US4376016A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Baths for electrodeposition of metal chalconide films
Assignee: TDC TECHNOLOGY
•
Filing: 1981-11-16
•
Granted: 1983-03-08
•
Expires: 2001-11-16
Abstract
Abstract Metal chalconide films having improved photo-electrical properties are obtained from electrodeposition baths containing solvents having a low power for solvating metal cations such that decreased quantities of solvent molecules become intercalated into the chalconide film.
Inventors
- 👤 William R. Fawcett
- 👤 Andrzej S. Baranski
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 20:52
CPC Classifications
C; C25; C25D; C25D9/00; C25D9/04; C25D9/08
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
95 words
A bath for the electrodeposition of metal chalconides comprising an organic polar solvent having dissolved therein (a) an ionized salt of at least one metal selected from the group consisting of Cd, Pb, Hg, Cu, Bi, Co, Ni, Tl, Ag, In, and Fe, and (b) at least one chalcogen in elemental form selected from the group consisting of S and Se said solvent being characterized by having a power of intercalation into metal chalconide films electrodeposited therefrom lower than that of dimethylsulfoxide and having power for dissolving elemental chalcogen greater than that of ethylene glycol.
Claim 2
Dependent Claim
95 words
A bath for the electrodeposition of metal chalconides comprising an organic polar solvent having dissolved therein (a) an ionized salt of at least one metal selected from the group consisting of Cd, Pb, Hg, Cu, Bi, Co, Ni, Tl, Ag, In, and Fe, and (b) at least one chalcogen in elemental form selected from the group consisting of S and Se said solvent being characterized by having a power of intercalation into metal chalconide films electrodeposited therefrom lower than that of dimethylsulfoxide and having power for dissolving elemental chalcogen greater than that of ethylene glycol.
Claim 3
Dependent Claim
62 words
A bath as claimed in claim 1 wherein the solvent is selected from the group consisting of glycols of the formula HO(CH.sub.2 CH.sub.2 O).sub.n CH.sub.2 CH.sub.2 OH (I) wherein n is an integer from 1 to about 20, and glycol ethers of the formula CnH.sub.2n+1 -0-CH.sub.2 CH.sub.2 OH (II) wherein n is an integer from 1 to about 10, and mixtures thereof.
Claim 4
Dependent Claim
22 words
A bath as claimed in claim 2 wherein the solvent is a glycol of the formula (I), wherein n=1 to about 20.
Claim 5
Dependent Claim
20 words
A bath as claimed in claim 3 wherein n in formula (I) is an integer from 1 to about 12.
Claim 6
Dependent Claim
13 words
A bath as claimed in claim 4 wherein said glycol is diethylene glycol.
Claim 7
Dependent Claim
36 words
A bath as claimed in claim 4 wherein said glycol comprises a mixture of polyethylene glycols of formula (I) wherein n is about 6 to about 12 and having an average molecular weight of about 400.
Claim 8
Dependent Claim
23 words
A bath as claimed in claim 2 wherein the solvent is a glycol ether of the formula (II) wherein n=1 to about 10.
Claim 9
Dependent Claim
17 words
A bath as claimed in claim 7 wherein n in formula (II) is 1 to about 5.
Claim 10
Dependent Claim
14 words
A bath as claimed in claim 8 wherein said glycol ether is 2-ethoxy ethanol.
Claim 11
Dependent Claim
20 words
A bath as claimed in claim 1 wherein donor number N of the solvent is not substantially higher than 19.
Claim 12
Dependent Claim
17 words
A bath as claimed in claim 1 wherein the donor number of the solvent is about 19.
Claim 13
Dependent Claim
28 words
A bath as claimed in claim 1 in which the solvent is capable of dissolving at least about 0.15 g of sulfur per 100 ml at 120° C.
Claim 14
Dependent Claim
27 words
A bath as claimed in claim 12 wherein the solvent is capable of dissolving at least about 0.2 g of sulfur per 100 ml at 120° C.
Claim 15
Dependent Claim
25 words
A bath as claimed in claim 13 having dissolved therein about 0.16 to about 0.3 g of elemental chalcogen per 100 ml of the bath.
Claim 16
Dependent Claim
15 words
A bath as claimed in claim 1 or 14 wherein said elemental chalcogen is sulfur.
Claim 17
Dependent Claim
17 words
A bath as claimed in claim 1 wherein the solvent is water-miscible and is non-reactive with water.
Claim 18
Dependent Claim
15 words
A bath as claimed in claim 16 containing up to about 20% by volume water.
Claim 19
Dependent Claim
15 words
A bath as claimed in claim 17 containing up to about 15% by volume water.
Claim 20
Dependent Claim
25 words
A bath as claimed in claim 1 having dissolved therein a salt yielding an electron donor ion for the metal chalconide electrodepositable from the bath.
Claim 21
Dependent Claim
15 words
A bath as claimed in claim 1 wherein the electron donor-yielding salt is a halide.
Claim 22
Dependent Claim
20 words
A bath as claimed in claim 20 wherein the cationic moiety of the halide is heat-volatilisable in the solid state.
Claim 23
Dependent Claim
14 words
A bath as claimed in claim 21 wherein the halide is an ammonium halide.
Claim 24
Dependent Claim
16 words
A bath as claimed in claim 20, 21, or 22 wherein the halide is a chloride.
Claim 25
Dependent Claim
21 words
A bath as claimed in claim 20 containing from about 0.01 to about 0.5 mole of halide ion per 100 ml.
Claim 26
Dependent Claim
21 words
A bath as claimed in claim 24 containing from about 0.05 to about 0.2 mole of halide ion per 100 ml.
Claim 27
Dependent Claim
21 words
A bath as claimed in claim 25 containing from about 0.08 to about 0.2 mole of halide ion per 100 ml.
Claim 28
Dependent Claim
29 words
A bath as claimed in claim 20 wherein the solvent is capable of dissolving at least about 0.01 moles of NH 4 Cl per 100 ml at 120° C.
Claim 29
Dependent Claim
28 words
A bath as claimed in claim 27 wherein the solvent is capable of dissolving at least about 0.05 moles of NH 4 Cl per ml at 120° C.
Claim 30
Dependent Claim
27 words
A bath as claimed in claim 28 wherein the solvent is capable of dissolving at least about 0.08 moles of NH Cl per 100 ml 120° C.
Claim 31
Dependent Claim
36 words
A bath as claimed in claim 1 wherein said at least one ionized salt comprises a cadmium salt, and the bath contains halide ion in a molar ratio halide ion:cadmium ion of at least about 15:1.
Claim 32
Dependent Claim
69 words
A method for producing a non-dendritic coherent film of metal chalconide comprising subjecting a bath as claimed in claim 1 to electrolysis at such temperature and at a current density that is sufficiently low with respect to the surface area of the cathode that a non-dendritic coherent film is deposited in the cathode; and continuing the electrolysis until a desired thickness of film has built up on the cathode.
Claim 33
Dependent Claim
40 words
A method as claimed in claim 31 for producing a cadmium sulfide film wherein the solvent is 2-ethoxyethanol, the dissolved metal salt is a cadmium salt, and the dissolved chalcogen is sulfur, and the electrodeposition is conducted at room temperature.
Claim 34
Dependent Claim
45 words
A method as claimed in claim 31 for producing a bismuth sulfide film wherein the solvent is diethylene glycol, the dissolved metal salts is a bismuth salt, and the dissolved chalcogen is sulfur, and the electrodeposition is conducted at a temperature below about 100° C.
Claim 35
Dependent Claim
17 words
A method claimed in claim 33 wherein the temperature is about 80° C. to about 100° C.
Claim 36
Dependent Claim
44 words
A method as claimed in claim 31 wherein the bath composition includes up to about 20% by volume water, and including the step of subsequently annealing the film in an inert atmosphere for a period sufficient to evaporate substantially all water from the film.
Claim 37
Dependent Claim
46 words
A method as claimed in claim 31 for producing a halide-doped film wherein the bath composition has dissolved therein an ammonium halide, and including the step of subsequently annealing the film in an inert atmosphere for a period sufficient to volatilise substantially all ammonium ion therefrom.
Claim 38
Dependent Claim
28 words
A method as claimed in claim 35 or 36 wherein the annealing is conducted at a temperature of from about 150° to 250° C. for about 30 minutes.
Claim 39
Dependent Claim
25 words
A method as claimed in claim 35 or 36 wherein the annealing is conducted at a temperature of about 200° C. for about 30 minutes.
References Cited (Backward Citations)
US602873A
Cited
US2818374A
Cited
GB905888A
Cited
US3374108A
Cited
FR1562163A
Cited
US3616280A
Cited
US3888697A
Cited
US3884779A
Cited
DE2556716A1
Cited
US4064326A
Cited
GB2006268A
Cited
GB2016049B
Cited
US4167805A
Cited
US4192721A
Cited
US4260427A
Cited
US4261802A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-03-07 | 1986-09-06 | 1987-03-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-03-07 | 1990-09-06 | 1991-03-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-03-07 | 1994-09-06 | 1995-03-08 | $7700.00 | Window Closed / Lapsed |