本文選題：磷硼酸鹽玻璃與玻璃陶瓷 + 稀土離子��； 參考：《桂林電子科技大學(xué)》2017年碩士論文

【摘要】：稀土離子摻雜熒光材料憑借其優(yōu)異的發(fā)光性能在白光LED、顯示器件、太陽能電池、激光和光學(xué)溫度傳感器等諸多領(lǐng)域有著廣泛的潛在應(yīng)用價值,引起了社會各界的關(guān)注。熒光玻璃及玻璃陶瓷具有其他熒光材料不可比擬的優(yōu)勢,例如透明、均勻、成本低廉和易加工等,同時也是一種優(yōu)異的稀土離子基質(zhì)材料。因此,開展稀土摻雜熒光玻璃及玻璃陶瓷的研究有重要的科學(xué)意義和應(yīng)用價值。本文通過高溫熔融-淬冷法制備了Eu~(3+)、Tm~(3+)、Tb~(3+)和Sm~(3+)離子單摻和共摻Na2O-CaO-P2O5-B2O3-ZrO2磷硼酸鹽玻璃,并通過可控析晶法制備了Tb~(3+)和Eu~(3+)離子單摻和共摻磷硼酸鹽玻璃陶瓷。利用XRD、紅外光譜、TEM和密度測量對磷硼酸鹽玻璃及玻璃陶瓷進行了結(jié)構(gòu)分析;采用吸收光譜、激發(fā)光譜、發(fā)射光譜和色坐標(biāo)研究了熒光磷硼酸鹽玻璃及玻璃陶瓷的光學(xué)性能;利用熒光衰減結(jié)并合相關(guān)的理論及公式計算對稀土離子在磷硼酸鹽玻璃及玻璃陶瓷中的能量傳遞進行了研究;對Tb~(3+)/Eu~(3+)共摻磷硼酸鹽玻璃及玻璃陶瓷進行變溫發(fā)射光譜測試,并基于熒光強度比技術(shù)研究了其熒光溫敏特性。得到如下的研究結(jié)果:1.Eu~(3+)離子摻雜磷硼酸鹽玻璃:XRD圖譜表明,樣品中沒有任何析晶,呈典型的非晶態(tài)玻璃結(jié)構(gòu)。紅外光譜分析結(jié)果表明,玻璃的網(wǎng)絡(luò)結(jié)構(gòu)中主要有[BO3]、[BO4]和[PO4]三種基團,并通過P-O-P,P-O-B,B-O和P=O鍵互相連接。在393nm激發(fā)下,Eu~(3+)離子單摻磷硼酸鹽玻璃的發(fā)射光譜及熒光衰減顯示,Eu~(3+)離子摻雜濃度達到2.5mol%時樣品中發(fā)生稀土離子的濃度猝滅現(xiàn)象。通過對Eu~(3+)離子單摻磷硼酸鹽玻璃的色坐標(biāo)進行計算發(fā)現(xiàn)其色坐標(biāo)為(0.65,0.34)接近于標(biāo)準(zhǔn)紅光的色坐標(biāo)(0.67,033)。2.Tb~(3+)/Sm~(3+)離子共摻磷硼酸鹽玻璃:在374nm激發(fā)下玻璃樣品表現(xiàn)出黃色的發(fā)射光,通過改變Sm~(3+)離子濃度可調(diào)控發(fā)光性能。發(fā)射光譜與熒光衰減結(jié)果證實存在Tb~(3+)→Sm~(3+)的能量傳遞過程,能量傳遞過程主要是以無輻射躍遷的共振傳遞形式進行,相應(yīng)的傳遞機理為電四極子-電四極子相互作用。3.Tm~(3+)/Tb~(3+)/Sm~(3+)離子共摻磷硼酸鹽玻璃:在358nm激發(fā)下玻璃樣品發(fā)射光進入了白光區(qū)域,符合白光LED色坐標(biāo)的基本要求。隨著Sm~(3+)離子濃度的增加,玻璃樣品的發(fā)射光逐漸由冷色調(diào)向暖色調(diào)移動。當(dāng)Tm~(3+)、Tb~(3+)和Sm~(3+)離子的摻雜濃度分別為0.4、1.0和0.8mol%時,玻璃樣品的色坐標(biāo)為(0.3339,0.3241),這與標(biāo)準(zhǔn)白光的色坐標(biāo)(0.3333,0.3333)非常接近。發(fā)射光譜與熒光衰減結(jié)果證實存在Tm~(3+)→Sm~(3+)和Tb~(3+)→Sm~(3+)的能量傳遞,能量傳遞主要以無輻射躍遷的共振傳遞形式進行。4.Tb~(3+)/Eu~(3+)離子共摻磷硼酸鹽玻璃:在378nm激發(fā)下玻璃樣品的發(fā)射光主要在黃光區(qū),通過改變Eu~(3+)離子濃度可調(diào)控發(fā)光性能。發(fā)射光譜與熒光衰減結(jié)果證實存在Tb~(3+)→Eu~(3+)的能量傳遞過程,能量傳遞過程主要是以無輻射躍遷的共振傳遞和交叉馳豫傳遞的形式進行。353K-573K溫度范圍內(nèi)的變溫發(fā)射光譜表明,Tb~(3+)/Eu~(3+)離子共摻磷硼酸鹽玻璃具備優(yōu)良的熒光溫敏特性,其絕對靈敏度為0.0036K-1。5.Tb~(3+)/Eu~(3+)離子共摻磷硼酸鹽玻璃陶瓷:XRD圖譜表明,玻璃陶瓷中的納米晶體為NaCaPO4,根據(jù)謝樂公式以及TEM分析估算出晶體的尺寸大約13nm。在378nm激發(fā)下,Tb~(3+)/Eu~(3+)離子共摻磷硼酸鹽玻璃陶瓷的發(fā)射光處于黃光區(qū),通過改變Eu~(3+)離子濃度可調(diào)控發(fā)光性能。發(fā)射光譜與熒光衰減結(jié)果證實存在Tb~(3+)→Eu~(3+)的能量傳遞過程,能量傳遞過程主要是以無輻射躍遷的共振傳遞和交叉馳豫傳遞的形式進行。293-573K溫度范圍內(nèi)的變溫發(fā)射光譜表明,相對于Tb~(3+)/Eu~(3+)離子共摻磷硼酸鹽玻璃,玻璃陶瓷具備更加優(yōu)異的熒光溫敏特性,其最大絕對靈敏度為0.0066K-1,最大相對靈敏度為4.55%K-1。
[Abstract]:The rare earth ion doped fluorescent materials have a wide range of potential applications in many fields, such as white light LED, display parts, solar cells, laser and optical temperature sensors, because of their excellent luminescence properties. The fluorescent glass and glass ceramics have the incomparable advantages of other fluorescent materials, such as transparency, The study of rare earth doped fluorescent glass and glass ceramics is of great scientific significance and application value. This paper has prepared Eu~ (3+), Tm~ (3+), Tb~ (3+) and Sm~ (3+) ions single and Co doped Na2O-CaO-P2O5- by high temperature melting quenching. Tb~ (3+) and Eu~ (3+) ion and Co doped Borate Glass ceramics were prepared by controllable crystallization method. The structure of phosphborate glass and glass ceramics was analyzed by XRD, infrared spectroscopy, TEM and density measurements. The absorption spectra, excitation spectra, emission spectra and color coordinates were used to study phosphor phosphor. The optical properties of borate glass and glass ceramics were studied by using the theory and formula of fluorescence decay junctions and correlation. The energy transfer of rare earth ions in phosphborate glass and glass ceramics was studied. The temperature emission spectra of Tb~ (3+) /Eu~ (3+) Co doped Borate Glass and glass ceramics were measured and the fluorescence intensity was based on the fluorescence intensity. The fluorescence thermosensitive properties of the 1.Eu~ (3+) ion doped phosphborate glass were obtained. The XRD map showed that there was no crystallization in the sample and the typical amorphous glass structure. The results of infrared spectrum analysis showed that there were three main groups of [BO3], [BO4] and [PO4] in the network structure of the glass, and through P-O-P, P-. O-B, B-O and P=O bonds are interconnected. Under 393nm excitation, the emission spectra and fluorescence decay of Eu~ (3+) ion doped Borate Glass show that the concentration quenching of rare earth ions occurs in the samples when the doping concentration of Eu~ (3+) ions reaches 2.5mol%. The color coordinates of the Eu~ (3+) ion doped Borate Glass are calculated and the color coordinates are found. (0.65,0.34) a color coordinate (0.67033).2.Tb~ (3+) /Sm~ (3+) ion Co doped phosphate borate glass near standard red light: a yellow emission light is displayed in the glass sample excited by 374nm, and the luminescence properties can be regulated by changing the concentration of Sm~ (3+) ions. The emission spectra and fluorescence decay results confirm the existence of the energy transfer process of Tb~ (3+) to Sm~ (3+). The energy transfer process is carried out mainly in the form of resonance transfer without radiative transition, and the corresponding transfer mechanism is.3.Tm~ (3+) /Tb~ (3+) /Sm~ (3+) ion Co doped Borate Glass with electric quadrupole electrical quadrupole interaction. The emission light of glass sample into the white light region under the excitation of 358nm, which is in accordance with the basic requirements of the white LED color coordinates. With S When the concentration of m~ (3+) ions increases, the emission light of the glass samples gradually moves from the cold tone to the warm tone. When the doping concentration of Tm~ (3+), Tb~ (3+) and Sm~ (3+) ions is 0.4,1.0 and 0.8mol%, the color coordinates of the glass samples are (0.3339,0.3241), which are very close to the standard white light color coordinates (0.3333,0.3333). The emission spectra and fluorescence decay junctions are very close. The energy transfer of Tm~ (3+), Sm~ (3+) and Tb~ (3+) to Sm~ (3+) is confirmed. The energy transfer is mainly composed of.4.Tb~ (3+) /Eu~ (3+) ions Co doped Borate Glass in the form of non radiative transition. The emission light of the glass sample is mainly in the Yellow region. The energy transfer process of Tb~ (3+) to Eu~ (3+) is confirmed by the spectra and fluorescence decay results. The energy transfer process is mainly in the form of the.353K-573K temperature range in the form of the.353K-573K temperature range in the form of the resonance transfer and the cross relaxation transfer of the non radiative transition. It shows that the Tb~ (3+) /Eu~ (3+) ion Co doped Borate Glass has excellent fluorescence Wen Min. The absolute sensitivity is 0.0036K-1.5.Tb~ (3+) /Eu~ (3+) Co doped phosphate borate glass ceramics. The XRD atlas shows that the nanocrystals in glass ceramics are NaCaPO4. According to the xele formula and TEM analysis, the size of the crystal is estimated to be about 13nm. under 378nm excitation, and the emission light of Tb ~ (3+) /Eu~ (3+) ions Co doped Borate Glass Ceramics In the Yellow region, the luminescence properties can be regulated by changing the concentration of Eu~ (3+) ions. The energy transfer process of Tb~ (3+) to Eu~ (3+) is confirmed by the emission spectra and fluorescence attenuation results. The energy transfer process is mainly based on the temperature range emission spectra within the.293-573K temperature range in the form of resonance transfer of non radiative transition and cross relaxation transfer. Compared with Tb~ (3+) /Eu~ (3+) ions Co doped with phosphate borate glass, glass ceramics have more excellent fluorescence thermo sensitive properties. The maximum absolute sensitivity is 0.0066K-1, and the maximum relative sensitivity is 4.55%K-1..
【學(xué)位授予單位】：桂林電子科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ171.1

【參考文獻】

相關(guān)期刊論文 前5條

1 王家鑫;陳國華;李旭瓊;何志毅;袁昌來;楊會娟;楊云;;Ce/Tb/Mn共摻雜ZnO-SrO-P_2O_5玻璃陶瓷的制備與白光發(fā)射調(diào)控[J];中國有色金屬學(xué)報;2014年06期

2 馮志慶;白蘭;曹保勝;宮利東;董斌;;基于Er-Yb共摻雜硼硅酸鹽玻璃的光學(xué)溫度傳感[J];中國科學(xué):物理學(xué) 力學(xué) 天文學(xué);2010年08期

3 李慧娟;邵起越;董巖;蔣建清;梁超;何錦華;;白光LED用YAG∶Ce~(3+)熒光粉的溫度猝滅性質(zhì)[J];發(fā)光學(xué)報;2008年06期

4 夏上達;;稀土發(fā)光和光譜理論的研究進展[J];發(fā)光學(xué)報;2007年04期

5 孟婕,趙麗娟,余華,唐莉勤,梁沁,禹宣伊,唐柏權(quán),蘇靜,許京軍;微晶結(jié)構(gòu)對氟氧化物玻璃陶瓷發(fā)光特性的影響[J];物理學(xué)報;2005年03期

，

本文編號：1976218