基于主客体系金属—有机框架材料的光谱调控及其白光发射性能研究
发布时间：2018-07-22 14:38
【摘要】：白光发光二极管(White-light-emitting-diode,WLED)因其效率高、寿命长、环境友好等优势,有望成为第四代照明光源而被广泛应用。目前商用WLED用荧光粉绝大多数采用掺杂了稀土离子的无机材料。但稀土元素十分稀缺,且价格昂贵,因此无稀土 WLED用荧光粉的研究和开发亟需进行。本文提出了利用有机荧光染料组装的主客体系金属-有机框架材料(Metal-organic-frameworks,MOFs)作为WLED用荧光粉的设计思路,通过改变组装染料的种类和含量来调控复合材料的荧光光谱和发光颜色,以研制适合搭配紫外芯片和蓝光芯片的WLED用高性能荧光粉材料。为了研究染料在MOFs孔道内的发光性能和组装规律,合成了两个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)-吡啶盐(DM-n)和烷基化的(反式)-4-(4-(二苯氨基)苯乙烯基)-吡啶盐(DP-n)。将染料组装入三个具有一维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'-联苯二甲酸)、(Me2NH2)2[Zn8(Ad)4(MBPDC)6O]·guests(bio-MOF-Me,H2MBPDC=2-甲基-[1,1-联苯]-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'-联苯二甲酸)中。研究表明MOFs的一维孔道可以有效的分散染料,使其保持良好的发光性能。染料与孔道尺寸匹配程度能影响染料在孔道内的组装速度和分子取向规律。同时对染料组装的复合材料进行了二次谐波信号测定,最大为α石英的0.4倍。利用染料在MOFs孔道内发光增强的特性,制备了紫外激发的主客体系MOFs白光发射材料。在N,N-二甲基甲酰胺(DMF)溶液中,阳离子染料(反式)-4-(4-二甲氨基苯乙烯)-1-甲基吡啶(DSM)可通过离子交换作用组装入阴离子 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主客体系材料,并且DSM在ZJU-28内浓度富集达九十余倍。同时,由于ZJU-28孔道的分隔和限域作用,DSM在ZJU-28内的量子效率提升近十倍,使得DSM的发光显著增强。通过365nm紫外光激发ZJU-28(?)DSM复合材料,可同时发出ZJU-28的蓝色荧光和DSM的红色荧光,其荧光光谱和发光颜色可通过改变染料装载量进行可控调节。根据三基色原理,在ZJU-28(?)DSM复合材料中引入绿光发射的阳离子染料吖啶黄(AF),通过调整染料装载量对复合材料荧光光谱进行调控,可制得荧光色坐标为(0.34,0.32)的ZJU-28(?)DSM/AF白光发射材料,量子效率可达17.4%,显色指数为91,相关色温为5327 K。这种染料组装的主客体系MOFs材料为WLED用荧光粉材料的设计制备提供了新的思路。蓝光LED芯片涂覆黄色荧光粉是目前制备WLED的主要方式。通过在ZJU-28中组装入高效率有机染料的方法,制备了可搭配蓝光LED芯片的WLED用荧光粉。在ZJU-28内组装入绿光染料香豆素6(Cou-6)和红光染料4-(二氰基亚甲基)-2-甲基-6-(4-二甲基氨基苯乙烯基)-4H-吡喃(DCM),制备了 ZJU-28(?)Cou-6/DCM复合材料,其在460 nm蓝光激发下,可以分别发出Cou-6的绿色荧光和DCM的红色荧光,并且通过调节染料的装载量可以对荧光光谱及发光颜色进行调控。ZJU-28(?)Cou-6/DCM(0.016 wt%Cou-6,0.0018 wt%DCM)荧光粉在蓝光激发下发出黄色荧光,量子效率为74.34%。将该材料作为WLED用荧光粉与450-460 nm蓝光LED芯片封装制备成WLED并进行测试,在20 mA驱动电流下,光效为1071m/W,显色指数为67,相关色温为5075K。为了进一步改善荧光粉性能,采用另一种红光发射染料派洛宁.(Py)代替DCM染料,制备了具有黄色荧光的 ZJU-28(?)Cou-6/Py(0.016wt%Cou-6,0.036wt%Py)荧光粉,量子效率提升至77.49%。以ZJU-28(?)Cou-6/Py荧光粉制备的WLED,在20 mA驱动电流下,光效为149 lm/W,显色指数为79,相关色温为4326 K,较ZJ-U-28(?)Cou-6/DCM荧光粉性能有明显提升。染料在MOFs内能够保持其优异的发光性能,使得该复合材料制备的荧光粉十分高效,很有潜力应用于白光LED领域。在室内照明领域,对WLED的显色指数要求较高,通常要求在80以上。绿光染料Cou-6和橙黄色荧光染料罗丹明6G(R6G)组装的ZJU-28(?)Cou-6/R6G荧光粉的量子效率可达90%以上,制得的WLED光效高达179 lm/W,但显色指数仅为50,不适合作为室内照明光源使用。为了得到高显色性能的WLED用荧光粉,我们在ZJU-28(?)Cou-6/R6G复合材料中引入红光发射染料以提高荧光粉在红色光谱区域的发光强度,制备了三元染料体系荧光粉。通过在ZJU-28(?)Cou-6/R6G 体系中引入 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蓝光激发下发出黄色荧光,量子效率为79.30%。利用该荧光粉封装制备WLED,在20mA驱动电流下,光效为126 lm/W,显色指数为66,相关色温3103 K。显色性能较ZJU-28(?)Cou-6/R6G体系荧光粉有所提高。若采用更高效的红光发射染料罗丹明101(R101),制备得到的 ZJU-28(?)Cou-6/R6G/R101(0.016wt%Cou-6,0.010wt%R6G,0.014 wt%R101)荧光粉在460nm蓝光激发下的量子效率为82.91%。该荧光粉封装的WLED,在20mA驱动电流下,光效为1261m/W,显色指数可达88,相关色温为4446 K,色坐标为(0.36,0.34)。利用该荧光粉制备的WLED拥有极高的显色指数,解决了商用的掺铈钇铝石榴石(YAG:Ce)荧光粉因缺少红光发射,导致制得的WLED相关色温偏高、显色指数偏低的问题,极有潜力作为搭配蓝光LED芯片的荧光粉应用于室内照明领域。
[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.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ422
本文编号：2137786
[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.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ422
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