太阳能用稀土掺杂磷酸盐玻璃组成、结构、性能的研究
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摘要
随着能源危机的不断加重,太阳能发电越来越受到人们的重视。但硅太阳能电池作为使用得最广泛的一种太阳能电池,其最高转化效率一直在20%左右。玻璃盖板作为太阳能电池的一个必要部件,其性能直接影响到硅太阳能电池的转化效率。磷酸盐玻璃具有声子能量低,稀土离子溶解度高,发光性能较好等优点。磷酸盐玻璃作为激光玻璃已经被广泛的利用到了各个领域。为了提高太阳能电池的转化效率,本文总结了现阶段硅太阳能电池以及磷酸盐玻璃的研究现状,研究了通过掺杂稀土离子下转换来提高光电转化效率,比较了掺杂不同组分稀土的磷酸盐玻璃,提出了研究太阳能用下转换稀土掺杂磷酸盐玻璃的必要性。
本文研究了磷酸盐玻璃的基础组分,掺杂稀土,采用熔融法制备太阳能用下转换磷酸盐玻璃。研究了组分和工艺制度对热膨胀系数、化学稳定性、透过率、发光性能的影响；研究了玻璃的激发光谱和发射光谱的规律。通过以上的实验和理论分析可以得到如下结论：
1.探讨了PAB玻璃的形成区,确定了PAB玻璃的形成范围。PAB三元玻璃的形成区域偏向P205和BaO一侧,玻璃组成中A1203的摩尔含量不能超过22.5%。
2.以摩尔组成65P2O5-15Al2O3-20BaO为组分的PAB磷酸盐热膨胀系数、化学稳定性、透过率、发光性能最好。
3.在PAB系统的玻璃中,Y3+、Sm3+、Nd3+因其外层电子结构的特点,不能起到转换光子以提高太阳能电池效率的作用。
4.当Ce3+作为敏化剂与Tb3+双掺的时候,通过交叉弛豫的作用传递能量,可以使一个波长小于300nm的光子转化为两个波长(5Hi→5D4和5D4→7Fi)较长的光子,且当Ce3+含量为1%mol时,Tb3+/Ce3+比值越高,玻璃的下转化效率越高。
As the energy crisis are more serious day by day, solar power is considered more and more important.The highest conversion efficiency of th silicon solar cells is about20%while it's the most widely-used solar battery. Glass cover plate affects the performance and the conversion efficiency of silicon solar cells directly as a necessary component of the solar cell. Phosphate glasse has characters of low phonon energy, high solubility of rare earth ions, and good luminescent properties, etc.. Phosphate glass has been extensive used in various fields as laser glass. This paper summarized the status of studies of silicon solar cells and the phosphate glass at this stage to improve the photoelectric conversion efficiency of conversion by doping rare earth ions,compared the different components of rare earth doped phosphate glass and inferred the necessity of research of conversion of rare earth doped into phosphate glass for solar use.
In this article, rare-earth doped glass was prepared as a basement composition of phosphate glass via melting method.The effect of process and component to the coefficient of thermal expansion, chemical stability, transparency and light-emitting properties is determined, the emission and excitation spectra of the glass are tested, and its microstructure were studied. By the experimental and theoretical analysis above, we have the following conclusions:
1.The final component is irrelevant to the temperature of feeding; feeding at1100℃will result in the best glass mass and most economical use of raw materials; molten glass must be taken out and annealed in organized process to avoid burst of glass or impacts to the performance of the glass.
2.Explored forming area of PAB glass,the range of PAB glass has been decided.
3.PAB phosphate components of65P2O5-15Al2O3-20BaO has a best balanced thermal expansion, chemical stability, transmittance, the luminescent properties.
4. Y3+, Sm3+and Nd3+, because of their outer layer of electronic structure can not convert photons to improve efficiency of solar cell; glass doped Ce3+as a sensitizer and Tb3+as booster, can convert photons with wavelength lower than 300nm to two photons of which longer wavelength (5Hi→5D4和5D4→7Fi), and the ratio of Tb3+/Ce3+is higher with the content of Ce3+as1%mol, the higher the efficiency of the glass transition we will get.
本文研究了磷酸盐玻璃的基础组分,掺杂稀土,采用熔融法制备太阳能用下转换磷酸盐玻璃。研究了组分和工艺制度对热膨胀系数、化学稳定性、透过率、发光性能的影响；研究了玻璃的激发光谱和发射光谱的规律。通过以上的实验和理论分析可以得到如下结论：
1.探讨了PAB玻璃的形成区,确定了PAB玻璃的形成范围。PAB三元玻璃的形成区域偏向P205和BaO一侧,玻璃组成中A1203的摩尔含量不能超过22.5%。
2.以摩尔组成65P2O5-15Al2O3-20BaO为组分的PAB磷酸盐热膨胀系数、化学稳定性、透过率、发光性能最好。
3.在PAB系统的玻璃中,Y3+、Sm3+、Nd3+因其外层电子结构的特点,不能起到转换光子以提高太阳能电池效率的作用。
4.当Ce3+作为敏化剂与Tb3+双掺的时候,通过交叉弛豫的作用传递能量,可以使一个波长小于300nm的光子转化为两个波长(5Hi→5D4和5D4→7Fi)较长的光子,且当Ce3+含量为1%mol时,Tb3+/Ce3+比值越高,玻璃的下转化效率越高。
As the energy crisis are more serious day by day, solar power is considered more and more important.The highest conversion efficiency of th silicon solar cells is about20%while it's the most widely-used solar battery. Glass cover plate affects the performance and the conversion efficiency of silicon solar cells directly as a necessary component of the solar cell. Phosphate glasse has characters of low phonon energy, high solubility of rare earth ions, and good luminescent properties, etc.. Phosphate glass has been extensive used in various fields as laser glass. This paper summarized the status of studies of silicon solar cells and the phosphate glass at this stage to improve the photoelectric conversion efficiency of conversion by doping rare earth ions,compared the different components of rare earth doped phosphate glass and inferred the necessity of research of conversion of rare earth doped into phosphate glass for solar use.
In this article, rare-earth doped glass was prepared as a basement composition of phosphate glass via melting method.The effect of process and component to the coefficient of thermal expansion, chemical stability, transparency and light-emitting properties is determined, the emission and excitation spectra of the glass are tested, and its microstructure were studied. By the experimental and theoretical analysis above, we have the following conclusions:
1.The final component is irrelevant to the temperature of feeding; feeding at1100℃will result in the best glass mass and most economical use of raw materials; molten glass must be taken out and annealed in organized process to avoid burst of glass or impacts to the performance of the glass.
2.Explored forming area of PAB glass,the range of PAB glass has been decided.
3.PAB phosphate components of65P2O5-15Al2O3-20BaO has a best balanced thermal expansion, chemical stability, transmittance, the luminescent properties.
4. Y3+, Sm3+and Nd3+, because of their outer layer of electronic structure can not convert photons to improve efficiency of solar cell; glass doped Ce3+as a sensitizer and Tb3+as booster, can convert photons with wavelength lower than 300nm to two photons of which longer wavelength (5Hi→5D4和5D4→7Fi), and the ratio of Tb3+/Ce3+is higher with the content of Ce3+as1%mol, the higher the efficiency of the glass transition we will get.
引文
[1]常永远.太阳能光伏技术的研究与发展[J].中国科技博览,2011,17：103-107.
[2]李红波.重要能源的巧妙利用——光伏建筑[J].中国住宅设施,2011,6：14-23.
[3]刘贞先.太阳能综合利用技术探讨[J].应用能源技术,2006,11：31-33.
[4]张晓光.太阳能电池的发展历程[J].无线电,2008,8：83-83.
[5]殷志刚.太阳能光伏发电材料的发展现状[J].可再生能源,2008,5(26)：17-20.
[6]李天星.能源谋变——新能源：破冰之后的远航[J].中国石油企业,2009,4：34-40.
[7]李春鹏.太阳能光伏发电综述[J].电工材料,2006,3：45-48.
[8]C.Strumpela,M.McCanna,G.Beaucarne. Modifying the solar spectrum to enhance silicon solar cell efficiency—An overview of available materials[J]. Solar Energy Materials and Solar Cells,2007,91(4):238-249.
[9]张帅.太阳能电池工作原理简介[J].灯与照明,2009,3：49-51.
[10]梁宗存.太阳能电池及材料研究[J].材料导报,2000,8：72-82.
[11]成志秀.太阳能光伏电池综述[J].信息记录材料,2007,2：41-47.
[12]樊炀.上转换下转换聚光太阳电池及系统的初步研究[D].北京交通大学,2009:17-19.
[13]邹红叶.硅薄膜太阳能电池的原理及其应用[J].物理通报,2009,5：56-57.
[14]陈珍霞.LED用低熔点发光玻璃的研究[D].武汉理工大学,2010：17-21.
[15]孟闯.稀土掺杂氧化锌荧光粉的合成及其上转换发光性质的研究[D].大连海事大学,2008：23-25.
[16]许亮.白光二极管用宽激发带荧光体的微结构和光谱研究[D].天津理工大学,2007：18-22.
[17]Wisniewski.D,Boatner L.A. Exploratory Research on the Development of Novel Ce3+ Activated Phosphate Glass Scintillators[J]. Nuclear Science,2008,55(6):3692-3702.
[18]F. Auzel. A general fundamental condition for flat gain optical amplification: Application to Er3+-doped glasses and glass ceramics[J]. Journal of Non-Crystalline Solids,2008,354(42-44): 4765-4769.
[19]魏葳.太阳能光电-光热综合利用系统[J].上海节能,2010,5：32-36.
[20]苏锵.稀土发光材料的进展与新兴技术产业[J].稀土信息,2010,9：5-8.
[21]Horn.D.S,Messing G L. Characterization of up-converter layers on bifacial silicon solar cells [J]. Materials Science and Engineering: B,2009,159-160:212-215.
[22]J.F.Suyver.Novel materials doped with trivalent lanthanides and transition metal ions showing near-infrared to visible photon upconversion[J]. Optical Materials,2005,27,(6):1111-1130.
[23]P.I.Paulose.Sensitized fluorescence of Ce3+Mn2+ system in phosphate glass[J]. Journal of Physics and Chemistry of Solids,2003,64(5):841-846.
[24]H.Ebendorff-Heidepriem, Messing GL. Effect of glass composition on Judd-Ofelt parameters and radiative decay rates of Er3+ in fluoride phosphate and phosphate glasses[J]. Journal of Non-Crystalline Solids,1998,240(1-3):66-78.
[25]徐美君.磷酸盐玻璃国内外发展概况[J].建材世界,2009,3：53-57.
[26]J.L.Rygel,C.G.Pantano. Synthesis and properties of cerium aluminosilicophosphate glasses[J]. Journal of Non-Crystalline Solids,2009,355(52-54):2622-2629.
[27]王国梅.P2O5-Li2O-MnO2系统玻璃结构的红外光谱研究[J].中国建筑材料科学研究院学报,1990,4：158-164.
[28]胡丽丽.磷酸盐激光玻璃研究进展[J].硅酸盐通报,2005,5：125-129.
[29]潘杏平.稀土功能材料应用的新进展[J].科技情报开发与经济,2008,5：130-131.
[30]张希艳.稀土发光材料[M].北京：国防工业出版社,2005：22-30.
[31]赵彦钊.玻璃工艺学[M].北京：化学工业出版社,2006：185-190.
[32]杨刚.P2O5-BaO-Al2O3-K2O磷酸盐激光玻璃的表面处理[J].无机材料学报,2010,2：198-203.
[33]Chonggeng MA, Sha JIANG, Xianju ZHOU. Energy transfer from Ce3+ to Tb3+ and Eu3+ in zinc phosphate glasses[J]. Journal of Rare Earths,2010,28(1):40-42.
[34]赵彦钊.玻璃工艺学[M].北京：化学工业出版社,2006：223-230.
[35]P.I. Paulose. Energy transfer studies of Ce:Eu system in phosphate glasses [J]. Journal of Non-Crystalline Solids,2010,356(2):93-97.
[36]M.Chromcikova. Structural relaxation of scintillating Ce-doped NaGd(PO3)4 glass[J]. Journal of Thermal Analysis and Calorimetry,2010,4(5):961-964.
[37]卢安贤.P2O5-PbO-Bi2O3系统玻璃和微晶玻璃的结构[J].中国有色金属学报,1997,1：203-210.
[38]王国梅.Li2O-P2O5-MnO2系统玻璃的光谱学研究[J].玻璃,1990,5：23-30.
[39]K. Kawanoa,B.C. Honga,K. Sakamotoa,T.Tsuboib, H.J.Seoc. Improvement of the conversion efficiency of solar cell by rare earth ion[J]. Optical Materials,2005,31(9):1353-1356.
[40]姜中宏主编.新型光功能玻璃[M].北京：化学工业出版社,2008：44-53.
[41]S Dongbing He. Intense near-infrared emission of Yb3+ related with charge transfer in phosphate glass[J]. Solid State Communications,2007,150(47-48):2354-2356.
[42]B.S. Richards. Enhancing the performance of silicon solar cells via the application of passive luminescence conversion layers [J]. Solar Energy Materials and Solar Cells,2006,90(15):2329-2337.
[43]Oskam K D, Wegh R T, Donker H. Downconversion:a new route to visible quantum cutting.[J] Alloys and Compounds,2000,300-301:421425.
[2]李红波.重要能源的巧妙利用——光伏建筑[J].中国住宅设施,2011,6：14-23.
[3]刘贞先.太阳能综合利用技术探讨[J].应用能源技术,2006,11：31-33.
[4]张晓光.太阳能电池的发展历程[J].无线电,2008,8：83-83.
[5]殷志刚.太阳能光伏发电材料的发展现状[J].可再生能源,2008,5(26)：17-20.
[6]李天星.能源谋变——新能源：破冰之后的远航[J].中国石油企业,2009,4：34-40.
[7]李春鹏.太阳能光伏发电综述[J].电工材料,2006,3：45-48.
[8]C.Strumpela,M.McCanna,G.Beaucarne. Modifying the solar spectrum to enhance silicon solar cell efficiency—An overview of available materials[J]. Solar Energy Materials and Solar Cells,2007,91(4):238-249.
[9]张帅.太阳能电池工作原理简介[J].灯与照明,2009,3：49-51.
[10]梁宗存.太阳能电池及材料研究[J].材料导报,2000,8：72-82.
[11]成志秀.太阳能光伏电池综述[J].信息记录材料,2007,2：41-47.
[12]樊炀.上转换下转换聚光太阳电池及系统的初步研究[D].北京交通大学,2009:17-19.
[13]邹红叶.硅薄膜太阳能电池的原理及其应用[J].物理通报,2009,5：56-57.
[14]陈珍霞.LED用低熔点发光玻璃的研究[D].武汉理工大学,2010：17-21.
[15]孟闯.稀土掺杂氧化锌荧光粉的合成及其上转换发光性质的研究[D].大连海事大学,2008：23-25.
[16]许亮.白光二极管用宽激发带荧光体的微结构和光谱研究[D].天津理工大学,2007：18-22.
[17]Wisniewski.D,Boatner L.A. Exploratory Research on the Development of Novel Ce3+ Activated Phosphate Glass Scintillators[J]. Nuclear Science,2008,55(6):3692-3702.
[18]F. Auzel. A general fundamental condition for flat gain optical amplification: Application to Er3+-doped glasses and glass ceramics[J]. Journal of Non-Crystalline Solids,2008,354(42-44): 4765-4769.
[19]魏葳.太阳能光电-光热综合利用系统[J].上海节能,2010,5：32-36.
[20]苏锵.稀土发光材料的进展与新兴技术产业[J].稀土信息,2010,9：5-8.
[21]Horn.D.S,Messing G L. Characterization of up-converter layers on bifacial silicon solar cells [J]. Materials Science and Engineering: B,2009,159-160:212-215.
[22]J.F.Suyver.Novel materials doped with trivalent lanthanides and transition metal ions showing near-infrared to visible photon upconversion[J]. Optical Materials,2005,27,(6):1111-1130.
[23]P.I.Paulose.Sensitized fluorescence of Ce3+Mn2+ system in phosphate glass[J]. Journal of Physics and Chemistry of Solids,2003,64(5):841-846.
[24]H.Ebendorff-Heidepriem, Messing GL. Effect of glass composition on Judd-Ofelt parameters and radiative decay rates of Er3+ in fluoride phosphate and phosphate glasses[J]. Journal of Non-Crystalline Solids,1998,240(1-3):66-78.
[25]徐美君.磷酸盐玻璃国内外发展概况[J].建材世界,2009,3：53-57.
[26]J.L.Rygel,C.G.Pantano. Synthesis and properties of cerium aluminosilicophosphate glasses[J]. Journal of Non-Crystalline Solids,2009,355(52-54):2622-2629.
[27]王国梅.P2O5-Li2O-MnO2系统玻璃结构的红外光谱研究[J].中国建筑材料科学研究院学报,1990,4：158-164.
[28]胡丽丽.磷酸盐激光玻璃研究进展[J].硅酸盐通报,2005,5：125-129.
[29]潘杏平.稀土功能材料应用的新进展[J].科技情报开发与经济,2008,5：130-131.
[30]张希艳.稀土发光材料[M].北京：国防工业出版社,2005：22-30.
[31]赵彦钊.玻璃工艺学[M].北京：化学工业出版社,2006：185-190.
[32]杨刚.P2O5-BaO-Al2O3-K2O磷酸盐激光玻璃的表面处理[J].无机材料学报,2010,2：198-203.
[33]Chonggeng MA, Sha JIANG, Xianju ZHOU. Energy transfer from Ce3+ to Tb3+ and Eu3+ in zinc phosphate glasses[J]. Journal of Rare Earths,2010,28(1):40-42.
[34]赵彦钊.玻璃工艺学[M].北京：化学工业出版社,2006：223-230.
[35]P.I. Paulose. Energy transfer studies of Ce:Eu system in phosphate glasses [J]. Journal of Non-Crystalline Solids,2010,356(2):93-97.
[36]M.Chromcikova. Structural relaxation of scintillating Ce-doped NaGd(PO3)4 glass[J]. Journal of Thermal Analysis and Calorimetry,2010,4(5):961-964.
[37]卢安贤.P2O5-PbO-Bi2O3系统玻璃和微晶玻璃的结构[J].中国有色金属学报,1997,1：203-210.
[38]王国梅.Li2O-P2O5-MnO2系统玻璃的光谱学研究[J].玻璃,1990,5：23-30.
[39]K. Kawanoa,B.C. Honga,K. Sakamotoa,T.Tsuboib, H.J.Seoc. Improvement of the conversion efficiency of solar cell by rare earth ion[J]. Optical Materials,2005,31(9):1353-1356.
[40]姜中宏主编.新型光功能玻璃[M].北京：化学工业出版社,2008：44-53.
[41]S Dongbing He. Intense near-infrared emission of Yb3+ related with charge transfer in phosphate glass[J]. Solid State Communications,2007,150(47-48):2354-2356.
[42]B.S. Richards. Enhancing the performance of silicon solar cells via the application of passive luminescence conversion layers [J]. Solar Energy Materials and Solar Cells,2006,90(15):2329-2337.
[43]Oskam K D, Wegh R T, Donker H. Downconversion:a new route to visible quantum cutting.[J] Alloys and Compounds,2000,300-301:421425.