CN106520121A - Preparation method of rare earth-doped gadolinium oxysulfide and oxygen-containing gadolinium sulphate up-conversion phosphor - Google Patents
Preparation method of rare earth-doped gadolinium oxysulfide and oxygen-containing gadolinium sulphate up-conversion phosphor Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 77
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- 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 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000001301 oxygen Substances 0.000 title claims abstract description 23
- QLAFITOLRQQGTE-UHFFFAOYSA-H gadolinium(3+);trisulfate Chemical compound [Gd+3].[Gd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QLAFITOLRQQGTE-UHFFFAOYSA-H 0.000 title abstract 2
- 239000000843 powder Substances 0.000 claims abstract description 32
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000006227 byproduct Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 229910005563 Gd2O2SO4 Inorganic materials 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
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 20
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- -1 rare earth ion Chemical class 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 9
- 229910002617 Gd(NO3)3·6H2O Inorganic materials 0.000 claims description 8
- 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 description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 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
- 239000000463 material Substances 0.000 abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 9
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 229910005560 Gd(NO3)3.6H2O Inorganic materials 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 13
- 238000000295 emission spectrum Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000008246 gaseous mixture Substances 0.000 description 5
- 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
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 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
- 230000005855 radiation Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 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
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229950000845 politef Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides a preparation method of rare earth-doped gadolinium oxysulfide and oxygen-containing gadolinium sulphate up-conversion phosphor, and belongs to the field of material science. The method comprises the following steps that 1, Gd(NO3)3.6H2O, Yb(NO3)3.6H2O and Ln(NO3)3.6H2O are mixed, deionized water is added, and a RE(NO3)3 solution is obtained; 2, ammonium sulfate is dissolved into the RE(NO3)3 solution, stirring is conducted, stirring continues, ammonia water is added, the pH value is regulated, and suspension is obtained; 3, the suspension is subjected to a hydrothermal reaction for 1-72 h at the temperature of 100 DEG C to 150 DEG C and then naturally cooled to room temperature, and a reaction product is obtained; 4, the reaction product is centrifugally separated, washed and dried, and a white powder precursor is obtained; 5, the white powder precursor is calcined, and the rare earth ion-doped Gd2O2S or Gd2O2SO4 up-conversion phosphor is obtained. According to the method, the problems of usage of sulfur-containing raw materials and discharge of harmful by-products in a conventional method are effectively solved, and the method is a green and environment-friendly preparation technique.
Description
Technical field
The invention belongs to material science, changes on more particularly to a kind of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate
The preparation method of fluorescent material.
Background technology
Up-conversion luminescent material, with the ability that long-wave radiation can be converted into shortwave radiation of its uniqueness, is widely used in
The fields such as upconversion laser, DSSC, medicament transport, biological fluorescent labelling and infrared anti-false.Imitate at present
The higher upper converting system of rate is fluoride (such as NaYF4：Yb/Er), fluoride has phonon energy low and upper high conversion efficiency
The advantages of.But fluoride raw material toxicity is larger, this shortcoming significantly limit the big rule of converting luminescent material of fluoride
Mould is produced and practical application.On rare earth oxide, converting system is although nontoxic, but phonon energy is higher, and upper conversion efficiency is low.
Therefore explore the upper converting system that other types are nontoxic and phonon energy is relatively low and there is higher actual application value.
Gadolinium oxysulfide (Gd2O2S) phonon energy is relatively low and chemical stability is good.Therefore, research worker have studied Yb/Ho
Adulterate in Gd with Yb/Er2O2Up-conversion luminescence performance in S, it is found which has good up-conversion luminescence performance.But at present
The problem of presence has：(1) other doping such as Yb/Tm are in Gd2O2Up-conversion luminescence in S is rarely reported；(2) such compound
Prepare inevitable use environment it is harmful containing sulfur feedstock or be related to the harmful sulfur byproduct species of environment.
Oxygen-containing Digadolinium trisulfate (Gd2O2SO4) extensive concern that luminous host has obtained research worker is changed mainly as lower.Closely
Phase is it was discovered by researchers that Yb/Er adulterates 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 Y2O2SO4Compare, Gd2O2SO4's
Covalency is higher than Y2O2SO4, while Gd2O2SO4In Gd3+With half-full 4f shells, 2 points of features of the above have the system
Prestige presents more preferable luminescent properties.The same Gd of such compound traditional preparation methods2O2The similar presence of preparation method of S uses ring
Border it is harmful containing sulfur feedstock or the problems such as be related to the discharge of environment harmful sulfur byproduct species, until 2010 Nian You research worker
It was found that the new sulfate type rare earth layered hydroxide Gd of a class2(OH)4SO4·nH2O, and by calcining such change in atmosphere
Compound green prepares Gd2O2SO4, but Gd2(OH)4SO4·nH2The preparation method of O is mainly limited to the sedimentation method.Obtained by the sedimentation method
Product is irregular aggregate.Calcined product Gd2O2SO4Pattern and its presoma Gd2(OH)4SO4·nH2The pattern of O is close
It is related.Therefore can not still realize at present preparing Gd in green2O2SO4While reach the Effective Regulation to its pattern.And precipitate
Method conventional precipitant such as hexamethylenetetramine (HMT, (CH2)6N4) have hydrolysis under room temperature slow, and generate in air under high temperature
Formaldehyde and its derivant and the shortcomings of reduce the yield for sinking to the bottom reaction.Because of Gd2(OH)4SO4·nH2In O water of crystallization and rare earth from
Son directly coordination, therefore whether occur in structure during water of crystallization directly affects the crystal structure feature of product and with rare earth ion be
The coordination mode of the coordination polyhedrom of the heart.
The content of the invention
Rear-earth-doped Gd is prepared for existing2O2Harmful the asking containing sulfur feedstock of use environment present in S technology paths
Topic, the present invention provide a kind of preparation method of rear-earth-doped gadolinium oxysulfide up-conversion phosphor, and the preparation method adopts hydro-thermal method
Prepare rear-earth-doped Gd2(OH)4SO4·nH2O and Gd2(OH)4SO4Two class presomas, and using in this two classes presoma
The mol ratio of RE/S and RE2O2The characteristics of completely the same in S, the two classes compound is calcined in reducing atmosphere, green is prepared
Rear-earth-doped Gd2O2S.Used in the preparation process of presoma, gentle ammonium sulfate is sulphur source, and the by-product in calcination process is only
For water vapour.The method efficiently solves the harmful use containing sulfur feedstock of environment and harmful side product discharge in conventional method
Problem, be a kind of technology of preparing of environmental protection.
Rear-earth-doped Gd is prepared for existing2O2SO4Reach while can not realizing prepared by green present in technology path
To the problem effectively regulated and controled to its pattern, a kind of preparation of rear-earth-doped oxygen-containing Digadolinium trisulfate up-conversion phosphor of present invention offer
Method, the method are to prepare rear-earth-doped Gd using hydro-thermal method2(OH)4SO4·nH2O, by calcining the change in air
Compound realizes the rear-earth-doped Gd of uniform reunion spheroid2O2SO4Preparation, 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 atmosphere
Thing 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 present invention a kind of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor preparation method, according to
Lower step is carried out：
(1) by Gd (NO3)3·6H2O、Yb(NO3)3·6H2O and Ln (NO3)3·6H2O mixes, and adds deionized water, room temperature
Transparence is stirred into, RE (NO are obtained3)3Solution；
Wherein, in molar ratio, Gd3+∶Yb3+∶Ln3+=(90～97): (5～2): (5～1)；
Described Ln is the one kind in Ho, Er or Tm；
Described RE3+For Gd3+、Yb3+And Ln3+Hybrid ionic；
(2) ammonium sulfate is dissolved in into RE (NO3)3In solution, stir, then, continue stirring, and add ammonia, adjust pH
It is worth for 7.0～10.0, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=(1～5): (2～1)；
(3) suspension is moved in reactor, at 100～150 DEG C, 1～72h of hydro-thermal reaction, after reaction terminates, takes out,
Room temperature is naturally cooled to, product is obtained；
(4) by product centrifugation, cleaning, drying, obtain white powder presoma (Gd, Yb, Ln)2(OH)4SO4·nH2O, wherein, n=0 or 1.9～2.2；
(5) by white powder presoma, calcined, rare earth ion doped Gd is obtained2O2S and Gd2O2SO4Upper conversion is glimmering
Light powder；Wherein, calcination parameter is (a) or (b)：
A () calcination environment is air, calcining heat is 800～1000 DEG C, and calcination time is 0.5～4h, corresponding obtained
Rare earth ion doped Gd2O2SO4Up-conversion phosphor is rare earth oxysulfate (Gd, Yb, Ln)2O2SO4；
B () calcination environment is reducing atmosphere, calcining heat is 800～1200 DEG C, and calcination time is 0.5～4h, corresponding
Obtained rare earth ion doped Gd2O2S up-conversion phosphors are rare-earth oxide sulfate (Gd, Yb, Ln)2O2S。
Wherein,
Described RE (NO3)3The RE of solution3+Concentration is 0.05～0.5mol/L；
In step (2), described stirring, time are 15～20min.
In step (2), ammonia is added using the method being added dropwise over.
In step (4), described centrifugation is that product is centrifuged, and removes supernatant, to being centrifuged
To precipitate processed；
In step (4), described cleaning adds washes of absolute alcohol once, mesh using adding water to clean three times
Be remove white powder presoma in impurity；
In step (4), described drying, drying temperature are 50～80 DEG C.
In step (4), described white powder presoma is sulfate type rare earth layered hydroxide, and its pattern is
One kind in reunion ball or quasi- hexagon micron plate, by adjusting the techniques such as pH, reaction temperature, response time, calcining heat
Parameter, can regulate and control to its pattern, reach the morphology controllable to fluorescent material, programmable effect.
In the step 5, described reducing atmosphere is H2And N2It is mixed in proportion, wherein, H2Percentage by volume be 5～
100%, balance of N2。
The preparation method of the rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor of the present invention, prepares rare earth sulfur
The chemical equation of oxide is：
RE2(OH)4SO4·nH2O→RE2(OH)4SO4+nH2O (3)
RE2(OH)4SO4→RE2O2SO4+2H2O (4)
RE2O2SO4+4H2→RE2O2S+4H2O (5)
The chemical equation for preparing rare earth oxysulfate is：
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 characteristics of of the invention and beneficial effect is：
Using rear-earth-doped Gd2(OH)4SO4And Gd2(OH)4SO4·nH2RE/S mol ratios and RE in O2O2S is completely the same
The characteristics of, this two classes compound is calcined in reducing atmosphere, green prepares rear-earth-doped Gd2O2S, effectively solves 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.
Using Hydrothermal Synthesiss route, by modulating response parameter, such as pH value, temperature and response time, size is prepared equal
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 and control have been carried out to its pattern.
Description of the drawings
Fig. 1 is the process chart that the present invention prepares rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor；
Fig. 2 is sulfate type rare earth layered hydroxide (Gd, Yb, Ln) prepared by embodiment of the present invention 1-62(OH)4SO4·nH2The XRD spectrum of O, wherein, (a) is obtained by embodiment 1 and embodiment 2, (b) is obtained by embodiment 3 and embodiment 4,
C () is obtained by embodiment 5 and embodiment 6；
Fig. 3 is sulfate type rare earth layered hydroxide (Gd, Yb, Ln) prepared by embodiment of the present invention 1-62(OH)4SO4·nH2The SEM shape appearance figures of O, wherein, (a) are obtained by embodiment 1 and embodiment 2, (b) are made by embodiment 3 and embodiment 4
, (c) it is obtained 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) be obtained by embodiment 1, (b) be obtained by embodiment 3, (c) be obtained 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 figures, wherein, (a) be obtained by embodiment 1, (b) be obtained by embodiment 3, (c) be obtained 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 phosphors
XRD spectrum, wherein, (a) is obtained by embodiment 2, (b) is obtained by embodiment 4, (c) be obtained 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 phosphors
SEM shape appearance figures, wherein, (a) are obtained by embodiment 2, (b) are obtained by embodiment 4, (c) be obtained by embodiment 6；
Fig. 8 is that embodiment of the present invention 7-12 prepares (Gd, Yb, Ln)2(OH)4SO4XRD spectrum, wherein, (a) by implementing
Example 7 and embodiment 8 are obtained, and (b) are obtained by embodiment 9 and embodiment 10, (c) are obtained by embodiment 11 and embodiment 12；
Fig. 9 is that embodiment of the present invention 7-12 prepares (Gd, Yb, Ln)2(OH)4SO4SEM shape appearance figures, wherein, (a) by reality
Apply example 7 and embodiment 8 is obtained, (b) be obtained by embodiment 9 and embodiment 10, (c) be obtained 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 obtained by embodiment 7, (b) is obtained by embodiment 9, (c) be obtained 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 figures of powder, wherein, (a) are obtained by embodiment 7, (b) are obtained by embodiment 9, (c) be obtained 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 obtained by embodiment 7, (b) is obtained by embodiment 9, (c) be obtained 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 phosphors
XRD spectrum, wherein, (a) be obtained by embodiment 8, (b) be obtained by embodiment 10, (c) be obtained 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 phosphors
SEM shape appearance figures, wherein, (a) be obtained by embodiment 8, (b) be obtained by embodiment 10, (c) be obtained 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 phosphors
Up-conversion emission spectrum, wherein, (a) be obtained by embodiment 8, (b) be obtained by embodiment 10, (c) be obtained by embodiment 12；
Specific embodiment
Chemical reagent employed in following instance is the pure level product of analysis；
Following examples carry out XRD analysis using the RINT2200V/PC types x-ray diffractometer of Rigaku companies of Japan；
Using S-5000 type field emission scanning electron microscope (FE-SEM) observing samples patterns (SEM) of Japanese Hitachi companies；
Using the up-conversion luminescence performance of the FP-6500 type spectrofluorophotometer test samples of Japanese JASCO companies, with
978nm near-infrared laser diodes (KS3-12322-105, Beijing Kaipu Lin Photoelectricity Science Co., Ltd) conduct is exciting light
Source.
Hydrothermal reaction kettle inner bag material is politef, and specification 100ml, steel bushing material are rustless steel, and baking oven is electronics
Temperature control oven, the temperature difference are less than 1 DEG C；High temperature furnace is tube furnace, 1550 DEG C of rated temperature；
In the present invention, the measure and calculation of sample crystallization water content is that the thermogravimetric of employing is divided according to depending on thermogravimetric analysiss (TGA)
Analysing INSTRUMENT MODEL is：The STA449F3 type thermogravimetric analyzers of German Netzsch companies.
With reference to embodiment, the present invention is described in further detail, is the preferred embodiment of the present invention below.
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 mixes, and adds 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 into 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 over ammonia, it is 7.0 to adjust pH value, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=1: 1；
(3) suspension is moved in reactor, at 100 DEG C, hydro-thermal reaction 72h, after reaction terminates, is taken out, natural cooling
To room temperature, product is obtained；
(4) by product centrifugation, add water to clean three times, add washes of absolute alcohol once, dry 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 its XRD spectrum such as Fig. 2 (a)；Its pattern is reunion ball, and size is 80～110 μm, such 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, its 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, are reunion ball, a diameter of 80～110 μm, such 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 with embodiment 1；
(5) white powder presoma is placed in into H2And N2Gaseous mixture (volume ratio, H2∶N2=50: 50) in atmosphere, 800 DEG C
Calcining 1h, obtains rare-earth oxide sulfate (Gd0.90Yb0.05Ho0.05)2O2S fluorescent material, its 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, is reunion ball, a diameter of 80～110 μm, such 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 mixes, and adds 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 into 0.5mol/L RE (NO3)3In solution, RE (NO3)3The volume of solution is 60mL, in room
Under temperature, 20min is stirred, then, continue to stir and be added dropwise over ammonia, it is 7.0 to adjust pH value, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=1: 1；
(3) suspension is moved in reactor, at 100 DEG C, hydro-thermal reaction 1h, after reaction terminates, is taken out, naturally cooled to
Room temperature, obtains product；
(4) by product centrifugation, add water to clean three times, add washes of absolute alcohol once, dry 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), its XRD spectrum such as Fig. 2 (b), its pattern is reunion ball, a diameter of 80～110 μm, such as Fig. 3 (b) institutes
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, its 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, are reunion ball, a diameter of 80～110 μm, such 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 with embodiment 3；
(5) white powder presoma is placed in into 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 material, its XRD are shown in Fig. 6 (b), can from figure
Go out product for pure phase；Its pattern is similar to its presoma, is reunion ball, a diameter of 80～110 μm, such 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 mixes, and adds 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 into 0.1mol/L RE (NO3)3In solution, RE (NO3)3The volume of solution is 60mL,
Under room temperature, 15min is stirred, then, continue to stir and be added dropwise over ammonia, it is 7.0 to adjust pH value, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=1: 1；
(3) suspension is moved in reactor, at 100 DEG C, hydro-thermal reaction 24h, after reaction terminates, is taken out, natural cooling
To room temperature, product is obtained；
(4) by product centrifugation, add water to clean three times, add washes of absolute alcohol once, dry 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 its XRD spectrum such as Fig. 2 (c), its pattern is reunion ball, and size is 80～110 μm, such 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, its 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, are reunion ball, a diameter of 80～110 μm, such 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 with embodiment 5；
(5) white powder presoma is placed in into H2And N2Gaseous mixture (volume ratio, H2∶N2=5: 95) in atmosphere, 1200 DEG C
Calcining 1h, obtains rare-earth oxide sulfate (Gd0.97Yb0.02Tm0.01)2O2S fluorescent material, its 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, is reunion ball, a diameter of 80～110 μm, such 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 mixes, and adds 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 into 0.1mol/L RE (NO3)3In solution, RE (NO3)3The volume of solution is 60mL, in room
Under temperature, 20min is stirred, then, continue to stir and be added dropwise over ammonia, it is 10.0 to adjust pH value, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=5: 1；
(3) suspension is moved in reactor, at 150 DEG C, hydro-thermal reaction 24h, after reaction terminates, is taken out, natural cooling
To room temperature, product is obtained；
(4) by product centrifugation, add water to clean three times, add washes of absolute alcohol once, dry at 70 DEG C
It is dry, obtain white powder presoma sulfate type rare earth layered hydroxide (Gd0.97Yb0.01Ho0.02)2(OH)4SO4, its
XRD spectrum is shown in Fig. 8 (a), and XRD shows which is pure phase, and its pattern is defined hexagon micron plate, and thick is 0.5～0.8 μm, long
For 4～8 μm, such 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, its 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, and be defined hexagon micron plate, thick for 0.5～0.8 μm, a length of 4～8 μm, such as Figure 11 (a) institutes
Show, its 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 with embodiment 7；
(5) white powder presoma is placed in into 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 material, its XRD are shown in that Figure 13 (a), XRD show which is
Pure phase, its pattern are similar to its presoma, and be defined hexagon micron plate, thick for 0.5～0.8 μm, a length of 4～8 μm, such as Figure 14
A, shown in (), its 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 mixes, and adds 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 into 0.1mol/L RE (NO3)3In solution, RE (NO3)3The volume of solution is 60mL,
Under room temperature, 15min is stirred, then, continue to stir and be added dropwise over ammonia, it is 10.0 to adjust pH value, obtains suspension；
Wherein, in molar ratio, sulfate radical: RE3+=1: 2；
(3) suspension is moved in reactor, at 150 DEG C, hydro-thermal reaction 24h, after reaction terminates, is taken out, natural cooling
To room temperature, product is obtained；
(4) by product centrifugation, add water to clean three times, add washes of absolute alcohol once, dry at 50 DEG C
It is dry, obtain white powder presoma sulfate type rare earth layered hydroxide (Gd0.97Yb0.01Er0.02)2(OH)4SO4, its
XRD spectrum is shown in that Fig. 8 (b), XRD show which is pure phase, and its pattern is defined hexagon micron plate, and thick is 0.5～0.8 μm, a length of 4
～8 μm, such 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, its XRD are shown in that Figure 10 (b), XRD show which is pure phase；Its pattern with its before
Drive body phase seemingly, be defined hexagon micron plate, thick is 0.5～0.8 μm, and a length of 4～8 μm, such as Figure 11 (b) is shown；Change 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 with embodiment 9；
(5) white powder presoma is placed in into H2Reducing atmosphere in, 1200 DEG C calcining 4h, obtain rare-earth oxide sulfate
(Gd0.97Yb0.01Er0.02)2O2S fluorescent material, its XRD are shown in that Figure 13 (b), XRD show which is pure phase, its pattern and its forerunner's body phase
Seemingly, be defined hexagon micron plate, and thick is 0.5～0.8 μm, and a length of 4～8 μm, such as Figure 14 (b) is shown, its 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 mixes, and adds 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 into 0.1mol/L RE (NO3)3In solution, RE (NO3)3The volume of solution is 60mL,
Under room temperature, 20min is stirred, then, continue to stir and be added dropwise over ammonia, it is 10.0 to adjust pH value, obtains suspension；
Wherein, in molar ratio, sulfate radical：RE3+=1: 1；
(3) suspension is moved in reactor, at 150 DEG C, hydro-thermal reaction 24h, after reaction terminates, is taken out, natural cooling
To room temperature, product is obtained；
(4) by product centrifugation, add water to clean three times, add washes of absolute alcohol once, dry at 80 DEG C
It is dry, obtain white powder presoma sulfate type rare earth layered hydroxide (Gd0.97Yb0.01Tm0.02)2(OH)4SO4, its
XRD spectrum is shown in that Fig. 8 (c), XRD show which is pure phase；Its pattern is defined hexagon micron plate, and thick is 0.5～0.8 μm, and a length of 4
～8 μm, such 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, its XRD are shown in that Figure 10 (c), XRD show which is pure phase, its pattern with its before
Drive body phase seemingly, be defined hexagon micron plate, thick is 0.5～0.8 μm, a length of 4～8 μm, such as shown in Figure 11 (c), is changed 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 with embodiment 11；
(5) white powder presoma is placed in into 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 material, its XRD are shown in that Figure 13 (c), XRD show which
For pure phase, its pattern is similar to its presoma, and be defined hexagon micron plate, and thick is 0.5～0.8 μm, a length of 4～8 μm, is such as schemed
Shown in 14 (c), its Up-conversion emission spectrum is shown in Figure 15 (c).
Claims (8)
1. the preparation method of a kind of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor, it is characterised in that according to
Following steps are carried out：
(1) by Gd (NO3)3·6H2O、Yb(NO3)3·6H2O and Ln (NO3)3·6H2O mixes, and adds deionized water, is stirred at room temperature
Into transparence, RE (NO are obtained3)3Solution；
Wherein, in molar ratio, Gd3+∶Yb3+∶Ln3+=(90～97): (5～2): (5～1)；
Described Ln is the one kind in Ho, Er or Tm；
Described RE3+For Gd3+、Yb3+And Ln3+Hybrid ionic；
(2) ammonium sulfate is dissolved in into RE (NO3)3In solution, stir, then, continue stirring, and add ammonia, 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 reactor, at 100～150 DEG C, 1～72h of hydro-thermal reaction, after reaction terminates, takes out, natural
Room temperature is cooled to, product is obtained；
(4) by product centrifugation, cleaning, drying, obtain white powder presoma (Gd, Yb, Ln)2(OH)4SO4·
nH2O, wherein, n=0 or 1.9～2.2；
(5) by white powder presoma, calcined, rare earth ion doped Gd is obtained2O2S and Gd2O2SO4Up-conversion fluorescence
Powder；Wherein, calcination parameter is (a) or (b)：
A () calcination environment is air, calcining heat is 800～1000 DEG C, and calcination time is 0.5～4h, corresponding obtained rare earth
The Gd of ion doping2O2SO4Up-conversion phosphor is rare earth oxysulfate (Gd, Yb, Ln)2O2SO4；
B () calcination environment is reducing atmosphere, calcining heat is 800～1200 DEG C, and calcination time is 0.5～4h, corresponding to be obtained
Rare earth ion doped Gd2O2S up-conversion phosphors are rare-earth oxide sulfate (Gd, Yb, Ln)2O2S。
2. the preparation method of rear-earth-doped gadolinium oxysulfide as claimed in claim 1 and oxygen-containing Digadolinium trisulfate up-conversion phosphor, its
It is characterised by, described RE (NO3)3The RE of solution3+Concentration is 0.05～0.5mol/L.
3. the preparation method of rear-earth-doped gadolinium oxysulfide as claimed in claim 1 and oxygen-containing Digadolinium trisulfate up-conversion phosphor, its
It is characterised by, in step (2), described stirring, time are 15～20min.
4. the preparation method of rear-earth-doped gadolinium oxysulfide as claimed in claim 1 and oxygen-containing Digadolinium trisulfate up-conversion phosphor, its
It is characterised by, in step (2), ammonia is added using the method being added dropwise over.
5. the preparation method of rear-earth-doped gadolinium oxysulfide as claimed in claim 1 and oxygen-containing Digadolinium trisulfate up-conversion phosphor, its
It is characterised by, in step (4), described cleaning adds washes of absolute alcohol once using adding water to clean three times.
6. the preparation method of rear-earth-doped gadolinium oxysulfide as claimed in claim 1 and oxygen-containing Digadolinium trisulfate up-conversion phosphor, its
It is characterised by, in step (4), described drying, drying temperature are 50～80 DEG C.
7. the preparation method of rear-earth-doped gadolinium oxysulfide as claimed in claim 1 and oxygen-containing Digadolinium trisulfate up-conversion phosphor, its
It is characterised by, in step (4), described white powder presoma is sulfate type rare earth layered hydroxide, its pattern
For the one kind in reunion ball or quasi- hexagon micron plate.
8. the preparation method of rear-earth-doped gadolinium oxysulfide as claimed in claim 1 and oxygen-containing Digadolinium trisulfate up-conversion phosphor, its
It is characterised by, in the step 5, described reducing atmosphere is H2And N2It is mixed in proportion, wherein, H2Percentage by volume be 5～
100%, balance of N2。
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