CN1082633A - The purification process of electrolyte components - Google Patents
The purification process of electrolyte components Download PDFInfo
- Publication number
- CN1082633A CN1082633A CN93106085A CN93106085A CN1082633A CN 1082633 A CN1082633 A CN 1082633A CN 93106085 A CN93106085 A CN 93106085A CN 93106085 A CN93106085 A CN 93106085A CN 1082633 A CN1082633 A CN 1082633A
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- family
- powder material
- metal powder
- solution
- metal
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 6
- 238000000746 purification Methods 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 23
- 238000004070 electrodeposition Methods 0.000 claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000010408 film Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 239000010409 thin film Substances 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000000151 deposition Methods 0.000 claims abstract 2
- 102000040350 B family Human genes 0.000 claims description 38
- 108091072128 B family Proteins 0.000 claims description 38
- 239000012535 impurity Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical group [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229910004613 CdTe Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003556 assay Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Weting (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Be applicable to a kind of preparation method of the IIB family aqueous metal salt of thin film semiconductor of IIB/VIB family electro-deposition process.This method comprises the following steps: that (a) makes IIB family metal salt solution and be the IIB family metallic contact that purity is higher than 99.99% powder form accordingly; (b) will contain minimum 10 minutes of the solution stirring of this metal; (c) metal powder material is removed from solution.Disclose in addition with the cathodic deposition method from containing the preparation of electrolyte electro-deposition film IIB/VIB method for semiconductor of II group metal ion.
Description
The present invention relates to the production process of film II B/ VI B family semiconductor material electricity consumption sedimentation.
Film II B/ VI B family semi-conductor is very important in the manufacturing of photovoltaic cell.
The production process of film II B/ VI B family's semi-conductor (for example CdTe) electricity consumption sedimentation is disclosed in many documents, for example, article and U.S. Pat 4,425,194 that people such as Panicher deliver on the 125th the 4th phase of volume " electrochemical society magazine " the 556th～572 page.The application of film II B/ VI B family semi-conductor in photovoltaic cell is made that the electro-deposition legal system is produced also disclosed in many documents.
We find, the II B/ VI B family semi-conductor made from the electro-deposition method is a basic raw material when preparing photovoltaic cell, foreign matter content is controlled to very low level can obtain best performance.
That sells on the market contains some more metallic impurity in order to preparation electrolyte solution in the electro-deposition groove usually with the semi-conductive chemical of deposit II B/ VI B.Concentration is very big in the electro-deposition process in ionogen for the impurity that some electrochemical activity is big (being those standard electric chemical reduction current potentials impurity more more positive than cadmium), and in other words, the concentration of the concentration ratio in the electro-deposition material in solution is big.
Therefore needing a method purifies the electrolyte solution that uses in the II B/ VI B semi-conductor electricity deposition process.
The present invention is applicable to that the preparation method of the II B family aqueous metal salt of thin film semiconductor of II B/ VI B family electro-deposition process comprises the following steps:
(a) make II B family metal salt solution and the II B family metallic contact that is high purity (preferably being higher than 99.99%) material forms accordingly;
(b) will contain the above-mentioned solution stirring of metal powder material, churning time is wanted fully, with extraction impurity wherein; Then
(c) metal powder material is removed from solution.
According to another aspect of the present invention, the present invention has following characteristics with the anode sedimentation from the film II B/ VI B family method for semiconductor of the preparation of electrolyte electro-deposition that contains II B family metal ion; Ionogen is to produce from the solution of II B family metal-salt, make this metal salt solution and the II B family metallic contact that is the powder form accordingly, want duration of contact fully, be advisable with 10 minutes at least, with extraction impurity wherein, from solution, remove II B group metal powder material then.
The II B family that mentions in this specification sheets and VI B family are meant the relevant family in the periodic table of chemical element.Periodictable has various forms, and their difference is to represent with word line A and B the mode of subfamily.The periodictable of mentioning in this specification sheets is meant the periodictable of listing in the 4th edition " Advanced Inorganic Chemistry " book that Corron and Wilkinson write, wherein II B family comprises Elements C d, Zn and Hg, VI B family comprises each element in the VI group master group, for example, and O, S, Se and Te.
II B family metal is cadmium preferably.The II B family salt of preparation used for electrolyte is preferably CdSO.
The granularity of metal powder material is big more, and the surface-area of unit weight is just more little.The maximum particle size of metal powder material is preferably 300 microns.
Maximum particle size depends on the effect of filtering operation.Metal powder material does not preferably contain the particle less than 0.2 micron substantially.Better situation is that metal powder material does not contain the particle less than 10 microns substantially.
Metal powder material is can be advisable by 100 orders (mesh) British Standard sieve and with the metal powder material that 200 order British Standard sieves are collected basically.100 orders are equivalent between the sieve wire 250 microns spacing, and 200 orders are equivalent to 130 millimeters.
The concentration of II B family salt brine solution can be at the 0.01M(mol) to the scope of 3M, but be advisable with 2M.Solution can be in for example 0-80 ℃ scope in the temperature for the treatment of processes, but is advisable in the scope with room temperature (18 °～25 ℃).
The purity of II B group metal powder material is 99.99% at least, and better situation should be 99.999% at least.The metal powder material of this purity has sale on the market.
The duration of contact of the metal powder material and the aqueous solution can be in 10 minutes to 2 hours scope for example.
Then II B family metal powder material is removed from solution.This can be by solution filtration or allow metal powder precipitate then liquid to be decanted to carry out.When thinking filtering separation, can carry out with the detailed catalogue filtering net that does not contain the impurity that can influence ionogen purity.Filter screen is advisable with the polymkeric substance filter screen that employing resembles polypropylene and so on, and the maximum diameter of hole is 0.1 micron.
Solution organizes contacting of metal powder material with II B and separation circuit preferably carries out repeatedly.The metal powder material that uses is preferably fresh.
The electro-deposition process of thin film semiconductor of II B/ VI B family is well-known, therefore at this moment there is no need to describe in detail.English Patent GB1 for example discloses electro-deposition technology in 532,616.In order to reduce the content of impurity to greatest extent, the most handyly resemble among we the co-pending European application EP-A-0538041 disclosed cation exchange polymer film and the employed electrolytic solution of semi-conductor is produced in anode and deposit separated.
It is well-known that thin film semiconductor of II B/ VI B family is deposited to the process of producing photovoltaic cell on the negative electrode that is coated with the cds film, thereby there is no need here to describe in detail again.Usually, the II B/ VI B family semiconductor film that deposit is come out is to need heating, so that be translated into P-type semiconductor.United States Patent (USP) 4,388,483 disclose this technology.Then can be with known the whole bag of tricks contact in deposit on the II B/ VI B family film.
Referring now to some following examples content of the present invention is described, wherein the simultaneous test of carrying out not according to the present invention indicates with letter, and example of the present invention indicates with figure.
Simultaneous test A
Be deposited with the glass preparation photovoltaic cell of cds with traditional method from being covered with stannic oxide, stannic oxide.NR Pavaska, C.A.Menzes, ABP S nha promptly disclose this method on " the electrochemical society magazine " of 1967 the 124th volumes the 743rd page.Adopted the sheet glass that the cds layer is arranged as negative electrode in the electro-deposition process of deposit CdTe.
The electro-deposition liquid that water becomes contains Cd, the 600ppm(PPM that 0.9M adds with the form of CdSO) Cl-and the Te that adds with the form of TeO of 50ppm.The electro-deposition operation is carried out under 70 ℃.
Photovoltaic cell is to produce from the glass/stannic oxide that draws thus/cds/CdTe structure: as U.S. Pat P 4,388, disclosed such in 483, with this structure heating, so that Cdte is changed into P-type material, as described in the U.S. Pat P 4456630, corrode then, add some golden point type contacts of 2 flat millimeters again by thermal evaporation.
Under standard test condition, the photovoltaic cell that is drawn is tested, and respectively be marked with A, B on the assay plate, the characteristic of the C lines respectively account for whole plate 1/3 different sites.The results are shown in table 1.
Table 1
Lines V (volt) J (milliampere/centimetre) FF %
A 0.605 13.5 0.48 4.1
B 0.427 16.5 0.50 3.6
C 0.402 16.4 0.51 3.4
Example 1
By simultaneous test 1 preparation photovoltaic cell, just electrolytic solution is to prepare from the CdSO aqueous solution by following described processing.Under churned mechanically situation, in CdSO solution, add the Cd powder, add in the ratio of 1 gram Cd powder 1 liter of CdSO solution.The purity of Cd powder is 99.999%.This powder can pass through 100 purpose screen clothes, but (British Standard is collected with 200 purpose screen clothes.Solution and powder at room temperature stirred 20 minutes together.With 0.1 micron polypropylene filter screen solution is filtered then, with filtering Cd powder wherein.By above-mentioned the solution that is drawn is handled once more with the Cd powder, filtered then.Its test-results of photovoltaic cell by example 1 preparation is listed in table 2.
Table 2
Lines V (volt) J (milliampere/centimetre) FF %
A 0.696 21.2 0.60 8.8
B 0.697 18.2 0.62 7.8
C 0.697 18.2 0.62 7.8
Claims (14)
1, is applicable to a kind of preparation method of the II B family aqueous metal salt of thin film semiconductor of II B/ VI B family electro-deposition process, comprises the following steps:
(a) make II B family metal salt solution and the II B family metallic contact that is high purity powder form accordingly;
(b) the above-mentioned solution that will contain metal powder material is stirred, and churning time is wanted fully, with extraction impurity wherein; Then
(c) metal powder material is removed from solution.
2, with the film II B/ VI B family semi-conductive a kind of method of cathodic deposition method from the preparation of electrolyte electro-deposition that contains II B family metal ion, it is characterized in that, ionogen is to produce from the solution of II B family metal-salt, make this metal salt solution in the II B family metallic contact that is the powder form accordingly, want duration of contact fully, with extraction impurity wherein, from solution, remove II B family metal powder material then.
According to the described method of above arbitrary claim, it is characterized in that 3, described II B family metal is a cadmium.
4, method according to claim 2 is characterized in that, described II B family metal-salt is a Cadmium Sulphate.
According to the described method of above arbitrary claim, it is characterized in that 5, metal powder material does not contain the particle of granularity below 0.2 micron haply.
6, method according to claim 5 is characterized in that, metal powder material does not contain the particle of granularity below 10 microns haply.
According to the described method of above arbitrary claim, it is characterized in that 7, metal powder material does not contain granularity haply at the particle more than 300 microns.
According to the described method of above arbitrary claim, it is characterized in that 8, the concentration of II B family salt is in the scope of 0.01M to 3M.
According to the described method of above arbitrary claim, it is characterized in that 9, temperature range is 0～80 ℃.
10, method according to claim 9 is characterized in that, temperature is in 18 ℃ to 25 ℃ scope.
According to the described method of above arbitrary claim, it is characterized in that 11, the purity of metal powder material is 99.999% at least.
12, according to the described method of above arbitrary claim, it is characterized in that metal powder material is removed from solution with filtration method.
13, method according to claim 12 is characterized in that, the metal powder material polymkeric substance filter screen filtering of 0.1 micron of maximum diameter of hole.
14, according to the described method of above arbitrary claim, it is characterized in that, this method is to make II B family salts solution contact with fresh metal powder material after removing wherein metal powder material, stirs then metal powder material to be separated, just as 1 to 12 arbitrary claim is described.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9210945.3 | 1992-05-22 | ||
| GB929210945A GB9210945D0 (en) | 1992-05-22 | 1992-05-22 | Chemical process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1082633A true CN1082633A (en) | 1994-02-23 |
Family
ID=10715903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93106085A Pending CN1082633A (en) | 1992-05-22 | 1993-05-21 | The purification process of electrolyte components |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN1082633A (en) |
| AU (1) | AU4077793A (en) |
| GB (1) | GB9210945D0 (en) |
| MX (1) | MX9303008A (en) |
| WO (1) | WO1993024962A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400244A (en) * | 1976-06-08 | 1983-08-23 | Monosolar, Inc. | Photo-voltaic power generating means and methods |
| US4345107A (en) * | 1979-06-18 | 1982-08-17 | Ametek, Inc. | Cadmium telluride photovoltaic cells |
| US4465565A (en) * | 1983-03-28 | 1984-08-14 | Ford Aerospace & Communications Corporation | CdTe passivation of HgCdTe by electrochemical deposition |
-
1992
- 1992-05-22 GB GB929210945A patent/GB9210945D0/en active Pending
-
1993
- 1993-05-07 WO PCT/GB1993/000946 patent/WO1993024962A1/en active Application Filing
- 1993-05-07 AU AU40777/93A patent/AU4077793A/en not_active Abandoned
- 1993-05-21 CN CN93106085A patent/CN1082633A/en active Pending
- 1993-05-21 MX MX9303008A patent/MX9303008A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU4077793A (en) | 1993-12-30 |
| MX9303008A (en) | 1993-11-01 |
| GB9210945D0 (en) | 1992-07-08 |
| WO1993024962A1 (en) | 1993-12-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |