CN102936497B - Main emission peak changeable and adjustable fluorescent material and preparation method thereof - Google Patents
Main emission peak changeable and adjustable fluorescent material and preparation method thereof Download PDFInfo
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Abstract
一种发射主峰变化可调的荧光材料及其制备方法。涉及一种LED照明/显示的荧光材料及其制备方法,是一种碱土氟氧硅铝酸盐荧光材料,化学通式表示为:Mx-zY6-x-y-zAl11-xLxO25.5-0.5kFk:yCe3+,zMn2+,其中Ce3+和Mn2+为发光中心离子,通式中:0≤x≤1.5,0.01≤y≤0.16,0≤z≤0.2,0<k≤0.01;M为Mg2+或Ba2+,L为Si4+或Zr4+;按照化学通式,将MgO、MgF2、Al2O3、AlF3、SiO2、ZrO2、BaF2、BaCO3、MnCO3和CeO2,在密闭容器中混料,将混合物在H2气氛下,1620℃还原炉中保温,冷却、破碎分级,过筛,得到碱土氟氧硅铝酸盐荧光材料。本发明提供一种白光LED照明/显示用绿色、黄色、橙色发射主峰变化可调,在蓝光LED激发下具有较高的发光效率、波长530~585nm的荧光材料及其制备方法。
A fluorescent material with adjustable emission main peak and a preparation method thereof. The invention relates to a fluorescent material for LED lighting/display and a preparation method thereof, which is an alkaline earth oxyfluorosilicate fluorescent material, and the general chemical formula is: M xz Y 6-xyz Al 11-x L x O 25.5-0.5 k F k : yCe 3+ , zMn 2+ , where Ce 3+ and Mn 2+ are luminescent center ions, in the general formula: 0≤x≤1.5, 0.01≤y≤0.16, 0≤z≤0.2, 0<k ≤0.01; M is Mg 2+ or Ba 2+ , L is Si 4+ or Zr 4+ ; according to the general chemical formula, MgO, MgF 2 , Al 2 O 3 , AlF 3 , SiO 2 , ZrO 2 , BaF 2 , BaCO 3 , MnCO 3 and CeO 2 , mixed in a closed container, kept the mixture in a reduction furnace at 1620°C under H 2 atmosphere, cooled, crushed and classified, and sieved to obtain alkaline earth fluorooxyaluminosilicate fluorescent materials . The invention provides a fluorescent material with a wavelength of 530-585nm, a fluorescent material with a wavelength of 530-585nm, which can be adjusted for white light LED lighting/display, and whose main emission peaks are adjustable in green, yellow, and orange.
Description
技术领域 technical field
本发明涉及一种荧光材料及其制备方法,特别涉及一种LED照明/显示等应用领域的荧光材料及其制备方法。The invention relates to a fluorescent material and a preparation method thereof, in particular to a fluorescent material and a preparation method thereof in application fields such as LED lighting/display.
背景技术 Background technique
白光LED是一种高效、节能、环保的新型固态绿色照明技术,被誉为21世纪第四代照明光源。白光LED的实现方案主要有:1)采用红、绿、蓝三基色芯片制备高显色性白光LED;2)采用InGaN蓝光LED激发钇铝石榴石结构Y3Al5O12:Ce(YAG:Ce3+)黄色荧光粉;3)采用UV-LED激发红、绿、蓝荧光粉制备高显色性白光LED。从目前白光LED照明发展技术趋势来看,白光LED实现方式主要以荧光转化为主,即通过蓝光LED(450~470nm)激发黄色荧光粉YAG:Ce,(Ba,Sr)SiO4:Eu2+,即蓝光LED+黄色荧光粉;或紫外LED(380~400nm))激发蓝色、绿色和红色荧光粉,即紫光LED+RGB荧光粉组合获得白光LED。因此,荧光材料性能优劣对白光LED的光效、光衰及显色性等起到了至关重要的作用。White LED is a new solid-state green lighting technology with high efficiency, energy saving and environmental protection, and is known as the fourth generation lighting source in the 21st century. The realization scheme of white light LED mainly includes: 1) using red , green and blue three primary color chips to prepare high color rendering white light LED ; Ce 3+ ) yellow phosphor; 3) using UV-LED to excite red, green and blue phosphors to prepare white LED with high color rendering. Judging from the current development trend of white light LED lighting technology, the realization of white light LED is mainly based on fluorescence conversion, that is, through blue LED (450~470nm) to excite yellow phosphor YAG:Ce, (Ba,Sr)SiO 4 :Eu 2+ , that is, blue LED + yellow phosphor; or ultraviolet LED (380 ~ 400nm)) to excite blue, green and red phosphor, that is, the combination of purple LED + RGB phosphor to obtain a white LED. Therefore, the performance of fluorescent materials plays a vital role in the light efficiency, light decay and color rendering of white LEDs.
CN201110309206.9公开了一种高温固相法制备钇铝石榴石结构YAG:Ce稀土荧光粉的方法,按照Y3Al5O12:Ce荧光粉化学式摩尔比称取Y2O3或Gd2O3或它们的混合物、Al2O3或Ga2O3或它们的混合物、CeO2及助熔剂,在高温炉还原性气氛中焙烧2~6小时,得到YAG:Ce稀土荧光粉。CN201110309206.9 discloses a method for preparing yttrium aluminum garnet structure YAG:Ce rare earth phosphor by a high-temperature solid phase method, and weighs Y 2 O 3 or Gd 2 O according to the molar ratio of Y 3 Al 5 O 12 :Ce phosphor chemical formula 3 or their mixtures, Al 2 O 3 or Ga 2 O 3 or their mixtures, CeO 2 and flux, and bake in a reducing atmosphere of a high-temperature furnace for 2 to 6 hours to obtain YAG:Ce rare earth phosphors.
CN201110132661.6公开了一种LED荧光粉,该荧光粉是以铈、铬离子或者Ce+Cr共掺为激活中心的石榴石相材料,其元素至少一种从Y和稀土中选取,至少有一种从Al、Ga、In、Sc、V中选取,在基质中引入元素钒有利于荧光效率的改善,钒的引入有助于改善基质掺杂的晶格完整性,同时,钒掺杂能对基质中的发光中心起到荧光敏化作用,而铬的引入更能带来600nm以上丰富的红色荧光成分,改善荧光粉的显示性。CN201110132661.6 discloses a LED phosphor, which is a garnet phase material with cerium, chromium ions or Ce+Cr co-doped as the active center, at least one element selected from Y and rare earth, at least one Selected from Al, Ga, In, Sc, V, the introduction of element vanadium in the matrix is conducive to the improvement of fluorescence efficiency, the introduction of vanadium helps to improve the lattice integrity of matrix doping, and at the same time, vanadium doping can affect the matrix The luminescent center in the luminescence plays a role of fluorescence sensitization, and the introduction of chromium can bring more abundant red fluorescent components above 600nm, and improve the display of the phosphor.
CN201110186964.6公开了一种硅酸盐黄橙色荧光粉,用通式Sr2-x-y-zLuyBazSiO4:xEu2+表示的材料组成,式中x为铕原子的摩尔数,y为镥原子的摩尔数,z为钡原子的摩尔数,0.005≤x≤0.15,0.01≤y≤0.15,0≤z≤1.5。在460nm蓝光激发下,其发射光谱为位于470~700nm的带状谱线,随着钡掺入量的增加,中心波长在515~570nm之间移动。CN201110186964.6 discloses a silicate yellow-orange fluorescent powder, which is composed of materials represented by the general formula Sr 2-xyz Lu y B z SiO 4 :xEu 2+ , where x is the number of moles of europium atoms, and y is lutetium The number of moles of atoms, z is the number of moles of barium atoms, 0.005≤x≤0.15, 0.01≤y≤0.15, 0≤z≤1.5. Under the excitation of 460nm blue light, its emission spectrum is a band line at 470-700nm, and the central wavelength moves between 515-570nm with the increase of barium doping amount.
上述CN201110309206.9,CN201110132661.6的LED用荧光粉属铝酸盐YAG:Ce体系;CN201110186964.6属硅酸盐(Sr,Ba)2SiO4:Eu2+荧光粉,CN201110132661.6的荧光粉添加了有毒元素铬作为发光离子。The above-mentioned CN201110309206.9 and CN201110132661.6 phosphor powders for LEDs belong to the aluminate YAG:Ce system; CN201110186964.6 belongs to silicate (Sr, Ba) 2 SiO 4 :Eu 2+ phosphor powders, and the phosphor powders of CN201110132661.6 Chromium, a toxic element, is added as a luminescent ion.
目前,人们使用的照明光源白炽灯和荧光灯的色温一般都低于6000K,因低色温光线具有穿透雾和水汽的能力强、光线柔和、路面反射率高等诸多优点,然而商用YAG:Ce荧光粉的发射光谱,发射主峰只能达到560nm,红光成分较少,导致白光LED器件的色温偏高(6000~8000K),显色指数偏低(<80)。因此,需要通过添加橙色、红色荧光粉来提高白光LED的显色性。尽管硅酸盐荧光粉(Sr,Ba)2SiO4:Eu2+具有发射主峰515~570nm变化可调特点,但是硅酸盐材料体系荧光粉存在较大的光衰,热稳定性低等缺点,特别是红光部分只能达到570nm左右,远远不能满足提高白光LED显色性的要求。At present, the color temperature of incandescent lamps and fluorescent lamps used by people is generally lower than 6000K, because low color temperature light has many advantages such as strong ability to penetrate fog and water vapor, soft light, and high reflectivity of the road surface. However, commercial YAG:Ce phosphors In the emission spectrum, the main emission peak can only reach 560nm, and the red light component is less, resulting in a high color temperature (6000-8000K) and a low color rendering index (<80) of the white LED device. Therefore, it is necessary to improve the color rendering of white LEDs by adding orange and red phosphors. Although the silicate phosphor (Sr, Ba) 2 SiO 4 :Eu 2+ has the characteristics of adjustable emission main peak 515-570nm, the silicate material system phosphor has the disadvantages of large light attenuation and low thermal stability. , especially the red light part can only reach about 570nm, which is far from meeting the requirements of improving the color rendering of white light LEDs.
发明内容 Contents of the invention
本发明的目的是克服现有技术的不足,提供一种白光LED照明/显示用绿色、黄色、橙色发射主峰变化可调,在蓝光LED激发下具有较高的发光效率、波长530~585nm的荧光材料及其制备方法。The purpose of the present invention is to overcome the deficiencies of the prior art, to provide a white light LED lighting/display with green, yellow and orange emission main peaks that can be adjusted, has higher luminous efficiency under the excitation of blue light LEDs, and has a fluorescent light with a wavelength of 530-585nm. Materials and their preparation methods.
本发明的应广泛为碱土氟氧硅铝酸盐荧光材料,其化学通式表示为:Mx-zY6-x-y-zAl11-xLxO25.5-0.5kFk:yCe3+,zMn2+,其中Ce3+和Mn2+为发光中心离子,通式中:0≤x≤1.5,0.01≤y≤0.16,0≤z≤0.2,0<k≤0.01;M为Mg2+或Ba2+,L为Si4+或Zr4+;按照化学通式,将分析纯的MgO、MgF2、NH4F、Al2O3、AlF3、SiO2、ZrO2、BaF2、BaCO3、MnCO3和CeO2,按化学组成比例配料混合,在密闭容器中混料40小时,然后将混合物在H2%<5%气氛下,1620℃还原炉中保温6小时,冷却、破碎分级,过500目筛网,得到粒度为3~20μm左右的碱土氟氧硅铝酸盐荧光材料。The present invention should be widely used as alkaline earth oxyfluorosilicate fluorescent material, and its general chemical formula is expressed as: M xz Y 6-xyz Al 11-x L x O 25.5-0.5k F k : yCe 3+ , zMn 2+ , where Ce 3+ and Mn 2+ are luminescent central ions, in the general formula: 0≤x≤1.5, 0.01≤y≤0.16, 0≤z≤0.2, 0<k≤0.01; M is Mg 2+ or Ba 2 + , L is Si 4+ or Zr 4+ ; according to the general chemical formula, analytically pure MgO, MgF 2 , NH 4 F, Al 2 O 3 , AlF 3 , SiO 2 , ZrO 2 , BaF 2 , BaCO 3 , MnCO 3 and CeO 2 were mixed according to the chemical composition ratio, and mixed in a closed container for 40 hours, and then the mixture was kept in a reduction furnace at 1620°C for 6 hours under the atmosphere of H 2 %<5%, cooled, crushed and classified, and passed 500-mesh sieve to obtain the alkaline earth oxyfluorosilicate fluorescent material with a particle size of about 3-20 μm.
碱土氟氧硅锆铝酸盐荧光材料晶体结构如图1所示,在该材料体系中存在一种Y3+格位,两种Al3+的格位。因为Al3+、Si4+、Zr4+离子半径分别为0.061,0.040和0.065nm,而Y3+、Mg2+、Ba2+、Mn2+和Ce3+离子半径分别为0.089,0.072,0.135,0.08和0.13nm。根据离子半径相似相近原理,Si4+,Zr4+优先取代碱土氟氧硅锆铝酸盐荧光材料晶体结构中的AlO4和AlO6格位,而Mg2+、Ba2+、Mn2+和Ce3+等离子则取代碱土氟氧硅锆铝酸盐荧光材料晶体结构中的YO8格位。The crystal structure of the alkaline earth oxysilicoaluminate zirconate fluorescent material is shown in Figure 1. There is one Y 3+ site and two Al 3+ sites in the material system. Because the ionic radii of Al 3+ , Si 4+ , and Zr 4+ are 0.061, 0.040, and 0.065 nm, respectively, while the ionic radii of Y 3+ , Mg 2+ , Ba 2+ , Mn 2+ , and Ce 3+ are 0.089, 0.072 nm, respectively. , 0.135, 0.08 and 0.13nm. According to the principle of similar ionic radii, Si 4+ and Zr 4+ preferentially replace the AlO 4 and AlO 6 sites in the crystal structure of the alkaline earth oxyfluorosilicoaluminate fluorescent material, while Mg 2+ , Ba 2+ , and Mn 2+ And Ce 3+ plasma replaces the YO 8 site in the crystal structure of the alkaline earth oxysilica zirconium aluminate fluorescent material.
Ce3+的晶体场能级劈裂与周围配位环境有着较大影响。Si4+电负性为1.9,而Al3+的电负性为1.6。当一个电负性较大的Si4+离子取代电负性较小的Al3+时,使得Ce3+周围配位场的共价性增强,导致Ce3+产生更大的能级劈裂,最低的5d轨道能级d1能级重心明显下降,从而使得Ce3+的发射出现红移。同样原理,当Zr4+取代Al3+时,因为Zr4+的电负性为1.33,使得Ce3+周围配位场的共价性降低,从而降低了Ce3+的晶体场能级劈裂,最低的5d轨道能级d1能级重心明显上升,从而使得Ce3+的发射出现蓝移。The crystal field level splitting of Ce 3+ has great influence on the surrounding coordination environment. Si 4+ has an electronegativity of 1.9, while Al 3+ has an electronegativity of 1.6. When a Si 4+ ion with a higher electronegativity replaces the Al 3+ with a lower electronegativity, the covalency of the coordination field around Ce 3+ is enhanced, resulting in greater energy level splitting of Ce 3+ , the center of gravity of the lowest 5d orbital energy level d 1 level drops obviously, which makes the emission of Ce 3+ appear red shifted. The same principle, when Zr 4+ replaces Al 3+ , because the electronegativity of Zr 4+ is 1.33, the covalency of the coordination field around Ce 3+ is reduced, thereby reducing the crystal field energy level split of Ce 3+ The center of gravity of the lowest 5d orbital energy level d 1 level rises obviously, which makes the emission of Ce 3+ appear blue-shifted.
因此,根据上述机理,调整基质组分中Zr4+,Si4+含量,可调整Ce3+格位所处的晶体场劈裂能级大小,从而使Ce3+离子发射从绿色(530nm)到黄色(570nm)变化可调。Therefore, according to the above mechanism, adjusting the content of Zr 4+ and Si 4+ in the matrix components can adjust the crystal field splitting level of the Ce 3+ site, so that the emission of Ce 3+ ions from green (530nm) Adjustable to yellow (570nm).
由于Zr4+,Si4+取代Al3+离子时,将产生不等价取代,容易形成缺陷,从而形成发光淬灭中心,这一点对提高稀土荧光材料发光效率是非常不利。因此,在本发明荧光材料体系中引入碱土离子如Mg2+、Ba2+,采用Mg2+、Ba2+不等价取代Y3+的格位,从而使得荧光材料晶体结构保持电荷平衡。When Zr 4+ and Si 4+ replace Al 3+ ions, unequal substitutions will occur, and defects are easily formed, thereby forming luminescent quenching centers, which is very unfavorable for improving the luminous efficiency of rare earth fluorescent materials. Therefore, alkaline earth ions such as Mg 2+ and Ba 2+ are introduced into the fluorescent material system of the present invention, and Mg 2+ and Ba 2+ are unequivalently substituted for the sites of Y 3+ , so that the crystal structure of the fluorescent material maintains charge balance.
然而,尽管通过掺入Si4+可使荧光粉中Ce3+离子发射从545nm红移到570nm左右,但是为了提高低色温白光LED的显色指数,需要把Ce3+发射进一步红移。因Ce3+的最低的5d轨道能级位于蓝光460nm,在蓝光激发下具有较高的发光效率,然而,Mn2+虽然在430nm一些吸收,但是发光比较弱。因此,在本发明中我们设计一种Ce3+和Mn2+共掺的荧光材料体系,利用Ce3+→Mn2+能量传递原理(ET),获得橙色荧光材料。首先通过Ce3+离子d1轨道能级吸收蓝光,然后把能量无辐射传递给Mn2+离子4T1(G)匹配能级,最后通过Mn2+的4T1(G)→6A1能级跃迁,实现橙色光宽带发射,发射主峰位于585nm。However, although the emission of Ce 3+ ions in the phosphor can be red-shifted from 545nm to about 570nm by doping Si 4+ , in order to improve the color rendering index of low color temperature white LEDs, it is necessary to further red-shift the emission of Ce 3+ . Because the lowest 5d orbital energy level of Ce 3+ is located at 460nm of blue light, it has higher luminous efficiency under blue light excitation. However, although Mn 2+ absorbs some at 430nm, the luminescence is relatively weak. Therefore, in the present invention, we design a Ce 3+ and Mn 2+ co-doped fluorescent material system, and use the Ce 3+ →Mn 2+ energy transfer principle (ET) to obtain an orange fluorescent material. First, the blue light is absorbed through the Ce 3+ ion d 1 orbital energy level, and then the energy is non-radiatively transferred to the Mn 2+ ion 4 T 1 (G) matching energy level, and finally through the 4 T 1 (G) of Mn 2+ → 6 A 1 energy level transition to achieve orange light broadband emission, the main emission peak is located at 585nm.
本发明的碱土氟氧硅锆铝酸盐荧光材料在蓝光激发下具有较高的发光效率,同时弥补了YAG:Ce荧光粉缺少红光部分等缺点。The alkaline earth oxyfluoride silicon zirconium aluminate fluorescent material of the present invention has higher luminous efficiency under blue light excitation, and at the same time makes up for the shortcomings of YAG:Ce fluorescent powder such as lack of red light parts.
图2,3分别给出了实施例1,2,3,4制备的荧光材料的XRD和发射光谱图,由图2,3可见,添加少量硅并不影响该材料晶体结构,随着荧光材料中的Si含量增加,发射光谱从545nm逐渐红移动到570nm。图4给出了实施例1制备的荧光材料扫描电镜SEM照片,该荧光材料为类球形颗粒,颗粒粒度为3~10μm之间。图5,6给出了封装得到白光LED发射光谱图及色品坐标图,该白光LED在350mA电流激发下,色温Tc=5823K,色坐标X=0.3241,Y=0.3676,光效为121.5流明/瓦,显色指数78.5。Fig. 2, 3 has respectively provided the XRD and the emission spectrogram of the fluorescent material prepared by embodiment 1, 2, 3, 4, as seen from Fig. 2, 3, adding a small amount of silicon does not affect this material crystal structure, along with the fluorescent material As the content of Si increases, the emission spectrum gradually shifts from 545nm to 570nm. Fig. 4 shows the scanning electron microscope (SEM) photo of the fluorescent material prepared in Example 1. The fluorescent material is a spherical particle with a particle size of 3-10 μm. Figures 5 and 6 show the emission spectrum and chromaticity coordinates of the packaged white LED. Under the excitation of 350mA current, the white LED has a color temperature Tc=5823K, color coordinates X=0.3241, Y=0.3676, and a luminous efficacy of 121.5 lumens/ Watts, color rendering index 78.5.
图7,8给出了实施例5,6,7制备的荧光材料激发、发射光谱图,随着Ce浓度增加时,激发、发射光谱逐渐红移。图9,10给出了封装得到白光LED发射光谱图及色品坐标图,该白光LED在350mA电流激发下,色温Tc=5430K,色坐标X=0.3352,Y=0.4072,光效为113.2流明/瓦,显色指数79.2。Figures 7 and 8 show the excitation and emission spectra of the fluorescent materials prepared in Examples 5, 6 and 7. As the Ce concentration increases, the excitation and emission spectra gradually red shift. Figures 9 and 10 show the emission spectrum and chromaticity coordinates of the packaged white LED. Under the excitation of 350mA current, the white LED has a color temperature Tc=5430K, color coordinates X=0.3352, Y=0.4072, and a luminous efficacy of 113.2 lumens/ watts, color rendering index 79.2.
图11,12,13,14给出了实施例8制备的荧光材料XRD晶体结构衍射,激发、发射光谱图和X射线荧光光谱(XPS)。通过掺杂Zr4+元素,晶体结构基本不变,但是从图14荧光材料X射线光电子能谱图(XPS)发现,该材料结构中除了Y,Al,O,Ce之外,包含了Zr4+和Mg2+等元素,说明本发明的荧光材料中,Zr4+和Mg2+离子进入了晶格中。从Ce3+激发光谱发现,360nm激发带明显降低,而Ce3+的最低5d轨道能级明显蓝移。同样在发射光谱发现,发射光谱逐渐蓝移动545nm左右,从而实现发射光谱蓝移获得更绿的荧光材料。图15,16给出了封装得到白光LED发射光谱图及色品坐标图,该白光LED在350mA电流激发下,色温Tc=5658K,色坐标X=0.3282,Y=0.3818,光效为106.9流明/瓦,显色指数79.2。Figures 11, 12, 13 and 14 show the XRD crystal structure diffraction, excitation and emission spectra and X-ray fluorescence spectrum (XPS) of the fluorescent material prepared in Example 8. By doping Zr 4+ elements, the crystal structure is basically unchanged, but from the X-ray photoelectron spectroscopy (XPS) of the fluorescent material in Figure 14, it is found that in addition to Y, Al, O, and Ce, the material structure contains Zr 4 + and Mg 2+ and other elements, indicating that in the fluorescent material of the present invention, Zr 4+ and Mg 2+ ions have entered the crystal lattice. From the Ce 3+ excitation spectrum, it is found that the 360nm excitation band is obviously reduced, and the lowest 5d orbital energy level of Ce 3+ is obviously blue-shifted. It is also found in the emission spectrum that the emission spectrum gradually shifts blue by about 545nm, thereby achieving a blue shift of the emission spectrum to obtain a greener fluorescent material. Figures 15 and 16 show the emission spectrum and chromaticity coordinates of the packaged white LED. Under the excitation of 350mA current, the white LED has a color temperature Tc=5658K, color coordinates X=0.3282, Y=0.3818, and a luminous efficacy of 106.9 lumens/ watts, color rendering index 79.2.
图17,18,19,20给出了实施例11制备的荧光材料XRD晶体结构衍射,激发、发射光谱图和X射线荧光光谱(XPS)。通过掺杂Si4+和Mn2+元素,晶体结构基本不变,但是从图20荧光材料X射线光电子能谱图(XPS)发现,该材料结构中除了Y,Al,O,Ce之外,包含了Si4+、Mn2+等元素,说明本发明的荧光材料中,Si4+和Mg2+离子进入了晶格中。从Ce3+激发光谱发现,共出现三处激发带,分别为297,334和462nm激发带明显降低,其中297nm来自Mn2+的激发带,如图18所示。图19给出了Ce3+和Mn2+离子共掺荧光材料的发射光谱图,通过高斯拟合分峰发现,该发射带主要530和585和733nm三个发射带构成,其中530nm发射带来自Ce3+的5d→2F5/2能级跃迁,585nm和733nm则来自Mn2+的4T1→1A6的能级跃迁。图21,图22给出了封装得到白光LED发射光谱图及色品坐标图,该白光LED在350mA电流激发下,色温Tc=3947K,色坐标X=0.4109,Y=0.4778,光效为98.5流明/瓦,显色指数86.6。Figures 17, 18, 19 and 20 show the XRD crystal structure diffraction, excitation and emission spectra and X-ray fluorescence spectrum (XPS) of the fluorescent material prepared in Example 11. By doping Si 4+ and Mn 2+ elements, the crystal structure is basically unchanged, but from the X-ray photoelectron spectrum (XPS) of the fluorescent material in Figure 20, it is found that in addition to Y, Al, O, and Ce in the material structure, Elements such as Si 4+ and Mn 2+ are contained, indicating that in the fluorescent material of the present invention, Si 4+ and Mg 2+ ions enter the crystal lattice. From the Ce 3+ excitation spectrum, it is found that there are three excitation bands in total, the excitation bands at 297, 334 and 462nm are significantly reduced, and the excitation band at 297nm comes from the Mn 2+ excitation band, as shown in Figure 18. Figure 19 shows the emission spectrum of Ce 3+ and Mn 2+ ion co-doped fluorescent materials. Through Gaussian fitting and peak division, it is found that the emission band is mainly composed of three emission bands at 530, 585 and 733nm, and the 530nm emission band comes from The 5d → 2 F 5/2 energy level transition of Ce 3+ , and the 585nm and 733nm are from the 4 T 1 → 1 A 6 energy level transition of Mn 2+ . Figure 21 and Figure 22 show the emission spectrum and chromaticity coordinate diagram of the packaged white LED. Under the excitation of 350mA current, the white LED has a color temperature Tc=3947K, color coordinates X=0.4109, Y=0.4778, and a luminous efficacy of 98.5 lumens / watt, color rendering index 86.6.
附图说明 Description of drawings
图1本发明荧光材料晶体结构示意图;Fig. 1 schematic diagram of crystal structure of fluorescent material of the present invention;
图2实施例1,2,3,4荧光材料的晶体结构X衍射图(XRD);The crystal structure X-ray diffractogram (XRD) of Fig. 2 embodiment 1,2,3,4 fluorescent material;
图3实施例1,2,3,4荧光材料发射光谱;Fig. 3 embodiment 1,2,3,4 fluorescent material emission spectrum;
图4实施例1得到的荧光粉扫描电镜图(SEM);The fluorescent powder scanning electron microscope picture (SEM) that Fig. 4 embodiment 1 obtains;
图5封装得到的白光LED光谱图;The spectrum diagram of white light LED obtained by packaging in Fig. 5;
图6封装得到的白光LED色品图;The chromaticity diagram of the white light LED obtained by packaging in Fig. 6;
图7实施例5、6、7荧光材料激发光谱图;Fig. 7 embodiment 5,6,7 fluorescent material excitation spectrogram;
图8实施例5、6、7荧光材料发射光谱图;Fig. 8 embodiment 5,6,7 fluorescent material emission spectrogram;
图9封装得到的白光LED光谱图;The spectrum diagram of the white light LED obtained by packaging in Fig. 9;
图10封装得到的白光LED色品图;The chromaticity diagram of white light LED obtained by packaging in Fig. 10;
图11实施例8制备的荧光材料的晶体结构X衍射图(XRD);The crystal structure X-ray diffractogram (XRD) of the fluorescent material prepared in Fig. 11 embodiment 8;
图12实施例8制备的荧光材料激发光谱图;The excitation spectrum of the fluorescent material prepared in Fig. 12 Example 8;
图13实施例8制备的荧光材料发射光谱图;The emission spectrum diagram of the fluorescent material prepared in Fig. 13 embodiment 8;
图14实施例8制备的荧光材料X射线光电子能谱图(XPS);The fluorescent material X-ray photoelectron spectrum (XPS) that Fig. 14 embodiment 8 prepares;
图15封装得到的白光LED光谱图;Figure 15 is a white light LED spectral diagram obtained by packaging;
图16封装得到的白光LED色品图;The chromaticity diagram of the white LED obtained by packaging in Fig. 16;
图17实施例11制备的荧光材料的晶体结构X衍射图(XRD);The crystal structure X-ray diffractogram (XRD) of the fluorescent material prepared in Fig. 17 embodiment 11;
图18实施例11制备的荧光材料激发光谱图;The excitation spectrum of the fluorescent material prepared in Fig. 18 embodiment 11;
图19实施例11制备的荧光材料发射光谱图;The emission spectrum diagram of the fluorescent material prepared in Fig. 19 embodiment 11;
图20实施例11制备的荧光材料X射线光电子能谱图(XPS);The fluorescent material X-ray photoelectron spectrum (XPS) that Fig. 20 embodiment 11 prepares;
图21封装得到的白光LED光谱图;Fig. 21 is a white light LED spectral diagram obtained by packaging;
图22封装得到的白光LED色品图。Fig. 22 The chromaticity diagram of the packaged white LED.
具体实施方式 Detailed ways
按照化学通式Mx-zY6-x-y-zAl11-xLxO25.5-0.5kFk:y.Ce3+,z.Mn2+,将分析纯的MgO、MgF2、NH4F、Al2O3、AlF3、SiO2、ZrO2、BaF2、MnCO3和CeO2,按表1,2和3化学组成比例配料混合,在密闭容器中混料40小时,然后将混合物在H2%<5%气氛下,1620℃还原炉中保温6小时,冷却、破碎分级,过500目筛网,得到粒度为3~20μm左右的碱土氟氧硅铝酸盐荧光材料。与蓝光LED芯片(450~460nm)组合封装,得到白光LED。According to the general chemical formula M xz Y 6-xyz Al 11-x L x O 25.5-0.5k F k : y.Ce 3+ , z.Mn 2+ , analytically pure MgO, MgF 2 , NH 4 F, Al 2 O 3 , AlF 3 , SiO 2 , ZrO 2 , BaF 2 , MnCO 3 and CeO 2 were mixed according to the chemical composition ratio of Table 1, 2 and 3, mixed in a closed container for 40 hours, and then the mixture was heated in H 2 %<5% atmosphere, keep warm in a reduction furnace at 1620°C for 6 hours, cool, crush and classify, and pass through a 500-mesh sieve to obtain an alkaline earth fluorooxyaluminosilicate fluorescent material with a particle size of about 3-20 μm. Combine and package with blue LED chip (450-460nm) to obtain white LED.
荧光粉发射主峰由国家荧光粉测试标准GB/T 14634.2-2010测试确定,激发光谱由FLS-920瞬态稳态荧光光谱仪测试。荧光粉的晶体结构(XRD)由GB/T 19421.1-2003测试标准确定。白光LED的色温(CCT)、显色指数(Ra)、发射光谱、发光效率(lm/w)由GB/T 24982-2010测试方法确定。荧光粉光电子能谱(XPS)由ISO15472-2001测试方法确定。The main peak of phosphor emission is determined by the national phosphor test standard GB/T 14634.2-2010, and the excitation spectrum is tested by FLS-920 transient steady-state fluorescence spectrometer. The crystal structure (XRD) of the phosphor is determined by the GB/T 19421.1-2003 test standard. The color temperature (CCT), color rendering index (Ra), emission spectrum, and luminous efficiency (lm/w) of white LEDs are determined by the GB/T 24982-2010 test method. The phosphor photoelectron spectroscopy (XPS) is determined by the ISO15472-2001 test method.
表1荧光材料化学组成Table 1 Chemical Composition of Fluorescent Materials
表2荧光材料化学组成Table 2 Chemical Composition of Fluorescent Materials
表3荧光材料化学组成Table 3 Chemical Composition of Fluorescent Materials
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