Ink deposition processes for photovoltaic absorbers

Abstract

Processes for making a process for making a photovoltaic absorber by depositing various layers of components on a substrate and converting the components into a thin film photovoltaic absorber material. Processes for depositing an ink containing compounds having the formula M B (ER) 3 wherein M B is In, Ga or Al, and polymeric precursor compounds.

1 . A process for making a photovoltaic absorber on a substrate comprising:
 (a) providing a substrate coated with an electrical contact layer;   (b) depositing an ink onto the contact layer of the substrate, the ink comprising one or more compounds having the formula M B (ER) 3 , wherein M B  is In, Ga or Al, E is S or Se, and R is selected from alkyl, aryl, heteroaryl, alkenyl, amido, and silyl;   (c) heating the initial layer;   (d) depositing a polymeric precursor compound onto the substrate; and   (e) heating the substrate.   
     
     
         2 . The process of  claim 1 , wherein M B  is In or Ga. 
     
     
         3 . The process of  claim 1 , wherein M B  is In or Al. 
     
     
         4 . The process of  claim 1 , wherein M B  is Ga or Al. 
     
     
         5 . The process of  claim 1 , wherein M B  is In or Ga, E is Se, and R is alkyl. 
     
     
         6 . The process of  claim 1 , wherein R is (C1)alkyl, (C2)alkyl, (C3)alkyl, (C4)alkyl, (C5)alkyl, or (C6)alkyl. 
     
     
         7 . The process of  claim 1 , wherein R is (C3)alkyl or (C4)alkyl. 
     
     
         8 . The process of  claim 1 , wherein M B (ER) 3  is In(SeR) 3 , wherein R is alkyl. 
     
     
         9 . The process of  claim 1 , wherein M B (ER) 3  is Ga(SeR) 3 , wherein R is alkyl. 
     
     
         10 . The process of  claim 1 , wherein M B (ER) 3  is In(SeR) 3 , wherein R is n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and mixtures thereof. 
     
     
         11 . The process of  claim 1 , wherein M B (ER) 3  is Ga(SeR) 3 , wherein R is n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and mixtures thereof. 
     
     
         12 . The process of  claim 1 , wherein M B (ER) 3  is In(Se sec Bu) 3 , In(Se t Bu) 3 , In(Se n Bu) 3 , Ga(Se sec Bu) 3 , Ga(Se t Bu) 3 , Ga(SEt) 3 , Ga(S t Bu) 3 , or Ga(Se n Bu) 3 . 
     
     
         13 . The process of  claim 1 , wherein the ink is a solution of the compounds having the formula M B (ER) 3  dissolved in an organic carrier. 
     
     
         14 . The process of  claim 13 , wherein the carrier is selected from aliphatic hydrocarbons, aromatic hydrocarbons, pentane, hexane, heptane, octane, isooctane, decane, cyclohexane, p-xylene, m-xylene, o-xylene, benzene, toluene, xylene, ethers, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, siloxanes, cyclosiloxanes, silicone fluids, acetonitrile, esters, acetates, ethyl acetate, butyl acetate, acrylates, isobornyl acrylate, ketones, acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, lactams, N-methylpyrrolidone, N-(2-hydroxyethyl)-pyrrolidone, cyclic acetals, cyclic ketals, aldehydes, alcohol, methanol, ethanol, isopropyl alcohol, thiols, butanol, butanediol, glycerols, alkoxyalcohols, glycols, 1-methoxy-2-propanol, acetone, ethylene glycol, propylene glycol, propylene glycol laurate, ethylene glycol ethers, diethylene glycol, triethylene glycol monobutylether, propylene glycol monomethylether, 1,2-hexanediol, and mixtures thereof. 
     
     
         15 . The process of  claim 1 , further comprising a dopant, or an alkali dopant, or a compound having the formula M alk  MB(ER) 4  or M alk (ER), wherein M alk  is Li, Na, or K, M B  is In, Ga, or Al, E is S or Se, and R is alkyl or aryl. 
     
     
         16 . The process of  claim 1 , further comprising one or more components selected from the group of a surfactant, a dispersant, an emulsifier, an anti-foaming agent, a dryer, a filler, a resin binder, a thickener, a viscosity modifier, an anti-oxidant, a flow agent, a plasticizer, a conductivity agent, a crystallization promoter, an extender, a film conditioner, and an adhesion promoter. 
     
     
         17 . The process of  claim 1 , wherein each heating process is a process comprising converting the layer at a temperature of from 100° C. to 400° C., or annealing the layer at a temperature of from 450° C. to 650° C., or annealing the layer at a temperature of from 450° C. to 650° C. in the presence of selenium vapor. 
     
     
         18 . The process of  claim 1 , wherein the ink contains from 0.01 to 2.0 atom percent sodium ions. 
     
     
         19 . The process of  claim 1 , wherein steps (b) and (c), or steps (d) and (e), or steps (b), (c), (d) and (e) are repeated. 
     
     
         20 . The process of  claim 1 , wherein steps (b) and (d) are interchanged so that the polymeric precursor compound is deposited onto the substrate before the ink. 
     
     
         21 . The process of  claim 1 , wherein the polymeric precursor compound is a CIS or CIGS precursor. 
     
     
         22 . The process of  claim 1 , wherein the polymeric precursor compound is enriched or deficient in Cu. 
     
     
         23 . The process of  claim 1 , wherein the polymeric precursor compound is a CAIGS precursor containing silver atoms or CAIGAS precursor containing aluminum atoms. 
     
     
         24 . The process of  claim 1 , wherein the depositing is done by spraying, spray coating, spray deposition, spray pyrolysis, printing, screen printing, inkjet printing, aerosol jet printing, ink printing, jet printing, stamp printing, transfer printing, pad printing, flexographic printing, gravure printing, contact printing, reverse printing, thermal printing, lithography, electrophotographic printing, electrodepositing, electroplating, electroless plating, bath deposition, coating, wet coating, dip coating spin coating, knife coating, roller coating, rod coating, slot die coating, meyerbar coating, lip direct coating, capillary coating, liquid deposition, solution deposition, layer-by-layer deposition, spin casting, solution casting, or any combination of the foregoing. 
     
     
         25 . The process of  claim 1 , wherein the substrate is a semiconductor, a doped semiconductor, silicon, gallium arsenide, insulators, glass, molybdenum glass, silicon dioxide, titanium dioxide, zinc oxide, silicon nitride, a metal, a metal foil, molybdenum, aluminum, beryllium, cadmium, cerium, chromium, cobalt, copper, gallium, gold, lead, manganese, molybdenum, nickel, palladium, platinum, rhenium, rhodium, silver, stainless steel, steel, iron, strontium, tin, titanium, tungsten, zinc, zirconium, a metal alloy, a metal silicide, a metal carbide, a polymer, a plastic, a conductive polymer, a copolymer, a polymer blend, a polyethylene terephthalate, a polycarbonate, a polyester, a polyester film, a mylar, a polyvinyl fluoride, polyvinylidene fluoride, a polyethylene, a polyetherimide, a polyethersulfone, a polyetherketone, a polyimide, a polyvinylchloride, an acrylonitrile butadiene styrene polymer, a silicone, an epoxy, paper, coated paper, or a combination of any of the foregoing. 
     
     
         26 . A photovoltaic absorber made by the process of  claim 1 . 
     
     
         27 . A process for depositing an ink on a substrate, the process comprising:
 (a) providing a substrate coated with an electrical contact layer;   (b) depositing an ink onto the contact layer of the substrate, wherein the ink contains one or more compounds having the formula M B (SeR) 3 , wherein M B  is In, Ga or Al, and R is alkyl dissolved in an organic solvent;   (c) heating the substrate.   
     
     
         28 . The process of  claim 27 , wherein M B  is In or Ga. 
     
     
         29 . The process of  claim 27 , wherein M B  is In or Al. 
     
     
         30 . The process of  claim 27 , wherein M B  is Ga or Al. 
     
     
         31 . The process of  claim 27 , wherein R is (C1)alkyl, (C2)alkyl, (C3)alkyl, (C4)alkyl, (C5)alkyl, or (C6)alkyl. 
     
     
         32 . The process of  claim 27 , wherein R is (C3)alkyl or (C4)alkyl. 
     
     
         33 . The process of  claim 27 , wherein M B (ER) 3  is In(SeR) 3 , wherein R is alkyl. 
     
     
         34 . The process of  claim 27 , wherein M B (ER) 3  is Ga(SeR) 3 , wherein R is alkyl. 
     
     
         35 . The process of  claim 27 , wherein M B (ER) 3  is In(SeR) 3 , wherein R is n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and mixtures thereof. 
     
     
         36 . The process of  claim 27 , wherein M B (ER) 3  is Ga(SeR) 3 , wherein R is n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and mixtures thereof. 
     
     
         37 . The process of  claim 27 , wherein M B (ER) 3  is In(Se sec Bu) 3 , In(S t Bu) 3 , In(Se n Bu) 3 , Ga(Se sec Bu) 3 , Ga(Se t Bu) 3 , Ga(SEt) 3 , Ga(S t Bu) 3 , or Ga(Se n Bu) 3 . 
     
     
         38 . The process of  claim 27 , wherein steps (b) and (c) are repeated.