CN1223696C - A solid electrolyte crystal material and process for preparing crystal film - Google Patents
A solid electrolyte crystal material and process for preparing crystal film Download PDFInfo
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- CN1223696C CN1223696C CN 02121109 CN02121109A CN1223696C CN 1223696 C CN1223696 C CN 1223696C CN 02121109 CN02121109 CN 02121109 CN 02121109 A CN02121109 A CN 02121109A CN 1223696 C CN1223696 C CN 1223696C
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- molybdenum
- crystal
- powder
- tungsten boat
- boat
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- 239000013078 crystal Substances 0.000 title claims abstract description 38
- 239000007784 solid electrolyte Substances 0.000 title claims description 14
- 239000000463 material Substances 0.000 title abstract description 20
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000000843 powder Substances 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000003776 cleavage reaction Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 36
- 229910052750 molybdenum Inorganic materials 0.000 claims description 36
- 239000011733 molybdenum Substances 0.000 claims description 36
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 36
- 229910052721 tungsten Inorganic materials 0.000 claims description 36
- 239000010937 tungsten Substances 0.000 claims description 36
- 239000002178 crystalline material Substances 0.000 claims description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 230000007017 scission Effects 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 238000007740 vapor deposition Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002226 superionic conductor Substances 0.000 description 6
- 238000000407 epitaxy Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
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Abstract
The present invention relates to a solid electrolytical crystal material and a method for preparing crystal films of the crystal material, which belongs to a solid electrolytical material field. The present invention provides a solid electrolytical crystal material and a method for preparing crystal films of the crystal material. The material has the chemical formula of Rb0.5Cs0.5Ag4I5, and has a cubic crystal structure at a room temperature. The lattice constant a is equal to 0.031 nm. The preparation method for crystal films comprises: RbI powder, CsI powder and AgI powder are prepared into a mixture of (Rb<x>Cs<1-x>I)y (AgI) <1-y> according to the molar ratio that x is equal to 0.5 and y is equal to 0.15 to 0.16. By utilizing a vacuum thermal vapor deposition method, the mixture is put on a new-cleavage NaCl crystal substrate which is heated to 55 to 75 DEG C for epitaxial growth when the pressure in the vacuum chamber is smaller than 2*10<3>Pa. The rate of film deposition is about 5 to 15 nm/s.
Description
Technical field
The present invention relates to the vacuum thermal evaporation method of a kind of solid electrolyte crystalline material and crystal film thereof preparation, particularly a kind of method of utilizing binary iodide crystal powder to prepare quaternary compound belongs to the solid electrolyte material field.
Background technology
About method epitaxy MAg on the NaCl crystal substrates with vacuum thermal evaporation
4I
5Type solid ionogen (or being referred to as superionic conductor(s)) crystal film has been an effective means through experiment confirm repeatedly.It is for preparation and research type material, particularly crystalline material is a kind of very convenient approach efficiently, at document [J.L.Sun, Spectroscopy of ternarycompounds on the basis of iodide of silver and copper, Dissertation to achieve thedegree of Ph.D., Kharkov State University, Kharkov, Ukraine, 1996, detailed argumentation is arranged in p.159.].
This type of sample is in preparation process, the main binary iodide crystal powders (KI, RbI, CsI, AgI etc.) that use, be mixed in together with suitable chemistry mole proportioning, under vacuum condition, make it fusing with molybdenum boat (or tungsten boat) heating, then slowly evaporation to the NaCl monocrystal chip that is heated to assigned temperature, the superionic conductor(s) film that makes new advances of epitaxy thus.According to experience in the past, may contain binary compound MI (M=K, Rb, Cs) and AgI in the film that on substrate, obtains, multi-element compounds is [(MI)
y(MI)
1-y]
x[AgI]
1-xExist mutually in crystal, but the control of the condition (as factors such as substrate temperature, sedimentation rate, pressures in vacuum tank) what can form depend primarily on the value of chemical mol ratio X in its original plating material and Y and evaporated film mutually the time.We once prepared crystal film AgI, RbI, CsI, the MAg of pure phase to utilize this method
2I
3, MAg
4I
5And M
2AgI
3(see document J.L. Sun etc. polytype crystal film, Spectroscopy of ternary compounds on the basis of iodideof silver and copper, Dissertation to achieve the degree of Ph.D., Kharkov StateUniversity, Kharkov, Ukraine, 1996, p.159.).
About MAg
4I
5The solid electrolyte of type structure early has the article (B.B.Owens and G.R.Argue, Science, 157 (1967) 308.) of Science it to be done detailed argumentation.Form 2 from this article has obtained MAg as can be seen
4I
5N-type waferN all belongs to solid electrolyte.With regard to the M of basic metal gang, also lack CsAg in this Science article
4I
5And Rb
0.5Cs
0.5Ag
4I
5For CsAg
4I
5Data, in article (A.M.Pogrebnoi, L.S.Kudin and K.V.Rakov, Russian journal of physical Chemistry, 75 (2001) 733.), report was arranged once, and Rb
0.5Cs
0.5Ag
4I
5Then worldwide do not see and disclosed.
Summary of the invention
The purpose of this invention is to provide a kind of novel solid electrolyte crystalline material and the preparation method of film thereof, utilize binary iodide powder, adopt method epitaxy on the NaCl monocrystal chip of vacuum heat steaming degree to go out a kind of brand-new superionic conductor(s) film, be the crystal film of solid electrolyte material, to fill up MAg
4I
5The vacancy of type superionic conductor(s) material family.
The crystalline material of a kind of solid electrolyte provided by the present invention, this material has following chemical structural formula: Rb
0.5Cs
0.5Ag
4I
5, its lattice parameter a=1.131nm.
The preparation method of the crystal film of above-mentioned crystalline material provided by the present invention comprises the steps:
(1) RbI, CsI and three kinds of binary iodide of AgI powder obtain (RbxCsl-xI) y (AgI) l-y mixture after mixing in x=0.5 and y=0.15～0.16 in molar ratio, utilize mortar that it is fully ground, again powder is inserted in the molybdenum or tungsten boat of vacuum plating unit, when pressure in vacuum tank less than 2 * 10
-3During Pa, cover molybdenum or tungsten boat, and make the energising of molybdenum or tungsten boat be heated to powder to begin fusing, remain under this temperature, treat behind whole powder smeltings and when not having bubble and producing, molybdenum or the outage of tungsten boat with baffle plate;
(2) the NaCl crystal substrates of the new cleavage of putting into the vacuum chamber top in advance is heated to 55 ℃～75 ℃, remove the baffle plate on molybdenum or the tungsten boat again and be heated to rapidly and occur white residue in the boat, the film sedimentation rate is 5～15nm/s, cover molybdenum or tungsten boat with baffle plate more immediately, cut off heating current, so far, can make Rb
0.5Cs
0.5Ag
4I
5Crystal film.
The Rb that the present invention is prepared
0.5Cs
0.5Ag
4I
5Crystalline material, belong to the MAg that mentions in the background technology
4I
5The newcomer of type superionic conductor(s) material family, thus MAg filled up
4I
5The vacancy of type superionic conductor(s) material family; This material has very high ionic conductivity, is a kind of novel solid electrolyte material, can be applicable in the fields such as manufacturing of high capacity solid battery and miniature capacitor.
Description of drawings
Fig. 1 is the on-chip Rb of NaCl
0.5Cs
0.5AgI
5Energy dispersive spectrum-the EDS of the scanning electron microscope of crystal film.
Fig. 2 a and Fig. 2 b are Rb
0.5Cs
0.5Ag
4I
5Selected area diffraction patterns-the SAD of the transmission electron microscope of crystal film.
Fig. 3 is the on-chip Rb of NaCl
0.5Cs
0.5Ag
4I
5X-ray diffraction spectrum-the XRD of crystal film.
Embodiment
For accurately judging the mol ratio of each element in the new compound film that obtains, we have done the measurement (Fig. 1) of the energy dispersive spectrum-EDS of scanning electron microscope to it, the result shows that the mol ratio of Rb in the film, Cs, Ag, I is 1: 1: 8: 10, determine that thus the gained quaternary compound is Rb
0.5Cs
0.5Ag
4I
5
Selected area diffraction patterns-the SAD of transmission electron microscope (Fig. 2 a and Fig. 2 b) shows: gained quaternary compound Rb
0.5Cs
0.5Ag
4I
5Film at room temperature has cubic crystal structure.
Calculate by X-ray diffraction spectrum-XRD (Fig. 3): Rb
0.5Cs
0.5Ag
4I
5Lattice parameter a=1.131nm.
Embodiment 1
Obtain (Rb after x=0.5 and y=0.15 mix in molar ratio with RbI, CsI and three kinds of binary iodide of AgI powder
xCs
1-xI)
y(AgI)
1-yMixture utilizes mortar that it is fully ground, and powder is inserted in molybdenum (or tungsten) boat of vacuum plating unit, when pressure in vacuum tank is 2 * 10 again
-3During Pa, cover molybdenum or tungsten boat, and make the energising of molybdenum or tungsten boat be heated to powder to begin fusing, remain under this temperature, treat behind whole powder smeltings and when not having bubble and producing, molybdenum or the outage of tungsten boat with baffle plate.The NaCl crystal substrates of the new cleavage of putting into the vacuum chamber top in advance is heated to 75 ℃, remove the baffle plate on molybdenum or the tungsten boat again and be heated to rapidly and occur white residue (the film sedimentation rate is 5nm/s) in the boat, cover molybdenum or tungsten boat with baffle plate more immediately, cut off the heating current of molybdenum or tungsten boat, so far, a kind of new solid electrolyte material Rb
0.5Cs
0.5Ag
4I
5Crystal film preparation finish.
Embodiment 2
Obtain (Rb after x=0.5 and y=0.16 mix in molar ratio with RbI, CsI and three kinds of binary iodide of AgI powder
xCs
1-x[)
v(AgI)
1-yMixture utilizes mortar that it is fully ground, and powder is inserted in molybdenum (or tungsten) boat of vacuum plating unit, when pressure in vacuum tank is 1.4 * 10 again
-3During Pa, cover molybdenum or tungsten boat, and make the energising of molybdenum or tungsten boat be heated to powder to begin fusing, remain under this temperature, treat behind whole powder smeltings and when not having bubble and producing, molybdenum or the outage of tungsten boat with baffle plate.The NaCl crystal substrates of the new cleavage of putting into the vacuum chamber top in advance is heated to 55 ℃, remove the baffle plate on molybdenum or the tungsten boat again and molybdenum or tungsten boat be heated to rapidly and occur white residue (the film sedimentation rate is 15nm/s) in the boat, cover molybdenum or tungsten boat with baffle plate more immediately, cut off the heating current of molybdenum or tungsten boat, so far, a kind of new solid electrolyte material Rb
0.5Cs
0.5Ag
4I
5Crystal film preparation finish.
Embodiment 3
Obtain (Rb after x=0.5 and y=0.155 mix in molar ratio with RbI, CsI and three kinds of binary iodide of AgI powder
xCs
1-xI)
y(AgI)
1-yMixture utilizes mortar that it is fully ground, again powder is inserted in molybdenum (or tungsten) boat of vacuum plating unit, when pressure in vacuum tank less than 1.6 * 10
-3During Pa, cover molybdenum or tungsten boat, and make the energising of molybdenum or tungsten boat be heated to powder to begin fusing, remain under this temperature, treat behind whole powder smeltings and when not having bubble and producing, molybdenum or the outage of tungsten boat with baffle plate.The NaCl crystal substrates of the new cleavage of putting into the vacuum chamber top in advance is heated to 65 ℃, remove the baffle plate on molybdenum or the tungsten boat again and molybdenum or tungsten boat be heated to rapidly and occur white residue (the film sedimentation rate is 10nm/s) in the boat, cover molybdenum or tungsten boat with baffle plate more immediately, cut off the heating current of molybdenum or tungsten boat, so far, a kind of new solid electrolyte material Rb
0.5Cs
0.5Ag
4I
5Crystal film preparation finish.
Though the film preparation condition difference of above-mentioned three embodiment all obtains the result same with accompanying drawing.
Claims (2)
1. a solid electrolyte crystalline material is characterized in that having following chemical structural formula: Rb
0.5Cs
0.5Ag
4I
5, and at room temperature have cubic crystal structure, lattice parameter a=1.131nm.
2. prepare the method for the crystal film of crystalline material formation as claimed in claim 1, this method comprises the steps:
(1) RbI, CsI and three kinds of binary iodide of AgI powder obtain (Rb after mixing in x=0.5 and y=0.15～0.16 in molar ratio
xCs
1-xI)
y(AgI)
1-yMixture utilizes mortar that it is fully ground, again powder is inserted in the molybdenum or tungsten boat of vacuum plating unit, when pressure in vacuum tank less than 2 * 10
-3During Pa, cover molybdenum or tungsten boat, and make the energising of molybdenum or tungsten boat be heated to powder to begin fusing, remain under this temperature, treat behind whole powder smeltings and when not having bubble and producing, molybdenum or the outage of tungsten boat with baffle plate;
(2) the NaCl crystal substrates of the new cleavage of putting into the vacuum chamber top in advance is heated to 55 ℃～75 ℃, remove the baffle plate on molybdenum or the tungsten boat again and it is heated to rapidly in the boat and white residue occurs, the film sedimentation rate is 5～15nm/s, cover molybdenum or tungsten boat with baffle plate more immediately, and cut-out heating current, so far, can make Rb
0.5Cs
0.5Ag
4I
5Crystal film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02121109 CN1223696C (en) | 2002-06-07 | 2002-06-07 | A solid electrolyte crystal material and process for preparing crystal film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02121109 CN1223696C (en) | 2002-06-07 | 2002-06-07 | A solid electrolyte crystal material and process for preparing crystal film |
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| Publication Number | Publication Date |
|---|---|
| CN1464074A CN1464074A (en) | 2003-12-31 |
| CN1223696C true CN1223696C (en) | 2005-10-19 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390524C (en) * | 2006-05-26 | 2008-05-28 | 北京科技大学 | Method for preparing film sample for use in transmitted electron microscope |
| KR20210002985A (en) * | 2019-07-01 | 2021-01-11 | 삼성전자주식회사 | Luminescent compound, method of manufacturing the same and light emitting device including the same |
| CN110817929B (en) * | 2019-12-03 | 2021-04-20 | 吉林大学 | Simple and efficient synthesis CsAgBr2Method for perovskite |
| CN112520781B (en) * | 2020-12-03 | 2022-02-11 | 吉林大学 | Copper-doped ternary metal halide and preparation method thereof |
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| Publication number | Publication date |
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