光電元件與構裝模組之界面穩定性與材料特性

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研究生：	林士剛 Shih-kang Lin
論文名稱：	光電元件與構裝模組之界面穩定性與材料特性 Interfacial Stabilities and Materials Characterizaztions in Optoelectronic Devices and Packaging Modules
指導教授：	陳信文 Sinn-wen Chen
口試委員:
學位類別：	博士 Doctor
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2008
畢業學年度：	96
語文別：	英文
論文頁數：	300
中文關鍵詞：	錫、銦、銅、鎳、相平衡、液相線投影圖、界面反應、無鉛銲料、構裝、光電、氮化銦鎵、負型氮化鎵、軟性電子、錫鬚、擴散、電遷移效應、歐姆接觸、釩、鋁、銀
外文關鍵詞：	Sn, In, Cu, Ni, Phase equilibria, Liquidus projection, Interfacial reaction, Pb-free solder, Packaging, Optoelectroic, InxGa1-xN, n-GaN, Fflexible electronic, Sn whisker, Diffusion, Electromigration, Ohmic contact, V, Al, Ag
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Optoelectronic (OE) systems play important roles in advanced applications of various fields, such as energy-saving light source, solar cell, flat-panel display technology, wireless communication technology, etc. These OE systems are composed of OE devices and packaging modules which contain a large number of thin-film or bulk heterogeneous materials joints. The interfacial stabilities of the interfaces are crucial for the functionalities and reliabilities of the OE products. Metallurgical reactions in the thin-film and bulk joints are of essential importance in materials design and manufacture conditioning. The aim of the study is at the important materials systems in OE applications and to make efforts on evaluation of the interfacial stabilities. The materials systems investigated in the thesis are the interfacial reactions between thin Ni film and InxGa1-xN, V/Al/Ag Ohmic contacts to n-GaN, interfacial reactions in the Sn-In/Cu and Sn-In/Ni couples, electromigration effect upon the Sn-In/Cu interfacial reaction, and the Sn whisker formation on the thick pure Sn film. These interfacial problems are analyzed by using various materials characterization techniques and evaluated based on the knowledge of materials phase equilibria and transport. The mechanisms of phase transformations and morphological developments are proposed. In addition, the 250 oC isothermal section and liquidus projection of the Sn-In-Cu ternary system are experimentally determined in order to fulfill the lack of data in the literatures.

光電系統(optoelectronic system)已被廣泛地應用於各式前瞻技術當中
，包括目前倍受重視的低耗能照明設備與發電裝置，如白光發光二極體(light emitting diode, LED)及太陽能電池(solar cell)，以及平面顯示器與無線通訊技術等。這些光電系統中包含了大量的異質材料相接界面，包括各式功能性元件中的薄膜異質界面，以及構裝模組中的塊材接點。這些異質界面的穩定性直接決定了光電產品的功能性以及可靠度。適度的界面反應(interfacial reaction)可產生良好的歐姆接觸(Ohmic contact)於元件，以及可靠的電子接點於構裝模組中；而過度的反應則會造成元件失效以及接點破壞。因此，開發新穎光電材料與製程時，必須對系統中的薄膜與塊材界面反應有所了解。本研究探討的範圍涵蓋光電產品中重要的材料系統與其界面行為，包括光電元件中的薄膜界面：氮化銦鎵(InxGa1-xN)對鎳薄膜之反應、與釩/鋁/銀(V/Al/Ag)薄膜對負型氮化鎵(n-GaN)之歐姆接觸，以及光電構裝中之塊材界面：錫銦無鉛銲料(Pb-free solder)與銅、鎳界面之反應與電遷移效應(electromigration effect)、以及純錫厚膜之錫鬚(Sn whisker)生長。運用各式形態(morphology)、組成與結構之材料分析技術，配合材料相平衡與輸送的知識，對這些異質界面的相變化與形態發展進行討論，並提出反應的機制。此外，本研究同時以實驗方法測定錫-銦-銅三元系統之液相線投影圖(liquidus projection)，與250度等溫橫截面圖(isothermal section)，以補充文獻上之不足。

ABSTRACT...................................................i

摘要......................................................ii

致謝.....................................................iii

LIST OF FIGURES...........................................vi

LIST OF TABLES............................................xx

CHAPTER I: INTRODUCTION....................................1
I.1 Optoelectronics Systems and Their Applications.........1
I.2 Optoelectronic Packaging and Soldering Technology......4
I.3 Lead (Pb) Free Solders and Sn-In Based Alloys..........8
I.4 Frame Structure of the Proposal.......................10

CHAPTER II: PHASE EQUILIBRIA AND LIQUIDUS PROJECTION OF THE SN-IN-CU TERNARY SYSTEM...................................11
II.1 Literature Review....................................13
II.1-1 Phase Equilibria and Liquidus Projection...........13
II.1-2 Sn-In Binary Phase Diagram.........................16
II.1-3 Cu-In Binary Phase Diagram.........................18
II.1-4 Sn-Cu Binary Phase Diagram.........................23
II.1-5 Sn-In-Cu Isothermal Sections.......................27
II.1-6 Sn-In-Cu Liquidus Projection.......................30
II.2 Experimental Procedures..............................32
II.2-1 Alloy Preparation, Annealing, and Solidification...32
II.2-2 Analyses...........................................33
II.3 Results and Discussion...............................34
II.3-1 Sn-In-Cu Isothermal Section at 250 oC..............34
II.3-2 Sn-In-Cu Liquidus Projection.......................59
II.4 Summary..............................................82

CHAPTER III: INTERFACIAL REACTIONS IN THE SN-IN/CU AND SN-IN/NI COUPLES.............................................83
III.1 Literature Review...................................85
III.1-1 Diffusion in Solid................................85
III.1-2 Interfacial Reaction..............................87
III.1-3 Sn-In-Cu Isothermal Sections......................93
III.1-4 Sn-In/Cu Interfacial Reactions....................93
III.1-5 Sn-In-Ni Isothermal Sections......................94
III.1-6 Sn-In/Ni Interfacial Reactions....................95
III.2 Experimental Procedures.............................96
III.2-1 Reaction Couples Preparation......................96
III.2-2 Heat Treatments and Reaction Couple Analyses......98
III.3 Results and Discussion..............................99
III.3-1 DTA and the Solidus Temperature of Sn-20at.%In....99
III.3-2 Sn-20at.%In/Cu and Sn-20at.%In/Ni Interfacial Reactions at 160 oC......................................101
III.3-3 Sn-20at.%In/Ni Interfacial Reactions at 130 oC and 140 oC...................................................113
III.3-3 Sn-20at.%In/Ni Interfacial Reactions at 150 oC and 160 oC...................................................119
III.4 Summary............................................126

CHAPTER IV: ELECTROMIGRATION EFFECT UPON INTERFACIAL REACTIONS IN THE SN-IN/CU COUPLES........................127
IV.1 Literature Review...................................128
IV.1-1 Electromigration Effect...........................128
IV.1-2 Electromigration Effect in the Solder Joints......131
IV.2 Experimental Procedures.............................133
IV.2-1 Reaction Couples Preparation......................133
IV.2-2 Electrifying Experiments..........................133
IV.2-3 Reaction Couples Analyses.........................134
IV.3 Results and Discussion..............................136
IV.3-1 Sn-20at.%In/Cu Interfacial Reactions at 160 oC....136
IV.3-2 Sn-20at.%In/Cu Interfacial Reactions at 160 oC with current stressing.    ......................................137
IV.3-3 Sn-20at.%In/Cu Interfacial Reactions at 250 oC....148
IV.3-3 Reaction Paths Shifting Under Current Stressing...150
IV.4 Summary.............................................154

CHAPTER V: MECHANICAL DEFORMATION INDUCED-TIN WHISKER FORMATION................................................155
V.1 Literature Review....................................158
V.1-1 Sn Whisker Formation...............................158
V.1-2 Driving Forces of Sn Whiskers Formation............160
V.2 Experimental Procedures..............................170
V.2-1 Pb-Free Thin Films Design..........................170
V.2-2 Compression Tests..................................171
V.2-3 Compressed Film Analyses...........................172
V.3 Results and Discussion...............................173
V.3-1 As-Prepared Thin Films: Six Conditions.............173
V.3-2 900 □m Diameter ZrO2 Ball Indenters: Constant Compressive Force........................................178
V.3-3 900 □m Diameter ZrO2 Ball Indenters: Microstructure Development..............................................193
V.3-4 900 □m Diameter ZrO2 Ball Indenters: Constant Compressed Strain........................................203
V.3-5 Tetrahedron Diamond Indenters: Constant Compressive Force.............    ......................................210
V.4 Summary.............................................214

CHAPTER VI: INTERFACIAL REACTIONS BETWEEN NICKEL THIN FILM AND INDIUM GALLIUM NITRIDE...............................215
VI.1 Literature Review...................................217
VI.1-1 Phase diagrams of the Ni-In-Ga-N Related Systems..217
VI-1-2 Interfacial Reactions between Ni Thin Film and InxGa1-xN................................................226
VI.2 Experimental Procedures.............................229
VI.2-1 Ni/InxGa1-xN Contact Preparation..................229
VI.2-2 Thermo-treatments.................................230
VI.2-3 Metallurgical and Compositional Analysis..........231
VI.3 Results and Discussion..............................233
VI.3-1 Ni/In0.25Ga0.75N – As-deposited..................233
VI.3-2 Ni/In0.16Ga0.84N – 600 oC-60s....................235
VI.3-3 Ni/In0.16Ga0.84N – 700 oC-60s....................239
VI.3-4 Ni/In0.16Ga0.84N – 700 oC-120s...................244
VI.3-5 Ni/In0.16Ga0.84N – 700 oC-1h.....................249
VI.3-6 Ni/In0.16Ga0.84N – 750 oC-60s....................250
VI.3-7 Surface Morphology of the In0.16Ga0.84N Epitaxial Film.......................    .............................252
VI.3-8 Possible Consequences of the Composition Shift in InxGa1-xN...............................................253
VI.4 Summary............................................254

CHAPTER VII: V/AL/AG OHMIC CONTACT TO N-TYPE GALLIUM NITRIDE..................................................255
VII.1 Literature Review..................................256
VII.1-1 Metal/Semiconductor Interfaces...................256
VII.1-2 Schottky Barriers................................257
VII.1-3 Ohmic Contacts...................................260
VII. 1-4 Ohmic Contacts to n-GaN.........................261
VII.2 Experimental Procedures............................263
VII.2-1 Contact Preparation and Thermo-treatment.........263
VII.2-2 Metallurgical Analysis and Electrical Measurement..............................................264
VII.3 Results and Discussion.............................266
VII.3-1 Gap Spacing Measurement and Calibration..........266
VII.3-2 Morphological Examination........................268
VII.3-3 Electrical Examination...........................271
VII.4 Summary............................................273

CHAPTER VIII: SUMMARY AND SUGGESTED FUTURE WORKS.........274

REFERENCES...............................................279

PUBLICATIONS LIST........................................290

ACADEMIC HONORS..........................................295

                                

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