Bath for electroplating a i-iii-vi compound, use thereof and structures containing same

Abstract

A bath for electroplating a I-III-VI compound comprising: water; a copper containing precursor dissolved in said water; a selenium containing precursor dissolved in said water; and at least one member selected from the group consisting of an indium containing precursor dissolved in said water, a gallium containing precursor dissolved in said water and mixtures thereof, and at least one member selected from the group consisting of sulfur-containing organic compound dissolved in said water wherein one or more sulfur atoms directly bond with at least one carbon atom, a phosphorus-containing organic compound dissolved in said water wherein one or more phosphorus atoms directly bond with at least one carbon atom and mixtures thereof is provided along with its use to fabricate thin films, solar devices and tuned thin films.

1 . A bath for electroplating a I-III-VI compound comprising: water; a copper containing precursor dissolved in said water; a selenium containing precursor dissolved in said water ; and at least one member selected from the group consisting of an indium containing precursor dissolved in said water, a gallium containing precursor dissolved in said water and mixtures thereof; and at least one member selected from the group consisting of sulfur-containing organic compound dissolved in said water wherein one or more sulfur atoms directly bond with at least one carbon atom, a phosphorus-containing organic compound dissolved in said water wherein one or more phosphorus atoms directly bond with at least one carbon atom and mixtures thereof. 
   
   
       2 . The bath according to  claim 1  wherein said I-III-VI compound is copper indium gallium selenide. 
   
   
       3 . The bath according to  claim 2  wherein said copper indium gallium selenide has 0 atomic % to 90 atomic % indium and 0 atomic % to 60 atomic % gallium provided that at least one of said indium and gallium is a positive atomic % greater than 0. 
   
   
       4 . The bath according to  claim 1  wherein said copper containing precursor is copper sulfate, said selenium containing precursor is selenium oxide, said indium precursor is indium sulfate, said gallium precursor is gallium nitrate. 
   
   
       5 . The bath according to  claim 1  wherein said sulfur containing organic compound is at least one member selected from the group consisting of sulfonate, sulfonic acid, sulfinic acid, sulfinate, sulfonide, sulfinide, sulfide and disulfide. 
   
   
       6 . The bath according to  claim 1  wherein said phosphorus containing organic compound is at least one member selected from the group consisting of phosphonate, phosphonic acid, phosphinate, phosphinic acid, phosphonite and phosphinite. 
   
   
       7 . The bath according to  claim 1  wherein said bath comprises one or more inorganic chemicals to provide conductivity of the solution selected from the group consisting of sodium sulfate, potassium nitrate, and sodium phosphate. 
   
   
       8 . The bath according to  claim 1  wherein said bath further comprises one or more organic compounds as surfactant, wherein surfactant may or may not contains sulfur or phosphorus. 
   
   
       9 . The bath according to  claim 1  wherein said bath comprises one or more organic or inorganic chemicals to complex with the precursor chemicals selected from the group consisting of organic acids and ammonium salts. 
   
   
       10 . The bath according to  claim 1  wherein said bath comprises one or more organic or inorganic chemicals to buffer the solution pH. 
   
   
       11 . (canceled) 
   
   
       12 . The bath according to  claim 1  wherein said bath further comprises one or more organic or inorganic chemicals to incorporate other elements into the film selected from the group consisting of C, B, N, O, S, H, Cl, Ag, Au, Cd, Zn, Al, Te, Ge, Sn and As. 
   
   
       13 . A method of producing a I-III-VI compound in a thin film form by electroplating which comprises obtaining a bath comprising: water; a copper containing precursor dissolved in said water; a selenium containing precursor dissolved in said water; and at least one member selected from the group consisting of an indium containing precursor dissolved in said water, a gallium containing precursor dissolved in said water and mixtures thereof, and at least one member selected from the group consisting of sulfur-containing organic compound dissolved in said water wherein one or more sulfur atoms directly bond with at least one carbon atom, a phosphorus-containing organic compound dissolved in said water wherein one or more phosphorus atoms directly bond with at least one carbon atom and mixtures thereof;
 immersing a cathode and an anode into said solution; and   applying a electric current or potential across said cathode and said anode to deposit a film of the I-III-VI compounds on the said cathode.   
   
   
       14 . The method according to  claim 13  wherein said I-III-VI compound is copper indium gallium selenide. 
   
   
       15 . The method according to  claim 13  wherein said sulfur containing organic compound is at least one member selected from the group consisting of sulfonate, sulfonic acid, sulfinic acid, sulfinate, sulfonide, sulfinide, sulfide and disulfide. 
   
   
       16 . The method according to  claim 13  wherein said phosphorus containing organic compound is at least one member selected from the group consisting of phosphonate, phosphonic acid, phosphinate, phosphinic acid, phosphonite and phosphinite. 
   
   
       17 . The method according to  claim 13  wherein said cathode is a conductive material selected from the group consisting of metal, conductive compound, conductive polymer, conductive glass, and a layer of conductive material on a substrate selected from the group consisting of Si, SiO 2 , Si 3 N 4 , and steel. 
   
   
       18 . (canceled) 
   
   
       19 . The method according to  claim 13  wherein said cathode comprises both conductive and nonconductive materials with one or more conductive materials exposed to the said solution. 
   
   
       20 . The method according to  claim 13  wherein the temperature of said solution is from about 5° C. to 80° C. 
   
   
       21 . The method according to  claim 13  wherein said potential and current is a constant, and has a current density from −1 mA/cm 2  to −100 mA/cm 2 . 
   
   
       22 . The method according to  claim 13  wherein said potential and current is controlled in a waveform comprising sweeps, pulses, pulse reverses, sinusoidal. 
   
   
       23 . The method according to  claim 13  wherein said I-III-VI compound is annealed at a temperature higher than 20° C. after electroplating. 
   
   
       24 . A method of producing a copper indium gallium selenide compound in a thin film form by electroplating, wherein the film has a composition gradient of gallium from 0 atomic % to 60 atomic % or a composition gradient of indium from 0 atomic % to 90 atomic %, comprising:
 obtaining a bath comprising: water; a copper containing precursor dissolved in said water; a selenium containing precursor dissolved in said water; and at least one member selected from the group consisting of an indium containing precursor dissolved in said water, a gallium containing precursor dissolved in said water and mixtures thereof; and at least one member selected from the group consisting of sulfur-containing organic compound dissolved in said water wherein one or more sulfur atoms directly bond with at least one carbon atom, a phosphorus-containing organic compound dissolved in said water wherein one or more phosphorus atoms directly bond with at least one carbon atom and mixtures thereof;   immersing a cathode and an anode into said solution; and   applying a electric current or potential across the said cathode and said anode to deposit a film of I-III-VI compounds in a thin film form on the said cathode.   
   
   
       25 . The method according to  claim 24  wherein said cathode is rotating with the rotation rate controlled. 
   
   
       26 . The method according to  claim 24  wherein the temperature of said bath is controlled. 
   
   
       27 . The method according to  claim 24  wherein the cathode comprises a substrate for a solar device.