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WO2018043725A1 - Matériau semi-conducteur organique, composé organique et dispositif semi-conducteur organique - Google Patents

Matériau semi-conducteur organique, composé organique et dispositif semi-conducteur organique Download PDF

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WO2018043725A1
WO2018043725A1 PCT/JP2017/031671 JP2017031671W WO2018043725A1 WO 2018043725 A1 WO2018043725 A1 WO 2018043725A1 JP 2017031671 W JP2017031671 W JP 2017031671W WO 2018043725 A1 WO2018043725 A1 WO 2018043725A1
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unit
group
semiconductor material
aliphatic chain
organic semiconductor
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PCT/JP2017/031671
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English (en)
Japanese (ja)
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純一 半那
タンジョウ ヤン
裕明 飯野
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国立大学法人東京工業大学
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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
    • C07D471/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]

Definitions

  • the present invention relates to an organic semiconductor material and an organic compound exhibiting liquid crystallinity, and an organic semiconductor device. More specifically, the present invention exhibits liquid crystallinity and can be suitably used as an organic semiconductor (for example, an n-type organic semiconductor) in at least one of a liquid crystal phase and a crystal phase, and an organic semiconductor material and an organic semiconductor material thereof.
  • the present invention relates to an organic semiconductor device using an organic compound.
  • a substance having a “rod-like” molecular structure and exhibiting liquid crystallinity having an extended aromatic ⁇ -conjugated site is characterized by a relatively flexible long-chain hydrocarbon chain.
  • it has a structure similar to a soluble organic transistor material.
  • Non-patent Document 1 Since an organic transistor using a pentacene crystal material (Non-patent Document 1) was reported, oligothiophene (Non-patent Document 2), TIPS-pentacene (Non-patent Document 13), and benzothienobenzothiophene [ 5,10] derivatives and the like are synthesized to produce transistors.
  • n-type organic semiconductor material requires a material having a low LUMO level (deep LUMO level)
  • organic semiconductor materials capable of n-type operation (electron transportable) in the atmosphere are extremely limited.
  • Non-Patent Documents 4 to 6 There are limited reports of materials that can operate n-type transistors. For this reason, an n-type organic transistor material necessary for manufacturing a CMOS is still eagerly searched.
  • the main object of the present invention is to provide an organic semiconductor material exhibiting liquid crystallinity, which has a deep LUMO level and can be preferably used as an n-type organic semiconductor, which can eliminate the above-mentioned drawbacks of the prior art. It is in.
  • Another object of the present invention is to provide an organic semiconductor device and a novel compound using the organic semiconductor material.
  • IQIQ isoquinolino-isoquinoline
  • the organic semiconductor material of the present invention is based on the above knowledge, and more specifically, a unit A having a IQIQ (isoquinolino-isoquinoline) type skeleton structure; and a carbon main chain linked to the unit A by a single bond.
  • An aliphatic chain unit B in which one or more of the constituent carbon atoms may be substituted with an oxygen atom; a group containing an aliphatic chain and / or a cyclic structure connected to the unit A with a single bond; Or an organic semiconductor material having at least a unit C which is a hydrogen atom; wherein the organic semiconductor material exhibits liquid crystallinity.
  • IQIQ isoquinolinoisoquinoline
  • the unit A is represented by the following formula (2) (In the formula, each a is independently a hydrogen atom, a single bond, or a saturated and / or unsaturated cyclic group, and the saturated and / or unsaturated cyclic group is a hydrocarbon group. Or it may contain one or more heteroatoms.)
  • the unit B and the unit C are each connected to two a by a single bond, and when the a is a single bond, the unit B and / or the unit C is connected to IQIQ.
  • the organic semiconductor material according to [1] which is directly bonded by a single bond.
  • each a independently represents the following structural formula (In the formula, R is a hydrogen atom or an aliphatic chain group.)
  • R in the above formula is a hydrogen atom In the case, it is substituted with R, or when R is an aliphatic chain group, the hydrogen atom of the aliphatic chain group of R can be substituted and bonded to the unit A.
  • the aliphatic chain of the unit C is an aliphatic chain group having 3 to 20 carbon atoms, and the group including the cyclic structure of the unit C is an aromatic group, a heterocyclic group or an aliphatic ring group.
  • Unit A including a skeleton structure based on isoquinolino-isoquinoline (IQIQ) represented by the following formula (1), an aliphatic chain unit B linked to the unit A by a single bond, and the unit A An organic compound having at least a group containing an aliphatic chain and / or a cyclic structure, or a unit C which is a hydrogen atom, connected by a single bond.
  • IQIQ isoquinolino-isoquinoline
  • the unit A is represented by the following formula (2) (In the formula, each a is independently a hydrogen atom, a single bond, or a saturated and / or unsaturated cyclic group, and the saturated and / or unsaturated cyclic group is a hydrocarbon group. Or it may contain one or more heteroatoms.)
  • Each of unit B and unit C is bonded to two a by a single bond, and when the a is a single bond, unit B and / or unit C is an IQIQ skeleton.
  • the organic compound according to the above [12] which is directly bonded to a single bond.
  • a in the formula (2) is each independently the following structural formula (In the formula, R is a hydrogen atom or an aliphatic chain group.)
  • R is a hydrogen atom or an aliphatic chain group.
  • Each of unit B and unit C is substituted with R when R is a hydrogen atom, or R is an aliphatic chain group.
  • the aliphatic chain of the unit C is an aliphatic chain group having 3 to 20 carbon atoms, and the group including the cyclic structure of the unit C is an aromatic group, a heterocyclic group, or an aliphatic cyclic group.
  • a layer formed by using the organic semiconductor material according to any one of [1] to [11] or the organic compound according to any one of [12] to [20] A semiconductor device comprising: a positive electrode and a negative electrode electrically connected to the semiconductor layer.
  • an organic semiconductor material exhibiting suitable characteristics for example, liquid crystallinity, solvent solubility, deep LUMO level, excellent semiconductor characteristics, particularly n-type organic semiconductor characteristics
  • suitable characteristics for example, liquid crystallinity, solvent solubility, deep LUMO level, excellent semiconductor characteristics, particularly n-type organic semiconductor characteristics
  • a semiconductor device using the organic semiconductor material is also provided.
  • a novel compound having a skeleton structure based on IQIQ is provided.
  • FIG. 3 is a schematic diagram of an Sm phase X-ray diffraction pattern of H12-IQIQ-12 at 150 ° C. and a liquid crystal molecule arrangement in a liquid crystal layer. It is a UV spectrum of a chloroform solution of 12-Chrysene-12 and 12-IQIQ-12. 2 is a photoelectron yield spectrum of 12-Chrysene-12 and 12-IQIQ-12 measured at 25 ° C. by photoelectron spectroscopy. It is a transient photocurrent waveform plotted by logarithm plotting measured by TOF method at 146 ° C. of 12-IQIQ-12, and is a result of (a) positive charge and (b) negative charge photocurrent. The insets in the photocurrent waveform diagrams of (a) and (b) show the respective linear plots. Electric field strength of 12-IQIQ-12: Temperature dependence of mobility of positive charge and negative charge at 6.6 ⁇ 10 4 V / cm.
  • the organic semiconductor material of the present invention comprises a unit A having an isoquinolino-isoquinoline (IQIQ) type skeleton structure; an aliphatic chain unit B (carbon atoms constituting a carbon main chain) linked to the unit A by a single bond; One or more of them may be substituted with “O (oxygen atom)”; a group containing an aliphatic chain and / or a cyclic structure connected to the unit A by a single bond, or a hydrogen atom
  • IQIQ isoquinolino-isoquinoline
  • the organic semiconductor material exhibits liquid crystallinity means that the organic semiconductor material exhibits liquid crystallinity at any temperature.
  • the organic semiconductor material of the present invention exhibits electron transport properties, and can be used as an excellent semiconductor particularly in a liquid crystal phase or a (solid) crystal phase.
  • the organic compound constituting the organic semiconductor material of the present invention is preferably a compound in which unit B and unit C are bonded to both ends of unit A by a single bond. That is, the organic compound constituting the organic semiconductor material of the present invention can have a configuration of ⁇ unit C> ⁇ ⁇ unit A> ⁇ ⁇ unit B>.
  • the “unit A” of the organic compound constituting the organic semiconductor material of the present invention will be described.
  • the unit A is a unit including a skeleton structure based on isoquinolino-isoquinoline (IQIQ) represented by the following formula (1).
  • the skeleton structure based on isoquinolino-isoquinoline (IQIQ) can have a group as described below.
  • Unit A has a modified structure of IQIQ of formula (1) in that unit B and unit C are connected by a single bond.
  • the organic semiconductor material of the present invention includes a skeletal structure based on isoquinolino-isoquinoline (IQIQ) as an extended aromatic ⁇ -conjugated system, so that a semiconductor property having a deeper LUMO level, particularly a LUMO level deeper than 3 eV can be obtained. It has the effect that it can utilize suitably as an n-type organic semiconductor.
  • IQIQ isoquinolino-isoquinoline
  • “Unit A” may be composed of “IQIQ” represented by the formula (1) alone, and the following formula (2) Wherein each a is independently a hydrogen atom, a single bond, or a saturated and / or unsaturated cyclic group, the cyclic group being a hydrocarbon group or one or more May include heteroatoms; at least one a is the cyclic group.) As shown in the above, at least one “cyclic group a” (since at least one a is a cyclic group, all a or a that is a cyclic group may be referred to as “cyclic group a”) is included in the IQIQ. Some may be connected by a single bond.
  • each of the unit B and the unit C is bonded to two a in the above formula by a single bond, so that the unit B and / or When the a to which unit C is bonded is a saturated and / or unsaturated cyclic group, unit B and / or unit C will be bonded to the cyclic group with a single bond, and unit B and When the a itself to which the unit C is bonded is a single bond, the unit B and / or the unit C is directly bonded to the IQIQ skeleton of the unit A with a single bond.
  • the liquid crystallinity is effectively expressed by the property of the cyclic group a.
  • unit A includes at least one other substitution in the IQIQ skeleton in place of the cyclic group a or in addition to the cyclic group a, particularly at positions R 5 to R 8 in the following formula (4).
  • a group, particularly an aliphatic group may be linked by a single bond.
  • This substituent, particularly an aliphatic group can be the same as the substituent and the aliphatic group constituting the units B and C described later. In the embodiment in which the unit A has such a substituent, it is effective to suitably exhibit liquid crystallinity depending on the nature of the substituent.
  • Suitable cyclic group a In the above formula (2), at least one of the cyclic groups a is a saturated and / or unsaturated cyclic group.
  • the cyclic structure constituting the cyclic group a is preferably a 5-membered ring and / or a 6-membered ring and / or a composite structure thereof.
  • the cyclic group a may be a hydrocarbon group or may contain one or more heteroatoms (for example, O, N and / or S).
  • the “suitable cyclic group a” can include, for example, the following structure.
  • R is a hydrogen atom or an aliphatic chain group. It is preferably a hydrogen atom.
  • the aliphatic chain group may contain an oxygen atom in the main chain, and the number of carbon atoms in R is preferably 20 or less.
  • Each of the units B and C is substituted when R in the above formula is a hydrogen atom, or when R is an aliphatic chain group, the aliphatic chain group of the R It may be bonded to the unit A in the form of substitution with a hydrogen atom.
  • unit B and unit C are bonded to unit A by a single bond.
  • the unit B and the unit C are “coupled by a single bond” to the unit A, the unit B and the unit C are single-bonded to the carbon atom constituting the skeleton structure including the IQIQ of the unit A. Therefore, a single bond (directly between unit B and unit C and the carbon atom is used in the form of substitution with a hydrogen atom bonded to the carbon atom in the skeleton structure represented by the above formulas (1) to (3). Bond) is formed. That is, it should be noted that the structures represented by the formulas (1) to (3) are structures before the unit B and the unit C are substituted and bonded.
  • the carbon atom constituting the skeletal structure in which the unit B and the unit C are bonded by a single bond is the carbon atom constituting the IQIQ itself represented by the formula (1), as well as represented by the formula (2) and the formula (3). It may be a cyclic group a bonded to IQIQ or a carbon atom constituting the substituents R 5 to R 8 .
  • the organic compound has a structure of ⁇ unit C>- ⁇ unit A>- ⁇ unit B>, that is, a chain molecule in which unit B is bonded to one end of unit A and unit C is bonded to the other end. It preferably has a structure.
  • the both ends of the unit A are the 2, 3, 8, and 9 positions of IQIQ (positions where a is bonded to the pyridine ring of the formula (2)).
  • Unit B is coupled to one end of unit A (eg, at least one of positions 2 and 3 of IQIQ), and unit C is coupled to the other end (eg, at least one of positions 8 and 9 of IQIQ).
  • the unit at the remaining end (the position of a in formula (2), that is, if there are positions where units B and C are not coupled among positions 2, 3, 8, and 9 of IQIQ) B and / or unit C may or may not be combined.
  • the unit B and the unit C are bonded directly to the carbon atoms at the 2nd and 8th positions (position to which a is bonded) of IQIQ represented by the following formula (5) or bonded to the 2nd and 8th position carbon atoms. It is preferably bonded to a carbon atom of the cyclic group a.
  • Unit B is an aliphatic chain group connected to unit A by a single bond.
  • the unit B is indispensable, and the unit B, which is a relatively flexible long chain, is bonded to the rigid unit A, so that the liquid crystallinity of the material can be suitably expressed. , Effective in improving solubility.
  • the aliphatic chain group may be either a saturated or unsaturated aliphatic chain group.
  • the main chain is a saturated or unsaturated group (for example, an alkyl group) composed of carbon atoms, or the carbon thereof. It is preferably a saturated or unsaturated aliphatic chain group containing “O (oxygen atom)” in the main chain composed of atoms.
  • the number of carbon atoms constituting the aliphatic chain of unit B is preferably 3-20, more preferably 10-14, and particularly preferably 12. If the number of atoms of the aliphatic chain group is 2 or less, it is difficult to impart flexibility to the molecule, and it may exceed 20, but if it exceeds 20, it may be difficult to obtain.
  • the aliphatic chain group constituting “unit B” is a C 3 to C 20 alkyl group.
  • one or more “O (oxygen) atoms” in the aliphatic chain group of “unit B” may be present in the carbon main chain.
  • a preferable “unit B” in this embodiment has one or more structures represented by the following formula as its partial structure.
  • the terminal of the aliphatic chain group having this partial structure is —CH 3 . (-X 1- (CH 2 ) r -X 2- ), (In the formula, X 1 and X 2 ⁇ O or CH 2 , and r is an integer of 1 to 19, except for the aspect of X 1 ⁇ X 2 ⁇ O (oxygen atom)).
  • the number of carbon atoms in the main chain is preferably 3-20.
  • X O or CH 2
  • n + m 3 to 19
  • the number of carbon atoms in the main chain is preferably 3-20.
  • -(CH 2 ) n -X- (CH 2 ) m -CH 3 — (CH 2 ) p —X— (CH 2 ) n —X— (CH 2 ) m —CH 3
  • X O or CH 2
  • n + m 3 to 19
  • p + n + m 3 to 19
  • p +... + N + m 3 to 19
  • m and n may include 0 Good.
  • the number of carbon atoms in the main chain is preferably
  • unit B is bonded to one of the ends of unit A, that is, any of positions 2, 3, 8, and 9 (positions where a is bonded to the pyridine ring of formula (2)) of IQIQ. Is preferred.
  • unit A is present at the end of those structures in the structures shown in the above formulas (1) to (3) or the structure shown as an example of cyclic group a.
  • a structure in which unit B is substituted for a hydrogen atom bonded to a carbon atom can be obtained.
  • the aliphatic chain group constituting the unit B can be the same group as the aliphatic chain group that may be contained in the unit A. Therefore, when unit A includes an aliphatic chain group and the aliphatic chain group satisfies the requirements of unit B, the aliphatic chain group of unit B is different from the aliphatic chain group of unit A. It may be additionally present, or the aliphatic chain group of the unit A itself may be the aliphatic chain group of the unit B, but the aliphatic chain group of the unit A When itself constitutes the aliphatic chain group of unit B, the aliphatic chain group constituting the aliphatic chain group of unit B is not regarded as a part constituting unit A.
  • the cyclic group a When the unit A has a cyclic group a added to the IQIQ skeleton, the cyclic group a has an aliphatic chain group R, and the unit B is linked to the aliphatic chain group of the cyclic group a, the cyclic group a
  • the aliphatic chain group R and the aliphatic chain group of the unit B preferably have 3 to 20 carbon atoms in their main chain.
  • the reason why the total length of the aliphatic chain group formed by combining unit A and unit B is preferably 3 to 20 carbon atoms is that the length of the aliphatic chain group of unit B is described. The same reason as above.
  • unit C is a group containing a hydrogen atom, an aliphatic chain, or a cyclic structure connected to unit A by a single bond.
  • the unit C can suitably exhibit the liquid crystal properties of the organic semiconductor material according to the properties of the unit C.
  • the “group containing a cyclic structure” includes an aromatic group (for example, a phenyl group), a heterocyclic group (for example, a thiophene group), or an aliphatic group (for example, a cyclohexyl group). it can.
  • the “group containing a cyclic structure” in the unit C can be the same as the cyclic group a in the unit A.
  • the meaning of the “aliphatic chain” in the “group containing an aliphatic chain” in the unit C is the same as that described for the aliphatic chain group in the “unit B”.
  • Examples of the aromatic group in the group containing a cyclic structure include phenyl, naphthyl, anthranyl, phenanthrenyl, fluorenyl, indenyl, azulenyl, biphenyl, terphenyl, cyclohexylphanyl, and naphthylphenyl.
  • heterocyclic group in the group containing a cyclic structure examples include thienyl, benzothienyl, naphthothienyl, furyl, oxadiazolyl, thiazoyl, thiadiazoyl, benzofuranyl, pyrrolyl, pyrazolyl, imidazolyl, pyridyl, pyrazinyl, pyrimidunyl, pyridazinyl, indolyl, quinolyl, Examples include isoquinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, tinolinyl, carbazoyl, acridinyl, phenanthridinyl, phenazinyl, and fetalidinyl.
  • Examples of the aliphatic group in the group including a cyclic structure include cyclopentyl, cyclohexyl, cycloheptyl, phenylcyclohexyl, and the like, and some of the structures include heteroatoms such as O, S, and N and unsaturated bonds. .
  • the unit C is preferably bonded to the end of the unit A, particularly to IQIQ positions 2, 3, 8, and 9 (positions where a is bonded to the pyridine ring of the formula (2)).
  • unit C is bonded to unit A by a single bond, unit C is bonded to unit A by substituting hydrogen atoms bonded to the carbon atoms constituting unit A shown in formulas (1) to (3). become.
  • the unit C is preferably connected to the end of the unit A opposite to the end to which the unit B is connected.
  • the group containing a cyclic structure or the group containing an aliphatic chain constituting the unit C can be the same group as the cyclic group or the aliphatic chain group that may be contained in the unit A. Therefore, when the unit A includes a cyclic group or an aliphatic chain group, and the cyclic group or the aliphatic chain group satisfies the requirements of the unit C, the cyclic group or the aliphatic chain group of the unit C is The cyclic group or aliphatic chain group may be present separately from the cyclic group or aliphatic chain group that the unit A has, or the cyclic group or aliphatic chain group of the unit A itself is the cyclic group or aliphatic chain group of the unit C.
  • the cyclic group or aliphatic chain group of unit A itself constitutes the cyclic group or aliphatic chain group of unit C
  • the cyclic group or aliphatic system of unit C may be used.
  • the cyclic group or aliphatic chain group constituting the chain group is not regarded as a part constituting the unit A.
  • the cyclic group a When the unit A has a cyclic group a added to the IQIQ skeleton, the cyclic group a has an aliphatic chain group R, and the unit C is linked to the aliphatic chain group of the cyclic group a, the cyclic group a
  • the aliphatic chain group R and the aliphatic chain group of unit C preferably have 3 to 20 carbon atoms in their main chain.
  • the reason why the total length of the aliphatic chain group formed by combining unit A and unit C is preferably 3 to 20 carbon atoms is that the length of the aliphatic chain group of unit B is described. The same reason as above.
  • a preferred example of the structure of an organic compound having a configuration of the organic semiconductor material of the present invention that is, an organic compound having a configuration of ⁇ unit C> ⁇ ⁇ unit A> ⁇ ⁇ unit B> is represented by the following structural formula (3). Street.
  • a 1 , a 2 , a 3 and a 4 are each independently a hydrogen atom, a single bond, or a saturated and / or unsaturated cyclic group
  • the unsaturated cyclic group may be a hydrocarbon group or may contain one or more heteroatoms, but at least one of a 1 , a 2 , a 3 and a 4 is a single bond Or a saturated and / or unsaturated cyclic group; at least one of R 1 , R 2 , R 3 and R 4 is each independently an aliphatic chain group, R 1 , R When any of 2 , R 3 and R 4 is not an aliphatic chain group, the remaining R 1 , R 2 , R 3 and R 4 can be hydrogen atoms.
  • the organic compound in which the units A, B, and C are bonded in such a form is preferable.
  • R 1 and R 3 may be the same (ie, symmetric) or different (ie, asymmetric).
  • R 2 and R 4 may be a hydrogen atom, an aliphatic chain, or a group containing a cyclic structure.
  • R 2 and R 4 may be the same (ie, symmetric) or different (ie, asymmetric).
  • the unit A is IQIQ alone.
  • at least one of R 1 to R 4 , particularly R 1 and R 3 is located. Two cyclic groups a may be bonded.
  • Suitable structures of the organic compound having the structure of the organic semiconductor material of the present invention that is, the organic compound having the structure of ⁇ unit C> ⁇ ⁇ unit A> ⁇ ⁇ unit B> are exemplified below.
  • H- ⁇ unit A> -alkyl group alkyl group- ⁇ unit A> -alkyl group phenyl group- ⁇ unit A> -alkyl group thiophene group- ⁇ unit A> -alkyl group
  • unit A is IQIQ skeleton alone
  • a 1 and a 3 are each independently a hydrogen atom, a single bond, or a saturated and / or unsaturated cyclic group, and the saturated and / or unsaturated
  • the cyclic group may be a hydrocarbon group or may contain one or more heteroatoms; one of R 1 and R 3 is an aliphatic chain group (eg, an alkyl group), and R 1 and R
  • the remainder of 3 is a hydrogen atom, an aliphatic chain group (eg, an alkyl group), a group containing a cyclic structure (eg, a phenyl group), or a cyclic hydrocarbon group containing one or more heteroatoms (eg, a thiophene group).
  • a 1 and a 3 are each independently a hydrogen atom, a single bond, or a saturated and / or unsaturated cyclic group, and the saturated and / or unsaturated
  • the cyclic group may be a hydrocarbon group or may contain one or more hetero
  • the organic semiconductor material exhibits liquid crystallinity means that the organic semiconductor material exhibits liquid crystallinity in “any temperature range” in which the organic semiconductor material exhibits semiconductivity.
  • the liquid crystallinity can be confirmed by various methods, and can be confirmed by, for example, observation with a polarizing microscope, or a combination of observation with a polarizing microscope, suggested thermal analysis, and X-ray diffraction.
  • the organic material is a material capable of exhibiting liquid crystallinity, it is possible to control molecular orientation in an aggregated state and realize excellent semiconductor characteristics. Although it has solubility as an excellent characteristic of liquid crystallinity, solubility can be easily confirmed by dissolving in a solvent.
  • the organic semiconductor material of the present invention exhibits liquid crystallinity, but is preferably in a liquid crystal or solid crystal state. It is more preferable to use higher-order smectic liquid crystals such as smectic liquid crystals, SmE, SmI, SmH, and SmK. Since the organic semiconductor material of the present invention is in a state of either a liquid crystal or a solid crystal, it can control molecular orientation and exhibits excellent semiconductor characteristics as compared with a case where liquid crystallinity is not exhibited.
  • the liquid crystal can be confirmed by, for example, polarization microscope texture (texture) observation, a combination of a polarization microscope, suggested thermal analysis, and X-ray diffraction analysis.
  • the solid crystal phase can be confirmed by, for example, X-ray diffraction analysis. Can do. Refer to the following literature for details.
  • the organic semiconductor material of the present invention “shows electronic conductivity”.
  • a well-known general evaluation method for semiconductor characteristics is a method in which mobility is directly obtained by the TOF method or a mobility is obtained by fabricating a transistor (FET).
  • FET transistor
  • the latter is a widely used method for evaluating crystalline thin film materials.
  • n-channels that is, when electrons are carriers, there are significant restrictions, and it is necessary to select electrode materials and insulating film materials appropriately. There is.
  • liquid crystal substances include high-molecular liquid crystals and low-molecular liquid crystals.
  • the liquid crystal phase generally has a high viscosity, so that ion conduction tends not to occur.
  • a low-order liquid crystal having a strong liquid property such as a nematic phase (N phase), a smectic A phase (SmA phase, hereinafter described in the same manner) or an SmC phase. In the phase, ionic conduction tends to be induced.
  • ionized impurity refers to an electrically active impurity (that is, a HOMO level, a LUMO level, or both of them, which can become a trap of ions and charges generated by dissociation of ionic impurities.
  • An impurity whose level is between the HOMO and LUMO levels of a liquid crystal substance is ionized by photoionization or charge trapping (for example, M. Funahashi and J. Hanna, Impurity effect on charge carrier transport in smectic liquid crystals, Chem. Phys. Lett., 397,319-323 (2004), H. Ahn, A. Ohno, and J. Hanna, Detection of Trace Amount of Impurity in Smectic Liquid Cry Appl. Phys., Vol. 44, No.6a, 2005, pp.3764-37687).
  • the HOMO and LUMO of the core part (in the present invention, the ⁇ -electron conjugate part including the IQIQ skeleton part, that is, the part related to charge transport, particularly IQIQ itself).
  • the energy level of becomes important.
  • the HOMO level of an organic semiconductor is determined by dissolving a test substance in a dehydrated organic solvent such as dichloromethane to a concentration of, for example, 1 mmol / L to 10 mmol / L, and adding a supporting electrolyte such as a tetrabutylammonium salt.
  • the HOMO level and LUMO level can be estimated from the difference between the peak potential and the reference potential, for example, a known substance such as ferrocene.
  • the HOMO-LUMO energy gap is determined from the absorption edge of the UV-visible absorption spectrum, and subtracted from the measured level.
  • the level and LUMO level can be estimated. This method can be referred to J. Pommerehne, H. Vestweber, W.ussGuss, R. F.rtMahrt, H. Bassler, M. Porsch, and J. Daub, Adv. Mater., 7, 551 (1995). it can.
  • the HOMO and LUMO levels of an organic semiconductor material provide a measure of electrical contact with the anode and cathode, respectively, and charge injection is limited by the size of the energy barrier determined by the difference from the work function of the electrode material. So be careful.
  • the work function of a metal is often silver (Ag) 4.0 eV, aluminum (Al) 4.28 eV, gold (Au) 5.1 eV, calcium (Ca) 2.87 eV, as examples of materials used as electrodes.
  • the difference in work function between the organic semiconductor material and the electrode substance is preferably 1 eV or less, more preferably 0.8 eV or less, and still more preferably 0.6 eV or less.
  • the work function of the metal the following documents can be referred to as necessary. Literature A: Handbook of Chemistry Fundamentals Revised 5th Edition II-608-61014.1b Work Function (Maruzen Publishing Co., Ltd.) (2004)
  • the size of the conjugated system can be used as a reference when selecting materials.
  • a method for changing the HOMO and LUMO energy levels it is effective to introduce, for example, an electron-withdrawing group such as F, another halogen element, or a cyano group into the core portion.
  • a substance that exhibits a higher-order smectic liquid crystal phase and is useful as an organic semiconductor can be screened as necessary from among compounds satisfying the above-described molecular design.
  • this screening basically, when used as an organic semiconductor in a liquid crystal phase, a higher order smectic phase is expressed, and when used as an organic semiconductor in a crystal phase, when cooled from a temperature higher than the crystal phase temperature, It is preferable to select one that does not develop a low-order liquid crystal phase adjacent to the crystal phase.
  • This selection method can select a substance useful as an organic semiconductor material by making a determination according to a “screening method” described later.
  • test substance After the isolated test substance is purified by column chromatography and recrystallization, it is confirmed by thin layer chromatography on silica gel that the test substance shows a single spot (that is, not a mixture).
  • a characteristic schlieren texture expressed as a pincushion is observed (see FIG. 3: typical schlieren texture).
  • a sample shows a SmA phase or an SmC phase a fan-like texture A characteristic texture having a uniform structure is observed in the fan-shaped area (see FIG. 4: a typical fan-like texture), and can be easily determined from the characteristic texture.
  • the visual field changes instantaneously at the phase transition temperature, but the phase transition texture almost changes.
  • the texture of the formed SmB phase, SmF phase, and SmI phase may be mistaken for the SmA phase and the SmC phase, so care should be taken.
  • the LUMO energy level is obtained by dissolving a test substance in an organic solvent such as dehydrated THF, adding about 0.2 mol / L of a supporting electrolyte such as tetrabutylammonium salt, and adding a working electrode such as Pt and Pt to this solution. After inserting a counter electrode and a reference electrode such as Ag / AgCl, the potentiostat is swept at a speed of about 50 mV / sec, and a CV curve is drawn, and the peak potential appears at a voltage lower than about -1.8V. It can be estimated that the LUMO level is deeper than about -3 eV.
  • solubility screening To measure the presence or absence of solubility of 0.1 wt% or more in toluene at room temperature, put about 5 mg of the test substance and about 5 g of toluene in a sample tube, heat it moderately on a hot stage, etc., and then dissolve it in toluene once. After cooling to room temperature (25 ° C.) and holding at room temperature for 1 hour, if no crystals appear, it can be judged that the solubility is 0.1 wt% or more.
  • a liquid crystal material having an isoquino [8,7-h] isoquinoline (IQIQ) skeleton which is a nitrogen-containing condensed ring, is designed and actually synthesized, and its phase transition behavior, energy level, optical characteristics, The charge transport properties were investigated.
  • An organic semiconductor material (or organic compound) having such a skeleton and also having liquid crystallinity is a novel organic compound by itself in that it has an isoquino [8,7-h] isoquinoline (IQIQ) skeleton. .
  • a unit A including a skeleton structure based on isoquinolino-isoquinoline (IQIQ) represented by the following formula (1) and a carbon main chain linked to the unit A by a single bond are formed.
  • An organic compound having at least unit C as an atom is provided.
  • One preferred embodiment of the novel organic compound of the present invention is represented by the following formula (3).
  • a 1 , a 2 , a 3 and a 4 are each independently a hydrogen atom, a single bond, or a saturated and / or unsaturated cyclic group, And / or the unsaturated cyclic group may be a hydrocarbon group or may contain one or more heteroatoms, but at least one of a 1 , a 2 , a 3 and a 4 is a single bond Or a saturated and / or unsaturated cyclic hydrocarbon group; at least one of R 1 , R 2 , R 3 and R 4 is each independently an aliphatic chain group, R 1 , When any of R 2 , R 3 and R 4 is not an aliphatic chain group, the remaining R 1 , R 2 , R 3 and R 4 can be hydrogen atoms.
  • the organic compound of the present invention has the following formula (6): (In the formula, at least one of R 1 , R 2 , R 3 and R 4 is each independently an alkyl group having 3 to 20 carbon atoms or other aliphatic chain group, and R 1 , R 2 , R 3 and R 4 are not aliphatic chain groups, the remaining R 1 , R 2 , R 3 and R 4 can be hydrogen atoms.) Can be.
  • R 1 , R 2 , R 3 and R 4 is each independently an aliphatic chain group described in Unit B or Unit C, particularly a carbon atom.
  • An aliphatic chain group having a number of 3 to 20 and containing one or more oxygen atoms, such as — (CH 2 ) n —X— (CH 2 ) m —CH 3 (wherein X ⁇ O or CH 2 N + m 3 to 19, and m and n may include 0), but any of R 1 , R 2 , R 3 and R 4 is not an aliphatic chain group
  • the remaining R 1 , R 2 , R 3 and R 4 can be hydrogen atoms.
  • Suitable examples of the organic compound of the present invention include 2,8-didecylisoquino [8,7-h] isoquinoline (10-IQIQ-10), 2.8-didodecylisoquino [8,7-h] isoquinoline ( 12-IQIQ-12) or 2.8-ditetradecylisoquino [8,7-h] isoquinoline (14-IQIQ-14).
  • the organic compound of the present invention (and / or the organic semiconductor material of the present invention) is useful as a liquid crystal material, an organic semiconductor material, or the like.
  • the method for producing the organic compound of the present invention (and / or the organic semiconductor material of the present invention) is not particularly limited, but the following production method can be suitably used from the viewpoint of simplicity.
  • the raw material compounds (compound 1, compound 2 and compound 3 shown in the synthesis scheme) can be prepared, and then the compound of the present invention (compound 4 shown in the synthesis scheme I) can be synthesized.
  • alkynes having various substituents R in the compound 1 obtained above for example, 1-alkynes such as 1-dodecine and 1-tetradecine, so-called Sonogashira reaction from 1-alkyne.
  • 1-alkynes such as 1-dodecine and 1-tetradecine
  • Sonogashira reaction from 1-alkyne can give 2,6-diarsynylnaphthalene-1,5-dicarbaldehyde (compound 2).
  • the Sonogashira reaction 2,6-Diorganylnaphthalene-1,5-dicarbaldehyde (Compound 2) having various substituents (organo groups) R other than alkyl groups can be obtained.
  • “typical Sonogashira reaction conditions” the literature (A. V. Malkov, M. M. Westwater, A. Gutnov, P. Ramirez-Lopez, F. Friscourt, A. Kadicikova, J. Hodacova, Z. Randkovic, M. Kotora, P. Kocovsky, Tetrahedron, 2008, 64, 11335).
  • an asymmetric compound is produced using the mixture of R, it is separated by a recrystallization method, column chromatography, or a combination thereof.
  • the target compound 4 is obtained by a cyclization reaction of the compound 3 with a cocatalyst of AgOTf and TfOH. They can be easily isolated as colorless crystals and purified by column chromatography and recrystallization. The structure of the resulting compound can be confirmed by a 1H NMR spectrum and a high resolution mass spectrometer.
  • the synthesis method is basically the same as that in Scheme 1, but only one bromine is supported in the Sonogashira reaction of compound 1, which is a key intermediate.
  • the product reacted with the alkyne compound is first isolated and then used to synthesize the remaining bromo group and the alkyne compound corresponding to the final product by the same coupling reaction by Sonogashira reaction. Can do.
  • various substituents such as an alkyl group and an aryl cage can be introduced at positions 3 and 9 of IQIQ by performing various known substitution reactions on the heterocyclic ring with respect to compound 4.
  • Known substitution reactions include those that selectively substitute the 3-position of pyridine and the 4-position of isoquinoline, such as J. Org. Chem., 53 (11), 2653-5 (1988) and J. Amer. Chem. Soc., 93 (5) 1294-6 (1971) can be used to synthesize compounds in which two B and C are substituted on the same pyridine unit of IQIQ.
  • organic compound of the present invention can be suitably obtained by “Synthesis route 1” or “Synthesis route 2” shown below.
  • the organic semiconductor material of the present invention is an organic semiconductor material that exhibits liquid crystallinity, has excellent solubility in a solvent, has high mobility, and has a deep LUMO level. In addition, since it has a deep LUMO level, it can be used not only as an organic transistor but also as an n-type organic semiconductor having an electron transport property.
  • the semiconductor device includes a layer formed using the novel organic semiconductor material or the novel organic compound of the present invention as a semiconductor layer, and includes a positive electrode and a negative electrode electrically coupled to the semiconductor layer.
  • the organic semiconductor material of the present invention is expected to be used as a high-mobility charge injection / transport layer when used in an organic EL, and also has a deep HOMO level, so it works as a hole blocking layer and is advantageous for charge containment. Furthermore, since it is a liquid crystal material, it can be controlled in parallel and can be used for a vertical device.
  • the organic semiconductor material of the present invention is used as a material for an n-channel transistor having a LUMO level of about 3 to 5 eV in combination with a p-channel transistor material having a HOMO level of about 5 to 6 eV. It can be used and is also useful as an n-channel transistor material for realizing a CMOS.
  • Such a semiconductor device using the organic semiconductor material of the present invention has a layer formed using the organic semiconductor material of the present invention as a semiconductor layer, and a positive electrode and a negative electrode electrically coupled to the semiconductor layer. It is characterized by comprising.
  • N-bromosuccinimide (6.8 g, 38.2 mmol) and AIBN (0.1 g, 0.64 mmol) were added to a carbon tetrachloride solution of 2,6-dibromo-1,5-dimethylnaphthalene (2 g, 6.35 mmol) under reflux conditions. ) was added in three portions, and the mixture was further heated under reflux for 12 hours. After cooling, the mixture solution was filtered and washed with methanol and ethyl acetate to obtain 2,6-dibromo-1,5-dibromodimethylnaphthalene as a white powder in 94% yield.
  • 1 HNMR (CDCl 3 , 400 MHz): 7.97 (d, 2H), 7.77 (d, 2H), 5.06 (s, 4H).
  • Measuring instrument High-resolution mass spectrum measuring device (HRMS: JEOL JMS-700) Measurement conditions: As the ionization method, a fast atom bombardment (FAB) method was used.
  • HRMS High-resolution mass spectrum measuring device
  • FAB fast atom bombardment
  • Example 4 Synthesis of Compound IV
  • a dichloroethane solution of compound III (1 eq) obtained in Example 3 was added to a Pyrex (registered trademark) glass flask.
  • AgOTf (0.1 eq) and TfOH (0.1 eq .; 0.10 M in dichloroethane) were added to an inert gas in the dark with respect to a dichloroethane solution of the compound III (1 eq) under stirring by a magnetic stirrer.
  • the mixture was added and further heated at 75 ° C. for 12 hours under the same stirring.
  • AgOTf / TfOH (0.1 eq) was further added under the same stirring.
  • the completion of the reaction was confirmed by TLC (trade name: silica gel 70F 254 manufactured by Wako Pure Chemical Industries, Ltd.).
  • silica column chromatography conditions used at this time are as follows. Column size: ID 3.5 cm x length 18 cm Silica filler: manufactured by Kanto Chemical Co., Ltd., trade name: silica gel 60 100-210 ⁇ m
  • Example 5 (Suggested thermal analysis of compound IVa, structure by polarizing microscope, X-ray diffraction)
  • the phase transition behavior of 10-IQIQ-10 (Compound IVa) was measured by suggested thermal analysis (DSC), structural observation with a polarizing microscope, and X-ray diffraction measurement.
  • DSC suggested thermal analysis
  • Optiphot 2-pol manufactured by Nikon hot stage: manufactured by Mettler: FP900 thermo-system was used, and an observed image was recorded.
  • Rigaku RAD-2B manufactured by Rigaku Corporation was used to identify phases.
  • FIGS. According to the DSC chart in FIG. 1, 10-IQIQ-10 (compound IVa) exhibits a plurality of exothermic and endothermic peaks in the temperature lowering and temperature rising processes, respectively, and has a clear phase transition to a liquid crystal phase around 160 ° C. Behavior is seen. Further, according to the polarizing microscope of FIG. 1 and the X-ray diffraction of FIG. 2, a fan-shaped structure characteristic to a low-order liquid crystal phase such as SmA or SmC phase was observed. FIG. 2 is an X-ray diffraction image in the crystal phase.
  • Example 6 (Suggested thermal analysis of compound 4b, organization by polarizing microscope, X-ray diffraction)
  • the phase transition behavior of 12-IQIQ-12 was measured by suggestive thermal analysis (DSC), structure observation with a polarizing microscope, and X-ray diffraction measurement under the same conditions as in Example 5.
  • FIG. 4 shows X-ray diffraction charts of 12-IQIQ-12 (Compound IVb) at 150 ° C. (upper diagram) and 130 ° C. (lower diagram).
  • FIG. 5 showing an X-ray diffraction chart at 150 ° C. of 12-IQIQ-12 (compound IVb), which is the same as the upper diagram in FIG. 4, when the interlayer distance is estimated from the diffraction peak of (111) plane, This value is shorter than the molecular length of 38.16 mm of 12-IQIQ-12 (compound IVb) calculated by MOPAC PM7, and the molecule is arranged at an angle of about 42.5 ° with respect to the molecular layer.
  • the alignment state of the liquid crystal molecules forming the liquid crystal layer is schematically shown on the right side of FIG.
  • this liquid crystal phase was identified as the SmH phase.
  • Several other peaks in the wide-angle diffraction are difficult to identify and some of these are believed to be due to diffraction from the crystalline domains remaining in the sample. This is because it was difficult to control the temperature of the sample in a narrow temperature range of about 10 ° C. from 140 ° C. to 150 ° C. in X-ray diffraction measurement. From the X-ray diffraction peak at 130 ° C. shown in FIG. 4, the crystal phase was identified in the temperature region of 140 ° C. or lower.
  • phase transition temperatures of 10-IQIQ-10 (compound IVa) and 12-IQIQ-12 (compound IVb) determined from DSC analysis are shown in Table 1 below.
  • Table 1 also shows the rearrangement temperature of 14-IQIQ-14 prepared in Example 10.
  • Iso represents an isotropic phase
  • SmC and “SmH” represent a smectic C phase and a smectic H phase
  • Cr represents a crystalline (solid) phase.
  • Example 7 Measurement of optical absorption characteristics and ionization potential of compound IVb
  • 12-IQIQ-12 Compound IVb
  • UV spectrum optical absorption characteristics
  • IP ionization potential
  • a solution in which the sample is dissolved is drop-cast on a glass substrate with ITO to form a film, and under a vacuum of 1.3 ⁇ 10 ⁇ 2 Pa, a Xe light source (HAMAMATSU C9559) and a deuterium light source (USHIO, XB-50101AA) -A) was irradiated with light (3 eV to 9 eV), and the emitted photoelectrons were measured at room temperature using a photoelectron yield spectrometer PYS-202 manufactured by Sumitomo Heavy Industries, Ltd.
  • FIG. 6 shows the UV spectra of the chloroform solutions of 12-Chrysene-12 and 12-IQIQ-12 obtained as described above.
  • FIG. 7 shows photoelectron yield spectra of 12-Chrysene-12 and 12-IQIQ-12 measured by photoelectron spectroscopy at 25 ° C.
  • the horizontal axis in FIG. 7 is the irradiation photon energy, and the vertical axis is the signal intensity corresponding to the photoelectron yield.
  • the ionization potentials (IP) of 12-IQIQ-12 and 12-Chrysene-12 were determined to be ⁇ 6.47 eV and ⁇ 5.85 eV, respectively. Further, as expected from the aza-acene skeleton, the LUMO level of 12-IQIQ-12 is 0.85 eV lower than 12-Chrysene-12, and the HOMO level is 0.62 eV lower as well. It became clear.
  • Example 8 Measurement of charge transport properties of compound IVb
  • the charge transport property of 12-IQIQ-12 was evaluated by the time-of-flight (TOF) method.
  • TOF time-of-flight
  • “12-IQIQ-12” to be measured was purified by repeating column chromatography and recrystallization several times (more than 6 times).
  • the column chromatography conditions and recrystallization conditions used at this time are as follows.
  • the sample purified as described above was injected into a liquid crystal cell having an ITO electrode having a thickness of 9 ⁇ m to obtain a sample.
  • a cell with a cell thickness of 9 ⁇ m (commercially available product: manufactured by EHC), in which two glass substrates with ITO transparent electrodes are bonded together with a thermosetting resin containing a spacer, is heated to the isotropic phase temperature of each compound, and a small amount of sample is prepared.
  • the sample was injected into the cell by contacting the cell opening and utilizing capillary action.
  • the cell was fixed to a sample stage having a heater, and a DC voltage was applied to the electrode.
  • a nitrogen pulse laser with a pulse width of 600 ps was irradiated, and the current flowing at that time was measured with a digital oscilloscope.
  • the intensity of light irradiation is adjusted so that the integral value (charge amount) of the photocurrent flowing by light irradiation is within 10% of the geometric electric capacity of the cell so as not to cause waveform distortion due to space charge. Noted that.
  • FIG. 8 (a) and 8 (b) show the logarithmically plotted transient photocurrent waveforms measured by the 12-IQIQ-12 TOF method at 164 ° C. and 130 ° C., respectively.
  • FIG. 8A shows the result by the positively charged photocurrent
  • FIG. 8B shows the result by the negatively charged photocurrent.
  • the “inset” in each figure shows the respective “linear plot”.
  • FIG. 9 shows the temperature dependence of the mobility of positive and negative charges at an electric field strength of 6.6 ⁇ 10 4 V / cm of 12-IQIQ-12 determined by the above-described measurement of charge transport characteristics.
  • the mobility of electrons and the mobility of holes in the Sm liquid crystal phase are 1.86 ⁇ 10 ⁇ 4 cm 2 / Vs and 1.08, respectively. It was estimated to be ⁇ 10 ⁇ 4 cm 2 / Vs. Although these mobilities have a limited temperature of 10K, the temperature dependence of the mobility was not observed in this region. In addition, no electric field dependency was observed.
  • both negative and positive charge mobilities in the isotropic phase are on the order of 10 ⁇ 5 cm 2 / Vs, and a slight electric field dependence It was observed.
  • the crystalline phase a significant decrease in photocurrent was observed, suggesting the formation of deep levels due to grain boundaries.
  • Example 10 In the same manner as in Examples 1 to 9, 2.8-ditetradecylisoquino [8,7-h] isoquinoline (14-IQIQ-14) was synthesized, and its physical properties and semiconductor properties were measured. Similar to 10-IQIQ-10 and 12-IQIQ-12, it exhibits a smectic phase around 150 ° C., and its LUMO level is deeper than ⁇ 3 eV, so this material is effective for electron conduction. Similarly, it can be determined that 10-IQIQ-10 and 14-IQIQ-14 have LUMO levels deeper than -3 eV.
  • 2,8-didecylisoquino is a new rod-like liquid crystal having a low electron density isoquino [8,7-h] isoquinoline (IQIQ) skeleton at the core and an IQIQ derivative expected as an organic semiconductor.
  • [8,7-h] isoquinoline (10-IQIQ-10) and 2.8-didodecylisoquino [8,7-h] isoquinoline (12-IQIQ-12) and 2.8-ditetradecylisoquinolino [8,7-h] isoquinoline (14-IQIQ-14) was synthesized in a relatively high yield using a simple technique.
  • 10-IQIQ-10 and 2.8-ditetradecylisoquinolino [8,7-h] isoquinoline are low-order smectic liquid crystals in a limited temperature range.
  • 12-IQIQ-12 developed a high-order smectic phase around 140 ° C. to 150 ° C., its LUMO level was ⁇ 3.33 eV. This material is expected to conduct electrons.
  • the LUMO level of 10-IQIQ-10 and 2.8-ditetradecylisoquinolino [8,7-h] isoquinoline (14-IQIQ-14) having the same skeleton structure as 12-IQIQ-12 is 12 Similar to -IQIQ-12, it is confirmed to be deeper than -3 eV.
  • the mobility of both electrons and holes was in the order of 10 ⁇ 4 cm 2 / Vs in the high-order smectic phase, and was in the order of 10 ⁇ 5 cm 2 / Vs in the isotropic phase.
  • This IQIQ material is expected to be applied to organic transistors.
  • Example 11 In the same manner as in the above example, 2-phenyl-8-decyl-benzothienobenzothiophene (Ph-BTBT-10) was synthesized and the LUMO level was measured and found to be -2.5 eV, and 12-Chrysene-12 The results were as expected by the BTBT skeleton structure, as was the shallow LUMO level of 3 eV or less.

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  • Organic Chemistry (AREA)
  • Thin Film Transistor (AREA)
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  • Photovoltaic Devices (AREA)

Abstract

Ce matériau semi-conducteur organique contient au moins les éléments suivants : une unité A comprenant une structure de squelette à base d'isoquinolino-isoquinoline (IQIQ) représentée par la formule (1); une unité de chaîne à base d'acide gras B reliée par une liaison simple avec l'unité A; et une unité C qui est un atome d'hydrogène, ou un groupe contenant une chaîne d'acides gras et/ou une structure cyclique, l'unité C étant connectée par une liaison simple avec l'unité A le matériau semi-conducteur organique présente des propriétés de cristaux liquides, a un niveau LUMO profond, et peut être utilisé de préférence en tant que matériau de transistor organique de type n. L'invention concerne également un nouveau composé.
PCT/JP2017/031671 2016-09-02 2017-09-01 Matériau semi-conducteur organique, composé organique et dispositif semi-conducteur organique WO2018043725A1 (fr)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
WO2012121393A1 (fr) * 2011-03-10 2012-09-13 国立大学法人東京工業大学 Matériau semi-conducteur organique
WO2013058844A1 (fr) * 2011-07-06 2013-04-25 Northwestern University Système et procédé de génération et/ou de criblage de réseaux métallo-organiques potentiels
JP2014506246A (ja) * 2010-12-15 2014-03-13 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 電気活性材料およびそのような材料を用いて製造されるデバイス

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014506246A (ja) * 2010-12-15 2014-03-13 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 電気活性材料およびそのような材料を用いて製造されるデバイス
WO2012121393A1 (fr) * 2011-03-10 2012-09-13 国立大学法人東京工業大学 Matériau semi-conducteur organique
WO2013058844A1 (fr) * 2011-07-06 2013-04-25 Northwestern University Système et procédé de génération et/ou de criblage de réseaux métallo-organiques potentiels

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YANG, TENGZHOU ET AL.: "Novel Calamitic Liquid Crystals Based on Electron-deficient Mesogen of Isoquino[8,7-h]isoquinoline: Synthesis, Mesomorphism, and Charge-transport Properties", CHEMISTRY LETTERS, vol. 45, no. 9, 5 September 2016 (2016-09-05), pages 1129 - 1131, XP055470810, DOI: doi:10.1246/cl.160559 *

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