CN105255496B - A kind of up-conversion luminescent material and preparation method thereof - Google Patents
A kind of up-conversion luminescent material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of up-conversion luminescent material and preparation method thereof, belong to luminescent material technical field.The material formula is Gd2‑y‑zO3‑xSx：Ery 3+,Mz n+, wherein 0≤x≤1,0.01≤y≤0.2,0.01≤z≤0.12, Mn+For Tm3+And/or Tb3+Rare earth ion, or Li+.First by Gd2O3And Er2O3Compound is obtained according to the stoichiometric proportion of material is well mixed, is then mixed with addition salpeter solution and obtains sediment；By after the sediment prepared drying, grinding according to metering than addition elemental sulfur or other raw materials and cosolvent NaCO3, it is that 0.1~10Pa, temperature are that 2~5h of insulation prepares Gd under the conditions of 700~1100 DEG C in vacuum2‑y‑zO3‑xSx：Ery 3+,Mz n+Luminescent material, wherein 0≤x≤1,0.01≤y≤0.2,0.01≤z≤0.12.The up-conversion luminescent material that the present invention is prepared has about 100 nanometers to about 10 microns of particle diameter, and under near ultraviolet excitation, realizes the luminous of different colours.
Description
Technical field
The present invention relates to a kind of up-conversion luminescent material and preparation method thereof, belong to luminescent material technical field.
Background technology
Conversion is highly important method in physics in optical frequency, material and device based on upper transfer principle laser,
Highly important application prospect is suffered from communication, the energy, medical treatment, military affairs, Aero-Space and people's daily life.Upper conversion skill
Art should obtain application widely in many fields, but at present, due to production technology in terms of limitation, many products are not up to
To the requirement needed for up-conversion luminescence.
Recent years, the up-conversion of research was various, and its shape phase is also varied.Such as glass, ceramics, list
Brilliant and polycrystal powder etc., its chemical combination composition is oxide, fluoride, sulfide, oxysulfide and oxyhalide etc..And rare earth sulphur
Oxide has lower phonon energy with respect to fluoride（200-300cm-1）, physicochemical properties stabilization, excitation intensity requirement phase
To relatively low.
The production method that current fluorescent material prepares comparative maturity has a high temperature solid-state method and the precipitation method, but high temperature solid-state method and heavy
All also there is respective shortcoming in shallow lake method.High temperature solid-state method reaction time length, it is necessary to temperature it is high, crystal grain is thick, and process is difficult to control；
Precipitation method crystallization is poor, causes luminous efficiency poor.Therefore the hair of rare earth luminescent material can be improved by further improving production method
Light efficiency.The invention propose under vacuum, by control vacuum, temperature, soaking time etc. study its under the conditions of crystal
The formation of growth mechanism and impurities phase, volatilization situation of sulphur etc..What synthesis can be quickly under vacuum condition reaches required temperature, preparation
Particle size is smaller, is conducive to the practical application of this kind of luminescent material.
The present invention is preparing rare-earth oxide sulfate（Gd2O2S) on the basis of single-matrix, design one kind has more for sunshine
The material of wide absorption band assists rare earth ion to turn light, is absorbed using this material in the broadband range that can not be utilized
Light, then transfers energy to rare earth ion, rare earth ion converts the light to the light that can be utilized again, so that erbium ion is at this
Realize that broadband turns light in host material luminous with cooperateing with.
The content of the invention
The problem of existing for above-mentioned prior art and deficiency, the present invention provide a kind of up-conversion luminescent material and its preparation
Method.The up-conversion luminescent material that the present invention is prepared has about 100 nanometers to about 10 microns of particle diameter, and in black light
Excite down, realize the luminous of different colours, compared with other materials, its crystal structure and luminescent properties are more excellent, quantum efficiency is high,
It is more suitable for actual application, the present invention is achieved through the following technical solutions.
A kind of up-conversion luminescent material, the material formula is Gd2-y-zO3-xSx：Ery 3+,Mz n+, wherein 0≤x≤1,0.01≤
Y≤0.2,0.01≤z≤0.12, Mn+For Tm3+And/or Tb3+Rare earth ion, or Li+。
A kind of preparation method of up-conversion luminescent material, it is comprised the following steps that：
（1）First by Gd2O3And Er2O3Compound is obtained according to the stoichiometric proportion of material is well mixed, nitre is then added
In acid solution mix, temperature be 90~120 DEG C at stir to solution clarification, then add LiOH precipitating reagents until pH be 12,
Sealing thermal insulation 2h, sediment is prepared after finally cleaning；
（2）By step（1）According to metering than adding elemental sulfur and cosolvent after the sediment drying for preparing, grinding
NaCO3, it is that 0.1~10Pa, temperature are that 2~5h of insulation prepares Gd under the conditions of 700~1100 DEG C in vacuum2-y-zO3-xSx：
Ery 3+,Mz n+Luminescent material, wherein 0≤x≤1,0.01≤y≤0.2,0.01≤z≤0.12, Mn+For Li+。
The step（1）The concentration of middle salpeter solution is 0.8~1.8mol/l.
The step（2）Middle cosolvent NaCO3Addition be sediment quality 20~50%.
A kind of preparation method of up-conversion luminescent material, it is comprised the following steps that：
（1）First by Gd2O3And Er2O3Compound is obtained according to the stoichiometric proportion of material is well mixed, nitric acid is added molten
Mix, stirred in the case where temperature is 90~120 DEG C to solution clarification in liquid, then add precipitating reagent until pH is 12, sealing thermal insulation
2h, sediment is prepared after finally cleaning；
（2）By step（1）Prepare sediment drying, grinding after according to metering than add elemental sulfur, Tm2O3And/or
Tb2O3, cosolvent NaCO3, it is that 0.1~30Pa, temperature are that 2~5h of insulation is prepared under the conditions of 700~1100 DEG C in vacuum
Gd2-y-zO3-xSx：Ery 3+,Mz n+Luminescent material, wherein 0≤x≤1,0.01≤y≤0.2,0.01≤z≤0.12, Mn+For Tm3+
And/or Tb3+Rare earth ion.
The step（1）The concentration of middle salpeter solution is 0.8~1.8mol/l.
The step（1）Middle precipitating reagent is NaOH.
The step（2）Middle cosolvent NaCO3Addition be sediment quality 20~50%.
The beneficial effects of the invention are as follows：
（1）The up-conversion luminescent material that the present invention is prepared has about 100 nanometers to about 10 microns of particle diameter, and near
Under ultraviolet excitation, the luminous of different colours is realized, compared with other materials, its crystal structure and luminescent properties are more excellent, quantum
Efficiency high, is more suitable for actual application；
（2）The method of the present invention is compared with other method, and it is more uniform that co-precipitation is distributed Doped ions, and vacuum solid phase is anti-
Reaction temperature should be made substantially to reduce, be conducive to improving the crystal structure and luminescent properties of material and energy is cost-effective.
Brief description of the drawings
Fig. 1 is the Gd that the embodiment of the present invention 1 is prepared1.75O2S：Er0.2 3+ ,Li0.05 +It is upper in the case where 980nm wavelength is excited
Switch illumination spectra figure.
Embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
The up-conversion luminescent material, the materials chemistry formula is Gd1.75O2S：Er0.2 3+ ,Li0.05 +。
The preparation method of the up-conversion luminescent material, it is comprised the following steps that：
（1）First by Gd2O3And Er2O3It is 0.875 according to mol ratio：0.1 well mixed obtains 5g compounds, Ran Houjia
Enter to 250mL salpeter solutions（Concentration is 0.8mol/l）Middle mixing, is stirred in the case where temperature is 120 DEG C to solution clarification, Ran Houjia
Enter LiOH precipitating reagents up to pH is 12, sealing thermal insulation 2h, sediment is prepared after finally cleaning；
（2）By step（1）Prepare sediment drying, grinding after be according to Gd in sediment and S mol ratio
1.75:1 adds elemental sulfur and cosolvent NaCO3（Cosolvent NaCO3Addition be sediment quality 50%, in vacuum
It is that insulation 2h prepares Gd under the conditions of 1100 DEG C for 10Pa, temperature1.75O2S：Er0.2 3+ ,Li0.05 +Luminescent material.
The Gd that the present embodiment is prepared1.75O2S：Er0.2 3+ ,Li0.05 +Luminescent material in the case where 980nm wavelength is excited upper turn
Luminescent spectrum figure is changed as shown in figure 1, the material has substantially within the scope of feux rouges, green glow and blue light three as can be seen from Figure 1
Transmitting light.
Embodiment 2
The up-conversion luminescent material, the materials chemistry formula is Gd1.84O2.5S0.5：Er0.08 3+,Tm0.08 3+。
The preparation method of the up-conversion luminescent material, it is comprised the following steps that：
（1）First by Gd2O3And Er2O3According to mol ratio 0.92：0.04 it is well mixed obtain 10g compounds, then add
To 150mL salpeter solutions（Concentration is 1.8mol/l）Middle mixing, is stirred to solution clarification, it is heavy then to add in the case where temperature is 90 DEG C
Shallow lake agent is 12, sealing thermal insulation 2h up to pH, and sediment is prepared after finally cleaning；Wherein precipitating reagent is NaOH；
（2）By step（1）Prepare sediment drying, grinding after according to mole according to Gd, S and Tm in sediment
Than 1.84：0.5：0.04 adds elemental sulfur, Tm2O3, cosolvent NaCO3（Cosolvent NaCO3Addition for sediment quality
20%, it is that 0.1Pa, temperature be that insulation 5h prepares chemical formula under the conditions of 700 DEG C are Gd in vacuum1.84O2.5S0.5：Er0.08 3 +,Tm0.08 3+Luminescent material.
Embodiment 3
The up-conversion luminescent material, the materials chemistry formula is Gd1.76O2S：Er0.08 3+,Tm0.08 3+,Tb0.08 3+。
The preparation method of the up-conversion luminescent material, it is comprised the following steps that：
（1）First by Gd2O3And Er2O3According to mol ratio 0.88：0.04 it is well mixed obtain 50g compounds, then add
To 200mL salpeter solutions（Concentration is 1.5mol/l）Middle mixing, stirs to solution clarification in the case where temperature is 100 DEG C, then adds
Precipitating reagent is 12, sealing thermal insulation 2h up to pH, and sediment is prepared after finally cleaning；Wherein precipitating reagent is NaOH；
（2）By step（1）Prepare sediment drying, grinding after according to according to Gd, S, Tm and Tb in sediment
Mol ratio 1.76：1：0.04：0.04 adds elemental sulfur, Tm2O3、Tb2O3, cosolvent NaCO3（Cosolvent NaCO3Addition be
The 35% of sediment quality）, it is that 5Pa, temperature are that insulation 2.5h prepares chemical formula and is under the conditions of 1000 DEG C in vacuum
Gd1.76O2S：Er0.08 3+,Tm0.08 3+,Tb0.08 3+Luminescent material.
Embodiment 4
The up-conversion luminescent material, the materials chemistry formula is Gd1.96O2S：Er0.02 3+,Tb0.02 3+。
The preparation method of the up-conversion luminescent material, it is comprised the following steps that：
（1）First by Gd2O3And Er2O3According to mol ratio 0.98：0.01 well mixed obtains 100g compounds, Ran Houjia
Enter to 150mL salpeter solutions（Concentration is 1.2mol/l）Middle mixing, is stirred in the case where temperature is 110 DEG C to solution clarification, Ran Houjia
Enter precipitating reagent up to pH is 12, sealing thermal insulation 2h, sediment is prepared after finally cleaning；Wherein precipitating reagent is NaOH；
（2）By step（1）Prepare sediment drying, grinding after according to mole according to Gd, S and Tb in sediment
Than 1.96：1：0.01 adds elemental sulfur, Tb2O3, cosolvent NaCO3（Cosolvent NaCO3Addition for sediment quality
40%）, it is that 1Pa, temperature be that insulation 3.5h prepares chemical formula under the conditions of 1100 DEG C are Gd in vacuum1.96O2S：Er0.02 3+,
Tb0.02 3+Luminescent material.
Above in association with accompanying drawing to the present invention embodiment be explained in detail, but the present invention be not limited to it is above-mentioned
Embodiment, can also be before present inventive concept not be departed from the knowledge that those of ordinary skill in the art possess
Put that various changes can be made.
Claims (8)
1. a kind of up-conversion luminescent material, it is characterised in that：The material formula is Gd2-y-zO3-xSx：Ery 3+,Mz n+, wherein 0 ＜ x
≤ 1,0.01≤y≤0.2,0.01≤z≤0.12, Mn+For Tm3+And/or Tb3+Rare earth ion, or Li+。
2. a kind of preparation method of up-conversion luminescent material according to claim 1, it is characterised in that comprise the following steps that：
（1）First by Gd2O3And Er2O3Compound is obtained according to the stoichiometric proportion of material is well mixed, nitric acid is then added molten
Mix, stirred in the case where temperature is 90~120 DEG C to solution clarification in liquid, then add LiOH precipitating reagents until pH is 12, sealed
2h is incubated, sediment is prepared after finally cleaning；
（2）By step（1）According to metering than adding elemental sulfur and cosolvent after the sediment drying for preparing, grinding
Na2CO3, it is that 0.1~10Pa, temperature are that 2~5h of insulation prepares Gd under the conditions of 700~1100 DEG C in vacuum2-y-zO3-xSx：
Ery 3+,Mz n+Luminescent material, wherein 0 ＜ x≤1,0.01≤y≤0.2,0.01≤z≤0.12, Mn+For Li+。
3. the preparation method of up-conversion luminescent material according to claim 2, it is characterised in that：The step（1）Middle nitre
The concentration of acid solution is 0.8~1.8mol/l.
4. the preparation method of up-conversion luminescent material according to claim 2, it is characterised in that：The step（2）In help
Solvent Na2CO3Addition be sediment quality 20~50%.
5. a kind of preparation method of up-conversion luminescent material according to claim 1, it is characterised in that comprise the following steps that：
（1）First by Gd2O3And Er2O3Compound is obtained according to the stoichiometric proportion of material is well mixed, is added in salpeter solution
Mixing, is stirred in the case where temperature is 90~120 DEG C to solution clarification, then adds precipitating reagent until pH is 12, sealing thermal insulation 2h, most
Sediment is prepared after cleaning afterwards；
（2）By step（1）Prepare sediment drying, grinding after according to metering than add elemental sulfur, Tm2O3And/or
Tb2O3, cosolvent Na2CO3, it is that 0.1~30Pa, temperature are that 2~5h of insulation is prepared under the conditions of 700~1100 DEG C in vacuum
To Gd2-y-zO3-xSx：Ery 3+,Mz n+Luminescent material, wherein 0 ＜ x≤1,0.01≤y≤0.2,0.01≤z≤0.12, Mn+For Tm3+
And/or Tb3+Rare earth ion.
6. the preparation method of up-conversion luminescent material according to claim 5, it is characterised in that：The step（1）Middle nitre
The concentration of acid solution is 0.8~1.8mol/l.
7. the preparation method of up-conversion luminescent material according to claim 5, it is characterised in that：The step（1）In sink
Shallow lake agent is NaOH.
8. the preparation method of up-conversion luminescent material according to claim 5, it is characterised in that：The step（2）In help
Solvent Na2CO3Addition be sediment quality 20~50%.
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