【摘要】：七鋁酸十二鈣(C12A7)晶體是一種具備很好集成性能的新型功能材料,在固態(tài)多色激光器及3D顯示等領(lǐng)域具有廣闊的應(yīng)用前景。本論文通過Ho~(3+),Yb~(3+)和Tm~(3+)離子按照一定摩爾比例進(jìn)行摻雜,在C12A7單晶中成功實現(xiàn)上轉(zhuǎn)換白光輸出,并對上轉(zhuǎn)換白光產(chǎn)生的機(jī)制進(jìn)行了詳細(xì)的分析。通過摻雜Mg~(2+)和Mn~(2+)離子分別對上轉(zhuǎn)換白光的光強(qiáng)和色度進(jìn)行了調(diào)節(jié),實現(xiàn)了對C12A7單晶體系上轉(zhuǎn)換白光性能的精細(xì)調(diào)節(jié)。采用高溫固相法合成Ho~(3+)/Yb~(3+)/Tm~(3+)摻雜的C12A7多晶粉末,在980 nm激光激發(fā)下,樣品在477 nm和652 nm處輸出了對應(yīng)于Tm~(3+)的1G4→3H6和1G4→3F4能級躍遷引起的上轉(zhuǎn)換藍(lán)光和紅光;在550 nm處輸出了對應(yīng)于Ho~(3+)的5S2/5F4→5I8能級躍遷產(chǎn)生的上轉(zhuǎn)換綠光,在665 nm處輸出了對應(yīng)于Ho~(3+)的5F5→5I8能級躍遷所引起的上轉(zhuǎn)換紅光。通過設(shè)計正交試驗來研究Ho~(3+),Yb~(3+)和Tm~(3+)三種稀土離子濃度對C12A7多晶上轉(zhuǎn)換發(fā)光性能的影響,并最終在C12A7多晶材料中實現(xiàn)白光輸出。采用提拉法生長不同濃度Ho~(3+),Yb~(3+)和Tm~(3+)離子摻雜的C12A7單晶體,研究晶體生長過程中的各參數(shù)對晶體質(zhì)量的影響。利用Crysmas軟件模擬不同尺寸保溫罩下的晶體生長溫度場,并在模擬結(jié)果的基礎(chǔ)上,測量實際晶體生長過程中的溫度梯度來與模擬結(jié)果做對比,以保證建立最適合C12A7晶體生長的溫度場(27℃/cm)。通過CGsim軟件模擬不同轉(zhuǎn)速下熔體的界面形狀,尋找最合適的晶體生長速度和旋轉(zhuǎn)速度(1mm/h和25 rpm)。研究了生長氣氛對晶體質(zhì)量的影響,發(fā)現(xiàn)隨著氧氣含量的增加,晶體中的銥雜質(zhì)含量也隨之增加,這也是晶體著色的原因。最終確定了完整的稀土摻雜C12A7晶體生長工藝,并生長出質(zhì)量較好的C12A7單晶。通過XRD、紫外-可見吸收光譜和上轉(zhuǎn)換發(fā)光光譜研究Ho~(3+),Yb~(3+)和Tm~(3+)離子濃度對C12A7晶體結(jié)構(gòu)和上轉(zhuǎn)換發(fā)光性能的影響。稀土離子所引起的晶格形狀變化以及稀土離子之間能量傳遞作用的變化是影響上轉(zhuǎn)換發(fā)光性能的主要因素。Ho~(3+)和Tm~(3+)離子濃度主要對輸出光的色度有很好的調(diào)節(jié)作用,Yb~(3+)離子則主要改變上轉(zhuǎn)換發(fā)光的光強(qiáng)。通過上轉(zhuǎn)換功率曲線、發(fā)光能級壽命、中間態(tài)能級壽命測試以及穩(wěn)態(tài)速率方程,分析了Ho~(3+)/Yb~(3+)/Tm~(3+)/C12A7晶體中上轉(zhuǎn)換白光的激發(fā)過程。在980 nm激光激發(fā)下,Ho~(3+)/Yb~(3+)/Tm~(3+)/C12A7晶體產(chǎn)生的477 nm波長的藍(lán)光為三光子連續(xù)能量傳遞過程,波長為550 nm的上轉(zhuǎn)換綠光以及波長為652 nm和665 nm的上轉(zhuǎn)換紅光均為兩光子連續(xù)能量傳遞過程。且上轉(zhuǎn)換藍(lán)光、綠光和紅光的光子數(shù)排序為:藍(lán)光綠光紅光。研究了激發(fā)功率對Ho~(3+)/Yb~(3+)/Tm~(3+)/C12A7晶體上轉(zhuǎn)換白光性能的影響。隨著激發(fā)功率的增加,上轉(zhuǎn)換藍(lán)光、綠光和紅光光強(qiáng)均呈現(xiàn)逐漸增強(qiáng)的趨勢,但增強(qiáng)幅度不同。上轉(zhuǎn)換發(fā)光的色度逐漸由白光中心向藍(lán)紫光交界區(qū)域偏移,這也是由于上轉(zhuǎn)換藍(lán)光的激發(fā)過程為三光子連續(xù)能量傳遞,而上轉(zhuǎn)換綠光和紅光的激發(fā)過程僅為兩光子連續(xù)能量傳遞。研究了Ho~(3+)/Yb~(3+)/Tm~(3+)/C12A7晶體中Tm~(3+)離子3F2,3和3H4能級的熱耦合行為,獲得了C12A7材料較高的光學(xué)溫度探測靈敏度,比較適合用于溫度探測,并且較高的靈敏度來源于較高的晶體結(jié)晶度。利用第一性原理計算了Yb~(3+)摻雜C12A7晶體的能帶結(jié)構(gòu)圖和態(tài)密度圖,并與未摻雜的理想C12A7晶體模型進(jìn)行對比,發(fā)現(xiàn)稀土離子的摻入使得禁帶寬度減小,但并沒有改變費(fèi)米能級位置。對C12A7與Yb~(3+)摻雜C12A7的結(jié)構(gòu)進(jìn)行分析,確定了稀土離子并沒有進(jìn)入C12A7晶體的籠狀結(jié)構(gòu)內(nèi)部,而是以取代Ca~(2+)的形式存在。運(yùn)用Judd-Ofelt理論計算了Ho~(3+)及Tm~(3+)摻雜C12A7材料的J-O強(qiáng)度參數(shù)以及光譜品質(zhì)因子,計算結(jié)果表明稀土摻雜C12A7單晶材料是一種能夠?qū)崿F(xiàn)很好上轉(zhuǎn)換發(fā)光的晶體材料。研究了金屬離子Mg~(2+)和Mn~(2+)對Ho~(3+)/Yb~(3+)/Tm~(3+)/C12A7晶體上轉(zhuǎn)換白光性能的影響。Mg~(2+)離子的摻雜對Ho~(3+)/Yb~(3+)/Tm~(3+)/C12A7晶體的上轉(zhuǎn)換發(fā)光強(qiáng)度有很好的調(diào)節(jié)作用。Mg~(2+)離子的摻雜使得上轉(zhuǎn)換發(fā)光過程中的中間態(tài)能級壽命增加,發(fā)光能級壽命降低,使得上轉(zhuǎn)換過程所需光子數(shù)減少,宏觀表現(xiàn)為上轉(zhuǎn)換發(fā)光強(qiáng)度增強(qiáng)。Mn~(2+)離子的摻雜對Ho~(3+)/Yb~(3+)/Tm~(3+)/C12A7晶體的上轉(zhuǎn)換白光色度有較好的調(diào)節(jié)作用。Mn~(2+)離子的摻雜會影響Ho~(3+)離子在5F5能級的粒子布居數(shù),增加紅光的發(fā)射幾率,對上轉(zhuǎn)換白光的色度有積極的調(diào)節(jié)作用。
[Abstract]:The seven calcium aluminate (C12A7) crystal is a new functional material with good integration properties. It has a broad application prospect in the fields of solid-state polychromatic laser and 3D display. In this paper, Ho~ (3+), Yb~ (3+) and Tm~ (3+) ions are doped in a certain molar ratio, and the upconversion white light output is successfully realized in the C12A7 single crystal. The mechanism of the upconversion white light was analyzed in detail. The light intensity and chromaticity of the upconversion white light were adjusted by doping Mg~ (2+) and Mn~ (2+) ions respectively. The fine regulation of the conversion of white light on the C12A7 single crystal system was realized. A high-temperature solid-phase method was used to synthesize the Ho~ (3+) /Yb~ (3+) /Tm~ (3+) doped C12A7 polycrystalline powder. Under the excitation of M laser, up conversion blue light and red light caused by 1G4 to 3H6 and 1G4 to 3F4 level transitions corresponding to Tm~ (3+) were output at 477 nm and 652 nm, and the upconversion green light corresponding to Ho~ (3+) transition was output at 550 nm. The effect of three rare earth ions concentration of Ho~ (3+), Yb~ (3+) and Tm~ (3+) on the performance of upconversion luminescence of C12A7 polycrystals was investigated by the orthogonal experiment, and the white light output was realized in the C12A7 polycrystalline material. The crystal of C12A7 with different concentration Ho~ (3+), Yb~ (3+) and ionic doping was studied by the drawing method. The influence of the parameters on the crystal quality during the growth process. Crysmas software is used to simulate the temperature field of the crystal growth under the different sizes of thermal insulation. On the basis of the simulation results, the temperature gradient in the actual crystal growth is measured to compare with the simulation results, so as to ensure the establishment of the temperature field (27 C /cm) suitable for the growth of C12A7 crystal. The interface shape of the melt at different rotational speeds was simulated by CGsim software to find the most suitable crystal growth speed and rotation speed (1mm/h and 25 RPM). The influence of the growth atmosphere on the crystal quality was studied. It was found that the iridium impurity content in the crystal increased with the increase of oxygen content, which was also the reason for the crystal coloring. Complete rare-earth doped C12A7 crystal growth process and high quality C12A7 single crystal have been grown. The effects of Ho~ (3+), Yb~ (3+) and Tm~ (3+) ion concentration on the crystal structure and upconversion luminescence properties of C12A7 are studied by XRD, UV Vis absorption and upconversion luminescence spectra. The lattice shape changes and rare earth ionization caused by rare earth ions are caused by rare earth ions. The change of energy transfer between the subgroups is the main factor affecting the performance of the upconversion luminescence. The concentration of.Ho~ (3+) and Tm~ (3+) ion mainly regulates the chromaticity of the output light, and the Yb~ (3+) ion mainly changes the light intensity of the upconversion luminescence. Through the upconversion power curve, the lifetime of the luminescent energy level, the lifetime test of the middle state and the stability of the light. The excited process of up conversion white light in the Ho~ (3+) /Yb~ (3+) /Tm~ (3+) /C12A7 crystal is analyzed by the state rate equation. The blue light of the Ho~ (3+) /Yb~ (3+) /Yb~ (3+) /Yb~ (3+) /Yb~ (3+) crystal is three photon continuous energy transfer process under the excitation of the 980 nm laser. The up conversion green light of the wave length of 550 and the up conversion red of the wavelength is 652 and 665. The light is two photon continuous energy transfer process. And up conversion blue light, the number of photons of green and red light is: blue and green light red light. The effect of excitation power on the performance of Ho~ (3+) /Yb~ (3+) /Tm~ (3+) /C12A7 crystal up conversion white light is studied. With the increase of the excitation power, the upconversion blue light, green light and red light intensity are gradually enhanced. Trend, but the enhancement range is different. The chromaticity of upconversion luminescence is gradually shifted from white light center to blue violet light junction area, which is due to the continuous energy transfer of three photons in the process of up conversion blue light, while the process of up conversion green light and red light is only two photon continuous energy transfer. The Ho~ (3+) /Yb~ (3+) /Tm~ (3+) /C12A7 crystal is studied. The thermal coupling behavior of the Tm~ (3+) ion 3F2,3 and 3H4 level in the body has obtained the higher sensitivity of the optical temperature detection of the C12A7 material, which is more suitable for the temperature detection, and the higher sensitivity is derived from the higher crystal crystallinity. The band structure diagram and the state density diagram of Yb~ (3+) doped C12A7 crystals are calculated by the first principle, and they are not used. The doping of the ideal C12A7 crystal model shows that the doping of rare earth ions reduces the band gap, but does not change the position of the Fermi level. The structure of the C12A7 and Yb~ (3+) doped C12A7 is analyzed, and the rare earth ions do not enter the cage like structure of the C12A7 crystal, but instead of the form of Ca~ (2+). The udd-Ofelt theory is used to calculate the J-O strength parameters and spectral quality factors of the Ho~ (3+) and Tm~ (3+) doped C12A7 materials. The calculation results show that the rare earth doped C12A7 single crystal material is a kind of crystal material which can achieve good upconversion luminescence. The conversion of white light on the crystal of metal ions Mg~ (2+) and Mn~ (2+) is studied. The doping of.Mg~ (2+) ion has a good regulating effect on the upconversion luminescence intensity of Ho~ (3+) /Yb~ (3+) /Tm~ (3+) /C12A7 crystal, the doping of.Mg~ (2+) ions makes the lifetime of the middle state of the middle state of the upconversion luminescence increases and the lifetime of the luminescent energy level decreases, which makes the number of photons in the upconversion process decrease and the macroscopic performance is the upturn. The doping of.Mn~ (2+) ion has a good regulating effect on the upconversion white light chromaticity of Ho~ (3+) /Yb~ (3+) /Tm~ (3+) /C12A7 crystal. The doping of.Mn~ (2+) ions will affect the number of particles in the energy level, increasing the emission probability of the red light, and has a positive effect on the chromaticity of the upconversion white light.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O734

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