Photopatternable compositions, patterned high k thin film dielectrics and related devices
The present teachings relate to a photopatternable composition including a vinylidene fluoride-based polymer, a photosensitive non-nucleophilic base, and a crosslinking agent. The photopatternable composition can be used to prepare a patterned thin film component for use in an electronic, optical, or optoelectronic device such as an organic thin film transistor. The patterned thin film component can be used as a gate dielectric with a high dielectric constant, for example, a dielectric constant greater than 10.
1. A method of forming a patterned thin film component for use in an electronic, optical, or optoelectronic device, the method comprising:
depositing onto a substrate a photopatternable composition to provide a thin film;
exposing the thin film to radiation in an imagewise pattern such that unexposed areas of the thin film are soluble in a developing agent and exposed areas of the thin film become insoluble in the developing agent; and
removing the unexposed areas of the thin film with the developing agent to provide a patterned thin film component;
wherein the photopatternable composition comprises a vinylidene fluoride-based polymer, a photosensitive non-nucleophilic base, and a crosslinking agent, wherein:
the vinylidene fluoride-based polymer comprises a first repeating unit that is vinylidene fluoride, a second repeating unit selected from the group consisting of vinyl fluoride, trifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene, vinylidene chloride, and hexafluoropropylene;
the photosensitive non-nucleophilic base is represented by one of the formulae selected from the group consisting of:
wherein
Y is selected from the group consisting of C═C, CR 2 , NR, O, S, and Se, wherein R is H, a C 1-6 alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group;
Z is selected from the group consisting of NR, an optionally substituted pyridyl group, or a covalent bond;
R a , R b , R c , and R d independently are H, a C 1-6 alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group, or R a and R b together and/or R c and R d together can be joined with the nitrogen atom to form a guanidinyl group or a triaminophosphazenyl group;
R e and R f independently are a halo group, a cyano group, a nitro group, a C 1-6 alkyl group, a C 1-6 haloalkyl group, or a C 1-6 alkoxy group;
R g , R h , R i , and R j independently are H, a halo group, a cyano group, a nitro group, a C 1-6 alkyl group, a C 1-6 haloalkyl group, or a C 1-6 alkoxy group, an optionally substituted phenyl group, or an optionally substituted benzyl group, or R g and R h together or R h and R i together or R i and R j together can be joined with the two carbon atoms therebetween to form an optionally substituted C 6-14 aryl group or an optionally substituted 5-14 membered heteroaryl group;
R k , R l , R m and R n independently are H, a halo group, a cyano group, a nitro group, a C 1-6 alkyl group, a C 1-6 haloalkyl group, or a C 1-6 alkoxy group, an optionally substituted phenyl group, or an optionally substituted benzyl group, or R k and R l together or R l and R m together or R m and R n together can be joined with the two carbon atoms therebetween to form an optionally substituted C 6-14 aryl group or an optionally substituted 5-14 membered heteroaryl group; or
if neither R g and R h together nor R m and R n together join to form an optionally substituted C 6-14 aryl group or an optionally substituted 5-14 membered heteroaryl group, then R g and R n together can be joined with Q and the four carbon atoms therebetween to form an optionally substituted C 6-14 aryl group or an optionally substituted 5-14 membered heteroaryl group; and
n is 0, 1, 2 or 3; and
the crosslinking agent is not thermally activated and is not peroxide-based.
2. The method of claim 1 , wherein the photosensitive non-nucleophilic base is represented by one of the formulae selected from the group consisting of:
wherein each R 1 and R 2 independently is H or a C 1-6 alkyl group; each R 3 independently is a C 1-6 alkyl group or an optionally substituted benzyl group; and m is 0, 1, or 2.
3. The method of claim 1 , wherein the photosensitive non-nucleophilic base is selected from the group consisting of:
4. The method of claim 1 , wherein the vinylidene fluoride-based polymer is a copolymer selected from the group consisting of a copolymer of vinylidene fluoride and trifluoroethylene (P(VDF-TrFE)), a copolymer of vinylidene fluoride and chlorotrifluoroethylene (P(VDF-CTFE)), and a copolymer of vinylidene fluoride and hexafluoropropylene (P(VDF-HFP)), or a terpolymer selected from the group consisting of poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene), poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene), poly(vinylidene fluoride-trifluoroethylene-hexafluoropropylene), poly(vinylidene fluoride-trifluoroethylene-vinyl fluoride), and poly(vinylidene fluoride-trifluoroethylene-vinylidene chloride).
5. The method of claim 1 , wherein the vinylidene fluoride-based polymer is represented by formula (I):
wherein X 1 is H or Cl;
X 2 , X 3 , and X 4 are selected from the group consisting of H, F and Cl, provided that no more than one of X 2 , X 3 , and X 4 is Cl and not all of X 2 , X 3 , and X 4 are F;
x is between about 30 mol % and about 85 mol %;
y is between about 10 mol % and about 65 mol %; and
x+y≤100 mol %.
6. The method of claim 5 , wherein xis between about 55 mol % and about 75 mol %, and y is between about 15 mol % and about 35 mol %.
7. The method of claim 1 , wherein the crosslinking agent comprises two or more crosslinking groups independently selected from the group consisting of maleimide, amine, thiol, phenol, cinnamate and coumarin groups.
8. The method of claim 1 , wherein the crosslinking agent does not absorb in the same wavelengths as the photosensitive non-nucleophilic base.
9. The method of claim 1 , wherein the photosensitive non-nucleophilic base and the crosslinking agent individually are present in the composition at less than about 10 wt % of the vinylidene fluoride-based polymer.
10. The method of claim 1 , wherein the photopatternable composition comprises an organic solvent selected from the group consisting of ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, cyclohexyl acetate, heptyl acetate, ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, γ-butyrolactone, acetone, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, 2-butanone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, cyclopentanone, and cyclohexanone.
11. The method of claim 10 , wherein the vinylidene fluoride-based polymer and the organic solvent have a weight-to-volume ratio between about 20 mg/ml and about 100 mg/ml.
12. The method of claim 1 comprising providing an organic thin film adjacent to the patterned thin film component, wherein the organic thin film comprises a non-ferroelectric polymer.
13. The method of claim 12 , wherein the non-ferroelectric polymer is selected from the group consisting of perfluoro(1-butenyl vinyl ether) homocyclopolymer polystyrene, polyethylene, poly-alpha-methyl styrene, polyisobutene, polypropylene, polyvinylcyclohexane, and polymethylmethacrylate.
14. The method of claim 1 , wherein the electronic, optical, or optoelectronic device is an organic field-effect transistor comprising the patterned thin film component as the gate dielectric, wherein the organic field-effect transistor operates at voltages less than about |40| V.
15. The method of claim 1 , wherein the electronic, optical, or optoelectronic device is an organic light-emitting transistor comprising the patterned thin film component as the gate dielectric, wherein the organic light-emitting transistor operates at voltages less than about |40| V.
16. The method of claim 15 , wherein the organic light-emitting transistor comprises a trilayer active layer, wherein the trilayer active layer comprises an emissive sublayer disposed between a hole transport sublayer and an electron transport sublayer.
17. An organic thin film transistor comprising a patterned thin film component as the gate dielectric, wherein the patterned thin film component is made by the method of claim 1 and comprises a crosslinked polymer material, the crosslinked polymer material comprising a vinylidene fluoride-based polymer, a non-nucleophilic base, and a crosslinking agent, wherein the vinylidene fluoride-based polymer is crosslinked by the crosslinking agent, and wherein:
the vinylidene fluoride-based polymer comprises a first repeating unit that is vinylidene fluoride, a second repeating unit selected from the group consisting of vinyl fluoride, trifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene, vinylidene chloride, and hexafluoropropylene;
the photosensitive non-nucleophilic base is represented by one of the formulae selected from the group consisting of:
wherein
Y is selected from the group consisting of C═C, CR 2 , NR, O, S, and Se, wherein R is H, a C 1-6 alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group;
Z is selected from the group consisting of NR, an optionally substituted pyridyl group, or a covalent bond;
R a , R b , R c , and R d independently are H, a C 1-6 alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group, or R a and R b together and/or R c and R d together can be joined with the nitrogen atom to form a guanidinyl group or a triaminophosphazenyl group;
R e and R f independently are a halo group, a cyano group, a nitro group, a C 1-6 alkyl group, a C 1-6 haloalkyl group, or a C 1-6 alkoxy group;
R g , R h , R i , and R j independently are H, a halo group, a cyano group, a nitro group, a C 1-6 alkyl group, a C 1-6 haloalkyl group, or a C 1-6 alkoxy group, an optionally substituted phenyl group, or an optionally substituted benzyl group, or R g and R h together or R h and R i together or R i and R j together can be joined with the two carbon atoms therebetween to form an optionally substituted C 6-14 aryl group or an optionally substituted 5-14 membered heteroaryl group;
R k , R l , R m and R n independently are H, a halo group, a cyano group, a nitro group, a C 1-6 alkyl group, a C 1-6 haloalkyl group, or a C 1-6 alkoxy group, an optionally substituted phenyl group, or an optionally substituted benzyl group, or R k and R l together or R l and R m together or R m and R n together can be joined with the two carbon atoms therebetween to form an optionally substituted C 6-14 aryl group or an optionally substituted 5-14 membered heteroaryl group; or
if neither R g and R h together nor R m and R n together join to form an optionally substituted C 6-14 aryl group or an optionally substituted 5-14 membered heteroaryl group, then R g and R n together can be joined with Q and the four carbon atoms therebetween to form an optionally substituted C 6-14 aryl group or an optionally substituted 5-14 membered heteroaryl group; and
n is 0, 1, 2 or 3; and
the crosslinking agent comprises two or more crosslinking groups independently selected from the group consisting of maleimide, amine, thiol, phenol, and cinnamate; and
wherein the organic thin film transistor further comprises a substrate, a gate electrode, source and drain electrodes, and an organic semiconductor layer, wherein the gate dielectric is positioned between the gate electrode and the organic semiconductor layer.
18. The organic thin film transistor of claim 17 further comprises an organic thin film comprising a non-ferroelectric polymer adjacent to the patterned thin film component, wherein the organic thin film prevents the vinylidene fluoride-based polymer in the patterned thin film component from forming ferroelectric domains when an electric field is applied to the patterned thin film component, and wherein the organic thin film is positioned between the patterned thin film component and either the organic semiconductor layer or the gate electrode.
19. A display device comprising at least one driving element, wherein the driving element comprises the organic thin film transistor of claim 17 .
20. A display device comprising at least one switching element, wherein the switching element comprises the organic thin film transistor of claim 17 .
21. The method according to claim 1 , wherein the vinylidene fluoride-based polymer further comprises a third repeating unit different from the second repeating unit that is selected from the group consisting of vinyl fluoride, chlorofluoroethylene, chlorotrifluoroethylene, vinylidene chloride, and hexafluoropropylene.
22. The method of claim 1 , wherein the crosslinking agent is selected from the group consisting of a bisphenol, a diamine having two amines that can react with the double bonds present in a dehydrohalogenated polymer via hydroamination, a bismaleimide, a multifunctional thiol, and a bis(cinnamate).
23. The method of claim 1 , wherein R a , R b , R c , and R d independently are a C 1-6 alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group, or R a and R b together and/or R c and R d together can be joined with the nitrogen atom to form a guanidinyl group or a triaminophosphazenyl group.
24. The method of claim 1 , wherein R a and R c independently are a H, C 1-6 alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group, or R a and R b together and/or R c and R d together can be joined with the nitrogen atom to form a guanidinyl group or a triaminophosphazenyl group; and R b and R d independently are a C 1-6 alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group, or R a and R b together and/or R c and R d together can be joined with the nitrogen atom to form a guanidinyl group or a triaminophosphazenyl group.