WO2018070670A1 - Organic semiconductor compound and electronic device using same - Google Patents

Organic semiconductor compound and electronic device using same Download PDF

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WO2018070670A1
WO2018070670A1 PCT/KR2017/009847 KR2017009847W WO2018070670A1 WO 2018070670 A1 WO2018070670 A1 WO 2018070670A1 KR 2017009847 W KR2017009847 W KR 2017009847W WO 2018070670 A1 WO2018070670 A1 WO 2018070670A1
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organic semiconductor
formula
semiconductor compound
monovalent non
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French (fr)
Korean (ko)
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김봉수
이명재
정아라
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이화여자대학교 산학협력단
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    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • 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 potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a novel organic semiconductor compound and an electronic device using the same.
  • Organic semiconductor compounds have been recognized as materials that can replace inorganic silicon semiconductors due to various advantages such as flexibility, light weight, ease of controlling photoelectric properties through molecular structure control, and low process cost.
  • Such an organic semiconductor compound can be used in a wide range of electronic devices, the performance of such electronic devices are many, but an important evaluation measure is the charge mobility, the higher the charge mobility is preferred.
  • An organic semiconductor compound having excellent charge mobility and an electronic device using the same are provided.
  • an organic semiconductor compound represented by Formula 1 is provided:
  • X 1 and X 2 are each independently selected from O, S and Se,
  • a is selected from an integer of 1 to 10,
  • L is a substituted or unsubstituted C 5 -C 60 carbocyclic group or a substituted or unsubstituted C 1 -C 60 heterocyclic group
  • b is selected from an integer of 1 to 30, when b is 2 or more, two or more L may be the same or different from each other,
  • n is selected from an integer of 5 to 100,000
  • At least one of the substituents of the substituted C 5 -C 60 carbocyclic group or substituted C 1 -C 60 heterocyclic group is deuterium, -F, -Cl, -Br, -I, hydroxyl group, oxo Group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group , C 1 -C 60 alkylthio group, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocycloalkenyl group, C 6 -C Import 60 aryl group, C 6 -C 60 aryloxy, C 6 -C 60 aryl come T, C
  • Q 1 to Q 3 and Q 11 to Q 13 are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group , hydride tank group, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 come alkylthio, C 3 -C 10 Cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocycloalkenyl group, C 6 -C 60 aryl group, C 1 -C 60 heteroaryl group, monovalent Non-aromatic condensed polycyclic groups and monovalent non-aromatic condensed polycyclic groups.
  • an electronic device including an organic semiconductor film including at least one organic semiconductor compound represented by Chemical Formula 1 is provided.
  • An electronic device including the organic semiconductor compound may have a high charge mobility.
  • FIG. 2 is a graph showing cyclic voltammetry test results of an organic semiconductor film including Compound 1 according to an embodiment of the present invention.
  • FIG 3 and 4 are graphs of current-voltage (J-V) curves of an organic thin film transistor according to an exemplary embodiment of the present invention.
  • J-V current-voltage
  • a C 5 -C 60 carbocyclic group means a monocyclic or polycyclic group having 5 to 60 carbon atoms including only carbon as a ring-forming atom.
  • the C 5 -C 60 carbocyclic group can be an aromatic carbocyclic group or a non-aromatic carbocyclic group.
  • the C 5 -C 60 carbocyclic group may be a ring such as benzene, a monovalent group such as a phenyl group, or a divalent group such as a phenylene group.
  • a C 5 -C 60 carbocyclic group during the various modifications can be made, such as in 3 or 4 is the group number of a group.
  • a C 1 -C 60 heterocyclic group has the same structure as the C 5 -C 60 carbocyclic group, and as a ring-forming atom, in addition to carbon (carbon number may be 1 to 60), N A group containing at least one hetero atom selected from among O, Si, P, S, Se, Te, and Ge.
  • the monovalent non-aromatic condensed polycyclic group herein includes two or more rings condensed with each other, contains only carbon as a ring forming atom, and the entire molecule is non-aromatic. It means a monovalent group having (for example, having 8 to 60 carbon atoms). Specific examples of the monovalent non-aromatic condensed polycyclic group include fluorenyl groups and the like.
  • a monovalent non-aromatic condensed heteropolycyclic group includes two or more rings condensed with each other, and in addition to carbon, N, O, Si, P, S, Se, Te and It means a monovalent group (eg, having 1 to 60 carbon atoms) containing at least one hetero atom selected from Ge, and the whole molecule is non-aromatic.
  • Specific examples of the monovalent non-aromatic heterocondensed polycyclic group include carbazolyl groups and the like.
  • the organic semiconductor compound is represented by the following Chemical Formula 1:
  • X 1 and X 2 may be independently selected from O, S, and Se.
  • X 1 and X 2 may be O or S independently of each other.
  • X 1 and X 2 may both be S, but is not limited thereto.
  • R 1 and R 2 are each independently hydrogen, C 1 -C 30 alkyl group, C 2 -C 30 alkenyl group, C 2 -C 30 alkynyl group, C 1 -C 30 alkoxy group and C 1 -C 30 alkylthio group.
  • the R 1 and R 2 may be each independently hydrogen, but are not limited thereto.
  • a may be selected from integers of 1 to 10.
  • A denotes the number of groups described in parentheses. When a is 2 or more, two or more of the groups may be the same or different. For example, a may be selected from an integer of 1 to 5. According to one embodiment, the a may be 1, but is not limited thereto.
  • L may be a substituted or unsubstituted C 5 -C 60 carbocyclic group or a substituted or unsubstituted C 1 -C 60 heterocyclic group, the substituted C 5 -C 60 carbosi
  • At least one of the substituents of the click group or substituted C 1 -C 60 heterocyclic group is deuterium, -F, -Cl, -Br, -I, hydroxyl group, oxo group, cyano group, nitro group, amidino group, a hydrazino group import, Hydra tank group, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 alkyl group, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -
  • Y 1 to Y 3 are independently of each other, C (Z 5 ) (Z 6 ), O, S, Se, Te, N (Z 5 ), Si (Z 5 ) (Z 6 ) and Ge (Z 5 ) ( Z 6 ),
  • Q 11 to Q 13 are independently of each other, hydrogen, C 1 -C 30 alkyl, C 1 -C 30 alkoxy group, C 1 -C 30 alkylthio, C 6 -C 30 aryl group and C 1 -C 30 Selected from heteroaryl groups,
  • d3 is selected from an integer of 1 to 3
  • d4 is selected from an integer of 1 to 4,
  • L may be selected from the group represented by the following formulas 3-1 to 3-19:
  • Z 31 to Z 34 are each independently selected from hydrogen, a C 1 -C 30 alkyl group, a C 1 -C 30 alkoxy group and a C 1 -C 30 alkylthio group,
  • e3 is selected from an integer of 1 to 3
  • e4 is selected from an integer of 1 to 4,
  • L may be a group represented by Formula 4-1 or 4-2, but is not limited thereto.
  • Z 51 and Z 52 are, independently from each other, hydrogen or a C 1 -C 30 alkyl group
  • b may be selected from an integer of 1 to 30.
  • B represents the number of L, and when b is 2 or more, two or more L may be the same or different from each other.
  • b may be selected from an integer of 1 to 10.
  • b may be selected from an integer of 1 to 5.
  • the b may be 1 or 3, but is not limited thereto.
  • n may be selected from an integer of 5 to 100,000.
  • N denotes the number of groups described in brackets, and the groups described in brackets may be the same or different from each other.
  • n may be selected from an integer of 10 to 10,000.
  • n may be selected from an integer of 20 to 1,000, but is not limited thereto.
  • the organic semiconductor compound may be represented by the following Chemical Formula 1A:
  • organic semiconductor compound may be represented by the following Chemical Formula 1-A:
  • b 1 to b 3 is an integer of 0 or more, the sum of b 1 to b 3 is 1 to 30,
  • Y 1 to Y 4 are each independently selected from O, S, Se, and N (Z 5 ),
  • Z 1 to Z 5 are independently of each other hydrogen, a C 1 -C 30 alkyl group, a C 2 -C 30 alkenyl group, a C 2 -C 30 alkynyl group, a C 1 -C 30 alkoxy group, a C 1 -C 30 alkylti Group, a C 6 -C 30 aryl group, a C 1 -C 30 heteroaryl group, a monovalent non-aromatic condensed polycyclic group and a monovalent non-aromatic condensed polycyclic group.
  • X 1 and X 2 may each be S, R 1 and R 2 may each be hydrogen, a may be 1, and b 1 , b 2, and b 3 may be 1, respectively.
  • X 1 and X 2 are each S, R 1 and R 2 are each hydrogen, a is 1, b 1 , b 2 and b 3 are each 1, and Y 1 and Y 2 are each N (Z 5 ), wherein Z 5 is a C 1 -C 30 alkyl group, Y 3 and Y 4 are each S, and Z 1 to Z 4 may be hydrogen.
  • the organic semiconductor compound may be Compound 1, but is not limited thereto.
  • n is selected from an integer of 5 to 100,000.
  • the organic semiconductor compound may have a number average molecular weight (Mn) of 5,000 g / mol to 100,000,000 g / mol.
  • Mn number average molecular weight
  • the organic semiconductor compound may have a number average molecular weight of 10,000 g / mol to 10,000,000 g / mol.
  • the organic semiconductor compound may have a number average molecular weight of 20,000 g / mol to 1,000,000 g / mol.
  • the organic semiconductor compound may have a number average molecular weight of 25,000 g / mol to 100,000 g / mol, but is not limited thereto.
  • the organic semiconductor compound may have a molecular weight distribution (polydispersity (PDI) of 1 to 10).
  • PDI polydispersity
  • the organic semiconductor compound may have a molecular weight distribution of 1 to 3, but is not limited thereto.
  • the organic semiconductor compound represented by Chemical Formula 1 may increase the planarity of the compound through an intramolecular interaction (see Chemical Formula 1 ′) between X 1 and F and X 2 and F in the molecule. This may narrow the distance between the organic semiconductor compounds and improve the charge mobility of the electronic device including the organic semiconductor compound.
  • the organic semiconductor compound may include -F in the molecule, thereby inducing polarity in the organic semiconductor compound, thereby increasing interchain interaction.
  • the organic semiconductor compound may include -F in the molecule, thereby inducing polarity in the organic semiconductor compound, thereby increasing interchain interaction.
  • the intermolecular interaction between X 1 and F and the X 2 and F between the organic semiconductor compounds the distance between the organic semiconductor compounds is narrowed, and thus the charge mobility of the electronic device including the organic semiconductor compound is reduced. Can improve.
  • an electronic device employing the organic semiconductor compound represented by Formula 1 for example, an organic thin film transistor, may have high charge mobility.
  • an organic semiconductor film including at least one organic semiconductor compound represented by Chemical Formula 1 is provided.
  • the organic semiconductor film including at least one organic semiconductor compound may be any one of an n-type organic semiconductor film, a p-type organic semiconductor film, and a bipolar organic semiconductor film. According to an embodiment, the organic semiconductor film may be a p-type organic semiconductor film or a bipolar organic semiconductor film.
  • the manufacturing method of the said organic semiconductor film is not specifically limited, For example, it can form by depositing 1 or more types of said organic semiconductor compounds, or coating by a solution process.
  • the organic semiconductor film may be manufactured using thermal deposition, vacuum deposition, laser deposition, screen printing, printing, imprinting, spin coating, dipping, inkjetting, drop casting, spray coating, or the like.
  • the method may further include a heat treatment step after the deposition or coating, thereby further improving the compactness and uniformity of the organic semiconductor film.
  • the heat treatment step may be appropriately selected in consideration of an organic semiconductor compound, a solvent, and the like used by a person skilled in the art (hereinafter, referred to as 'an expert'), for example, 1 minute to 2 hours at 60 ° C to 300 ° C. May be performed.
  • one or more conventional organic solvents may be used as the solvent, and for example, chloroform, chlorobenzene, dichlorobenzene, toluene, xylene, 1,2, 4-trimethylbenzene, tetralin and the like can be used.
  • the organic semiconductor film is a non-halogen solvent (i.e., a solvent which does not contain a halogen group in the molecule), which is a solvent having relatively environmentally friendly properties, not a halogen solvent having high corrosion resistance and human toxicity, such as toluene, xylene , 1,2,4-trimethylbenzene, tetralin and the like can be prepared, but still has the advantage of obtaining a high charge mobility.
  • a non-halogen solvent i.e., a solvent which does not contain a halogen group in the molecule
  • a solvent having relatively environmentally friendly properties not a halogen solvent having high corrosion resistance and human toxicity, such as toluene, xylene , 1,2,4-trimethylbenzene, tetralin and the like can be prepared, but still has the advantage of obtaining a high charge mobility.
  • a method of manufacturing an organic semiconductor thin film is provided.
  • the non-halogenous solvent may include, for example, a substituted or unsubstituted aliphatic hydrocarbon solvent containing no halogen group; Substituted or unsubstituted aromatic hydrocarbon solvent containing no halogen group; Substituted or unsubstituted ketone solvent containing no halogen group; Substituted or unsubstituted ether solvent containing no halogen group; Substituted or unsubstituted acetate solvent containing no halogen group; Substituted or unsubstituted alcohol solvent containing no halogen group; Substituted or unsubstituted amide solvent containing no halogen group; Substituted or unsubstituted silicone solvent containing no halogen group; And combinations of the above solvents,
  • One of the substituents of the substituted silicone solvent that does not contain a halogen group is, for example, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C 1 -C 60 alkyl group, C 2- C 60 alkenyl, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 come alky
  • Q 1 to Q 3 are independently of each other, hydrogen, deuterium, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2 -C 60 alke group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 come alkylthio, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkyl Selected from alkenyl groups, C 1 -C 10 heterocycloalkenyl groups, C 6 -C 60 aryl groups, C 1 -C 60 heteroaryl groups, monovalent non-aromatic condensed polycyclic groups and monovalent non-aromatic condensed polycyclic groups It may be, but is not limited thereto.
  • the non-halogenous solvent may be an aliphatic hydrocarbon solvent such as hexane or heptane; Aromatic hydrocarbon solvents such as toluene, pyridine, quinoline, anisole, trimethylbenzene, xylene and tetralin; Ketone solvents such as methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, cyclohexanone and acetone; Ether solvents such as tetrahydrofuran and isopropyl ether; Acetate solvents such as ethyl acetate, butyl acetate and propylene glycol methyl ether acetate; Alcohol solvents such as isopropyl alcohol and butyl alcohol; Amide solvents such as dimethylacetiamide and dimethylformamide; Silicone solvents; And one or more selected from a combination of the above solvents.
  • the non-halogenous solvent may be an aromatic hydrocarbon solvent such as toluene,
  • the content of the organic semiconductor compound dissolved in the solvent may be appropriately selected by those skilled in the art in consideration of solubility and coating property.
  • the thickness of the organic semiconductor film may be appropriately selected in consideration of the type of organic semiconductor compound used by those skilled in the art and the use of the film, and may be, for example, a thickness of several nm to several hundred ⁇ m.
  • an electronic device comprising an organic semiconductor film containing at least one organic semiconductor compound.
  • the electronic device including the organic semiconductor film may include, for example, an organic thin-film transistor (OTFT), an organic light emitting diode (OLED), an organic solar cell (OSC), and an organic device. It may be any one of an organic photo sensor (OPD).
  • OFT organic thin-film transistor
  • OLED organic light emitting diode
  • OSC organic solar cell
  • OPD organic photo sensor
  • the electronic device including the organic semiconductor film may be an organic thin film transistor.
  • the organic thin film transistor in the case of an organic thin film transistor having a bottom-gate / bottom-contact (BGBC) structure, the organic thin film transistor includes a substrate; A gate electrode disposed on a predetermined region of the substrate; A gate insulator disposed on the gate electrode; An organic semiconductor film including at least one organic semiconductor compound represented by Formula 1 disposed on the insulator; And a source electrode and a drain electrode respectively disposed on the organic semiconductor film.
  • BGBC bottom-gate / bottom-contact
  • the organic thin film transistor in the case of an organic thin film transistor having a top-gate / bottom-contact (TGBC) structure, includes a substrate; Source and drain electrodes doubled on predetermined regions of the substrate; An organic semiconductor film including at least one organic semiconductor compound represented by Chemical Formula 1, respectively disposed on the source electrode and the drain electrode; A gate insulator disposed on the organic semiconductor film; And a gate electrode disposed on the gate insulator.
  • the organic semiconductor film including at least one organic semiconductor compound represented by Formula 1 may be any one of an n-type organic semiconductor film, a p-type organic semiconductor film, and a bipolar organic semiconductor film.
  • ODTS octadecyltrichlorosilane
  • the solution obtained by dissolving the compound 1 (5 mg) in o-xylene (1 mL) was spin-coated at a speed of 1000 rpm for 35 seconds, and then dried at a temperature of 25 ° C. for 30 minutes, to a thickness of 0.050 ⁇ m. An organic semiconductor film was formed.
  • a source electrode and a drain electrode were formed by depositing gold on the organic semiconductor thin film using a mask, thereby manufacturing an organic thin film transistor having a bottom-gate / bottom-contact (BGBC) structure.
  • the channel length of the organic thin film transistor was 100 ⁇ m and the channel width was 800 ⁇ m.
  • An organic thin film transistor was manufactured in the same manner as in Example 1, except that 1,2,4-trimethylbenzene was used instead of o-xylene and dried at a temperature of 25 ° C., 100 ° C. or 200 ° C. It was.
  • UV-Vis spectrophotometer was used for the compound 1 in the solution state and the compound 1 in the thin film state dissolved in o-xylene, using a UV-Vis spectrophotometer.
  • the Vis absorption spectrum was measured and the results are shown in FIG. 1 and Table 1 below.
  • the maximum absorption wavelength of the compound 1 was shifted to the long wavelength as it changes from the solution state to the thin film state, it can be seen that the band gap is smaller. Through this, it can be seen that the intermolecular pi ( ⁇ ) bond of Compound 1 increases as the solution state changes from the thin film state.
  • the organic semiconductor film obtained by spin coating the solution obtained by dissolving Compound 1 (5 mg) in o-xylene (1 mL) on a carbon glass electrode for 35 seconds at a speed of 1000 rpm was prepared as a working electrode, Platinum wire was prepared as a counter electrode and Ag / Ag + was prepared as a reference electrode.
  • a voltage (V) was applied to the reference electrode (Ag / Ag + ) using a potentiometer, the redox reaction of the analyte occurred at the lower part of the working electrode, and the current flowing at the counter electrode was measured.
  • the redox potential of ferrocene / ferrocenenium (Fc / Fc + ) was calibrated and the redox potential of ferrocene / ferrocenenium (Fc / Fc + ) was assumed to be 4.8 eV.
  • the voltage ( ⁇ ox ) at the point where oxidation starts and the voltage ( ⁇ red ) at the point where reduction starts, respectively, are used to determine the highest occupied molecular orbital (HOMO)
  • the energy levels of the lowest unoccupied molecular orbital (LUMO) were calculated.
  • the voltage at the start of oxidation ( ⁇ ox ) and the voltage at the start of reduction ( ⁇ red ) were measured at 0.55 V and -1.30 V, respectively.
  • the calculated energy level was -5.35 eV for HOMO energy level and -3.50 eV for LUMO energy level.
  • the characteristics of the organic thin film transistors manufactured in Examples 1 and 2 were measured using a Keithley 2400 source / measure units, and the drain voltage-drain current according to the gate voltage and the gate voltage-drain current curve according to the drain voltage were measured. Various characteristics were evaluated using Equation 2 below in the saturation region.
  • V T is a threshold voltage
  • V gs is an applied gate voltage
  • ⁇ is a field effect charge mobility
  • W and L are channel width and length
  • C i is capacitance of an insulating film.
  • Ids is determined as the gate voltage with zero
  • FIG. 3 and 4 are graphs of current-voltage (J-V) curves showing transfer characteristics of the organic thin film transistors prepared in Examples 1 and 2.
  • FIG. 3 and 4 are graphs of current-voltage (J-V) curves showing transfer characteristics of the organic thin film transistors prepared in Examples 1 and 2.
  • Compound 1 exhibited p-type and n-type bipolar current flow characteristics, and in the case of the organic thin film transistor manufactured in Example 1, the hole mobility was 0.167 cm 2 V -1 S -1 , and the electron mobility was 0.021. cm 2 V ⁇ 1 S ⁇ 1 .
  • the hole mobility was 0.367 cm 2 V -1 S -1
  • the electron mobility was 0.051 cm 2 V -1 S -1 .
  • the hole mobility was 0.826 cm 2 V -1 S -1 and the electron mobility was 0.078 cm 2 V -1 S -1 when dried at °C, and the hole mobility was 1.377 when dried at 200 °C. cm 2 V -1 S -1 , electron mobility was 0.283 cm 2 V -1 S -1 .
  • Example 2 As a comparative example, the same method as in Example 1 was used except that Comparative Example A was used instead of Compound 1 in Example 1 and dried at a temperature of 25 ° C, 100 ° C, 150 ° C or 200 ° C. The organic thin film transistor was manufactured, and the characteristic was evaluated.
  • J-V current-voltage
  • the hole mobility when dried at room temperature, the hole mobility was 0.040 cm 2 V -1 S -1 , the electron mobility was 0.0019 cm 2 V -1 S -1 , and the temperature was 100 ° C.
  • the hole mobility was 0.56 cm 2 V -1 S -1 and the electron mobility was 0.0033 cm 2 V -1 S -1 when dried at, and the hole mobility was 0.68 cm when dried at 150 ° C. 2 V -1 S -1 , the electron mobility was 0.026 cm 2 V -1 S -1 , and when dried at 200 °C hole mobility 0.85 cm 2 V -1 S -1 , electron mobility 0.029 cm 2 V ⁇ 1 S ⁇ 1 .
  • the electronic device including the organic semiconductor compound according to the embodiment of the present invention has high charge mobility.
  • the organic thin film transistor including the organic semiconductor compound according to the embodiment of the present invention exhibits higher charge mobility than the organic thin film transistor of the comparative example using Comparative Compound A without -F.
  • using the organic semiconductor compound according to an embodiment of the present invention dissolved in a non-halogen solvent it was possible to manufacture an electronic device having a high charge mobility environmentally friendly.

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Abstract

A novel organic semiconductor compound and an electronic device using the same are disclosed.

Description

유기 반도체 화합물 및 이를 이용한 전자 소자Organic semiconductor compound and electronic device using same
신규 유기 반도체 화합물 및 이를 이용한 전자 소자에 관한 것이다.The present invention relates to a novel organic semiconductor compound and an electronic device using the same.
본 출원은 2016년 10월 11일에 한국특허청에 제출된 한국 특허 출원 제10-2016-0131615호의 출원일의 이익을 주장하며, 그 내용 전부는 본 명세서에 포함된다.This application claims the benefit of the application date of Korean Patent Application No. 10-2016-0131615 filed with the Korea Intellectual Property Office on October 11, 2016, the entire contents of which are incorporated herein.
유기 반도체 화합물은 유연성, 경량성, 분자 구조 제어를 통한 광전자적 특성 제어의 용이성, 낮은 공정비용 등의 다양한 장점으로 인해 무기물 실리콘 반도체를 대체할 수 있는 소재로 인식되고 있다.Organic semiconductor compounds have been recognized as materials that can replace inorganic silicon semiconductors due to various advantages such as flexibility, light weight, ease of controlling photoelectric properties through molecular structure control, and low process cost.
이러한 유기 반도체 화합물은 광범위한 전자 소자에 사용될 수 있는데, 이러한 전자 소자의 성능은 여러 가지가 있으나, 그 중 중요한 평가 척도가 전하이동도이며, 전하이동도는 더 높을수록 바람직하다.Such an organic semiconductor compound can be used in a wide range of electronic devices, the performance of such electronic devices are many, but an important evaluation measure is the charge mobility, the higher the charge mobility is preferred.
전하이동도가 우수한 유기 반도체 화합물 및 이를 이용한 전자 소자를 제공하는 것이다. An organic semiconductor compound having excellent charge mobility and an electronic device using the same are provided.
일 측면에 따르면, 하기 화학식 1로 표시되는 유기 반도체 화합물이 제공된다:According to one aspect, an organic semiconductor compound represented by Formula 1 is provided:
<화학식 1><Formula 1>
Figure PCTKR2017009847-appb-I000001
Figure PCTKR2017009847-appb-I000001
상기 화학식 1 중,In Formula 1,
X1 및 X2는 서로 독립적으로, O, S 및 Se로부터 선택되고,X 1 and X 2 are each independently selected from O, S and Se,
R1 및 R2는 서로 독립적으로, 수소, 중수소(-D), 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C1-C60알킬티오기, -Si(Q1)(Q2)(Q3), -N(Q1)(Q2), -B(Q1)(Q2), -C(=O)(Q1), -OC(=O)(Q1), -C(=O)N(Q1)(Q2), -S(=O)2(Q1) 및 -P(=O)(Q1)(Q2) 중에서 선택되고,R 1 and R 2 are each independently hydrogen, deuterium (-D), hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2- C 60 alkenyl, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 alkylthio group, -Si (Q 1) (Q 2) (Q 3), -N (Q 1 ) (Q 2 ), -B (Q 1 ) (Q 2 ), -C (= O) (Q 1 ), -OC (= O) (Q 1 ), -C (= O) N (Q 1 ) (Q 2 ), -S (= O) 2 (Q 1 ), and -P (= O) (Q 1 ) (Q 2 ),
a는 1 내지 10의 정수 중에서 선택되고,a is selected from an integer of 1 to 10,
L은 치환 또는 비치환된 C5-C60카보시클릭 그룹 또는 치환 또는 비치환된 C1-C60헤테로시클릭 그룹이고,L is a substituted or unsubstituted C 5 -C 60 carbocyclic group or a substituted or unsubstituted C 1 -C 60 heterocyclic group,
b는 1 내지 30의 정수 중에서 선택되되, b가 2 이상일 경우, 2 이상의 L은 서로 동일하거나 상이할 수 있고,b is selected from an integer of 1 to 30, when b is 2 or more, two or more L may be the same or different from each other,
n은 5 내지 100,000의 정수 중에서 선택되고,n is selected from an integer of 5 to 100,000,
상기 치환된 C5-C60카보시클릭 그룹 또는 치환된 C1-C60헤테로시클릭 그룹의 치환기 중 적어도 하나는, 중수소, -F, -Cl, -Br, -I, 히드록실기, 옥소기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C1-C60알킬티오기, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C6-C60아릴옥시기, C6-C60아릴티오기, C1-C60헤테로아릴기, C1-C60헤테로아릴옥시기, C1-C60헤테로아릴티오기, 1가 비-방향족 축합다환 그룹, 1가 비-방향족 헤테로축합다환 그룹, -Si(Q11)(Q12)(Q13), -N(Q11)(Q12), -B(Q11)(Q12), -C(=O)(Q11), -OC(=O)(Q11), -C(=O)N(Q11)(Q12), -S(=O)2(Q11) 및 -P(=O)(Q11)(Q12) 중에서 선택되고,At least one of the substituents of the substituted C 5 -C 60 carbocyclic group or substituted C 1 -C 60 heterocyclic group is deuterium, -F, -Cl, -Br, -I, hydroxyl group, oxo Group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group , C 1 -C 60 alkylthio group, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocycloalkenyl group, C 6 -C Import 60 aryl group, C 6 -C 60 aryloxy, C 6 -C 60 aryl come T, C 1 -C 60 heteroaryl groups, C 1 -C 60 heteroaryloxy group, C 1 -C 60 heteroaryl T , Monovalent non-aromatic condensed polycyclic group, monovalent non-aromatic condensed polycyclic group, -Si (Q 11 ) (Q 12 ) (Q 13 ), -N (Q 11 ) (Q 12 ),-B (Q 11 ) (Q 12 ), -C (= O) (Q 11 ), -OC (= O) (Q 11 ), -C (= O) N (Q 11 ) (Q 12 ), -S (= O ) 2 (Q 11 ) and -P (= O) (Q 11 ) (Q 12 ),
상기 Q1 내지 Q3 및 Q11 내지 Q13은 서로 독립적으로, 수소, 중수소, -F, -Cl, -Br, -I, 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C1-C60알킬티오기, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C1-C60헤테로아릴기, 1가 비-방향족 축합다환 그룹 및 1가 비-방향족 헤테로축합다환 그룹 중에서 선택된다.Q 1 to Q 3 and Q 11 to Q 13 are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group , hydride tank group, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 come alkylthio, C 3 -C 10 Cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocycloalkenyl group, C 6 -C 60 aryl group, C 1 -C 60 heteroaryl group, monovalent Non-aromatic condensed polycyclic groups and monovalent non-aromatic condensed polycyclic groups.
다른 측면에 따르면, 상기 화학식 1로 표시되는 유기 반도체 화합물을 1종 이상 포함한 유기 반도체 막을 포함하는 전자 소자가 제공된다.According to another aspect, an electronic device including an organic semiconductor film including at least one organic semiconductor compound represented by Chemical Formula 1 is provided.
상기 유기 반도체 화합물을 포함한 전자 소자는 높은 전하이동도를 가질 수 있다. An electronic device including the organic semiconductor compound may have a high charge mobility.
도 1은 본 발명의 일 구현예에 따른 화합물 1의 UV-Vis 흡수 스펙트럼을 도시한다.1 shows UV-Vis absorption spectra of compound 1 according to one embodiment of the invention.
도 2는 본 발명의 일 구현예에 따른 화합물 1을 포함한 유기 반도체 막의 사이클릭 볼타메트리(cyclic voltammetry) 시험 결과를 나타낸 그래프이다.FIG. 2 is a graph showing cyclic voltammetry test results of an organic semiconductor film including Compound 1 according to an embodiment of the present invention.
도 3 및 도 4는 본 발명의 일 구현예에 따른 유기 박막 트랜지스터의 전류-전압(J-V) 곡선 그래프이다.3 and 4 are graphs of current-voltage (J-V) curves of an organic thin film transistor according to an exemplary embodiment of the present invention.
도 5는 본 발명의 일 비교예에 따른 유기 박막 트랜지스터의 전류-전압(J-V) 곡선 그래프이다.5 is a graph showing current-voltage (J-V) curves of an organic thin film transistor according to a comparative example of the present invention.
이하, 본 발명을 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 명세서 중 "포함하다" 또는 "가지다" 등의 용어는 명세서 상에 기재된 특징 또는 구성 요소가 존재함을 의미하는 것이고, 하나 이상의 다른 특징들 또는 구성 요소가 부가될 가능성을 미리 배제하는 것은 아니다.The term "comprise" or "having" in this specification means that there is a feature or component described in the specification and does not preclude the possibility of adding one or more other features or components.
본 명세서 중 C5-C60카보시클릭 그룹이란, 고리-형성 원자로서 탄소만을 포함한 탄소수 5 내지 60의 모노시클릭 또는 폴리시클릭 그룹을 의미한다. 상기 C5-C60카보시클릭 그룹은 방향족 카보시클릭 그룹 또는 비-방향족 카보시클릭 그룹일 수 있다. 상기 C5-C60카보시클릭 그룹은 벤젠과 같은 고리, 페닐기와 같은 1가 그룹 또는 페닐렌기와 같은 2가 그룹일 수 있다. 또는, 상기 C5-C60카보시클릭 그룹에 연결된 치환기에 개수에 따라, 상기 C5-C60카보시클릭 그룹은 3가 그룹 또는 4가 그룹일 수 있는 등 다양한 변형이 가능하다. As used herein, a C 5 -C 60 carbocyclic group means a monocyclic or polycyclic group having 5 to 60 carbon atoms including only carbon as a ring-forming atom. The C 5 -C 60 carbocyclic group can be an aromatic carbocyclic group or a non-aromatic carbocyclic group. The C 5 -C 60 carbocyclic group may be a ring such as benzene, a monovalent group such as a phenyl group, or a divalent group such as a phenylene group. Alternatively, it is the C 5 -C according to the number attached to the substituent at the 60 carbocyclic group, a C 5 -C 60 carbocyclic group during the various modifications can be made, such as in 3 or 4 is the group number of a group.
본 명세서 중 C1-C60헤테로시클릭 그룹이란, 상기 C5-C60카보시클릭 그룹과 동일한 구조를 갖되, 고리-형성 원자로서, 탄소(탄소수는 1 내지 60일 수 있음) 외에, N, O, Si, P, S, Se, Te 및 Ge 중에서 선택된 적어도 하나의 헤테로 원자를 포함한 그룹을 의미한다. As used herein, a C 1 -C 60 heterocyclic group has the same structure as the C 5 -C 60 carbocyclic group, and as a ring-forming atom, in addition to carbon (carbon number may be 1 to 60), N A group containing at least one hetero atom selected from among O, Si, P, S, Se, Te, and Ge.
본 명세서 중 1가 비-방향족 축합다환 그룹(non-aromatic condensed polycyclic group)은 2 이상의 고리가 서로 축합되어 있고, 고리 형성 원자로서 탄소만을 포함하고, 분자 전체가 비-방향족성(non-aromaticity)을 갖는 1가 그룹(예를 들면, 탄소수 8 내지 60을 가짐)을 의미한다. 상기 1가 비-방향족 축합다환 그룹의 구체예에는, 플루오레닐기 등이 포함된다.The monovalent non-aromatic condensed polycyclic group herein includes two or more rings condensed with each other, contains only carbon as a ring forming atom, and the entire molecule is non-aromatic. It means a monovalent group having (for example, having 8 to 60 carbon atoms). Specific examples of the monovalent non-aromatic condensed polycyclic group include fluorenyl groups and the like.
본 명세서 중 1가 비-방향족 헤테로축합다환 그룹(non-aromatic condensed heteropolycyclic group)은 2 이상의 고리가 서로 축합되어 있고, 고리 형성 원자로서 탄소 외에 N, O, Si, P, S, Se, Te 및 Ge 중에서 선택된 적어도 하나의 헤테로 원자를 포함하고, 분자 전체가 비-방향족성을 갖는 1가 그룹(예를 들면, 탄소수 1 내지 60을 가짐)을 의미한다. 상기 1가 비-방향족 헤테로축합다환 그룹의 구체예에는, 카바졸일기 등이 포함된다.In the present specification, a monovalent non-aromatic condensed heteropolycyclic group includes two or more rings condensed with each other, and in addition to carbon, N, O, Si, P, S, Se, Te and It means a monovalent group (eg, having 1 to 60 carbon atoms) containing at least one hetero atom selected from Ge, and the whole molecule is non-aromatic. Specific examples of the monovalent non-aromatic heterocondensed polycyclic group include carbazolyl groups and the like.
본 명세서 중 * 및 *'은, 다른 정의가 없는 한, 해당 화학식 중 이웃한 원자와의 결합 사이트를 의미한다.In the present specification, * and * 'means a binding site with a neighboring atom in the chemical formula, unless otherwise defined.
본 발명의 일 측면에 따르면, 상기 유기 반도체 화합물은 하기 화학식 1로 표시된다:According to an aspect of the present invention, the organic semiconductor compound is represented by the following Chemical Formula 1:
<화학식 1><Formula 1>
Figure PCTKR2017009847-appb-I000002
Figure PCTKR2017009847-appb-I000002
상기 화학식 1 중, X1 및 X2는 서로 독립적으로, O, S 및 Se로부터 선택될 수 있다. 예를 들어, 상기 X1 및 X2는 서로 독립적으로, O 또는 S일 수 있다. 일 구현예에 따르면, 상기 X1 및 X2는 모두 S일 수 있으나, 이에 한정되는 것은 아니다.In Formula 1, X 1 and X 2 may be independently selected from O, S, and Se. For example, X 1 and X 2 may be O or S independently of each other. According to one embodiment, X 1 and X 2 may both be S, but is not limited thereto.
상기 화학식 1 중, R1 및 R2는 서로 독립적으로, 수소, 중수소(-D), 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C1-C60알킬티오기, -Si(Q1)(Q2)(Q3), -N(Q1)(Q2), -B(Q1)(Q2), -C(=O)(Q1), -OC(=O)(Q1), -C(=O)N(Q1)(Q2), -S(=O)2(Q1) 및 -P(=O)(Q1)(Q2) 중에서 선택되고, 상기 Q1 내지 Q3은 서로 독립적으로, 수소, 중수소, -F, -Cl, -Br, -I, 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C1-C60알킬티오기, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C1-C60헤테로아릴기, 1가 비-방향족 축합다환 그룹 및 1가 비-방향족 헤테로축합다환 그룹 중에서 선택될 수 있다. 예를 들어, 상기 R1 및 R2는 서로 독립적으로, 수소, C1-C30알킬기, C2-C30알케닐기, C2-C30알키닐기, C1-C30알콕시기 및 C1-C30알킬티오기 중에서 선택될 수 있다. 일 구현예에 따르면, 상기 R1 및 R2는 서로 독립적으로, 모두 수소일 수 있으나, 이에 한정되는 것은 아니다.In Formula 1, R 1 and R 2 are each independently hydrogen, deuterium (-D), hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group import, C 1 -C 60 alkyl group, -Si (Q 1) (Q 2) (Q 3), -N (Q 1 ) (Q 2 ), -B (Q 1 ) (Q 2 ), -C (= O) (Q 1 ), -OC (= O) (Q 1 ), -C (= O) N (Q 1 ) (Q 2 ), —S (═O) 2 (Q 1 ) and —P (═O) (Q 1 ) (Q 2 ), wherein Q 1 to Q 3 are independently of each other , Hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 alkylthio, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocycloalkenyl group, C 6 -C 60 aryl group, C 1 -C 60 heteroaryl group, monovalent non-aromatic It may be selected from a condensed polycyclic group and a monovalent non-aromatic heterocondensed polycyclic group. For example, R 1 and R 2 are each independently hydrogen, C 1 -C 30 alkyl group, C 2 -C 30 alkenyl group, C 2 -C 30 alkynyl group, C 1 -C 30 alkoxy group and C 1 -C 30 alkylthio group. According to an embodiment, the R 1 and R 2 may be each independently hydrogen, but are not limited thereto.
상기 화학식 1 중, a는 1 내지 10의 정수 중에서 선택될 수 있다. 상기 a는 소괄호로 내에 기재된 그룹의 개수를 나타내는 것으로서, a가 2 이상일 경우, 2 이상의 상기 그룹은 서로 동일하거나 상이할 수 있다. 예를 들어, 상기 a는 1 내지 5의 정수 중에서 선택될 수 있다. 일 구현예에 따르면, 상기 a는 1일 수 있으나, 이에 한정되는 것은 아니다.In Formula 1, a may be selected from integers of 1 to 10. A denotes the number of groups described in parentheses. When a is 2 or more, two or more of the groups may be the same or different. For example, a may be selected from an integer of 1 to 5. According to one embodiment, the a may be 1, but is not limited thereto.
상기 화학식 1 중, L은 치환 또는 비치환된 C5-C60카보시클릭 그룹 또는 치환 또는 비치환된 C1-C60헤테로시클릭 그룹일 수 있고, 상기 치환된 C5-C60카보시클릭 그룹 또는 치환된 C1-C60헤테로시클릭 그룹의 치환기 중 적어도 하나는, 중수소, -F, -Cl, -Br, -I, 히드록실기, 옥소기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C1-C60알킬티오기, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C6-C60아릴옥시기, C6-C60아릴티오기, C1-C60헤테로아릴기, C1-C60헤테로아릴옥시기, C1-C60헤테로아릴티오기, 1가 비-방향족 축합다환 그룹, 1가 비-방향족 헤테로축합다환 그룹, -Si(Q11)(Q12)(Q13), -N(Q11)(Q12), -B(Q11)(Q12), -C(=O)(Q11), -OC(=O)(Q11), -C(=O)N(Q11)(Q12), -S(=O)2(Q11) 및 -P(=O)(Q11)(Q12) 중에서 선택되고, 상기 Q1 내지 Q3 및 Q11 내지 Q13은 서로 독립적으로, 수소, 중수소, -F, -Cl, -Br, -I, 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C1-C60알킬티오기, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C1-C60헤테로아릴기, 1가 비-방향족 축합다환 그룹 및 1가 비-방향족 헤테로축합다환 그룹 중에서 선택될 수 있다. 예를 들어, 상기 L은 하기 화학식 2-1 내지 2-35로 표시되는 그룹 중에서 선택될 수 있다:In Formula 1, L may be a substituted or unsubstituted C 5 -C 60 carbocyclic group or a substituted or unsubstituted C 1 -C 60 heterocyclic group, the substituted C 5 -C 60 carbosi At least one of the substituents of the click group or substituted C 1 -C 60 heterocyclic group is deuterium, -F, -Cl, -Br, -I, hydroxyl group, oxo group, cyano group, nitro group, amidino group, a hydrazino group import, Hydra tank group, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 alkyl group, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocycloalkenyl group, C 6 -C 60 aryl group, C 6 -C 60 aryl aryloxy, C 6 -C 60 arylthio, C 1 -C 60 heteroaryl groups, C 1 -C 60 heteroaryloxy group, C 1 -C 60 hetero arylthio group, a monovalent non-aromatic condensed polycyclic group, Monovalent non-aromatic heterocondensed polycyclic group, -Si (Q 11 ) (Q 12 ) (Q 13 ), -N (Q 11 ) (Q 12 ), -B (Q 11 ) (Q 12 ), -C (= O) (Q 11 ), -OC (= O) (Q 11 ) , -C (= 0) N (Q 11 ) (Q 12 ), -S (= 0) 2 (Q 11 ), and -P (= 0) (Q 11 ) (Q 12 ), wherein Q 1 To Q 3 and Q 11 to Q 13 independently of each other, hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazo group, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 alkylthio, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocycloalkenyl group, C 6 -C 60 aryl group, C 1 -C 60 heteroaryl group, monovalent non-aromatic It may be selected from condensed polycyclic groups and monovalent non-aromatic heterocondensed polycyclic groups. For example, L may be selected from the group represented by the following Chemical Formulas 2-1 to 2-35:
Figure PCTKR2017009847-appb-I000003
Figure PCTKR2017009847-appb-I000003
Figure PCTKR2017009847-appb-I000004
Figure PCTKR2017009847-appb-I000004
Figure PCTKR2017009847-appb-I000005
Figure PCTKR2017009847-appb-I000005
상기 화학식 2-1 내지 2-35 중,In Formulas 2-1 to 2-35,
Y1 내지 Y3는 서로 독립적으로, C(Z5)(Z6), O, S, Se, Te, N(Z5), Si(Z5)(Z6) 및 Ge(Z5)(Z6) 중에서 선택되고,Y 1 to Y 3 are independently of each other, C (Z 5 ) (Z 6 ), O, S, Se, Te, N (Z 5 ), Si (Z 5 ) (Z 6 ) and Ge (Z 5 ) ( Z 6 ),
Z1 내지 Z6은 서로 독립적으로, 수소, 중수소, -F, -Cl, -Br, -I, 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C30알킬기, C2-C30알케닐기, C2-C30알키닐기, C1-C30알콕시기, C1-C30알킬티오기, C6-C30아릴기, C1-C30헤테로아릴기, 1가 비-방향족 축합다환 그룹, 1가 비-방향족 헤테로축합다환 그룹, -Si(Q11)(Q12)(Q13), -N(Q11)(Q12), -B(Q11)(Q12), -C(=O)(Q11), -OC(=O)(Q11), -C(=O)N(Q11)(Q12), -S(=O)2(Q11) 및 -P(=O)(Q11)(Q12) 중에서 선택되고,Z 1 to Z 6 independently of each other, hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl group, C 1 -C 30 alkoxy group, C 1 -C 30 alkylthio, C 6 -C 30 aryl group, C 1 -C 30 heteroaryl group, monovalent non-aromatic condensed polycyclic group, monovalent non-aromatic condensed polycyclic group, -Si (Q 11 ) (Q 12 ) (Q 13 ), -N (Q 11 ) (Q 12 ), -B (Q 11 ) (Q 12 ), -C (= O) (Q 11 ), -OC (= O) (Q 11 ), -C (= O) N (Q 11 ) (Q 12 ),- S (= O) 2 (Q 11 ) and -P (= O) (Q 11 ) (Q 12 ),
상기 Q11 내지 Q13은 서로 독립적으로, 수소, C1-C30알킬기, C1-C30알콕시기, C1-C30알킬티오기, C6-C30아릴기 및 C1-C30헤테로아릴기 중에서 선택되고,Wherein Q 11 to Q 13 are independently of each other, hydrogen, C 1 -C 30 alkyl, C 1 -C 30 alkoxy group, C 1 -C 30 alkylthio, C 6 -C 30 aryl group and C 1 -C 30 Selected from heteroaryl groups,
d3은 1 내지 3의 정수 중에서 선택되고,d3 is selected from an integer of 1 to 3,
d4는 1 내지 4의 정수 중에서 선택되고,d4 is selected from an integer of 1 to 4,
* 및 *'은 이웃한 원자와의 결합 사이트이다.* And * 'are binding sites with neighboring atoms.
일 구현예에 따르면, 상기 L은 하기 화학식 3-1 내지 3-19로 표시되는 그룹 중에서 선택될 수 있다:According to one embodiment, L may be selected from the group represented by the following formulas 3-1 to 3-19:
Figure PCTKR2017009847-appb-I000006
Figure PCTKR2017009847-appb-I000006
Figure PCTKR2017009847-appb-I000007
Figure PCTKR2017009847-appb-I000007
상기 화학식 3-1 내지 3-19 중,In Formulas 3-1 to 3-19,
Z31 내지 Z34는 서로 독립적으로, 수소, C1-C30알킬기, C1-C30알콕시기 및 C1-C30알킬티오기 중에서 선택되고,Z 31 to Z 34 are each independently selected from hydrogen, a C 1 -C 30 alkyl group, a C 1 -C 30 alkoxy group and a C 1 -C 30 alkylthio group,
e3은 1 내지 3의 정수 중에서 선택되고,e3 is selected from an integer of 1 to 3,
e4는 1 내지 4의 정수 중에서 선택되고,e4 is selected from an integer of 1 to 4,
* 및 *'은 이웃한 원자와의 결합 사이트이다.* And * 'are binding sites with neighboring atoms.
다른 구현예에 따르면, 상기 L은 하기 화학식 4-1 또는 4-2로 표시되는 그룹일 수 있으나, 이에 한정되는 것은 아니다:According to another embodiment, L may be a group represented by Formula 4-1 or 4-2, but is not limited thereto.
Figure PCTKR2017009847-appb-I000008
Figure PCTKR2017009847-appb-I000008
상기 화학식 4-1 및 4-2 중,In Formulas 4-1 and 4-2,
Z51 및 Z52는 서로 독립적으로, 수소 또는 C1-C30알킬기이고,Z 51 and Z 52 are, independently from each other, hydrogen or a C 1 -C 30 alkyl group,
* 및 *'은 이웃한 원자와의 결합 사이트이다.* And * 'are binding sites with neighboring atoms.
상기 화학식 1 중, b는 1 내지 30의 정수 중에서 선택될 수 있다. 상기 b는 L의 개수를 나타낸 것으로, b가 2 이상일 경우, 2 이상의 L은 서로 동일하거나 상이할 수 있다. 예를 들어, 상기 b는 1 내지 10의 정수 중에서 선택될 수 있다. 또 다른 예를 들면, 상기 b는 1 내지 5의 정수 중에서 선택될 수 있다. 일 구현예에 따르면, 상기 b는 1 또는 3일 수 있으나, 이에 한정되는 것은 아니다.In Formula 1, b may be selected from an integer of 1 to 30. B represents the number of L, and when b is 2 or more, two or more L may be the same or different from each other. For example, b may be selected from an integer of 1 to 10. As another example, b may be selected from an integer of 1 to 5. According to one embodiment, the b may be 1 or 3, but is not limited thereto.
상기 화학식 1 중, n은 5 내지 100,000의 정수 중에서 선택될 수 있다. 상기 n은 대괄호로 내에 기재된 그룹의 개수를 나타내는 것으로서, 상기 대괄호로 내에 기재된 그룹은 서로 동일하거나 상이할 수 있다. 예를 들어, 상기 n은 10 내지 10,000의 정수 중에서 선택될 수 있다. 일 구현예에 따르면, 상기 n은 20 내지 1,000의 정수 중에서 선택될 수 있으나, 이에 한정되는 것은 아니다.In Formula 1, n may be selected from an integer of 5 to 100,000. N denotes the number of groups described in brackets, and the groups described in brackets may be the same or different from each other. For example, n may be selected from an integer of 10 to 10,000. According to one embodiment, n may be selected from an integer of 20 to 1,000, but is not limited thereto.
일 구현예에 따르면, 상기 유기 반도체 화합물은 하기 화학식 1A로 표시될 수 있다:According to an embodiment, the organic semiconductor compound may be represented by the following Chemical Formula 1A:
<화학식 1A><Formula 1A>
Figure PCTKR2017009847-appb-I000009
Figure PCTKR2017009847-appb-I000009
상기 화학식 1A 중, X1, X2, R1, R2, a, L, b 및 n에 대한 설명은 본 명세서에 기재된 바를 참조한다.In Formula 1A, description of X 1 , X 2 , R 1 , R 2 , a, L, b, and n may be referred to herein.
또 다른 구현예에 따르면, 상기 유기 반도체 화합물은 하기 화학식 1-A로 표시될 수 있다:According to another embodiment, the organic semiconductor compound may be represented by the following Chemical Formula 1-A:
<화학식 1-A><Formula 1-A>
Figure PCTKR2017009847-appb-I000010
Figure PCTKR2017009847-appb-I000010
상기 화학식 1-A 중, In Formula 1-A,
X1, X2, R1, R2, a 및 n에 대한 설명은 본 명세서에 기재된 바를 참조하고,For descriptions of X 1 , X 2 , R 1 , R 2 , a and n, refer to what is described herein,
b1 내지 b3는 0 이상의 정수이되, b1 내지 b3의 합은 1 내지 30이고, b 1 to b 3 is an integer of 0 or more, the sum of b 1 to b 3 is 1 to 30,
Y1 내지 Y4는 서로 독립적으로, O, S, Se 및 N(Z5) 중에서 선택되고,Y 1 to Y 4 are each independently selected from O, S, Se, and N (Z 5 ),
Z1 내지 Z5는 서로 독립적으로, 수소, C1-C30알킬기, C2-C30알케닐기, C2-C30알키닐기, C1-C30알콕시기, C1-C30알킬티오기, C6-C30아릴기, C1-C30헤테로아릴기, 1가 비-방향족 축합다환 그룹 및 1가 비-방향족 헤테로축합다환 그룹 중에서 선택된다. 예를 들어, 상기 화학식 1-A 중, X1 및 X2는 각각 S이고, R1 및 R2는 각각 수소이고, a는 1이고, b1, b2 및 b3는 각각 1일 수 있다. 또는, X1 및 X2는 각각 S이고, R1 및 R2는 각각 수소이고, a는 1이고, b1, b2 및 b3는 각각 1이고, Y1 및 Y2는 각각 N(Z5) (여기서, Z5는 C1-C30알킬기임) 이고, Y3 및 Y4는 각각 S이고, Z1 내지 Z4는 수소일 수 있다.Z 1 to Z 5 are independently of each other hydrogen, a C 1 -C 30 alkyl group, a C 2 -C 30 alkenyl group, a C 2 -C 30 alkynyl group, a C 1 -C 30 alkoxy group, a C 1 -C 30 alkylti Group, a C 6 -C 30 aryl group, a C 1 -C 30 heteroaryl group, a monovalent non-aromatic condensed polycyclic group and a monovalent non-aromatic condensed polycyclic group. For example, in Formula 1-A, X 1 and X 2 may each be S, R 1 and R 2 may each be hydrogen, a may be 1, and b 1 , b 2, and b 3 may be 1, respectively. . Or X 1 and X 2 are each S, R 1 and R 2 are each hydrogen, a is 1, b 1 , b 2 and b 3 are each 1, and Y 1 and Y 2 are each N (Z 5 ), wherein Z 5 is a C 1 -C 30 alkyl group, Y 3 and Y 4 are each S, and Z 1 to Z 4 may be hydrogen.
상기 유기 반도체 화합물은 하기 화합물 1일 수 있으나, 이에 한정되는 것은 아니다:The organic semiconductor compound may be Compound 1, but is not limited thereto.
<화합물 1><Compound 1>
Figure PCTKR2017009847-appb-I000011
Figure PCTKR2017009847-appb-I000011
상기 화합물 1 중, n은 5 내지 100,000의 정수 중에서 선택된다.In the compound 1, n is selected from an integer of 5 to 100,000.
일 구현예에 따르면, 상기 유기 반도체 화합물은 5,000 g/mol 내지 100,000,000 g/mol의 수평균 분자량(number average molecular weight: Mn)을 가질 수 있다. 예를 들어, 상기 유기 반도체 화합물은 10,000 g/mol 내지 10,000,000 g/mol의 수평균 분자량을 가질 수 있다. 일 구현예에 따르면, 상기 유기 반도체 화합물은 20,000 g/mol 내지 1,000,000 g/mol의 수평균 분자량을 가질 수 있다. 또 다른 구현예에 따르면, 상기 유기 반도체 화합물은 25,000 g/mol 내지 100,000 g/mol의 수평균 분자량을 가질 수 있으나, 이에 한정되는 것은 아니다.According to one embodiment, the organic semiconductor compound may have a number average molecular weight (Mn) of 5,000 g / mol to 100,000,000 g / mol. For example, the organic semiconductor compound may have a number average molecular weight of 10,000 g / mol to 10,000,000 g / mol. According to one embodiment, the organic semiconductor compound may have a number average molecular weight of 20,000 g / mol to 1,000,000 g / mol. According to another embodiment, the organic semiconductor compound may have a number average molecular weight of 25,000 g / mol to 100,000 g / mol, but is not limited thereto.
일 구현예에 따르면, 상기 유기 반도체 화합물은 1 내지 10의 분자량 분포(polydispersity: PDI)를 가질 수 있다. 예를 들어, 유기 반도체 화합물은 1 내지 3의 분자량 분포를 가질 수 있으나, 이에 한정되는 것은 아니다.According to one embodiment, the organic semiconductor compound may have a molecular weight distribution (polydispersity (PDI) of 1 to 10). For example, the organic semiconductor compound may have a molecular weight distribution of 1 to 3, but is not limited thereto.
상기 화학식 1로 표시되는 유기 반도체 화합물은 분자 내의 X1과 F 사이 및 X2와 F 사이의 상호작용(intramolecular interaction)(하기 화학식 1' 참조)을 통하여 화합물의 평면성(planarity)을 증가시킬 수 있고, 이는 상기 유기 반도체 화합물들 사이의 거리를 좁혀, 상기 유기 반도체 화합물을 포함한 전자 소자의 전하이동도를 향상시킬 수 있다.The organic semiconductor compound represented by Chemical Formula 1 may increase the planarity of the compound through an intramolecular interaction (see Chemical Formula 1 ′) between X 1 and F and X 2 and F in the molecule. This may narrow the distance between the organic semiconductor compounds and improve the charge mobility of the electronic device including the organic semiconductor compound.
<화학식 1'> <Formula 1 '>
Figure PCTKR2017009847-appb-I000012
Figure PCTKR2017009847-appb-I000012
또한, 상기 유기 반도체 화합물은 분자 내 -F를 포함함으로써, 상기 유기 반도체 화합물에 극성을 유도하여, 분자간 상호작용(interchain interaction)을 증가시킬 수 있다. 또한, 상기 유기 반도체 화합물들 사이의 X1와 F 사이 및 X2와 F 사이의 분자간 상호작용에 의하여, 상기 유기 반도체 화합물들 사이의 거리를 좁혀, 상기 유기 반도체 화합물을 포함한 전자 소자의 전하이동도를 향상시킬 수 있다.In addition, the organic semiconductor compound may include -F in the molecule, thereby inducing polarity in the organic semiconductor compound, thereby increasing interchain interaction. In addition, by the intermolecular interaction between X 1 and F and the X 2 and F between the organic semiconductor compounds, the distance between the organic semiconductor compounds is narrowed, and thus the charge mobility of the electronic device including the organic semiconductor compound is reduced. Can improve.
따라서, 상기 화학식 1로 표시되는 유기 반도체 화합물을 채용한 전자 소자, 예를 들어 유기 박막 트랜지스터는 높은 전하이동도를 가질 수 있다.Therefore, an electronic device employing the organic semiconductor compound represented by Formula 1, for example, an organic thin film transistor, may have high charge mobility.
상기 화학식 1로 표시되는 유기 반도체 화합물의 합성 방법은 후술하는 실시예를 참조하여 당업자가 인식할 수 있다.The synthesis method of the organic semiconductor compound represented by Chemical Formula 1 may be recognized by those skilled in the art with reference to the following examples.
본 발명의 다른 측면에 따르면, 상기 화학식 1로 표시되는 유기 반도체 화합물을 1종 이상 포함한 유기 반도체 막이 제공된다.According to another aspect of the present invention, an organic semiconductor film including at least one organic semiconductor compound represented by Chemical Formula 1 is provided.
상기 유기 반도체 화합물을 1종 이상 포함한 유기 반도체 막은 n-형 유기 반도체 막, p-형 유기 반도체 막 및 양극성 유기 반도체 막 중 어느 하나일 수 있다. 일 구현예에 따르면, 상기 유기 반도체 막은 p-형 유기 반도체 막 또는 양극성 유기 반도체 막일 수 있다.The organic semiconductor film including at least one organic semiconductor compound may be any one of an n-type organic semiconductor film, a p-type organic semiconductor film, and a bipolar organic semiconductor film. According to an embodiment, the organic semiconductor film may be a p-type organic semiconductor film or a bipolar organic semiconductor film.
상기 유기 반도체 막의 제조 방법은 특별히 한정되지 않으나, 예를 들어 1종 이상의 상기 유기 반도체 화합물을 증착하거나, 또는 용액 공정으로 코팅함으로써 형성할 수 있다. 예를 들어, 상기 유기 반도체 막은 열 증착, 진공 증착, 레이저 증착, 스크린 인쇄, 프린팅, 임프린팅(imprinting), 스핀 코팅, 딥핑(dipping), 잉크젯팅, 드롭 캐스팅, 스프레이 코팅 등을 사용하여 제조될 수 있다. 선택적으로, 상기 증착 또는 코팅 후에 열처리 단계를 더 포함할 수 있으며, 이를 통해 상기 유기 반도체 막의 치밀성 및 균일성을 보다 향상시킬 수 있다. 상기 열처리 단계는 당해 분야의 통상의 기술자(이하, '당업자'라 함)가 사용된 유기 반도체 화합물 및 용매 등을 고려하여 적절히 선택할 수 있으며, 예를 들어 60℃ 내지 300℃에서 1분 내지 2시간 동안 수행될 수 있다.Although the manufacturing method of the said organic semiconductor film is not specifically limited, For example, it can form by depositing 1 or more types of said organic semiconductor compounds, or coating by a solution process. For example, the organic semiconductor film may be manufactured using thermal deposition, vacuum deposition, laser deposition, screen printing, printing, imprinting, spin coating, dipping, inkjetting, drop casting, spray coating, or the like. Can be. Optionally, the method may further include a heat treatment step after the deposition or coating, thereby further improving the compactness and uniformity of the organic semiconductor film. The heat treatment step may be appropriately selected in consideration of an organic semiconductor compound, a solvent, and the like used by a person skilled in the art (hereinafter, referred to as 'an expert'), for example, 1 minute to 2 hours at 60 ° C to 300 ° C. May be performed.
용액 공정을 통해 상기 유기 반도체 막을 제조하는 경우, 사용될 수 있는 용매로는 통상의 유기 용매를 1종 이상 사용할 수 있으며, 예를 들어 클로로포름, 클로로벤젠, 디클로로벤젠, 톨루엔, 자일렌, 1,2,4-트리메틸벤젠, 테트랄린 등을 사용할 수 있다. 특히, 상기 유기 반도체 막은 내부식성 및 인체유해성이 높은 할로겐 용매가 아닌, 상대적으로 친환경 특성을 갖는 용매인 비할로겐성 용매(즉, 분자 내에 할로겐기를 포함하지 않는 용매), 예를 들어 톨루엔, 자일렌, 1,2,4-트리메틸벤젠, 테트랄린 등을 사용하여 제조될 수 있는데, 이때에도 여전히 높은 전하이동도를 얻을 수 있는 장점을 갖는다.When the organic semiconductor film is prepared through a solution process, one or more conventional organic solvents may be used as the solvent, and for example, chloroform, chlorobenzene, dichlorobenzene, toluene, xylene, 1,2, 4-trimethylbenzene, tetralin and the like can be used. In particular, the organic semiconductor film is a non-halogen solvent (i.e., a solvent which does not contain a halogen group in the molecule), which is a solvent having relatively environmentally friendly properties, not a halogen solvent having high corrosion resistance and human toxicity, such as toluene, xylene , 1,2,4-trimethylbenzene, tetralin and the like can be prepared, but still has the advantage of obtaining a high charge mobility.
따라서, 본 발명의 또 다른 측면에 따르면, 상기 화학식 1로 표시되는 1종 이상의 유기 반도체 화합물을 제공하는 단계; 상기 유기 반도체 화합물을 비할로겐성 용매 중에 용해시켜 유기 반도체 화합물 용액을 제조하는 단계; 상기 유기 반도체 화합물 용액을 기재 상에 증착 또는 코팅하여 유기 반도체 막을 제조하는 단계; 및 선택적으로 상기 기재를 제거하는 단계;를 포함한 유기 반도체 박막의 제조 방법이 제공된다. Thus, according to another aspect of the invention, providing at least one organic semiconductor compound represented by Formula 1; Dissolving the organic semiconductor compound in a non-halogenous solvent to prepare an organic semiconductor compound solution; Preparing an organic semiconductor film by depositing or coating the organic semiconductor compound solution on a substrate; And optionally removing the substrate. A method of manufacturing an organic semiconductor thin film is provided.
상기 비할로겐성 용매는, 예를 들어 할로겐기를 포함하지 않는 치환 또는 비치환된 지방족 탄화수소 용매; 할로겐기를 포함하지 않는 치환 또는 비치환된 방향족 탄화수소 용매; 할로겐기를 포함하지 않는 치환 또는 비치환된 케톤계 용매; 할로겐기를 포함하지 않는 치환 또는 비치환된 에테르계 용매; 할로겐기를 포함하지 않는 치환 또는 비치환된 아세테이트계 용매; 할로겐기를 포함하지 않는 치환 또는 비치환된 알코올계 용매; 할로겐기를 포함하지 않는 치환 또는 비치환된 아미드계 용매; 할로겐기를 포함하지 않는 치환 또는 비치환된 실리콘계 용매; 및 상기 용매들의 조합에서 선택될 수 있고, The non-halogenous solvent may include, for example, a substituted or unsubstituted aliphatic hydrocarbon solvent containing no halogen group; Substituted or unsubstituted aromatic hydrocarbon solvent containing no halogen group; Substituted or unsubstituted ketone solvent containing no halogen group; Substituted or unsubstituted ether solvent containing no halogen group; Substituted or unsubstituted acetate solvent containing no halogen group; Substituted or unsubstituted alcohol solvent containing no halogen group; Substituted or unsubstituted amide solvent containing no halogen group; Substituted or unsubstituted silicone solvent containing no halogen group; And combinations of the above solvents,
상기 할로겐기를 포함하지 않는 치환된 지방족 탄화수소 용매; 할로겐기를 포함하지 않는 치환된 방향족 탄화수소 용매; 할로겐기를 포함하지 않는 치환된 케톤계 용매; 할로겐기를 포함하지 않는 치환된 에테르계 용매; 할로겐기를 포함하지 않는 치환된 아세테이트계 용매; 할로겐기를 포함하지 않는 치환된 알코올계 용매; 할로겐기를 포함하지 않는 치환된 아미드계 용매; 할로겐기를 포함하지 않는 치환된 실리콘계 용매의 치환기 중 하나는, 예를 들어 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C1-C60알킬티오기, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C6-C60아릴옥시기, C6-C60아릴티오기, C1-C60헤테로아릴기, C1-C60헤테로아릴옥시기, C1-C60헤테로아릴티오기, 1가 비-방향족 축합다환 그룹, 1가 비-방향족 헤테로축합다환 그룹, Si(Q1)(Q2)(Q3), -N(Q1)(Q2), -B(Q1)(Q2), -C(=O)(Q1), -OC(=O)(Q1), -C(=O)N(Q1)(Q2), -S(=O)2(Q1) 및 -P(=O)(Q1)(Q2) 중에서 선택되고,A substituted aliphatic hydrocarbon solvent not containing the halogen group; Substituted aromatic hydrocarbon solvents containing no halogen groups; Substituted ketone solvents containing no halogen group; Substituted ether solvents containing no halogen groups; Substituted acetate solvents that do not contain halogen groups; Substituted alcohol solvent which does not contain a halogen group; Substituted amide solvents not including a halogen group; One of the substituents of the substituted silicone solvent that does not contain a halogen group is, for example, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C 1 -C 60 alkyl group, C 2- C 60 alkenyl, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 come alkylthio, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 - C 10 cycloalkenyl group, C 1 -C 10 heteroaryl cycloalkenyl group, C 6 -C 60 aryl group, C 6 -C 60 aryloxy, C 6 -C 60 arylthio, C 1 -C 60 heteroaryl group, , C 1 -C 60 heteroaryloxy group, C 1 -C 60 heteroarylthio group, monovalent non-aromatic condensed polycyclic group, monovalent non-aromatic condensed polycyclic group, Si (Q 1 ) (Q 2 ) ( Q 3 ), -N (Q 1 ) (Q 2 ), -B (Q 1 ) (Q 2 ), -C (= O) (Q 1 ), -OC (= O) (Q 1 ), -C (= O) N (Q 1 ) (Q 2 ), -S (= O) 2 (Q 1 ), and -P (= O) (Q 1 ) (Q 2 ),
상기 Q1 내지 Q3은 서로 독립적으로, 수소, 중수소, 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C1-C60알킬티오기, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C1-C60헤테로아릴기, 1가 비-방향족 축합다환 그룹 및 1가 비-방향족 헤테로축합다환 그룹 중에서 선택될 수 있으나, 이에 한정되는 것은 아니다. 예를 들어, 상기 비할로겐성 용매는 헥산, 헵탄 등의 지방족 탄화수소 용매; 톨루엔, 피리딘, 퀴놀린, 아니솔, 트리메틸벤젠, 자일렌, 테트랄린 등의 방향족계 탄화수소 용매; 메틸 이소부틸 케톤, 1-메틸-2-피롤리디논, 시클로헥산온, 아세톤 등의 케톤계 용매; 테트라하이드로퓨란, 이소프로필 에테르 등의 에테르계 용매; 에틸 아세테이트, 부틸 아세테이트, 프로필렌 글리콜 메틸 에테르 아세테이트 등의 아세테이트계 용매; 이소프로필 알코올, 부틸 알코올 등의 알코올계 용매; 디메틸아세티아미드, 디메틸포름아마이드 등의 아미드계 용매; 실리콘계 용매; 및 상기 용매들의 조합에서 선택되는 1종 이상을 사용할 수 있다. 일 구현예에 따르면, 상기 비할로겐성 용매는 톨루엔, 자일렌, 트리메틸벤젠, 및 이들의 조합 등의 방향족계 탄화수소 용매일 수 있으나, 이에 한정되는 것은 아니다.Q 1 to Q 3 are independently of each other, hydrogen, deuterium, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2 -C 60 alke group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 come alkylthio, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkyl Selected from alkenyl groups, C 1 -C 10 heterocycloalkenyl groups, C 6 -C 60 aryl groups, C 1 -C 60 heteroaryl groups, monovalent non-aromatic condensed polycyclic groups and monovalent non-aromatic condensed polycyclic groups It may be, but is not limited thereto. For example, the non-halogenous solvent may be an aliphatic hydrocarbon solvent such as hexane or heptane; Aromatic hydrocarbon solvents such as toluene, pyridine, quinoline, anisole, trimethylbenzene, xylene and tetralin; Ketone solvents such as methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, cyclohexanone and acetone; Ether solvents such as tetrahydrofuran and isopropyl ether; Acetate solvents such as ethyl acetate, butyl acetate and propylene glycol methyl ether acetate; Alcohol solvents such as isopropyl alcohol and butyl alcohol; Amide solvents such as dimethylacetiamide and dimethylformamide; Silicone solvents; And one or more selected from a combination of the above solvents. According to one embodiment, the non-halogenous solvent may be an aromatic hydrocarbon solvent such as toluene, xylene, trimethylbenzene, and combinations thereof, but is not limited thereto.
상기 용매 중에 용해되는 유기 반도체 화합물의 함량은 당업자가 용해도 및 코팅성을 고려하여 적절히 선택할 수 있다.The content of the organic semiconductor compound dissolved in the solvent may be appropriately selected by those skilled in the art in consideration of solubility and coating property.
상기 유기 반도체 막의 두께는 당업자가 사용된 유기 반도체 화합물의 종류 및 상기 막의 용도를 고려하여 적절히 선택할 수 있으며, 예를 들어 수 nm 내지 수백 μm의 두께일 수 있다.The thickness of the organic semiconductor film may be appropriately selected in consideration of the type of organic semiconductor compound used by those skilled in the art and the use of the film, and may be, for example, a thickness of several nm to several hundred μm.
본 발명의 또 다른 측면에 따르면, 상기 유기 반도체 화합물을 1종 이상 포함한 유기 반도체 막을 포함하는 전자 소자가 제공된다.According to another aspect of the invention, there is provided an electronic device comprising an organic semiconductor film containing at least one organic semiconductor compound.
상기 유기 반도체 막을 포함하는 전자 소자는, 예를 들어 유기 박막 트랜지스터(organic thin-film transistor: OTFT), 유기 발광 다이오드(organic light emitting diode: OLED), 유기 태양 전지(organic solar cell: OSC) 및 유기 광 센서(organic photo sensor: OPD) 중 어느 하나일 수 있다.The electronic device including the organic semiconductor film may include, for example, an organic thin-film transistor (OTFT), an organic light emitting diode (OLED), an organic solar cell (OSC), and an organic device. It may be any one of an organic photo sensor (OPD).
일 구현예에 따르면, 상기 유기 반도체 막을 포함하는 전자 소자는 유기 박막 트랜지스터일 수 있다. 예를 들어 바텀-게이트/바텀-컨택(bottom-gate/bottom-contact: BGBC) 구조를 갖는 유기 박막 트랜지스터인 경우, 이러한 유기 박막 트랜지스터는 기판; 상기 기판의 소정 영역 상에 배치된 게이트 전극; 상기 게이트 전극 상에 배치된 게이트 절연체; 상기 절연체 상에 배치된, 상기 화학식 1로 표시되는 유기 반도체 화합물을 1종 이상 포함한 유기 반도체 막; 상기 유기 반도체 막 상에 각각 배치된 소스 전극 및 드레인 전극;을 포함할 수 있다. 또는, 예를 들어 탑-게이트/바텀-컨택(top-gate/bottom-contact: TGBC) 구조를 갖는 유기 박막 트랜지스터인 경우, 이러한 유기 박막 트랜지스터는 기판; 상기 기판의 소정 영역 상에 각각 배이된 소스 전극 및 드레인 전극; 상기 소스 전극 및 드레인 전극 상에 각각 배치된, 상기 화학식 1로 표시되는 유기 반도체 화합물을 1종 이상 포함한 유기 반도체 막; 상기 유기 반도체 막 상에 배치된 게이트 절연체; 및 상기 게이트 절연체 상에 배치된 게이트 전극;을 포함할 수 있다. 상기 화학식 1로 표시되는 유기 반도체 화합물을 1종 이상 포함한 유기 반도체 막은 n-형 유기 반도체 막, p-형 유기 반도체 막 및 양극성 유기 반도체 막 중 어느 하나일 수 있다.According to an embodiment, the electronic device including the organic semiconductor film may be an organic thin film transistor. For example, in the case of an organic thin film transistor having a bottom-gate / bottom-contact (BGBC) structure, the organic thin film transistor includes a substrate; A gate electrode disposed on a predetermined region of the substrate; A gate insulator disposed on the gate electrode; An organic semiconductor film including at least one organic semiconductor compound represented by Formula 1 disposed on the insulator; And a source electrode and a drain electrode respectively disposed on the organic semiconductor film. Or, for example, in the case of an organic thin film transistor having a top-gate / bottom-contact (TGBC) structure, the organic thin film transistor includes a substrate; Source and drain electrodes doubled on predetermined regions of the substrate; An organic semiconductor film including at least one organic semiconductor compound represented by Chemical Formula 1, respectively disposed on the source electrode and the drain electrode; A gate insulator disposed on the organic semiconductor film; And a gate electrode disposed on the gate insulator. The organic semiconductor film including at least one organic semiconductor compound represented by Formula 1 may be any one of an n-type organic semiconductor film, a p-type organic semiconductor film, and a bipolar organic semiconductor film.
이하에서, 합성예 및 실시예를 들어 본 발명의 일 구현예를 따르는 화합물 및 전자 소자 중 하나인 유기 박막 트랜지스터에 대하여 보다 구체적으로 설명한다. 하기 합성예 및 실시예 중 "A 대신 B를 사용하였다"란 표현 중 A의 몰당량과 B의 몰당량은 서로 동일하다.Hereinafter, an organic thin film transistor, which is one of a compound and an electronic device, according to one embodiment of the present invention will be described in more detail with reference to Synthesis Examples and Examples. The molar equivalents of A and the molar equivalents of B are identical to each other in the following expressions "B was used instead of A" in Synthesis Examples and Examples.
[실시예]EXAMPLE
합성예: 화합물 1의 합성Synthesis Example: Synthesis of Compound 1
<반응식><Scheme>
Figure PCTKR2017009847-appb-I000013
Figure PCTKR2017009847-appb-I000013
3,6-비스(5-브로모티오펜-2-일)-2,5-비스(2-옥틸도데실)피롤로[3,4-c]피롤-1,4(2H,5H)-디온 (300 mg, 0.265 mmol),(3,3'-디플루오로-[2,2'-비티오펜]-5,5'-디일)비스(트리메틸스탄난) (139.9 mg, 0.265 mmol), 테트라키스(트리페닐포스핀)팔라듐 (12.2 mg, 0.0106 mmol)을 DMF (1 mL) 및 톨루엔 (5 mL)에 녹였다. 상기 용액을 2℃/10 min의 속도로 60℃에서 90℃까지 승온하면서 교반하였다. 90℃에서 23분간 교반한 후, 온도를 상온으로 낮추었다. 상온으로 식은 상기 용액을 클로로포름으로 묽힌 후, 메탄올에 한방울씩 떨어뜨려 침전시켰다. 침전된 화합물을 팀블 튜브(thimble tube)에 거른 뒤, 메탄올, 아세톤, 헥산, 디클로로메탄, 클로로포름의 순으로 속슬렛 추출법(soxhlet)으로 추출하여 정제하였다. 클로로포름에 녹아 나온 상기 화합물을 일부 용매만을 남기고 제거한 뒤, 다시 메탄올에 침전시키고 거른 뒤, 상온에서 진공 건조하여 화합물 1을 얻었다. 수율: 260.9 mg, 83.8%, GPC: Mn = 43 kg/mol, PDI = 2.1.3,6-bis (5-bromothiophen-2-yl) -2,5-bis (2-octyldodecyl) pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione (300 mg, 0.265 mmol), (3,3'-difluoro- [2,2'-bithiophene] -5,5'-diyl) bis (trimethylstannan) (139.9 mg, 0.265 mmol), tetra Kis (triphenylphosphine) palladium (12.2 mg, 0.0106 mmol) was dissolved in DMF (1 mL) and toluene (5 mL). The solution was stirred while raising the temperature from 60 ° C to 90 ° C at a rate of 2 ° C / 10 min. After stirring at 90 ° C. for 23 minutes, the temperature was lowered to room temperature. The solution cooled to room temperature was diluted with chloroform, and then dropped by dropping into methanol to precipitate. The precipitated compound was filtered through a thimble tube and extracted by soxhlet extraction in the order of methanol, acetone, hexane, dichloromethane and chloroform. The compound dissolved in chloroform was removed leaving only some solvent, precipitated again in methanol, filtered, and dried in vacuo at room temperature to obtain compound 1. Yield: 260.9 mg, 83.8%, GPC: Mn = 43 kg / mol, PDI = 2.1.
실시예 1: 유기 박막 트랜지스터의 제조Example 1 Fabrication of Organic Thin Film Transistor
300 nm 두께의 산화규소층이 열적으로 성장된 고도핑 n-타입 실리콘 웨이퍼를 100℃의 피라나 용액으로 세척한 뒤, 증류수로 세척하였다. 이후, 옥타데실트리클로로실란(octadecyltrichlorosilane: ODTS)(Gelest, Inc.)으로 상기 산화규소층을 패시베이션(passivation)하였다. 그 위에, 상기 화합물 1 (5 mg)을 o-자일렌 (1 mL)에 녹여 얻은 용액을 1000 rpm의 속도로 35초간 스핀코팅한 후, 25℃의 온도에서 30분간 건조시켜, 0.050 μm 두께의 유기 반도체 막을 형성하였다. 상기 유기 반도체 박막 위에 마스크를 사용하여 금을 증착시킴으로써 소스 전극 및 드레인 전극을 형성하여, 바텀-게이트/바텀-컨택(BGBC) 구조를 갖는 유기 박막 트랜지스터를 제조하였다. 상기 유기 박막 트랜지스터의 채널 길이는 100 μm였고, 채널 폭은 800 μm로 하였다.The highly doped n-type silicon wafer, on which a 300 nm thick silicon oxide layer was thermally grown, was washed with 100 ° C. of Pirana solution and then with distilled water. Subsequently, the silicon oxide layer was passivated with octadecyltrichlorosilane (ODTS) (Gelest, Inc.). The solution obtained by dissolving the compound 1 (5 mg) in o-xylene (1 mL) was spin-coated at a speed of 1000 rpm for 35 seconds, and then dried at a temperature of 25 ° C. for 30 minutes, to a thickness of 0.050 μm. An organic semiconductor film was formed. A source electrode and a drain electrode were formed by depositing gold on the organic semiconductor thin film using a mask, thereby manufacturing an organic thin film transistor having a bottom-gate / bottom-contact (BGBC) structure. The channel length of the organic thin film transistor was 100 μm and the channel width was 800 μm.
실시예 2Example 2
o-자일렌 대신 1,2,4-트리메틸벤젠을 사용하고, 25℃, 100℃ 또는 200℃의 온도에서 건조시켰다는 점을 제외하고는, 실시예 1과 동일한 방법을 사용하여 유기 박막 트랜지스터를 제조하였다.An organic thin film transistor was manufactured in the same manner as in Example 1, except that 1,2,4-trimethylbenzene was used instead of o-xylene and dried at a temperature of 25 ° C., 100 ° C. or 200 ° C. It was.
평가예 1: 유기 반도체 화합물의 광학 특성 평가Evaluation Example 1 Evaluation of Optical Properties of Organic Semiconductor Compound
화합물 1의 광학 특성을 평가하기 위하여, o-자일렌에 용해시킨 용액 상태의 화합물 1과 박막 상태의 화합물 1에 대하여 UV-Vis 분광광도계(Perkin Elmer Lambda 9 UV/Vis spectrophotometer)를 사용하여, UV-Vis 흡수 스펙트럼을 측정하고, 그 결과를 도 1 및 하기 표 1에 나타냈다.In order to evaluate the optical properties of compound 1, UV-Vis spectrophotometer was used for the compound 1 in the solution state and the compound 1 in the thin film state dissolved in o-xylene, using a UV-Vis spectrophotometer. The Vis absorption spectrum was measured and the results are shown in FIG. 1 and Table 1 below.
도 1 및 표 1에 나타난 바와 같이, 화합물 1의 최대 흡광 파장이 용액 상태에서 박막 상태로 변화함에 따라 장파장으로 이동하였고, 밴드갭도 더 작아졌음을 확인할 수 있다. 이를 통해, 화합물 1의 분자간 파이(π) 결합이 용액 상태에서 박막 상태로 변화함에 따라 더 증가한다는 것을 알 수 있다.As shown in FIG. 1 and Table 1, the maximum absorption wavelength of the compound 1 was shifted to the long wavelength as it changes from the solution state to the thin film state, it can be seen that the band gap is smaller. Through this, it can be seen that the intermolecular pi (π) bond of Compound 1 increases as the solution state changes from the thin film state.
최대흡광(λmax)Absorption (λ max ) 시작지점에서의 흡광(λonset)Λ onset at the starting point 광학적 밴드갭(Eg,opt)Optical bandgap (E g, opt )
용액상태의 화합물 1Compound in solution 1 788 nm788 nm 854 nm854 nm 1.45 eV1.45 eV
박막상태의 화합물 1Thin film compound 1 818 nm818 nm 900 nm900 nm 1.38 eV1.38 eV
평가예 2: 유기 반도체 화합물의 전기적 특성 평가Evaluation Example 2: Evaluation of Electrical Properties of Organic Semiconductor Compound
화합물 1의 전기적 특성을 평가하기 위하여, 사이클릭 볼타메트리법을 사용하였다.In order to evaluate the electrical properties of compound 1, the cyclic voltammetry method was used.
탄소유리 전극 상에 상기 화합물 1 (5 mg)을 o-자일렌 (1 mL)에 녹여 얻은 용액을 1000 rpm의 속도로 35초간 스핀코팅하여 얻은 유기 반도체 막을 작업전극(working electrode)으로 준비하고, 백금 와이어를 상대전극(counter electrode)으로 준비하고, Ag/Ag+를 기준전극(reference electrode)으로 준비하였다. 기준전극(Ag/Ag+)에 전위차계(Potentiometer)를 이용해 전압(V)을 걸어주면 작업전극 아래 부분에서 분석물질의 산화 환원반응이 일어나고, 이때 흐르는 전류를 상대전극에서 측정하였다. 같은 조건에서 페로센/페로센늄(Fc/Fc+)의 산화 환원 포텐셜 측정을 통해서 보정하였으며, 페로센/페로센늄(Fc/Fc+)의 산화 환원 포텐셜 값을 4.8 eV로 가정하였다. 산화가 시작되는 지점에서의 전압(ψox)과 환원이 시작되는 지점에서의 전압(ψred)을 각각 측정하여, 아래 수학식 1을 통해 최고준위 점유 분자궤도(highest occupied molecular orbital: HOMO)의 에너지 준위와 최저준위 비점유 분자궤도(lowest unoccupied molecular orbital: LUMO)의 에너지 준위를 계산하였다.The organic semiconductor film obtained by spin coating the solution obtained by dissolving Compound 1 (5 mg) in o-xylene (1 mL) on a carbon glass electrode for 35 seconds at a speed of 1000 rpm was prepared as a working electrode, Platinum wire was prepared as a counter electrode and Ag / Ag + was prepared as a reference electrode. When a voltage (V) was applied to the reference electrode (Ag / Ag + ) using a potentiometer, the redox reaction of the analyte occurred at the lower part of the working electrode, and the current flowing at the counter electrode was measured. Under the same conditions, the redox potential of ferrocene / ferrocenenium (Fc / Fc + ) was calibrated and the redox potential of ferrocene / ferrocenenium (Fc / Fc + ) was assumed to be 4.8 eV. The voltage (ψ ox ) at the point where oxidation starts and the voltage (ψ red ) at the point where reduction starts, respectively, are used to determine the highest occupied molecular orbital (HOMO) The energy levels of the lowest unoccupied molecular orbital (LUMO) were calculated.
[수학식 1][Equation 1]
EHOMO = -4.8 - (ψox)(eV)E HOMO = -4.8-(ψ ox ) (eV)
ELUMO = -4.8 - (ψred)(eV)E LUMO = -4.8-(ψ red ) (eV)
도 2는 사이클릭볼타메트리법으로 측정된 그래프이다. 산화가 시작되는 지점에서의 전압(ψox)과 환원이 시작되는 지점에서의 전압(ψred)은 각각 0.55 V, -1.30 V로 측정되었다. 이를 통해 계산된 에너지 준위는, HOMO 에너지 준위의 경우 -5.35 eV였고, LUMO 에너지 준위의 경우는 -3.50 eV였다.2 is a graph measured by the cyclic voltammetry method. The voltage at the start of oxidation (ψ ox ) and the voltage at the start of reduction (ψ red ) were measured at 0.55 V and -1.30 V, respectively. The calculated energy level was -5.35 eV for HOMO energy level and -3.50 eV for LUMO energy level.
평가예 3: 유기 박막 트랜지스터의 특성 평가Evaluation Example 3: Evaluation of Characteristics of Organic Thin Film Transistor
실시예 1 및 2에서 제조된 유기 박막 트랜지스터의 특성을 Keithley 2400 source/measure units 장비를 이용하여, 게이트 전압에 따른 드레인 전압-드레인 전류, 및 드레인 전압에 따른 게이트 전압-드레인 전류 곡선을 측정하고, 포화영역(saturation) 영역에서 아래의 수학식 2를 이용하여 제반 특성들을 평가하였다.The characteristics of the organic thin film transistors manufactured in Examples 1 and 2 were measured using a Keithley 2400 source / measure units, and the drain voltage-drain current according to the gate voltage and the gate voltage-drain current curve according to the drain voltage were measured. Various characteristics were evaluated using Equation 2 below in the saturation region.
[수학식 2][Equation 2]
Figure PCTKR2017009847-appb-I000014
Figure PCTKR2017009847-appb-I000014
상기 수학식 2 중, VT는 문턱전압, Vgs는 인가된 게이트 전압, μ는 전계효과 전하이동도, W와 L은 채널의 폭과 길이, Ci는 절연막의 커패시턴스이다. 또한, 문턱전압은
Figure PCTKR2017009847-appb-I000015
와 Vgs의 그래프로부터 Ids가 0인 게이트 전압으로 결정되고, 전계효과 전하이동도는
Figure PCTKR2017009847-appb-I000016
와 Vgs의 그래프의 기울기로부터 산출하였다.In Equation 2, V T is a threshold voltage, V gs is an applied gate voltage, μ is a field effect charge mobility, W and L are channel width and length, and C i is capacitance of an insulating film. In addition, the threshold voltage
Figure PCTKR2017009847-appb-I000015
From the graph of and V gs , Ids is determined as the gate voltage with zero, and the field effect charge mobility
Figure PCTKR2017009847-appb-I000016
It was computed from the slope of the graph of and V gs .
도 3 및 4는 실시예 1 및 2에서 제조된 유기 박막 트랜지스터의 전달 특성을 나타내는 전류-전압(J-V) 곡선 그래프이다.3 and 4 are graphs of current-voltage (J-V) curves showing transfer characteristics of the organic thin film transistors prepared in Examples 1 and 2. FIG.
상기 화합물 1은 p-형, n-형 양극성 전류 흐름 특성을 나타냈으며, 실시예 1에서 제조된 유기 박막 트랜지스터의 경우, 정공이동도가 0.167 cm2V-1S-1, 전자이동도가 0.021 cm2V-1S-1로 나타났다. 실시예 2에서 제조된 유기 박막 트랜지스터의 경우, 상온에서 건조시킨 경우에는 정공이동도가 0.367 cm2V-1S-1, 전자이동도가 0.051 cm2V-1S-1로 나타났고, 100℃에서 건조시킨 경우에는 정공이동도가 0.826 cm2V-1S-1, 전자이동도가 0.078 cm2V-1S-1로 나타났으며, 200℃에서 건조시킨 경우에는 정공이동도가 1.377 cm2V-1S-1, 전자이동도가 0.283 cm2V-1S-1로 나타났다. Compound 1 exhibited p-type and n-type bipolar current flow characteristics, and in the case of the organic thin film transistor manufactured in Example 1, the hole mobility was 0.167 cm 2 V -1 S -1 , and the electron mobility was 0.021. cm 2 V −1 S −1 . In the case of the organic thin film transistor manufactured in Example 2, when dried at room temperature, the hole mobility was 0.367 cm 2 V -1 S -1 , and the electron mobility was 0.051 cm 2 V -1 S -1 . The hole mobility was 0.826 cm 2 V -1 S -1 and the electron mobility was 0.078 cm 2 V -1 S -1 when dried at ℃, and the hole mobility was 1.377 when dried at 200 ℃. cm 2 V -1 S -1 , electron mobility was 0.283 cm 2 V -1 S -1 .
또한, 비교예로서, 상기 실시예 1에서 화합물 1 대신 하기 비교 화합물 A를 사용하고 25℃, 100℃, 150℃ 또는 200℃의 온도에서 건조시켰다는 점을 제외하고는 실시예 1과 동일한 방법을 사용하여 유기 박막 트랜지스터를 제조하고, 그 특성을 평가하였다.As a comparative example, the same method as in Example 1 was used except that Comparative Example A was used instead of Compound 1 in Example 1 and dried at a temperature of 25 ° C, 100 ° C, 150 ° C or 200 ° C. The organic thin film transistor was manufactured, and the characteristic was evaluated.
<비교 화합물 A><Comparative Compound A>
Figure PCTKR2017009847-appb-I000017
Figure PCTKR2017009847-appb-I000017
도 5는 비교예에서 제조된 유기 박막 트랜지스터의 전달 특성을 나타내는 전류-전압(J-V) 곡선 그래프이다.5 is a current-voltage (J-V) curve graph showing the transfer characteristics of the organic thin film transistor manufactured in Comparative Example.
비교예에서 제조된 유기 박막 트랜지스터의 경우, 상온에서 건조시킨 경우에는 정공이동도가 0.040 cm2V-1S-1, 전자이동도가 0.0019 cm2V-1S-1로 나타났고, 100℃에서 건조시킨 경우에는 정공이동도가 0.56 cm2V-1S-1, 전자이동도가 0.0033 cm2V-1S-1로 나타났으며, 150℃에서 건조시킨 경우에는 정공이동도가 0.68 cm2V-1S-1, 전자이동도가 0.026 cm2V-1S-1로 나타났고, 200℃에서 건조시킨 경우에는 정공이동도가 0.85 cm2V-1S-1, 전자이동도가 0.029 cm2V-1S-1로 나타났다.In the case of the organic thin film transistor manufactured in Comparative Example, when dried at room temperature, the hole mobility was 0.040 cm 2 V -1 S -1 , the electron mobility was 0.0019 cm 2 V -1 S -1 , and the temperature was 100 ° C. The hole mobility was 0.56 cm 2 V -1 S -1 and the electron mobility was 0.0033 cm 2 V -1 S -1 when dried at, and the hole mobility was 0.68 cm when dried at 150 ° C. 2 V -1 S -1 , the electron mobility was 0.026 cm 2 V -1 S -1 , and when dried at 200 ℃ hole mobility 0.85 cm 2 V -1 S -1 , electron mobility 0.029 cm 2 V −1 S −1 .
이를 통해, 본 발명의 일 구현예에 따른 유기 반도체 화합물을 포함한 전자 소자는 높은 전하이동도를 가짐을 확인할 수 있다. 특히, 본 발명의 일 구현예에 따른 유기 반도체 화합물을 포함한 유기 박막 트랜지스터는, -F를 비포함한 비교 화합물 A를 이용한 비교예의 유기 박막 트랜지스터에 비하여 높은 전하 이동도를 나타냄을 확인할 수 있다. 또한, 비할로겐 용매에 용해시킨 본 발명의 일 구현예에 따른 유기 반도체 화합물을 사용하여 친환경적으로 높은 전하이동도를 갖는 전자 소자를 제조할 수 있었다.Through this, it can be seen that the electronic device including the organic semiconductor compound according to the embodiment of the present invention has high charge mobility. In particular, it can be seen that the organic thin film transistor including the organic semiconductor compound according to the embodiment of the present invention exhibits higher charge mobility than the organic thin film transistor of the comparative example using Comparative Compound A without -F. In addition, using the organic semiconductor compound according to an embodiment of the present invention dissolved in a non-halogen solvent it was possible to manufacture an electronic device having a high charge mobility environmentally friendly.

Claims (10)

  1. 하기 화학식 1로 표시되는 유기 반도체 화합물:An organic semiconductor compound represented by Formula 1 below:
    <화학식 1><Formula 1>
    Figure PCTKR2017009847-appb-I000018
    Figure PCTKR2017009847-appb-I000018
    상기 화학식 1 중,In Formula 1,
    X1 및 X2는 서로 독립적으로, O, S 및 Se로부터 선택되고,X 1 and X 2 are each independently selected from O, S and Se,
    R1 및 R2는 서로 독립적으로, 수소, 중수소(-D), 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C1-C60알킬티오기, -Si(Q1)(Q2)(Q3), -N(Q1)(Q2), -B(Q1)(Q2), -C(=O)(Q1), -OC(=O)(Q1), -C(=O)N(Q1)(Q2), -S(=O)2(Q1) 및 -P(=O)(Q1)(Q2) 중에서 선택되고,R 1 and R 2 are each independently hydrogen, deuterium (-D), hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2- C 60 alkenyl, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 alkylthio group, -Si (Q 1) (Q 2) (Q 3), -N (Q 1 ) (Q 2 ), -B (Q 1 ) (Q 2 ), -C (= O) (Q 1 ), -OC (= O) (Q 1 ), -C (= O) N (Q 1 ) (Q 2 ), -S (= O) 2 (Q 1 ), and -P (= O) (Q 1 ) (Q 2 ),
    a는 1 내지 10의 정수 중에서 선택되고,a is selected from an integer of 1 to 10,
    L은 치환 또는 비치환된 C5-C60카보시클릭 그룹 또는 치환 또는 비치환된 C1-C60헤테로시클릭 그룹이고,L is a substituted or unsubstituted C 5 -C 60 carbocyclic group or a substituted or unsubstituted C 1 -C 60 heterocyclic group,
    b는 1 내지 30의 정수 중에서 선택되되, b가 2 이상일 경우, 2 이상의 L은 서로 동일하거나 상이할 수 있고,b is selected from an integer of 1 to 30, when b is 2 or more, two or more L may be the same or different from each other,
    n은 5 내지 100,000의 정수 중에서 선택되고,n is selected from an integer of 5 to 100,000,
    상기 치환된 C5-C60카보시클릭 그룹 또는 치환된 C1-C60헤테로시클릭 그룹의 치환기 중 적어도 하나는, 중수소, -F, -Cl, -Br, -I, 히드록실기, 옥소기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C1-C60알킬티오기, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C6-C60아릴옥시기, C6-C60아릴티오기, C1-C60헤테로아릴기, C1-C60헤테로아릴옥시기, C1-C60헤테로아릴티오기, 1가 비-방향족 축합다환 그룹, 1가 비-방향족 헤테로축합다환 그룹, -Si(Q11)(Q12)(Q13), -N(Q11)(Q12), -B(Q11)(Q12), -C(=O)(Q11), -OC(=O)(Q11), -C(=O)N(Q11)(Q12), -S(=O)2(Q11) 및 -P(=O)(Q11)(Q12) 중에서 선택되고,At least one of the substituents of the substituted C 5 -C 60 carbocyclic group or substituted C 1 -C 60 heterocyclic group is deuterium, -F, -Cl, -Br, -I, hydroxyl group, oxo Group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group , C 1 -C 60 alkylthio group, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocycloalkenyl group, C 6 -C Import 60 aryl group, C 6 -C 60 aryloxy, C 6 -C 60 aryl come T, C 1 -C 60 heteroaryl groups, C 1 -C 60 heteroaryloxy group, C 1 -C 60 heteroaryl T , Monovalent non-aromatic condensed polycyclic group, monovalent non-aromatic condensed polycyclic group, -Si (Q 11 ) (Q 12 ) (Q 13 ), -N (Q 11 ) (Q 12 ),-B (Q 11 ) (Q 12 ), -C (= O) (Q 11 ), -OC (= O) (Q 11 ), -C (= O) N (Q 11 ) (Q 12 ), -S (= O ) 2 (Q 11 ) and -P (= O) (Q 11 ) (Q 12 ),
    상기 Q1 내지 Q3 및 Q11 내지 Q13은 서로 독립적으로, 수소, 중수소, -F, -Cl, -Br, -I, 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C1-C60알킬티오기, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C1-C60헤테로아릴기, 1가 비-방향족 축합다환 그룹 및 1가 비-방향족 헤테로축합다환 그룹 중에서 선택된다.Q 1 to Q 3 and Q 11 to Q 13 are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group , hydride tank group, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 1 -C 60 come alkylthio, C 3 -C 10 Cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocycloalkenyl group, C 6 -C 60 aryl group, C 1 -C 60 heteroaryl group, monovalent Non-aromatic condensed polycyclic groups and monovalent non-aromatic condensed polycyclic groups.
  2. 제1항에 있어서,The method of claim 1,
    상기 X1 및 X2는 각각 S인, 유기 반도체 화합물.X 1 and X 2 are each S, an organic semiconductor compound.
  3. 제1항에 있어서,The method of claim 1,
    상기 R1 및 R2는 각각 수소인, 유기 반도체 화합물.And R 1 and R 2 are each hydrogen.
  4. 제1항에 있어서,The method of claim 1,
    상기 L은 하기 화학식 2-1 내지 2-35로 표시되는 그룹 중에서 선택된, 유기 반도체 화합물:The L is selected from the group represented by the formula 2-1 to 2-35, an organic semiconductor compound:
    Figure PCTKR2017009847-appb-I000019
    Figure PCTKR2017009847-appb-I000019
    Figure PCTKR2017009847-appb-I000020
    Figure PCTKR2017009847-appb-I000020
    Figure PCTKR2017009847-appb-I000021
    Figure PCTKR2017009847-appb-I000021
    상기 화학식 2-1 내지 2-35 중,In Formulas 2-1 to 2-35,
    Y1 내지 Y3는 서로 독립적으로, C(Z5)(Z6), O, S, Se, Te, N(Z5), Si(Z5)(Z6) 및 Ge(Z5)(Z6) 중에서 선택되고,Y 1 to Y 3 are independently of each other, C (Z 5 ) (Z 6 ), O, S, Se, Te, N (Z 5 ), Si (Z 5 ) (Z 6 ) and Ge (Z 5 ) ( Z 6 ),
    Z1 내지 Z6은 서로 독립적으로, 수소, 중수소, -F, -Cl, -Br, -I, 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C30알킬기, C2-C30알케닐기, C2-C30알키닐기, C1-C30알콕시기, C1-C30알킬티오기, C6-C30아릴기, C1-C30헤테로아릴기, 1가 비-방향족 축합다환 그룹, 1가 비-방향족 헤테로축합다환 그룹, -Si(Q11)(Q12)(Q13), -N(Q11)(Q12), -B(Q11)(Q12), -C(=O)(Q11), -OC(=O)(Q11), -C(=O)N(Q11)(Q12), -S(=O)2(Q11) 및 -P(=O)(Q11)(Q12) 중에서 선택되고,Z 1 to Z 6 independently of each other, hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl group, C 1 -C 30 alkoxy group, C 1 -C 30 alkylthio, C 6 -C 30 aryl group, C 1 -C 30 heteroaryl group, monovalent non-aromatic condensed polycyclic group, monovalent non-aromatic condensed polycyclic group, -Si (Q 11 ) (Q 12 ) (Q 13 ), -N (Q 11 ) (Q 12 ), -B (Q 11 ) (Q 12 ), -C (= O) (Q 11 ), -OC (= O) (Q 11 ), -C (= O) N (Q 11 ) (Q 12 ),- S (= O) 2 (Q 11 ) and -P (= O) (Q 11 ) (Q 12 ),
    상기 Q11 내지 Q13은 서로 독립적으로, 수소, C1-C30알킬기, C1-C30알콕시기, C1-C30알킬티오기, C6-C30아릴기 및 C1-C30헤테로아릴기 중에서 선택되고,Wherein Q 11 to Q 13 are independently of each other, hydrogen, C 1 -C 30 alkyl, C 1 -C 30 alkoxy group, C 1 -C 30 alkylthio, C 6 -C 30 aryl group and C 1 -C 30 Selected from heteroaryl groups,
    d3은 1 내지 3의 정수 중에서 선택되고,d3 is selected from an integer of 1 to 3,
    d4는 1 내지 4의 정수 중에서 선택되고,d4 is selected from an integer of 1 to 4,
    * 및 *'은 이웃한 원자와의 결합 사이트이다.* And * 'are binding sites with neighboring atoms.
  5. 제1항에 있어서,The method of claim 1,
    하기 화학식 1A로 표시되는 유기 반도체 화합물:An organic semiconductor compound represented by Formula 1A:
    <화학식 1A><Formula 1A>
    Figure PCTKR2017009847-appb-I000022
    Figure PCTKR2017009847-appb-I000022
    상기 화학식 1A 중, X1, X2, R1, R2, a, L, b 및 n에 대한 설명은 제1항에 기재된 바와 동일하다.In the formula (1A), the description of X 1 , X 2 , R 1 , R 2 , a, L, b, and n is the same as described in claim 1.
  6. 제1항에 있어서,The method of claim 1,
    하기 화학식 1-A로 표시되는 유기 반도체 화합물:An organic semiconductor compound represented by Formula 1-A:
    <화학식 1-A><Formula 1-A>
    Figure PCTKR2017009847-appb-I000023
    Figure PCTKR2017009847-appb-I000023
    상기 화학식 1-A 중, In Formula 1-A,
    X1, X2, R1, R2, a 및 n에 대한 설명은 제1항에 기재된 바와 동일하고,The description of X 1 , X 2 , R 1 , R 2 , a and n is the same as described in claim 1,
    b1 내지 b3는 0 이상의 정수이되, b1 내지 b3의 합은 1 내지 30이고, b 1 to b 3 is an integer of 0 or more, the sum of b 1 to b 3 is 1 to 30,
    Y1 내지 Y4는 서로 독립적으로, O, S, Se 및 N(Z5) 중에서 선택되고,Y 1 to Y 4 are each independently selected from O, S, Se, and N (Z 5 ),
    Z1 내지 Z5는 서로 독립적으로, 수소, C1-C30알킬기, C2-C30알케닐기, C2-C30알키닐기, C1-C30알콕시기, C1-C30알킬티오기, C6-C30아릴기, C1-C30헤테로아릴기, 1가 비-방향족 축합다환 그룹 및 1가 비-방향족 헤테로축합다환 그룹 중에서 선택된다.Z 1 to Z 5 are independently of each other hydrogen, a C 1 -C 30 alkyl group, a C 2 -C 30 alkenyl group, a C 2 -C 30 alkynyl group, a C 1 -C 30 alkoxy group, a C 1 -C 30 alkylti Group, a C 6 -C 30 aryl group, a C 1 -C 30 heteroaryl group, a monovalent non-aromatic condensed polycyclic group and a monovalent non-aromatic condensed polycyclic group.
  7. 제6항에 있어서,The method of claim 6,
    X1 및 X2는 각각 S이고,X 1 and X 2 are each S,
    R1 및 R2는 각각 수소이고,R 1 and R 2 are each hydrogen,
    a는 1이고,a is 1,
    b1, b2 및 b3는 각각 1인, 유기 반도체 화합물.b 1 , b 2 and b 3 are each 1 an organic semiconductor compound.
  8. 제1항에 있어서,The method of claim 1,
    하기 화합물 1인 유기 반도체 화합물:The organic semiconductor compound which is the following compound 1:
    <화합물 1><Compound 1>
    Figure PCTKR2017009847-appb-I000024
    Figure PCTKR2017009847-appb-I000024
    상기 화합물 1 중, n은 5 내지 100,000의 정수 중에서 선택된다.In the compound 1, n is selected from an integer of 5 to 100,000.
  9. 제1항 내지 제8항 중 어느 한 항의 유기 반도체 화합물을 1종 이상 포함한 유기 반도체 막을 포함하는 전자 소자.An electronic device comprising an organic semiconductor film containing at least one organic semiconductor compound of any one of claims 1 to 8.
  10. 제9항에 있어서,The method of claim 9,
    상기 전자 소자는 유기 박막 트랜지스터(OTFT), 유기 발광 다이오드(OLED), 유기 태양 전지(OSC) 및 유기 광 센서(OPD) 중 어느 하나인 전자 소자.The electronic device is any one of an organic thin film transistor (OTFT), an organic light emitting diode (OLED), an organic solar cell (OSC), and an organic light sensor (OPD).
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