Patent Application
20100187514
The present invention relates to an organic thin film transistor having an organic semiconductor layer and an organic thin film light emitting transistor. In particular, the present invention relates to an organic thin film transistor containing a compound with a high field effect mobility and capable of undergoing a high-speed operation, an organic thin film light emitting transistor using the same as a light emitting device and a compound suitable for this.
A thin film transistor (TFT) is widely used as a switching element for display of a liquid crystal display, etc. A sectional structure of a representative TFT is shown in
A TFT has hitherto been prepared by using amorphous or polycrystalline silicon. However, there was a problem that a CVD apparatus which is used for the preparation of a TFT using such silicon is very expensive so that increasing in size of a display, etc. using a TFT is accompanied by a significant increase of manufacturing costs. Also, since a process for fabricating amorphous or polycrystalline silicon is carried out at a very high temperature, the kind of a material which can be used as a substrate is limited, causing a problem that a lightweight resin substrate or the like cannot be used.
In order to solve such a problem, there has been proposed a TFT using an organic material in place of amorphous or polycrystalline silicon (this TFT will be hereinafter often abbreviated as “organic TFT”). As a fabrication method which is adopted during forming a TFT by an organic material, there are known a vacuum vapor deposition method, a coating method and so on. According to such a fabrication method, it is possible to realize increasing in size of a device while suppressing an increase of the manufacturing costs, and the process temperature which is necessary at the time of fabrication can be made relatively low. For that reason, in the organic TFT, there is an advantage that limitations at the time of selection of a material to be used for the substrate are few; its practical implementation is expected; and studies have been eagerly reported.
As an organic semiconductor which is used for the organic TFT, so far as a p-type is concerned, multimers such as conjugated polymers, thiophenes, etc.; metallophthalocyanine compounds; condensed aromatic hydrocarbons such as pentacene, etc.; and the like are used singly or in a state of a mixture with other compounds. Also, as a material of an n-type FET (field effect transistor), for example, 1,4,5,8-naphthalenetetracarboxyl dianhydride (NTCDA), 11,11,12,12-tetracyanonaphth-2,5-guinodimethane (TCNNQD), 1,4,5,8-naphthalenetetracarboxyl diimide (NTCDI) and phthalocyanine fluoride are known.
On the other hand, there is an organic electroluminescence (EL) device as a device similarly using electric conduction. However, the organic EL device generally forcedly feeds charges upon application of a strong electric field of 105 V/cm or more in the thickness direction of a ultra-thin film of not more than 100 nm; whereas in the case of the organic TFT, it is necessary to feed charges at a high speed over a distance of several μm or more in an electric field of not more than 105 V/cm, and thus, the organic material itself is required to become more conductive. However, the foregoing compounds in the conventional organic TFTs involved a problem in high-speed response as a transistor because the field effect mobility is low, and the response speed is slow. Also, the ON/OFF ratio was small.
The terms “ON/OFF ratio” as referred to herein refer to a value obtained by dividing a current flowing between a source and a drain when a gate voltage is applied (ON) by a current flowing between the source and the drain when no gate voltage is applied (OFF). The terms “ON current” as referred to herein usually refer to a current value (saturated current) at the time when the gate voltage is increased, and the current flowing between the source and the drain is saturated.
Also, Patent Document 1 and Non-Patent Documents 1 and disclose organic compounds displaying a high mobility through a combination of an olefin structure with an aromatic hydrocarbon group or an aromatic heterocyclic group. However, these involve such a defect that the response speed is slow.
Also, Non-Patent Document 3 discloses that a tetramer structure in which an acetylene structure is combined with a benzene ring displays an organic transistor characteristic. However, there is involved a defect that the mobility is low.
[Patent Document 1] PCT International Patent Publication No. WO 2006/113205
[Non-Patent Document 1] Hong Meng, et al., Journal of American Chemical Society, Vol. 128, page 9304 (2006)
[Non-Patent Document 2] Lay-Lay Chua, et al., Nature, Vol. 434, page 194 (2005)
[Non-Patent Document 3] T. Oyamada, et al., Japanese Journal of Applied Physics, Vol. 45, page L1331 (2006)
In order to solve the foregoing problems, the present invention has been made. An object of the present invention is to provide an organic thin film transistor having a high response speed (driving speed) and a large ON/OFF ratio, an organic thin film light emitting transistor utilizing the same and an organic compound suitable for this.
In order to achieve the foregoing object, the present inventors made extensive and intensive investigations. As a result, it has been found that the response speed (driving speed) can be made high by using an organic compound having a structure represented by the following general formula (1) in an organic semiconductor layer of an organic thin film transistor, leading to accomplishment of the present invention.
That is, the present invention is to provide an organic thin film transistor comprising a substrate having thereon at least three terminals of a gate electrode, a source electrode and a drain electrode, an insulator layer and an organic semiconductor layer, with a current between a source and a drain being controlled upon application of a voltage to the gate electrode, wherein the organic semiconductor layer includes an organic compound having a structure represented by the following general formula (1).
[In the formula, B1 and B2 each independently represents a divalent aromatic hydrocarbon group having from 6 to 60 carbon atoms or a divalent aromatic heterocyclic group having from 1 to 60 carbon atoms; R1 to R10 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having from 1 to 30 carbon atoms, a haloalkyl group having from 1 to 30 carbon atoms, an alkoxyl group having from 1 to 30 carbon atoms, a haloalkoxyl group having from 1 to 30 carbon atoms, an alkylamino group having from 1 to 30 carbon atoms, a dialkylamino group having from 2 to 60 carbon atoms (the alkyl groups may be bonded to each other to form a nitrogen atom-containing cyclic structure), an alkylsulfonyl group having from 1 to 30 carbon atoms, a haloalkylsulfonyl group having from 1 to 30 carbon atoms, an alkylthio group having from 1 to 30 carbon atoms, a haloalkylthio group having from 1 to 30 carbon atoms, an alkylsilyl group having from 3 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 60 carbon atoms or an aromatic heterocyclic group having from to 60 carbon atoms; each of these groups may have a substituent; and R1 to R5 and R6 to R10 may each form a saturated or unsaturated cyclic structure together with an adjacent group thereto.]
Also, the present invention is to provide an organic thin film light emitting transistor in which in an organic thin film transistor, light emission is obtained while utilizing a current flowing between a source and a drain, and the light emission is controlled upon application of a voltage to a gate electrode.
Also, the present invention is to provide an organic compound represented by the following general formula (2).
[In the formula, R11 and R12 each independently represents an alkyl group having from 1 to 30 carbon atoms.]
Also, the present invention is to provide an organic compound represented by the following general formula (3).
[In the formula, R13 to R22 each independently represents an alkyl group having from 1 to 30 carbon atoms; and B3 and B4 each independently represents a divalent, bicyclic or polycyclic condensed aromatic hydrocarbon group having from 10 to 60 carbon atoms or a divalent, bicyclic or polycyclic condensed aromatic heterocyclic group having from 4 to 60 carbon atoms.]
The organic thin film transistor of the present invention is made high with respect to the response speed (driving speed), has a large ON/OFF ratio and has a high performance as a transistor, and thus, it can also be utilized as an organic thin film light emitting transistor which can achieve light emission.
The present invention is concerned with an organic thin film transistor comprising a substrate having thereon at least three terminals of a gate electrode, a source electrode and a drain electrode, an insulator layer and an organic semiconductor layer, with a current between a source and a drain being controlled upon application of a voltage to the gate electrode, wherein the organic semiconductor layer includes an organic compound having a structure represented by the following general formula (1).
In the foregoing formula (1), B1 and B2 each independently represents a divalent aromatic hydrocarbon group having from 6 to 60 carbon atoms or a divalent aromatic heterocyclic group having from 1 to 60 carbon atoms; and each of these groups may have a substituent.
In the foregoing general formula (1), it is preferable that B1 and B2 each independently represents a benzene ring-containing group.
In the foregoing general formula (1), it is preferable that B1 and B2 each independently represents a 5-membered aromatic heterocyclic ring-containing group.
Specific examples of the aromatic hydrocarbon group for the foregoing B1 and B2 include optionally substituted divalent residues of benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene, chrysene, triphenylene, corannulene, coronene, hexabenzotriphenylene, hexabenzocoronene, sumanene, etc.
Also, specific examples of the aromatic heterocyclic group for B1 and B2 include optionally substituted divalent residues of pyridine, pyrazine, quinoline, naphthylidine, quinoxaline, phenazine, diazaanthracene, pyridoquinoline, pyrimidoquinazoline, pyrazinoquinoxaline, phenanthroline, carbazole, dibenzothiophene, thienothiophene, dithienothiophene, dibenzofuran, benzodifuran, dithiaindacene, dithiaindenoindene, dibenzoselenophene, diselenaindacene, diselenaindenoindene, dibenzosilole, etc.
In the foregoing general formula (1), it is preferable that B1 and B2 have a symmetric structure to each other about a double bond interposed between B1 and B2; and it is more preferable that a π-conjugated structure represented by B1-=-B2 takes a plane.
Examples of the substituent which each of the foregoing B1 and B2 may have are the same as those in R1 to R10 as described later.
In the foregoing general formula (1), R1 to R10 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having from 1 to 30 carbon atoms, a haloalkyl group having from 1 to 30 carbon atoms, an alkoxyl group having from 1 to 30 carbon atoms, a haloalkoxyl group having from 1 to 30 carbon atoms, an alkylamino group having from 1 to 30 carbon atoms, a dialkylamino group having from 2 to 60 carbon atoms (the alkyl groups may be bonded to each other to form a nitrogen atom-containing cyclic structure), an alkylsulfonyl group having from 1 to 30 carbon atoms, a haloalkylsulfonyl group having from 1 to 30 carbon atoms, an alkylthio group having from 1 to 30 carbon atoms, a haloalkylthio group having from 1 to 30 carbon atoms, an alkylsilyl group having from 3 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 60 carbon atoms or an aromatic heterocyclic group having from 1 to 60 carbon atoms; each of these groups may have a substituent; and R1 to R5 and R6 to R10 may each form a saturated or unsaturated cyclic structure together with an adjacent group thereto.
Also, in the general formula (1), it is preferable that R1 to R10 each independently represents a hydrogen atom, a halogen atom, an alkyl group having from 1 to 30 carbon atoms or a haloalkyl group having from 1 to 30 carbon atoms.
Also, in the general formula (1), the case where R1, R2, R4, R5, R6, R7, R9 and R10 are each a hydrogen atom, and at least one of R3 and R8 is an alkyl group having from 1 to 30 carbon atoms, a haloalkyl group having from 1 to 30 carbon atoms, a halogen atom or a cyano group is preferable because the compound takes a more minute orientation structure.
Also, the organic compound having a specified structure to be used in the organic thin film transistor of the present invention is basically bipolar displaying p-type (hole conduction) and n-type (electron conduction) and can be driven as a p-type device or an n-type device through a combination with source and drain electrodes as described later. However, in the foregoing general formula (1), by employing an electron accepting group for the groups substituting on B1 to B2 or R1 to R10, the lowest unoccupied molecular orbital (LUMO) level is reduced, thereby enabling it to work as an n-type semiconductor. Preferred examples of the electron accepting group include a hydrogen atom, a halogen atom, a cyano group, a haloalkyl group having from 1 to 30 carbon atoms, a haloalkoxyl group having from 1 to 30 carbon atoms and a haloalkylsulfonyl group having from 1 to 30 carbon atoms. Also, by employing an electron donating group for the groups substituting on R1 to R10 and B1 to B2, the highest occupied molecular orbital (HOMO) level is increased, thereby enabling it to work as a p-type semiconductor. Preferred examples of the electron donating group include a hydrogen atom, an alkyl group having from 1 to 30 carbon atoms, an alkoxyl group having from 1 to 30 carbon atoms, an alkylamino group having from 1 to 30 carbon atoms and a dialkylamino group having from 2 to 60 carbon atoms (the alkyl group may be bonded to each other to form a nitrogen atom-containing cyclic structure).
Specific examples of each of the groups represented by R1 to R10 in the general formula (1) are hereunder described.
Examples of the foregoing halogen atom include fluorine, chlorine, bromine and iodine atoms.
Examples of the foregoing alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-icosane group, an n-henicosane group, an n-docosane group, an n-tricosane group, an n-tetracosane group, an n-pentacosane group, an n-hexacosane group, an n-heptacosane group, an n-octacosane group, an n-nonacosane group, an n-triacontane group, etc.
Examples of the foregoing haloalkyl group include a chloromethyl group, a 1-chloroethyl group, a 2-chloroethyl group, a 2-chloroisobutyl group, a 1,2-dichloroethyl group, a 1,3-dichloroisopropyl group, a 2,3-dichloro-t-butyl group, a 1,2,3-trichloropropyl group, a bromomethyl group, a 1-bromoethyl group, a 2-bromoethyl group, a 2-bromoisobutyl group, a 1,2-dibromoethyl group, a 1,3-dibromoisopropyl group, a 2,3-dibromo-t-butyl group, a 1,2,3-tribromopropyl group, an iodomethyl group, a 1-iodoethyl group, a 2-iodoethyl group, a 2-iodoisobutyl group, a 1,2-diiodoethyl group, a 1,3-diiodoisopropyl group, a 2,3-diiodo-t-butyl group, a 1,2,3-triiodopropyl group, a fluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group a 2-fluoroisobutyl group, a 1,2-difluoroethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorocyclohexyl group, etc.
The foregoing alkoxyl group is a group represented by —OX1, and examples of X1 are the same as those described for the foregoing alkyl group; and the foregoing haloalkoxyl group is a group represented by —OX2, and examples of X2 are the same as those described for the foregoing haloalkyl group.
The foregoing alkylthio group is a group represented by —SX1, and examples of X1 are the same as those described for the foregoing alkyl group; and the haloalkylthio group is a group represented by —SX2, and examples of X2 are the same as those described for the foregoing haloalkyl group.
The foregoing alkylamino group is a group represented by —NHX1; the dialkylamino group is a group represented by —NX1X3; and examples of each of X1 and X3 are the same as those described for the foregoing alkyl group. The alkyl groups of the dialkylamino group may be bonded to each other to form a nitrogen atom-containing cyclic structure; and examples of the cyclic structure include pyrrolidine, piperidine, etc.
The foregoing alkylsulfonyl group is a group represented by —SO2X1, and examples of X1 are the same as those described for the foregoing alkyl group; and the foregoing haloalkylsulfonyl group is a group represented by —SO2X2, and examples of X2 are the same as those described for the foregoing haloalkyl group.
Examples of the foregoing aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a perylenyl group, a tetracenyl group, a pentacenyl group, etc.
Examples of the foregoing aromatic heterocyclic group include a dithienophenyl group, a benzofuranyl group, a benzothiophenyl group, a quinolinyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzothiadiazonyl group, etc.
The foregoing alkylsilyl group is a group represented by —SiX1X2X3, and examples of each of X1, X2 and X3 are the same as those described for the foregoing alkyl group.
Examples of the foregoing saturated cyclic structure include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1,4-dioxanyl group, etc.
Examples of the foregoing unsaturated cyclic structure are the same as those described for the foregoing aromatic hydrocarbon group and the foregoing aromatic heterocyclic group.
Examples of a substituent which may be further substituted on each of the groups represented in the foregoing general formula (1) include an aromatic hydrocarbon group, an aromatic heterocyclic group, an alkyl group, an alkoxy group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, an amino group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, etc.
Also, the present invention provides an organic compound represented by the following general formula (2).
In the foregoing general formula (2), R11 and R12 each independently represents an alkyl group having from 1 to 30 carbon atoms. Specific examples thereof include the same groups as in the specific examples of the alkyl group having from 1 to 30 carbon atoms represented by R1 to R10 in the foregoing general formula (1).
Also, the present invention provides an organic compound represented by the following general formula (3).
In the foregoing general formula (3), R13 to R22 each independently represents an alkyl group having from 1 to 30 carbon atoms. Specific examples thereof include the same groups as in the specific examples of the alkyl group having from 1 to 30 carbon atoms represented by R1 to R10 in the foregoing general formula (1).
In the foregoing general formula (3), B3 and B4 each independently represents a divalent, bicyclic or polycyclic condensed aromatic hydrocarbon group having from 10 to 60 carbon atoms or a divalent, bicyclic or polycyclic condensed aromatic heterocyclic group having from 4 to 60 carbon atoms. Specific examples thereof include bicyclic or polycyclic groups among the aromatic groups represented by B1 and B2 in the foregoing general formula (1) and having the corresponding carbon atom number.
Specific examples of the organic compound represented by the general formula (1), (2) or (3) which is used in the organic semiconductor layer of the organic thin film transistor of the present invention will be given below, but it should not be construed that the present invention is limited thereto.
Also, in electronic devices such as transistors, a device with a high electric field effect mobility and a high ON/OFF ratio can be obtained by using a high-purity material. In consequence, it is desirable to apply purification by a technique such as column chromatography, recrystallization, distillation, sublimation, etc. to the organic compound having a structure of the foregoing general formula (1), as the need arises. Preferably, it is possible to more enhance the purity by repeating such a purification method or combining plural methods. Furthermore, it is desirable to repeat the sublimation purification as a final step of the purification at least two times or more. By using such a technique, it is preferred to use a material having a purity, as measured by HPLC, of 90% or more. More preferably, by using a material having a purity of more preferably 95% or more, and especially preferably 99% or more, the electric field effect mobility and the ON/OFF ratio of the organic thin film transistor can be increased, thereby revealing an inherent performance of the material.
The device configuration of the organic thin film transistor of the present invention is hereunder described.
The device configuration of the organic thin film transistor of the present invention is not limited so far as it is a thin film transistor comprising a substrate having thereon at least three terminals of a gate electrode, a source electrode and a drain electrode, an insulator layer and an organic semiconductor layer, with a current between a source and a drain being controlled upon application of a voltage to the gate electrode. It may be one having a known device configuration except for the components of the organic semiconductor layer.
Of these, representative device configurations of the organic thin film transistor are shown as devices A to D in
Among the devices A to D, the device B of
With respect to the organic thin film transistor of the present invention, various configurations are proposed as the organic thin film transistor for the device configuration other than the foregoing devices A to D. The device configuration is not limited to these device configurations so far as it has a mechanism revealing an effect for undergoing an ON/OFF operation or amplification or the like, with a current flowing between the source electrode and the drain electrode being controlled by a voltage to be applied to the gate electrode. Examples of the device configuration include a top and bottom contact type organic thin film transistor (see
The substrate in the organic thin film transistor of the present invention bears a role of supporting the structure of the organic thin film transistor. Besides glasses, inorganic compounds such as metal oxides or nitrides, etc., plastic films (for example, PET, PES or PC), metal substrates, composites or laminates thereof and so on can also be used as a material of the substrate. Also, in the case where the structure of the organic fin film transistor can be sufficiently supported by a configuration element other than the substrate, there is a possibility that the substrate is not used. Also, a silicon (Si) wafer is frequently used as a material of the substrate. In that case, Si itself can be used as the substrate which also serves as the gate electrode. Also, it is possible to oxidize the surface of Si to form SiO2, thereby applying it as an insulating layer. In that case, there may be the case where a metal layer such as Au, etc. is fabricated as an electrode for connecting a lead wire on the Si substrate of the gate electrode which also serves as the substrate.
Materials of the gate electrode, the source electrode and the drain electrode in the organic thin film transistor of the present invention are not particularly limited so far as they are a conductive material. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony, lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, antimony tin oxide, indium tin oxide (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glassy carbon, a silver paste and a carbon paste, lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, a sodium-potassium alloy, a magnesium/copper mixture, a magnesium/silver mixture, a magnesium/aluminum mixture, a magnesium/indium mixture, an aluminum/aluminum oxide mixture, a lithium/aluminum mixture, etc. are useful, and the electrode is formed by means of fabrication by a sputtering method or a vacuum vapor deposition method.
In the organic thin film transistor of the present invention, an electrode formed using a fluidic electrode material containing the foregoing conductive material, such as a solution, a paste, an ink, a dispersion, etc., can be utilized as the source electrode and the drain electrode. Also, for the purpose of suppressing damage to the organic semiconductor, it is preferable that the solvent or dispersion medium is a solvent or a dispersion medium each containing 60% by mass or more, and preferably 90% by mass or more of water. As a dispersion containing a metal fine particle, for example, a known conductive paste or the like may be used. In general, it is preferable that the dispersion is a dispersion containing a metal fine particle having a particle size of from 0.5 nm to 50 nm, and preferably from 1 nm to 10 nm. As a material of this metal fine particle, for example, platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony, lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, zinc, etc. can be used.
It is preferable that an electrode is formed by using a dispersion stabilizer composed mainly of an organic material and using a dispersion prepared by dispersing such a metal fine particle in water or a dispersion medium as an arbitrary organic solvent. Examples of a method for manufacturing a dispersion of such a metal fine particle include a physical formation method such as a gas evaporation method, a sputtering method, a metal vapor synthesis method, etc.; and a chemical formation method for reducing a metal ion in a liquid phase to form a metal fine particle, such as a colloid method, a coprecipitation method, etc. Dispersions of a metal fine particle manufactured by a colloid method disclosed in JP-A-11-76800, JP-A-11-80647, JP-A-11-319538, JP-A-2000-239853, etc., or a gas evaporation method disclosed in JP-A-2001-254185, JP-A-2001-53028, JP-A-2001-35255, JP-A-2000-124157, JP-A-2000-123634, etc. are preferable.
The foregoing electrode is molded by using such a metal fine particle dispersion; the solvent is dried; and thereafter, the molded article is heated in a desired shape at a temperature in the range of from 100° C. to 300° C., and preferably from 150° C. to 200° C. as the need arises, thereby thermally fusing the metal fine particle. There is thus formed an electrode pattern having a desired shape.
Furthermore, it is also preferable that a known conductive polymer whose conductivity has been enhanced by means of doping or the like is used as each of the materials of the gate electrode, the source electrode and the drain electrode. For example, conductive polyanilines, conductive polypyrroles, conductive polythiophenes (for example, a complex of polyethylene dioxythiophene and polystyrene sulfonate, etc.), and so on are also suitably used. These materials are able to reduce the contact resistance of each of the source electrode and the drain electrode with the organic semiconductor layer.
Among the foregoing examples, those materials having small electric resistance on the contact surface with the organic semiconductor layer are preferable with respect to the material for forming each of the source electrode and the drain electrode. On that occasion, when a current control device is prepared, the electric resistance is corresponding to the electric effect mobility, and it is necessary that the resistance is as small as possible for the purpose of obtaining a large mobility. In general, this is determined by a large and small relation between a work function of the electrode material and an energy level of the organic semiconductor layer.
In the organic thin film transistor of the present invention, it is preferable that at least one of the source electrode and the drain electrode is made of a material having a work function of 4.2 eV or more, and/or at least one of them is made of a material having a work function of not more than 4.3 eV.
When a work function (W) of the electrode material is defined as “a”, an ionized potential (Ip) of the organic semiconductor layer is defined as “b”, and an electron affinity (Af) of the organic semiconductor layer is defined as “c”, it is preferable that they meet the following relational expression. Here, each of a, b and c is a positive value on the basis of vacuum level.
In the case of a p-type organic thin film transistor, (b−a)<1.5 eV (expression (I)) is preferable; and (b−a)<1.0 eV is more preferable. In the relation with the organic semiconductor layer, when the foregoing relation can be maintained, a device with high performance can be obtained. In particular, it is preferred to choose an electrode material having a large work function as far as possible. The work function is preferably 4.0 eV or more, and the work function is more preferably 4.2 eV or more.
A value of the work function of the metal may be selected from the list of effective metals having a work function of 4.0 eV or more, which is described in, for example, Kagaku Binran Kiso-hen II (Handbook of Chemistry, Fundamentals II), page 493 (Third Edition, edited by the Chemical Society of Japan and published by Maruzen Co., Ltd., 1983). A metal having a high work function is mainly Ag (4.26, 4.52, 4.64, 4.74 eV), Al (4.06, 4.24, 4.41 eV), Au (5.1, 5.37, 5.47 eV), Be (4.98 eV), Bi (4.34 eV), Cd (4.08 eV), Co (5.0 eV), Cu (4.65 eV), Fe (4.5, 4.67, 4.81 eV), Ga (4.3 eV), Hg (4.4 eV), Ir (5.42, 5.76 eV), Mn (4.1 eV), Mo (4.53, 4.55, 4.95 eV), Nb (4.02, 4.36, 4.87 eV), Ni (5.04, 5.22, 5.35 eV), Os (5.93 eV), Pb (4.25 eV), Pt (5.64 eV), Pd (5.55 eV), Re (4.72 eV), Ru (4.71 eV), Sb (4.55, 4.7 eV), Sn (4.42 eV), Ta (4.0, 4.15, 4.8 eV), Ti (4.33 eV), V (4.3 eV), W (4.47, 4.63, 5.25 eV) or Zr (4.05 eV). Of these, noble metals (for example, Ag, Au, Cu or Pt), Ni, Co, Os, Fe, Ga, Ir, Mn, Mo, Pd, Re, Ru, V and W are preferable. Besides the metals, ITO, conductive polymers such as polyanilines and PEDOT:PSS, and carbon are preferable. Even when one or plural kinds of such a material having a high work function are included as the electrode material, so far as the work function meets the foregoing expression (I), there are no particular limitations.
In the case of an n-type organic thin film transistor, (a−c)<1.5 eV (expression (II)) is preferable; and (a−c)<1.0 eV is more preferable. In the relation with the organic semiconductor layer, when the foregoing relation can be maintained, a device with high performance can be obtained. In particular, it is preferred to choose an electrode material having a small work function as far as possible. The work function is preferably not more than 4.3 eV, and the work function is more preferably not more than 3.7 eV.
A value of the work function of the metal having a low work function may be selected from the list of effective metalshaving a work function of not more than 4.3 eV, which is described in, for example, Kagaku Binran Kiso-hen II (Handbook of Chemistry, Fundamentals II), page 493 (Third Edition, edited by the Chemical Society of Japan and published by Maruzen Co., Ltd., 1983). Examples thereof include Ag (4.26 eV), Al (4.06, 4.28 eV), Ba (2.52 eV), Ca (2.9 eV), Ce (2.9 eV), Cs (1.95 eV), Er (2.97 eV), Eu (2.5 eV), Gd (3.1 eV), Hf (3.9 eV), In (4.09 eV), K (2.28 eV), La (3.5 eV), Li (2.93 eV), Mg (3.66 eV), Na (2.36 eV), Nd (3.2 eV), Rb (4.25 eV), Sc (3.5 eV), Sm (2.7 eV), Ta (4.0, 4.15 eV), Y (3.1 eV), Yb (2.6 eV), Zn (3.63 eV), etc. Of these, Ba, Ca, Cs, Er, Eu, Gd, Hf, K, La, Li, Mg, Na, Nd, Rb, Y, Yb and Zn are preferable. Even when one or plural kinds of such a material having a low work function are included as the electrode material, so far as the work function meets the foregoing expression (II), there are no particular limitations. However, it is desirable that the metal having a low work function is coated by a metal which is stable in air, such as Ag and Au, as the need arises because when it comes into contact with moisture or oxygen in the air, it is easily deteriorated. The thickness necessary for achieving coating is required to be 10 nm or more, and as the thickness becomes thick, the metal can be protected from oxygen or water. However, it is desirable that the thickness is not more than 1 μm for the reasons of practical use, an increase of productivity, etc.
With respect to a method for forming the electrode, the electrode is formed by a measure, for example, vapor deposition, electron beam vapor deposition, sputtering, an atmospheric pressure plasma method, ion plating, chemical vapor phase vapor deposition, electrodeposition, electroless plating, spin coating, printing, inkjetting, etc. Also, with respect to a patterning method of a conductive thin film formed by adopting the foregoing method, which is carried out as the need arises, there are a method for forming an electrode by adopting a known photo lithographic method or a liftoff method; and a method of forming a resist by means of heat transfer, inkjetting, etc. onto a metal foil such as aluminum, copper, etc. and etching it. Also, a conductive polymer solution or dispersion, a metal fine particle-containing dispersion or the like may be subjected to patterning directly by an inkjetting method or may be formed from a coated film by means of lithography, laser abrasion, etc. Furthermore, a method for patterning a conductive ink, a conductive paste, etc. containing a conductive polymer or a metal fine particle by a printing method such as relief printing, intaglio printing, planographic printing, screen printing, etc. can be adopted.
The thickness of the thus formed electrode is not particularly limited so far as the electrode is electrically conductive. It is preferably in the range of from 0.2 nm to 10 μm, and more preferably from 4 nm to 300 nm. When the thickness of the electrode falls within this preferred range, the resistance is high because of the fact that the thickness is thin, whereby any voltage drop is not caused. Also, since the thickness is not excessively thick, it does not take a long period of time to form a film, and in the case of laminating other layers such as a protective layer, an organic semiconductor layer, etc., a laminated film can be smoothly formed without causing a difference in level.
Also, in the organic thin film transistor of the present embodiment, for example, for the purpose of enhancing injection efficiency, a buffer layer may be provided between the organic semiconductor layer and each of the source electrode and the drain electrode. With respect to the buffer layer, a compound having an alkali metal or alkaline earth metal ionic bond, which is used for a negative electrode of an organic EL device, such as LiF, Li2O, CsF, Na2CO3, KCl, MgF2, CaCO3, etc., is desirable for the n-type organic thin film transistor. Also, a compound which is used as an electron injection layer or an electron transport layer in an organic EL device, such as Alq, etc., may be inserted.
Cyano compounds such as FeCl3, TCNQ, F4-TCNQ, HAT, etc.; CFx; oxides of a metal other than alkali metals or alkaline earth metals, such as GeO2, SiO2, MoO3, V2O5, VO2, V2O3, MnO, Mn3O4, ZrO2, WO3, TiO2, In2O3 ZnO, NiO, HfO2, Ta2O5, ReO3, PbO2 etc.; and inorganic compounds such as ZnS, ZnSe, etc. are desirable for the p-type organic thin film transistor. In many cases, the most of these oxides cause oxygen deficiency, and this is suitable for hole injection. Furthermore, compounds which are used for a hole injection layer or a hole transport layer in an organic EL device, such as amine based compounds, for example, TPD, NPD, etc., CuPc, etc., may be used. Also, a combination of two or more kinds of the foregoing compounds is desirable.
It is known that the buffer layer decreases a threshold voltage upon lowering an injection barrier of a carrier, thereby bringing an effect for driving a transistor at a low voltage. We have found that the buffer layer brings not only the low voltage effect but an effect for enhancing the mobility with respect to the compound of the present invention. This is because a carrier trap exists at the interface between the organic semiconductor and the insulator layer; and when carrier injection is caused upon application of a gate voltage, the first injected carrier is used for burying the trap; however, when the buffer layer is inserted, the trap is buried at a low voltage, thereby enhancing the mobility. It would be better that the buffer layer exists thinly between the electrode and the organic semiconductor layer, and its thickness is from 0.1 nm to 30 nm, and preferably from 0.3 nm to 20 nm.
A material of the insulator layer in the organic thin film transistor of the present invention is not particularly limited so far as it is electrically insulative and can be formed as a thin film. Materials having an electric resistivity of 10 Ωom or more at room temperature, such as metal oxides (including an oxide of silicon), metal nitrides (including a nitride of silicon), polymers, organic low-molecular weight compounds, etc., can be used; and inorganic oxide films having a high dielectric constant are especially preferable.
Examples of the inorganic oxide include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, zirconic acid barium titanate, zirconic acid lead titanate, lanthanum lead titanate, strontium titanate, barium titanate, lanthanum oxide, fluorine oxide, magnesium oxide, bismuth oxide, bismuth titanate, niobium oxide, bismuth strontium titanate, bismuth strontium tantalate, tantalum pentoxide, tantalic acid bismuth niobate, trioxide yttrium and combinations thereof, with silicon oxide, aluminum oxide, tantalum oxide and titanium oxide being preferable.
Also, inorganic nitrides such as silicon nitrides (for example, Si3N4 or SixNy (x, y>0)), aluminum nitride, etc. can be suitably used.
Furthermore, the insulator layer may be formed of a precursor including a metal alkoxide. For example, the insulator layer is formed by coating a solution of this precursor on a substrate and subjecting this to a chemical solution treatment including a heat treatment.
The metal of the foregoing metal alkoxide is, for example, selected among transition metals, lanthanoids or main group elements. Specific examples thereof include barium (Ba), strontium (Sr), titanium (Ti), bismuth (Bi), tantalum (Ta), zirconium (Zr), iron (Fe), nickel (Ni), manganese (Mn), lead (Pb), lanthanum (La), lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium (Ca), niobium (Nb), thallium (Tl), mercury (Hg), copper (Cu), cobalt (Co), rhodium (Rh), scandium (Sc), yttrium (Y), etc. Also, examples of the alkoxide in the foregoing metal alkoxide include those derived from alcohols, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, etc.; alkoxy alcohols, for example, methoxyethanol, ethoxyethanol, propoxyethanol, butoxyethanol, pentoxyethanol, heptoxyethanol, methoxypropanol, ethoxypropanol, propoxypropanol, butoxypropanol, pentoxypropanol, heptoxypropanol, etc.; and so on.
In the present invention, when the insulator layer is constituted of the foregoing material, a depletion layer is easily generated in the insulator layer, whereby the threshold voltage of the transistor operation can be reduced. Also, in particular, when the insulator layer is formed of a silicon nitride such as Si3N4, SiNy, SiONx (x, y>0), etc. among the foregoing materials, the depletion layer is more easily generated, whereby the threshold voltage of the transistor operation can be more reduced.
With respect to the insulator layer using an organic compound, polyimides, polyamides, polyesters, polyacrylates, photo radical polymerization based or photo cationic polymerization based photocurable resins, copolymers containing an acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, novolak resins, cyanoethyl pullulan, etc. can also be used.
Besides, in addition to waxes, polyethylene, polychloroprene, polyethylene terephthalate, polyoxymethylene, polyvinyl chloride, polyvinylidene fluoride, polysulfone, polyimide cyanoethyl pullulan, poly(vinyl phenol) (PVP), poly(methyl methacrylate) (PMMA), polycarbonate (PC), polystyrene (PS), polyolefins, polyacrylamide, poly(acrylic acid), novolak resins, resol resins, polyimides, polyxylylene and epoxy resins, polymer materials having a high dielectric constant, such as pullulan, etc., can be used.
With respect to the organic compound material or polymer material which is used in the insulator layer, organic compounds having water repellency are especially preferable. When the material has water repellency, an interaction between the insulator layer and the organic semiconductor layer is suppressed, and the crystallinity of the organic semiconductor layer is enhanced while utilizing the cohesiveness which the organic semiconductor originally possesses, whereby the device performance can be enhanced. Examples thereof include polyparaxylylene derivatives described in Yasuda, et al., Jpn. J. Appl Phys., Vol. 42 (2003), pages 6614 to 6618; and those described in Janos Veres, et al., Chem. Mater., Vol. 16 (2004), pages 4543 to 4555.
Also, when a top gate structure as shown in
The foregoing insulator layer may be a mixed layer using a plurality of the foregoing inorganic or organic compound materials or may be of a laminated structure thereof. In that case, the performance of the device can be controlled by mixing a material having a high dielectric constant and a material having water repellency or laminating the both as the need arises.
Also, the foregoing insulator layer may be an anodic oxide film or may include the subject anodic oxide film as a constituent. It is preferable that the anodic oxide film is subjected to a sealing treatment. The anodic oxide film is formed by anodically oxidizing an anodic oxidizable metal by a known method. Examples of the anodic oxidizable metal include aluminum and tantalum. The method of the anodic oxidation treatment is not particularly limited, and known methods can be adopted. By carrying out the anodic oxidation treatment, an oxide film is formed. As an electrolytic solution which is used for the anodic oxidation treatment, any material can be used so far as it is able to form a porous oxide film. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, boric acid, sulfamic acid, benzenesulfonic acid, etc., or mixed acids composed of a combination of two or more kinds of those acids or salts thereof are useful. The treatment condition of the anodic oxidation variously varies depending upon the electrolytic solution to be used and cannot be unequivocally specified. However, in general, it is appropriate that the concentration of the electrolytic solution is in the range of from 1 to 80% by mass; that the temperature of the electrolytic solution is in the range of from 5 to 70° C.; that the current density is in the range of from 0.5 to 60 A/cm2; that the voltage is in the range of from 1 to 100 volts; and that the electrolysis time is in the range of from 10 seconds to 5 minutes. A preferred anodic oxidation treatment is a method for carrying out the treatment with a direct current by using, as the electrolytic solution, an aqueous solution of sulfuric acid, phosphoric acid or boric acid; however, an alternating current can also be applied. The concentration of such an acid is preferably from 5 to 45% by mass; and it is preferable that the electrolysis treatment is carried out at a temperature of the electrolytic solution of from 20 to 50° C. and a current density of from 0.5 to 20 A/cm2 for from 20 to 250 seconds.
With respect to the thickness of the insulator layer, when the thickness of the layer is thin, an effective voltage which is applied to the organic semiconductor becomes large, and therefore, it is possible to lower a driving voltage and a threshold voltage of the device itself. However, on the contrary, a leak current between the source and the gate becomes large. Therefore, it is necessary to select an appropriate thickness of the film. The thickness of the film is usually from 10 nm to 5 μm, preferably from 50 nm to 2 μm, and more preferably from 100 nm to 1 μm.
Also, an arbitrary orientation treatment may be applied between the foregoing insulator layer and organic semiconductor layer. A preferred embodiment thereof is a method in which a water repelling treatment or the like is applied onto the surface of the insulator layer, thereby reducing an interaction between the insulator layer and the organic semiconductor layer and enhancing the crystallinity of the organic semiconductor layer. Specifically, there is exemplified a method in which a silane coupling agent, for example, materials of self-assembled oriented film such as octadecyltrichlorosilane, trichloromethylsilazane, alkane phosphoric acids, alkane sulfonic acids, alkane carboxylic acids, etc., is brought into contact with the surface of an insulating film in a liquid phase or vapor phase state, thereby forming a self-assembled monolayer, which is then properly dried. Also, as used in the orientation of a liquid crystal, a method of disposing a film constituted of a polyimide or the like on the surface of an insulating film and subjecting the resulting surface to a rubbing treatment is also preferable.
Examples of the method for forming the foregoing insulator layer include dry processes such as a vacuum vapor deposition method, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, an atmospheric pressure plasma method disclosed in JP-A-11-61406, JP-A-11-133205, JP-A-2000-121804, JP-A-2000-147209 and JP-A-2000-185362, etc.; and wet processes such as methods by coating, for example, a spray coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roller coating method, a bar coating method, a die coating method, etc., and methods by patterning, for example, printing, inkjetting, etc. They can be applied depending upon the material. As the wet process, a method of coating and drying a solution prepared by dispersing a fine particle of an inorganic oxide in an arbitrary organic solvent or water while optionally using a dispersing agent such as surfactants, etc.; and a so-called sol-gel method of coating and drying a solution of an oxide precursor, for example, an alkoxide are used.
Though the thickness of the organic semiconductor layer in the organic thin film transistor of the present invention is not particularly limited, it is usually from 0.5 nm to 1 μm, and preferably from 2 nm to 250 nm.
Also, a method for forming the organic semiconductor layer is not particularly limited, and a known method is employable. For example, the organic semiconductor layer is formed from the foregoing materials of the organic semiconductor layer by a molecular beam epitaxy method (MBE method), a vacuum vapor deposition method, chemical vapor deposition, a printing or coating method of a solution having a material dissolved in a solvent, such as a dipping method, a spin coating method, a casting method, a bar coating method, a roller coating method, etc., baking, electro-polymerization, molecular beam vapor deposition, self-assembling from a solution, or a method of a combination of those measures.
When the crystallinity of the organic semiconductor layer is enhanced, the field effect mobility is enhanced. Therefore, in the case of adopting fabrication (for example, vapor deposition, sputtering, etc.) from a vapor phase, it is desirable to keep the temperature of the substrate during the fabrication at a high temperature. The temperature is preferably from 50 to 250° C., and more preferably from 70 to 150° C. Also, regardless of the fabrication method, it is preferable that annealing is carried out after the fabrication because a high-performance device is obtained. With respect to the annealing, the temperature is preferably from 50 to 200° C., and more preferably from 70 to 200° C.; and the time is preferably from 10 minutes to 12 hours, and more preferably from 1 to 10 hours.
In the present invention, one kind of materials selected from the general formula (1) may be used in the organic semiconductor layer. A plurality of these materials may be combined or used as plural mixed thin films or laminated using a known semiconductor such as a pentacene or thiophene oligomer, etc.
A method for forming the organic thin film transistor of the present invention is not particularly limited but may be carried out in accordance with a known method. It is preferable that the formation is carried out in accordance with a desired device configuration through a series of device preparation steps including charging a substrate, forming a gate electrode, forming an insulator layer, forming an organic semiconductor layer, forming a source electrode and forming a drain electrode without utterly coming into contact with the air because the hindrance of a device performance to be caused due to the moisture or oxygen or the like in the air upon contact with the air can be prevented. When it is unable to evade the contact with the air once, it is preferable that steps after the fabrication of the organic semiconductor layer are a step of not contacting with the air at all; and that immediately before the fabrication of the organic semiconductor layer, the surface on which the organic semiconductor layer is laminated (for example, in the case of the device II, the surface of the insulating layer on which are partially laminated the source electrode and the drain electrode) is cleaned and activated by means of irradiation with ultraviolet rays, irradiation with ultraviolet rays/ozone, oxygen plasma, argon plasma, etc., and the organic semiconductor layer is then laminated.
Furthermore, for example, taking into consideration influences of oxygen, water, etc. contained in the air against the organic semiconductor layer, a gas barrier layer may be formed entirely or partially on the peripheral surface of the organic transistor device. As a material for forming the gas barrier layer, those which are commonly used in this field can be used, and examples thereof include polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene, etc. Furthermore, the inorganic materials having insulating properties, which are exemplified in the foregoing insulator layer, can be used.
Also, the present invention provides an organic thin film light emitting transistor in which in the foregoing organic thin film transistor, light emission is obtained while utilizing a current flowing between a source and a drain, and the light emission is controlled upon application of a voltage to a gate electrode.
The organic thin film transistor in the present invention can also be used as a light emitting device using charges injected from the source and drain electrodes. The emission intensity is controlled by controlling a current flowing between the source and drain electrodes by the gate electrode. That is, it is meant that the organic thin film transistor is used as a light emitting device (organic EL device). Since the transistor for controlling the emission and the light emitting device can be consolidated, the costs can be reduced due to an enhancement of the degree of opening of a display or simplification of the preparation process, resulting in great advantages from the standpoint of practical use. When used as an organic light emitting transistor, the contents which have been described previously in detail are sufficient. However, in order to make the organic thin film transistor of the present invention operate as an organic light emitting transistor, it is necessary to inject holes from one of a source and a drain and to inject electrons from the other; and in order to enhance the emission performance, it is preferable that the following condition is met.
For the purpose of enhancing the injection properties of holes, it is preferable that at least one of the electrodes is a hole injection electrode. The hole injection electrode as referred to herein is an electrode including a material having the foregoing work function of 4.2 eV or more.
Also, for the purpose of enhancing the injection properties of electrons, it is preferable that at least one of the electrodes is an electron injection electrode. The electron injection electrode as referred to herein is an electrode including a material having the foregoing work function of not more than 4.3 eV. An organic thin film light emitting transistor provided with electrodes such that one of the electrodes has hole injection properties, with the other having electron injection properties, is more preferable.
For the purpose of enhancing the hole injection properties, it is preferable that a hole injection layer is inserted between at least one of the electrodes and the organic semiconductor layer. With respect to the hole injection layer, amine based materials which are used as a hole injection material or a hole transport material in organic EL devices are exemplified.
Also, for the purpose of enhancing the electron injection properties, it is preferable that an electron injection layer is inserted between at least one of the electrodes and the organic semiconductor layer. Similar to the hole injection layer, electron injection materials which are used in organic EL devices can be used.
An organic thin film light emitting transistor in which a hole injection layer is provided beneath at least one of the electrodes, and an electron injection layer is provided beneath the other electrode is more preferable.
Also, in the organic thin film light emitting transistor of the present embodiment, for example, for the purpose of enhancing injection efficiency, a buffer layer may be provided between the organic semiconductor layer and each of the source electrode and the drain electrode.
Next, the present invention is described in more detail with reference to the following Examples.
The foregoing Compound (2) was synthesized in the following manner. A synthesis route is described below.
A 300-mL three-necked flask was charged with 3.00 g (8.87 mmoles) of 4,4′-dibromostilbene, 0.513 g (0.443 moles) of tetrakistriphenylphosphine palladium and 0.169 g (0.886 mmoles) of copper(I) iodide and then purged with argon. 22 mL of triethylamine and 3.09 g (26.6 mmoles) of 4-ethynyltoluene were added thereto, and the mixture was refluxed under heating for 9 hours in an argon atmosphere. The reaction solution was filtered, and the obtained solid was cleaned with dichloromethane and methanol, thereby obtaining 2.36 g (5.77 mmoles, yield: 65%) of Compound (2). This compound was confirmed to be a desired compound by the measurement of 90 MHz 1H-NMR and FD-MS (field desorption mass analysis). The measurement results of FD-MS are shown below. FD-MS, calculated for C48H30S2=408, found, m/z=408 (M+, 100)
Also, the present compound was subjected to sublimation purification at 280° C. Compound (2) obtained by the sublimation purification had a purity of 99.5%.
The apparatus and measurement condition used for the measurement of FD-MS (field desorption mass analysis) in
HX110 (manufactured by JEOL Ltd.)
Accelerating voltage: 8 kV
Scan range: m/z=50 to 1,500
The foregoing Compound (29) was synthesized in the following manner. A synthesis route is described below.
A 300-mL three-necked flask was charged with 10.9 g (36.2 mmoles) of Compound (A) and 12.0 g (72.3 mmoles) of triethyl phosphite. The reactor was refluxed under heating at 150° C. for 3 hours, and the reaction mixture was then distilled in vacuo, thereby removing impurities therefrom. The residue remaining in the flask was purified by column chromatography, thereby obtaining 9.71 g (27.2 mmoles, yield: 75%) of Compound (B).
A 300-mL three-necked flask was charged with 4.00 g (11.2 mmoles) of Compound (B), 0.647 g (0.560 mmoles) of tetrakistriphenylphosphine palladium and 0.213 g (1.12 mmoles) of copper (I) iodide and then purged with argon. 16 mL of triethylamine, 56 mL of tetrahydrofuran and 2.60 g (22.4 moles) of 4-ethynyltoluene were added thereto, and the mixture was refluxed under heating for 8 hours in an argon atmosphere. The reaction solution was filtered, and the obtained solid was cleaned with dichloromethane and methanol, thereby obtaining 3.41 g (8.69 moles, yield: 78%) of Compound (C).
A 300-mL three-necked flask was charged with 2.00 g (8.51 mmoles) of Compound (D), 0.492 g (0.426 mmoles) of tetrakistriphenylphosphine palladium and 0.162 g (0.852 mmoles) of copper (1) iodide and then purged with argon. 20 mL of triethylamine, 20 mL of tetrahydrofuran and 1.48 g (12.8 mmoles) of 4-ethynyltoluene were added thereto, and the mixture was refluxed under heating for 9 hours in an argon atmosphere. The reaction solution was filtered, and the obtained solid was cleaned with dichloromethane and methanol, thereby obtaining 1.73 g (6.40 mmoles, yield: 75%) of Compound (E).
A 300-mL three-necked flask is charged with 1.35 g (3.44 mmoles) of Compound (C) and further charged with 10 mL of THF. 0.463 g (4.13 mmoles) of potassium tertiary butoxide is added thereto step by step. After stirring the reactor at room temperature for 30 minutes, 10 mL of a THF solution of 1.40 g (3.78 mmoles) of Compound (E) was further added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was filtered, and the obtained solid was cleaned with dichloromethane and methanol, thereby obtaining 0.874 g (1.72 mmoles, yield: 50%) of Compound (29). This compound was confirmed to be a desired compound by the measurement of 90 MHz 1H-NMR and ED-MS (field desorption mass analysis). The measurement results of FD-MS are shown below. The apparatus and measurement condition used for the measurement of FD-MS are the same as those in Synthesis Example 1.
FD-MS, calculated for C48H30S2=508, found, m/z=508 (M+, 100)
An organic thin film transistor was prepared according to the following procedures. First of all, the surface of an Si substrate (p-type also serving as a gate electrode, specific resistivity: 1 Ωcm) was oxidized by a thermal oxidation method to prepare a 300 nm-thick thermally oxidized film on the substrate, which was then used as an insulator layer. Furthermore, after completely removing the SiO2 film fabricated on one surface of the substrate by means of dry etching, chromium was fabricated in a thickness of 20 nm thereon by a sputtering method; and gold (Au) was further fabricated in a thickness of 100 nm thereon by means of sputtering, thereby forming a lead-out electrode. This substrate was ultrasonically cleaned with a neutral detergent, pure water, acetone and ethanol each for 30 minutes, followed by further cleaning with ozone.
Subsequently, the foregoing substrate was placed in a vacuum vapor deposition apparatus (EX-400, manufactured by ULVAC, Inc.), and the foregoing Compound (2) was fabricated in a thickness of 50 nm as an organic semiconductor layer on the insulator layer at a vapor deposition rate of 0.05 nm/s. Subsequently, gold was fabricated in a thickness of 50 nm through a metal mask, thereby forming a source electrode and a drain electrode which did not come into contact with each other at a space (channel length L) of 75 μm. At that time, the fabrication was carried out such that a width (channel width W) between the source electrode and the drain electrode was 5 mm, thereby preparing an organic thin film transistor (see
A gate voltage of −40 V was applied to the gate electrode of the obtained organic thin film transistor, and a voltage was applied between the source and the drain, thereby allowing a current to flow therethrough. In that case, holes are induced in a channel region (between the source and the drain) of the organic semiconductor layer, whereby the organic thin film transistor works as a p-type transistor. As a result, an ON/OFF ratio of the current between the source and drain electrodes in a current saturation region was 3×105. Also, an electric field effect mobility μ of the hole was calculated in accordance with the following expression (A) and found to be 6×10−2 cm2/Vs.
I
D=(W/2L)·Cμ·(VG−VT)2 (A)
In the expression, ID represents a current between the source and the drain; W represents a channel width; L represents a channel length; C represents an electric capacitance per unit area of the gate insulator layer; VT represents a gate threshold voltage; and VG represents a gate voltage.
An organic thin film transistor was prepared in the same manner as in Example 1, except for using Compound (75) as the material of the organic semiconductor layer in place of the Compound (2). The obtained organic thin film transistor was subjected to p-type driving at a gate voltage VG of −40 V in the same manner as in Example 1. An ON/OFF ratio of the current between the source and drain electrodes was measured, and a field effect mobility μ of the hole was calculated. The results are shown in Table 1.
An organic semiconductor layer was fabricated in the same manner as in Example 1, except for using Compound (21) as the material of the organic semiconductor layer in place of the Compound (2). Subsequently, Ca was vacuum vapor deposited in a thickness of 20 nm as the source and drain electrodes through the metal mask in place of Au at a vapor deposition rate of 0.05 nm/s. Thereafter, Ag was vapor deposited in a thickness of 50 nm at a vapor deposition rate of 0.05 nm/s, thereby coating Ca. There was thus prepared an organic thin film transistor. The obtained organic thin film transistor was subjected to n-type driving at a gate voltage VG of +40 V in the same manner as in Example 1. An ON/OFF ratio of the current between the source and drain electrodes was measured, and a field effect mobility μ of the electron was calculated. The results are shown in Table 1.
An organic thin film transistor was prepared in the same manner as in Example 1, except for vacuum vapor depositing a buffer layer MoO3 in a thickness of 10 nm as the source and drain electrodes in place of Au singly at a vapor deposition rate 0.05 nm/s, thereby inserting it between Au and the thin film of Compound (2). The obtained organic thin film transistor was subjected to p-type driving at a gate voltage VG of −40 V in the same manner as in Example 1. An ON/OFF ratio of the current between the source and drain electrodes was measured, and a field effect mobility μ of the hole was calculated. The results are shown in Table 1.
Cleaning of a substrate, fabrication of a gate electrode and fabrication of an insulator layer were carried out in the same manner as in Example 1. Subsequently, 3% by mass of polyparaphenylene vinylene (PPV) [molecular weight (Mn): 86,000, molecular weight distribution (Mw/Mn)=5.1] was dissolved in toluene, and the solution was fabricated on the substrate which had been fabricated up to the foregoing insulating layer by a spin coating method and dried at 120° C. in a nitrogen atmosphere, thereby fabricating it as an organic semiconductor layer. Subsequently, gold (Au) was fabricated in a thickness of 50 nm through a metal mask by a vacuum vapor deposition apparatus, thereby forming source and drain electrodes which did not come into contact with each other. There was thus prepared an organic thin film transistor.
The obtained organic thin film transistor was subjected to p-type driving at a gate voltage VG of −40 V in the same manner as in Example 1. An ON/OFF ratio of the current between the source and drain electrodes was measured, and a field effect mobility μ of the hole was calculated. The results are shown in Table 1.
Fabrication up to the organic semiconductor layer was carried out in exactly the same manner as in Comparative Example 1 by using polyparaphenylene vinylene (PPV) as the material of the organic semiconductor layer. Thereafter, Ca was fabricated as the source and drain electrodes through a metal mask in the same manner as in Example 3, and Ag was then coated thereon, thereby preparing an organic thin film transistor.
The obtained organic thin film transistor was subjected to n-type driving at a gate voltage VG of +40 V in the same manner as in Example 3. An ON/OFF ratio of the current between the source and drain electrodes was measured, and a field effect mobility μ of the hole was calculated. The results are shown in Table 1.
An organic thin film light emitting transistor was prepared according to the following procedures. First of all, the surface of an Si substrate (p-type also serving as a gate electrode, specific resistivity: 1 Ωcm) was oxidized by a thermal oxidation method to prepare a 300 nm-thick thermally oxidized film on the substrate, which was then used as an insulator layer. Furthermore, after completely removing the SiO2 film fabricated on one surface of the substrate by means of dry etching, chromium was fabricated in a thickness of 20 nm thereon by a sputtering method; and gold (Au) was further fabricated in a thickness of 100 nm thereon by means of sputtering, thereby forming a lead-out electrode. This substrate was ultrasonically cleaned with a neutral detergent, pure water, acetone and ethanol each for 30 minutes.
Subsequently, the resulting substrate was placed in a vacuum vapor deposition apparatus (EX-900, manufactured by ULVAC, Inc.), and the foregoing Compound (2) was fabricated in a thickness of 100 nm as an organic semiconductor light emitting layer on the insulator layer (SiO2) at a vapor deposition rate of 0.05 nm/s. Subsequently, a metal mask having a channel length of 75 μm and a channel width 5 mm was placed in the same manner as described previously, and gold was fabricated in a thickness of 50 nm through the mask in a state of inclining the substrate at 45° against an evaporation source. Subsequently, Mg was vapor deposited in a thickness of 100 nm in a state of inclining the substrate at 45° in the reverse direction, thereby preparing an organic thin film light emitting transistor in which a source electrode and a drain electrode which did not come into contact with each other were each substantially provided with a hole injection electrode (Au) and an electron transport electrode (Mg) (see
When −100 V was applied between the source and the drain, and −100 V was applied to the gate electrode, blue emission of 40 cd/m2 was obtained. An emission spectrum is shown in
As described above in detail, by using a compound having a specified structure with high electron mobility as a material of an organic semiconductor layer, the organic thin film transistor of the present invention has a fast response speed (driving speed), has a large ON/OFF ratio and is high in performance as a transistor; and it is also able to be utilized as an organic thin film light emitting transistor which can achieve light emission.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2007-163617 | Jun 2007 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2008/061160 | 6/18/2008 | WO | 00 | 12/18/2009 |
