根据固体掺杂发光的一般规律，开展了材料制备和成分结构分析认证，进行基于光谱的物质局域结构辅助分析及探索其在温度传感方面的应用研究，为研究新型发光材料的性能和温度传感的应用提供了依据。具体研究体系涵盖了以Mn²⁺和Eu³⁺为激活离子的含氧酸盐，本文主要研究内容和成果如下： 第一章首先介绍了发光的定义、分类和性能参数。其次，介绍了发光机理分析中常用的位形坐标模型、能量传递机制和能量传递理论。接着介绍了稀土离子性质、过渡金属离子性质和晶体场作用对离子能级的影响。最后对实验中采用的X射线光电子能谱技术进行了简单介绍。 第二章的内容为研究Zn₂GeO₄:Mn²⁺材料的发光性质及其热猝灭机理。通过高温固相法合成了不同Mn²⁺浓度掺杂的Zn₂GeO₄样品，利用X射线衍射、漫反射谱、光致激发和发射谱、温度依赖的发射谱、X射线光电子能谱及余辉衰减曲线对材料的性质进行了系统的研究。对样品光激发过程中的发光和热猝灭机理进行了详细的分析和计算，认为Zn₂GeO₄基质的绿光发射来自施主能级(Zn〓和V〓)中电子与受主能级中空穴(V〓和V〓)的复合发光，而其蓝光发射则是由施主能级中电子与价带中空穴的复合发光产生。Mn²⁺的绿光发射来自第一激发态⁴T₁(G)到基态⁶A₁(S)的d-d跃迁，对Mn²⁺发光进行了浓度优化，发现2％Mn²⁺具有最强的绿光发射。通过温度依赖的发射光谱并结合第一性原理计算结果构建了位形坐标模型，对Zn₂GeO₄:2％Mn²⁺样品的热稳定性和热猝灭进行了深入的分析，认为高温下Mn²⁺发光的猝灭主要是由于被激发的电子从激发态到离化态的退局域过程所导致。最后详细的讨论了Zn₂GeO₄:2％Mn²⁺材料的光致发光和长余辉发光过程，并给出了相应的能级和跃迁过程示意图。这些实验和分析结果将有助于理解和优化Mn²⁺掺杂的无机发光材料的发光性能。 在第二章实验结果的基础上，可以进一步探索材料在温度传感方面的应用价值。因此，第三章主要为研究基于Zn₂GeO₄:Mn²⁺时间分辨发光特性的温度成像的应用。在250 K到420 K温度范围内测量分析了Mn²⁺离子掺杂的Zn₂GeO₄的发光强度和荧光衰减寿命的温度依赖特性。结果表明，发光强度和荧光衰减寿命的温度探测模式的相对灵敏度的最大值分别达到了4.5％K⁻¹和4.6％K⁻¹。基于时间分辨技术，提出了一种新的利用两段时间范围内的积分强度比的温度探测方案。采用这种温度探测方法得到的相对灵敏度最大值可以达到11.8％K⁻¹，最佳的温度分辨率可以达到0.65 K。采用这种时间分辨的温度探测系统，在荧光显微镜下对印刷电路板上微电路温度分布变化进行了监测，实现了具有高空间分辨率和温度分辨率的温度成像应用。 第四章主要内容为研究Ca₃Ga₂Ge₃O₁₂:Eu³⁺材料的局域结构和变温发光特性。通过固相法合成了不同Eu³⁺掺杂浓度的具有石榴石结构的Ca₃Ga₂Ge₃O₁₂粉末材料。在394 nm光激发下，这些粉末样品展现出较强的⁵D₀→⁷F₄跃迁的光发射，通过浓度优化，得到了发光最强的为10％Eu³⁺掺杂的Ca₃Ga₂Ge₃O₁₂样品。通过晶体结构分析，判断⁵D₀→⁷F₄跃迁的发光增强是由于晶体中Eu³⁺格位的畸变形成了具有D₂对称性8配位结构，可以看作在六面体的上下底面间发生了大角度扭转，导致⁵D₀→⁷F₂跃迁被一定程度上抑制，而⁵D₀→⁷F₄跃迁得到增强。在610.8 nm脉冲激光激发下，热布居在⁷F₂能级上的Eu³⁺离子被激发到⁵D₀能级，从而其布居数对温度具有较大依赖，进而产生温度依赖的发光特性。在所讨论的温度范围内(160K到360K)和610.8nm脉冲激光激发下，⁵D₀→⁷F₄发光跃迁的强度随着温度的升高单调增加，其变化决定的温度测量相对灵敏度在160 K时达到最大值3.66％K⁻¹，而在室温300K时的相对灵敏度亦维持于1.04％K⁻¹。总之，结果表明合成的样品具有良好的温度探测性能，从而有望用于光学温度探测领域。 第五章的研究工作主要围绕基于光谱和X射线光电子能谱对不同Ca／Ti比例的CaTiO₃:Eu³⁺样品的格位占据分析指认。通过高温固相法合成了纯的CaTiO₃和1％Eu³⁺离子掺杂的具有不同Ca／Ti比例的CaTiO₃样品，X射线衍射谱、元胞参数的计算结果和X射线光电子能谱分析表明Eu³⁺离子进入了Ca格位。在20 K温度下，采用不同波长的脉冲激光激发下得到的高分辨光致发光谱并没有明显的改变，表明Eu³⁺离子在基质中只取代了一类格位。考虑到⁵D₀→⁷F₁跃迁的光谱劈裂范围较小，而⁵D₀→⁷F₂与⁵D₀→⁷F₁的跃迁强度比值较大，更符合Eu³⁺离子取代12配位的Ca格位的特征，而非6配位的Ti格位。进一步发现，在所合成的样品中，通过改变Ca／Ti的比例值并不影响Eu³⁺离子在晶体中的格位占据。此实验结果有助于澄清稀土离子掺杂的钙钛矿结构中稀土离子的格位占据情况，并为优化材料的发光性能提供参考信息。 第六章主要分析讨论Yb³⁺-Er³⁺共掺的K₂GdF₅材料的发光温度特性。利用固相法制备了K₂GdF₅:18％Yb³⁺，2％Er³⁺粉末样品，再通过对X射线衍射谱的结果的分析，表明成功合成了样品。对样品上转化发光的过程和机理研究表明绿光和红光发射都是双光子过程，并且在上转换过程中Yb³⁺离子到Er³⁺离子的能量传递占据主要地位。在307 K到570 K温度范围内，测量了来自²H〓→⁴I〓和⁴S〓→⁴I〓跃迁的绿光发射的温度依赖关系。荧光强度比与温度之间的关系可以由指数函数进行很好的拟合，拟合得到的有效能量间隔为690 ㎝⁻。在307 K时，样品的相对灵敏度达到最大值1.1％K⁻。实验结果表明所合成的上转换发光材料可以作为一种潜在的光学温度传感材料。 最后对本文的主要内容做了总结与展望。 关键词：发光材料，发光性质，稀土离子，过渡金属离子，局域结构，发光温度特性，时间分辨光谱，X射线光电子能谱，温度探测

 We carried out the preparation and characterization of materials based on the general luminescent law of solids doping. The spectra-based local structure analysis and the application of materials in temperature sensing were performed. It provided a basis for investigating the performance of new luminescent materials and the application of temperature sensing. The specific research system covered the Mn²⁺ and Eu³⁺ activated oxysalts. The main research contents and results were listed as follows. In chapter 1, we first introduced the definition, classification and performance parameters of luminescence. Secondly, the configuration coordinate model, energy transfer mechanism and energy transfer theory were discussed. Then we presented the rare-earth ions, transition-metal ions and effects of crystal field on ion energy levels. Finally, the employed X-ray photonelectron spectroscopy (XPS) technology in the experiment was briefly introduced. The second chapter is the study of luminescence properties for Zn₂GeO₄:Mn²⁺ material and its thermal quenching mechanism. Different Mn²⁺ concertrations doping Zn₂GeO₄ phosphors were synthesized via the high temperature solid state reaction. Systematic investigations were performed using X-ray powder diffraction, diffuse reflectance spectroscopy, photoluminescence spectroscopy, temperature dependence of photoluminescence spectra, X-ray photoelectron spectroscopy and afterglow decay curve. We elaborated the luminescence and thermal quenching mechanisms arising in optical excitation of the investigated samples. We attributed the green emission of Zn₂GeO₄ host to the radiative transition from the shallow donor levels (Zn〓 and V〓) to the acceptor levels (V〓 and V〓), whereas the blue emission of Zn₂GeO₄ is due to the recombination of electrons from the local defect level of shallow donor centers with holes at the VB. The green emission of Mn²⁺ doped Zn₂GeO₄ powder is due to the d-d transition from the first excited state of ⁴T¹(G) to the ground state of ⁶A¹(S). The concentration optimization of Mn²⁺ luminescence was performed, and 2%Mn²⁺ was found to have the strongest green light emission. The thermal stability and quenching of Zn₂GeO₄:2%Mn²⁺ samples were analyzed by using the temperature dependent emission spectra and the calculation results of the first principle. Thermal luminescent quenching of Mn²⁺ is proposed to be due to the delocalized process of excited electrons from excited state to ionized state. Finally, the detailed luminescence mechanism for photoluminescence and long persistent luminescence is demonstrated, and the corresponding energy level and transition process diagram were given. This may contribute to the understanding and optimization of luminescent properties for other Mn²⁺ doped inorganic phosphors On the basis of the experimental results in chapter 2, we further explored the application value in temperature sensing of Zn₂GeO₄:Mn²⁺ material. In chapter 3, we introduced the application of temperature imaging for Zn₂GeO₄:Mn²⁺ material based on the time resolution technic. Temperature dependencies of emission intensity and decay lifetime of Mn²⁺ doped Zn₂GeO₄ phosphor in the range from 250 K to 420 K were investigated. The relative sensitivity for sensing modal of emission intensity and decay lifetime reaches the maximum of 4.5% K⁻¹ and 4.6% K⁻¹, respectively. We proposed a new temperature sensing protocol based on time resolved technique. The relative sensitivity can reach the maximum of 11.8% K⁻¹ and the best temperature resolution is about 0.65 K. Adopting the temperature measuring system, we realized monitoring the change of a micro circuit temperature distribution on printed circuit board. Temperature imaging with high spatial and temperature resolutions were successfully performed in this work. In chapter 4, the main content is the research of the local structure and temperature dependent photoluminescence of Ca₃Ga₂Ge₃O₁₂:Eu³⁺ material. A series of concentrations of Eu³⁺ activated garnet type Ca₃Ga₂Ge₃O₁₂ phosphors were successfully prepared by solid state reaction. Under the excitation of 394 nm, the phosphors show unusual red emission from ⁵D₀→⁷F₄ transition of Eu³⁺. The emission intensity of the phosphors gradually increases with the concentration of Eu³⁺, and decreases from the quenching concentration of 10 mol%. Through the analysis of crystal structure, the enhancement of ⁵D₀→⁷F₄ transition is due to the distortion of Eu³⁺ site in the crystal. It can be seen that, there is a large angle twist between the upper and lower sides of the hexahedron, resulting in the inhibition of ⁵D₀→⁷F₄ in a certain degree, while ⁵D₀→⁷F₄ transition is enhanced. Under the excitation of 610.8 nm pulse laser, the Eu³⁺ ions populated on the ⁷F₂ level are excited to the ⁵D₀ level, so that the number of populations is dependent on the temperature, thus generating the temperature dependent luminescence characteristics. The intensity of ⁵D₀→⁷F₄ transition increases monotonously as the temperature rises in the range of 160-360 K when excited by 610.8 nm pulse laser. The temperature measurement relative sensitivity maximizes 3.66% K⁻¹ at 160 K and keep in 1.04% K⁻¹ at 300 K, which is determined by the variation of intensity. It is indicated that our prepared sample has good temperature sensing performance and can be applied to the field of optical temperature detection. The research in chapter 5 mainly focuses on the analysis and identification of CaTiO₃:Eu³⁺ samples with different Ca/Ti ratios based on spectra and X-ray photoelectron spectroscopy. Un-doped and 1% Eu³⁺ ions doped CaTiO₃ samples with different Ca/Ti ratios were synthesized using solid-state reaction method. Measuring results of X-ray powder diffraction patterns, unit-cell parameters and X-ray photoelectron spectroscopy show that Eu³⁺ ions enter into the Ca²⁺ site. The high-resolution photoluminescence spectra of Eu³⁺ ions at 20 K in all samples did not witness a significant change under the excitation at different wavelength, implying that Eu³⁺ ions occupy only one type of site. Considering the small spectral splitting range of ⁵D₀→⁷F₂ transition and the large intensity ratio of ⁵D₀→⁷F₂ / ⁵D₀→⁷F₁, it can be concluded that Eu³⁺ occupies the 12-coordinated Ca²⁺ site without inversion symmetry rather than Ti⁴⁺ site. Changing the Ca/Ti ratio doesn’t affect the site occupancy of Eu³⁺ ions in our research. These results may help clarifying the site occupancy of rare-earth ions, and optimizing the performance of rare earth doped perovskite materials. The temperature dependent luminescent characteristics of Yb³⁺-Er³⁺ codoped K₂GdF₅ material were discussed in chapter 6. K₂GdF₅: 18% Yb³⁺, 2% Er³⁺ sample was synthesized by solid state reaction, and the results of X-ray powder diffraction pattern was analyzed to show that the well-crystalized sample was successfully synthesized. The investigations on the possible upconversion (UC) processes and mechanism indicate that both the green and red emissions are two-photon processes and the energy transfer from Yb³⁺ to Er³⁺ plays an important role in UC process. The thermal behavior of green emissions originating from ²H〓 → ⁴I〓 and ⁴S〓→⁴I〓 transitions was investigated in the temperature range from 307 K to 570 K. The relationship between the fluorescence intensity ratio and temperature is well-fitted with an effective energy gap of 690 ㎝⁻. The relative sensitivity of the sample reaches the maximum 1.1% K⁻ at 307 K. The results indicate that the present UC sample could be used as a promising candidate for optical temperature sensor. At last, the main content of this thesis were summarized and prospected. Keywords: luminescent materials, luminescent properties, rare-earth ions, transition-metal ions, local structure, luminescent temperature characteristic, time resolved spectroscopy, X-ray photoelectron spectroscopy, temperature sensing