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chi20181127上海光机所陈伟557460Nd-doped laser glasses are the core gain mediums of high-power laser facilities. Nd-doped phosphate glasses have been widely used in high-energy/ high-power laser applications because of the high solubility of rare earth ions, and low nonlinear coefficient. Nd-doped aluminate glasses can be used in pulse amplification due to their ultra-wide effective bandwidth. Further, spectroscopic properties, such as the emission cross section, the effective bandwidth, and radiative lifetime, etc. are important parameters for evaluating the laser properties of glasses. Thus, the study of the relationship between spectroscopic properties and structure of laser glasses is of significant interest for further exploring and improving their laser properties. In this dissertation, the spectroscopic properties and structure of Nd-doped phosphate and aluminate glasses have been systematically discussed. This dissertation is divided into five chapters. The first chapter is the introduction. The second chapter presents the experimental methods and theoretic basis. The third chapter describes the study on the spectroscopic properties and glass structure of Nd-doped phosphate glasses. The fourth chapter presents the study on the spectroscopic properties and glass structure of Nd-doped aluminate glasses. The fifth chapter is the conclusion Chapter 1 introduces the development and history of Nd-doped glasses, the energy levels of Nd3+ ions, and the network structure of phosphate and aluminate glasses. It also summarizes the contents of this dissertation. Chapter 2 describes the preparations of glasses, methods for testing properties and glass structure, the spectroscopy theory, and partial least squares regression. Chapter 3 introduces the investigation of the effects of the Al2O3 content, P/Al ratio, and K2O content on spectroscopic properties and structure of P2O5-Al2O3-K2O-Nd2O3 (P-Al-K)glasses, respectively. First, 60P2O5-xAl2O3-(40-x) K2O-2Nd2O3 (x = 3, 6, 9, 12, 15) glasses were prepared by the melting method. Then, the influence of the Al2O3 content on the glass transition temperature, density, and refractive index were studied. Thereafter, the Judd-Ofelt intensity parameters, emission cross section, effective bandwidth, radiative lifetime, etc. were calculated and discussed. The network structure was studied using Raman spectroscopy. The regression models of properties and network structure were established by the partial least squares regression method. Analysis results show that Q21Al (2 represents two bridged oxygen bonds, and 1Al represents one non-bridged oxygen bond to an Al) is an important factor affecting spectroscopic properties. With the increase in the relative content and symmetric stretching vibration frequency of Q21Al, the emission cross section decreases, while the effective bandwidth and radiative lifetime increase. Second, (60-x)P2O5-xAl2O3-40K2O-0.5Nd2O3 (x=5, P/Al=11; x=10, P/Al=5; x=15, P/Al=3) glasses were prepared by the melting method. Then the influence of P/Al ratio on the glass transition temperature, density, and refractive index were studied. Thereafter, the Judd-Ofelt intensity parameters, emission cross section, effective bandwidth, radiative lifetime, etc. were calculated and discussed. The network structure was studied using Raman and X-ray photoelectron spectroscopy (XPS) spectroscopies. The coordination environment of Nd3+ ions was investigated using electron paramagnetic resonance (EPR). The results show that the most ions around Nd3+ ions are 31P and 27Al. In addition, with the decreases in the P/Al ratio, the number of the 27Al surrounding Nd3+ ions increases. With a decreases in the P/Al ratio, the emission cross section decreases, while the effective bandwidth and radiative lifetime increase. Third, 3xP2O5-xAl2O3-(100-4x)K2O-0.5Nd2O3 (x=15, K2O=40; x=22.5, K2O=10; x=25, K2O =0) glasses were prepared by the melting method. Then, the influence of the K2O content on the glass transition temperature, density, and refractive index were studied. Thereafter, the Judd-Ofelt intensity parameters, emission cross section, effective bandwidth, radiative lifetime, etc. were calculated and discussed. The network structure was studied using Raman and XPS spectroscopies. The coordination environment of Nd3+ ions was investigated using EPR. The results show that the most ions around Nd3+ ions are 31P and 27Al. In addition, with the increases in the K2O content, the number of the 27Al ions surrounding Nd3+ ions decreases. Fourth, the effect of temperature on the network structure of 60P2O5-3Al2O3-37K2O-2Nd2O3 glass was investigated by high-temperature infrared spectroscopy. The glass transition temperature is 318.5 °C, and the highest temperature is 400 °C. The infrared spectral signals disappeared when the temperature reached 400 °C in the heating process. The infrared spectra obtained in the cooling process were different from those obtained in the heating process, and the network structure changes. The rults also show that when temperature was over glass transition temperature about 100 °C, dehydroxylation may occur. Chapter 4 introduces the investigation of the effects of the Al2O3 content and glass fomers on the spectroscopic properties and structure of Al2O3-CaO-Nd2O3 (Al-Ca) glasses, respectively. First, xAl2O3-(30-x)Ga2O3-55CaO-15PbO-0.2Nd2O3 (x=0, 10, 15, 20, 30) glasses were prepared by the melting method. The influence of Al2O3 content on the glass transition temperature, density, and refractive index were studied. Thereafter, the Judd-Ofelt intensity parameters, emission cross section, effective bandwidth, radiative lifetime, etc. were calculated and discussed. The network structure was studied using nuclear magnetic resonance (NMR), Raman and infrared spectroscopies. The coordination environment of Nd3+ ions was investigated using EPR. The results show that with an increase in the Al2O3 content, the content of [AlO4] increases and that of [GaO4] decreases. Moreover, the coordination environment of the Nd3+ ions changes from a Pb-rich environment to an Al-rich environment. With an increases in the Al2O3 content, the emission cross section decreases, while effective bandwidth and radiative lifetime increase. Second, (36Al2O3-64CaO)-x(B2O3, or SiO2, or Ga2O3)-1Nd2O3 (x=0, 2, 4, 6, 8, 10) glasses were prepared by the melting method. The influence of glass formers on the glass transition temperature, density, and refractive index were studied. Thereafter, the Judd-Ofelt intensity parameters, emission cross section, effective bandwidth, radiative lifetime, etc. were calculated and discussed. The network structure was studied using NMR, Raman spectroscopies. The coordination environment of Nd3+ ions was investigated using EPR. The results of NMR show that B is mainly three coordinated, however, Al, Si, and Ga are four coordinated. The results of EPR show that with an increase in B2O3 content, the coordination environment of the Nd3+ ions changes from an Al-rich environment to a mixed Al/B environment. B2O3 has a greater effect on the spectroscopic properties of the Nd3+ ions. Chapter 5 summarizes the dissertation, and presents the limitations of the research. Futher, it outlines the potential future course of study.2019atalunwen21911414464623phosphate glass, aluminate glass, spectroscopic parameters, glass structureStudy on the spectroscopic properties and structure of Nd3+-doped P-Al-K phosphate and Al-Ca aluminate glasses掺钕P-Al-K磷酸盐和Al-Ca铝酸盐激光钕玻璃是高功率激光聚变装置的核心增益介质。磷酸盐钕玻璃具有声子能量适中、稀土离子溶解度高、非线性系数小等优点,被广泛应用于大型激光装置中。铝酸盐钕玻璃因具有超宽的荧光线宽,可被应用于脉冲放大技术中。激光玻璃的光谱性质如受激发射截面、辐射寿命和有效线宽等是评价激光性能的重要参数。这些光谱性质与基质玻璃结构具有密切的关系。虽然非晶态材料的结构和光谱性质的关系非常复杂,但研究两者之间可能的对应关系,对进一步探索提高激光玻璃性能具有重要意义。本课题分别研究了掺钕的磷酸盐和铝酸盐玻璃的光谱性质与玻璃结构。 本论文共包括五章:第一章为引言,第二章为实验方法和理论基础,第三章为磷酸盐钕玻璃光谱性质与玻璃结构的研究,第四章为铝酸盐钕玻璃光谱性质与玻璃结构的研究,第五章是结论。 第一章介绍了钕玻璃的研究历史,Nd3+离子的能级结构和光谱性质,磷酸盐玻璃和铝酸盐玻璃的结构特征,以及本文的研究内容。 第二章介绍了玻璃的制备方法、性质测试和结构测试、光谱理论基础和偏最小二乘法。 第三章分别研究了Al2O3含量、P/Al比和K2O含量的变化对P2O5-Al2O3-K2O-Nd2O3(简写为P-Al-K)磷酸盐玻璃的光谱性质和玻璃结构的影响,以及不同温度下红外光谱的变化。1.熔融法制备60P2O5-xAl2O3-(40-x)K2O-2Nd2O3(x=3,6,9,12,15)玻璃;研究了玻璃化转变温度、折射率和密度随Al2O3含量的变化;计算并讨论了Judd-Ofelt参数、受激发射截面、有效线宽和辐射寿命等的变化;应用拉曼光谱研究了玻璃结构变化;采用偏最小二乘法建立了玻璃性质和玻璃结构的回归模型。经过分析得出,Q21Al基团(2表示两个桥氧键,1Al表示非桥氧与1个Al连接)是影响玻璃荧光性质的重要因素,随着Q21Al基团的相对含量和对称伸缩振动频率的增加,受激发射截面下降,而有效线宽和辐射寿命增大。2.熔融法制备了(60-x)P2O5-xAl2O3-40K2O-0.5Nd2O3(x=5,P/Al=11;x=10,P/Al=5;x=15,P/Al=3)玻璃;研究了玻璃化转变温度、折射率和密度随P/Al比的变化;计算并讨论了Judd-Ofelt参数、受激发射截面、有效线宽和辐射寿命等的变化;应用拉曼光谱、X射线光电子能谱研究了网络结构的变化;应用电子顺磁共振研究了P/Al对Nd3+离子配位环境的影响。结果表明:Nd3+离子周围主要是31P和27Al,并随着P/Al的减小,Nd3+离子周围的27Al数目增加。随着P/Al减小,受激发射截面减小,而有效线宽和辐射寿命增大。3.熔融法制备了3xP2O5-xAl2O3-(100-4x)K2O-0.5Nd2O3(x=15,K2O=40;x=22.5,K2O=10;x=25,K2O =0)玻璃;研究了玻璃化转变温度、折射率和密度随K2O含量的变化;计算并讨论了Judd-Ofelt参数、受激发射截面和有效线宽等的变化;应用拉曼光谱和X射线光电子能谱研究了网络结构的变化;采用电子顺磁共振研究了K2O含量对Nd3+离子的配位环境的影响。结果表明,Nd3+离子周围主要是31P和27Al,且随着K2O含量增加,Nd3+离子周围的27Al数目减少。4.研究了60P2O5-3Al2O3-37K2O-2Nd2O3玻璃的高温红外光谱,玻璃化转变温度为318.5 °C,温度最高升至400 °C。在升温过程中,当温度升高至400 °C时,红外光谱信号消失。降温过程中测得的红外光谱和升温过程中测得的红外光谱不同,玻璃结构发生了改变。本实验结果还表明,当升温至高于玻璃化转变温度约100 °C时,玻璃可能发生脱羟基。 第四章分别研究了Al2O3含量和网络形成体变化对Al2O3-CaO-Nd2O3(简写为Al-Ca)铝酸盐钕玻璃的光谱性质和玻璃结构的影响。1.熔融法制备了xAl2O3-(30-x)Ga2O3-55CaO-15PbO-0.2Nd2O3(x=0,10,15,20,30)玻璃。研究了玻璃化转变温度、折射率和密度随Al2O3含量的改变;计算并分析了Judd-Ofelt参数、受激发射截面、有效线宽、辐射寿命的变化;应用固态核磁共振、拉曼光谱、红外光谱研究了玻璃结构的变化;应用电子顺磁共振研究了Al2O3含量对Nd3+离子配位环境的影响。实验结果表明,随着Al2O3含量增加,玻璃中[AlO4]基团不断增加而[GaO4]基团不断减小,且Nd3+离子的配位环境从富Pb的环境向富Al环境转变。随着Al2O3含量增加,有效线宽和辐射寿命增加,而受激发射截面减小。2.熔融法制备了(36Al2O3-64CaO)-x(B2O3或SiO2或Ga2O3)-1Nd2O3(x=0,2,4,6,8,10)玻璃。研究了玻璃化转变温度、折射率和密度随网络形成体(B2O3或SiO2或Ga2O3)含量的改变;计算并讨论了Judd-Ofelt参数、受激发射截面、有效线宽和辐射寿命的变化;应用核磁共振、拉曼光谱研究了玻璃结构的变化;应用电子顺磁共振研究了Nd3+离子配位环境的变化。核磁共振结果表明,B主要是三配位,而Al、Si和Ga均是四配位。电子顺磁共振的结果表明,随着B2O3含量增加,Nd3+离子配位环境从富Al环境向Al/B混合环境转变。 第五章对全文进行了总结,同时指出本研究存在的不足和对今后工作的建议。磷酸盐玻璃,铝酸盐玻璃,荧光参数,玻璃结构中国科学院上海光学精密机械研究所岳玉材料学博士
中文题目: 掺钕P-Al-K磷酸盐和Al-Ca铝酸盐
外文题目: Study on the spectroscopic properties and structure of Nd3+-doped P-Al-K phosphate and Al-Ca aluminate glasses
作者: 岳玉
导师姓名: 陈伟
学位授予机构: 中国科学院上海光学精密机械研究所
答辩时间: 20181127
中文关键词:
磷酸盐玻璃,铝酸盐玻璃,荧光参数,玻璃结构
英文关键词:
phosphate glass, aluminate glass, spectroscopic parameters, glass structure
中文摘要:
英文摘要:
文献类型:学位论文
学位级别: 博士
正文语种: chi
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