本實驗利用微乳膠法合成添加稀土離子之二氧化矽球形粒子，藉由改變油水(W/O)的比例、溫度及固結劑(APTES)添加量調整其粒子大小及球形外觀。由實驗發現當W/O=8%有相對穩定的微胞產生對於球形粒子的合成有顯著的影響；而溫度影響TEOS的水解縮合速率，若溫度過低使其反應速率過慢，微胞彼此容易團聚成團，反之溫度過高則會使的界面活性劑崩解而微胞破裂無法形成球形粒子，研究發現50˚C溫度區間有較適當的合成溫度；而不同固結劑的添加量影響著合成球形粒徑大小，實驗發現需要有足夠的APTES包附球體表面才能產生均一的粒徑分布且APTES/TEOS=2%為較理想的添加量，可合成均一粒徑約1-2 μm之球形粒子。在螢光性質方面，在添加Eu3+於球形SiO2中發現添加3 mole % Eu3+有最好的發光效率，一旦Eu3+之添加濃度大於3 mole %時，則會因為濃度焠滅的緣故使得螢光效率反而減弱。此外，適當添加Al離子於SiO2粒子中，有助於誘發部份Eu3+還原成具有藍色螢光特徵之Eu2+，使合成之SiO2: (Eu, Al)粒子成為同時具有藍、紅光特性之螢光材料。最後，添加具有綠光特徵之Tb於SiO2: (Eu, Al)粒子中，即可獲得同時具有藍、綠、紅三原色螢光之SiO2球形粒子。唯Tb與Eu間有明顯的能量轉移現象發生，因此Tb之綠光強度受此影響而效率相對較低。本研究成功藉由Eu, Tb, Al三種離子的添加，合成具有多色螢光性質之SiO2球形粒子，並透過離子濃度以及激發波長的控制，適當調整合成粒子之最終螢光色彩表現。

Silica microspheres doped with rare-earth were successfully synthesized by sol-gel microencapsulation method. In the Water-to-oil system, the effects of the synthetic procedure on spherical silica microcapsules have been investigated. This study was found that the effect of parameters on spherical morphology according to the four parameters: the amount of solidifier (APTES), W/O ratio, temperature and concentration of europium nitrate. The results of this study showed that the particle size around 1-2 m was obtained when the amount of APTES/Si = 2 %, the stable emulsion droplets was observed at W/O= 8 % and the synthesis temperature is suitable at 50 ˚C due to the appropriate hydrolysis rate of TEOS. In the optical property, the emission intensity is found at 3 mole% Eu3+ and a concentration quenching is occurred when the doping concentration increases up to 6 mole%. When Al3+ is incorporated in SiO2: Eu microspheres, it is confirmed that a reduction of Eu3+ to Eu2+ can be spontaneous in air. In the SiO2: (Eu, Tb) into silica microspheres, the excitation spectrum of Tb3+ is strongly modified by with Eu. The fluorescent properties of Tb3+ are strongly modified by with Eu2+ in (Eu, Tb, Al) co-doped silica microspheres. Owing to the energy transfer between Eu2+ and Tb3+, the fluorescent intensity of Tb3+ decreases. In the tricolor fluorescence system, the SiO2: (Eu, Tb, Al) exhibiting blue, green and red colors are successfully obtained.

1. Afify, N. D., Mountjoy, G., “Molecular-dynamics modeling of Eu3+-ion clustering in SiO2 glass”,Physical Review B”, 2009. 79(2)024202. p.1.
2. Armellini, C.,Ferrari, M.,Montagna, M.,Pucker, G.,Bernard, C.,Monteil, A, “Terbium(III) doped silica-xerogels: effect of aluminium(III) co-doping”, Journal of Non-Crystalline Solids, 1999. 245: p. 115.
3. Hu, X. Y., Fan, J., Li, T., Zhang, D. K., Bai, J. T., Ren, Z. Y., Hou, X., “ Novel trichromatic phosphor co-doped with Eu, Tb in SiO2 gel matrix”,Chinese Science Bulletin, 2007. 52(4): p. 444.
4. Song, C. F., Yang, P., Lu, M. K., Xu, D., Yuan, D. R., Liu, Z. Q., “Enhanced blue emission from Eu, Dy co-doped sol-gel Al2O3-SiO2 glasses”, Journal of Physics and Chemistry of Solids, 2003. 64(3): p. 491.
5. Ntwaeaborwa, O. M., Swart, H. C., Kroon, R. E., Holloway, P. H., Botha, J. R., “Photoluminescence of cerium-europium co-doped SiO2 phosphor prepared by a sol-gel process”, Surface and Interface Analysis, 2006. 38(4): p. 458.
6. Chang, S.M., Lee, M., and Kim, W.-S., “Preparation of large monodispersed spherical silica particles using seed particle growth”, Journal of Colloid and Interface Science, 2005. 286(2): p. 536.
7. Stiefelhagen, J.C.P., “Incorporating lanthanides into silica colloids”, Universiteit Utrecht Soft Condensed Matter, 2006.
8. Kobayashi, Y., Imai, J., Nagao, D., Konno, M., “Fabrication of Eu-coated silica particles by homogeneous precipitation method”, Colloids and Surfaces a-Physicochemical and Engineering Aspects, 2008. 326(1-2): p. 109.
9. Matsumoto, T., Takayama, Y., Onoda, H., Kojima, K., Wada, N., “Synthesis of Rhodamine B-Doped and Monodispersed Spherical Particles of Polyorganosiloxane Using a W/O Emulsion”, Journal of the American Ceramic Society, 2005. 88(12): p. 3458.
10.Park, S.K., Kim, K. Do, and Kim, H.T., “Preparation of silica nanoparticles: determination of the optimal synthesis conditions for small and uniform particles”, Colloids and Surfaces a-Physicochemical and Engineering Aspects, 2002. 197(1-3): p. 7.
11.張俊鴻, 以EDTA、藻酸鈉對砷及鉻污染土壤萃取效率之研究. 國立中央大學, 2006.
12.林永璋, 以臭氧/紫外光程序去除乙二胺四乙酸之研究. 國立中山大學碩論, 2003.
13.Bauer, H., Blanc, J., and Ross, D.L., “ Octacoordinate Chelates of Lanthanides. Two Series of Compounds,” Journal of the American Chemical Society, 1964( 5125 ): p. 5125 .
14.Sievers, R.E., “Nuclear Magnetic Resonance Shift Reagents”, Academic Press: New York, 1973.
15.葉怡燕, 雙酮基銪化物之發光性質探討. 國立中山大學化學研究所碩士論文, 2002.
16.林清安, 界面活性劑與紡織工業應用, 2004.
17.Tabor, R. F., Eastoe, J., Dowding, P. J., Grillo, I., Heenan, R. K., Hollamby, M., “Formation of Surfactant-Stabilized Silica Organosols”, Langmuir, 2008. 24(22): p. 12793.
18.Barbé, C., Kong, L., Finnie, K., Calleja, S., Hanna, J., Drabarek, E., Cassidy, D., Blackford, M., “Sol-gel matrices for controlled release: from macro to nano using emulsion polymerisation”, Journal of Sol-Gel Science and Technology, 2008. 46(3): p. 393.
19.Jafelicci, M., Davolos, M. R., dos Santos, F. J., de Andrade, S. J., “Hollow silica particles from microemulsion”, Journal of Non-Crystalline Solids, 1999. 247: p. 98.
20.Chang, C.L. and Fogler, H.S., “Controlled formation of silica particles from tetraethyl orthosilicate in nonionic water-in-oil microemulsions”, Langmuir, 1997. 13(13): p. 3295.
21.Kim, M. S., Seok, S. I., Ahn, B. Y., Koo, S. M., Paik, S. U., “Encapsulation of water-soluble dye in spherical sol-gel silica matrices”. Journal of Sol-Gel Science and Technology, 2003. 27(3): p. 355.
22.Ahn, B.Y., Seok, S.I.L and Baek, I.C., “Sol-gel micro encapsulation of hydrophilic active compounds from the modified silicon alkoxides: The control of pore and particle size”, Materials Science & Engineering C-Biomimetic and Supramolecular Systems, 2008. 28(7): p. 1183.
23.Granadeiro, C.M., Ferreira, R.A.S., Soares-Santos, P C.R., Carlos, L.D., Trindade, T.,Nogueira, H.I.S., “Lanthanopolyoxotungstates in silica nanoparticles: multi-wavelength photoluminescent core/shell materials”, Journal of Materials Chemistry, 2010. 20(16): p. 3313.
24.Nogami, M., Shiiba, H., Kleine, G. A., Nakayama, M., Hayakawa, T., “Hydrogen Gas Permeation Through Al2O3-SiO2 Glasses Containing Metal Ions”, Journal of the American Ceramic Society, 2010. 93(11): p. 3752.
25.Yamashita, N., “Coexistence of the Eu2+ and Eu3+ centers in the CaO: Eu powder phosphor”, Journal of the Electrochemical Society, 1993. 140(3): p. 840.
26.Chen, W., Sammynaiken R., and Huang, Y., “Photoluminescence and photostimulated luminescence of Tb3+ and Eu3+ in zeolite-Y”, Journal of Applied Physics, 2000. 88(3): p. 1424.
27.Gao, Y., Shi C.S., and Wu Y., “Luminescence properties of SrB4O7: Eu, Tb phosphors. Materials Research Bulletin”, 1996. 31(5): p. 439.
28.Liu, S. M., Zhao, G. L., Ruan, W. G., Yao, Z. W., Xie, T. T., Jin, J., Ying, H., Wang, J. X., Han, G. R., “Reduction of Eu3+ to Eu2+ in aluminoborosilicate glasses prepared in air”, Journal of the American Ceramic Society, 2008. 91(8): p. 2740.
29.Nogami, M., Hayakawa, N., Sugioka, N., Abe, Y., “Formation of Sm2+ ions in sol-gel-derived glasses of the system Na2O-Al2O3-SiO2”, Journal of the American Ceramic Society, 1996. 79(5): p. 1257.
30.Solé, J.G., Bausá L.E., and Jaque D., “An Introduction to the Optical Spectroscopy of Inorganic Solids”, John Wiley & Sons, 2005: p. 6.
31.Chunlei, Y., Shixun, D., Gang, Z., Junjie, Z., Lili, H., Zhonghong J., “The effect of OH- groups on the spectroscopic properties of erbium-doped tellurite glasses”, Science in China Series E-Engineering & Materials Science, 2005. 48(6): p. 638.
32.Son, H.S., Roh, J., Shin, S.K., Park, J.W. and Ku, J.K., “ Luminescence spectroscopy of Eu(Bis-tris)3+ complexes in anhydrous DMF Bis-tris=2,2-bis(hydroxymethyl)-2,2',2'-nitrilotriethanol:luminescence quenching rate constants for the 5D0 state of Eu3+ by DMF and polyalcoholic OH groups”, Journal of the Chemical Society-Dalton Transactions, 2001(9): p. 1524.
33.Pei, Z.W., Zeng, Q.H., and Su, Q.A., “The application and a substitution defect model for Eu3+ → Eu2+ reduction in non-reducing atmospheres in borates containing BO4 anion groups”, Journal of Physics and Chemistry of Solids, 2000. 61(1): p. 9.
34.Zeng, Q., Pei, Z., Wang, S., Su, Q., “The Reduction of Eu3+ in SrB6O10 Prepared in Air and the Luminescence of SrB6O10:Eu”, Spectroscopy Letters: An International Journal for Rapid Communication, 1999. 32(6): p. 895.
35.Machida, K., Adachi, G., Moriwaki, Y., Shiokawa, J., “The crystal structure and luminescence properties of europium (ii) haloborates”, Bulletin of the Chemical Society of Japan, 1981. 54(4): p. 1048.
36.Sen, S., “Atomic environment of high-field strength Nd and Al cations as dopants and major components in silicate glasses: a Nd L-III-edge and AlK-edge X-ray absorption spectroscopic study”, Journal of Non-Crystalline Solids, 2000. 261(1-3): p. 226
37.Lochhead, M.J. and Bray, K.L., “Rare-Earth Clustering and Aluminum Codoping in Sol-Gel Silica: Investigation Using Europium(III) Fluorescence Spectroscopy”, Chemistry of Materials, 1995. 7(3): p. 572
38.Thornton, W.A., “Luminosity and color-rendering capability of white light”, Journal of the Optical Society of America, 1971. 61(9): p. 1155.
39. 要之勤, MgSiO3:Eu3+螢光粉體之製備及其光性質之研究. 國立成功大學 材料科學及工程學碩士論文, 2005.
40.Photopic and scotopic vision. http://www.prismalenceuk.com/light_vision.
41.Justel, T., Nikol, H., and Ronda, C., “New developments in the field of luminescent materials for lighting and displays”, Angewandte Chemie-International Edition, 1998. 37(22): p. 3085.
42.Park, J.K., Lim, M.A., Kim, C.H., Park, H.D., Choi, S.Y., “Effect of composition on luminescence properties of Eu2+-activated mullite”, Journal of the Electrochemical Society, 2003. 150(10): p. H246.
43.國家同步輻射中心, http://www.srrc.gov.tw/chi/about/index.html.
44.Sinex, S.A., “EDTA - A Molecule with a Complex Story”, Department of Physical Sciences and Engineering Prince George's Community College
45.Changqing H., Ting, S., Baoping Z., Weijian, T., Yaoxiang, W., “Synthesis and Fluorescence Properties of Eu(TTFA)3-doped Colloidal SiO2 Microspheres”, Actaphotonica sinica, 2006. 35.
46.Auerj, H., Blanca, O.S., and Ross N.D., “Octacoordinate Chelates of Lanthanides. Two Series of Compounds”, 1964. 86: p. 5125.
47.Kim, K.B., Koo, K.W., Cho, T.Y., Chun, H.G., “ Effect of heat treatment on photoluminescence behavior of BaMgAl10O17 : Eu phosphors”, Materials Chemistry and Physics, 2003. 80(3): p. 682.
48.Stillwell, M.T., Holdich, R.G., Kosvintsev, S.R., Gasparini, G., Cumming, I.W., “ Stirred Cell Membrane Emulsification and Factors Influencing Dispersion Drop Size and Uniformity”, Industrial & Engineering Chemistry Research, 2007. 46(3): p. 965.
49.Nogami, M. and Abe, Y., “Properties of sol--gel-derived Al2O3---SiO2 glasses using Eu3+ ion fluorescence spectra”, Journal of Non-Crystalline Solids, 1996. 197(1): p. 73.
50.Jung, H.C., Park, J.Y., Seeta Rama Raju, G., Jeong, J. H., Moon, B. K., Kim, J. H., Choi, H. Y., “Crystalline structure dependence of luminescent properties of Eu3+-activated Y2O3-Al2O3 system phosphors”, Current Applied Physics, 2009. 9(3, Supplement 1): p. S217.
51.Zhang, Q. Y., Pita, K., Ye, W., Que, W. X., “Influence of annealing atmosphere and temperature on photoluminescence of Tb3+ or Eu3+-activated zinc silicate thin film phosphors via sol-gel method”, Chemical Physics Letters, 2002. 351(3-4): p. 163.
52.Wang, Y., Ling, L.S., Zhu, H.Q., Ding, R.Q., “Anneal and Concentration Effect on PL Properties of Sol-Gel Derived Eu3+ Doped SiO2 Glass”, Journal of Rare Earths, 2006. 24(1, Supplement 1): p. 199.
53. Kamata, N., Tosaka, K., Honda, Z., Yamada, K., “Formation of Eu2+ in SiO2-Al2O3 glass during thermal treatment in sol-gel process”, Japanese Journal of Applied Physics Part 2-Letters & Express Letters, 2004. 43(3A): p. L372.
54.Yang, Y., Yu, L., Tao, C., Dai, Z., Yang, H., “ Luminescence of YAl3 (BO3)4: Eu2+, Dy3+ phosphor and its luminescence decay characteristics”, Journal of Electroceramics, 2010. 25(1): p. 56.
55.Zhang, X., Zhang, Z., and Seo, H.J., “Photoluminescence and time-resolved luminescence spectroscopy of novel NaBa4(BO3)3:Tb3+ phosphor. Journal of Alloys and Compounds”, 2011. 509(14): p. 4875.
56.Jun-Gill, K., Min-Kook, N., and Youngku, S.,“Luminescence from KCl co-doped with Eu2+ and Eu3+ ions”, Journal of Physics-Condensed Matter, 2000. 12(10): p. L199.
57.Hayakawa, T. and Nogami, M., “ Dynamical Faraday rotation effects of sol-gel derived Al2O3-SiO2 glass containing Eu2+ ions”, Solid State Communications, 2000. 116(2): p. 77.