本文選題：白光LED + 熒光材料　； 參考：《蘭州大學》2017年博士論文

【摘要】：白光LED被稱為第四代照明光源,因其具有節(jié)能、環(huán)保、壽命長、低功耗,亮度高等優(yōu)點。熒光材料是熒光轉換型白光LED的重要組成部分,通過與藍光或近紫外LED芯片組合產(chǎn)生白光,白光LED的顯色性、色溫和發(fā)光效率等發(fā)光表現(xiàn)由熒光材料性能的優(yōu)劣直接決定。氮化物熒光材料因其優(yōu)秀發(fā)光性能而受到研究者的廣泛關注。本論文針對目前存在的大部分熒光材料的性能有待進一步提高、氮化物紅色熒光材料種類太少和相關機理研究不夠完善等問題,從以下四個方面開展研究工作:1.(1)通過氣壓燒結法,金屬氮化物為原料,成功合成了純氮Ca-α-sialon:Eu~(2+)(Ca_(1.4-x)Al_(2.8)Si_(9.2)N_(16):xEu~(2+)-CASN:xEu~(2+),x=0-0.3)熒光材料并研究其發(fā)光性能。相比于含氧的Ca-α-sialon:Eu~(2+)和商用黃粉YAG:Ce~(3+)(P46-Y3),CASN:x Eu~(2+)具有更長波長的發(fā)射和更好地熱穩(wěn)定性。結果表明,CASN:xEu~(2+)是一種有極具潛力的白光LED氮化物黃色熒光材料。(2)研究了Ce~(3+)摻雜的CASN的光致發(fā)光和陰極射線發(fā)光性能。通過改變激活劑離子濃度和基質(zhì)組成的手段實現(xiàn)調(diào)控熒光材料的發(fā)光性能。在395nm激發(fā)下,樣品的CASN:xCe~(3+)發(fā)射峰中心波長位于525nm,半高寬為135 nm。在150℃時,樣品的發(fā)射強度只降低了13%。在陰極射線激發(fā)下,樣品CASN:xCe~(3+)具有良好的耐電流飽和性和優(yōu)異的抗退化性能及色彩穩(wěn)定性。(3)通過陽離子取代(Al~(3+)→Si4+)的方式調(diào)控CASN:Eu~(2+)的結構和發(fā)光性能,探索了樣品發(fā)射強度增強、發(fā)射紅移和熱穩(wěn)定性提高的機理,結果表明,隨著Al~(3+)對Si4+的取代,樣品結晶度也逐漸提高,從而導致CASN:x Al的發(fā)射強度逐漸增強。發(fā)射光譜的紅移和熱穩(wěn)定性能的提高是因Eu-N共價性增強的增強導致的。2.(1)通過氣壓燒結法,合成了Eu~(2+)摻雜和Eu~(2+),Ce~(3+)共摻的鋰氮化物LiSi_2N_3熒光材料。LiSi_2N_3:Eu~(2+)的最強激發(fā)在~355nm,最強發(fā)射位于~592 nm。基質(zhì)中含氧量的不同使本文合成的LiSi_2N_3:Eu~(2+)的激發(fā)和發(fā)射比之前文獻報道的位于更長波長范圍。再者,研究了Ce~(3+)與Eu2之間能量傳遞機制和光譜紅移的機理。(2)探究AlN的固溶對LiSi_2N_3:Eu~(2+)晶體結構、形貌、熱穩(wěn)定性和發(fā)光性能的影響。AlN的固溶能夠提高樣品的發(fā)射強度。而AlN的固溶沒有改變發(fā)光中心的配位環(huán)境,樣品的發(fā)射光譜的形狀和峰位沒有發(fā)生變化。結果表明,通過固溶體的形式是一種有效的提高熒光材料發(fā)射強度的手段。3.采用傳統(tǒng)固相反應成功合成了鋰氮化物Ca_3Li_(4-x)Si_2N_(6-y)O_y:Eu~(2+)/Ce~(3+)(CLSN:Eu~(2+)/Ce~(3+))(0≤y≤1.5)熒光材料,,并研究了其發(fā)光性能和能帶結構。基質(zhì)CLSN具有缺陷紅光發(fā)光特性。Eu~(2+)和Ce~(3+)激活的CLSN同樣表現(xiàn)出深紅光發(fā)射。同時,研究了CLSN:Eu~(2+)/Ce~(3+)的熱穩(wěn)定性。結果表明,鋰氮化物(M-Li-Si/Al-N,M=Ca,Sr,Ba)熒光材料對熒光轉換型LED用熒光材料的發(fā)展有一定的意義。4.采用傳統(tǒng)固相反應成功合成系列鋰氮化物LiCaAlN_2:Eu~(3+)/Tb~(3+)(LCAN:Eu~(3+)/Tb~(3+))熒光材料。系統(tǒng)研究了LiCaAlN_2:Eu~(3+)/Tb~(3+)的光致發(fā)光性能和LCAN:Tb~(3+)的陰極射線發(fā)光性能。Eu~(3+)/Tb~(3+)摻雜的LCAN表現(xiàn)出位于615nm/550nm的紅光/綠光發(fā)射。在615nm/550nm監(jiān)控下,有趣的發(fā)現(xiàn)LiCaAlN_2:Eu~(3+)/Tb~(3+)有一個位于350-450 nm/275-375 nm寬的電荷遷移帶。在電子束激發(fā)下,樣品LCAN:Tb~(3+)表現(xiàn)出良好的耐電流飽和性。將紅色LiCaAlN_2:Eu~(3+)與藍色、綠色熒光材料封裝得到白光LED器件。結果表明,三價稀土離子激活的鋰氮化物對高效窄帶發(fā)射熒光材料的開發(fā)有很大意義。
[Abstract]:White light LED is known as the fourth generation lighting source. Because of its advantages of energy saving, environmental protection, long life, low power consumption and high brightness, fluorescent material is an important part of the fluorescent conversion white light LED. White light is produced by combination with blue or near ultraviolet LED chips. The color display, color temperature and luminous efficiency of white LED are characterized by fluorescent material The advantages and disadvantages of the energy are directly determined. The nitride fluorescent materials have been widely concerned because of their excellent luminescence properties. In this paper, the performance of most of the existing fluorescent materials needs to be further improved, the species of nitride red fluorescent materials are too few and the related mechanism is not perfect, and the following four aspects are carried out. 1. (1) the pure nitrogen Ca- alpha -sialon:Eu~ (2+) (Ca_ (1.4-x) Al_ (2.8) Si_ (9.2) N_ (16): xEu~ (2+) -CASN:xEu~ (2+) -CASN:xEu~ (2+)) was synthesized by the pressure sintering method, and the luminescence properties of the pure nitrogen (1.4-x) Al_ (2.8) Si_ (9.2) N_ (2+) were studied. The longer wavelength emission and better geothermal stability. The results show that CASN:xEu~ (2+) is a potential white light LED nitride yellow fluorescent material. (2) the photoluminescence and cathodoluminescence of Ce~ (3+) doped CASN are studied. The regulation of fluorescent materials by means of changing the concentration of activator ion concentration and matrix composition is realized. Under 395nm excitation, the center wavelength of the sample CASN:xCe~ (3+) emission peak is located at 525nm, and the emission strength of the sample is only reduced by the cathode ray excitation at 135 nm. at 150 centigrade. The sample CASN:xCe~ (3+) has good current saturation and excellent resistance to degradation and color stability. (3) through cation substitution The structure and luminescence properties of CASN:Eu~ (2+) are regulated by (Al~ (3+) (Si4+)). The mechanism of the enhancement of the emission intensity, the emission of red shift and the increase of thermal stability is explored. The results show that the crystallinity of the sample increases gradually with the substitution of Al~ (3+) to Si4+, which leads to the increase of the emission intensity of CASN:x Al. The enhancement of the fixed properties is due to the enhancement of Eu-N covalent enhancement..2. (1) has synthesized the strongest excitation of the Eu~ (2+) doping and Eu~ (2+), Ce~ (3+) Co doped LiSi_2N_3 fluorescent material.LiSi_2N_3:Eu~ (2+) in the ~355nm, the difference in the oxygen content in the strongest emitter matrix. The excitation and emission of 2+) is in a longer wavelength range than that previously reported in the literature. Furthermore, the mechanism of energy transfer between Ce~ (3+) and Eu2 and the mechanism of spectral redshift are studied. (2) to explore the effect of solid solution of AlN on the crystal structure, morphology, thermal stability and luminescence energy of LiSi_2N_3:Eu~ (2+), the solid solution of.AlN can improve the emission strength of the sample. The solid solution does not change the coordination environment of the luminescent center, and the shape and peak of the emission spectra of the samples have not changed. The results show that the solid solution is an effective means to improve the emission strength of the fluorescent materials,.3. (4-x) Si_2N_ (6-y) O_y:Eu~ (2+) /Ce~ (3+) (C) has been successfully synthesized by the traditional solid phase reaction. LSN:Eu~ (2+) /Ce~ (3+)) (0 < < < y < 1.5) fluorescent material, and its luminescence property and band structure are studied. Matrix CLSN with defective red light luminescence properties.Eu~ (2+) and Ce~ (3+) activation also shows deep red light emission. The optical materials have certain significance for the development of fluorescent materials for fluorescent converted LED..4. (LCAN:Eu~ (3+) /Tb~ (3+)) fluorescent material has been successfully synthesized by the traditional solid phase reaction. The photoluminescence properties of LiCaAlN_2:Eu~ (3+) LiCaAlN_2:Eu~ (LCAN:Eu~ (3+) /Tb~ (3+)) are systematically studied. /Tb~ (3+) doped LCAN shows red / green light emission at 615nm/550nm. Under the monitoring of 615nm/550nm, it is interesting to find that LiCaAlN_2:Eu~ (3+) /Tb~ (3+) has a 350-450 nm/275-375 nm wide charge transfer zone. The white light LED devices are encapsulated in blue and green fluorescent materials. The results show that lithium nitride activated by trivalent rare earth ions is of great significance for the development of efficient narrow band emission fluorescent materials.

【學位授予單位】：蘭州大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O482.31

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