CN104046984B - A kind of method preparing the lutetium pyrosilicate flicker film mixing cerium - Google Patents
A kind of method preparing the lutetium pyrosilicate flicker film mixing cerium Download PDFInfo
- Publication number
- CN104046984B CN104046984B CN201310081938.6A CN201310081938A CN104046984B CN 104046984 B CN104046984 B CN 104046984B CN 201310081938 A CN201310081938 A CN 201310081938A CN 104046984 B CN104046984 B CN 104046984B
- Authority
- CN
- China
- Prior art keywords
- monocrystalline silicon
- aqueous solution
- silicon piece
- molar concentration
- volumetric molar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 34
- 229910052765 Lutetium Inorganic materials 0.000 title claims abstract description 34
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000002156 mixing Methods 0.000 title claims abstract description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 53
- 238000003486 chemical etching Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000002203 pretreatment Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 76
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000007864 aqueous solution Substances 0.000 claims description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 32
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 238000005530 etching Methods 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 235000011194 food seasoning agent Nutrition 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 14
- 239000010703 silicon Substances 0.000 description 14
- 229910002651 NO3 Inorganic materials 0.000 description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 7
- 229910021426 porous silicon Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000009206 nuclear medicine Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 238000002600 positron emission tomography Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Weting (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a kind of method preparing the lutetium pyrosilicate flicker film mixing cerium, it comprises the steps: a) to carry out surface cleaning and oxide layer pre-treatment to monocrystalline silicon piece; B) adopt chemical etching method through step a) pretreated monocrystalline silicon sheet surface etch porous; C) by step b) surface etch that obtains has the monocrystalline silicon piece of porous to insert Ce
xlu
1-x(NO
3)
3in acetic acid solution, flood at 25 ~ 60 DEG C after 8 ~ 12 hours, drying for standby; Wherein, Ce
xlu
1-x(NO
3)
3in x=0.001 ~ 0.040; D) by step c) monocrystalline silicon piece that obtains heat-treats 2 ~ 4 hours in an inert atmosphere, at 1000 ~ 1200 DEG C.The present invention can realize preparing thickness with simple operations, low cost, big area can reach 30 ~ 60 microns and film to be combined the lutetium pyrosilicate firmly mixing cerium glimmers film with substrate, has application prospect.
Description
Technical field
The present invention relates to a kind of method preparing the lutetium pyrosilicate flicker film mixing cerium, particularly relate to a kind of direct for metal catalytic chemical etching silicon method being combined with dipping coating method prepare the lutetium pyrosilicate mixing cerium and to glimmer the method for film, belong to technology of thin film material preparation field of glimmering.
Background technology
2000, it is found that the lutetium pyrosilicate (Lu mixing cerium
2si
2o
7: Ce
3+, be abbreviated as LPS:Ce
3+) crystal has higher light output (being about 13000-22000Ph/MeV), and fluorescence decay time short (38ns), what is more important without twilight sunset, energy resolution good (9%), therefore scintillation properties is excellent, meanwhile, LPS:Ce
3+chemical stability and high-temperature stability be excellent, deliquescence, physical strength are not high, therefore, mix the lutetium pyrosilicate (LPS:Ce of cerium
3+) scintillation crystal is particularly suitable as oil well exploration, nuclear medicine diagnostic (particularly positron emission tomography PET, XCT), XRF display applications, is a kind of scintillation material having much the high comprehensive performance of potentiality.But, due to LPS:Ce
3+ce in monocrystalline
3+skewness, cause its scintillation properties unstable, the fusing point of LPS is more than 1900 DEG C in addition, and single crystal preparation cost is high, the cycle is long, limits its large-scale application to a certain extent.Given this, if by LPS:Ce
3+be prepared into flicker film, greatly can reduce preparation temperature on the one hand, can shorten the production cycle on the other hand, this will be LPS:Ce
3+an important research direction of scintillation material.
At present, the method preparing film has a lot, such as: magnetron sputtering method, atomic layer deposition method, pulsed laser deposition, hot vapour deposition method, liquid phase epitaxial method, collosol and gel are in conjunction with dip-coating method etc.Collosol and gel wherein in conjunction with dip-coating method compared to additive method have equipment simple and convenient, with low cost, big area can prepare the advantages such as film.A kind of sol-gel method that adopts is disclosed at (Lu in Chinese patent CN1588607A
1-yre
y)
2si
2o
7single crystalline substrate grows one deck (Ce
xre
ylu
1-x-y)
2si
2o
7the method of the transparent cathode-ray screen that flicker film is formed, wherein x=0.001 ~ 0.01, y=0 ~ 0.3.But collosol and gel also has the defect of himself in conjunction with dip-coating method, such as: need repeatedly the bonding force of Best-Effort request, film and substrate more weak, not easily prepare thicker film and ftracture as the film of tens micron levels, high-temperature heat treatment easily make film produce.
Summary of the invention
The problems referred to above existed for prior art and defect, the object of this invention is to provide a kind of method preparing the lutetium pyrosilicate flicker film mixing cerium, realize with simple operations, low cost, big area can prepare thickness and can reach tens microns and film to be combined the lutetium pyrosilicate firmly mixing cerium to glimmer film with substrate, to meet the application requiring of this flicker film in fields such as X-ray scintillation conversion screen, X-ray safety check instrument, industrial non-destructive detections.
For achieving the above object, the technical solution used in the present invention is as follows:
Prepare a method for the lutetium pyrosilicate flicker film mixing cerium, comprise the steps:
A) surface cleaning and oxide layer pre-treatment are carried out to monocrystalline silicon piece;
B) adopt chemical etching method through step a) pretreated monocrystalline silicon sheet surface etch porous;
C) by step b) surface etch that obtains has the monocrystalline silicon piece of porous to insert Ce
xlu
1-x(NO
3)
3in acetic acid solution, flood at 25 ~ 60 DEG C after 8 ~ 12 hours, drying for standby; Wherein, Ce
xlu
1-x(NO
3)
3in x=0.001 ~ 0.040;
D) by step c) monocrystalline silicon piece that obtains heat-treats 2 ~ 4 hours in an inert atmosphere, at 1000 ~ 1200 DEG C.
As a kind of preferred version, step a) described in pre-treatment comprise following operation: after monocrystalline silicon piece is cut into desired size, at room temperature successively through acetone, alcohol, deionized water ultrasonic cleaning monocrystalline silicon sheet surface, then dry up, be immersed in hydrofluoric acid aqueous solution to remove the zone of oxidation of monocrystalline silicon sheet surface.
As further preferred version, the mass concentration of described hydrofluoric acid aqueous solution is 5 ~ 10wt%.
As a kind of preferred version, described step b) comprise following operation: by through step a) pretreated monocrystalline silicon piece insert in the mixed aqueous solution A be made up of hydrofluoric acid and Silver Nitrate and carry out etching 30 ~ 180 seconds, insert again in the mixed aqueous solution B be made up of hydrofluoric acid and hydrogen peroxide, at 25 ~ 50 DEG C after with deionized water, ethanol wash and carry out etching 30 ~ 60 minutes, insert again in aqueous nitric acid after with deionized water, ethanol wash and carry out immersion 1 ~ 1.5 hour.
As further preferred version, in described mixed aqueous solution A, hydrofluoric volumetric molar concentration is 4.6 ~ 4.8mol/L, and the volumetric molar concentration of Silver Nitrate is 0.005 ~ 0.01mol/L.
As further preferred version, in described mixed aqueous solution B, hydrofluoric volumetric molar concentration is 4.6 ~ 4.8mol/L, and the volumetric molar concentration of hydrogen peroxide is 0.2 ~ 0.6mol/L.
As further preferred version, described aqueous nitric acid or volumetric molar concentration be 3.5 ~ 7.0mol/L.
As a kind of preferred version, described Ce
xlu
1-x(NO
3)
3the volumetric molar concentration of acetic acid solution is 0.05 ~ 0.4mol/L.
Described Ce
xlu
1-x(NO
3)
3the preparation of acetic acid solution the compound as lutetium source and the compound as cerium source is stoichiometrically added in acetic acid solvent to obtain; Compound as lutetium source can be lutecium oxide, lutecium chloride or its hydrate, lutecium nitrate or its hydrate etc., preferential oxidation lutetium; Compound as cerium source can be soluble inorganic cerium salt and hydrate thereof, comprises cerous nitrate and hydrate, cerous acetate and hydrate thereof, Cerium II Chloride and hydrate thereof etc., preferably six nitric hydrate ceriums.
As a kind of preferred version, step c) described in drying refer to seasoning in air at room temperature.
As a kind of preferred version, steps d) described in inert atmosphere be argon gas atmosphere.
Compared with prior art, the present invention has following beneficial effect:
1, creatively adopt the method for argent catalysis direct chemical etching silicon and flood coating method and combine, achieve with simple operations, low cost, big area can prepare thickness and can reach 30 ~ 60 microns and film to be combined the lutetium pyrosilicate firmly mixing cerium glimmers film with substrate;
2, show after testing: the crystallised component adopting the film prepared by the inventive method is Lu
2si
2o
7phase, its UV, visible light fluorescence spectrum and excitation of X-rays spectrum all show the Lu at about 378nm
2si
2o
7(LPS): Ce
3+characteristic luminescence peak, and film is even, the fall time of film is 34.25ns; Be expected, in fields such as X-ray scintillation conversion screen, X-ray safety check instrument, industrial non-destructive detections, there is good application prospect.
Accompanying drawing explanation
Fig. 1 has the surface topography map of the monocrystalline silicon piece of porous for surface etch that embodiment 1 obtains;
Fig. 2 has the Cross Section Morphology figure of the monocrystalline silicon piece of porous for surface etch that embodiment 1 obtains;
The XRD figure spectrum of mixing the lutetium pyrosilicate flicker film of cerium of Fig. 3 obtained by embodiment 3;
The XRD figure spectrum of mixing the lutetium pyrosilicate flicker film of cerium of Fig. 4 obtained by embodiment 4;
The lutetium pyrosilicate flicker photoluminescence spectra (PL) of film and the comparison diagram of photoluminescence laser spectrum (PLE) of mixing cerium of Fig. 5 obtained by embodiment 2,3,4;
Excitation of X-rays spectrum (XEL) figure that mix the lutetium pyrosilicate flicker film of cerium of Fig. 6 obtained by embodiment 4, illustration is collection of illustrative plates fall time;
The surface topography map of mixing the lutetium pyrosilicate flicker film of cerium of Fig. 7 obtained by embodiment 4;
The Cross Section Morphology figure that mix the lutetium pyrosilicate flicker film of cerium of Fig. 8 obtained by embodiment 4.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further elaborated.
Embodiment 1
One, choose P type (100) monocrystalline silicon piece, being cut into area is after 25.4mm × 25.4mm square, at room temperature successively through acetone, alcohol, deionized water ultrasonic cleaning 20 minutes, dries up; Then to be immersed in the hydrofluoric acid aqueous solution of 5wt% 2 minutes, to remove the zone of oxidation of silicon chip surface, and then to wash about 3 times respectively with deionized water, alcohol.
Two, etching is carried out 60 seconds by inserting through above-mentioned pretreated monocrystalline silicon piece in the mixed aqueous solution A that is made up of hydrofluoric acid and Silver Nitrate, make silicon chip surface deposit one deck Ag particle uniformly, the hydrofluoric acid in described mixed aqueous solution A and the volumetric molar concentration of Silver Nitrate are respectively 4.8mol/L and 0.005mol/L; Insert in the mixed aqueous solution B be made up of hydrofluoric acid and hydrogen peroxide, at 50 DEG C after with deionized water, ethanol wash again and carry out etching 60 minutes, the hydrofluoric acid in described mixed aqueous solution B and the volumetric molar concentration of hydrogen peroxide are respectively 4.8mol/L and 0.3mol/L; Inserting volumetric molar concentration again after with deionized water, ethanol wash is carry out immersion in the aqueous nitric acid of 7.0mol/L 1 hour, to remove the Ag particle among porous silicon; The surface etch obtained has the surface topography of the monocrystalline silicon piece of porous as shown in Figure 1, and its Cross Section Morphology as shown in Figure 2.
Three, preparing volumetric molar concentration is the Ce of 0.4mol/L
0.01lu
0.99(NO
3)
3acetic acid solution: 3.9395g lutecium oxide is added in 10mL concentrated nitric acid, heated and stirred is to dissolving, evaporate to dryness solution obtains the lutecium nitrate solid of white again, then adds in 50mL acetic acid by described lutecium nitrate solid and 0.08685g six nitric hydrate cerium, stirs and makes formation clear soln; Then the monocrystalline silicon piece of porous there is is to insert prepared Ce the surface etch that step 2 obtains
0.01lu
0.99(NO
3)
3in acetic acid solution, flood 12 hours at 60 DEG C, then to take out under air at room temperature seasoning 12 hours.
Four, the monocrystalline silicon piece after step 3 process is put into box-type furnace, in argon gas atmosphere, (Ar airshed is 60sccm) is in 1100 DEG C, constant temp. heating process 2 hours under 0.02MPa pressure, then be cooled to room temperature, on monocrystalline silicon piece, namely prepare the lutetium pyrosilicate flicker film mixing cerium that thickness is about 60 μm.
Embodiment 2
One, choose P type (100) monocrystalline silicon piece, being cut into area is after 25.4mm × 25.4mm square, at room temperature successively through acetone, alcohol, deionized water ultrasonic cleaning 20 minutes, dries up; Then to be immersed in the hydrofluoric acid aqueous solution of 5wt% 2 minutes, to remove the zone of oxidation of silicon chip surface, and then to wash about 3 times respectively with deionized water, alcohol.
Two, etching is carried out 60 seconds by inserting through above-mentioned pretreated monocrystalline silicon piece in the mixed aqueous solution A that is made up of hydrofluoric acid and Silver Nitrate, make silicon chip surface deposit one deck Ag particle uniformly, the hydrofluoric acid in described mixed aqueous solution A and the volumetric molar concentration of Silver Nitrate are respectively 4.8mol/L and 0.005mol/L; Insert in the mixed aqueous solution B be made up of hydrofluoric acid and hydrogen peroxide, at 50 DEG C after with deionized water, ethanol wash again and carry out etching 30 minutes, the hydrofluoric acid in described mixed aqueous solution B and the volumetric molar concentration of hydrogen peroxide are respectively 4.8mol/L and 0.3mol/L; Inserting volumetric molar concentration again after with deionized water, ethanol wash is carry out immersion in the aqueous nitric acid of 7.0mol/L 1 hour, to remove the Ag particle among porous silicon.
Three, preparing volumetric molar concentration is the Ce of 0.4mol/L
0.01lu
0.99(NO
3)
3acetic acid solution: 3.9395g lutecium oxide is added in 10mL concentrated nitric acid, heated and stirred is to dissolving, evaporate to dryness solution obtains the lutecium nitrate solid of white again, then adds in 50mL acetic acid by described lutecium nitrate solid and 0.08685g six nitric hydrate cerium, stirs and makes formation clear soln; Then the monocrystalline silicon piece of porous there is is to insert prepared Ce the surface etch that step 2 obtains
0.01lu
0.99(NO
3)
3in acetic acid solution, flood 8 hours at 60 DEG C, then to take out under air at room temperature seasoning 12 hours.
Monocrystalline silicon piece after step 3 process is put into box-type furnace, in argon gas atmosphere, (Ar airshed is 60sccm) is in 1000 DEG C, constant temp. heating process 2 hours under 0.03MPa pressure, then be cooled to room temperature, on monocrystalline silicon piece, namely prepare the lutetium pyrosilicate flicker film mixing cerium that thickness is about 30 μm.
Embodiment 3
One, choose P type (100) monocrystalline silicon piece, being cut into area is after 25.4mm × 25.4mm square, at room temperature successively through acetone, alcohol, deionized water ultrasonic cleaning 20 minutes, dries up; Then to be immersed in the hydrofluoric acid aqueous solution of 5wt% 2 minutes, to remove the zone of oxidation of silicon chip surface, and then to wash about 3 times respectively with deionized water, alcohol.
Two, etching is carried out 60 seconds by inserting through above-mentioned pretreated monocrystalline silicon piece in the mixed aqueous solution A that is made up of hydrofluoric acid and Silver Nitrate, make silicon chip surface deposit one deck Ag particle uniformly, the hydrofluoric acid in described mixed aqueous solution A and the volumetric molar concentration of Silver Nitrate are respectively 4.8mol/L and 0.005mol/L; Insert in the mixed aqueous solution B be made up of hydrofluoric acid and hydrogen peroxide, at 50 DEG C after with deionized water, ethanol wash again and carry out etching 30 minutes, the hydrofluoric acid in described mixed aqueous solution B and the volumetric molar concentration of hydrogen peroxide are respectively 4.8mol/L and 0.3mol/L; Inserting volumetric molar concentration again after with deionized water, ethanol wash is carry out immersion in the aqueous nitric acid of 7.0mol/L 1 hour, to remove the Ag particle among porous silicon.
Three, preparing volumetric molar concentration is the Ce of 0.4mol/L
0.01lu
0.99(NO
3)
3acetic acid solution: 3.9395g lutecium oxide is added in 10mL concentrated nitric acid, heated and stirred is to dissolving, evaporate to dryness solution obtains the lutecium nitrate solid of white again, then adds in 50mL acetic acid by described lutecium nitrate solid and 0.08685g six nitric hydrate cerium, stirs and makes formation clear soln; Then the monocrystalline silicon piece of porous there is is to insert prepared Ce the surface etch that step 2 obtains
0.01lu
0.99(NO
3)
3in acetic acid solution, flood 8 hours at 60 DEG C, then to take out under air at room temperature seasoning 12 hours.
Monocrystalline silicon piece after step 3 process is put into box-type furnace, in argon gas atmosphere, (Ar airshed is 60sccm) is in 1100 DEG C, constant temp. heating process 2 hours under 0.03MPa pressure, then be cooled to room temperature, on monocrystalline silicon piece, namely prepare the lutetium pyrosilicate flicker film mixing cerium that thickness is about 30 μm.
The XRD figure spectrum of mixing the lutetium pyrosilicate flicker film of cerium of Fig. 3 obtained by the present embodiment, as seen from Figure 3: the thing of prepared thin-film material is Lu mutually
2si
2o
7phase, and in collection of illustrative plates, there is a small amount of cristobalite SiO
2phase, cristobalite SiO
2be obtain by after porous silicon oxide mutually, the crystallinity of XRD figure spectrum display film is good.
Embodiment 4
One, choose P type (100) monocrystalline silicon piece, being cut into area is after 25.4mm × 25.4mm square, at room temperature successively through acetone, alcohol, deionized water ultrasonic cleaning 20 minutes, dries up; Then to be immersed in the hydrofluoric acid aqueous solution of 5wt% 2 minutes, to remove the zone of oxidation of silicon chip surface, and then to wash about 3 times respectively with deionized water, alcohol.
Two, etching is carried out 60 seconds by inserting through above-mentioned pretreated monocrystalline silicon piece in the mixed aqueous solution A that is made up of hydrofluoric acid and Silver Nitrate, make silicon chip surface deposit one deck Ag particle uniformly, the hydrofluoric acid in described mixed aqueous solution A and the volumetric molar concentration of Silver Nitrate are respectively 4.8mol/L and 0.005mol/L; Insert in the mixed aqueous solution B be made up of hydrofluoric acid and hydrogen peroxide, at 50 DEG C after with deionized water, ethanol wash again and carry out etching 30 minutes, the hydrofluoric acid in described mixed aqueous solution B and the volumetric molar concentration of hydrogen peroxide are respectively 4.8mol/L and 0.3mol/L; Inserting volumetric molar concentration again after with deionized water, ethanol wash is carry out immersion in the aqueous nitric acid of 7.0mol/L 1 hour, to remove the Ag particle among porous silicon.
Three, preparing volumetric molar concentration is the Ce of 0.4mol/L
0.01lu
0.99(NO
3)
3acetic acid solution: 3.9395g lutecium oxide is added in 10mL concentrated nitric acid, heated and stirred is to dissolving, evaporate to dryness solution obtains the lutecium nitrate solid of white again, then adds in 50mL acetic acid by described lutecium nitrate solid and 0.08685g six nitric hydrate cerium, stirs and makes formation clear soln; Then the monocrystalline silicon piece of porous there is is to insert prepared Ce the surface etch that step 2 obtains
0.01lu
0.99(NO
3)
3in acetic acid solution, flood 8 hours at 60 DEG C, then to take out under air at room temperature seasoning 12 hours.
Monocrystalline silicon piece after step 3 process is put into box-type furnace, in argon gas atmosphere, (Ar airshed is 60sccm) is in 1200 DEG C, constant temp. heating process 2 hours under 0.03MPa pressure, then be cooled to room temperature, on monocrystalline silicon piece, namely prepare the lutetium pyrosilicate flicker film mixing cerium that thickness is about 30 μm.
The XRD figure spectrum of mixing the lutetium pyrosilicate flicker film of cerium of Fig. 4 obtained by the present embodiment, as seen from Figure 4: the thing of prepared thin-film material is Lu mutually
2si
2o
7phase, cristobalite SiO
2substantially disappear mutually, the crystallinity of XRD figure spectrum display film is good.
The lutetium pyrosilicate of mixing cerium of Fig. 5 obtained by the present embodiment and embodiment 2,3 glimmers the photoluminescence spectra (PL) of film and the comparison diagram of photoluminescence laser spectrum (PLE), as seen from Figure 5: the peak value of its emission wavelength is at about 378nm, and the peak value of excitation wavelength has 300nm and 348nm two place; Can find out that from luminescent spectrum luminous intensity is the strongest when thermal treatment temp is 1200 DEG C.
Excitation of X-rays spectrum (XEL) figure that mix the lutetium pyrosilicate flicker film of cerium of Fig. 6 obtained by the present embodiment, illustration is collection of illustrative plates fall time; As seen from Figure 6: the peak value of the excitation of X-rays spectrum of this film is positioned at about 378nm, and carry out the bimodal matching of Gauss to it, peak position lays respectively at 375nm, 402nm, corresponding to Ce
3+5d lowest vibration energy level to the transition of 4f two splitted levels.Illustration wherein provides curve fall time of corresponding film, obtains being about 34.25ns fall time to its matching.
The surface topography map of mixing the lutetium pyrosilicate flicker film of cerium of Fig. 7 obtained by the present embodiment, the Cross Section Morphology figure that mix the lutetium pyrosilicate flicker film of cerium of Fig. 8 obtained by the present embodiment; From Fig. 7 and 8: prepared film is even, surface is slightly in apertures pattern, and the arrangement of section crystal grain closely.
Embodiment 5
One, choose P type (100) monocrystalline silicon piece, being cut into area is after 25.4mm × 25.4mm square, at room temperature successively through acetone, alcohol, deionized water ultrasonic cleaning 20 minutes, dries up; Then to be immersed in the hydrofluoric acid aqueous solution of 5wt% 1 minute, to remove the zone of oxidation of silicon chip surface, and then to wash about 3 times respectively with deionized water, alcohol.
Two, etching is carried out 90 seconds by inserting through above-mentioned pretreated monocrystalline silicon piece in the mixed aqueous solution A that is made up of hydrofluoric acid and Silver Nitrate, make silicon chip surface deposit one deck Ag particle uniformly, the hydrofluoric acid in described mixed aqueous solution A and the volumetric molar concentration of Silver Nitrate are respectively 4.6mol/L and 0.01mol/L; Insert in the mixed aqueous solution B be made up of hydrofluoric acid and hydrogen peroxide, at 50 DEG C after with deionized water, ethanol wash again and carry out etching 30 minutes, the hydrofluoric acid in described mixed aqueous solution B and the volumetric molar concentration of hydrogen peroxide are respectively 4.6mol/L and 0.3mol/L; Inserting volumetric molar concentration again after with deionized water, ethanol wash is carry out immersion in the aqueous nitric acid of 7.0mol/L 1 hour, to remove the Ag particle among porous silicon.
Three, preparing volumetric molar concentration is the Ce of 0.2mol/L
0.005lu
0.995(NO
3)
3acetic acid solution: 3.9594g lutecium oxide is added in 10mL concentrated nitric acid, heated and stirred is to dissolving, evaporate to dryness solution obtains the lutecium nitrate solid of white again, then adds in 100mL acetic acid by described lutecium nitrate solid and 0.04343g six nitric hydrate cerium, stirs and makes formation clear soln; Then the monocrystalline silicon piece of porous there is is to insert prepared Ce the surface etch that step 2 obtains
0.005lu
0.995(NO
3)
3in acetic acid solution, flood 12 hours at 60 DEG C, then to take out under air at room temperature seasoning 12 hours.
Monocrystalline silicon piece after step 3 process is put into box-type furnace, in argon gas atmosphere, (Ar airshed is 100sccm) is in 1100 DEG C, constant temp. heating process 4 hours under 0.04MPa pressure, then be cooled to room temperature, on monocrystalline silicon piece, namely prepare the lutetium pyrosilicate flicker film mixing cerium that thickness is about 30 μm.
Embodiment 6
One, choose N-type (100) monocrystalline silicon piece, being cut into area is after 25.4mm × 25.4mm square, at room temperature successively through acetone, alcohol, deionized water ultrasonic cleaning 20 minutes, dries up; Then to be immersed in the hydrofluoric acid aqueous solution of 5wt% 3 minutes, to remove the zone of oxidation of silicon chip surface, and then to wash about 3 times respectively with deionized water, alcohol.
Two, etching is carried out 60 seconds by inserting through above-mentioned pretreated monocrystalline silicon piece in the mixed aqueous solution A that is made up of hydrofluoric acid and Silver Nitrate, make silicon chip surface deposit one deck Ag particle uniformly, the hydrofluoric acid in described mixed aqueous solution A and the volumetric molar concentration of Silver Nitrate are respectively 4.8mol/L and 0.005mol/L; Insert in the mixed aqueous solution B be made up of hydrofluoric acid and hydrogen peroxide, at 35 DEG C after with deionized water, ethanol wash again and carry out etching 60 minutes, the hydrofluoric acid in described mixed aqueous solution B and the volumetric molar concentration of hydrogen peroxide are respectively 4.8mol/L and 0.3mol/L; Inserting volumetric molar concentration again after with deionized water, ethanol wash is carry out immersion in the aqueous nitric acid of 7.0mol/L 1 hour, to remove the Ag particle among porous silicon.
Three, preparing volumetric molar concentration is the Ce of 0.2mol/L
0.01lu
0.99(NO
3)
3acetic acid solution: 3.9395g lutecium oxide is added in 10mL concentrated nitric acid, heated and stirred is to dissolving, evaporate to dryness solution obtains the lutecium nitrate solid of white again, then adds in 100mL acetic acid by described lutecium nitrate solid and 0.08685g six nitric hydrate cerium, stirs and makes formation clear soln; Then the monocrystalline silicon piece of porous there is is to insert prepared Ce the surface etch that step 2 obtains
0.01lu
0.99(NO
3)
3in acetic acid solution, flood 8 hours at 60 DEG C, then to take out under air at room temperature seasoning 12 hours.
Monocrystalline silicon piece after step 3 process is put into box-type furnace, in argon gas atmosphere, (Ar airshed is 60sccm) is in 1200 DEG C, constant temp. heating process 2 hours under 0.03MPa pressure, then be cooled to room temperature, on monocrystalline silicon piece, namely prepare the lutetium pyrosilicate flicker film mixing cerium that thickness is about 40 μm.
The preparation technology parameter of table 1 embodiment 1 ~ 6 and the performance data of gained film
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (9)
1. prepare a method for the lutetium pyrosilicate flicker film mixing cerium, it is characterized in that, comprise the steps:
A) surface cleaning and oxide layer pre-treatment are carried out to monocrystalline silicon piece;
B) adopt chemical etching method through step a) pretreated monocrystalline silicon sheet surface etch porous, specifically comprise following operation: by through step a) pretreated monocrystalline silicon piece insert in the mixed aqueous solution A be made up of hydrofluoric acid and Silver Nitrate and carry out etching 30 ~ 180 seconds, insert again in the mixed aqueous solution B be made up of hydrofluoric acid and hydrogen peroxide, at 25 ~ 50 DEG C after with deionized water, ethanol wash and carry out etching 30 ~ 60 minutes, insert again in aqueous nitric acid after with deionized water, ethanol wash and carry out immersion 1 ~ 1.5 hour;
C) by step b) surface etch that obtains has the monocrystalline silicon piece of porous to insert Ce
xlu
1-x(NO
3)
3in acetic acid solution, flood at 25 ~ 60 DEG C after 8 ~ 12 hours, drying for standby; Wherein, Ce
xlu
1-x(NO
3)
3in x=0.001 ~ 0.040;
D) by step c) monocrystalline silicon piece that obtains heat-treats 2 ~ 4 hours in an inert atmosphere, at 1000 ~ 1200 DEG C.
2. method according to claim 1, it is characterized in that, step a) described in pre-treatment comprise following operation: after monocrystalline silicon piece is cut into desired size, at room temperature successively through acetone, alcohol, deionized water ultrasonic cleaning monocrystalline silicon sheet surface, then dry up, be immersed in hydrofluoric acid aqueous solution to remove the zone of oxidation of monocrystalline silicon sheet surface.
3. method according to claim 2, is characterized in that: the mass concentration of described hydrofluoric acid aqueous solution is 5 ~ 10wt%.
4. method according to claim 1, is characterized in that: in described mixed aqueous solution A, and hydrofluoric volumetric molar concentration is 4.6 ~ 4.8mol/L, and the volumetric molar concentration of Silver Nitrate is 0.005 ~ 0.01mol/L.
5. method according to claim 1, is characterized in that: in described mixed aqueous solution B, and hydrofluoric volumetric molar concentration is 4.6 ~ 4.8mol/L, and the volumetric molar concentration of hydrogen peroxide is 0.2 ~ 0.6mol/L.
6. method according to claim 1, is characterized in that: the volumetric molar concentration of described aqueous nitric acid is 3.5 ~ 7.0mol/L.
7. method according to claim 1, is characterized in that: described Ce
xlu
1-x(NO
3)
3the volumetric molar concentration of acetic acid solution is 0.05 ~ 0.4mol/L.
8. method according to claim 1, is characterized in that: step c) described in drying refer to seasoning in air at room temperature.
9. method according to claim 1, is characterized in that: steps d) described in inert atmosphere be argon gas atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310081938.6A CN104046984B (en) | 2013-03-14 | 2013-03-14 | A kind of method preparing the lutetium pyrosilicate flicker film mixing cerium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310081938.6A CN104046984B (en) | 2013-03-14 | 2013-03-14 | A kind of method preparing the lutetium pyrosilicate flicker film mixing cerium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104046984A CN104046984A (en) | 2014-09-17 |
| CN104046984B true CN104046984B (en) | 2016-03-23 |
Family
ID=51500369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310081938.6A Active CN104046984B (en) | 2013-03-14 | 2013-03-14 | A kind of method preparing the lutetium pyrosilicate flicker film mixing cerium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104046984B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1588607A (en) * | 2004-08-04 | 2005-03-02 | 中国科学院上海光学精密机械研究所 | Process fo preparing cerium doped lutetium pyrosilicate submicron imaging fluorescent screen |
| CN1587447A (en) * | 2004-08-04 | 2005-03-02 | 中国科学院上海光学精密机械研究所 | Process for preparing high temperature cerium blended lutetium pyrosilicate scintillation monocrystal |
| CN1896342A (en) * | 2006-06-19 | 2007-01-17 | 中国科学院上海光学精密机械研究所 | Ytterbium-doped lutecium disilicate laser crystal and its preparation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4110246B2 (en) * | 2003-03-31 | 2008-07-02 | 独立行政法人産業技術総合研究所 | Rare earth silicate high temperature steam corrosion prevention coating and method for producing the same |
| JP4385123B2 (en) * | 2003-12-26 | 2009-12-16 | 独立行政法人産業技術総合研究所 | High heat resistant silicon nitride sintered body and method for producing the same |
-
2013
- 2013-03-14 CN CN201310081938.6A patent/CN104046984B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1588607A (en) * | 2004-08-04 | 2005-03-02 | 中国科学院上海光学精密机械研究所 | Process fo preparing cerium doped lutetium pyrosilicate submicron imaging fluorescent screen |
| CN1587447A (en) * | 2004-08-04 | 2005-03-02 | 中国科学院上海光学精密机械研究所 | Process for preparing high temperature cerium blended lutetium pyrosilicate scintillation monocrystal |
| CN1896342A (en) * | 2006-06-19 | 2007-01-17 | 中国科学院上海光学精密机械研究所 | Ytterbium-doped lutecium disilicate laser crystal and its preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104046984A (en) | 2014-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Sr 2 Y 8 (SiO 4) 6 O 2: Bi 3+/Eu 3+: a single-component white-emitting phosphor via energy transfer for UV w-LEDs | |
| Gupta et al. | Combustion synthesis of YAG: Ce and related phosphors | |
| Yu et al. | Luminescence properties of RP1− xVxO4: A (R= Y, Gd, La; A= Sm3+, Er3+ x= 0, 0.5, 1) thin films prepared by Pechini sol–gel process | |
| Silver et al. | Yttrium oxide upconverting phosphors. Part 2: temperature dependent upconversion luminescence properties of erbium in yttrium oxide | |
| CN109943336A (en) | A kind of rare earth ion doped bismuth oxychloride semiconductor material and preparation method thereof | |
| CN102676170B (en) | Method for synthesizing one-dimension red long afterglow luminous nano-tube array | |
| CN105679546B (en) | A kind of InWO4:Eu3+/TiO2Complex light anode and preparation method thereof | |
| CN102061521A (en) | Er-Yb codoping ZnO nano crystal and preparation method thereof | |
| CN104046984B (en) | A kind of method preparing the lutetium pyrosilicate flicker film mixing cerium | |
| Park et al. | Luminescent properties of BaSi 2 O 5: Eu 2+ phosphor film fabricated by spin-coating of Ba-Eu precursor on SiO 2 glass | |
| Cheng et al. | Down-conversion emission of Ce3+-Tb3+ co-doped CaF2 hollow spheres and application for solar cells | |
| CN103666473B (en) | Method for preparing europium ion doped lanthanum aluminum long afterglow light-emitting film | |
| Shen et al. | Fabrication, structure and luminescence properties of polycrystalline Tb3+-doped Lu2SiO5 films by Pechini sol–gel method | |
| CN102503549A (en) | Preparation method for polycrystalline thin film made of lutecium silicate doped with rare earth ions | |
| Tsuchiya et al. | Preparation of Y 2 O 3: Eu thin films by excimer-laser-assisted metal organic deposition | |
| Lü et al. | Eu2+-Activated Ca8Zn (SiO4) 4Cl2: an intense green emitting phosphor for blue light emitting diodes | |
| CN104830344B (en) | A kind of Er3+,Yb3+The preparation method being co-doped with YOF redness upconverting fluorescent material | |
| Liu et al. | Deposition of NaGd (WO4) 2: Eu3+/Bi3+ films on glass substrates and potential applications in white light emitting diodes | |
| CN110184063B (en) | Rare earth luminescent material and preparation method and application thereof | |
| CN103422058B (en) | A kind of boron-doping Si-rich silicon oxide film and its preparation method and application | |
| CN103911154B (en) | Micro nanocrystalline of a kind of single dispersing up-conversion luminescence and preparation method thereof | |
| Xiumei et al. | Photoluminescent properties of Ca2RE8 (SiO4) 6O2: A (RE= Y, Gd; A= Pb2+, Mn2+) phosphor films prepared by sol-gel process | |
| Yadav et al. | One step combustion synthesis of YAG: Ce phosphor for solid state lighting | |
| CN104745188A (en) | Lanthanum titanate red fluorescent material taking Sm<3+> as luminescence center, and preparation method thereof | |
| CN104449732A (en) | A seed crystal method is used to prepare nanometer KYF4: yb3+, er3+materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200430 Address after: 215400 No. 6 Liangfu Road, Taicang City, Suzhou City, Jiangsu Province Patentee after: SUZHOU Research Institute SHANGHAI INSTITUTE OF CERAMICS CHINESE ACADEMY OF SCIENCES Address before: 200050 No. 1295 Dingxi Road, Shanghai, Changning District Patentee before: SHANGHAI INSTITUTE OF CERAMICS, CHINESE ACADEMY OF SCIENCES |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 215400 No.6 Liangfu Road, Taicang City, Suzhou City, Jiangsu Province Patentee after: Jiangsu Institute of advanced inorganic materials Address before: 215400 No.6 Liangfu Road, Taicang City, Suzhou City, Jiangsu Province Patentee before: SUZHOU Research Institute SHANGHAI INSTITUTE OF CERAMICS CHINESE ACADEMY OF SCIENCES |