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| ???org.dspace.app.webui.jsptag.ItemTag.dcfield??? | Value | Language |
|---|---|---|
| dc.contributor.advisor | 劉如熹 | zh_TW |
| dc.contributor.advisor | Ru-Shi Liu | en |
| dc.contributor.author | 陳冠群 | zh_TW |
| dc.contributor.author | Kuan-Chun Chen | en |
| dc.date.accessioned | 2025-08-21T16:32:32Z | - |
| dc.date.available | 2025-08-22 | - |
| dc.date.copyright | 2025-08-21 | - |
| dc.date.issued | 2025 | - |
| dc.date.submitted | 2025-07-30 | - |
| dc.identifier.citation | (1) Newton, I. Opticks, or, a Treatise of the Reflections, Refractions, Inflections & Colours of Light; Courier Corporation, 1952.
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/99139 | - |
| dc.description.abstract | 短波紅外線因其獨特性質，於不同領域具高應用潛力。於固態照明中，螢光粉轉化發光二極體已為現今常見之光源，且短波紅外線螢光粉亦可應用於此類發光二極體，且具可調控放光波段之優勢，為短波紅外線光源提供另一選擇。然短波紅外線螢光粉應用於光纖放大器之應用仍待發展與研究。故於本研究中，將探討短波紅外光螢光粉之調控與其應用於光纖放大器與發光二極體。
本研究中前半(Chapters 3 and 4)部分，著重短波紅外線螢光粉之合成與分析研究，且將最佳條件之螢光粉進行晶體光纖之生長，評估其應用潛力。因現今商用Y3Al5O12:Cr4+晶體光纖無法調整Cr4+之濃度導致其發光強度受限，故其一(Chapter 3)為Y3Al5O12:Cr3+/4+,Ca2+,Mg2+，藉Cr離子濃度調整與二價陽離子摻雜，最佳化Cr4+之放光表現，且所生長之晶體光纖於短波紅外線之放光強度，高於商用Y3Al5O12:Cr4+商用晶體光纖。此外，晶體光纖研究領域之材料多樣性受局限，故其二(Chapter 4)為開發全新晶體光纖系統(Ga,Ge)2O3:Cr3+,Ni2+，藉Cr3+與Ni2+雙活化劑摻雜與Ge4+摻雜進行價數補償。因Cr3+得有效能量轉移至Ni2+，故得獲寬譜帶放射峰於短波紅外線之波段。除生長為晶體光纖之應用，因Cr3+可有效藉藍光激發，故此系列螢光粉亦可應用於短波紅外線光源。 本研究後半(Chapters 5 and 6)部分，致力於短波紅外線尖晶石螢光粉之研究，建立有效調控放光波段之策略與延伸放光波段之策略，亦評估其於短波紅外線光源之應用可行性。其一(Chapter 5)為Cr3+與Ni2+雙活化劑摻雜之MgAl2O4–MgGa2O4–Mg2SnO4固態溶液系統，探討尖晶石系統結構轉換於放光性質之影響，且著重探討Cr3+團簇之消長與Ni2+放光波段之調控。將合成之螢光粉進行發光二極體封裝測試，展現其短波紅外線光源之應用示範。其二(Chapter 6)為MgGa2O4:Cr3+,Er3+，藉Cr3+濃度變化探討Cr3+離子團簇於能量轉移至Er3+之影響，並藉Er3+濃度調整得最佳化之放光強度於短波紅外線波段，搭配局部結構與進階光譜分析揭示Cr3+團簇於Er3+放光強度之影響，得改善稀土元素低吸收導致之螢光強度受限窘境。 綜上所述，本研究致力於推動短波紅外線螢光粉之發展，藉系統性之陽離子取代策略、結構調控及能量轉移機制探討，提升螢光粉之放光表現且建立有效調控放光位置之策略，同時藉螢光粉之配方設計思維改良與開發晶體光纖材料，揭示螢光粉於晶體光纖與發光二極體之應用潛力，為短波紅外線螢光粉領域提供嶄新之設計思路與應用方向。 | zh_TW |
| dc.description.abstract | Shortwave infrared (SWIR) phosphors possess high application potential in various fields due to their unique properties. In solid-state lighting, phosphor-converted light-emitting diodes (pc-LEDs) have become common light sources nowadays. SWIR phosphors can also be applied to such pc-LEDs and have the advantage of tunable emission wavelengths, providing another option for SWIR light sources. However, the application of SWIR phosphors in optical fiber amplifiers still needs development and research. Therefore, this study will explore the emission tuning of SWIR phosphors and their applications in optical fiber amplifiers and pc-LEDs.
The first half (Chapters 3 and 4) of this study focused on the synthesis and analysis of SWIR phosphors, and crystal fibers were grown using the optimized phosphors to evaluate their application potential. The current commercial crystal fiber faces the challenge of low photoluminescence intensity because of the limited Cr4+ content in commercial Y3Al5O12:Cr4+ crystal fiber. Hence, the first part (Chapter 3) is Y3Al5O12:Cr3+/4+,Ca2+,Mg2+, which optimizes Cr4+ photoluminescence performance through Cr ion concentration tuning and divalent cations doping. The grown crystal fiber shows higher SWIR emission intensity than commercial Y3Al5O12:Cr4+ crystal fibers. Besides, the crystal fiber research field also encounters the challenge of low material diversity. Therefore, the second part (Chapter 4) aims to develop a new material system, (Ga,Ge)2O3:Cr3+,Ni2+, using Cr3+ and Ni2+ co-activators doping for obtaining SWIR emission and Ge4+ doping for charge compensation. Due to effective energy transfer from Cr3+ to Ni2+, a broadband emission peak in the SWIR band is obtained. In addition to crystal fiber applications, since Cr3+ can be effectively excited by blue light, this series of phosphors can also be applied to SWIR light sources. The latter half (Chapters 5 and 6) of this study focused on SWIR spinel phosphor research and evaluated their feasibility for SWIR light source applications. The effective emission tuning strategy and emission range extension method were established. The first part (Chapter 5) is the MgAl2O4–MgGa2O4–Mg2SnO4 spinel solid-solution system doped with Cr3+ and Ni2+ activators, investigating the effects of spinel system structural evolution on photoluminescence properties, with emphasis on exploring the relationship between Cr3+ clusters and Ni2+ emission band tuning. Pc-LED packaging tests were conducted on the synthesized phosphors, demonstrating their potential for application as SWIR light sources. The second part (Chapter 6) is MgGa2O4:Cr3+,Er3+, exploring the effect of Cr3+ clusters on Er3+ through Cr3+ concentration tuning and optimizing emission intensity in the SWIR band through Er3+ concentration tuning. Local structure investigation and advanced photoluminescence analysis are also conducted to reveal the effect of Cr3+ clusters on Er3+ emission intensity, which can overcome the issue of low absorption for rare-earth elements. In summary, this study is dedicated to advancing the development of SWIR phosphors through systematic cation substitution strategies, structural regulation, and energy transfer investigations to enhance the luminescence performance of phosphors and establish effective emission position-controlling strategies. Meanwhile, by developing optical crystal fiber through phosphor design concepts, this work reveals the potential of phosphors in optical crystal fibers and pc-LEDs, providing novel design approaches and directions for the application of SWIR phosphors. | en |
| dc.description.provenance | Submitted by admin ntu (admin@lib.ntu.edu.tw) on 2025-08-21T16:32:32Z No. of bitstreams: 0 | en |
| dc.description.provenance | Made available in DSpace on 2025-08-21T16:32:32Z (GMT). No. of bitstreams: 0 | en |
| dc.description.tableofcontents | 口試委員審定書 I
誌謝 II 摘要 III Abstract V Contents VII Figure Contents XV Table Contents XXIX Abbreviation List XXXII Chapter 1 Introduction 1 1.1 Light 1 1.1.1 Infrared light 2 1.1.2 Photoluminescence 5 1.2 Optical Communication 5 1.2.1 Optical fiber 6 1.2.2 Optical fiber amplifiers 10 1.3 Solid-State Lighting 13 1.3.1 Light-emitting diodes 14 1.3.2 Inorganic phosphor materials 17 1.4 Fundamentals of Photoluminescence in Inorganic Phosphor Materials 18 1.4.1 Jabłoński diagram 19 1.4.2 Franck-Condon principle 22 1.4.3 Electron-phonon coupling and Stokes shift 24 1.4.4 Nephelauxetic effect 26 1.4.5 Quenching effect 27 1.5 Selection Principle of Activators 30 1.5.1 Advantages of 3d transition metal activators 32 1.5.2 Characteristics of the Cr3+ activators 33 1.5.3 Characteristics of the Cr4+ activators 35 1.5.4 Characteristics of the Ni2+ activators 37 1.6 Photoluminescence Tunning Strategies for Phosphors 38 1.6.1 Crystal field theory 39 1.6.2 Tanabe–Sugano diagram 43 1.6.3 Charge compensation 46 1.6.4 Energy transfer 46 1.7 Research Motivation 50 Chapter 2 Experimental Approaches and Techniques 52 2.1 Chemical Reagents 52 2.2 Synthesis of Inorganic Phosphor and Growth of Crystal Fiber 53 2.2.1 Design and synthesis of Y3Al5O12:Cr3+/4+,Ca2+,Mg2+ phosphor 54 2.2.2 Crystal fiber growth of Y3Al5O12:Cr3+/4+,Ca2+,Mg2+ 57 2.2.3 Design and synthesis of (Ga,Ge)2O3:Cr3+Ni2+ phosphor 59 2.2.4 Crystal fiber growth of (Ga,Ge)2O3:Cr3+,Ni2+ 61 2.2.5 Design and synthesis of MgAl2O4–MgGa2O4–Mg2SnO4 solid-solution phosphor 62 2.2.6 Design and synthesis of MgGa2O4:Cr3+,Er3+ phosphor 66 2.3 Instrumental Analysis 68 2.3.1 Structural investigation 69 2.3.1.1 Powder X-ray diffraction 70 2.3.1.2 Synchrotron X-ray diffraction 74 2.3.1.3 Structural refinement 75 2.3.1.4 X-ray absorption spectroscopy 78 2.3.1.5 Transmission electron microscope 83 2.3.1.6 Electron paramagnetic resonance 85 2.3.2 Photoluminescence analysis 88 2.3.2.1 Photoluminescence spectroscopy 88 2.3.2.2 Absolute photoluminescence quantum yield spectrometer 89 2.3.2.3 Time-resolved photoluminescence spectroscopy 91 2.3.2.4 Temperature-dependent photoluminescence spectroscopy 93 2.3.2.5 Pressure-dependent photoluminescence spectroscopy 95 2.3.3 Crystal fiber analysis 96 2.3.3.1 Electron probe microanalysis 97 2.3.3.2 Optical spectrum analysis 98 2.3.3.3 Laser scanning confocal microscopy 99 2.3.4 Phosphor applications 100 2.3.4.1 Phosphor-converted light-emitting diode 101 2.3.4.2 Shortwave infrared camera 102 Chapter 3 High-Concentration Cr4+-Doped Garnet Phosphors Development for Broadband Shortwave Infrared Optical Fiber Amplifiers by Divalent Cations Substitutions 103 3.1 Introduction 103 3.2 Experimental Section 106 3.2.1 Synthesis of Y3−yAl5−xO12:xCr3+/4+,yCa2+ (x = 0.02–0.16, y = 0; x = 0.1, y = 0–0.22) and Y3−y−zAl5−xO12:xCr3+/4+,yCa2+,zMg2+ (x = 0.1, y = 0.16, z = 0.08–0.24; x = 0.1, y = 0.08, z = 0.08; x = 0.1 y = 0, z = 0.16, 0.24) phosphor 106 3.2.2 Crystal fiber growth of Y3−yAl5−xO12:xCr3+/4+,yCa2+ (x = 0.1, y = 0, 0.16) and Y3−y−zAl5−xO12:xCr3+/4+,yCa2+,zMg2+ (x = 0.1, y = 0.16, z = 0.08) 106 3.2.3 Powder X-ray diffraction and synchrotron X-ray diffraction analyses 107 3.2.4 Transmission electron microscope (TEM)/Scanning TEM with energy dispersive X-ray spectroscopy 108 3.2.5 X-ray absorption spectroscopy 108 3.2.6 Electron paramagnetic resonance spectroscopy 109 3.2.7 Photoluminescence excitation/emission spectrum measurements 109 3.2.8 Internal quantum efficiency 110 3.2.9 Temperature- and pressure-dependent photoluminescence spectrum measurements 110 3.2.10 Luminescence kinetics measurements 111 3.2.11 Optical spectrum analysis 111 3.2.12 Electron probe microanalysis 112 3.3 Results and Discussion 112 3.3.1 Crystal structure and morphology of Y3−yAl5−xO12:xCr3+/4+,yCa2+ 112 3.3.2 Local environment of Y3−yAl5−xO12:xCr3+/4+,yCa2+ 119 3.3.3 Photoluminescence of Y3−yAl5−xO12:xCr3+/4+,yCa2+ 123 3.3.4 Crystal fiber growth and demonstration of Y3−yAl5−xO12:xCr3+/4+,yCa2+ 135 3.3.5 Crystal structure and morphology of Y3−y−zAl5−xO12:xCr3+/4+,yCa2+,zMg2+ 138 3.3.6 Local environment of Y3−y−zAl5−xO12:xCr3+/4+,yCa2+,zMg2+ 146 3.3.7 Photoluminescence of Y3−y−zAl5−xO12:xCr3+/4+,yCa2+,zMg2+ 150 3.3.8 Crystal fiber growth and demonstration of Y3−y−zAl5−xO12:xCr3+/4+,yCa2+,zMg2+ 156 3.4 Summary 157 Chapter 4 Blue Light-Pumped Ga1.98−2xGexO3:0.02Cr3+,xNi2+ Energy Transfer Shortwave Infrared Phosphor for Broadband Optical Fiber Amplifiers and Light-Emitting Diodes Applications 159 4.1 Introduction 159 4.2 Experimental Section 161 4.2.1 Synthesis of Ga1.98−2xGexO3:0.02Cr3+,xNi2+ (x = 0–0.020) and Ga1.97Ge0.015O3:0.015Ni2+ 161 4.2.2 Crystal fiber growth of Ga1.95Ge0.015O3:0.02Cr3+,0.015Ni2+ 161 4.2.3 Powder X-ray diffraction and synchrotron X-ray diffraction analyses 162 4.2.4 X-ray absorption spectroscopy 162 4.2.5 Electron paramagnetic resonance spectroscopy 162 4.2.6 Photoluminescence excitation/emission spectrum measurements 163 4.2.7 Internal quantum efficiency 163 4.2.8 Temperature- and pressure-dependent photoluminescence spectrum measurements 163 4.2.9 Luminescence kinetics measurements 164 4.2.10 Optical spectrum analysis 165 4.2.11 Electron probe microanalysis 165 4.3 Results and Discussion 166 4.3.1 Crystal structure of Ga1.98−2xGexO3:0.02Cr3+,xNi2+ 166 4.3.2 Local environment of Ga1.98−2xGexO3:0.02Cr3+,xNi2+ 169 4.3.3 Photoluminescence of Ga1.98−2xGexO3:0.02Cr3+,xNi2+ 173 4.3.4 Crystal fiber growth and LED package Ga1.98−2xGexO3:0.02Cr3+,xNi2+ 185 4.4 Summary 191 Chapter 5 Tuning Shortwave Infrared Emission Wavelengths by Chemical Pressure in Cr3+,Ni2+ Co-Doped Spinel Phosphors 192 5.1 Introduction 192 5.2 Experimental Section 194 5.2.1 Synthesis of Mg0.98Ga1.94−2xAl2xO4:0.06Cr3+,0.02Ni2+ (x = 0–0.9) and Mg0.98+yGa1.94−2ySnyO4:0.06Cr3+,0.02Ni2+ (y = 0–0.9) spinel phosphor 194 5.2.2 Powder X-ray diffraction and synchrotron X-ray diffraction analyses 194 5.2.3 X-ray absorption spectroscopy 195 5.2.4 Electron paramagnetic resonance spectroscopy 196 5.2.5 Photoluminescence excitation/emission spectrum measurements 196 5.2.6 Internal quantum efficiency 197 5.2.7 Temperature- and pressure-dependent photoluminescence spectrum measurements 197 5.2.8 Luminescence kinetics measurements 199 5.3 Results and Discussion 199 5.3.1 Crystal structure of Mg0.98Ga1.94−2xAl2xO4:0.06Cr3+,0.02Ni2+ and Mg0.98+yGa1.94−2ySnyO4:0.06Cr3+,0.02Ni2+ spinel phosphor 199 5.3.2 Local environment of Mg0.98Ga1.94−2xAl2xO4:0.06Cr3+,0.02Ni2+ and Mg0.98+yGa1.94−2ySnyO4:0.06Cr3+,0.02Ni2+ spinel phosphor 208 5.3.3 Photoluminescence of Mg0.98Ga1.94−2xAl2xO4:0.06Cr3+,0.02Ni2+ and Mg0.98+yGa1.94−2ySnyO4:0.06Cr3+,0.02Ni2+ spinel phosphor 216 5.3.4 LED package and demonstration of Mg0.98Ga1.94−2xAl2xO4:0.06Cr3+,0.02Ni2+ and Mg0.98+yGa1.94−2ySnyO4:0.06Cr3+,0.02Ni2+ spinel phosphor 237 5.4 Summary 239 Chapter 6 Enhancement of Er3+ Shortwave Infrared Emission through Cr3+ Cluster Energy Transfer Pathway in Partially Inverse Spinel Phosphor 240 6.1 Introduction 240 6.2 Experimental Section 242 6.2.1 Synthesis of MgGa2−x−yO4:xCr3+,yEr3+ (x = 0.02, y = 0–0.036; x = 0.06, y = 0–0.028) spinel phosphor 242 6.2.2 Powder X-ray diffraction and synchrotron X-ray diffraction analyses 242 6.2.3 X-ray absorption spectroscopy 243 6.2.4 Transmission electron microscope (TEM)/Scanning TEM with energy dispersive X-ray spectroscopy 243 6.2.5 Electron paramagnetic resonance spectroscopy 243 6.2.6 Photoluminescence excitation/emission spectrum measurements 244 6.2.7 Internal quantum efficiency 244 6.2.8 Temperature- and pressure-dependent photoluminescence spectrum measurements 245 6.2.9 Luminescence kinetics measurements 246 6.3 Results and Discussion 246 6.3.1 Crystal structure of MgGa2−x−yO4:xCr3+,yEr3+ spinel phosphor 246 6.3.2 Local environment of MgGa2−x−yO4:xCr3+,yEr3+ spinel phosphor 254 6.3.3 Photoluminescence of MgGa2−x−yO4:xCr3+,yEr3+ spinel phosphor 256 6.3.4 LED package and demonstration of MgGa2−x−yO4:xCr3+,yEr3+ spinel phosphor 274 6.4 Summary 277 Chapter 7 Conclusions and Future Perspectives 278 References 281 Publications in International Scientific Journals 304 Patents 308 | - |
| dc.language.iso | en | - |
| dc.subject | 螢光粉 | zh_TW |
| dc.subject | 短波紅外線 | zh_TW |
| dc.subject | 晶體光纖 | zh_TW |
| dc.subject | 光纖放大器 | zh_TW |
| dc.subject | 能量轉移 | zh_TW |
| dc.subject | 發光二極體 | zh_TW |
| dc.subject | Light-emitting diode | en |
| dc.subject | Shortwave infrared | en |
| dc.subject | Crystal fiber | en |
| dc.subject | Optical fiber amplifier | en |
| dc.subject | Energy transfer | en |
| dc.subject | Phosphor | en |
| dc.title | 短波紅外線螢光粉調控及其於光纖放大器與發光二極體之應用 | zh_TW |
| dc.title | Control of Shortwave Infrared Phosphors and Their Applications in Optical Fiber Amplifiers and Light-Emitting Diodes | en |
| dc.type | Thesis | - |
| dc.date.schoolyear | 113-2 | - |
| dc.description.degree | 博士 | - |
| dc.contributor.oralexamcommittee | 陳威廷;彭之皓;吳學亮;許火順;蘇昭瑾;李育群 ;蔡易州 | zh_TW |
| dc.contributor.oralexamcommittee | Wei-Tin Chen;Chi-How Peng;Hsyueh-Liang Wu;Hwo-Shuenn Sheu;Chaochin Su;Yu-Chun Lee;Yi-Chou Tsai | en |
| dc.subject.keyword | 螢光粉,短波紅外線,晶體光纖,光纖放大器,能量轉移,發光二極體, | zh_TW |
| dc.subject.keyword | Phosphor,Shortwave infrared,Crystal fiber,Optical fiber amplifier,Energy transfer,Light-emitting diode, | en |
| dc.relation.page | 308 | - |
| dc.identifier.doi | 10.6342/NTU202502961 | - |
| dc.rights.note | 同意授權(限校園內公開) | - |
| dc.date.accepted | 2025-07-31 | - |
| dc.contributor.author-college | 理學院 | - |
| dc.contributor.author-dept | 化學系 | - |
| dc.date.embargo-lift | 2025-08-22 | - |
| Appears in Collections: | 化學系 | |
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