CN102746844B - CaIn2O4-based up-conversion luminescent material and preparation methods thereof - Google Patents

CaIn2O4-based up-conversion luminescent material and preparation methods thereof Download PDF

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CN102746844B
CN102746844B CN 201210215571 CN201210215571A CN102746844B CN 102746844 B CN102746844 B CN 102746844B CN 201210215571 CN201210215571 CN 201210215571 CN 201210215571 A CN201210215571 A CN 201210215571A CN 102746844 B CN102746844 B CN 102746844B
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luminescent material
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conversion luminescent
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CN102746844A (en
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郭崇峰
李琳
李婷
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Northwest University
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Northwest University
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Abstract

The invention belongs to the technical field of luminescent materials and discloses a CaIn2O4-based up-conversion luminescent material. The CaIn2O4-based up-conversion luminescent material is characterized in that CaIn2O4 is utilized as a base material and rare-earth metal ions are added into the base material. The invention also discloses a solid-phase preparation method and a sol-gel preparation method of the CaIn2O4-based up-conversion luminescent material. The CaIn2O4-based up-conversion luminescent material has low phonon energy of the base material, and stable physical and chemical properties. The two preparation methods have simple processes and low costs and are suitable for industrial production.

Description

A kind of with CaIn 2o 4for up-conversion luminescent material of matrix and preparation method thereof
Technical field
The invention belongs to the luminescent material technical field in physics, be specifically related to a kind of with CaIn 2o 4for up-conversion luminescent material of matrix and preparation method thereof.
Background technology
Up-conversion luminescent material is a kind of material at infrared ray excited lower emission visible ray, it is at short wavelength's solid laser, in the devices such as infrared laser detecting, play a part very importantly, so the good up-conversion luminescent material of processability has very great meaning.
Traditional up-conversion luminescent material is substantially all to using fluorochemical or oxyfluoride as matrix, as the ZL200710009067.1 patent discloses rare earth ion doped NaYF 4for up-conversion phosphor of matrix tool adjustable light color and preparation method thereof, its up-conversion phosphor provided exists that water absorbability is strong, poor chemical stability, bad mechanical strength and be difficult for the shortcoming of preparation, has greatly limited its practical application effect.Its preparation method commonly used is hydrothermal method, as ZL200710144828.4 discloses the hydrothermal method preparation of the red up-conversion phosphor that NaYF4 is matrix, it has, and synthesis temperature is low, the product purity advantages of higher, but its reaction process is under high pressure to carry out, and synthetic cost is higher, this kind of method is not easy to a large amount of production.
Summary of the invention
The object of the invention is to provide that a kind of stability is high, good luminous performance rare earth ion doped with CaIn 2o 4novel up-conversion luminescent material for matrix.
The structural formula of luminescent material provided by the present invention is: CaIn 2x-y-z(Yb xm yn z) O 4, wherein: M is Er, Ho, and Tm, Pr or Nd, N is Er, Ho, Tm, Pr or Nd, and M is different from N; 0≤x≤0.3,0≤y≤0.05,0≤z≤0.05, and y and z can not be O simultaneously.
Further, the structural formula of described luminescent material is: CaIn 2-x-y(Yb xer y) O 4, wherein: 0≤x≤0.3,0<y≤0.05.
Further, the structural formula of described luminescent material is: CaIn 2-x-y(Yb xho y) O 4, wherein: 0≤x≤0.3,0<y≤0.05.
Further, the structural formula of described luminescent material is: CaIn 2-x-y(Yb xnd y) O 4, wherein: 0≤x≤0.3,0<y≤0.05.
Further, the structural formula of described luminescent material is: CaIn 2-x-y(Yb xtmy) O 4, wherein: 0≤x≤0.3,0<y≤0.05.
Further, the structural formula of described luminescent material is: CaIn 2-x-y(Yb xpr y) O 4, wherein: 0≤x≤0.3,0<y≤0.05.
Further, the structural formula of described luminescent material is: CaIn 2-x-y-z(Yb xer ytm z) O 4, wherein: 0≤x≤0.3,0<y≤0.05,0<z≤0.05.
CaIn of the present invention 2o 4the phonon of the up-conversion luminescent material matrix of matrix can low, physics and chemistry stable in properties.
For different systems, by adjusting fill a prescription (x, y, z value) can obtain tangerine red, green, blue and several VISIBLE LIGHT EMISSION of white light.
The CaIn of above-mentioned formula 2-x-y(Yb xer y) O 4the up-conversion luminescent material of system can produce 507～530nm and 530～580nm wave band green emission and 630～695nm wave band red emission under the exciting of 980nm laser;
CaIn 2-x-y(Yb xho y) O 4the up-conversion luminescent material of system can produce red emission a little less than the strong green emission of 525～565nm wave band and 640～670nm wave band under the exciting of 980nm laser;
CaIn 2-x-y(Yb xnd y) O 4the up-conversion luminescent material of system can produce the emission that the strong green glow of 525～565nm wave band, 470～495nm wave band blue light region, 595～610nm wave band tangerine red light district and 645～665nm wave band red light district have the low light level under the exciting of 980nm laser;
CaIn 2-x-y(Yb xtm y) O 4the up-conversion luminescent material of system can produce red emission a little less than the strong blue light of 455～510nm wave band and 645～660nm under 980nm and optical excitation;
CaIn 2-x-y-z(Yb xer ytm z) O 4/ CaIn 2-x-y(Yb xpr y) O 4the up-conversion luminescent material of system can produce the light of three wave bands of red, green, blue under 980nm laser excitation; CaIn wherein 2-x-y(Yb xpr y) O 4produce 465～520nm wave band blue light, 525～575nm wave band green glow and 610～670nm wave band ruddiness, by adjusting Er, the concentration of Tm and Pr can obtain white luminous.
Another object of the present invention is to provide the preparation method of above-mentioned luminescent material.The preparation method who provides is as follows:
The step that the employing high temperature solid-state method prepares above-mentioned luminescent material is as follows:
Step 1, will containing the In compound, containing the Ca compound, containing the Yb compound, containing the M compound and containing the N compound by formula general formula CaIn 2-x-y-z(Yb xm yn z) O 4batching is mixed, and mix is ground and obtains powder A, wherein: be In containing the In compound 2o 3or In (NO 3) 3, containing the Ca compound, be CaCO 3or Ca (NO 3) 2, containing the Yb compound, be Yb 2o 3, containing the M compound, be M 2o 3, M 6o 11or M (NO 3) 3, containing the N compound, be N 2o 3, N 6o 11or N (NO 3) 3;
Step 2, by powder A pre-burning 2～6h under 400～600 ℃ of conditions, grind to obtain powder material B after cooling;
Step 3 is calcined 8～24h by powder material B under 700～1400 ℃ of conditions, grinds to obtain up-conversion luminescent material after cooling.
The step that the employing sol-gel method prepares above-mentioned luminescent material is as follows:
Step 1, will be containing In compound powder, containing Ca compound powder, Yb (NO 3) 3solution, M (NO 3) 3solution and N (NO 3) 3solution is by formula general formula CaIn 2-x-y-z(Yb xm yn z) O 4batching, obtain solution A after stirring, then citric acid is added in solution A, obtains solution B after complete reaction, and the citrate ion in institute's adding citric acid and the metal ion mol ratio in solution A are: (1～4): 1;
Step 2 first is incubated 48～72h by solution B under 60～80 ℃ of conditions, then under 120 ℃ of conditions, is incubated 12～24h, obtains presoma;
Step 3, after presoma is ground under 400～600 ℃ of conditions pre-burning 2 ~ 6h, obtain original material, calcine 2～10h after then will original material grinding under 700～1400 ℃ of conditions, grind to obtain up-conversion luminescent material after cooling.
The present invention adopts conventional high-temperature solid phase method and sol-gel method to prepare rare earth ion doped CaIn 2o 4for the up-conversion luminescent material of matrix, its preparation technology is simple, chemosynthesis is with low cost, be applicable to commercial scale production.
The accompanying drawing explanation
Fig. 1 is the CaIn in the embodiment of the present invention 1 2-0.1-0.025(Yb 0.1er 0.025) O 4up-conversion luminescent material is calcined the XRD figure spectrum of 16h under differing temps;
Fig. 2 is the CaIn in the embodiment of the present invention 1 2-0.1-0.025(Yb 0.1er 0.025) O 4the emmission spectrum of up-conversion luminescent material;
Fig. 3 is the CaIn in the embodiment of the present invention 7 2-0.1-0.005(Yb 0.1ho 0.005) O 4the emmission spectrum of fluorescent material;
Fig. 4 is the CaIn in the embodiment of the present invention 9 2-0.1-0.005(Yb 0.1nd 0.005) O 4the emmission spectrum of up-conversion luminescent material;
Fig. 5 is the CaIn in the embodiment of the present invention 10 2-0.1-0.001(Yb 0.1tm 0.001) O 4the emmission spectrum of up-conversion luminescent material;
Fig. 6 is the CaIn in the embodiment of the present invention 16 2-0.1-0.005(Yb 0.1pr 0.005) O 4the emmission spectrum of up-conversion luminescent material.
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment
Embodiment 1:
This embodiment is CaIn 2-0.1-0.025(Yb 0.1er 0.025) O 4the solid phase method preparation method of up-conversion luminescent material, concrete preparation process is as follows:
1) press CaIn 2-0.1-0025(Yb 0.1er 0.025) O 4the mol ratio of stoichiometric equation takes In 2o 3(SP) 0.5205g, CaCO 3(AR) 0.2001g, Yb 2o 3(3N5) 0.0394g and Er 2o 3(3N) 0.0097g, mix the raw material after preparation, grinds to obtain powder A;
2) powder A is heat-treated under retort furnace Air atmosphere to 500 ℃ of pre-burning 5h, the cooling rear powder material B of fully grinding to obtain;
3) powder material B is calcined to 16h under 1300 ℃ of conditions, grind to such an extent that send out the fluorescent material of Exocarpium Citri Rubrum light after naturally cooling.
The CaIn that Fig. 1 is this embodiment 2-0.1-0.025(Yb 0.1er 0.025) O 4up-conversion luminescent material is calcined the XRD figure spectrum of 16h under differing temps, in Fig. 1, X-coordinate be 2 times of diffraction angle (°), ordinate zou is diffracted intensity (a.u.); As can be seen from the figure, the diffraction peak of sample and CaIn 2o 4identical fine of standard card (PDF17-0643), dephasign does not appear, illustrate that the doping of rare earth ion does not affect CaIn 2o 4crystalline structure.
Fig. 2 is this Embodiment C aIn 2-0.1-0.025(Yb 0.1er 0.025) O 4the emmission spectrum of up-conversion luminescent material, in Fig. 2, X-coordinate is wavelength (nm), ordinate zou is luminous intensity (a.u.), each emmission spectrum is respectively 550nm, 660nm from left to right.
Embodiment 2:
This embodiment is CaIn 2-0.05er 0.05o 4the solid phase method preparation method of up-conversion luminescent material, concrete preparation process is as follows:
1) press CaIn 2-0.05er 0.05o 4the mol ratio of stoichiometric equation takes In (NO 3) 34.5H 2o (AR) 1.4895g, Ca (NO 3) 24H 2o (AR) 0.4723g and Er 2o 3(3N) 0.0191g, mix the raw material after preparation, grinds to obtain powder A;
2) powder A is heat-treated under retort furnace Air atmosphere, 400 ℃ of pre-burning 2h, fully grind after cooling again, obtains powder material B;
3) powder material B is carried out to high-temperature heat treatment again, 700 ℃ of calcining 8h, grind to such an extent that send out the fluorescent material of Exocarpium Citri Rubrum light after naturally cooling.
Embodiment 3:
This embodiment is CaIn 2-0.1-0.025(Yb 0.1er 0.025) O 4the preparation of fluorescent material, the concrete preparation process of sol-gel method is as follows:
1) press reactant positively charged ion mol ratio Ca 2+: In 2+: Er 3+: Yb 3+=1:1.875:0.025:0.1 takes respectively CaCO 3(AR) 0.1504g, In (NO 3) 34.5H 2o (AR) 1.0741g powder, measure the Yb (NO of 0.02mol/L 3) 3er (the NO of solution 7.5mL, 0.01mol/L 3) 3solution 3.75mL mix and blend obtains solution A; Be that 2:1 takes citric acid 1.9003g in citrate ion and metal ion ratio, slowly add in solution A, the limit edged stirs, and makes it complete reaction, and the deionized water constant volume obtains colourless transparent solution B;
2) solution B is put into to baking oven, under 80 ℃ of environment, be incubated 48h, form the transparent and homogeneous colloid, then be warming up to 120 ℃, insulation 12h, obtain yellow presoma;
3) presoma is ground fully, at 600 ℃ of lower pre-burning 6h, obtain the original material of fluffy yellow powder powder, at 1400 ℃ of calcining 8h, coolingly grind to such an extent that send out the fluorescent material of Exocarpium Citri Rubrum light afterwards after original material is fully ground.
Embodiment 4:
This embodiment is CaIn 2-0.3-0.025(Yb 0.3er 0.025) O 4the preparation of fluorescent material, the concrete preparation process of sol-gel method is as follows:
1) press reactant positively charged ion mol ratio Ca 2+: In 2+: Er 3+: Yb 3+=1:1.675:0.025:0.3 takes respectively Ca (NO 3) 24H 2o (AR) 0.3546g, In (NO 3) 34.5H 2o (AR) 0.9596g powder, measure the Yb (NO of 0.04mol/L 3) 3er (the NO of solution 11.25mL, 0.02mol/L 3) 3solution 1.875mL mix and blend obtains solution A; Be that 2:1 takes citric acid 1.9002g in citrate ion and metal ion ratio, slowly add in solution A, the limit edged stirs, and makes it complete reaction, and the deionized water constant volume obtains colourless transparent solution B;
2) solution B is put into to baking oven, under 80 ℃ of environment, be incubated 48h, form the transparent and homogeneous colloid, then be warming up to 120 ℃, insulation 12h, obtain yellow presoma;
3) presoma is ground fully, at 600 ℃ of lower pre-burning 5h, obtain the original material of fluffy yellow powder powder, then original material is fully ground, at 1400 ℃ of calcining 2h, the cooling rear up-conversion luminescent material of an Exocarpium Citri Rubrum light of grinding to obtain.
Embodiment 5:
This embodiment is CaIn 2-0.1-0.005(Yb 0.1ho 0.005) O 4the solid phase method preparation method of fluorescent material, concrete preparation process is as follows:
1) press CaIn 2-0.1-0.005(Yb 0.1ho 0.005) O 4the mol ratio of stoichiometric equation takes In 2o 3(SP) 0.5262g, CaCO 3(AR) 0.2001g, Yb 2o 3(3N5) 0.0394g and Ho 2o 3(3N5) 0.0021g, mix the raw material after preparation, fully grinds to obtain powder A;
2) powder A is heat-treated under retort furnace Air atmosphere, 500 ℃ of pre-burning 4h, fully grind after cooling again, obtains powder material B;
3) powder material B is carried out to high-temperature heat treatment again, 700 ℃ of calcining 16h, grind to such an extent that send out the fluorescent material of purer green glow after naturally cooling.
Embodiment 6:
This embodiment is CaIn 2-0.05ho 0.05o 4the solid phase method preparation method of fluorescent material, concrete preparation process is as follows:
1) press CaIn 2-0.05ho 0.05o 4the mol ratio of stoichiometric equation takes In (NO 3) 34.5H 2o (AR) 1.4890g, Ca (NO 3) 24H 2o (AR) 0.4723g and Ho 2o 3(3N5) 0.0189g, mix the raw material after preparation, grinds the abundant powder A of obtaining;
2) powder A is heat-treated under retort furnace Air atmosphere, 400 ℃ of pre-burning 2h, fully grind after cooling again, obtains powder material B;
3) powder material B is carried out to high-temperature heat treatment again, 1300 ℃ of calcining 8h, grind to obtain the fluorescent material of green light after naturally cooling.
Embodiment 7:
This embodiment is CaIn 2-0.1-0005(Yb 0.1ho 0.005) O 4the sol-gel method for preparing of fluorescent material, concrete preparation process is as follows:
1) press reactant positively charged ion mol ratio Ca 2+: In 2+: Ho 3+: Yb 3+=1:1.895:0.005:0.1 takes respectively CaCO 3(AR) 0.1504g, In (NO 3) 34.5H 2o (AR) 1.0858g powder, measure the Yb (NO of 0.02mol/L 3) 3ho (the NO of solution 7.5mL, 0.01mol/L 3) 3solution 0.75mL mix and blend obtains solution A; Be that 2:1 takes citric acid 1.9007g in citrate ion and metal ion ratio, slowly add in solution A, the limit edged stirs, and makes it complete reaction, and the deionized water constant volume obtains colourless transparent solution B;
2) solution B is put into to baking oven, under 80 ℃ of environment, be incubated 48h, form the transparent and homogeneous colloid, then be warming up to 120 ℃, insulation 12h, obtain yellow presoma;
3) presoma is ground fully, at 500 ℃ of lower pre-burning 5h, obtain the original material of fluffy yellow powder powder, then original material is fully ground, at 1300 ℃ of calcining 8h, the cooling rear fluorescent material of a purer green glow of grinding to obtain.
Fig. 3 is this Embodiment C aIn 2-0.1-0.005(Yb 0.1ho 0.005) O 4the emmission spectrum of up-conversion luminescent material, in Fig. 3, X-coordinate is wavelength (nm), ordinate zou is luminous intensity (a.u.), each emmission spectrum is respectively 542nm and 650nm from left to right.
Embodiment 8:
This embodiment is CaIn 2-0.3-0005(Yb 0.3ho 0.005) O 4the sol-gel method for preparing of fluorescent material, concrete preparation process is as follows:
1) press reactant positively charged ion mol ratio Ca 2+: In 2+: Ho 3+: Yb 3+=1:1.695:0.005:0.3 takes respectively Ca (NO 3) 24H 2o (AR) 0.3544g, In (NO 3) 34.5H 2o (AR) 0.9710g powder, measure the Yb (NO of 1mol/L 3) 3ho (the NO of solution 0.45mL, 0.03mol/L 3) 3solution 0.25mL mix and blend obtains solution A.Be that 2:1 takes citric acid 1.8949g in citrate ion and metal ion ratio, slowly add in solution A, the limit edged stirs, and makes it complete reaction, and the deionized water constant volume obtains colourless transparent solution B;
2) solution B is put into to baking oven, under 80 ℃ of environment, be incubated 48h, form the transparent and homogeneous colloid.Be warming up to 120 ℃, insulation 12h, obtain yellow presoma;
3) presoma is ground fully, at 600 ℃ of lower pre-burning 4h, obtain fluffy yellow powder powder original material, then original material is fully ground, at 1400 ℃ of calcining 2h, the cooling rear fluorescent material of a purer green glow of grinding to obtain.
Embodiment 9:
This embodiment is CaIn 2-0.1-0.005(Yb 0.1nd 0.005) O 4the process for preparing sol-gel of fluorescent material, concrete preparation process is as follows:
1) press reactant positively charged ion mol ratio Ca 2+: In 2+: Nd 3+: Yb 3+=1:1.895:0.005:0.1 takes respectively CaCO 3(AR) 0.1001g, In (NO 3) 34.5H 2o (AR) 0.7241g powder, measure the Yb (NO of 0.02mol/L 3) 3nd (the NO of solution 5mL, 0.01mol/L 3) 3solution 0.5mL mix and blend obtains solution A; Be that 2:1 takes citric acid 1.2623g in citrate ion and metal ion ratio, slowly add in solution A, the limit edged stirs, and makes it complete reaction, and the deionized water constant volume obtains colourless transparent solution B;
2) solution B is put into to baking oven, under 80 ℃ of environment, be incubated 48h, form the transparent and homogeneous colloid, then be warming up to 120 ℃, insulation 12h, obtain yellow presoma;
3) presoma is ground fully, at 500 ℃ of lower pre-burning 5h, obtain fluffy yellow powder powder original material, original material is fully ground, at 1300 ℃ of calcining 8h, coolingly grind to such an extent that send out the fluorescent material of purer green glow afterwards.
The CaIn that this embodiment makes 2-0.1-0.005(Yb 0.1nd 0.005) O 4the emmission spectrum of up-conversion luminescent material is shown in Fig. 4, and in Fig. 4, X-coordinate is wavelength (nm), and ordinate zou is luminous intensity (a.u.), and each emmission spectrum is respectively 486nm from left to right, 542nm, 603nm, 655nm.
Embodiment 10:
This embodiment is CaIn 2-0.1-0.001(Yb 0.1tm 0.001) O 4the solid phase preparation method of up-conversion luminescent material, concrete preparation process is as follows:
1) press CaIn 2-0.1-0.001(Yb 0.1tm 0.001) O 4the mol ratio of stoichiometric equation takes In 2o 3(SP) 0.5262g, CaCO 3(AR) 0.2002g, Yb 2o 3(3N5) 0.0394g and Tm 2o 3(2N5) 0.0006g, mix the raw material after preparation, grinds fully, obtains powder A;
2) powder A is heat-treated under retort furnace Air atmosphere, 500 ℃ of pre-burning 5h, fully grind after cooling again, obtains powder material B;
3) powder material B is carried out to high-temperature heat treatment again, 1300 ℃ of calcining 16h, grind to such an extent that send out than the fluorescent material of ethereal blue light after naturally cooling.
The CaIn that Fig. 5 is this embodiment 2-0.1-0.001(Yb 0.1tm 0.001) O 4the emmission spectrum of up-conversion luminescent material, in Fig. 5, each emmission spectrum is respectively 484nm and 655nm from left to right.
Embodiment 11:
This embodiment is CaIn 2-0.05tm 0.05o 4the solid phase preparation method of fluorescent material, concrete preparation process is as follows:
1) press CaIn 2-0.05tm 0.05o 4the mol ratio of stoichiometric equation takes In (NO 3) 34.5H 2o (AR) 1.4891g, Ca (NO 3) 24H 2o (AR) 0.4723g and Tm 2o 3(2N5) 0.0193g, mix the raw material after preparation, grinds fully, obtains powder A;
2) powder A is heat-treated under retort furnace Air atmosphere, 400 ℃ of pre-burning 2h, fully grind after cooling again, obtains powder material B;
3) powder material B is carried out to high-temperature heat treatment again, 700 ℃ of calcining 24h, grind to such an extent that send out than the fluorescent material of ethereal blue light after naturally cooling.
Embodiment 12:
This embodiment is CaIn 2-0.1-0.001(Yb 0.1tm 0.001) O 4the preparation of sol-gel method of fluorescent material, concrete preparation process is as follows:
1) press reactant positively charged ion mol ratio Ca 2+: In 2+: Tm 3+: Yb 3+=1:1.899:0.001:0.1 takes respectively Ca (NO 3) 24H 2o (AR) 0.2365g, In (NO 3) 34.5H 2o (AR) 0.7253g powder, measure the Yb (NO of 0.01mol/L 3) 3tm (the NO of solution 10ml, 0.01mol/L 3) 3solution 0.1mL mix and blend obtains solution A.Be that 2:1 takes citric acid 1.2618g in citrate ion and metal ion ratio, slowly add in solution A, the limit edged stirs, and makes it complete reaction, and the deionized water constant volume obtains colourless transparent solution B;
2) solution B is put into to baking oven, under 80 ℃ of environment, be incubated 48h, form the transparent and homogeneous colloid; Then be warming up to 120 ℃, insulation 12h, obtain yellow presoma;
3) presoma is ground fully, at 600 ℃ of lower pre-burning 6h, obtain fluffy yellow powder powder original material, after original material is fully ground, at 1400 ℃ of calcining 8h, coolingly grind to such an extent that send out than the fluorescent material of ethereal blue light afterwards.
Embodiment 13:
This embodiment is CaIn 2-0.3-0.005(Yb 0.3tm 0.005) O 4the preparation of sol-gel method of fluorescent material, concrete preparation process is as follows:
1) press reactant positively charged ion mol ratio Ca 2+: In 2+: Tm 3+: Yb 3+=1:1.695:0.005:0.3 takes respectively CaCO 3(AR) 0.1005g, In (NO 3) 34.5H 2o (AR) 0.6475g powder, measure the Yb (NO of 0.02mol/L 3) 3tm (the NO of solution 15mL, 0.005mol/L 3) 3solution 1mL mix and blend obtains solution A.Be that 2:1 takes citric acid 1.2625g in citrate ion and metal ion ratio, slowly add in solution A, the limit edged stirs, and makes it complete reaction, and the deionized water constant volume obtains colourless transparent solution B;
2) solution B is put into to baking oven, under 80 ℃ of environment, be incubated 48h, form the transparent and homogeneous colloid, then be warming up to 120 ℃, insulation 12h, obtain yellow presoma;
3) presoma is ground fully, at 500 ℃ of lower pre-burning 4h, obtain fluffy yellow powder powder original material, at 1100 ℃ of calcining 10h, coolingly grind than the fluorescent material of ethereal blue light afterwards after then original material fully being ground.
Embodiment 14:
This embodiment is CaIn 2-0.1-0.005(Yb 0.1pr 0.005) O 4the solid phase preparation method of fluorescent material, concrete preparation process is as follows:
1) press CaIn 2-0.1-0.005(Yb 0.1pr 0.005) O 4the mol ratio of stoichiometric equation takes In 2o 3(SP) 0.5263g, CaCO 3(AR) 0.2004g, Yb 2o 3(3N5) 0.0394g and Pr 6o 11(3N5) 0.0018g, mix the raw material after preparation, grinds fully, obtains powder A;
2) powder A is heat-treated under retort furnace Air atmosphere, 400 ℃ of pre-burning 5h, fully grind after cooling again, obtains powder material B;
3) powder material B is carried out to high-temperature heat treatment again, 1300 ℃ of calcining 16h, grind to such an extent that send out the fluorescent material of more pure white light after naturally cooling.
Embodiment 15:
This embodiment is CaIn 2-0.05pr 0.05o 4the solid phase preparation method of fluorescent material, concrete preparation process is as follows:
1) press CaIn 2-0.05pr 0.05o 4the mol ratio of stoichiometric equation takes In (NO 3) 34.5H 2o (AR) 1.4891g, Ca (NO 3) 24H 2o (AR) 0.4725g and Pr 6o 11(3N5) 0.0170g, mix the raw material after preparation, grinds the abundant powder A of obtaining;
2) powder A is heat-treated under retort furnace Air atmosphere, 500 ℃ of pre-burning 2h, fully grind after cooling again, obtains powder material B;
3) powder material B is carried out to high-temperature heat treatment again, 700 ℃ of calcining 24h, grind to such an extent that send out the fluorescent material of more pure white light after naturally cooling.
Embodiment 16:
This embodiment is CaIn 2-0.1-0.005(Y b0.1pr 0.005) O 4the preparation of fluorescent material, the concrete preparation process of sol-gel method is as follows:
1) press reactant positively charged ion mol ratio Ca 2+: In 2+: Pr 3+: Yb 3+=1:1.895:0.005:0.1 takes respectively CaCO 3(AR) 0.1002g, In (NO 3) 34.5H 2o (AR) 0.7240g powder, measure the Yb (NO of 0.02mol/L 3) 3pr (the NO of solution 5mL, 0.01mol/L 3) 3solution 0.5mL mix and blend obtains solution A, in citrate ion and metal ion ratio, is that 2:1 takes citric acid 1.2609g, slowly adds in solution A, and the limit edged stirs, and makes it complete reaction, and the deionized water constant volume obtains colourless transparent solution B;
2) solution B is put into to baking oven, under 80 ℃ of environment, be incubated 48h, form the transparent and homogeneous colloid, then be warming up to 120 ℃, insulation 12h, obtain yellow presoma;
3) presoma is ground fully, at 500 ℃ of lower pre-burning 5h, obtain fluffy yellow powder powder original material, then original material is fully ground, at 1300 ℃ of calcining 8h, the cooling rear fluorescent material of a more pure white light of grinding to obtain.
Fig. 6 is this Embodiment C aIn 2-0.1-0.005(Yb 0.1pr 0.005) O 4the emmission spectrum of up-conversion luminescent material, in Fig. 6, each emmission spectrum is respectively 495nm from left to right, 542nm, 623nm, 655nm.
Embodiment 17:
This embodiment is CaIn 2-0.3-0005(Yb 0.3pr 0.005) O 4the preparation of fluorescent material, the concrete preparation process of sol-gel method is as follows:
1) press reactant positively charged ion mol ratio Ca 2+: In 2+: Pr 3+: Yb 3+=1:1.695:0.005:0.3 takes respectively Ca (NO 3) 24H 2o (AR) 0.1003g, In (NO 3) 34.5H 2o (AR) 0.6474g powder, measure the Yb (NO of 0.03mol/L 3) 3pr (the NO of solution 10mL, 0.005mol/L 3) 3solution 1ML mix and blend obtains solution A.Be that 2:1 takes citric acid 1.2608g in citrate ion and metal ion ratio, slowly add in solution A, the limit edged stirs, and makes it complete reaction, and the deionized water constant volume obtains colourless transparent solution B;
2) solution B is put into to baking oven, under 80 ℃ of environment, be incubated 48h, form the transparent and homogeneous colloid, then be warming up to 120 ℃, insulation 12h, obtain yellow presoma.
3) presoma is ground fully, at 600 ℃ of lower pre-burning 6h, obtain fluffy yellow powder powder original material, then original material is fully ground, at 1400 ℃ of calcining 2h, the cooling rear fluorescent material of a more pure white light of grinding to obtain.
It should be noted that Yb (NO used in preparation of sol-gel method provided by the present invention 3) 3solution, M (NO 3) 3solution and N (NO 3) 3the concentration of solution can configure suitable concentration according to experiment condition, and principle is that the consumption of each raw material meets prepared luminescent material CaIn 2-x-yz(Yb xm yn z) O 4in the amount proportioning of each element.

Claims (8)

1. one kind with CaIn 2o 4up-conversion luminescent material for matrix, is characterized in that, the structural formula of described luminescent material is: CaIn 2-x-y-z(Yb xm yn z) O 4, wherein: M is Er, Ho, and Tm, Pr or Nd, N is Er, Ho, Tm, Pr or Nd, and M is different from N; 0<x≤0.3,0≤y≤0.05,0≤z≤0.05, and y and z can not be 0 simultaneously.
2. as claimed in claim 1 with CaIn 2o 4up-conversion luminescent material for matrix, is characterized in that, the structural formula of described luminescent material is: CaIn 2-x-y(Yb xer y) O 4, wherein: 0<x≤0.3,0<y≤0.05.
3. as claimed in claim 1 with CaIn 2o 4up-conversion luminescent material for matrix, is characterized in that, the structural formula of described luminescent material is: CaIn 2-x-y(Yb xho y) O 4, wherein: 0<x≤0.3,0<y≤0.05.
4. as claimed in claim 1 with CaIn 2o 4up-conversion luminescent material for matrix, is characterized in that, the structural formula of described luminescent material is: CaIn 2-x-y(Yb xnd y) O 4, wherein: 0<x≤0.3,0<y≤0.05.
5. as claimed in claim 1 with CaIn 2o 4up-conversion luminescent material for matrix, is characterized in that, the structural formula of described luminescent material is: CaIn 2-x-y(Yb xtm y) O 4, wherein: 0<x≤0.3,0<y≤0.05.
6. as claimed in claim 1 with CaIn 2o 4up-conversion luminescent material for matrix, is characterized in that, the structural formula of described luminescent material is: CaIn 2-x-y(Yb xpr y) O 4, wherein: 0<x≤0.3,0<y≤0.05.
7. as claimed in claim 1 with CaIn 2o 4up-conversion luminescent material for matrix, is characterized in that, the structural formula of described luminescent material is: CaIn 2-x-y-z(Yb xer ytm z) O 4, wherein: 0<x≤0.3,0<y≤0.05,0<z≤0.05.
One kind claimed in claim 1 with CaIn 2o 4high temperature solid-state preparation method for the up-conversion luminescent material of matrix, is characterized in that, this high temperature solid-state preparation method carries out according to the following steps:
Step 1, will containing the In compound, containing the Ca compound, containing the Yb compound, containing the M compound and containing the N compound by formula general formula CaIn 2-x-y-z(Yb xm yn z) O 4batching is mixed, and mix is ground and obtains powder A, wherein: be In containing the In compound 2o 3or In (NO 3) 3, containing the Ca compound, be CaCO 3or Ca (NO 3) 2, containing the Yb compound, be Yb 2o 3, containing the M compound, be M 2o 3, M 6o 11or M (NO 3) 3, containing the N compound, be N 2o 3, N 6o 11or N (NO 3) 3;
Step 2, by powder A pre-burning 2～6h under 400～600 ℃ of conditions, grind to obtain powder material B after cooling;
Step 3 is calcined 8～24h by powder material B under 700～1400 ℃ of conditions, grinds to obtain up-conversion luminescent material after cooling.
CN 201210215571 2012-06-27 2012-06-27 CaIn2O4-based up-conversion luminescent material and preparation methods thereof Expired - Fee Related CN102746844B (en)

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