WO2010057984A2 - Photocurable polymeric dielectrics and methods of preparation and use thereof - Google Patents

Photocurable polymeric dielectrics and methods of preparation and use thereof Download PDF

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Publication number
WO2010057984A2
WO2010057984A2 PCT/EP2009/065569 EP2009065569W WO2010057984A2 WO 2010057984 A2 WO2010057984 A2 WO 2010057984A2 EP 2009065569 W EP2009065569 W EP 2009065569W WO 2010057984 A2 WO2010057984 A2 WO 2010057984A2
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group
alkyl
aryl
divalent
alkenyl
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PCT/EP2009/065569
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English (en)
French (fr)
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WO2010057984A3 (en
Inventor
Silke Koehler
Thomas Breiner
Jordan Quinn
He Yan
Yan Zheng
Christopher Newman
Antonio Facchetti
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Basf Se
Polyera Corporation
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Priority to CN200980146851.4A priority Critical patent/CN102224611B/zh
Priority to EP09759719.9A priority patent/EP2368281B1/en
Priority to US13/128,961 priority patent/US8937301B2/en
Priority to KR1020117014710A priority patent/KR101712680B1/ko
Priority to JP2011536876A priority patent/JP5684715B2/ja
Priority to KR1020157036689A priority patent/KR101717398B1/ko
Publication of WO2010057984A2 publication Critical patent/WO2010057984A2/en
Publication of WO2010057984A3 publication Critical patent/WO2010057984A3/en
Priority to US14/467,839 priority patent/US9923158B2/en

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    • H—ELECTRICITY
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
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    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
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    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C08F12/24—Phenols or alcohols
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • a critical component in most organic electronic devices is a polymeric dielectric layer that serves as the gate insulator material in thin- film transistors, which are key building blocks of any electronic circuit.
  • the polymer dielectric layer can be formed on either the gate contact (for bottom-gate transistor structures) or the semiconductor layer (for top-gate transistor structures) by depositing a solution of an electrically insulating (i.e., dielectric) polymer via a solution phase process such as spin-coating or printing.
  • a crosslinking step usually is required.
  • Figure 2 provides representative output plots of poly(3-hexylthiophene)-based organic field effect transistors fabricated in a top-gate structure with dielectric materials of the present teachings (a crosslinked dielectric film prepared from PVP0.55-co-PMMA0.45- 6HOC-Ac).
  • Figure 3 provides representative transfer plots of poly(3-hexylthiophene)-based organic field effect transistors fabricated in a top-gate structure with dielectric materials of the present teachings (a crosslinked dielectric film prepared from PVP0.55-co-PMMA0.45- 6HOC-Ac).
  • Figure 9 provides representative transfer plots of PDI-based organic field effect transistors fabricated in a bottom-gate bottom-contact structure with dielectric materials of the present teachings (a crosslinked dielectric film prepared from PVP0.55-co-PMMA0.45- 6HOC-Ac).
  • Figure 10 provides representative transfer plots of pentacene-based organic field effect transistors fabricated in a bottom-gate top-contact structure with dielectric materials of the present teachings (a crosslinked dielectric film prepared from PVP0.55-co-PMMA0.45- 6HOC-Ac).
  • Figure 12 provides a typical differential scanning calorimetry (DSC) plot of a polymer of the present teachings (PVP-6HOC-Ac).
  • Figure 13 provides leakage current density (J) versus electric field (E) plots of metal- insulator-metal capacitor structures incorporating dielectric materials of the present teachings (a crosslinked dielectric film prepared from PVP-6HOC-Ac) before and after post- crosslinking solvent treatment.
  • Figure 14 illustrates four different configurations of thin film transistors: a) bottom- gate top contact, b) bottom-gate bottom-contact, c) top-gate bottom-contact, and d) top-gate top-contact; each of which can be used to incorporate one or more polymers of the present teachings, particularly as the dielectric layer or part of the dielectric component.
  • 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.
  • a "polymer” or “polymeric compound” refers to a molecule (e.g., a macro molecule) including a plurality of repeating units connected by covalent chemical bonds.
  • a polymer can be represented by the general formula:
  • a "pendant group” or “side group” is part of a repeating unit of a polymer and refers to a moiety that is attached covalently to the backbone of the polymer.
  • solution-processable refers to polymers, materials, or compositions that can be used in various solution-phase processes including spin-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, “solution-processable” also include dispersions of polymers, materials, or compositions as long as they can be processed by the processes mentioned above.
  • printing e.g., inkjet printing, screen printing, pad printing, offset printing, gravure printing, flexographic printing, lithographic printing, mass-printing and the like
  • spray coating e.g., electrospray coating, drop casting, dip coating, and blade coating
  • dispersions of polymers, materials, or compositions as long as they can be processed by the processes mentioned above.
  • halo or halogen refers to fluoro, chloro, bromo, and iodo.
  • alkyl refers to a straight-chain or branched saturated hydrocarbon group.
  • alkyl groups include methyl (Me), ethyl (Et), propyl (e.g., n-propyl and ⁇ o-propyl), butyl (e.g., n-butyl, ⁇ o-butyl, sec-butyl, tert-buty ⁇ ), pentyl groups (e.g., n-pentyl, ⁇ o-pentyl, neopentyl), hexyl groups, and the like.
  • haloalkyl refers to an alkyl group having one or more halogen substituents.
  • a haloalkyl group can have 1 to 40 carbon atoms (i.e., Ci_4o haloalkyl group), for example, 1 to 20 carbon atoms (i.e., Ci_2o haloalkyl group).
  • Examples of haloalkyl groups include CF 3 , C 2 F 5 , CHF 2 , CH 2 F, CCl 3 , CHCl 2 , CH 2 Cl, C 2 Cl 5 , and the like.
  • Perhaloalkyl groups i.e., alkyl groups where all of the hydrogen atoms are replaced with halogen atoms (e.g., CF 3 and C 2 F 5 ), are included within the definition of "haloalkyl.”
  • a Ci_4o haloalkyl group can have the formula -C z H 2z+ i-tX°t, where X 0 , at each occurrence, is F, Cl, Br or I, z is an integer in the range of 1 to 40, and t is an integer in the range of 1 to 81 , provided that t is less than or equal to 2z+l .
  • Haloalkyl groups that are not perhaloalkyl groups can be substituted as described herein.
  • alkoxy refers to -O-alkyl group.
  • alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy (e.g., n-propoxy and isopropoxy), t-butoxy, pentoxyl, hexoxyl groups, and the like.
  • the alkyl group in the -O-alkyl group can be substituted as described herein.
  • alkylthio refers to an -S-alkyl group.
  • alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio (e.g., n-propylthio and isopropylthio), t-butylthio, pentylthio, hexylthio groups, and the like.
  • the alkyl group in the -S-alkyl group can be substituted as described herein.
  • arylalkyl refers to an -alkyl-aryl group, where the arylalkyl group is covalently linked to the defined chemical structure via the alkyl group.
  • An arylalkyl group is within the definition of a -Y-C ⁇ - ⁇ aryl group, where Y is as defined herein.
  • An example of an arylalkyl group is a benzyl group (-CH 2 -C 6 H 5 ).
  • An arylalkyl group can be optionally substituted, i.e., the aryl group and/or the alkyl group, can be substituted as disclosed herein.
  • cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, norbornyl, norpinyl, norcaryl, adamantyl, and spiro[4.5]decanyl groups, as well as their homo logs, isomers, and the like.
  • cycloalkyl groups can be substituted as described herein.
  • heteroatom refers to an atom of any element other than carbon or hydrogen and includes, for example, nitrogen, oxygen, silicon, sulfur, phosphorus, and selenium.
  • cycloheteroalkyl refers to a non-aromatic cycloalkyl group that contains at least one ring heteroatom selected from O, S, Se, N, P, and Si (e.g., O, S, and N), and optionally contains one or more double or triple bonds.
  • a cycloheteroalkyl group can have 3 to 20 ring atoms, for example, 3 to 14 ring atoms (i.e., 3-14 membered cycloheteroalkyl group).
  • One or more N, P, S, or Se atoms (e.g., N or S) in a cycloheteroalkyl ring may be oxidized
  • nitrogen or phosphorus atoms of cycloheteroalkyl groups can bear a substituent, for example, a hydrogen atom, an alkyl group, or other substituents as described herein.
  • Cycloheteroalkyl groups can also contain one or more oxo groups, such as oxopiperidyl, oxooxazolidyl, dioxo-(lH,3H)-pyrimidyl, oxo-2(lH)-pyridyl, and the like.
  • cycloheteroalkyl groups include, among others, morpholinyl, thiomorpholinyl, pyranyl, imidazolidinyl, imidazolinyl, oxazolidinyl, pyrazolidinyl, pyrazolinyl, pyrrolidinyl, pyrrolinyl, tetrahydrofuranyl, tetrahydrothiophenyl, piperidinyl, piperazinyl, and the like.
  • cycloheteroalkyl groups can be substituted as described herein.
  • 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 cycloalkyl and/or cycloheteroalkyl rings.
  • An aryl group can have 6 to 20 carbon atoms in its ring system (e.g., C 6-14 aryl group), which can include multiple fused rings.
  • a polycyclic aryl group can have from 8 to 20 carbon atoms. Any suitable ring position of the aryl group can be covalently linked to the defined chemical structure.
  • aryl groups having only aromatic carbocyclic ring(s) include phenyl, 1-naphthyl (bicyclic), 2-naphthyl (bicyclic), anthracenyl (tricyclic), phenanthrenyl (tricyclic), and like groups.
  • Perhaloaryl groups i.e., aryl groups where all of the hydrogen atoms are replaced with halogen atoms (e.g., -C 6 F 5 ), are included within the definition of "haloaryl.”
  • an aryl group is substituted with another aryl group and can be referred to as a biaryl group.
  • Each of the aryl groups in the biaryl group can be substituted as disclosed herein.
  • Polymers of the present teachings can include a "divalent group" defined herein as a linking group capable of forming a covalent bond with two other moieties.
  • polymers of the present teachings can include a divalent Ci_2o alkyl group (e.g., a methylene group), a divalent C2-20 alkenyl group (e.g., a vinylyl group), a divalent C2-20 alkynyl group (e.g., an ethynylyl group), a divalent C 6 _i 4 aryl group (e.g., a phenylyl group); a divalent 3-14 membered cycloheteroalkyl group (e.g., a pyrrolidylyl), and/or a divalent 5-14 membered heteroaryl group (e.g., a thienylyl group).
  • a divalent Ci_2o alkyl group e.g., a methylene
  • 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.
  • 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.
  • the coumarin moiety can be unsubstituted, in which case, R 1 and R 2 are H, and b is 0.
  • the coumarin moiety can be substituted with one or more functional groups.
  • at least one of R 1 and R 2 can be a non- hydrogen substituent and/or at least one R 3 group is present.
  • the crosslinkable coumarin moiety can be covalently linked to the polymeric backbone directly or via a linker (or spacer) group at a specific carbon atom:
  • the crosslinkable coumarin moiety can be covalently linked to the polymeric backbone at C6 or C7 as shown below, respectively: wherein the crosslinkable coumarin moiety can be covalently linked to the polymeric backbone at C6.
  • polymers having C6-linked coumarin moieties can be crosslinked at a faster rate than their counterparts having C7-linked coumarin moieties. That is, in using the present polymers to prepare a dielectric material (e.g., film), it often is desirable to ensure that the dielectric material achieves a sufficient degree of crosslinking, such that subsequent device processing conditions will not jeopardize the properties of the dielectric material.
  • a dielectric material can be considered "sufficiently crosslinked” if, after the crosslinking step, the thickness of the dielectric film does not decrease by more than about 10% when treated with the solvent used to prepare the dielectric material ("mother solvent").
  • a dielectric material can be considered "sufficiently crosslinked" if, after the crosslinking step, the leakage current does not increase by more than about 5 times at 2 MV/cm when the crossinked dielectric film has been in contact with the mother solvent.
  • the polymers having C6-linked coumarin moieties can achieve a sufficient degree of crosslinking at least 2 times (e.g., at least 3 times) faster than their counterparts having C7-linked coumarin moieties.
  • the present polymers can include a coumarin-containing repeating unit where the coumarin moiety is the terminal moiety of the pendant group.
  • any substitutent(s) on the coumarin moiety generally are small functional groups such as F, Cl, OH, or other non-cyclic organic groups such as R, OR, C(O)R, OC(O)R, OC(O)OR, where R is a Ci -6 alkyl group.
  • the present polymers can include a coumarin- containing repeating unit where the coumarin moiety is not the terminal moiety of the pendant group.
  • R 1 , R 2 , or R 3 can represent the terminal moiety of the pendant group.
  • R 1 , R 2 , or R 3 can be a larger functional group (e.g., including 6 carbon atoms or more), which optionally can include one or more crosslinkable groups (e.g., cinnamoyl groups, azobenzenes, and the like).
  • the present polymers can be derived from one or more vinyl phenol monomers or derivatives thereof.
  • the derivatization can occur before or after polymerization.
  • the hydrogen atom of the hydroxyl group of the phenol moiety is replaced with a different functional group.
  • the present polymers can include vinyl phenol polymers (e.g., poly-4-vinylphenol, PVP), where at least some of the phenol pendant groups are derivatived to include the coumarin moiety described herein.
  • the present polymers can include copolymers of vinyl phenol and/or vinyl phenol derivatives and methyl methacrylate and/or methacrylate derivatives, where at least some of the vinyl phenol repeating units are derivatized with a coumarin moiety.
  • the coumarin moiety also can be introduced into the non- vinyl phenol units instead of or in addition to the vinyl phenol units.
  • L and Q at each occurrence, independently can be a linker group or a covalent bond
  • R 6 and R 7 at each occurrence, independently can be selected from a) H, b) a halogen, c) a Ci_io alkyl group, and d) a C 6-14 aryl group, wherein each of the C 1-10 alkyl group and the C 6 -14 aryl group optionally can be substituted with 1-5 R 5 groups;
  • R , Q, b and n are as defined herein.
  • substantially all of the phenol pendant groups can be derivatized with the crosslinkable coumarin moiety (e.g., x' ⁇ 0.1).
  • a percentage of the phenol pendant groups can be derivatized with the crosslinkable coumarin moiety (e.g., 0.1 ⁇ x ⁇ 0.8), while the remaining phenol pendant groups can remain underivatized.
  • a "derivative" of a compound or a moiety should be understood as a modified form of the compound or moiety, wherein the modified form has replaced at least one atom in the compound or moiety with another atom or group of atoms. The derivatization can take place before or after polymerization or copolymerization.
  • the phenol pendant groups can be derivatized to provide a third unit (monomer C) that is different from the first unit containing the coumarin moiety (monomer A).
  • the present polymers can be a copolymer of monomers A and C, and optionally monomer B (i.e., y and y' can be 0). Accordingly, the present polymers can be represented by the formula:
  • Q and/or W" can include a functional group that can confer some advantageous property to the polymer as a whole.
  • the functional group can help improve solubility or more generally, processability of the polymer, and/or stability of the polymer (e.g., by increasing hydrophobicity).
  • the present teachings can provide a vinyl phenol copolymer including a repeating unit that includes a pendant group L-W. Accordingly, the present polymers can be represented by the formula:
  • x can be larger than about 0.25; and x + x' + x" can be larger than about 0.5.
  • x can be larger than about 0.6; y can be larger than about 0.2; 0 ⁇ x' ⁇ 0.10; and 0 ⁇ x" ⁇ 0.10.
  • the present teachings can provide a vinyl phenol copolymer including a repeating unit that includes a pendant group L-W and a repeating unit that includes a pendant group L-W, where L-W and L-W' are different.
  • x can be larger than about 0.25; and x + x' can be larger than about 0.5.
  • x can be larger than about 0.6; y' can be larger than about 0.2; 0 ⁇ x' ⁇ 0.10; and 0 ⁇ y ⁇ 0.10.
  • the repeating unit above can be methyl methacrylate.
  • the repeating unit above can be vinyl acetate-co-vinyl alcohol.
  • L-W can be a derivative of L-W, wherein L and W are as defined herein.
  • W can be OH
  • W can be OCH 3 .
  • L and Q at each occurrence, independently can be a linker group selected from a divalent Ci_ 2 o alkyl group, a divalent C 2 _ 2 o alkenyl group or a divalent C 2 _ 2 o alkynyl group, where 1-5 methylene groups (adjacent or non-adjacent) of each of these groups optionally can be replaced with a functionality independently selected from O, S(O)k, C(O), OSiR 4 2 , NR 4 , N(C(O)R 4 ), C(NR 4 ), and a divalent C 6 -I 4 aryl group, and each of the Ci -20 alkyl group, the C2-20 alkenyl group, the C2-20 alkynyl group, and the C 6- I 4 aryl group optionally can be substituted with 1-5 R 5 groups, wherein k is 0, 1 or 2; and R 4 and R 5 are as defined herein.
  • L at each occurrence, independently can be a covalent bond or a linker group of the formula:
  • L' is linked to the backbone of the polymer and can be selected from-Y'-O-, -Y'-NR 4 -, -Y'-N(C(O)R 4 )-, -V-S-, -Y'-C(O)-, -V-C(O)O-, -V-OC(O)-, -V- NR 4 C(O)-, -Y'-C(0)NR 4 -, -Y'-Si(R 4 ) 2 - and a covalent bond;
  • Y' can be selected from a divalent Ci_6 alkyl group, a divalent C 2 _6 alkenyl group, a divalent C 2 _6 alkynyl group, a divalent C 6-14 aryl group, and a covalent bond, wherein each of the Ci_6 alkyl group, the C 2 _6 alkenyl group, the C 2 _6 alkynyl group, and the C 6-14 aryl group optionally can be substituted with 1-5 R 5 groups;
  • Y at each occurrence, can be selected from a divalent Ci_6 alkyl group, a divalent C 2 _6 alkenyl group, and a divalent C 6-14 aryl group, wherein each of the Ci_6 alkyl group, the C 2 _6 alkenyl group, and the C 6-14 aryl group optionally can be substituted with 1-5 R 5 groups;
  • Y"' can be selected from a divalent Ci_6 alkyl group, a divalent C 2 _6 alkenyl group, and a divalent C 6-14 aryl group, wherein each of the Ci_6 alkyl group, the C 2 _6 alkenyl group, and the C 6 -14 aryl group optionally can be substituted with 1-5 R 5 groups; k is O, 1 or 2; m is 1, 2, 3, 4, 5 or 6; p is O, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; and R 4 and R 5 are as defined herein.
  • L can be a linker group of the formula -L'-(L") P -L"'-, wherein L' can be selected from -V-O-, -Y'-C(O)-, -Y'-OC(O)-, -V-C(O)O-, and a covalent bond; L", at each occurrence, independently can be selected from -Y"-, -(Y") m -O-, and a covalent bond; L"' can be selected from -C(O)-, -C(O)-O-, -C(O)-Y" -0-, -C(O)-Y" -NR 4 -, and a covalent bond, provided that at least one of L', L", and L"' is not a covalent bond; wherein R 4 , Y', Y", Y"' and m are as defined herein.
  • L at each occurrence, independently can be selected from -(CH 2 CH 2 O) P' -, -0-, -0-(CH 2 CH 2 O) P -, -O-C(O) -, -O-C(O)(CH 2 CH 2 O)p ' -, -C(O)-O-, -C(O)-O-(CH 2 CH 2 O) P -, -C 6 H 4 -O-(CH 2 CH 2 O) P -, -C 6 H 4 -O-, -C 6 H 4 -O-C(O)-, -C 6 H 4 -O-C(O)-, -C 6 H 4 -O-C(O)(CH 2 CH 2 O) P -, -C(O)-O-CF 2 CF 2 -O-, -(CH 2 CH 2 O) P -C(O)-CH 2 -O-, -C(O)-CH 2 -O-, -0-
  • L at each occurrence, independently can be selected from -CH 2 CH 2 O-C(O)-CH 2 -O-, -OC(O)-CH 2 -O-, -0-CH 2 CH 2 O-C(O)-CH 2 -O-, -0-C(O)CH 2 CH 2 O-C(O)-CH 2 -O-, -C(O)-O-CH 2 CH 2 O-C(O)-CH 2 -O-, -C 6 H 4 -O-C(O)-CH 2 -O-, -C 6 H 4 -O-CH 2 CH 2 O-C(O)-CH 2 -O-, -C 6 H 4 -O-C(O)-CH 2 CH 2 O-C(O)-CH 2 -O-, and -C(O)-O-CF 2 CF 2 -O-C(O)-CH 2 -O-.
  • Q at each occurrence, independently can be a covalent bond or a linker group of the formula:
  • L at each occurrence, independently can be selected from -Y"-, -(Y") m -0-Y"-, -Y"-NR 4 -Y"-,-Y"-C(NR 4 )-Y"-, -Y"-Si(R 4 ) 2 -Y"-, -O-Si(R 4 ) 2 -Y"-, and a covalent bond;
  • L"' is linked to the coumarin moiety and can be selected from -C(O)-, -C(O)-O-, -0-C(O)- -C(O)-Y"'-, -C(O)-Y"'-O- -O-Y"'-C(O)-, -C(O)-NR 4 -, -NR 4 -C(0)-, -C(0)-Y'"-NR 4 -, -NR 4 -Y"'-C(0)-, -0-S(0) k -, -O-Y"'-S(O) k -, and a covalent bond; provided that at least one of L" and L"' is not a covalent bond;
  • Y"' is selected from a divalent Ci_6 alkyl group, a divalent C2-6 alkenyl group, and a divalent C 6-14 aryl group, wherein each of the Ci_6 alkyl group, the C2-6 alkenyl group, and the C 6-14 aryl group optionally is substituted with 1-5 R 5 groups; k is 0, 1 or 2; m is 1, 2, 3, 4, 5 or 6; p is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; and
  • R 4 and R 5 are as defined herein.
  • W, W, and W" independently can be selected from H, a C 1-10 alkyl group, a C 2-10 alkenyl group, a C 1-10 haloalkyl group, a phenyl group, and a 5-14 membered heteroaryl group, wherein each of the C 1-10 alkyl group, the C 2-10 alkenyl group, the Ci_io haloalkyl group, the phenyl group, and the 5-14 membered heteroaryl group optionally can be substituted with 1 to 5 substituents independently selected from a halogen, -CN, an oxo group, a Ci_6 alkyl group, a Ci_6 haloalkyl group, a Ci_6 alkoxy group, a -C(O)-Ci -6 alkyl group, a -C(O)-Ci -6 haloalkyl group, and a -C(O)-O-Ci -6 alky
  • x can be larger than about 0.25; and x + x' + x" can be larger than about 0.5.
  • x can be larger than about 0.6; y can be larger than about 0.2; 0 ⁇ x' ⁇ 0.10; and 0 ⁇ x" ⁇ 0.10.
  • monomer C can be selected from:
  • Q and W" can be a -C(O)-C 1-20 alkyl group (e.g., -C(O)-CHs), thereby providing a monomer C having a formula such as:
  • R is a Ci_2o alkyl group (e.g., CH 3 ), and n is as defined herein.
  • n is as defined herein.
  • n can be an integer between 3 and 10,000. In some embodiments, n can be 10-10,000, 20-10,000, 50-10,000, or 100-10,000. For example, n can be 10-5,000, 10-1,000, 10-500, 10-400, 10-300, or 10-200. In certain embodiments, n can be 8-1,000. In various embodiments, the present polymers can have a molecular weight (M w ) between about 1,000 and about 5,000,000, for example, between about 2,000 and about 1,000,000; or between about 5,000 Da and about 500,000 Da.
  • M w molecular weight
  • Formulations of the polymers of the present teachings can be used in various solution-phase processes including, but not limited to, spin-coating, printing, drop casting, dip coating, spraying, and blade coating.
  • Spin-coating involves applying an excess amount of the coating solution onto a substrate, then rotating the substrate at high speed to spread the fluid by centrifugal force.
  • the thickness of the resulting dielectric film prepared by this technique is 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 flexo printing press, pad printing, screen printing or an inkjet printer.
  • the present polymers are particularly useful for preparing dielectric layers in electronic devices, in preferably thin film transistor devices, most preferably thin film transistor devices based on organic semiconducting materials.
  • One of the advantages of the polymer formulations disclosed herein is their ability to crosslink, for example, photocrosslink, after deposition onto a substrate.
  • the crosslinking functionality allows formation of a densely crosslinked polymeric matrix.
  • the crosslinked polymeric matrix is robust enough to withstand various conditions that are common in device fabrication processes, including patterning and subsequent solution-phase processes, for example, to form/deposit overlying layers (e.g., the semiconductor layer in a bottom-gate OTFT structure or the gate layer for a top-gate OTFT structure).
  • the crosslinking chemistry can include a 2+2 photo-stimulated cycloaddition that provides stable cyclobutane moieties.
  • the crosslinking chemistry can also involve free radical additions affording C-C and C-O bonds.
  • Polymers of the present teachings can be cured, for example, photocrosslinked, by exposure to ultraviolet light, for example, at a wavelength of about 250-500 nm (e.g., between about 300 nm and about 450 nm). Shorter wavelengths of light can be filtered through, for example, an optical filter such as pyrex (cutoff ca. 300 nm).
  • Crosslinking also can be achieved by other types of radiation, for example, with ion beams of charged particles, and electron beams with radioactive sources.
  • the dielectric material of the present teachings can be subject to further patterning and process steps, by which additional layers, including additional dielectric, semiconductor and/or conducting layers, can be formed on top of the dielectric material.
  • compositions (formulations) including one or more polymers of the present teachings can be used to prepare dielectric materials that can exhibit a wide range of desirable properties and characteristics including, but not limited to, low leakage current densities, high breakdown voltages, low hysteresis, tuned capacitance values, uniform film thickness, solution-processability, fabricability at low temperatures and/or atmospheric pressures, air and moisture stability, and/or compatibility with diverse gate materials and/or semiconductors.
  • Polymers of the present teachings can have a relatively high glass transition temperature (T g ).
  • T g glass transition temperature
  • the present polymers can have a T g between about 100 0 C and about 200 0 C.
  • the manufacturing process of many electronic devices can include an annealing step at a temperature of 100 0 C or above, and a polymer having a T g less than about 100 0 C may not be as useful in those processes.
  • the present polymers also can have a dielectric constant between about 1.1 and about 5.0, wherein the dielectric constant can be determined using any procedures known in the art, including the procedures described in the standard test method ASTM D 150. Without wishing to be bound by any particular theory, it is believed that copolymerization with PMMA can lead to a higher dielectric constant for certain particular embodiments of the present polymers, for example, those having a coumarin-containing vinyl phenol derivative repeating unit.
  • 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 oxide in a metal-oxide-semiconductor (MOS) structure.
  • MOS metal-oxide-semiconductor
  • Polymers of the present teachings and their crosslinked products can have very low leakage current densities as measured from standard MIS and MIM capacitor structures.
  • Dielectric materials prepared from polymers of the present teachings also can withstand very high breakdown voltages (i.e., the maximum voltage difference that can be applied across the dielectric before it breaks down and begins to conduct).
  • dielectric materials of the present teachings can withstand a breakdown voltage of 4 MV/cm or higher, a breakdown voltage of 6 MV/cm or higher, or a breakdown voltage of 7 MV/cm or higher.
  • the present teachings further provide articles of manufacture, for example, composites, that includes a dielectric material of the present teachings and a substrate component and/or a semiconductor component.
  • the substrate component can be selected from, but is not limited to, doped silicon, an indium tin oxide (ITO), ITO-coated glass, ITO- coated polyimide or other plastics, aluminum or other metals alone or coated on a polymer or other substrate, a doped polythiophene, and the like.
  • the composite can include a semiconductor component.
  • the semiconductor component can be selected from, but is not limited to, various fused heterocycles, aromatic hydrocarbons, polythiophenes, fused (hetero)aromatics (e.g., perylene imides and naphthalene imides), and other such organic semiconductor compounds or materials, whether p-type or n-type, otherwise known or found useful in the art.
  • the semiconductor component can be prepared from one or more compounds and/or polymers as described in U.S. Patent Nos. 6,585,914, 6,608,323, and 6,991,749; and U.S. Patent Publication Nos.
  • the semiconductor component also can include inorganic semiconductor materials such as silicon, germanium, gallium arsenide, metal oxide, and the like.
  • the composite can include one or more interlayers between the semiconductor layer and the dielectric layer.
  • Such interlayers can be electrically insulating and can be prepared from various dielectric polymers.
  • the one or more interlayers can be prepared from polymers such as fluoropolymers (e.g., Cytop®, Asahi Glass Co., Wilmington, DE; and Teflon® AF, Dupont, Wilmington, DE), poly(isobutylene), poly( vinyl phenol-co- methyl methacrylate), poly(vinyl alcohol), poly(propylene), poly( vinyl chloride), polycyanopulluane, polyvinyl phenol), poly(vinyl cyclohexane), benzocyclobutene-based polymers, poly(methyl methacrylate), poly(styrene-co-butadiene), poly( vinyl pyridine), poly(vinylidine fluoride), polyacrylonitrile, poly(4-vinylpyridine), poly(2-ethymer (ethylene
  • the composite can include one or more electrical contacts.
  • Such electrical contacts can be made of a metal (e.g., gold) or any other organic or inorganic electrically conducting material and can function as source, drain, or gate contacts.
  • One or more of the composites described herein can be embodied within various organic electronic, optical, and optoelectronic devices such as organic thin film transistors (OTFTs), specifically, organic field effect transistors (OFETs), as well as sensors, capacitors, unipolar circuits, complementary circuits (e.g., inverter circuits), and the like.
  • OFTs organic thin film transistors
  • OFETs organic field effect transistors
  • sensors capacitors, unipolar circuits, complementary circuits (e.g., inverter circuits), and the like.
  • the present polymers and polymeric materials also can be used to prepare an ancillary component in articles of manufacture such as organic light-emitting diodes, photovoltaics or solar cells. Exploitation of polymers of the present teachings
  • the method can include preparing a polymer composition (formulation) by dissolving one or more polymers described herein in a solvent, and printing the formulation onto a substrate to form a dielectric layer.
  • the method can include exposing the dielectric layer to a radiation source (e.g., ultraviolet light) to induce crosslinking, thereby forming a crosslinked dielectric material.
  • the method can also include printing an additional dielectric layer onto the crosslinked dielectric layer to form a multilayer dielectric material.
  • An aspect of the present teachings relates to a thin film transistor device including a dielectric layer including a dielectric material as described herein, a semiconductor layer, a gate electrode, a source electrode, and a drain electrode.
  • the dielectric layer typically is disposed between the semiconductor layer and the gate electrode.
  • the dielectric layer can be coupled to the semiconductor layer either directly or via optionally present intervening layer(s) such as a protective interlayer.
  • the source and drain electrodes can be disposed above the semiconductor layer (top-contact), or the semiconductor layer can be disposed above the source and drain electrodes (bottom-contact).
  • the dielectric layer can include a polymeric film (e.g., a photocrosslinked polymeric film), wherein the polymeric film can include a polymer having a repeating unit that has a pendant group including a photocrosslinkable pendant group, more specifically, a coumarin-6-yl group, of the formula:
  • a polymeric film e.g., a photocrosslinked polymeric film
  • the polymeric film can include a polymer having a repeating unit that has a pendant group including a photocrosslinkable pendant group, more specifically, a coumarin-6-yl group, of the formula:
  • R 1 R 2 , R 3 , and b are as defined herein.
  • FIG. 14 illustrates the four common types of OFET structures: (a) bottom-gate top-contact structure (14a), (b) bottom-gate bottom-contact structure (14b), (c) top-gate bottom-contact structure (14c), and (d) top-gate top-contact structure (14d).
  • an OFET can include a dielectric layer (8, 8', 8", and 8'"), a semiconductor/channel layer (6, 6', 6", and 6'"), a gate contact (10, 10', 10", and 10'"), a substrate (12, 12', 12", and 12'"), and source (2, 2', 2", and 2'") and drain contacts (4, 4', 4", and 4'").
  • the method can include preparing a polymer formulation that includes one or more polymers described herein, printing the formulation onto a substrate (gate) to form a dielectric layer, forming a semiconductor layer above the dielectric material, and forming a first electrical contact and a second electrical contact (source and drain) on the semiconductor layer, to fabricate a top-contact bottom-gate organic field effect transistor.
  • the method can include exposing the dielectric layer to radiation to induce crosslinking to form a crosslinked dielectric material.
  • the method can include forming a first electrical contact and a second electrical contact (source and drain) on a substrate, forming a semiconductor layer above the substrate and the first and second electrical contacts (to cover the electrical contacts and an area of the substrate between the electrical contacts), preparing a polymer formulation that includes one or more polymers described herein, printing the formulation above the semiconductor layer to form a dielectric layer, forming a third electrical contact (gate) on the dielectric material, wherein the third electrical contact is above an area between the first and second electrical contacts, to fabricate a bottom-contact top-gate organic field effect transistor.
  • the method can include exposing the dielectric layer to radiation to induce crosslinking to form a crosslinked dielectric material.
  • the method can include forming an interlayer above the semiconductor layer before depositing the dielectric polymer formulation.
  • the method can include forming a semiconductor layer on a substrate, forming a first electrical contact and a second electrical contact (source and drain) above the semiconductor layer, preparing a polymer formulation that includes one or more polymers described herein, printing the formulation above the first and second electrical contacts and an area of the semiconductor layer between the first and second electrical contacts to form a dielectric layer, and forming a third electrical contact (gate) above the dielectric material, wherein the third electrical contact is above an area between the first and second electrical contacts, to fabricate a top-contact top-gate organic field effect transistor.
  • the method can include exposing the dielectric layer to radiation to induce crosslinking to form a crosslinked dielectric material.
  • Electrical contacts can be formed by processes such as, but not limited to, thermal evaporation and radio frequency or e-beam sputtering, as well as various deposition processes, including but not limited to those described immediately above (e.g., flexo printing, litho printing, gravure printing, ink-jetting, pad printing, screen printing, drop casting, dip coating, doctor blading, roll coating, and spin- coating).
  • processes such as, but not limited to, thermal evaporation and radio frequency or e-beam sputtering, as well as various deposition processes, including but not limited to those described immediately above (e.g., flexo printing, litho printing, gravure printing, ink-jetting, pad printing, screen printing, drop casting, dip coating, doctor blading, roll coating, and spin- coating).
  • polymers and dielectric materials according to the present teachings were prepared and characterized by NMR, UV- Vis spectroscopy, differential scanning calorimetry (DSC), AFM, and metal-insulator-semiconductor (MIS) device leakage and impedance spectroscopy measurements, to demonstrate, among other things, their dielectric properties and their compatibility with various p-type and n-type organic semiconductors.
  • Organic electronic devices for example, organic thin film transistors (OTFTs), specifically, organic field effect transistors (OFETs), based on these dielectric films also have been fabricated and characterized, data of which are provided below.
  • Example 2 Preparation of PVP O 55 -CO-PMMA 0 45 -OHOC-AC
  • the supernatant was decanted and the remaining residue was precipitated once from 20 mL cyclopentanone/60 mL methanol and once from 20 mL cyclopentanone/60 mL diethyl ether.
  • the residue was dissolved in 50 mL of cyclopentanone and filtered.
  • the filtrate was concentrated to 20 rnL and treated with 70 mL of diethyl ether.
  • the cloudy supernatant was removed and the remaining residue was treated with 50 mL of diethyl ether and shaken and/or stirred for 15 minutes.
  • the suspension was filtered and the filter cake was dried in vacuo to give 5.4 g (76% yield) of PVP-6HOC-Ac as a white powder.
  • the mixture was poured into 100 mL of methanol and the resulting suspension was reduced in volume by half using a rotary evaporator.
  • the mixture was treated with 50 mL of methanol and the supernatant was decanted.
  • the remaining residue was dissolved in chloroform (15 mL) and pyridine (1 mL) and precipitated using methanol (30 mL).
  • the supernatant was decanted and the remaining residue was precipitated three times from chloroform (15 mL)/methanol (30 mL), each time decanting the supernatant.
  • the remaining residue was dissolved in 50 mL of chloroform and added dropwise into 200 mL of methanol cooled to -78 0 C.
  • the precipitate was filtered off and dried in vacuo to give 5.7 g of PVPo.55-co-PMMAo. 45 -7HOC-Ac as a pale yellow powder.
  • the remaining residue was treated first with 10 mL cyclopentanone to dissolve the oily portion and then with 50 mL of methanol. The supernatant was decanted and the remaining residue was precipitated twice from 30 mL cyclopentanone/ 100 mL methanol, each time decanting the supernatant. The remaining residue was dissolved in 30 mL of cyclopentanone and filtered directly into -78 0 C methanol with vigorous stirring. The suspension was filtered and the filter cake was dried in vacuo to give 3.2 g of (PVP-6HOC-Ac)o.8o-co-(PVP-Ac)o.2o as an off-white powder.
  • Example 9 Polymerization of VP-6HOC-Ac
  • Example 10 Solubility of photopolymer materials before and after photocrosslinking
  • photopolymers of the present teachings are soluble in common organic solvents including, but not limited to, tetrahydrofuran, bis(2-methoxyethyl) ether, dioxane, chloroform, ethyl acetate, acetone, toluene, dichlorobenzene, cyclohexylbenzene, dimethylformamide, N-methyl pyrrolidone, dimethyl sulfoxide, cyclopentanone and cyclohexanone.
  • Photopolymers from Examples 2-7 and 9, for example, have excellent solubility in common organic solvents.
  • PVPo.ss-co-PMMAo ⁇ - ⁇ HOC-Ac from Example 2 can be dissolved in cyclopentanone without heating to give a solution having a concentration of 350 mg/mL. Such a solution is sufficiently viscous for use in gravure printing.
  • photopolymers of the present teachings can be cured by exposure to ultraviolet light (e.g., via treatment in a 400 W UV oven for 0.5-5 minutes), which renders them insoluble in the organic solvents in which they were initially soluble prior to the photocrosslinking step.
  • the cured dielectric films were found to be robust enough to withstand relatively harsh processes. For example, a photocrosslinked dielectric film was soaked in cyclopentanone for 1-5 min, after which its thickness and physical appearance was found to be substantially the same as before the soaking step. This feature of the present dielectric materials makes them attractive candidates for solution-processed bottom-gate OFETs, which requires that the dielectric layer be insoluble in the solution-processing solvent for the deposition of the semiconductor layer.
  • Example 11 Dielectric film fabrication
  • bottom-contact top-gate OFETs were fabricated using a dielectric material of the present teachings (PVPo.ss-co-PMMAo ⁇ - ⁇ HOC-Ac from Example 2) as the dielectric layer.
  • Step 1 Substrate: Glass slides 1" x 1 ", 0.4 mm thickness (PGO) were cleaned by sonication in ethanol three times and kept in ethanol before the next step.
  • Step 2. Source and drain electrodes: Glass substrates from Step 2 were loaded onto a CV302-FR metal evaporator (Cooke Vacuum).
  • the films were transferred to a Dymax UV curing system and exposed to UV irradiation for 4 minutes under a 320 nm filter (ca. 8 mW/cm 2 lamp intensity) and baked at 110 0 C in a vacuum oven for 20 minutes.
  • Pentacene Sigma- Aldrich, St. Louis, MO
  • Pentacene was vacuum-deposited at about 2 x 10 "6 Torr (500 A, 0.3 A/s) while maintaining the substrate temperature at about 50 0 C to about 70 0 C.
  • Gold (Au) electrodes were vacuum-deposited through shadow masks at 3-4 x 10 ⁇ 6 Torr (500 A, 0.3 A/s).
  • the channel length was 50 ⁇ m, and the channel width was 5000 ⁇ m. Measurement was performed as in Example 10. Representative OFET transfer plots are shown in Figures 10-11.
  • Example 19 Effects of solvent treatment on crosslinked dielectric films

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US20110215334A1 (en) 2011-09-08
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US9923158B2 (en) 2018-03-20
EP2660889A2 (en) 2013-11-06
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TWI491622B (zh) 2015-07-11
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US8937301B2 (en) 2015-01-20
CN102224611A (zh) 2011-10-19
TW201030028A (en) 2010-08-16
US20140363690A1 (en) 2014-12-11
KR20110106320A (ko) 2011-09-28
JP5684715B2 (ja) 2015-03-18
EP2660889A3 (en) 2014-11-12
EP2368281B1 (en) 2015-05-20
WO2010057984A3 (en) 2010-09-23
CN102224611B (zh) 2014-01-22
EP2368281A2 (en) 2011-09-28
JP2012510149A (ja) 2012-04-26
KR20160005138A (ko) 2016-01-13

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