films 159
5.4.4. Defect origin analysis of S-deficient ZnS films 160
5.5. Surface leakage currents of ZnS passivated InSb PDs 165
5.5.1. Theroertical background 165
5.5.2. The dependence of deposition rates on the surfae leakage currents 166
5.6. Device performance 172
5.6.1. Dark current 172
5.6.2. Spectral response 173
5.6.3. Responsivity and Detectivity (D*) 179
5.7. Summary 183
5.8. Bibliography 185

Chapter 6. Conclusions 192

Abstract (in Korean) 196

Publication List 200
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dc.formatapplication/pdf-
dc.format.extent7233391 bytes-
dc.format.mediumapplication/pdf-
dc.language.isoen-
dc.publisher서울대학교 대학원-
dc.subject인듐안티모나이드-
dc.subject저압 유기화학기상증착법-
dc.subject.ddc620-
dc.titleInvestigation on InSb Epitaxial Growth and Surface Passivation to Improve Device Performances-
dc.title.alternative적외선 검출소자 특성향상을 위한 InSb 성장 및 표면 보호막에 대한 연구-
dc.typeThesis-
dc.description.degreeDoctor-
dc.citation.pages210-
dc.contributor.affiliation공과대학 재료공학부-
dc.date.awarded2016-02-
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