Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/10—Semiconductor bodies
  • H10F77/12—Active materials
  • H10F77/121—Active materials comprising only selenium or only tellurium
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/29—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by the substrates
  • H10P14/2901—Materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/10—Semiconductor bodies
  • H10F77/12—Active materials
  • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/26—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using liquid deposition
  • H10P14/265—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using liquid deposition using solutions
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/34—Deposited materials, e.g. layers
  • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
  • H10P14/3436—Deposited materials, e.g. layers characterised by the chemical composition being chalcogenide semiconductor materials not being oxides, e.g. ternary compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/541—CuInSe2 material PV cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• This invention relates to molecular precursors and processes for preparing coated substrates and films of copper indium gallium
• This invention also relates to processes for preparing coated substrates and for making photovoltaic devices.
• solution-based processes to CIGS/Se are not only less expensive than vacuum-based processes, but typically have lower energy input and can utilize close to 100% of the raw materials by precisely and directly depositing materials on a substrate.
• solution-based processes are readily adaptable to high-throughput roll-to-roll processing on flexible substrates.
• Solution-based processes to CIGS/Se fall into three general categories: (1 ) Electro-, electroless and chemical bath deposition, where (electro)chemical reactions in a solution lead to the coating of an immersed substrate; (2) Particulate-based processes that use solid particles dispersed in a solvent to form an ink, which can be coated onto a substrate; and (3) Processes that coat molecular precursor solutions onto a substrate by mechanical means such as spraying or spin coating.
• molecular precursor routes the semiconductor can be synthesized in situ with direct film deposition from solution. High-boiling capping agents, which often introduce carbon-based impurities into the semiconductor film, are used in many particulate-based processes, but can be avoided in molecular precursor routes.
• CIGS/Se Molecular precursor routes to CIGS/Se have been reported using metal salts (e.g., chlorides and nitrates).
• metal salts e.g., chlorides and nitrates
• aqueous solutions of copper-, indium- and gallium chlorides and an excess of thio- or selenourea have been deposited via spray pyrolysis to give CIGS/Se.
• salt solutions By mixing salt solutions with binders or chelating agents, viscosity can be increased and deposition techniques other than spraying can be
• CulnSe 2 films have been formed from a solution of Cu and In naphthenates, wherein the naphthenates are derived from an acidic fraction of processed petroleum and are composed of a mixture of organic acids.
• the solutions were spun-coated onto substrates, which were then then treated with a 10% mixture of hydrogen in nitrogen gas at 450 °C and then selenized in vacuum-sealed ampoules with Se vapor to give coatings with a thickness of 250 nm.
• the above molecular precursor routes rely on sulfo- and seleno- ureas or thioacetamide as the chalcogen source and/or annealing in reducing H 2 , H 2 S, S-, or Se-containing atmosphere for chalcogenization.
• a molecular precursor approach to CIGS/Se involving the preparation of a solution of copper and indium chalcogenides and elemental chalcogen has been reported.
• the use of hydrazine as the solvent was required.
• CIS/Se a highly reactive and potentially explosive solvent that is described in the Merck Index as a "violent poison.”
• Single-source organometallic precursors to CIS/Se e.g., (Ph 3 P) 2 Cu(mu-SEt)2ln(SEt)2] have been prepared and used to form CIS/Se films via spray chemical vapor deposition. However, the synthesis of these single-source precursors is involved and limits the compositional tuning of film
• One aspect of this invention is a molecular precursor to CIGS/Se comprising:
• a copper source selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands, copper sulfides, copper selenides, and mixtures thereof
• an indium source selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands, indium sulfides, indium selenides, and mixtures thereof;
• a gallium source selected from the group consisting of gallium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands, gallium sulfides, gallium selenides, and mixtures thereof; and
• a vehicle comprising a liquid chalcogen compound, a solvent, or a mixture thereof;
• the vehicle does not comprise hydrazine.
• Another aspect of this invention is a process comprising disposing a molecular precursor to CIGS/Se onto a substrate to form a coated substrate, wherein molecular precursor comprises:
• a copper source selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands, copper sulfides, copper selenides, and mixtures thereof
• an indium source selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands, indium sulfides, indium selenides, and mixtures thereof
• a gallium source selected from the group consisting of gallium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands, gallium sulfides, gallium selenides, and mixtures thereof;
• a vehicle comprising a liquid chalcogen compound, a solvent, or a mixture thereof;
• the vehicle does not comprise hydrazine.
• Another aspect of this invention is a coated substrate comprising: A) a substrate; and
• a copper source selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands, copper sulfides, copper selenides, and mixtures thereof;
• an indium source selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands, indium sulfides, indium selenides, and mixtures thereof;
• a gallium source selected from the group consisting of gallium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands, gallium sulfides, gallium selenides, and mixtures thereof;
• At least one of the copper or indium sources comprises
• Another aspect of this invention is a process for producing a photovoltaic cell.
• band gap energy refers to the energy required to generate electron-hole pairs in a semiconductor material, which in general is the minimum energy needed to excite an electron from the valence band to the conduction band.
• grain size refers to the diameter of a grain of granular material, wherein the diameter is defined as the longest distance between two points on its surface.
• crystallite size is the size of a single crystal inside the grain.
• a single grain can be composed of several crystals.
• a useful method for obtaining grain size is electron microscopy.
• ASTM test methods are available for determining planar grain size, that is, characterizing the two-dimensional grain sections revealed by the sectioning plane. Manual grain size measurements are described in ASTM E 1 12 (equiaxed grain structures with a single size distribution) and E 1 182 (specimens with a bi-modal grain size distribution), while ASTM E 1382 describes how any grain size type or condition can be measured using image analysis methods.
• chalcogen refers to Group VIA elements
• metal chalcogenides or “chalcogenides” refer to materials that comprise metals and Group VIA elements. Suitable Group VIA elements include sulfur, selenium and tellurium. Metal chalcogenides are important candidate materials for photovoltaic applications, since many of these compounds have optical band gap values well within the terrestrial solar spectra.
• binary-metal chalcogenide refers to a
• chalcogenide composition comprising one metal.
• ternary-metal chalcogenide refers to a chalcogenide composition comprising two metals.
• quaternary-metal chalcogenide refers to a
• multinary- metal chalcogenide refers to a chalcogenide composition comprising two or more metals, and encompasses ternary and quaternary metal chalcogenide compositions.
• the terms “copper indium sulfide” and “CIS” refer to CulnS 2 .
• “Copper indium selenide” and “CISe” refer to CulnSe 2 .
• “Copper indium sulfide/selenide,” “CIS/Se,” and “CIS-Se” encompass all possible combinations of Culn(S,Se)2, including CulnS2, CulnSe2, and CulnS x Se2 -x , where 0 ⁇ x ⁇ 2.
• sulfide/selenide and "CIGS/Se” and “CIGS-Se” encompass all possible combinations of ⁇ ( ⁇ ⁇ 03 ⁇ - ⁇ )(5 ⁇ 5 ⁇ 2 - ⁇ ) where O ⁇ y ⁇ I and 0 ⁇ x ⁇ 2.
• the terms "CIS,” “CISe,” “CIS/Se,” and “CIGS/Se” further encompass copper indium gallium sulfide/selenide semiconductors with fractional
• stoichiometries e.g., Cuo.7ln 1 1 S 2 . That is, the stoichiometry of the elements can vary from a strictly 1 :1 :2 molar ratio for Cu:(ln+Ga):(S+Se). Materials designated as CIGS/Se can also contain small amounts of other elements such as sodium. Highly efficient CIGS/Se solar cells are often copper poor, that is the molar ratio of Cu:(ln+Ga) is less than one.
• coherent domain size refers to the size of crystalline domains over which a defect-free, coherent structure can exist. The coherency comes from the fact that the three-dimensional ordering is not broken inside of these domains. When the coherent grain size is less than about 100 nm, appreciable broadening of the x-ray diffraction lines will occur. The domain size can be estimated by measuring the full width at half maximum intensity of the diffraction peak.
• metal salts refers to compositions wherein metal cations and inorganic anions are joined by ionic bonding.
• Relevant classes of inorganic anions comprise oxides, sulfides, selenides, carbonates, sulfates and halides.
• metal complexes refers to compositions wherein a metal is bonded to a surrounding array of molecules or anions, typically called “ligands” or “complexing agents.”
• the atom within a ligand that is directly bonded to the metal atom or ion is called the “donor atom” and, herein, often comprises nitrogen, oxygen, selenium, or sulfur.
• ligands are classified according to M. L. H. Green's
• X-function ligand is one which interacts with a metal center via a normal two-electron covalent bond, composed of one electron from the metal and one electron from the X ligand.
• Simple examples of X-type ligands include alkyls and thiolates.
• nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands refers specifically to carbon-containing X-function ligands, wherein the donor atom comprises nitrogen, oxygen, carbon, sulfur, or selenium.
• complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands refers to the metal complexes comprising these ligands.
• hydrocarbyl group is a univalent group containing only carbon and hydrogen.
• hydrocarbyl groups include unsubstituted alkyls, cycloalkyls, and aryl groups, including alkyl- subsituted aryl groups.
• Suitable hydrocarbyl groups and alkyl groups contain 1 to about 30 carbons, or 1 to 25, 1 to 20, 1 to 15, 1 to 10, 1 to 5, 1 to 4, or 1 to 2 carbons.
• heteroatom-substituted hydrocarbyl is meant a hydrocarbyl group that contains one or more heteroatoms, wherein the free valence is located on carbon, not on the heteroatom.
• Examples include hydroxyethyl and carbomethoxyethyl.
• Suitable heteroatom substituents include O-, N-, S-, Se-, halogen, and tri(hydrocarbyl)silyl.
• a substituted hydrocarbyl all of the hydrogens can be substituted, as in trifluoromethyl.
• tri(hydrocarbyl)silyl encompasses silyl substituents, wherein the substituents on silicon are hydrocarbyls.
• ⁇ -, N-, S-, or Se-based functional groups is meant univalent groups other than hydrocarbyl and substituted hydrocarbyl that comprise O-, N-, S-, or Se-heteroatoms, wherein the free valence is located on this heteroatom.
• O-, N-, S-, and Se-based functional groups include alkoxides, amidos, thiolates, and selenolates.
• One aspect of this invention is a molecular precursor to CIGS/Se comprising:
• a copper source selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands, copper sulfides, copper selenides, and mixtures thereof;
• an indium source selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands, indium sulfides, indium selenides, and mixtures thereof;
• a gallium source selected from the group consisting of gallium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands, gallium sulfides, gallium selenides, and mixtures thereof; and
• a vehicle comprising a liquid chalcogen compound, a solvent, or a mixture thereof;
• the vehicle does not comprise hydrazine.
• the molecular precursor consists essentially of components (i) - (ii) and (iv).
• a gallium source is present. In some embodiments, a gallium source is present and the molecular precursor consists essentially of components (i) - (iv).
• the copper source is selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof.
• the copper source is selected from the group consisting of copper sulfides, copper selenides, and mixtures thereof.
• the indium source is selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof.
• the indium source is selected from the group consisting of indium sulfides, indium selenides, and mixtures thereof.
• the copper source is selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof
• the indium source is selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof.
• the copper source is selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof
• the indium source is selected from the group consisting of indium sulfides, indium selenides, and mixtures thereof.
• the copper source is selected from the group consisting of copper sulfides, copper selenides, and mixtures thereof
• the indium source is selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands and mixtures thereof.
• the molecular precursor further comprises a chalcogen compound. In some embodiments, the molecular precursor further comprises a chalcogen compound.
• the copper source is selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands and mixtures thereof, or the indium source is selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof, and the molecular precursor further comprises a chalcogen compound.
• the copper or indium source is selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof
• the molecular precursor further comprises a chalcogen compound.
• the copper or indium source is selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof.
• the molecular precursor further comprises a chalcogen compound.
• the copper and indium sources comprise a nitrogen-, oxygen-, or carbon-based organic ligand, and the molecular precursor further comprises a chalcogen compound.
• Suitable chalcogen compounds include: elemental S, elemental Se, CS 2 , CSe 2 , CSSe, R 1 S-Z, R 1 Se-Z, R 1 S-SR 1 , R 1 Se-SeR 1 , R 2 C(S)S-Z, R 2 C(Se)Se-Z, R 2 C(Se)S-Z, R 1 C(O)S-Z, R 1 C(O)Se-Z, and mixtures thereof, with each Z independently selected from the group consisting of: H, NR 4 , and SiR 5 3; wherein each R 1 and R 5 is independently selected from the group consisting of: hydrocarbyl and O-, N-, S-, Se-, halogen- or tri(hydrocarbyl)silyl-substituted hydrocarbyl; each R 2 is independently selected from the group consisting of hydrocarbyl, O-, N-, S-, Se-, halogen-, or tri(hydrocarbyl)silyl-
• elemental sulfur, elemental selenium, or a mixture of elemental sulfur and selenium is present.
• suitable R 1 S- and R 1 Se- of R 1 S-Z and R 1 Se-Z are selected from the following ligand lists of suitable thiolates and selenolates.
• suitable R 1 S-SR 1 and R 1 Se-SeR 1 include: methyl disulfide, 2,2'-dipyridyl disulfide, (2-thienyl) disulfide, (2-hydroxyethyl) disulfide, (2-methyl-3-furyl) disulfide, (6-hydroxy- 2-naphthyl) disulfide, ethyl disulfide, methylpropyl disulfide, allyl disulfide, propyl disulfide, isopropyl disulfide, butyl disulfide, sec-butyl disulfide,
• R 2 C(Se)S-Z, R 1 C(O)S-Z, and R 1 C(O)Se-Z are selected from the ligand lists (below) of suitable thio-, seleno-, and dithiocarboxylates; suitable dithio-, diseleno-, and thioselenocarbamates; and suitable
• Suitable NR 4 4 include: Et 2 NH 2 , Et 4 N, Et 3 NH, EtNH 3 , NH , Me 2 NH 2 ,
• Suitable SiR 5 3 include: SiMe 3 , SiEt 3 , SiPr 3 , SiBu 3 , Si(/ ' -Pr) 3 ,
• SiEtMe 2 SiMe 2 (/ ' -Pr), Si(f-Bu)Me 2 , Si(cyclohexyl)Me 2 , and mixtures thereof.
• chalcogen compounds are commercially available or readily synthesized by the addition of an amine, alcohol, or alkyl nucleophile to CS2 or CSe2 or CSSe.
• the molar ratio of Cu:(ln+Ga) is about 1 in the molecular precursor. In some embodiments, the molar ratio of Cu:(ln+Ga) is less than 1 . In some embodiments, the molar ratio of total chalcogen to (Cu+ln+Ga) is at least about 1 in the molecular precursor.
• sources for the total chalcogen include the metal chalcogenides (e.g., the copper, indium, and gallium sulfides and selenides of the molecular precursor), the sulfur- and selenium-based organic ligands and the optional chalcogen compound of the molecular precursor.
• metal chalcogenides e.g., the copper, indium, and gallium sulfides and selenides of the molecular precursor
• sulfur- and selenium-based organic ligands e.g., the sulfur- and selenium-based organic ligands and the optional chalcogen compound of the molecular precursor.
• the moles of total chalcogen are determined by multiplying the moles of each metal chalcogenide by the number of equivalents of chalcogen that it contains and then summing these quantities together with the number of moles of any sulfur- or selenium- based organic ligands and optional chalcogen compound.
• Each sulfur- or selenium-based organic ligand and compound is assumed to contribute just one equivalent of chalcogen in this determination of total chalcogen. This is because not all of the chalcogen atoms contained within each ligand and compound will necessarily be available for incorporation into CIGS/Se; some of the chalcogen atoms from these sources can be incorporated into organic by-products.
• the moles of (Cu+ln+Ga) are determined by multiplying the moles of each Cu-, or In-, or Ga-containing species by the number of equivalents of Cu, In or Ga that it contains and then summing these quantities.
• CuDTC 2-mercaptoethanol
• MCE 2-mercaptoethanol
• sulfur [2(moles of CuDTC) + (moles of MCE) + (moles of S)] / [(moles of In acetate) + (moles of
• elemental sulfur, elemental selenium, or a mixture of elemental sulfur and selenium is present in the molecular precursor, and the molar ratio of elemental (S+Se) is about 0.2 to about 5, or about 0.5 to about 2.5, relative to the copper source of the molecular precursor.
• the nitrogen-, oxygen-, carbon-, sulfur- or selenium-based organic ligands are selected from the group consisting of: amidos; alkoxides; acetylacetonates; carboxylates; hydrocarbyls; O-, N-, S-, Se-, halogen-, or tri(hydrocarbyl)silyl-substituted hydrocarbyls; thiolates and selenolates; thio-, seleno-, and
• dithiocarboxylates dithio-, diseleno-, and thioselenocarbamates; and dithioxanthogenates. Many of these are commercially available or readily synthesized by the addition of an amine, alcohol, or alkyl nucleophile to CS 2 or CSe 2 or CSSe.
• Amidos. Suitable amidos include: bis(trimethylsilyl)amino, dimethylamino, diethylamino, diisopropylamino, /V-methyl-f-butylamino, 2-(dimethylamino)-/V-methylethylamino, /V-methylcyclohexylamino, dicydohexylamino, W-ethyl-2-methylallylamino, bis(2-methoxyethyl)amino, 2-methylaminomethyl-1 ,3-dioxolane, pyrrolidino, f-butyl- 1 -piperazinocarboxylate, /V-methylanilino, /V-phenylbenzylamino, /V-ethyl-
• ligands can chelate the metal center, and, in some cases, comprise more than one type of donor atom, e.g., the dianion of A/-benzyl-2-aminoethanol is a suitable ligand comprising both amino and alkoxide groups.
• alkoxides include: methoxide, ethoxide, n-propoxide, / ' -propoxide, n-butoxide, f-butoxide, neopentoxide, ethylene glycol dialkoxide, 1 -methylcyclopentoxide, 2-fluoroethoxide,
• Acetylacetonates refers to the anion of 1 ,3-dicarbonyl compounds, A 1 C(O)CH(A 2 )C(O)A 1 , wherein each A 1 is independently selected from hydrocarbyl, substituted hydrocarbyl, and O-, S-, or N-based functional groups and each A 2 is independently selected from hydrocarbyl, substituted hydrocarbyl, halogen, and O-, S-, or N-based functional groups.
• Suitable acetylacetonates include:
• 2,4-pentanedionate 3-methyl-2,4-pentanedionate, 3-ethyl- 2,4-pentanedionate, 3-chloro-2,4-pentanedionate, 1 ,1 ,1 -trifluoro- 2,4-pentanedionate, 1 ,1 ,1 ,5,5,5-hexafluoro-2,4-pentanedionate,
• Carboxylates include: formate, acetate, trifluoroacetate, propionate, butyrates, hexanoate, octanoate, decanoate, stearate, isobutyrate, f-butylacetate, heptafluorobutyrate, methoxyacetate, ethoxyacetate, methoxypropionate, 2-ethylhexanoate,
• Hydrocarbyls include: methyl, ethyl, n-propyl, / ' -propyl, n-butyl, / ' -butyl, sec-butyl, f-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, neopentyl, 3-methylbutyl, phenyl, benzyl, 4-f-butylbenzyl,
• Suitable O-, N-, S-, halogen- or tri(hydrocarbyl)silyl-substituted hydrocarbyls include: 2-methoxyethyl, 2-ethoxyethyl, 4-methoxyphenyl, 2-methoxybenzyl, 3-methoxy-1 -butyl,
• Suitable thiolates and selenolates include:
• thiog lycerol phenylthio, ethylthio, methylthio, n-propylthio, /-propylthio, n-butylthio, / ' -butylthio, f-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio, n-dodecylthio, 2-methoxyethylthio,
• Carboxylates, Carbamates, and Xanthogenates include: thioacetate, thiobenzoate, selenobenzoate, dithiobenzoate, and mixtures thereof.
• Suitable dithio-, diseleno-, and thioselenocarbamates include: dimethyldithiocarbamate, diethyldithiocarbamate, dipropyldithiocarbamate, dibutyldithiocarbamate, bis(hydroxyethyl)dithiocarbamate, dibenzyldithiocarbamate,
• dithioxanthogenates include: methylxanthogenate, ethylxanthogenate, /-propylxanthogenate, and mixtures thereof.
• the molecular precursor comprises a vehicle, comprising a liquid chalcogen compound, a solvent, or a mixture thereof.
• the vehicle comprises about 99 to about 1 wt%, 95 to about 5 wt%, 90 to 10 wt%, 80 to 20 wt%, 70 to 30 wt%, or 60 to 40 wt% of the molecular precursor, based upon the total weight of the molecular precursor.
• the vehicle comprises at least about 2 wt%, 5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, or 95 wt% of the molecular precursor, based upon the total weight of the molecular precursor.
• the vehicle comprises a liquid chalcogen compound.
• the vehicle comprises a solvent.
• the boiling point of the solvent is greater than about 100 °C, 1 10 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C or 190 °C at atmospheric pressure.
• the process is conducted at atmospheric pressure.
• Suitable solvents include: aromatics, heteroaromatics, nitriles, amides, alcohols, pyrrolidinones, amines, and mixtures thereof.
• Suitable heteroaromatics include pyridine and substituted pyridines.
• Suitable amines include compounds of the form R 6 NH 2 , wherein each R 6 is independently selected from the group consisting of: O-, N-, S-, or Se-substituted hydrocarbyl.
• the solvent comprises an amino-substituted pyridine.
• Aromatics include: benzene, toluene, ethylbenzene, chlorobenzene, o-xylene, m-xylene, p-xylene, mesitylene, / ' -propylbenzene, 1 -chlorobenzene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, f-butylbenzene, n-butylbenzene, /-butylbenzene, s-butylbenzene, 1 ,2-dichlorobenzene, 1 ,3-dichlorobenzene,
• Heteroaromatics include:
• Suitable nitrile solvents include: acetonitrile,
• Suitable amide solvents include: ⁇ /,/V-diethylnicotinamide,
• Alcohols include: methoxyethoxyethanol, methanol, ethanol, isopropanol, 1 -butanol, 2-pentanol, 2-hexanol, 2-octanol, 2-nonanol, 2-decanol, 2-dodecanol, ethylene glycol, 1 ,3-propanediol, 2,3-butanediol, 1 ,5-pentanediol,
• di(ethyleneglycol) ethylether di(ethylene glycol) ethylether, diethylene glycol, 2,4-dimethylphenol, and mixtures thereof.
• Suitable pyrrolidinone solvents include: /V-methyl- 2-pyrrolidinone, 5-methyl-2-pyrrolidinone, 3-methyl-2-pyrrolidinone,
• Suitable amine solvents include: butylamine, hexylamine, octylamine, 3-methoxypropylamine, 2-methylbutylamine, isoamylamine,
• diethylaminoacetaldehyde diethyl acetal 4-aminobutyraldehyde diethyl acetal, 2-methylaminomethyl-1 ,3-dioxolane, ethanolamine, 3-amino- 1 -propanol, 2-hydroxyethylhydrazine, ⁇ /,/V-diethylhydroxylamine, 4-amino-
• Preparing the molecular precursor typically comprises mixing the components (i) - (iv) by any conventional method. If one or more of the chalcogen sources is a liquid at room temperature or at the processing temperatures, the use of a separate solvent is optional. Otherwise, a solvent is used. In some embodiments, the molecular precursor is a solution; in other
• the molecular precursor is a suspension or dispersion.
• the preparation is conducted under an inert atmosphere, taking precautions to protect the reaction mixtures from air and light.
• the molecular precursor is initially prepared at low temperatures and/or with slow additions, e.g., when larger amounts of reagents and/or low boiling point and/or highly reactive reagents such as CS 2 are utilized. In such cases, the ink is typically stirred at room temperature prior to heat-processing. In some embodiments, the molecular precursor is prepared at about 20 - 100 °C, e.g., when smaller amounts of reagents are used, when the reagents are solids or have high boiling points and/or when one or more of the solvents is a solid at room temperature, e.g., 2-aminopyridine or 3-aminopyridine. In some
• all of the ink components are added together at room temperature, e.g., when smaller amounts of reagents are used.
• elemental chalcogen is added last, following the mixing of all the other components for about half an hour at room temperature.
• the components are added consecutively.
• the indium source can be added slowly with mixing to a suspension of the copper source in the vehicle, followed by the addition of the chalcogen source(s).
• the molecular precursor is heat-processed at a temperature of greater than about 90 °C, 100 °C, 1 10 °C, 120 °C, 130 °C, 140 °C, 150 C°, 160 °C, 170 °C ,180 °C or, 190 °C before coating on the substrate.
• Suitable heating methods include conventional heating and microwave heating.
• this heat- processing step aids the formation of CIGS/Se.
• This optional heat- processing step is typically carried out under an inert atmosphere.
• the molecular precursor produced at this stage can be stored for extended periods (e.g., months) without any noticeable decrease in efficacy.
• the molecular precursor can further comprise one or more additives. These additives are typically added to the molecular precursor at room temperature, following the mixing and optional heat processing of components (i) - (iv) of the molecular precursor. These additives are typically mixed with the molecular precursor under an inert atmosphere using conventional methods.
• Suitable additives include dispersants, surfactants, polymers, binders, ligands, capping agents, defoamers, thickening agents, corrosion inhibitors, plasticizers, thixotropic agents, viscosity modifiers, and dopants.
• additives are selected from the group consisting of: capping agents, dopants, polymers, and surfactants.
• the ink comprises up to about 10 wt%, 7.5 wt%, 5 wt%, 2.5 wt% or 1 wt% additives, based upon the total weight of the ink.
• Suitable capping agents include:
• polycarboxylates polyphosphates, polyamines, pyridine, alkylpyridines, aminopyridines, peptides comprising cysteine and/or histidine residues, ethanolamines, citrates, thioglycolic acid, oleic acid, and polyethylene glycol;
• Inorganic chalcogenides including metal chalcogenides, and zintl ions
• Degradable capping agents including dichalcogenocarbamates, monochalcogenocarbamates, xanthates, trithiocarbonates,
• chalcogenosemicarbazides and tetrazoles.
• These capping agents can be degraded by thermal and/or chemical processes, such as acid- and base- catalyzed processes.
• Degradable capping agents include: dialkyi dithiocarbamates, dialkyi monothiocarbamates, dialkyi
• diselenocarbamates dialkyi monoselenocarbamates, alkyi xanthates, alkyi trithiocarbonates, disulfidoimidodiphosphates, diselenoimidodiphosphates, tetraalkyl thiobiurets, tetraalkyl dithiobiurets, thiosemicarbazides, selenosemicarbazides, tetrazole, alkyi tetrazoles, amino-tetrazoles, thio- tetrazoles, and carboxylated tetrazoles;
• Ligands for these molecular precursor complexes include: thio groups, seleno groups, thiolates, selenolates, and thermally degradable ligands, as described above;
• the Lewis base can be chosen such that it has a boiling
• the capping agent comprises a surfactant or a dispersant.
• Suitable capping agents include volatile capping agents.
• a capping agent is considered volatile if, instead of decomposing and introducing impurities, it evaporates during film
• Volatile capping agents include those having a boiling point less than about 200 °C, 150 °C, 120 °C, or 100 °C at ambient pressure. Suitable volatile capping agents include: ammonia, methyl amine, ethyl amine, propylamine, butylamine, tetramethylethylene diamine, acetonitrile, ethyl acetate, butanol, pyridine, ethanethiol, propanethiol, butanethiol, f-butylthiol, pentanethiol, hexanethiol,
• Suitable volatile capping agents can also include: amines, amidos, amides, nitriles, isonitriles, cyanates, isocyanates, thiocyanates, isothiocyanates, azides, thiocarbonyls, thiols, thiolates, sulfides, sulfinates, sulfonates, phosphates, phosphines, phosphites, hydroxyls, hydroxides, alcohols, alcoholates, phenols, phenolates, ethers, carbonyls, carboxylates, carboxylic acids, carboxylic acid anhydrides, glycidyls, and mixtures thereof.
• Suitable dopants include sodium and alkali-containing compounds.
• the alkali-containing compounds are selected from the group consisting of: alkali compounds comprising N-, O-, C-, S-, or Se-based organic ligands, alkali sulfides, alkali selenides, and mixtures thereof.
• the dopant comprises an alkali-containing compound selected from the group consisting of: alkali- compounds comprising amidos; alkoxides; acetylacetonates; carboxylates; hydrocarbyls; O-, N-, S-, Se-, halogen-, or tri(hydrocarbyl)silyl-substituted hydrocarbyls; thiolates and selenolates; thio-, seleno-, and
• dithiocarboxylates dithio-, diseleno-, and thioselenocarbamates; and dithioxanthogenates.
• Other suitable dopants include antimony
• chalcogenides selected from the group consisting of antimony sulfide and antimony selenide.
• Suitable polymeric additives include vinylpyrrolidone-vinylacetate copolymers and (meth)acrylate copolymers, including PVPA/A E-535 (International Specialty Products), and Elvacite® 2028 binder and Elvacite® 2008 binder (Lucite International, Inc.).
• polymers can function as binders or dispersants.
• Suitable surfactants comprise siloxy-, fluoryl-, alkyl-, alkynyl-, and ammonium-substituted surfactants. These include, for example, Byk® surfactants (Byk Chemie), Zonyl® surfactants (DuPont), Triton®
• surfactants Air Products
• Tego® surfactants Evonik Industries AG
• surfactants can function as coating aids, capping agents, or dispersants.
• the molecular precursor comprises one or more binders or surfactants selected from the group consisting of:
• decomposable binders include: homo- and co-polymers of polyethers; homo- and co-polymers of polylactides; homo- and copolymers of polycarbonates including, for example, Novomer PPC
• a suitable low-boiling surfactant is Surfynol ® 61 surfactant from Air Products.
• Cleavable surfactants useful herein as capping agents include Diels-Alder adducts, thiirane oxides, sulfones, acetals, ketals, carbonates, and ortho esters.
• Cleavable surfactants include: alkyl-substituted Diels Alder adducts, Diels Alder adducts of furans; thiirane oxide; alkyl thiirane oxides; aryl thiirane oxides; piperylene sulfone, butadiene sulfone, isoprene sulfone, 2,5-dihydro-3-thiophene carboxylic acid-1 ,1 -dioxide-alkyl esters, alkyl acetals, alkyl ketals, alkyl 1 ,3-dioxolanes, alkyl 1 ,3-dioxanes, hydroxyl acetals, alkyl glucosides, ether acetals, polyoxyethylene acetals, alkyl carbonates, ether carbonates, polyoxyethylene carbonates, ortho esters of formates, alkyl ortho esters, ether ortho esters, and
• each molecular precursor comprises a complete set of reagents, e.g., each molecular precursor comprises at least a copper source, an indium source and a vehicle.
• the two or more molecular precursors can then be combined following mixing or following heat-processing. This method is especially useful for controlling stoichiometry and obtaining CIGS/Se of high purity, as prior to combining, separate films from each molecular precursor can be coated, annealed, and analyzed by XRD. The XRD results can then guide the selection of the type and amount of each molecular precursor to be combined.
• a molecular precursor yielding an annealed film of CIGS/Se with traces of copper sulfide can be combined with a molecular precursor yielding an annealed film of CIGS/Se with traces of indium sulfide, to form a molecular precursor that yields an annealed film comprising only CIGS/Se, as determined by XRD.
• an ink comprising a complete set of reagents is combined with ink(s) comprising a partial set of reagents.
• an ink containing only an indium source can be added in varying amounts to an ink comprising a complete set of reagents, and the stoichiometry can be optimized based upon the resulting device performances of annealed films of the mixtures.
• Another aspect of this invention is a process comprising disposing a molecular precursor to CIGS/Se onto a substrate to form a coated substrate, wherein molecular precursor comprises:
• a copper source selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands, copper sulfides, copper selenides, and mixtures thereof
• an indium source selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands, indium sulfides, indium selenides, and mixtures thereof
• a gallium source selected from the group consisting of gallium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands, gallium sulfides, gallium selenides, and mixtures thereof;
• a vehicle comprising a liquid chalcogen compound, a solvent, or a mixture thereof;
• the vehicle does not comprise hydrazine.
• Another aspect of this invention is a coated substrate comprising: A) a substrate; and
• a copper source selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands, copper sulfides, copper selenides, and mixtures thereof;
• an indium source selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands, indium sulfides, indium selenides, and mixtures thereof;
• a gallium source selected from the group consisting of gallium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands, gallium sulfides, gallium selenides, and mixtures thereof;
• At least one of the copper or indium sources comprises
• the coated substrate further comprises one or more additional layers.
• the copper source is selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof.
• the copper source is selected from the group consisting of copper sulfides, copper selenides, and mixtures thereof.
• the indium source is selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof.
• the indium source is selected from the group consisting of indium sulfides, indium selenides, and mixtures thereof.
• the copper source is selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof
• the indium source is selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof.
• the copper source is selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium-based organic ligands and mixtures thereof
• the indium source is selected from the group consisting of indium sulfides, indium selenides, and mixtures thereof.
• the copper source is selected from the group consisting of copper sulfides, copper selenides, and mixtures thereof
• the indium source is selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, or selenium- based organic ligands and mixtures thereof.
• the molecular precursor consists essentially of components (i) - (ii). In some embodiments, the gallium source is present and the molecular precursor consists essentially of components (i) - (iii). In some embodiments, the molecular precursor further comprises a chalcogen compound.
• the copper source is selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, and selenium-based organic ligands and mixtures thereof, or the indium source is selected from the group consisting of indium complexes of nitrogen-, oxygen-, carbon-, sulfur-, and selenium-based organic ligands and mixtures thereof, and the molecular precursor further comprises a chalcogen compound. In some embodiments, the copper source is selected from the group consisting of copper complexes of nitrogen-, oxygen-, carbon-, sulfur-, and selenium-based organic ligands and mixtures thereof, or the indium source is selected from the group consisting of indium complexes of nitrogen-, oxygen
• the copper or indium source comprises a nitrogen-, oxygen-, or carbon-based organic ligand, and the molecular precursor further comprises a chalcogen compound.
• the copper and indium sources comprise a nitrogen-, oxygen-, or carbon- based organic ligand, and the molecular precursor further comprises a chalcogen compound.
• the molecular further comprises an additive.
• the molar ratio of Cu:ln in the at least one layer is about 1 . In some embodiments, the gallium source is present in the molecular precursor and the molar ratio of Cu:(ln+Ga) in the at least one layer is about 1 . In some embodiments, the molar ratio of Cu:ln in the at least one layer is less than 1 . In some embodiments, the gallium source is present in the molecular precursor and the molar ratio of
• Cu:(ln+Ga) in the at least one layer is less than 1 .
• the molar ratio of total chalcogen to (Cu+ln) in the at least one layer is at least about 1 .
• the gallium source is present in the molecular precursor and the molar ratio of total chalcogen to (Cu+ln+Ga) in the at least one layer is at least about 1 .
• the substrate onto which the ink is disposed can be rigid or flexible.
• the substrate comprises: (i) a base; and (ii) optionally, an electrically conductive coating on the base.
• the base material is selected from the group consisting of glass, metals, ceramics, and polymeric films. Suitable base materials include metal foils, plastics, polymers, metalized plastics, glass, solar glass, low-iron glass, green glass, soda-lime glass, metalized glass, steel, stainless steel, aluminum, ceramics, metal plates, metalized ceramic plates, and metalized polymer plates.
• the base material comprises a filled polymer (e.g., a polyimide and an inorganic filler).
• the base material comprises a metal (e.g., stainless steel) coated with a thin insulating layer (e.g., alumina).
• Suitable electrically conductive coatings include metal conductors, transparent conducting oxides, and organic conductors. Of particular interest are substrates of molybdenum-coated soda-lime glass,
• molybdenum-coated polyimide films and molybdenum-coated polyimide films further comprising a thin layer of a sodium compound (e.g., NaF, Na 2 S, or Na 2 Se).
• a sodium compound e.g., NaF, Na 2 S, or Na 2 Se.
• the ink is disposed on a substrate to provide a coated substrate by solution-based coating or printing techniques, including spin-coating, spray-coating, dip-coating, rod-coating, drop-cast coating, roller-coating, slot-die coating, draw-down coating, ink-jet printing, contact printing, gravure printing, flexographic printing, and screen printing.
• the coating can be dried by evaporation, by applying vacuum, by heating, by blowing, or by combinations thereof.
• the substrate and disposed ink are heated at a temperature from 80 - 350 °C, 100 - 300 °C, 120 - 250 °C, 150 -190 °C, or 120 - 170 °C to remove at least a portion of the solvent, if present, by-products, and volatile capping agents.
• the drying step can be a separate, distinct step, or can occur as the substrate and precursor ink are heated in an annealing step.
• the coated substrate is heated at about 100 - 800 °C, 200 - 800 °C, 250 - 800 °C, 300 - 800 °C, 350 - 800 °C, 400 - 650 °C, 450 - 600 °C, 450 - 550 °C, 450 - 525 °C, 100 - 700 °C, 200 - 650 °C, 300 - 600 °C, 350 - 575 °C, or 350 - 525 °C.
• the coated substrate is heated for a time in the range of about 1 min to about 48 h; 1 min to about 30 min; 10 min to about 10 h; 15 min to about 5 h; 20 min to about 3 h; or, 30 min to about 2 h.
• the annealing comprises thermal processing, rapid thermal processing (RTP), rapid thermal annealing (RTA), pulsed thermal processing (PTP), laser beam exposure, heating via IR lamps, electron beam exposure, pulsed electron beam processing, heating via microwave irradiation, or combinations thereof.
• RTP refers to a technology that can be used in place of standard furnaces and involves single-wafer processing, and fast heating and cooling rates.
• RTA is a subset of RTP, and consists of unique heat treatments for different effects, including activation of dopants, changing substrate interfaces, densifying and changing states of films, repairing damage, and moving dopants.
• Rapid thermal anneals are performed using either lamp-based heating, a hot chuck, or a hot plate.
• PTP involves thermally annealing structures at extremely high power densities for periods of very short duration, resulting, for example, in defect reduction.
• pulsed electron beam processing uses a pulsed high-energy electron beam with short pulse duration. Pulsed processing is useful for processing thin films on temperature-sensitive substrates. The duration of the pulse is so short that little energy is transferred to the substrate, leaving it undamaged.
• the annealing is carried out under an atmosphere comprising: an inert gas (nitrogen or a Group VINA gas, particularly argon); optionally hydrogen; and optionally, a chalcogen source such as selenium vapor, sulfur vapor, hydrogen sulfide, hydrogen selenide, diethyl selenide, or mixtures thereof.
• the annealing step can be carried out under an atmosphere comprising an inert gas, provided that the molar ratio of total chalcogen to (Cu+ln+Ga) in the coating is greater than about 1 .
• the annealing step is carried out in an atmosphere comprising an inert gas and a chalcogen source.
• a chalcogen source e.g., S
• the chalcogen present in the coating can be exchanged (e.g., S can be replaced by Se) by conducting the annealing step in the presence of a different chalcogen (e.g., Se).
• annealings are conducted under a combination of atmospheres.
• a first annealing is carried out under an inert atmosphere and a second annealing is carried out in an atmosphere comprising an inert gas and a chalcogen source as described above, or vice versa.
• the annealing is conducted with slow heating and/or cooling steps, e.g., temperature ramps and declines of less than about 15 °C/ min, 10 °C/ min, 5 °C/ min, 2 °C/ min, or 1 °C/ min.
• the annealing is conducted with rapid heating and/or cooling steps, e.g., temperature ramps and declines of greater than about 15 °C per min, 20 °C per min, 30 °C per min, 45 °C per min, or 60 °C per min.
• rapid heating and/or cooling steps e.g., temperature ramps and declines of greater than about 15 °C per min, 20 °C per min, 30 °C per min, 45 °C per min, or 60 °C per min.
• the coated substrate further comprises one or more additional layers. These one or more layers can be of the same composition as the at least one layer or can differ in composition.
• particularly suitable additional layers comprise CIGS/Se precursors selected from the group consisting of: CIGS/Se molecular precursors, CIGS/Se particles, elemental Cu-, In- or Ga-containing particles; binary or ternary Cu-, In- or Ga-containing chalcogenide particles; and mixtures thereof.
• the one or more additional layers are coated on top of the at least one layer. In some embodiments, the one or more additional layers are coated prior to coating the at least one layer. In some embodiments, the additional layers are coated both prior to and
• a soft-bake step and/or annealing step occurs between coating the at least one layer and the one or more additional layers.
• CIGS/Se Composition An annealed film comprising CIGS/Se is produced by the above annealing processes.
• the coherent domain size of the CIGS/Se film is greater than about 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 100 nm, as determined by XRD.
• the molar ratio of Cu:ln or Cu:(ln+Ga) in the film is about 1 . In some embodiments, the molar ratio of Cu:ln or
• Cu:(ln+Ga) in the film is less than 1 .
• Coating and Film Thickness By varying the ink concentration and/or coating technique and temperature, layers of varying thickness can be coated in a single coating step. In some embodiments, the coating thickness can be increased by repeating the coating and drying steps. Annealing steps can also be carried out between the coating of multiple layers. These multiple coatings can be conducted with the same ink or with different inks. As described above, wherein two or more inks are mixed, the coating of multiple layers with different inks can be used to fine- tune stoichiometry and purity of the CIGS/Se films. It can also be used to tune the absorption of the film, e.g., by creating films with gradient
• the annealed film typically has an increased density and/or reduced thickness versus that of the wet precursor layer.
• the film thicknesses of the dried and annealed coatings are 0.1 - 200 microns; 0.1 - 100 microns; 0.1 - 50 microns; 0.1 - 25 microns; 0.1 - 10 microns; 0.1 - 5 microns; 0.1 - 3 microns; 0.3 - 3 microns; or 0.5 - 2 microns.
• the coated substrate can be dried and then a second coating can be applied and coated by spin-coating.
• the spin- coating step can wash organics out of the first coating.
• the coated film can be soaked in a solvent and then spun to wash out the organics.
• useful solvents for removing organics in the coatings include alcohols, e.g., methanol or ethanol, and hydrocarbons, e.g., toluene.
• dip-coating the substrate into the ink can be alternated with dip-coating the coated substrate into a solvent bath to remove impurities and organic compounds. Removal of non-volatile capping agents from the coating can be further facilitated by exchanging these capping agents with volatile capping agents.
• the volatile capping agent can be used as the washing solution or as a component in a bath.
• a layer of a coated substrate comprising a first capping agent is contacted with a second capping agent, thereby replacing the first capping agent with the second capping agent to form a second coated substrate.
• Advantages of this method include film densification, along with lower levels of carbon-based impurities in the film, particularly if and when it is later annealed.
• binary sulfides and other impurities can be removed by etching the annealed film using standard techniques for CIGS/Se films.
• Another aspect of this invention is a process for preparing a photovoltaic cell comprising a film comprising CIGS/Se.
• the film is the absorber or buffer layer of a photovoltaic cell.
• One aspect of this invention provides a process for making an electronic device and comprises depositing one or more layers in layered sequence onto the annealed film of the substrate.
• the layers can be selected from the group consisting of conductors, semiconductors, and insulators.
• Another aspect of this invention provides a process for
• a typical photovoltaic cell includes a substrate, a back contact layer (e.g., molybdenum), an absorber layer (also referred to as the first
• the photovoltaic cell can also include an electrode pad on the top contact layer, and an anti- reflective (AR) coating on the front (light-facing) surface of the substrate to enhance the transmission of light into the semiconductor layer.
• the buffer layer, top contact layer, electrode pads and antireflective layer can be deposited onto the annealed CIGS/Se film in layered sequence.
• the process provides a photovoltaic device and comprises depositing the following layers in layered sequence onto the annealed coating of the substrate having an electrically conductive layer present: (i) a buffer layer; (ii) a transparent top contact layer, and (iii) optionally, an antireflective layer.
• the process provides a photovoltaic device and comprises disposing one or more layers selected from the group consisting of buffer layers, top contact layers, electrode pads, and antireflective layers onto the annealed
• construction and materials for these layers are analogous to those of known CIGS/Se photovoltaic cells.
• Suitable substrate materials for the photovoltaic cell substrate are as described above.
• Advantages of the inks of the present invention are numerous: 1 .
• Molecular precursors to CIGS/Se can be prepared that form stable dispersions that can be stored for long periods without settling or agglomeration, while keeping the amount of dispersing agent in the ink at a minimum. 2.
• chalcogenide in the molecular precursor can be easily varied to achieve optimum performance of the photovoltaic cell.
• the use of molecular precursors enables low annealing temperatures and dense film packing.
• the molecular precursor can be prepared and deposited using a small number of operations and scalable, inexpensive processes.
• Films of thickness suitable for thin film photovoltaic devices can be deposited in one coating operation.
• Coatings derived from the molecular precursor can be annealed at atmospheric pressure. Moreover, for certain molecular precursor compositions, only an inert atmosphere is required. For other ink compositions, the use of H 2 S or H 2 Se is not required to form CIGS/Se, since sulfurization or selenization can be achieved with sulfur or selenium vapor.
• isopropanol dried at 1 10 °C, and coated on the non-float surface of the SLG substrate. All formulations and coatings were prepared in a nitrogen- purged drybox. Vials containing formulations were heated and stirred on a magnetic hotplate/stirrer. Coatings were dried in the drybox.
• Annealing of Coated Substrates in a Tube Furnace were carried out either under an inert atmosphere (nitrogen or argon) or under an inert atmosphere comprising a chalcogen source (nitrogen/sulfur, argon/sulfur, or argon/selenium).
• Annealings were carried out in either a single-zone Lindberg/Blue tube furnace (Ashville, NC) equipped with an external temperature controller and a one-inch quartz tube, or in a
• a 3-inch long ceramic boat was loaded with 2.5 g of elemental sulfur and placed near the gas inlet, outside of the direct heating zone.
• the coated substrates were placed on quartz plates inside the tube.
• the substrates When annealing under selenium, the substrates were placed inside a graphite box (Industrial Graphite Sales, Harvard, IL) with a lid with a center hole in it of 1 mm in diameter.
• the box dimensions were 5" length x 1 .4" width x 0.625" height with a wall and lid thickness of 0.125".
• the selenium was placed in small ceramic boats within the graphite box. Details of the Procedures Used for Device Manufacture
• Substrates for photovoltaic devices were prepared by coating an SLG substrate with a 500 nm layer of patterned molybdenum using a Denton Sputtering System. Deposition conditions were: 150 watts of DC Power, 20 seem Ar, and 5 mT pressure.
• Mo-sputtered SLG substrates were purchased from Thin Film Devices, Inc. (Anaheim, CA).
• Cadmium Sulfide Deposition CdSO 4 (12.5 mg, anhydrous) was dissolved in a mixture of nanopure water (34.95 mL) and 28% NH OH (4.05 mL). Then a 1 mL aqueous solution of 22.8 mg thiourea was added rapidly to form the bath solution. Immediately upon mixing, the bath solution was poured into a double-walled beaker (with 70 °C water circulating between the walls), which contained the samples to be coated. The solution was continuously stirred with a magnetic stir bar. After 23 min, the samples were taken out, rinsed with and then soaked in nanopure water for 1 h. The samples were dried under a nitrogen stream and then annealed under a nitrogen atmosphere at 200 °C for 2 min.
• Insulating ZnO and AZO Deposition A transparent conductor was sputtered on top of the CdS with the following structure: 50 nm of insulating ZnO (150 W RF, 5 mTorr, 20 seem) followed by 500 nm of Al- doped ZnO using a 2% AI 2 O 3 , 98% ZnO target (75 or 150 W RF, 10 mTorr, 20 seem).
• ITO Transparent Conductor Deposition A transparent conductor was sputtered on top of the CdS with the following structure: 50 nm of insulating ZnO [100 W RF, 20 mTorr (19.9 mTorr Ar + 0.1 mTorr O 2 )] followed by 250 nm of ITO [100 W RF, 12 mTorr (12 mTorr Ar + 5x10 "6 Torr O2)] .
• the sheet resistivity of the resulting ITO layer was around 30 ohms per square.
• Silver was deposited at 150 WDC, 5 mTorr, 20 seem Ar, with a target thickness of 750 nm.
• Powder X-ray diffraction was used to identify crystalline phases. Data were obtained with a Philips X'PERT automated powder diffractonneter, Model 3040. The diffractonneter was equipped with automatic variable anti-scatter and divergence slits, X'Celerator RTMS detector, and Ni filter. The radiation was CuK(alpha) (45 kV, 40 imA). Data were collected at room temperature from 4 to 120°. 2-theta, using a continuous scan with an equivalent step size of 0.02°, and a count time of from 80 sec to 240 sec per step in theta-theta geometry. Thin film samples were presented to the X-ray beam as made. MDI/Jade software version 9.1 was used with the International Committee for Diffraction Data database PDF4+ 2008 for phase identification and data analysis.
• EQE Analysis External Quantum Efficiency (EQE) determinations were carried out as described in ASTM Standard E1021 -06 ("Standard Test Method for Spectral Responsivity Measurements of Photovoltaic Devices").
• the reference detector in the apparatus was a pyroelectric radiometer (Laser Probe (Utica, NY), LaserProbe Model RkP-575 controlled by a LaserProbe Model Rm-6600 Universal Radiometer).
• the excitation light source was a xenon arc lamp with wavelength selection provided by a monochrometer in conjunction with order sorting filters.
• Optical bias was provided by a broad band tungsten light source focused to a spot slightly larger than the monochromatic probe beam.
• Measurement spot sizes were approximately 1 mm x 2 mm.
• Optical beam induced current measurements were determined with a purpose-constructed apparatus employing a focused monochromatic laser as the excitation source.
• the excitation beam was focused to a spot -100 microns in diameter.
• the excitation spot was rastered over the surface of the test sample while simultaneously measuring photocurrent so as to build a map of photocurrent vs position for the sample.
• the resulting photocurrent map characterizes the photoresponse of the device vs. position.
• the apparatus can operate at various wavelengths via selection of the excitation laser. Typically, 440, 532 or 633 nm excitation sources were employed.
• This example illustrates: (a) the preparation of a molecular precursor to CIS 2 ; (b) the formation of an annealed film of CIS 2 from the molecular precursor using only an inert gas in the annealing atmosphere; and (c) the production of an active photovoltaic device from an annealed film of the molecular precursor (Example 1A).
• Indium(lll) 2,4-pentanedionate (0.6734 g, 1 .634 mmol) and copper(ll) bis(2-hydroxyethyl)dithiocarbamate (0.6932 g, 1 .635 mmol) were placed together in a 40 mL amber septum-capped vial equipped with a stir bar.
• Example 1A Example 1 was repeated with the exception that the molecular precursor was deposited on a Mo-patterned SLG slide with a spin-coating speed of 3000 rpm. The Mo layer had a resisitivity of ⁇ 20 ohms/square. Cadmium sulfide, insulating ZnO, ITO, and silver lines were deposited. The device efficiency was 0.200%.
• This example illustrates: (a) the preparation of a molecular precursor to CIS/Se; (b) the formation of an annealed film of CIS 2 and CISe 2 from the molecular precursor using only an inert gas in the annealing atmosphere; (c) the production of an active photovoltaic device from an annealed film of the molecular precursor (Example 2A); and (d) in Example 2B, the formation of an annealed film of the molecular precursor under a sulfur/nitrogen atmosphere with large grain sizes (according to scanning electron microscopy), and a crystalline composition consisting only of CIS and CIS/Se (according to XRD).
• the coating was then dried in the drybox on a hotplate at 170 °C for 15 min and then at 230 °C for 5 min. The coating (3,250 rpm for 10 sec) and drying procedures were repeated.
• the dried film was then annealed under argon in a 3-inch tube furnace by heating to 250 °C at a rate of 15 °C/ min and then heating to 500 °C at a rate of 2 °C/min. The temperature was then held at 500 °C for 1 hr. Analysis of the annealed sample by XRD indicated the presence of CulnSe2 Cuo.79lno.7eSei.8 and two forms of CulnS2 along with small amounts of CuS, Se, and S6.
• Example 2A Example 2 was repeated, but the molecular precursor was deposited on a Mo-patterned SLG slide. Cadmium sulfide, insulating ZnO, ITO, and silver lines were deposited. The Mo layer had a resisitivity of ⁇ 20 ohms/square. The device efficiency was 0.066%. Analysis by OBIC at 440 nm gave a photoresponse with J90 of 4.1 micro-Amp and dark current of 0.23 micro-Amp. The EQE onset was at 880 nm with an EQE of 5.76% at 640 nm.
• Example 2B A molecular precursor was prepared and heated as in Example 2. The resulting molecular precursor was spun-coated onto an SLG slide at 450 rpm for 3 sec and then at 3000 rpm for 4 sec. The coating was then dried in the drybox on a hotplate at 65 °C for several hours and then at 170 °C for -0.5 hr. The coating (3,250 rpm for 10 sec) and drying procedures were repeated. The dried film was then annealed under nitrogen in a 3-inch tube by raising the temperature to 500 °C at a rate of 15 °C/ min and then holding the temperature at 500 °C for 1 hr. The film was then further annealed at 550 °C for 0.5 hr under a
• Examples 3 and 3A illustrate the formation of molecular precursor inks to CIS.
• Annealed films prepared from both of the inks have a crystalline composition consisting only of CIS2, according to XRD. Both films were formed under an atmosphere consisting only of an inert gas.
• the resulting molecular precursor was spun-coated onto an SLG slide at 2,250 rpm for 10 sec. The coating was then dried in the drybox on a hotplate at 170 °C for 15 min and then at 230 °C for 5 min. The coating (3,500 rpm for 10 sec) and drying
• the dried film was then annealed under argon in a 3-inch tube furnace by heating to 250 °C at a rate of 15 °C/ min and then heating to 500 °C at a rate of 2 °C/ min. The temperature was then held at 500 °C for 1 hr. Analysis of the annealed sample by XRD indicated the presence of one crystalline phase: CIS2.
• the coating (3,500 rpm for 8 sec) and drying procedures were repeated.
• the dried film was then annealed under argon in a 3-inch tube furnace by heating to 250 °C at a rate of 15 °C/ min and then heating to 500 °C at a rate of 2 °C/ min. The temperature was then held at 500 °C for 1 hr. Analysis of the annealed sample by XRD indicated the presence of one crystalline phase: CIS 2 .
• Examples 4A - 4D illustrate the formation of molecular precursor inks to CIS/Se utilizing either ln 2 S 3 or ln 2 Se 3 , Cu(l) acetate,
• Example 4A diethylselenide, and selenium or sulfur powder. Butanethiol was used as an additive in the inks, and the films were annealed under a Se/argon atmosphere.
• the phase of the resulting CIS/Se varied from tetragonal to cubic to a mixture of cubic and tetragonal.
• Example 4D an active device from an ink containing ln 2 S3 was formed.
• Example 4A In the drybox, copper(l) acetate (0.4000 g, 3.263 mmol) and indium(lll) selenide (0.7636 g, 1 .637 mmol) were placed together with a stir bar in a 40 ml_ vial. Solvent ( ⁇ 1 .5 g of 3,5-lutidine) and ethyl diselenide (0.3666 g, 1 .697 mmol) were placed together in a 20 ml_ vial. Both vials were cooled to -25 °C in the drybox freezer. The cold ethyl diselenide solution was added to the mix of copper and indium reagents.
• the reaction mixture was stirred as it was allowed to warm to room temperature.
• Chalcogen powder (selenium, 0.3666 g, 1 .697 mmol) was added to the reaction mixture, which was then capped with a vented septum and stirred for more than one week at 100 °C. Additional solvent (2 g of 3,5-lutidine) was added, and the reaction mixture was then stirred for 4 days at 150 °C.
• the reaction mixture was allowed to cool to room temperature.
• Butanethiol (0.42 g) was added, and the resulting ink was stirred several days at room temperature and then filtered twice through small plugs of glass wool in pipettes. A small portion of the ink was drawn into a pipette and spread onto a Mo-sputtered SLG substrate.
• the coating was then dried in the drybox at 175 °C for -30 min on a hotplate. The same coating and drying procedure was repeated two times to form a second and third coated layer. The resulting 3-layer coating was dried at 250 °C for ⁇ 30 min.
• the coated substrate was placed in a graphite box along with four other coated substrates and three ceramic boats containing a total of 150 mg of Se pellets. The box was placed in a 3-inch tube furnace which was evacuated and then placed under argon. The temperature was increased to 585 °C.
• the furnace was allowed to cool to 500 °C and held at 500 °C for 30 min.
• the XRD of the annealed film had peaks for Mo, trace MoSe2, and tetragonal Culn(S/Se)2 with a S/Se ratio of 1 .7/98.3 and a coherent domain size of 87.1 +/-1 .3 nm.
• Example 4B An ink was prepared using the reagents and procedure of Example 4A with the exception that a 2:1 mixture of 3,5- lutidine/3-aminopyridine was used as the solvent.
• a 2:1 mixture of 3,5- lutidine/3-aminopyridine was used as the solvent.
• two-layer coatings were produced on a number of Mo-sputtered SLG substrates.
• One of the coated substrates was dried at 250 °C for ⁇ 30 min and then placed in a graphite box, along with four other coated substrates and three ceramic boats containing a total of 150 mg of Se pellets.
• the box was placed in a 3-inch tube furnace which was evacuated and then placed under argon. The temperature was increased to 600 °C. Once it reached the set point, the furnace lid was opened briefly to cool the temperature to 500 °C.
• the lid was closed and the furnace was held at 500 °C for 30 min.
• the XRD of the annealed film had peaks for Mo, trace MoSe 2 , tetragonal CulnSe 2 , cubic Cuo.5lno .5 Se, a S/Se ratio of approx. 0/100, and a coherent domain size of greater than 100 nm.
• Example 4C An ink was prepared using the reagents and procedures of Example 4A with the following exceptions: ln 2 S3 was used as the indium source, a mixture of 1 .5 g of pyridine and 0.165 g of
• Example 4A 3-aminopyridine was used as the solvent, the chalcogen powder consisted of sulfur, and the ink was heated at 100 °C for one week, but not to 150 °C.
• the coating and annealing procedure of Example 4A was followed with the following three exceptions: (1 ) A 2-layer coated substrate was formed and was dried at 175 °C for ⁇ 30 min. (2) A total of only 5-10 mg of selenium were placed in two ceramic boats inside of the graphite box. (3) The furnace temperature was increased to 575 °C, held there for 20 min, and then allowed to cool to room temperature.
• the XRD of the annealed film had peaks for Mo, cubic Cuo.5lno .5 Se, and possibly trace CuO, and a coherent domain size of 16.3 +/-0.2 nm.
• the S/Se ratio was 13.8/86.2.
• Example 4D The procedure of Example 4C was followed with the following two exceptions: (1 ) Three ceramic boats containing a total of 150 mg of Se pellets were placed in the graphite box. (2) During the anneal, the furnace temperature was increased to 585 °C. Once it reached the set point, the tube was allowed to cool to 500 °C and held at 500 °C for 30 min. The annealed film was brought into the drybox and heated to 300 °C on a hotplate for 45 min. Cadmium sulfide (the above procedure was repeated two times), insulating ZnO, ITO, and silver lines were deposited on the annealed film. The device efficiency was 0.106%.

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