Method for making devices having dielectric layers with thiosulfate-containing polymers

1. A method for preparing an electronic device comprising:

independently applying a precursor dielectric composition and an organic semiconductor composition to a substrate to form an applied precursor dielectric composition and an applied organic semiconductor composition, respectively, and

subjecting the applied precursor dielectric composition to curing conditions to form a gate dielectric layer comprising a photochemically cured or thermally cured product of a photocurable or thermally curable thiosulfate-containing polymer, which gate dielectric layer is in physical contact with the applied organic semiconductor composition,

wherein the precursor dielectric composition comprises:

(1) the photocurable or thermally curable thiosulfate-containing polymer that has a T g of at least 50° C. and that comprises: an organic polymer backbone that comprises at least one repeating unit comprising (a) recurring units comprising pendant thiosulfate groups; and the photocurable or thermally curable thiosulfate-containing polymers further comprises, either within the (a) recurring units or within recurring units different from the (a) recurring units, charge balancing cations,

wherein the photocurable thiosulfate-containing polymer has sensitivity to irradiation at a wavelength of from 150 nm to 700 nm to cause the pendant thiosulfate groups to form disulfide bonds;

(2) optionally, an electron-accepting photosensitizer component; and

(3) optionally, one or more organic solvents in which the photocurable or thermally curable thiosulfate polymer is dissolved or dispersed.

2. The method of claim 1 comprising, in order:

applying the precursor dielectric composition to the substrate to form the applied precursor dielectric composition,

removing any solvents from the applied precursor dielectric composition,

simultaneously or subsequently, curing the applied precursor dielectric composition to form a gate dielectric layer comprising a crosslinked disulfide polymer,

applying the organic semiconductor composition to the gate dielectric layer to form the applied organic semiconductor layer, and

forming one or more sets of electrically conductive source and drain electrodes on the applied organic semiconductor layer.

3. The method of claim 1 , wherein the precursor dielectric composition further comprises one or more organic solvents in which the photocurable or thermally curable thiosulfate-containing polymer is dissolved or dispersed.

4. The method of claim 1 , wherein the charge balancing cations are within the (a) recurring units and form binary salts with the pendant thiosulfate groups in the (a) recurring units that are represented by the following structure (I):

wherein R represents the organic polymer backbone, G is a single bond or a divalent linking group, M represents a charge balancing cation, and “a” represents at least 0.5 mol % and up to and including 100 mol % of (a) recurring units, based on the total recurring units in the photocurable or thermally curable thiosulfate-containing polymer.

5. The method of claim 1 , wherein the charge balancing cations are part of the organic polymer backbone of the photocurable or thermally curable thiosulfate-containing polymer and are not part of pendant groups attached to the organic polymer backbone.

6. The method of claim 1 , wherein the charge balancing cations are within the (a) recurring units and form zwitterionic groups with the pendant thiosulfate groups in the (a) recurring units that are represented by the following structure (II):

wherein R represents the organic polymer backbone, G is a single bond or divalent linking group, Q + is an organic charge balancing cation, and “a” represents at least 0.5 mol % and up to and including 100 mol % of (a) recurring units, based on the total recurring units in the photocurable or thermally curable thiosulfate-containing polymer.

7. The method of claim 6 , wherein Q + is a quaternary ammonium cation, pyridinium cation, morpholinium cation, or thiazolium cation.

8. The method of claim 1 , wherein the photocurable or thermally curable thiosulfate-containing polymer further comprises (b) recurring units that comprise the charge balancing cations, which photocurable or thermally curable thiosulfate-containing polymer is represented by the following structure (III):

wherein R represents the organic polymer backbone, G is a single bond or a divalent linking group, M + represents a charge balancing cation, “a” represents at least 0.5 mol % and up to and including 50 mol % of (a) recurring units, and “b” represents (b) recurring units and is at least equal to the “a” mol %, based on the total recurring units in the photocurable or thermally curable thiosulfate-containing polymer.

9. The method of claim 1 , wherein the photocurable or thermally curable thiosulfate-containing polymer further comprises:

(c) recurring units that are represented by the following structure (IV);

(d) recurring units that are represented by the following structure (V); or both (c) recurring units and (d) recurring units:

wherein R′ represents the organic polymer backbone, G′ is a single bond or a divalent linking group, R 2 is a electron-accepting photosensitizer component, and “c” represents at least 1 mol % and up to and including 10 mol % of (c) recurring units, based on the total recurring units in the photocurable or thermally curable thiosulfate-containing polymer;

wherein R″ represents the organic polymer backbone, G″ is a carbonyloxy group, R 3 comprises a monovalent linear, branched, or carbocyclic non-aromatic hydrocarbon group having 1 to 18 carbon atoms, or it comprises a phenyl group that has one or more linear, branched, or carbocyclic non-aromatic hydrocarbon substituents, at least one of which linear, branched, or carbocyclic non-aromatic hydrocarbon substituents has at least 6 carbon atoms and up to and including 18 carbon atoms, and “d” represents at least 1 mol % and up to and including 40 mol % of (d) recurring units, based on the total recurring units in the photocurable or thermally curable thiosulfate-containing polymer.

10. The method of claim 1 , wherein the precursor dielectric composition further comprises the electron-accepting photosensitizer component.

11. The method of claim 1 , wherein the photocurable or thermally curable thiosulfate-containing polymer comprises the (a) recurring units in an amount of at least 0.5 mol % and up to and including 50 mol %, based on total recurring units in the photocurable or thermally curable thiosulfate-containing polymer.

12. The method of claim 1 , further providing a gate electrode, and source and drain electrodes on the substrate that is glass substrate, silicon wafer, or a flexible polymeric film.

13. The method of claim 1 , wherein the precursor dielectric composition comprises a photocurable thiosulfate-containing polymer that has a sensitivity to irradiation at a wavelength of at least 150 nm and up to and including 450 nm to cause the pendant thiosulfate groups to form disulfide bonds.

14. The method of claim 1 , wherein the photocurable or thermally curable thiosulfate-containing polymer is present in the gate dielectric layer in an amount of at least 90 weight % and up to and including 100 weight %, based on the total dry weight of the gate dielectric layer.

15. The method of claim 1 , wherein the substrate is a flexible substrate and the method is carried out in a roll-to-roll manufacturing operation.

16. The method of claim 1 , wherein the substrate is combined with a temporary support that is detachable adhered or mechanically affixed to the substrate.

17. A process for fabricating a thin-film semiconductor device, comprising:

providing a substrate,

providing a gate electrode material over the substrate,

providing a gate dielectric layer over the gate electrode material,

providing a thin film of an organic semiconductor material, and

providing a source electrode and a drain electrode contiguous to the thin-film of the organic semiconductor material,

wherein the dielectric gate layer comprises:

(1) a photochemically or thermally crosslinked product of a photocurable or thermally curable thiosulfate-containing polymer that has a T g of at least 50° C. and that comprises: an organic polymer backbone that comprises at least one recurring unit comprising: (a) recurring units comprising pendant thiosulfate groups; and the photocurable or thermally curable thiosulfate-containing polymer further comprises, either within the (a) recurring units or within recurring units different from the (a) recurring units, charge balancing cations,

wherein the photocurable thiosulfate-containing polymer has sensitivity to irradiation to a wavelength of from 150 nm to 700 nm to cause the pendant thiosulfate groups to form disulfide bonds; and

(2) optionally, an electron-accepting photosensitizer component.

18. The process of claim 17 , wherein the substrate is a flexible polymeric substrate.

19. The method of claim 17 , wherein:

(A) the photocurable or thermally curable thiosulfate-containing polymer comprises:

(a) recurring units that are represented by the following structure (I) or structure (II), or both structures (I) and (II):

wherein R represents the organic polymer backbone, G is a single bond or divalent linking group, Q + is an organic charge balancing cation, M represents a charge balancing cation, and “a” represents at least 0.5 mol % and up to and including 100 mol % of (a) recurring units, based on the total recurring units in the photocurable or thermally curable thiosulfate-containing polymer; or

(B) the photocurable or thermally curable thiosulfate-containing polymer is represented by the following structure (III):

wherein R represents the organic polymer backbone, G is a single bond or a divalent linking group, M + is a charge balancing cation, “a” represents at least 0.5 mol % and up to and including 50 mol % of (a) recurring units, and “b” represents the mol % of (b) recurring units and is at least equal to the “a” mol %, based on the total recurring units in the photocurable or thermally curable thiosulfate-containing polymer; and

(C) wherein the photocurable or thermally curable thiosulfate-containing polymer of (A) or (B) optionally further comprises:

(c) recurring units that are represented by the following structure (IV);

(d) recurring units that are represented by the following structure (V); or

both (c) recurring units and (d) recurring units:

wherein R′ represents the organic polymer backbone, G′ is a single bond or a divalent linking group, R 2 is a electron-accepting photosensitizer component, and “c” represents at least 1 mol % and up to and including 10 mol % of (c) recurring units, based on the total recurring units in the photocurable or thermally-curable thiosulfate-containing polymer;

wherein R″ represents the organic polymer backbone, G″ is a carbonyloxy group, R 3 comprises a monovalent linear, branched, or carbocyclic non-aromatic hydrocarbon group having 1 to 18 carbon atoms, or it comprises a phenyl group having one or more linear, branched, or carbocyclic non-aromatic hydrocarbon substituents, at least one of which linear, branched, or carbocyclic non-aromatic hydrocarbon substituents has at least 6 carbon atoms and up to and including 18 carbon atoms, and “d” represents at least 1 mol % and up to and including 40 mol % of (d) recurring units, based on the total recurring units in the photocurable or thermally-curable thiosulfate-containing polymer.