JP4752269B2 - Porphyrin compound and method for producing the same, organic semiconductor film, and semiconductor device - Google Patents

Description

  The present invention relates to a porphyrin compound and a manufacturing method thereof, an organic semiconductor film and a manufacturing method thereof, and a semiconductor device and a manufacturing method thereof.

  Currently, various semiconductor devices such as transistors and diodes are mainly formed of inorganic semiconductor materials such as silicon. The manufacturing method is based on patterning of a semiconductor layer by photolithography and etching, and requires an expensive apparatus and a large number of processes, so that the production cost is high. In addition, since heat treatment at a high temperature is necessary, materials such as a substrate are limited.

  On the other hand, an organic semiconductor device can be manufactured by a simple process such as a coating method or a dipping method, and a large-area device can be manufactured at a lower cost than an inorganic semiconductor device. Further, it can be formed on a soft substrate that is soft and easy to bend, is flexible but does not have heat resistance, and is stable against mechanical shock.

  Therefore, in recent years, assuming a thin film transistor (hereinafter abbreviated as TFT) used in an active matrix circuit of a display device, an attempt is made to replace the channel layer of the transistor from a silicon layer to an organic semiconductor layer. Research and development of organic field effect transistors using organic semiconductor materials has been actively conducted.

  Organic channel materials include pentacene (S. Nelson et al., Appl. Phys. Lett., (1998), 72, 1854-1856), oligothiophene ((a) G. Horowitz et al., Solid State Commun., (1989). , 72, 381-384, (b) F. Garnier, Pure Appl. Chem., (1996), 68, 1455-1462, (c) HEKatz, J. Mater. Chem., (1997), 7, 369 -379) and other materials that form a semiconductor layer by vapor deposition, and regioregular polythiophene, such as high molecular weight materials that form a semiconductor layer by application of a solution ((a) Z. Bao et al., Appl. Phys Lett., (1996), 69, 4108-4110, (b) Z. Bao et al., Chem. Mater., (1997), 9, 1299-1301, BSOng et al., J. Am. Chem. Soc., (2004), 126, 3378-3379) are the mainstream.

  In addition, research for forming a film by coating a precursor such as oligothiophene, pentacene, porphyrin has attracted attention (ARMurphy et al., J. Am. Chem. Soc., (2004), 126, 1596-1597, ( a) PTHerwig et al., Adv. Mater., (1999), 11, 480-483, (b) A. Afzali et al., J. Am. Chem. Soc., (2002), 124, 8812-8813, S. Aramaki et al., Appl. Phys. Lett., (2004), 84,2085-2087, (a) G. Horowitz et al., Adv. Mater., (1998), 10, 365-377, (b) HEKatz, Acc Chem. Res., (2001), 34, 359-369, (c) CDDimitrakopoulos et al., Adv. Mater., (2002), 14, 99-117).

  In addition, as described in Patent Document 1 described later, an organic material using a complex molecule having a porphyrin ring and an oligothiophene chain in which porphyrin and oligothiophene T, each of which is applied as a channel material of a transistor, is incorporated into one molecule. Field effect transistors and the like have also been prototyped.

JP 2004-6758 A (Pages 5-14, 17 and 18; FIG. 1)

However, in organic semiconductor materials, carrier mobility, which is a characteristic index of TFT, is only 10 ^{−3 to 1} cm ² / Vs as a typical value (CDDimitrakopoulos et al., Adv. Mater., (2002). ), 14, 99-117). This value is lower than the mobility of amorphous silicon of several cm ² / Vs and the mobility of polycrystalline silicon of about 100 cm ² / Vs, and the mobility required for display TFTs is 1 to 3 cm ² / Vs. Not reached. For this reason, improving the mobility is a major issue in the development of organic semiconductor materials.

  The mobility of organic semiconductor materials is determined by intramolecular charge transfer and intermolecular charge transfer. Intramolecular charge transfer is made possible by the delocalization of π electrons to form a conjugated π electron system. Charge transfer between molecules is performed by intermolecular coupling, conduction due to overlapping of molecular orbitals due to π-π interaction, or hopping conduction through trap levels between molecules.

In this case, the mobility in the molecule is μ-intra, the mobility due to the bond between molecules is μ-inter, and the mobility of hopping conduction between molecules is μ-hop.
μ-intra ≫ μ-inter ＞ μ-hop
In the organic semiconductor material, since the charge transfer between slow molecules restricts the mobility as a whole, the mobility of charges is small.

  Therefore, in order to realize high carrier mobility of the organic semiconductor material, it is most important how to arrange and pack molecules having a conjugated π electron system.

  On the other hand, from the viewpoint of simplifying the manufacturing process, it is desirable to have a device manufacturing method in which an organic semiconductor layer is formed by dissolving an organic semiconductor material in an appropriate solvent and applying or printing this solution. Development of organic semiconductor materials is an important issue for the future.

  In order to increase the solubility of an organic semiconductor material in an organic solvent and facilitate the process of forming a semiconductor layer from a solution, it is known to introduce an oleophilic group such as an alkyl group into the organic semiconductor material. However, when a semiconductor layer deposition process from a solution such as a spin coating method is used, the substituents introduced for improving the solubility are arranged between molecules that realize good intermolecular carrier transfer, It may inhibit packing (C. Videlotet et al., Adv. Mater .. (2003), 15, 306-310). In fact, when the carrier mobility of a semiconductor layer formed from a solution is compared with the carrier mobility of a semiconductor layer formed by vapor deposition, the carrier mobility is as small as 1 to 1 / 1,000, and transistor characteristics are low. Low (W. Geens et al., Synth. Met., (2001), 122, 191-194).

  In addition, the organic semiconductor molecules used in the transistor channels have a stable structure in which the molecular long axes are arranged almost perpendicular to the substrate surface (thin film phase), and the molecules are stacked and stacked in a direction parallel to the substrate. In this case, high carrier mobility is obtained.

  The present invention has been made in view of such circumstances, and the object thereof is a porphyrin compound that can form a semiconductor film that realizes good intermolecular carrier transfer from a solution, a method for producing the same, an organic A semiconductor film and a manufacturing method thereof, and a semiconductor device and a manufacturing method thereof.

That is, the present invention relates to a porphyrin compound represented by the following general formula [I] or [II].
[However, in the above general formula [I] or [II], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different from each other and have 1 carbon atom. 10 or a substituted or unsubstituted alkyl group, a, b, c, d, e and f are the same or different integers of 1 to 6, and M is a metal ion. ]

Moreover, it is the 1st manufacturing method of the said porphyrin compound, Comprising: Alkyl di (2-pyrrolyl) methane shown by the following general formula [III] is synthesize | combined by condensation reaction of aldehyde R ^B CHO and pyrrole, A compound represented by the following general formula [V] is synthesized by a condensation reaction between the oligothiophenecarbaldehyde represented by the general formula [IV] and the alkyldi (2-pyrrolyl) methane, and then this compound is oxidized to produce porphyrin. The present invention relates to a method for producing a porphyrin compound, in which a ring is completed and then a metal ion M ²⁺ is introduced into the porphyrin ring to synthesize a porphyrin compound represented by the general formula [I].
[However, in the general formulas [III] to [V], R ^A and R ^B are the same or different, each having a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. It is an integer of 6. ]

Further, in the second production method of the porphyrin compound, a compound represented by the following general formula [VI] is synthesized by a condensation reaction of oligothiophenecarbaldehyde represented by the following general formula [IV] and pyrrole, Next, the compound is oxidized to complete a porphyrin ring, and then a metal ion M ²⁺ is introduced into the porphyrin ring to synthesize a porphyrin compound represented by the general formula [II]. Is.
[However, in the said general formula [IV] and [VI], ^RA is a C1-C10 substituted or unsubstituted alkyl group, and n is an integer of 1-6. ]

Further, in the third production method of the porphyrin compound, an alkyldi (2-pyrrolyl) methane represented by the following general formula [III] is synthesized by a condensation reaction of aldehyde R ^B CHO and pyrrole, and then A step of synthesizing a porphyrin core compound represented by the following general formula [VIII] by a condensation reaction of the oligothiophenecarbaldehyde represented by the general formula [VII] and the alkyldi (2-pyrrolyl) methane and a subsequent oxidation reaction; A step of synthesizing a porphyrin compound represented by the general formula [I] from the porphyrin core compound by a reaction for introducing a metal ion M ²⁺ into the porphyrin ring and a coupling reaction with a compound represented by the following general formula [IX]. The present invention relates to a method for producing a porphyrin compound.
[However, in the general formulas [III] and [VII] to [IX], R ^A and R ^B are the same or different from each other, and are substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, X is a halogen atom, R ^D is a substituted or unsubstituted alkyl group, and the sum of i and j is an integer of 2-6. ]

  Further, the present invention relates to an organic semiconductor film made of the porphyrin compound, and a solution in which the porphyrin compound is dissolved in a polar solvent and a nonpolar solvent or a solvent having a polarity smaller than that of the polar solvent are mixed, and this mixed solution Is applied to a method for producing an organic semiconductor film in which the solvent is evaporated.

  Further, the present invention relates to a semiconductor device having a conductive path made of the porphyrin compound, and also a method for manufacturing the semiconductor device, comprising: a solution in which the porphyrin compound is dissolved in a polar solvent; and a nonpolar solvent or the polar solvent. The present invention also relates to a method for manufacturing a semiconductor device, in which a solvent having a small polarity is mixed, the mixed solution is applied, the solvent is evaporated, and the conductive path is formed.

  The porphyrin compounds represented by the general formulas [I] and [II] (hereinafter abbreviated as porphyrin compounds [I] and [II]) have two or four oligothiophene chains bonded to the meso position of the porphyrin ring. Furthermore, it is a novel compound in which an alkyl group is bonded to the end of the oligothiophene chain bonded to the meso position of the porphyrin ring or the meso position.

  Porphyrin is a molecule having a two-dimensional conjugated π electron system with 18 π electrons. Since the energy level of HOMO (Highest Occupied Molecular Orbital) is about 5.4 eV, electrons can be easily injected from a gold electrode (work function: 5.1 eV) at room temperature. In the porphyrin compounds [I] and [II], since the oligothiophene chain is bonded to the meso position of the porphyrin ring, each of the porphyrin ring and the oligothiophene chain functions as a charge carrier conduction path in the molecule. Is possible.

  Between molecules, a strong π-π interaction acts between porphyrin molecules, and a π-π interaction also acts between oligothiophene molecules. A strong intermolecular force due to a further strengthened π-π interaction acts between each of the porphyrin compounds [I] and [II] incorporated in the molecule. Since the molecular symmetry and the length of the oligothiophene chain influence the formation of self-assembly by molecular arrangement and packing, it is desirable that the oligothiophene chain length in the molecule is the same ( NEGruhn et al., J. Am. Chem. Soc., (2004), 126, 3430-3431).

  For the above reasons, high molecular mobility between molecules and between molecules can be expected in each of the molecular aggregates of the porphyrin compounds [I] and [II]. Actually, as will be described later in Examples, a field effect transistor (FET) produced using a porphyrin compound [I] having three thiophene chains and a porphyrin compound [I] having five thiophene chains are used. Comparing the characteristics with the FETs fabricated using the latter, the latter FET is 4 times the hole mobility and 10 times the On / Off ratio superior to the former FET, which demonstrates the effect of the thiophene chain. The result is considered.

  On the other hand, in the porphyrin compounds [I] and [II], four alkyl groups are arranged around the conjugated π electron system unit of the porphyrin ring and the thiophene chain. Conjugated π-electron systems are polar units, whereas alkyl chains are nonpolar units. That is, porphyrin compounds [I] and [II] are amphiphilic substances composed of a polar unit at the center and a nonpolar unit at the outer edge. For this reason, it has high solubility not only in polar solvents such as chloroform, dichloromethane and tetrahydrofuran (THF) but also in low-polar or nonpolar organic solvents such as toluene and hexane due to its strong affinity with alkyl chains. be able to. Therefore, the porphyrin compounds [I] and [II] can easily form an organic semiconductor film composed of molecular aggregates by a solution process.

  In addition, in the porphyrin compounds [I] and [II], by changing the polarity of the solvent, the association between the porphyrin compound [I] or [II] and the solvent molecule is changed, and thereby the porphyrin compound [I] or It is possible to control the interaction between molecules of [II] (N.Kiriy et al., Nano Lett., (2003), 3, 707).

  Therefore, in the present invention, a solution in which the porphyrin compound [I] or [II] is dissolved in a polar solvent is mixed with a nonpolar solvent or a solvent having a smaller polarity than the polar solvent, and this mixed solution is applied. The solvent is evaporated to produce an organic semiconductor film made of the porphyrin compound [I] or [II]. For example, when a nonpolar or low polarity solvent such as hexane is added to a solution in which a porphyrin compound [I] or [II] is dissolved in a polar solvent such as chloroform, the conjugated π-electron unit becomes a solvent molecule. It becomes difficult to solvate. As a result, the conjugated π electron system unit repelled by the solvent has a strong tendency to assemble the conjugated π electron system units between molecules, and the conjugated π electron system unit such as a porphyrin ring is stacked and stacked, Formation of a molecular assembly of a porphyrin compound [I] or [II] having a structure that solvates with an alkyl group at the outer edge of the solvent is induced (the mechanism of formation of such an assembly is a soap molecule in an aqueous soap solution. It is a mechanism similar to the formation of micelles).

However, alkyl chains have the effect of strengthening intermolecular interactions by van der Waals forces ((a) HEKatz et al., Chem. Mater., (1995), 7, 2238, (b) CDDimitrakopoulos et al., Synth. Met., (1998), 92, 47), however, it is said that the characteristics of the transistor are degraded if the length is too short or too long. In general, as an alkyl group for improving the solubility of an organic semiconductor molecule in an organic solvent, a hexyl group (—C ₆ H ₁₃ ), an octyl group (—C ₈ H ₁₇ ), or a decyl group (—C ₁₀ H) is used. ₂₁ ) is often used (M.Halik et al., Adv. Mater., (2003), 15, 917-922). Therefore, 1-10 is suitable for the carbon number of the alkyl chain of porphyrin compounds [I] and [II].

  Moreover, since the 1st, 2nd and 3rd manufacturing methods of the porphyrin compound of this invention are all implement | achieved by the combination of the already established reaction, the said porphyrin compound can be obtained reliably.

  The semiconductor device of the present invention and the method for manufacturing the same include a semiconductor device having a conductive path composed of the porphyrin compound [I] or [II], and, as described above, the porphyrin compound [I] or [II] is polar. A solution dissolved in a solvent is mixed with a nonpolar solvent or a solvent having a polarity smaller than that of the polar solvent, and the mixture is applied to evaporate the solvent, thereby forming the conductive path made of the molecular assembly. Therefore, the semiconductor device utilizes the characteristics of the porphyrin compound [I] or [II] and the method for manufacturing the semiconductor device.

  In the porphyrin compound of the present invention, the metal ion may be an ion of any metal element of zinc, magnesium, copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, or platinum.

  In the method for producing an organic semiconductor film of the present invention, the coating is preferably performed by a spin coating method. According to the spin coating method, an effect of aligning the molecular assembly can be expected.

  In the semiconductor device and the manufacturing method thereof according to the present invention, it is preferable that a means for applying an electric field is formed and the conductivity of the conductive path is controlled by the electric field.

  In that case, the semiconductor device has an insulated gate electric field in which a channel region having the conductive path is formed, source and drain electrodes are provided on both sides of the channel region, and a gate electrode is provided between the two electrodes. It may be configured as an effect transistor. In addition, the semiconductor device can be applied to various sensors.

  Next, a preferred embodiment of the present invention will be described specifically and in detail with reference to the drawings.

Synthesis of Porphyrin Compounds [I] and [II] FIG. 1 is an explanatory diagram showing a synthesis scheme of porphyrin compounds [I] and [II] (PAvan Hal et al., Chem. Eur. J., (2002), 8 , 5415-5429, B. Li et al., J. Am. Chem. Soc., (2004), 126, 3430-3431).

Synthesis scheme 1 in FIG. 1 is an example of the first production method of the porphyrin compound. In this synthesis scheme 1, first, alkyldi (2-pyrrolyl) methane [III] is produced by a condensation reaction of a normal aldehyde R ^B CHO and pyrrole. Next, the alkyl di (2-pyrrolyl) and methane, by condensation reaction with oligothiophene-carbaldehyde [IV] with an alkyl group -R ^A, to synthesize a compound represented by the following general formula [V].
Next, this compound [V] is oxidized with p-chloroanil (tetrachloro-p-benzoquinone) to complete a porphyrin ring. Next, a metal ion M ²⁺ is introduced into the porphyrin ring, and the general formula [I] The indicated porphyrin compound is synthesized.

Synthesis scheme 1 is a synthesis method in which an oligothiophene chain is introduced only at two opposing meso positions. In addition, the alkyl group —R ^B introduced directly into the meso position and the alkyl group —R ^A introduced via the oligothiophene chain can be made different to synthesize various porphyrin compounds [I]. Can do.

Synthesis scheme 2 in FIG. 1 is an example of the second production method of the porphyrin compound. In the synthetic scheme 2, firstly, by a condensation reaction with oligothiophene-carbaldehyde [IV] pyrrole having the alkyl group -R ^A, to synthesize a compound represented by the following general formula [VI].
Next, compound [VI] is oxidized with p-chloroanil to complete a porphyrin ring, and then a metal ion M ²⁺ is introduced into the porphyrin ring to synthesize a porphyrin compound represented by general formula [II]. This synthesis method is simple because it can introduce oligothiophene chains at four meso positions.

  Synthesis scheme 3 in FIG. 1 is an example of the third production method of the porphyrin compound. This synthetic scheme 3 is a method that can be regarded as a modified example of the synthetic scheme 1 or 2 (FIG. 1 shows a modified example of the synthetic scheme 1, but instead of alkyldi (2-pyrrolyl) methane [III]. If pyrrole is used, a modification of Synthesis Scheme 2 can be configured.)

Synthetic scheme 3 in FIG. 1 is the same as synthetic scheme 1 except that oligothiophenecarbaldehyde [X] having a bromine group is used instead of oligothiophenecarbaldehyde [IV] used in synthetic scheme 1. Is reacted with alkyldi (2-pyrrolyl) methane [III], and this product is oxidized with p-chloroanil to synthesize a porphyrin core compound [XI] represented by the following general formula.
Next, after introducing a metal ion M ²⁺ into the porphyrin core compound [XI], the porphyrin core compound [XI] is converted into the general formula [I] by a coupling reaction with the compound represented by the general formula [XII]. A porphyrin compound represented by is synthesized.

  According to this synthesis scheme 3, a porphyrin compound [I] or [II] having an oligothiophene chain longer than synthesis scheme 1 or 2 can be synthesized.

  FIG. 2 is an explanatory diagram showing reactions for synthesizing various oligothiophene derivatives used in the above synthesis scheme. Although FIG. 2 shows an example in which oligothiophene is a trimer as an example, the present invention is not limited to this, and a similar reaction can be performed from a monomer to a hexamer (PAvan Hal et al., Chem. Eur. J., (2002), 8, 5415-5429, B. Li et al., J. Am. Chem. Soc., (2004), 126, 3430-3431).

Reaction (1) is a reaction in which carbonyl chloride ROCl is allowed to act on oligothiophene and an acyl group —COR is introduced into oligothiophene. Reaction (2) is a reaction in which this acyl group is reduced with lithium aluminum hydride LiAlH ₄ , and an alkyl group can be introduced into oligothiophene by reactions (1) and (2).

Reaction (3) is a reaction for introducing a tributylstannyl group —SnBu ₃ into oligothiophene by allowing butyllithium BuLi and tributylchlorostannane to act on oligothiophene.

Reaction (4) is a reaction in which an aldehyde group —CHO is introduced into oligothiophene by allowing N, N-dimethylformamide (DMF) to act on oligothiophene in the presence of phosphoryl chloride POCl ₃ .

  Reaction (5) is a reaction in which oligothiophene is selectively brominated by allowing N-bromosuccinimide (NBS) to act on oligothiophene in the presence of N, N-dimethylformamide (DMF).

Reaction (6) consists of tributylstane synthesized by reaction with brominated oligothiophene in the presence of a palladium catalyst such as tetrakis (triphenylphosphine) palladium (0) Pd (PPh ₃ ) ₄ catalyst. This is a reaction in which an oligothiophene having a nyl group —SnBu ₃ is coupled to couple two oligothiophene chains.

Formation of molecular assembly In the porphyrin compounds [I] and [II], four alkyl groups are arranged at the outer edge of the conjugated π-electron system unit of the porphyrin ring and the thiophene chain. Conjugated π-electron systems are polar units, whereas alkyl chains are nonpolar units. Therefore, as described above, by changing the polarity of the solvent molecule, the association between the porphyrin compound [I] or [II] and the solvent molecule is changed, and through this, the intermolecularity of the porphyrin compound [I] or [II] is changed. Can be controlled (N.Kiriy et al., Nano Lett., (2003), 3, 707).

  FIG. 3 is a flowchart showing a process for producing an organic semiconductor film made of a molecular assembly of porphyrin compound [I] or [II]. For example, when a nonpolar or low polarity solvent such as hexane is added to a solution in which a porphyrin compound [I] or [II] is dissolved in a polar solvent such as chloroform, the conjugated π-electron unit becomes a solvent molecule. It becomes difficult to solvate. As a result, the conjugated π electron system unit repelled by the solvent has a strong tendency to assemble the conjugated π electron system units between molecules, and the conjugated π electron system unit such as a porphyrin ring is stacked and stacked, Formation of a molecular assembly of the porphyrin compound [I] or [II] having a structure that solvates with the alkyl group at the outer edge of the solvent is induced. The formation mechanism of such aggregates is similar to the formation of micelles of soap molecules in an aqueous soap solution. As the solvent used in this case, for example, chloroform (polarity index: 4.1), toluene (polarity index: 2.1), and hexane (polarity index: 0) can be used.

  FIG. 4 is a schematic diagram showing a stacking structure of porphyrin molecules. As shown in FIG. 4, the stacking structure of porphyrin molecules has a face-type structure in which the center positions of the rings overlap on a straight line perpendicular to the plane of the ring without displacement of the porphyrin rings in the plane direction of the rings. H-aggregates stacked on the to-face and porphyrin rings are displaced in the plane direction of the rings so that the centers of the rings are aligned on a straight line that is slanted with respect to the plane of the ring There are two types of J-aggregates to be stacked.

  The two stacking structures of porphyrin can be distinguished by measuring the visible ultraviolet light absorption spectrum. The porphyrin molecule has a strong Soray band absorption band around 400-500 nm, as will be described later. This Soray band causes a unique spectral change depending on the intermolecular interaction. In the H-aggregate, the Soray band shifts to the short wavelength side (the blue shift), and the J-type aggregate (J-aggregate) ) The red shift of the Soray band ((a) M. Shirakawa et al., J. Org. Chem., (2003), 68, 5037-5044, (b) V. Kral et al., Org Lett., (2002), 4, 51-54, M. Kasha et al., Pure. Appl. Chem., (1965), 11, 371).

  The organic semiconductor molecular assemblies with high regularity generated in the solution as described above are transferred and aligned on the surface of the gate insulating film of the FET by using a solution process such as spin coating, and the organic to be the conductive path. Since a semiconductor film can be formed, an organic FET with high carrier mobility can be realized.

Fabrication of organic FET

  FIG. 5 is a cross-sectional view showing a device structure of an insulated gate FET according to the present embodiment. For the insulated gate FET according to the present invention, the bottom gate type device structure shown in FIG. 4 is suitable. In this FET, a gate electrode 3 made of gold or the like, a gate insulating film 2 made of silicon oxide or the like, a source electrode 4 and a drain electrode 5 made of gold or the like are formed on a substrate 1 such as a silicon substrate, and gate insulation is performed. A conductive layer 6 made of an organic semiconductor film is formed on the film 2 in a region between the source electrode 4 and the drain electrode 5.

  FIG. 6 is a cross-sectional view showing a device structure of a desirable insulated gate FET. The molecular assembly of the highly ordered porphyrin compound [I] or [II] generated in the solution as described above is transferred onto the surface of the gate insulating film 2 of the FET using a solution process such as spin coating, and the molecule Since the major axis is arranged substantially perpendicular to the substrate surface and molecules are stacked and aligned in a direction parallel to the substrate, the organic semiconductor film serving as the conductive path can be formed. It is expected that organic FETs with high mobility can be realized.

  Although the preferable Example of this invention is described concretely below, this invention is not limited to a following example.

Synthesis of Porphyrin Compounds [I] and [II] Porphyrin compounds (9) and (10), which are porphyrin compounds [I] having 3 and 5 oligothiophene chains, were synthesized according to the synthesis schemes 1 and 3 described above. According to Synthesis Scheme 2, a porphyrin compound (11), which is a porphyrin compound [II] having three oligothiophene chains, was synthesized. Molecular identification is performed by ¹ H NMR measurement and MALDI-TOF-MS (Matrix Assisted Laser Desorption Ionization-Time of Flight-Mass Spectroscopy) measurement, and the visible ultraviolet light absorption spectra of porphyrin compounds (9) to (11) are examined. did. The measurement results are shown below together with the detailed synthesis method.

<Synthesis of 5-hexanoyl-2,2 ′: 5 ′, 2 ″ -terthiophene (2)>

Under argon atmosphere, 30 ml of anhydrous dichloromethane CH ₂ Cl ₂ was added to 5.0 g (20 mmol) of 2,2 ′: 5 ′, 2 ″ -terthiophene (1) and cooled to 4 ° C. with stirring. 2.6 ml (20 mmol) of noyl chloride CH ₃ CH ₂ CH ₂ CH ₂ CH ₂ COCl was gradually added dropwise, followed by dropwise addition of 20 ml of a 1.0 M solution of tin (II) chloride SnCl ₂ at 4 ° C. After stirring for 1 hour, the mixture was further stirred at room temperature for 2 hours.

The reaction solution was gradually added to 0.5 M hydrochloric acid, extracted thoroughly with dichloromethane, and washed with saturated aqueous sodium hydrogen carbonate NaHCO ₃ solution and saturated brine. After drying over anhydrous sodium sulfate Na ₂ SO ₄ , the product was purified by silica gel column chromatography using dichloromethane as a developing solvent to obtain solid 5-hexanoyl-2,2 ′: 5 ′, 2 ″ -terthiophene (2) 4.8 g (70% yield) was obtained.

¹ H NMR (400 MHz, CDCl ₃ , 23 ° C.): δ (ppm) = 0.98 (t, 3H; CH ₃ ), 1.44 (m, 4H, CH ₂ ), 1.82 (t, 2H, CH ₂ ), 2.93 (t, 2H, CH ₂ ), 7.10-7.60 (m, 6H, Ar-H), 7.66 (d, 1H, Ar-H).
MALDI-TOF-MS: [M] ⁺ m / z: calcd: 346.052; obsd: 345.900.

<Synthesis of 5-hexyl-2,2 ': 5', 2 "-terthiophene (3)>

Under an argon atmosphere, 300 ml of anhydrous ether was added to 2.5 g (18.9 mmol) of aluminum chloride AlCl ₃ and 2.8 g (75.6 mmol) of lithium aluminum hydride LiAlH ₄ and cooled to 4 ° C. with stirring. A solution prepared by dissolving 4.2 g (12.6 mmol) of the product (2) in 200 ml of anhydrous toluene was gradually added dropwise to this solution. After dropping, the mixture was stirred at 4 ° C. for 30 minutes, and further stirred at room temperature for 2 hours.

  After cooling the solution to 4 ° C., 38 ml of ethyl acetate was added dropwise to decompose excess lithium aluminum hydride. Further, when 12 ml of concentrated hydrochloric acid was gradually added and stirred, a clear light green solution was obtained. After filtration, the filtrate was concentrated, hexane was added, washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous sodium sulfate. This was purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane in a volume ratio of 1: 1 as a developing solvent to give oily 5-hexyl-2,2 ′: 5 ′, 2 ″ -terthiophene (3 ) 3.0 g (yield 72%) was obtained.

¹ H NMR (400 MHz, CDCl ₃ , 23 ° C.): δ (ppm) = 0.87 (d, 3H; CH ₃ ), 1.30 (s, 6H, CH ₂ ), 1.65 (t, 2H, CH ₂ ), 2.75 (t, 2H, CH ₂ ), 6.64-6.97 (m, 6H, Ar-H), 7.16 (d, 1H, Ar-H).
MALDI-TOF-MS: [M] ⁺ m / z: calcd: 332.073; obsd: 331.932.

<Synthesis of 5-hexyl-5 "-tributylstannyl-2,2 ': 5', 2" -terthiophene (4)>

  Under an argon atmosphere, 100 ml of anhydrous tetrahydrofuran (THF) was added to 3.0 g (9 mmol) of the product (3), and the mixture was cooled to −78 ° C. with stirring. To this solution, 7.4 ml of a 1.6 M hexane solution of butyllithium BuLi (11.7 mmol) was gradually added dropwise, and further 3.2 ml (11.7 mmol) of tributylchlorostannane was gradually added. After dropping, the mixture was stirred at −78 ° C. for 1 hour, and further stirred at room temperature for 16 hours.

  After the reaction solution was concentrated, 200 ml of hexane was added, washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous sodium sulfate. This was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane in a volume ratio of 1: 5 as a developing solvent to give oily 5-hexyl-5 "-tributylstannyl-2,2 ': 5' 5.6 g (100% yield) of 2,2 "-terthiophene (4) were obtained.

¹ H NMR (400 MHz, CDCl ₃ , 23 ° C.): δ (ppm) = 0.87 (t, 3H; CH ₃ ), 1.30 (s, 6H, CH ₂ ), 1.65 (t, 2H, CH ₂ ), 2.75 (t, 2H, CH ₂ ), 6.64-6.97 (m, 6H, Ar-H), 7.16 (d, 1H, Ar-H).
MALDI-TOF-MS: [M] ⁺ m / z: calcd: 622.178; obsd: 622.035.

<Synthesis of 5 "-hexyl-2,2 ': 5', 2" -terthiophene-5-carbaldehyde (5)>

Under an argon atmosphere, 60 ml of anhydrous 1,2-dichloroethane and 0.84 ml (10.8 mmol) of anhydrous N, N-dimethylformamide (DMF) are added to 3.0 g (9 mmol) of the product (3), and while stirring, -4 Cooled to ° C. To this solution, 0.96 ml (10.8 mmol) of phosphoryl chloride POCl ₃ was gradually added dropwise. After the dropwise addition, the mixture was stirred for 1 hour, and further heated at reflux for 18 hours.

  The reaction solution was poured into 200 ml of a saturated aqueous sodium acetate solution and stirred for 1 hour. The organic layer was washed with water and dried over anhydrous sodium sulfate. This was purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane in a volume ratio of 1: 1 as a developing solvent to obtain solid 5 "-hexyl-2,2 ': 5', 2" -terthiophene. 2.3 g (yield 72%) of -5-carbaldehyde (5) was obtained.

¹ H NMR (400 MHz, CDCl ₃ , 23 ° C.): δ (ppm) = 0.94 (t, 3H; CH ₃ ), 1.33 (d, 6H, CH ₂ ), 1.71 (t, 2H, CH ₂ ), 2.81 (t, 2H, CH ₂ ), 7.00-7.27 (m, 6H, Ar-H), 9.88 (s, 1H, CHO).
MALDI-TOF-MS: [M] ⁺ m / z: calcd: 360.068; obsd: 359.676.

<Synthesis of pentyldi (2-pyrrolyl) methane (7)>

  Under an argon atmosphere, gradually add 2 ml of trifluoroacetic acid (TFA) to 150 ml (1.5 mol) of pyrrole containing 6.1 ml (0.05 mol) of hexanal, stir for 40 minutes, and then add 2 ml of triethylamine (TEA). The reaction was stopped. Concentrate under reduced pressure to remove unreacted pyrrole. The concentrated reaction solution was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane in a volume ratio of 1: 4 as a developing solvent to obtain 3.3 g of oily pentyldi (2-pyrrolyl) methane (7) ( Yield 30%).

¹ H NMR (400 MHz, CDCl ₃ , 23 ° C.): δ (ppm) = 0.89 (t, 3H; CH ₃ ), 1.31 (s, 6H, CH ₂ ), 1.95 (q, 2H, CH ₂ ), 3.99 (t, 1H, methane-H), 6.09-6.18 (m, 4H, Ar-H), 6.65 (d, 2H, Ar-H), 7.77 (s, 2H, NH).

<Synthesis of Porphyrin Compound (9)>

In an argon atmosphere, trifluoroacetic acid (TFA) was added to 400 ml of a chloroform solution containing 1.5 g (4.2 mmol) of carbaldehyde (5) and 0.96 g (4.2 mmol) of pentyldi (2-pyrrolyl) methane (7). After gradually adding 0.5 ml, the mixture was stirred for 17 hours. Thereafter, 1.0 g (4.1 mmol) of p-chloroanil (tetrachloro-p-benzoquinone) was added and stirred for 30 minutes, and then 1.0 ml of triethylamine (TEA) was added to stop the reaction. The reaction solution was concentrated as it was, washed with water, and dried over anhydrous sodium sulfate. Further, a methanol saturated solution of zinc acetate Zn (CH ₃ COO) ₂ was added and stirred for 1 hour, zinc ions were introduced into the porphyrin ring and washed with water.

  This was purified by silica gel column chromatography using dichloromethane as a developing solvent to remove the polymer, and then purified by preparative gel permeation chromatography (GPC) using THF as a solvent, using a column consisting of BioBeads S-X1, 0.7 g (yield 30%) of a solid porphyrin compound (9) was obtained. However, Pen in the above formula represents a pentyl group, and Hex represents a hexyl group.

¹ H NMR (400 MHz, CDCl ₃ , 23 ° C): δ (ppm) = 0.94-0.98 (m, 12H; CH ₃ ), 1.29-1.62 (m, 20H, CH ₂ ), 1.75-1.86 (m, 8H , CH ₂ ), 2.57 (t, 4H, CH ₂ ), 4.94 (s, 4H, CH ₂ ), 7.10-7.19 (m, 4H, thiophene-H), 7.28 (2H, thiophene-H, overlapped with CDCl ₃ peak), 7.33 (d, 2H, thiophene-H), 7.59 (d, 2H, thiophene-H), 7.80 (d, 2H, thiophene-H), 9.31 (d, 4H, pyrrole-H), 9.52 (d , 4H, pyrrole-H).
UV-Vis (CHCl ₃ ): λ _max /nm=359.5, 435, 562, 616.5.
MALDI-TOF-MS: [M + H] ⁺ m / z: calcd: 1172.306; obsd: 1172.160.

<Synthesis of Porphyrin Core Compound (8)>

Chloroform containing 1.6 g (7.0 mmol) of pentyldi (2-pyrrolyl) methane (7) and 1.9 g (7.0 mmol) of 5′-bromo-2,2′-bithiophene-5-carbaldehyde under an argon atmosphere To 700 ml of the solution, 0.82 ml of trifluoroacetic acid (TFA) was gradually added and stirred for 18 hours. Thereafter, 1.7 g (7.0 mmol) of p-chloroanil was added and stirred for 30 minutes, and then 1.5 ml of triethylamine (TEA) was added to stop the reaction. The reaction solution was concentrated as it was and washed with water. Further, a methanol saturated solution of zinc acetate Zn (CH ₃ COO) ₂ was added and stirred for 1 hour, zinc ions were introduced into the porphyrin ring and washed with water.

  This was purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane in a volume ratio of 3: 2 as a developing solvent to obtain 2.1 g (yield 46%) of a solid porphyrin core compound (8). . However, Pen in the above formula represents a pentyl group.

¹ H NMR (400 MHz, CDCl ₃ , 23 ° C.): δ (ppm) = 1.01 (m, 6H; CH ₃ ), 1.60 (t, 4H, CH ₂ ), 1.87 (t, 4H, CH ₂ ), 2.54 (t, 4H, CH ₂ ), 4.96 (t, 4H, CH ₂ ), 7.12 (d, 2H, thiophene-H), 7.19 (d, 2H, thiophene-H), 7.54 (d, 2H, thiophene-H ), 7.79 (d, 2H, thiophene-H), 9.28 (d, 4H, pyrrole-H), 9.53 (d, 4H, pyrrole-H).
MALDI-TOF-MS: [M] ⁺ m / z: calcd: 997.962; obsd: 997.732.

<Synthesis of Porphyrin Compound (10)>

In an argon atmosphere, 56 mg (0.09 mmol) of the thiophene derivative (4) synthesized from terthiophene, 30 mg (0.03 mmol) of the porphyrin core compound (8), tetrakis (triphenylphosphine) palladium (0) Pd (PPh ₃ ) 5 ml of an anhydrous toluene solution containing 4.3 mg (0.0037 mmol) of ₄ catalysts was heated to reflux for 18 hours.

  The reaction solution is concentrated as it is, purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane in a volume ratio of 1: 1 as a developing solvent to remove the polymer, and then a column made of BioBeadsS-X1 is used to remove THF. Was purified by preparative gel permeation chromatography (GPC) to obtain 1.8 mg (yield 4%) of a solid porphyrin compound (10). However, Pen in the above formula represents a pentyl group, and Hex represents a hexyl group.

¹ H NMR (400 MHz, CDCl ₃ , 23 ° C.): δ (ppm) = 0.92 (t, 12H; CH ₃ ), 1.00-1.33 (m, 20H, CH ₂ ), 1.70 (t, 4H, CH ₂ ) , 1.84 (t, 4H, CH ₂ ), 2.57 (t, 4H, CH ₂ ), 4.96 (t, 4H, CH ₂ ), 6.84 (d, 2H, thiophene-H), 6.98-7.23 (m, 12H, thiophene-H), 7.36 (q, 2H, thiophene-H), 7.62 (d, 2H, thiophene-H), 7.81 (d, 2H, thiophene-H), 9.32 (d, 4H, pyrrole-H), 9.54 (d, 4H, pyrrole-H).
UV-Vis (CHCl ₃ ): λ _max /nm=430.5, 560.5, 615.
MALDI-TOF-MS: [M + H] ⁺ m / z: calcd: 1501.257; obsd: 1501.954.

<Synthesis of Porphyrin Compound (11)>

Under an argon atmosphere, 0.16 ml of trifluoroacetic acid (TFA) was gradually added to 130 ml of a chloroform solution containing 0.50 g (1.4 mmol) of terthiophenecarbaldehyde (5) and 95 μl (1.4 mmol) of pyrrole. Thereafter, the mixture was stirred for 17 hours. Thereafter, 0.33 g (1.3 mmol) of p-chloroanil was added and stirred for 30 minutes, and then 0.33 ml of triethylamine (TEA) was added to stop the reaction. The reaction solution was concentrated as it was, washed with water, and dried over anhydrous sodium sulfate. Further, a methanol saturated solution of zinc acetate Zn (CH ₃ COO) ₂ was added and stirred for 1 hour, zinc ions were introduced into the porphyrin ring and washed with water.

  This was purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane in a volume ratio of 1: 1 as a developing solvent to remove the polymer, and then a column consisting of BioBeads S-X1 was used and fractionated using THF as the solvent. Purification by gel permeation chromatography (GPC) gave 0.1 g (yield 9%) of a solid porphyrin compound (11). However, Hex in the above formula represents a hexyl group.

The ¹ H NMR (400 MHz, CDCl ₃ ) spectrum was not detectable due to rather broadening of each peaks even at an elevated temperature such as 55 ° C.
UV-Vis (CHCl ₃ ): λ _max / nm = 362, 448, 568, 615.
MALDI-TOF-MS: [M + H] ⁺ m / z: calcd. 1693.264; obsd. 1693.744.

<MALDI-TOF-MS>
FIG. 7 is a mass spectrum of porphyrin compounds (9) to (11) by MALDI-TOF-MS. In these mass spectra, the measured molecular weight agreed well with the calculated value.

<Visible UV light absorption spectrum>
FIG. 8 is a visible ultraviolet light absorption spectrum of porphyrin compounds (9) to (11) in chloroform. As absorption derived from porphyrin, there is a strong Soray band between 400 and 500 nm, and two absorption peaks of Q band between 550 and 650 nm. The absorption derived from thiophene is absorption around 350 nm.

  In the case of the porphyrin compound (9), the absorption peak of the thiophene trimer appears at 359.5 nm, the absorption peak of the porphyrin sorter band appears at 435 nm, and the absorption peaks of the Q band appear at 562 nm and 616.5 nm. In the case of the porphyrin compound (10), since the absorption peak of the thiophene pentamer overlaps with the absorption peak of the porphyrin sorter band, the sorter band is slightly broadened. In the case of the porphyrin compound (11), since it has four thiophene trimers, a larger absorption peak derived from thiophene appears at 362 nm. Moreover, when the interaction between the thiophene unit and the porphyrin unit is increased, the porphyrin solay band is shifted to a longer wavelength side, and an absorption peak appears at 448 nm.

Formation of Self-Assembly 10 μl of high-concentration chloroform solution was added to 3 ml of chloroform and hexane, respectively, shaken gently, and then sonicated for 30 seconds to form a sample solution. The concentration of the porphyrin compound in the sample solution is 3.0 × 10 ⁻⁶ M. The polarities of the two organic solvents with different polarities are chloroform: 4.1 and hexane: 0.

<Examination by measurement of visible light absorption spectrum>
FIG. 9 shows the results of examining changes in the visible ultraviolet light absorption spectra of the porphyrin compounds (9) to (11) depending on the solvent. According to these absorption spectra, when the polarity of the solvent was lowered, the porphyrin Soray band tended to shift to the short wavelength side (blue shift).

  It is not clear whether such shift of the absorption wavelength is a generally observed deep color shift or the formation of the H-aggregate described above. If this shift in absorption wavelength is due to the formation of an H-aggregate, the result is that a nonpolar solvent such as hexane is added to the chloroform solution of the porphyrin compounds (9) to (11). This indicates that the formation of an H-aggregate can be induced.

<Observation of self-assembly by transmission electron microscope (TEM)>
FIG. 10 is a TEM photograph in which a hexane solution of porphyrin compounds (9) to (11) is dropped onto a microgrit-attached mesh, air-dried, and surface observation is performed with a transmission electron microscope with an acceleration voltage of 200 kV. . It was observed that rods were gathering.

  In the TEM photograph of the porphyrin compound (9) shown in FIG. 10 (a), it was observed that the granular materials were gathered. However, the individual shapes appear to be constricted rods or dumbbells rather than grains. In the TEM photograph of the porphyrin compound (10) shown in FIG. 10 (b), the length of each bar was several hundred nm and the thickness was about 50 nm. In the TEM photograph of the porphyrin compound (11) shown in FIG. 10 (c), it was observed that the particulate matter was attached around the lump. In the granular materials, small strips (several tens of nm) and random striped patterns such as fine fibers were observed.

  From this result, it was revealed that the porphyrin compound (10) molecule shown in FIG. 10 (b) forms a stable rod-like molecular aggregate having a length of about several hundreds of nanometers. From now on, the size control of molecular assemblies will be the next issue for application to FETs.

Production of Organic FET and Confirmation of Operation The bottom gate type insulated gate FET shown in FIG. 5 was produced. In this FET, a gate electrode 3 made of gold, a gate insulating film 2 made of silicon oxide, a source electrode 4 and a drain electrode 5 made of gold are formed on a silicon substrate 1. A conductive layer 6 made of an organic semiconductor film was formed in a region between the source electrode 4 and the drain electrode 5.

The conductive layer 6 is formed on the gate insulating film 2 made of HMDS-treated silicon oxide on the silicon substrate 1 by spin coating a chloroform solution (0.1 mg / ml) of the porphyrin compounds (9) and (10). did. The HMDS treatment is a treatment aimed at improving the adhesion between the oxide film on the wafer and the resist film, and is generally applied by vaporizing HMDS ((CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ ). .

FIGS. 11 and 12 are a graph (a) showing the relationship between the drain current I _d and the gate voltage V _g and the drain current in an organic FET manufactured using the porphyrin compounds (9) and (10), respectively. is a graph showing the relationship between I _d and the drain voltage V _d (b).

From the change in the drain current I _d accompanying the change in the gate voltage V _g shown in FIGS. 11 (a) and 12 (a), the On / Off ratio of the organic FET is produced using the porphyrin compound (9). The organic FET was about 10 ⁴ , and the organic FET produced using the porphyrin compound (10) was 10 ⁵ . Moreover, hole mobility is about 1.08 * 10 < ^-5 > cm < ² > / Vs by organic FET produced using the porphyrin compound (9), and is organic FET produced using the porphyrin compound (10). 4.17 × 10 ⁻⁵ cm ² / Vs.

  The organic FET manufactured using the porphyrin compound (10) has higher FET performance such as carrier mobility than the organic FET manufactured using the porphyrin compound (9). This is thought to be due to the strong interaction between molecules and the close packing of molecules.

  As described above, in the FETs using the novel porphyrin compounds (9) and (10), the curve hysteresis was small and high-quality FET operation was confirmed. Further, if it is possible to transfer the H-aggregate structure of the self-assembly having a controlled length to the FET as a channel layer of the FET, it is expected that the carrier transfer speed is improved.

  Although the present invention has been described based on the embodiments and examples, it is needless to say that the present invention is not limited to these examples and can be appropriately changed without departing from the gist of the invention. .

  The porphyrin compound and the manufacturing method thereof, the organic semiconductor film and the manufacturing method thereof, and the semiconductor device and the manufacturing method thereof according to the present invention are widely used as switching elements for various electronic circuits, particularly display active matrix circuits. It is used as a semiconductor device such as TFT) and a manufacturing method thereof, and can contribute to the development of new uses such as cost reduction and application to a flexible substrate having no heat resistance such as plastic.

It is explanatory drawing which shows the synthetic scheme of the porphyrin compound based on embodiment of this invention. It is explanatory drawing which shows reaction which synthesize | combines the various oligothiophene derivatives used in the said synthetic scheme. It is a flowchart which shows the process of producing the semiconductor film which consists of a molecular assembly of a porphyrin compound [I] or [II] similarly. FIG. 2 is a schematic diagram showing a stacking structure of porphyrin molecules. It is sectional drawing which shows the structure of an insulated gate FET similarly. It is sectional drawing which shows the structure of the desirable insulated gate FET similarly. It is a mass spectrum of porphyrin compounds (9)-(11) by MALDI-TOF-MS by the example of the present invention. It is a visible ultraviolet light absorption spectrum of porphyrin compounds (9) to (11) in chloroform. It is a change by the solvent of the visible ultraviolet light absorption spectrum of porphyrin compounds (9)-(11). 2 is an electron micrograph of molecular aggregates of porphyrin compounds (9) to (11). Same is a graph (a) showing the relationship between the drain current I _d and the gate voltage V _g in organic FET, a graph showing the relationship between the drain current I _d and the drain voltage V _d and (b). Same is a graph (a) showing the relationship between the drain current I _d and the gate voltage V _g in organic FET, a graph showing the relationship between the drain current I _d and the drain voltage V _d and (b).

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Gate insulating layer, 3 ... Gate electrode, 4 ... Source electrode, 5 ... Drain electrode, 6 ... Organic-semiconductor film (conductive path)

Claims (6)

A porphyrin compound represented by the following general formula [I].
[In the general formula [I], R ¹ , R ² , R ^3, and R ⁴ are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a and b is the same or different integer of 1-6, and M is a metal ion. ]   The porphyrin compound according to claim 1, wherein the metal ion is an ion of a metal element of any one of zinc, magnesium, copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, or platinum. A method for producing a porphyrin compound according to claim 1 or 2, wherein an alkyldi (2-pyrrolyl) methane represented by the following general formula [III] is synthesized by a condensation reaction between aldehyde R ^B CHO and pyrrole, A compound represented by the following general formula [V] was synthesized by a condensation reaction of the oligothiophenecarbaldehyde represented by the following general formula [IV] with the above alkyldi (2-pyrrolyl) methane, and then this compound was oxidized. complete a porphyrin ring Te, then by introducing the metal ion M ²⁺ to the porphyrin ring, to synthesize a porphyrin compound represented by the general formula [I], the production method of the porphyrin compound.
[However, in the general formulas [III] to [V], R ^A and R ^B are the same or different, each having a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. It is an integer of 6. ] A method for producing a porphyrin compound according to claim 1 or 2, wherein an alkyldi (2-pyrrolyl) methane represented by the following general formula [III] is synthesized by a condensation reaction between aldehyde R ^B CHO and pyrrole, Step of synthesizing a porphyrin core compound represented by the following general formula [VIII] by a condensation reaction of the oligothiophenecarbaldehyde represented by the following general formula [VII] with the alkyldi (2-pyrrolyl) methane and a subsequent oxidation reaction When the reaction for introducing the metal ion M ²⁺ to the porphyrin ring, and by a coupling reaction with a compound represented by the following general formula [IX], a porphyrin compound represented by the porphyrin core compound by the general formula [I] And a method for producing a porphyrin compound.
[However, in the general formulas [III] and [VII] to [IX], R ^A and R ^B are the same or different from each other, and are substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, X is a halogen atom, R ^D is a substituted or unsubstituted alkyl group, and the sum of i and j is an integer of 2-6. ]   An organic semiconductor film comprising the porphyrin compound according to claim 1. Have a conductive path consisting of a porphyrin compound described in claim 1 or 2, the conductivity of the conductive path is configured to be controlled by an electric field, a semiconductor device, a channel region having a conductive path An insulated gate field effect transistor formed and provided with source and drain electrodes on both sides of the channel region, and a gate electrode for controlling the conductivity of the conductive path by an electric field between the electrodes. A semiconductor device configured as: