Method to electrochemically deposit compound semiconductors

• US 5,320,736 A
• Filed: 05/06/1991
• Issued: 06/14/1994
• Est. Priority Date: 01/11/1991
• Status: Expired due to Term

• Current Assignee: University of Georgia Research Foundation BOYD Graduate Studies Research Center
• Original Assignee: The University of Georgia Research Foundation, Inc.
• Inventors: Villegas, Ignacio, Gregory, Brian W., Stickney, John L.
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): Leader, William T.
• Application Number:
  US07/695,969
• Time in Patent Office: 1,135 Days
• Field of Search: 205/170, 205/171, 205/123, 205/148, 205/157, 205/915, 205/177, 205/182, 204/86, 204/92, 156/611
• US Class Current: 205/157
• CPC Class Codes: H01L 21/02425 Conductive materials, e.g. metallic silicides
• CPC Class Codes: H01L 21/02562 Tellurides
• CPC Class Codes: H01L 21/02568 Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
• CPC Class Codes: H01L 21/02628 using solutions
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• CPC Class Codes: Y10S 205/915 Electrolytic deposition of semiconductor

Abstract

A method to electrochemically deposit semiconductors and for the electrochemical formation of epitaxial thin-film, single-crystalline compound semiconductors comprising alternating electrodeposition of atomic layers of selected pairs of elements using underpotential deposition.

Claims

1. A method for producing epitaxial single-crystalline compound semiconductors by depositing semiconductor material onto a substrate using underpotential deposition, comprising the steps of:

(a) providing said substrate;

(b) providing a first reactant in a first solution;

(c) providing a second reactant in a second solution;

(d) providing a means for controlling the electrochemical potential of said substrate relative to a reference electrode;

(e) sequentially electrodepositing an atomic layer of said first reactant and said second reactant on said substrate by sequentially contacting said first solution containing said first reactant with said substrate and said second solution containing said second reactant with said substrate and by sequentially adjusting the electrochemical potential of said substrate relative to said reference electrode, said first reactant being deposited on said substrate at a first electrochemical potential and said second reactant being deposited on said substrate at a second electrochemical potential lower than the potential necessary to deposit a layer of said second reactant onto itself, said reference electrode being in contact with said first solution when said first solution is in contact with said substrate and in contact with said second solution when said second solution is in contact with said substrate; and

(f) repeating step (e) until and epitaxial single-crystalline compound semiconductor of a desired thickness is obtained.

2. The method as claimed in claim 1, wherein each of said atomic layers of said reactants comprises a half-monolayer of a monolayer of the resulting compound.

3. The method as claimed in claim 1, wherein said first reactant is a metal.

4. The method as claimed in claim 3, wherein said first reactant is selected from the group consisting of Group IB, Group IIB, Group IIIA, Group IVA and Group VIA elements.

5. The method as claimed in claim 1, wherein said second reactant is selected from the group consisting of Group IVA, Group VA and Group VIA elements.

6. The method as claimed in claim 5, wherein said second reactant is selected from the group of elements consisting of Tellurium, Selemium, Sulfur, Arsenic, Antimony, Bismuth, Germanium, Tin and Lead.

7. The method as claimed in claim 1, wherein said second reactant is a metal.

8. The method as claimed in claim 7, wherein said first reactant is selected from the group consisting of Group IB, Group IIB, Group IIIA, Group IVA and Group VIA elements.

9. The method as claimed in claim 1, wherein said first reactant is selected from the group consisting of Group IVA, Group VA and Group VIA elements.

10. The method as claimed in claim 9, wherein said first reactant is selected from the group of elements consisting of Tellurium, Selemium, Sulfur, Arsenic, Antimony, Bismuth, Germanium, Tin and Lead.

11. The method as claimed in claim 1, wherein said substrate is polycrystalline.

12. The method as claimed in claim 1, wherein said substrate is a single crystal.

13. The method as claimed in claim 1, wherein said substrate is selected from the group consisting of Copper, Gold, Silver, Platinum, Compound semiconductors, Germanium, Silicon, Carbon, Nickel, and Titanium.

14. The method as claimed in claim 1, wherein said first reactant is delivered to said substrate in a first solution comprising said first reactant and an electrolyte and said second reactant is delivered to said substrate in a second solution comprising said second reactant and an electrolyte.

15. The method as claimed in claim 14 wherein said reactants are delivered to said substrate as dissolved gases.

16. The method as claimed in claim 1, wherein said substrate is lattice-matched.

17. A method for producing epitaxial single-crystalline compound semiconductors using underpotential electrochemical deposition, comprising the steps of

(a) providing a substrate;

(b) providing a first reactant selected from the group consisting of Group IB, Group IIB, Group IIIA, Group IVA, Group VA, Group VIA, and Group VIIA elements;

(c) providing a second reactant selected from the group consisting of Group IVA, Group VA and Group VIA elements;

(d) providing means for controlling the electrochemical potential of said substrate;

(e) delivering said first reactant to said substrate in a first solution, selecting and applying a first electrochemical potential to said substrate relative to a reference electrode, both said substrate and said reference electrode being in contact with said first solution containing said first reactant, and electrodepositing an atomic layer of said first reactant on said substrate;

(f) delivering said second reactant to said substrate in a second solution, selecting and applying a second electrochemical potential to said substrate relative to said reference electrode, both said substrate and said reference electrode being in contact with said second solution containing said second reactant, and electrodepositing an atomic layer of said second reactant on said substrate using underpotential electrochemical deposition wherein said second electrochemical potential is lower than the potential necessary to deposit a layer of said second reactant onto itself; and

(g) sequentially repeating steps (e) and (f) until an epitaxial single-crystalline compound semiconductor of a desired thickness is obtained.

18. The method as claimed in claim 17, further comprising the steps of:

(e1) rinsing any of said first reactant greater than a single atomic layer remaining on said substrate from said substrate;

after step (e) and prior to step (f), and the step of;

(f1) rinsing any of said second reactant greater than a single atomic layer remaining on said substrate from said substrate;

after step (f) and prior to step (g).

19. The method as claimed in claim 18, wherein steps (e), (e1), (f), and (f1) are repeated sequentially until an epitaxial single-crystalline compound semiconductor of a desired thickness is obtained.

20. The method as claimed in claim 18, wherein said rinsing steps (e1) and (f1) are accomplished using an electrolytic solution.