GB2259098A - Electrochemical preparation of single phase lead telluride - Google Patents
Electrochemical preparation of single phase lead telluride Download PDFInfo
- Publication number
- GB2259098A GB2259098A GB9118659A GB9118659A GB2259098A GB 2259098 A GB2259098 A GB 2259098A GB 9118659 A GB9118659 A GB 9118659A GB 9118659 A GB9118659 A GB 9118659A GB 2259098 A GB2259098 A GB 2259098A
- Authority
- GB
- United Kingdom
- Prior art keywords
- lead
- reaction medium
- range
- tellurium
- sulphamate
- 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.)
- Granted
Links
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title description 3
- 239000012429 reaction media Substances 0.000 claims abstract description 19
- 230000008021 deposition Effects 0.000 claims abstract description 10
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 10
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 10
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 sulphamate ions Chemical class 0.000 claims abstract description 5
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000003 Lead carbonate Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 10
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002019 doping agent Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000000151 deposition Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001215 Te alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrodes Of Semiconductors (AREA)
Abstract
Single phase lead telluride is electrodeposited from a reaction medium containing free sulphamate ions, reactive lead species eg. lead carbonate and reactive tellurium species eg. tellurium dioxide, the deposition electrode being maintained at a potential of minus 0.25V to minus 0.4V.
Description
Preparation of Lead Telluride
The present invention is concerned with a method of preparation of lead telluride.
Single phase lead telluride has a very narrow stoichiometric range (Te: 49.994 to 50.013 at 700"C) and co-existence of a second phase is easily caused by deviation from this stoichiometry. Biphasic lead telluride however has inferior mechanical and semiconductive properties compared to single phase lead telluride.
In order to try to avoid the unwanted effect of segregation on solidification, various complex methods have been suggested for the production of single phase lead telluride, such methods include melting the lead and tellurium in a sealed atmosphere, single crystal growth or rapid solidification, mechanical pulverisation, cold pressing, and sintering in a hydrogen atmosphere.
Direct alloy formation methods such as molecular beam epitaxy or chemical vapour deposition have also been suggested, but the cost of the manufacturing equipment remains expensive and the methods are therefore impractical for commercial production.
It has also been tried to electrochemically deposit tellurium alloys from aqueous solutions containing two or more metal elements. However, reports of such methods are limited, because lead readily reacts with typical electrolytes such as sulphuric acid to form insoluble compounds such as lead sulphate.
We have developed a method of electrochemically producing single phase lead telluride which alleviates the above problems.
According to the present invention, therefore, there is provided a method of preparing substantially single phase lead telluride, which method comprises:a) arranging electrodes in contact with a reaction medium comprising substantially free sulphamate ions, electrical contact being provided between said electrodes; b) contacting electrochemically reactive species comprising lead and tellurium in said reaction medium; and c) maintaining a deposition electrode at a potential in the range of about -0.25V to -0.4V (referenced to a calomel electrode) so as to produce a deposit of lead telluride.
Preferably the free sulphamate ions are initially present in the reaction medium as sulphamic acid, the concentration of the latter in the reaction medium being preferably in the range of about 0.1 to 0.4 mole/litre. It is beneficial that the above concentration range is achieved because at higher concentrations the hydrolysis of lead sulphamate becomes significant whereas at lower concentrations the product deposition rate becomes unacceptably low. The use of sulphamic acid as the electrolyte alleviates the problem of lead compound precipitation experienced with previously used electrolytes such as sulphuric acid.
It is preferred that the precursors for the reactive species comprising lead and tellurium are lead sulphamate and tellurium dioxide respectively. The lead sulphamate itself may however be produced in situ from the reaction of a suitable lead-containing reagent (such as lead carbonate) and sulphamic acid.
Preferably the lead sulphamate is included in the reaction medium at a concentration in the range of about 0.03 to 0.5 mole/litre; at higher concentrations the hydrolysis of lead sulphamate becomes significant, whereas at lower concentrations the composition uniformity of the lead telluride may be unacceptable. Preferably the tellurium dioxide is present at a concentration in the range of 0.002 to 0.05 mole/litre, in which range the reaction medium is essentially saturated with the tellurium dioxide; additional tellurium dioxide may however be added as tellurium is consumed during the reaction with lead.
Although it is generally preferred that the lead telluride is produced by the reaction of separate compounds such as lead sulphamate and tellurium dioxide as described above, it is of course envisaged that the lead telluride may be obtained from a single complex containing both lead and tellurium. In the latter case, the electrochemically reactive leaN2nd tellurium could be generated resulting from discharge and decomposition of the complex.
The deposition electrode is preferably the cathode which is typically in the form of a metal sheet; the anode is typically an insoluble anode formed from a suitable material such as graphite or platinum. As previously described the potential of the deposition electrode is maintained in the range of about -0.25V to -0.4V, because at higher potentials the concentration of lead in the deposit becomes unacceptably high, whereas at lower potentials the concentration of lead in the deposit becomes unacceptably low.
Preferably the reaction medium is maintained at a temperature in the range of about 20 to 50"C; above this temperature range the hydrolysis of lead sulphamate again becomes significant whereas below this range the deposition rate may become unacceptably slow.
It is further preferred that the reaction medium should be substantially agitated during operation of the method so as to increase the rate of deposition of the lead telluride on the electrode.
In some embodiments, it is preferred that a dopant should be added to the reaction medium so as to improve the resulting semi-conductive properties of the product.
Typical dopants include oxides of silver, tin, indium, or bismuth. The semi-conductive properties of the product may alternatively or additionally be modified by controlling the lead/telluride ratio present in the product. Tertiary or quaternary lead telluride may also be deposited by controlling the concentration of ions present in the reaction medium.
The invention will now be further illustrated by the following example which does not limit the scope of the invention in any way.
Example
The following components were mixed together in the order specified:a) 7.5g of sulphamic acid dissolved in 150ml of distilled water; b) lOg of lead carbonate; and c) 7.5g of sulphamic acid.
The mixture was then filtered and 100mg of tellurium dioxide was then added.
The resultant mixture contained 0.26 mole/litre of free sulphamic acid, 0.26 mole/litre of lead sulphamate and 0.002 mole/litre of tellurium.
A finely polished copper sheet exposing 2x2cm area for deposition was used as the cathode, and a graphite plate was used as the insoluble anode. The cathode potential was kept at - 0.35V (referenced to a saturated calomel electrode) and the temperature was maintained at 350C.
A cathode current density of 0.6mA/cm2 was measured and maintained at this value for about 30 minutes until a deposit analysed to be 50% lead, 50% telluride was obtained.
Claims (15)
1. A method of preparing substantially single phase lead telluride, which method
comprises:
a) arranging electrodes in contact with a reaction medium comprising
substantially free sulphamate ions, electrical contact being provided between said
electrodes;
b) contacting electrochemically reactive species comprising lead and tellurium in
said reaction medium; and
c) maintaining a deposition electrode at a potential in the range of minus 0.25V
to minus 0.4V so as to produce a deposit of lead telluride.
2. A method according to claim 1, wherein the free sulphamate ions are initially present
in the reaction medium as sulphamic acid.
3. A method according to claim 2, wherein the sulphamic acid concentration in the
reaction medium is in the range of 0.1 to 0.4 mole/litre.
4. A method according to any of claims 1 to 3, wherein the reactive species comprising
lead is lead sulphamate, or precursor reagents therefor.
5. A method according to claim 4, wherein the lead sulphamate is included in the
reaction medium at a concentration in the range of 0.03 to 0.5 mole/litre.
6. A method according to claim 4, wherein said precursor reagents comprise lead
carbonate and sulphamic acid.
7. A method according to any of claims 1 to 6, wherein said reactive species comprising
tellurium is tellurium dioxide.
8. A method according to claim 7, wherein said tellurium dioxide is present at a
concentration in the range of 0.002 to 0.05 mole/litre.
9. A method according to any of claims 1 to 8, wherein said deposition electrode is the
cathode.
10. A method according to any of claims 1 to 9, wherein the anode comprises graphite
or platinum.
11. A method according to any of claims 1 to 10, wherein said reaction medium is
maintained at a temperature in the range of 20 to SOOC.
12. A method according to any of claims 1 to 11, wherein said reaction medium is
substantially agitated.
13. A method according to any of claims 1 to 12, wherein a dopant is added to the
reaction medium.
14. A method according to claim 13, wherein said dopant includes one or more oxide of
silver, tin, indium or bismuth.
15. A method substantially as described herein, as illustrated by the Example.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9118659A GB2259098B (en) | 1991-08-30 | 1991-08-30 | Preparation of lead telluride |
| JP29896791A JP3152976B2 (en) | 1991-08-30 | 1991-11-14 | Method for manufacturing lead telluride semiconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9118659A GB2259098B (en) | 1991-08-30 | 1991-08-30 | Preparation of lead telluride |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9118659D0 GB9118659D0 (en) | 1991-10-16 |
| GB2259098A true GB2259098A (en) | 1993-03-03 |
| GB2259098B GB2259098B (en) | 1995-01-18 |
Family
ID=10700721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9118659A Expired - Fee Related GB2259098B (en) | 1991-08-30 | 1991-08-30 | Preparation of lead telluride |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3152976B2 (en) |
| GB (1) | GB2259098B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005114755A3 (en) * | 2004-05-18 | 2006-05-11 | Basf Ag | Tellurides having novel property combinations |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6603173B1 (en) | 1991-07-26 | 2003-08-05 | Denso Corporation | Vertical type MOSFET |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3887446A (en) * | 1974-07-26 | 1975-06-03 | Us Navy | Electrochemical preparation of metallic tellurides |
| JPS50122892A (en) * | 1974-03-14 | 1975-09-26 | ||
| GB2006268A (en) * | 1977-10-14 | 1979-05-02 | Univ Queensland | Preparation of semiconductor films on electrically conductive substrates |
| SU1516929A1 (en) * | 1988-01-29 | 1989-10-23 | Московский химико-технологический институт им.Д.И.Менделеева | Method of producing semiconductor sensitive elements for gas analysis |
-
1991
- 1991-08-30 GB GB9118659A patent/GB2259098B/en not_active Expired - Fee Related
- 1991-11-14 JP JP29896791A patent/JP3152976B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50122892A (en) * | 1974-03-14 | 1975-09-26 | ||
| US3887446A (en) * | 1974-07-26 | 1975-06-03 | Us Navy | Electrochemical preparation of metallic tellurides |
| GB2006268A (en) * | 1977-10-14 | 1979-05-02 | Univ Queensland | Preparation of semiconductor films on electrically conductive substrates |
| SU1516929A1 (en) * | 1988-01-29 | 1989-10-23 | Московский химико-технологический институт им.Д.И.Менделеева | Method of producing semiconductor sensitive elements for gas analysis |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005114755A3 (en) * | 2004-05-18 | 2006-05-11 | Basf Ag | Tellurides having novel property combinations |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9118659D0 (en) | 1991-10-16 |
| GB2259098B (en) | 1995-01-18 |
| JPH0558796A (en) | 1993-03-09 |
| JP3152976B2 (en) | 2001-04-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19990830 |