WO2016121589A1 - Matériau semi-conducteur organique - Google Patents

Matériau semi-conducteur organique Download PDF

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WO2016121589A1
WO2016121589A1 PCT/JP2016/051525 JP2016051525W WO2016121589A1 WO 2016121589 A1 WO2016121589 A1 WO 2016121589A1 JP 2016051525 W JP2016051525 W JP 2016051525W WO 2016121589 A1 WO2016121589 A1 WO 2016121589A1
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group
carbon atoms
formula
hydrocarbon group
organosilyl
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Japanese (ja)
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淳志 若宮
一剛 萩谷
光 田中
良樹 今西
崇 倉田
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東洋紡株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices

Definitions

  • the present invention relates to a compound having a specific benzobisthiazole skeleton and a production method thereof.
  • Organic semiconductor materials are one of the most important materials in the field of organic electronics, and can be classified into electron-donating p-type organic semiconductor materials and electron-accepting n-type organic semiconductor materials.
  • Various elements can be manufactured by appropriately combining p-type organic semiconductor materials and n-type organic semiconductor materials. For example, such elements are excitons formed by recombination of electrons and holes. It is applied to organic electroluminescence that emits light by the action of (exciton), an organic thin film solar cell that converts light into electric power, an organic thin film transistor that controls the amount of current and voltage, and the like.
  • organic thin-film solar cells are useful for environmental conservation because they do not release carbon dioxide into the atmosphere, and demand is increasing because they are easy to manufacture with a simple structure.
  • the photoelectric conversion efficiency of the organic thin film solar cell is still not sufficient.
  • FF fill factor
  • the open circuit voltage (Voc) is proportional to the energy difference between the HOMO (highest occupied orbital) level of the p-type organic semiconductor and the LUMO (lowest unoccupied orbital) level of the n-type organic semiconductor, the open circuit voltage (Voc) ) Needs to be deepened (reduced) in the HOMO level of the p-type organic semiconductor.
  • the short circuit current density (Jsc) correlates with the amount of energy received by the organic semiconductor material.
  • the short circuit current density (Jsc) of the organic semiconductor material In order to improve the short circuit current density (Jsc) of the organic semiconductor material, from the visible region to the near infrared region. It is necessary to absorb light in a wide wavelength range. Of the light that can be absorbed by the organic semiconductor material, the wavelength of the light with the lowest energy (the longest wavelength) is the absorption edge wavelength, and the energy corresponding to this wavelength corresponds to the band gap energy. Therefore, in order to absorb light in a wider wavelength range, it is necessary to narrow the band gap (energy difference between the HOMO level and the LUMO level of the p-type organic semiconductor).
  • Patent Document 1 As one of such organic semiconductor materials, although a compound having a benzobisthiazole skeleton in a repeating unit has been proposed (Patent Document 1), performance as an organic semiconductor material such as photoelectric conversion efficiency is not specified.
  • Patent Document 1 JP 2007-238530 A
  • An object of the present invention is to provide an organic semiconductor material excellent in conversion efficiency. Another object of the present invention is to provide a raw material compound that can introduce more various skeletons and substituents because the organic semiconductor material is closely related to the chemical structure and the conversion efficiency. Furthermore, it is providing the manufacturing method of such an organic-semiconductor material and its raw material compound.
  • the present inventors have made the p-type organic semiconductor absorb light in a wide wavelength range and simultaneously perform HOMO. We found it useful to make the level moderately deep. And as a result of earnestly examining paying attention to the correlation between the conversion efficiency and the chemical structure in the p-type organic semiconductor material, by using an organic semiconductor polymer having a specific structure, the entire visible light region has a wide light absorption. At the same time, it was found that the short circuit current density (Jsc) can be improved while improving the open circuit voltage (Voc) because the HOMO level and the LUMO level can be adjusted to appropriate ranges. And when such an organic-semiconductor polymer was used, it discovered that a charge separation could be easily caused between a p-type organic semiconductor and an n-type organic semiconductor, and completed this invention.
  • the polymer compound according to the present invention includes a repeating unit having a benzobisthiazole structure represented by the following formula (1) and a repeating unit having a thiophene structure represented by the following formula (2).
  • T 1 and T 2 are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group.
  • R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • the polymer compound according to the present invention preferably includes a repeating unit represented by the following formula (3).
  • T 1 , T 2 and R 1 each represent the same group as described above, and p represents an integer of 1 to 10.
  • the high molecular compound which concerns on this invention contains the repeating unit represented by following formula (6).
  • T 1 , T 2 , T 3 , T 4 are each independently a thiophene ring, carbonized, which may be substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group.
  • R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • T 1 , T 2 , T 3 , and T 4 are all the same, and R 1 , R 2 , R 3 , and R 4 are not all the same. ]
  • T 1 , T 2 , T 3 and T 4 are groups represented by any of the following formulas (t1) to (t5), respectively. It is preferable.
  • R 21 to R 22 each independently represents a hydrocarbon group having 6 to 30 carbon atoms.
  • R 23 to R 24 each independently represents a hydrocarbon group having 6 to 30 carbon atoms or a group represented by **-Si (R 26 ) 3 .
  • R 25 each independently represents a hydrocarbon group having 6 to 30 carbon atoms, ** — O—R 27 , ** — S—R 28 , ** — Si (R 26 ) 3 , a halogen atom, or **. It represents a -CF 3.
  • R 26 each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the plurality of R 26 may be the same or different.
  • R 27 to R 28 each represents a hydrocarbon group having 6 to 30 carbon atoms. * Represents a bond bonded to the thiazole ring of benzobisthiazole. ** represents a bond that binds to (t3) to (t5). ]
  • the technical scope of the present invention also includes an organic semiconductor material containing the compound of the present invention and that the organic semiconductor material is a p-type semiconductor or an n-type semiconductor. Furthermore, the technical scope of the present invention also includes an organic electronic device including the organic semiconductor material, and that the organic electronic device is a photoelectric conversion element or a solar cell.
  • a dihalogenobenzobisthiazole compound represented by the following formula (4) (hereinafter sometimes referred to as “compound (4)”); [In Formula (4), T 1 and T 2 each represent the same group as described above, and X 1 and X 2 each represent a halogen atom. ]
  • a thiophene compound represented by the following formula (5) (hereinafter sometimes referred to as “compound (5)”), [In Formula (5), R 1 represents the same group as described above, and p represents the same integer as described above.
  • R 10 to R 13 each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
  • M 1 and M 2 each independently represent a boron atom or a tin atom.
  • R 10 and R 11 may form a ring with M 1
  • R 12 and R 13 may form a ring with M 2 .
  • m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R 10 and R 12 may be the same or different.
  • T 1 , T 2 and R 1 each represent the same group as described above, and p represents the same integer as described above.
  • p represents the same integer as described above.
  • T 1 and T 2 are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group.
  • R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • X 1 and X 2 represent a halogen atom.
  • a benzobisthiazole compound represented by the following formula (8) (hereinafter sometimes referred to as “compound (8)”), [In formula (8), T 3 and T 4 are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group.
  • R 3 and R 4 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • R 10 to R 13 each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
  • M 1 and M 2 each independently represent a boron atom or a tin atom.
  • R 10 and R 11 may form a ring with M 1
  • R 12 and R 13 may form a ring with M 2 .
  • m and n each represents an integer of 1 or 2.
  • the plurality of R 10 and R 12 may be the same or different.
  • T 1 , T 2 , T 3 , T 4 , R 1 , R 2 , R 3 , R 4 each represents the same group as described above.
  • T 1 and T 2 are each independently a thiophene ring, hydrocarbon group, or organosilyl optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group.
  • R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • X 1 and X 2 represent a halogen atom.
  • a thiophene compound represented by the following formula (5) (hereinafter sometimes referred to as “compound (5)”), [In Formula (5), R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. p represents an integer of 1 to 10.
  • R 10 to R 13 each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
  • M 1 and M 2 each independently represent a boron atom or a tin atom.
  • R 10 and R 11 may form a ring with M 1
  • R 12 and R 13 may form a ring with M 2 .
  • m and n each represents an integer of 1 or 2.
  • the plurality of R 10 and R 12 may be the same or different.
  • T 1 , T 2 and R 1 each represent the same group as described above, and p represents the same integer as described above.
  • the benzobisthiazole compound of the present invention can form a planar cruciform skeleton by intramolecular SN interaction.
  • ⁇ conjugation is extended to a planar cross-shaped skeleton, so that multiband light absorption derived from a plurality of ⁇ - ⁇ * transitions is exhibited, and the entire visible light region has wide light absorption.
  • high charge transport characteristics can be achieved. Therefore, it is useful as an organic semiconductor material, particularly a solar cell material.
  • benzobisthiazole compounds into which more various skeletons and substituents are introduced can be obtained.
  • FIG. 1 shows an ultraviolet-visible absorption spectrum (diluted chloroform solution) of the polymer compound of Example 1.
  • FIG. 2 shows an ultraviolet-visible absorption spectrum (diluted chloroform solution) of the polymer compound of Example 2.
  • FIG. 3 shows an ultraviolet-visible absorption spectrum (diluted chloroform solution) of the polymer compound of Example 3.
  • FIG. 4 shows an ultraviolet-visible absorption spectrum (diluted chloroform solution) of the polymer compound of Example 4.
  • FIG. 5 shows the UV-visible absorption spectrum (chloroform dilute solution) of the polymer compound of Example 5.
  • FIG. 6 shows an ultraviolet-visible absorption spectrum (diluted chloroform solution) of the polymer compound of Example 6.
  • FIG. 7 shows an ultraviolet-visible absorption spectrum (chloroform dilute solution) of the polymer compound of Example 7.
  • FIG. 8 shows the UV-visible absorption spectrum (chloroform dilute solution) of the polymer compound of Example 8.
  • FIG. 9 shows an ultraviolet-visible absorption spectrum (chloroform dilute solution) of the polymer compound of Example 9.
  • FIG. 10 shows an ultraviolet-visible absorption spectrum (diluted chloroform solution) of the polymer compound of Example 10.
  • the polymer compound of the present invention has a repeating unit having a benzothiazole structure represented by the following formula (1) and a repeating unit having a thiophene structure represented by the formula (2).
  • T 1 and T 2 are each independently a thiophene ring, hydrocarbon group, or organosilyl group optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon, or an organosilyl group.
  • R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • the polymer compound of the present invention has a benzobisthiazole structural unit represented by the formula (1) and a thiazole structural unit represented by the formula (2), it has a high planar structure due to intramolecular SN interaction.
  • the ⁇ -conjugated system spreads through the cruciform skeleton and exhibits multiband light absorption characteristics derived from a plurality of ⁇ - ⁇ * transitions. As a result, the entire visible light region has a wide absorption.
  • the band gap can be narrowed while deepening the HOMO level, which is advantageous in increasing the photoelectric conversion efficiency.
  • the polymer compound of the present invention preferably contains a repeating unit having a benzobisthiazole structure represented by the following formula (3).
  • T 1 , T 2 and R 1 each represent the same group as described above, and p represents an integer of 1 to 10.
  • the polymer compound of the present invention preferably has a repeating unit having a benzobisthiazole structure represented by the following formula (6).
  • T 1 , T 2 , T 3 , T 4 are each independently a thiophene ring, carbonized, which may be substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group.
  • R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • T 1 , T 2 , T 3 , and T 4 are all the same, and R 1 , R 2 , R 3 , and R 4 are not all the same. ]
  • T 1 and T 2 may be the same or different from each other, but are the same from the viewpoint of easy production. Preferably there is.
  • T 1 , T 2 , T 3 , and T 4 may be the same or different from each other, but at least one of them is different. It is preferable. Further, from the viewpoint of easy production, it is preferable that T 1 and T 2 are the same and T 3 and T 4 are the same.
  • Each of 4 is preferably a group represented by the following formulas (t1) to (t5).
  • the alkoxy group of T 1 , T 2 , T 3 , and T 4 is preferably a group represented by the following formula (t1)
  • the thioalkoxy group is represented by the following formula (t2).
  • a thiophene ring optionally substituted with a hydrocarbon group or an organosilyl group is preferably a group represented by the following formula (t3), and a thiazole optionally substituted with a hydrocarbon group or an organosilyl group
  • a group represented by the following formula (t4) is preferable, and as a phenyl group optionally substituted by a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group Is preferably a group represented by the following formula (t5).
  • T 1 , T 2 , T 3 , and T 4 are groups represented by the following formulas (t1) to (t5), it is possible to absorb short-wavelength light and to have high planarity, thereby improving efficiency. Since ⁇ - ⁇ stacking is formed, the photoelectric conversion efficiency can be further increased.
  • R 21 to R 22 each independently represents a hydrocarbon group having 6 to 30 carbon atoms.
  • R 23 to R 24 each independently represents a hydrocarbon group having 6 to 30 carbon atoms or a group represented by **-Si (R 26 ) 3 .
  • R 25 each independently represents a hydrocarbon group having 6 to 30 carbon atoms, ** — O—R 27 , ** — S—R 28 , ** — Si (R 26 ) 3 , a halogen atom, or * * Represents CF 3 .
  • R 26 each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the plurality of R 26 may be the same or different.
  • R 27 to R 28 each represents a hydrocarbon group having 6 to 30 carbon atoms. * Represents a bond bonded to the thiazole ring of benzobisthiazole. ** represents a bond that binds to (t3) to (t5). ]
  • the hydrocarbon group having 6 to 30 carbon atoms of R 21 to R 25 and R 27 to R 28 is preferably a branched hydrocarbon group, more preferably It is a branched chain saturated hydrocarbon group. Since the hydrocarbon groups of R 21 to R 25 and R 27 to R 28 have a branch, the solubility in an organic solvent can be increased, and the polymer compound of the present invention can obtain appropriate crystallinity. .
  • the larger the carbon number of the hydrocarbon group of R 21 to R 25 and R 27 to R 28 the more the solubility in an organic solvent can be improved. Therefore, the synthesis of the polymer compound becomes difficult. Therefore, the carbon number of the hydrocarbon group of R 21 to R 25 and R 27 to R 28 is preferably 8 to 28, more preferably 8 to 26, and still more preferably 8 to 24.
  • Examples of the hydrocarbon group having 6 to 30 carbon atoms represented by R 21 to R 25 and R 27 to R 28 include an n-hexyl group, an n-heptyl group, an n-octyl group, and 1-n-butylbutyl.
  • R 21 to R 25 and R 27 to R 28 are the above groups, the polymer compound of the present invention has improved solubility in an organic solvent and has appropriate crystallinity.
  • the number of carbon atoms of the aliphatic hydrocarbon group of R 26 is preferably 1 to 18, more preferably 1-8.
  • the aliphatic hydrocarbon group for R 26 include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, an octyl group, and an octadecyl group.
  • the number of carbon atoms of the aromatic hydrocarbon group for R 26 is preferably 6 to 8, more preferably 6 to 7, and particularly preferably 6.
  • R 26 examples include a phenyl group.
  • R 26 is preferably an aliphatic hydrocarbon group, more preferably a branched aliphatic hydrocarbon group, and particularly preferably an isopropyl group.
  • the plurality of R 26 may be the same or different, but are preferably the same.
  • R 23 to R 25 are groups represented by **-Si (R 26 ) 3
  • the polymer compound of the present invention has improved solubility in an organic solvent.
  • the groups represented by **-Si (R 26 ) 3 in R 23 to R 25 are specifically a trimethylsilyl group, an ethyldimethylsilyl group, an isopropyldimethylsilyl group.
  • R 25 is a halogen atom
  • any of fluorine, chlorine, bromine and iodine can be used.
  • T 1 , T 2 , T 3 , and T 4 are represented by the formulas (t1) to (t5) from the viewpoint of excellent planarity as the whole structural unit represented by the formula (1), the formula (3), or the formula (6).
  • a group represented by the formula (t3) is more preferred, and groups represented by the following formulas (t3-1) to (t3-12) are particularly preferred.
  • * represents a bond bonded to the thiazole ring of benzobisthiazole.
  • the carbon number of the hydrocarbon group of R 1 , R 2 , R 3 , R 4 is preferably 1-30, more preferably 1-16, and even more preferably 1-8.
  • Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 1 , R 2 , R 3 and R 4 include a methyl group having 1 carbon atom; an ethyl group having 2 carbon atoms.
  • alkyl group of several tens An alkyl group of several tens; n-undecyl group, 1-n-butylheptyl group, 2-n-butylheptyl group, 1-n-propyloctyl group, 2-n-propyloctyl group, 1- An alkyl group having 11 carbon atoms such as tilnonyl group, 2-ethylnonyl group; n-dodecyl group, 1-n-pentylheptyl group, 2-n-pentylheptyl group, 1-n-butyloctyl group, 2-n-butyl 12 alkyl groups such as octyl, 1-n-propylnonyl, 2-n-propylnonyl; n-tridecyl, 1-n-pentyloctyl, 2-n-pentyloctyl, 1- Alkyl groups having 13 carbon atoms such as n-butylnonyl
  • it is an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 16 carbon atoms, still more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. Or a hydrogen atom is preferable.
  • R 1 , R 2 , R 3 , and R 4 are the above groups, the polymer compound of the present invention has improved solubility in an organic solvent and has appropriate solubility and crystallinity.
  • T 1 , T 2 , and R 1 in the structural unit of the polymer compound represented by the formula (3) are the same as described above.
  • p is an integer of 1 to 10, but is preferably an alkyl group of 1 to 7, more preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 to 2.
  • the weight average molecular weight and number average molecular weight of the polymer compound of the present invention are generally 2,000 or more and 500,000 or less, more preferably 3,000 or more and 200,000 or less.
  • the weight average molecular weight and number average molecular weight of the polymer compound of the present invention can be calculated based on a calibration curve prepared using polystyrene as a standard sample using gel permeation chromatography.
  • the ionization potential of the polymer compound of the present invention is preferably 4 eV or more, more preferably 4.5 eV or more, still more preferably 5 eV or more, and particularly preferably 5.1 eV or more.
  • the upper limit of ionization potential is not specifically limited, For example, it is 7 eV or less, it is preferable that it is 6.5 eV or less, and it is preferable that it is 6 eV or less.
  • the HOMO level is appropriately deepened (lowered), so that both a high open-circuit voltage (Voc) and a short-circuit current density (Jsc) can be obtained. It becomes possible, and higher photoelectric conversion efficiency can be obtained.
  • the polymer compound represented by the formula (3) of the present invention is: [In Formula (3), T 1 , T 2 and R 1 each represent the same group as described above, and p represents the same integer as described above. ]
  • the polymer compound represented by the formula (6) of the present invention is [In Formula (6), T 1 , T 2 , T 3 , T 4 , R 1 , R 2 , R 3 , R 4 each represents the same group as described above. ]
  • the polymer compound represented by the formula (3) of the present invention is obtained by cross-coupling a dihalogenobenzobisthiazole compound represented by the formula (7) and a thiophene compound represented by the formula (5). It can also be produced by reacting.
  • examples of the halogen atom for X 1 and X 2 include chlorine, bromine, and iodine. Any of them can be used, but bromine and iodine are particularly preferable from the viewpoint of a balance between reactivity and stability.
  • the hydrocarbon group having 1 to 30 carbon atoms represented by R 1 , R 2 , R 3 , and R 4 is a methyl group
  • An ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group are preferred.
  • a hydrogen atom is preferable.
  • the compound (7) is preferably used as an intermediate compound of the polymer compound represented by the formulas (3) and (6) of the present invention. Since this compound (7) has the above-mentioned predetermined group, it has high temporal stability and can react efficiently to form the polymer compound of the present invention.
  • the compound represented by a following formula can be illustrated, for example.
  • a compound in which bromine is substituted with iodine in formulas (7-1) to (7-6) can also be preferably exemplified as compound (7).
  • the number of carbon atoms of the aliphatic hydrocarbon group of R 10 to R 13 is preferably 1 to 5, and more preferably 1 to 4.
  • the aliphatic hydrocarbon group for R 10 to R 13 is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, more preferably a methyl group or a butyl group.
  • the number of carbon atoms of the alkoxy group of R 10 to R 13 is preferably 1 to 3, and more preferably 1 to 2.
  • R 10 to R 13 As the alkoxy group for R 10 to R 13 , a methoxy group, an ethoxy group, a propoxy group and the like are preferable, and a methoxy group and an ethoxy group are more preferable.
  • the number of carbon atoms of the aryloxy group of R 10 to R 13 is preferably 6 to 9, and more preferably 6 to 8.
  • Examples of the aryloxy group for R 10 to R 13 include a phenyloxy group, a benzyloxy group, and a phenylenebis (methyleneoxy) group.
  • R 10 to R 13 may be the same or different from each other.
  • R 10 to R 13 are preferably a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, m, And n is preferably 1.
  • ***-M 1 (R 10 ) m R 11 , ***-M 2 (R 12 ) n R 13 when M 1 and M 2 are boron atoms are represented by, for example, the following formulae: Group. However, *** represents a bond with a thiophene ring.
  • R 10 to R 13 are preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and m and n are preferably 2.
  • ***-M 1 (R 10 ) m R 11 , ***-M 2 (R 12 ) n R 13 in the case where M 1 and M 2 are tin atoms are represented by, for example, the following formulae: Group. However, *** represents a bond with a thiophene ring or a thiazole ring.
  • the compound (5) is an intermediate compound used for the synthesis of the polymer compound of the present invention. Since this compound (5) has the above-mentioned predetermined group, it has high temporal stability and can react efficiently to form the polymer compound of the present invention.
  • compound (5) the compound represented by a following formula can be illustrated, for example.
  • compounds represented by formulas (5-1) to (5-10) in which the methyl group on the tin atom is substituted with a butyl group are also preferred as the compound (5).
  • the molar ratio of the dihalogenobenzobisthiazole compound represented by formula (4) or formula (7) and the thiophene compound represented by formula (5) is: Generally, it is about 1: 0.8 to 1:10, and is not particularly limited, but is preferably 1: 0.8 to 1: 8, more preferably 1: 0.9 to 1: 6 from the viewpoint of yield and reaction efficiency. More preferably, the ratio is 1: 1 to 1: 5.
  • the compound (8) is preferably used as an intermediate compound used for the synthesis of the polymer compound represented by the formula (6) of the present invention. Since this compound (8) has the above-mentioned predetermined group, it has high temporal stability and can react efficiently to form the polymer compound of the present invention.
  • the compound represented by a following formula can be illustrated, for example.
  • a compound in which the methyl group on the tin atom is substituted with a butyl group can also be preferably exemplified as the compound (8).
  • the molar ratio of the dihalogenobenzobisthiazole compound represented by the formula (7) and the benzobisthiazole compound represented by the formula (8) is generally 1: Although it is about 0.8 to 1:10 and is not particularly limited, it is preferably 1: 0.8 to 1: 8, more preferably 1: 0.9 to 1: 6, from the viewpoint of yield and reaction efficiency. 1 to 1: 5 is more preferable.
  • the dihalogenobenzobisthiazole compound represented by the formula (4) or the formula (7) is reacted with the thiophene compound represented by the formula (5).
  • the metal catalyst used include transition metal catalysts such as a palladium catalyst, a nickel catalyst, an iron catalyst, a copper catalyst, a rhodium catalyst, and a ruthenium catalyst. Among these, a palladium-based catalyst is preferable. Note that the valence of palladium is not particularly limited, and may be zero or divalent.
  • Metal catalyst used in the reaction of the dihalogenobenzobisthiazole compound represented by formula (7) and the benzobisthiazole compound represented by formula (8) in the production of the polymer compound represented by formula (6) examples thereof include transition metal catalysts such as palladium catalysts, nickel catalysts, iron catalysts, copper catalysts, rhodium catalysts, and ruthenium catalysts. Among these, a palladium-based catalyst is preferable. Note that the valence of palladium is not particularly limited, and may be zero or divalent.
  • the palladium-based catalyst examples include palladium (II) chloride, palladium (II) bromide, palladium (II) iodide, palladium (II) oxide, palladium (II) sulfide, palladium (II) telluride, palladium hydroxide ( II), palladium selenide (II), palladium cyanide (II), palladium acetate (II), palladium trifluoroacetate (II), palladium acetylacetonate (II), diacetate bis (triphenylphosphine) palladium (II) ), Tetrakis (triphenylphosphine) palladium (0), dichlorobis (triphenylphosphine) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (benzonitrile) palladium (II), dichloro [1,2 Bis (diphenyl
  • These catalysts may be used individually by 1 type, and may mix and use 2 or more types.
  • tris (dibenzylideneacetone) dipalladium (0) and tris (dibenzylideneacetone) dipalladium (0) chloroform adduct are particularly preferred.
  • the molar ratio of the dihalogenobenzobisthiazole compound represented by formula (4) or formula (7) to the metal catalyst is generally about 1: 0.0001 to 1: 0.5 and is not particularly limited, but is preferably 1: 0.001 to 1: 0.4 from the viewpoint of yield and reaction efficiency. 005 to 1: 0.3 is more preferable, and 1: 0.01 to 1: 0.2 is more preferable.
  • the molar ratio of the dihalogenobenzobisthiazole compound represented by formula (7) to the metal catalyst is generally although it is about 1: 0.0001 to 1: 0.5 and is not particularly limited, it is preferably 1: 0.001 to 1: 0.4 from the viewpoint of yield and reaction efficiency, and 1: 0.005 to 1: 0. .3 is more preferable, and 1: 0.01 to 1: 0.2 is more preferable.
  • a specific ligand may be coordinated to a metal catalyst such as a palladium-based catalyst.
  • the ligands include trimethylphosphine, triethylphosphine, tri (n-butyl) phosphine, tri (isopropyl) phosphine, tri (tert-butyl) phosphine, tri-tert-butylphosphonium tetrafluoroborate, bis (tert-butyl) ) Methylphosphine, tricyclohexylphosphine, diphenyl (methyl) phosphine, triphenisphosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, tris (p-tolyl) phosphine, tris (2-methoxyphenyl) phosphine , Tris (3-methoxyphenyl)
  • triphenylphosphine tris (o-tolyl) phosphine, and tris (2-methoxyphenyl) phosphine are particularly preferable.
  • the molar ratio of the metal catalyst to the ligand Is generally about 1: 0.5 to 1:10 and is not particularly limited, but is preferably 1: 1 to 1: 8, more preferably 1: 1 to 1: 7, from the viewpoint of yield and reaction efficiency. 1 to 1: 5 is more preferable.
  • the dihalogenobenzobisthiazole compound represented by formula (4) or formula (7) is represented by formula (5) in the presence of a metal catalyst.
  • a base may coexist.
  • the dihalogenobenzobisthiazole compound represented by formula (7) is added to the benzobisthiazole represented by formula (8) in the presence of a metal catalyst.
  • a base may coexist.
  • M 1 and M 2 are boron atoms, it is preferable to coexist with a base, and when M 1 and M 2 are tin atoms, it is not necessary to coexist with a base.
  • Examples of the base include lithium metal hydride, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate and other alkali metal salt compounds; magnesium hydroxide, calcium hydroxide, barium hydroxide, Alkaline earth metal salt compounds such as magnesium carbonate, calcium carbonate, barium carbonate; lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium isopropoxide, sodium isopropoxide Potassium isopropoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, lithium tert-amyl alkoxide, sodium tert-amyl alkoxide Alkoxymethyl alkali metal compounds such as potassium tert- amyl alkoxide; lithium hydride, sodium hydride, metal hydride compounds such as potassium hydride.
  • an alkoxyalkali metal compound is preferable, and lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, and cesium carbonate are more preferable.
  • the molar ratio of the dihalogenobenzobisthiazole compound represented by formula (4) or formula (7) to the base Is generally about 1: 1 to 1:10 and is not particularly limited, but is preferably 1: 1.5 to 1: 8, more preferably 1: 1.8 to 1: 6, from the viewpoint of yield and reaction efficiency. 1: 2 to 1: 5 is more preferable.
  • the molar ratio of the dihalogenobenzobisthiazole compound represented by formula (7) to the base is generally 1: Although it is about 1 to 1:10 and is not particularly limited, it is preferably 1: 1.5 to 1: 8, more preferably 1: 1.8 to 1: 6, and more preferably 1: 2 to 1: 8 from the viewpoint of yield and reaction efficiency. 1: 5 is more preferable.
  • the dihalogenobenzobisthiazole compound represented by formula (4) or formula (7) is represented by formula (5) in the presence of a metal catalyst.
  • the solvent for reacting the thiophene compound is not particularly limited as long as it does not affect the reaction, ether solvent, aromatic solvent, ester solvent, hydrocarbon solvent, halogen solvent, ketone solvent, An amide solvent or the like can be used.
  • ether solvent examples include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane.
  • aromatic solvent examples include benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, and tetralin.
  • ester solvent examples include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate.
  • hydrocarbon solvent examples include pentane, hexane, heptane, octane, and decalin.
  • halogen solvent examples include dichloromethane, chloroform, dichloroethane, and dichloropropane.
  • ketone solvent examples include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • amide solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro- ( 1H) -pyrimidine.
  • a nitrile solvent such as acetonitrile, a sulfoxide solvent such as dimethyl sulfoxide, and a sulfone solvent such as sulfolane can be used.
  • a nitrile solvent such as acetonitrile, a sulfoxide solvent such as dimethyl sulfoxide, and a sulfone solvent such as sulfolane
  • tetrahydrofuran, toluene, chlorobenzene, and N, N-dimethylformamide are particularly preferable.
  • the benzobisthiazole compound represented by the formula (8) is added to the dihalogenobenzobisthiazole compound represented by the formula (7) in the presence of a metal catalyst.
  • the said solvent can be used also about the solvent made to react.
  • the amount of the solvent used in the production of the polymer compound represented by formula (3) is generally 1 mL or more with respect to 1 g of the dihalogenobenzobisthiazole compound represented by formula (4) or formula (7), although it is about 150 mL or less and it is not specifically limited, From a viewpoint of a yield or reaction efficiency, 5 mL or more and 100 mL or less are preferable, 8 mL or more and 90 mL or less are more preferable, 10 mL or more and 80 mL or less are more preferable.
  • the amount of the solvent used in the production of the polymer compound represented by formula (6) is the sum of the dihalogenobenzobisthiazole compound represented by formula (7) and the benzobisthiazole compound represented by formula (8). Although it is generally 1 mL or more and about 150 mL or less with respect to 1 g, it is preferably 5 mL or more and 100 mL or less from the viewpoint of yield or reaction efficiency, more preferably 8 mL or more and 90 mL or less, more preferably 10 mL or more and 80 mL or less. Further preferred.
  • the reaction temperature is not particularly limited, but is preferably 0 ° C. or higher and 200 ° C. or lower from the viewpoint of increasing the reaction yield, 30 ° C. As mentioned above, it is more preferable that it is 180 degrees C or less, and it is still more preferable that it is 40 degrees C or more and 150 degrees C or less.
  • the measurement method used in the examples is as follows.
  • NMR spectrum measurement Regarding the benzobisthiazole compound, an NMR spectrum measuring apparatus (manufactured by Agilent (formerly Varian), “400MR”, and Bruker, “AVANCE”) 500 ”) and NMR spectra were measured.
  • the molecular weight of the benzobisthiazole compound was measured using gel permeation chromatography (GPC).
  • GPC Gel permeation chromatography
  • the benzobisthiazole compound was dissolved in a mobile phase solvent (chloroform) so as to have a concentration of 0.5 g / L, measured under the following conditions, and based on a calibration curve prepared using polystyrene as a standard sample. By converting, the weight average molecular weight of the benzobisthiazole compound was calculated.
  • the GPC conditions in the measurement are as follows.
  • UV-visible absorption spectrum The obtained benzobisthiazole compound was dissolved in chloroform so as to have a concentration of 0.03 g / L, and an ultraviolet / visible spectroscopic device (manufactured by Shimadzu Corporation, “UV-2450”, “UV-3150”), and The UV-visible absorption spectrum was measured using a cell having an optical path length of 1 cm.
  • a benzobisthiazole compound was formed on a glass substrate so as to have a thickness of 50 nm to 100 nm.
  • the ionization potential of this membrane was measured with an ultraviolet photoelectron analyzer (“AC-3” manufactured by Riken Keiki Co., Ltd.) at room temperature and normal pressure.
  • DI-DBTH-DMOTH 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole DI-DBTH-DMOTH
  • 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-DMOTH, 1.4 g) 2.12 mmol) and tetrahydrofuran (27 mL) were added, and the mixture was cooled to ⁇ 40 ° C., and then lithium diisopropylamide (2M solution, 2.3 mL, 4.66 mmol) was added dropwise and stirred for 30 minutes.
  • DI-DBTH-TDTH 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH-TDTH) Synthesis of In a 200 mL flask, 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-TDTH, 4.1 g, 3.97 mmol) and tetrahydrofuran (80 mL) were added and cooled to ⁇ 40 ° C., and then lithium diisopropylamide (2M solution, 4.4 mL, 8.8 mmol) was added dropwise and stirred for 30 minutes.
  • donor material P-THDT-DBTH-T obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material
  • donor material: acceptor material 1: 2 (weight) (total concentration 30 mg / mL) and 1,8-diiodooctane (0.03 mL / mL) were dissolved in chlorobenzene and passed through a 0.45 ⁇ m filter to obtain a mixed solution.
  • a glass substrate on which ITO is formed is subjected to surface treatment by ozone UV treatment, and then a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion is spun. It was applied and annealed with a coater. Next, the mixed solution of the above donor material and acceptor material was formed into a film with a spin coater and dried under reduced pressure at room temperature. On top of that, an ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated, and a film converted into titanium oxide by moisture in the atmosphere was prepared.
  • PEDOT-PSS [poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)
  • Example 4 P-THDT-DBTH-DT To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH). -HDTH, 100 mg, 0.09 mmol), 5,5′-bis (trimethylstannyl) -2,2′-bithiophene (47 mg, 0.09), dipalladium (0) -chloroform adduct (3 mg, 3.
  • a glass substrate on which ITO is formed is subjected to surface treatment by ozone UV treatment, and then a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion is spun. It was applied and annealed with a coater. Next, the mixed solution of the above donor material and acceptor material was formed into a film with a spin coater and dried under reduced pressure at room temperature. On top of that, an ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated, and a film converted into titanium oxide by moisture in the atmosphere was prepared.
  • PEDOT-PSS [poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)
  • a glass substrate on which ITO is formed is subjected to surface treatment by ozone UV treatment, and then a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion is spun. It was applied and annealed with a coater. Next, the mixed solution of the above donor material and acceptor material was formed into a film with a spin coater and dried under reduced pressure at room temperature. On top of that, an ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated, and a film converted into titanium oxide by moisture in the atmosphere was prepared.
  • PEDOT-PSS [poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)
  • donor material P-TTDT-DBTH-TT obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material
  • donor material: acceptor material 1: 2 (weight) (total concentration 24 mg / mL) and 1,8-diiodooctane (0.03 mL / mL) were dissolved in chlorobenzene and passed through a 0.45 ⁇ m filter to obtain a mixed solution.
  • a glass substrate on which ITO is formed is subjected to surface treatment by ozone UV treatment, and then a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion is spun. It was applied and annealed with a coater. Next, the mixed solution of the above donor material and acceptor material was formed into a film with a spin coater and dried under reduced pressure at room temperature. On top of that, an ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated, and a film converted into titanium oxide by moisture in the atmosphere was prepared.
  • PEDOT-PSS [poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)
  • the polymer compound of the present invention has high photoelectric conversion efficiency, it is useful for organic electro devices such as organic electroluminescence elements and organic thin film transistor elements.

Abstract

L'invention concerne un composé polymère pour l'obtention d'un matériau semi-conducteur organique ayant un excellent rendement de conversion, ou un composé de matériau de départ ayant un degré de liberté élevé dans la conception de matériau, et un procédé de fabrication de celui-ci. L'invention concerne un composé polymère caractérisé en ce qu'il comprend des unités récurrentes d'une structure benzobisthiazole représentée par la formule (1) et des unités récurrentes d'une structure thiophène représentée par la formule (2). (Dans la formule (1), T1 et T2 représentent chacun indépendamment : un cycle thiophène qui peut être substitué par un groupe alcoxy, un groupe thioalcoxy, un groupe hydrocarbure ou un groupe organosilyle; un cycle thiazole qui peut être substitué par un groupe hydrocarbure ou un groupe organosilyle; ou un groupe phényle qui peut être substitué par un groupe hydrocarbure, un groupe alcoxy, un groupe thioalcoxy, un groupe organosilyle, un atome d'halogène ou un groupe trifluorométhyle.) (Dans la formule (2), R1 représente un atome d'hydrogène ou un groupe hydrocarbure C1-3.)
PCT/JP2016/051525 2015-01-27 2016-01-20 Matériau semi-conducteur organique WO2016121589A1 (fr)

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WO2020218189A1 (fr) * 2019-04-26 2020-10-29 東洋紡株式会社 Compose haut polymere
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