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WO2016100983A1 - Compositions photoréticulables, diélectriques structurés en couche mince à constante k élevée et dispositifs associés - Google Patents

Compositions photoréticulables, diélectriques structurés en couche mince à constante k élevée et dispositifs associés Download PDF

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WO2016100983A1
WO2016100983A1 PCT/US2015/067217 US2015067217W WO2016100983A1 WO 2016100983 A1 WO2016100983 A1 WO 2016100983A1 US 2015067217 W US2015067217 W US 2015067217W WO 2016100983 A1 WO2016100983 A1 WO 2016100983A1
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group
optionally substituted
thin film
alkyl group
membered heteroaryl
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Antonio Facchetti
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ETC SRL
Polyera Corp
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ETC SRL
Polyera Corp
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/471—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising only organic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/30—Organic light-emitting transistors

Definitions

  • the dielectric constants of state-of-the-art PVDF-based polymers e.g., poly(vinylidene fluoride- trifluoroethylene), P(VDF-TrFE); poly(vinylidene fluoride-trifluoroethylene- chlorofluoroethylene), P(VDF-TrFE-CFE); and poly(vinylidene fluoride-tetrafluoroethylene- hexafluoropropylene), P(VDF-TFE-FIFP)
  • P(VDF-TFE-FIFP) have been reported to be 20 or higher, and in some cases, 40 or higher, depending on the comonomers, backbone regiochemistry, and the ratio of the different repeating units.
  • Their applicability in low-voltage devices has been confirmed by incorporating such PVDF-based polymers as gate dielectrics in OFETs.
  • the present teachings relate to a photocrosslinkable composition that can be used to prepare a patterned thin film having a high dielectric constant, for example, a dielectric constant greater than 10.
  • the photocrosslinkable composition also may include a photocrosslinker.
  • the present teachings also relate to various electronic, optical, and optoelectronic devices including a gate dielectric component composed of a patterned thin film prepared from the photocrosslinkable composition.
  • Fig. 1 shows exemplary organic field-effect transistors (OFETs) having,
  • a bottom-gate top-contact (a), a bottom-gate bottom-contact structure (b), a top- gate bottom-contact structure (c), and a top-gate top-contact structure (d).
  • Fig. 2 shows the structure of an exemplary organic light-emitting transistor (OLET).
  • OLET organic light-emitting transistor
  • compositions are described as having, including, or comprising specific components, or where processes are described as having, including, or comprising specific process steps, it is contemplated that compositions of the present teachings also consist essentially of, or consist of, the recited components, and that the processes of the present teachings also consist essentially of, or consist of, the recited process steps.
  • halo or halogen refers to fluoro, chloro, bromo, and iodo.
  • alkyl refers to a straight-chain, branched, or cyclic saturated hydrocarbon group.
  • an alkyl group can have 1 to 40 carbon atoms (i.e., Ci-40 alkyl group), for example, 1-20 carbon atoms (i.e., C 1-20 alkyl group).
  • aryl refers to an aromatic monocyclic hydrocarbon ring system or a polycyclic ring system in which two or more aromatic hydrocarbon rings are fused (i.e., having a bond in common with) together or at least one aromatic monocyclic hydrocarbon ring is fused to one or more saturated (or nonaromatic) cyclic rings.
  • An aryl group can have 6 to 40 carbon atoms in its ring system, which can include multiple fused rings.
  • a polycyclic aryl group can have from 8 to 40 carbon atoms. Any suitable ring position of the aryl group can be covalently linked to the defined chemical
  • aryl groups having only aromatic carbocyclic ring(s) include phenyl, 1-naphthyl (bicyclic), 2-naphthyl (bicyclic), anthracenyl (tricyclic), phenanthrenyl (tricyclic), and like groups.
  • polycyclic ring systems in which at least one aromatic carbocyclic ring is fused to one or more saturated (or nonaromatic) cyclic rings include, among others, benzo derivatives of cyclopentane (i.e., an indanyl group, which is a 5,6- bicyclic cycloalkyl/aromatic ring system), cyclohexane (i.e., a tetrahydronaphthyl group, which is a 6,6-bicyclic cycloalkyl/aromatic ring system), imidazoline (i.e., a
  • benzimidazolinyl group which is a 5,6-bicyclic cycloheteroalkyl/aromatic ring system
  • pyran i.e., a chromenyl group, which is a 6,6-bicyclic cycloheteroalkyl/aromatic ring system
  • aryl groups include benzodioxanyl, benzodioxolyl, chromanyl, indolinyl groups, and the like. In some embodiments, aryl groups can be substituted as described herein.
  • heteroaryl refers to an aromatic monocyclic ring system
  • a heteroaryl group as a whole, can have, for example, 5 to 40 ring atoms and contain 1-5 ring
  • heteroaryl group can be attached to the defined chemical structure at any heteroatom or carbon atom that results in a stable structure.
  • C 1-6 alkyl is specifically intended to individually disclose Ci, C 2 , C 3 , C 4 , C 5 , C 6 , Ci-C 6 , C1-C5, C1-C4, C1-C3, C1-C2, C2-C6, C2-C5, C2-C4, C2-C3, C3-C6, C3-C5, C3-C4, C 4 -C 6 , C4-C 5 , and C 5 -C 6 alkyl.
  • an integer in the range of 0 to 40 is specifically intended to individually disclose 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40, and an integer in the range of 1 to 20 is specifically intended to individually disclose 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.
  • phrases "optionally substituted with 1-5 substituents” is specifically intended to individually disclose a chemical group that can include 0, 1, 2, 3, 4, 5, 0-5, 0-4, 0-3, 0-2, 0-1, 1-5, 1-4, 1-3, 1-2, 2-5, 2-4, 2-3, 3-5, 3-4, and 4-5 substituents.
  • a "dielectric material” has a conductivity in the order of 10 "6 Scm "1 or less to avoid current leakage to an adjacent electrical conductor.
  • the two components can be directly in contact (e.g., directly coupled to each other), or the two components can be coupled to each other via one or more intervening components or layers.
  • polymer refers to a molecule including a plurality of repeating units connected by covalent chemical bonds.
  • a polymeric compound can be represented by the general formula:
  • M is the repeating unit or monomer.
  • the polymeric compound can have only one type of repeating unit as well as two or more types of different repeating units. When a polymeric compound has only one type of repeating unit, it can be referred to as a homopolymer. When a polymeric compound has two or more types of different repeating units, the term "copolymer" can be used instead. For example, a copolymer can include repeating units
  • the assembly of the repeating units in the copolymer can be head-to-tail, head-to-head, or tail-to- tail.
  • the copolymer can be a random copolymer, an alternating copolymer, or a block co olymer. For example, the general formula:
  • a polymeric compound can be further characterized by its degree of polymerization (n) and molar mass (e.g., number average molecular weight (M n ) and/or weight average molecular weight (M w ) depending on the measuring technique(s)).
  • the present teachings relate to a photocrosslinkable composition
  • the partially fluorinated polymer can include (a) about 60-99 mol % of at least one of the following fluorinated repeating units:
  • X 2 , X 3 and X 4 independently are selected from the group consisting of H, F and CI, provided that no more than one of X 2 , X 3 , and X 4 is CI;
  • Z is selected from the group consisting of H, a C 1-20 alkyl group, an optionally substituted C 6 -i4 aryl group, and an optionally substituted 5-14 membered heteroaryl group; and n is 1 or 2;
  • Z is selected from the group consisting of H, a C 1-20 alkyl group, an optionally substituted C 6 -i4 aryl group, and an optionally substituted 5-14 membered heteroaryl group; and n is 1 or 2;
  • the partially fluorinated polymer can be characterized by a dielectric constant (k) that is greater than about 10, preferably greater than about 15, and more preferably, greater than about 20.
  • the present partially fluorinated polymer can include vinylidene fluoride (VDF) as at least one of the fluorinated repeating units.
  • VDF vinylidene fluoride
  • the present partially fluorinated polymer can be P(VDF-co-W), where W is a photocrosslinkable repeating unit as described herein.
  • the partially fluorinated polymer can include vinylidene fluoride as a first fluorinated repeating unit and at least a second fluorinated repeating unit selected from the group consisting of vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorofluoroethylene, and chlorotrifluoroethylene.
  • the partially fluorinated polymer can include vinylidene fluoride as a first fluorinated repeating unit, a second fluorinated repeating unit selected from the group consisting of vinyl fluoride, trifluoroethylene, and tetrafluoroethylene, and an optionally third fluorinated repeating unit different from the second fluorinated repeating unit that is selected from the group consisting of vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorofluoroethylene, and chl orotrifluoroethy 1 ene .
  • the one or more fluorinated repeating units and the one or more photocrosslinkable repeating units can be arranged such that they are regularly alternating (i.e., as an alternating polymer); or arranged in a repeating sequence (i.e., as a periodic polymer).
  • photocrosslinkable repeating units can provide a statistical or random polymer.
  • the partially fluorinated polymer can be represented by formula 1:
  • Xi is H or F
  • X 2 , X 3 , and X 4 are selected from the group consisting of H, F and CI, provided that no more than one of X 2 , X 3 , and 3 ⁇ 4 is CI;
  • W is a photocrosslinkable repeating unit having a formula selected from the group consisting of:
  • each Y independently is selected from the group consisting of H, halogen, and a C 1-20 alkyl group; x is between about 0 mol% and about 60 mol%, preferably between about 30 mol% and about 50 mol%; y is between about 0 mol% and about 60 mol%; z is between about 0 mol% and about 60 mol%; provided that x+y+z is between about 60 mol% and about 99 mol%.
  • the partially fluorinated polymer can be represented by formula 2:
  • W can have a formula selected from (1), (2), (3) and (4), where Z can be an unsubstituted or substituted C 6-14 aryl or 5-14 membered heteroaryl group.
  • Z can be a phenyl, naphthyl, or anthracenyl group optionally substituted with 1-5 groups independently selected from a halogen, CN, R, -O-R, -S-R, -C(0)-R, and -C(0)-0-R, wherein R, at each occurrence, is selected from a Ci-io alkyl group, a C 1-10 haloalkyl group, a C 2-10 alkenyl group, and a C 2-10 alkynyl group.
  • Z can be an unsubstituted 5- or 6-membered heteroaryl group or a 5- or 6-membered heteroaryl group substituted with 1-5 groups independently selected from a halogen, CN, oxo, R, -O-R, -S-R, -C(0)-R, and -C(0)-0-R, wherein R, at each occurrence, is selected from a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 2-10 alkenyl group, and a C 2-10 alkynyl group.
  • Examples of 5- or 6-membered heteroaryl groups include, without limitation, pyrrolyl, furyl, thienyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, and oxadiazolyl groups.
  • Z can be an unsubstituted 5-6 bicyclic heteroaryl group or a 5-6 bicyclic heteroaryl group substituted with 1-5 groups independently selected from a halogen, CN, oxo, R, -O-R, -S-R, -C(0)-R, and -C(0)-0-R, wherein R, at each occurrence, is selected from a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 2-10 alkenyl group, and a C 2-10 alkynyl group.
  • Examples of 5-6 bicyclic heteroaryl groups include, without limitation, indolyl, isoindolyl, benzofuryl, benzothienyl, quinolyl, 2-methylquinolyl, isoquinolyl, quinoxalyl, quinazolyl, benzotriazolyl,
  • benzimidazolyl benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxadiazolyl, benzoxazolyl, cinnolinyl, lH-indazolyl, 2H-indazolyl, indolizinyl, isobenzofuyl,
  • Z can be a C 1-20 alkyl group or a C 1-20 haloalkyl group.
  • W can have formula (V), where each Y independently is selected from H, CI, F, and CH 3 .
  • the partially fluorinated polymer can be synthesized using procedures known in the art for preparing copolymers comprising vinylidene fluoride.
  • the most common synthesis involves reacting a mixture of the appropriate vinyl monomers by free radical polymerization using a free radical initiator and optionally in the presence of a suitable catalyst.
  • organic free radical initiators include peroxides such as benzoyl peroxide,
  • acetylcyclohexanesulfonyl peroxide diacetylperoxydicarbonate, dialkylperoxydicarbonates, di-tertiary-butyl peroxide, and particularly, chlorocarbon-based and fluorocarbon-based acyl peroxides including trichloroacetyl peroxide, bis(perfluoro-2-propoxy propionyl) peroxide, and so forth.
  • Redox systems comprising an amine and a peroxide also may be used as free radical initiators to initiate the polymerization process. Examples of such redox systems include dimethylaniline-benzoyl peroxide, diethylaniline-benzoyl peroxide, and
  • the present polymer can be prepared by a combination of a bulk polymerization process and an oxygen-activated organoborane initiator at ambient temperature as described in U.S. Patent No. 6,355,769 and Chung et al., Macromolecules, 35: 7678-7684 (2002).
  • the polymerization reaction can be performed in a suspension, emulsion, or solution, and the monomers can be selected and contacted in the desired proportion as described herein.
  • the unsaturated repeating unit (W) can be initially
  • the precursor monomer can be hydroxyethyl methacrylate (HEMA) which, after polymerization with the
  • VP vinyl phenol
  • VA vinyl alcohol
  • acetylated analogs may be employed in the polymerization with fluoroolefins, followed by deacetylation with base, then reaction between the deprotected hydroxyl group and the appropriate acetyl chloride.
  • HEMA hydroxyl-functional monomers
  • VP VP
  • VA VP
  • acetylated analogs may be employed in the polymerization with fluoroolefins, followed by deacetylation with base, then reaction between the deprotected hydroxyl group and the appropriate acetyl chloride.
  • 4-acetoxystyrene may be used to provide a precursor copolymer of fluorinated repeating units and 4-acetoxystyrene.
  • Deacetylation can be performed by reacting the precursor copolymer with a strong base such as ammounium hydroxide to provide 4-hydroxystyrene.
  • Schemes 5 and 6 below illustrate possible synthetic schemes for preparing a polymer having an unsaturated repeating unit of formula (V).
  • acetylene is used as the monomer.
  • the present photocrosslinkable composition can include a crosslinker.
  • the crosslinker can be selected from various crosslinking agents that are known by those skilled in the art to be reactive with double bonds upon irradiaton.
  • the crosslinker can be a small molecule or a polymer having one or more thiol groups that can react with the double bonds present in the polymer via thiol-ene click chemistry, examples of which include poly(mercaptopropyl)methylsiloxane and pentaerythritol tetrakis(3-mercaptopropionate).
  • the crosslinker can be a small molecule or a polymer having one or more amine groups that can react with the double bonds present in the polymer via hydroamination, examples of which include ⁇ , ⁇ , ⁇ ' -trimethylethylenediamine, 1 ,2-diamino-4, 5-difluorobenzene, 4,7, 10-trioxo- 1,13- tridecanediamine, N,N'-bis(2-hydroxybenzyl) ethylenediamine, branched polyethylenimine, ethylenediamine, and Versalink® P-650 (an oligomeric diamine).
  • the crosslinker can be a small molecule or a polymer that can promote a [2+2] or a [2+4] cycloaddition; for example, such small molecule or polymer can have one or more vinyl groups such as one or more cinnamate groups.
  • the crosslinker can be a small molecule or a polymer having one or more maleimide groups that can react with the double bonds present in the polymer via, for example, conjugate addition. Specific examples include:
  • the partially fluorinated polymer, and if present, the crosslinker can be mobilized in a liquid medium to provide a composition (a photocrosslinkable composition) for forming a photocrosslinkable material.
  • the composition can be a solution, a dispersion, a suspension, an emulsion, or a gel, although in most embodiments, the composition is a solution or a dispersion suitable for solution-phase processes.
  • the term "mobilized in a liquid medium” broadly means that the designated liquid medium causes a designated solid to take on properties of a liquid. For example, the solid can be dissolved in the liquid medium to form a single-phase solution, or the solid can be dispersed in the liquid medium to form a two-phase dispersion.
  • the solid and the liquid medium can be combined together to form an emulsion, a suspension, or a gel.
  • solution means that a substantial proportion of a designated solute has formed a single phase with a designated solvent, but a substantial second phase that can include dispersed particulate matter also can be present.
  • the liquid medium can be an organic solvent or a solvent mixture in which the partially fluorinated polymer has satisfactory solubility.
  • a compound can be considered soluble in a solvent when at least 1 mg of the compound can be dissolved in 1 ml of the solvent. Examples of organic solvents that can be used in the present
  • photocrosslinkable composition include, but are not limited to, ester solvents such as 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 and ⁇ -butyrolactone; ketone solvents such as acetone, acetyl acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-butanone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, cyclopentanone, and cyclohexanone; halogenated solvents such as chloroform, carbon tet
  • the present photocrosslinkable composition can be used to deposit thin film materials via various solution-phase processes known in the art, where the thin film materials can be subsequently photocrosslinked and become insoluble in the mother liquid medium used for film deposition.
  • the solution-phase process can be selected from spin-coating, slot coating, printing (e.g., inkjet printing, screen printing, pad printing, offset printing, gravure printing, flexographic printing, lithographic printing, mass- printing and the like), spray coating, electrospray coating, drop casting, dip coating, and blade coating.
  • spin-coating involves applying an excess amount of the coating solution onto the substrate, then rotating the substrate at high speed to spread the fluid by centrifugal force.
  • the thickness of the resulting film prepared by this technique can be dependent on the spin- coating rate, the concentration of the solution, as well as the solvent used.
  • Printing can be performed, for example, with a rotogravure printing press, a flexoprinting press, pad printing, screen printing or an inkjet printer.
  • the thickness of the resulting film as processed by these printing methods can be dependent on the concentration of the solution, the choice of solvent, and the number of printing repetitions.
  • Ambient conditions such as temperature, pressure, and humidity also can affect the resulting thickness of the film.
  • printing quality can be affected by different parameters including, but not limited to, rheological properties of the formulations/compositions such as tension energy and viscosity.
  • the solubility requirement generally can be less stringent and a solubility range as low as about 1-4 mg/ml can suffice.
  • a solubility range may be necessary, often in the range of about 20-100 mg/ml.
  • Other contact printing techniques such as screen- printing and flexo printing can require even higher solubility ranges, for example, about 100- 1000 mg/ml.
  • the strength of the polymer in the present photocrosslinkable composition can be between about 1 mg/ml and about 200 mg/ml, preferably between about 20 mg/ml and about 100 mg/ml.
  • the present photocrosslinkable composition also can include one or more photosensitizers which absorb at an irradiation wavelength and then transfer either energy or an electron to the polymer and/or the crosslinker.
  • a photosensitizer can be added to make the polymer and/or the crosslinker more sensitive to (i.e., have stronger absorption at) longer wavelengths.
  • photosensitizers include a-acyloxy esters, acylphosphine oxides, benzoins, benzophenones, thioxanthones, anthracenes, perylenes, tetracenes, acetophenones, phenothiazones, 1,2-benzathracenes, phenothiazines, phenanthrenes, chrysenes, coronenes, benzpyrenes, fluoranthenes, rubrenes, pyrenes, indanthrenes, anthraquinones, acridones, coumarins and ketocoumarins, and derivatives thereof.
  • a combination of photosensitizers may be used. Specific examples include 4,4-bis(diethylamino)benzophenone,
  • the polymer, the crosslinker and if present, the photosensitizer can be photoactive to exposure to wavelengths between about 200 nm and about 500 nm.
  • the polymer, the crosslinker and if present, the photosensitizer can be photoactive to exposure to G (435.8 nm), H (404.7 nm), or I (365.4 nm) line of the spectrum.
  • the present composition also can include one or more additives, processing aids and/or fillers (e.g., metal oxide nanoparticles).
  • the present photocrosslinkable composition can exclude any inorganic (e.g., metal) fillers.
  • the total solid loading of all the non-polymer components i.e., the crosslinker, the photosensitizer, and any optional additives
  • Materials prepared from the present photocrosslinkable composition can be photopatterned directly (without using a photoresist). Accordingly, a patterned dielectric component can be formed by depositing a photocrosslinkable
  • composition according to the present teachings to provide an uncrosslinked film, subjecting the uncrosslinked film to actinic radiation in an imagewise pattern (for example, through a photomask) such that exposed areas of the film become crosslinked; and removing the unexposed areas (which remain uncrosslinked and soluble).
  • the process can include depositing the photocrosslinkable composition on a substrate to form a film of desired thickness, exposing the film to actinic radiation (for example, flood exposure or irradiation at specific wavelengths in the UV region e.g., the H, I, or G line wavelengths) through a photomask (one having the desired imagewise pattern) to provide crosslinked areas and uncrosslinked areas, and subjecting the film to a developing agent to remove the uncrosslinked areas, thereby transferring the pattern of the photomask in a negative-tone manner to the film.
  • actinic radiation for example, flood exposure or irradiation at specific wavelengths in the UV region e.g., the H, I, or G line wavelengths
  • a photomask one having the desired imagewise pattern
  • Thin film materials prepared from the present photocrosslinkable composition can have good mechanical properties and chemical resistance. For example, after
  • the thin film materials can become substantially insoluble in various organic solvents in which the pristine polymer is soluble. More specifically, the photocrosslinked film can be immersed in the mother solvent, for example, for a period of time sufficient to develop the desired pattern, and the loss in the thickness of the film
  • thickness loss can be less than about 50%, preferably less than about 20%, and more preferably less than about 10%.
  • the present thin film materials generally have excellent dielectric properties.
  • the present thin film materials typically have a dielectric constant of 10 or greater.
  • the present thin film materials can have a dielectric constant of about 15 or greater.
  • the present thin film materials can have a dielectric constant of about 20.
  • the present thin film materials can exhibit very low leakage current densities. Leakage current density typically is defined as a vector whose magnitude is the leakage current per cross-sectional area.
  • leakage current refers to uncontrolled (“parasitic") current flowing across region(s) of a semiconductor structure or device in which no current should be flowing, for example, current flowing across the gate dielectric in a metal-oxide-semiconductor (MOS) structure.
  • MOS metal-oxide-semiconductor
  • the leakage current density of a dielectric material can be determined by fabricating a standard metal-insulator-semiconductor (MIS) and/or metal- insulator-metal (MIM) capacitor structures with the dielectric material, then measuring the leakage current, and dividing the measured current by the area of the metal electrodes.
  • photopatterned thin film dielectrics according to the present teachings can have a leakage current density of less than or equal to about 2 x 10 "3 A/cm 2 at 1 MV/cm, less than or equal to about 5 x 10 "4 A/cm 2 at 1 MV/cm, or less than or equal to about 2 x 10 "4 A/cm 2 at 1 MV/cm.
  • photocrosslinked thin films according to the present teachings can be used as a patterned gate dielectric component in various electronic, optical, and
  • Such gate dielectric components can exhibit a wide range of desirable properties and characteristics including, but not limited to, low leakage current densities, high breakdown voltages, large capacitance values, thermal, air and moisture stability, resistance to harsh reagents, and/or compatibility with diverse interlayer, semiconductor and/or metal contact materials (including interfacial compatibility and compatibility with methods used to process such interlayer, semiconductor and/or metallic materials).
  • the electronic, optical, or optoelectronic devices incorporating the present gate dielectric component in turn, can have improved device performance including, but not limited to, low hysteresis, better stability, and lower operating voltages.
  • Non-limiting examples of electronic, optical, and optoelectronic devices that can include a gate dielectric component composed of the present thin film materials include capacitors, organic field-effect transistors, metal oxide field-effect transistors, and organic light-emitting transistors. Referring to Fig.
  • a field-effect transistor generally includes source and drain electrodes (2, 2', 2", 2"' and 4, 4', 4", 4"'), a semiconductor layer (6, 6', 6", 6"'), a gate dielectric layer (8, 8', 8", 8"'), a gate electrode (10, 10', 10", 10"'), a substrate (12, 12', 12", 12"'), and optionally one or more interlayers (e.g., a surface-modifying layer, a passivation layer, or an encapsulation layer).
  • the gate electrode, and the source and drain electrodes can be arranged in different configurations relative to the gate dielectric layer and the semiconductor layer to provide, for example, a bottom-gate top- contact (Fig.
  • a potential is applied on the gate electrode, charge carriers are accumulated in the semiconductor layer at an interface with the gate dielectric. As a result, a conductive channel is formed between the source electrode and the drain electrode and a current will flow if a potential is applied to the drain electrode.
  • a field-effect transistor has a gate dielectric layer prepared from a photocrosslinkable composition described herein, and can be characterized by an operating voltage that is less than about
  • the semiconductor layer of a field-effect transistor can be composed of one or more organic (small molecule or polymeric) semiconducting compounds or semiconducting metal oxides.
  • the semiconducting metal oxide can be selected from indium oxide (ln 2 0 ), indium zinc oxide (IZO), zinc tin oxide (ZTO), indium gallium oxide (IGO), indium-gallium-zinc oxide (IGZO), indium-gallium-oxide (IGO), indium-ittrium-oxide (IYO), indium tin zinc oxide (ITZO), tin oxide (Sn0 2 ), and zinc oxide (ZnO).
  • IGO indium gallium oxide
  • IGZO indium-gallium-zinc oxide
  • IGO indium-gallium-oxide
  • IYO indium-ittrium-oxide
  • IYO indium tin zinc oxide
  • tin oxide Sn0 2
  • ZnO zinc oxide
  • the organic semiconductor layer can be composed of one or more small molecule and/or polymeric compounds that exhibit n-type (electron-transporting), p-type (hole-transporting), or ambipolar (both n-type and p-type) semiconducting activity.
  • a "p-type semiconductor material” or a “p-type semiconductor” refers to a semiconductor material having holes as the majority current carriers. In some embodiments, when a p-type semiconductor material is deposited on a substrate, it can provide a hole mobility in excess of about 10 "5 cm 2 /V s. In the case of field- effect devices, a p-type semiconductor can also exhibit a current on/off ratio of greater than about 10.
  • An "n-type semiconductor material” or an “n-type semiconductor” refers to a semiconductor material having electrons as the majority current carriers. In some
  • an n-type semiconductor material when it is deposited on a substrate, it can provide an electron mobility in excess of about 10 "5 cm 2 /V s. In the case of field-effect devices, an n-type semiconductor can also exhibit a current on/off ratio of greater than about 10.
  • the term "mobility” refers to a measure of the velocity with which charge carriers, for example, holes (or units of positive charge) in the case of a p-type semiconductor material and electrons in the case of an n-type semiconductor material, move through the material under the influence of an electric field. This parameter, which depends on the device architecture, can be measured using a field-effect device or space-charge limited current measurements.
  • Exemplary p-type semiconductors include soluble pentacenes (e.g., those described in U.S. Patent No. 7, 125,989); oligothiophenes and polythiophenes (e.g., dihexyl
  • C n -DNTTs Organic Semiconductors for High-Performance Thin-Film Transistors
  • p-type semiconductors include linear acenes, bent acenes, arylvinylenes, phenylenes, and fused (hetero)arenes substituted with alkyl and/or alkoxy groups.
  • Exemplary n-type semiconductors include fluorocarbon substituted-oligothiophenes (e.g., ⁇ , ⁇ -diperfluorohexylsexithiophenes and other fluorocarbon- substituted thiophene oligomers are described in U.S. Patent No. 6,585,914); fused ring tetracarboxylic diimides and their derivatives (e.g., cyanated perylene diimides (PDIs) or naphthalene diimides (NDIs) such as those described in U.S. Patent No.
  • fluorocarbon substituted-oligothiophenes e.g., ⁇ , ⁇ -diperfluorohexylsexithiophenes and other fluorocarbon- substituted thiophene oligomers are described in U.S. Patent No. 6,585,914
  • fused ring tetracarboxylic diimides and their derivatives e.g.
  • n-type semiconductors include linear acenes, bent acenes, arylvinylenes, phenylenes, and fused (hetero)arenes substituted with alkylcarbonyl, arylcarbonyl, and/or cyano groups.
  • a plurality of organic and/or metal oxide field-effect transistors can be arranged in an array which can be used as switching devices or peripheral drivers in active matrix liquid crystal displays (AMLCDs) and as pixel drivers for active matrix organic light-emitting diodes (AMOLEDs).
  • AMLCDs active matrix liquid crystal displays
  • AMOLEDs active matrix organic light-emitting diodes
  • OLET Organic light-emitting transistor
  • an organic light-emitting transistor includes a number of layers and can be configured in various ways. For example, a trilayer
  • heterostructure bottom-gate top-contact OLET can include, from bottom to top, a transparent substrate (1), a gate electrode (2), a gate dielectric (3), an active layer consisting of the superposition of three organic layers (4, 5, 6), and source and drain electrodes (7, 8) on top of the active layer.
  • the trilayer active layer generally includes a light-emitting host-guest matrix sandwiched between an n-type (electron-transporting) semiconductor and a p-type (hole-transporting) semiconductor.
  • One or more optional layers (e.g., charge injection layers) and/or additional electrodes can be present, for example, as described in U.S. Patent
  • An OLET can be operated by applying a first appropriate bias voltage to the gate electrode, and injecting electrons from the electron electrode and holes from the hole electrode, while maintaining a second bias voltage between the latter two electrodes.
  • the first and second bias voltages can be continuous voltages. Alternatively, the first and second bias voltages also can be pulsed voltages.
  • OLETs of different architectures can be fabricated using processes known to those skilled in the art as described in, for example, International Publication Nos.
  • WO2013/018000 and WO2013/128344 For example, in a bottom-gate configuration, an optional planarization or surface-modifying layer can be formed onto a transparent substrate, e.g., by spin-coating. A metallic thin film can be thermally evaporated thereon, followed by etching or other patterning techniques to form the gate electrode.
  • An OLET incorporates a patterned high-k thin film dielectric herein as the gate electric, wherein the patterned high-k thin film dielectric can be prepared by depositing (e.g., spin-coating) onto the gate electrode a film from a photocrosslinkable composition comprising a partially fluorinated polymer and a crosslinker as described herein; drying the film; photopatterning the film (exposing the film to actinic radiation through a photomask thereby inducing photocrosslinking in the exposed areas, and subsequently using a developer to remove the soluble, unexposed areas), and optionally annealing the film.
  • a photocrosslinkable composition comprising a partially fluorinated polymer and a crosslinker as described herein
  • the active channel layer can be prepared over the gate dielectric via sequential deposition of a first charge transport sublayer (e.g., hole transport sublayer), an emissive sublayer, and a second charge transport sublayer (e.g., electron transport sublayer).
  • a first charge transport sublayer e.g., hole transport sublayer
  • an emissive sublayer e.g., a second charge transport sublayer
  • the various organic layers can be formed by chemical vapor deposition, physical vapor deposition, different types of printing techniques (e.g., flexo printing, litho printing, gravure printing, ink-jetting, pad printing, and so forth), drop casting, slot coating, dip coating, doctor blading, roll coating, or spin-coating.
  • the hole transport sublayer can be used as the hole transport sublayer, the electron transport sublayer, and the emissive sublayer.
  • the channel layer can comprise one or more of the small molecule or polymeric p-type and n-type semiconducting compounds described hereinabove in connection with organic field-effect transistors.
  • the energy of the hole- transporting semiconductor material must match that of the electron transporting
  • the energy difference between the highest occupied molecular orbital (HOMO) of the hole-transporting semiconductor material and the lowest unoccupied molecular orbital (LUMO) of the electron-transporting semiconductor material should be, at a minimum, between about 1.6V and about 1.8 eV.
  • the energy difference between the HOMO of the hole-transporting semiconductor material and the LUMO of the electron-transporting semiconductor material has to be, at a minimum, between about 2.2 eV and about 2.5 eV.
  • the energy difference between the HOMO of the hole- transporting semiconductor material and the LUMO of the electron-transporting semiconductor material has to be, at a minimum, between about 2.8 eV and about 3.2 eV.
  • the emissive sublayer can be a blend that includes a host material and a guest emitter selected from a fluorescent emitter and a phosphorescent emitter.
  • the emissive sublayer can be prepared from a single-component host-emitting material. Suitable organic electroluminescent light-emitting materials include those having been used in OLED applications.
  • the emissive sublayer can be composed of a blend of host tris(8- hydroxyquinolinato)aluminium (Alq 3 ) and guest 4-(dicyanomethylene)-2-methyl-6-(p- dimethylaminostyryl)-4H-pyran (DCM).
  • Some exemplary host materials include polymers such as poly(p-phenylene vinylene), poly(alkyphenylphenylvinylene), poly(alkyphenylphenylvinylene-co- alkoxyphenylenevinylene), polyfluorene, poly(n-vinylcarbazole), and copolymers thereof.
  • polymers such as poly(p-phenylene vinylene), poly(alkyphenylphenylvinylene), poly(alkyphenylphenylvinylene-co- alkoxyphenylenevinylene), polyfluorene, poly(n-vinylcarbazole), and copolymers thereof.
  • Various carbazole compounds, triphenylamine compounds, including hybrids with oxadiazole or benzimidazole also have been used as host materials.
  • Some exemplary guest emitters include fluorescent dyes such as various perylene derivatives, anthracene derivatives, rubrene derivatives, carbazole dervatives, fluorene derivatives, and quinacridone derivatives, and phosphorescent emitters such as various transition metal complexes including Ir, Os, or Pt.
  • Some exemplary host-emitting materials include phosphorescent host-emitting compounds based on carbazole derivatives, fluorene derivatives, or 9 -naphthyl anthracene derivatives, and fluorescent host-emitting compounds based on organometallic chelates such as tris(8-quinolinol) aluminum complexes.
  • the hole/electron (or souce/drain) electrodes can be formed using similar or different techniques as the gate electrode.
  • any of the electrical contacts can be deposited through a mask, or can be deposited then etched or lifted off (photolithography).
  • Suitable deposition techniques include electrodeposition, vaporization, sputtering, electroplating, coating, laser ablation and offset printing, from metal or metal alloy including copper, aluminum, gold, silver, molybdenum, platinum, palladium, and/or nickel, or an electrically conductive polymer such as polyethylenethioxythiophene (PEDOT).
  • PEDOT polyethylenethioxythiophene
  • Charge carrier injection can be facilitated by the use of a material for the injection electrode (hole electrode or electron electrode) that has a low barrier against injection of a charge carrier type into the hole transport sublayer and the electron transport sublayer, respectively.
  • the hole electrode can comprise at least one material selected from the group consisting of Au, indium tin oxide, Cr, Cu, Fe, Ag, poly(3,4-ethylenedioxthiophene) combined with poly(styrenesulfonate) (PEDOT:PSS), and a perovskite manganite (Rei -x A x Mn03).
  • the hole electrode and the electron electrode can be made of conductors with different work functions to favor both hole and electron injection.
  • the hole and electron injection layers can be prepared by self-assembly of thiolates, phosphonates, or aliphatic or aromatic carboxylates; by thermal evaporation of various charge transfer complexes and other heteroaromatic or organometallic complexes; or by thermal evaporation or sputtering of various metal oxides, fluorides, or carbonates.
  • the hole injection layer and the electron injection layer can be made of materials that provide a staircase of electronic levels between the energy level of the hole electrode and the electron electrode, and the energy level required for injection into the hole transport sublayer and the electron transport sublayer, respectively.
  • OLETs can be fabricated on various substrates including plastic, flexible substrates that have a low temperature resistance.
  • flexible substrates include polyesters such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate; polyolefins such as polypropylene, polyvinyl chloride, and polystyrene; polyphenylene sulfides such as polyphenylene sulfide; polyamides; aromatic polyamides; polyether ketones; polyimides; acrylic resins; polymethylmethacrylate, and blends and/or copolymers thereof.
  • the substrate can be a rigid transparent substrate such as glass, quartz and VYCOR®.
  • Substrate-gate materials commonly used in thin-film transistors also can be used. Examples include doped silicon wafer, tin-doped indium oxide (ITO) on glass, tin-doped indium oxide on polyimide or mylar film, aluminum or other metals alone or coated on a polymer such as polyethylene terephthalate, a doped polythiophene, and the like.
  • ITO tin-doped indium oxide
  • polyimide or mylar film aluminum or other metals alone or coated on a polymer such as polyethylene terephthalate, a doped polythiophene, and the like.
  • a plurality of OLETs can be arranged in a matrix to provide a display device.
  • the display device can include optional driving and switching elements, compensating transistor elements, capacitors, and/or light-emitting diodes.

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  • Chemical & Material Sciences (AREA)
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Abstract

La présente invention concerne des diélectriques structurés en couche mince à constante k élevée préparés à partir d'une composition photostructurable à base d'un polymère partiellement fluoré qui comprend un motif répété fluoré et au moins un motif répété photoréticulable de formule (I), (II), (III), (IV) et/ou (V). Ces diélectriques structurés peuvent être incorporés dans un transistor organique en couche mince conçu pour fonctionner à des tensions inférieures à environ 40 V.
PCT/US2015/067217 2014-12-19 2015-12-21 Compositions photoréticulables, diélectriques structurés en couche mince à constante k élevée et dispositifs associés Ceased WO2016100983A1 (fr)

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WO2020036761A1 (fr) * 2018-08-17 2020-02-20 Corning Incorporated Réticulation uv de polymères à base de pvdf pour isolants diélectriques de grille de transistors à couches minces organiques
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