# Patent

## Title
Group 6a/group 3a ink and methods of making and using same

## Abstract

A selenium/Group 3a ink, comprising (a) a selenium/Group 3a complex which comprises a combination of, as initial components: a selenium component comprising selenium; an organic chalcogenide component having a formula selected from RZ—Z′R′ and R2—SH; wherein Z and Z′ are each independently selected from sulfur, selenium and tellurium; wherein R is selected from H, C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; wherein R′ and R2 are selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; and, a Group 3a complex, comprising at least one Group 3a material selected from aluminum, indium, gallium and thallium complexed with a multidentate ligand; and, (b) a liquid carrier; wherein the selenium/Group 3a complex is stably dispersed in the liquid carrier.

## Background
The present invention relates to a selenium/Group 3a ink comprising, as initial components: a selenium component comprising selenium, an organic chalcogenide component having a formula selected from RZ—Z′R′ and R2—SH; and a Group 3a complex stably dispersed in a liquid carrier. The present invention further relates to a method of preparing the selenium/Group 3a ink and for using the selenium/Group 3a ink.
The fabrication of thin films of Group III/Group VI semiconductors (e.g., InxSey) have been studied extensively over the past two decades for use in a number of potential applications including, for example, switching devices, photovoltaics, nonlinear optics, ionic batteries and high density phase change data storage devices. Of these potential applications use of the Group III/Group VI semiconductors in the preparation of a CIGS absorber layers and in the preparation of an γ-In2Se3 window layers (i.e., a CdS buffer layer substitute for use in photovoltaic cells) are extremely promising.
One challenge for these promising uses for Group III/Group VI semiconductors is the development of cost-effective manufacturing techniques. Conventional methods for depositing Group III/Group VI semiconductors typically involve the use of vacuum based processes, including, for example, vacuum evaporation, sputtering and chemical vapor deposition (e.g., metal-organic chemical vapor deposition). Such deposition techniques tend to exhibit low throughput capabilities and high cost. To facilitate the large scale, high throughput, low cost, manufacture of systems incorporating the use of Group III/Group VI semiconductor materials, it would be desirable to provide liquid based deposition techniques.
A method for the liquid deposition of a semiconductor precursor film is disclosed in U.S. Pat. No. 6,126,740 to Schulz et al. Schulz et al. disclose a colloidal suspension comprising metal chalcogenide nanoparticles and a volatile capping agent, wherein the colloidal suspension is made by the reaction of a metal salt with a chalcogenide salt in an organic solvent to precipitate a metal chalcogenide, recovery of the metal chalcogenide precipitate, and mixing of the metal chalcogenide precipitate with a volatile capping agent in a nonaqueous organic solvent. Schulz et al. further disclose that the colloidal suspension can be spray deposited onto a substrate to produce a semiconductor precursor film. Schulz et al. disclose that particular preferred metals for use in its colloidal suspension and method of use are copper, indium, gallium and cadmium.
A method for depositing indium selenide is disclosed by Mitzi, et al. in Low-Voltage Transistor Employing a High-Mobility Spin-Coated chalcogenide Semiconductor, ADVANCED MATERIALS vol. 17, pp. 1285-89 (2005). Mitzi, et al. disclose the use of a hydrazinium precursor material for deposition of indium selenide to form an indium selenide channel of a thin film transistor.
The hydrazinium precursor materials disclosed by Mitzi, et al. remove hydrazine from the manufacturing step to produce semiconductor films. Notwithstanding, Mitzi, et al. do not eliminate the need for hydrazine. Rather, Mitzi, et al. still utilize hydrazine in the preparation of the hydrazinium precursor materials. Moreover, hydrazinium ion precursors pose a significant explosion risk, as documented by Eckart W. Schmidt in his book, Hydrazine and Its Derivatives: Preparation, Properties, and Applications, JOHN WILEY & SONS pp 392-401 (1984). The presence of numerous metal ions exacerbates the risk of hydrazinium explosion or detonation. This can be a problem because residual hydrazinium salts may accumulate in process equipment during manufacture, presenting an unacceptable safety risk.
Notwithstanding, there remains a need for a selenium/Group 3a ink for use in the manufacture of systems incorporating selenium/Group 3a semiconductors (e.g., switching devices, photovoltaics, nonlinear optics, ionic batteries and high density phase change data storage devices). In particular, a selenium/Group 3a ink that facilitates the deposition of an MaSeh material, wherein M is a Group 3a material and wherein the mole ratio of M to Se in the deposited MaSeh material is tailorable, which selenium/Group 3a ink formulations are preferably hydrazine and hydrazinium free.
The present invention provides a selenium/Group 3a ink, comprising a selenium/Group 3a complex which comprises a combination of, as initial components: (a) a selenium component comprising selenium; an organic chalcogenide component having a formula selected from RZ—Z′R′ and R2—SH; wherein Z and E are each independently selected from sulfur, selenium and tellurium; wherein R is selected from H, C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; wherein R′ and R2 are selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; and, a Group 3a complex, comprising at least one Group 3a material selected from aluminum, indium, gallium and thallium complexed with a multidentate ligand; and, (b) a liquid carrier; wherein the selenium/Group 3a complex is stably dispersed in the liquid carrier.
The present invention also provides a method of preparing a selenium/Group 3a ink according to claim 1, comprising: providing a selenium component, comprising selenium; providing an organic chalcogenide component having a formula selected from RZ—Z′R′ and R2—SH; wherein Z and Z′ are each independently selected from sulfur, selenium and tellurium; wherein R is selected from H, C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; wherein R′ and R2 are selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; providing a liquid carrier; combining the selenium component, the organic chalcogenide component and the liquid carrier; heating the combination with agitation to produce a combined selenium/organic chalcogenide component; providing a Group 3a complex, comprising at least one Group 3a material selected from aluminum, indium, gallium and thallium complexed with a multidentate ligand; and, combining the combined selenium/organic chalcogenide component and the Group 3a complex to form the selenium/Group 3a ink; wherein the selenium/Group 3a ink is a stable dispersion.
The present invention also provides a method for depositing a MaSeh material on a substrate, comprising: providing a substrate; forming a selenium/Group 3a ink, comprising: providing a selenium component, comprising selenium; providing an organic chalcogenide component having a formula selected from RZ—Z′R′ and R2—SH; wherein Z and Z′ are each independently selected from sulfur, selenium and tellurium; wherein R is selected from H, C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; wherein R′ and R2 are selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; providing a liquid carrier; combining the selenium component, the organic chalcogenide component and the liquid carrier; heating the combination with agitation to produce a combined selenium/organic chalcogenide component; providing a Group 3a complex, comprising at least one Group 3a material selected from aluminum, indium, gallium and thallium complexed with a multidentate ligand; and, combining the combined selenium/organic chalcogenide component and the Group 3a complex to form the selenium/Group 3a ink; wherein the selenium/Group 3a ink is a stable dispersion; depositing the selenium/Group 3a ink on the substrate; heating the deposited selenium/Group 3a ink to eliminate the liquid carrier leaving a MaSeh material, wherein the mole ratio of M to Se in the deposited MaSeh material on the substrate is 6:1 to 1:6; and, optionally, annealing the deposited MaSeh material.


DETAILED DESCRIPTION
The Group 3a complex of the present invention is not a salt. Without wishing to be bound by theory, the selenium/Group 3a ink of the present invention can comprise (i) a selenium complex and a Group 3a complex stably dispersed together in a liquid carrier; (ii) a complex incorporating both selenium and a Group 3a material; or (iii) a combination of (i) and (ii). As distinguished from the nonaqueous colloidal suspension taught by Schultz et al. in U.S. Pat. No. 6,126,740; any selenium/Group 3a complex present in the selenium/Group 3a ink of the present invention is not precipitated, isolated from solution and then redispersed. Rather, any selenium/Group 3a complex present in the selenium/Group 3a ink of the present invention is stable in the liquid carrier upon creation and remains stable pending its use.
The term “stable” as used herein and in the appended claims in reference to the selenium/Group 3a ink means that the selenium component, the organic chalcogenide component and the Group 3a complex do not form a precipitate upon mixing to form the selenium/Group 3a ink in a liquid carrier at 22° C. under nitrogen.
The term “storage stable” as used herein and in the appended claims in reference to the selenium/Group 3a ink means that the selenium component, the organic chalcogenide component and the Group 3a complex do not form a precipitate upon mixing in a liquid carrier to form the selenium/Group 3a ink or upon subsequent storage of the selenium/Group 3a ink at 22° C. under nitrogen for a period of at least five (5) minutes.
The term “extended stability” as used herein and in the appended claims in reference to the selenium/Group 3a ink means that the selenium component, the organic chalcogenide component and the Group 3a complex do not form a precipitate upon mixing in a liquid carrier to form the selenium/Group 3a ink or upon subsequent storage of the selenium/Group 3a ink at 22° C. under nitrogen for a period of at least two (2) hours.
The term “hydrazine free” as used herein and in the appended claims in reference to the selenium/Group 3a ink means that the selenium/Group 3a ink contains <100 ppm hydrazine.
The term “hydrazinium free or (N2H5)+ free” as used herein and in the appended claims in reference to the selenium/Group 3a ink means that the selenium/Group 3a ink contains <100 ppm hydrazinium complexed with selenium.
The selenium component of the present invention comprises selenium. Preferably, the selenium component is selenium.
The organic chalcogenide component has a formula selected from RZ—Z′R′ and R2—SH; wherein Z and are each independently selected from sulfur, selenium and tellurium (preferably sulfur and selenium; most preferably sulfur); wherein R is selected from H, a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group (preferably R is selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, a C7-20 arylether group and a C3-20 alkylether group; more preferably R is selected from a C1-20 alkyl group and a C6-20 aryl group; still more preferably R is a C1-10 alkyl group; most preferably R is a C1-5 alkyl group); wherein R′ is selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group (preferably R′ is selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, a C7-20 arylether group and a C3-20 alkylether group; more preferably R′ is selected from a C1-20 alkyl group and a C6-20 aryl group; still more preferably R′ is a C1-10 alkyl group; most preferably R′ is a C1-5 alkyl group). Preferably, R, R′ and R2 are selected to enhance the solubility of the organic chalcogenide in the liquid carrier.
The organic chalcogenide component is believed to provide the selenium/Group 3a ink of the present invention with enhanced stability. The molar ratio of selenium to the organic chalcogenide having a formula selected from RZ—Z′R′ and R2—SH in the selenium/Group 3a ink is selected to tailor the properties of the selenium/Group 3a ink as desired. Without wishing to be bound by theory, it is believed that a higher molar ratio of organic chalcogenide having a formula selected from RZ—Z′R′ and R2—SH to selenium in the selenium/Group 3a ink of the present invention correlates with greater stability of the selenium/Group 3a ink. Preferably, the molar ratio of selenium to the organic chalcogenide having a formula selected from RZ—Z′R′ and R2—SH in the selenium/Group 3a ink is 2:1 to 20:1, more preferably 2:1 to 14:1, still more preferably 2:1 to 10:1, most preferably 2:1 to 8:1.
Optionally, Z and Z′ are both sulfur. Preferably, when both Z and Z′ are sulfur, R and R′ are each independently selected from a phenyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group and a tert-butyl group. More preferably, when both Z and Z′ are sulfur, R and R′ are each independently selected from a n-butyl group and a tert-butyl group. Most preferably, when both Z and Z′ are sulfur, R and R′ are both a tert-butyl group.
Optionally, Z and Z′ are both selenium. Preferably, when both Z and Z′ are selenium, R and R′ are each independently selected from a phenyl group, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group and a tert-butyl group. More preferably, when both Z and Z′ are selenium, R and R′ are both a phenyl group.
Optionally, the selenium component and the organic chalcogenide component are combined to form a selenium/organic chalcogenide component. Preferably, the combined selenium/organic chalcogenide component comprises, a chemical compound having a formula RZ—Set—Z′R′ dispersed in a liquid carrier; wherein Z and Z′ are as previously described; wherein R and R′ are as previously described; wherein t is 2 to 20 (preferably 2 to 14; more preferably 2 to 10; most preferably 2 to 8); wherein the selenium component comprises ≧1 wt % selenium; wherein the selenium component is a stable dispersion and wherein the selenium component is hydrazine and hydrazinium free.
The Group 3a complex of the present invention comprises: (a) a Group 3a material selected from aluminum, gallium, indium and thallium; preferably selected from gallium and indium; most preferably indium; and (b) a multidentate ligand coordinated with the Group 3a ion. Without wishing to be bound by theory, it is believed that, relatively speaking, the use of higher denticity ligands in the preparation of the Group 3a complex decreases the reactivity of the Group 3a material in the Group 3a complex with selenium in the selenium component while the selenium component and the Group 3a complex are dispersed in the liquid carrier (e.g., tridentate ligands result in higher stability relative to bidentate or monodentate ligands). It is believed that higher denticity ligands exhibit a higher affinity for the Group 3a material in the Group 3a complex and are therefore more difficult for selenium to displace from the Group 3a material while dispersed in the liquid carrier.
The multidentate ligands in the Group 3a complex preferably include diketones. More preferably, the Group 3a complex includes a multidentate ligand selected from butanedionate, pentanedionate, hexanedionate, heptanedionate, cyclohexanedionate, 1,1,1,5,5,5-hexafluoroacetylacetone complexed with the Group 3a material. Most preferably, the Group 3a complex includes pentanedionate complexed with the Group 3a material.
The Group 3a complex of the present invention is preferably indium, gallium or a mixture thereof; complexed with a multidentate ligand. Optionally, the Group 3a complex is a gallium complex, preferably gallium complexed with a diketone, most preferably gallium complexed with pentanedionate. Optionally, the Group 3a complex is an indium complex, preferably indium complexed with a diketone, most preferably indium complexed with pentanedionate.
Liquid carrier used in the selenium/Group 3a ink of the present invention can be any solvent in which the selenium component, the organic chalcogenide component and the Group 3a complex are stably dispersible. Given the teachings provided herein, one of ordinary skill in the art will know, through routine experimentation, how to determine what solvents are suitable for use in the invention. That is, one of ordinary skill in the art will know, through routine experimentation, which solvents result in gelation. For example, monodentate amine solvents exhibit reduced solubility of Group 3a complexes and are also poor solvents for the selenium component. Preferably, the liquid carrier is selected from amine solvents (a) having two nitrogen atoms per molecule, wherein the nitrogen atoms are either (i) separated by at least 3 carbon atoms (e.g., “—C—C—C—”) in the molecular formula of the amine solvent or (ii) the nitrogen atoms are constituents of an unsaturated ring structure in the molecular formula of the amine solvent (e.g., an imidazole ring); and (b) having at least three nitrogen atoms per molecule of the amine solvent. More preferably, the liquid carrier is selected from 1,3-diaminopropane; diethylenetriamine; 1-methylimidazole; tris(2-aminoethyl)amine; triethylenetetramine; tetraethylenepentamine and tetramethyl guanidine. Still more preferably, the liquid carrier is selected from 1,3-diaminopropane; diethylenetriamine; triethylenetetramine; tetramethylquanidine and 1-methylimidazole. Most preferably, the liquid carrier is 1,3-diaminopropane.
The selenium/Group 3a ink of the present invention can, optionally, further comprise a cosolvent. Cosolvents suitable for use with the present invention are miscible with the liquid carrier contained in the selenium/Group 3a ink and do not have the effect of destabilizing the selenium/Group 3a ink. Preferred cosolvents further exhibit a boiling point within 30° C. of the boiling point of the liquid carrier contained in the selenium/Group 3a ink.
The selenium/Group 3a ink of the present invention can, optionally, further comprise an additive selected from the group consisting of aromatic thiols, saturated cyclic thiols and carboxylic acids that do not have the effect of destabilizing the selenium/Group 3a ink. Given the teachings provided herein, one of ordinary skill in the art will know through routine experimentation how to determine what optional additives are suitable for use in the invention. Preferred optional additives for use in indium containing selenium/Group 3a inks of the present invention are selected from p-toluene thiol, cyclohexyl mercaptan, 2-mercaptopropionic acid; formic acid; trifluoroacetic acid; acetic acid; propionic acid and mixtures thereof. Preferred optional additives for use in gallium containing selenium/Group 3a inks of the present invention are selected from p-toluene thiol, cyclohexyl mercaptan, 2-ethylbutyric acid, mercaptoproprionic acid, formic acid, trifluoroacetic acid, acetic acid, propionic acid and mixtures thereof.
The selenium/Group 3a ink of the present invention can, optionally, further comprise an agent selected from a dispersant, a wetting agent, a polymer, a binder, an anti-foaming agent, an emulsifying agent, a drying agent, a filler, an extender, a film conditioning agent, an antioxidant, a plasticizer, a preservative, a thickening agent, a flow control agent, a leveling agent, a corrosion inhibitor and a dopant (e.g., sodium to improve electrical performance of CIGS absorber materials). Optional agents can be incorporated into the selenium/Group 3a ink of the present invention to, for example, facilitate increased shelf life, to improve flow characteristics to facilitate the method of application to a substrate (e.g., printing, spraying), to modify the wetting/spreading characteristics of the ink onto the substrate, to enhance the compatibility of the selenium/Group 3a ink with other inks used to deposit other components on the substrate (e.g., other constituents of a CIGS absorber material, such as Cu), and to modify the decomposition temperature of the selenium/Group 3a ink.
Preferably, the selenium/Group 3a ink of the present invention is a non-aqueous ink (i.e., contains ≦10 wt %, more preferably ≦1 wt %, most preferably ≦0.1 wt % water). It is believed that water present in the raw materials (e.g., liquid vehicle, optional agent) used can react with the Group 3a complex to produce insoluble Group 3a oxides.
The selenium content of the selenium/Group 3a ink of the present invention can be selected to suit the particular application need and the processing technology and equipment used to apply the selenium/Group 3a ink to a given substrate. Preferably, the selenium/Group 3a ink exhibits a selenium content selected from 1 to 50 wt %; 1 to 5 wt %; 4 to 15 wt % and 5 to 10 wt % (based on the weight of the selenium/Group 3a ink). Optionally, the selenium/Group 3a ink exhibits a selenium content of 1 to 50 wt % (based on the weight of the selenium/Group 3a ink). Optionally, the selenium/Group 3a ink exhibits a selenium content of 1 to 5 wt % (based on the weight of the selenium/Group 3a ink). Optionally, the selenium/Group 3a ink exhibits a selenium content of 4 to 15 wt % (based on the weight of the selenium/Group 3a ink). Optionally, the selenium/Group 3a ink exhibits a selenium content of 5 to 10 wt % (based on the weight of the selenium/Group 3a ink).
The mole ratio of selenium to Group 3a material in the selenium/Group 3a ink of the present invention is tailorable. Preferably, the mole ratio of the selenium to Group 3a material in the selenium/Group 3a ink of the present invention is tailored to be 6:1 to 1:6. More preferably, the mole ratio of the selenium to Group 3a material in the selenium/Group 3a ink of the present invention is tailored to be 3:1 to 1:3. Still more preferably, the mole ratio of selenium to Group 3a material in the selenium/Group 3a ink of the present invention is tailored to be 2:1 to 1:2. Most preferably, the mole ratio of the selenium to Group 3a material in the selenium/Group 3a ink of the present invention is tailored to be 1.5:1 to 1:1.5.
Without wishing to be bound by theory, it is believed that the stability of the selenium/Group 3a ink is determined by five main factors, namely 1) the solubility of the Group 3a complex in the liquid carrier; 2) selection of R, R′ and R2 in the organic chalcogenide component; 3) selection of the molar ratio of the organic chalcogenide component to selenium in the selenium component; 4) selection of the liquid carrier; and, 5) coordination of the Group 3a material in the Group 3a complex by ligands capable of regulating reaction of the Group 3a material with selenium while dispersed in the liquid carrier. By selection and control of these five main factors, it is believed possible to tailor the stability of the selenium/Group 3a ink for a given application. That is, the desired stability may vary depending on the method used to deposit the selenium/Group 3a ink onto a substrate. In some cases, it will be desirable to mix the selenium component and the Group 3a complex well in advance of the time when the selenium/Group 3a ink is to be deposited onto a substrate (e.g., hours). In these situations, the selenium/Group 3a ink can be formulated to exhibit extended stability. In some cases, it will be desirable for the customer/user to combine the selenium component and the Group 3a complex shortly before the selenium/Group 3a ink is to be deposited onto a substrate (e.g., within minutes of deposition onto a substrate). In these situations, the selenium/Group 3a ink can be formulated to be at least storage stable. In some cases, it will be desirable for the customer/user to combine the selenium component and the Group 3a complex contemporaneously with the deposition of the selenium/Group 3a ink onto a substrate (e.g., simultaneous co-deposition of the selenium component and the Group 3a complex wherein the components are mixed momentarily before or as they contact the substrate). In these situations, the selenium/Group 3a ink can be formulated to be at least stable.
Preferably the selenium/Group 3a ink of the present invention is hydrazine free and hydrazinium free.
A method of preparing a selenium/Group 3a ink of the present invention, comprises: providing a selenium component; providing an organic chalcogenide component; providing a Group 3a complex; providing a liquid carrier; and forming a combination of the selenium component, the organic chalcogenide component, the Group 3a complex and the liquid carrier, providing the selenium/Group 3a ink.
In providing the selenium component for use in the preparation of the selenium/Group 3a ink of the present invention, the selenium and the liquid carrier are preferably combined by adding the liquid carrier to the selenium. More preferably, the selenium and liquid carrier are combined using inert techniques, followed with continuous agitation and heating to reflux until the selenium is dissolved in the liquid carrier. Preferably, the liquid carrier is maintained at a temperature of 20 to 240° C. during the combining of the liquid carrier and the selenium. Optionally, the liquid carrier and selenium can be heated above the melting point of selenium (220° C.) during the combining process.
Providing a combined selenium/organic chalcogenide component for use in the preparation of the selenium/Group 3a ink of the present invention, comprises: providing selenium, providing an organic chalcogenide having a formula selected from RZ—Z′R′ and R2—SH, and providing a liquid carrier; combining the selenium, the organic chalcogenide and the liquid carrier; heating the combination (preferably to a temperature within 25° C. of the boiling point temperature of the liquid carrier, most preferably to heating to reflux) with agitation (preferably for a period of 0.1 to 40 hrs; more preferably for a period of 0.1 to 8 hrs) to form the combined selenium/organic chalcogenide component stably dispersed in the liquid carrier. Preferably, the molar ratio of selenium to the organic chalcogenide having a formula selected from RZ—Z′R′ and R2—SH in the combined selenium/organic chalcogenide component is 2:1 to 20:1, more preferably 2:1 to 14:1, still more preferably 2:1 to 10:1, most preferably 2:1 to 8:1.
In providing the combined selenium/organic chalcogenide component for use in the preparation of the selenium/Group 3a ink of the present invention, the organic chalcogenide provided is selected from a thiol and an organic dichalcogenide. When a thiol is used, the thiol preferably has a formula R2—SH, wherein R2 is selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; preferably R2 is selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, a C7-20 arylether group and a C3-20 alkylether group; more preferably R2 is selected from a C1-20 alkyl group and a C6-20 aryl group; still more preferably R2 is a C1-10 alkyl group; most preferably R2 is a C1-5 alkyl group. When an organic dichalcogenide is used, the organic dichalcogenide preferably has a formula RZ—Z′R′, wherein R is selected from H, a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group (preferably R is selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, a C7-20 arylether group and a C3-20 alkylether group; more preferably R is selected from a C1-20 alkyl group and a C6-20 aryl group; still more preferably R is a C1-10 alkyl group; most preferably R is a C1-5 alkyl group); wherein R′ is selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group (preferably R′ is selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, a C7-20 arylether group and a C3-20 alkylether group; more preferably R′ is selected from a C1-20 alkyl group and a C6-20 aryl group; still more preferably R′ is a C1-10 alkyl group; most preferably R′ is a C1-5 alkyl group); and, wherein Z and Z′ are each independently selected from sulfur, selenium and tellurium; preferably sulfur and selenium; most preferably sulfur. The R2, R and R′ groups in the thiol and organic dichalcogenide used can be selected to enhance the solubility of the resulting combined selenium/organic chalcogenide component in the liquid carrier.
Preferably, in providing the combined selenium/organic chalcogenide component for use in the preparation of the selenium/Group 3a ink of the present invention, the timing of the addition of the organic chalcogenide depends on the physical state of the organic chalcogenide used. For solid organic chalcogenides, the solid organic chalcogenide is preferably combined with the selenium before addition of the liquid carrier. For liquid organic chalcogenides, the liquid organic chalcogenide is preferably added to the combined selenium and liquid carrier.
When using a liquid organic chalcogenide, providing the combined selenium/organic chalcogenide component for use in the preparation of the selenium/Group 3a ink of the present invention, optionally, further comprises heating the combined selenium and liquid carrier before adding the liquid organic chalcogenide. Preferably, providing the combined selenium/organic chalcogenide component for use in preparation of the selenium/Group 3a ink of the present invention, optionally, further comprises: heating the combined liquid carrier and selenium powder before and during the addition of the liquid organic chalcogenide. More preferably, the combined liquid carrier and selenium powder are maintained at a temperature of 20 to 240° C. during the addition of the liquid organic chalcogenide. Most preferably, any liquid organic chalcogenides are added to the combined selenium and liquid carrier by gradually adding the liquid organic chalcogenide to the combined selenium and liquid carrier with continuous agitation and heating to reflux.
The Group 3a complex can, optionally, be prepared by combining simple salts of Group 3a material with a ligand in an appropriate liquid vehicle, wherein the liquid vehicle is selected from a liquid carrier (as defined herein), a cosolvent (as defined herein) or a mixture thereof. For instance, indium nitrate or gallium nitrate can be reacted with a deprotonated pentanedione in an appropriate liquid vehicle to form an indium pentanedionate or gallium pentanedionate, respectively. Some Group 3a complexes are also available commercially, for example indium pentanedionate and gallium pentanedionate. For commercially available Group 3a complexes, the Group 3a complex can, optionally, be combined with an appropriate liquid vehicle, wherein the liquid vehicle is selected from a liquid carrier (as defined herein), a cosolvent (as defined herein), or mixtures thereof. Some raw materials used in combination with a Group 3a material with ligand or a Group 3a complex (e.g., optional additive, optional agent and liquid vehicle) can result in the formation of a precipitate. For example, in cases where the raw materials (e.g., optional additive, optional agent, liquid vehicle) contain water, it is believed that the water will react with the Group 3a complex to form an insoluble Group 3a oxide. For combinations where a precipitate is formed, the Group 3a complex, optional additive, and optional agent in liquid vehicle will be present as the supernate, which can be withdrawn from the container for use in the preparation of a selenium/Group 3a ink of the present invention using well known methods such as by decanting and by cannula.
In providing the selenium component and the Group 3a complex for use in the preparation of the selenium/Group 3a ink of the present invention, the liquid carrier used is any solvent or combination of solvents in which the selenium component and the Group 3a complex are stably dispersible. Preferably, the liquid carrier is selected from amine solvents (a) having two nitrogen atoms per molecule, wherein the nitrogen atoms are either (i) separated by at least 3 carbon atoms (e.g., “—C—C—C—”) in the molecular formula of the amine solvent or (ii) the nitrogen atoms are both constituents of an unsaturated ring structure in the molecular formula of the amine solvent (e.g., an imidazole ring); and (b) having at least three nitrogen atoms per molecule of the amine solvent. More preferably, the liquid carrier is selected from 1,3-diaminopropane; diethylenetriamine; 1-methylimidazole; tris(2-aminoethyl)amine; triethylenetetramine; tetraethylenepentamine and tetramethylquanidine. Still more preferably, the liquid carrier is selected from 1,3-diaminopropane; diethylenetriamine; triethylenetetramine; tetramethylquanidine and 1-methylimidazole. Most preferably, the liquid carrier is 1,3-diaminopropane.
Optionally, the method of preparing the selenium/Group 3a ink of the present invention, further comprises: providing a cosolvent; and, combining the cosolvent with the selenium component, the Group 3a complex and the liquid carrier. Optionally, the cosolvent is used in the preparation of the Group 3a complex. Suitable cosolvents are miscible with the liquid carrier contained in the selenium/Group 3a ink and do not have the effect of destabilizing the selenium/Group 3a ink. Preferred cosolvents further exhibit a boiling point within 30° C. of the boiling point of the liquid carrier contained in the selenium/Group 3a ink.
Optionally, the method of preparing the selenium/Group 3a ink of the present invention, further comprises: providing an optional additive selected from the group consisting of aromatic thiols, saturated cyclic thiols and carboxylic acids that do not have the effect of destabilizing the selenium/Group 3a ink; and, combining the optional additive with the selenium component, the Group 3a complex and the liquid carrier. Preferably, optional additives provided in solid form (e.g., p-toluene thiol which is a solid under atmospheric conditions) are combined with solid Group 3a complexes before the addition of liquid carrier. Preferably, optional additives provided in liquid form (e.g., acetic acid) are added to an already combined Group 3a complex and liquid carrier. Preferred optional additives for use in indium containing selenium/Group 3a inks of the present invention are selected from p-toluene thiol, cyclohexyl mercaptan, 2-mercaptopropionic acid; formic acid; trifluoroacetic acid; acetic acid; propionic acid and mixtures thereof. Preferred optional additives for use in gallium containing selenium/Group 3a inks of the present invention are selected from p-toluene thiol, cyclohexyl mercaptan, 2-ethylbutyric acid, mercaptoproprionic acid, formic acid, trifluoroacetic acid, acetic acid, propionic acid and mixtures thereof.
Optionally, the method of preparing the selenium/Group 3a ink of the present invention, further comprises: providing an optional agent; and, combining the optional agent with the liquid carrier; wherein the optional agent is selected from a dispersant, a wetting agent, a polymer, a binder, an anti-foaming agent, an emulsifying agent, a drying agent, a filler, an extender, a film conditioning agent, an antioxidant, a plasticizer, a preservative, a thickening agent, a flow control agent, a leveling agent, a corrosion inhibitor and a dopant.
The selenium/Group 3a ink of the present invention can be used in, for example, the manufacture of switches, photovoltaics (either in preparation of a CIGS absorber layer or a γ-In2Se3 window layer), nonlinear optics, ionic batteries and high density phase change data storage devices.
The method of applying a MaSeh material on a substrate using the selenium/Group 3a ink of the present invention, comprises: providing a substrate; providing a selenium/Group 3a ink of the present invention and applying the selenium/Group 3a ink to the substrate forming a MaSeh precursor on the substrate; treating the MaSeh precursor to remove the liquid carrier depositing a MaSeh material on the substrate; wherein the mole ratio of selenium to M in the selenium/Group 3a ink is 6:1 to 1:6 (preferably 3:1 to 1:3; more preferably 2:1 to 1:2; most preferably 1, 5:1 to 1:1.5); wherein M is at least one Group 3a material selected from aluminum, gallium, indium and thallium (preferably gallium and indium; most preferably indium); and wherein the mole ratio of M to Se in the deposited MaSeh material on the substrate is 6:1 to 1:6 (preferably 3:1 to 1:3; more preferably 2:1 to 1:2; most preferably 1.5:1 to 1:1.5).
In the method of applying a MaSeh material on a substrate using a selenium/Group 3a ink of the present invention, the selenium/Group 3a ink of the present invention can be applied to the substrate using conventional liquid processing techniques such as wet coating, spray coating, spin coating, doctor blade coating, contact printing, top feed reverse printing, bottom feed reverse printing, nozzle feed reverse printing, gravure printing, microgravure printing, reverse microgravure printing, comma direct printing, roller coating, slot die coating, meyerbar coating, lip direct coating, dual lip direct coating, capillary coating, ink-jet printing, jet deposition, spray pyrolysis and spray deposition. Optionally, the selenium/Group 3a ink of the present invention can be applied to the substrate using conventional spray pyrolysis techniques. Preferably, the selenium/Group 3a ink of the present invention is applied to the substrate under an inert atmosphere (e.g., under nitrogen).
After applying a selenium/Group 3a ink of the present invention to a substrate, the deposited material is heated to remove any residual liquid carrier or cosolvent. Preferably, the deposited material is further annealed by subjecting it to a temperature of 200 to 650° C. with an annealing time of 0.5 to 60 minutes. When using the selenium/Group 3a ink of the present invention to deposit a In2Se3 window layer in a photovoltaic cell, it is desirable to anneal the deposited material with an annealing temperature of 350 to 450° C.
The substrate used in the method depositing a selenium/Group 3a ink of the present invention can be selected from conventional materials used in conjunction with the preparation of semiconductor systems. In some applications, the substrate can be a coating on a carrier substance, such as, glass, foil, and plastic (e.g., polyethylene terephthalate and polyimides). Optionally, the substrate is sufficiently flexible to facilitate roll-to-roll production of CIGS materials for use in photovoltaic devices. When used in the preparation of a CIGS absorber material, the substrate is preferably molybdenum. When used in the preparation of a window layer in a photovoltaic device, the substrate is preferably the absorber layer material.
Some embodiments of the present invention will now be described in detail in the following Examples. Note that the In(acac)3 (also known as indium (III) acetylacetonate and indium 2,4-pentanedionate) and Ga(acac)3 (also known as gallium (III) acetylacetonate and gallium 2,4-pentanedionate) used in the examples was obtained from Sigma-Aldrich.
EXAMPLES1-7
Preparation of Group 3a Complex in Liquid Carrier
The Group 3a complex and the liquid carrier identified in TABLE 1 were weighed out in air in the amount indicated in TABLE 1. The Group 3a complex and the liquid carrier were then combined in a glass vial with a stir bar and placed on a hot plate. The glass vial was then sealed and the contents stirred for 30 minutes with a hot plate set point temperature of 70° C. The hot plate set point temperature was then lowered to 50° C. and stirring continued for 3 hours. The hot plate was switched off and stirring was discontinued. Observations are provided in TABLE 1. Note that in some instances a white precipitate formed. In those instances where a white precipitate formed, the supernate (Group 3a complex in liquid carrier) was decanted drawn from the glass vial for use in the preparation of selenium/Group 3a inks.












TABLE 1






Group 3a
Mass of

Mass




Complex
3aC

of LC


Ex
(3aC)
(in g)
Liguid Carrier (LC)
(in g)
Observations




















1
In(acac)3
0.1007
1,3-diaminopropane
1.300
A


2
In(acac)3
0.071
diethylenetriamine
1.910
B


3
In(acac)3
0.073
triethylenetetramine
1.964
B


4
In(acac)3
0.068
tetramethylguanidine
1.836
B


5
In(acac)3
0.1007
tetramethylguanidine
1.300
B


6
In(acac)3
0.1007
1-methylimidazole
1.300
B


7
Ga(acac)3
0.102
tetramethylguanidine
1.836
B





A A gel formed after storage at room temperature (RT) for 24 hours.


B No precipitate (ppt) following storage at RT for 24 hrs.






EXAMPLES 8-36
Preparation of Group 3a Complex in Liquid Carrier+Additive
Group 3a complex plus additive in liquid carrier combinations were prepared using the materials and the amounts thereof indicated in TABLE 2. Specifically, the indicated Group 3a complex was weighed out in air in a glass vial with a stir bar in the amount indicated in TABLE 2. Any indicated additive in the solid state (e.g., p-toluene thiol) were then added to the glass vial in the amount indicated in TABLE 2, followed by addition of the indicated liquid carrier in the indicated amount and then the addition of any indicated additive in the liquid state in the indicated amount. The glass vial was then sealed up and inerted under nitrogen gas. The glass vial was then placed on a hot plate with stirring for 1 hour with a hot plate temperature set point of 23° C. The hot plate set point temperature was then raised to 70° C. and the vial was left on the hot plate with stirring for an hour. The hot plate was then turned off. Observations are provided in TABLE 2. Note that in some instances a white precipitate formed. In those instances where a white precipitate formed, the supernate product (Group 3a complex+additive in liquid carrier) was decanted drawn from the glass vial for use in the preparation of selenium/Group 3a inks.














TABLE 2






Group 3a
Mass

Mass

Mass




Complex
3aC
Liguid Carrier
LC
Additive
Ad


Ex
(3aC)
(in g)
(LC)
(in g)
(Ad)
(in g)
Observ






















8
In(acac)3
0.1006
1,3-diaminopropane
1.29
formic acid
0.011
C


9
In(acac)3
0.2015
1,3-diaminopropane
2.576
formic acid
0.023
F


10
In(acac)3
0.2010
1,3-diaminopropane
2.55
formic acid
0.045
E


11
In(acac)3
0.2018
1,3-diaminopropane
2.5424
trifluoro acetic acid
0.056
E


12
In(acac)3
0.2001
1,3-diaminopropane
2.4892
trifluoro acetic acid
0.111
E


13
In(acac)3
0.2004
1,3-diaminopropane
2.5704
acetic acid
0.029
E


14
In(acac)3
0.2016
1,3-diaminopropane
2.5396
acetic acid
0.059
E


15
In(acac)3
0.2008
1,3-diaminopropane
2.5631
propionic acid
0.036
E


16
In(acac)3
0.0210
1,3-diaminopropane
2.5267
propionic acid
0.072
E


17
In(acac)3
0.1006
1,3-diaminopropane
1.27
2-mercaptopropionic acid
0.026
C


18
In(acac)3
0.2014
1,3-diaminopropane
2.4948
2-mercaptopropionic acid
0.104
D


19
In(acac)3
0.2008
1,3-diaminopropane
2.5253
p-toluene thiol
0.074
D


20
In(acac)3
0.2001
1,3-diaminopropane
2.4528
p-toluene thiol
0.147
D


21
In(acac)3
0.2009
1,3-diaminopropane
2.5424
cyclohexyl mercaptan
0.113
D


22
In(acac)3
0.2005
1,3-diaminopropane
2.4864
cyclohexyl mercaptan
0.104
D


23
In(acac)3
0.1006
tetramethyl guanidine
1.29
formic acid
0.011
C


24
In(acac)3
0.1006
tetramethyl guanidine
1.27
2-mercaptopropionic acid
0.026
C


25
Ga(acac)3
0.296
1,3-diaminopropane
2.46
acetic acid
0.048
D


26
Ga(acac)3
0.295
1,3-diaminopropane
2.41
acetic acid
0.097
D


27
Ga(acac)3
0.297
1,3-diaminopropane
2.44
propionic acid
0.060
D


28
Ga(acac)3
0.297
1,3-diaminopropane
2.38
propionic acid
0.120
D


29
Ga(acac)3
0.295
1,3-diaminopropane
2.41
2-ethylbutyric acid
0.093
D


30
Ga(acac)3
0.297
1,3-diaminopropane
2.32
2-ethylbutyric acid
0.188
D


31
Ga(acac)3
0.296
1,3-diaminopropane
2.41
trifluoroacetic acid
0.092
F


32
Ga(acac)3
0.297
1,3-diaminopropane
2.32
trifluoroacetic acid
0.185
F


33
Ga(acac)3
0.2953
1,3-diaminopropane
2.3828
p-toluene thiol
0.122
F


34
Ga(acac)3
0.296
1,3-diaminopropane
2.2596
p-toluene thiol
0.244
F


35
Ga(acac)3
0.295
1,3-diaminopropane
2.4116
cyclohexyl mercaptan
0.093
G


36
Ga(acac)3
0.2957
1,3-diaminopropane
2.317
cyclohexyl mercaptan
0.187
G


37
Ga(acac)3
0.2954
1,3-diaminopropane
2.3338
2-mercaptopropionic acid
0.171
F


38
Ga(acac)3
0.2936
1,3-diaminopropane
2.4696
formic acid
0.037
F


39
Ga(acac)3
0.295
1,3-diaminopropane
2.43
formic acid
0.074
F





C No precipitate (ppt) upon storing at room temperature (RT) for 18 hrs.


D Slightly hazy solution, very small amount of white ppt following storage at RT for 18-36 hrs.


E Clear solution, very small amount of white ppt following storage at RT for 18-36 hrs.


F Clear solution, no ppt following storage at RT for 18-36 hrs.


G Hazy solution, no ppt following storage at RT for 18-36 hrs.






EXAMPLES 40-56
Preparation of Group 3a Complex in Liquid Carrier+Additives
Group 3a complex plus additives in liquid carrier combinations were prepared using the materials and the amounts thereof indicated in TABLE 3. Specifically, the indicated Group 3a complex was weighed out in air in a glass vial with a stir bar in the amount indicated in TABLE 3. Any indicated additives in the solid state (e.g., p-toluene thiol) were then added to the glass vial in the amount indicated in TABLE 3, followed by addition of the indicated liquid carrier in the indicated amount and then the addition of any indicated additives in the liquid state in the indicated amount. The glass vial was then sealed up and inerted under nitrogen gas. The glass vial was then placed on a hot plate with stirring for 1 hour with a hot plate temperature set point of 23° C. The hot plate set point temperature was then raised to 70° C. and the vial was left on the hot plate with stirring for an hour. The hot plate was then turned off. Observations are provided in TABLE 3. Note that in some instances a white precipitate formed. In those instances where a white precipitate formed, the supernate product (Group 3a complex+additives in liquid carrier) was decanted drawn from the glass vial.
















TABLE 3






Group 3a
Mass

Mass

Mass

Mass




Complex
3aC
Liguid Carrier
LC
Additive 1
Ad1
Additive 2
Ad2


Ex
(3aC)
(ing)
(LC)
(in g)
(Ad1)
(in g)
(Ad2)
(in g)
Observ.
























40
In(acac)3
0.201
1,3-diaminopropane
2.50
p-toluenethiol
0.074
formic acid
0.022
D


41
In(acac)3
0.201
1,3-diaminopropane
2.43
p-toluenethiol
0.148
formic acid
0.022
H


42
In(acac)3
0.201
1,3-diaminopropane
2.52
cyclohexyl mercaptan
0.057
formic acid
0.022
D


43
In(acac)3
0.201
1,3-diaminopropane
2.46
cyclohexyl mercaptan
0.113
formic acid
0.022
D


43
In(acac)3
0.200
1,3-diaminopropane
2.53
2-mercaptopropionic acid
0.052
formic acid
0.022
D


44
In(acac)3
0.2004
1,3-diaminopropane
2.548
acetic acid
0.029
formic acid
0.022
E


45
In(acac)3
0.2009
1,3-diaminopropane
2.52
2-ethyl butyric acid
0.057
formic acid
0.022
E


46
In(acac)3
0.2016
1,3-diaminopropane
2.5396
propionic acid
0.036
formic acid
0.023
E


47
In(acac)3
0.2017
1,3-diaminopropane
2.52
trifluoroacetic acid
0.056
formic acid
0.023
E


48
Ga(acac)3
0.295
1,3-diaminopropane
2.42
acetic acid
0.048
formic acid
0.037
D


49
Ga(acac)3
0.296
1,3-diaminopropane
2.37
2-ethylbutyric acid
0.094
formic acid
0.037
D


50
Ga(acac)3
0.295
1,3-diaminopropane
2.41
propionic acid
0.060
formic acid
0.037
D


51
Ga(acac)3
0.296
1,3-diaminopropane
2.37
trifluoroacetic acid
0.092
formic acid
0.037
D


52
Ga(acac)3
0.295
1,3-diaminopropane
2.35
p-toluenethiol
0.122
formic acid
0.037
F


53
Ga(acac)3
0.294
1,3-diaminopropane
2.23
p-toluenethiol
0.243
formic acid
0.037
F


54
Ga(acac)3
0.295
1,3-diaminopropane
2.37
cyclohexyl mercaptan
0.093
formic acid
0.037
F


55
Ga(acac)3
0.296
1,3-diaminopropane
2.28
cyclohexyl mercaptan
0.188
formic acid
0.037
F


56
Ga(acac)3
0.295
1,3-diaminopropane
2.38
2-mercaptopropionic acid
0.085
formic acid
0.037
F





C No precipitate (ppt) upon storing at room temperature (RT) for 18 hrs.


D Slightly hazy solution, very small amount of white ppt following storage at RT for 18-36 hrs.


E Clear solution, very small amount of white ppt following storage at RT for 18-36 hrs.


F Clear solution, no ppt following storage at RT for 18-36 hrs.


G Hazy solution, no ppt following storage at RT for 18-36 hrs.


H Large amount of white ppt following storage at RT for 18-36 hrs.






EXAMPLE 57
Preparation of Combined Selenium/Organic Chalcogenide Component
To a 250 mL 3-neck flask with a magnetic stir bar, 4.80 grams of selenium and 112.49 grams of ethylene diamine were added. The flask was equipped with a reflux condenser and septa. The flask was inerted under nitrogen. Then 2.94 mL of di-tert butylsulfide was added to the flask. The contents of the flask were refluxed at about 120° C. for 6.5 hours and then allowed to cool to room temperature providing a product combined selenium/organic chalcogenide component.
EXAMPLES 58-61
Preparation of Selenium/Group 3a Inks
The Selenium/Group 3a inks were prepared in a glove box. In each example, to a 2 mL vial, the noted mass of the combined selenium/organic chalcogenide component of Example 57 and the Group 3a complex in liquid carrier (G3aCinLC) noted in TABLE 4 in the amount noted in TABLE 4 were added. The contents of the vial were then mixed by vortexing for 5 seconds. After mixing of the contents of the 2 mL vial, observations were made as noted in TABLE 4.











TABLE 4






Product of

G3aCinLC




Ex. 57
Group 3a complex in
Mass



Mass added
liquid carrier
added


Ex
(in g)
(G3aCinLC)
(in g)
Observ.







58
0.354
Product of Example 2
10
I


59
0.473
Product of Example 2
10
I


60
0.354
Product of Example 3
10
I


61
0.473
Product of Example 3
10
I





I No precipitate (ppt) upon initial mixing, ppt formed after storage for 30 min at room temperature (RT).






EXAMPLE 62
Preparation of Combined Selenium/Organic Chalcogenide Component
To a 40 mL vial with a stir bar, 0.80 grams of selenium and 18.9 grams of 1,3-diaminopropane were added. The vial was equipped with a reflux condenser and septa. The vial was inerted under nitrogen. Then 326 μL of di-tert butyl-disulfide was added to the vial. The contents of the vial were refluxed at about 140° C. for 3.75 hours and then allowed to cool to room temperature providing a product combined selenium/organic chalcogenide component.
EXAMPLES 63-102
Preparation of Selenium/Group 3a Inks
The Selenium/Group 3a inks were prepared in a glove box. In each example, to a 2 mL vial, 5 drops of the combined selenium/organic chalcogenide component noted in TABLE and the Group 3a complex in liquid carrier (G3aCinLC) noted in TABLE 5 in the amount noted in TABLE 5 were added. The contents of the vial were then mixed by vortexing for 5 seconds. After mixing of the contents of the 2 mL vial, observations were made as noted TABLE 5.











TABLE 5






Combined
Group 3a
Vol.




selenium/organic
complex in
added



chalcogenide
liquid carrier
G3aCinLC
Ob-


Ex
component
(G3aCinLC)
(in drops)
serv.



















63
Product of Example 57
Product of Example 7
6
M


64
Product of Example 62
Product of Example 19
10
J


65
Product of Example 62
Product of Example 18
10
K


66
Product of Example 62
Product of Example 9
10
J


67
Product of Example 62
Product of Example 43
10
J


68
Product of Example 62
Product of Example 10
10
J


69
Product of Example 62
Product of Example 13
10
J


70
Product of Example 62
Product of Example 14
10
J


71
Product of Example 62
Product of Example 15
10
J


72
Product of Example 62
Product of Example 16
10
J


73
Product of Example 62
Product of Example 44
10
J


74
Product of Example 62
Product of Example 45
10
J


75
Product of Example 62
Product of Example 46
10
J


76
Product of Example 62
Product of Example 47
10
J


77
Product of Example 62
Product of Example 11
10
J


78
Product of Example 62
Product of Example 12
10
J


79
Product of Example 62
Product of Example 25
6
L


80
Product of Example 62
Product of Example 26
6
L


81
Product of Example 62
Product of Example 27
6
L


82
Product of Example 62
Product of Example 28
6
L


83
Product of Example 62
Product of Example 29
6
J


84
Product of Example 62
Product of Example 30
6
J


85
Product of Example 62
Product of Example 48
6
L


86
Product of Example 62
Product of Example 49
6
J


87
Product of Example 62
Product of Example 50
6
L


88
Product of Example 62
Product of Example 51
6
L


89
Product of Example 62
Product of Example 31
6
L


90
Product of Example 62
Product of Example 32
6
L


91
Product of Example 62
Product of Example 33
6
L


92
Product of Example 62
Product of Example 34
6
L


93
Product of Example 62
Product of Example 35
6
L


94
Product of Example 62
Product of Example 36
6
L


95
Product of Example 62
Product of Example 37
6
J


96
Product of Example 62
Product of Example 38
6
L


97
Product of Example 62
Product of Example 52
6
L


98
Product of Example 62
Product of Example 53
6
L


99
Product of Example 62
Product of Example 54
6
L


100
Product of Example 62
Product of Example 55
6
L


101
Product of Example 62
Product of Example 56
6
L


102
Product of Example 62
Product of Example 39
6
L





J No precipitate (ppt) upon initial mixing, no ppt after storage for 2 hrs at room temperature (RT).


K No ppt upon initial mixing, ppt formed after storage for 5 min. at RT.


L No ppt upon initial mixing; no ppt after storage for 5 min. at RT; no ppt after storage for 2 hrs at RT; thin layer attracted to bottom of container after storage for 2 hrs at RT.


M No ppt upon initial mixing, ppt formed after storage for 16 hrs at RT.






EXAMPLES 103-109
Preparation of Selenium/Group 3a Films
The films of Examples 103-109 were prepared in a glove box under a nitrogen atmosphere. The substrate used for the preparation of the films in Examples 103-109 was a 5×5 mm piece of molybdenum-coated glass. In each example, the substrate was heated on a hotplate set at 80° C. In each example, one drop of the Selenium/Group 3a ink noted in TABLE 6 was placed onto the substrate. After dropping the Selenium/Group 3a ink on the substrate, the hotplate set point temperature was ramped to 400° C. over a ramp time of about 15 minutes. The hotplate set point temperature was then held for 5 minutes at 400° C., before being switched off. The substrate was then allowed to cool to room temperature on the surface of the hotplate. The product films were then analyzed by at least one of x-ray defraction (2-theta scan) (“XRD”) and energy dispersive x-ray spectroscopy (“EDS”) as noted in TABLE 6. Those films analyzed by x-ray defraction (2-theta scan) were analyzed using a Rigaku D/MAX 2500 at 50 kV/200 mA of nickel filtered copper Kα radiation. The samples were scanned from 5 to 90 degrees of 2θ in steps of 0.03 degrees at 0.75 degrees/min. Reflection geometry was used and the samples were rotated at 20 RPM. The XRD scan output for Example 103 showed the presence of two phases; one of which can be matched to literature reports for a cubic InaSeh phase. (See Malik, et al., Atmospheric pressure synthesis of In2Se3, Cu2Se, and CuInSe2 without external selenization from solution precursors, J. MATER. RES., vol. 24, pp. 1375-1387 (2009)). The XRD scan output for Examples 104 and 105 showed the presence of only the cubic InaSeh phase. EDS samples were mounted on conductive carbon tape and examined uncoated in a Hitachi 3400 VP-SEM in variable pressure mode. EDS spectra were collected with a 30 mm2 SD Detector at 15 KeV. The XRD scan output for Examples 107 through 109 showed an unidentified GaaSeh phase that is believed to be analogous to the cubic InaSeh phase. The EDS data provide the weight % ratio between the Group 3a material and selenium in the deposited films. The EDS data also show from 5-15 wt % carbon content in the unoptimized films and a signal from the underlying molybdenum substrate.









TABLE 6









Results









EDS Film



Composition














Selenium/Group 3a


In
Ga
Se


Ex
Ink
XRD
EDS
(wt %)
(wt %)
(wt %)





103
Product of Example 64
Yes
Yes
55
—
45






46

54


104
Product of Example 68
Yes
No
—
—
—


105
Product of Example 72
Yes
Yes
54
—
46


106
Product of Example 71
No
Yes
56
—
44


107
Product of Example 71
Yes
Yes
—
47
53


108
Product of Example 96
Yes
Yes
—
55
45


109
Product of Example 99
Yes
No
—
—
—

## Claims

1. A selenium/Group 3a ink, comprising
(a) a selenium/Group 3a complex which comprises a combination of, as initial components:
a selenium component comprising selenium;
an organic chalcogenide component having a formula selected from RZ—Z′R′and R2—SH; wherein Z and Z′ are each independently selected from sulfur, selenium and tellurium; wherein R is selected from H, C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; wherein R′ and R2 are selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; and,
a Group 3a complex, comprising at least one Group 3a material selected from aluminum, indium, gallium and thallium complexed with a multidentate ligand; and,

(b) a liquid carrier;

wherein the selenium/Group 3a complex is stably dispersed in the liquid carrier.

2. The ink of claim 1, wherein Z and Z′ are both sulfur and wherein R and R′ are each independently selected from a phenyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group and a tert-butyl group.

3. The ink of claim 1, wherein the Group 3a complex is an indium complex.

4. The ink of claim 3, wherein the Group 3a complex further comprises an additive; wherein the additive is selected from p-toluene thiol, cyclohexyl mercaptan, 2-mercaptopropionic acid, formic acid, trifluoroacetic acid, acetic acid, propionic acid and mixtures thereof.

5. The ink of claim 1, wherein the Group 3a complex is a gallium complex.

6. The ink of claim 5, wherein the Group 3a complex further comprises an additive; wherein the additive is selected from p-toluene thiol, cyclohexyl mercaptan, 2-ethylbutyric acid, 2-mercaptopropionic acid, formic acid, trifluoroacetic acid, acetic acid, propionic acid and mixtures thereof.

7. The ink of claim 1, wherein the liquid carrier is a nitrogen containing solvent selected from (a) an amine solvent having two nitrogen atoms per molecule, wherein (i) the nitrogen atoms are separated by at least 3 carbon atoms in the molecular formula of the amine solvent or (ii) the nitrogen atoms are both constituents of an unsaturated ring structure in the molecular formula of the amine solvent; and (b) an amine solvent having three or more nitrogen atoms per molecule of the amine solvent.

8. The ink of claim 1, wherein the selenium component and the organic chalcogenide component are combined to form a combined selenium/organic chalcogenide component; wherein the combined selenium/organic chalcogenide component comprise a chemical compound having a formula RZ—Set—Z′R′; wherein 2≦t≦20.

9. A method of preparing a selenium/Group 3a ink according to claim 1, comprising:
providing a selenium component, comprising selenium;
providing an organic chalcogenide component having a formula selected from RZ—Z′R′ and R2—SH; wherein Z and Z′ are each independently selected from sulfur, selenium and tellurium; wherein R is selected from H, C1-20 alkyl group, a C6-20aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; wherein R′ and R2 are selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group;
providing a liquid carrier;
combining the selenium component, the organic chalcogenide component and the liquid carrier; heating the combination with agitation to produce a combined selenium/organic chalcogenide component;
providing a Group 3a complex, comprising at least one Group 3a material selected from aluminum, indium, gallium and thallium complexed with a multidentate ligand; and,
combining the combined selenium/organic chalcogenide component and the Group 3a complex to form the selenium/Group 3a ink; wherein the selenium/Group 3a ink is a stable dispersion.

10. A method for depositing a MaSeh material on a substrate, comprising:
providing a substrate;
forming a selenium/Group 3a ink, comprising:
providing a selenium component, comprising selenium;
providing an organic chalcogenide component having a formula selected from RZ—Z′R′ and R2—SH; wherein Z and Z′ are each independently selected from sulfur, selenium and tellurium; wherein R is selected from H, C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group; wherein R′ and R2 are selected from a C1-20 alkyl group, a C6-20 aryl group, a C1-20 hydroxyalkyl group, an arylether group and an alkylether group;
providing a liquid carrier;
combining the selenium component, the organic chalcogenide component and the liquid carrier; heating the combination with agitation to produce a combined selenium/organic chalcogenide component;
providing a Group 3a complex, comprising at least one Group 3a material selected from aluminum, indium, gallium and thallium complexed with a multidentate ligand; and,
combining the combined selenium/organic chalcogenide component and the Group 3a complex to form the selenium/Group 3a ink; wherein the selenium/Group 3a ink is a stable dispersion;

depositing the selenium/Group 3a ink on the substrate;
heating the deposited selenium/Group 3a ink to eliminate the liquid carrier leaving a MaSeh material, wherein the mole ratio of M to Se in the deposited MaSeh material on the substrate is 6:1 to 1:6; and,
optionally, annealing the deposited MaSeh material.