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研究生:CAO PHUONG THAO
研究生(外文):PHUONG-THAO CAO
論文名稱:Processing and Property Characteristics of Doped and Codoped Gallium Nitride Films Grown by RF Reactive Sputtering Technique
論文名稱(外文):Processing and Property Characteristics of Doped and Codoped Gallium Nitride Films Grown by RF Reactive Sputtering Technique
指導教授:郭東昊
指導教授(外文):Dong-Hau Kuo
口試委員:郭東昊柯文政陳詩芸Ren-Kae ShiueJenn-Ming Song
口試委員(外文):Dong-Hau KuoWen-Cheng KeShih-Yun ChenRen-Kae ShiueJenn-Ming Song
口試日期:2019-01-03
學位類別:博士
校院名稱:國立臺灣科技大學
系所名稱:材料科學與工程系
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2019
畢業學年度:107
語文別:英文
論文頁數:163
中文關鍵詞:RF sputteringdopingGaNelectrical propertydiode
外文關鍵詞:RF sputteringdopingGaNelectrical propertydiode
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The nitride-based material had excellent properties such as high thermal conductivity, high electron mobility, high electron saturation velocity, and a wide band gap, which have been considerably studied by many researchers in recent years. The GaN and its alloys materials have achieved promising future for the application of electronic devices such as metal–oxide–semiconductor field effect transistors (MOSFETs), hetero-junction field-effect transistors (HJ-FETs), Schottky diodes, p–n junction diodes, laser diodes, light emitting diodes (LEDs) etc. However, high-quality GaN and III-V nitride semiconductor layers for employing of optoelectronic and electronic devices often have been deposited on sapphire, Si and SiC substrates by metal organic chemical vapor deposition (MOCVD) and molecular beam epitaxy (MBE) at high temperature. Besides, the physical properties and applications of various semiconductor materials were determined by doping techniques. It is important that the applications of low-cost methods at low processing temperatures, safe working environment could develop III-V nitride materials and their devices.
In this study, GaN materials have been prepared by radio-frequency (RF) reactive sputtering technique with the low temperature and effective economic. To study the effects of doping and co-doping technique on the semiconductor properties, a systematic change in film composition is the basic strategy to study the solid solubility, the structure, properties, and their relationship for the purpose of understanding the possible defect nature. Additionally, this study has investigated influences of RF sputtering power and deposition temperature on the structure, electrical and optical properties of films.
For donor doped in GaN material, the Ge-x-GaN thin films were grown on Si (100) substrates by RF reactive sputtering technology with single cermet targets at the Ge/(Ge+Ga) molar ratios of x= 0, 0.03, 0.07 and 1. The Ge-x-GaN films had a wurtzite structure with a preferential ( ) plane. The SEM images showed that Ge-GaN films were smooth, continuous, free from cracks and holes, and possessed grains in nanometer-size. All Ge-x-GaN films remained as n-type. While the highest conductivity was found to be 1.46 Scm-1 in Ge-0.03-GaN film due to the highest carrier concentration of 2.55  1018 cm-3. Additionally, we made the n/p diodes with Ge-doped GaN films as n-type layers deposited on Si (100) substrate as a p-type layer using by RF reactive sputtering technique. Their electronics characteristics were evaluated in terms of the barrier height, ideality factor, and series resistance. Additionally, effects of deposition temperature and sputtering power on film properties were systematically investigated.
For acceptor doped in GaN material, Sb anion-substituted gallium nitride films were fabricated by RF reactive sputtering technology with single cermet targets containing different Sb contents under Ar/N2 atmosphere. n-type GaN films with electron concentration of 1.311017 cm-3 inverted to the p-type semiconductor of Sb-GaN with high hole concentration of 5.491017 cm-3. The bandgap energy of Sb anion-added Sb-GaN films decreased from 3.20 to 2.72 eV with increasing the Sb content. The formation of p-type Sb-GaN is attributed to the formation of Ga vacancy at the higher Sb content. The coexistence of Sb at the Ga cation site and N anion site can be the interesting and important result, as GaNSb had been well developed for highly mismatched alloys. The hetero-junction with p-type Sb-GaN/n-Si diodes were all made by RF reactive sputtering technique. The electrical characteristics of Sb-GaN diode devices were fully investigated at room temperature from -20 to 20 V.
For studying co-doping of acceptor and donor in GaN material, Zn acceptor/Ge donor (Zn/Ge)-codoped GaN films with different Zn contents have been deposited on Si substrates at 300 oC and at 90-150 W by RF reactive sputtering technique with cermet targets at the composition atomic ratios of Zn:Ge:(Ga+GaN) at x:0.03:(0.97-x) with x= 0, 0.03, 0.06, and 0.09 and Ga:GaN = 3:7. The films made with such targets were presented in an abbreviated symbol of Zn-x-GeGaN at x= 0, 0.03, 0.06, and 0.09. The morphology, structure, electrical properties, optical property, and hetero-junction diode devices involved in the Zn-x-GeGaN films were thoroughly investigated. The systematic Zn increment into the n-type Zn-0-GeGaN through property evaluation provides the supporting information in studying solid solutions. Zn-x-GeGaN films converted into p-type semiconductor at x= 0.06 and 0.09. The values of bandgap were in the range of 2.87 – 3.17 eV with the lower value for the higher Zn content in Zn-x-GeGaN films. The higher RF power led to the faster growth, highly deficient in nitrogen, a higher Zn atom ratio in the deposited film. The 120W-deposited Zn-0.06-GeGaN film had hole concentration of 7.21 × 1016 cm-3, the hole mobility of 39 cm2.V-1.s-1, and the electrical conductivity of 0.45 S/cm.
The nitride-based material had excellent properties such as high thermal conductivity, high electron mobility, high electron saturation velocity, and a wide band gap, which have been considerably studied by many researchers in recent years. The GaN and its alloys materials have achieved promising future for the application of electronic devices such as metal–oxide–semiconductor field effect transistors (MOSFETs), hetero-junction field-effect transistors (HJ-FETs), Schottky diodes, p–n junction diodes, laser diodes, light emitting diodes (LEDs) etc. However, high-quality GaN and III-V nitride semiconductor layers for employing of optoelectronic and electronic devices often have been deposited on sapphire, Si and SiC substrates by metal organic chemical vapor deposition (MOCVD) and molecular beam epitaxy (MBE) at high temperature. Besides, the physical properties and applications of various semiconductor materials were determined by doping techniques. It is important that the applications of low-cost methods at low processing temperatures, safe working environment could develop III-V nitride materials and their devices.
In this study, GaN materials have been prepared by radio-frequency (RF) reactive sputtering technique with the low temperature and effective economic. To study the effects of doping and co-doping technique on the semiconductor properties, a systematic change in film composition is the basic strategy to study the solid solubility, the structure, properties, and their relationship for the purpose of understanding the possible defect nature. Additionally, this study has investigated influences of RF sputtering power and deposition temperature on the structure, electrical and optical properties of films.
For donor doped in GaN material, the Ge-x-GaN thin films were grown on Si (100) substrates by RF reactive sputtering technology with single cermet targets at the Ge/(Ge+Ga) molar ratios of x= 0, 0.03, 0.07 and 1. The Ge-x-GaN films had a wurtzite structure with a preferential ( ) plane. The SEM images showed that Ge-GaN films were smooth, continuous, free from cracks and holes, and possessed grains in nanometer-size. All Ge-x-GaN films remained as n-type. While the highest conductivity was found to be 1.46 Scm-1 in Ge-0.03-GaN film due to the highest carrier concentration of 2.55  1018 cm-3. Additionally, we made the n/p diodes with Ge-doped GaN films as n-type layers deposited on Si (100) substrate as a p-type layer using by RF reactive sputtering technique. Their electronics characteristics were evaluated in terms of the barrier height, ideality factor, and series resistance. Additionally, effects of deposition temperature and sputtering power on film properties were systematically investigated.
For acceptor doped in GaN material, Sb anion-substituted gallium nitride films were fabricated by RF reactive sputtering technology with single cermet targets containing different Sb contents under Ar/N2 atmosphere. n-type GaN films with electron concentration of 1.311017 cm-3 inverted to the p-type semiconductor of Sb-GaN with high hole concentration of 5.491017 cm-3. The bandgap energy of Sb anion-added Sb-GaN films decreased from 3.20 to 2.72 eV with increasing the Sb content. The formation of p-type Sb-GaN is attributed to the formation of Ga vacancy at the higher Sb content. The coexistence of Sb at the Ga cation site and N anion site can be the interesting and important result, as GaNSb had been well developed for highly mismatched alloys. The hetero-junction with p-type Sb-GaN/n-Si diodes were all made by RF reactive sputtering technique. The electrical characteristics of Sb-GaN diode devices were fully investigated at room temperature from -20 to 20 V.
For studying co-doping of acceptor and donor in GaN material, Zn acceptor/Ge donor (Zn/Ge)-codoped GaN films with different Zn contents have been deposited on Si substrates at 300 oC and at 90-150 W by RF reactive sputtering technique with cermet targets at the composition atomic ratios of Zn:Ge:(Ga+GaN) at x:0.03:(0.97-x) with x= 0, 0.03, 0.06, and 0.09 and Ga:GaN = 3:7. The films made with such targets were presented in an abbreviated symbol of Zn-x-GeGaN at x= 0, 0.03, 0.06, and 0.09. The morphology, structure, electrical properties, optical property, and hetero-junction diode devices involved in the Zn-x-GeGaN films were thoroughly investigated. The systematic Zn increment into the n-type Zn-0-GeGaN through property evaluation provides the supporting information in studying solid solutions. Zn-x-GeGaN films converted into p-type semiconductor at x= 0.06 and 0.09. The values of bandgap were in the range of 2.87 – 3.17 eV with the lower value for the higher Zn content in Zn-x-GeGaN films. The higher RF power led to the faster growth, highly deficient in nitrogen, a higher Zn atom ratio in the deposited film. The 120W-deposited Zn-0.06-GeGaN film had hole concentration of 7.21 × 1016 cm-3, the hole mobility of 39 cm2.V-1.s-1, and the electrical conductivity of 0.45 S/cm.
Abstract i
Acknowledgment iii
Table of Contents iv
List of Figures vi
List of Tables xv
Chapter 1: Introduction 1
1.1 Background of study…………………………………………………………… 1
1.2 Gallium nitride materials and devices………………………………………….. 2
1.3 Motivation and objectives of this study……………………………………….. 6
The Basic Theory and Literature Review 8
2.1 Gallium Nitride materials…………………………………………………… 8
2.2 Donor-Doped Gallium Nitride………………………………………………… 14
2.3 Acceptor-Doped Gallium Nitride……………………………………………… 18
2.4 Donor-Acceptor Co-doped Gallium Nitride……………………………….. 27
2.5 p-n junction diodes …………………………………………………………… 33
Chapter 3: Experimental Procedure 36
3.1 Experiment materials ………………………………………………………… 36
3.2 Description of experimental instruments ……………………………………. 37
3.2.1 Chemical vapor deposition (CVD) machine 37
3.2.2 Vacuum hot pressing machine 38
3.2.3 RF reactive magnetron sputtering 38
3.3 Experimental procedure ……………………………………………………… 40
3.3.1 Powder configuration and hot pressure target 41
3.3.2 Target Fabrication 43
3.3.3 Slice and cleaning of the substrate 43
3.3.4 Sputtering films 44
3.3.5 The modeling of the diodes 47
3.4. Material characterization techniques ………………………………………… 51
Chapter 4: Results and Discussions 53
4.1 Characteristics of Ge-doped GaN thin film deposited by RF reactive sputtering technique …………………………………………………………………………………. 53
4.1.1 Influences of Ge dopant on the electrical, optical and structural properties of Ge-doped GaN thin films 53
4.1.2 Influences of deposition temperature on the electrical, optical and structural properties of Ge-doped GaN thin films 63
4.1.3 Influences of RF sputtering power on the electrical, optical and structural properties of Ge-doped GaN thin films 71
4.1.4 The hetero-junction diode devices made by Ge-x-GaN films 79
4.2 Electrical and structural characteristics of Sb-doped GaN thin films and its hetero-junction diode made all by RF reactive sputtering ………………………………………. 82
4.2.1 Influences of Sb dopant content on structural and properties of the sputtered Sb-x-GaN films 82
4.2.1.1 XPS analyse of Sb-0.14-GaN film 82
4.2.2 Influences of deposition temperature on the electrical, optical and structural properties of Sb-doped GaN thin films 93
4.2.3 The hetero-junction Sb-x-GaN/ n-Si diodes 101
4.3. Processing and property characterization of Zn-Ge codoped Gallium Nitride by radio frequency reactive sputtering technique ………………………………………….. 109
4.3.1 Influences of Zn dopant content on structural and properties of the sputtered Zn-x-GeGaN films 109
4.3.2. Effects of sputtering power on structural and electrical properties 121
4.3.3 The hetero-junction diode devices made by Zn-x-GeGaN films 128
Chapter 5: Conclusions 131
References 133
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