稀土摻雜硅酸鹽電子俘獲型材料及其發(fā)光性能的研究
發(fā)布時(shí)間：2018-07-26 19:36
【摘要】：電子俘獲型材料(Electron trapping materials)具有存儲(chǔ)的特性,并且材料被長波波長的光激勵(lì)時(shí),可以輻射出短波波長的光,因此它在光學(xué)領(lǐng)域的另外一個(gè)名稱為光激勵(lì)發(fā)光材料。光激勵(lì)發(fā)光材料因其獨(dú)特的性質(zhì),其在紅外探測、紅外光轉(zhuǎn)換、光存儲(chǔ)及X射線成像等諸多方面有其廣泛的應(yīng)用前景。目前,可以商業(yè)化光激勵(lì)材料主要是堿土金屬硫化物系列,這種材料的光激勵(lì)發(fā)光初始激發(fā)亮度強(qiáng)度高,并且光存儲(chǔ)量大等諸多優(yōu)點(diǎn)。但是,硫化物的本身的致命缺陷就是熱穩(wěn)定差。同時(shí),我們知道硫化物的分解,將會(huì)產(chǎn)生有毒害的物質(zhì),可以對(duì)自然環(huán)境造成嚴(yán)重的污染。因此,尋找一種化學(xué)性質(zhì)穩(wěn)定,并且對(duì)環(huán)境污染少的光激勵(lì)材料已經(jīng)成為當(dāng)前的光激勵(lì)材料研究的重點(diǎn)。從所周知,硅酸鹽體系具有較好的化學(xué)穩(wěn)定性,并且耐高溫、抗腐蝕等優(yōu)點(diǎn),是目前被廣泛的用作稀土發(fā)光材料的基質(zhì)材料。其中,基質(zhì)材料RSrSiO4:Eu2+(R=Sr/Li2)是一類傳統(tǒng)的LED (light emitting diodes)用的熒光粉,本論文以RSrSiO4:Eu2+(R=Sr/Li2)為研究對(duì)象,通過摻入另一種共激活劑的方式引入陷阱以提高其光激勵(lì)發(fā)光性能。主要的研究成果如下：1)在基質(zhì)材料β-SrSiO4:Eu2+中,通過La3+離子摻雜有效的提高了樣品長余輝發(fā)光性能與光激勵(lì)發(fā)光性能。樣品的長余輝時(shí)間從幾分鐘增長到五十多分鐘,同時(shí)其光激勵(lì)初始強(qiáng)度、光激勵(lì)光存儲(chǔ)量等性能都有不同程度的提高。其原因是由于摻雜La3+離子的樣品本征存在的氧空位更加穩(wěn)定,因此其俘獲電子的能力得到很大的提高,這些增加的陷阱可以很大程度的提高材料的光激勵(lì)發(fā)光性能。2)在Li2SrSi04:Eu2+材料中,我們通過摻入四種不同的稀土離子(La3+/Nd3+/Dy3+ /Tm3+),研究發(fā)現(xiàn)不同的稀土離子對(duì)基質(zhì)材料內(nèi)部的微觀結(jié)構(gòu)影響不同,通過比較發(fā)現(xiàn)La3+離子能有效的增強(qiáng)材料的不同溫度范圍的熱釋光強(qiáng)度,因此其對(duì)樣品的光激勵(lì)發(fā)光性能是有較大貢獻(xiàn)。同時(shí)發(fā)現(xiàn)Nd3+/Dy3+離子對(duì)樣品材料的長余輝發(fā)光性能是有貢獻(xiàn)的,而對(duì)光激發(fā)光性能影響較小,因而可以忽略,其中Dy3+離子對(duì)樣品的長余輝發(fā)光性能影響最大。而Tm3+離子可以有效的提高深陷阱區(qū)的熱釋光峰,不過在我們用近紅外光激勵(lì)時(shí),不能使陷阱中的電子釋放出來,因而Tm3+離子對(duì)光激勵(lì)發(fā)光幾乎沒有貢獻(xiàn)。3)系統(tǒng)的研究了不同濃度La3+離子摻雜下Li2Sr0.997SiO4: 0.003Eu2+光激勵(lì)發(fā)光性能的變化。通過比較樣品的光致發(fā)光和光激勵(lì)發(fā)光光譜,說明樣品的發(fā)光都來自同一個(gè)發(fā)光中心,即Eu2+離子4f65d1→4f7的躍遷。經(jīng)研究我們發(fā)現(xiàn),隨著La3+離子濃度增加樣品的光激勵(lì)發(fā)光性能逐漸提升,當(dāng)La3+的摻雜濃度為0.008時(shí),基質(zhì)材料的光激勵(lì)發(fā)光初始強(qiáng)度和光激勵(lì)光存儲(chǔ)量性能均達(dá)到了最優(yōu)。同時(shí)研究了Dy3+離子對(duì)材料Li2Sr0.997SiO4:0.003Eu2+的熒光發(fā)光、長余輝發(fā)光性能的影響。通過實(shí)驗(yàn)發(fā)現(xiàn),Dy3+離子的引入在一定程度上使得材料的熒光發(fā)光強(qiáng)度有所降低,這是因?yàn)镈yr3+的引入使得材料本征存在的氧空位更加穩(wěn)定,增強(qiáng)了其俘獲載流子的能力,因此,在光致發(fā)光過程中,這些陷阱將會(huì)俘獲部分載流子造成基質(zhì)材料發(fā)光強(qiáng)度的降低。同時(shí)我們發(fā)現(xiàn)材料的長余輝性能隨著Dy3+離子的引入有所增強(qiáng)。
[Abstract]:Electron trapping materials has the characteristics of storage, and when the material is stimulated by long wave wavelengths, it can radiate the light of the short wave wavelength. Therefore, the other name in the optical field is the light excited luminescent material. The light excitation luminescent material is detected in infrared and infrared light conversion because of its unique properties. There are extensive applications in optical storage and X ray imaging. At present, commercialized light excitation materials are mainly alkaline earth metal sulfide series. The light excitation luminescence intensity of this material is high, and the amount of light storage is large. However, the fatal defect of the sulphide itself is the thermal stability. It is known that the decomposition of sulfides will produce toxic substances and can cause serious pollution to the natural environment. Therefore, looking for a light excitation material with stable chemical properties and less pollution to the environment has become the focus of current research on light excitation materials. It is well known that the silicate system has good chemical stability. With the advantages of high temperature resistance and corrosion resistance, it is widely used as a matrix material for rare earth luminescent materials. The matrix material RSrSiO4:Eu2+ (R=Sr/Li2) is a kind of traditional LED (light emitting diodes) phosphor. This paper is based on RSrSiO4:Eu2+ (R=Sr/Li2) as the research object and introduced by adding another Co activator. The main research results are as follows: 1) in the matrix material beta -SrSiO4:Eu2+, the long afterglow and light excitation properties of the sample are improved effectively by doping La3+ ions. The long afterglow time of the sample increases from a few minutes to more than 50 minutes, and the light excitation intensity and light excitation are also stimulated. The performance of the stored reserves has been improved in varying degrees. The reason is that the oxygen vacancies in the samples of the doped La3+ ions are more stable, so the ability to capture electrons is greatly improved. These increased traps can greatly improve the light excitation performance of the material.2) in the Li2SrSi04:Eu2+ material. Over the addition of four different rare earth ions (La3+/Nd3+/Dy3+ /Tm3+), it is found that different rare earth ions have different effects on the microstructure of the matrix materials. By comparison, it is found that La3+ ions can effectively enhance the thermoluminescence intensity of the materials at different temperature ranges, so it has a great contribution to the photoluminescence properties of the samples. It is found that the Nd3+/Dy3+ ions contribute to the long afterglow luminescence properties of the sample materials, but have little effect on the luminescence properties, and can be ignored, in which the Dy3+ ions have the greatest influence on the long afterglow luminescence properties of the samples, and the Tm3+ ions can effectively improve the thermal Shi Guangfeng in the deep trap region, but when we are excited by near infrared light, The electrons in the trap can not be released, so the Tm3+ ions have little contribution to the light excited luminescence. The system has studied the changes in the luminescence properties of the Li2Sr0.997SiO4: 0.003Eu2+ light stimulated by different concentrations of La3+ ions. By comparing the photoluminescence of the samples and the light excitation luminescence spectra, the luminescence of the samples comes from the same one. The luminescence center, that is, the transition of the Eu2+ ion 4f65d1 to 4F7. We have found that the luminescent properties of the samples increase gradually with the increase of the concentration of La3+ ions. When the doping concentration of La3+ is 0.008, the initial light excitation intensity and the optical storage performance of the matrix material have reached the best performance. At the same time, the Dy3+ ion pair is studied. The effect of fluorescent luminescence of Li2Sr0.997SiO4:0.003Eu2+ on the properties of long afterglow luminescence. It is found through experiments that the introduction of Dy3+ ions reduces the fluorescence intensity of the material to some extent. This is because the introduction of Dyr3+ makes the oxygen vacancies in the material more stable and the ability to capture the carrier. Therefore, the ability of the carrier to capture the carrier is enhanced. In the photoluminescence process, these traps will capture part of the carrier to reduce the luminescence intensity of the matrix material. We also find that the long afterglow properties of the material are enhanced with the introduction of Dy3+ ions.
【學(xué)位授予單位】：昆明理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB34;TQ422
本文編號(hào)：2147075
[Abstract]:Electron trapping materials has the characteristics of storage, and when the material is stimulated by long wave wavelengths, it can radiate the light of the short wave wavelength. Therefore, the other name in the optical field is the light excited luminescent material. The light excitation luminescent material is detected in infrared and infrared light conversion because of its unique properties. There are extensive applications in optical storage and X ray imaging. At present, commercialized light excitation materials are mainly alkaline earth metal sulfide series. The light excitation luminescence intensity of this material is high, and the amount of light storage is large. However, the fatal defect of the sulphide itself is the thermal stability. It is known that the decomposition of sulfides will produce toxic substances and can cause serious pollution to the natural environment. Therefore, looking for a light excitation material with stable chemical properties and less pollution to the environment has become the focus of current research on light excitation materials. It is well known that the silicate system has good chemical stability. With the advantages of high temperature resistance and corrosion resistance, it is widely used as a matrix material for rare earth luminescent materials. The matrix material RSrSiO4:Eu2+ (R=Sr/Li2) is a kind of traditional LED (light emitting diodes) phosphor. This paper is based on RSrSiO4:Eu2+ (R=Sr/Li2) as the research object and introduced by adding another Co activator. The main research results are as follows: 1) in the matrix material beta -SrSiO4:Eu2+, the long afterglow and light excitation properties of the sample are improved effectively by doping La3+ ions. The long afterglow time of the sample increases from a few minutes to more than 50 minutes, and the light excitation intensity and light excitation are also stimulated. The performance of the stored reserves has been improved in varying degrees. The reason is that the oxygen vacancies in the samples of the doped La3+ ions are more stable, so the ability to capture electrons is greatly improved. These increased traps can greatly improve the light excitation performance of the material.2) in the Li2SrSi04:Eu2+ material. Over the addition of four different rare earth ions (La3+/Nd3+/Dy3+ /Tm3+), it is found that different rare earth ions have different effects on the microstructure of the matrix materials. By comparison, it is found that La3+ ions can effectively enhance the thermoluminescence intensity of the materials at different temperature ranges, so it has a great contribution to the photoluminescence properties of the samples. It is found that the Nd3+/Dy3+ ions contribute to the long afterglow luminescence properties of the sample materials, but have little effect on the luminescence properties, and can be ignored, in which the Dy3+ ions have the greatest influence on the long afterglow luminescence properties of the samples, and the Tm3+ ions can effectively improve the thermal Shi Guangfeng in the deep trap region, but when we are excited by near infrared light, The electrons in the trap can not be released, so the Tm3+ ions have little contribution to the light excited luminescence. The system has studied the changes in the luminescence properties of the Li2Sr0.997SiO4: 0.003Eu2+ light stimulated by different concentrations of La3+ ions. By comparing the photoluminescence of the samples and the light excitation luminescence spectra, the luminescence of the samples comes from the same one. The luminescence center, that is, the transition of the Eu2+ ion 4f65d1 to 4F7. We have found that the luminescent properties of the samples increase gradually with the increase of the concentration of La3+ ions. When the doping concentration of La3+ is 0.008, the initial light excitation intensity and the optical storage performance of the matrix material have reached the best performance. At the same time, the Dy3+ ion pair is studied. The effect of fluorescent luminescence of Li2Sr0.997SiO4:0.003Eu2+ on the properties of long afterglow luminescence. It is found through experiments that the introduction of Dy3+ ions reduces the fluorescence intensity of the material to some extent. This is because the introduction of Dyr3+ makes the oxygen vacancies in the material more stable and the ability to capture the carrier. Therefore, the ability of the carrier to capture the carrier is enhanced. In the photoluminescence process, these traps will capture part of the carrier to reduce the luminescence intensity of the matrix material. We also find that the long afterglow properties of the material are enhanced with the introduction of Dy3+ ions.
【學(xué)位授予單位】：昆明理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB34;TQ422
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