WO2011103721A1 - 掺铽的硼酸钆盐基绿色发光材料及其制备方法 - Google Patents
掺铽的硼酸钆盐基绿色发光材料及其制备方法 Download PDFInfo
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- WO2011103721A1 WO2011103721A1 PCT/CN2010/070776 CN2010070776W WO2011103721A1 WO 2011103721 A1 WO2011103721 A1 WO 2011103721A1 CN 2010070776 W CN2010070776 W CN 2010070776W WO 2011103721 A1 WO2011103721 A1 WO 2011103721A1
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- luminescent material
- borate
- green luminescent
- earth metal
- alkaline earth
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/778—Borates
Definitions
- the invention belongs to the technical field of luminescent materials, and in particular relates to a bismuth borate-based green luminescent material excited by vacuum ultraviolet light and a preparation method thereof.
- PDPs plasma flat panel displays
- circuits and luminescent materials are important technologies. With the improvement of circuit design, the selection of luminescent materials has become the most critical technology in PDP display. Therefore, research on trichromatic phosphors for PDP and mercury-free fluorescent lamps is essential.
- trichromatic phosphors are mainly red powder Y 2 O 3 : Eu 3+ , (Y, Gd) BO 3 : Eu 3+ , green powder Zn 2 SiO 4 : Mn 2+ , BaAl 12 O 19 : Mn 2 + and blue powder BaMgAl 10 O 17 :Eu 2+ .
- green powder Zn 2 SiO 4 :Mn 2+ due to the spin inhibition of Mn 2+ ( 4 T 1 ⁇ 6 A 1 ), the afterglow time is long, which is not conducive to the display of fast motion pictures, and is not suitable. On the requirements of TV monitors.
- the luminescent materials based on the strontium borate salt M 3 Gd(BO 3 ) 3 are mainly concentrated on the laser characteristics of rare earth doping as a single crystal, in terms of vacuum ultraviolet excitation. Less research.
- Tb 3+ Compared with the long afterglow characteristics of Mn 2+ , Tb 3+ has characteristic green light emission (540-545nm), and its spin coupling shields the spin-forbidden ring, which makes it have a shorter afterglow time and overcomes Hysteresis effect.
- the technical problem to be solved by the present invention is to provide a cerium-doped barium strontium borate-based green luminescent material with high luminescence intensity and a method for preparing a cerium-doped cerium borate-based green luminescent material.
- the alkaline earth metal element M is one or more of Ca, Sr and Ba.
- Step two mixing the source compounds
- Step 3 The mixture is subjected to sintering pretreatment and then cooled;
- Step 4 The cooled sinter is taken out for grinding, and the ground product is calcined in a reducing atmosphere to obtain the cerium-doped cerium borate-based green luminescent material after cooling.
- the source compound of the alkaline earth metal ion is at least one of an oxide, a hydroxide, a nitrate, and a carbonate of an alkaline earth metal
- the source compound of the borate ion is boric acid.
- At least one of boron oxide, the source compound of Gd 3+ and Tb 3+ being a corresponding rare earth oxide or nitrate.
- the respective source compounds are uniformly mixed together with the flux when mixed.
- the fluxing agent is one or more of boric acid and cesium fluoride.
- the sintering pretreatment temperature is 200 to 700 ° C for 2 to 7 hours.
- the calcination treatment temperature is 900 to 1100 ° C, and the time is 3 to 24 hours.
- the source compound of the borate ion is in an amount of 10% to 20% by weight.
- the reducing atmosphere is a reducing atmosphere formed by a mixed gas of nitrogen and hydrogen, hydrogen or carbon monoxide.
- the luminescent material of the present invention transmits energy to Gd ions through the strong absorption of vacuum ultraviolet light (VUV) of 150 nm to 175 nm by the matrix M 3 Gd 1-x Tb x (BO 3 ) 3 , and Gd 3+ 6 P J can There is energy transfer between the stage and Tb 3+ . After Tb 3+ absorbs energy, it emits green photons through ff transition radiation, and the energy transfer process between Gd 3+ 6 P J energy level and Tb 3+ increases Tb. 3+ green light emission intensity. Compared with the prior art, the luminescent material of the invention has the following advantages: 1.
- Gd 3+ in the strontium borate salt M 3 Gd(BO 3 ) 3 (M Ca, Sr, Ba) as a skeleton structure, Gd 3+ ⁇ Tb There is energy transfer between 3+ , which is beneficial to increase the green emission intensity of Tb 3+ ; 2.
- Tb 3+ has characteristic green emission (540 ⁇ 545nm) and its spin The coupling shields the spin-forbidden ring so that it has a shorter afterglow time and overcomes the hysteresis effect.
- the luminescent material can be obtained by sintering and calcining, thereby making the preparation process simple, the cost is low, and the invention has broad application prospects.
- Example 1 is an excitation spectrum of a Sr 3 Gd 0.85 Tb 0.15 (BO 3 ) 3 luminescent material according to Example 1 of the present invention, and the monitoring wavelength is 543 nm;
- FIG. 4 is a flow chart of a method for preparing a cerium-doped barium borate-based green luminescent material according to the present invention.
- VUV vacuum ultraviolet light
- Tb 3+ absorbs energy, it passes.
- Ff transition radiation, emitting green photons the energy transfer process between Gd 3+ 6 P J level and Tb 3+ increases the green emission intensity of Tb 3+ .
- the strong absorption peak between 150-200 nm in the vacuum ultraviolet range is the matrix absorption peak.
- the luminescent material in the first embodiment has strong absorption in the vacuum ultraviolet region, and can effectively transfer energy to the Gd 3+ ions, thereby finally realizing Gd-Tb energy transfer and improving the characteristic emission intensity of Tb 3+ at 543 nm.
- curve 1 shows the emission spectrum of Sr 3 Gd 0.85 Tb 0.15 (BO 3 ) 3 at an excitation wavelength of 172 nm
- curve 2 shows the commercial green powder BaAl 12 O 19 : Mn 2+ at an excitation wavelength of 172 nm.
- Emission spectrum Obviously, the emission peak intensity of Sr 3 Gd 0.85 Tb 0.15 (BO 3 ) 3 near 543 nm is significantly higher than that of commercial green powder BaAl 12 O 19 :Mn 2+ at around 525 nm.
- the emission intensity of 0.85 Tb 0.15 (BO 3 ) 3 at the excitation wavelength of 543 nm was 1.8 times that of the commercial powder BaAl 12 O 19 :Mn 2+ .
- the luminescent material of the first embodiment has high luminous efficiency, has a short afterglow time, and overcomes the hysteresis effect.
- the preparation method includes the following steps:
- S01 selecting a source compound of an alkaline earth metal ion, a source compound of a borate ion, a source compound of Gd 3+ and Tb 3+ according to a stoichiometric ratio, and a stoichiometric ratio of each source compound is according to a chemical formula M 3 Gd 1-x Tb x a molar ratio of the corresponding element in (BO 3 ) 3 , wherein the source compound of the borate ion is in an amount of 10% to 30% by weight, preferably, the source compound of the borate ion is 10% to 20% by weight.
- the source compound of the alkaline earth metal ion is at least one of an oxide, a hydroxide, a nitrate, and a carbonate of an alkaline earth metal
- the source compound of the borate ion is at least at least boric acid and boron oxide.
- the source compounds of the Gd 3+ and Tb 3+ are corresponding rare earth oxides or nitrates.
- each source compound is uniformly mixed with a small amount of a flux, which is one or a combination of boric acid and cesium fluoride.
- step S03 the sintering pretreatment temperature is 200 to 700 ° C for 2 to 7 hours, and is cooled to room temperature.
- step S04 it is calcined at 900 to 1100 ° C for 3 to 24 hours in a box type high temperature furnace, and then naturally cooled.
- the reducing atmosphere is a reducing atmosphere formed by a mixed gas of nitrogen and hydrogen, hydrogen or carbon monoxide.
- compositions of the erbium-doped barium strontium sulphate-based green luminescent material and the preparation method thereof are exemplified below by various embodiments.
- cerium nitrate Ba(NO 3 ) 2 3.9201g, cerium oxide Gd 2 O 3 0.9017g, boric acid H 3 BO 3 1.2057g (15% excess), cerium oxide Tb 4 O 7 0.0047g, barium fluoride BaF 2 0.0438 g (5%) was thoroughly ground in an agate mortar, placed in a corundum crucible and calcined at 200 ° C for 2 h, then cooled to room temperature, taken out and thoroughly ground again.
- strontium carbonate SrCO 3 0.0370g of calcium hydroxide Ca(OH) 2 , 0.7703g of yttrium oxide Gd 2 O 3 , 1.0202g of boric acid H 3 BO 3 (10% excess), strontium oxide Tb 4 O 7 0.1402g
- the barium fluoride BaF 2 0.0438 g (5%) was sufficiently ground in an agate mortar, placed in a corundum crucible and calcined at 700 ° C for 2 h, then cooled to room temperature, taken out and thoroughly ground again.
- the intensity of Tb 3+ doping is low, as shown in Figure 3.
- Curve 3 shows the emission spectrum of the Sr 3 Y 0.85 Tb 0.15 (BO 3 ) 3 luminescent material at an excitation wavelength of 172 nm
- curve 4 shows the emission of the Sr 3 Gd 0.85 Tb 0.15 (BO 3 ) 3 luminescent material at an excitation wavelength of 172 nm. spectrum.
- the luminescent material can be obtained by sintering and calcination treatment, thereby making the preparation process simple, the cost low, and having broad application prospects.
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Description
Claims (10)
- 一种掺铽的硼酸钆盐基绿色发光材料,其特征在于:所述掺铽的硼酸钆盐基绿色发光材料的化学式为:M3Gd1-xTbx(BO3)3 ,其中,M为碱土金属元素,x=0.005~0.5。
- 如权利要求1所述的掺铽的硼酸钆盐基绿色发光材料,其特征在于:所述碱土金属元素M为Ca、Sr及Ba中的一种或几种。
- 一种掺铽的硼酸钆盐基绿色发光材料制备方法,包括如下步骤:步骤一:按照化学计量比选取碱土金属离子的源化合物、硼酸根离子的源化合物、Gd3+和 Tb3+的源化合物,各源化合物的化学计量比是按照化学式M3Gd1-xTbx(BO3)3 中的相应元素的摩尔比例,其中,所述硼酸根离子的源化合物按摩尔比过量10%-30%,M为碱土金属元素,x=0.005~0.5;步骤二:将各源化合物混合;步骤三:将混合物进行烧结预处理,然后冷却;步骤四:将冷却后的烧结物进行研磨,再将研磨后产物在还原气氛中煅烧,冷却后得到所述掺铽的硼酸钆盐基绿色发光材料。
- 如权利要求3所述的掺铽的硼酸钆盐基绿色发光材料制备方法,其特征在于:所述碱土金属离子的源化合物为碱土金属的氧化物、氢氧化物、硝酸盐、碳酸盐中的至少一种,所述硼酸根离子的源化合物为硼酸、氧化硼中的至少一种,所述Gd3+和Tb3+的源化合物为相对应的稀土氧化物或硝酸盐。
- 如权利要求3所述的掺铽的硼酸钆盐基绿色发光材料制备方法,其特征在于:所述各源化合物混合时与助熔剂一起均匀混合。
- 如权利要求5所述的掺铽的硼酸钆盐基绿色发光材料制备方法,其特征在于:所述助熔剂为硼酸和氟化钡中的一种或几种。
- 如权利要求3所述的掺铽的硼酸钆盐基绿色发光材料制备方法,其特征在于:所述烧结预处理温度为200~700°C,时间为2~7小时。
- 如权利要求3所述的掺铽的硼酸钆盐基绿色发光材料制备方法,其特征在于:所述煅烧处理温度为900~1100°C,时间为3~24小时。
- 如权利要求3所述的掺铽的硼酸钆盐基绿色发光材料制备方法,其特征在于:所述硼酸根离子的源化合物按摩尔比过量10%-20%。
- 如权利要求3所述的掺铽的硼酸钆盐基绿色发光材料制备方法,其特征在于:所述还原气氛为氮气和氢气的混合气体、氢气或一氧化碳形成的还原气氛。
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EP10846344.9A EP2540799B1 (en) | 2010-02-26 | 2010-02-26 | Green luminescent material of terbiuim doped gadolinium borate and preparing method thereof |
CN2010800478189A CN102575163A (zh) | 2010-02-26 | 2010-02-26 | 掺铽的硼酸钆盐基绿色发光材料及其制备方法 |
US13/574,409 US8765016B2 (en) | 2010-02-26 | 2010-02-26 | Green luminescent material of terbium doped gadolinium borate and preparing method thereof |
PCT/CN2010/070776 WO2011103721A1 (zh) | 2010-02-26 | 2010-02-26 | 掺铽的硼酸钆盐基绿色发光材料及其制备方法 |
JP2012554192A JP5529980B2 (ja) | 2010-02-26 | 2010-02-26 | テルビウムをドープしたホウ酸ガドリニウム塩緑色発光材料及びその製造方法 |
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CN107011903A (zh) * | 2017-05-27 | 2017-08-04 | 陕西科技大学 | 一种铥掺杂三硼酸镧锶基蓝光荧光粉及其制备方法 |
CN115216300B (zh) * | 2021-04-20 | 2023-09-29 | 中国科学院理化技术研究所 | 一种三价铽掺杂的硫氧化钆发光材料的制备方法及其产品和应用 |
CN113292995A (zh) * | 2021-05-19 | 2021-08-24 | 中山大学 | 一种Sm3+离子激活硼酸镥钡橙红色荧光粉及其制备方法和应用 |
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CN1640984A (zh) * | 2004-12-17 | 2005-07-20 | 中国科学院上海硅酸盐研究所 | 一种发射绿色荧光的荧光粉及其制备方法 |
US20050230689A1 (en) * | 2004-04-20 | 2005-10-20 | Gelcore Llc | Ce3+ and Eu2+ doped phosphors for light generation |
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US4926091A (en) * | 1988-09-07 | 1990-05-15 | U.S. Philips Corporation | Luminescent terbium-activated borate, luminescent screen provided with such a borate and low-pressure mercury vapor discharge lamp provided with such a screen |
US6090310A (en) | 1999-01-12 | 2000-07-18 | Council Of Scientific And Industrial Research | Green emitting TB3+ activated borate phosphors used in low pressure mercury vapour lamps and a process for synthesizing the same |
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US20050230689A1 (en) * | 2004-04-20 | 2005-10-20 | Gelcore Llc | Ce3+ and Eu2+ doped phosphors for light generation |
CN1640984A (zh) * | 2004-12-17 | 2005-07-20 | 中国科学院上海硅酸盐研究所 | 一种发射绿色荧光的荧光粉及其制备方法 |
Non-Patent Citations (2)
Title |
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LIANG HONGBIN ET AL.: "The VUV-vis spectroscopic properties of phosphors Ca3Gd2(1-X)Ln2X(BO3)4(Ln3+=Ce,Sm,Eu,Tb)", MATERIALS RESEARCH BULLETIN, vol. 41, 2006, pages 1468 - 1475, XP008168682 * |
LU, JUNYE ET AL.: "Exploration of crystal growth and giant faraday rotation of terbium doped Sr3Gd(BO3)3", THE PAPER COLLECTION OF THE 15TH ACADEMIC CONFERENCE ON CRYSTAL GROWTH AND MATERIALS, 2009, pages 144, XP008168675 * |
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CN116574505A (zh) * | 2023-04-27 | 2023-08-11 | 桂林电子科技大学 | 一种镓酸盐应力发光材料的制备方法 |
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JP5529980B2 (ja) | 2014-06-25 |
EP2540799B1 (en) | 2015-11-25 |
JP2013520535A (ja) | 2013-06-06 |
US8765016B2 (en) | 2014-07-01 |
EP2540799A4 (en) | 2014-05-21 |
US20120286206A1 (en) | 2012-11-15 |
EP2540799A1 (en) | 2013-01-02 |
CN102575163A (zh) | 2012-07-11 |
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