臺灣博碩士論文加值系統

本研究是以溶膠–凝膠法製備鎂橄欖石(Forsterite; Mg2SiO4)螢光粉末，並探討不同活化劑濃度及熱處理條件對其結構、微結構及發光特性之影響。
乾燥粉末經熱處理溫度達500oC時開始產生鎂橄欖石結晶相，隨著溫度上升至1100oC皆為純相鎂橄欖石，至1300oC主要為鎂橄欖石相但含有少量頑火輝石(Enstatite)結晶。粉末的激發與放射強度均隨著熱處理溫度增加而增加，歸因於較高的熱處理溫度可以使晶粒的結晶性增強。摻雜錳或銪之粉末分別經469 nm及393 nm波長激發後，放射峰分別位於510 nm及614 nm，具有綠光、橘紅光發光特性。經還原氣氛後摻雜錳會增強綠光發光強度，而摻雜銪則會改變激發波長為343 nm進而產生446 nm放射峰，具有藍光特性，活化劑種類與濃度及熱處理條件會影響粉末晶粒大小、結晶性以及發光特性。

In this study, forsterite (Mg2SiO4) phosphor powders were synthesized by the sol–gel method. The effects of various activators and heat treatment conditions on the structure, microstructure and luminescent properties were investigated.
Mg2SiO4 powder started to crystallize into forsterite phase after heat treatment at 500oC. After heat treatment at 1100oC, forsterite is still the main crystalline phase. With heating to 1300oC, forsterite is still the dominant phase with a small amount of enstatite.
Both the excitation and emission intensity of the powder increase with the increase of the heating temperature, due to the higher heat treatment temperature can increase their crystallinity.
Under excited at 469 nm or 393 nm, the powders doped with manganese or europium show green or orange-red light emission with the peaks at 510 or 614 nm, respectively. When the phosphor powders heat treatment in reducing atmosphere, an enhancement of emission intensity is observed in the manganese-doped powders. While europium-doped powders change the excitation wavelength to 343 nm and generate an emission peak of 446 nm, with blue light characteristics. The microstructure and luminescence of powders were dependent on the species and concentration of activator as well as the heat treatment conditions.

摘要..i
Abstract..ii
誌謝..iv
目錄..v
表目錄..ix
圖目錄..x
第一章 緒論...1
1.1 前言..1
1.2 研究動機..2
第二章 基礎理論及文獻回顧..4
2.1鎂橄欖石晶體結構..4
2.2鎂橄欖石特性與應用..4
2.3鎂橄欖石螢光粉末之製備方法...9
2.3-1固態反應法(Solid state reaction)...9
2.3-2水熱法（Hydrothermal method）...9
2.3-3燃燒法(Combustion Synthesis)....9
2.3-4溶膠–凝膠法(Sol–gel method)...9
2.4溶膠–凝膠法..11
2.4-1溶膠-凝膠法原理..11
2.4-2 影響溶膠-凝膠製程的因素..11
2.5螢光材料的特性..13
2.5-1 發光原理...13
2.5-2 發光機制..13
2.5-3史托克位移...13
2.5-4發光材料組成...13
2.5-5發光種類...14
2.5-6影響螢光材料之發光效率因素...14
2.5-7 CIE色度座標......15
2.6研究目的... 16
第三章 實驗方法與步驟.. 22
3.1 實驗流程... 22
3.2 分析儀器與原理介紹 ...24
3.2-1 X光繞射分析(XRD).. 24
3.2-2示差掃描熱量分析/熱重分析 (DSC-TGA) ...24
3.2-3傅立葉紅外線轉換光譜 (FT-IR)... 24
3.2-4場發射掃描式電子顯微鏡 (FE-SEM )... 24
3.2-5場發射穿透式電子顯微鏡 (FE-TEM )... 24
3.2-6紫外光/可見光光譜 (UV-Vis)... 24
3.2-7光光電子能譜 (XPS)... 25
3.2.8 電子順磁共振光譜 (EPR)... 25
3.2-9螢光光譜 (PL)... 25
第四章 結果與討論... 31
4.1 溶膠–凝膠反應... 31
4.2 X光繞射圖分析(XRD)... 33
4.3傅立葉紅外線轉換光譜 (FT-IR)...38
4.4熱重分析與熱示差掃描分析...40
4.5 SEM分析..44
4.6 TEM分析..48
4.7 XPS分析..51
4.8 EPR分析..57
4.9 UV-Vis分析..59
4.10 PL分析..63
4.11 衰減時間量測分析..74
4.12 色度座標分析..76
第五章 結論.....82
參考文獻........83
Extended Abstract....87


















表目錄
Table 1.1 Luminescence properties of Mg2SiO4 prepared by different processes...3
Table 2.1 Physical properties and applications of Mg2SiO4.....6
Table 2.2 Luminescence properties of some Mn-, Eu- ,or Cr-doped prepared by different processes...7
Table 3.1 Experimental Materials..22
Table 4.1 Effect of different concentrations of manganese activator on the sol-gel state...32
Table 4.2 Effect of different concentrations of europium activator on the sol-gel state..32
Table 4.3 Average grain size of Mg2SiO4 powders after heat treatment at 600~1300oC.......34
Table 4.4 Effect of doping concentration on the grain size and lattice constant of samples heat treatment at 1300oC....37
Table 4.5 The glass transition temperature and activation energy of undoped Mg2SiO4 powder.....43
Table 4.6 Calculation of the ratio of Mn2+, Mn3+, Eu3+, Eu2+,after annealing in defferent atmosphere.....56
Table 4.7 Absorption edge and band gap energy of samples....62
Table 4.8 Decay time of Mg2SiO4: Eu phosphors.....75














圖目錄
Figure 2.1 Crystal structure of Mg2SiO4.....5
Figure 2.2 Phase diagram of Mg2SiO4....8
Figure 2.3 Sol-gel process ....10
Figure 2.4 Schematic diagram of hydrolysis and condensation polymerization by Sol-gel method....12
Figure 2.5 Schematic diagram of Stokes shift of phosphor.....17
Figure 2.6 Schematic diagram of activator energy transfer in the host lattice.....18
Figure 2.7 Schematic diagram of energy transfer between sensitizer and activator in the host lattice....19
Figure 2.8 Schematic diagram of thermal quenching....20
Figure 2.9 Schematic diagram of concentration quenching....21
Figure 3.1 Experimental flow chart.....23
Figure 3.2 X-ray Diffractometer...26
Figure 3.3 Thermogravimetric Analysis/ Differential Scanning Calorimeter.....26
Figure 3.4 FT-IR spectrometers.....27
Figure 3.5 Field-Emission Scanning Electron Microscope....27
Figure 3.6 Field-Emission Scanning Electron Microscope.....28
Figure 3.7 UV-Vis spectrometer....28
Figure 3.8 X-ray photoelectron spectroscopy....29
Figure 3.9 Electron paramagnetic resonance....29
Figure 3.10 Photoluminescence spectrometer.....30
Figure 4.1 XRD patterns of Mg2SiO4 powders after heat treatment at 400~1300oC....34
Figure 4.2 (a) XRD patterns of Mg2SiO4:x Mn with various dopant contents heat treatment at 1300oC.(b) The peak positions of (112) diffraction plane....35
Figure 4.3 (a) XRD patterns of Mg2SiO4:y Eu with various dopant contents heat treatment at 1300oC.(b) The peak positions of (112) diffraction plane.....36
Figure 4.4 FT-IR spectra of sample undoped Mg2SiO4 heat treatment at different temperatures....39
Figure 4.5 TGA/DSC curves of sample undoped Mg2SiO4 with heat rate of 10°C/min....41
Figure 4.6 TGA/DSC curves of sample undoped Mg2SiO4 with heat rate of 5°C/min....41
Figure 4.7 TGA/DSC curves of sample undoped Mg2SiO4 with heat rate of 20°C/min...42
Figure 4.8 SEM images of samples undoped Mg2SiO4 with different heat treatment temperature: (a)600oC, (b)1100oC, and (c) 1300oC....45
Figure 4.9 SEM image of samples M2 (Mn=1%) after heat treatment at 1300oC.....46
Figure 4.10 SEM image of samples E3 (Eu=5%) after heat treatment at 1300oC.....47
Figure 4.11 TEM images of samples F5 (a)600 oC, (b) 1100oC, (c) 1300oC, (d)SAD image, (e)HR-TEM image and (f) EDS spectrum.....49
Figure 4.12 TEM image of samples M2 after heat treatment at 1300oC.....50
Figure 4.13 TEM image of samples E3 after heat treatment at 1300oC....50
Figure 4.14 XPS patterns of Mn2p: (a) heat treatment at 1300oC in air, (b) heat treatment at 1300oC and then heat treatment at 1100oC in reducing atmosphere....52
Figure 4.15 XPS patterns of Eu3d: (a) heat treatment at 1300oC in air, (b) heat treatment at 1300oC and then heat treatment at 1100oC in reducing atmosphere....53
Figure 4.16 XPS spectra of the O1s level for undoped Mg2SiO4...54
Figure 4.17 XPS spectra of the O1s level for Mn-doped Mg2SiO4...54
Figure 4.18 XPS spectra of the O1s level for Eu-doped Mg2SiO4....55
Figure.4.19 EPR spectrum of sample M2 heat treatment at 1300℃...58
Figure.4.20 EPR spectrum of sample E3 heat treatment at 1300℃...58
Figure 4.21 Absorption spectra of Mg2SiO4:x Mn with various dopant contents heat treatment at 1300oC in air: (a)absorption spectra and (b)tauc curves....60
Figure 4.22 Absorption spectra of Mg2SiO4: y%Eu with various dopant contents heat treatment at 1300oC in air: (a) absorption spectra and (b) tauc curves.....61
Figure 4.23 (a) Excitation and (b) emission spectra of Mg2SiO4:1%Mn phosphor heat treatment at 600~1300oC in air....65
Figure 4.24 (a) Excitation and (b) emission spectra of Mg2SiO4:x%Mn phosphor heat treatment at 1300oC in air....66
Figure 4.25 (a) Excitation and (b) emission spectra of Mg2SiO4:1%Mn phosphor heat treatment at 1300oC in air and then at 1100oC in reducing atmosphere....67
Figure 4.26 (a) Excitation and (b) emission spectra of Mg2SiO4:5%Eu phosphor heat treatment at 600~1300oC in air....68
Figure 4.27 (a) Excitation and (b) emission spectra of Mg2SiO4:y%Eu phosphor heat treatment at 1300oC in air....69
Figure 4.28 (a) Excitation and (b) emission spectra of Mg2SiO4: y%Eu heat treatment at 1300oC and then at 1100oC in reducing atmosphere.....70
Figure 4.29 (a) Excitation and (b) emission spectra of Mg2SiO4: y%Eu heat treatment at 1100oC in reducing atmosphere.....71
Figure 4.30 (a) Excitation and (b) emission spectra of Mg2SiO4: 5%Eu heat treatment at 1300oC and 1100oC in reducing atmosphere......72
Figure 4.31 Emission spectra of Mg2SiO4: 1%Mn and 5%Eu heat treatment at 1300oC in air.....73
Figure 4.32 Emission spectra of Mg2SiO4: 1%Mn and 5%Eu heat treatment at 1300oC in air and then 1100oC in reducing atmosphere..........................73
Figure 4.33 Decay time curves of Mg2SiO4: y%Eu phosphors heat treatment at 1300oC ( λem = 614 nm)....75
Figure 4.34 CIE color coordinates for Mg2SiO4: xMn% powders heat treatment at 1300oC in air and 1%Mn in reducing atmosphere.....77
Figure 4.35 CIE color coordinates for Mg2SiO4: yEu% heat treatment at 1300oC in air......78
Figure 4.36 CIE color coordinates for Mg2SiO4: y%Eu heat treatment at 1300oC in air and then at 1100oC in reducing atmosphere......79
Figure 4.37 CIE color coordinates for Mg2SiO4: y%Eu heat treatment at 1100oC in reducing atmosphere.....80
Figure 4.38 CIE color coordinates for Mg2SiO4: 1%Mn and 5%Eu heat treatment at 1300oC in air.....81

[1]L. Lin, M. Yin, C. Shi, & W. Zhang, 2008, “Luminescence properties of a new red long-lasting phosphor:Mg2SiO4: Dy3+, Mn2+”, Journal of Alloys and Compounds, 455, 327–330.
[2]Y. Nanai, R. Ishida, Y. Urabe, S. Nishimura, & S. Fuchi, 2019,“ Octave-spanning broad luminescence of Cr3+, Cr4+-codoped Mg2SiO4 phosphor for ultra-wideband near-infrared LEDs” ,Journal of Applied Physics 58, SFFD02.
[3]C. Zhao, Y. H. Wu, D.H. Wang, S.X.Cao, S.Y.Chen, L.L.Peng, & D.C.Zhu, 2019,“A near-ultraviolet (NUV) converting blue-violet Mg2SiO4:Ce3+ phosphor for white light-emitting-diodes (w-LEDs)”,Journal of Luminescence,Volume 207, March, 241-245.
[4]S. C. Prashanthaa, B. N. Lakshminarasappa, & B. M. Nagabhushana, 2011, “Photoluminescence and thermoluminescence studies of Mg2SiO4:Eu3+ nano phosphor”, Journal of Alloys and Compounds,509 10185–10189.
[5]R. Naik, S.C. Prashantha, & H. Nagabhushana, 2017, “Effect of Li+ codoping on structural and luminescent properties of Mg2SiO4:RE3+ (RE=Eu, Tb) nanophosphors for displays and eccrine latent fingerprint detection”, Optical Materials,72,295-304.
[6]H. Yang, J. Shi, M. Gong, & K.W. Cheah, 2006,“Synthesis and photoluminescence of Eu3+- or Tb3+-doped Mg2SiO4 nanoparticles prepared by a combined novel approach”, Journal of Luminescence,118,257–264.
[7]L.Lin, Y.Min, S.Chaoshu, & Z.Weiping, 2006, “Synthesis and Luminescence Properties of Red Phosphors : Mn-Doped MgSiO3 and Mg2SiO4 Prepared by Sol-Gel Method”, Journal of Rare Earth Vol. 24, Spec. Issue, Dee, p.104.
[8]D.G.Park,J.M.Burlitch,R.F.Geray,R.Dieckmann,D.B.Barber,& .R.Pollock, 1993,“Sol-Gel Synthesis of Chromium-Doped Forsterite”, J. Mater. Chem,5,518-524.
[9]Nora H. de Leeuw, 2001,“Density Functional Theory Calculations of Hydrogen-Containing Defects in Forsterite, Periclase, and r-Quartz”, J. Phys. Chem. B, 105, 9747-9754
[10]R.Michel, M.R.Ammar, J.Poirier, & P.Simon,2013,“Phase transformation characterization of olivine subjected to high temperature in air”,Ceramics International,39,5287–5294.
[11]K. Mondal, P. Kumari, & J. Manam, 2016, “Influence of doping and annealing temperature on the structural and optical properties of Mg2SiO4:Eu3+ synthesized by combustion method”Current Applied Physics,16 707-719.
[12]R. Lv, C. Zhong, A.Gulzar, S.Gai, F.He, R. Gu, S. Zhang, G.Yang, & P.Yang, 2012,“Synthesis, luminescence,and anti-tumor properties of MgSiO3:Eu-DOX-DPP-RGD hollow microspheres”, J. Name,00,1-3.
[13]K. Mostafavi, M. Ghahari,S. Baghshahi, & A.M. Arabi, 2013,“Synthesis of Mg2SiO4:Eu3+ by combustion method and investigating its luminescence properties”, Journal of Alloys and Compounds, 555, 62–67.
[14]Y.Li, Y.Wang, X.Xu, G.Yu, & F. Zhang, 2010, “Photoluminescence Properties and Valence Stability of Eu in CaMgSiO4”Journal of The Electrochemical Society, 157 ,2, J39-J43.
[15]H.K. Jung, & K.S.Seo, 2006,“Luminescent properties of Eu2+-activated(Ba, Sr)3MgSi2O8 phosphor under VUV irradiation”, Optical Materials 28, 602–605.
[16]R. Naik, S.C. Prashantha, H. Nagabhushana, S.C. Sharma, H.P.Nagaswarupa,& K.M. Girish,2016 ,“Effect of fuel on auto ignition route, photoluminescence and photometric studies of tunable red emitting Mg2SiO4:Cr3+ nanophosphors for solid state lighting applications”Journal of Alloys and Compounds Volume 682,815-824.
[17]S.M.Kaczmarek, W.Chen, & G. Boulon, 2006,“Recharging processes of Cr ions in Mg2SiO4 and Y3Al5O12 crystals under influence of annealing and γ - irradiation”,Cryst.Res.Technol.41,No.1,41-47.
[18]W. Chen, R. Sammynaiken, Y. Huang, J.O. Malm, R. Wallenberg, J.O. Bovin, V. Zwiller,& N.A.Kotov, 2001,“Crystal field, phonon coupling and emission shift of Mn2+ in ZnS:Mn nanoparticles”, Journal of Applied Physics 89,1120.
[19]K.W. Park, H.S. Lim, S.W. Park, G. Deressa, & J.S. Kim, 2015,“Strong blue absorption of green Zn2SiO4:Mn2+ phosphor by doping heavy Mn2+ concentrations”, Chemical Physics Letters, 636,141–145.
[20]I.H.Jung, S.A.Decterov, & A.D.Pelton, 2005,“Critical thermodynamic evaluation and optimization of the CaO–MgO–SiO2 system”, Journal of the European Ceramic Societ,25, 313–333
[21]S.K.Tripathi, R. Kaur, & M.Rani, 2015,“Oxide Nanomaterials and their Applications as a Memristor”,Solid State Phenomena,Vol. 222,67-97.
[22]C.J.Brinker, G.W.Scherer, 1990,“Sol-Gel Science:The Physics and Chemistry of Sol-Gel Processing”.
[23]N.Dutta,2016,“Hybrid Organic/Inorganic Coatings Through Dual-Cure Processes: State of the Art and Perspectives”,Coatings,6,10.
[24]L.Bao, Z.L.Zhang, Z.Q.Tian, L.Zhang, C.Liu, Y.Lin, B.Qi, & D.W.Pang, 2011,“Electrochemical Tuning of Luminescent Carbon Nanodots: From Preparation to Luminescence Mechanism” Adv. Mater,23,5801–5806.
[25]S.Bakhoda, M.K.Assadi, S.A.Kandjani, H. H.Al_Kayiem, & A.H.Bhat, 2018,“Application of Quantum Dot nanocrystal in Luminescent solar concentrators”, Materials Science and Engineering,328,12-22.
[26]K.Liu, N.Zhao, C.Wang, B.Qu, & L.Wang, 2020,“Synthesis and Photoluminescent Properties of Deep-Red Emission Phosphor BaZnAl10O17:Cr3+”,Applied Physics,10(4),246-256.
[27]柯韋志，陳奕光，粘群，林皇羽，林芳宇，曾敬媛，盧弘毅，王博漢，羅英豪，陳維翔，“化學與光電”，日期不詳。
[28]P.Halappa, & C.Shivakumara, 2017, “Synthesis and Characterization of Luminescent La2Zr2O7/Sm3+ Polymer Nanocomposites”,Trends and Applications in Advanced Polymeric Materials,163–190.
[29]M. JABOYEDOFF, B. KUÈ BLER, & PH.THELIN,1999,“An empirical Scherrer equation for weakly swelling mixed-layer minerals, especially illite-smectite”, Clay Minerals,34,601-617.
[30]簡文昱，2015，“A study of the crystal structural variations related to alkaline earth orthosilicate (Sr1-xBax)2SiO4 solid solutions”,國立成功大學地球科學研究所碩士論文。
[31]M.T. Tsai, 2003, “Preparation and crystallization of forsterite fibrous gels”, Journal of the European Ceramic Society, 23,1283–1291.
[32]F.Ghariani, R.Fezei, & A. H. Hamzaoui, 2018,“Synthesis,characterization, and application of sol gel derived Mg2SiO4 powder”, Journal of Sol-Gel Science and Technology,volume 88,100–104.
[33]S.Rastegari, O.S.M.Kani, E.Salahinejad, S.Fadavi, N.Eftekhari,A.Nozariasbmarz, L.Tayebi, & D.Vashaee, 2016,“Non-hydrolytic sol-gel processing of chloride precursors loaded at forsterite stoichiometry”, Journal of Alloys and Compounds,688,235-241.
[34]T.S.Sasikala,M.T.Sebastian, 2016,“Mechanical,thermal and microwave dielectric properties of Mg2SiO4 filled Polyteterafluoroethylene composites”,Ceramics International,42,7551–7563.
[35]M.I.Martın, F.Andreolab , L.Barbieri , F.Bondioli , I. Lancellotti , J.Ma. Rinco´n, & M. Romeroa, 2013,“Crystallisation and microstructure of nepheline–forsterite glass-ceramics”,Ceramics International,39,2955–2966.
[36]H.Schulz, 2018,“From the Kissinger equation to model-free kinetics:reaction kinetics of thermally initiated solid-state reactions”, Article number:9.
[37]C. Chai, C. Fan, J. Liu, X. Zhang, Y. Wang, R. Li, D. Duan, 2019, “Photoinduced g–C3N4–promoted Mn2+/Mn3+/Mn4+ redox cycles for activation of peroxymonosulfate” Journal of Solid State Chemistry,277,466–474.
[38]D.Li, X.Zhang, L.Jin, & D. Yang, 2010,“ Structure and luminescence evolution of annealed Europium-doped silicon oxides films” ,Optics Express, No. 26, Vol. 18,27191
[39]R.A.Shepherd, & W.R.M.Graham,1984, “EPR of Mn2+ in polycrystalline dolomite”,J. Chem. Phys.81,6080.
[40]N.Dhananjaya, C.Shivakumara, Rohit Saraf, & H.Nagabhushana, 2016,“Red-emitting LaOF:Eu3+ phosphors: Synthesis, structure and their Judd–Ofelt analysis for LED applications”, Materials Research Bulletin,75,100–109.
[41]K.Baishya, J.S.Ray, P. Dutta, P.P.Das, S.K.Das,2018,“Graphene-mediated band gap engineering of WO3 nanoparticle and a relook at Tauc equation for band gap evaluation”, Applied Physics A volume 124, Article number:704.
[42]G.Lakshminarayana, & S.Buddhudu, 2006,“Spectral analysis of Mn2+, Co2+ and Ni2+: B2O3–ZnO–PbO glasses”, Spectrochimica Acta Part A ,63, 295–304
[43]J.Ha, Z.Wang, E.Novitskaya,G.A. Hirata, O.A. Graeve, S.P.Ong, & J.McKittrick , 2016,“An integrated first principles and experimental investigation of the relationship between structural rigidity and quantum efficiency in phosphors for solid state lighting”, Journal of Luminescence Volume 179, 297-305.
[44]R.Vijayakumar, & K.Marimuthu,2016,“Luminescence studies on Ag nanoparticles embedded Eu3+doped Boro-phosphate glasses”, Journal of Alloys and Compounds,Volume 665,294-303.
[45]C.Huang,P.J.Wu, J.F.Lee, & T.M.Chen,2011,“(Ca,Mg,Sr)9Y(PO4)7:Eu2+,Mn2+: Phosphors for white-light near-UV LEDs through crystal field tuning and energy transfer”, J. Mater. Chem., 2011, 21,10489–10495.