CN105778913B - A kind of list matrix three adulterates white light phosphor and preparation method and application - Google Patents
A kind of list matrix three adulterates white light phosphor and preparation method and application Download PDFInfo
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- 239000011159 matrix material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 52
- 229910004283 SiO 4 Inorganic materials 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 26
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 60
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 43
- 230000004907 flux Effects 0.000 claims description 25
- 239000004570 mortar (masonry) Substances 0.000 claims description 20
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 18
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- 229910001940 europium oxide Inorganic materials 0.000 claims description 17
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 2
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 2
- 230000005284 excitation Effects 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- -1 rare earth ions Chemical class 0.000 abstract description 5
- 229910052693 Europium Inorganic materials 0.000 abstract description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052771 Terbium Inorganic materials 0.000 abstract description 3
- 239000003086 colorant Substances 0.000 abstract description 3
- 239000002019 doping agent Substances 0.000 abstract description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 abstract description 3
- 241001085205 Prenanthella exigua Species 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 18
- HEQHIXXLFUMNDC-UHFFFAOYSA-N O.O.O.O.O.O.O.[Tb].[Tb].[Tb].[Tb] Chemical compound O.O.O.O.O.O.O.[Tb].[Tb].[Tb].[Tb] HEQHIXXLFUMNDC-UHFFFAOYSA-N 0.000 description 16
- 238000005245 sintering Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000000695 excitation spectrum Methods 0.000 description 9
- 230000009102 absorption Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009877 rendering Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000002354 daily effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7792—Aluminates
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/85—Packages
- H10H20/851—Wavelength conversion means
- H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
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Abstract
本发明公开了一种单基质三掺杂白色荧光材料及其制备方法与应用。化学组成表达式为：LiY1‑x‑y‑zCexTbyEuzSiO4，式中x，y，z分别为掺杂离子Ce3+，Tb3+，Eu3+相对基质稀土离子Y3+占的摩尔百分含量，取值范围：x=0.01，0.03≤y≤0.05，0≤z≤0.09。本发明上述白色荧光材料的基质材料为硅酸盐LiYSiO4，发光中心分别为三价稀土离子铈Ce3+，铽Tb3+，铕Eu3+。在近紫外光激发下，三价稀土离子Ce3+在该基质中发蓝光，Tb3+产生绿光，而Eu3+发射红光，将三种光色进行混合，即可得到明亮的白光。由于该发光材料中存在Ce3+，因此在近紫外有很强的吸收，在自身发射蓝光的同时能通过能量传递的方式敏化Tb3+及Eu3+,使其高效地产生荧光发射。通过对相关组分的调节，可以得到发光效率优异的白光荧光粉，可以很好的用作白光LED荧光粉。
The invention discloses a single-matrix triple-doped white fluorescent material as well as a preparation method and application thereof. The chemical composition expression is: LiY 1‑x‑y‑z Ce x Tb y Eu z SiO 4 , where x, y, z are dopant ions Ce 3+ , Tb 3+ , Eu 3+ relative matrix rare earth ions The molar percentage of Y 3+ , the value range: x=0.01, 0.03≤y≤0.05, 0≤z≤0.09. The matrix material of the above-mentioned white fluorescent material of the present invention is silicate LiYSiO 4 , and the light emitting centers are trivalent rare earth ions Ce 3+ , Tb 3+ terbium and Eu 3+ europium respectively. Under the excitation of near-ultraviolet light, the trivalent rare earth ion Ce 3+ emits blue light in the matrix, Tb 3+ emits green light, and Eu 3+ emits red light. By mixing the three light colors, a bright white light can be obtained . Due to the presence of Ce 3+ in the luminescent material, it has strong absorption in the near ultraviolet, and can sensitize Tb 3+ and Eu 3+ through energy transfer while emitting blue light itself, so that it can efficiently generate fluorescence emission. By adjusting related components, a white light phosphor with excellent luminous efficiency can be obtained, which can be well used as a white light LED phosphor.
Description
技术领域technical field
本发明属于LED的光转换材料技术领域。更具体地，涉及一种单基质三掺杂白色荧光材料及其制备方法与应用。The invention belongs to the technical field of light conversion materials for LEDs. More specifically, it relates to a single-matrix triple-doped white fluorescent material and its preparation method and application.
背景技术Background technique
白光发光二极管（LED）具有长寿命、高效率、低能耗和环境友好等优点，迅速在照明显示等领域获得了广泛应用，并被誉为下一代固体照明光源。目前实现白光LED的主流方案是将半导体芯片和荧光粉组合成荧光粉转换型白光LED。因此，荧光粉的性能决定着最终LED器件的一系列光电特性参数，如光转换效率、流明效率、色温（T c）、色坐标值（CIE）和显色指数（R a）等。White light-emitting diodes (LEDs) have the advantages of long life, high efficiency, low energy consumption, and environmental friendliness. They have quickly been widely used in lighting and display fields, and are known as the next-generation solid-state lighting sources. At present, the mainstream solution for realizing white light LED is to combine semiconductor chips and phosphor powder into a phosphor powder conversion white light LED. Therefore, the performance of the phosphor determines a series of photoelectric characteristic parameters of the final LED device, such as light conversion efficiency, lumen efficiency, color temperature ( T c ), color coordinate value (CIE) and color rendering index ( R a ), etc.
目前，实现荧光粉转换型白光LED的主要方法是将蓝光GaN芯片与YAG: Ce3+黄色荧光粉组合，利用芯片发出的蓝光和荧光粉被激发后产生的黄色荧光组合得到高亮度的白光。然而这种组合由于缺少红色荧光成份，使得最终器件的显色指数较低。另外，利用近紫外InGaN芯片与红、绿和蓝色不同基质荧光粉组合实现白光LED的方法同样被广泛采用。但是由于不同基质之间对芯片能量的利用效率存在差异及相应辐射再吸收过程的干扰，使用这类方法得到的LED器件的发光效率仍有待提高。At present, the main method to realize phosphor-converted white LED is to combine blue GaN chip with YAG: Ce 3+ yellow phosphor, and use the combination of blue light emitted by the chip and yellow fluorescence generated after the phosphor is excited to obtain high-brightness white light. However, due to the lack of red fluorescent components in this combination, the color rendering index of the final device is low. In addition, the method of using near-ultraviolet InGaN chips combined with red, green and blue matrix phosphors to realize white LEDs is also widely used. However, the luminous efficiency of LED devices obtained by using this method still needs to be improved due to the differences in the utilization efficiency of chip energy among different substrates and the interference of the corresponding radiation reabsorption process.
为改善上述情况，单基质三色荧光粉的研制得到了极大的关注。通过使用近紫外InGaN芯片进行激发，使得材料中同时产生三种不同光色的发射，直接符合得到高亮度的白光。由于这种方法获得的白光LED具有高显色指数的优点，更加适用于室内照明，为白光LED提供了更为广阔的发展空间。因此，研究适用于近紫外光激发的单基质三掺杂白色荧光材料具有非常重要的意义。In order to improve the above situation, the development of single-matrix three-color phosphors has received great attention. By using a near-ultraviolet InGaN chip for excitation, the material emits three different light colors at the same time, which directly corresponds to obtaining high-brightness white light. Because the white light LED obtained by this method has the advantage of high color rendering index, it is more suitable for indoor lighting, and provides a broader development space for white light LED. Therefore, it is of great significance to study single-matrix triple-doped white fluorescent materials suitable for near-ultraviolet excitation.
发明内容Contents of the invention
本发明的目的是克服现有白光LED器件的缺陷和不足，提供一种可被近紫外光有效激发、Ce3+-Tb3+-Eu3+之间能量传递效率高、色纯度好且物理化学性能稳定的单基质三掺杂白色荧光粉。The purpose of the present invention is to overcome the defects and deficiencies of the existing white light LED devices, to provide a kind of LED that can be effectively excited by near ultraviolet light, has high energy transfer efficiency between Ce 3+ -Tb 3+ -Eu 3+ , good color purity and physical Chemically stable single-matrix triple-doped white phosphor.
本发明另一目的是提供上述高亮度白色荧光材料的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned high-brightness white fluorescent material.
本发明的进一步目的是提供上述高亮度白色荧光材料在LED领域的应用。A further object of the present invention is to provide the application of the above-mentioned high-brightness white fluorescent material in the LED field.
本发明上述目的通过以下技术方案实现：The above object of the present invention is achieved through the following technical solutions:
一种单基质三掺杂白色荧光材料，其化学组成表达式为：LiY1-x-y-zCexTbyEuzSiO4，式中x，y，z分别为掺杂离子Ce3+，Tb3+，Eu3+相对基质稀土离子Y3+占的摩尔百分含量，取值范围：x=0.01，0.03≤y≤0.05，0≤z≤0.09。A single-matrix triple-doped white fluorescent material, its chemical composition expression is: LiY 1-xyz Ce x Tb y Eu z SiO 4 , where x, y, z are dopant ions Ce 3+ , Tb 3+ , the molar percentage of Eu 3+ relative to the matrix rare earth ion Y 3+ , the value range: x=0.01, 0.03≤y≤0.05, 0≤z≤0.09.
上述单基质三掺杂白色荧光材料的基质材料为硅酸盐LiYSiO4，发光中心分别为三价稀土离子铈Ce3+，铽Tb3+，铕Eu3+。在近紫外光激发下，三价稀土离子Ce3+在该基质中发蓝光，Tb3+产生绿光，而Eu3+发射红光，将三种光色进行混合，即可得到明亮的白光。The host material of the above-mentioned single-matrix triple-doped white fluorescent material is silicate LiYSiO 4 , and the light-emitting centers are trivalent rare earth ions Ce 3+ , terbium Tb 3+ , and europium Eu 3+ . Under the excitation of near-ultraviolet light, the trivalent rare earth ion Ce 3+ emits blue light in the matrix, Tb 3+ emits green light, and Eu 3+ emits red light. By mixing the three light colors, a bright white light can be obtained .
上述单基质三掺杂白色荧光材料的制备方法，包括如下步骤：The preparation method of the above-mentioned single-matrix three-doped white fluorescent material comprises the following steps:
S1.按照权利要求1所述化学组成表达式中体现的化学组成，准确称取原料，并加入相应助熔剂，充分研磨混合均匀，得混合物；S1. According to the chemical composition embodied in the chemical composition expression of claim 1, the raw materials are accurately weighed, and the corresponding flux is added, fully ground and mixed to obtain a mixture;
S2.将混合物置于还原气氛程序升温并焙烧，自然冷却到室温；S2. The mixture is placed in a reducing atmosphere to program the temperature and roasted, and naturally cooled to room temperature;
S3.步骤S2所得产物取出研磨，即得到终产品。S3. The product obtained in step S2 is taken out and ground to obtain the final product.
其中，步骤S1所述原料为碳酸锂、氧化钇、氧化铈、氧化铽、氧化铕和二氧化硅。Wherein, the raw materials in step S1 are lithium carbonate, yttrium oxide, cerium oxide, terbium oxide, europium oxide and silicon dioxide.
优选地，步骤S1所述相应助熔剂为碳酸锂。Preferably, the corresponding flux described in step S1 is lithium carbonate.
优选地，步骤S1所述相应助熔剂碳酸锂的含量为1-10%。Preferably, the content of the corresponding flux lithium carbonate described in step S1 is 1-10%.
更优选地，步骤S1所述相应助熔剂碳酸锂的含量为5%。More preferably, the content of the corresponding flux lithium carbonate described in step S1 is 5%.
另外，优选地，步骤S1所述充分研磨是于玛瑙研钵中充分研磨。In addition, preferably, the sufficient grinding in step S1 is fully grinding in an agate mortar.
优选地，步骤S2所述置于还原气氛中焙烧是指置于通过加热炭块产生的一氧化碳气氛中焙烧。Preferably, roasting in a reducing atmosphere in step S2 refers to roasting in a carbon monoxide atmosphere generated by heating the carbon block.
优选地，步骤S2所述升温时间为2-5h。Preferably, the heating time in step S2 is 2-5 hours.
更优选地，步骤S2所述升温时间为3h。More preferably, the heating time in step S2 is 3 hours.
另外，优选地，步骤S2所述焙烧的条件为1000~1200℃焙烧8~12h。In addition, preferably, the calcination condition in step S2 is 1000-1200° C. for 8-12 hours.
更优选地，步骤S2所述焙烧的条件为1000~1200℃焙烧10h。More preferably, the calcination condition in step S2 is 1000-1200° C. for 10 h.
最优选地，步骤S2所述焙烧的条件为1100℃焙烧10h。Most preferably, the calcination condition in step S2 is 1100° C. for 10 h.
上述高亮度白色荧光材料的应用也应在本发明的保护范围之内。具体是指在作为近紫外激发的白光LED材料方面的应用。The application of the above-mentioned high-brightness white fluorescent material should also be within the protection scope of the present invention. Specifically, it refers to the application as a near-ultraviolet excited white light LED material.
优选地，所述白光LED是指对照明显示要求的暖白光LED。因为本发明的白色荧光材料中存在可发射明亮红光的Eu3+，相比普通蓝光GaN芯片+YAG: Ce3+的荧光粉转换型白光LED，本材料显色指数较高，产生的白光色温更加合适与日常照明。Preferably, the white LED refers to a warm white LED required for lighting display. Because there is Eu 3+ that can emit bright red light in the white fluorescent material of the present invention, compared with the phosphor powder conversion white light LED of ordinary blue light GaN chip + YAG: Ce 3+ , the color rendering index of this material is higher, and the white light produced The color temperature is more suitable for everyday lighting.
根据本发明上述方法制备得到的一系列材料具有相似的光谱性质：在250~400 nm有很强的宽带吸收，符合近紫外LED芯片的激发要求；在345 nm光激发下，能得到很强的蓝，绿，红光发射，分别位于360-400 nm (Ce3+)，525-560 nm (Tb3+)及600-625 nm(Eu3+)，均属于标准光色范围，符合之后可产生高亮度白光；是一种可应用于照明LED的白色荧光材料。A series of materials prepared according to the above method of the present invention have similar spectral properties: there is strong broadband absorption at 250-400 nm, which meets the excitation requirements of near-ultraviolet LED chips; under 345 nm light excitation, a strong Blue, green, and red light emission are located at 360-400 nm (Ce 3+ ), 525-560 nm (Tb 3+ ) and 600-625 nm (Eu 3+ ), respectively, all of which belong to the standard light color range. Produces high-brightness white light; it is a white fluorescent material that can be applied to lighting LEDs.
本发明具有以下有益效果：The present invention has the following beneficial effects:
（1）本发明的白色荧光材料具有非常宽的激发光谱，在250~400 nm范围内均具有吸收，可有效的吸收LED芯片发出的近紫外光。(1) The white fluorescent material of the present invention has a very wide excitation spectrum, has absorption in the range of 250-400 nm, and can effectively absorb the near-ultraviolet light emitted by the LED chip.
（2）本发明的白色荧光材料的发射峰分别位于360-400 nm (Ce3+)，525-560 nm(Tb3+)及600-625 nm(Eu3+)，均属于标准光色范围，复合之后可产生高亮度白光。(2) The emission peaks of the white fluorescent material of the present invention are respectively located at 360-400 nm (Ce 3+ ), 525-560 nm (Tb 3+ ) and 600-625 nm (Eu 3+ ), all of which belong to the standard light color range , can produce high-brightness white light after compounding.
（3）本发明的白色荧光材料中存在可发射明亮红光的Eu3+，相比普通蓝光GaN芯片+YAG: Ce3+的荧光粉转换型白光LED，本材料显色指数较高，产生的白光色温更加合适与日常照明。(3) There is Eu 3+ that can emit bright red light in the white fluorescent material of the present invention. Compared with ordinary blue GaN chip + YAG: Ce 3+ phosphor conversion white LED, the color rendering index of this material is higher, resulting in The color temperature of white light is more suitable for daily lighting.
（4）本发明的白色荧光材料属于为硅酸盐，较其他化合物有更优越的物理化学稳定性。(4) The white fluorescent material of the present invention is silicate, which has better physical and chemical stability than other compounds.
（5）本发明所述白色荧光材料的制备工艺方法简单，易于实现，且成本较低，大规模工业应用前景广阔。(5) The preparation process of the white fluorescent material of the present invention is simple, easy to realize, and low in cost, and has broad prospects for large-scale industrial application.
附图说明Description of drawings
图1中a为本发明（实施例1）的白色荧光材料在监测611 nm主发射峰时的激发光谱，b为本发明（实施例1）的白色荧光材料在345 nm光激发下的发射光谱。In Figure 1, a is the excitation spectrum of the white fluorescent material of the present invention (Example 1) when monitoring the main emission peak at 611 nm, and b is the emission spectrum of the white fluorescent material of the present invention (Example 1) under 345 nm light excitation .
图2为实施例1、9、10的发光材料监测400 nm (Ce3+)发光下的激发光谱。Fig. 2 shows the excitation spectra of the luminescent materials in Examples 1, 9, and 10 under 400 nm (Ce 3+ ) luminescence monitoring.
图3为实施例1、9、10的发光材料监测550 nm (Tb3+)发光下的激发光谱。Fig. 3 is the excitation spectra of the luminescent materials of Examples 1, 9, and 10 under monitoring 550 nm (Tb 3+ ) luminescence.
图4为实施例1、9、10的发光材料监测611 nm (Eu3+)发光下的激发光谱。Fig. 4 shows the excitation spectra of the luminescent materials of Examples 1, 9, and 10 under 611 nm (Eu 3+ ) luminescence monitoring.
图5为实施例1、8、9、10、11的发光材料的发射光谱，插图显示的样品的实际发光照片。Fig. 5 is the emission spectra of the luminescent materials of Examples 1, 8, 9, 10, and 11, and the actual luminescence photos of the samples shown in the inset.
图6为本发明白色荧光材料LiY0.96-zCe0.01Tb0.03EuzSiO4 [z = 0 (D1), 0.01 (D2),0.03 (D3), 0.05 (D4), 0.09 (D5)]的色坐标在CIE-1931色度图中的位置，以及LiY0.99Ce0.01SiO4，LiY0.95Tb0.05SiO4，LiY0.99Eu0.01SiO4和LiY0.96-zCe0.01Tb0.03EuzSiO4发光照片。Figure 6 shows the white fluorescent material LiY 0.96-z Ce 0.01 Tb 0.03 Eu z SiO 4 [z = 0 (D 1 ), 0.01 (D 2 ), 0.03 (D 3 ), 0.05 (D 4 ), 0.09 (D 5 )] in the CIE-1931 chromaticity diagram, and the positions of LiY 0.99 Ce 0.01 SiO 4 , LiY 0.95 Tb 0.05 SiO 4 , LiY 0.99 Eu 0.01 SiO 4 and LiY 0.96-z Ce 0.01 Tb 0.03 Eu z SiO 4 glow photos.
具体实施方式Detailed ways
以下结合说明书附图和具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
除非特别说明，以下实施例所用试剂和材料均为市购。Unless otherwise specified, the reagents and materials used in the following examples are commercially available.
实施例1Example 1
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5250 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0264 g，氧化铽(Tb4O7) 0.0280 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结10小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.93Ce0.01Tb0.03Eu0.03SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5250 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0264 g, terbium oxide (Tb 4 O 7 ) 0.0280 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 3 hours in a reducing atmosphere and roasted. Sintering at 1100°C for 10 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.93 Ce 0.01 Tb 0.03 Eu 0.03 SiO 4 .
实施例2Example 2
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5250 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0264 g，氧化铽(Tb4O7) 0.0280 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1000℃下烧结8小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.93Ce0.01Tb0.03Eu0.03SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5250 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0264 g, terbium oxide (Tb 4 O 7 ) 0.0280 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 3 hours in a reducing atmosphere and roasted. Sintering at 1000°C for 8 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.93 Ce 0.01 Tb 0.03 Eu 0.03 SiO 4 .
实施例3Example 3
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5250 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0264 g，氧化铽(Tb4O7) 0.0280 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温5h并进行焙烧，1000℃下烧结8小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.93Ce0.01Tb0.03Eu0.03SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5250 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0264 g, terbium oxide (Tb 4 O 7 ) 0.0280 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 5 hours in a reducing atmosphere and roasted. Sintering at 1000°C for 8 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.93 Ce 0.01 Tb 0.03 Eu 0.03 SiO 4 .
实施例4Example 4
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5250 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0264 g，氧化铽(Tb4O7) 0.0280 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结8小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.93Ce0.01Tb0.03Eu0.03SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5250 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0264 g, terbium oxide (Tb 4 O 7 ) 0.0280 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 3 hours in a reducing atmosphere and roasted. Sintered at 1100°C for 8 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.93 Ce 0.01 Tb 0.03 Eu 0.03 SiO 4 .
实施例5Example 5
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5250 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0264 g，氧化铽(Tb4O7) 0.0280 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1200℃下烧结8小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.93Ce0.01Tb0.03Eu0.03SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5250 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0264 g, terbium oxide (Tb 4 O 7 ) 0.0280 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 3 hours in a reducing atmosphere and roasted. Sintered at 1200°C for 8 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.93 Ce 0.01 Tb 0.03 Eu 0.03 SiO 4 .
实施例6Example 6
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5250 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0264 g，氧化铽(Tb4O7) 0.0280 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温2h并进行焙烧，1000℃下烧结8小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.93Ce0.01Tb0.03Eu0.03SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5250 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0264 g, terbium oxide (Tb 4 O 7 ) 0.0280 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up in a reducing atmosphere for 2 hours and roasted. Sintering at 1000°C for 8 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.93 Ce 0.01 Tb 0.03 Eu 0.03 SiO 4 .
实施例7Example 7
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5250 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0264 g，氧化铽(Tb4O7) 0.0280 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结12小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.93Ce0.01Tb0.03Eu0.03SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5250 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0264 g, terbium oxide (Tb 4 O 7 ) 0.0280 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 3 hours in a reducing atmosphere and roasted. Sintering at 1100°C for 12 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.93 Ce 0.01 Tb 0.03 Eu 0.03 SiO 4 .
实施例8Example 8
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5419 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铽(Tb4O7) 0.0280 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结10小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.96Ce0.01Tb0.03SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5419 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, terbium oxide (Tb 4 O 7 ) 0.0280 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 3 hours in a reducing atmosphere and fired, and sintered at 1100 ° C for 10 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.96 Ce 0.01 Tb 0.03 SiO 4 .
实施例9Example 9
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5363 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0088 g，氧化铽(Tb4O7) 0.0280 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结10小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.95Ce0.01Tb0.03Eu0.01SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5363 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0088 g, terbium oxide (Tb 4 O 7 ) 0.0280 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 3 hours in a reducing atmosphere and roasted. Sintering at 1100°C for 10 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.95 Ce 0.01 Tb 0.03 Eu 0.01 SiO 4 .
实施例10Example 10
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5137 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0440 g，氧化铽(Tb4O7) 0.0280 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结10小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.91Ce0.01Tb0.03Eu0.05SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5137 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0440 g, terbium oxide (Tb 4 O 7 ) 0.0280 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 3 hours in a reducing atmosphere and roasted. Sintering at 1100°C for 10 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.91 Ce 0.01 Tb 0.03 Eu 0.05 SiO 4 .
实施例11Example 11
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.4911 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0792 g，氧化铽(Tb4O7) 0.0280 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结10小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.87Ce0.01Tb0.03Eu0.09SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.4911 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0792 g, 0.0280 g of terbium oxide (Tb 4 O 7 ) and 0.0092 g of flux lithium carbonate (Li 2 CO 3 ) were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 3 hours in a reducing atmosphere and roasted. Sintering at 1100°C for 10 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.87 Ce 0.01 Tb 0.03 Eu 0.09 SiO 4 .
实施例12Example 12
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5250 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0088 g，氧化铽(Tb4O7) 0.0467 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结10小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.93Ce0.01Tb0.05Eu0.01SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5250 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0088 g, terbium oxide (Tb 4 O 7 ) 0.0467 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 3 hours in a reducing atmosphere and roasted. Sintering at 1100°C for 10 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.93 Ce 0.01 Tb 0.05 Eu 0.01 SiO 4 .
实施例13Example 13
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5137 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0264 g，氧化铽(Tb4O7) 0.0467 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结10小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.91Ce0.01Tb0.05Eu0.03SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5137 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0264 g, terbium oxide (Tb 4 O 7 ) 0.0467 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 3 hours in a reducing atmosphere and roasted. Sintering at 1100°C for 10 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.91 Ce 0.01 Tb 0.05 Eu 0.03 SiO 4 .
实施例14Example 14
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5024 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0440 g，氧化铽(Tb4O7) 0.0467 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结10小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.89Ce0.01Tb0.05Eu0.05SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5024 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0440 g, terbium oxide (Tb 4 O 7 ) 0.0467 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated up for 3 hours in a reducing atmosphere and roasted. Sintering at 1100°C for 10 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.89 Ce 0.01 Tb 0.05 Eu 0.05 SiO 4 .
实施例15Example 15
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.4798 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g，氧化铕(Eu2O3) 0.0792 g，氧化铽(Tb4O7) 0.0467 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结10小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.85Ce0.01Tb0.05Eu0.09SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.4798 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g, europium oxide (Eu 2 O 3 ) 0.0792 g, terbium oxide (Tb 4 O 7 ) 0.0467 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g were placed in an agate mortar and thoroughly ground and mixed uniformly, then heated in a reducing atmosphere for 3 hours and roasted. Sintering at 1100°C for 10 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.85 Ce 0.01 Tb 0.05 Eu 0.09 SiO 4 .
实施例16Example 16
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5589 g，二氧化硅(SiO2) 0.3004g，氧化铈(CeO2) 0.0086 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结10小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.99Ce0.01SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5589 g, silicon dioxide (SiO 2 ) 0.3004 g, cerium oxide (CeO 2 ) 0.0086 g and flux lithium carbonate (Li 2 CO 3 ) 0.0092 g was placed in an agate mortar and thoroughly ground and mixed uniformly, then the temperature was raised in a reducing atmosphere for 3 hours and calcined, and sintered at 1100° C. for 10 hours. Cool naturally to room temperature. The sample is taken out and ground, and finally the product is obtained, and its chemical composition expression is: LiY 0.99 Ce 0.01 SiO 4 .
实施例17Example 17
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5363 g，二氧化硅(SiO2) 0.3004g，氧化铽(Tb4O7) 0.0467 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结10小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.95Tb0.05SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5363 g, silicon dioxide (SiO 2 ) 0.3004 g, terbium oxide (Tb 4 O 7 ) 0.0467 g and flux lithium carbonate ( Li 2 CO 3 ) 0.0092 g was placed in an agate mortar and thoroughly ground and mixed uniformly, then the temperature was raised in a reducing atmosphere for 3 hours and then calcined, and sintered at 1100°C for 10 hours. Cool naturally to room temperature. The sample was taken out and ground to obtain the final product, the chemical composition expression of which was: LiY 0.95 Tb 0.05 SiO 4 .
实施例18Example 18
称取碳酸锂(Li2CO3) 0.1847 g，氧化钇(Y2O3) 0.5589 g，二氧化硅(SiO2) 0.3004g，氧化铕(Eu2O3) 0.0088 g及助熔剂碳酸锂(Li2CO3) 0.0092 g置于玛瑙研钵中充分研磨并混合均匀后，在还原气氛中升温3h并进行焙烧，1100℃下烧结10小时。自然冷却到室温。将样品取出研磨，最终得到产品，其化学组成表达式为：LiY0.99Eu0.01SiO4。Weigh lithium carbonate (Li 2 CO 3 ) 0.1847 g, yttrium oxide (Y 2 O 3 ) 0.5589 g, silicon dioxide (SiO 2 ) 0.3004 g, europium oxide (Eu 2 O 3 ) 0.0088 g and flux lithium carbonate ( Li 2 CO 3 ) 0.0092 g was placed in an agate mortar and thoroughly ground and mixed uniformly, then the temperature was raised in a reducing atmosphere for 3 hours and then calcined, and sintered at 1100°C for 10 hours. Cool naturally to room temperature. The sample is taken out and ground to obtain the final product, the chemical composition expression of which is: LiY 0.99 Eu 0.01 SiO 4 .
测试实验：Test experiment:
1、针对测试上述实施例1~18所制备的系列材料的光谱性质等，结果显示，按照本发明所述的制备方法获得的一系列具有不同离子（离子分别为三价稀土离子铈Ce3+，铽Tb3 +，铕Eu3+）浓度的白色荧光粉样品 (LiY1-x-y-zCexTbyEuzSiO4，式中x，y，z分别为掺杂离子Ce3 +，Tb3+，Eu3+相对基质稀土离子Y3+占的摩尔百分含量，取值范围：x=0.01，0.03≤y≤0.05，0≤z≤0.09) (实施例1~15)具有相似的光谱性质。1. For testing the spectral properties of the series of materials prepared in the above-mentioned Examples 1 to 18, the results show that a series of materials with different ions obtained according to the preparation method of the present invention (the ions are respectively trivalent rare earth ions cerium Ce 3+ , terbium Tb 3 + , europium Eu 3+ ) concentration white phosphor sample (LiY 1-xyz Ce x Tb y Eu z SiO 4 , where x, y, z are dopant ions Ce 3 + , Tb 3+ , the molar percentage of Eu 3+ relative to the matrix rare earth ion Y 3+ , the value range: x=0.01, 0.03≤y≤0.05, 0≤z≤0.09) (Examples 1~15) have similar spectral properties .
而且本发明的实验也显示了，在该类型材料的制备过程中，助熔剂应选择碳酸锂(Li2CO3)，其加入量应控制在5%。制备过程中焙烧的条件为1100℃焙烧10h，最佳升温时间控制在3h。Moreover, the experiment of the present invention also shows that in the preparation process of this type of material, the flux should be lithium carbonate (Li 2 CO 3 ), and its addition should be controlled at 5%. The calcination condition in the preparation process is 1100° C. for 10 h, and the optimal heating time is controlled at 3 h.
下面以实施例1制备的材料为例，呈现说明按照本发明方法制备的材料的性质。Taking the material prepared in Example 1 as an example, the properties of the material prepared according to the method of the present invention are presented below.
2、实施例1的白色荧光材料的性质测定结果。2. Measurement results of the properties of the white fluorescent material of Example 1.
如图1中a所示，在监测发射峰611 nm时测得发光材料的激发光谱，可以观察到：LiY1-x-y-zCexTbyEuzSiO4系列发光材料在近紫外区有很强的宽带吸收，样品的激发光谱（图1中a所示）显示宽带吸收从250 nm~400 nm，表明该材料能满足近紫外LED芯片的激发要求。As shown in a in Figure 1, the excitation spectrum of the luminescent material was measured when the emission peak was monitored at 611 nm. It can be observed that the LiY 1-xyz Ce x Tb y Eu z SiO 4 series luminescent material has a strong Broadband absorption, the excitation spectrum of the sample (shown in a in Figure 1) shows that the broadband absorption ranges from 250 nm to 400 nm, indicating that the material can meet the excitation requirements of near-ultraviolet LED chips.
如图1中b所示，本白色荧光材料在345 nm光激发下测得发射光谱，可以观察到：LiY1-x-y-zCexTbyEuzSiO4系列发光材料在蓝，绿，红光谱区域均具有较为优异的发射，其发射峰位置分别位于：360-400 nm (Ce3+)，525-560 nm (Tb3+)及600-625 nm(Eu3+)，均属于标准光色范围，复合之后可产生高亮度白光。As shown in b in Figure 1 , the emission spectrum of this white fluorescent material is measured under the excitation of 345 nm light, and it can be observed that : All have relatively excellent emission, and their emission peak positions are located at: 360-400 nm (Ce 3+ ), 525-560 nm (Tb 3+ ) and 600-625 nm (Eu 3+ ), all of which belong to the standard light color range , can produce high-brightness white light after compounding.
图2-4为实施例1、9、10的发光材料监测不同发射波长位置的激发光谱，激发光谱有相似的性质，即呈现从250 nm到400 nm的宽带吸收。Figures 2-4 are the excitation spectra of the luminescent materials of Examples 1, 9, and 10 monitored at different emission wavelengths. The excitation spectra have similar properties, that is, broadband absorption from 250 nm to 400 nm.
图5为实施例1、8、9、10、11的发光材料的发射光谱。从图5看出，改变样品中铕(Eu3 +)离子的掺杂量，样品的各发射峰强度会随之变化，从而实现光色可调。另外，图5插图显示的样品的实际发光照片，从中可以看出：LiY1-x-y-zCexTbyEuzSiO4系列白色荧光材料在345nm激发下具有较高的亮度，满足日常照明及显示要求。FIG. 5 is the emission spectra of the luminescent materials of Examples 1, 8, 9, 10, and 11. It can be seen from Fig. 5 that by changing the doping amount of europium (Eu 3 + ) ions in the sample, the intensity of each emission peak of the sample will change accordingly, so that the light color can be adjusted. In addition, the actual luminescent photo of the sample shown in the inset of Figure 5 shows that: LiY 1-xyz Ce x Tb y Eu z SiO 4 series white fluorescent materials have high brightness under excitation at 345nm, meeting the requirements of daily lighting and display .
图6展示了本发明白色荧光材料LiY0.96-zCe0.01Tb0.03EuzSiO4 [0≤z≤0.09](实施例1、8、9、10、11)的色坐标在CIE-1931色度图中的位置，以及LiY0.99Ce0.01SiO4(实施例16)，LiY0.95Tb0.05SiO4(实施例17)，LiY0.99Eu0.01SiO4(实施例18)和LiY0.93Ce0.01Tb0.03Eu0.03SiO4(实施例1)的发光照片。可以看出本发明的荧光材料色坐标均位于白光区，并随着Eu3+掺杂量的增加逐渐改变光色及色温，是一种新型高亮度的白色荧光材料。Figure 6 shows the color coordinates of the white fluorescent material LiY 0.96-z Ce 0.01 Tb 0.03 Eu z SiO 4 [0≤z≤0.09] (Example 1, 8, 9, 10, 11) of the present invention in CIE-1931 chromaticity position in the figure, and LiY 0.99 Ce 0.01 SiO 4 (Example 16), LiY 0.95 Tb 0.05 SiO 4 (Example 17), LiY 0.99 Eu 0.01 SiO 4 (Example 18) and LiY 0.93 Ce 0.01 Tb 0.03 Eu 0.03 Photoluminescence of SiO 4 (Example 1). It can be seen that the color coordinates of the fluorescent material of the present invention are all located in the white light region, and the light color and color temperature gradually change with the increase of Eu 3+ doping amount, and it is a new type of high-brightness white fluorescent material.
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