Devices having dielectric layers with thiosulfate-containing polymers
View Patent ↗A semiconductor device can be prepared with a gate dielectric layer that 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 comprising (a) recurring units comprising pendant thiosulfate groups; and further comprises charge balancing cations, and (2) optionally, an electron-accepting photosensitizer component.
1. A device comprising a gate dielectric layer that comprises:
(1) a photochemically crosslinked product derived from a photocurable curable thiosulfate-containing polymer that has a T g of at least 50° C.,
wherein the photocurable thiosulfate-containing polymer comprises: an organic polymer backbone that comprises at least one repeating unit comprising: (a) recurring units comprising pendant thiosulfate groups; and the photocurable thiosulfate-containing polymer further comprises, either within the (a) recurring units or within recurring units different from the (a) recurring units, charge balancing cations, and 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, and
(2) optionally, an electron-accepting photosensitizer component.
2. The device of claim 1 , wherein the gate dielectric layer comprises a crosslinked disulfide polymer derived from the photocurable thiosulfate-containing polymer provided in a precursor dielectric composition that further comprises one or more organic solvents in which the photocurable thiosulfate-containing polymer is dissolved or dispersed.
3. The device of claim 1 , wherein the photochemically crosslinked product comprises less than 2 mol % of the original pendant thiosulfate groups that are not crosslinked.
4. The device 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 thiosulfate-containing polymer.
5. The device of claim 1 , wherein the charge balancing cations are part of the organic polymer backbone of the photocurable curable thiosulfate-containing polymer and are not part of pendant groups attached to the organic polymer backbone.
6. The device 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 thiosulfate-containing polymer.
7. The device of claim 6 , wherein Q + is a quaternary ammonium cation, pyridinium cation, morpholinium cation, or thiazolium cation.
8. The device of claim 1 , wherein the photocurable thiosulfate-containing polymer further comprises (b) recurring units that comprise the charge balancing cations, which photocurable 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 thiosulfate-containing polymer.
9. The device of claim 1 , wherein the photocurable 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 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 thiosulfate-containing polymer.
10. The device of claim 1 , wherein the gate dielectric layer further comprises the electron-accepting photosensitizer component.
11. The device of claim 1 , wherein the photocurable 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 thiosulfate-containing polymer.
12. The device of claim 1 further comprising an organic semiconductor layer that is in physical contact with the gate dielectric layer.
13. The device of claim 1 that is a thin film transistor that comprises a gate electrode, the gate dielectric layer, an organic semiconductor layer, and source and drain electrodes formed on a substrate that is glass substrate, silicon wafer, or a flexible polymeric film.
14. A device comprising:
a substrate,
a gate electrode disposed over the substrate,
a gate dielectric layer,
a thin film of a semiconductor material adjacent the gate dielectric layer, and
a source electrode and a drain electrode contiguous to the thin film of the semiconductor material,
wherein the gate dielectric layer comprises a crosslinked disulfide polymer product that is derived from a precursor dielectric composition comprising:
(1) a photochemically crosslinked product derived from a photocurable curable thiosulfate-containing polymer that has a T g of at least 50° C.,
wherein the photocurable thiosulfate-containing polymer comprises: an organic polymer backbone that comprises at least one repeating unit comprising: (a) recurring units comprising pendant thiosulfate groups; and the photocurable thiosulfate-containing polymer further comprises, either within the (a) recurring units or within recurring units different from the (a) recurring units, charge balancing cations, and 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, and
(2) optionally, an electron-accepting photosensitizer component.