CN102559179B - Single-matrix white light fluorescent powder for white light light-emitting diode (LED) and preparation method thereof - Google Patents
Single-matrix white light fluorescent powder for white light light-emitting diode (LED) and preparation method thereof Download PDFInfo
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
本发明涉及一种白光LED用单基质白光荧光粉，化学式为MxNy(PO4)2-z-(BO3)z:aEu2+，bMn2+，M为Ba、Ca或Sr的一种、两种或三种的组合；N为Mg或Zn的一种或两种的组合；a，b，x，y，z为各自的摩尔分数，1.5＜x＜3，0.5＜y＜2，0≤z＜1，0.001＜a＜0.2，0≤b＜0.4，其中z和b不同时为零。并公开了所述白光LED用单基质白光荧光粉的制备方法。本发明有益效果：产品性能稳定、激发和发射光谱范围宽、显色指数高；工艺简单、易于操作、无污染、成本低。The invention relates to a single-matrix white light phosphor powder for white light LED, the chemical formula is M x N y (PO 4 ) 2-z -(BO 3 ) z : aEu 2+ , bMn 2+ , M is Ba, Ca or Sr A combination of one, two or three; N is a combination of one or two of Mg or Zn; a, b, x, y, z are the respective mole fractions, 1.5<x<3, 0.5<y< 2. 0≤z<1, 0.001<a<0.2, 0≤b<0.4, wherein z and b are not zero at the same time. It also discloses a preparation method of the single-matrix white light phosphor powder for the white light LED. The invention has beneficial effects: stable product performance, wide excitation and emission spectrum range, high color rendering index; simple process, easy operation, no pollution and low cost.
Description
(一)技术领域 (1) Technical field
本发明属于稀土发光材料和半导体固态照明领域，特别涉及一种可被近紫外光LED芯片有效激发而发白光的单基质荧光粉及其制备方法。The invention belongs to the field of rare earth luminescent materials and semiconductor solid-state lighting, and particularly relates to a single-matrix fluorescent powder that can be effectively excited by a near-ultraviolet LED chip to emit white light and a preparation method thereof.
(二)背景技术 (2) Background technology
半导体发光二极管(light emitting diode，简称LED)是一种新型固态照明光源，具有体积小、光效高、节能、寿命长、无污染等优点，可广泛应用于城市景观照明、汽车灯、LCD背光源、室内外普通照明等领域，被誉为第四代照明光源，对节能、环保、改善人们生活质量等都具有重大的意义。目前白光LED的实现方式主要有芯片组合型和荧光体光转换型。芯片组合型是指通过红、绿、蓝三色LED芯片组合实现白光。由于红光LED的光转化效率明显高于绿光LED和蓝光LED，必须通过复杂的控制电路才能实现混色平衡，因此该方法的成本较高、工艺性较差。荧光体光转换型是指通过蓝光LED激发荧光材料发射黄光，剩余的蓝光透射出来与黄光互补混合产生白光；或者利用涂敷在紫外或近紫外LED芯片上的荧光材料完全吸收LED的发射产生红、绿、蓝光，进而混合形成白光。当今LED固体光源的主流方案是荧光体光转换白光LED，其核心问题在于研制高效荧光体。但是由于白光是由荧光体的黄色荧光与LED的蓝光混合而成，器件的发光颜色随驱动电压和荧光体涂层厚度的变化而变化，色彩还原性差，显色指数低。为解决上述问题，采用近紫外光InGaN管芯激发三基色荧光体实现白光LED已成为目前国际上该领域研发的热点之一。但目前，与近紫外光管芯相匹配的三色基荧光体缺乏，并且荧光体混合物之间存在颜色再吸收和配比调控问题，流明效率和显色指数受到较大影响。全色单基质白光荧光粉能在一定程度上克服混合荧光体的不足，提高了流明效率和显色指数；同时也能简化封装工艺。因此开发适合紫外激发的高效单基质白光荧光粉将是新一代白光LED照明的研究热点，具有广阔的经济应用价值。Semiconductor light emitting diode (light emitting diode, referred to as LED) is a new type of solid-state lighting source, which has the advantages of small size, high luminous efficiency, energy saving, long life, and no pollution. It can be widely used in urban landscape lighting, car lights, LCD backlights, etc. Source, indoor and outdoor general lighting and other fields, known as the fourth generation of lighting sources, has great significance for energy saving, environmental protection, and improving people's quality of life. At present, the implementation methods of white light LED mainly include chip combination type and phosphor light conversion type. The chip combination type refers to the realization of white light through the combination of red, green and blue LED chips. Since the light conversion efficiency of red LEDs is significantly higher than that of green LEDs and blue LEDs, complex control circuits must be used to achieve color mixing balance, so this method has high costs and poor manufacturability. Phosphor light conversion type means that the blue light is used to excite the fluorescent material to emit yellow light, and the remaining blue light is transmitted and mixed with the yellow light to generate white light; or the fluorescent material coated on the ultraviolet or near-ultraviolet LED chip is used to completely absorb the emission of the LED Red, green, and blue light are produced, which are then mixed to form white light. Today's mainstream solution for LED solid-state light sources is phosphor light-conversion white light LEDs, and the core problem is to develop high-efficiency phosphors. However, since the white light is composed of the yellow fluorescence of the phosphor and the blue light of the LED, the luminescent color of the device changes with the change of the driving voltage and the thickness of the phosphor coating, the color reproduction is poor, and the color rendering index is low. In order to solve the above problems, the use of near-ultraviolet light InGaN dies to excite trichromatic phosphors to realize white LEDs has become one of the research and development hotspots in this field in the world. However, at present, there is a lack of three-color base phosphors that match the near-ultraviolet light dies, and there are color reabsorption and ratio control problems between the phosphor mixtures, which greatly affect the lumen efficiency and color rendering index. The full-color single-matrix white phosphor can overcome the shortcomings of mixed phosphors to a certain extent, improve lumen efficiency and color rendering index; at the same time, it can also simplify the packaging process. Therefore, the development of high-efficiency single-matrix white light phosphors suitable for ultraviolet excitation will be a research hotspot in the new generation of white light LED lighting, and has broad economic application value.
(三)发明内容 (3) Contents of the invention
本发明针对目前缺乏与近紫外光管芯相匹配的三色基荧光体，并且荧光体混合物之间存在颜色再吸收和配比调控的问题，提出了一种具有高显色指数、适合于紫外光LED芯片激发的白光LED用单基质白光荧光粉及其制备方法。Aiming at the lack of three-color-based phosphors matching the near-ultraviolet tube core, and the problems of color reabsorption and ratio control among the phosphor mixtures, the present invention proposes a high color rendering index suitable for ultraviolet The invention discloses a single-matrix white light phosphor powder for white light LED excited by a light LED chip and a preparation method thereof.
本发明采用的技术方案是：The technical scheme adopted in the present invention is:
一种白光LED用单基质白光荧光粉，所述荧光粉的化学表达式为：A single-matrix white light phosphor powder for white light LEDs, the chemical expression of the phosphor powder is:
MxNy(PO4)2-z-(BO3)z:aEu2+，bMn2+ M x N y (PO 4 ) 2-z -(BO 3 ) z : aEu 2+ , bMn 2+
其中，所述的M为Ba、Ca或Sr的一种或两种以上的任意组合；所述的N为Mg或Zn的一种或两种的任意组合；O代表氧；Eu2+和Mn2+是掺杂离子。所述的a，b，x，y，z为各自的摩尔分数，其中1.5＜x＜3，0.5＜y＜2，0≤z＜1，0.001＜a＜0.2，0≤b＜0.4，其中z和b不同时为零。优选的，所述化学表达式中，x+y+a+b＝3。Wherein, said M is one or any combination of two or more of Ba, Ca or Sr; said N is any combination of one or two of Mg or Zn; O represents oxygen; Eu 2+ and Mn 2+ is a dopant ion. The a, b, x, y, z are the respective mole fractions, wherein 1.5<x<3, 0.5<y<2, 0≤z<1, 0.001<a<0.2, 0≤b<0.4, wherein z and b are not both zero. Preferably, in the chemical expression, x+y+a+b=3.
z为0时，表示所述荧光粉中不含B元素。b为0时，表示所述荧光粉中不掺杂Mn2+。When z is 0, it means that the phosphor does not contain B element. When b is 0, it means that the phosphor is not doped with Mn 2+ .
所述的M优选为Ba和Sr任意比例的混合，更优选Ba与Sr以摩尔比1∶0.6～1∶1.4的混合。Said M is preferably a mixture of Ba and Sr in any proportion, more preferably a mixture of Ba and Sr in a molar ratio of 1:0.6˜1:1.4.
所述的N优选为Mg。Said N is preferably Mg.
进一步，本发明优选白光LED用单基质白光荧光粉，所述的M为Ba和Sr的组合；所述的N为Mg；所述的a，b，x，y，z为各自的摩尔分数，其中1.8＜x＜2.5，0.6＜y＜1.5，0.01＜z＜0.2，0.005＜a＜0.08，0.001＜b＜0.2。Further, the present invention preferably uses single-matrix white light phosphors for white light LEDs, said M is a combination of Ba and Sr; said N is Mg; said a, b, x, y, and z are respective mole fractions, Wherein 1.8<x<2.5, 0.6<y<1.5, 0.01<z<0.2, 0.005<a<0.08, 0.001<b<0.2.
本发明还提供了所述白光LED用单基质白光荧光粉的制备方法，所述方法为下列之一：The present invention also provides a preparation method of the single-matrix white light phosphor for white light LED, and the method is one of the following:
(A)0＜z＜1，即荧光粉中含有B元素时，所述制备方法为：(A) 0<z<1, that is, when the fluorescent powder contains B element, the preparation method is:
(1)以各自含M、N、Eu或Mn的化合物，含B的化合物，和含P的化合物为原料，按照所述白荧光粉化学表达式中各元素的摩尔比例称取相应的所述原料，直接以固体粉末或加入少量乙醇或丙酮润湿，混和均匀得混合物；所述的含M、N、Eu或Mn的化合物为含M、N、Eu或Mn各自对应的氧化物、氢氧化物、碳酸盐、硝酸盐、磷酸盐、硼酸盐或有机酸盐；所述的含B的化合物为含硼的氧化物、硼酸或硼酸盐；所述的含P的化合物为含磷的氧化物、磷酸或磷酸盐。(1) Using the compounds containing M, N, Eu or Mn, the compounds containing B, and the compounds containing P as raw materials, weigh the corresponding molar ratio of each element in the chemical expression of the white phosphor powder. The raw material is directly wetted with solid powder or added a small amount of ethanol or acetone, and mixed uniformly to obtain a mixture; the compound containing M, N, Eu or Mn is the corresponding oxide, hydroxide substances, carbonates, nitrates, phosphates, borates or organic acid salts; the B-containing compounds are boron-containing oxides, boric acid or borates; the P-containing compounds are phosphorus-containing oxides, phosphoric acid or phosphates.
(2)将步骤(1)得到的混合物在空气或还原性气氛中于600～1500℃焙烧1～5次(优选1～2次)，得最终焙烧产物，每次焙烧时间为1～25h；每两次焙烧之间冷却到室温进行研磨处理，最后一次焙烧在还原性气氛下进行；所述的还原性气氛为含5-10v％氢气的氮气混合气，含5-10v％一氧化碳的氮气混合气，或活性炭在高温下和空气中的氧气反应产生的一氧化碳气氛。(2) Calcining the mixture obtained in step (1) in air or a reducing atmosphere at 600-1500°C for 1-5 times (preferably 1-2 times) to obtain the final calcined product, and the calcining time for each time is 1-25 hours; Cool to room temperature between every two roastings for grinding treatment, and the last roasting is carried out under a reducing atmosphere; the reducing atmosphere is a nitrogen mixture containing 5-10v% hydrogen, and a nitrogen mixture containing 5-10v% carbon monoxide Gas, or a carbon monoxide atmosphere produced by the reaction of activated carbon with oxygen in the air at high temperature.
(3)将步骤(2)得到的最终焙烧产物经过破碎、磨细、粒径分级，并经洗涤除杂、烘干制得所述白光LED用单一基质白光荧光粉；(B)z＝0，即荧光粉中不含B元素时，所述制备方法为：(3) The final calcined product obtained in step (2) is crushed, ground, classified in particle size, washed to remove impurities, and dried to obtain the single-matrix white light phosphor for white light LED; (B) z=0 , that is, when the fluorescent powder does not contain B element, the preparation method is:
(1)以各自含M、N、Eu或Mn的化合物，和含P的化合物为原料，按照所述白荧光粉化学表达式中各元素的摩尔比例称取相应的所述原料，在反应助熔剂的存在下，直接以固体粉末或加入少量乙醇或丙酮润湿，混和均匀得混合物；所述的反应助熔剂为含M的卤化物或含N的卤化物中的至少一种；所述反应助熔剂的用量为所述荧光粉原料的总重量的0.001～5wt％；所述的含M、N、Eu或Mn的化合物为含M、N、Eu或Mn各自对应的氧化物、氢氧化物、碳酸盐、硝酸盐、磷酸盐、硼酸盐或有机酸盐；所述的含P的化合物为含磷的氧化物、磷酸或磷酸盐。(1) With the compounds containing M, N, Eu or Mn respectively, and the compounds containing P as raw materials, the corresponding raw materials are weighed according to the molar ratio of each element in the chemical expression of the white fluorescent powder, and the reaction aids In the presence of a flux, wet directly with solid powder or add a small amount of ethanol or acetone, and mix uniformly to obtain a mixture; the reaction flux is at least one of M-containing halides or N-containing halides; the reaction The amount of fluxing agent is 0.001-5wt% of the total weight of the phosphor raw material; the compound containing M, N, Eu or Mn is the corresponding oxide or hydroxide containing M, N, Eu or Mn , carbonate, nitrate, phosphate, borate or organic acid salt; the compound containing P is phosphorus oxide, phosphoric acid or phosphate.
(2)将步骤(1)得到的混合物在空气或还原性气氛中于600～1500℃焙烧1～5次(优选1～2次)，得最终焙烧产物，每次焙烧时间为1～25h；每两次焙烧之间冷却到室温进行研磨处理，最后一次焙烧在还原性气氛下进行；所述的还原性气氛为含5-10v％氢气的氮气混合气，含5-10v％一氧化碳的氮气混合气，或活性炭在高温下和空气中的氧气反应产生的一氧化碳气氛。(2) Calcining the mixture obtained in step (1) in air or a reducing atmosphere at 600-1500°C for 1-5 times (preferably 1-2 times) to obtain the final calcined product, and the calcining time for each time is 1-25 hours; Cool to room temperature between every two roastings for grinding treatment, and the last roasting is carried out under a reducing atmosphere; the reducing atmosphere is a nitrogen mixture containing 5-10v% hydrogen, and a nitrogen mixture containing 5-10v% carbon monoxide Gas, or a carbon monoxide atmosphere produced by the reaction of activated carbon with oxygen in the air at high temperature.
(3)将步骤(2)得到的最终焙烧产物经过破碎、磨细、粒径分级，并经洗涤除杂、烘干制得所述白光LED用单一基质白光荧光粉。(3) The final calcined product obtained in step (2) is crushed, ground, classified in particle size, washed to remove impurities, and dried to obtain the single-matrix white light phosphor for white light LEDs.
本发明所述研磨可在玛瑙研钵或球磨机中进行。所述研磨可以加入少量乙醇或丙酮润湿，起到均匀介质的作用，通常加入量使固体原料成糊状即可，这是本领域技术人员公知的。The grinding of the present invention can be carried out in an agate mortar or a ball mill. A small amount of ethanol or acetone can be added to the grinding to act as a uniform medium for wetting. Usually, the amount added is enough to make the solid raw material into a paste, which is well known to those skilled in the art.
其中步骤(3)所述的分级所用的方法选自沉降法、筛分法或气流法中的一种或几种。这是本领域技术人员公知的粒径分级方法。Wherein the method used for the classification described in step (3) is selected from one or more of sedimentation method, sieving method or air flow method. This is a particle size fractionation method well known to those skilled in the art.
步骤(3)中，所述最终焙烧产物经破碎、磨细、粒径分级，是采用手工破碎后再以球磨方式使烧结体的颗粒尺寸磨细，经沉降法、筛分法或气流法分级，取粒度为3～10微米的固体粉末。In step (3), the final calcined product is crushed, ground, and particle size classified, and the particle size of the sintered body is ground by ball milling after manual crushing, and then classified by sedimentation method, sieving method or air flow method , take solid powder with a particle size of 3-10 microns.
本发明方法中，所述洗涤除杂、烘干可使用酸、碱、醇或水中的一种或两种以上依次进行洗涤，再取固相于100～115℃烘干。In the method of the present invention, one or more of acid, alkali, alcohol or water can be used for the washing, removing impurities and drying in sequence, and then the solid phase is dried at 100-115°C.
本发明所述的白光LED用单基质白光荧光粉的制备方法，所述的原料中含M的化合物优选为碳酸钡和碳酸锶、含N的化合物优选为氧化镁(MgO)、含Eu的化合物优选为三氧化二铕、含Mn的化合物优选为碳酸锰。优选所述的含B的化合物为硼酸。优选所述的含P的化合物为磷酸氢二铵。In the preparation method of the single-matrix white phosphor powder for white LED according to the present invention, the compound containing M in the raw material is preferably barium carbonate and strontium carbonate, the compound containing N is preferably magnesium oxide (MgO), and the compound containing Eu Europium trioxide is preferred, and the Mn-containing compound is preferably manganese carbonate. Preferably, the B-containing compound is boric acid. Preferably, the compound containing P is diammonium hydrogen phosphate.
所述方法(A)中，在原料中有含B的化合物时，研磨时没有加入反应助熔剂，这是因为含B的化合物可以起到助熔剂的作用，并且B和Mn的存在能有效提高荧光粉的显色指数。In the method (A), when there is a compound containing B in the raw material, no reaction flux is added during grinding, because the compound containing B can act as a flux, and the presence of B and Mn can effectively improve The color rendering index of the phosphor.
所述方法(B)中，由于原料中没有含B的化合物，研磨时需要加入少量的反应助熔剂。所述方法(B)中，所述反应助熔剂为含M的卤化物或含N的卤化物中的至少一种，其中含有的M或N元素的摩尔数并不计入荧光粉表达式中，因为反应助熔剂会在之后的洗涤除杂中经酸洗或碱洗除去。In the method (B), since there is no compound containing B in the raw material, a small amount of reaction flux needs to be added during grinding. In the method (B), the reaction flux is at least one of M-containing halides or N-containing halides, and the moles of M or N elements contained therein are not included in the phosphor expression , because the reaction flux will be removed by acid washing or alkali washing in the subsequent washing and impurity removal.
本发明的有益效果是：采用本发明的方法制备的荧光粉的化学组成决定了其激发光谱非常宽，在250～430nm范围内具有强的吸收，适合于紫外光LED芯片激发。本发明荧光粉的发射光谱覆盖了从390nm到750nm的整个可见光区，是一种具有高显色指数、非常适合于白光LED的新型荧光粉。同时该荧光粉具有性能稳定，发光效率高等优点。并且制备方法工艺简单、易于操作、无污染、成本低。The beneficial effects of the invention are: the chemical composition of the fluorescent powder prepared by the method of the invention determines that its excitation spectrum is very broad, and has strong absorption in the range of 250-430nm, which is suitable for excitation of ultraviolet LED chips. The emission spectrum of the fluorescent powder of the invention covers the entire visible light region from 390nm to 750nm, and is a new type of fluorescent powder with high color rendering index, which is very suitable for white LEDs. At the same time, the phosphor has the advantages of stable performance and high luminous efficiency. Moreover, the preparation method has simple process, easy operation, no pollution and low cost.
(四)附图说明(4) Description of drawings
图1是实施例1制得的荧光粉的激发光谱和发射光谱，虚线部分是激发光谱，实线部分是发射光谱；横坐标代表波长(nm)，纵坐标代表相对强度(A.U.)。Fig. 1 is the excitation spectrum and emission spectrum of the fluorescent powder that embodiment 1 makes, and dotted line part is excitation spectrum, and solid line part is emission spectrum; Abscissa represents wavelength (nm), and ordinate represents relative intensity (A.U.).
(五)具体实施方式 (5) Specific implementation methods
下面结合具体实施例对本发明进行进一步描述，但本发明的保护范围并不仅限于此：The present invention is further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto:
实施例1：化学式为Ba0.87Sr1.09Mg0.9(PO4)1.94-(BO3)0.06:0.04Eu2+、0.10Mn2+荧光粉的制备。Example 1: Preparation of fluorescent powder with chemical formula Ba 0.87 Sr 1.09 Mg 0.9 (PO 4 ) 1.94 -(BO 3 ) 0.06 :0.04Eu 2+ , 0.10Mn 2+ .
制备方法如下：The preparation method is as follows:
分别称取0.8584g碳酸钡(BaCO3)、0.8046g碳酸锶(SrCO3)、0.1814g氧化镁(MgO)，1.2810g磷酸氢二铵[(NH4)2HPO4]、0.0185g硼酸(H3BO3)、0.0352g三氧化二铕(Eu2O3)、0.0575g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中，添加2mL丙酮进行研磨，研磨均匀以后得混合物，装入刚玉坩埚中，用高温炉先以800℃焙烧8小时，冷却至室温，取出研磨粉碎；然后以含5-10％氢气的氮气混合气为，在1100℃温度下烧结20小时，冷却至室温。第二次得到的烧结产品经破碎，用球磨磨细，筛分法得到粒度在3～10微米的固体粉末。接着依次用1M的氢氧化钠溶液(30ml)、去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 0.8584g barium carbonate (BaCO 3 ), 0.8046g strontium carbonate (SrCO 3 ), 0.1814g magnesium oxide (MgO), 1.2810g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0185g boric acid (H 3 BO 3 ), 0.0352g of europium trioxide (Eu 2 O 3 ), and 0.0575g of manganese carbonate (MnCO 3 ), all of which are analytically pure. Put the above raw material mixture in an agate mortar, add 2mL of acetone to grind, and grind the mixture evenly, put it into a corundum crucible, bake it in a high temperature furnace at 800°C for 8 hours, cool it to room temperature, take it out and grind it; The mixed gas of 5-10% hydrogen and nitrogen is sintered at 1100°C for 20 hours and cooled to room temperature. The sintered product obtained for the second time is crushed, finely ground by a ball mill, and sieved to obtain a solid powder with a particle size of 3-10 microns. Then wash twice with 1M sodium hydroxide solution (30ml), deionized water (30ml) and methanol (20ml) in sequence, and finally filter and separate the phosphor powder, and dry it in an oven at 110°C for 20 hours to obtain the phosphor powder product. The emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例2：化学式为Ba0.67Sr1.29Mg0.95(PO4)1.8-(BO3)0.2:0.04Eu2+，0.05Mn2+荧光粉的制备。Example 2: Preparation of phosphor powder with chemical formula Ba 0.67 Sr 1.29 Mg 0.95 (PO 4 ) 1.8 -(BO 3 ) 0.2 :0.04Eu 2+ , 0.05Mn 2+ .
制备方法如下：The preparation method is as follows:
分别称取0.6611g碳酸钡(BaCO3)、0.9522g碳酸锶(SrCO3)、0.1914g氧化镁(MgO)、1.1885g磷酸氢二铵[(NH4)2HPO4]、0.0618g硼酸(H3BO3)、0.0352g三氧化二铕(Eu2O3)、0.0287g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中，添加2mL乙醇进行研磨，研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧5小时，冷却至室温，取出研磨粉碎；然后以活性炭粉作为产生还原气氛的条件，在1200℃温度下烧结5小时，冷却至室温。第二次得到的烧结产品经破碎后，经球磨磨细，筛分法后得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh respectively 0.6611g barium carbonate (BaCO 3 ), 0.9522g strontium carbonate (SrCO 3 ), 0.1914g magnesium oxide (MgO), 1.1885g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0618g boric acid (H 3 BO 3 ), 0.0352g of europium trioxide (Eu 2 O 3 ), 0.0287g of manganese carbonate (MnCO 3 ), all of which are analytically pure. Put the above raw material mixture in an agate mortar, add 2mL of ethanol for grinding, after grinding evenly, put it into a corundum crucible, first roast it in a high temperature furnace at 800°C for 5 hours, cool to room temperature, take it out and grind it; then use activated carbon powder as The conditions for generating a reducing atmosphere are sintering at 1200°C for 5 hours and cooling to room temperature. After the sintered product obtained for the second time is crushed, it is ball milled and sieved to obtain phosphor powder with a particle size of 3-10 microns. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder product. The emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例3：化学式为Ba0.995SrMg0.99(PO4)1.94-(BO3)0.06:0.005Euw、0.01Mn2+荧光粉的制备。Example 3: Preparation of phosphor powder with chemical formula Ba 0.995 SrMg 0.99 (PO 4 ) 1.94 -(BO 3 ) 0.06 :0.005Euw, 0.01Mn 2+ .
制备方法如下：The preparation method is as follows:
分别称取0.9818g碳酸钡(BaCO3)、0.7382g碳酸锶(SrCO3)、0.1995g氧化镁(MgO)，1.2810g磷酸氢二铵[(NH4)2HPO4]、0.0185g硼酸(H3BO3)、0.0044g三氧化二铕(Eu2O3)、0.0057g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧4小时，冷却至室温，取出研磨粉碎；然后以含5-10v％一氧化碳的氮气混合气为还原气氛，在1200℃温度下烧结10小时，冷却至室温。第二次得到的烧结产品经破碎后，经球磨磨细，筛分法后得到粒度在3～10微米的荧光粉，依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh respectively 0.9818g barium carbonate (BaCO 3 ), 0.7382g strontium carbonate (SrCO 3 ), 0.1995g magnesium oxide (MgO), 1.2810g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0185g boric acid (H 3 BO 3 ), 0.0044g of europium trioxide (Eu 2 O 3 ), 0.0057g of manganese carbonate (MnCO 3 ), all of which are analytically pure. Grind the above-mentioned raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 4 hours, cool it to room temperature, take it out and grind it; then use a nitrogen mixture containing 5-10v% carbon monoxide In a reducing atmosphere, sinter at 1200°C for 10 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball mill, and sieved to obtain phosphor powder with a particle size of 3 to 10 microns, which is washed twice with deionized water (30ml) and methanol (20ml) successively, and finally The fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder product. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例4：化学式为Ba0.87Sr1.09Mg0.9(PO4)2:0.04Eu2+、0.10Mn2+荧光粉的制备。Example 4: Preparation of phosphor powder with chemical formula Ba 0.87 Sr 1.09 Mg 0.9 (PO 4 ) 2 :0.04Eu 2+ , 0.10Mn 2+ .
制备方法如下：The preparation method is as follows:
分别称取1.1893g乙酸钡((CH3COO)2Ba·H2O)、0.8046g碳酸锶(SrCO3)、0.1814g氧化镁(MgO)，1.3206g磷酸氢二铵[(NH4)2HPO4]、0.0359g氟化钡(BaF2)、0.0352g三氧化二铕(Eu2O3)、0.0575g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧8小时，冷却至室温，取出研磨粉碎；然后以含5-10％氢气的氮气混合气为还原气氛，在1100℃温度下烧结20小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，气流法得到粒度在3～10微米的荧光粉。接着依次用1M盐酸溶液(30ml)，去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在105℃的烘箱中烘干24小时即得到荧光粉产品。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 1.1893g barium acetate ((CH 3 COO) 2 Ba H 2 O), 0.8046g strontium carbonate (SrCO 3 ), 0.1814g magnesium oxide (MgO), 1.3206g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0359g barium fluoride (BaF 2 ), 0.0352g europium trioxide (Eu 2 O 3 ), 0.0575g manganese carbonate (MnCO 3 ), the above raw materials are all analytically pure. Grind the above-mentioned raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 8 hours, cool it to room temperature, take it out and grind it; then mix it with nitrogen containing 5-10% hydrogen In a reducing atmosphere, sinter at 1100°C for 20 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball milling, and phosphor powder with a particle size of 3-10 microns is obtained by airflow method. Then wash twice with 1M hydrochloric acid solution (30ml), deionized water (30ml) and methanol (20ml) respectively, and finally filter and separate the fluorescent powder, and dry it in an oven at 105°C for 24 hours to obtain the fluorescent powder product. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例5：化学式为Ba0.77Sr1.19Mg(PO4)1.9-(BO3)0.1:0.04Eu2+荧光粉的制备Example 5: Preparation of Phosphor Powder with Chemical Formula Ba 0.77 Sr 1.19 Mg(PO 4 ) 1.9 -(BO 3 ) 0.1 :0.04Eu 2+
制备方法如下：The preparation method is as follows:
分别称取0.7598g碳酸钡(BaCO3)、0.8784g碳酸锶(SrCO3)、0.2015g氧化镁(MgO)，1.2546g磷酸氢二铵[(NH4)2HPO4]、0.0309g硼酸(H3BO3)、0.0352g三氧化二铕(Eu2O3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧5小时，冷却至室温，取出研磨粉碎；然后以活性炭粉作为产生还原气氛的条件，在1400℃温度下烧结5小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，沉降法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 0.7598g barium carbonate (BaCO 3 ), 0.8784g strontium carbonate (SrCO 3 ), 0.2015g magnesium oxide (MgO), 1.2546g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0309g boric acid (H 3 BO 3 ), 0.0352g of europium trioxide (Eu 2 O 3 ), the above raw materials are all analytically pure. Grind the above raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 5 hours, cool it to room temperature, take it out and grind it; then use activated carbon powder as the condition for generating a reducing atmosphere. Sinter at 1400°C for 5 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by a ball mill, and the phosphor powder with a particle size of 3-10 microns is obtained by a sedimentation method. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder product. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例6：化学式为Ba0.85Sr1.1Mg0.88(PO4)1.94-(BO3)0.06:0.05Eu2+、0.12Mn2+荧光粉的制备Example 6: Preparation of Phosphor Powder with Chemical Formula Ba 0.85 Sr 1.1 Mg 0.88 (PO 4 ) 1.94 -(BO 3 ) 0.06 :0.05Eu 2+ , 0.12Mn 2+
制备方法如下：The preparation method is as follows:
分别称取0.8387g碳酸钡(BaCO3)、0.8120g碳酸锶(SrCO3)、0.1773g氧化镁(MgO)，1.2810g磷酸氢二铵[(NH4)2HPO4]、0.0185g硼酸(H3BO3)、0.0440g三氧化二铕(Eu2O3)、0.0690g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以900℃焙烧5小时，冷却至室温，取出研磨粉碎；然后以活性炭粉作为产生还原气氛的条件，在1200℃温度下烧结8小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，筛分法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 0.8387g barium carbonate (BaCO 3 ), 0.8120g strontium carbonate (SrCO 3 ), 0.1773g magnesium oxide (MgO), 1.2810g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0185g boric acid (H 3 BO 3 ), 0.0440g of europium trioxide (Eu 2 O 3 ), 0.0690g of manganese carbonate (MnCO 3 ), all of which are analytically pure. Grind the above raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 900°C for 5 hours, cool it to room temperature, take it out and grind it; then use activated carbon powder as the condition for generating a reducing atmosphere. Sinter at 1200°C for 8 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball milling, and sieved to obtain phosphor powder with a particle size of 3-10 microns. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder product. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例7：化学式为Ba0.86Ca1.05Mg0.9(PO4)1.8-(BO3)0.2:0.04Eu2+、0.15Mn2+荧光粉的制备制备方法如下：Example 7: The chemical formula is Ba 0.86 Ca 1.05 Mg 0.9 (PO 4 ) 1.8 -(BO 3 ) 0.2 : The preparation method of phosphor powder of 0.04Eu 2+ and 0.15Mn 2+ is as follows:
分别称取0.8486g碳酸钡(BaCO3)、0.5255g碳酸钙(CaCO3)、0.1814g氧化镁(MgO)，1.1885g磷酸氢二铵[(NH4)2HPO4]、0.0618g硼酸(H3BO3)、0.0352g三氧化二铕(Eu2O3)、0.0862g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以700℃焙烧10小时，冷却至室温，取出研磨粉碎；然后以活性炭粉作为产生还原气氛的条件，在1100℃温度下烧结25小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，筛分法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh respectively 0.8486g barium carbonate (BaCO 3 ), 0.5255g calcium carbonate (CaCO 3 ), 0.1814g magnesium oxide (MgO), 1.1885g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0618g boric acid (H 3 BO 3 ), 0.0352g of europium trioxide (Eu 2 O 3 ), and 0.0862g of manganese carbonate (MnCO 3 ), all of which are analytically pure. Grind the above raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 700°C for 10 hours, cool it to room temperature, take it out and grind it; then use activated carbon powder as the condition for generating a reducing atmosphere. Sinter at 1100°C for 25 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball milling, and sieved to obtain phosphor powder with a particle size of 3-10 microns. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder product. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例8：化学式为Ca0.7Sr1.2Mg0.82(PO4)1.8-(BO3)0.2:0.08Eu2+、0.2Mn2+荧光粉的制备制备方法如下：Example 8: The chemical formula is Ca 0.7 Sr 1.2 Mg 0.82 (PO 4 ) 1.8 -(BO 3 ) 0.2 : 0.08Eu 2+ , 0.2Mn 2+ phosphor preparation The preparation method is as follows:
分别称取0.3503g碳酸钙(CaCO3)、0.8858g碳酸锶(SrCO3)、0.1652g氧化镁(MgO)，1.1885g磷酸氢二铵[(NH4)2HPO4]、0.0618g硼酸(H3BO3)、0.0704g三氧化二铕(Eu2O3)、0.1150g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧5小时，冷却至室温，取出研磨粉碎；然后以活性炭粉作为产生还原气氛的条件，在1200℃温度下烧结5小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，沉降法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh respectively 0.3503g calcium carbonate (CaCO 3 ), 0.8858g strontium carbonate (SrCO 3 ), 0.1652g magnesium oxide (MgO), 1.1885g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0618g boric acid (H 3 BO 3 ), 0.0704g of europium trioxide (Eu 2 O 3 ), and 0.1150g of manganese carbonate (MnCO 3 ), all of which are analytically pure. Grind the above raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 5 hours, cool it to room temperature, take it out and grind it; then use activated carbon powder as the condition for generating a reducing atmosphere. Sinter at 1200°C for 5 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by a ball mill, and the phosphor powder with a particle size of 3-10 microns is obtained by a sedimentation method. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder product. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例9：化学式为Ba0.85Sr1.1Zn0.88(PO4)1.9-(BO3)0.1:0.05Eu2+、0.12Mn2+荧光粉的制备。Example 9: Preparation of phosphor powder with chemical formula Ba 0.85 Sr 1.1 Zn 0.88 (PO 4 ) 1.9 -(BO 3 ) 0.1 :0.05Eu 2+ , 0.12Mn 2+ .
分别称取0.8387g碳酸钡(BaCO3)、0.8120g碳酸锶(SrCO3)、0.3581g氧化锌(ZnO)，1.2546g磷酸氢二铵[(NH4)2HPO4]、0.0309g硼酸(H3BO3)、0.0440g三氧化二铕(Eu2O3)、0.0690g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧5小时，冷却至室温，取出研磨粉碎；然后以活性炭粉作为产生还原气氛的条件，在1200℃温度下烧结5小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，气流法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh respectively 0.8387g barium carbonate (BaCO 3 ), 0.8120g strontium carbonate (SrCO 3 ), 0.3581g zinc oxide (ZnO), 1.2546g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0309g boric acid (H 3 BO 3 ), 0.0440g of europium trioxide (Eu 2 O 3 ), 0.0690g of manganese carbonate (MnCO 3 ), all of which are analytically pure. Grind the above raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 5 hours, cool it to room temperature, take it out and grind it; then use activated carbon powder as the condition for generating a reducing atmosphere. Sinter at 1200°C for 5 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball milling, and phosphor powder with a particle size of 3-10 microns is obtained by airflow method. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder product. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例10：化学式为Ba1.3Ca0.62Zn0.92(PO4)1.95-(BO3)0.05:0.04Eu2+、0.12Mn2+荧光粉的制备制备方法如下：Example 10: The chemical formula is Ba 1.3 Ca 0.62 Zn 0.92 (PO 4 ) 1.95 -(BO 3 ) 0.05 :0.04Eu 2+ , 0.12Mn 2+ The preparation method of the phosphor is as follows:
分别称取1.2827g碳酸钡(BaCO3)、0.3103g碳酸钙(CaCO3)、0.3743g氧化锌(ZnO)，1.2876g磷酸氢二铵[(NH4)2HPO4]、0.0155g硼酸(H3BO3)、0.0352g三氧化二铕(Eu2O3)、0.0690g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧5小时，冷却至室温，取出研磨粉碎；然后以活性炭粉作为产生还原气氛的条件，在1200℃温度下烧结10小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，筛分法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 1.2827g barium carbonate (BaCO 3 ), 0.3103g calcium carbonate (CaCO 3 ), 0.3743g zinc oxide (ZnO), 1.2876g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0155g boric acid (H 3 BO 3 ), 0.0352g of europium trioxide (Eu 2 O 3 ), and 0.0690g of manganese carbonate (MnCO 3 ), all of which are analytically pure. Grind the above raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 5 hours, cool it to room temperature, take it out and grind it; then use activated carbon powder as the condition for generating a reducing atmosphere. Sinter at 1200°C for 10 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball milling, and sieved to obtain phosphor powder with a particle size of 3-10 microns. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例11：化学式为Ba0.88Sr0.62Ca0.45Mg0.91(PO4)1.85-(BO3)0.15:0.04Eu2+、0.10Mn2+荧光粉的制备制备方法如下：Example 11: The chemical formula is Ba 0.88 Sr 0.62 Ca 0.45 Mg 0.91 (PO 4 ) 1.85 -(BO 3 ) 0.15 :0.04Eu 2+ , 0.10Mn 2+ phosphor. The preparation method is as follows:
分别称取0.8683g碳酸钡(BaCO3)、0.4577g碳酸锶(SrCO3)、0.2882g草酸钙(CaC2O4)、0.1834g氧化镁(MgO)，1.2216g磷酸氢二铵[(NH4)2HPO4]、0.0464g硼酸(H3BO3)、0.0352g三氧化二铕(Eu2O3)、0.0575g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧5小时，冷却至室温，取出研磨粉碎；然后以活性炭粉作为产生还原气氛的条件，在1300℃温度下烧结5小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，筛分法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 0.8683g barium carbonate (BaCO 3 ), 0.4577g strontium carbonate (SrCO 3 ), 0.2882g calcium oxalate (CaC 2 O 4 ), 0.1834g magnesium oxide (MgO), 1.2216g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0464g boric acid (H 3 BO 3 ), 0.0352g europium trioxide (Eu 2 O 3 ), 0.0575g manganese carbonate (MnCO 3 ), the above raw materials are all analytically pure. Grind the above raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 5 hours, cool it to room temperature, take it out and grind it; then use activated carbon powder as the condition for generating a reducing atmosphere. Sinter at 1300°C for 5 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball milling, and sieved to obtain phosphor powder with a particle size of 3-10 microns. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例12：化学式为Ba0.72Sr1.2Mg0.4Zn0.5(PO4)1.94-(BO3)0.06:0.08Eu2+、0.10Mn2+荧光粉的制备制备方法如下：Example 12: The chemical formula is Ba 0.72 Sr 1.2 Mg 0.4 Zn 0.5 (PO 4 ) 1.94 -(BO 3 ) 0.06 :0.08Eu 2+ , 0.10Mn 2+ phosphor. The preparation method is as follows:
分别称取0.7104g碳酸钡(BaCO3)、0.8858g碳酸锶(SrCO3)、0.0806g氧化镁(MgO)，0.2035g氧化锌(ZnO)、1.2810g磷酸氢二铵[(NH4)2HPO4]、0.0185g硼酸(H3BO3)、0.0704g三氧化二铕(Eu2O3)、0.0575g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧5小时，冷却至室温，取出研磨粉碎；然后以活性炭粉作为产生还原气氛的条件，在1200℃温度下烧结5小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，筛分法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 0.7104g barium carbonate (BaCO 3 ), 0.8858g strontium carbonate (SrCO 3 ), 0.0806g magnesium oxide (MgO), 0.2035g zinc oxide (ZnO), 1.2810g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0185g boric acid (H 3 BO 3 ), 0.0704g europium trioxide (Eu 2 O 3 ), 0.0575g manganese carbonate (MnCO 3 ), the above raw materials are analytically pure. Grind the above raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 5 hours, cool it to room temperature, take it out and grind it; then use activated carbon powder as the condition for generating a reducing atmosphere. Sinter at 1200°C for 5 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball milling, and sieved to obtain phosphor powder with a particle size of 3-10 microns. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例13：化学式为Ba0.87Sr1.09Mg0.9(PO4)1.94-(BO3)0.06:0.04Eu2+、0.10Mn2+荧光粉的制备。Example 13: Preparation of phosphors with chemical formula Ba 0.87 Sr 1.09 Mg 0.9 (PO 4 ) 1.94 -(BO 3 ) 0.06 :0.04Eu 2+ , 0.10Mn 2+ .
制备方法如下：The preparation method is as follows:
分别称取0.8584g碳酸钡(BaCO3)、0.8046g草酸锶(SrC2O4)、0.1814g氧化镁(MgO)，1.2810g磷酸氢二铵[(NH4)2HPO4]、0.0185g硼酸(H3BO3)、0.0352g三氧化二铕(Eu2O3)、0.0575g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧8小时，冷却至室温，取出研磨粉碎；然后以含5-10％氢气的氮气混合气为还原气氛，在1100℃温度下烧结20小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，筛分法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 0.8584g barium carbonate (BaCO 3 ), 0.8046g strontium oxalate (SrC 2 O 4 ), 0.1814g magnesium oxide (MgO), 1.2810g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0185g boric acid (H 3 BO 3 ), 0.0352g of europium trioxide (Eu 2 O 3 ), 0.0575g of manganese carbonate (MnCO 3 ), the above raw materials are all analytically pure. Grind the above-mentioned raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 8 hours, cool it to room temperature, take it out and grind it; then mix it with nitrogen containing 5-10% hydrogen In a reducing atmosphere, sinter at 1100°C for 20 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball milling, and sieved to obtain phosphor powder with a particle size of 3-10 microns. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例14：化学式为Ba0.975r0.99Mg0.9(PO4)1.94-(BO3)0.06:0.04Eu2+、0.10Mn2+荧光粉的制备。Example 14: Preparation of phosphors with chemical formula Ba 0.97 5r 0.99 Mg 0.9 (PO 4 ) 1.94 -(BO 3 ) 0.06 :0.04Eu 2+ , 0.10Mn 2+ .
制备方法如下：The preparation method is as follows:
分别称取0.9571g碳酸钡(BaCO3)、0.7308g碳酸锶(SrCO3)、1.1542g硝酸镁(MgN2O6.6H2O)，1.2810g磷酸氢二铵[(NH4)2HPO4]、0.0185g硼酸(H3BO3)、0.0352g三氧化二铕(Eu2O3)、0.0575g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧8小时，冷却至室温，取出研磨粉碎；然后以含5-10v％氢气的氮气混合气为还原气氛，在1050℃温度下烧结24小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，沉降法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在105℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 0.9571g barium carbonate (BaCO 3 ), 0.7308g strontium carbonate (SrCO 3 ), 1.1542g magnesium nitrate (MgN 2 O 6 .6H 2 O), 1.2810g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0185g boric acid (H 3 BO 3 ), 0.0352g europium trioxide (Eu 2 O 3 ), 0.0575g manganese carbonate (MnCO 3 ), the above raw materials are all analytically pure. Grind the above-mentioned raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 8 hours, cool it to room temperature, take it out and grind it; then use a nitrogen mixture containing 5-10v% hydrogen In a reducing atmosphere, sinter at 1050°C for 24 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by a ball mill, and the phosphor powder with a particle size of 3-10 microns is obtained by a sedimentation method. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 105° C. for 20 hours to obtain the fluorescent powder product. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例15：化学式为Ba0.98Sr0.98Mg0.9(PO4)1.94-(BO3)0.06:0.04Eu2+、0.10Mn2+荧光粉的制备。Example 15: Preparation of phosphor powder with chemical formula Ba 0.98 Sr 0.98 Mg 0.9 (PO 4 ) 1.94 -(BO 3 ) 0.06 :0.04Eu 2+ , 0.10Mn 2+ .
制备方法如下：The preparation method is as follows:
分别称取0.9669g碳酸钡(BaCO3)、0.5078g氧化锶(SrO)、0.1814g氧化镁(MgO)，1.2810g磷酸氢二铵[(NH4)2HPO4]、0.0185g硼酸(H3BO3)、0.0352g三氧化二铕(Eu2O3)、0.0575g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧8小时，冷却至室温，取出研磨粉碎；然后以含5-10％氢气的氮气混合气为还原气氛，在1300℃温度下烧结20小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，气流法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在115℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 0.9669g barium carbonate (BaCO 3 ), 0.5078g strontium oxide (SrO), 0.1814g magnesium oxide (MgO), 1.2810g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0185g boric acid (H 3 BO 3 ), 0.0352g of europium trioxide (Eu 2 O 3 ), and 0.0575g of manganese carbonate (MnCO 3 ), all of which are analytically pure. Grind the above-mentioned raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 8 hours, cool it to room temperature, take it out and grind it; then mix it with nitrogen containing 5-10% hydrogen In a reducing atmosphere, sinter at 1300°C for 20 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball milling, and phosphor powder with a particle size of 3-10 microns is obtained by airflow method. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 115° C. for 20 hours to obtain the fluorescent powder product. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例16：化学式为Ba0.87Sr1.09Mg0.9(PO4)1.9-(BO3)0.1:0.04Eu2+、0.10Mn2+荧光粉的制备。Example 16: Preparation of phosphor powder with chemical formula Ba 0.87 Sr 1.09 Mg 0.9 (PO 4 ) 1.9 -(BO 3 ) 0.1 :0.04Eu 2+ , 0.10Mn 2+ .
制备方法如下：The preparation method is as follows:
分别称取0.8584g碳酸钡(BaCO3)、0.8046g碳酸锶(SrCO3)、0.2625g氢氧化镁(Mg(OH)2)，1.2546g磷酸氢二铵[(NH4)2HPO4]、0.0309g硼酸(H3BO3)、0.0352g三氧化二铕(Eu2O3)、0.0575g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧8小时，冷却至室温，取出研磨粉碎；然后以含5-10％氢气的氮气混合气为还原气氛，在1050℃温度下烧结20小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，筛分法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在115℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 0.8584g of barium carbonate (BaCO 3 ), 0.8046g of strontium carbonate (SrCO 3 ), 0.2625g of magnesium hydroxide (Mg(OH) 2 ), 1.2546g of diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0309g of boric acid (H 3 BO 3 ), 0.0352g of europium trioxide (Eu 2 O 3 ), and 0.0575g of manganese carbonate (MnCO 3 ), all of which are analytically pure. Grind the above-mentioned raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 8 hours, cool it to room temperature, take it out and grind it; then mix it with nitrogen containing 5-10% hydrogen In a reducing atmosphere, sinter at 1050°C for 20 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball milling, and sieved to obtain phosphor powder with a particle size of 3-10 microns. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 115° C. for 20 hours to obtain the fluorescent powder product. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例17：化学式为Ba0.87Sr1.09Mg0.4Zn0.5(PO4)1.9-(BO3)0.1:0.04Eu2+、0.10Mn2+荧光粉的制备。Example 17: Preparation of phosphor powder with chemical formula Ba 0.87 Sr 1.09 Mg 0.4 Zn 0.5 (PO 4 ) 1.9 -(BO 3 ) 0.1 :0.04Eu 2+ , 0.10Mn 2+ .
制备方法如下：The preparation method is as follows:
分别称取0.6670g氧化钡(BaO)、0.8046g碳酸锶(SrCO3)、0.0806g氧化镁(MgO)，0.2035g氧化锌(ZnO)，1.2546g磷酸氢二铵[(NH4)2HPO4]、0.0309g硼酸(H3BO3)、0.0575g碳酸锰(MnCO3)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧8小时，冷却至室温，取出研磨粉碎；然后以含5-10％氢气的氮气混合气为还原气氛，在1100℃温度下烧结20小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，筛分法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 0.6670g barium oxide (BaO), 0.8046g strontium carbonate (SrCO 3 ), 0.0806g magnesium oxide (MgO), 0.2035g zinc oxide (ZnO), 1.2546g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0309g boric acid (H 3 BO 3 ), 0.0575g manganese carbonate (MnCO 3 ), the above raw materials are all analytically pure. Grind the above-mentioned raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 8 hours, cool it to room temperature, take it out and grind it; then mix it with nitrogen containing 5-10% hydrogen In a reducing atmosphere, sinter at 1100°C for 20 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball milling, and sieved to obtain phosphor powder with a particle size of 3-10 microns. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder product. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
实施例18：化学式为Ba0.87Sr1.09Mg0.9(PO4)1.94-(BO3)0.06:0.04Eu2+、0.10Mn2+荧光粉的制备。Example 18: Preparation of phosphor powder with chemical formula Ba 0.87 Sr 1.09 Mg 0.9 (PO 4 ) 1.94 -(BO 3 ) 0.06 :0.04Eu 2+ , 0.10Mn 2+ .
制备方法如下：The preparation method is as follows:
分别称取0.8584g碳酸钡(BaCO3)、0.8046g碳酸锶(SrCO3)、0.1814g氧化镁(MgO)，1.2810g磷酸氢二铵[(NH4)2HPO4]、0.0185g硼酸(H3BO3)、0.0352g三氧化二铕(Eu2O3)、0.0435g二氧化锰(MnO2)，以上原料均为分析纯。将上述原料混合物在玛瑙研钵中研磨均匀以后，装入刚玉坩埚中，用高温炉先以800℃焙烧8小时，冷却至室温，取出研磨粉碎；然后以含5-10％氢气的氮气混合气为还原气氛，在1100℃温度下烧结20小时，冷却至室温。第二次得到的烧结产品经破碎，经球磨磨细，筛分法得到粒度在3～10微米的荧光粉。接着依次用去离子水(30ml)和甲醇(20ml)各洗涤两次，最后过滤分离出荧光粉，在110℃的烘箱中烘干20小时即得到荧光粉产品。该荧光粉的主发射峰在390nm到750nm之间，是覆盖了整个可见光范围的白光。该荧光粉可被从250nm到430nm的紫外光激发，适合于紫外光LED芯片激发的白光LED应用的新型荧光粉。Weigh 0.8584g barium carbonate (BaCO 3 ), 0.8046g strontium carbonate (SrCO 3 ), 0.1814g magnesium oxide (MgO), 1.2810g diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], 0.0185g boric acid (H 3 BO 3 ), 0.0352g of europium trioxide (Eu 2 O 3 ), and 0.0435g of manganese dioxide (MnO 2 ), all of which are analytically pure. Grind the above-mentioned raw material mixture evenly in an agate mortar, put it into a corundum crucible, bake it in a high-temperature furnace at 800°C for 8 hours, cool it to room temperature, take it out and grind it; then mix it with nitrogen containing 5-10% hydrogen In a reducing atmosphere, sinter at 1100°C for 20 hours and cool to room temperature. The sintered product obtained for the second time is crushed, finely ground by ball milling, and sieved to obtain phosphor powder with a particle size of 3-10 microns. Then it was washed twice with deionized water (30ml) and methanol (20ml) respectively, and finally the fluorescent powder was separated by filtration, and dried in an oven at 110° C. for 20 hours to obtain the fluorescent powder product. The main emission peak of the phosphor is between 390nm and 750nm, which is white light covering the entire visible light range. The phosphor can be excited by ultraviolet light from 250nm to 430nm, and is a new phosphor suitable for the application of white light LEDs excited by ultraviolet LED chips.
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