【摘要】：白光發(fā)光二極管(White-light-emitting-diode,WLED)因其效率高、壽命長(zhǎng)、環(huán)境友好等優(yōu)勢(shì),有望成為第四代照明光源而被廣泛應(yīng)用。目前商用WLED用熒光粉絕大多數(shù)采用摻雜了稀土離子的無(wú)機(jī)材料。但稀土元素十分稀缺,且價(jià)格昂貴,因此無(wú)稀土 WLED用熒光粉的研究和開(kāi)發(fā)亟需進(jìn)行。本文提出了利用有機(jī)熒光染料組裝的主客體系金屬-有機(jī)框架材料(Metal-organic-frameworks,MOFs)作為WLED用熒光粉的設(shè)計(jì)思路,通過(guò)改變組裝染料的種類和含量來(lái)調(diào)控復(fù)合材料的熒光光譜和發(fā)光顏色,以研制適合搭配紫外芯片和藍(lán)光芯片的WLED用高性能熒光粉材料。為了研究染料在MOFs孔道內(nèi)的發(fā)光性能和組裝規(guī)律,合成了兩個(gè)系列具有不同尺寸的半菁染料,烷基化的(反式)-4-(4-二甲氨基苯乙烯)-吡啶鹽(DM-n)和烷基化的(反式)-4-(4-(二苯氨基)苯乙烯基)-吡啶鹽(DP-n)。將染料組裝入三個(gè)具有一維孔道但孔道尺寸不同的MOFs材料(Me2NH2)2[Zn8(Ad)4(BPDC)6O]·guests(bio-MOF-1,HAd=腺嘌呤,H2BPDC=4,4'-聯(lián)苯二甲酸)、(Me2NH2)2[Zn8(Ad)4(MBPDC)6O]·guests(bio-MOF-Me,H2MBPDC=2-甲基-[1,1-聯(lián)苯]-4,4-二羧酸)和(Me2NH2)2[Zn8(Ad)4(DMBPDC)60]· guests(bio-MOF-2Me,H2DMBPDC=2,2'-二甲基-4,4'-聯(lián)苯二甲酸)中。研究表明MOFs的一維孔道可以有效的分散染料,使其保持良好的發(fā)光性能。染料與孔道尺寸匹配程度能影響染料在孔道內(nèi)的組裝速度和分子取向規(guī)律。同時(shí)對(duì)染料組裝的復(fù)合材料進(jìn)行了二次諧波信號(hào)測(cè)定,最大為α石英的0.4倍。利用染料在MOFs孔道內(nèi)發(fā)光增強(qiáng)的特性,制備了紫外激發(fā)的主客體系MOFs白光發(fā)射材料。在N,N-二甲基甲酰胺(DMF)溶液中,陽(yáng)離子染料(反式)-4-(4-二甲氨基苯乙烯)-1-甲基吡啶(DSM)可通過(guò)離子交換作用組裝入陰離子 MOF 材料(Me2NH2)3[In3(BTB)4]·guests(ZJU-28,H3BTB=1,3,5-三(4-苯羧基)苯)孔道中得到ZJU-28(?)DSM主客體系材料,并且DSM在ZJU-28內(nèi)濃度富集達(dá)九十余倍。同時(shí),由于ZJU-28孔道的分隔和限域作用,DSM在ZJU-28內(nèi)的量子效率提升近十倍,使得DSM的發(fā)光顯著增強(qiáng)。通過(guò)365nm紫外光激發(fā)ZJU-28(?)DSM復(fù)合材料,可同時(shí)發(fā)出ZJU-28的藍(lán)色熒光和DSM的紅色熒光,其熒光光譜和發(fā)光顏色可通過(guò)改變?nèi)玖涎b載量進(jìn)行可控調(diào)節(jié)。根據(jù)三基色原理,在ZJU-28(?)DSM復(fù)合材料中引入綠光發(fā)射的陽(yáng)離子染料吖啶黃(AF),通過(guò)調(diào)整染料裝載量對(duì)復(fù)合材料熒光光譜進(jìn)行調(diào)控,可制得熒光色坐標(biāo)為(0.34,0.32)的ZJU-28(?)DSM/AF白光發(fā)射材料,量子效率可達(dá)17.4%,顯色指數(shù)為91,相關(guān)色溫為5327 K。這種染料組裝的主客體系MOFs材料為WLED用熒光粉材料的設(shè)計(jì)制備提供了新的思路。藍(lán)光LED芯片涂覆黃色熒光粉是目前制備WLED的主要方式。通過(guò)在ZJU-28中組裝入高效率有機(jī)染料的方法,制備了可搭配藍(lán)光LED芯片的WLED用熒光粉。在ZJU-28內(nèi)組裝入綠光染料香豆素6(Cou-6)和紅光染料4-(二氰基亞甲基)-2-甲基-6-(4-二甲基氨基苯乙烯基)-4H-吡喃(DCM),制備了 ZJU-28(?)Cou-6/DCM復(fù)合材料,其在460 nm藍(lán)光激發(fā)下,可以分別發(fā)出Cou-6的綠色熒光和DCM的紅色熒光,并且通過(guò)調(diào)節(jié)染料的裝載量可以對(duì)熒光光譜及發(fā)光顏色進(jìn)行調(diào)控。ZJU-28(?)Cou-6/DCM(0.016 wt%Cou-6,0.0018 wt%DCM)熒光粉在藍(lán)光激發(fā)下發(fā)出黃色熒光,量子效率為74.34%。將該材料作為WLED用熒光粉與450-460 nm藍(lán)光LED芯片封裝制備成WLED并進(jìn)行測(cè)試,在20 mA驅(qū)動(dòng)電流下,光效為1071m/W,顯色指數(shù)為67,相關(guān)色溫為5075K。為了進(jìn)一步改善熒光粉性能,采用另一種紅光發(fā)射染料派洛寧.(Py)代替DCM染料,制備了具有黃色熒光的 ZJU-28(?)Cou-6/Py(0.016wt%Cou-6,0.036wt%Py)熒光粉,量子效率提升至77.49%。以ZJU-28(?)Cou-6/Py熒光粉制備的WLED,在20 mA驅(qū)動(dòng)電流下,光效為149 lm/W,顯色指數(shù)為79,相關(guān)色溫為4326 K,較ZJ-U-28(?)Cou-6/DCM熒光粉性能有明顯提升。染料在MOFs內(nèi)能夠保持其優(yōu)異的發(fā)光性能,使得該復(fù)合材料制備的熒光粉十分高效,很有潛力應(yīng)用于白光LED領(lǐng)域。在室內(nèi)照明領(lǐng)域,對(duì)WLED的顯色指數(shù)要求較高,通常要求在80以上。綠光染料Cou-6和橙黃色熒光染料羅丹明6G(R6G)組裝的ZJU-28(?)Cou-6/R6G熒光粉的量子效率可達(dá)90%以上,制得的WLED光效高達(dá)179 lm/W,但顯色指數(shù)僅為50,不適合作為室內(nèi)照明光源使用。為了得到高顯色性能的WLED用熒光粉,我們?cè)赯JU-28(?)Cou-6/R6G復(fù)合材料中引入紅光發(fā)射染料以提高熒光粉在紅色光譜區(qū)域的發(fā)光強(qiáng)度,制備了三元染料體系熒光粉。通過(guò)在ZJU-28(?)Cou-6/R6G 體系中引入 DCM染料制得 ZJU-28(?)Cou-6/R6G/DCM(0.016 wt%Cou-6,0.008wt%R6G,0.0017wt%DCM)材料,在460nm藍(lán)光激發(fā)下發(fā)出黃色熒光,量子效率為79.30%。利用該熒光粉封裝制備WLED,在20mA驅(qū)動(dòng)電流下,光效為126 lm/W,顯色指數(shù)為66,相關(guān)色溫3103 K。顯色性能較ZJU-28(?)Cou-6/R6G體系熒光粉有所提高。若采用更高效的紅光發(fā)射染料羅丹明101(R101),制備得到的 ZJU-28(?)Cou-6/R6G/R101(0.016wt%Cou-6,0.010wt%R6G,0.014 wt%R101)熒光粉在460nm藍(lán)光激發(fā)下的量子效率為82.91%。該熒光粉封裝的WLED,在20mA驅(qū)動(dòng)電流下,光效為1261m/W,顯色指數(shù)可達(dá)88,相關(guān)色溫為4446 K,色坐標(biāo)為(0.36,0.34)。利用該熒光粉制備的WLED擁有極高的顯色指數(shù),解決了商用的摻鈰釔鋁石榴石(YAG:Ce)熒光粉因缺少紅光發(fā)射,導(dǎo)致制得的WLED相關(guān)色溫偏高、顯色指數(shù)偏低的問(wèn)題,極有潛力作為搭配藍(lán)光LED芯片的熒光粉應(yīng)用于室內(nèi)照明領(lǐng)域。
[Abstract]:White-light-emitting-diode (WLED) is widely used because of its high efficiency, long life, friendly environment and so on. It is expected to be the fourth generation lighting source and is widely used. At present, most of commercial WLED fluorescent powders are doped with rare earth ions, but rare earth elements are very scarce and expensive, so there is no rare earth WL. The research and development of ED phosphor is urgently needed. In this paper, the main and guest system metal organic frame material (Metal-organic-frameworks, MOFs), which is assembled by organic fluorescent dyes, is proposed as the design idea of phosphor for WLED. By changing the variety and content of the dyestuffs, the fluorescence spectrum and luminescence color of the composite materials are controlled and controlled. In order to study the luminescence properties of WLED with UV chips and blue light chips, two series of semi cyanine dyes with different sizes, alkylated (trans) -4- (4- two methylamino styrene) pyridinium salt (DM-n) and alkylated (trans) -4- (two benzene) were synthesized to study the luminescence properties and assembly laws of dyes in the channel of the dye. Amino) - styrene - pyridinium salt (DP-n). The dye is assembled into three MOFs materials (Me2NH2) 2[Zn8 (Ad) 4 (BPDC) 6O] / guests (bio-MOF-1, HAd= adenine, H2BPDC=4,4'- biphenyl two formic acid) with one dimensional channel but different pore size, and (Me2NH2) 4 E2NH2) 2[Zn8 (Ad) 4 (DMBPDC) 60]. Guests (bio-MOF-2Me, H2DMBPDC=2,2'- two methyl -4,4'- biphenyl two formic acid). The study shows that the one-dimensional channel of MOFs can effectively disperse dyes and maintain good luminescence properties. The matching degree of dye and pore size can affect the assembly speed and molecular orientation of the dye in the channel. The dyestuff composite was measured by two times harmonic signal, the maximum was 0.4 times of the alpha quartz. Using the characteristic of the dye in the MOFs channel, the MOFs white light emitting material was prepared by UV excitation. In N, N- two methyl formamide (DMF) solution, the cationic -4- (4- two methylamino styrene) -1- methyl Pyridine (DSM) can be assembled into the anionic MOF material (Me2NH2) 3[In3 (BTB) 4]. Guests (ZJU-28, H3BTB=1,3,5- three (4- phenyl carboxyl) benzene) through ion exchange and obtained the ZJU-28 (?) DSM main guest system material. The quantum efficiency increases nearly ten times, making the luminescence of DSM significantly enhanced. The blue fluorescence of ZJU-28 and the red fluorescence of DSM can be emitted simultaneously with the ZJU-28 (?) DSM composite excited by 365nm ultraviolet light. The fluorescence spectrum and the color of the luminescence can be controlled by changing the load of the dye. According to the principle of three color, the ZJU-28 (?) DSM composite material The cationic dye acridine yellow (AF), a cationic dye, is introduced to regulate the fluorescence spectrum of the composite by adjusting the loading amount of the dye. The ZJU-28 (?) DSM/AF white light emitting materials with fluorescent color coordinates (0.34,0.32) can be obtained. The quantum efficiency is 17.4%, the color rendering index is 91, and the relative color temperature is 5327 K., the main and guest MOFs material of the dye assembly. A new way of thinking for the design and preparation of phosphor materials for WLED is provided. The main way to prepare WLED by using blue light LED chip with yellow fluorescent powder is to prepare WLED with high efficiency organic dyes in ZJU-28. The WLED phosphor can be prepared with the blue light LED chip. In ZJU-28, the green dye coumarin 6 (Cou-6) is installed in ZJU-28. The red dye 4- (two cyanyl methylene) -2- methyl -6- (4- two methyl amino styrene) -4H- Piran (DCM) is prepared for ZJU-28 (?) Cou-6/DCM composite. Under the excitation of 460 nm blue light, the green fluorescence and DCM red fluorescence of Cou-6 can be emitted respectively, and the fluorescence and luminescence colors can be obtained by adjusting the loading of the dye. .ZJU-28 (?) Cou-6/DCM (?) Cou-6/DCM (0.016 wt%Cou-6,0.0018 wt%DCM) phosphor emitted yellow fluorescence under blue light. The quantum efficiency was 74.34%., which was prepared as WLED with phosphor and 450-460 nm blue LED chip to prepare WLED and tested. Under 20 mA driven electric current, the light effect was 1071m/W, the color index was 67, and the relative color temperature was 50. 75K., in order to further improve the performance of the phosphor, uses another red light emitting dye Luoning. (Py) instead of DCM dye, the ZJU-28 (?) Cou-6/Py (0.016wt%Cou-6,0.036wt%Py) phosphor with yellow fluorescence is prepared, the quantum efficiency is raised to WLED with ZJU-28 (?) Cou-6/Py phosphor, and the light efficiency is 149 lm/ under the 20 mA drive current. W, the color rendering index is 79, the correlation color temperature is 4326 K, and the performance of ZJ-U-28 (?) Cou-6/DCM phosphor is obviously improved. The dye can keep its excellent luminescence performance in MOFs, making the phosphor prepared by the composite very efficient and has the potential to be applied to the white light LED field. In the field of indoor lighting, the color index of WLED is higher and the passage is higher. It is often required to be more than 80. The quantum efficiency of the ZJU-28 (?) Cou-6/R6G phosphor assembled by green dye Cou-6 and orange yellow fluorescent dye Luo Danming 6G (R6G) is more than 90%, and the obtained WLED light efficiency is up to 179 lm/W, but the color index is only 50. It is not suitable to be used as an indoor lighting source. In order to obtain the high color performance of WLED fluorescent powder, we are in The ZJU-28 (?) Cou-6/R6G composite was introduced with red light emitting dyes to improve the luminescence intensity of the phosphor in the red spectrum region. The three element dye system phosphor was prepared. The ZJU-28 (?) Cou-6/R6G/DCM (0.016 wt%Cou-6,0.008wt%R6G, 0.0017wt%DCM) material was produced by introducing DCM dye into the ZJU-28 (?) Cou-6/R6G system and excited in the 460nm blue light. Under the 20mA drive current, the light efficiency is 126 lm/W, the color rendering index is 66, the color temperature 3103 K. is higher than that of the ZJU-28 (?) Cou-6/R6G system fluorescent powder. If a more efficient red light emitting dye Luo Danming 101 (R101) is used, the obtained ZJU-28 is prepared. The quantum efficiency of Cou-6/R6G/R101 (0.016wt%Cou-6,0.010wt%R6G, 0.014 wt%R101) phosphor excited by 460nm blue light is 82.91%. encapsulated WLED. Under the 20mA drive current, the light efficiency is 1261m/W, the color index is up to 88, the color temperature is 4446 K, the color coordinates are (0.36,0.34). The WLED with this phosphor has a very high color display. As a result of the lack of red light emission, the commercial cerium doped yttrium aluminum garnet (YAG:Ce) fluorescent powder has a problem of high WLED color temperature and low color index, and has the potential to be used as a fluorescent powder with blue light LED chips to be used in the field of indoor lighting.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ422

【參考文獻(xiàn)】

相關(guān)博士學(xué)位論文 前5條

1 喬君;鈧硅酸鹽白光LED熒光粉的研究[D];中國(guó)科學(xué)院研究生院(長(zhǎng)春光學(xué)精密機(jī)械與物理研究所);2014年

2 郁建燦;離子型金屬—有機(jī)框架材料及其主—客體系的設(shè)計(jì)、合成與非線性光學(xué)性能[D];浙江大學(xué);2013年

3 于泓;白光LED用硅酸鹽熒光粉的合成與性能研究[D];吉林大學(xué);2013年

4 陳觀通;M_3Si_6O_(12)N_2：RE（M=Sr，，Ba）綠色熒光粉的制備及熒光性能研究[D];北京有色金屬研究總院;2013年

5 嚴(yán)小松;白光LED用熒光材料的制備與性能研究[D];上海交通大學(xué);2011年

相關(guān)碩士學(xué)位論文 前2條

1 羅海濱;白光LED用Ba_2Si_3O_8：Eu~（2+）綠色熒光粉制備及其表征[D];浙江大學(xué);2010年

2 陳濤;白光LED用紅色熒光粉的研究[D];華中科技大學(xué);2008年

本文編號(hào)：2137786