CN102337130B - Bismuth ion-doped germanosilicate luminescent material and preparation method thereof - Google Patents

Bismuth ion-doped germanosilicate luminescent material and preparation method thereof Download PDF

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CN102337130B
CN102337130B CN201010227119.4A CN201010227119A CN102337130B CN 102337130 B CN102337130 B CN 102337130B CN 201010227119 A CN201010227119 A CN 201010227119A CN 102337130 B CN102337130 B CN 102337130B
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luminescent material
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raw materials
bismuth ion
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CN102337130A (en
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周明杰
黄杰
汪磊
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention belongs to the field of photoelectric materials, disclosing a bismuth ion-doped germanosilicate luminescent material. The bismuth ion-doped germanosilicate luminescent material is characterized in that a chemical general formula of the bismuth ion-doped germanosilicate luminescent material is AB1-xBixCO4, wherein x is more than 0 and not more than 0.08, A is one of Na, K and Li, B is one or two of Y, Gd, Lu, La and Sc and C is one or two of Ge and Si. The invention further discloses a preparation method of the bismuth ion-doped germanosilicate luminescent material. The luminescent material disclosed by the invention is the bismuth ion-doped germanosilicate luminescent material, has the characteristics of favorable stability and better luminescent performance and can be suitable for UV (Ultraviolet)-LED (Light Emitting Diode).

Description

Germanium silicate luminescent material of bismuth ion doping and preparation method thereof
Technical field
The present invention relates to a kind of germanium silicate luminescent material, relate in particular to a kind of germanium silicate luminescent material of bismuth ion doping.The invention still further relates to a kind of preparation method of germanium silicate luminescent material of bismuth ion doping.
Background technology
At present, transition element and rare earth luminescent material are as a kind of new and effective luminescent material, the important luminescent materials in field such as information demonstration, lighting source, photoelectric device have been developed into, by improving the luminous intensity of luminescent material, can effectively improve the performance of luminescent device, the luminous efficiency that simultaneously improves device is also effectively energy-conservation.Therefore, the research of the luminescent material of high-luminous-efficiency and application are the important research contents in materials chemistry and materials physics field always.
Rare earth ion doped germanium silicate luminescent material has good photoluminescence performance, and fluorescence color purity and the brightness of after being stimulated, sending are all higher.The research of existing ultraviolet LED (UV-LED, lower same) concentrates on UV chip on the one hand, mainly concentrates on the other hand the light-emitting phosphor material that UV-LED uses.Can be applicable at present fluorescent material that UV-LED uses few, thus development of new to be applicable to the luminescent material that UV-LED uses be a research emphasis.
Summary of the invention
The present invention solves the germanium silicate luminescent material that its technical problem is to provide a kind of bismuth (Bi, lower same) ion doping.
The technical scheme adopting is: this germanium silicate luminescent material has following chemical general formula: AB 1-xbi xcO 4wherein, the value of x is 0 < x≤0.08, a kind of for receiving (Na), in potassium (K), lithium (Li) of A, B is a kind of in yttrium (Y), gadolinium (Gd), lutetium (Lu), lanthanum (La), scandium (Sc) or two kinds, and C is a kind of in germanium (Ge), silicon (Si) or two kinds; Wherein, the value of x is preferably 0.001≤x≤0.06.
The present invention also provides a kind of method of preparing the germanium silicate luminescent material of bismuth ion doping, comprises the following steps:
(1), press chemical general formula AB 1-xbi xcO 4in the stoichiometric ratio of each element, the raw materials of compound of A, the raw materials of compound of B, the raw materials of compound of C and Bi are provided 3+raw materials of compound, grind to form mixed powder; Wherein, the raw materials of compound of A is A +carbonate; The raw materials of compound of B is B 3+oxide compound, nitrate, carbonate, oxalate at least one; The raw materials of compound of C is C 4+oxide compound; The raw materials of compound of Bi is Bi 3+oxide compound, one or both in oxalate; The value of x is 0 < x≤0.08, and the value of x is preferably 0.001≤x≤0.06; A kind of for receiving (Na), in potassium (K), lithium (Li) of A, B is a kind of in yttrium (Y), gadolinium (Gd), lutetium (Lu), lanthanum (La), scandium (Sc) or two kinds, and C is a kind of in germanium (Ge), silicon (Si) or two kinds;
(2), by mixed powder high temperature sintering 2～20h at 800～1350 ℃ of temperature, in air atmosphere, resulting product is cooled to room temperature, grinds and to obtain Bi 3+the germanium silicate luminescent material of ion doping.
Luminescent material of the present invention is the germanium silicate luminescent material of bismuth ion of having adulterated, and has good stability, the good feature of luminescent properties, goes for the use of UV-LED.
Preparation method's technique of the present invention is simple, quality product is high, cost is low, can be widely used in luminescent material manufacture.
Accompanying drawing explanation
Fig. 1 is the prepared NaY of embodiment 2 0.99bi 0.01geO 4the emmission spectrum of luminescent material.
Wherein, the excitation wavelength of emmission spectrum is 350nm.The instrument of testing this spectrum use is Shimadzu RF-5301PC fluorescence spectrophotometer;
Fig. 2 is preparation technology's schema of germanium silicate luminescent material of the present invention.
Embodiment
The invention provides a kind of germanium silicate luminescent material of bismuth ion doping, the present invention also provides a kind of method of preparing the germanium silicate luminescent material of bismuth ion doping, as shown in Figure 2, comprises the following steps:
S1, press chemical general formula AB 1-xbi xcO 4in the stoichiometric ratio of each element, the raw materials of compound of A, the raw materials of compound of B, the raw materials of compound of C and Bi are provided 3+raw materials of compound, grind to form mixed powder; Wherein, the raw materials of compound of A is A +carbonate; The raw materials of compound of B is B 3+oxide compound, nitrate, carbonate, oxalate at least one; The raw materials of compound of C is C 4+oxide compound; The raw materials of compound of Bi is Bi 3+oxide compound, one or both in oxalate; The value of x is 0 < x≤0.08, and the value of x is preferably 0.001≤x≤0.06; A kind of for receiving (Na), in potassium (K), lithium (Li) of A, B is a kind of in yttrium (Y), gadolinium (Gd), lutetium (Lu), lanthanum (La), scandium (Sc) or two kinds, and C is a kind of in germanium (Ge), silicon (Si) or two kinds;
S2, by mixed powder high temperature sintering 2～20h at 800～1350 ℃ of temperature, in air atmosphere, resulting product is cooled to room temperature, grinds and to obtain Bi 3+the germanium silicate luminescent material of ion doping.
In above-mentioned steps S2, the sintering process of described mixed powder is carried out in air atmosphere.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
NaY 0.999bi 0.001siO 4the preparation of luminescent material
First weighing sodium carbonate (Na 2cO 3) 0.2650g, yttrium oxide (Y 2o 3) 0.5639g, bismuth oxide (Bi 2o 3) 0.0012g, silicon-dioxide (SiO 2) 0.3005g, then load weighted raw material ground and mixed in agate mortar is packed in corundum crucible after evenly, this corundum crucible is put into high temperature box furnace, under air atmosphere, be warmed up to 1100 ℃, insulation calcining is after 10 hours with this understanding, cool to room temperature, grinds cooled product again, can obtain NaY 0.999bi 0.001siO 4luminescent material.
The NaY of the present embodiment 0.999bi 0.001siO 4under the excitation that luminescent material is 350nm at wavelength, launch blue white light.
Embodiment 2
NaY 0.99bi 0.01geO 4the preparation of luminescent material
First weighing sodium carbonate (Na 2cO 3) 0.2650g, yttrium oxide (Y 2o 3) 0.5589g, bismuth oxide (Bi 2o 3) 0.0116g, germanium dioxide (GeO 2) 0.5230g, then load weighted raw material ground and mixed in agate mortar is packed in corundum crucible after evenly, this corundum crucible is put into high temperature box furnace, under air atmosphere, be warmed up to 1200 ℃, insulation calcining is after 5 hours with this understanding, cool to room temperature, grinds cooled product again, can obtain NaY 0.99bi 0.01geO 4luminescent material.
The NaY of the present embodiment 0.99bi 0.01geO 4under the excitation that luminescent material is 350nm at wavelength, launch blue white light.
Fig. 1 is the NaY that the present embodiment prepares 0.99bi 0.01geO 4emmission spectrum under the excitation that luminescent material is 350nm at 350nm wavelength, spectral range is from 380nm to 620nm, and peak wavelength is 445nm.
Embodiment 3
LiLa 0.994bi 0.006siO 4the preparation of luminescent material
First take Quilonum Retard (Li 2cO 3) 0.1847g, lanthanum nitrate (La (NO 3) 3) 1.6148g, bismuth oxide (Bi 2o 3) 0.0070g, silicon-dioxide (SiO 2) 0.3005g, then load weighted raw material ground and mixed in agate mortar is packed in corundum crucible after evenly, this corundum crucible is put into high temperature box furnace, under air atmosphere, be warmed up to 800 ℃, insulation calcining is after 20 hours with this understanding, cool to room temperature, grinds cooled product again, can obtain LiLa 0.994bi 0.006siO 4luminescent material.
The LiLa of the present embodiment 0.994bi 0.006siO 4under the excitation that luminescent material is 350nm at wavelength, launch blue white light.
Embodiment 4
LiSc 0.992bi 0.008geO 4the preparation of luminescent material
First take and get Quilonum Retard (Li 2cO 3) 0.1847g, Scium trioxide (Sc 2o 3) 0.3420g, bismuth oxide (Bi 2o 3) 0.0093g, germanium dioxide (GeO 2) 0.5230g, then load weighted raw material ground and mixed in agate mortar is packed in corundum crucible after evenly, this corundum crucible is put into high temperature box furnace, under air atmosphere, be warmed up to 1000 ℃, insulation calcining is after 10 hours with this understanding, cool to room temperature, grinds cooled product again, can obtain LiSc 0.992bi 0.008geO 4luminescent material.
The LiSc of the present embodiment 0.992bi 0.008geO 4under the excitation that luminescent material is 350nm at wavelength, launch blue white light.
Embodiment 5
KLu 0.99bi 0.01ge 0.7si 0.3o 4the preparation of luminescent material
First take and get salt of wormwood (K 2cO 3) 0.3455g, oxalic acid lutetium (Lu 2(C 2o 4) 3) 1.5196g, Oxalic acid bismuth salt (Bi 2(C 2o 4) 3) 0.0170g, germanium dioxide (GeO 2) 0.3661g, silicon-dioxide (SiO 2) 0.0901g, then load weighted raw material ground and mixed in agate mortar is packed in corundum crucible after evenly, this corundum crucible is put into high temperature box furnace, under air atmosphere, be warmed up to 1350 ℃, insulation calcining is after 2 hours with this understanding, cool to room temperature, grinds cooled product again, can obtain KLu 0.99bi 0.01ge 0.7si 0.3o 4luminescent material.
The KLu of the present embodiment 0.99bi 0.01ge 0.7si 0.3o 4under the excitation that luminescent material is 350nm at wavelength, launch blue white light.
Embodiment 6
KGd 0.92bi 0.08siO 4the preparation of luminescent material
First take salt of wormwood (K 2cO 3) 0.3455g, gadolinium sesquioxide (Gd 2o 3) 0.8337g, Oxalic acid bismuth salt (Bi 2(C 2o 4) 3) 0.1364g, silicon-dioxide (SiO 2) 0.3005g, then load weighted raw material ground and mixed in agate mortar is packed in corundum crucible after evenly, this corundum crucible is put into high temperature box furnace, under air atmosphere, be warmed up to 1300 ℃, insulation calcining is after 5 hours with this understanding, cool to room temperature, grinds cooled product again, can obtain KGd 0.92bi 0.08siO 4luminescent material.
The KGd of the present embodiment 0.92bi 0.08siO 4under the excitation that luminescent material is 350nm at wavelength, launch blue white light.
Embodiment 7
NaY 0.85gd 0.1bi 0.05geO 4the preparation of luminescent material
First weighing sodium carbonate (Na 2cO 3) 0.2650g, gadolinium carbonate (Gd 2(CO 3) 3) 0.1236g, yttrium carbonate (Y 2(CO 3) 3) 1.5206g, bismuth oxide (Bi 2o 3) 0.0582g, germanium dioxide (GeO 2) 0.5230g, then load weighted raw material ground and mixed in agate mortar is packed in corundum crucible after evenly, this corundum crucible is put into high temperature box furnace, under air atmosphere, be warmed up to 1250 ℃, insulation calcining is after 6 hours with this understanding, cool to room temperature, grinds cooled product again, can obtain NaY 0.85gd 0.1bi 0.05geO 4luminescent material.
The NaY of the present embodiment 0.85gd 0.1bi 0.05geO 4under the excitation that luminescent material is 350nm at wavelength, launch blue white light.
Embodiment 8
KLu 0.47sc 0.5bi 0.03ge 0.3si 0.7o 4the preparation of luminescent material
First take salt of wormwood (K 2cO 3) 0.3455g, oxalic acid lutetium (Lu 2(C 2o 4) 3) 0.7214g, oxalic acid scandium (Sc 2(C 2o 4) 3) 0.8849g, Oxalic acid bismuth salt (Bi 2(C 2o 4) 3) 0.0511g, germanium dioxide (GeO 2) 0.1569g, silicon-dioxide (SiO 2) 0.2103g, then load weighted raw material ground and mixed in agate mortar is packed in corundum crucible after evenly, this corundum crucible is put into high temperature box furnace, under air atmosphere, be warmed up to 1200 ℃, insulation calcining is after 10 hours with this understanding, cool to room temperature, grinds cooled product again, can obtain KLu 0.47sc 0.5bi 0.03ge 0.3si 0.7o 4luminescent material.
The KLu of the present embodiment 0.47sc 0.5bi 0.03ge 0.3si 0.7o 4under the excitation that luminescent material is 350nm at wavelength, launch blue white light.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.

Claims (9)

1. a germanium silicate luminescent material for bismuth ion doping, is characterized in that, its chemical general formula is AB 1-xbi xcO 4; Wherein, the value of x is 0<x≤0.08, and A is a kind of in Na, K, Li, and B is a kind of in Y, Gd, Lu, La, Sc or two kinds, and C is a kind of in Ge, Si or two kinds.
2. the germanium silicate luminescent material of bismuth ion doping according to claim 1, is characterized in that, the value of described x is 0.001≤x≤0.06.
3. a preparation method for the germanium silicate luminescent material of bismuth ion doping, is characterized in that, comprises the steps:
Press chemical general formula AB 1-xbi xcO 4in the stoichiometric ratio of each element, the raw materials of compound of A, the raw materials of compound of B, the raw materials of compound of C and Bi are provided 3+raw materials of compound, grind to form mixed powder; Wherein, the value of x is 0<x≤0.08, and A is a kind of in Na, K, Li, and B is a kind of in Y, Gd, Lu, La, Sc or two kinds, and C is a kind of in Ge, Si or two kinds;
Described mixed powder is placed in to sintering 2～20h at 800～1350 ℃ of temperature, is cooled to after room temperature, grind the germanium silicate luminescent material that obtains described bismuth ion doping.
4. preparation method according to claim 3, is characterized in that, in described raw material grinding steps, the value of described x is 0.001≤x≤0.06.
5. preparation method according to claim 3, is characterized in that, in described raw material grinding steps, the raw materials of compound of described A is A +carbonate.
6. preparation method according to claim 3, is characterized in that, in described raw material grinding steps, the raw materials of compound of described B is B 3+oxide compound, nitrate, carbonate, oxalate at least one.
7. preparation method according to claim 3, is characterized in that, in described raw material grinding steps, the raw materials of compound of described C is C 4+oxide compound.
8. preparation method according to claim 3, is characterized in that, in described raw material grinding steps, the raw materials of compound of described Bi is Bi 3+oxide compound, one or both in oxalate.
9. preparation method according to claim 3, is characterized in that, in described mixture powder sintering step, the sintering process of described mixed powder is carried out in air atmosphere.
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CN102906223B (en) * 2010-07-19 2014-07-02 海洋王照明科技股份有限公司 Luminescent material and preparation method thereof
CN104211079B (en) * 2014-09-05 2016-04-13 齐鲁工业大学 A kind of preparation method of high thermal stability STW type germanium silicate molecular sieve
CN115161028B (en) * 2022-07-18 2023-11-14 中国计量大学 Fluorescence-adjustable anti-counterfeiting material and preparation method thereof
CN116103045B (en) * 2023-02-16 2023-12-29 华侨大学 LiSc (LiSc) 1-x Lu x GeO 4 :Ln 3+ ,Eu 3+ Optical storage material, preparation method and application thereof

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