本文選題：發(fā)光材料 + 固溶體�。� 參考：《中國(guó)科學(xué)技術(shù)大學(xué)》2017年博士論文

【摘要】：作為常見(jiàn)的固態(tài)發(fā)光材料之一,稀土離子激活的發(fā)光材料如今已被廣泛應(yīng)用于白光LED、上轉(zhuǎn)換發(fā)光、長(zhǎng)余輝以及量子剪裁等領(lǐng)域。固溶體發(fā)光材料的出現(xiàn)為尋找新型功能材料提供了更豐富的素材,其結(jié)構(gòu)性質(zhì)在很大程度上決定了該材料的光、電、磁、熱等性質(zhì)。對(duì)固溶體材料結(jié)構(gòu)組成的研究,并建立其結(jié)構(gòu)組成和各方面應(yīng)用性能之間的聯(lián)系,因其對(duì)新型功能材料的開發(fā)具有指導(dǎo)意義而成為當(dāng)今固態(tài)無(wú)機(jī)化學(xué)材料科學(xué)領(lǐng)域的重要研究方向之一。固溶體發(fā)光材料對(duì)發(fā)光材料的性能調(diào)控具有重要意義,其在稀土摻雜和過(guò)渡族金屬離子摻雜發(fā)光材料中占據(jù)著越來(lái)越重要的地位。發(fā)光材料的結(jié)構(gòu)性質(zhì)在很大程度上決定了其發(fā)光性質(zhì),例如直接影響激發(fā)和發(fā)射光譜中峰型、峰值位置以及峰寬等,它們直接決定了該材料的性能和使用前景。這意味著深入研究發(fā)光材料結(jié)構(gòu)性質(zhì)和發(fā)光性質(zhì)之間的聯(lián)系顯得尤為必要,它對(duì)開發(fā)新型發(fā)光材料具有十分重要的指導(dǎo)意義。因此,本論文的主要工作是通過(guò)建立與實(shí)驗(yàn)結(jié)果相符的理論模型來(lái)試圖尋找材料結(jié)構(gòu)性質(zhì)和發(fā)光性質(zhì)之間的聯(lián)系,并為尋找性能更為優(yōu)異的新型發(fā)光材料提供一定的理論依據(jù)。本文主要內(nèi)容和研究成果如下:第一章是本文的緒論部分,主要介紹了固溶體發(fā)光材料性質(zhì)探究的選題意義、研究背景和現(xiàn)狀,并對(duì)稀土摻雜發(fā)光材料以及固溶體材料的基礎(chǔ)知識(shí)、基本原理和基本研究手段做了簡(jiǎn)單介紹,主要包括稀土元素的分類、稀土的光譜理論、稀土發(fā)光材料的應(yīng)用以及稀土光譜的表征手段。同時(shí),介紹了固溶體材料的定義、形成、類型、性能、作用以及研究方法等基本知識(shí)。第二章主要介紹了自激活固溶體發(fā)光材料Ba2xSr1-2xV207的結(jié)構(gòu)和發(fā)光性質(zhì)。首先,我們通過(guò)高溫固相法合成了不同固溶比例下的樣品,并通過(guò)X射線衍射譜對(duì)材料的結(jié)構(gòu)性質(zhì)做了表征。XRD結(jié)果表明我們成功合成固溶體。此外,我們還測(cè)得了不同固溶比例下樣品的激發(fā)和發(fā)射光譜。實(shí)驗(yàn)結(jié)果表明激發(fā)和發(fā)射峰的位置和峰寬均隨固溶比例變化呈現(xiàn)非單調(diào)變化。通過(guò)展示與實(shí)驗(yàn)結(jié)果相符的位形坐標(biāo)圖,我們把這種非單調(diào)性歸結(jié)于固溶導(dǎo)致的非均勻程度的增加。Ba(2+)和Sr(2+)的非均勻分布不僅造成能級(jí)組的非均勻增寬,還通過(guò)增大交換作用常數(shù)使得激發(fā)態(tài)自旋單態(tài)和三重態(tài)之間的能級(jí)組間隔增大。此外,當(dāng)Sr的占比達(dá)到3/4時(shí)譜線峰值位置和半高寬均出現(xiàn)極值,這表明度量無(wú)序程度的標(biāo)準(zhǔn)在此處發(fā)生變化。第三章主要介紹了摻雜稀土離子的長(zhǎng)余輝固溶體發(fā)光材料BaxSr1-xAl204:Eu~(2+)的結(jié)構(gòu)和發(fā)光性質(zhì)。與第二章工作類似,不同固溶比例下樣品的合成同樣通過(guò)高溫固相法實(shí)現(xiàn),而材料的結(jié)構(gòu)性質(zhì)同樣通過(guò)X射線衍射譜表征。XRD結(jié)果在證明成功合成固溶體的同時(shí)顯示了我們的材料中出現(xiàn)的結(jié)構(gòu)相變,同時(shí)我們還通過(guò)第一性原理計(jì)算估計(jì)了相變點(diǎn),其結(jié)果與XRD結(jié)果相符。對(duì)于特定的固溶區(qū)間,我們監(jiān)測(cè)了不同固溶比例下樣品的發(fā)射光譜,并發(fā)現(xiàn)了發(fā)射光譜峰值位置與固溶比例的非單調(diào)依賴關(guān)系。與第二章內(nèi)容不同的是,這里涉及的發(fā)光中心是摻雜離子而非具有電荷遷移帶的自激活基團(tuán),因而我們需要建立不同于第二章的理論模型來(lái)解釋此實(shí)驗(yàn)中出現(xiàn)的現(xiàn)象。通過(guò)分析,我們發(fā)現(xiàn)這種反常的光譜現(xiàn)象與Eu~(2+)在不同固溶比例樣品中占據(jù)兩種Ba格位的不同傾向性有關(guān)。第四章主要介紹了摻雜稀土離子Eu~(2+)和過(guò)渡族金屬離子Mn~(2+)的鹵磷酸鹽Ca5(PO4)3(F0.8Cl0.2)樣品的發(fā)光性質(zhì)。與前兩章內(nèi)容不同的是,前兩章主要考慮陽(yáng)離子取代形成的固溶體,而本章則考慮陰離子取代所形成的固溶體。本實(shí)驗(yàn)中,所有樣品均由高溫固相法合成,并由X射線衍射譜表征。XRD結(jié)果顯示我們成功合成了固溶樣品,同時(shí)說(shuō)明一定占比Cl-的引入并不會(huì)對(duì)Ca5(PO4)3F原本的晶格結(jié)構(gòu)造成較大影響。在此材料中,我們研究了 Eu~(2+)向Mn~(2+)的能量傳遞以及如何通過(guò)調(diào)節(jié)Eu~(2+)、Mn~(2+)的摻雜濃度來(lái)實(shí)現(xiàn)白光。第五章主要介紹了摻雜Tb~(3+)、Ho~(3+)兩種稀土離子的磷酸鹽材料YPO4的發(fā)光性質(zhì)以及其應(yīng)用于熒光溫度探測(cè)的可行性。我們通過(guò)水熱法合成該樣品,并通過(guò)X射線衍射譜對(duì)其結(jié)構(gòu)進(jìn)行了表征。XRD結(jié)果顯示成功合成所需晶相。在本章中,我們提出了一種與傳統(tǒng)的基于熱耦合能級(jí)的上轉(zhuǎn)換熒光溫度探測(cè)不同的測(cè)溫機(jī)制,并通過(guò)YPO4:3.2%Tb~(3+),0.8%Ho~(3+)樣品展示了其原理。此測(cè)溫機(jī)制主要利用到Tb~(3+)的基態(tài)熱耦合能級(jí),而Ho~(3+)的摻入則作為參照。實(shí)驗(yàn)結(jié)果表明該材料具有較高的測(cè)溫靈敏度,因而具有一定的實(shí)用價(jià)值;同時(shí)也說(shuō)明我們的測(cè)溫方案具有一定的可行性,能夠?yàn)閷ふ揖哂休^好性能的熒光溫度探測(cè)材料提供幫助。最后一章對(duì)本論文的主要內(nèi)容做了總結(jié)并對(duì)固溶體發(fā)光材料的應(yīng)用前景做了展望。
[Abstract]:As one of the common solid state luminescent materials, rare earth ions activated luminescent materials have been widely used in the fields of white light LED, upconversion luminescence, long afterglow and quantum cutting. The appearance of solid solution luminescent materials provides more abundant material for finding new functional materials. The structure and properties of the materials determine the material to a great extent. The study of the structure composition of solid solution materials and the relationship between the structure and the application properties of the solid solution materials have been established. Because of their guiding significance for the development of new functional materials, it has become one of the most important research directions in the field of solid inorganic chemical materials science. The performance control of the material is of great significance. It occupies an increasingly important position in the rare earth doped and transition metal ion doped luminescent materials. The structure and properties of the luminescent materials determine their luminescence properties to a large extent, such as the direct influence of the peak type, peak position and peak width in the excitation and emission spectra. They are directly determined by them. It is very necessary to study the relationship between the structural properties and luminescent properties of the luminescent materials, which is of great significance to the development of new luminescent materials. Therefore, the main work of this paper is to try to find the material by establishing a theoretical model consistent with the results of the test. The relationship between the properties of the material structure and the luminescence properties and the theoretical basis for finding new luminescent materials with more excellent properties are provided. The main contents and research results of this paper are as follows: the first chapter is the introduction part of this article, which mainly introduces the significance of the selection of the properties of solid solution luminescent materials, the background and the present situation, and the rare earth. The basic knowledge, basic principles and basic research methods of doped luminescent materials and solid solution materials are briefly introduced, including the classification of rare earth elements, the spectral theory of rare earth, the application of rare earth luminescent materials and the characterization means of rare earth spectra. At the same time, the definition, formation, type, properties, function and effect of solid solution materials are introduced. The second chapter mainly introduces the structure and luminescence properties of the self activated solid solution luminescent material Ba2xSr1-2xV207. First, we synthesized the samples with different solid solution ratio by high temperature solid phase method and characterized the structure and properties of the material by the X ray diffraction spectrum. The results show that we have successfully synthesized the solid solution. In addition, we have also measured the excitation and emission spectra of the samples with different solid solution ratios. The experimental results show that the position and peak width of the excitation and emission peaks are not monotonically changed with the change of the solid solution ratio. By displaying the coordinate maps consistent with the experimental results, we attribute this non monotonicity to the nonuniformity caused by the solution of solid solution. Increasing the non-uniform distribution of.Ba (2+) and Sr (2+) not only causes the inhomogeneous broadening of the energy level group, but also increases the energy level interval between the excited state spin singlet and the three heavy state by increasing the exchange constant. In addition, the peak value of the peak position and the half width of the spectral line of the Sr is reached to 3/4, which indicates the standard of measuring the degree of disorder. The third chapter mainly introduces the structure and luminescence properties of the long afterglow solid solution luminescent material BaxSr1-xAl204:Eu~ (2+) doped with rare earth ions. Similar to the second chapter, the synthesis of samples under different solid solution ratios is also realized by high temperature solid phase method, and the structure and properties of the material are also characterized by X ray diffraction (.XR). The D results show that the successful synthesis of solid solution shows the structural phase transition in our material. At the same time, we have estimated the phase transition point by the first principle. The results are in agreement with the XRD results. For a specific solution interval, we monitored the emission spectra of the samples with different solid solution ratios and found the emission spectrum peak. The non monotonic dependence of the position of the value on the solid solution ratio. Unlike the second chapter, the luminescent center involved is the doping ion rather than the self activating group with the charge transfer band, so we need to establish a theoretical model different from the second chapter to explain the phenomenon in this experiment. The spectral phenomena are related to the different tendencies of the Eu~ (2+) Eu~ (Ba) in different solid solution ratios. The fourth chapter mainly introduces the luminescence properties of the halophosphate Ca5 (PO4) 3 (F0.8Cl0.2) samples doped with the rare earth ions Eu~ (2+) and the transition metal ions Mn~ (2+). Unlike the previous two chapters, the first two chapters mainly consider cations. Instead of the solid solution formed, Moto Akinori considered the solid solution formed by the substitution of anions. In this experiment, all the samples were synthesized by the high temperature solid state method, and the results of the X ray diffraction spectrum showed that we have successfully synthesized the solid solution samples, and that the introduction of a certain proportion of Cl- does not cause the lattice structure of the original Ca5 (PO4) 3F to be more than that of the Ca5 (PO4) 3F. In this material, we have studied the energy transfer of Eu~ (2+) to Mn~ (2+) and how to achieve white light by adjusting the doping concentration of Eu~ (2+), Mn~ (2+). The fifth chapter mainly introduces the luminescence properties of the phosphate materials doped Tb~ (3+), Ho~ (3+) and two kinds of rare earth ions, and the feasibility of its application to the detection of fluorescence temperature. The sample was synthesized by hydrothermal method, and its structure was characterized by X ray diffraction..XRD results showed that the crystalline phase was successfully synthesized. In this chapter, we proposed a different temperature measurement mechanism which is different from the conventional upconversion temperature detection based on the thermal coupling energy level, and through YPO4:3.2%Tb~ (3+), 0.8%Ho~ (3+) samples are displayed. Principle. The temperature measurement mechanism is mainly used in the ground state thermal coupling energy level of Tb~ (3+), and the incorporation of Ho~ (3+) is used as reference. The experimental results show that the material has a high sensitivity of temperature measurement and therefore has a certain practical value. It also shows that our temperature measurement scheme has a definite feasibility for finding good performance of the fluorescence. Temperature detection materials provide help. In the last chapter, the main contents of this paper are summarized and the application prospects of solid solution luminescent materials are prospected.

【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O482.31

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