CN106520121B - The preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor - Google Patents
The preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 84
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 28
- MCVAAHQLXUXWLC-UHFFFAOYSA-N [O-2].[O-2].[S-2].[Gd+3].[Gd+3] Chemical compound [O-2].[O-2].[S-2].[Gd+3].[Gd+3] MCVAAHQLXUXWLC-UHFFFAOYSA-N 0.000 title claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 40
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 18
- -1 rare earth ion Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910005563 Gd2O2SO4 Inorganic materials 0.000 claims abstract description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 11
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 10
- 229910002617 Gd(NO3)3·6H2O Inorganic materials 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 20
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 20
- 150000002910 rare earth metals Chemical class 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 9
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000007796 conventional method Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000000295 emission spectrum Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000008246 gaseous mixture Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910009500 Y2O2SO4 Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- MIKCAECBBIRHCH-UHFFFAOYSA-N gadolinium(3+);oxygen(2-);trisulfide Chemical compound [O-2].[O-2].[O-2].[S-2].[S-2].[S-2].[Gd+3].[Gd+3].[Gd+3].[Gd+3] MIKCAECBBIRHCH-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- C09K11/7781—Sulfates
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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
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
- C09K11/7789—Oxysulfides
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
A kind of preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor, belongs to materials science field.Method includes the following steps: (1) is by Gd (NO3)3·6H2O、Yb(NO3)3·6H2O and Ln (NO3)3·6H2O mixing, adds deionized water, obtains RE (NO3)3Solution；(2) ammonium sulfate is dissolved in RE (NO3)3Solution stirring, continues to stir, and ammonium hydroxide is added, and adjusts pH value, obtains suspension；(3) by suspension, at 100~150 DEG C, 1~72h of hydro-thermal reaction, cooled to room temperature obtains reaction product；(4) by reaction product centrifuge separation, cleaning, drying, white powder presoma is obtained；(5) by white powder presoma, rare earth ion doped Gd is made in calcining2O2S or Gd2O2SO4Up-conversion phosphor.This method efficiently solves the use in conventional method containing sulfur feedstock and the discharge of harmful side product, is a kind of environmentally protective technology of preparing.
Description
Technical field
The invention belongs to materials science field, in particular to converted on a kind of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate
The preparation method of fluorescent powder.
Background technique
Up-conversion luminescent material is widely used in its unique ability that long-wave radiation can be converted into shortwave radiation
The fields such as upconversion laser, dye-sensitized solar cells, medicament transport, biological fluorescent labelling and infrared anti-false.Effect at present
The higher upper converting system of rate is fluoride (such as NaYF4: Yb/Er), fluoride has the low and upper high conversion efficiency of phonon energy
The advantages that.But fluoride raw material are more toxic, this disadvantage significantly limits the big rule of converting luminescent material of fluoride
Mould production and practical application.Converting system is although nontoxic on rare earth oxide, but phonon energy is higher, and upper transfer efficiency is relatively low.
Therefore explore that other types are nontoxic and the lower upper converting system practical application value with higher of phonon energy.
Gadolinium oxysulfide (Gd2O2S) phonon energy is lower and chemical stability is good.Therefore, researcher has studied Yb/Ho
It adulterates with Yb/Er in Gd2O2Up-conversion luminescence performance in S finds it with good up-conversion luminescence performance.But at present
There are the problem of have: (1) Yb/Tm etc. other doping in Gd2O2Up-conversion luminescence in S is rarely reported；(2) such compound
Prepare that inevitable use environment is harmful containing sulfur feedstock or to be related to the harmful sulfur byproduct species of environment.
Oxygen-containing Digadolinium trisulfate (Gd2O2SO4) mainly as lower conversion luminous host obtain the extensive concern of researcher.Closely
Phase is it was discovered by researchers that Yb/Er is adulterated in Y2O2SO4In good up-conversion luminescence performance can be presented.Therefore, same conduct
The Gd of such compound2O2SO4It is expected to show good up-conversion luminescence performance, and and Y2O2SO4It compares, Gd2O2SO4's
Covalency is higher than Y2O2SO4, while Gd2O2SO4In Gd3+With half-full 4f shell, above two point feature has the system
Prestige shows better luminescent properties.The same Gd of such compound traditional preparation methods2O2The similar presence of the preparation method of S uses ring
Border is harmful containing sulfur feedstock or the problems such as be related to the discharge of the harmful sulfur byproduct species of environment, until 2010 Nian You researchers
It was found that a kind of novel sulfate type rare earth layered hydroxide Gd2(OH)4SO4·nH2O, and by calcining such change in air
It closes object green and prepares Gd2O2SO4, but Gd2(OH)4SO4·nH2The preparation method of O is mainly limited to the precipitation method.Obtained by the precipitation method
Product is irregular aggregate.Calcined product Gd2O2SO4Pattern and its presoma Gd2(OH)4SO4·nH2The pattern of O is close
It is related.Therefore it still can not achieve at present and prepare Gd in green2O2SO4While reach Effective Regulation to its pattern.And it precipitates
Method is often with precipitating reagent such as hexa (HMT, (CH2)6N4) there is room temperature to be lauched solution slowly, and generated in air under high temperature
Formaldehyde and its derivative and the disadvantages of reduce the yield for sinking to the bottom reaction.Because of Gd2(OH)4SO4·nH2In O the crystallization water and rare earth from
Son directly coordination, therefore whether occur during the crystallization water directly affects the crystal structure feature of product and with rare earth ion be in structure
The coordination mode of the coordination polyhedrom of the heart.
Summary of the invention
Rear-earth-doped Gd is prepared for existing2O2Harmful the asking containing sulfur feedstock of use environment present in S technology path
Topic, the present invention provide a kind of preparation method of rear-earth-doped gadolinium oxysulfide up-conversion phosphor, which uses hydro-thermal method
Prepare rear-earth-doped Gd2(OH)4SO4·nH2O and Gd2(OH)4SO4Two class presomas, and using in these two types of presomas
The molar ratio and RE of RE/S2O2Completely the same feature in S, calcines the two classes compound in reducing atmosphere, and green is prepared
Rear-earth-doped Gd2O2S.It is sulphur source that mild ammonium sulfate is used in the preparation process of presoma, and the by-product in calcination process is only
For water vapour.This method efficiently solves harmful use and the harmful side product discharge containing sulfur feedstock of environment in conventional method
The problem of, it is a kind of environmentally protective technology of preparing.
Rear-earth-doped Gd is prepared for existing2O2SO4It is reached while can not achieve green preparation present in technology path
To the problem of effectively regulation to its pattern, the present invention provides a kind of preparation of rear-earth-doped oxygen-containing Digadolinium trisulfate up-conversion phosphor
Method, this method are to prepare rear-earth-doped Gd using hydro-thermal method2(OH)4SO4·nH2O, by calcining the change in air
Closing object realizes the rear-earth-doped Gd of uniform reunion sphere2O2SO4Preparation, while providing a kind of quasi- hexagon micron plate
Rear-earth-doped sulfate type rare earth layered hydroxide Gd2(OH)4SO4Hydrothermal preparing process, calcine the chemical combination in air
Object prepares the rear-earth-doped Gd of quasi- hexagon micron plate2O2SO4.The technology path realize green prepare it is rear-earth-doped
Gd2O2SO4While its pattern is effectively regulated and controled.
The preparation method of a kind of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor of the invention, according to
Lower step carries out:
(1) by Gd (NO3)3·6H2O、Yb(NO3)3·6H2O and Ln (NO3)3·6H2O mixing, is added deionized water, room temperature
Transparence is stirred into, RE (NO is obtained3)3Solution；
Wherein, in molar ratio, Gd3+∶Yb3+∶Ln3+=(90~97): (5~2): (5~1)；
The Ln is one of Ho, Er or Tm；
The RE3+For Gd3+、Yb3+And Ln3+Hybrid ionic；
(2) ammonium sulfate is dissolved in RE (NO3)3It in solution, stirs evenly, then, continues to stir, and ammonium hydroxide is added, adjust pH
Value is 7.0~10.0, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=(1~5): (2~1)；
(3) suspension is moved in reaction kettle, at 100~150 DEG C, 1~72h of hydro-thermal reaction, after reaction, is taken out,
Cooled to room temperature obtains reaction product；
(4) by reaction product centrifuge separation, cleaning, drying, white powder presoma (Gd, Yb, Ln) is obtained2(OH)4SO4·nH2O, wherein n=0 or 1.9~2.2；
(5) it by white powder presoma, is calcined, rare earth ion doped Gd is made2O2S and Gd2O2SO4Upper conversion is glimmering
Light powder；Wherein, calcination parameter is (a) or (b):
(a) calcination environment is air, and calcination temperature is 800~1000 DEG C, and calcination time is 0.5~4h, it is corresponding made from
Rare earth ion doped Gd2O2SO4Up-conversion phosphor is rare earth oxysulfate (Gd, Yb, Ln)2O2SO4；
(b) calcination environment is reducing atmosphere, and calcination temperature is 800~1200 DEG C, and calcination time is 0.5~4h, corresponding
Rare earth ion doped Gd obtained2O2S up-conversion phosphor is rare-earth oxide sulfate (Gd, Yb, Ln)2O2S。
Wherein,
RE (the NO3)3The RE of solution3+Concentration is 0.05~0.5mol/L；
In the step (2), the stirring, the time is 15~20min.
In the step (2), ammonium hydroxide is added using the method being added dropwise.
In the step (4), the centrifuge separation is to be centrifuged reaction product, supernatant is removed, to being centrifuged
To sediment handled；
In the step (4), the cleaning is using water cleaning is added three times, and it is primary to add washes of absolute alcohol, mesh
Be remove white powder presoma in impurity；
In the step (4), the drying, drying temperature is 50~80 DEG C.
In the step (4), the white powder presoma is sulfate type rare earth layered hydroxide, and pattern is
One of reunion ball or quasi- hexagon micron plate, by adjusting techniques such as pH, reaction temperature, reaction time, calcination temperatures
Parameter can regulate and control its pattern, reach the morphology controllable to fluorescent powder, programmable effect.
In the step 5, the reducing atmosphere is H2And N2It mixes in proportion, wherein H2Percentage by volume be 5~
100%, surplus N2。
The preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor of the invention, prepares rare earth sulphur
The chemical equation of oxide are as follows:
RE2(OH)4SO4·nH2O→RE2(OH)4SO4+nH2O (3)
RE2(OH)4SO4→RE2O2SO4+2H2O (4)
RE2O2SO4+4H2→RE2O2S+4H2O (5)
Prepare the chemical equation of rare earth oxysulfate are as follows:
RE2(OH)4SO4·nH2O→RE2(OH)4SO4+nH2O (3)
RE2(OH)4SO4→RE2O2SO4+2H2O (4)
The rare earth ion doped Gd of the present invention2O2S and Gd2O2SO4The preparation method of up-conversion phosphor, with prior art phase
Than the features of the present invention and beneficial effect are:
Utilize rear-earth-doped Gd2(OH)4SO4And Gd2(OH)4SO4·nH2RE/S molar ratio and RE in O2O2S is completely the same
The characteristics of, these two types of compounds are calcined in a reducing atmosphere, and green prepares rear-earth-doped Gd2O2S, effective solution are dilute
The Gd of soil doping2O2Unavoidably it is related to the environmentally harmful use containing sulfur feedstock or noxious products in S traditional preparation methods
The problem of discharge.
It is equal to prepare size by modulating response parameter, such as pH value, temperature and reaction time using hydrothermal synthesis route
The rear-earth-doped Gd of the quasi- hexagon micron plate of even reunion ball or favorable dispersibility2O2SO4, realize the same of green preparation
When effective regulation has been carried out to its pattern.
Detailed description of the invention
Fig. 1 is the process flow chart that the present invention prepares rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor；
Fig. 2 is the sulfate type rare earth layered hydroxide (Gd, Yb, Ln) of 1-6 of embodiment of the present invention preparation2(OH)4SO4·nH2The XRD spectrum of O, wherein (a) is made by embodiment 1 and embodiment 2, (b) is made by embodiment 3 and embodiment 4,
(c) it is made by embodiment 5 and embodiment 6；
Fig. 3 is the sulfate type rare earth layered hydroxide (Gd, Yb, Ln) of 1-6 of embodiment of the present invention preparation2(OH)4SO4·nH2The SEM shape appearance figure of O, wherein (a) is made by embodiment 1 and embodiment 2, (b) is made by embodiment 3 and embodiment 4
, (c) it is made by embodiment 5 and embodiment 6；
Fig. 4 is that the embodiment of the present invention 1, embodiment 3 and embodiment 5 prepare (Gd, Yb, Ln)2O2SO4Up-conversion phosphor
XRD spectrum, wherein (a) is made by embodiment 1, and (b) is made by embodiment 3, (c) is made by embodiment 5；
Fig. 5 is that the embodiment of the present invention 1, embodiment 3 and embodiment 5 prepare (Gd, Yb, Ln)2O2SO4Up-conversion phosphor
SEM shape appearance figure, wherein (a) is made by embodiment 1, and (b) is made by embodiment 3, (c) is made by embodiment 5；
Fig. 6 is that the embodiment of the present invention 2, embodiment 4 and embodiment 6 prepare (Gd, Yb, Ln)2O2S up-conversion phosphor
XRD spectrum, wherein (a) is made by embodiment 2, (b) is made by embodiment 4, (c) is made by embodiment 6；
Fig. 7 is that the embodiment of the present invention 2, embodiment 4 and embodiment 6 prepare (Gd, Yb, Ln)2O2S up-conversion phosphor
SEM shape appearance figure, wherein (a) is made by embodiment 2, (b) is made by embodiment 4, (c) is made by embodiment 6；
Fig. 8 is 7-12 of embodiment of the present invention preparation (Gd, Yb, Ln)2(OH)4SO4XRD spectrum, wherein (a) is by implementing
Example 7 and embodiment 8 are made, and (b) are made by embodiment 9 and embodiment 10, (c) are made by embodiment 11 and embodiment 12；
Fig. 9 is 7-12 of embodiment of the present invention preparation (Gd, Yb, Ln)2(OH)4SO4SEM shape appearance figure, wherein (a) is by reality
It applies example 7 and embodiment 8 is made, (b) be made by embodiment 9 and embodiment 10, (c) be made by embodiment 11 and embodiment 12；
Figure 10 is that the embodiment of the present invention 7, embodiment 9 and embodiment 11 prepare (Gd, Yb, Ln)2O2SO4Up-conversion fluorescence
The XRD spectrum of powder, wherein (a) is made by embodiment 7, (b) is made by embodiment 9, (c) is made by embodiment 11；
Figure 11 is that the embodiment of the present invention 7, embodiment 9 and embodiment 11 prepare (Gd, Yb, Ln)2O2SO4Up-conversion fluorescence
The SEM shape appearance figure of powder, wherein (a) is made by embodiment 7, (b) is made by embodiment 9, (c) is made by embodiment 11；
Figure 12 is that the embodiment of the present invention 7, embodiment 9 and embodiment 11 prepare (Gd, Yb, Ln)2O2SO4Up-conversion fluorescence
The Up-conversion emission spectrum of powder, wherein (a) is made by embodiment 7, (b) is made by embodiment 9, (c) is made by embodiment 11；
Figure 13 is that the embodiment of the present invention 8, embodiment 10 and embodiment 12 prepare (Gd, Yb, Ln)2O2S up-conversion phosphor
XRD spectrum, wherein (a) is made by embodiment 8, (b) is made by embodiment 10, (c) is made by embodiment 12；
Figure 14 is that the embodiment of the present invention 8, embodiment 10 and embodiment 12 prepare (Gd, Yb, Ln)2O2S up-conversion phosphor
SEM shape appearance figure, wherein (a) is made by embodiment 8, (b) is made by embodiment 10, (c) is made by embodiment 12；
Figure 15 is that the embodiment of the present invention 8, embodiment 10 and embodiment 12 prepare (Gd, Yb, Ln)2O2S up-conversion phosphor
Up-conversion emission spectrum, wherein (a) is made by embodiment 8, (b) is made by embodiment 10, (c) is made by embodiment 12；
Specific embodiment
Chemical reagent employed in following instance is the pure grade product of analysis；
Following embodiment carries out XRD analysis using the RINT2200V/PC type x-ray diffractometer of Rigaku company of Japan；
Using S-5000 type field emission scanning electron microscope (FE-SEM) the observing samples pattern (SEM) of Japanese Hitachi company；
Using the up-conversion luminescence performance of the FP-6500 type sepectrophotofluorometer test sample of Japanese JASCO company, with
It is exciting light that 978nm near-infrared laser diode (KS3-12322-105, Beijing Kaipu Lin Photoelectricity Science Co., Ltd), which is used as,
Source.
Hydrothermal reaction kettle liner material is polytetrafluoroethylene (PTFE), and specification 100ml, steel bushing material is stainless steel, and baking oven is electronics
Temperature control oven, the temperature difference is less than 1 DEG C；High temperature furnace is tube furnace, 1550 DEG C of rated temperature；
The measure and calculation of sample crystallization water content is according to depending on thermogravimetric analysis (TGA) in the present invention, and the thermogravimetric of use is divided
Analysis instrument model is: the STA449F3 type thermogravimetric analyzer of German Netzsch company.
Below with reference to embodiment, the present invention is described in further detail, and the following are the preferred embodiment of the present invention.
Embodiment 1
A kind of preparation method of rear-earth-doped oxygen-containing Digadolinium trisulfate up-conversion phosphor, follows the steps below:
(1) by Gd (NO3)3·6H2O、Yb(NO3)3·6H2O and Ho (NO3)3·6H2O mixing, is added deionized water, room temperature
Transparence is stirred into, RE is obtained3+Ion concentration is 0.05mol/L RE (NO3)3Solution；
Wherein, in molar ratio, Gd3+∶Yb3+∶Ho3+=90: 5: 5；
(2) 0.4g ammonium sulfate is dissolved in 0.05mol/L RE (NO3)3In solution, RE (NO3)3The volume of solution is 60mL,
At room temperature, 20min is stirred, then, continues to stir and be added dropwise ammonium hydroxide, adjusting pH value is 7.0, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=1: 1；
(3) suspension is moved in reaction kettle, at 100 DEG C, hydro-thermal reaction 72h, after reaction, is taken out, natural cooling
To room temperature, reaction product is obtained；
(4) reaction product is centrifugated, water cleaning is added three times, it is primary to add washes of absolute alcohol, dries at 70 DEG C
It is dry, obtain white powder presoma-sulfate type rare earth layered hydroxide (Gd0.90Yb0.05Ho0.05)2(OH)4SO4·nH2O
(n=1.9), shown in XRD spectrum such as Fig. 2 (a)；Its pattern is reunion ball, having a size of 80~110 μm, as shown in Fig. 3 (a)；
(5) white powder presoma is placed in air, at 800 DEG C, calcines 1h, obtain rare earth oxysulfate
(Gd0.90Yb0.05Ho0.05)2O2SO4Up-conversion phosphor, XRD are shown in Fig. 4 (a), and as can be seen from the figure product is pure phase；Its shape
Looks are similar to its presoma, and for reunion ball, diameter is 80~110 μm, as shown in Fig. 5 (a).
Embodiment 2
A kind of preparation method of rear-earth-doped gadolinium oxysulfide up-conversion phosphor, follows the steps below:
Step (1), (2), (3), (4) are the same as embodiment 1；
(5) white powder presoma is placed in H2And N2Gaseous mixture (volume ratio, H2∶N2=50: 50) in atmosphere, 800 DEG C
1h is calcined, rare-earth oxide sulfate (Gd is obtained0.90Yb0.05Ho0.05)2O2S fluorescent powder, XRD are shown in Fig. 6 (a), as can be seen from the figure
Product is pure phase；Its pattern is similar to its presoma, and for reunion ball, diameter is 80~110 μm, as shown in Fig. 7 (a).
Embodiment 3
A kind of preparation method of rear-earth-doped oxygen-containing Digadolinium trisulfate up-conversion phosphor, follows the steps below:
(1) by Gd (NO3)3·6H2O、Yb(NO3)3·6H2O and Er (NO3)3·6H2O mixing, is added deionized water, room temperature
Transparence is stirred into, RE is obtained3+Ion concentration is 0.5mol/L RE (NO3)3Solution；
Wherein, in molar ratio, Gd3+∶Yb3+∶Er3+=97: 2: 1；
(2) 4g ammonium sulfate is dissolved in 0.5mol/L RE (NO3)3In solution, RE (NO3)3The volume of solution is 60mL, in room
Under temperature, 20min is stirred, then, continues to stir and be added dropwise ammonium hydroxide, adjusting pH value is 7.0, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=1: 1；
(3) suspension is moved in reaction kettle, at 100 DEG C, hydro-thermal reaction 1h, after reaction, takes out, naturally cool to
Room temperature obtains reaction product；
(4) reaction product is centrifugated, water cleaning is added three times, it is primary to add washes of absolute alcohol, dries at 70 DEG C
It is dry, obtain white powder presoma --- sulfate type rare earth layered hydroxide (Gd0.97Yb0.02Er0.01)2(OH)4SO4·
nH2Shown in O (n=2.2), XRD spectrum such as Fig. 2 (b), pattern is reunion ball, and diameter is 80~110 μm, such as Fig. 3 (b) institute
Show.
(5) white powder presoma is placed in air, at 1000 DEG C, calcines 1h, obtain rare earth oxysulfate
(Gd0.97Yb0.02Er0.01)2O2SO4Up-conversion phosphor, XRD are shown in Fig. 4 (b), and as can be seen from the figure product is pure phase；Its shape
Looks are similar to its presoma, and for reunion ball, diameter is 80~110 μm, as shown in Fig. 5 (b).
Embodiment 4
A kind of preparation method of rear-earth-doped gadolinium oxysulfide up-conversion phosphor, follows the steps below:
Step (1), (2), (3), (4) are the same as embodiment 3；
(5) white powder presoma is placed in H2And N2Gaseous mixture (volume ratio, H2∶N2=60: 40) in atmosphere, 1200
DEG C calcining 1h, obtain rare-earth oxide sulfate (Gd0.97Yb0.02Er0.01)2O2S fluorescent powder, XRD are shown in Fig. 6 (b), can from figure
Product is pure phase out；Its pattern is similar to its presoma, and for reunion ball, diameter is 80~110 μm, as shown in Fig. 7 (b).
Embodiment 5
A kind of preparation method of rear-earth-doped oxygen-containing Digadolinium trisulfate up-conversion phosphor, follows the steps below:
(1) by Gd (NO3)3·6H2O、Yb(NO3)3·6H2O and Tm (NO3)3·6H2O mixing, is added deionized water, room temperature
Transparence is stirred into, RE is obtained3+Ion concentration is 0.1mol/L RE (NO3)3Solution；
Wherein, in molar ratio, Gd3+∶Yb3+∶Tm3+=97: 2: 1；
(2) 0.8g ammonium sulfate is dissolved in 0.1mol/L RE (NO3)3In solution, RE (NO3)3The volume of solution is 60mL,
At room temperature, 15min is stirred, then, continues to stir and be added dropwise ammonium hydroxide, adjusting pH value is 7.0, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=1: 1；
(3) suspension is moved in reaction kettle, at 100 DEG C, hydro-thermal reaction for 24 hours, after reaction, is taken out, natural cooling
To room temperature, reaction product is obtained；
(4) reaction product is centrifugated, water cleaning is added three times, it is primary to add washes of absolute alcohol, dries at 70 DEG C
It is dry, obtain white powder presoma-sulfate type rare earth layered hydroxide (Gd0.97Yb0.02Tm0.01)2(OH)4SO4·nH2O
(n=2.1), shown in XRD spectrum such as Fig. 2 (c), pattern is reunion ball, having a size of 80~110 μm, as shown in Fig. 3 (c)；
(5) white powder presoma is placed in air, at 1000 DEG C, calcines 1h, obtain rare earth oxysulfate
(Gd0.97Yb0.02Tm0.01)2O2SO4Up-conversion phosphor, XRD are shown in Fig. 4 (c), and as can be seen from the figure product is pure phase；Its shape
Looks are similar to its presoma, and for reunion ball, diameter is 80~110 μm, as shown in Fig. 5 (c).
Embodiment 6
A kind of preparation method of rear-earth-doped gadolinium oxysulfide up-conversion phosphor, follows the steps below:
Step (1), (2), (3), (4) are the same as embodiment 5；
(5) white powder presoma is placed in H2And N2Gaseous mixture (volume ratio, H2∶N2=5: 95) in atmosphere, 1200 DEG C
1h is calcined, rare-earth oxide sulfate (Gd is obtained0.97Yb0.02Tm0.01)2O2S fluorescent powder, XRD are shown in Fig. 6 (c), as can be seen from the figure
Product is pure phase.Its pattern is similar to its presoma, and for reunion ball, diameter is 80~110 μm, as shown in Fig. 7 (c).
Embodiment 7
A kind of preparation method of rear-earth-doped oxygen-containing Digadolinium trisulfate up-conversion phosphor, follows the steps below:
(1) by Gd (NO3)3·6H2O、Yb(NO3)3·6H2O and Ho (NO3)3·6H2O mixing, is added deionized water, room temperature
Transparence is stirred into, RE is obtained3+Ion concentration is 0.1mol/L RE (NO3)3Solution；
Wherein, in molar ratio, Gd3+∶Yb3+∶Ho3+=97: 1: 2；
(2) 4g ammonium sulfate is dissolved in 0.1mol/L RE (NO3)3In solution, RE (NO3)3The volume of solution is 60mL, in room
Under temperature, 20min is stirred, then, continues to stir and be added dropwise ammonium hydroxide, adjusting pH value is 10.0, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=5: 1；
(3) suspension is moved in reaction kettle, at 150 DEG C, hydro-thermal reaction for 24 hours, after reaction, is taken out, natural cooling
To room temperature, reaction product is obtained；
(4) reaction product is centrifugated, water cleaning is added three times, it is primary to add washes of absolute alcohol, dries at 70 DEG C
It is dry, obtain white powder presoma --- sulfate type rare earth layered hydroxide (Gd0.97Yb0.01Ho0.02)2(OH)4SO4,
XRD spectrum is shown in Fig. 8 (a), and XRD shows it as pure phase, and hexagon micron plate subject to pattern, thickness is 0.5~0.8 μm, long
It is 4~8 μm, as shown in Fig. 9 (a)；
(5) white powder presoma is placed in air, at 1000 DEG C, calcines 1h, obtain rare earth oxysulfate
(Gd0.97Yb0.01Ho0.02)2O2SO4Up-conversion phosphor, XRD are shown in Figure 10 (a), and as can be seen from the figure product is pure phase；Its
Pattern is similar to its presoma, subject to hexagon micron plate, thickness be 0.5~0.8 μm, a length of 4~8 μm, such as Figure 11 (a) institute
Show, Up-conversion emission spectrum is shown in Figure 12 (a).
Embodiment 8
A kind of preparation method of rear-earth-doped gadolinium oxysulfide up-conversion phosphor, follows the steps below:
Step (1), (2), (3), (4) are the same as embodiment 7；
(5) white powder presoma is placed in H2And N2Gaseous mixture (volume ratio, H2∶N2=70: 30) in atmosphere, 1200
DEG C calcining 1h, obtain rare-earth oxide sulfate (Gd0.97Yb0.01Ho0.02)2O2S fluorescent powder, XRD are shown in that Figure 13 (a), XRD show that it is
Pure phase, pattern is similar to its presoma, subject to hexagon micron plate, thickness be 0.5~0.8 μm, a length of 4~8 μm, such as Figure 14
(a) shown in, Up-conversion emission spectrum is shown in Figure 15 (a).
Embodiment 9
A kind of preparation method of rear-earth-doped oxygen-containing Digadolinium trisulfate up-conversion phosphor, follows the steps below:
(1) by Gd (NO3)3·6H2O、Yb(NO3)3·6H2O and Er (NO3)3·6H2O mixing, is added deionized water, room temperature
Transparence is stirred into, RE is obtained3+Ion concentration is 0.1mol/L RE (NO3)3Solution；
Wherein, in molar ratio, Gd3+∶Yb3+∶Er3+=97: 1: 2；
(2) 0.4g ammonium sulfate is dissolved in 0.1mol/L RE (NO3)3In solution, RE (NO3)3The volume of solution is 60mL,
At room temperature, 15min is stirred, then, continues to stir and be added dropwise ammonium hydroxide, adjusting pH value is 10.0, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=1: 2；
(3) suspension is moved in reaction kettle, at 150 DEG C, hydro-thermal reaction for 24 hours, after reaction, is taken out, natural cooling
To room temperature, reaction product is obtained；
(4) reaction product is centrifugated, water cleaning is added three times, it is primary to add washes of absolute alcohol, dries at 50 DEG C
It is dry, obtain white powder presoma --- sulfate type rare earth layered hydroxide (Gd0.97Yb0.01Er0.02)2(OH)4SO4,
XRD spectrum is shown in that Fig. 8 (b), XRD show it as pure phase, and hexagon micron plate subject to pattern, thickness is 0.5~0.8 μm, a length of 4
~8 μm, as shown in Fig. 9 (b)；
(5) white powder presoma is placed in air, at 1000 DEG C, calcines 4h, obtain rare earth oxysulfate
(Gd0.97Yb0.01Er0.02)2O2SO4Up-conversion phosphor, XRD are shown in that Figure 10 (b), XRD show it for pure phase；Its pattern and its before
Drive body it is similar, subject to hexagon micron plate, thickness be 0.5~0.8 μm, a length of 4~8 μm, as shown in Figure 11 (b)；It converts thereon
Emission spectrum is shown in Figure 12 (b).
Embodiment 10
A kind of preparation method of rear-earth-doped gadolinium oxysulfide up-conversion phosphor, follows the steps below:
Step (1), (2), (3), (4) are the same as embodiment 9；
(5) white powder presoma is placed in H2Reducing atmosphere in, 1200 DEG C of calcining 4h obtain rare-earth oxide sulfate
(Gd0.97Yb0.01Er0.02)2O2S fluorescent powder, XRD are shown in that Figure 13 (b), XRD show it for pure phase, pattern and its presoma phase
Seemingly, hexagon micron plate subject to, thickness be 0.5~0.8 μm, a length of 4~8 μm, as shown in Figure 14 (b), Up-conversion emission light
Spectrum is shown in Figure 15 (b).
Embodiment 11
A kind of preparation method of rear-earth-doped oxygen-containing Digadolinium trisulfate up-conversion phosphor, follows the steps below:
(1) by Gd (NO3)3·6H2O、Yb(NO3)3·6H2O and Tm (NO3)3·6H2O mixing, is added deionized water, room temperature
Transparence is stirred into, RE is obtained3+Ion concentration is 0.1mol/L RE (NO3)3Solution；
Wherein, in molar ratio, Gd3+∶Yb3+∶Tm3+=97: 1: 2；
(2) 0.8g ammonium sulfate is dissolved in 0.1mol/L RE (NO3)3In solution, RE (NO3)3The volume of solution is 60mL,
At room temperature, 20min is stirred, then, continues to stir and be added dropwise ammonium hydroxide, adjusting pH value is 10.0, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=1: 1；
(3) suspension is moved in reaction kettle, at 150 DEG C, hydro-thermal reaction for 24 hours, after reaction, is taken out, natural cooling
To room temperature, reaction product is obtained；
(4) reaction product is centrifugated, water cleaning is added three times, it is primary to add washes of absolute alcohol, dries at 80 DEG C
It is dry, obtain white powder presoma --- sulfate type rare earth layered hydroxide (Gd0.97Yb0.01Tm0.02)2(OH)4SO4,
XRD spectrum is shown in that Fig. 8 (c), XRD show it for pure phase；Hexagon micron plate subject to its pattern, thickness be 0.5~0.8 μm, a length of 4
~8 μm, as shown in Fig. 9 (c).
(5) white powder presoma is placed in air, at 1000 DEG C, calcines 0.5h, obtain rare earth oxysulfate
(Gd0.97Yb0.01Tm0.02)2O2SO4Up-conversion phosphor, XRD see Figure 10 (c), XRD show its for pure phase, pattern and its before
Drive body it is similar, subject to hexagon micron plate, thickness be 0.5~0.8 μm, a length of 4~8 μm, as shown in Figure 11 (c), convert thereon
Emission spectrum is shown in Figure 12 (c).
Embodiment 12
A kind of preparation method of rear-earth-doped gadolinium oxysulfide up-conversion phosphor, follows the steps below:
Step (1), (2), (3), (4) are the same as embodiment 11；
(5) white powder presoma is placed in H2And N2Gaseous mixture (volume ratio, H2∶N2=80: 20) in atmosphere, 1200
DEG C calcining 0.5h, obtain rare-earth oxide sulfate (Gd0.97Yb0.01Tm0.02)2O2S fluorescent powder, XRD are shown in that Figure 13 (c), XRD show it
For pure phase, pattern is similar to its presoma, subject to hexagon micron plate, thickness be 0.5~0.8 μm, a length of 4~8 μm, such as scheme
Shown in 14 (c), Up-conversion emission spectrum is shown in Figure 15 (c).
Claims (7)
1. the preparation method of a kind of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor, which is characterized in that according to
Following steps carry out:
(1) by Gd (NO3)3·6H2O、Yb(NO3)3·6H2O and Ln (NO3)3·6H2O mixing, is added deionized water, is stirred at room temperature
At transparence, RE (NO is obtained3)3Solution；
Wherein, in molar ratio, Gd3+:Yb3+:Ln3+=(90~97):(5~2):(5~1)；
The Ln is one of Ho or Tm；
The RE3+For Gd3+、Yb3+And Ln3+Hybrid ionic；
(2) ammonium sulfate is dissolved in RE (NO3)3It in solution, stirs evenly, then, continues to stir, and ammonium hydroxide is added, adjusting pH value is
7.0 ~ 10.0, obtain suspension；
Wherein, in molar ratio, sulfate radical: RE3+=(1~5):(2~1)；
(3) suspension is moved in reaction kettle, at 100 ~ 150 DEG C, 1 ~ 72h of hydro-thermal reaction, after reaction, is taken out, it is naturally cold
But to room temperature, reaction product is obtained；
(4) by reaction product centrifuge separation, cleaning, drying, white powder presoma (Gd, Yb, Ln) is obtained2(OH)4SO4·nH2O, whereinn=0 or 1.9 ~ 2.2；
The white powder presoma is sulfate type rare earth layered hydroxide, and pattern is that reunion ball or quasi- hexagon are micro-
One of rice plate；
(5) it by white powder presoma, is calcined, rare earth ion doped Gd is made2O2S and Gd2O2SO4Up-conversion fluorescence
Powder；Wherein, calcination parameter is (a) or (b):
(a) calcination environment is air, and calcination temperature is 800 ~ 1000 DEG C, and calcination time is 0.5 ~ 4h, corresponding obtained rare earth from
The Gd of son doping2O2SO4Up-conversion phosphor is rare earth oxysulfate (Gd, Yb, Ln)2O2SO4；
(b) calcination environment is reducing atmosphere, and calcination temperature is 800 ~ 1200 DEG C, and calcination time is 0.5 ~ 4h, it is corresponding made from
Rare earth ion doped Gd2O2S up-conversion phosphor is rare-earth oxide sulfate (Gd, Yb, Ln)2O2S。
2. the preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor as described in claim 1,
It is characterized in that, the RE (NO3)3The RE of solution3+Concentration is 0.05 ~ 0.5mol/L.
3. the preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor as described in claim 1,
It is characterized in that, in the step (2), the stirring, the time is 15 ~ 20min.
4. the preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor as described in claim 1,
It is characterized in that, in the step (2), ammonium hydroxide is added using the method being added dropwise.
5. the preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor as described in claim 1,
It is characterized in that, in the step (4), it is primary to add washes of absolute alcohol using water cleaning is added three times for the cleaning.
6. the preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor as described in claim 1,
It is characterized in that, in the step (4), the drying, drying temperature is 50 ~ 80 DEG C.
7. the preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor as described in claim 1,
It is characterized in that, in the step 5, the reducing atmosphere is H2And N2It mixes in proportion, wherein H2Percentage by volume be 5 ~
100%, surplus N2。
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