Fused ring compounds, semiconductor materials and electronic devices

Abstract

This fused ring compound C has a fused ring F that includes a plurality of monocyclic aromatic rings M. The fused ring F has 11 monocyclic aromatic rings M. Of the 11 monocyclic aromatic rings, no more than two are thiophene. The fused ring F includes two naphthacene structures. A semiconductor material S includes the fused ring compound C. An electronic device 10 includes the semiconductor material S.

Description

Fused ring compounds, semiconductor materials and electronic devices

[0001] The present disclosure relates to fused ring compounds, semiconductor materials, and electronic devices.

[0002] In recent years, numerous electronic devices using semiconductor films formed from organic materials have been proposed, and their research and development is actively underway. Examples of electronic devices include thin film transistors (TFTs). In this disclosure, the semiconductor film may be referred to as a semiconductor layer. Using organic materials for the semiconductor layer offers various advantages. For example, conventional inorganic thin film transistors based on inorganic materials such as inorganic amorphous silicon require a heating process at temperatures of approximately 350°C to 400°C during fabrication. On the other hand, organic TFTs can be fabricated using a heating process at low temperatures of approximately 50°C to 200°C. Therefore, organic TFTs enable the fabrication of devices on substrates with low heat resistance, such as plastic films. Furthermore, the use of organic materials offers the advantage of being able to form semiconductor layers using simple methods such as spin coating, inkjet printing, and printing. These methods enable the fabrication of large-area devices at low cost.

[0003] One of the indices used to evaluate the performance of a TFT is the carrier mobility of the semiconductor layer. Much research has been conducted to improve the carrier mobility of the organic semiconductor layer in an organic TFT. For example, Patent Documents 1 to 4, etc., focus on organic materials for forming the organic semiconductor layer. Specifically, Patent Documents 1 to 3 disclose fused thiophene molecules having a structure in which two thiophene rings are fused with two to seven other monocyclic aromatic rings. Patent Document 4 discloses fused thiophene molecules having a structure in which four thiophene rings are fused with four to nine other monocyclic aromatic rings. Organic semiconductors and organic semiconductor films with excellent properties can improve the performance of electronic devices. Therefore, research to further improve the properties of organic semiconductors and organic semiconductor films is needed.

[0004] Examples of fused thiophene molecules that function as p-type organic semiconductor materials include benzothieno-benzothiophene (BTBT), dinaphthothienothiophene (DNTT), etc. These fused thiophene molecules are known to exhibit relatively high carrier mobility.

[0005] International Publication No. 2017 / 150474 International Publication No. 2016 / 152889 Patent No. 6318452 European Patent Application Publication No. 3050887

[0006] There is a need for new fused ring compounds suitable for semiconductor materials.

[0007] In one embodiment of the present disclosure, the fused ring compound has a fused ring containing a plurality of monocyclic aromatic rings, wherein the number of the monocyclic aromatic rings in the fused ring is 11, the number of thiophene rings among the 11 monocyclic aromatic rings is 2 or less, and the fused ring contains two naphthacene structures.

[0008] The present disclosure provides new fused ring compounds suitable for semiconductor materials.

[0009] Fig. 1 is a structural schematic diagram showing an example of an electronic device using the fused ring compound of the present disclosure. Fig. 2 is a structural schematic diagram showing another example of an electronic device using the fused ring compound of the present disclosure.

[0010] (Findings that form the basis of the present disclosure) According to the studies of the present inventors, the carrier mobility of conventional fused thiophene molecules cannot be said to be sufficiently high. Therefore, it is difficult to obtain an electronic device with a sufficiently high operating speed using conventional fused thiophene molecules. As an example, the hole mobility of fused thiophene molecules such as BTBT and DNTT is at most 5 to 10 cm 2 / Vs. When a fused thiophene molecule having this level of hole mobility is used, an element having a gate length of 10 μm can only achieve an operating speed of about 1 MHz. Furthermore, even when an element having a gate length adjusted to about 1 μm is used, an operating speed of only about 10 MHz can be achieved. Note that a gate length of about 1 μm corresponds to the lower limit of the gate length achievable using a coating method. For this reason, in the field of RF-ID (Radio Frequency Identification), which requires an operating speed of about 100 MHz, organic semiconductor materials with higher carrier mobility are required.

[0011] Reorganization energy is known as a physical quantity that significantly contributes to carrier mobility. Reorganization energy is a physical quantity that depends on the elemental arrangement and three-dimensional shape of a single molecule. Specifically, reorganization energy represents the amount of energy change that accompanies structural deformation of a molecule when carriers are hopping-conducted between multiple molecules. The smaller the reorganization energy, the higher the carrier mobility of a semiconductor material tends to be. Semiconductor materials with improved carrier mobility can realize electronic devices with high operating speeds.

[0012] As a result of extensive research, the present inventors have newly discovered that compounds having specific fused rings tend to have sufficiently small reorganization energies, leading to the completion of the fused ring compounds of the present disclosure.

[0013] (Summary of one aspect of the present disclosure) A fused ring compound according to a first aspect of the present disclosure has a fused ring containing a plurality of monocyclic aromatic rings, wherein the number of the monocyclic aromatic rings in the fused ring is 11, and among the 11 monocyclic aromatic rings, the number of thiophene rings is 2 or less, and the fused ring contains two naphthacene structures.

[0014] According to the first aspect, the fused ring compound tends to have a sufficiently small reorganization energy and a large carrier mobility, and can be said to be suitable for use as a semiconductor material.

[0015] In the second aspect of the present disclosure, for example, in the fused ring compound according to the first aspect, the eleven monocyclic aromatic rings may each independently be a benzene ring or a thiophene ring.

[0016] In the third aspect of the present disclosure, for example, in the fused ring compound according to the first or second aspect, the fused ring may have a linear structure.

[0017] In a fourth aspect of the present disclosure, for example, the fused ring compound according to any one of the first to third aspects may be represented by the following formula (I): In the formula (I), R A1 From R A18 are each independently a hydrogen atom or a hydrocarbon group, and Ar A1 and Ar A2 are each independently an optionally substituted benzene ring or an optionally substituted thiophene ring.

[0018] In a fifth aspect of the present disclosure, for example, the fused ring compound according to any one of the first to fourth aspects may be represented by the following formula (I-1), (I-2), (I-3), (I-4), or (I-5): In the formula (I-1), R a1 From R a26 are each independently a hydrogen atom or a hydrocarbon group. In the formula (I-2), R b1 From R b22 are each independently a hydrogen atom or a hydrocarbon group. In the formula (I-3), R c1 From R c22 are each independently a hydrogen atom or a hydrocarbon group. In the formula (I-4), R d1 From R d24 are each independently a hydrogen atom or a hydrocarbon group. In the formula (I-5), R e1 From R e24 are each independently a hydrogen atom or a hydrocarbon group.

[0019] The fused ring compounds according to the second to fifth aspects are suitable for semiconductor materials.

[0020] In a sixth aspect of the present disclosure, for example, in the fused ring compound according to any one of the first to fifth aspects, the fused ring is C 2V The symmetry may be:

[0021] The fused ring compound according to the sixth embodiment tends to be easy to synthesize.

[0022] A semiconductor material according to a seventh aspect of the present disclosure includes a fused ring compound according to any one of the first to sixth aspects.

[0023] According to the seventh aspect, the semiconductor material tends to have high carrier mobility.

[0024] An electronic device according to an eighth aspect of the present disclosure includes the semiconductor material according to the seventh aspect.

[0025] According to the eighth aspect, the operating speed of the electronic device tends to be high.

[0026] An electronic device according to a ninth aspect of the present disclosure comprises: a source electrode; a drain electrode; a gate electrode; and a semiconductor film including the semiconductor material according to the seventh aspect.

[0027] According to the ninth aspect, the operating speed of the electronic device tends to be high.

[0028] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. The present disclosure is not limited to the following embodiments.

[0029] (Embodiment of Fused Ring Compound) The fused ring compound C of this embodiment has a fused ring F containing a plurality of monocyclic aromatic rings M. In the fused ring F, the number of monocyclic aromatic rings M is 11. Of the 11 monocyclic aromatic rings M, the number of thiophene rings is 2 or less. The fused ring F contains two naphthacene structures.

[0030] The monocyclic aromatic ring M means one ring structure having aromaticity. In the present disclosure, the monocyclic aromatic ring M may be simply referred to as "aromatic ring M". The aromatic ring M typically contains carbon atoms. The aromatic ring M may be composed of only carbon atoms, or may contain heteroatoms such as sulfur atoms in addition to carbon atoms. The number of carbon atoms in the aromatic ring M is not particularly limited and is 4 or more and 10 or less. Specific examples of the aromatic ring M include a benzene ring and a thiophene ring.

[0031] The eleven aromatic rings M may each independently be a benzene ring or a thiophene ring. For example, the fused ring F may be composed of eleven benzene rings, one thiophene ring and ten benzene rings, or two thiophene rings and nine benzene rings.

[0032] In this embodiment, when the number of thiophene rings contained in the fused ring F is 2 or less, the fused ring compound C tends to have sufficiently high carrier mobility. Furthermore, when the number of thiophene rings contained in the fused ring F is 2 or less and the number of aromatic rings M constituting the fused ring F is 11, the fused ring compound C tends to have sufficiently high carrier mobility. As described below, the fused ring compound C can typically be used as a p-type semiconductor material. Therefore, in the present disclosure, the carrier mobility of the fused ring compound C may be referred to as hole mobility.

[0033] In the fused ring F, 11 aromatic rings M are fused. In the present disclosure, "aromatic rings M are fused" means that two adjacent aromatic rings M share two carbon atoms and a covalent bond formed between these carbon atoms.

[0034] The fused ring F has, for example, a linear structure. In the present disclosure, "fused ring F has a linear structure" means that in the fused ring F, 11 aromatic rings M are arranged in a single line without branching. That is, each of all aromatic rings M constituting the fused ring F is fused with only one or two adjacent aromatic rings M. In the fused ring F having a linear structure, there is no aromatic ring M fused with three or more adjacent aromatic rings M. If there is even one aromatic ring M fused with three or more adjacent aromatic rings M, the fused ring F can be considered not to have a linear structure but to have a branched structure.

[0035] In the fused ring F having a linear structure, the eleven aromatic rings M do not have to be arranged in a straight line. For example, the fused ring F may have a bent structure. In the present disclosure, "the fused ring F has a bent structure" means that in the fused ring F, some of the aromatic rings M are arranged in a bent manner.

[0036] In the fused ring F having a linear structure, the two aromatic rings M present at the terminals are each fused to only one adjacent aromatic ring M. The two aromatic rings M present at the terminals may each independently be a benzene ring or a thiophene ring. When the aromatic ring M present at the terminal is a thiophene ring, the thiophene ring may be fused to one adjacent aromatic ring M so as to share the second and third carbon atoms, or may be fused to one adjacent aromatic ring M so as to share the fourth and fifth carbon atoms. Usually, the first atom in the thiophene ring is a sulfur atom.

[0037] In the fused ring F having a linear structure, the other aromatic rings M other than the two aromatic rings M present at the terminals are each fused with two adjacent aromatic rings M. When the other aromatic ring M is a benzene ring, the benzene ring may be fused with one adjacent aromatic ring M so as to share the first and second carbon atoms, and may also be fused with the other adjacent aromatic ring M so as to share the third and fourth carbon atoms, may be fused with the other adjacent aromatic ring M so as to share the fourth and fifth carbon atoms, or may be fused with the other adjacent aromatic ring M so as to share the fifth and sixth carbon atoms.

[0038] As described above, the fused ring F contains two naphthacene structures. The naphthacene structure is represented by the following formula (1): In the two naphthacene structures of the fused ring F, the benzene rings constituting the naphthacene structures do not overlap with each other.

[0039] In this embodiment, the fused ring F has two naphthacene structures, and therefore the fused ring compound C tends to have sufficiently high carrier mobility.

[0040] The fused ring F may be symmetrical or may not be symmetrical. From the viewpoints of facilitating synthesis of the fused ring compound C, reducing the production cost, and further improving the hole mobility of the fused ring compound C, the fused ring F is preferably C 2V "The fused ring F may have the symmetry of C 2V "Having symmetry of 2-fold" means that the fused ring F has a two-fold rotational symmetry axis and a mirror plane parallel to the rotational symmetry axis. In the present disclosure, the rotational symmetry axis may be referred to as the principal axis of the fused ring F. 2V An example of the fused ring F having the symmetry is a structure represented by the following formula (2): In formula (2), the dashed line indicates the axis of rotational symmetry. At the position of the axis of rotational symmetry, a mirror plane extends in a direction perpendicular to the paper surface.

[0041] In the fused ring compound C, a hydrogen atom or a substituent is connected to the fused ring F. The substituent connected to the fused ring F is not particularly limited. For example, this substituent does not contain a heteroatom. A specific example of the substituent is a hydrocarbon group. The number of carbon atoms in the hydrocarbon group is not particularly limited, and is, for example, 1 to 20. The hydrocarbon group may be linear, branched, or cyclic. Examples of the hydrocarbon group include an alkyl group and an aryl group.

[0042] The number of carbon atoms in the alkyl group may be from 1 to 20, from 1 to 10, or from 3 to 8. Examples of the alkyl group include a methyl group, an ethyl group (Et), an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group (i-Bi), a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0043] The number of carbon atoms in the aryl group may be 6 or more and 18 or less, or 6 or more and 12 or less. Examples of the aryl group include a phenyl group (Ph), a naphthyl group, a 4-biphenyl group, a 3-biphenyl group, and a 2-biphenyl group.

[0044] The fused ring compound C is represented, for example, by the following formula (I): The fused ring compound C represented by formula (I) tends to have a smaller reorganization energy than the fused ring compound C represented by formula (II) described below.

[0045] In formula (I), R A1 From R A18 are each independently a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include those described above.

[0046] In formula (I), Ar A1 and Ar A2 are each independently a benzene ring which may have a substituent or a thiophene ring which may have a substituent. Specific examples of the substituent on the benzene ring and the thiophene ring are hydrocarbon groups. Examples of the hydrocarbon group include those described above.

[0047] The fused ring compound C may be represented by the following formula (I-1).

[0048] In formula (I-1), R a1 From R a26 are each independently a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include those mentioned above. The fused ring compound C represented by formula (I-1) is a fused polycyclic hydrocarbon having a fused ring F having a linear structure. In this fused ring compound C, the fused ring F is C 2V It has the symmetry of

[0049] From the viewpoint of further improving the solubility of the fused ring compound C in an organic solvent and the hole mobility of the fused ring compound C, R a1 From R a26 At least one selected from R may be an alkyl group or an aryl group. a1 From R a26 may each independently be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Examples of the alkyl group and the aryl group include those described above. a1 From R a26 Specific examples of combinations of R are shown in Table 1 below. In Table 1, the compound entries are a1 From R a26 The abbreviation of the fused ring compound C having the formula:

[0050]

[0051] The fused ring compound C may be represented by the following formula (I-2).

[0052] In formula (I-2), R b1 From R b22 are each independently a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include those described above. The fused ring compound C represented by formula (I-2) is a fused ring thiophene molecule having a fused ring F with a linear structure. In this fused ring compound C, the fused ring F is 2V It has the symmetry of

[0053] From the viewpoint of further improving the solubility of the fused ring compound C in an organic solvent and the hole mobility of the fused ring compound C, R b1 From R b22 At least one selected from R may be an alkyl group or an aryl group. b1 From R b22 may each independently be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Examples of the alkyl group and the aryl group include those described above. b1 From R b22 Specific examples of combinations of R are shown in Table 2 below. In Table 2, the compound entries are b1 From R b22 The abbreviation of the fused ring compound C having the formula:

[0054]

[0055] The fused ring compound C may be represented by the following formula (I-3).

[0056] In formula (I-3), R c1 From R c22 are each independently a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include those described above. The fused ring compound C represented by formula (I-3) is a fused ring thiophene molecule having a fused ring F with a linear structure. In this fused ring compound C, the fused ring F is 2V It has the symmetry of

[0057] From the viewpoint of further improving the solubility of the fused ring compound C in an organic solvent and the hole mobility of the fused ring compound C, R c1 From R c22 At least one selected from may be an alkyl group or an aryl group, or may be an alkyl group. c1 From R c22 may each independently be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Examples of the alkyl group and the aryl group include those described above. c1 From R c22Specific examples of combinations of R are shown in Table 3 below. In Table 3, the compound entries are c1 From R c22 The abbreviation of the fused ring compound C having the formula:

[0058]

[0059] The fused ring compound C may be represented by the following formula (I-4).

[0060] In formula (I-4), R d1 From R d24 are each independently a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include those described above. The fused ring compound C represented by formula (I-4) is a fused ring thiophene molecule having a fused ring F with a linear structure. In this fused ring compound C, the fused ring F is not symmetrical.

[0061] From the viewpoint of further improving the solubility of the fused ring compound C in an organic solvent and the hole mobility of the fused ring compound C, R d1 From R d24 At least one selected from may be an alkyl group or an aryl group, or may be an alkyl group. d1 From R d24 may each independently be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Examples of the alkyl group and the aryl group include those described above. d1 From R d24 Specific examples of combinations of R are shown in Table 4 below. In Table 4, the compound entries are d1 From R d24 The abbreviation of the fused ring compound C having the formula:

[0062]

[0063] The fused ring compound C may be represented by the following formula (I-5).

[0064] In formula (I-5), R e1 From R e24are each independently a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include those described above. The fused ring compound C represented by formula (I-5) is a fused ring thiophene molecule having a fused ring F with a linear structure. In this fused ring compound C, the fused ring F is not symmetrical.

[0065] From the viewpoint of further improving the solubility of the fused ring compound C in an organic solvent and the hole mobility of the fused ring compound C, R e1 From R e24 At least one selected from may be an alkyl group or an aryl group, or may be an alkyl group. e1 From R e24 may each independently be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Examples of the alkyl group and the aryl group include those described above. e1 From R e24 Specific examples of combinations of R are shown in Table 5 below. In Table 5, the compound entries are e1 From R e24 The abbreviation of the fused ring compound C having the formula:

[0066]

[0067] The fused ring compound C may be represented by formula (I-1), (I-2), (I-3), (I-4), or (I-5), or may be represented by formula (I-1), (I-2), or (I-3). The fused ring compound C represented by formula (I-1), (I-2), or (I-3) has a high symmetry of the fused ring F and tends to be easily synthesized.

[0068] The fused ring compound C may be represented by the following formula (II):

[0069] In formula (II), R B1 From R B18 are each independently a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include those described above.

[0070] In formula (II), Ar B1 and ArB2 are each independently a benzene ring which may have a substituent or a thiophene ring which may have a substituent. Specific examples of the substituent on the benzene ring and the thiophene ring are hydrocarbon groups. Examples of the hydrocarbon group include those described above.

[0071] The fused ring compound C may be represented by the following formula (II-1).

[0072] In formula (II-1), R f1 From R f26 are each independently a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include those mentioned above. The fused ring compound C represented by formula (II-1) is a fused polycyclic hydrocarbon having a fused ring F having a linear structure. In this fused ring compound C, the fused ring F is C 2V It has the symmetry of

[0073] From the viewpoint of further improving the solubility of the fused ring compound C in an organic solvent and the hole mobility of the fused ring compound C, R f1 From R f26 At least one selected from R may be an alkyl group or an aryl group. f1 From R f26 may each independently be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Examples of the alkyl group and the aryl group include those described above. f1 From R f26 Specific examples of combinations of R are shown in Table 6 below. In Table 6, the compound entries are f1 From R f26 The abbreviation of the fused ring compound C having the formula:

[0074]

[0075] The fused ring compound C may be represented by the following formula (II-2).

[0076] In formula (II-2), R g1 From R g22are each independently a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include those described above. The fused ring compound C represented by formula (II-2) is a fused ring thiophene molecule having a fused ring F with a linear structure. In this fused ring compound C, the fused ring F is 2V It has the symmetry of

[0077] From the viewpoint of further improving the solubility of the fused ring compound C in an organic solvent and the hole mobility of the fused ring compound C, R g1 From R g22 At least one selected from R may be an alkyl group or an aryl group. g1 From R g22 may each independently be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Examples of the alkyl group and the aryl group include those described above. g1 From R g22 Specific examples of combinations of R are shown in Table 7 below. In Table 7, the compound entries are g1 From R g22 The abbreviation of the fused ring compound C having the formula:

[0078]

[0079] The fused ring compound C may be represented by the following formula (II-3).

[0080] In formula (II-3), R h1 From R h22 are each independently a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include those described above. The fused ring compound C represented by formula (II-3) is a fused ring thiophene molecule having a fused ring F with a linear structure. In this fused ring compound C, the fused ring F is 2V It has the symmetry of

[0081] From the viewpoint of further improving the solubility of the fused ring compound C in an organic solvent and the hole mobility of the fused ring compound C, R h1 From R h22At least one selected from may be an alkyl group or an aryl group, or may be an alkyl group. h1 From R h22 may each independently be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Examples of the alkyl group and the aryl group include those described above. h1 From R h22 Specific examples of combinations of R are shown in Table 8 below. In Table 8, the compound entries are h1 From R h22 The abbreviation of the fused ring compound C having the formula:

[0082]

[0083] The fused ring compound C may be represented by the following formula (II-4).

[0084] In formula (II-4), R i1 From R i24 are each independently a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include those described above. Fused ring compound C represented by formula (II-4) is a fused ring thiophene molecule having a fused ring F with a linear structure. In this fused ring compound C, the fused ring F is not symmetrical.

[0085] From the viewpoint of further improving the solubility of the fused ring compound C in an organic solvent and the hole mobility of the fused ring compound C, R i1 From R i24 At least one selected from may be an alkyl group or an aryl group, or may be an alkyl group. i1 From R i24 may each independently be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Examples of the alkyl group and the aryl group include those described above. i1 From R i24 Specific examples of combinations of R are shown in Table 9 below. In Table 9, the compound entries are i1 From R i24The abbreviation of the fused ring compound C having the formula:

[0086]

[0087] The fused ring compound C may be represented by the following formula (II-5).

[0088] In formula (II-5), R j1 From R j24 are each independently a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include those described above. Fused ring compound C represented by formula (II-5) is a fused ring thiophene molecule having a fused ring F with a linear structure. In this fused ring compound C, the fused ring F is not symmetrical.

[0089] From the viewpoint of further improving the solubility of the fused ring compound C in an organic solvent and the hole mobility of the fused ring compound C, R j1 From R j24 At least one selected from may be an alkyl group or an aryl group, or may be an alkyl group. j1 From R j24 may each independently be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Examples of the alkyl group and the aryl group include those described above. j1 From R j24 Specific examples of combinations of R are shown in Table 10 below. In Table 10, the compound entries are j1 From R j24 The abbreviation of the fused ring compound C having the formula:

[0090]

[0091] [Method for Producing Fused Ring Compound] Fused ring compound C can be synthesized by using a commercially available compound as a raw material and performing a combination of known reactions such as a halogenation reaction and a Sonogashira coupling reaction. If by-products are produced by the reaction, they may be separated and purified by known methods such as column chromatography.

[0092] [Method for Identifying Fused Ring Compound] The fused ring compound C of the present disclosure can be identified by elemental analysis, mass spectrometry, and 13 The compound C can be identified by C-NMR. That is, the ratio of the number of atoms constituting one molecule of the fused ring compound C is determined by elemental analysis. The molecular weight of the fused ring compound C is determined by mass spectrometry. Based on these results, the molecular formula of the fused ring compound C can be determined. Furthermore, 13 By analyzing the chemical shift amount of each peak obtained by C-NMR, it is possible to determine the structural formula of fused ring compound C. These methods also allow the type and position of the substituent to be identified.

[0093] [Characteristics of the fused ring compound] The fused ring compound C of this embodiment tends to have a sufficiently small reorganization energy and a high carrier mobility. The reorganization energy due to hole migration of the fused ring compound C is not particularly limited, and may be, for example, 0.10 eV or less, 0.08 eV or less, 0.07 eV or less, or 0.06 eV or less. The lower limit of the reorganization energy of the fused ring compound C is not particularly limited, and is, for example, 0.04 eV.

[0094] The charge hopping rate, which corresponds to the carrier mobility, can be calculated by the following formula (F1): Formula (F1) is reported in, for example, David R. Evans et al., Organic Electronics, 2016, Vol. 29, p. 50.

[0095] In formula (F1), κ is the charge hopping rate. ΔG is the amount of change in free energy accompanying charge transfer. λ is the reorganization energy in Marcus theory. H is the electron coupling between molecules. k B is the Boltzmann constant. T is the temperature. h- (hbar) is the Planck constant.

[0096] Reorganization energy is a physical quantity that depends on the atomic arrangement and three-dimensional shape of a single molecule. Specifically, reorganization energy represents the amount of energy change that accompanies the structural deformation of a molecule when carriers are hopping between multiple molecules. Reorganization energy contributes significantly to the charge transport speed, and the smaller its value, the more likely carrier mobility is to improve. The good correlation between reorganization energy and carrier mobility has been reported, for example, by Shigeyoshi Sakaki et al., J. Phys. Chem. A, 1999, Vol. 103, pp. 5551-5556.

[0097] The reorganization energy λ is E (neutral state in neutral geometry), E * (neutral state in ionic geometry), E ± (ionic state in ionic geometry) and E ± * It is defined by the following formula (F2) using the energy values ​​of the four points of the ionic state in neutral geometry.

[0098] The reorganization energy λ can be calculated, for example, by density functional theory. This calculation can be performed using known software such as Gaussian09. In this case, B3LYP can be used as the functional. 6-31G(d,p) can be used as the basis function.

[0099] [Uses of Fused Ring Compounds] The fused ring compounds C of the present disclosure tend to have excellent carrier mobility. Therefore, the fused ring compounds C are suitable as semiconductor materials. In another aspect, the present disclosure provides a semiconductor material S containing the fused ring compound C. The fused ring compound C has, for example, excellent hole mobility. The semiconductor material S containing such a fused ring compound C can be used, for example, as a p-type semiconductor material. In the present disclosure, the semiconductor material S containing the fused ring compound C may be referred to as a molecular-based organic semiconductor material or a carbon-based hole transport material.

[0100] The semiconductor material S containing the fused ring compound C of the present disclosure can be used in an electronic device. In another aspect, the present disclosure provides an electronic device containing the semiconductor material S. Specifically, the electronic device includes a semiconductor film containing the semiconductor material S. In the present disclosure, the electronic device may be referred to as an electronic element. By using the fused ring compound C in an electronic device, the frequency characteristics of the electronic device can be improved. A specific example of the electronic device is a transistor.

[0101] (Embodiment of Electronic Device) FIG. 1 is a structural schematic diagram showing an example of an electronic device using the fused ring compound C of the present disclosure. As shown in FIG. 1, the electronic device 10 includes a gate electrode 1, a source electrode 3, a drain electrode 4, and a semiconductor film 5. The electronic device 10 may further include a gate insulating film 2. In the electronic device 10, the semiconductor film 5 contains a semiconductor material S. The electronic device 10 of FIG. 1 is typically a transistor. In detail, FIG. 1 shows the basic structure of a transistor.

[0102] The gate electrode 1 is, for example, plate-shaped, and supports the gate insulating film 2, the source electrode 3, the drain electrode 4, and the semiconductor film 5. The gate insulating film 2 is located on the gate electrode 1 and covers the main surface of the gate electrode 1. The gate insulating film 2 may cover the entire main surface of the gate electrode 1.

[0103] The source electrode 3 and the drain electrode 4 are each, for example, strip-shaped. The source electrode 3 and the drain electrode 4 are located on the gate insulating film 2 so as not to contact each other. A space is formed between the source electrode 3 and the drain electrode 4. The source electrode 3 and the drain electrode 4 are each in contact with the gate insulating film 2. The source electrode 3 and the drain electrode 4 each extend from one to the other of a pair of end faces of the gate electrode 1.

[0104] The semiconductor film 5 is in contact with each of the gate insulating film 2, the source electrode 3, and the drain electrode 4. In particular, the semiconductor film 5 covers the surface of the gate insulating film 2 that is exposed between the source electrode 3 and the drain electrode 4, and also covers each of the source electrode 3 and the drain electrode 4. The semiconductor film 5 fills the space that exists between the source electrode 3 and the drain electrode 4.

[0105] The material of the gate electrode 1 is not particularly limited as long as it is used as an electrode material in the field of electronic devices. The material of the gate electrode 1 is, for example, a metal. Examples of the material of the gate electrode 1 include silicon, gold, copper, nickel, and aluminum.

[0106] The material of the gate insulating film 2 is not particularly limited as long as it has electrical insulation properties. Examples of materials for the gate insulating film 2 include metal oxides, metal nitrides, and polymeric materials. Examples of metal oxides include silicon oxides such as SiO2, tantalum oxides such as Ta2O5, aluminum oxides such as Al2O3, titanium oxides such as TiO2, yttrium oxides such as Y2O3, and lanthanum oxides such as La2O3. Examples of metal nitrides include silicon nitrides such as Si3N4. Examples of polymeric materials include epoxy resins, polyimide (PI) resins, polyphenylene ether (PPE) resins, polyphenylene oxide (PPO), and polyvinylpyrrolidone (PVP) resins.

[0107] Materials for the source electrode 3 and the drain electrode 4 include the materials mentioned above for the gate electrode 1 .

[0108] As described above, the semiconductor film 5 contains the semiconductor material S. Specifically, the semiconductor film 5 is a p-type semiconductor film containing a fused ring compound C. The content of the fused ring compound C in the semiconductor film 5 is not particularly limited and may be, for example, 0.1% by mass or more, or 1% by mass or more. From the viewpoint of improving hole mobility, the content of the fused ring compound C may be 10% by mass or more, 50% by mass or more, or even 100% by mass.

[0109] Semiconductor film 5 may further contain a material other than fused ring compound C. Examples of the other material include fullerene, perylene diimide, polythiophene, and fused ring thiophene molecules other than fused ring compound C.

[0110] The semiconductor film 5 can be formed by known methods such as vacuum deposition, coating, etc. When the semiconductor film 5 is formed by vacuum deposition, the semiconductor film 5 can be formed with a fused ring compound C content of 100 mass % by using only the fused ring compound C as a deposition material.

[0111] (Modified Example of Electronic Device) Fig. 2 is a structural schematic diagram showing another example of an electronic device using the fused ring compound C of the present disclosure. As shown in Fig. 2, the electronic device 11 includes a gate electrode 17, a source electrode 13, a drain electrode 14, and a semiconductor film 15. The electronic device 11 may further include an underlying substrate 12 and a gate insulating film 16. In the electronic device 11, the semiconductor film 15 contains a semiconductor material S. The electronic device 11 in Fig. 2 is typically a transistor. In detail, Fig. 2 shows another basic structure of a transistor.

[0112] The base substrate 12 is, for example, plate-shaped and supports the source electrode 13, the drain electrode 14, the semiconductor film 15, the gate insulating film 16, and the gate electrode 17. The base substrate 12 has, for example, an insulating layer. The base substrate 12 may have a silicon wafer and an insulating layer located on the silicon wafer. In the base substrate 12, the insulating layer may cover the entire main surface of the silicon wafer.

[0113] The source electrode 13 and the drain electrode 14 are each, for example, strip-shaped. The source electrode 13 and the drain electrode 14 are located on the underlying substrate 12 so as not to contact each other. A space is formed between the source electrode 13 and the drain electrode 14. The source electrode 13 and the drain electrode 14 are each in contact with the underlying substrate 12, more specifically, in contact with the insulating layer of the underlying substrate 12. The source electrode 13 and the drain electrode 14 each extend from one to the other of a pair of end faces of the underlying substrate 12.

[0114] The semiconductor film 15 is in contact with the underlying substrate 12, the source electrode 13, and the drain electrode 14. Specifically, the semiconductor film 15 covers the surface of the underlying substrate 12 exposed between the source electrode 13 and the drain electrode 14, and also covers each of the source electrode 13 and the drain electrode 14. The semiconductor film 15 is in contact with the insulating layer of the underlying substrate 12. The semiconductor film 15 fills the space between the source electrode 13 and the drain electrode 14.

[0115] The gate insulating film 16 is located on the semiconductor film 15 and covers the main surface of the semiconductor film 15. The gate insulating film 16 may cover the entire main surface of the semiconductor film 15.

[0116] The gate electrode 17 has, for example, a strip shape. The gate electrode 17 is located on the gate insulating film 16 and is in contact with the gate insulating film 16. The gate electrode 17 extends from one to the other of a pair of end faces of the base substrate 12. When the electronic device 11 is viewed in plan, the gate electrode 17 is located between the source electrode 13 and the drain electrode 14.

[0117] The material of the insulating layer of the base substrate 12 is not particularly limited as long as it has electrical insulation properties. Examples of insulating layer materials include metal oxides, metal nitrides, and polymeric materials. Metal oxides include silicon oxides such as SiO2, tantalum oxides such as Ta2O5, aluminum oxides such as Al2O3, titanium oxides such as TiO2, yttrium oxides such as Y2O3, and lanthanum oxides such as La2O3. Metal nitrides include silicon nitrides such as Si3N4. Polymeric materials include epoxy resins, polyimide (PI) resins, polyphenylene ether (PPE) resins, polyphenylene oxide (PPO), and polyvinylpyrrolidone (PVP) resins.

[0118] The material of the source electrode 13 and the drain electrode 14 is not particularly limited as long as it is an electrode material used in the field of electronic devices. The material of the source electrode 13 and the drain electrode 14 is, for example, a metal. Examples of the material of the source electrode 13 and the drain electrode 14 include silicon, gold, copper, nickel, and aluminum.

[0119] As described above, the semiconductor film 15 contains the semiconductor material S. Specifically, the semiconductor film 15 is a p-type semiconductor film containing a fused ring compound C. The content of the fused ring compound C in the semiconductor film 15 is not particularly limited and may be, for example, 0.1% by mass or more, or 1% by mass or more. From the viewpoint of improving hole mobility, the content of the fused ring compound C may be 10% by mass or more, 50% by mass or more, or even 100% by mass.

[0120] Semiconductor film 15 may further contain a material other than fused ring compound C. Examples of the other material include fullerene, perylene diimide, polythiophene, and fused ring thiophene molecules other than fused ring compound C.

[0121] There are no particular limitations on the material of the gate insulating film 16 as long as it has electrical insulation properties. Examples of materials for the gate insulating film 16 include the materials mentioned above for the insulating layer of the base substrate 12.

[0122] The gate electrode 17 may be made of the materials mentioned above for the source electrode 13 and the drain electrode 14 .

[0123] The present disclosure will be described in more detail below with reference to examples. Note that the following examples are merely illustrative and the present disclosure is not limited to the following examples.

[0124] Experimental Example 1 The reorganization energy due to hole migration was calculated for dinaphthothienothiophene (DNTT), compounds (i-1) to (i-9) in Table 1, compounds (ii-1) to (ii-3) in Table 2, compounds (iii-1) to (iii-3) in Table 3, compound (iv-1) in Table 4, compound (v-1) in Table 5, compound (vi-1) in Table 6, and compound (vii-1) in Table 7. DNTT is known as a p-type organic semiconductor material with high hole mobility. The reorganization energy was calculated using density functional theory based on the above-mentioned formula (F2). Specifically, the reorganization energy was calculated using the calculation software Gaussian09. The functional used was B3LYP. The basis function used was 6-31G(d,p). The results are shown in Table 11.

[0125]

[0126] Table 11 shows that fused ring compound C of the present disclosure exhibits a sufficiently small reorganization energy compared to DNTT. As described above, reorganization energy and hole mobility are well correlated. In particular, reorganization energy and hole mobility show a negative correlation. From the results in Table 11, it is estimated that fused ring compound C of the present disclosure has a higher hole mobility than DNTT. From this, it can be said that fused ring compound C is suitable as a semiconductor material.

[0127] Experimental Example 2 (Production of Compound (i-1)) Compound (i-1) was synthesized by the following method. First, a tetrachloromethane solution containing commercially available 1-bromo-2,3-dimethylbenzene and bromosuccinimide was prepared. This solution was kept at room temperature for 1.5 hours to obtain a compound represented by the following formula (3).

[0128] Next, 1,4-anthraquinone and potassium iodide were added to the obtained compound, and the mixture was kept in N,N-dimethylformamide (DMF) at 110°C for 20 hours to obtain a compound represented by the following formula (4).

[0129] Next, aluminum, tetrabromomethane, and mercury(II) chloride were added to the obtained compound, and the mixture was kept in cyclohexanol at 100° C. for about 3 days. Further, hydrochloric acid and ethanol were added, and the mixture was kept at 100° C. for 2 hours, thereby obtaining Compound A represented by the following formula (5).

[0130] Next, trimethylsilylacetylene, diisopropylamine, CuI, and PdCl(PPh) were added to the compound A, and the mixture was refluxed in tetrahydrofuran for 24 hours. Potassium fluoride and methanol were then added to the resulting mixture, and the mixture was refluxed for 12 hours to obtain a compound represented by the following formula (6).

[0131] Next, compound A represented by formula (5), triethylamine, CuI, Pd(PPh3)4, and DI-μ-iododicopper were added to the compound represented by formula (6), and the mixture was kept in DMF at 55°C to obtain a compound represented by formula (7) below.

[0132] Next, PdCaCo3, Pd(OCOCH3)2 and quinoline were added to the obtained compound, and the mixture was kept in a hydrogen atmosphere in ethyl acetate at room temperature for 1 hour to obtain a compound represented by the following formula (8).

[0133] Next, iodine was added to the obtained compound, and the mixture was kept in an oxygen atmosphere in toluene at room temperature for 6 minutes, thereby obtaining a compound (i-1) represented by the following formula (9).

[0134] Compound (i-1) was analyzed by elemental analysis, mass spectrometry, and 13 Identification was performed by C-NMR. Elemental analysis revealed that the ratio of the number of carbon atoms to the number of hydrogen atoms was C:H=23:13. Mass analysis revealed that the molecular weight was 578.7.

[0135] Experimental Example 3 (Production of Compound (ii-1)) Compound (ii-1) was synthesized by the following method: First, Ph(OAc)2 and dichloro(p-cymene)ruthenium(II) were added to commercially available 1-bromoanthraquinone, and the mixture was kept in trifluoroacetic anhydride at 80°C for 12 hours to obtain a compound represented by the following formula (10).

[0136] Next, sodium dithionite was added to the obtained compound, and the mixture was kept in dioxane at room temperature overnight to obtain a compound represented by the following formula (11).

[0137] Next, 2,3-thiophenedicarboxaldehyde and sodium hydroxide were added to the obtained compound, and the mixture was kept at room temperature for 1 hour in a mixed solution of ethanol, water, and tetrahydrofuran, to obtain a compound represented by the following formula (12).

[0138] Next, sodium borohydride was added to the obtained compound, and the mixture was kept in tetrahydrofuran at 60° C. for one day or more. Further, hydrochloric acid and tin(II) chloride were added, and the mixture was kept at 60° C. for one hour, thereby obtaining compound B represented by the following formula (13).

[0139] Next, trimethylsilylacetylene, piperidine, CuI, and PdCl(PPh) were added to the compound B, and the mixture was kept in tetrahydrofuran at 120° C. for 2.5 hours. Potassium carbonate, tin chloride, and methanol were added to the resulting mixture, and the mixture was kept at room temperature for 40 minutes, thereby obtaining a compound represented by the following formula (14).

[0140] Next, compound B represented by formula (13), triethylamine, CuI, and PdCl(PPh) were added to the compound represented by formula (14), and the mixture was kept in DMF at 130° C. for 16 hours to obtain a compound represented by formula (15).

[0141] Next, potassium hydroxide and palladium acetate were added to the obtained compound, and the mixture was kept in DMF at 145° C. for 6 hours to obtain a compound represented by the following formula (16).

[0142] Next, iron(III) chloride was added to the obtained compound, and the mixture was kept at room temperature for 1 hour in a mixed solution of MeNO and CHCl to obtain compound (ii-1) represented by the following formula (17).

[0143] Compound (ii-1) was analyzed by elemental analysis, mass spectrometry, and 13 Identification was performed by C-NMR. Elemental analysis revealed that the ratio of the number of carbon atoms, the number of hydrogen atoms, and the number of sulfur atoms was C:H:S=21:11:1. Mass analysis revealed that the molecular weight was 590.756.

[0144] The fused ring compound C of the present disclosure tends to have excellent carrier mobility. Therefore, the fused ring compound C is suitable for semiconductor materials. In particular, the fused ring compound C is useful as a p-type semiconductor material. The semiconductor material S containing the fused ring compound C can be used in electronic devices. By using the fused ring compound C in electronic devices, the frequency characteristics of the electronic devices can be improved. A specific example of the electronic device is a transistor.

Claims

1. A fused ring compound having a fused ring containing a plurality of monocyclic aromatic rings, wherein the number of the monocyclic aromatic rings in the fused ring is 11, and among the 11 monocyclic aromatic rings, the number of thiophene rings is 2 or less, and the fused ring contains two naphthacene structures.

2. The fused ring compound of claim 1, wherein each of the eleven monocyclic aromatic rings is independently a benzene ring or a thiophene ring.

3. The fused ring compound according to claim 1 or 2, wherein the fused ring has a linear structure.

4. The fused ring compound according to any one of claims 1 to 3, represented by the following formula (I): In the formula (I), R A1 From R A18 are each independently a hydrogen atom or a hydrocarbon group; Ar A1 and Ar A2 each independently represents a benzene ring which may have a substituent or a thiophene ring which may have a substituent.

5. The fused ring compound according to any one of claims 1 to 4, which is represented by the following formula (I-1), (I-2), (I-3), (I-4) or (I-5): In the formula (I-5), R e1 From R e24 are each independently a hydrogen atom or a hydrocarbon group.

6. The condensed ring is C 2V The fused ring compound according to claim 1 , having the symmetry:

7. A semiconductor material comprising the fused ring compound according to any one of claims 1 to 6.

8. An electronic device comprising the semiconductor material of claim 7.

9. An electronic device comprising: a source electrode; a drain electrode; a gate electrode; and a semiconductor film comprising the semiconductor material according to claim 7.

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