WO2021118242A1 - Novel polymer and organic electronic device including same - Google Patents
Novel polymer and organic electronic device including same Download PDFInfo
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- WO2021118242A1 WO2021118242A1 PCT/KR2020/018010 KR2020018010W WO2021118242A1 WO 2021118242 A1 WO2021118242 A1 WO 2021118242A1 KR 2020018010 W KR2020018010 W KR 2020018010W WO 2021118242 A1 WO2021118242 A1 WO 2021118242A1
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- 0 CC(C)C(*)*C(C(N(*(C)C*C(*)*)C(C1=C(C(*)=CC(C2(*)*)=*C(C(*)*3)=C2C=C3*(*)*)N2*C*C(C)*)=O)=C1C2=O)=CCC(C)(*)* Chemical compound CC(C)C(*)*C(C(N(*(C)C*C(*)*)C(C1=C(C(*)=CC(C2(*)*)=*C(C(*)*3)=C2C=C3*(*)*)N2*C*C(C)*)=O)=C1C2=O)=CCC(C)(*)* 0.000 description 3
- QARNQBJYRJQLMY-UHFFFAOYSA-N CC(C)(c1c-2[s]cc1)c1c-2[s]c(C#N)c1 Chemical compound CC(C)(c1c-2[s]cc1)c1c-2[s]c(C#N)c1 QARNQBJYRJQLMY-UHFFFAOYSA-N 0.000 description 1
- JVGFIIIGJPSPMD-UHFFFAOYSA-N CC(C)(c1c-2[s]cc1)c1c-2[s]c(C(NC(C2=C(c3cc(C(C)(C)C4=C5CC=C4)c5[s]3)N3)=O)=C2C3=O)c1 Chemical compound CC(C)(c1c-2[s]cc1)c1c-2[s]c(C(NC(C2=C(c3cc(C(C)(C)C4=C5CC=C4)c5[s]3)N3)=O)=C2C3=O)c1 JVGFIIIGJPSPMD-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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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
Definitions
- the present invention relates to a novel polymer and an organic electronic device including the same, and more particularly, to a novel polymer including a diketopyrrolopyrrole skeleton as an organic semiconductor compound, and an organic electronic device including the same.
- an organic transistor using an organic semiconductor may be used as a display device such as a portable computer, an organic EL device, a smart card, an electronic tag, a pager, and a mobile phone.
- the organic transistor can be used as an active element in a plastic circuit part such as a memory element inside an ATM, and thus has been the subject of many studies.
- a thin-film field-effect transistor consists of a source electrode, a drain electrode, a gate electrode, an insulating layer, and a semiconductor layer. Consists of.
- the organic transistor having the above structure may have a top gate or a bottom gate structure depending on the position of the gate electrode, and in the lower gate structure, the source/drain electrode is located above or below the semiconductor layer. It can be divided into a top contact (top contact) or bottom contact (bottom contact) structure.
- the upper gate structure may be advantageous in terms of performance because the semiconductor layer has a relatively large contact area with the source electrode and the drain electrode, and may be advantageous in terms of air stability because the upper electrode is applied on the semiconductor layer.
- organic transistors have advantages in that the manufacturing process is simple and can be produced at low cost compared to the thin film transistors using amorphous silicon and polysilicon so far.
- bending bending is possible due to the nature of the organic material, it has excellent compatibility with plastic substrates for realization of flexible displays and electronic devices.
- organic transistors still have low mobility of charge, poor performance, and low solubility in solution process.
- the present invention provides a novel polymer having high solubility, which is very easy to process in solution, and has surprisingly improved electron transport properties.
- the present invention also provides an organic electronic device comprising the novel polymer of the present invention.
- the present invention also provides novel diketopyrrolopyrrole compounds for use in preparing the novel polymers of the present invention.
- the present invention provides a novel polymer comprising diketopyrrolopyrrole having a controlled functional group, and the polymer of the present invention is represented by the following formula (1).
- Z 1 to Z 4 are each independently O, S or Se;
- R 1 and R 2 are each independently C1-C40 alkyl
- R 3 to R 6 are each independently hydrogen or C1-C10 alkyl
- X is selected from the following structures.
- Z 5 to Z 15 are each independently O, S or Se;
- R 11 to R 30 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl.
- Z 1 to Z 4 are each independently S or Se; R 1 and R 2 are each independently C10-C40 alkyl; R 3 to R 6 may be each independently C1-C7 alkyl.
- R 1 and R 2 may each independently be branched-chain C10-C40 alkyl.
- X may be selected from the following structure.
- Z 5 to Z 11 are each independently S or Se;
- R 11 to R 24 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl.
- the polymer according to an embodiment of the present invention may include a repeating unit represented by the following Chemical Formula 2 or Chemical Formula 3.
- Z 1 to Z 8 are each independently O, S or Se;
- R 3 to R 6 are each independently C1-C10 alkyl
- R 11 to R 18 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl;
- R 41 to R 44 are each independently C6-C30 alkyl
- n and m are each independently an integer from 1 to 8.
- Z 1 to Z 8 are each independently S or Se;
- R 3 to R 6 are each independently C1-C5 alkyl;
- R 11 to R 18 are each independently hydrogen, halogen, C1-C5 alkyl or haloC1-C5 alkyl;
- R 41 to R 44 are each independently C8-C20 alkyl;
- n and m may be each independently an integer of 1 to 7.
- the polymer according to an embodiment of the present invention may include a repeating unit represented by the following Chemical Formula 4 or the following Chemical Formula 5.
- Z 1 to Z 4 and Z 9 to Z 11 are each independently O, S or Se;
- R 3 to R 6 are each independently C1-C10 alkyl
- R 19 to R 24 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl;
- R 41 to R 44 are each independently C6-C30 alkyl
- n and m are each independently an integer from 1 to 8.
- Z 1 to Z 4 and Z 9 to Z 11 are each independently S or Se;
- R 3 to R 6 are each independently C1-C5 alkyl;
- R 19 to R 24 are each independently hydrogen, halogen, C1-C5 alkyl or haloC1-C5 alkyl;
- R 41 to R 44 are each independently C8-C20 alkyl;
- n and m may be each independently an integer of 1 to 7.
- the organic electronic device may be an organic solar cell, an organic thin film transistor, an organic memory, an organophotoreceptor, or an organic photosensor, but is not limited thereto.
- the diketopyrrolopyrrole compound is represented by the following formula (11).
- Z 1 to Z 4 are each independently O, S or Se;
- R 1 and R 2 are each independently C1-C40 alkyl
- R 3 to R 6 are each independently hydrogen or C1-C10 alkyl
- X 1 and X 2 are each independently hydrogen or halogen.
- Z 1 to Z 4 are each independently S or Se; R 1 and R 2 are each independently C10-C40 alkyl; R 3 to R 6 are each independently C1-C10 alkyl; X 1 and X 2 may be each independently halogen.
- charge mobility is remarkably improved by introducing a compound in which a controlled aromatic ring or heteroaromatic ring is fused to a diketopyrrolopyrrole backbone, so that the efficiency of an organic electronic device including the same is surprisingly improved.
- the polymer of the present invention is spin-coated by introducing a controlled substituent to N of a compound in which a controlled aromatic ring or a heteroaromatic ring is fused and a diketopyrrolopyrrole, while improving the charge mobility and excellent solubility in a solvent. It is very easy to manufacture large-area organic electronic devices through solution processes such as or printing.
- the polymer of the present invention is a compound in which an aromatic ring or a heteroaromatic ring having an extended conjugation is fused, specifically, a substituted or unsubstituted 4H-cyclopenta[2,1-b:3,4-b]dithiophene, By introducing a compound such as 4H-cyclopenta[2,1-b:3,4-b]difuran and 4H-cyclopenta[2,1-b:3,4-b]diselenophen, the charge mobility was improved. By improving, organic electronic devices employing the polymers of the present invention have improved efficiency.
- Figure 1 is a diagram showing a graph of a polymer 3 to 6 of the present invention.
- Example 2 is a view showing the results of measuring the stress stability of the memory device manufactured in Example 8 of the present invention (a: polymer 3, b: polymer 5).
- alkyl (when the number of carbon atoms is not particularly limited) has 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably denotes a saturated straight-chain or branched non-cyclic hydrocarbon having 1 to 6 carbon atoms.
- “Lower alkyl” means straight-chain or branched alkyl having 1 to 6 carbon atoms.
- Alkyl according to an embodiment of the present invention is saturated having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, preferably 10 to 40 carbon atoms, even more preferably 10 to 35 carbon atoms.
- saturated straight chain alkyls are -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl and -n- contains decyl, whereas saturated branched alkyl is -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3- Methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,
- aryl refers to a carbocyclic aromatic group containing 5 to 10 ring atoms. Representative examples include phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, etc. including, but not limited to. Carbocyclic aromatic groups may be optionally substituted.
- the present invention provides a substituted or unsubstituted 4H-cyclopenta[2,1-b:3,4-b]dithiophene, 4H-cyclopenta[2,1-b:
- 4H-cyclopenta[2,1-b: To provide a polymer having improved charge mobility by introducing compounds such as 3,4-b]difuran and 4H-cyclopenta[2,1-b:3,4-b]diselenophen, the present invention
- the polymer includes a repeating unit represented by the following formula (1).
- Z 1 to Z 4 are each independently O, S or Se;
- R 1 and R 2 are each independently C1-C40 alkyl
- R 3 to R 6 are each independently hydrogen or C1-C10 alkyl
- X is selected from the following structures.
- Z 5 to Z 15 are each independently O, S or Se;
- R 11 to R 30 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl.
- the polymers of the present invention are substituted or unsubstituted 4H-cyclopenta[2,1-b:3,4-b]dithiophene, 4H-cyclopenta[2,1- Conjugation such as b:3,4-b]difuran and 4H-cyclopenta[2,1-b:3,4-b]diselenophene has improved charge mobility by introducing extended compounds, thus The organic electronic device employing this has improved flicker ratio and high device efficiency.
- the polymer of the present invention is formed on both sides of the backbone of diketopyrrolopyrrole. and Conjugation is expanded by the introduction of the substituent of , and the overlap of pi electrons increases, which facilitates electron transfer and greatly improves charge mobility.
- the polymer of the present invention is and By introducing a compound with extended conjugation of , overlapping of high pi electrons is generated, and thus the band gap of the polymer is lowered and the charge mobility is very excellent.
- the solubility in the solvent is excellent, which is more advantageous for the solution process.
- Z 1 to Z 4 are each independently S or Se; R 1 and R 2 are each independently C10-C40 alkyl; R 3 to R 6 may be each independently C1-C7 alkyl, more preferably Z 1 to Z 4 are S; R 1 and R 2 are each independently branched C10-C30 alkyl; R 3 to R 6 may be each independently C1-C5 alkyl.
- R 1 and R 2 may each independently be branched-chain C10-C40 alkyl, more preferably branched-chain C20-C40 alkyl.
- X may be selected from the following structures.
- Z 5 to Z 11 are each independently S or Se;
- R 11 to R 24 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl.
- Z 5 to Z 10 are S; R 11 to R 24 may be each independently hydrogen, halogen, C1-C5 alkyl or haloC1-C5 alkyl.
- the polymer according to an embodiment of the present invention may include a repeating unit represented by the following Chemical Formulas 2 to 5.
- Z 1 to Z 11 are each independently O, S or Se;
- R 3 to R 6 are each independently C1-C10 alkyl
- R 11 to R 24 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl;
- R 41 to R 44 are each independently C6-C30 alkyl
- n and m are each independently an integer from 1 to 8.
- the repeating units of Chemical Formulas 2 to 5 according to an embodiment of the present invention have improved charge mobility in a preferred combination with diketopyrrolopyrrole in which the conjugated functional group of the present invention is introduced, and organic electronic device employing the same has improved short-circuit current (J SC ) and open-circuit voltage (V OC ), has an excellent flashing ratio, and has a high solubility in organic solvents.
- Z 1 to Z 11 are each independently S or Se;
- R 3 to R 6 are each independently C1-C5 alkyl;
- R 11 to R 24 are each independently hydrogen, halogen, C1-C5 alkyl or haloC1-C5 alkyl;
- R 41 to R 44 are each independently C8-C20 alkyl;
- n and m may be each independently an integer of 1 to 7, more preferably Z 1 to Z 8 are S;
- Z 9 to Z 8 are S or Se;
- R 3 to R 6 are each independently C1-C5 alkyl;
- R 11 to R 24 are each independently hydrogen, halogen, C1-C5 alkyl or haloC1-C5 alkyl;
- R 41 to R 44 are each independently branched-chain C8-C20 alkyl;
- n and m may be each independently an integer of 1 to 7.
- the polymer according to an embodiment of the present invention may have a weight average molecular weight of 100 to 200,000 g
- the polymer according to an embodiment of the present invention may be prepared as in the following reaction scheme, but of course, it may also be prepared through a conventional organic synthesis method that can be recognized by those skilled in the art.
- the organic solvent used in the reaction is not limited, and the reaction time and temperature can also be changed within a range that does not deviate from the core of the invention.
- Z 1 to Z 4 , R 1 to R 6 and X are the same as defined in Formula 1,
- R 51 to R 56 are each independently C1-C10 alkyl
- X 1 and X 2 are each independently halogen
- n is an integer from 2 to 100,000.
- the present invention also provides an organic electronic device comprising the polymer of the present invention.
- the organic electronic device is not limited as long as it is a device in which the polymer of the present invention can be used, and as a non-limiting example thereof, the organic electronic device may be an organic solar cell, an organic thin film transistor, an organic memory, or an organic electronic device. and a photoreceptor, an organic photosensor, and the like, and preferably an organic solar cell or an organic thin film transistor.
- the organic electronic device according to an embodiment of the present invention may be an organic transistor, and the polymer may be included in an organic semiconductor layer of the organic transistor.
- the polymer of the present invention is used in the organic semiconductor layer of the organic transistor, and the organic transistor employing the same has an improved flashing ratio.
- the organic electronic device may be an organic solar cell, and the polymer may be included in a photoactive layer of the organic solar cell.
- the polymer of the present invention is used as an electron donor in the photoactive layer of an organic solar cell, and an organic solar cell employing the same has improved photoelectric conversion efficiency.
- the present invention also provides a diketopyrrolopyrrole compound for preparing the polymer of the present invention, and the diketopyrrolopyrrole compound of the present invention is represented by the following formula (11).
- Z 1 to Z 4 are each independently O, S or Se;
- R 1 and R 2 are each independently C1-C40 alkyl
- R 3 To R 6 are each independently hydrogen or C1-C10 alkyl
- X 1 and X 2 are each independently hydrogen or halogen.
- Z 1 to Z 4 are each independently S or Se; R 1 and R 2 are each independently C10-C40 alkyl; R 3 to R 6 may be each independently C1-C10 alkyl; X 1 and X 2 may be each independently halogen.
- the diketopyrrolopyrrole compound represented by Formula 11 is an intermediate for preparing the polymer represented by Formula 1 of the present invention.
- the polymer can be easily prepared.
- the organic transistor according to an embodiment of the present invention may have a bottom contact structure among a bottom gate structure. Specifically, a gate electrode and an insulating layer may be sequentially formed on the substrate, and then a source electrode and a drain electrode may be formed on the insulating layer, and finally, an organic semiconductor layer may be formed on the source electrode and the drain electrode.
- the organic transistor according to an embodiment of the present invention may have a top contact structure among a bottom gate structure. Specifically, the gate electrode and the insulating layer are sequentially formed on the substrate, and then the organic semiconductor layer is formed on the insulating layer, and finally the source electrode and the drain electrode are formed on the organic semiconductor layer.
- the insulating layer may be provided in contact with the organic semiconductor layer, and the source electrode and the drain electrode may be provided with a predetermined interval therebetween so as not to contact each other.
- the source electrode and the drain electrode according to one embodiment of the present invention may be provided in partial contact with the surface opposite to the surface in which the organic semiconductor layer is in contact with the insulating layer.
- the organic transistor according to the embodiment of the present invention may be manufactured using materials and methods known in the art, except that at least one layer of the organic semiconductor layer includes the polymer of Formula 1 above.
- the organic semiconductor layers may be formed of the same material or different materials.
- the organic semiconductor layer according to the embodiment of the present invention may be provided as a single layer. When provided as a single layer, the organic semiconductor layer includes the polymer of the present invention.
- the substrate according to the embodiment of the present invention may be formed of a transparent substrate such as glass, a silicon substrate, or plastic.
- Plastic substrate materials include polyethersulfone (PES, polyethersulfone), polyacrylate (PAR, polyacrylate), polyetherimide (PET, polyetherimide), polyethylenenaphthalate (PEN, polyethylenenaphthalate), polyethyleneterephthalate (PET, polyethyleneterephthalate), Polyphenylene sulfide (PPS), polyarylate (polyarylate), polyimide (polyimide), polycarbonate (PC, polycarbonate), triacetyl cellulose (TAC, tri-acetyl-cellulose) and cellulose acetate propionate (CAP, cellulose acetate propionate) may be used at least one selected from.
- a transparent substrate such as glass that can transmit UV can be used.
- the gate electrode according to the present embodiment of the present invention may be in the form of a pattern, but the present invention is not limited thereto.
- the gate electrode is selected from among gold (Au), nickel (Ni), copper (Cu), silver (Ag), aluminum (Al), aluminum alloy (Al-alloy), molybdenum (Mo), and molybdenum alloy (Mo-alloy). It can be formed by any one selected.
- the gate electrode according to an embodiment of the present invention may be formed using a method selected from a photolithography method, an offset printing method, a silkscreen printing method, an inkjet printing method, a thermal evaporation method, and a method using a shadow mask. However, the present invention is not limited thereto.
- the thickness of the gate electrode may be 10 nm to 300 nm, preferably 10 nm to 50 nm.
- the insulating layer according to an embodiment of the present invention may be composed of a single film or a multilayer film of an organic insulating film or an inorganic insulating film, or may be composed of an organic-inorganic hybrid film.
- the inorganic insulating film any one or a plurality of silicon oxide films, silicon nitride films, Al 2 O 3 , Ta 2 O 5 , BST, and PZT may be used.
- the organic insulating film examples include CYTOP TM, polymethylmethacrylate (PMMA, polymethylmethacrylate), polystyrene (PS, polystyrene), phenolic polymers, acrylic polymers, imide-based polymers such as polyimide, arylether-based polymers, amide-based polymers, Any one or a plurality of fluorine-based polymers, p-xylylene-based polymers, vinyl alcohol-based polymers, and parylene may be used, but the present invention is not limited thereto.
- the insulating layer according to an embodiment of the present invention may be formed through a solution process, and may be applied over a large area through spin coating, bar coating, slit die coating, doctor blade, or the like. Preferably, the insulating layer may be formed through spin coating, but is not limited thereto. When the insulating layer is formed, heat treatment is performed at 100° C. to 150° C. for 30 minutes or more so that the solvent used is completely evaporated.
- the source electrode and the drain electrode according to an embodiment of the present invention may be made of a conductive material, for example, carbon, aluminum, vanadium, chromium, copper, zinc, silver, gold, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, tin, lead, neodymium, platinum, nickel, similar metals and alloys thereof; p- or n-doped silicon; zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide, similar tin oxide and tin oxide indium-based complex compounds; mixtures of oxides and metals such as ZnO:Al, SnO 2 :Sb; and poly(3-methylthiophene)), poly[3,4-(ethylene-1,2-dioxy)thiophene] (poly[3,4-(ethylene-1,2) -dioxy) thiophene]), polypyrrole (polypyrrole), and conductive polymers such as polyaniline
- the organic semiconductor layer according to an embodiment of the present invention may be formed through a solution process.
- the organic semiconductor layer may be applied over a large area through spin coating, bar coating, slit die coating, doctor blade, inkjet coating, or the like, but is not limited thereto.
- the source electrode and the drain electrode when the source electrode and the drain electrode are formed on the substrate, the source electrode and the drain electrode may be formed using a thermal evaporation method, but the present invention is not limited thereto. It can be formed by other methods known in the art. In this case, the distance between the source electrode and the drain electrode typically has a channel length of 2 ⁇ m to several hundreds of ⁇ m, and the channel width may be 10 to 1000 times the channel length.
- the source and drain electrodes are usually made of gold and nickel, but other electrodes such as silver, copper, and molybdenum may also be used.
- the source electrode and the drain electrode may be formed using a photoetch process or a shadow mask process, but only in this case It is not limited, and may be formed by other methods known in the art.
- the P-type characteristic according to the embodiment of the present invention is checked by measuring the current flowing between the source electrode and the drain electrode after applying a negative voltage to the gate electrode. If a negative voltage is applied to the gate electrode in the case of exhibiting the P-type characteristic, holes move in the organic semiconductor layer.
- the polymer of the present invention has improved charge mobility by introducing a functional group having extended conjugation instead of conventional thiophene, and thus an organic solar cell employing the same can realize high efficiency.
- the present invention provides an organic solar cell employing the novel polymer of the present invention in the photoactive layer or a quantum dot solar cell employing the novel polymer in the photoactive layer.
- the organic solar cell according to an embodiment of the present invention may include a substrate, a first electrode, a photoactive layer and a second electrode, and may further include a hole transport layer, an electron transport layer, and the like.
- the organic solar cell according to an embodiment of the present invention may be an inverted type organic solar cell.
- the substrate is PET (polyethylene terephthalate), PEN (polyethylene naphthelate), PP (polyperopylene), PI (polyimide), PC (polycarbornate), PS (polystylene), POM (polyoxyethlene), AS resin (acrylonitrile styrene) copolymer), ABS resin (acrylonitrile butadiene styrene copolymer), and TAC (Triacetyl cellulose) may be made of a flexible and transparent material such as plastic.
- the first electrode is formed by coating a transparent electrode material on one surface of the substrate or coating it in a film form using sputtering, E-Beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing method. do.
- the first electrode is a part functioning as an anode, and is a material having a greater work function compared to a second electrode to be described later, and any material having transparency and conductivity may be used.
- ITO indium tin oxide
- FTO fluorine doped tin oxide
- AZO aluminum doped zinc oxide
- IZO indium zink oxide
- ZnO-Ga 2 O 3 ZnO-Al 2 O 3 and antimony tin oxide (ATO, SnO 2 -Sb 2 O 3 ), etc.
- ITO indium tin oxide
- Au gold
- silver fluorine doped tin oxide
- FTO fluorine doped tin oxide
- AZO aluminum doped zinc oxide
- IZO indium zink oxide
- ZnO-Ga 2 O 3 ZnO-Al 2 O 3
- antimony tin oxide ATO, SnO 2 -Sb 2 O 3
- a hole transport layer may be inserted between the first electrode and the photoactive layer, and the hole transport layer may be formed through spin coating or dip coating.
- a material for forming the hole transport layer it is preferable to use a conductive polymer, PEDOT:PSS (poly(3,4-ethylenedioxythiophene):polystyrene sulfonate), in which electrons move to the anode, ITO (indium tin oxide) layer. It helps to facilitate the transport of holes while preventing
- An electron transport layer may be inserted between the second electrode and the photoactive layer, and the electron transport layer is a metal oxide layer including a metal oxide, the metal oxide being, but not limited to, titanium dioxide (TiO 2 ), tin dioxide (SnO 2 ), zinc oxide (ZnO), and the like may be formed of a nanoparticle oxide.
- the photoactive layer may include an electron donor as an electron donor and an electron acceptor as an electron acceptor.
- the polymer may be used as an electron donor of the photoactive layer to realize improved external quantum efficiency.
- the electron donor and the electron acceptor of the photoactive layer constitute a bulk heterojunction (BHJ, Bulk-heterojunction).
- the bulk heterojunction means that each compound corresponding to an electron donor and an electron acceptor is mixed with each other in the photoactive layer.
- the photoactive layer may include the polymer as an electron donor of the photoactive layer and constitute a bulk heterojunction together with the electron acceptor.
- the photoactive layer may include the polymer of the present invention as an electron donor, and the blending amount thereof may be appropriately adjusted according to the use.
- the polymer may include a solvent and an electron acceptor.
- the electron acceptor for example, C60, C70, [60]PCBM (Phenyl C 61 -butyric acid methyl ester), [70]PCBM (Phenyl C 71 -butyric acid methyl ester), [60]ICBA (Indene-C) 60 Bis-Adduct), [60]PCBCR (phenyl-C 61 -butyric acid cholestryl ester), [70]PCBCR (phenyl-C 71 -butyric acid cholestryl ester), perylene, PBI (polybenzimidazole), PTCBI (3,4,9,10-perylene-tetracarboxylic bis-benzimidazole), P(NDI2HD-Se), etc. may be used, but is not limited thereto
- the band gap is lowered to have an improved flashing ratio.
- the photoactive layer may further include an additional additive in order to realize excellently improved efficiency by controlling the morphology and crystallinity of the active layer.
- the additive include 1,8-diiodooctane (DIO: 1,8-diiodooctane), 1-chloronaphthalene (1-CN: 1-chloronaphthalene), diphenyl ether (DPE: diphenylether), octanedithiol (octane dithiol) and tetrabromothiophene (tetrabromothiophene), and the like, and may be appropriately combined according to the intended use.
- DIO 1,8-diiodooctane
- 1-chloronaphthalene (1-CN: 1-chloronaphthalene
- DPE diphenylether
- octanedithiol octane dithiol
- tetrabromothiophene
- the polymer according to the present invention realizes significantly improved crystallinity when used with 1,8-diiodooctane, thereby significantly improving short-circuit current density ( J sc ) and filling factor (FF) as well as significantly improved External quantum efficiency can be implemented.
- the polymer of the present invention may be used by dissolving it in a solvent, and the solvent may be used as acetone, methanol, THF, toluene, xylene, tetralin, chloroform, chlorobenzene, dichlorobenzene, or a mixed solvent thereof. it is not
- the polymer of the present invention is preferably introduced into the photoactive layer with a thickness of 60 to 120 nm, but is not limited thereto.
- due to high electron density and low bandgap short circuit current density and open circuit voltage are increased as well as the flashing ratio is improved.
- the organic solar cell according to an embodiment of the present invention may further include an electron transport layer.
- the electron transport layer may be prepared by adding a surfactant to improve the morphology of the electron transport layer.
- the electron transport layer may be prepared by dissolving a water-soluble polymer having an electrophilic function in water, ethanol or a mixed solvent thereof, adding a surfactant to the polymer solution, and then filtering to form a thin film. have.
- the water-soluble polymer having the electrophilic functional group is preferably poly[9,9-bis(6'-diethanolamino)hexyl)-fluorene], and the surfactant is 2,4,7,9- It is preferably, but not limited to, tetramethyl-5-decyne-4,7-diol.
- the electron transport layer may be applied by methods such as dip coating, screen printing, inkjet printing, gravure printing, spray coating, doctor blade or brush painting in addition to the spin coating method, but the present invention is not limited thereto.
- the second electrode may be deposited using a thermal evaporator in a state in which the electron transport layer is introduced.
- usable electrode materials include lithium fluoride/aluminum, lithium fluoride/calcium/aluminum, aluminum/calcium, barium/aluminum fluoride, barium fluoride/barium/aluminum, barium/aluminum, aluminum, gold, silver, magnesium: silver and lithium.
- It can be selected from aluminum, and it is preferable to use an electrode made of silver, aluminum, aluminum/calcium or barium fluoride/barium/aluminum structure.
- M n and PDI values were measured in o -DCB ( o -dichlorobenzene) solvent at 80 ° C. at a rate of 1 mL / min using a GPC consisting of a Waters 1515 Isocratic HPLC pump, a temperature control module, and a Waters 2414 differential refraction detector. Molecular weight was calibrated using polystyrene standards.
- TGA was measured by raising the nitrogen flow rate to 50 ml/min to a temperature range of 0 to 800 °C at a rate of 10 °C per minute.
- Step 1 Preparation of compound 1-1 (4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2-carbonitrile)
- Step 2 Compound 1-2 (3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-dihydropyrrolo[ Preparation of 3,4-c]pyrrole-1,4-dione)
- Step 3 Compound 1-3(2,5-bis(5-decylheptadecyl)-3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophen- Preparation of 2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione)
- reaction mixture was stirred at 120 °C for 24 h and then cooled to room temperature. After extraction by addition of dichloromethane and water, the product was purified by column chromatography on silica gel using hexane:dichloromethane (9:1) to give the product as a dark blue solid (1.6 g, 64%).
- Step 4 Compound 1-4(2,5-bis(5-decylheptadecyl)-3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen- Preparation of 2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione)
- the polymer was prepared using a palladium catalyzed Stille coupling reaction. 3,6-bis(6-bromo-4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-bis(2) in Schlenk flask -decyltetradecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (compound 1-4, 0.3 g, 0.1978 mmol) and 5,6-difluoro-4,7-bis(5- (trimethylstannyl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole (0.1309 g, 0.1978 mmol) was dissolved in anhydrous chlorobenzene (12.0 mL).
- the polymer was prepared using a palladium catalyzed Stille coupling reaction.
- Mn 160 kDa
- Mw 190 kDa
- PDI 1.18.
- Polymer 4 was prepared in the same manner as in Example 3, except that compound B was used instead of compound A in Example 3 above (0.16 g, 82%).
- Mn 110 kDa
- Mw 130 kDa
- PDI 1.18.
- Polymer 5 was prepared in the same manner as in Example 3, except that compound C was used instead of compound C in Example 3 above (0.17 g, 82%).
- Polymer 5 was prepared in the same manner as in Example 3, except that compound C was used instead of compound C in Example 3 above (0.16 g, 72%).
- the polymers 1 to 6 prepared in Examples 1 to 6 were dissolved in chloroform and the light absorption regions of the polymers were measured in solution state and film state, and the results are shown in Table 1 below.
- this invention measured TGA of polymers 3 to 6 by the method, and showed the results in diagram 1 (A: Polymer 3, Polymer 3, Polymer 4, Polymer 4) From Figure 1, it is known that this invention is excellent in thermal stability of the polymer.
- a highly n-doped Si ++ /SiO 2 (100 nm) waiter was cleaned using a piranha solution and oxygen plasma. After the cleaning process, the substrate was deposited with OTS (octadecyltrichlorosilane) and then annealed at 120°C for 30 minutes.
- Polymers 3 to 6 prepared in Examples 3 to 6 of the present invention were respectively dissolved in chlorobenzene to prepare polymer solutions having a concentration of 5 mg/mL, respectively.
- the prepared polymer solution was spin coated on the OTS-treated substrate. This was annealed at 200°C for 20 minutes in a glove box filled with nitrogen. Finally, an organic transistor was manufactured by depositing an electrode (80 nm) on the active layer with a channel length of 150 ⁇ m and 1500 ⁇ m, respectively.
- the polymer of the present invention has excellent charge mobility (cm 2 V -1 s - 1 ) and the flashing ratio (I on /I off ) It can be seen that it has.
- the CFA solution was spin-coated on the substrate and then annealed at 200°C for 1 hour.
- the AA layer (2 nm) was thermally evaporated using thermal evaporation to form AA.
- the CFC layer used as the tunneling layer (7 NPM) was annealed and then deposited on the AFA2O 0°C NPM for 1 hour.
- the thin films of Polymer 3 and Polymer 5 were deposited on the CFA layer by spin-coating the polymer solution in chloroform. This sample was annealed at 200 °C for 20 minutes, and then an 80 kmm thick electrode was deposited on the annealed film to make it.
- the ID reduction rates of Polymer 3 and Polymer 5 of the present invention were measured to be 22% and 19%, respectively.
- the ⁇ and ⁇ values of Polymer 3 and Polymer 5 of the present invention were 3.38 ⁇ 10 5 s, 5.30 ⁇ 10 5 s, and 0.41 0.50, respectively. From this, it can be seen that the memory device of the present invention is excellent in bias stress by using the polymer of the present invention.
- the memory device employing the polymer 5 of the present invention has very high hysteresis and bias stress stability.
- non-volatile memory operation was investigated by fabricating a floating gate memory transistor having AuNP as a charge storage layer using polymer 5 of the present invention.
- the fabricated memory device accurately responded to (+) and (-) gate bias, and the maximum memory window was 28V. As a result, ON and OFF bistable current states were clearly obtained, and these states were distinguishable for one year. In addition, the memory device of the present invention exhibited a reproducible switching operation for 100 repeated WRER cycles in one process of writing and erasing.
- the organic memory transistor including the polymer of the present invention has a very good effect.
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Abstract
The present invention pertains to a novel polymer and an organic electronic device including same. More specifically, the present invention pertains to a polymer containing a diketopyrrolopyrrole having a specific functional group, an organic electronic device including same, and a diketopyrrolopyrrole compound for preparing the polymer.
Description
본 발명은 신규한 중합체 및 이를 포함하는 유기 전자 소자에 관한 것으로, 보다 상세하게는 유기 반도체 화합물로 다이케토피롤로피롤 골격을 포함하는 신규한 중합체 및 이를 포함하는 유기 전자 소자에 관한 것이다.The present invention relates to a novel polymer and an organic electronic device including the same, and more particularly, to a novel polymer including a diketopyrrolopyrrole skeleton as an organic semiconductor compound, and an organic electronic device including the same.
21세기에 들어와 정보통신의 발달과 개인 휴대용 통신기기의 발달로 인해 크기가 작고, 중량이 가볍고, 두께가 얇고, 사용하기 편리한 정보통신기기에 대한 욕구가 급증하고 있다. 이에 무엇보다 이를 가능하게 하는 초미세 가공, 초고집적회로를 제작할 수 있는 고성능 전기전자재료, 신개념의 디스플레이를 가능케 하는 새로운 정보통신 재료가 필요한 실정이다.In the 21st century, due to the development of information communication and personal portable communication devices, the demand for information communication devices that are small in size, light in weight, thin in thickness, and convenient to use is rapidly increasing. Therefore, above all else, there is a need for high-performance electrical and electronic materials capable of producing ultra-fine processing and ultra-high integrated circuits that make this possible, and new information and communication materials that enable a new concept of display.
이 중에서도 유기 반도체를 이용한 유기트랜지스터(Organic Transistor)는 휴대용 컴퓨터, 유기EL 소자, 스마트카드, 전자 태그, 호출기, 휴대폰 등과 같은 디스플레이 장치로 사용될 수 있다. 또한 유기트랜지스터는 현금인출기 내부의 메모리 소자 등의 플라스틱 회로부의 능동소자로서 사용될 수 있어, 많은 연구의 대상이 되고 있다.Among them, an organic transistor using an organic semiconductor may be used as a display device such as a portable computer, an organic EL device, a smart card, an electronic tag, a pager, and a mobile phone. In addition, the organic transistor can be used as an active element in a plastic circuit part such as a memory element inside an ATM, and thus has been the subject of many studies.
유기트랜지스터는 단분자, 고분자 및 올리고머와 같은 유기물질을 반도체층에 적용한 것으로, 박막형태의 전계효과 트랜지스터(field-effect transistor, FET)는 소스 전극, 드레인 전극, 게이트 전극, 절연층 및 반도체층으로 구성되어 있다.Organic transistors apply organic materials such as monomolecules, polymers, and oligomers to a semiconductor layer. A thin-film field-effect transistor (FET) consists of a source electrode, a drain electrode, a gate electrode, an insulating layer, and a semiconductor layer. Consists of.
상기와 같은 구조의 유기트랜지스터는 게이트 전극의 위치에 따라 상부 게이트(top gate) 또는 하부 게이트(bottom gate) 구조를 가질 수 있으며, 하부 게이트 구조에서는 소스/드레인 전극이 반도체층 위 또는 아래에 위치하느냐에 따라 상부 접촉(top contact) 또는 하부 접촉(bottom contact) 구조로 나뉠 수 있다.The organic transistor having the above structure may have a top gate or a bottom gate structure depending on the position of the gate electrode, and in the lower gate structure, the source/drain electrode is located above or below the semiconductor layer. It can be divided into a top contact (top contact) or bottom contact (bottom contact) structure.
상부 게이트 구조는 반도체층이 소스 전극 및 드레인 전극과 접촉하는 면적이 상대적으로 넓기 때문에 성능면에서 유리할 수 있으며, 반도체층 위에 상부 전극을 도포하기 때문에 공기 안정성 면에서 유리할 수 있다.The upper gate structure may be advantageous in terms of performance because the semiconductor layer has a relatively large contact area with the source electrode and the drain electrode, and may be advantageous in terms of air stability because the upper electrode is applied on the semiconductor layer.
이러한 유기트랜지스터는 지금까지의 비정질 실리콘 및 폴리실리콘을 이용한 박막 트랜지스터에 비하여 제조 공정이 간단하고, 저비용으로 생산할 수 있다는 장점을 가지고 있다. 특히, 유기물의 특성상 휨(구부러짐)이 가능하여 플렉시블(flexible) 디스플레이나, 전자소자의 구현을 위한 플라스틱 기판들과도 호환성이 뛰어나다.These organic transistors have advantages in that the manufacturing process is simple and can be produced at low cost compared to the thin film transistors using amorphous silicon and polysilicon so far. In particular, since bending (bending) is possible due to the nature of the organic material, it has excellent compatibility with plastic substrates for realization of flexible displays and electronic devices.
그러나 유기트랜지스터는 여전히 전하의 이동도(Mobility)가 낮아, 성능이 떨어지고 용액공정상 용해도가 낮은 단점을 가진다.However, organic transistors still have low mobility of charge, poor performance, and low solubility in solution process.
따라서 보다 우수한 물성을 가져 고성능 유기 전자 소자, 특히 유기트랜지스터의 효율을 획기적으로 향상시킬 수 있으며, 유기용매에 대한 용해도가 우수한 유기 반도체 화합물에 대한 연구가 필요하다.Therefore, it is possible to dramatically improve the efficiency of high-performance organic electronic devices, particularly organic transistors, by having superior physical properties, and there is a need for research on organic semiconductor compounds having excellent solubility in organic solvents.
본 발명은 높은 용해도를 가져 용액공정이 매우 용이한 동시에 전자 전달 특성이 놀랍도록 향상된 신규한 중합체를 제공한다.The present invention provides a novel polymer having high solubility, which is very easy to process in solution, and has surprisingly improved electron transport properties.
또한 본 발명은 본 발명의 신규한 중합체를 포함하는 유기 전자 소자를 제공한다.The present invention also provides an organic electronic device comprising the novel polymer of the present invention.
또한 본 발명은 본 발명의 신규한 중합체 제조에 사용되는 신규한 다이케토피롤로피롤 화합물을 제공한다.The present invention also provides novel diketopyrrolopyrrole compounds for use in preparing the novel polymers of the present invention.
본 발명은 제어된 작용기를 가지는 다이케토피롤로피롤을 포함하는 신규한 중합체를 제공하는 것으로, 본 발명의 중합체는 하기 화학식 1로 표시된다.The present invention provides a novel polymer comprising diketopyrrolopyrrole having a controlled functional group, and the polymer of the present invention is represented by the following formula (1).
[화학식 1][Formula 1]
(상기 화학식 1에서,(In Formula 1,
Z
1 내지 Z
4는 서로 독립적으로 O, S 또는 Se이며;Z 1 to Z 4 are each independently O, S or Se;
R
1 및 R
2는 서로 독립적으로 C1-C40알킬이며;R 1 and R 2 are each independently C1-C40 alkyl;
R
3 내지 R
6은 서로 독립적으로 수소 또는 C1-C10알킬이며;R 3 to R 6 are each independently hydrogen or C1-C10 alkyl;
X는 하기 구조에서 선택된다.)X is selected from the following structures.)
(상기 구조식에서,(In the above structural formula,
Z
5 내지 Z
15는 서로 독립적으로 O, S 또는 Se이며;Z 5 to Z 15 are each independently O, S or Se;
R
11 내지 R
30는 서로 독립적으로 수소, 할로겐, C1-C10알킬 또는 할로C1-C10알킬이다.)R 11 to R 30 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl.)
바람직하게 본 발명의 일 실시예에 따른 화학식 1에서, Z
1 내지 Z
4는 서로 독립적으로 S 또는 Se이며; R
1 및 R
2는 서로 독립적으로 C10-C40알킬이며; R
3 내지 R
6은 서로 독립적으로 C1-C7알킬일 수 있다.Preferably, in Formula 1 according to an embodiment of the present invention, Z 1 to Z 4 are each independently S or Se; R 1 and R 2 are each independently C10-C40 alkyl; R 3 to R 6 may be each independently C1-C7 alkyl.
보다 바람직하게 본 발명의 일 실시예에 따른 화학식 1에서 R
1 및 R
2는 서로 독립적으로 분지쇄C10-C40알킬일 수 있다.More preferably, in Formula 1 according to an embodiment of the present invention, R 1 and R 2 may each independently be branched-chain C10-C40 alkyl.
보다 향상된 성능을 가지는 유기 전자 소자를 제조하기 위한 측면에서 바람직하게 X는 하기 구조에서 선택되는 것일 수 있다.In terms of manufacturing an organic electronic device having more improved performance, preferably X may be selected from the following structure.
(상기 구조식에서,(In the above structural formula,
Z
5 내지 Z
11은 서로 독립적으로 S 또는 Se이며;Z 5 to Z 11 are each independently S or Se;
R
11 내지 R
24는 서로 독립적으로 수소, 할로겐, C1-C10알킬 또는 할로C1-C10알킬이다.)R 11 to R 24 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl.)
바람직하게 본 발명의 일 실시예에 따른 중합체는 하기 화학식 2 또는 화학식 3으로 표시되는 반복단위를 포함할 수 있다.Preferably, the polymer according to an embodiment of the present invention may include a repeating unit represented by the following Chemical Formula 2 or Chemical Formula 3.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
(상기 화학식 2 및 화학식 3에서, (In Formula 2 and Formula 3,
Z
1 내지 Z
8은 서로 독립적으로 O, S 또는 Se이며;Z 1 to Z 8 are each independently O, S or Se;
R
3 내지 R
6은 서로 독립적으로 C1-C10알킬이며;R 3 to R 6 are each independently C1-C10 alkyl;
R
11 내지 R
18은 서로 독립적으로 수소, 할로겐, C1-C10알킬 또는 할로C1-C10알킬이며;R 11 to R 18 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl;
R
41 내지 R
44는 서로 독립적으로 C6-C30알킬이며;R 41 to R 44 are each independently C6-C30 alkyl;
n 및 m은 서로 독립적으로 1 내지 8의 정수이다.)n and m are each independently an integer from 1 to 8.)
본 발명의 일 실시예에 따른 화학식 2 또는 3에서 Z
1 내지 Z
8은 서로 독립적으로 S 또는 Se이며; R
3 내지 R
6은 서로 독립적으로 C1-C5알킬이며; R
11 내지 R
18은 서로 독립적으로 수소, 할로겐, C1-C5알킬 또는 할로C1-C5알킬이며; R
41 내지 R
44는 서로 독립적으로 C8-C20알킬이며; n 및 m은 서로 독립적으로 1 내지 7의 정수일 수 있다.In Formula 2 or 3 according to an embodiment of the present invention, Z 1 to Z 8 are each independently S or Se; R 3 to R 6 are each independently C1-C5 alkyl; R 11 to R 18 are each independently hydrogen, halogen, C1-C5 alkyl or haloC1-C5 alkyl; R 41 to R 44 are each independently C8-C20 alkyl; n and m may be each independently an integer of 1 to 7.
바람직하게 본 발명의 일 실시예에 따른 중합체는 하기 화학식 4 또는 하기 화학식 5로 표시되는 반복단위를 포함하는 것일 수 있다.Preferably, the polymer according to an embodiment of the present invention may include a repeating unit represented by the following Chemical Formula 4 or the following Chemical Formula 5.
[화학식 4][Formula 4]
[화학식 5][Formula 5]
(상기 화학식 4 및 화학식 5에서, (In Chemical Formulas 4 and 5,
Z
1 내지 Z
4 및 Z
9 내지 Z
11은 서로 독립적으로 O, S 또는 Se이며;Z 1 to Z 4 and Z 9 to Z 11 are each independently O, S or Se;
R
3 내지 R
6은 서로 독립적으로 C1-C10알킬이며;R 3 to R 6 are each independently C1-C10 alkyl;
R
19 내지 R
24는 서로 독립적으로 수소, 할로겐, C1-C10알킬 또는 할로C1-C10알킬이며;R 19 to R 24 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl;
R
41 내지 R
44는 서로 독립적으로 C6-C30알킬이며;R 41 to R 44 are each independently C6-C30 alkyl;
n 및 m은 서로 독립적으로 1 내지 8의 정수이다.)n and m are each independently an integer from 1 to 8.)
보다 좋기로는 본 발명의 일 실시예에 따른 화학식 4 및 화학식 5에서 Z
1 내지 Z
4 및 Z
9 내지 Z
11은 서로 독립적으로 S 또는 Se이며; R
3 내지 R
6은 서로 독립적으로 C1-C5알킬이며; R
19 내지 R
24는 서로 독립적으로 수소, 할로겐, C1-C5알킬 또는 할로C1-C5알킬이며; R
41 내지 R
44는 서로 독립적으로 C8-C20알킬이며; n 및 m은 서로 독립적으로 1 내지 7의 정수일 수 있다.More preferably, in Formulas 4 and 5 according to an embodiment of the present invention, Z 1 to Z 4 and Z 9 to Z 11 are each independently S or Se; R 3 to R 6 are each independently C1-C5 alkyl; R 19 to R 24 are each independently hydrogen, halogen, C1-C5 alkyl or haloC1-C5 alkyl; R 41 to R 44 are each independently C8-C20 alkyl; n and m may be each independently an integer of 1 to 7.
또한 본 발명의 본 발명의 신규한 중합체를 포함하는 유기 전자 소자를 제공한다.It also provides an organic electronic device comprising the novel polymer of the present invention.
본 발명의 일 실시예에 따른 유기 전자 소자는 유기 태양 전지, 유기 박막 트랜지스터, 유기메모리, 유기감광체 또는 유기 광센서일 수 있으나, 이에 한정이 있는 것은 아니다.The organic electronic device according to an embodiment of the present invention may be an organic solar cell, an organic thin film transistor, an organic memory, an organophotoreceptor, or an organic photosensor, but is not limited thereto.
또한 본 발명의 본 발명의 중합체를 제조하기위한 신규한 다이케토피롤로피롤 화합물을 제공하는 것으로, 다이케토피롤로피롤 화합물은 하기 화학식 11로 표시된다.In addition, to provide a novel diketopyrrolopyrrole compound for preparing the polymer of the present invention, the diketopyrrolopyrrole compound is represented by the following formula (11).
[화학식 11][Formula 11]
(상기 화학식 11에서,(In Formula 11,
Z
1 내지 Z
4는 서로 독립적으로 O, S 또는 Se이며;Z 1 to Z 4 are each independently O, S or Se;
R
1 및 R
2는 서로 독립적으로 C1-C40알킬이며;R 1 and R 2 are each independently C1-C40 alkyl;
R
3 내지 R
6은 서로 독립적으로 수소 또는 C1-C10알킬이며;R 3 to R 6 are each independently hydrogen or C1-C10 alkyl;
X
1 및 X
2는 서로 독립적으로 수소 또는 할로겐이다.)X 1 and X 2 are each independently hydrogen or halogen.)
바람직하게 화학식 11에 있어서 Z
1 내지 Z
4는 서로 독립적으로 S 또는 Se이며; R
1 및 R
2는 서로 독립적으로 C10-C40알킬이며; R
3 내지 R
6은 서로 독립적으로 C1-C10알킬이며; X
1 및 X
2는 서로 독립적으로 할로겐일 수 있다.Preferably, in Formula 11, Z 1 to Z 4 are each independently S or Se; R 1 and R 2 are each independently C10-C40 alkyl; R 3 to R 6 are each independently C1-C10 alkyl; X 1 and X 2 may be each independently halogen.
본 발명의 신규한 중합체는 다이케토피롤로피롤 골격에 제어된 방향족고리 또는 헤테로방향족고리가 융합된 화합물을 도입함으로써 전하이동도가 현저하게 향상되어 이를 포함하는 유기 전자 소자의 효율이 놀랍도록 향상된다.In the novel polymer of the present invention, charge mobility is remarkably improved by introducing a compound in which a controlled aromatic ring or heteroaromatic ring is fused to a diketopyrrolopyrrole backbone, so that the efficiency of an organic electronic device including the same is surprisingly improved. .
뿐만 아니라 본 발명의 중합체는 제어된 방향족고리 또는 헤테로방향족고리가 융합된 화합물 및 다이케토피롤로피롤의 N에 제어된 치환기를 도입함으로써 전하 이동도가 향상되는 동시에 용매에 대한 용해도가 우수하여 스핀코팅이나 프린팅과 같은 용액 공정으로 대면적 유기 전자 소자의 제조가 매우 용이하다.In addition, the polymer of the present invention is spin-coated by introducing a controlled substituent to N of a compound in which a controlled aromatic ring or a heteroaromatic ring is fused and a diketopyrrolopyrrole, while improving the charge mobility and excellent solubility in a solvent. It is very easy to manufacture large-area organic electronic devices through solution processes such as or printing.
또한, 본 발명의 중합체는 컨쥬게이션이 확장된 방향족고리 또는 헤테로방향족고리가 융합된 화합물, 구체적으로 치환되거나 비치환된 4H-싸이클로펜타[2,1-b:3,4-b]디티오펜, 4H-싸이클로펜타[2,1-b:3,4-b]디퓨란, 4H-싸이클로펜타[2,1-b:3,4-b]디셀레노펜 등의 화합물을 도입하여 전하이동도를 향상시켜, 본 발명의 중합체를 채용한 유기 전자 소자는 향상된 효율을 가진다.In addition, the polymer of the present invention is a compound in which an aromatic ring or a heteroaromatic ring having an extended conjugation is fused, specifically, a substituted or unsubstituted 4H-cyclopenta[2,1-b:3,4-b]dithiophene, By introducing a compound such as 4H-cyclopenta[2,1-b:3,4-b]difuran and 4H-cyclopenta[2,1-b:3,4-b]diselenophen, the charge mobility was improved. By improving, organic electronic devices employing the polymers of the present invention have improved efficiency.
도 1은 본 발명의 중합체 3 내지 6의 TGA 그래프를 나타낸 도면이다.Figure 1 is a diagram showing a graph of a polymer 3 to 6 of the present invention.
도 2는 본 발명의 실시예 8에서 제조된 메모리 소자의 스트레스 안정성을 측정한 결과를나타낸 도면이다(a: 중합체 3, b:중합체 5).2 is a view showing the results of measuring the stress stability of the memory device manufactured in Example 8 of the present invention (a: polymer 3, b: polymer 5).
본 발명에 따른 신규한 중합체 및 이를 채용한 유기 전자 소자에 대하여 이하 상술하나, 이때 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다. The novel polymer according to the present invention and an organic electronic device employing the same will be described in detail below, but unless there are other definitions in the technical and scientific terms used at this time, those of ordinary skill in the art to which this invention pertains usually Descriptions of well-known functions and configurations that have an understanding meaning and may unnecessarily obscure the gist of the present invention in the following description will be omitted.
본 명세서에서 사용된 용어 "알킬"은 (탄소수가 특별히 한정되지 않은 경우) 탄소수 1 내지 40, 바람직하게 탄소수 1 내지 30, 보다 바람직하게 탄소수 1 내지 20, 좋기로는 탄소수 1 내지 10, 더욱 좋기로는 탄소수 1 내지 6을 가진 포화된 직쇄상 또는 분지상의 비-고리(cyclic) 탄화수소를 의미한다. "저급 알킬"은 탄소수가 1 내지 6인 직쇄상 또는 분지상 알킬을 의미한다. 본 발명의 일 실시예에 따른 알킬은 탄소수 1 내지 40, 바람직하게 탄소수 1 내지 30, 보다 바람직하게 탄소수 5 내지 30, 좋기로는 탄소수 10 내지 40, 더욱 좋기로는 탄소수 10 내지 35를 가진 포화된 또는 분지상의 비-고리(cyclic) 탄화수소일 수 있다. 대표적인 포화 직쇄상 알킬은 -메틸, -에틸, -n-프로필, -n-부틸, -n-펜틸, -n-헥실, -n-헵틸, -n-옥틸, -n-노닐 과 -n-데실을 포함하고, 반면에 포화 분지상 알킬은 -이소프로필, -sec-부틸, -이소부틸, -tert-부틸, 이소펜틸, 2-메틸헥실, 3-메틸부틸, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 2-메틸헥실, 3-메틸헥실, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 2-메틸헥실, 3-메틸헥실, 4-메틸헥실, 5- 메틸헥실, 2,3-디메틸부틸, 2,3-디메틸펜틸, 2,4-디메틸펜틸, 2,3-디메틸헥실, 2,4-디메틸헥실, 2,5-디메틸헥실, 2,2-디메틸펜틸, 2,2-디메틸헥실, 3,3-디메틸펜틸, 3,3-디메틸헥실, 4,4-디메틸헥실, 2-에틸펜틸, 3-에틸펜틸, 2-데틸헥실, 3-에틸헥실, 4-에틸헥실, 2-메틸-2-에틸펜틸, 2-메틸-3-에틸펜틸, 2-메틸-4-에틸펜틸, 2-메틸-2-에틸헥실, 2-메틸-3-에틸헥실, 2-메틸-4-에틸헥실, 2,2-디에틸펜틸, 3,3-디에틸헥실, 2,2-디에틸헥실, 및 3,3-디에틸헥실을 포함한다.As used herein, the term "alkyl" (when the number of carbon atoms is not particularly limited) has 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably denotes a saturated straight-chain or branched non-cyclic hydrocarbon having 1 to 6 carbon atoms. "Lower alkyl" means straight-chain or branched alkyl having 1 to 6 carbon atoms. Alkyl according to an embodiment of the present invention is saturated having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, preferably 10 to 40 carbon atoms, even more preferably 10 to 35 carbon atoms. or a branched, non-cyclic hydrocarbon. Representative saturated straight chain alkyls are -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl and -n- contains decyl, whereas saturated branched alkyl is -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3- Methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5- Methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethyl pentyl, 2,2-dimethylhexyl, 3,3-dimethylpentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-diethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.
본 명세서에서 사용된 용어 "아릴"은 5 내지 10의 고리 원자를 함유하는 탄소고리 방향족 그룹을 의미한다. 대표적인 예는 페닐, 톨일(tolyl), 자이릴(xylyl), 나프틸, 테트라하이드로나프틸, 안트라세닐(anthracenyl), 플루오레닐(fluorenyl), 인데닐(indenyl), 아주레닐(azulenyl) 등을 포함하나 이에 한정되는 것은 아니다. 탄소고리 방향족 그룹은 선택적으로 치환될 수 있다.As used herein, the term "aryl" refers to a carbocyclic aromatic group containing 5 to 10 ring atoms. Representative examples include phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, etc. including, but not limited to. Carbocyclic aromatic groups may be optionally substituted.
본 발명은 다이케토피롤로피롤에 콘쥬게이션이 확장된 치환되거나 비치환된 4H-싸이클로펜타[2,1-b:3,4-b]디티오펜, 4H-싸이클로펜타[2,1-b:3,4-b]디퓨란, 4H-싸이클로펜타[2,1-b:3,4-b]디셀레노펜 등의 화합물을 도입하여 향상된 전하 이동도를 가지는 중합체를 제공하는 것으로, 본 발명의 중합체는 하기 화학식 1로 표시되는 반복단위를 포함한다.The present invention provides a substituted or unsubstituted 4H-cyclopenta[2,1-b:3,4-b]dithiophene, 4H-cyclopenta[2,1-b: To provide a polymer having improved charge mobility by introducing compounds such as 3,4-b]difuran and 4H-cyclopenta[2,1-b:3,4-b]diselenophen, the present invention The polymer includes a repeating unit represented by the following formula (1).
[화학식 1][Formula 1]
(상기 화학식 1에서,(In Formula 1,
Z
1 내지 Z
4는 서로 독립적으로 O, S 또는 Se이며;Z 1 to Z 4 are each independently O, S or Se;
R
1 및 R
2는 서로 독립적으로 C1-C40알킬이며;R 1 and R 2 are each independently C1-C40 alkyl;
R
3 내지 R
6은 서로 독립적으로 수소 또는 C1-C10알킬이며;R 3 to R 6 are each independently hydrogen or C1-C10 alkyl;
X는 하기 구조에서 선택된다.X is selected from the following structures.
상기 구조식에서,In the above structural formula,
Z
5 내지 Z
15는 서로 독립적으로 O, S 또는 Se이며;Z 5 to Z 15 are each independently O, S or Se;
R
11 내지 R
30는 서로 독립적으로 수소, 할로겐, C1-C10알킬 또는 할로C1-C10알킬이다.)R 11 to R 30 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl.)
본 발명의 중합체는 다이케토피롤로피롤에 제어된 특정한 작용기인 치환되거나 비치환된 4H-싸이클로펜타[2,1-b:3,4-b]디티오펜, 4H-싸이클로펜타[2,1-b:3,4-b]디퓨란, 4H-싸이클로펜타[2,1-b:3,4-b]디셀레노펜 등의 컨쥬게이션이 확장된 화합물을 도입함으로써 향상된 전하 이동도를 가지며, 따라서 이를 채용한 유기 전자 소자는 점멸비가 개선되어 높은 소자 효율을 가진다.The polymers of the present invention are substituted or unsubstituted 4H-cyclopenta[2,1-b:3,4-b]dithiophene, 4H-cyclopenta[2,1- Conjugation such as b:3,4-b]difuran and 4H-cyclopenta[2,1-b:3,4-b]diselenophene has improved charge mobility by introducing extended compounds, thus The organic electronic device employing this has improved flicker ratio and high device efficiency.
본 발명의 중합체는 다이케토피롤로피롤의 골격을 중심으로 양쪽에
및
의 치환기가 도입됨으로서 컨주게이션이 확장되어 파이전자의 겹침이 많아짐으로써 전자 전달이 용이하여 전하 이동도가 극히 향상된다. The polymer of the present invention is formed on both sides of the backbone of diketopyrrolopyrrole. and Conjugation is expanded by the introduction of the substituent of , and the overlap of pi electrons increases, which facilitates electron transfer and greatly improves charge mobility.
즉, 본 발명의 중합체는
및
의 컨쥬게이션이 확장된 화합물을 도입함으로써 높은 파이전자끼리의 겹침이 발생되며, 따라서 중합체의 밴드갭이 보다 낮아져 전하 이동도가 매우 우수하다. That is, the polymer of the present invention is and By introducing a compound with extended conjugation of , overlapping of high pi electrons is generated, and thus the band gap of the polymer is lowered and the charge mobility is very excellent.
나아가 본 발명의 중합체의 다이케토피롤로피롤의 N에 제어된 치환기를 도입하여 용매에 대한 용해도가 우수하여 용액공정에 보다 유리하다. Furthermore, by introducing a controlled substituent to N of diketopyrrolopyrrole of the polymer of the present invention, the solubility in the solvent is excellent, which is more advantageous for the solution process.
높은 용해도와 우수한 전자 전달 특성을 가지기 위한 측면에서 바람직하게 Z
1 내지 Z
4는 서로 독립적으로 S 또는 Se이며; R
1 및 R
2는 서로 독립적으로 C10-C40알킬이며; R
3 내지 R
6은 서로 독립적으로 C1-C7알킬일 수 있으며, 보다 바람직하게는 Z
1 내지 Z
4는 S이며; R
1 및 R
2는 서로 독립적으로 분지쇄C10-C30알킬이며; R
3 내지 R
6은 서로 독립적으로 C1-C5알킬일 수 있다.In terms of high solubility and excellent electron transport properties, preferably Z 1 to Z 4 are each independently S or Se; R 1 and R 2 are each independently C10-C40 alkyl; R 3 to R 6 may be each independently C1-C7 alkyl, more preferably Z 1 to Z 4 are S; R 1 and R 2 are each independently branched C10-C30 alkyl; R 3 to R 6 may be each independently C1-C5 alkyl.
보다 바람직하게 화학식 1에서 R
1 및 R
2는 서로 독립적으로 분지쇄C10-C40알킬일 수 있으며, 더욱 좋기로는 분지쇄C20-C40알킬일 수 있다.More preferably, in Formula 1, R 1 and R 2 may each independently be branched-chain C10-C40 alkyl, more preferably branched-chain C20-C40 alkyl.
본 발명의 확장된 켄쥬게이션을 가지는 작용기인
및
이 도입된 다이케토피롤로피롤 골격과 바람직한 조합에 있어서 X는 하기 구조에서 선택되는 것일 수 있다.The functional group with extended conjugation of the present invention is and In a preferred combination with the introduced diketopyrrolopyrrole skeleton, X may be selected from the following structures.
(상기 구조식에서,(In the above structural formula,
Z
5 내지 Z
11은 서로 독립적으로 S 또는 Se이며;Z 5 to Z 11 are each independently S or Se;
R
11 내지 R
24는 서로 독립적으로 수소, 할로겐, C1-C10알킬 또는 할로C1-C10알킬이다.)R 11 to R 24 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl.)
X의 구조식에서 Z
5 내지 Z
10는 S이며; R
11 내지 R
24는 서로 독립적으로 수소, 할로겐, C1-C5알킬 또는 할로C1-C5알킬일 수 있다.In the structural formula of X, Z 5 to Z 10 are S; R 11 to R 24 may be each independently hydrogen, halogen, C1-C5 alkyl or haloC1-C5 alkyl.
바람직하게 본 발명의 일 실시예에 따른 중합체는 하기 화학식 2 내지 하기 화학식 5로 표시되는 반복단위를 포함할 수 있다.Preferably, the polymer according to an embodiment of the present invention may include a repeating unit represented by the following Chemical Formulas 2 to 5.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
(상기 화학식 2 내지 화학식 5에서, (In Formulas 2 to 5,
Z
1 내지 Z
11은 서로 독립적으로 O, S 또는 Se이며;Z 1 to Z 11 are each independently O, S or Se;
R
3 내지 R
6은 서로 독립적으로 C1-C10알킬이며;R 3 to R 6 are each independently C1-C10 alkyl;
R
11 내지 R
24는 서로 독립적으로 수소, 할로겐, C1-C10알킬 또는 할로C1-C10알킬이며;R 11 to R 24 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl;
R
41 내지 R
44는 서로 독립적으로 C6-C30알킬이며;R 41 to R 44 are each independently C6-C30 alkyl;
n 및 m은 서로 독립적으로 1 내지 8의 정수이다.)n and m are each independently an integer from 1 to 8.)
본 발명의 일 실시예에 따른 화학식 2 내지 화학식 5의 반복단위는 본 발명의 컨쥬게이션이 확장된 작용기가 도입된 다이케토피롤로피롤과 바람직한 조합으로 향상된 전하 이동도를 가져 이를 채용한 유기 전자 소자는 향상된 단락 전류(J
SC)와 개방전압(V
OC)을 가지며, 우수한 점멸비를 가지고 유기용매에 대한 용해도 또한 높은 값을 가진다.The repeating units of Chemical Formulas 2 to 5 according to an embodiment of the present invention have improved charge mobility in a preferred combination with diketopyrrolopyrrole in which the conjugated functional group of the present invention is introduced, and organic electronic device employing the same has improved short-circuit current (J SC ) and open-circuit voltage (V OC ), has an excellent flashing ratio, and has a high solubility in organic solvents.
바람직하게 본 발명의 일 실시예에 따른 화학식 2 내지 5에서 Z
1 내지 Z
11은 서로 독립적으로 S 또는 Se이며; R
3 내지 R
6은 서로 독립적으로 C1-C5알킬이며; R
11 내지 R
24는 서로 독립적으로 수소, 할로겐, C1-C5알킬 또는 할로C1-C5알킬이며; R
41 내지 R
44는 서로 독립적으로 C8-C20알킬이며; n 및 m은 서로 독립적으로 1 내지 7의 정수일 수 있으며, 보다 바람직하게 Z
1 내지 Z
8은 S이며; Z
9 내지 Z
8은 S 또는 Se이며; R
3 내지 R
6은 서로 독립적으로 C1-C5알킬이며; R
11 내지 R
24는 서로 독립적으로 수소, 할로겐, C1-C5알킬 또는 할로C1-C5알킬이며; R
41 내지 R
44는 서로 독립적으로 분지쇄C8-C20알킬이며; n 및 m은 서로 독립적으로 1 내지 7의 정수일 수 있다.본 발명의 일 실시예에 따른 중합체는 중량평균분자량이 100 내지 200,000g/mol, 바람직하게 5000 내지 200,000g/mol 일 수 있으며, PDI는 1이상일 수 있으나, 이에 한정이 있는 것은 아니다.Preferably, in Formulas 2 to 5 according to an embodiment of the present invention, Z 1 to Z 11 are each independently S or Se; R 3 to R 6 are each independently C1-C5 alkyl; R 11 to R 24 are each independently hydrogen, halogen, C1-C5 alkyl or haloC1-C5 alkyl; R 41 to R 44 are each independently C8-C20 alkyl; n and m may be each independently an integer of 1 to 7, more preferably Z 1 to Z 8 are S; Z 9 to Z 8 are S or Se; R 3 to R 6 are each independently C1-C5 alkyl; R 11 to R 24 are each independently hydrogen, halogen, C1-C5 alkyl or haloC1-C5 alkyl; R 41 to R 44 are each independently branched-chain C8-C20 alkyl; n and m may be each independently an integer of 1 to 7. The polymer according to an embodiment of the present invention may have a weight average molecular weight of 100 to 200,000 g/mol, preferably 5,000 to 200,000 g/mol, and PDI is It may be 1 or more, but is not limited thereto.
본 발명의 일 실시예에 따른 중합체는 하기 반응식에서와 같이 제조될 수 있으나, 이외에 당업자가 인식할 수 있는 통상의 유기합성방법을 통하여 제조될 수도 있음은 물론이다.The polymer according to an embodiment of the present invention may be prepared as in the following reaction scheme, but of course, it may also be prepared through a conventional organic synthesis method that can be recognized by those skilled in the art.
또한 반응에서 사용되는 유기 용매는 제한되지 않으며, 반응시간과 온도 또한 발명의 핵심을 벗어나지 않는 범위 내에서 변경이 가능하다. In addition, the organic solvent used in the reaction is not limited, and the reaction time and temperature can also be changed within a range that does not deviate from the core of the invention.
[반응식 1][Scheme 1]
(상기 반응식 1에서 (in Scheme 1 above
Z
1 내지 Z
4, R
1 내지 R
6 및 X는 화학식 1에서의 정의와 동일하며,Z 1 to Z 4 , R 1 to R 6 and X are the same as defined in Formula 1,
R
51 내지 R
56은 서로 독립적으로 C1-C10알킬이며,R 51 to R 56 are each independently C1-C10 alkyl;
X
1 및 X
2는 서로 독립적으로 할로겐이며;X 1 and X 2 are each independently halogen;
n은 2 내지 100,000의 정수이다.)n is an integer from 2 to 100,000.)
또한, 본 발명은 본 발명의 중합체를 포함하는 유기 전자 소자를 제공한다.The present invention also provides an organic electronic device comprising the polymer of the present invention.
본 발명의 일 실시예에 따른 유기 전자 소자는 본 발명의 중합체가 사용될 수 있는 소자라면 제한되지 않으며, 이의 비한정적인 일예로는 유기 전자 소자는 유기 태양 전지, 유기 박막 트랜지스터, 유기메모리, 또는 유기감광체, 유기 광센서 등을 들 수 있으며, 바람직하게는 유기태양전지 또는 유기박막트랜지스터일 수 있다.The organic electronic device according to an embodiment of the present invention is not limited as long as it is a device in which the polymer of the present invention can be used, and as a non-limiting example thereof, the organic electronic device may be an organic solar cell, an organic thin film transistor, an organic memory, or an organic electronic device. and a photoreceptor, an organic photosensor, and the like, and preferably an organic solar cell or an organic thin film transistor.
본 발명의 일 실시예에 따른 유기 전자 소자는 유기트랠지스터일 수 있으며, 상기 중합체는 유기트랜지스터의 유기반도체층에 포함될 수 있다.The organic electronic device according to an embodiment of the present invention may be an organic transistor, and the polymer may be included in an organic semiconductor layer of the organic transistor.
보다 구체적으로, 본 발명의 중합체는 유기트랜지스터의 유기반도체층에 사용되어 이를 채용한 유기트랜지스터는 향상된 점멸비를 가진다.More specifically, the polymer of the present invention is used in the organic semiconductor layer of the organic transistor, and the organic transistor employing the same has an improved flashing ratio.
본 발명의 일 실시예에 따른 유기 전자 소자는 유기 태양 전지일 수 있으며, 상기 중합체는 유기 태양 전지의 광활성층에 포함될 수 있다.The organic electronic device according to an embodiment of the present invention may be an organic solar cell, and the polymer may be included in a photoactive layer of the organic solar cell.
보다 구체적으로, 본 발명의 중합체는 유기 태양 전지의 광활성층에 전자공여체로 사용되어 이를 채용한 유기 태양 전지는 향상된 광전변환효율을 가진다.More specifically, the polymer of the present invention is used as an electron donor in the photoactive layer of an organic solar cell, and an organic solar cell employing the same has improved photoelectric conversion efficiency.
또한 본 발명은 본 발명의 중합체를 제조하기위한 다이케토피롤로피롤 화합물을 제공하는 것으로, 본 발명의 다이케토피롤로피롤 화합물은 하기 화학식 11로 표시된다.The present invention also provides a diketopyrrolopyrrole compound for preparing the polymer of the present invention, and the diketopyrrolopyrrole compound of the present invention is represented by the following formula (11).
[화학식 11][Formula 11]
(상기 화학식 11에서,(In Formula 11,
Z
1 내지 Z
4는 서로 독립적으로 O, S 또는 Se이며;Z 1 to Z 4 are each independently O, S or Se;
R
1 및 R
2는 서로 독립적으로 C1-C40알킬이며;R 1 and R 2 are each independently C1-C40 alkyl;
R
3 내지 R
6은 서로 독립적으로 수소 또는 C1-C10알킬이며;R 3 To R 6 are each independently hydrogen or C1-C10 alkyl;
X
1 및 X
2는 서로 독립적으로 수소 또는 할로겐이다.)X 1 and X 2 are each independently hydrogen or halogen.)
바람직하게 본 발명의 일 실시예에 따른 화학식 11에서 Z
1 내지 Z
4는 서로 독립적으로 S 또는 Se이며; R
1 및 R
2는 서로 독립적으로 C10-C40알킬이며; R
3 내지 R
6은 서로 독립적으로 C1-C10알킬이며; X
1 및 X
2는 서로 독립적으로 할로겐일 수 있다.Preferably, in Formula 11 according to an embodiment of the present invention, Z 1 to Z 4 are each independently S or Se; R 1 and R 2 are each independently C10-C40 alkyl; R 3 to R 6 may be each independently C1-C10 alkyl; X 1 and X 2 may be each independently halogen.
본 발명의 일 실시예에 따른 화학식 11로 표시되는 다이케토피롤로피롤 화합물은 본 발명의 화학식 1로 표시되는 중합체를 제조하기위한 중간체로 화학식 1의 화합물을 팔라듐 촉매 하 스틸러 커플링으로 본 발명의 중합체를 용이하게 제조할 수 있다.The diketopyrrolopyrrole compound represented by Formula 11 according to an embodiment of the present invention is an intermediate for preparing the polymer represented by Formula 1 of the present invention. The polymer can be easily prepared.
이하 본 발명이 일 양태에 따른 유기트랜지스터에 대하여 설명하나, 이에 한정이 있는 것은 아니다.Hereinafter, the present invention will be described with respect to the organic transistor according to the day and mode, but it is not limited to this.
본 발명의 일 실시에 따른 유기트랜지스터는 하부 게이트(bottom gate) 구조 중 하부 접촉 (bottom contact) 구조일 수 있다. 구체적으로, 기판 상에 게이트 전극 및 절연층이 순차적으로 형성되고 그 후에 절연층 상에 소스 전극 및 드레인 전극이 형성되며 마지막으로 소스 전극 및 드레인 전극 상에 유기반도체층이 형성될 수 있다. 본 발명의 일 실시에 따른 유기트랜지스터는 하부 게이트(bottom gate) 구조 중 상부 접촉(top contact) 구조일 수 있다. 구체적으로, 기판 상에 게이트 전극 및 절연층이 순차적으로 형성되고 그 후에 절연층 상에 유기반도체층이 형성되며, 마지막으로 유기반도체층 상에 소스 전극 및 드레인 전극이 형성될 수 있다. 본 발명의 일 실시예에 따른 절연층은 상기 유기반도체층과 접하여 구비될 수 있으며, 상기 소스 전극 및 상기 드레인 전극은 서로 접하지 않게 일정 간격을 사이에 두고 구비될 수 있다. 본 발명의 일 실시예에 따른 소스 전극 및 드레인 전극은 유기반도체층이 절연층과 접하는 면의 반대면에 부분적으로 접하여 구비될 수 있다. 본 발명의 일 실시예에 따른 유기트랜지스터는 유기반도체층 중 1층 이상이 상기 화학식 1의 중합체를 포함하는 것을 제외하고는 당 기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다. 본 발명의 일 실시예에 따른 유기트랜지스터가 복수개의 유기반도체층을 포함하는 경우, 유기반도체층은 동일한 물질 또는 다른 물질로 형성될 수 있다. 본 발명의 일 실시예에 따른 유기반도체층은 단층으로 구비될 수 있다. 단층으로 구비될 경우 유기 반도체층은 본 발명의 중합체를 포함한다. The organic transistor according to an embodiment of the present invention may have a bottom contact structure among a bottom gate structure. Specifically, a gate electrode and an insulating layer may be sequentially formed on the substrate, and then a source electrode and a drain electrode may be formed on the insulating layer, and finally, an organic semiconductor layer may be formed on the source electrode and the drain electrode. The organic transistor according to an embodiment of the present invention may have a top contact structure among a bottom gate structure. Specifically, the gate electrode and the insulating layer are sequentially formed on the substrate, and then the organic semiconductor layer is formed on the insulating layer, and finally the source electrode and the drain electrode are formed on the organic semiconductor layer. According to one embodiment of the present invention, the insulating layer may be provided in contact with the organic semiconductor layer, and the source electrode and the drain electrode may be provided with a predetermined interval therebetween so as not to contact each other. The source electrode and the drain electrode according to one embodiment of the present invention may be provided in partial contact with the surface opposite to the surface in which the organic semiconductor layer is in contact with the insulating layer. The organic transistor according to the embodiment of the present invention may be manufactured using materials and methods known in the art, except that at least one layer of the organic semiconductor layer includes the polymer of Formula 1 above. When the organic transistor according to the present embodiment includes a plurality of organic semiconductor layers, the organic semiconductor layers may be formed of the same material or different materials. The organic semiconductor layer according to the embodiment of the present invention may be provided as a single layer. When provided as a single layer, the organic semiconductor layer includes the polymer of the present invention.
본 발명의 일 실시예에 따른 기판은 유리와 같은 투명기판, 실리콘 기판, 또는 플라스틱으로 형성될 수 있다. 플라스틱 기판 물질로는 폴리에테르술폰(PES, polyethersulfone), 폴리아크릴레이트(PAR, polyacrylate), 폴리에테르이미드(PET, polyetherimide), 폴리에틸렌나프탈레이트(PEN, polyethylenenaphthalate), 폴리에틸렌테레프탈레이드(PET, polyethyleneterephthalate), 폴리페닐렌설파이드(PPS, polyphenylene sulfide), 폴리아릴레이트(polyarylate), 폴리이미드(polyimide), 폴리카보네이트(PC, polycarbonate), 트리아세틸셀룰로오스(TAC, tri-acetyl-cellulose) 및 셀룰로오스아세테이트 프로피오네이트(CAP, cellulose acetate propionate) 중에서 선택되는 1종 이상을 사용할 수 있다. 바람직하게는 UV 투과가 가능한 유리 같은 투명기판이 사용될 수 있다.The substrate according to the embodiment of the present invention may be formed of a transparent substrate such as glass, a silicon substrate, or plastic. Plastic substrate materials include polyethersulfone (PES, polyethersulfone), polyacrylate (PAR, polyacrylate), polyetherimide (PET, polyetherimide), polyethylenenaphthalate (PEN, polyethylenenaphthalate), polyethyleneterephthalate (PET, polyethyleneterephthalate), Polyphenylene sulfide (PPS), polyarylate (polyarylate), polyimide (polyimide), polycarbonate (PC, polycarbonate), triacetyl cellulose (TAC, tri-acetyl-cellulose) and cellulose acetate propionate (CAP, cellulose acetate propionate) may be used at least one selected from. Preferably, a transparent substrate such as glass that can transmit UV can be used.
본 발명의 일 실시예에 따른 게이트 전극은 패턴형태일 수 있으나, 이에 한정이 있는 것은 아니다. 게이트 전극은 금(Au), 니켈(Ni), 구리(Cu), 은(Ag), 알루미늄(Al), 알루미늄 합금(Al-alloy), 몰리브덴(Mo), 몰리 브덴 합금(Mo-alloy) 중에서 선택되는 어느 하나로 형성할 수 있다. 본 발명의 일 실시예에 따른 게이트 전극은 포토리소그래피법, 오프셋 인쇄법, 실크스크린 인쇄법, 잉크젯 인 쇄법, 열증착법 및 쉐도우 마스크(Shadow Mask)를 이용한 방법 중에서 선택되는 방법을 이용하여 형성될 수 있으나, 이에만 한정되는 것은 아니다. 게이트 전극의 두께는 10nm 내지 300nm일 수 있으며, 바람직하게는 10nm 내지 50nm이다. The gate electrode according to the present embodiment of the present invention may be in the form of a pattern, but the present invention is not limited thereto. The gate electrode is selected from among gold (Au), nickel (Ni), copper (Cu), silver (Ag), aluminum (Al), aluminum alloy (Al-alloy), molybdenum (Mo), and molybdenum alloy (Mo-alloy). It can be formed by any one selected. The gate electrode according to an embodiment of the present invention may be formed using a method selected from a photolithography method, an offset printing method, a silkscreen printing method, an inkjet printing method, a thermal evaporation method, and a method using a shadow mask. However, the present invention is not limited thereto. The thickness of the gate electrode may be 10 nm to 300 nm, preferably 10 nm to 50 nm.
본 발명의 일 실시예에 따른 절연층은 유기절연막 또는 무기절연막의 단일막 또는 다층막으로 구성되거나 유무기 하이브리드막으로 구성될 수 있다. 무기절연막으로는 실리콘 산화막, 실리콘 질화막, Al
2O
3, Ta
2O
5, BST, PZT 중에서 선택되는 어느 하나 또는 다수개가 사용될 수 있다. 유기절연막으로는 CYTOP TM, 폴리메틸메타크 릴레이트(PMMA, polymethylmethacrylate), 폴리스타이렌(PS, polystyrene), 페놀계 고분자, 아크릴계 고분자, 폴리이미드와 같은 이미드계 고분자, 아릴에테르계 고분자, 아마이드계 고분자, 불소계 고분자, p-자이리렌계 고분자, 비닐알콜계 고분자, 파릴렌(parylene) 중에서 선택되는 어느 하나 또는 다수 개를 사용할 수 있으나, 이에 한정되는 것은 아니다. 본 발명의 일 실시예에 따른 절연층은 용액공정을 통해서 형성할 수 있으며, 스핀코팅, 바코팅, 슬릿다이 코팅, 닥터 블레이드 등을 통해서 대면적으로 도포될 수 있다. 바람직하게는 스핀코팅을 통하여 절연층을 형성할 수 있으나, 이에 한정되는 것은 아니다. 절연층 형성시 100℃ 내지 150℃에서 30분 이상 열처리를 하여서 사용한 용매가 완전히 증발되도록 할 수 있다. The insulating layer according to an embodiment of the present invention may be composed of a single film or a multilayer film of an organic insulating film or an inorganic insulating film, or may be composed of an organic-inorganic hybrid film. As the inorganic insulating film, any one or a plurality of silicon oxide films, silicon nitride films, Al 2 O 3 , Ta 2 O 5 , BST, and PZT may be used. Examples of the organic insulating film include CYTOP TM, polymethylmethacrylate (PMMA, polymethylmethacrylate), polystyrene (PS, polystyrene), phenolic polymers, acrylic polymers, imide-based polymers such as polyimide, arylether-based polymers, amide-based polymers, Any one or a plurality of fluorine-based polymers, p-xylylene-based polymers, vinyl alcohol-based polymers, and parylene may be used, but the present invention is not limited thereto. The insulating layer according to an embodiment of the present invention may be formed through a solution process, and may be applied over a large area through spin coating, bar coating, slit die coating, doctor blade, or the like. Preferably, the insulating layer may be formed through spin coating, but is not limited thereto. When the insulating layer is formed, heat treatment is performed at 100° C. to 150° C. for 30 minutes or more so that the solvent used is completely evaporated.
본 발명의 일 실시예에 따른 소스 전극 및 드레인 전극은 도전성 물질로 이루어질 수 있으며, 예컨대, 탄 소, 알루미늄, 바나듐, 크롬, 구리, 아연, 은, 금, 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 주석, 납, 네오디뮴(neodymium), 백금, 니켈, 금속 유사물(similar metals) 및 이들의 합금; p- 또는 n-도프된(doped) 실리콘; 산화아연, 산화인듐, 인듐 주석 산화물(ITO), 인듐아연 산화물, 주석 유사 산화물(similar tin oxide) 및 주석 산화물 인듐계 복합 화합물(tin oxide indium-based complex compounds); ZnO:Al, SnO
2:Sb와 같은 산화물과 금속의 혼합물; 및 폴리(3-메틸티오펜)(poly(3-methylthiophene)), 폴리[3,4- (에틸렌-1,2-디옥시)티오펜] (poly[3,4-(ethylene-1,2-dioxy) thiophene]), 폴리피롤(polypyrrole) 및 폴리아 닐린(polyaniline)과 같은 도전성 고분자 등이 있으나, 이에 한정되는 것은 아니다. The source electrode and the drain electrode according to an embodiment of the present invention may be made of a conductive material, for example, carbon, aluminum, vanadium, chromium, copper, zinc, silver, gold, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, tin, lead, neodymium, platinum, nickel, similar metals and alloys thereof; p- or n-doped silicon; zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide, similar tin oxide and tin oxide indium-based complex compounds; mixtures of oxides and metals such as ZnO:Al, SnO 2 :Sb; and poly(3-methylthiophene)), poly[3,4-(ethylene-1,2-dioxy)thiophene] (poly[3,4-(ethylene-1,2) -dioxy) thiophene]), polypyrrole (polypyrrole), and conductive polymers such as polyaniline (polyaniline), but is not limited thereto.
본 발명의 일 실시예에따른 유기반도체층은 용액공정을 통하여 형성될 수 있다. 이때 유기반도체층은 통상적으로 스핀코팅, 바코팅, 슬릿다이 코팅, 닥터 블레이드, 잉크젯 코팅 등을 통해서 대면적으로 도포할 수 있 으나, 이에 한정되는 것은 아니다. The organic semiconductor layer according to an embodiment of the present invention may be formed through a solution process. In this case, the organic semiconductor layer may be applied over a large area through spin coating, bar coating, slit die coating, doctor blade, inkjet coating, or the like, but is not limited thereto.
본 발명의 일 실시예에 따른 유기박막트랜지스터에 있어서, 기판 상에 소스 전극 및 드레인 전극을 형성할 경우, 소스 전극 및 드레인 전극은 열증착 방법을 이용해서 형성할 수 있으나, 이에 한정되는 것은 아니며, 당업계에서 공지된 다른 방법에 의하여 형성 할 수 있다. 이때 소스 전극과 드레인 전극간의 간격은 통상적으로 2㎛ 내지 수 백㎛의 채널 길이를 지니고 있고 채널 넓이는 채널 길이의 10배 내지 1000배 정도로 구성될 수 있다. 소스 전극과 드레인 전극은 통상적으로 금 및 니켈로 제작되어 있으나 은, 구리, 몰리브덴 등 다른 전극을 사용할 수도 있다.In the organic thin film transistor according to the embodiment of the present invention, when the source electrode and the drain electrode are formed on the substrate, the source electrode and the drain electrode may be formed using a thermal evaporation method, but the present invention is not limited thereto. It can be formed by other methods known in the art. In this case, the distance between the source electrode and the drain electrode typically has a channel length of 2 μm to several hundreds of μm, and the channel width may be 10 to 1000 times the channel length. The source and drain electrodes are usually made of gold and nickel, but other electrodes such as silver, copper, and molybdenum may also be used.
본 발명의 일 실시예에 따른 유기트랜지스터에 있어서 유기반도체층 상에 소스 전극 및 드레인 전극을 형성할 경우, 소스 전극 및 드레인 전극은 광식각 공정이나 쉐도우 마스크 공정을 이용해서 형성할 수 있으나, 이에만 한정되는 것은 아니며, 당업계에서 공지된 다른 방법에 의하여 형성할 수 있다. In the case of forming the source electrode and the drain electrode on the organic semiconductor layer in the organic transistor according to the embodiment of the present invention, the source electrode and the drain electrode may be formed using a photoetch process or a shadow mask process, but only in this case It is not limited, and may be formed by other methods known in the art.
본 발명의 일 실시예에 따른 P-type 특성은 게이트 전극에 마이너스 전압을 가한 후 소스 전극과 드레인 전극 사이에서 흐르는 전류를 측정하여 확인한다. P-type 특성을 나타낼 경우, 게이트 전극에 마이너스 전압을 가하면, 유기반도체층 내에서 정공이 이동한다.The P-type characteristic according to the embodiment of the present invention is checked by measuring the current flowing between the source electrode and the drain electrode after applying a negative voltage to the gate electrode. If a negative voltage is applied to the gate electrode in the case of exhibiting the P-type characteristic, holes move in the organic semiconductor layer.
이하, 본 발명의 일 양태에 따른 유기 태양 전지에 대하여 설명하나, 이는 일 예를 들어 설명하는 것으로 이에 한정이 있는 것은 아니다.Hereinafter, an organic solar cell according to an aspect of the present invention will be described, but this is not limited thereto.
본 발명의 중합체는 종래의 싸이오펜 대신 확장된 컨쥬게이션을 가지는 작용기를 도입함으로써 향상된 전하 이동도를 가지며, 따라서 이를 채용한 유기 태양 전지는 높은 효율을 구현할 수 있다.The polymer of the present invention has improved charge mobility by introducing a functional group having extended conjugation instead of conventional thiophene, and thus an organic solar cell employing the same can realize high efficiency.
즉, 본 발명은 본 발명의 신규한 중합체를 광활성층에 채용한 유기 태양 전지 또는 신규한 중합체를 광활성층에 채용한 양자점 태양전지를 제공한다.That is, the present invention provides an organic solar cell employing the novel polymer of the present invention in the photoactive layer or a quantum dot solar cell employing the novel polymer in the photoactive layer.
본 발명의 일 실시예에 따른 유기 태양 전지는 기판, 제1전극, 광활성층 및 제2전극을 포함하는 것일 수 있으며, 정공수송층, 전자수송층 등을 더 포함할 수 있음은 물론이다.The organic solar cell according to an embodiment of the present invention may include a substrate, a first electrode, a photoactive layer and a second electrode, and may further include a hole transport layer, an electron transport layer, and the like.
또한 본 발명의 일 실시예에 따른 유기 태양 전지는 반전된 유형의 유기 태양 전지일 수 있다.Also, the organic solar cell according to an embodiment of the present invention may be an inverted type organic solar cell.
상기 기판은 유리 및 석영판 이외에도 PET(polyethylene terephthalate), PEN(polyethylene naphthelate), PP(polyperopylene), PI(polyimide), PC(polycarbornate), PS(polystylene), POM(polyoxyethlene), AS 수지(acrylonitrile styrene copolymer), ABS 수지(acrylonitrile butadiene styrene copolymer) 및 TAC(Triacetyl cellulose) 등을 포함하는 플라스틱과 같은 유연하고 투명한 물질로 제조될 수 있다.In addition to glass and quartz plate, the substrate is PET (polyethylene terephthalate), PEN (polyethylene naphthelate), PP (polyperopylene), PI (polyimide), PC (polycarbornate), PS (polystylene), POM (polyoxyethlene), AS resin (acrylonitrile styrene) copolymer), ABS resin (acrylonitrile butadiene styrene copolymer), and TAC (Triacetyl cellulose) may be made of a flexible and transparent material such as plastic.
또한 상기 제1전극은 스퍼터링, E-Beam, 열증착, 스핀코팅, 스크린 프린팅, 잉크젯 프린팅, 닥터 블레이드 또는 그라비아 프린팅법을 사용하여 투명전극 물질을 상기 기판의 일면에 도포되거나 필름형태로 코팅됨으로써 형성된다. 제1전극은 애노드의 기능을 하는 부분으로써, 후술하는 제2전극에 비해 일함수가 큰 물질로 투명성 및 도전성을 갖는 임의의 물질이 사용될 수 있다. 예를 들면, ITO(indium tin oxide), 금, 은, 플로린이 도핑된 틴 옥사이드(fluorine doped tin oxide; FTO), 알루미늄이 도핑된 징크 옥사이드(aluminium doped zink oxide, AZO), IZO(indium zink oxide), ZnO-Ga
2O
3, ZnO-Al
2O
3 및 ATO(antimony tin oxide, SnO
2-Sb
2O
3) 등이 있으며, 바람직하게는 ITO를 사용하는 것이 좋다.In addition, the first electrode is formed by coating a transparent electrode material on one surface of the substrate or coating it in a film form using sputtering, E-Beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing method. do. The first electrode is a part functioning as an anode, and is a material having a greater work function compared to a second electrode to be described later, and any material having transparency and conductivity may be used. For example, indium tin oxide (ITO), gold, silver, fluorine doped tin oxide (FTO), aluminum doped zinc oxide (AZO), indium zink oxide (IZO) ), ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 and antimony tin oxide (ATO, SnO 2 -Sb 2 O 3 ), etc., and preferably ITO.
상기 제1 전극과 광활성층의 사이에는 정공수송층이 삽입될 수도 있으며, 상기 정공수송층은 스핀코팅 또는 딥코팅 등의 방법을 통해 형성될 수 있다. 상기 정공수송층을 형성하기 위한 재료로는 전도성 고분자인 PEDOT:PSS (poly(3,4-ethylenedioxythiophene):polystyrene sulfonate)를 사용하는 것이 바람직하며, 이는 전자가 양극인 ITO(indium tin oxide)층으로 이동하는 것을 막아주면서 정공의 수송을 원활하게 도와준다.A hole transport layer may be inserted between the first electrode and the photoactive layer, and the hole transport layer may be formed through spin coating or dip coating. As a material for forming the hole transport layer, it is preferable to use a conductive polymer, PEDOT:PSS (poly(3,4-ethylenedioxythiophene):polystyrene sulfonate), in which electrons move to the anode, ITO (indium tin oxide) layer. It helps to facilitate the transport of holes while preventing
상기 제2전극과 광활성층 사이에 전자수송층이 삽입될 수도 있으며, 상기 전자수송층은 금속산화물을 포함하는 금속산화물층으로, 상기 금속산화물은 이에 한정되는 것은 아니나, 이산화티탄(TiO
2), 이산화주석(SnO
2), 산화아연(ZnO) 등의 나노입자 산화물로 형성될 수 있다.An electron transport layer may be inserted between the second electrode and the photoactive layer, and the electron transport layer is a metal oxide layer including a metal oxide, the metal oxide being, but not limited to, titanium dioxide (TiO 2 ), tin dioxide (SnO 2 ), zinc oxide (ZnO), and the like may be formed of a nanoparticle oxide.
상기 광활성층은 전자 주게인 전자공여체 및 전자 받게인 전자수용체를 포함하는 것일 수 있다. 이때, 상기 중합체는 광활성층의 전자공여체로 사용되어 향상된 외부 양자 효율을 구현할 수 있다. 이때, 상기 광활성층의 전자공여체 및 전자수용체는 벌크 헤테로 정션(BHJ, Bulk-heterojunction)을 구성한다. 벌크 헤테로 정션이란 광활성층에서 전자공여체 및 전자수용체에 해당하는 각 화합물이 서로 섞여 있는 것을 의미한다.The photoactive layer may include an electron donor as an electron donor and an electron acceptor as an electron acceptor. In this case, the polymer may be used as an electron donor of the photoactive layer to realize improved external quantum efficiency. At this time, the electron donor and the electron acceptor of the photoactive layer constitute a bulk heterojunction (BHJ, Bulk-heterojunction). The bulk heterojunction means that each compound corresponding to an electron donor and an electron acceptor is mixed with each other in the photoactive layer.
상기 광활성층은 상기 중합체는 광활성층의 전자공여체로 포함하고, 전자수용체와 함께 벌크 헤테로 정션을 구성하는 것일 수 있다.The photoactive layer may include the polymer as an electron donor of the photoactive layer and constitute a bulk heterojunction together with the electron acceptor.
또한 상기 광활성층에는 본 발명의 중합체를 전자공여체를 포함할 수 있으며, 이의 배합량은 용도에 따라 적절하게 조절될 수 있다. 또한 상기 중합체는 용매 및 전자수용체를 포함할 수 있다. 상기 전자수용체로는 예를 들어 C60, C70, [60]PCBM (Phenyl C
61-butyric acid methyl ester), [70]PCBM (Phenyl C
71-butyric acid methyl ester), [60]ICBA (Indene-C
60 Bis-Adduct), [60]PCBCR (phenyl-C
61-butyric acid cholestryl ester), [70]PCBCR (phenyl-C
71-butyric acid cholestryl ester), 페릴렌 (perylene), PBI (polybenzimidazole), PTCBI (3,4,9,10-perylene-tetracarboxylic bis-benzimidazole), P(NDI2HD-Se) 등이 사용될 수 있으나, 이에 한정되는 것은 아니다.In addition, the photoactive layer may include the polymer of the present invention as an electron donor, and the blending amount thereof may be appropriately adjusted according to the use. In addition, the polymer may include a solvent and an electron acceptor. As the electron acceptor, for example, C60, C70, [60]PCBM (Phenyl C 61 -butyric acid methyl ester), [70]PCBM (Phenyl C 71 -butyric acid methyl ester), [60]ICBA (Indene-C) 60 Bis-Adduct), [60]PCBCR (phenyl-C 61 -butyric acid cholestryl ester), [70]PCBCR (phenyl-C 71 -butyric acid cholestryl ester), perylene, PBI (polybenzimidazole), PTCBI (3,4,9,10-perylene-tetracarboxylic bis-benzimidazole), P(NDI2HD-Se), etc. may be used, but is not limited thereto.
이때, 본 발명에 따른 중합체를 광활성층의 전자공여체로 포함하는 경우, 밴드갭을 낮추어 향상된 점멸비를 가진다.In this case, when the polymer according to the present invention is included as an electron donor of the photoactive layer, the band gap is lowered to have an improved flashing ratio.
또한 상기 광활성층에는 활성층의 모폴로지와 결정성을 조절하여 탁월하게 향상된 효율을 구현하기 위하여, 추가의 첨가제를 더 포함할 수 있다. 상기 첨가제의 일 예로는 1,8-디아이오도옥탄(DIO:1,8-diiodooctane), 1-클로로나프탈렌(1-CN:1-chloronaphthalene), 다이페닐에테르(DPE:diphenylether), 옥탄디싸이올(octane dithiol) 및 테트라브로모싸이오펜(tetrabromothiophene) 등을 들 수 있으며, 용도에 따라 적절하게 배합되어 사용될 수 있다. 바람직하게, 본 발명에 따른 중합체는 1,8-디아이오도옥탄과 함께 사용되는 경우 현저하게 향상된 결정성을 구현하여, 단락전류밀도(
J
sc) 및 충전률(FF)의 향상은 물론 현저하게 향상된 외부 양자 효율을 구현할 수 있다.In addition, the photoactive layer may further include an additional additive in order to realize excellently improved efficiency by controlling the morphology and crystallinity of the active layer. Examples of the additive include 1,8-diiodooctane (DIO: 1,8-diiodooctane), 1-chloronaphthalene (1-CN: 1-chloronaphthalene), diphenyl ether (DPE: diphenylether), octanedithiol (octane dithiol) and tetrabromothiophene (tetrabromothiophene), and the like, and may be appropriately combined according to the intended use. Preferably, the polymer according to the present invention realizes significantly improved crystallinity when used with 1,8-diiodooctane, thereby significantly improving short-circuit current density ( J sc ) and filling factor (FF) as well as significantly improved External quantum efficiency can be implemented.
본 발명의 중합체는 용매에 용해시켜 사용될 수 있으며, 상기 용매는 아세톤, 메탄올, THF, 톨루엔, 자일렌, 테트랄린, 클로로포름, 클로로벤젠, 디클로로벤젠 또는 이들의 혼합용매로 사용될 수 있으나 이에 한정되는 것은 아니다. 또한 본 발명의 중합체는 60 내지 120 nm 두께로 광활성층에 도입되는 것이 바람직하나 이에 한정되는 것은 아니다. 또한 본 발명의 중합체를 포함하는 상기 광활성층은 높은 전자 밀도 및 낮은 밴드갭으로 인하여, 단락전류밀도(short circuit current density) 및 개방전압(open circuit voltage)이 증가할 뿐만 아니라 점멸비도 개선된다.The polymer of the present invention may be used by dissolving it in a solvent, and the solvent may be used as acetone, methanol, THF, toluene, xylene, tetralin, chloroform, chlorobenzene, dichlorobenzene, or a mixed solvent thereof. it is not In addition, the polymer of the present invention is preferably introduced into the photoactive layer with a thickness of 60 to 120 nm, but is not limited thereto. In addition, in the photoactive layer comprising the polymer of the present invention, due to high electron density and low bandgap, short circuit current density and open circuit voltage are increased as well as the flashing ratio is improved.
본 발명의 일 실시예에 따른 유기 태양 전지는 전자수송층을 더 포함할 수 있다. 상기 전자수송층은 전자수송층의 모폴로지를 향상시키기 위해 계면활성제(surfactant)를 첨가하여 제조 할 수 있다. 이때, 상기 전자수송층은 친전자성 기능을 가지는 수용성 고분자를 물, 에탄올 또는 이들의 혼합용매에 용해하고, 상기 고분자 용액에 계면활성제를 첨가한 후 여과하여 박막을 형성하는 단계를 포함하여 제조할 수 있다. 이때, 상기 친전자성 기능기를 가지는 수용성 고분자로는 폴리[9,9-비스(6'-디에탄올아미노)헥실)-플루오렌]이 바람직하며, 상기 계면활성제는 2,4,7,9-테트라메틸-5-데킨-4,7-디올인 것이 바람직하지만, 이에 한정되는 것은 아니다. 또한 상기 수용성 고분자 및 계면활성제가 혼합된 용액을 스핀 코팅 등의 방법으로 2 내지 20nm 코팅하여 열처리하는 것이 좋다. 이때, 상기 전자수송층은 스핀코팅의 방법 외에도 딥코팅, 스크린 프린팅, 잉크젯 프린팅, 그라비아 프린팅, 스프레이 코팅, 닥터블레이드 또는 브러쉬 페인팅 등의 방법을 응용할 수 있으며, 본 발명이 이에 제한되는 것은 아니다.The organic solar cell according to an embodiment of the present invention may further include an electron transport layer. The electron transport layer may be prepared by adding a surfactant to improve the morphology of the electron transport layer. In this case, the electron transport layer may be prepared by dissolving a water-soluble polymer having an electrophilic function in water, ethanol or a mixed solvent thereof, adding a surfactant to the polymer solution, and then filtering to form a thin film. have. In this case, the water-soluble polymer having the electrophilic functional group is preferably poly[9,9-bis(6'-diethanolamino)hexyl)-fluorene], and the surfactant is 2,4,7,9- It is preferably, but not limited to, tetramethyl-5-decyne-4,7-diol. In addition, it is preferable to heat-treat the solution in which the water-soluble polymer and the surfactant are mixed by coating 2 to 20 nm by a method such as spin coating. In this case, the electron transport layer may be applied by methods such as dip coating, screen printing, inkjet printing, gravure printing, spray coating, doctor blade or brush painting in addition to the spin coating method, but the present invention is not limited thereto.
또한 상기 제2 전극은 전자수송층이 도입된 상태에서 열증착기를 이용하여 증착될 수 있다. 이때 사용가능한 전극재료로는 불화리튬/알루미늄, 불화리튬/칼슘/알루미늄, 알루미늄/칼슘, 불화바륨/알루미늄, 불화바륨/바륨/알루미늄, 바륨/알루미늄, 알루미늄, 금, 은, 마그네슘:은 및 리튬:알루미늄 중에서 선택될 수 있으며, 바람직하게는 은, 알루미늄, 알루미늄/칼슘 또는 불화바륨/바륨/알루미늄 구조로 제작된 전극을 사용하는 것이 좋다.In addition, the second electrode may be deposited using a thermal evaporator in a state in which the electron transport layer is introduced. At this time, usable electrode materials include lithium fluoride/aluminum, lithium fluoride/calcium/aluminum, aluminum/calcium, barium/aluminum fluoride, barium fluoride/barium/aluminum, barium/aluminum, aluminum, gold, silver, magnesium: silver and lithium. : It can be selected from aluminum, and it is preferable to use an electrode made of silver, aluminum, aluminum/calcium or barium fluoride/barium/aluminum structure.
일반 유기 태양전지는 전자(electron)가 음극으로, 정공(Hole)이 양극으로 빠져나가는 원리이나, 반전 유기 태양전지는 반대로 전자(electron)가 양극으로, 정공(Hole)이 음극으로 빠져나가는 원리로, 본 발명은 이를 모두 포함한다.In general organic solar cells, electrons go to the anode and holes go to the anode, whereas in reverse organic solar cells, electrons go to the anode and holes go to the cathode. , the present invention includes all of them.
이하, 본 발명을 실시예에 의해 상세히 설명한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 내용이 하기 실시예에 의해 한정되는 것은 아니다. 이때, 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가진다. 또한, 종래와 동일한 기술적 구성 및 작용에 대한 반복되는 설명은 생략하기로 한다.Hereinafter, the present invention will be described in detail by way of Examples. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited by the following examples. At this time, unless there are other definitions in the technical terms and scientific terms used, those of ordinary skill in the art to which this invention belongs have the meanings commonly understood. In addition, repeated description of the same technical configuration and operation as in the prior art will be omitted.
[물성 평가 방법][Method for evaluating physical properties]
1H NMR 스펙트럼은 Varian Mercury Plus 300 MHz 및 Bruker FT NMR spectroscopy system으로 측정하였고, 자외선 흡수 스펙트럼은 UV-1800 spectrophotometer(Shimadzu Scientific Instruments)으로 측정하였다. 물질의 HOMO Level을 구하기 위하여 순환 전류-전압 분석(Cyclic Voltammetry, CV)은 CHI 600C electrochemical analyzer를 이용하여 측정하였다. 1 H NMR spectrum was measured with Varian Mercury Plus 300 MHz and Bruker FT NMR spectroscopy system, and ultraviolet absorption spectrum was measured with UV-1800 spectrophotometer (Shimadzu Scientific Instruments). Cyclic voltammetry (CV) was measured using a CHI 600C electrochemical analyzer to obtain the HOMO level of the material.
M
n 및 PDI 값은 Waters 1515 Isocratic HPLC 펌프, 온도 제어 모듈 및 Waters 2414 시차굴절 검출기로 구성된 GPC를 이용하여 80℃에서 1 mL/min의 속도로
o-DCB(
o-dichlorobenzene) 용매 하에서 측정하였으며, 폴리스티렌 표준물질을 사용하여 분자량을 보정하였다.M n and PDI values were measured in o -DCB ( o -dichlorobenzene) solvent at 80 ° C. at a rate of 1 mL / min using a GPC consisting of a Waters 1515 Isocratic HPLC pump, a temperature control module, and a Waters 2414 differential refraction detector. Molecular weight was calibrated using polystyrene standards.
TGA는 질소 유속을 50 ml/분으로 하여 온도 범위 0 내지 800 ℃까지 분 당 10℃씩 올려서 측정하였다.TGA was measured by raising the nitrogen flow rate to 50 ml/min to a temperature range of 0 to 800 °C at a rate of 10 °C per minute.
[실시예 1] 중합체
1의 제조[Example 1] Preparation of Polymer 1
단계1: 화합물 1-1(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2-carbonitrile)의 제조Step 1: Preparation of compound 1-1 (4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2-carbonitrile)
4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2-carbaldehyde (2.0 g, 8.54 mmol) 를 NMP(N-Methyl-2-pyrrolidone )(50.0 mL)에 녹인 후 Hydroxylamine hydrochloride (0.7 g, 10.1 mmol)를 서서히 첨가하였다. 반응 혼합물을 115 ℃에서 8 시간 동안 교반시킨 후 실온으로 냉각시켰다. 디클로로메탄 및 물을 첨가하여 추출한 후 헥산 : 에틸 아세테이트 (9 : 1)를 사용하여 실리카 겔상에서 컬럼 크로마토 그래피를 통해 정제하여 황색 고체인 표제 화합물을 수득 하였다(1.4 g, 71%). 4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2-carbaldehyde (2.0 g, 8.54 mmol) was mixed with NMP(N-Methyl-2-pyrrolidone) (50.0 mL) After dissolving in , Hydroxylamine hydrochloride (0.7 g, 10.1 mmol) was slowly added. The reaction mixture was stirred at 115 °C for 8 h and then cooled to room temperature. After extraction with dichloromethane and water, the mixture was purified by column chromatography on silica gel using hexane:ethyl acetate (9: 1) to obtain the title compound as a yellow solid (1.4 g, 71%).
1H NMR (300 MHz, CD
2Cl
2) δ 7.50 (s, 1 H), 7.39 (d, J = 4.9 Hz, 1 H), 7.07 (d, J = 4.9 Hz, 1 H), 1.46 (s, 6 H). 1 H NMR (300 MHz, CD 2 Cl 2 ) δ 7.50 (s, 1 H), 7.39 (d, J = 4.9 Hz, 1 H), 7.07 (d, J = 4.9 Hz, 1 H), 1.46 (s) , 6 H).
단계2: 화합물 1-2(3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione)의 제조Step 2: Compound 1-2 (3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-dihydropyrrolo[ Preparation of 3,4-c]pyrrole-1,4-dione)
20 mL 반응 플라스크에 sodium (0.152 g, 6.36 mmol), FeCl
3 (0.051 g, 0.318 mmol)를 첨가하고
5 mL tert-Amyl alcohol을 첨가 한 다음, 모든 고체가 용해 될 때까지 100 ℃로 가온 하였다. 이후, 4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2-carbonitrile (1.0 g, 4.32 mmol)을 한번에 첨가 한 다음 diisopropyl succinate (0.35 g, 1.73 mmol)를 첨가 하였다. 12 시간 동안 교반 한 후, 반응물을 40 ℃로 냉각시키고, 메탄올 (8mL) 및 아세트산 (3 mL)을 첨가 하였다. 반응 혼합물을 여과하고 물, 메탄올, 아세톤 및 헥산으로 세척하여 생성물을 진한 파란색 고체로 수득하였으며 (0.6 g 64%), 이를 추가 정제없이 다음 반응을 진행하였다.Add sodium (0.152 g, 6.36 mmol), FeCl 3 (0.051 g, 0.318 mmol) to a 20 mL reaction flask and 5 mL tert-Amyl alcohol was added and then warmed to 100 °C until all solids were dissolved. Then, 4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2-carbonitrile (1.0 g, 4.32 mmol) was added at once, followed by diisopropyl succinate (0.35 g, 1.73 mmol) ) was added. After stirring for 12 h, the reaction was cooled to 40 °C, and methanol (8 mL) and acetic acid (3 mL) were added. The reaction mixture was filtered and washed with water, methanol, acetone and hexane to give the product as a dark blue solid (0.6 g 64%), which was carried out without further purification.
단계 3: 화합물 1-3(2,5-bis(5-decylheptadecyl)-3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione)의 제조Step 3: Compound 1-3(2,5-bis(5-decylheptadecyl)-3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophen- Preparation of 2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione)
3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (1.0 g 1.83 mmol), KOH (0.31 g ,5.50 mmol), 촉매당량의 KI (0.015 g, 0.0915 mmol) 그리고 18-crown-6 (0.05 g, 0.183 mmol)를 DMF (60.0 mL)에 녹인 후 11-(6-bromohexyl)tricosane (2.68 g, 5.50 mmol)를 천천히 첨가하였다. 반응 혼합물을 120 ℃에서 24 시간 동안 교반시킨 다음 실온으로 냉각시켰다. 디클로로메탄 및 물을 첨가하여 추출한 후 헥산 : 디클로로메탄 (9 : 1)를 사용하여 실리카 겔상에서 컬럼 크로마토 그래피를 통해 정제하여 생성물을 진청색 고체로서 수득 하였다 (1.6 g, 64%). 3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole- 1,4-dione (1.0 g 1.83 mmol), KOH (0.31 g ,5.50 mmol), catalytic equivalent of KI (0.015 g, 0.0915 mmol) and 18-crown-6 (0.05 g, 0.183 mmol) in DMF (60.0 mL) ) and then slowly added 11-(6-bromohexyl)tricosane (2.68 g, 5.50 mmol). The reaction mixture was stirred at 120 °C for 24 h and then cooled to room temperature. After extraction by addition of dichloromethane and water, the product was purified by column chromatography on silica gel using hexane:dichloromethane (9:1) to give the product as a dark blue solid (1.6 g, 64%).
1H NMR (300 MHz, CD
2Cl
2) δ 8.95 (s, 1 H), 7.29 (d, J = 4.9 Hz, 1 H), 7.01 (d, J = 4.9 Hz, 1 H), 4.12 - 3.93 (m, 2 H), 1.78 - 1.60 (m, 2 H), 1.53 - 1.43 (m, 6 H), 1.36 (dd, J = 14.5, 4.4 Hz, 2 H), 1.19 (q, J = 7.2 Hz, 47 H), 0.84 - 0.73 (m, 6 H). 1 H NMR (300 MHz, CD 2 Cl 2 ) δ 8.95 (s, 1 H), 7.29 (d, J = 4.9 Hz, 1 H), 7.01 (d, J = 4.9 Hz, 1 H), 4.12 - 3.93 (m, 2 H), 1.78 - 1.60 (m, 2 H), 1.53 - 1.43 (m, 6 H), 1.36 (dd, J = 14.5, 4.4 Hz, 2 H), 1.19 (q, J = 7.2 Hz) , 47 H), 0.84 - 0.73 (m, 6 H).
단계4: 화합물 1-4(2,5-bis(5-decylheptadecyl)-3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione)의 제조Step 4: Compound 1-4(2,5-bis(5-decylheptadecyl)-3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen- Preparation of 2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione)
화합물1-3(2,5-bis(5-decylheptadecyl)-3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) (1.0 g, 0.74 mmol)를 Chloroform (30.0 mL)에 녹인 후 NBS (0.29 g, 1.61 mmol)를 천천히 첨가하였다. 실온에서 3 시간 동안 교반시킨 후, 용액을 디클로로메탄으로 추출하고 물로 세척 하였다. 추출물을 MgSO4로 건조시키고 감압 하에서 농축하고, 헥산 : 디클로로메탄 (3 : 2)을 사용하여 실리카 겔상에서 컬럼 크로마토그래피를 통해 정제하여 생성물을 진청색 고체로서 수득 하였다.(0.9 g, 81%). Compound 1-3(2,5-bis(5-decylheptadecyl)-3,6-bis(4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl )-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) (1.0 g, 0.74 mmol) was dissolved in Chloroform (30.0 mL), and then NBS (0.29 g, 1.61 mmol) was slowly added. . After stirring at room temperature for 3 h, the solution was extracted with dichloromethane and washed with water. The extract was dried over MgSO4, concentrated under reduced pressure, and purified via column chromatography on silica gel using hexanes:dichloromethane (3:2) to give the product as a dark blue solid (0.9 g, 81%).
1H NMR (300 MHz, CD
2Cl
2) δ 8.89 (s, 1 H), 7.04 (s, 1 H), 4.41 - 3.54 (m, 2 H), 1.82 - 1.62 (m, 2 H), 1.45 (d, J = 1.3 Hz, 6 H), 1.41 - 1.31 (m, 2 H), 1.31 - 1.06 (m, 47 H), 0.79 (t, J = 6.7 Hz, 6 H). 1 H NMR (300 MHz, CD 2 Cl 2 ) δ 8.89 (s, 1 H), 7.04 (s, 1 H), 4.41 - 3.54 (m, 2 H), 1.82 - 1.62 (m, 2 H), 1.45 (d, J = 1.3 Hz, 6 H), 1.41 - 1.31 (m, 2 H), 1.31 - 1.06 (m, 47 H), 0.79 (t, J = 6.7 Hz, 6 H).
단계5: 중합체1 의 제조Step 5: Preparation of Polymer 1
팔라듐 촉매화된 스틸레(Stille) 커플링 반응을 사용하여 중합체를 제조 하였다. Schlenk flask에 3,6-bis(6-bromo-4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-bis(2-decyltetradecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (화합물 1-4, 0.3 g, 0.1978 mmol) 및 5,6-difluoro-4,7-bis(5-(trimethylstannyl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole (0.1309 g, 0.1978 mmol)를 무수 클로로벤젠 (12.0 mL)에 녹였다. 질소 하에서 20 분 동안 탈기한 후, Pd
2(dba)
3 (0.0036 g, 0.003956 mmol) 및 P(o-Tol)
3 (0.0048 g, 0.015824 mmol)를 혼합물에 첨가 한 다음, 110 ℃에서 48 시간 동안 교반시켰다. 반응 혼합물에 2-Bromothiophene 및 tributyl(thiophen-2-yl)stannane을 순차적으로 주입하여 말단 캡핑하고, 6 시간 동안 교반시켰다. 그 후 중합체를 메탄올에 침전시켰다. 미정제 중합체를 여과에 의해 수집 한 다음, 메탄올, 아세톤, 헥산 및 클로로포름으로 순차적으로 속실렛 추출에 의해 정제 하였다. 최종 생성물은 메탄올에서 침전시키고 진공에서 건조시켜 진한 자주색 고체로서 수득되었다(0.24 g, 73%).The polymer was prepared using a palladium catalyzed Stille coupling reaction. 3,6-bis(6-bromo-4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-bis(2) in Schlenk flask -decyltetradecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (compound 1-4, 0.3 g, 0.1978 mmol) and 5,6-difluoro-4,7-bis(5- (trimethylstannyl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole (0.1309 g, 0.1978 mmol) was dissolved in anhydrous chlorobenzene (12.0 mL). After degassing under nitrogen for 20 min, Pd 2 (dba) 3 (0.0036 g, 0.003956 mmol) and P(o-Tol) 3 (0.0048 g, 0.015824 mmol) were added to the mixture, then at 110 °C for 48 h stirred. The reaction mixture was end-capped by sequentially injecting 2-Bromothiophene and tributyl(thiophen-2-yl)stannane, and stirred for 6 hours. The polymer was then precipitated in methanol. The crude polymer was collected by filtration and then purified by Soxhlet extraction sequentially with methanol, acetone, hexane and chloroform. The final product was precipitated in methanol and dried in vacuo to give as a dark purple solid (0.24 g, 73%).
[실시예 2] 중합체
2의 제조[Example 2] Preparation of Polymer 2
Schlenk flask에 3,6-bis(6-bromo-4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-bis(2-decyltetradecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (화합물 1-4, 0.3 g, 0.1978 mmol) 및 5,6-difluorobenzo[c][1,2,5]thiadiazole (0.034 g, 0.1978 mmol), Cs
2CO
3 (0.1933 g, 0.5934 mmol) 그리고 PivOH (0.0197 g, 0.1978 mmol)을 무수 클로로벤젠 (12.0 mL)에 녹였다. 질소 하에서 20 분 동안 탈기한 후, Pd
2(dba)
3 (0.0036 g, 0.003956 mmol) 및 (o-OMePhenyl)
3P
(0.0055 g, 0.015824 mmol)을 반응혼합물에 첨가한 다음, 110 ℃에서 48 시간 동안 교반시켰다. 그 후 중합체를 메탄올에 침전시켰다. 미정제 중합체를 여과에 의해 수집한 다음, 순차적으로 메탄올, 아세톤, 헥산 및 클로로포름으로 속실렛 추출에 의해 정제하였다. 최종 생성물은 메탄올에서 침전시키고 진공에서 건조시켜 진한 자주색 고체로서 수득되었다(0.22 g, 73%).3,6-bis(6-bromo-4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-bis(2) in Schlenk flask -decyltetradecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (compound 1-4, 0.3 g, 0.1978 mmol) and 5,6-difluorobenzo[c][1,2,5 ]thiadiazole (0.034 g, 0.1978 mmol), Cs 2 CO 3 (0.1933 g, 0.5934 mmol) and PivOH (0.0197 g, 0.1978 mmol) were dissolved in anhydrous chlorobenzene (12.0 mL). After degassing under nitrogen for 20 min, Pd 2 (dba) 3 (0.0036 g, 0.003956 mmol) and (o-OMePhenyl) 3 P (0.0055 g, 0.015824 mmol) was added to the reaction mixture, followed by stirring at 110 °C for 48 hours. The polymer was then precipitated in methanol. The crude polymer was collected by filtration and then purified by Soxhlet extraction sequentially with methanol, acetone, hexane and chloroform. The final product was precipitated in methanol and dried in vacuo to give as a dark purple solid (0.22 g, 73%).
[실시예 3] 중합체
3의 제조[Example 3] Preparation of Polymer 3
팔라듐 촉매화된 스틸레(Stille) 커플링 반응을 사용하여 중합체를 제조 하였다.The polymer was prepared using a palladium catalyzed Stille coupling reaction.
Schlenk flask에 3,6-bis(6-bromo-4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-bis(2-decyltetradecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (0.200 g, 0.145 mmol) 및 2,5-bis(trimethylstannyl)thiophene (0.059 g, 0.145 mmol)를 무수 클로로벤젠(7.0 mL)에 녹였다. 질소 하에서 15 분 동안 탈기한 후, Pd
2(dba)
3 (4.1 mg) 및 P(o-Tol)
3 (5.4 mg)를 혼합물에 첨가 한 다음, 110 ℃에서 48 시간 동안 교반시켰다. 그 후 온도를 상온으로 내린 후 , 중합체를 메탄올에 침전시켰다. 미정제 중합체를 여과에 의해 수집한 다음 메탄올, 아세톤, 헥산 및 클로로포름으로 순차적으로 속실렛 추출에 의해 정제하였다. 최종 생성물은 메탄올에서 침전시키고 진공에서 건조시켜 진한 자주색 고체로서 수득되었다 (0.14 g, 74%).3,6-bis(6-bromo-4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-2,5-bis(2) in Schlenk flask -decyltetradecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (0.200 g, 0.145 mmol) and 2,5-bis(trimethylstannyl)thiophene (0.059 g, 0.145 mmol) in anhydrous chloro It was dissolved in benzene (7.0 mL). After degassing under nitrogen for 15 min, Pd 2 (dba) 3 (4.1 mg) and P(o-Tol) 3 (5.4 mg) were added to the mixture and then stirred at 110 °C for 48 h. After the temperature was lowered to room temperature, the polymer was precipitated in methanol. The crude polymer was collected by filtration and then purified by Soxhlet extraction sequentially with methanol, acetone, hexane and chloroform. The final product was precipitated in methanol and dried in vacuo to give as a dark purple solid (0.14 g, 74%).
Mn =160kDa, Mw =190 kDa, PDI =1.18.Mn =160 kDa, Mw =190 kDa, PDI =1.18.
1H NMR (300 MHz, CDCl
3) δ 8.83-8.89 (broad, 2H), 6.91-7.16 (broad, 8H), 4.04-4.08 (broad, 4H), 2.01-2.03 (m, 2H), 1.53-1.59 (m, 12H), 1.42-1.15 (m, 80H), 0.84-0.86 (m, 12H). 1 H NMR (300 MHz, CDCl 3 ) δ 8.83-8.89 (broad, 2H), 6.91-7.16 (broad, 8H), 4.04-4.08 (broad, 4H), 2.01-2.03 (m, 2H), 1.53-1.59 (m, 12H), 1.42-1.15 (m, 80H), 0.84-0.86 (m, 12H).
[실시예 4] 중합체
4의 제조[Example 4] Preparation of Polymer 4
상기 실시예 3에서 화합물 A 대신 화합물 B를 사용한 것을 제외하고는 실시예 3과 동일하게 실시하여 중합체 4를 제조하였다(0.16g, 82%).Polymer 4 was prepared in the same manner as in Example 3, except that compound B was used instead of compound A in Example 3 above (0.16 g, 82%).
Mn =110kDa, Mw = 130kDa, PDI = 1.18.Mn = 110 kDa, Mw = 130 kDa, PDI = 1.18.
1H NMR (300 MHz, CDCl
3) δ 8.88-8.95 (broad, 2H), 6.90-7.18 (broad, 8H), 4.04-4.10 (broad, 4H), 2.01-2.03 (m, 2H), 1.53-1.59 (m, 12H), 1.42-1.15 (m, 80H), 0.84-0.86 (m, 12H). 1 H NMR (300 MHz, CDCl 3 ) δ 8.88-8.95 (broad, 2H), 6.90-7.18 (broad, 8H), 4.04-4.10 (broad, 4H), 2.01-2.03 (m, 2H), 1.53-1.59 (m, 12H), 1.42-1.15 (m, 80H), 0.84-0.86 (m, 12H).
[실시예 5] 중합체
5의 제조[Example 5] Preparation of polymer 5
상기 실시예 3에서 화합물 A 대신 화합물 C를 사용한 것을 제외하고는 실시예 3과 동일하게 실시하여 중합체 5를 제조하였다(0.17g, 82%).Polymer 5 was prepared in the same manner as in Example 3, except that compound C was used instead of compound C in Example 3 above (0.17 g, 82%).
Mn =130kDa, Mw = 146kDa, PDI = 1.12.Mn = 130 kDa, Mw = 146 kDa, PDI = 1.12.
1H NMR (300 MHz, CDCl
3) δ 8.95-9.14 (broad, 2H), 6.60-7.06 (broad, 8H), 4.04-4.10 (broad, 4H), 2.01-2.03 (m, 2H), 1.53-1.59 (m, 12H), 1.42-1.15 (m, 80H), 0.84-0.86 (m, 12H). 1 H NMR (300 MHz, CDCl 3 ) δ 8.95-9.14 (broad, 2H), 6.60-7.06 (broad, 8H), 4.04-4.10 (broad, 4H), 2.01-2.03 (m, 2H), 1.53-1.59 (m, 12H), 1.42-1.15 (m, 80H), 0.84-0.86 (m, 12H).
[실시예 6] 중합체
6의 제조[Example 6] Preparation of polymer 6
상기 실시예 3에서 화합물 A 대신 화합물 C를 사용한 것을 제외하고는 실시예 3과 동일하게 실시하여 중합체 5를 제조하였다 (0.16g, 72%).Polymer 5 was prepared in the same manner as in Example 3, except that compound C was used instead of compound C in Example 3 above (0.16 g, 72%).
Mn =126kDa, Mw = 144kDa, PDI = 1.14.Mn = 126 kDa, Mw = 144 kDa, PDI = 1.14.
1H NMR (300 MHz, CDCl
3) δ 8.95-9.11 (broad, 2H), 6.60-7.10 (broad, 8H), 4.04-4.10 (broad, 4H), 2.01-2.03 (m, 2H), 1.53-1.59 (m, 12H), 1.42-1.15 (m, 80H), 0.84-0.86 (m, 12H). 1 H NMR (300 MHz, CDCl 3 ) δ 8.95-9.11 (broad, 2H), 6.60-7.10 (broad, 8H), 4.04-4.10 (broad, 4H), 2.01-2.03 (m, 2H), 1.53-1.59 (m, 12H), 1.42-1.15 (m, 80H), 0.84-0.86 (m, 12H).
[실시예 7]중합체의 물성측정[Example 7] Measurement of physical properties of polymers
상기 실시예 1 내지 실시예 6에서 제조된 중합체 1 내지 6을 클로로포름에 녹여 중합체들의 광 흡수영역을 용액상태와 필름상태에서 측정하여, 그 결과를 하기 표 1에 기재하였다.The polymers 1 to 6 prepared in Examples 1 to 6 were dissolved in chloroform and the light absorption regions of the polymers were measured in solution state and film state, and the results are shown in Table 1 below.
중합체polymer | 용액 λ max (nm)solution λ max (nm) | 필름 λ max (nm)Film λ max (nm) | E g (eV)E g (eV) | E HOMO (eV)E HOMO (eV) | E LUMO (eV)E LUMO (eV) |
1One | 802.856(s)802.856(s) | 870(s)870(s) | 1.011.01 | -5.68-5.68 | -4.67-4.67 |
22 | 822(s)822(s) | 826(s)826(s) | 1.271.27 | -5.48-5.48 | -4.2-4.2 |
33 | 824824 | 821821 | 1.341.34 | 1.341.34 | -4.11-4.11 |
44 | 836836 | 835835 | 1.321.32 | 1.321.32 | -4.05-4.05 |
55 | 810810 | 813813 | 1.331.33 | 1.331.33 | -4.10-4.10 |
66 | 823823 | 824824 | 1.351.35 | 1.351.35 | -4.15-4.15 |
표 1이 시사하는 바와 같이 본 발명의 중합체의 광학적 특성을 살펴보면 용액 및 필름상에서 각각 802 내지 836nm 및 813 내지 870nm 범위에서 흡수 peak를 나타내었으며, 용액상태에서보다 필름상태에서 장파장영역으로 이동하였다. 이로부터 본 발명의 중합체는 분자간 또는 분자내에서 파이결합이 증가하는 것을 알 수 있다.또한 본 발명의 중합체는 low Band gap energy를 가져 유기반도체 재료로서 전하이동도가 향상됨을 알 수 있다. As Table 1 suggests, looking at the optical properties of the polymer of the present invention, absorption peaks were exhibited in the ranges of 802 to 836 nm and 813 to 870 nm, respectively, on the solution and film, and moved to a longer wavelength region in the film state than in the solution state. From this, it can be seen that the polymer of the present invention has an increased intermolecular or intramolecular pi bond. In addition, it can be seen that the polymer of the present invention has a low band gap energy and thus the charge mobility is improved as an organic semiconductor material.
또한 본 발명은 중합체 3 내지 6의 TGA를 방법으로 측정하여 그 결과를 도 1에 나타내었다(a:중합체3, b:중합체4,c:중합체5, d:중합체6). 도 1로부터 본 발명이 중합체가 열안정성이 우수함을 알 수 있다.In addition, this invention measured TGA of polymers 3 to 6 by the method, and showed the results in diagram 1 (A: Polymer 3, Polymer 3, Polymer 4, Polymer 4) From Figure 1, it is known that this invention is excellent in thermal stability of the polymer.
[실시예 8]유기트랜지스터의 제조[Example 8] Manufacturing of organic transistors
고도로 n-도핑된 Si
++/SiO
2 (100 nm)웨이터는 피라냐 용액과 산소 플라즈마를 사용하여 세척하였다. 세척공정 후 기판을 OTS(octadecyltrichlorosilane)로 증착한 다음 120℃에서 30분동안 어닐링하였다. 본 발명의 실시예 3 내지 6에서 제조된 중합체 3 내지 6을 각각 클로로벤젠에 녹여 농도가 5mg/mL인 중합체 용액을 각각 제조하였다.A highly n-doped Si ++ /SiO 2 (100 nm) waiter was cleaned using a piranha solution and oxygen plasma. After the cleaning process, the substrate was deposited with OTS (octadecyltrichlorosilane) and then annealed at 120°C for 30 minutes. Polymers 3 to 6 prepared in Examples 3 to 6 of the present invention were respectively dissolved in chlorobenzene to prepare polymer solutions having a concentration of 5 mg/mL, respectively.
제조된 중합체 용액을 OTS처리된 기판 상에 스핀 코팅하였다. 이를 질소가 충전된 글러브박스에서 200℃에서 20분동안 어닐링하였다. 마지막으로 채널길이가 각각 150μm와 1500μm인 활성층에 Au 전극(80nm)을 증착하여 유기트랜지스터를 제조하였다.The prepared polymer solution was spin coated on the OTS-treated substrate. This was annealed at 200°C for 20 minutes in a glove box filled with nitrogen. Finally, an organic transistor was manufactured by depositing an electrode (80 nm) on the active layer with a channel length of 150 μm and 1500 μm, respectively.
제조된 각 유기트랜지스터의 특성을 측정하여 하기 표 2에 나타내었다.The characteristics of each manufactured organic transistor were measured and shown in Table 2 below.
중합체polymer |
전하이동도
μ max (cm 2 V -1 s -1)charge mobility μ max (cm 2 V -1 s -1 ) |
평균전하이동도
μ ave (cm 2 V -1 s -1) * Average charge mobility μ ave (cm 2 V -1 s -1 ) * |
문턱전압
V th (V)threshold voltage V th (V) |
점멸비
I on/I off flashing ratio I on /I off |
33 | 0.130.13 | 0.11 ± 0.020.11 ± 0.02 | 0.41 ± 0.030.41 ± 0.03 | 10 4 10 4 |
44 | 0.150.15 | 0.13 ± 0.070.13 ± 0.07 | 2.86 ± 0.032.86 ± 0.03 | 10 4 10 4 |
55 | 0.190.19 | 0.17 ± 0.020.17 ± 0.02 | 3.65 ± 0.053.65 ± 0.05 | 10 4 10 4 |
66 | 0.220.22 | 0.20 ± 0.10.20 ± 0.1 | 5.83 ± 0.15.83 ± 0.1 | 10 4 10 4 |
*는 본 발명의 중합체를 이용하여 제조된 유기트랜지스터를 이용하여 32번 측정하여 얻어진 전하이동도 평균값이다.표 2에서 보이는 바와 같이 본 발명의 중합체는 우수한 전하이동도(cm
2 V
-1s
-1) 및 점멸비(I
on/I
off )를 가짐을 알 수 있다.* is the average value of charge mobility obtained by measuring 32 times using the organic transistor prepared using the polymer of the present invention. As shown in Table 2, the polymer of the present invention has excellent charge mobility (cm 2 V -1 s - 1 ) and the flashing ratio (I on /I off ) It can be seen that it has.
[실시예 9]메모리 소자의 제조[Example 9] Manufacturing of memory devices
먼저 Cytop 용액을 기판에 스핀코팅한 후 200℃에서 1시간동안 어닐링하였다. Au층(2nm)은 AuNP를 형성하기위해 열증발을 사용하여 열증착하였다. AuNP 증착 후 터널링 층으로 사용된 Cytop 층(7nm)을 Au NP위에 증착한 후 200℃에서 1시간동안 어닐링하였다. 중합체 3과 중합체 5의 박막은 클로로포름에서 중합체 용액을 스핀코팅하여 Cytop층에 증착하였다. 이 샘플을 200℃에서 20분동안 어닐링한 후 어닐링된 필름 상에 80nm 두께의 Au 전극을 증착하여 제조하였다.First, the CFA solution was spin-coated on the substrate and then annealed at 200°C for 1 hour. The AA layer (2 nm) was thermally evaporated using thermal evaporation to form AA. After deposition, the CFC layer used as the tunneling layer (7 NPM) was annealed and then deposited on the AFA2O 0℃ NPM for 1 hour. The thin films of Polymer 3 and Polymer 5 were deposited on the CFA layer by spin-coating the polymer solution in chloroform. This sample was annealed at 200 °C for 20 minutes, and then an 80 kmm thick electrode was deposited on the annealed film to make it.
제조된 메모리 소자의 스트레스 안정성을 VG=-20V 및 VD=-1V의 전압 바이어스에서 10,000초 동안 드레인 전류(ID)감소로 측정하였으며, 그 결과를 도 2에 나타내었다.The stress stability of the manufactured memory device was measured by decreasing the drain current (ID) for 10,000 seconds under voltage bias of VG=-20V and VD=-1V, and the results are shown in FIG.
주어진 시간동안 바이어스 스트레스 후 본 발명의 중합체 3과 중합체 5의 각각 ID감소 비율은 22%, 19%로 측정되었다. ID감소 플롯을 피팅하여 본 발명의 중합체 3과 중합체 5의 τ 및 β값을 측정한 결과 각각 3.38 Х 10
5 s, 5.30 Х 10
5 s 와 0.41 0.50이었다. 이로부터 본 발명의 메모리 소자는 본 발명의 중합체를 사용함으로써 바이어스 스트레스에 우수함을 알 수 있다.After the bias stress for a given time, the ID reduction rates of Polymer 3 and Polymer 5 of the present invention were measured to be 22% and 19%, respectively. As a result of measuring the τ and β values of Polymer 3 and Polymer 5 of the present invention by fitting the ID reduction plot, they were 3.38 Х 10 5 s, 5.30 Х 10 5 s, and 0.41 0.50, respectively. From this, it can be seen that the memory device of the present invention is excellent in bias stress by using the polymer of the present invention.
특히 본 발명의 중합체 5를 채용한 메모리 소자는 히스테리시스(hysteresis) 및 바이어스 응력 안정성이 매우 높음을 알 수 있다.In particular, it can be seen that the memory device employing the polymer 5 of the present invention has very high hysteresis and bias stress stability.
구체적으로 본 발명의 중합체 5를 전하저장층으로 AuNP를 갖는 플로팅 게이트 메모리 트랜지스터를 제작하여 비휘발성 메모리 동작을 조사하였다.Specifically, the non-volatile memory operation was investigated by fabricating a floating gate memory transistor having AuNP as a charge storage layer using polymer 5 of the present invention.
제조된 메모리 장치는 (+) 및 (-)게이트 바이어스에 정확하게 응답하였으며, 최대 메모리 창은 28V였다. 그 결과 ON 및 OFF 쌍 안정전류 상태가 명확하게 얻어졌으며, 이 상태는 이후 1년동안 구분할 수 있었다. 또한 본 발명의 메모리 소자는 쓰기 및 지우기를 하나의 과정으로 100회 반복 WRER 사이클 동안 재현 가능한 스위칭 동작을 나타냈다. The fabricated memory device accurately responded to (+) and (-) gate bias, and the maximum memory window was 28V. As a result, ON and OFF bistable current states were clearly obtained, and these states were distinguishable for one year. In addition, the memory device of the present invention exhibited a reproducible switching operation for 100 repeated WRER cycles in one process of writing and erasing.
따라서 본 발명의 중합체를 포함하는 유기 메모리 트랜지스터는 매우 우수한 작용효과를 가짐을 알 수 있다.Therefore, it can be seen that the organic memory transistor including the polymer of the present invention has a very good effect.
이상에서 살펴본 바와 같이 본 발명의 실시예에 대해 상세히 기술되었지만, 본 발명이 속하는 기술분야에 있어서 통상의 지식을 가진 사람이라면, 첨부된 청구범위에 정의된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 본 발명을 여러 가지로 변형하여 실시할 수 있을 것이다. 따라서 본 발명의 앞으로의 실시예들의 변경은 본 발명의 기술을 벗어날 수 없을 것이다.Although the embodiments of the present invention have been described in detail as described above, those of ordinary skill in the art to which the present invention pertains within the scope not departing from the technical spirit of the present invention as defined in the appended claims. The present invention may be practiced with various modifications. Accordingly, modifications of future embodiments of the present invention will not depart from the technology of the present invention.
Claims (12)
- 하기 화학식 1로 표시되는 반복단위를 포함하는 중합체:A polymer comprising a repeating unit represented by the following Chemical Formula 1:[화학식 1][Formula 1]상기 화학식 1에서,In Formula 1,Z 1 내지 Z 4는 서로 독립적으로 O, S 또는 Se이며;Z 1 to Z 4 are each independently O, S or Se;R 1 및 R 2는 서로 독립적으로 C1-C40알킬이며;R 1 and R 2 are each independently C1-C40 alkyl;R 3 내지 R 6은 서로 독립적으로 수소 또는 C1-C10알킬이며;R 3 to R 6 are each independently hydrogen or C1-C10 alkyl;X는 하기 구조에서 선택된다.X is selected from the following structures.상기 구조식에서,In the above structural formula,Z 5 내지 Z 15는 서로 독립적으로 O, S 또는 Se이며;Z 5 to Z 15 are each independently O, S or Se;R 11 내지 R 30는 서로 독립적으로 수소, 할로겐, C1-C10알킬 또는 할로C1-C10알킬이다.R 11 to R 30 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl.
- 제 1항에 있어서,The method of claim 1,상기 화학식 1에서, Z 1 내지 Z 4는 서로 독립적으로 S 또는 Se이며;In Formula 1, Z 1 to Z 4 are each independently S or Se;R 1 및 R 2는 서로 독립적으로 C10-C40알킬이며;R 1 and R 2 are each independently C10-C40 alkyl;R 3 내지 R 6은 서로 독립적으로 C1-C7알킬인, 중합체.R 3 to R 6 are independently of each other C 1 -C 7 alkyl.
- 제 1항에 있어서,The method of claim 1,상기 화학식 1에서, R 1 및 R 2는 서로 독립적으로 분지쇄C10-C40알킬인, 중합체.In Formula 1, R 1 and R 2 are each independently branched-chain C10-C40 alkyl, the polymer.
- 제 1항에 있어서,The method of claim 1,상기 X는 하기 구조에서 선택되는 것인, 중합체:wherein X is selected from the following structures:상기 구조식에서,In the above structural formula,Z 5 내지 Z 11은 서로 독립적으로 S 또는 Se이며;Z 5 to Z 11 are each independently S or Se;R 11 내지 R 24는 서로 독립적으로 수소, 할로겐, C1-C10알킬 또는 할로C1-C10알킬이다.R 11 to R 24 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl.
- 제 1항에 있어서,The method of claim 1,상기 중합체는 하기 화학식 2 또는 하기 화학식 3으로 표시되는 반복단위를 포함하는 중합체:The polymer is a polymer comprising a repeating unit represented by the following Chemical Formula 2 or Chemical Formula 3:[화학식 2][Formula 2][화학식 3][Formula 3]상기 화학식 2 및 화학식 3에서, In Formula 2 and Formula 3,Z 1 내지 Z 8은 서로 독립적으로 O, S 또는 Se이며;Z 1 to Z 8 are each independently O, S or Se;R 3 내지 R 6은 서로 독립적으로 C1-C10알킬이며;R 3 to R 6 are each independently C1-C10 alkyl;R 11 내지 R 18은 서로 독립적으로 수소, 할로겐, C1-C10알킬 또는 할로C1-C10알킬이며;R 11 to R 18 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl;R 41 내지 R 44는 서로 독립적으로 C6-C30알킬이며;R 41 to R 44 are each independently C6-C30 alkyl;n 및 m은 서로 독립적으로 1 내지 8의 정수이다.n and m are each independently an integer from 1 to 8;
- 제 5항에 있어서,6. The method of claim 5,상기 화학식 2 및 화학식 3에서, In Formula 2 and Formula 3,Z 1 내지 Z 8은 서로 독립적으로 S 또는 Se이며;Z 1 to Z 8 are each independently S or Se;R 3 내지 R 6은 서로 독립적으로 C1-C5알킬이며;R 3 to R 6 are each independently C1-C5 alkyl;R 11 내지 R 18은 서로 독립적으로 수소, 할로겐, C1-C5알킬 또는 할로C1-C5알킬이며;R 11 to R 18 are each independently hydrogen, halogen, C1-C5 alkyl or haloC1-C5 alkyl;R 41 내지 R 44는 서로 독립적으로 C8-C20알킬이며;R 41 to R 44 are each independently C8-C20 alkyl;n 및 m은 서로 독립적으로 1 내지 7의 정수인 중합체.n and m are independently of each other an integer from 1 to 7. A polymer.
- 제 1항에 있어서,The method of claim 1,상기 중합체는 하기 화학식 4 또는 하기 화학식 5로 표시되는 반복단위를 포함하는 중합체:The polymer is a polymer comprising a repeating unit represented by Formula 4 or Formula 5 below:[화학식 4][Formula 4][화학식 5][Formula 5]상기 화학식 4 및 화학식 5에서, In Formulas 4 and 5,Z 1 내지 Z 4 및 Z 9 내지 Z 11은 서로 독립적으로 O, S 또는 Se이며;Z 1 to Z 4 and Z 9 to Z 11 are each independently O, S or Se;R 3 내지 R 6은 서로 독립적으로 C1-C10알킬이며;R 3 to R 6 are each independently C1-C10 alkyl;R 19 내지 R 24는 서로 독립적으로 수소, 할로겐, C1-C10알킬 또는 할로C1-C10알킬이며;R 19 to R 24 are each independently hydrogen, halogen, C1-C10 alkyl or haloC1-C10 alkyl;R 41 내지 R 44는 서로 독립적으로 C6-C30알킬이며;R 41 to R 44 are each independently C6-C30 alkyl;n 및 m은 서로 독립적으로 1 내지 8의 정수이다.n and m are each independently an integer from 1 to 8;
- 제 7항에 있어서,8. The method of claim 7,상기 화학식 4 및 화학식 5에서, In Chemical Formulas 4 and 5,Z 1 내지 Z 4 및 Z 9 내지 Z 11은 서로 독립적으로 S 또는 Se이며;Z 1 to Z 4 and Z 9 to Z 11 are each independently S or Se;R 3 내지 R 6은 서로 독립적으로 C1-C5알킬이며;R 3 to R 6 are each independently C1-C5 alkyl;R 19 내지 R 24는 서로 독립적으로 수소, 할로겐, C1-C5알킬 또는 할로C1-C5알킬이며;R 19 to R 24 are each independently hydrogen, halogen, C1-C5 alkyl or haloC1-C5 alkyl;R 41 내지 R 44는 서로 독립적으로 C8-C20알킬이며;R 41 to R 44 are each independently C8-C20 alkyl;n 및 m은 서로 독립적으로 1 내지 7의 정수인 중합체.n and m are independently of each other an integer from 1 to 7. A polymer.
- 제 1항 내지 제 8항에서 선택되는 어느 한 항의 중합체를 포함하는 유기 전자 소자.An organic electronic device comprising the polymer of any one of claims 1 to 8.
- 제 9항에 있어서,10. The method of claim 9,상기 유기 전자 소자는 유기 태양 전지, 유기 박막 트랜지스터, 유기메모리, 유기감광체 또는 유기 광센서인 유기 전자 소자.The organic electronic device is an organic solar cell, an organic thin film transistor, an organic memory, an organic photoreceptor, or an organic optical sensor.
- 하기 화학식 11로 표시되는 다이케토피롤로피롤 화합물.A diketopyrrolopyrrole compound represented by the following formula (11).[화학식 11][Formula 11]상기 화학식 11에서,In the above formula (11),Z 1 내지 Z 4는 서로 독립적으로 O, S 또는 Se이며;Z 1 to Z 4 are each independently O, S or Se;R 1 및 R 2는 서로 독립적으로 C1-C40알킬이며;R 1 and R 2 are each independently C1-C40 alkyl;R 3 내지 R 6은 서로 독립적으로 수소 또는 C1-C10알킬이며;R 3 to R 6 are each independently hydrogen or C1-C10 alkyl;X 1 및 X 2는 서로 독립적으로 수소 또는 할로겐이다.X 1 and X 2 are each independently hydrogen or halogen.
- 제 11항에 있어서,12. The method of claim 11,상기 화학식 11에서 Z 1 내지 Z 4는 서로 독립적으로 S 또는 Se이며;In Formula 11, Z 1 to Z 4 are each independently S or Se;R 1 및 R 2는 서로 독립적으로 C10-C40알킬이며;R 1 and R 2 are each independently C10-C40 alkyl;R 3 내지 R 6은 서로 독립적으로 C1-C10알킬이며;R 3 to R 6 are each independently C1-C10 alkyl;X 1 및 X 2는 서로 독립적으로 할로겐인 다이케토피롤로피롤 화합물.X 1 and X 2 are each independently a halogen diketopyrrolopyrrole compound.
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