技术领域technical field
本发明涉及发光技术领域，具体涉及一种自带防水性能的红色荧光粉及其制备方法。The invention relates to the technical field of light emission, in particular to a red fluorescent powder with waterproof performance and a preparation method thereof.
背景技术Background technique
白光二极管(LED)的发展对节约全球能源具有重要的意义，因为其具有寿命长、能量转化效率高、稳定性良好、体积小、重量轻、结构紧凑等优点而被广泛应用于显示和照明领域。目前，最多商用WLED是通过将InGaN蓝色芯片和 YAG:Ce3+黄色荧光粉结合制成，GaN发出的蓝色光激发了YAG而得到黄色光，未被吸收的蓝光和黄光复合得到白光，因此在蓝光或紫光激发下发黄光的YAG 荧光粉是目前使用量最大的一类荧光粉，但由于YAG:Ce3+发射光谱中红色成分不足，导致WLED显色指数较低，相关色温较高，不能满足一般要求照明。实现高性能的具有高显色性和可调色温的大功率WLED，还需要红色荧光粉来补偿红色。现在，红色的荧光粉主要是稀土掺杂氮化物荧光粉，如Ca(Sr、 Ba)2Si5N8:Eu2+、CaAlSiN3:Eu2+等，但它们的合成条件苛刻会导致高成本，发生重吸收会导致发光效率低。此外，某些荧光粉明显超出了人眼的敏感范围，使 WLED的发光效率难以提高。因此，具有优良的性能的新型窄型红色荧光粉在简单或温和的合成条件下，发光性能被不断追求。The development of white light diodes (LEDs) is of great significance to saving global energy, because of their long life, high energy conversion efficiency, good stability, small size, light weight, and compact structure, they are widely used in display and lighting fields . At present, the most commercial WLEDs are made by combining InGaN blue chips and YAG:Ce3+ yellow phosphors. The blue light emitted by GaN excites YAG to obtain yellow light, and the unabsorbed blue light and yellow light combine to obtain white light. Therefore, YAG phosphors that emit yellow light when excited by blue or violet light are currently the most used type of phosphors. However, due to the lack of red components in the emission spectrum of YAG:Ce3+ , the color rendering index of WLED is low, and the correlated color temperature is low. High, can not meet the general requirements for lighting. Realizing high-performance high-power WLEDs with high color rendering and adjustable color temperature also requires red phosphors to compensate for the red color. At present, red phosphors are mainly rare earth doped nitride phosphors, such as Ca(Sr, Ba)2 Si5 N8 :Eu2+ , CaAlSiN3 :Eu2+ , etc., but their synthesis conditions are harsh and will lead to high Cost, the occurrence of reabsorption will lead to low luminous efficiency. In addition, some phosphors are obviously beyond the sensitive range of the human eye, making it difficult to improve the luminous efficiency of WLEDs. Therefore, new narrow-type red phosphors with excellent properties and luminescent properties under simple or mild synthesis conditions are constantly pursued.
近年来，Mn4+掺杂氟化合物，如A2XF6:Mn4+(A＝NH4，K，Na，Rb，Cs；X＝Si， Ge，Sn，Ti，Zr)作为新型非稀土红色荧光粉出现，与氮化红色荧光粉相比，系列A2XF6:Mn4+红色荧光粉具有以下优点：首先，它们表现出高效的窄带红发射，大部分红发射小于650nm，这保证了更好的颜色纯度和视觉比色参数；其次，它们表现出很高的量子效率；第三，它们有非常好的热淬火性能，热稳定性高；最后是合成条件相对简单，这使得其成本低廉。但是荧光粉包括卤化物和碱土元素(如Cl-、F-、Na+、K+等)在内均容易受潮，使得它们的发光性能降低，虽有研究者提出对荧光粉表面进行涂层保护或者使用表面包膜方案，避免荧光粉直接与水接触，从而提高荧光粉抗水性能，但是这种方法使得荧光粉耐候性差，在高温或紫外线环境下性能衰减很快。也有研究表明通过H2O2或者H2C2O4等进行钝化处理构建失活层作为隔离膜，这始终不能解决根本性的问题，在一些潮湿的环境中照明还是需要荧光粉自身具有防水性的功能。In recent years, Mn4+ doped fluorine compounds, such as A2 XF6 : Mn4+ (A=NH4, K, Na, Rb, Cs; X=Si, Ge, Sn, Ti, Zr) as a new type of non-rare earth red Phosphors appear, compared with nitrided red phosphors, series A2 XF6 :Mn4+ red phosphors have the following advantages: First, they exhibit efficient narrow-band red emission, most of which are less than 650nm, which guarantees Better color purity and visual colorimetric parameters; secondly, they exhibit high quantum efficiency; thirdly, they have very good thermal quenching properties and high thermal stability; lastly, the synthesis conditions are relatively simple, which makes their cost low. However, phosphors, including halides and alkaline earth elements (such as Cl- , F- , Na+ , K+ , etc.), are susceptible to moisture, which reduces their luminous performance. Although some researchers have proposed coating protection on the surface of phosphors Or use a surface coating solution to avoid direct contact of the phosphor with water, thereby improving the water resistance of the phosphor, but this method makes the phosphor poor in weather resistance, and its performance decays quickly in high temperature or ultraviolet environments. Some studies have also shown that H2 O2 or H2 C2 O4 is used to passivate the inactivation layer as an isolation film, which cannot solve the fundamental problem. In some humid environments, the phosphor itself still needs to be illuminated. A waterproof function.
发明内容Contents of the invention
本发明目的在于提供一种自带防水性能的红色荧光粉。The purpose of the present invention is to provide a red fluorescent powder with waterproof performance.
本发明还有另一目的在于提供上述一种自带防水性能的红色荧光粉的制备方法。Still another object of the present invention is to provide a method for preparing the above-mentioned red fluorescent powder with waterproof performance.
本发明通过如下技术方案实现：The present invention realizes through following technical scheme:
一种自带防水性能的红色荧光粉，其特征在于：所述自带防水性能的红色荧光粉的通式为：K2MxNyF6：zMn4+，其中K2MxNyF6作为其基质，所述基质中MN 为Si、Ge、Ti离子中任意两种组合，其中x、y、z分别为M、N和Mn4+的摩尔分数，0<x<1、0<y<1，且x+y＝1，0<z≦0.2。A red fluorescent powder with waterproof performance, characterized in that: the general formula of the red fluorescent powder with waterproof performance is: K2 Mx Ny F6 : zMn4+ , wherein K2 Mx Ny F6 as its matrix, MN in the matrix is any combination of Si, Ge, Ti ions, where x, y, z are the mole fractions of M, N and Mn4+ respectively, 0<x<1, 0 <y<1, and x+y=1, 0<z≦0.2.
更优选地，上述自带防水性能的红色荧光粉通式为K2M0.3N0.7F6：0.1Mn4+。More preferably, the general formula of the above-mentioned red phosphor powder with waterproof property is K2 M0.3 N0.7 F6 : 0.1Mn4+ .
上述K2MxNyF6作为基质在现有技术文献中没有报道过。发明人在研究中开发出了上述基质，并且掺杂Mn4+后得到的红色荧光粉K2MxNyF6：zMn4+具有发光效率高，显色效果好等特点，而且其本身自带非常好的防水效果，且防水稳定性高，可长期使用在潮湿环境中。The aforementioned K2 Mx Ny F6 as a matrix has not been reported in the prior art literature. The inventor developed the above-mentioned matrix in the research, and the red phosphor K2 Mx Ny F6 obtained after doping Mn4+ : zMn4+ has the characteristics of high luminous efficiency and good color rendering effect, and its own It has a very good waterproof effect and high waterproof stability, which can be used in a humid environment for a long time.
进一步，一种自带防水性能的红色荧光粉，其特征在于：所述荧光粉以 K2MxNyF6为基质，和KMnO4混合后与HF溶液反应制得；所述K2MxNyF6基质是由可溶性钾盐与H2AF6按照摩尔比为1:2～15配比反应制得，其中H2AF6溶液为H2SiF6、H2GeF6、H2TiF6溶液中两种混合的溶液，可溶性钾盐可以为KCl、 K2CO3、KNO3或者KOH其中之一。Further, a red fluorescent powder with waterproof performance is characterized in that: the fluorescent powder is made of K2 Mx Ny F6 as a matrix, mixed with KMnO4 and reacted with HF solution; the K2 M Thex Ny F6 matrix is prepared by reacting soluble potassium salt and H2 AF6 according to the molar ratio of 1:2~15, wherein the H2 AF6 solution is H2 SiF6 , H2 GeF6 , H2 In the mixed solution of the two kinds in the TiF6 solution, the soluble potassium salt can be one of KCl, K2 CO3 , KNO3 or KOH.
更进一步，上述荧光粉是在常温常压下，以K2MxNyF6为基质，与KMnO4混合后与HF溶液按照K2MxNyF6：KMnO4：HF＝1:0.1～0.5:1～300的摩尔比进行反应10～20h后，真空抽滤，无水乙醇清洗，再用80℃的真空干燥箱真空干燥8～ 10h，得到K2MxNyF6:zMn4+荧光粉。Furthermore, the above-mentioned fluorescent powder is based on K2 Mx Ny F6 at normal temperature and pressure, mixed with KMnO4 and mixed with HF solution according to K2 Mx Ny F6 : KMnO4 : HF=1: 0.1～0.5:1～300 molar ratio to react for 10～20h, vacuum filter, wash with anhydrous ethanol, and vacuum dry in a vacuum oven at 80°C for 8～10h to obtain K2 Mx Ny F6 : zMn4+ phosphor.
一种自带防水性能的红色荧光粉的制备方法，其特征在于：所述荧光粉是在常温常压下，由可溶性钾盐与H2AF6按照摩尔比为1:2～15配比反应制得 K2MxNyF6，其中H2AF6为H2SiF6、H2GeF6、H2TiF6溶液中任意两种混合的溶液；常温常压下，再以K2MxNyF6为基质，与KMnO4混合后与HF溶液按照K2MxNyF6： KMnO4：HF＝1:0.1～0.5:1～300的摩尔比进行反应10～20h后，真空抽滤，无水乙醇清洗1～3次，再用80℃的真空干燥箱真空干燥8～10h，得到K2MxNyF6:zMn4+荧光粉。A method for preparing red fluorescent powder with waterproof performance, characterized in that: the fluorescent powder is reacted with soluble potassium salt and H2 AF6 at a molar ratio of 1:2 to 15 under normal temperature and pressure Prepare K2 Mx Ny F6 , wherein H2 AF6 is a mixed solution of any two of H2 SiF6 , H2 GeF6 , and H2 TiF6 solutions;x Ny F6 as the substrate, mixed with KMnO4 and reacted with HF solution for 10 to 20 hours according to the molar ratio of K2 Mx Ny F6 : KMnO4 : HF=1:0.1～0.5:1～300, Vacuum filter, wash with absolute ethanol for 1-3 times, and then vacuum-dry in a vacuum oven at 80°C for 8-10 hours to obtain K2 Mx Ny F6 :zMn4+ phosphor.
更优选地说，上述可溶性钾盐与H2AF6的摩尔比为1:2～10；上述K2MxNyF6、 KMnO4和HF的摩尔比为K2MxNyF6：KMnO4：HF＝1:0.1～0.2:50～150。More preferably, the molar ratio of the above-mentioned soluble potassium salt to H2 AF6 is 1:2-10; the molar ratio of the above-mentioned K2 Mx Ny F6 , KMnO4 and HF is K2 Mx Ny F6 : KMnO4 : HF=1:0.1-0.2:50-150.
进一步优先地，上述H2AF6溶液的质量百分浓度为30～50％，上述可溶性钾盐溶液的质量百分浓度为10～40％；上述HF的水溶液质量百分浓度为30～40％。Further preferably, the mass percent concentration of the above- mentionedH2AF6 solution is 30-50%, the mass percent concentration of the above-mentioned soluble potassium salt solution is 10-40%; the mass percent concentration of the above-mentioned HF aqueous solution is 30-40% .
若在防水性荧光粉制备过程中控制不好，不能得到本发明红色荧光粉，其制得的红色荧光粉浸在蒸馏水中，先接触水的表面那层荧光粉已经完全不发光了，虽还有一部分中间粉在发光，但是发光效果骤降，直至荧光粉全部变黑。采用上述制备方法成功地制得了本发明自带显著防水性以及稳定性好的红色荧光粉。If the control is not good in the preparation process of the waterproof phosphor powder, the red phosphor powder of the present invention cannot be obtained, and the red phosphor powder prepared by it is immersed in distilled water, and the phosphor powder on the surface that first touches the water does not emit light at all. A part of the intermediate powder is glowing, but the luminous effect drops sharply until all the phosphors turn black. The red fluorescent powder with remarkable water resistance and good stability of the present invention is successfully prepared by using the above preparation method.
同时，在研究中发现，在制备过程中控制不好，会导致制得的荧光粉粉末颗粒均匀性变差，对荧光粉在水中的发光效果有一定的影响，按照本发明方法制得的荧光粉很好的避免了该技术问题。At the same time, it was found in the research that if the control in the preparation process is not good, the uniformity of the obtained phosphor powder particles will be deteriorated, and the luminescent effect of the phosphor powder in water will be affected to a certain extent. The fluorescent powder prepared according to the method of the present invention Powder well avoids this technical problem.
最具体地说，一种自带防水性能的红色荧光粉的制备方法，它是包括以下步骤制得：Most specifically, a method for preparing a red fluorescent powder with waterproof performance, which comprises the following steps:
(1)常温常压下将质量百分浓度为30～50％的H2AF6溶液缓慢滴入质量百分浓度为10～40％的可溶性钾盐溶液中，边滴加边进行同一方向规律搅拌，搅拌转速在60～80转/min，制得K2MxNyF6的基质溶液，其中可溶性钾盐与H2AF6的摩尔比为1:2～15；(1) Under normal temperature and pressure, slowly drop theH2AF 6solution with a mass percentage concentration of 30-50% into a soluble potassium salt solution with a mass percentage concentration of 10-40%, and carry out the same direction law while dropping. Stir at a stirring speed of 60-80 rpm to prepare a matrix solution of K2 Mx Ny F6 , wherein the molar ratio of soluble potassium salt to H2 AF6 is 1:2-15;
(2)用真空泵抽滤机抽滤，蒸馏水清洗至中性，用烘箱在90℃下干燥8～ 10h，制得K2MxNyF6基质粉末；(2) Filter with a vacuum pump filter, wash with distilled water until neutral, and dry in an oven at 90°C for 8-10 hours to obtain K2 Mx Ny F6 matrix powder;
(3)将步骤(2)中制得的K2MxNyF6粉末和KMnO4混合均匀后，加入质量百分浓度为40％的HF水溶液中进行反应，其中K2MxNyF6、KMnO4和HF的摩尔比为1:0.1～0.5:1～300；常温常压下反应时间为10～20h，生成目标产物 K2MxNyF6:zMn4+沉淀物；(3) After mixing the K2 Mx Ny F6 powder and KMnO4 prepared in the step (2) evenly, they are added to 40% HF aqueous solution for reaction, wherein K2 Mx Ny The molar ratio of F6 , KMnO4 and HF is 1:0.1-0.5:1-300; the reaction time is 10-20 hours at normal temperature and pressure, and the target product K2 Mx Ny F6 :zMn4+ precipitate is generated;
(4)使用真空泵抽滤机抽滤，无水乙醇清洗1～3次，再用80℃的真空干燥箱真空干燥8～10h，得到目标产物K2MxNyF6:zMn4+荧光粉。(4) Use a vacuum pump to filter, wash with absolute ethanol for 1 to 3 times, and then dry in a vacuum oven at 80°C for 8 to 10 hours to obtain the target product K2 Mx Ny F6 :zMn4+ fluorescence pink.
进一步，上述步骤(1)中H2AF6溶液滴入可溶性钾盐溶液完成后，还需继续搅拌30～40min。Further, after the H2 AF6 solution is dripped into the soluble potassium salt solution in the above step (1), it is necessary to continue stirring for 30-40 minutes.
本发明具有以下有益效果：The present invention has the following beneficial effects:
本发明提供了一种自带防水性能的红色荧光粉及其制备方法，使用本发明方法制备荧光粉简单，高效，不需要高温煅烧等步骤，常温常压条件下就可以制备；本发明红色荧光粉为窄带发射，颗粒均匀，其具有发光效率高，显色效果好，有很好防水效果等突出优点，很好的解决了传统红色荧光粉容易受潮水解的难题，而且荧光粉自身具有稳定的防水性，其在潮湿环境中保持长时间稳定不衰减，且最终发光强度可保持在原来的80％以上，不仅解决了传统涂层保护的防水手段中荧光粉性能衰减较快的问题，而且无需使用防水涂层，节约了生产成本，且广泛适用于潮湿环境中。The invention provides a red fluorescent powder with waterproof performance and a preparation method thereof. The preparation of the fluorescent powder by the method of the invention is simple, efficient, and does not require steps such as high-temperature calcination, and can be prepared under normal temperature and pressure conditions; the red fluorescent powder of the present invention The powder has narrow-band emission and uniform particles. It has outstanding advantages such as high luminous efficiency, good color rendering effect, and good waterproof effect. Waterproof, it remains stable for a long time in a humid environment without attenuation, and the final luminous intensity can be maintained at more than 80% of the original, which not only solves the problem of rapid attenuation of phosphor performance in traditional coating protection waterproof methods, but also does not require The use of waterproof coating saves production costs and is widely applicable in wet environments.
附图说明Description of drawings
图1：本发明实例1中所述红色荧光粉的XRD谱图；Fig. 1: the XRD spectrogram of red fluorescent powder described in the example 1 of the present invention;
图2：本发明实例1中所述红色荧光粉的激发光谱；Fig. 2: the excitation spectrum of the red fluorescent powder described in the example 1 of the present invention;
图3：本发明实例1中所述红色荧光粉的发射光谱；Fig. 3: the emission spectrum of the red fluorescent powder described in the example 1 of the present invention;
图4：本发明实例3中所述红色荧光粉的激发光谱；Fig. 4: the excitation spectrum of the red fluorescent powder described in the example 3 of the present invention;
图5：本发明实例3中所述红色荧光粉的发射光谱；Fig. 5: the emission spectrum of the red fluorescent powder described in the example 3 of the present invention;
图6：本发明实例1、2和3中所述红色荧光粉的浸水后发光强度对比图。Fig. 6: A comparison chart of the luminous intensity of the red phosphors described in Examples 1, 2 and 3 of the present invention after immersion in water.
具体实施方式Detailed ways
下面通过实施例对本发明进行具体的描述，有必要在此指出的是以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域技术人员可以根据本发明内容对本发明做出一些非本质的改进和调整。The present invention is specifically described below through the examples. It is necessary to point out that the following examples are only used to further illustrate the present invention, and cannot be interpreted as limiting the protection scope of the present invention. Those skilled in the art can understand the present invention according to the contents of the present invention. Invention to make some non-essential improvements and adjustments.
实施例1Example 1
一种自带防水性能的红色荧光粉的制备方法，按如下步骤：A kind of preparation method of the red fluorescent powder with self-waterproof performance, according to the following steps:
(1)常温常压下取质量百分浓度为50％的H2TiF6和H2GeF6组成的混合酸溶液，其中H2TiF6：H2GeF6的摩尔比为1:9，将混合溶液缓慢滴入质量百分浓度为 40％的KNO3溶液中，KNO3与混合酸溶液的施用量摩尔比1:2，边滴加边进行同一方向圆周规律搅拌，滴加完成后继续搅拌30min，搅拌转速为80转/min,制得含有K2Ge0.9Ti0.1F6的基质溶液；(1) Take a mixed acid solution composed of H2 TiF6 and H2 GeF6 with a concentration of 50% by mass at normal temperature and pressure, wherein the molar ratio of H2 TiF6 : H2 GeF6 is 1:9, and the The mixed solution is slowly dropped into theKNO3 solution with a mass percentage concentration of 40%. The molar ratio ofKNO3 to the mixed acid solution is 1:2. 30min, the stirring speed is 80 revs/min, and the matrix solution containing K2 Ge0.9 Ti0.1 F6 is obtained;
(2)再经循环水式多用真空泵抽滤机抽滤，用蒸馏水清洗至中性，再用烘箱在90℃下干燥10h，制得K2Ge0.9Ti0.1F6基质；(2) Suction filtration by a circulating water multi-purpose vacuum pump filter, wash with distilled water until neutral, and then dry in an oven at 90°C for 10 hours to obtain a K2 Ge0.9 Ti0.1 F6 matrix;
(3)取步骤(2)制得的K2Ge0.9Ti0.1F6粉末和KMnO4混合均匀后，加入质量百分浓度为40％的HF溶液；常温常压下反应20h，生成目标产物K2Ge0.9Ti0.1F6： 0.15Mn4+，其中各反应物的摩尔比为K2Ge0.9Ti0.1F6：KMnO4：HF＝1:0.15:150；(3) Take the K2 Ge0.9 Ti0.1 F6 powder prepared in step (2) and KMnO4 and mix evenly, then add HF solution with a concentration of 40% by mass; react for 20 hours at normal temperature and pressure, and generate the target product K2 Ge0.9 Ti0.1 F6 : 0.15Mn4+ , wherein the molar ratio of each reactant is K2 Ge0.9 Ti0.1 F6 : KMnO4 : HF=1:0.15:150;
(4)去掉上层悬液，使用经循环水式多用真空泵抽滤机抽滤，无水乙醇清洗3次，用真空干燥箱在80℃下干燥10h，得到目标产物K2Ge0.9Ti0.1F6：0.15Mn4+荧光粉。(4) Remove the upper suspension, filter with a circulating water multi-purpose vacuum pump filter, wash with absolute ethanol for 3 times, and dry at 80°C for 10 hours in a vacuum drying oven to obtain the target product K2 Ge0.9 Ti0.1 F6 : 0.15Mn4+ phosphor.
将实施例1中制得的K2Ge0.9Ti0.1F6：0.15Mn4+防水性红色荧光粉浸在蒸馏水中，静置一段时间，观察并检测该红色荧光粉在水中的发光情况如图6。Soak the K2 Ge0.9 Ti0.1 F6 : 0.15Mn4+ waterproof red phosphor powder prepared in Example 1 in distilled water, let it stand for a period of time, observe and detect the luminescence of the red phosphor powder in water as shown in the figure 6.
根据图1、图2、图3和图6所示可知：实施例1中采用本发明方法制得的K2Ge0.9Ti0.1F6：0.15Mn4+红色荧光粉，其激发峰位于362.8nm和462.8nm，发射光谱是在580～680nm之间的窄带发射，有590.4nm、603.2nm、616.0nm、634.8nm 和650.6nm 5个交叉发射峰，其中634.8nm为最强峰，最强峰的半峰宽为10nm。荧光粉随着浸水时间增长，短时间内发光强度有略微降低，降低到一定程度后趋于稳定，仍然具有不错的发光效果，发光性能不再衰减。According to Fig. 1, Fig. 2, Fig. 3 and Fig. 6, it can be known that the K2 Ge0.9 Ti0.1 F6 : 0.15Mn4+ red phosphor prepared by the method of the present invention in Example 1 has an excitation peak at 362.8nm and 462.8nm, the emission spectrum is a narrow-band emission between 580 and 680nm, and there are 5 cross emission peaks at 590.4nm, 603.2nm, 616.0nm, 634.8nm and 650.6nm, of which 634.8nm is the strongest peak, the strongest peak Half width is 10nm. As the water immersion time increases, the luminous intensity of the phosphor decreases slightly in a short period of time, and after a certain decrease, it tends to be stable, and still has a good luminous effect, and the luminous performance does not attenuate.
实施例2Example 2
一种自带防水性能的红色荧光粉的制备方法，按如下步骤：A kind of preparation method of the red fluorescent powder with self-waterproof performance, according to the following steps:
(1)常温常压下取质量百分浓度为30％的H2TiF6和H2SiF6组成的混合酸溶液，其摩尔比为H2TiF6:H2SiF6＝1:1，缓慢滴入质量百分浓度为10％的KCl溶液中，KCl 与混合酸溶液的施用量摩尔比为1:10，边滴加边进行同一方向圆周规律搅拌，滴加完成后继续搅拌40min搅拌转速在60转/min，制得含有K2Ti0.5Si0.5F6的基质溶液；(1) Take a mixed acid solution composed of H2 TiF6 and H2 SiF6 with a concentration of 30% by mass at normal temperature and pressure, the molar ratio of which is H2 TiF6 :H2 SiF6 =1:1, slowly Drop into the KCl solution with a mass percentage concentration of 10%. The molar ratio of KCl to the mixed acid solution is 1:10. While dripping, carry out circular stirring in the same direction, and continue stirring for 40 minutes after the dripping is completed. 60 turns/min, make the matrix solution that contains K2 Ti0.5 Si0.5 F6 ;
(2)循环水式多用真空泵抽滤机抽滤，经蒸馏水清洗至中性，再使用90℃真空干燥箱干燥8h，制得基质K2Ti0.5Si0.5F6；(2) Filtrate with a circulating water type multi-purpose vacuum pump filter, wash with distilled water until neutral, and then dry in a vacuum oven at 90°C for 8 hours to obtain the matrix K2 Ti0.5 Si0.5 F6 ;
(3)取步骤(2)制得的K2Ti0.5Si0.5F6粉末与KMnO4混合均匀后，加入质量百分浓度为30％的HF混合溶液中进行反应，各反应物摩尔比为K2Ti0.5Si0.5F6： KMnO4：HF＝1:0.2:80，在常温常压下反应20h后，生成目标产物 K2Ti0.5Si0.5F6:0.2Mn4+；(3) Get K2 Ti0.5 Si0.5 F6 powder prepared in step (2) and KMnO4 After mixing evenly, add mass percent concentration and be 30% in the HF mixed solution to react, each reactant molar ratio is K2 Ti0.5 Si0.5 F6 : KMnO4 : HF=1:0.2:80, after 20 hours of reaction at normal temperature and pressure, the target product K2 Ti0.5 Si0.5 F6 :0.2Mn4+ is generated;
(4)去掉上层悬液，用循环水式多用真空泵抽滤机抽滤，之后用无水乙醇清洗1次，在80℃的真空干燥箱中干燥8h，得到目标产物K2Ti0.5Si0.5F6:0.2Mn4+荧光粉。(4) Remove the upper layer suspension, filter it with a circulating water multi-purpose vacuum pump filter, wash it once with absolute ethanol, and dry it in a vacuum oven at 80°C for 8 hours to obtain the target product K2 Ti0.5 Si0.5 F6 : 0.2Mn4+ phosphor.
将实施例中制得的K2Ti0.5Si0.5F6:0.2Mn4+防水性红色荧光粉浸在蒸馏水中，静置一段时间，观察并检测该红色荧光粉在水中的发光情况如图6。Soak the K2 Ti0.5 Si0.5 F6 :0.2Mn4+ waterproof red phosphor powder prepared in the example in distilled water, let it stand for a period of time, observe and detect the luminescence of the red phosphor powder in water as shown in Figure 6 .
实施例2中采用本发明方法制得的K2Ti0.5Si0.5F6:0.2Mn4+红色荧光粉，其激发峰位于336.4.0nm和469.2nm，发射光谱在580～680nm之间窄带发射，有590.2nm、 605.6nm、617.2nm、636.2nm和651.4nm、5个交叉发射峰，其中636.2nm为最强峰，最强峰的半峰宽为10nm。如图6所示，荧光粉随着浸水时间增长，短时间内发光强度有略微降低，降低到一定程度后趋于稳定，仍然具有不错的发光效果，且发光性能不再衰减。The K2 Ti0.5 Si0.5 F6 :0.2Mn4+ red phosphor prepared by the method of the present invention in Example 2 has excitation peaks at 336.4.0nm and 469.2nm, and emission spectrum in a narrow band between 580nm and 680nm. There are 5 cross emission peaks at 590.2nm, 605.6nm, 617.2nm, 636.2nm and 651.4nm, among which 636.2nm is the strongest peak, and the half width of the strongest peak is 10nm. As shown in Figure 6, as the immersion time increases, the luminous intensity of the phosphor decreases slightly in a short period of time, and it tends to be stable after a certain decrease, and still has a good luminous effect, and the luminous performance no longer decays.
实施例3Example 3
一种自带防水性能的红色荧光粉的制备方法，按如下步骤：A kind of preparation method of the red fluorescent powder with self-waterproof performance, according to the following steps:
(1)常温常压下取质量百分浓度为40％的H2SiF6和H2GeF6组成的混合溶液，其摩尔比为H2GeF6:H2SiF6＝3:7，缓慢滴入质量百分浓度为26％的KOH溶液， KOH与混合酸溶液的使用量摩尔比为1:6，边滴加边进行同一方向圆周规律搅拌，滴加完成后继续搅拌35min，搅拌搅拌转速为70转/min，制得含有K2Si0.7Ge0.3F6的基质溶液；(1) Take a mixed solution of H2 SiF6 and H2 GeF6 with a concentration of 40% by mass at normal temperature and pressure. The molar ratio is H2 GeF6 :H2 SiF6 =3:7, slowly drop Add the KOH solution that the mass percent concentration is 26%, the molar ratio of KOH and mixed acid solution is 1:6, carry out the circular regularity stirring in the same direction while adding dropwise, continue to stir 35min after the dropwise addition is completed, the stirring speed of stirring is 70 revolutions/min to prepare a matrix solution containing K2 Si0.7 Ge0.3 F6 ;
(2)采用循环水式多用真空泵抽滤机抽滤，用蒸馏水清洗至中性，再用90℃真空干燥箱干燥9h，制得基质K2Si0.7Ge0.3F6；(2) Suction filtration with a circulating water type multi-purpose vacuum pump filter, wash with distilled water until neutral, and then dry in a vacuum oven at 90°C for 9 hours to obtain the matrix K2 Si0.7 Ge0.3 F6 ;
(3)取步骤(2)中制得的K2Si0.7Ge0.3F6粉末与KMnO4混合均匀后，加入质量百分浓度为36％的HF混合溶液中进行反应，其中各反应物的摩尔比为 K2Si0.7Ge0.3F6：KMnO4：HF＝1:0.1:50，常温常压下反应12h后，生成目标产物 K2Si0.7Ge0.3F6：0.1Mn4+；(3) Get the K2 Si0.7 Ge0.3 F6 powder prepared in step (2) and KMnO4 After mixing evenly, add the mass percent concentration and be 36% in the HF mixed solution and react, wherein the mole of each reactant The ratio is K2 Si0.7 Ge0.3 F6 : KMnO4 : HF=1:0.1:50, after 12 hours of reaction at normal temperature and pressure, the target product K2 Si0.7 Ge0.3 F6 : 0.1Mn4+ is generated;
(4)去掉上层悬液，用循环水式多用真空泵抽滤机抽滤，再用无水乙醇清洗3次，在80℃的真空干燥箱中干燥9h，得到目标产物K2Si0.7Ge0.3F6：0.1Mn4+荧光粉。(4) Remove the upper suspension, filter with a circulating water multi-purpose vacuum pump filter, wash with absolute ethanol for 3 times, and dry in a vacuum oven at 80°C for 9 hours to obtain the target product K2 Si0.7 Ge0.3 F6 : 0.1Mn4+ phosphor.
将实施例3中制得的K2Si0.7Ge0.3F6：0.1Mn4+防水性红色荧光粉浸在蒸馏水中，静置一段时间，观察并检测该红色荧光粉在水中的发光情况如图6所示。Soak the K2 Si0.7 Ge0.3 F6 : 0.1Mn4+ waterproof red phosphor powder prepared in Example 3 in distilled water, let it stand for a period of time, observe and detect the luminescence of the red phosphor powder in water as shown in the figure 6.
根据图4、图5和图6所示可知：实施例3中采用本发明方法制得的 K2Si0.7Ge0.3F6：0.1Mn4+红色荧光粉，其基质为K2Si0.7Ge0.3F6，其激发峰位于358.0nm和460.0nm，发射光谱在580～680nm之间窄带发射，有590.4nm、600.8nm、 615.2nm、623.8nm、633.6nm和649.8nm 6个交叉发射峰，其中633.6nm为最强峰，最强峰的半峰宽为10nm。荧光粉随着浸水时间增长，算时间内发光强度有略微降低，降低到一定程度后趋于稳定，仍然具有很好的发光效果，且发光性能不再衰减。According to Fig. 4, Fig. 5 and Fig. 6, it can be known that the K2 Si0.7 Ge0.3 F6 : 0.1Mn4+ red phosphor prepared by the method of the present invention in Example 3 is K2 Si0.7 Ge0.3 F6 , its excitation peaks are located at 358.0nm and 460.0nm, and its emission spectrum emits in a narrow band between 580nm and 680nm. nm is the strongest peak, and the half width of the strongest peak is 10nm. As the time of immersion increases, the luminous intensity of the phosphor decreases slightly within a certain period of time, and it tends to be stable after decreasing to a certain extent. It still has a good luminous effect, and the luminous performance is no longer attenuated.
经多次试验检测，上述防水性红色荧光粉的激发峰为360nm±10nm和 460nm±10nm，其发射光谱在580～680nm之间窄带发射：有5～6个交叉的发射峰；After multiple tests, the excitation peaks of the above-mentioned waterproof red phosphor are 360nm±10nm and 460nm±10nm, and its emission spectrum emits in a narrow band between 580-680nm: there are 5-6 crossed emission peaks;
当0<z≦0.1时，会出现6个发射波峰，峰位分别为590nm±2nm、602nm± 2nm、616nm±2nm、625nm±2nm、635nm±2nm和650nm±2nm，其中最强峰为635nm±2nm，且最强峰的半峰宽为10nm±2nm。When 0<z≦0.1, there will be 6 emission peaks, the peak positions are 590nm±2nm, 602nm±2nm, 616nm±2nm, 625nm±2nm, 635nm±2nm and 650nm±2nm, the strongest peak is 635nm±2nm 2nm, and the half width of the strongest peak is 10nm±2nm.
当0.1<z≦0.2时，会出现5个发射波峰，峰位分别为590nm±2nm、603nm ±3nm、616nm±2nm、635nm±2nm和650nm±2nm，其中最强峰为635nm±2nm，且最强峰的半峰宽为10nm±2nm。When 0.1<z≦0.2, there will be 5 emission peaks, the peak positions are 590nm±2nm, 603nm±3nm, 616nm±2nm, 635nm±2nm and 650nm±2nm, the strongest peak is 635nm±2nm, and the most The half width of the strong peak is 10nm±2nm.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910571374.1ACN110257065B (en) | 2019-06-28 | 2019-06-28 | A kind of red phosphor with waterproof performance and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910571374.1ACN110257065B (en) | 2019-06-28 | 2019-06-28 | A kind of red phosphor with waterproof performance and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN110257065Atrue CN110257065A (en) | 2019-09-20 |
| CN110257065B CN110257065B (en) | 2022-05-17 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910571374.1AActiveCN110257065B (en) | 2019-06-28 | 2019-06-28 | A kind of red phosphor with waterproof performance and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN110257065B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112410030A (en)* | 2020-12-03 | 2021-02-26 | 重庆文理学院 | A kind of preparation method of heterogeneous composite molybdate oxyfluoride nano fluorescent material |
| CN113097368A (en)* | 2021-03-26 | 2021-07-09 | 湖北三峡夷丰光电科技有限公司 | Production method of red fluorescent film |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013014715A (en)* | 2011-07-06 | 2013-01-24 | Nichia Corp | Fluoride phosphor and light-emitting device obtained using the fluoride phosphor |
| CN103003388A (en)* | 2010-07-27 | 2013-03-27 | 通用电气公司 | Moisture resistant phosphors and related methods |
| CN103980896A (en)* | 2014-04-29 | 2014-08-13 | 中国科学院福建物质结构研究所 | Preparation method of fluoride fluorescent powder material |
| CN105733575A (en)* | 2015-12-28 | 2016-07-06 | 温州大学 | Tetravalent manganese ion doped ammonium salt red light material and preparation method thereof |
| CN105980523A (en)* | 2014-01-30 | 2016-09-28 | 信越化学工业株式会社 | Method for producing and method for processing complex fluoride phosphor |
| CN106085428A (en)* | 2015-03-10 | 2016-11-09 | 重庆文理学院 | A kind of fluorescent material being applicable to LED illumination |
| JP2016210950A (en)* | 2015-04-28 | 2016-12-15 | 株式会社ネモト・ルミマテリアル | Fluoride phosphor and production method thereof, and semiconductor light-emitting device |
| CN106433626A (en)* | 2016-09-22 | 2017-02-22 | 陕西师范大学 | Method for preparing Mn(IV)-activated fluoride red fluorescent powder |
| CN106929015A (en)* | 2015-12-29 | 2017-07-07 | 有研稀土新材料股份有限公司 | Red fluorescence powder, its preparation method and the luminescent device comprising the red fluorescence powder |
| CN107236543A (en)* | 2017-06-15 | 2017-10-10 | 华南理工大学 | One kind improves Mn4+The method of doped fluoride red fluorescence powder material moisture resistance properties |
| WO2018215204A1 (en)* | 2017-05-23 | 2018-11-29 | Osram Opto Semiconductors Gmbh | Wavelength conversion element, light emitting device and method for producing a wavelength conversion element |
| CN109135739A (en)* | 2017-06-16 | 2019-01-04 | 隆达电子股份有限公司 | Manganese-doped red fluoride phosphor, light-emitting device and backlight module |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103003388A (en)* | 2010-07-27 | 2013-03-27 | 通用电气公司 | Moisture resistant phosphors and related methods |
| JP2013014715A (en)* | 2011-07-06 | 2013-01-24 | Nichia Corp | Fluoride phosphor and light-emitting device obtained using the fluoride phosphor |
| CN105980523A (en)* | 2014-01-30 | 2016-09-28 | 信越化学工业株式会社 | Method for producing and method for processing complex fluoride phosphor |
| CN103980896A (en)* | 2014-04-29 | 2014-08-13 | 中国科学院福建物质结构研究所 | Preparation method of fluoride fluorescent powder material |
| CN106085428A (en)* | 2015-03-10 | 2016-11-09 | 重庆文理学院 | A kind of fluorescent material being applicable to LED illumination |
| JP2016210950A (en)* | 2015-04-28 | 2016-12-15 | 株式会社ネモト・ルミマテリアル | Fluoride phosphor and production method thereof, and semiconductor light-emitting device |
| CN105733575A (en)* | 2015-12-28 | 2016-07-06 | 温州大学 | Tetravalent manganese ion doped ammonium salt red light material and preparation method thereof |
| CN106929015A (en)* | 2015-12-29 | 2017-07-07 | 有研稀土新材料股份有限公司 | Red fluorescence powder, its preparation method and the luminescent device comprising the red fluorescence powder |
| CN106433626A (en)* | 2016-09-22 | 2017-02-22 | 陕西师范大学 | Method for preparing Mn(IV)-activated fluoride red fluorescent powder |
| WO2018215204A1 (en)* | 2017-05-23 | 2018-11-29 | Osram Opto Semiconductors Gmbh | Wavelength conversion element, light emitting device and method for producing a wavelength conversion element |
| CN107236543A (en)* | 2017-06-15 | 2017-10-10 | 华南理工大学 | One kind improves Mn4+The method of doped fluoride red fluorescence powder material moisture resistance properties |
| CN109135739A (en)* | 2017-06-16 | 2019-01-04 | 隆达电子股份有限公司 | Manganese-doped red fluoride phosphor, light-emitting device and backlight module |
| Title |
|---|
| JIN YUMING ET AL.,: "Synthesis and photoluminescence properties of octahedral", 《JOURNAL OF RARE EARTHS》* |
| 陈三斌主编: "《农用化工产品手册》", 30 April 2008, 北京：金盾出版社* |
| 陈文威: "20170621", 《厦门大学硕士学位论文》* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112410030A (en)* | 2020-12-03 | 2021-02-26 | 重庆文理学院 | A kind of preparation method of heterogeneous composite molybdate oxyfluoride nano fluorescent material |
| CN112410030B (en)* | 2020-12-03 | 2022-09-13 | 重庆文理学院 | A kind of preparation method of heterogeneous composite molybdate oxyfluoride nano fluorescent material |
| CN113097368A (en)* | 2021-03-26 | 2021-07-09 | 湖北三峡夷丰光电科技有限公司 | Production method of red fluorescent film |
| Publication number | Publication date |
|---|---|
| CN110257065B (en) | 2022-05-17 |
| Publication | Publication Date | Title |
|---|---|---|
| CN107236543B (en) | A method for improving the moisture resistance of Mn4+-doped fluoride red phosphor materials | |
| CN107142102A (en) | A kind of Mn4+The surface modifying method of doped fluoride red fluorescence powder material | |
| JP5005759B2 (en) | Fluorescent powder, method for producing the same, and light-emitting device using the same | |
| CN112251219B (en) | Moisture-resistant fluoride red fluorescent powder and preparation method thereof | |
| CN106479485B (en) | A kind of fluoride red light fluorescent powder of high-temp resisting high-humidity resisting and preparation method thereof | |
| CN108003872B (en) | Fluoride red phosphor for white light LED excited by blue light and method for its preparation and modification | |
| CN113583656A (en) | Oleamidooleic acid modified tetravalent manganese doped fluoride red light material and preparation method thereof | |
| CN110257065B (en) | A kind of red phosphor with waterproof performance and preparation method thereof | |
| CN105950137A (en) | A kind of Mn4+ doped fluoride red fluorescent powder and its preparation method and application | |
| CN112175609A (en) | A kind of green preparation method of water-resistant fluoride red phosphor | |
| CN110157414B (en) | Red fluoromanganate fluorescent material and preparation method thereof | |
| CN102559173B (en) | Core-surface layer gradient nitrogen oxide fluorescent powder, manufacturing method thereof and light-emitting device adopting fluorescent powder | |
| CN109280551A (en) | High light-efficiency oxyfluoride phosphor, preparation method thereof, and semiconductor light-emitting device | |
| CN114933896B (en) | A kind of Mn4+ heterovalent doped oxyfluoride red phosphorescent material and preparation method thereof | |
| CN105567221A (en) | Red fluorescent material, preparation method and application thereof, and white LED (light emitting diode) device | |
| CN111978955B (en) | A kind of red phosphor and its preparation method and application | |
| CN110157425A (en) | A kind of manganese ion activated oxyfluoride phosphor and preparation method thereof | |
| CN110184057A (en) | A kind of oxygen fluoride red fluorescence powder and preparation method thereof | |
| CN106318381B (en) | A kind of Mn4+Sodium bifluoride red light material of doping and preparation method thereof | |
| CN114874774A (en) | Manganese ion activated tantalum-based oxyfluoride red luminescent material and preparation method thereof | |
| CN110172346A (en) | A kind of red fluorescence powder and preparation method thereof | |
| CN107603624B (en) | A blue light excited Mn4+ doped fluoroytterbium red light material and preparation method thereof | |
| CN103467648B (en) | A kind of ultralow second-order transition temperature mix europium fluorine Si acrylate red fluorescence agent and preparation method thereof | |
| CN116333735B (en) | Tetravalent manganese doped fluoride red fluorescent material with homogeneous core-shell structure and preparation method thereof | |
| CN115491200B (en) | A blue light-excited red phosphor and its preparation and white light LED device |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |