CN1186103A - Green fluorescent powder and preparation thereof - Google Patents

Green fluorescent powder and preparation thereof Download PDF

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Publication number
CN1186103A
CN1186103A CN 96123003 CN96123003A CN1186103A CN 1186103 A CN1186103 A CN 1186103A CN 96123003 CN96123003 CN 96123003 CN 96123003 A CN96123003 A CN 96123003A CN 1186103 A CN1186103 A CN 1186103A
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China
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phosphor
ce3
reducing atmosphere
flux
4cl2
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CN 96123003
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Chinese (zh)
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刘行仁
林海
张晓�
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中国科学院长春物理研究所
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Publication of CN1186103A publication Critical patent/CN1186103A/en

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Abstract

A green fluorescent powder is rare-earth element activated magnesium zinc calcium chlorosilicate. It has a chemical expression : Ca8Mg1-aZna(SiO4)4Cl2 : xEu2+, yM, where M=Ce3+ and Mn2+; Ca can be replaced by less Sr or Ba; a is 0-1.0; x is 0-0.2; and y is 0-0.1 mol. Said green fluorescent powder has stable performance and high energy transformation efficiency.

Description

一种绿色荧光粉及其制备方法 A green phosphor and a preparation method

本发明涉及一种以氯硅酸镁锌钙为基质的绿色荧光粉及其制备方法。 The present invention relates to a method for preparing a green phosphor and magnesium zinc calcium chloride to a substrate.

以往在长波紫外光激发下发射高效的绿色荧光材料中主要有:硫化锌型和碱土金属硫化物荧光粉,如ZnS:Cu,ZnS:Cu,Al,CaS:Ce等。 Conventional long wavelength emission efficiency of green fluorescent material excited by ultraviolet light are: type zinc sulfide and alkaline earth metal sulfide phosphor, such as ZnS: Cu, ZnS: Cu, Al, CaS: Ce and the like. 但它们是不稳定的材料,在空气中易分解,使荧光粉性能大大下降,甚至会分解放出有毒的硫化氢气体,危害环境和健康。 But they are unstable material, easy to decompose in the air, so that the phosphor performance greatly reduced, or even released by the decomposition of toxic hydrogen sulfide gas, harm the environment and health.

本发明的目的是提供一种性能稳定,能量转换率高的绿色荧光粉。 Object of the present invention is to provide a stable and high energy conversion green phosphor.

本发明的荧光粉为稀土激活的氯硅酸镁锌钙,其化学表达式如下:Ca3Mg1-aZna(SiO4)4Cl2:XEu2+,yM其中:M为Ce3+和Mn2+,少量Sr,Ba可取代Ca;式中,0≤a≤1,0≤x≤0.2,0≤y≤0.1摩尔。 Phosphor of the present invention is a rare earth activated magnesium zinc calcium chloride, its chemical formula is as follows: Ca3Mg1-aZna (SiO4) 4Cl2: XEu2 +, yM wherein: M is Ce3 + and Mn2 +, a small amount of Sr, Ba of Ca may be substituted; of formula in, 0≤a≤1,0≤x≤0.2,0≤y≤0.1 mol.

按化学计量比CaCO3∶MgO(ZnO)∶SiO2∶CaCl2=7∶1∶4∶1摩尔比制取荧光粉的基质,过量的CaCl2可起助熔剂作用,称取量为计算量的1.0-2.5倍,激活剂为Eu2+,敏化剂为Ce3+,助熔剂为Li2CO3,上述原料充分磨混均匀后,在1000-1200℃下的弱还原气氛中灼烧1-3小时,即可得到所需的荧光粉,其体色为黄绿色,随Eu2+浓度增加而加深,对含锌的化合物来说,先在空气中合成含锌的基质,然后该基质和掺杂的激活剂Eu2+、敏化剂Ce3+、助熔剂Li2CO3等混合,在高温还原性气氛中合成所需的荧光粉,还原气氛可以是95%N2+5%H2(体积比)混合气体,也可是碳粒在空气中燃烧产生的气体。 Stoichiometric ratio of phosphor to take CaCO3:MgO (ZnO) :SiO2:CaCl2 = 7:1:4:1 molar ratio of the matrix system, an excess of CaCl2 can play the role of flux weighed amount calculated amount of 1.0-2.5 times, activating agent is Eu2 +, sensitizer is Ce3 +, a flux of Li2CO3, the grinding of the raw material sufficiently uniformly mixed, fired in a weakly reducing atmosphere at 1000-1200 deg.] C in 1-3 hours, to give the desired phosphor, which is yellow-green in color, with increasing concentrations of Eu2 + deepened, zinc compounds, the first matrix synthesis zinc in air, and then the matrix and an activator doped Eu2 +, Ce3 + sensitizer , Li2CO3, etc. mixed flux, in a high temperature reducing atmosphere required for the synthesis of phosphors, the reducing atmosphere may be 95% N2 + 5% H2 (by volume) gas mixture of carbon particles may also be a gas generated by combustion in air.

下面给出实施例对本发明作具体描述。 The following Examples are given of the present invention will be specifically described.

实施例一、称取CaCO321.00g,MgO1.21g,SiO27.21g,CaCl25.01g,Eu2O30.528g及Li2CO31.03g。 Example a weighed CaCO321.00g, MgO1.21g, SiO27.21g, CaCl25.01g, Eu2O30.528g and Li2CO31.03g. 将上述原料磨混均匀,还原气氛中,1100℃灼烧3小时,取出,用去离子水洗涤,过筛,烘干,得到体色为黄绿色的,组成为Ca8Mg(SiO4)4Cl2∶0.1Eu2+的二价铕激活的氯硅酸镁钙荧光粉。 Uniformly mixing the above raw mill, a reducing atmosphere, fired 1100 ℃ 3 hours, removed, washed with deionized water, sieved, and drying, to obtain a yellow-green in color, composition Ca8Mg (SiO4) 4Cl2:0.1Eu2 + divalent europium-activated calcium chloride magnesium silicate phosphor. 该荧光粉在365nm激发下,发射明亮的绿光。 The phosphor at 365nm excitation, emit bright green light.

实施例二、称取CeO20.052g,其余条件同实施例一,得到Ca8Mg(SiO4)4Cl2∶0.1Eu2+,0.01Ce3+荧光粉,其体色为浅黄绿色,在紫外光和蓝光激发下,发射很强的带蓝的绿光,其亮度比没有掺Ce3+的荧光粉高。 Example II weighed CeO20.052g, a remaining conditions being the same, to give Ca8Mg (SiO4) 4Cl2:0.1Eu2 +, 0.01Ce3 + phosphors, which body color as a pale green, and blue under UV excitation, emit a strong bluish green high, the brightness ratio is not doped with Ce3 + phosphor.

实施例三、称取Eu2O30.158g,CeO20.155g,其它条件同实施例一,得到体色为浅黄绿色的Ca3Mg(SiO4)4Cl2:0.03Eu2+,0.03Ce3+荧光粉,在365nm激发下其绿色发光强度是没有掺Ce3+的1.5倍。 Embodiment 3 weighed Eu2O30.158g, CeO20.155g, other conditions being the same one, 4Cl2 obtained as a pale green in color Ca3Mg (SiO4): 0.03Eu2 +, 0.03Ce3 + phosphor, which is a green light emission intensity at excitation 365nm It is not doped with Ce3 1.5 times the +.

实施例四、称取CaCO321.00g,ZnO2.44g,SiO27.21g,CaCl210.00g,混磨均匀,于1220℃恒温数分钟,温度迅速降至1160℃恒温3小时,得到CaaZn(SiO4)4Cl2白色多晶基质材料。 Example IV weighed CaCO321.00g, ZnO2.44g, SiO27.21g, CaCl210.00g, uniformly mixing mill at 1220 ℃ temperature for several minutes, the temperature rapidly to 1160 ℃ temperature for 3 hours to give CaaZn (SiO4) 4Cl2 white polycrystalline matrix material. 称取Eu2O3激活剂0.158g,Li2CO3助熔剂1.03g,和上述获得的氯硅酸锌钙基质混磨均匀,于1000℃弱还原气氛中灼烧3小时,其余条件同实施例一,得到体色为浅黄绿色的二价铕激活的氯硅酸锌钙Ca8Zn(SiO4)4Cl2:0.03Eu2+荧光粉。 Weigh activator Eu2O3 0.158g, Li2CO3 1.03 g of the flux, zinc chloride and calcium silicate matrix obtained above was mixed uniformly mill at 1000 ℃ fired in a weakly reducing atmosphere for 3 hours and the remaining conditions were the same first embodiment, the body color obtained green light yellow activated by bivalent europium chloride, calcium zinc silicate Ca8Zn (SiO4) 4Cl2: 0.03Eu2 + phosphor.

实施例五、称取CeO20.052g,其余条件同实施例四,得到二价铕和三价铈共激活的Ca8Zn(SiO4)4Cl2:0.03Eu2+,0.01Ce3+荧光粉。 Example V. weighed CeO20.052g, other conditions in Example IV to give divalent europium and trivalent cerium co-activated Ca8Zn (SiO4) 4Cl2: 0.03Eu2 +, 0.01Ce3 + phosphor.

实施例六、称取CaCO321.00g,MgO0.61g,ZnO1.22g,CaCl26.66g,Li2CO31.03g,磨混均匀,放入高温炉中,于1220℃恒温数分钟,温度降至1160℃后恒温3小时,洗涤,过筛,烘干后得到Ca8Mg0.5Zn0.5(SiO4)4Cl2白色基质。 After the sixth embodiment, weighed CaCO321.00g, MgO0.61g, ZnO1.22g, CaCl26.66g, Li2CO31.03g, mill mixed uniformly, placed in a high temperature furnace for several minutes at 1220 ℃ thermostat, the thermostat temperature was reduced to 1160 ℃ 3 hours, washed, sieved to give after drying Ca8Mg0.5Zn0.5 (SiO4) 4Cl2 white mass. 然后称取Eu2O30.158g,CeO20.052g,和上述基质混磨均匀,于1100℃下在弱还原气氛灼烧3小时,得到浅黄色Ca8Mg0.5Zn0.5(SiO4)4Cl2:0.03Eu2+,0.01Ce3+荧光粉。 Then weighed Eu2O30.158g, CeO20.052g, and said matrix uniformly mixing mill, calcined at 1100 ℃ in a weakly reducing atmosphere for 3 hours, to give a pale yellow Ca8Mg0.5Zn0.5 (SiO4) 4Cl2: 0.03Eu2 +, 0.01Ce3 + fluorescence powder.

Claims (2)

1.一种绿色荧光粉,其特征在于荧光粉为稀土激活的氯硅酸镁锌钙,其化学表达式如下:Ca8Mg1-aZna(SiO4)4Cl2:XEu2+,yM其中:M为Ce3+和Mn2+,少量Sr,Ba可取代Ca;式中,0≤a≤1,0≤x≤0.2,0≤y≤0.1摩尔。 A green phosphor, wherein the phosphor is a rare earth-activated zinc silicate, calcium chloride, its chemical formula is as follows: Ca8Mg1-aZna (SiO4) 4Cl2: XEu2 +, yM wherein: M is Ce3 + and Mn2 +, a small amount of Sr, Ba of Ca may be substituted; wherein, 0≤a≤1,0≤x≤0.2,0≤y≤0.1 mol.
2.一种绿色荧光粉的制备方法,其特征在于按化学计量比CaCO3∶MgO(ZnO)∶SiO2∶CaCl2=7∶1∶4∶1摩尔比配制荧光粉的基质,过量的CaCl2可起助熔剂作用,称取量为计算量的1.0-2.5倍,激活剂为Eu2+、敏化剂为Ce3+、助熔剂为Ll2CO3,上述原料充分磨混均匀后,在1000-1200℃下的弱还原气氛中灼烧1-3小时,对含锌的化合物则先在空气中合成含锌的基质,然后该基质和掺杂的激活剂Eu2+、敏化剂Ce3+、助熔剂Li2CO3等混合,在高温还原性气氛中合成所需的荧光粉,还原气氛可以是95%N2+5%H2(体积比)混合气体,也可是碳粒在空气中燃烧产生的气体。 A method for preparing a green phosphor, characterized in that the stoichiometric CaCO3:MgO (ZnO) :SiO2:CaCl2 = 7:1:4:1 molar ratio of the phosphor matrix formulation, the excess can act as co-CaCl2 flux effect weighed amount of from 1.0 to 2.5 times the calculated amount of activating agent is Eu2 +, sensitizer is Ce3 +, is a flux Ll2CO3, after the grinding of the raw material mixed sufficiently uniformly, at 1000-1200 ℃ weakly reducing atmosphere burning 1-3 hours, then to a zinc-containing matrix synthesis zinc compound in air, and then mixing the matrix and an activator doped Eu2 +, the sensitizer Ce3 +, Li2CO3 flux etc., in a high temperature reducing atmosphere desired synthesized phosphor, a reducing atmosphere may be 95% N2 + 5% H2 (by volume) gas mixture of carbon particles may also be produced by the gas combustion in air.
CN 96123003 1996-12-26 1996-12-26 Green fluorescent powder and preparation thereof CN1186103A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1325603C (en) * 2003-11-27 2007-07-11 上海交通大学 Long-time afterglow luminescent silicate material and its producing method
CN101010413B (en) 2004-09-07 2010-08-25 住友化学株式会社 Phosphor, phosphor paste and light-emitting device
WO2012000176A1 (en) * 2010-06-29 2012-01-05 海洋王照明科技股份有限公司 Fluorescent powder of halogen silicate containing nano-metal particles and preparaion method thereof
CN101307229B (en) 2007-04-05 2012-07-04 株式会社小糸制作所 Phosphor
CN1729267B (en) 2002-12-20 2012-12-19 丰田合成株式会社 Phosphor and optical device using same
CN102925153A (en) * 2012-11-23 2013-02-13 中国科学院长春光学精密机械与物理研究所 Color-adjustable single-phase fluorescent material and application thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1729267B (en) 2002-12-20 2012-12-19 丰田合成株式会社 Phosphor and optical device using same
CN1325603C (en) * 2003-11-27 2007-07-11 上海交通大学 Long-time afterglow luminescent silicate material and its producing method
CN101010413B (en) 2004-09-07 2010-08-25 住友化学株式会社 Phosphor, phosphor paste and light-emitting device
CN101307229B (en) 2007-04-05 2012-07-04 株式会社小糸制作所 Phosphor
WO2012000176A1 (en) * 2010-06-29 2012-01-05 海洋王照明科技股份有限公司 Fluorescent powder of halogen silicate containing nano-metal particles and preparaion method thereof
CN102933685A (en) * 2010-06-29 2013-02-13 海洋王照明科技股份有限公司 Fluorescent powder of halogen silicate containing nano-metal particles and preparaion method thereof
US8956553B2 (en) 2010-06-29 2015-02-17 Ocean's King Lighting Science & Technology Co., Ltd. Fluorescent powder of halogen silicate containing nano-metal particles and preparation method thereof
CN102925153A (en) * 2012-11-23 2013-02-13 中国科学院长春光学精密机械与物理研究所 Color-adjustable single-phase fluorescent material and application thereof
CN102925153B (en) 2012-11-23 2014-01-15 中国科学院长春光学精密机械与物理研究所 Color-adjustable single-phase fluorescent material and application thereof

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