EP2707455A1 - Halogenierte perylen-basierte halbleitermaterialien - Google Patents

Halogenierte perylen-basierte halbleitermaterialien

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Publication number
EP2707455A1
EP2707455A1 EP12717702.0A EP12717702A EP2707455A1 EP 2707455 A1 EP2707455 A1 EP 2707455A1 EP 12717702 A EP12717702 A EP 12717702A EP 2707455 A1 EP2707455 A1 EP 2707455A1
Authority
EP
European Patent Office
Prior art keywords
substituents
optionally substituted
alkyl
cor
independently
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP12717702.0A
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English (en)
French (fr)
Inventor
Helmut Reichelt
Thomas Gessner
Chen Li
Klaus MÜLLEN
Glauco BATTAGLIARIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Original Assignee
BASF SE
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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Priority to EP12717702.0A priority Critical patent/EP2707455A1/de
Publication of EP2707455A1 publication Critical patent/EP2707455A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/08—Naphthalimide dyes; Phthalimide dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Definitions

  • Organic semiconducting materials can be used in electronic devices such as organic photo- voltaic (OPV) cells, organic field-effect transistors (OFETs) and organic light emitting diodes (OLEDs).
  • OCV organic photo- voltaic
  • OFETs organic field-effect transistors
  • OLEDs organic light emitting diodes
  • the organic semiconducting material-based devices show high charge carrier mobility and high stability, in particular towards oxi- dation, under ambient conditions.
  • the organic semiconducting materials are compatible with liquid processing techniques as liquid processing techniques are convenient from the point of proc- essability, and thus allow the production of low cost organic semiconducting material-based electronic devices.
  • liquid processing techniques are also compatible with plastic substrates, and thus allow the production of light weight and flexible organic semiconducting material-based electronic devices.
  • Perylene bisimide-based organic semiconducting materials suitable for use in electronic devices are known in the art.
  • Ar 1 is a first aromatic core and is a divalent, trivalent or tetravalent radical of a long list of formulae, including
  • EC is a first end capping group and is a monovalent radical of a long list of formulae, n is an integer of 2 to 4
  • Z is NH or CH 2
  • OFET organic thin film transistor
  • the organic semiconductor film is formed of pentacene.
  • the organic acceptor film is formed of at least one electron withdrawing material selected from a long list of compounds, including N,N'-bis(di-feri-butyphenyl)-3,4,9,10-perylenedicarboximide.
  • US 7,326,956 B2 describes a thin film transitor comprising a layer of organic semiconductor material comprising tetracarboxylic diimide perylene-based compound having attached to each of the imide nitrogen atoms a carbocyclic or heterocyclic aromatic ring system substituted with one or more fluorine containing groups.
  • the fluorine-containing N,N'-diaryl perylene-based tetracarboxylic diimide compound is represented by the following structure:
  • a 1 and A 2 are independently carbocyclic and/or heterocyclic aromatic ring systems comprising at least one aromatic ring in which one or more hydrogen atoms are substituted with at least one fluorine-containing group.
  • the perylene nucleus can be optionally substituted with up to eight independently selected X groups, wherein n is an integer from 0 to 8.
  • the X substituent groups on the perylene can include a long list of substituents, including halogens such as fluorine or chlorine.
  • each R 1 to R 8 can be independently selected from H, an electron-withdrawing substituent and a moiety comprising such substituent.
  • Electron-withdrawing substitutents include a long list of substituents, including cyano.
  • R 9 and R 10 are independently selected from H, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, polycyclic aryl and/or substi- tuted polycyclic aryl moieties.
  • WO 2005/124453 describes perylenetetracarboxylic diimide charge-transfer materials, for example a perylenetetracarboxylic diimide charge-transfer material having formula
  • Y in each instance can be independently selected from H, CN, acceptors, donors and a polymerizable group; and X in each instance can be independently selected from a large group of listed compounds.
  • WO 2008/063609 describes a compound having the following formula
  • A, B, I, D, E, F, G and H are independently selected from a group of substituents, including, CH and CR a , wherein R a can be selected from a list of substituents, including halogen.
  • A, B, I, D, E, F, G and H can be independently CH, C-Br or C-CN.
  • WO 2009/098252 describes semiconducting compounds having formula
  • R 1 and R 2 at each occurrence independently are selected from a large list of groups, including H, Ci-30-alkyl and C2-3o-alkenyl; and R 3 , R 4 , R 5 and R 6 are independently H or an electron-withdrawing group.
  • R 3 , R 4 , R 5 and R 6 can be independently from each other H, F, CI, Br, I or CN.
  • WO 2009/144205 describes bispolycyclic rylene-based semiconducting compounds, which can be prepared from a compound of formula
  • LG is a leaving group, including CI, Br or I,
  • ⁇ -1 can be
  • A, B, I, D, E, F, G and H are independently selected from a group of substituents, in eluding, CH and CR a , wherein R a can be selected from a list of substituents, including halogen.
  • the object is solved by the compound of claim 1 , the process of claim 5, and the electronic de- vice of claim 6.
  • the perylene-based semiconducting compound of the present invention is of formula 1
  • R 1 and R 2 are independently from each other selected from the group consisting of H, Ci-30-alkyl optionally substituted with 1 to 30 substituents R a , C2-3o-alkenyl optionally substituted with
  • -O-COR 3 -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -SO 2 -Ci- 30 -alkyl optionally substituted with 1 to 30 substituents R', -NH 2 , -NHR 3 , -NR 3 R 4 , -[NR 3 R 4 R 5 ] + , -NH-COR 3 , -COOH, -COOR 3 , -CONH 2 , -CONHR 3 , -CONR 3 R 4 , -CO-H, -COR 3 , Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C 2- 3o-alkenyl optionally substituted with 1 to 30 substituents R', C 2- 3o-alkynyl optionally substituted with 1 to 30 substituents R',
  • R 3 , R 4 and R 5 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C 2- 3o-alkenyl optionally substituted with 1 to 30 substituents R', C 2- 3o-alkynyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to
  • R 6 , R 7 and R 8 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C 2- 3o-alkenyl, C 2- 3o-alkynyl, C3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl,
  • X is -CI, -Br or -I.
  • Ci-io-alkyl and Ci-30-alkyl can be branched or unbranched.
  • Examples of Ci-10-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, fert-butyl, n-pentyl, neopentyl, isopentyl, n-(1 -ethyl)propyl, n-hexyl, n-heptyl, n-octyl, n-(2-ethyl)hexyl, n-nonyl and n-decyl.
  • C3-8-alkyl examples include n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, fert-butyl, n-pentyl, neopentyl, isopentyl, n-(1 -ethyl)propyl, n-hexyl, n-heptyl, n-octyl and n-(2-ethyl)hexyl.
  • Ci-30-alkyl examples are Ci-10-alkyl, and n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C 20 ), n-docosyl (C 22 ), n-tetracosyl (C 2 4), n-hexacosyl (C 2 6), n-octacosyl (C 2 s) and n-triacontyl (C30).
  • C3- 2 5-alkyl branched at the C attached to the N of formula I are isopropyl, sec-butyl, n-(1 -methyl)propyl, n-(1 - ethyl)propyl, n-(1 -methyl)butyl, n-(1 -ethyl)butyl, n-(1 -propyl)butyl, n-(1 -methyl)pentyl, n-(1 - ethyl)pentyl, n-(1 -propyl)pentyl, n-(1 -butyl)pentyl, n-(1 -butyl)hexyl, n-(1 -pentyl)hexyl, n-(1 -pentyl)hexyl, n-(1 - hexyl)heptyl, n-(1 -heptyl)oc
  • C2-3o-alkenyl can be branched or unbranched.
  • Examples of C2-3o-alkenyl are vinyl, propenyl, cis- 2-butenyl, frans-2-butenyl, 3-butenyl, c/s-2-pentenyl, frans-2-pentenyl, c/s-3-pentenyl, trans- 3-pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl, linoleyl (ds), linolenyl (Cis), oleyl (Cis), arachidonyl (C20), and erucyl (C22).
  • C2-3o-alkynyl can be branched or unbranched.
  • Examples of C2-3o-alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and decynyl, undecynyl, do- decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptade- cynyl, octadecynyl, nonadecynyl and icosynyl (C20).
  • C3-io-cycloalkyl are preferably monocyclic C3-io-cycloalkyls such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, but include also polycyclic
  • C3-io-cycloalkyls such as decalinyl, norbornyl and adamantyl.
  • Cs-io-cycloalkenyl are preferably monocyclic Cs-io-cycloalkenyls such as cyclopen- tenyl, cyclohexenyl, cyclohexadienyl and cycloheptatrienyl, but include also polycyclic
  • Examples of 3-14 membered cycloheteroalkyi are monocyclic 3-8 membered cycloheteroalkyi and polycyclic, for example bicyclic 7-12 membered cycloheteroalkyi.
  • Examples of monocyclic 3-8 membered cycloheteroalkyi are monocyclic 5 membered cycloheteroalkyi containing one heteroatom such as pyrrolidinyl, 1 -pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl, tetrahydrofuryl, 2,3-dihydrofuryl, tetrahydrothiophenyl and 2,3-dihydrothiophenyl, monocyclic
  • cycloheteroalkyi containing one heteroatom such as piperidyl, piperidino, tetrahy- dropyranyl, pyranyl, thianyl and thiopyranyl, monocyclic 6 membered cycloheteroalkyi containing two heteroatoms such as piperazinyl, morpholinyl and morpholino and thiazinyl, monocyclic 7 membered cycloheteroalkyi containing one hereoatom such as azepanyl, azepinyl, oxepanyl, thiepanyl, thiapanyl, thiepinyl, and monocyclic 7 membered cycloheteroalkyi containing two hereoatom such as 1 ,2-diazepinyl and 1 ,3-thiazepinyl.
  • C6-i4-aryl can be monocyclic or polycyclic.
  • Examples of C6-i4-aryl are monocyclic C6-aryl such as phenyl, bicyclic Cg-io-aryl such as 1 -naphthyl, 2-naphthyl, indenyl, indanyl and tetrahy- dronaphthyl, and tricyclic Ci2-i4-aryl such as anthryl, phenanthryl, fluorenyl and s-indacenyl.
  • 5-14 membered heteroaryl can be monocyclic 5-8 membered heteroaryl, or polycyclic 7-14 membered heteroaryl, for example bicyclic 7-12 membered or tricyclic 9-14 membered heteroaryl.
  • monocyclic 5-8 membered heteroaryl examples include monocyclic 5 membered heteroaryl con- taining one heteroatom such as pyrrolyl, furyl and thiophenyl, monocyclic 5 membered heteroaryl containing two heteroatoms such as imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, monocyclic 5 membered heteroaryl containing three heteroatoms such as
  • 1 ,2,3-triazolyl, 1 ,2,4-triazolyl and oxadiazolyl monocyclic 5 membered heteroaryl containing four heteroatoms such as tetrazolyl, monocyclic 6 membered heteroaryl containing one heteroa- torn such as pyridyl, monocyclic 6 membered heteroaryl containing two heteroatoms such as pyrazinyl, pyrimidinyl and pyridazinyl, monocyclic 6 membered heteroaryl containing three heteroatoms such as 1 ,2,3-triazinyl, 1 ,2,4-triazinyl and 1 ,3,5-triazinyl, monocyclic 7 membered heteroaryl containing one heteroatom such as azepinyl, and monocyclic 7 membered heteroaryl containing two heteroatoms such as 1 ,2-diazepinyl.
  • monocyclic 5 membered heteroaryl containing four heteroatoms such as
  • bicyclic 7-12 membered heteroaryl examples include bicyclic 9 membered heteroaryl containing one heteroatom such as indolyl, isoindolyl, indolizinyl, indolinyl, benzofuryl, isobenzofuryl, ben- zothiophenyl and isobenzothiophenyl, bicyclic 9 membered heteroaryl containing two heteroatoms such as indazolyl, benzimidazolyl, benzimidazolinyl, benzoxazolyl, benzisooxazolyl, benzthiazolyl, benzisothiazolyl, furopyridyl and thienopyridyl, bicyclic 9 membered heteroaryl containing three heteroatoms such as benzotriazolyl, benzoxadiazolyl, oxazolopyridyl, isooxa- zolopyridyl, thiazolopyridyl, iso
  • tricyclic 9-14 membered heteroaryls examples include dibenzofuryl, acridinyl, phenoxazinyl, 7H- cyclopenta[1 ,2-b:3,4-b']dithiophenyl and 4H-cyclopenta[2,1 -b:3,4-b']dithiophenyl.
  • halogen examples are -F, -CI, -Br and -I.
  • Ci-30-alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, fert-butoxy, n-pentoxy, neopentoxy, isopentoxy, hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, n-tridecoxy, n-tetradecoxy, n-pentadecoxy, n-hexadecoxy, n-heptadecoxy, n-octadecoxy and n-nonadecoxy.
  • Examples of C2-5-alkylene are ethylene, propylene, butylene and pentylene.
  • C2-5-alkylene are ethylene, prop
  • R 1 and R 2 are independently from each other selected from the group consisting of H, Ci-30-alkyl optionally substituted with 1 to 30 substituents R a , C2-3o-alkenyl optionally substituted with 1 to 30 substituents R a , C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R b , and C6-i4-aryl optionally substituted with 1 to 8 substituents R c , wherein
  • R 3 , R 4 and R 5 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R iH ,
  • R 6 , R 7 and R 8 at each occurrence are independently from each other selected from the group consisting of Ci -3 o-alkyl, C 2-3 o-alkenyl, C 3- io-cycloalkyl, and C6-i4-aryl, and
  • X is -CI, -Br or I.
  • R 1 and R 2 are independently from each other Ci -3 o-alkyl optionally substituted with 1 to 30 substituents R a , wherein
  • R 3 , R 4 and R 5 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R iH ,
  • R 6 , R 7 and R 8 at each occurrence are independently from each other selected from the group consisting of Ci -3 o-alkyl, C 2-3 o-alkenyl, C 3- io-cycloalkyl, and C6-i4-aryl, and
  • X is -CI, -Br or -I. Most preferably,
  • R 1 and R 2 are independently from each other C 3-2 5-alkyl branched at the C attached to the N of formula 1 and
  • X is -CI, -Br or -I. Particular preferred are the compounds of formulae
  • R 1 and R 2 are as defined above, which process comprises the steps of
  • R 1 and R 2 are as defined above, and L is a linking group
  • L is preferably C2-5-alkylene, which can be optionally substituted with 1 to 6 Ci-10-alkyl groups. More preferably L is ethylene or propylene and is substituted with 2 to 4 methyl groups.
  • the transition metal-containing catalyst can be an iridium-containing catalyst such as
  • the first step can be performed in the presence of a base such as di-feri-butylbipyridine. If the transition metal- containing catalyst is an iridium-containing catalyst, the first step is usually performed in a suitable organic solvent such as tetrahydrofuran or 1 ,4-dioxane. If the transition metal-containing catalyst is an iridium-containing catalyst, the first step is usually performed at elevated temperatures, such as at temperatures from 60 to 1 10 °C. In principal, if the transition metal-containing catalyst is an iridium-containing catalyst, the first step can be performed in analogy to the method described by C. W. Liskey; X. Liao; J. F.
  • the first step is usu- ally performed in a suitable organic solvent such as toluene, pinacolone and mesitylene or mixtures thereof. If the transition metal-containing catalyst is ruthenium-containing catalyst, the first step is usually performed at elevated temperatures, such as at temperatures from 120 to 160 °C.
  • the Cl-source source can be Cu(ll)Cl2.
  • the Br-source source can be Cu(ll)Br2.
  • the l-source source can be Nal in combination with chloroamine T.
  • the second step is usually performed in a suitable solvent such as water, methanol, THF and dioxane, or mixtures thereof.
  • the second step is usually performed at elevated temperatures, such as at temperatures from 40 to 140 °C.
  • the second step is preferably performed at elevated temperatures, such as at temperatures from 80 to 140 °C.
  • the second step is preferably performed at elevated temperatures, such as at temperatures from 40 to 80 °C.
  • the compounds of formulae (4) and (1 ) can be isolated by methods known in the art, such as column chromatography.
  • the compound of formula (2) can be obtained by methods known in the art, for example as described in the subsection titled "Synthesis" of F. Wurthner, Chem. Commun., 2004, 1564-1579.
  • an electronic device comprising the compound of formula (1 ) as semiconducting material.
  • the electronic device is an organic field effect transistor (OFET).
  • an organic field effect transistor comprises a dielectric layer, a semiconducting layer and a substrate.
  • an organic field effect transistor usually comprises a gate electrode and source/drain electrodes.
  • An organic field effect transistor can have various designs. The most common design of an organic field-effect transistor is the bottom-gate design. Examples of bottom-gate designs are shown in Figures 1.
  • top-gate design Another design of an organic field-effect transistor is the top-gate design. Examples of top-gate designs are shown in Figure 2.
  • the semiconducting layer comprises the semiconducting material of the present invention.
  • the semiconducting layer can have a thickness of 5 to 500 nm, preferably of 10 to 100 nm, more preferably of 20 to 50 nm.
  • the dielectric layer comprises a dielectric material.
  • the dielectric material can be silicon dioxide, or, an organic polymer such as polystyrene (PS), poly(methylmethacrylate) (PMMA), poly(4-vinylphenol) (PVP), polyvinyl alcohol) (PVA), benzocyclobutene (BCB), or polyimide (PI).
  • PS polystyrene
  • PMMA poly(methylmethacrylate)
  • PVP poly(4-vinylphenol)
  • PVA polyvinyl alcohol
  • BCB benzocyclobutene
  • PI polyimide
  • the dielectric layer can have a thickness of 10 to 2000 nm, preferably of 50 to 1000 nm, more preferably of 100 to 800 nm
  • the source/drain electrodes can be made from any suitable source/drain material, for example gold (Au) or tantalum (Ta).
  • the source/drain electrodes can have a thickness of 1 to 100 nm, preferably from 5 to 50 nm.
  • the gate electrode can be made from any suitable gate material such as highly doped silicon, aluminium (Al), tungsten (W), indium tin oxide, gold (Au) and/or tantalum (Ta).
  • the gate elec- trode can have a thickness of 1 to 200 nm, preferably from 5 to 100 nm.
  • the substrate can be any suitable substrate such as glass, or a plastic substrate such as poly- ethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).
  • a combination of the gate electrode and the dielectric layer can also function as substrate.
  • the organic field effect transistor can be prepared by methods known in the art.
  • a bottom-gate organic field effect transistor can be prepared as follows:
  • the gate electrode can be formed by depositing the gate material, for example highly doped silicon, on one side of the dielectric layer made of a suitable dielectric material, for example si- licium dioxide.
  • the other side of the dielectric layer can be optionally treated with a suitable reagent, for example with hexamethyldisilazane (HMDS).
  • Source/drain electrodes can be deposited on this side (the side which is optionally treated with a suitable reagent) of the dielectric layer for example by vapour deposition of a suitable source/drain material, for example tantalum (Ta) and/or gold (Au).
  • the source/drain electrodes can then be covered with the semiconducting layer by solution processing, for example drop coating, a solution of the semiconducting material of the present invention in s suitable solvent, for example in chloroform. Also part of the invention is the use of the compound of formula (1 ) as semiconducting material.
  • the advantage of the semiconducting materials of the present invention is the high solubility of these materials in solvents suitable for solution processing.
  • the semiconducting materials of the present invention show acceptable to high charge carrier mobility.
  • the semiconducting materials are stable, in particular towards oxidation, under ambient conditions.
  • A/,A/'-Bis(1 -heptyloctyl) perylene-3,4:9,10-tetracarboxylic acid bisimide (2b) (100 mg, 0.12 mmol) and bispinacolonediboronate (3a) (250 mg, 0.99 mmol) are mixed together and dissolved in 1 ml. anhydrous mesitylene and 1 ml. anhydrous pinacolone. Argon is bubbled through the solution for 30 minutes.
  • RuH2(CO)(PPh3)3 23 mg, 0,03 mmol
  • thermoly grown silicon dioxide (thickness: 200 nm) is used as dielectric layer.
  • the gate electrode is formed by depositing highly doped silicon on one side of the dielectric layer.
  • the other side of the dielectric layer is treated with hexamethyldisilazane (HMDS) by vapour deposition of hexamethyldisilazane.
  • HMDS hexamethyldisilazane
  • the contact angle of the surface of the HMPS-treated side of the dielectric layer is 93.2 ⁇ 1.3°.
  • Source/drain electrodes (Ta (thickness: 10 nm) covered by Au (thick- ness: 40 nm)) are deposited on the HMPS-treated side of the dielectric layer by vapour deposition.
  • the source/drain electrodes are then covered with the semiconducting layer (thickness: ca.
  • the drain current ISD [A] in relation to the gate voltage VSG [V] (top transfer curve) and the drain current ISD 0 5 [ ⁇ ° 5 ] in relation to the gate voltage VSG [V] (bottom transfer curve) for the bottom- gate organic field effect transistor of example 6 comprising compound 1c as semiconducting material at a drain voltage VSD of 100 V is determined in a nitrogen filled glove box (O2 content: 0.1 ppm, H 2 0 content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine is shown. The results are shown in Figure 4.
  • the drain current ISD in relation to the drain voltage VSD (output curve) for the bottom-gate organic field effect transistor of example 6 comprising compound 1c as semiconducting material at a gate voltage VSG of 100 V (first and top curve), 90 V (second curve), 80 V (third curve), 70 V (fourth curve) and 0 V (fifth and bottom curve) is determined in a nitrogen filled glove box (O2 content: 0.1 ppm, H2O content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine is shown. The results are shown in Figure 5.
  • drain current ISD [A] in relation to the gate voltage VSG [V] (top transfer curve) and the drain current ISD 0 5 [ ⁇ ° 5 ] in relation to the gate voltage VSG [V] (bottom transfer curve) for the bottom- gate, organic field effect transistor of example 6 comprising compound 1 b as semiconducting material at a drain voltage VSD of 100 V is determined in a nitrogen filled glove box (O2 content: 0.1 ppm, H 2 0 content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine is shown. The results are shown in Figure 6.
  • the drain current ISD in relation to the drain voltage VSD (output curve) for the bottom-gate organic field effect transistor of example 6 comprising compound 1 b as semiconducting material at a gate voltage VSG of 100 V (first and top curve), 90 V (second curve), 80 V (third curve) and 0 V (fourth and bottom curve) is determined in a nitrogen filled glove box (O2 content: 0.1 ppm, H2O content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine is shown. The results are shown in Figure 7.
  • the average values and the 90% confidence interval (in parentheses) of the charge carrier mobilities ⁇ 53 ⁇ [cmWs], the ION/IOFF ratios and the switch-on voltages Vso [V] for the bottom-gate organic field effect transistors of example 6 comprising compound 1 b, respectively, 1c, as semi- conducting material are given in table 1.
  • the switch-on voltage Vso [V] is the gate voltage VSG [V] where the drain current ISD [A] starts to increase (out of the off-state).
  • A/,A/'-Bis-octyl-2,5,8,1 1 -tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]perylene-3,4:9,10- tetracarboxylic acid bisimide (0.68 mg, 0.61 mmol) and copper(ll) bromide (1 ,62 g, 7.3 mmol) are suspended in a mixture of dioxane (10 mL), methanol (3 ml) and water (3 ml) and heated at 120°C for 12 hours. The reaction mixture is then poured into HCI (1 .0 M) and the solid so obtained filtered.

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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Thin Film Transistor (AREA)
EP12717702.0A 2011-05-11 2012-04-27 Halogenierte perylen-basierte halbleitermaterialien Withdrawn EP2707455A1 (de)

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