本文選題：稀土離子 + 能量轉(zhuǎn)移��； 參考：《中國(guó)計(jì)量學(xué)院》2015年碩士論文

【摘要】：~3μm波長(zhǎng)的中紅外熒光發(fā)射包含了許多大氣分子的特征譜線帶,在軍事對(duì)抗、醫(yī)療手術(shù)、環(huán)境污染檢測(cè)以及光通信等領(lǐng)域有重要應(yīng)用。本論文主要目的在于研究能夠適用于~3μm激光輸出的玻璃材料。通過(guò)對(duì)玻璃基質(zhì)的組分調(diào)整及稀土離子的濃度優(yōu)化,制備出了適用于~3μm發(fā)光的玻璃材料。本文首先制備了不同Ga2O3含量的鍺酸鹽玻璃,對(duì)玻璃樣品進(jìn)行了XRD分析。發(fā)現(xiàn)當(dāng)Ga2O3含量達(dá)到25 mol%時(shí),玻璃開(kāi)始變得不透明。對(duì)未析晶樣品進(jìn)行了熱分析、發(fā)現(xiàn)所制備的樣品具有較高的ΔT和kgl(140°C和0.176)。進(jìn)一步研究了玻璃的結(jié)構(gòu)、物理及光學(xué)性能,通過(guò)拉曼光譜分析發(fā)現(xiàn)玻璃的最大聲子振動(dòng)頻率隨著Ga2O3含量的增加逐漸向低波數(shù)方向移動(dòng)。測(cè)試了Er3+的吸收光譜,討論了J-O參數(shù)及輻射性質(zhì)。研究了玻璃的紅外透過(guò)光譜,發(fā)現(xiàn)樣品的最大透過(guò)率高達(dá)84%。中紅外熒光光譜表明2.7μm發(fā)射強(qiáng)度隨著Ga2O3含量增加先降低后增加。計(jì)算發(fā)現(xiàn)所制備樣品的最大發(fā)射截面可達(dá)4.68×10-21 cm2。利用速率方程和Inokuti-Hirayama模型計(jì)算了能量轉(zhuǎn)移參數(shù)及能量轉(zhuǎn)移上轉(zhuǎn)換系數(shù),解釋了2.7μm熒光行為。在前一章研究的基礎(chǔ)上,進(jìn)一步制備了R2O3(R=Al/Y/Gd/La)及Nb2O5改進(jìn)的鍺酸鹽玻璃。研究了R2O3對(duì)玻璃密度、折射率等物化參數(shù)的影響,比較了R2O3及Nb2O5對(duì)其熱穩(wěn)定性、析晶活化能等熱力學(xué)性能。發(fā)現(xiàn)Y2O3改進(jìn)的玻璃具有更高的ΔT及kgl值(175°C和0.224)。研究了樣品的拉曼光譜,對(duì)其玻璃結(jié)構(gòu)及最大聲子能量進(jìn)行了分析。中紅外熒光光譜分析表明Y2O3改進(jìn)的鍺酸鹽玻璃在2.7μm處具有較高的熒光強(qiáng)度及發(fā)射截面。研究了Er3+的能量轉(zhuǎn)移過(guò)程,討論了2.7μm熒光增強(qiáng)的機(jī)理。采用Y2O3改進(jìn)的鍺酸鹽玻璃為基質(zhì),研究了Er3+濃度對(duì)其2.7μm熒光性能的影響,發(fā)現(xiàn)所制備的樣品能實(shí)現(xiàn)6 mol%Er3+的高濃度摻雜而沒(méi)有熒光猝滅�；谏限D(zhuǎn)換及近紅外熒光光譜,提出了合理的能量轉(zhuǎn)移機(jī)理。研究發(fā)現(xiàn)激發(fā)態(tài)吸收(ESA2)、交叉弛豫(CR)及能量轉(zhuǎn)移上轉(zhuǎn)換(ETU2)過(guò)程隨著Er3+濃度的增加而變強(qiáng)。這些過(guò)程均有利于提高激光上下能級(jí)的粒子數(shù)反轉(zhuǎn),增強(qiáng)2.7μm熒光發(fā)射。制備了Er3+/Tm3+共摻鍺酸鹽玻璃,發(fā)現(xiàn)Tm3+能夠有效的敏化Er3+粒子,顯著增強(qiáng)了2.7μm發(fā)射。討論了Tm3+與Er3+間的能量轉(zhuǎn)移機(jī)理并計(jì)算了Tm3+與Er3+間的能量轉(zhuǎn)移微觀參數(shù)及能量轉(zhuǎn)移效率。結(jié)果表明Er3+:4I13/2→Tm3+:3F4的能量轉(zhuǎn)移系數(shù)(2.94×10-39cm6/s)遠(yuǎn)大于Er3+:4I11/2→Tm3+:3H5的值(0.93×10-40 cm6/s)。通過(guò)速率方程分析,進(jìn)一步證實(shí)了2.7μm,1.8及1.53μm熒光變化。制備了Er3+-Yb3+共摻鍺酸鹽玻璃,在980nm波長(zhǎng)泵浦下,Er3+-Yb3+共摻樣品的2.7μm、1.53μm及上轉(zhuǎn)換發(fā)射強(qiáng)度明顯高于Er3+單摻樣品。隨著Yb3+濃度的增加,其發(fā)射強(qiáng)度單調(diào)增加,沒(méi)有出現(xiàn)明顯的熒光猝滅現(xiàn)象。接著討論了Er3+與Yb3+的能量轉(zhuǎn)移機(jī)理,Yb3+:2F5/2→Er3+:4I11/2的能量轉(zhuǎn)移微觀參數(shù)高達(dá)1.42×10-39 cm6/s。本文最后研究了Ho3+/Yb3+共摻鍺酸鹽玻璃的2.9μm光譜性能�；谖展庾V及J-O理論,計(jì)算了Ho3+的Judd-Ofelt強(qiáng)度參數(shù)及輻射性質(zhì),發(fā)現(xiàn)Ho3+:5I6→5I7躍遷(2.9μm)的自發(fā)輻射躍遷幾率高達(dá)36.66 s-1。中紅外熒光光譜表明當(dāng)Ho3+:Yb3+的濃度比為0.1:2時(shí),2.9μm熒光最強(qiáng)。計(jì)算的2.9μm發(fā)射截面高達(dá)8.58×10-21 cm2,當(dāng)反轉(zhuǎn)粒子數(shù)P為0.5時(shí),在2866-3000nm處的增益為正。通過(guò)上轉(zhuǎn)換、近紅外及中紅外光譜分析,討論了Ho3+和Yb3+的能量轉(zhuǎn)移機(jī)理,計(jì)算了Yb3+到Ho3+的能量傳遞效率及能量傳遞系數(shù),分別為35.8%和4.06×10-40 cm6/s。最后利用YokotaTanimoto模型計(jì)算了不同Ho3+濃度的Yb3+到Ho3+的能量轉(zhuǎn)移系數(shù),發(fā)現(xiàn)隨著Ho3+濃度的增加,其值逐漸減小,這表明5I6能級(jí)的粒子數(shù)隨著Ho3+濃度而降低,與實(shí)驗(yàn)結(jié)果一致。
[Abstract]:The middle infrared fluorescence emission of ~3 mu m wavelength contains many characteristic spectral lines of atmospheric molecules. It has important applications in military confrontation, medical operation, environmental pollution detection and optical communication. The main purpose of this paper is to study glass materials that can be applied to the output of ~3 mu m laser. The glass material suitable for ~3 mu m luminescence was prepared. The germanate glass with different Ga2O3 content was prepared in this paper. The glass samples were analyzed by XRD. It was found that when the content of Ga2O3 reached 25 mol%, the glass began to become opaque. The structure, physical and optical properties of the glass are further studied. The vibration frequency of the maximum phonon of the glass is gradually moved to the low wave number with the increase of the Ga2O3 content. The absorption spectra of Er3+ are tested and the J-O parameters and radiation properties are discussed. The infrared transmittance of the glass is studied. The infrared transmittance of the glass is studied. It is found that the maximum transmittance of the sample up to 84%. mid infrared fluorescence spectra shows that the emission intensity of 2.7 mu m decreases first and then increases with the increase of Ga2O3 content. The maximum emission cross section of the prepared sample can reach 4.68 x 10-21 cm2. utilization rate equation and Inokuti-Hirayama model to calculate the energy transfer parameters and the energy transfer upconversion system The fluorescence behavior of 2.7 mu m was explained. On the basis of the previous chapter, R2O3 (R=Al/Y/Gd/La) and Nb2O5 improved germanate glass were further prepared. The effects of R2O3 on the physical parameters of glass density, refractive index and so on were studied. The thermodynamic properties of R2O3 and Nb2O5 on its thermal stability and crystallization activation energy were compared. The improved glass tool with Y2O3 was found. A higher Delta T and KGL value (175 degree C and 0.224). The Raman spectra of the samples were studied, and the glass structure and the maximum phonon energy were analyzed. The mid infrared fluorescence spectrum analysis showed that the Y2O3 improved germanate glass had high fluorescence intensity and the emission cross section at 2.7 mu m. The energy transfer process of Er3+ was studied, and 2.7 mu m fluorescence was discussed. Strengthening mechanism. Using Y2O3 improved germanate glass as matrix, the effect of Er3+ concentration on its 2.7 u m fluorescence is studied. It is found that the prepared samples can achieve high concentration of 6 mol%Er3+ without fluorescence quenching. Based on upconversion and near infrared fluorescence spectroscopy, the mechanism of energy transfer is proposed. ESA2, cross relaxation (CR) and energy transfer up conversion (ETU2) process become stronger with the increase of Er3+ concentration. These processes are beneficial to increase the number reversal of the particles in the upper and lower energy levels of the laser and enhance the fluorescence emission of 2.7 mu m. The Er3+/Tm3+ Co doped germanate glass is prepared, and it is found that Tm3+ can sensitize Er3+ particles effectively and significantly enhance the emission of 2.7 u m. The energy transfer mechanism between Tm3+ and Er3+ is discussed and the energy transfer micro parameters and energy transfer efficiency between Tm3+ and Er3+ are calculated. The results show that the energy transfer coefficient (2.94 x 10-39cm6/s) of Er3+: 4I13/2 to Tm3+ is far greater than Er3+: 4I11/2 > Tm3+: (0.93 x 10-40). Through the rate equation analysis, further confirmed 2.7 micron, Er3+-Yb3+ Co doped germanate glass was prepared by 1.8 and 1.53 m fluorescence. Under 980nm wavelength, 2.7 mu m, 1.53 mu m and upconversion emission intensity were significantly higher than those of Er3+ single doped samples. With the increase of Yb3+ concentration, the emission intensity of the samples increased monotonically, and no obvious fluorescence quenching was found. Then Er3+ and Yb were discussed. The energy transfer mechanism of 3+, Yb3+: 2F5/2 to Er3+: the micro parameters of energy transfer of 4I11/2 are as high as 1.42 x 10-39 cm6/s.. Finally, the spectral properties of 2.9 mu m of Ho3+/Yb3+ Co doped germanate glass are studied. Based on the absorption spectrum and J-O theory, the Judd-Ofelt intensity parameters and radiating properties of Ho3+ are calculated, and Ho3+: Ho3+: 2.9 micron transition (2.9 mu) self is found. The radiation transition probability up to 36.66 s-1. in the infrared fluorescence spectrum shows that when the concentration ratio of Ho3+: Yb3+ is 0.1:2, the fluorescence of 2.9 mu m is the strongest. The calculated 2.9 mu m emission cross section is up to 8.58 x 10-21 cm2, and the gain at 2866-3000nm is positive when the number P of the reverse is P. The Ho3+ and Yb3 are discussed by upconversion, near infrared and mid infrared spectroscopy. The energy transfer mechanism of + + is calculated. The energy transfer efficiency and energy transfer coefficient of Yb3+ to Ho3+ are calculated, 35.8% and 4.06 x 10-40 cm6/s. respectively. Finally, the energy transfer coefficient of Yb3+ to Ho3+ with different Ho3+ concentrations is calculated by YokotaTanimoto model. It is found that with the increase of Ho3+ concentration, the value gradually decreases, which indicates that the number of particles at the 5I6 level is dependent on the number of Ho3+. The decrease of Ho3+ concentration is consistent with the experimental results.
【學(xué)位授予單位】：中國(guó)計(jì)量學(xué)院
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TQ171.112

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