KR20220159635A - Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors OFETs)에 적용 가능한 전도성 고분자 제조방법 - Google Patents
Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors OFETs)에 적용 가능한 전도성 고분자 제조방법 Download PDFInfo
- Publication number
- KR20220159635A KR20220159635A KR1020210067473A KR20210067473A KR20220159635A KR 20220159635 A KR20220159635 A KR 20220159635A KR 1020210067473 A KR1020210067473 A KR 1020210067473A KR 20210067473 A KR20210067473 A KR 20210067473A KR 20220159635 A KR20220159635 A KR 20220159635A
- Authority
- KR
- South Korea
- Prior art keywords
- cfc
- conductive polymer
- cyclopentadithiophene
- organic
- ofets
- Prior art date
Links
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000011669 selenium Substances 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 230000005669 field effect Effects 0.000 claims abstract description 6
- 239000002861 polymer material Substances 0.000 claims abstract description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 5
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- 229930192474 thiophene Natural products 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 claims 1
- 230000005693 optoelectronics Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004630 atomic force microscopy Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920000547 conjugated polymer Polymers 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000009304 pastoral farming Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000012799 electrically-conductive coating Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000007523 nucleic acids Chemical class 0.000 description 2
- 102000039446 nucleic acids Human genes 0.000 description 2
- 108020004707 nucleic acids Proteins 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- 238000000584 ultraviolet--visible--near infrared spectrum Methods 0.000 description 2
- KVZDYOVYIHJETJ-UHFFFAOYSA-N 4,7-dibromo-5-fluoro-2,1,3-benzothiadiazole Chemical compound BrC1=C(F)C=C(Br)C2=NSN=C21 KVZDYOVYIHJETJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- -1 siloxanes Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- LGLMAWUUKPRGBF-UHFFFAOYSA-N trimethyl-(5-trimethylstannylfuran-2-yl)stannane Chemical compound C[Sn](C)(C)C1=CC=C([Sn](C)(C)C)O1 LGLMAWUUKPRGBF-UHFFFAOYSA-N 0.000 description 1
- DTJBEISROOTMQK-UHFFFAOYSA-N trimethyl-(5-trimethylstannylselenophen-2-yl)stannane Chemical compound C[Sn](C)(C)C1=CC=C([Sn](C)(C)C)[se]1 DTJBEISROOTMQK-UHFFFAOYSA-N 0.000 description 1
- KKRPPVXJVZKJON-UHFFFAOYSA-N trimethyl-(5-trimethylstannylthiophen-2-yl)stannane Chemical compound C[Sn](C)(C)C1=CC=C([Sn](C)(C)C)S1 KKRPPVXJVZKJON-UHFFFAOYSA-N 0.000 description 1
- UKHQRARQNZOXRL-UHFFFAOYSA-N trimethyltin Chemical compound C[SnH](C)C UKHQRARQNZOXRL-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
-
- 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
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/125—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one oxygen atom in the ring
-
- 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
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/143—Side-chains containing nitrogen
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/145—Side-chains containing sulfur
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/92—TFT applications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
본발명은 Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors, OFETs)에 적용 가능한 전도성 고분자 제조방법에 관한 것으로, 산소(O), 황(S), 셀레니움(Se)을 각각 갖는 퓨란(furan), 싸이오펜(thiophene), 셀레노펜(selenophene)을 활용하여 유기트랜지스터에 적용 가능한 CFC-O, CFC-S, CFC-Se 전도성 고분자 재료를 하기 화학식 1과 같이 각각 합성하는 것으로,
[화학식 1]
본발명의 제조방법에 의해 제조되는 전도성 고분자 (conjugated polymer)는 유연성 (flexibility), 광전기적 특성(optoelectronic properties)이 좋고,제조경비가 저렴하며, 고분자 배열의 정도가 증가하며, 유기트랜지스터의 성능이 열처리 후 증가하는 현저한 효과가 있다.
[화학식 1]
본발명의 제조방법에 의해 제조되는 전도성 고분자 (conjugated polymer)는 유연성 (flexibility), 광전기적 특성(optoelectronic properties)이 좋고,제조경비가 저렴하며, 고분자 배열의 정도가 증가하며, 유기트랜지스터의 성능이 열처리 후 증가하는 현저한 효과가 있다.
Description
본발명은 Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors, OFETs)에 적용 가능한 전도성 고분자 제조방법에 관한 것으로, 유연성 (flexibility), 광전기적 특성(optoelectronic properties)이 좋고, 제조경비가 저렴하며, 고분자 배열의 정도가 증가하며, 유기트랜지스터의 성능이 열처리 후 증가하는 전도성 고분자에 관한 것이다.
일반적으로 용액공정(solution-processable)이 가능한 전도성 고분자 (conjugated polymer)는 유연성 (flexibility), 광전기적 특성(optoelectronic properties), 매우 낮은 가격(low-cost) 등의 장점으로 유기반도체에 많이 사용한다. 유기반도체는 유비쿼터스 시대의 유연 디스플레이, RFID (radio frequency identification), 센서 등으로 활용이 가능하다. 유기트랜지스터 재료에 관한 개발은 많이 진행되었지만 원자 크기에 따른 전하 이동도의 차이를 체계적으로 개발한 기술은 없었다.
그리고 종래특허기술의 일례로서, 등록번호 10-0229581호에는 전기 전도 성페이스트재료 및 응용에 관한 것으로, 각각 Sn, Zn, In, Bi 및 Sb로 이루어진 군에서 선택된 전기 전도성 코팅을 갖는, Cu, Au, Ag, Al, Pd, Pt로 이루어진 군에서 선택된 재료로 형성된 복수개로 이루어지며, 이 입자들 중 적어도 일부는 다른 상기 입자들과 상기 전기 전도성 코팅을 통해 융합되며, 상기 복수개의 입자들이 폴리이미드, 실록산, 폴리이미드실록산 및 리그닌, 셀룰로오즈, 동유 및 작황유로부터 유도된 생물질-기재 고분자 수지로 이루어진 군에서 선택된 고분자 재료 내에 매립된 구조물이 공개되어 있다.
또한, 등록특허공보 등록번호 10-1771978호의 불소 함유 중합체 재료를 포함하는 패턴형성된 구조를 얻는 방법, 등록특허공보 등록번호 10-1359288호의 유기 전계 발광 소자 및 그 제조 공개특허공보 공개번호 10-2011-0051186의 중합체, 발광층 재료, 유기 전계 발광 소자 재료, 유기 전계 발광 소자용 조성물, 이들을 이용한 유기 전계 발광 소자, 태양 전지 소자, 유기 EL 표시 장치, 및 유기 EL 조명이 공개되어 있다.
그러나 상기 종래기술들은 원자 크기에 따른 전하 이동도의 차이를 체계적으로 개발하지 못하여, 유연성 (flexibility), 광전기적 특성(optoelectronic properties)이 좋지 않고, 제조경비가 고가인 문제점이 여전히 있었다.
따라서 본 발명은 상기와 같은 문제점을 해결하고자 안출된 것으로, 유연성 (flexibility), 광전기적 특성(optoelectronic properties)이 좋고,제조경비가 저렴하며, 고분자 배열의 정도가 증가하며, 유기트랜지스터의 성능이 열처리 후 증가하는 전도성 고분자 (conjugated polymer)를 제공하고자 하는 것이다.
본발명은 Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors, OFETs)에 적용 가능한 전도성 고분자 제조방법에 관한 것으로, 산소(O), 황(S), 셀레니움(Se)을 각각 갖는 퓨란(furan), 싸이오펜(thiophene), 셀레노펜(selenophene)을 활용하여 유기트랜지스터에 적용 가능한 CFC-O, CFC-S, CFC-Se 전도성 고분자 재료를 하기 화학식 1과 같이 합성하는 것을 특징으로 한다.
[화학식 1]
따라서 본발명의 제조방법에 의해 제조되는 전도성 고분자 (conjugated polymer)는 유연성 (flexibility), 광전기적 특성(optoelectronic properties)이 좋고,제조경비가 저렴하며, 고분자 배열의 정도가 증가하며, 유기트랜지스터의 성능이 열처리 후 증가하는 현저한 효과가 있다.
도 1. 4,7-bis(6-bromo-4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-5-fluorobenzo[c][1,2,5]thiadiazole 단량체를 합성공정도
도 2. (a) Cyclic voltammogram)s of and normalized UV-vis-NIR absorption spectra of CFC-O, CFC-S, CFC-Se in (b) thin film and (c) chlorobenzene solution. (d) HOMO and LUMO energy levels of the polymers.
도 3. (a) Two-dimensional grazing incidence wide-angle x-ray scattering (2D GI-WAXD) patterns obtained for CFC-O, CFC-S and CFC-Se films. (b) Vertical and (c) horizontal GIWAXS profiles of CFC-O, CFC-S and CFC-Se films, where qz and qxy are the perpendicular and parallel wave vector transfers with respect to sample surface, respectively.
도 4. Atomic force microscopy topographic images of as-cast polymers films: (a) CFC-O, (b) CFC-S, and (c) CFC-Se. Scale bars indicate 500 nm.
도 5. Atomic force microscopy topographic images of annealed polymers films: (a) CFC-O(210℃), (b) CFC-S(240℃), and (c) CFC-Se(210℃). Scale bars indicate 500 nm.
도 2. (a) Cyclic voltammogram)s of and normalized UV-vis-NIR absorption spectra of CFC-O, CFC-S, CFC-Se in (b) thin film and (c) chlorobenzene solution. (d) HOMO and LUMO energy levels of the polymers.
도 3. (a) Two-dimensional grazing incidence wide-angle x-ray scattering (2D GI-WAXD) patterns obtained for CFC-O, CFC-S and CFC-Se films. (b) Vertical and (c) horizontal GIWAXS profiles of CFC-O, CFC-S and CFC-Se films, where qz and qxy are the perpendicular and parallel wave vector transfers with respect to sample surface, respectively.
도 4. Atomic force microscopy topographic images of as-cast polymers films: (a) CFC-O, (b) CFC-S, and (c) CFC-Se. Scale bars indicate 500 nm.
도 5. Atomic force microscopy topographic images of annealed polymers films: (a) CFC-O(210℃), (b) CFC-S(240℃), and (c) CFC-Se(210℃). Scale bars indicate 500 nm.
본발명은 Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors, OFETs)에 적용 가능한 전도성 고분자 제조방법에 관한 것으로, 산소(O), 황(S), 셀레니움(Se)을 각각 갖는 퓨란(furan), 싸이오펜(thiophene), 셀레노펜(selenophene)을 활용하여 유기트랜지스터에 적용 가능한 CFC-O, CFC-S, CFC-Se 전도성 고분자 재료를 하기 화학식 1과 같이 각각 합성하는 것을 특징으로 한다.
[화학식 1]
또한, CFC-O, CFC-S, CFC-Se 고분자 합성과정은 4ml 톨루엔용매에 4,7-bis(6-bromo-4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-5-fluorobenzo[c][1,2,5]thiadiazole, tetrakis(triphenylphosphine)-palladium(0) 을 넣고, 교반하면서 가열하는 단계;
반응물을 메탄올에 침전시키고 결과로 나온 고체를 여과하는 단계;를 포함하여 제조되는 것을 특징으로 한다.
또한, 상기 여과후 잔여물은 클로로포름으로 추출하여 PTDPPSBS-SiC5를 합성하는 것을 특징으로 한다.
본발명을 첨부도면에 의해 상세히 설명하면 다음과 같다.
본 발명에서는 산소(O), 황(S), 셀레니움(Se)을 각각 갖는 퓨란(furan), 싸이오펜(thiophene), 셀레노펜(selenophene)을 활용하여 유기트랜지스터에 적용 가능한 3가지 종류의 고분자 재료를 합성하였고 화학구조는 아래와 같다.
아래는 CFC-O, CFC-S, CFC-Se의 화학구조도이다.
유기트랜지스터에 사용 가능한 전도성 고분자 CFC-O, CFC-S, CFC-Se을 합성하기 위하여
4,7-bis(6-bromo-4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-5-fluorobenzo[c][1,2,5]thiadiazole 단량체를 합성하였고 자세한 합성과정은 도 1과 같다.
4,7-bis(4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-5-fluorobenzo[c][1,2,5]thiadiazole (1)아르곤 환경에서 150 ml 톨루엔 용매에 (4,4-Dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)trimethylstannane (7.48 g, 9.99 mmol)과 4,7-dibromo-5-fluorobenzo[c][1,2,5]thiadiazole (1.25 g, 3.10 mmol)을 녹였다. 그리고 Pd(dba)2 (0.07 g, 0.12 mmol)와 tri(o-tolyl)phosphine (0.15g, 0.48mmol)을 첨가하고, 교반하면서 95℃로 24시간 가열하였다. 반응 혼합물을 냉각시킨후 후, 증류수로 반응을 중단시켰다. 이후 클로로포름으로 유기층을 추출하고, 증류수로 행군 다음 MgSO4로 수분을 제거했다. 용매는 회전증발 농축기를 이용해 증발시켰다. 혼합물은 헥산으로 고정된 실리카 크로마토그래피로 분리 정제했다. 처음에는 핵산으로만 분리한 후 핵산과 클로로포름의 부피비가 95 : 5인 용액까지 극성을 천천히 올리면서 분리 정제를 하여 5.06 g 의 생성물
4,7-bis(4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-5-fluorobenzo[c][1,2,5]thiadiazole를 수득률 75%로 합성하였다.
4,7-bis(6-bromo-4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-5-fluorobenzo[c][1,2,5]thiadiazole (2)
4,7-bis(4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-5-fluorobenzo[c][1,2,5]thiadiazole (4.2 g, 2.99 mmol) 용액을 넣은 후, N-Bromosuccinimide (NBS, 1.17 g, 6.58 mmol)을 천천히 첨가했다. 빛을 차단한 후, 실온에서 24시간동안 교반하였다. 반응물은 증류수로 반응을 중단시켰으며, 메틸렌클로라이드로 유기층을 추출한 후 NaCl 용액으로 다른층에 있을 유기물을 한 번 더 추출했다. 유기층에 남아있는 수분은 MgSO4를 이용해 수분을 제거했다. 용매는 회전증발농축기를 이용해 증발시켰으며, 헥산을 이용한 컬럼크로마토 그래피로 생성물을 분류 정제하여 3.5 g 의 4,7-bis(6-bromo-4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-5-fluorobenzo[c][1,2,5]thiadiazole 생성물을 75%의 수득률로 합성하였다.
도 1은 고분자 CFC-O, CFC-S, CFC-Se의 합성과정이다.
CFC-O, CFC-S, CFC-Se 고분자 합성과정
4ml 톨루엔용매에
4,7-bis(6-bromo-4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-5-fluorobenzo[c][1,2,5]thiadiazole (0.20 mmol), tetrakis(triphenylphosphine)-palladium(0) (4.0 ㎛ol)을 넣고, 교반하면서 24시간동안 95℃로 가열하였다. 반응물을 300ml 메탄올 침전시키고 결과로 나온 고체를 여과하였다. 작은 분자량을 가지는 물질을 제거하기 위해 메탄올, 아세톤, 헥산 그리고 메틸렌클로라이드 순으로 Soxhlet 추출을 거쳤다. 잔여물은 클로로포름으로 추출하여 PTDPPSBS-SiC5를 합성하였다. 수득율이 77%인 어두운 갈색을 띄는 CFC-O, CFC-S, CFC-Se를 합성하였다.
화합물 2와 2,5-bis(trimethylstannyl)furan, 2,5-bis(trimethylstannyl)thiophene, 2,5-bis(trimethylstannyl)selenophene를 Ph(PPh3)4 촉매를 사용하여 Stille polycondensation 반응으로 고분자 CFC-O, CFC-S, CFC-Se를 각각 합성하였다. 합성한 전도성 고분자의 광학적 특성과 에너지 준위를 분광광도법과 순환전압전류법으로 각각 분석을 하였다.
도 2. (a) Cyclic voltammogram)s of and normalized UV-vis-NIR absorption spectra of CFC-O, CFC-S, CFC-Se in (b) thin film and (c) chlorobenzene solution. (d) HOMO and LUMO energy levels of the polymers.
이 고분자의 분자배열을 알아보기 위하여 GIWAXS (Grazing incidence wide angle x-ray scattering)를 측정하였다. CFC-O, CFC-S, CFC-Se 모두 열처리 전과 후를 비교했을 때 고분자 배열의 정도가 증가하는 것을 알 수 있었고, 이러한 실험 결과는 유기트랜지스터의 성능이 열처리 후 증가하는 것을 뒷받침하는 실험 결과가 된다.
도 3. (a) Two-dimensional grazing incidence wide-angle x-ray scattering (2D GI-WAXD) patterns obtained for CFC-O, CFC-S and CFC-Se films. (b) Vertical and (c) horizontal GIWAXS profiles of CFC-O, CFC-S and CFC-Se films, where qz and qxy are the perpendicular and parallel wave vector transfers with respect to sample surface, respectively.
도 4. Atomic force microscopy topographic images of as-cast polymers films: (a) CFC-O, (b) CFC-S, and (c) CFC-Se. Scale bars indicate 500 nm.
도 5. Atomic force microscopy topographic images of annealed polymers films: (a) CFC-O(210℃), (b) CFC-S(240℃), and (c) CFC-Se(210℃). Scale bars indicate 500 nm.
CFC-O, CFC-S, CFC-Se의 모폴로지(morphology)를 확인하기 위하여 원자힘 현미경(atomic force microscopy)을 측정하였고 그 결과는 도 4와 5와 같다. 그림 5에서 보는 것과 같이 열처리 전과 후를 비교하였을 때 표면의 거칠기를 나타내는 CFC-O, CFC-S, CFC-Se은 대한 RMS의 값은 증가하는 것을 알 수 있다.
Claims (3)
- 산소(O), 황(S), 셀레니움(Se)을 각각 갖는 퓨란(furan), 싸이오펜(thiophene), 셀레노펜(selenophene)을 활용하여 유기트랜지스터에 적용 가능한 CFC-O, CFC-S, CFC-Se 전도성 고분자 재료를 하기 화학식 1과 같이 각각 합성하는 것을 특징으로 하는 Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors, OFETs)에 적용 가능한 전도성 고분자 제조방법
[화학식 1]
- 제1항에 있어서, 상기 CFC-O, CFC-S, CFC-Se 고분자 합성과정은
톨루엔용매에 4,7-bis(6-bromo-4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-5-fluorobenzo[c][1,2,5]thiadiazole, tetrakis(triphenylphosphine)-palladium(0) 을 넣고, 교반하면서 가열하는 단계;
반응물을 메탄올에 침전시키고 결과로 나온 고체를 여과하는 단계;를 포함하여 제조되는 것을 특징으로 하는 Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors, OFETs)에 적용 가능한 전도성 고분자 제조방법 - 제2항에 있어서, 상기 여과후 잔여물은 클로로포름으로 추출하여 PTDPPSBS-SiC5를 합성하는 것을 특징으로 하는 Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors, OFETs)에 적용 가능한 전도성 고분자 제조방법
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210067473A KR102560214B1 (ko) | 2021-05-26 | 2021-05-26 | Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors OFETs)에 적용 가능한 전도성 고분자 제조방법 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210067473A KR102560214B1 (ko) | 2021-05-26 | 2021-05-26 | Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors OFETs)에 적용 가능한 전도성 고분자 제조방법 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20220159635A true KR20220159635A (ko) | 2022-12-05 |
| KR102560214B1 KR102560214B1 (ko) | 2023-07-26 |
Family
ID=84392114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020210067473A KR102560214B1 (ko) | 2021-05-26 | 2021-05-26 | Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors OFETs)에 적용 가능한 전도성 고분자 제조방법 |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102560214B1 (ko) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015092909A1 (ja) * | 2013-12-19 | 2015-06-25 | リンテック株式会社 | 高分子化合物、有機光電変換素子、及び該素子の製造方法 |
| KR20190024258A (ko) * | 2017-08-31 | 2019-03-08 | 이화여자대학교 산학협력단 | 유기 반도체 화합물 및 이를 이용한 전자 소자 |
-
2021
- 2021-05-26 KR KR1020210067473A patent/KR102560214B1/ko active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015092909A1 (ja) * | 2013-12-19 | 2015-06-25 | リンテック株式会社 | 高分子化合物、有機光電変換素子、及び該素子の製造方法 |
| KR20190024258A (ko) * | 2017-08-31 | 2019-03-08 | 이화여자대학교 산학협력단 | 유기 반도체 화합물 및 이를 이용한 전자 소자 |
Non-Patent Citations (2)
| Title |
|---|
| Polym. Chem., vol.10, pp.2854-2862 * |
| Polymer Journal, vol.49, pp.113-122 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102560214B1 (ko) | 2023-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100960492B1 (ko) | 유기 트랜지스터 및 이의 제조방법 | |
| TWI472550B (zh) | 具有噻吩并〔３，２-b〕噻吩部分之聚合物 | |
| KR20110021772A (ko) | 카본 나노튜브 복합체, 유기 반도체 콤포지트 및 전계 효과형 트랜지스터 | |
| CN101479272B (zh) | 作为有机半导体的二酮基吡咯并吡咯聚合物 | |
| CN103068829B (zh) | 二锡稠合噻吩化合物与聚合物及其制备方法 | |
| An et al. | Benzodithiophene–Thiadiazoloquinoxaline as an acceptor for ambipolar copolymers with deep LUMO level and distinct linkage pattern | |
| KR20100101575A (ko) | 유기 반도체로서 케토피롤 | |
| JP2011151396A (ja) | ポリマー半導体、ポリマー半導体の製造法および電子デバイス | |
| Pyshkina et al. | Poly (3, 4-ethylenedioxythiophene): synthesis and properties | |
| KR20140007059A (ko) | 분지형 알킬 쇄를 갖는 화합물, 그 제조 방법, 및 광전 소자에서의 그의 용도 | |
| CN1610143A (zh) | 半导体聚合物及其装置 | |
| Fu et al. | Synthesis and properties of photodegradable poly (furan-amine) s by a catalyst-free multicomponent cyclopolymerization | |
| US20150194608A1 (en) | Building block for low bandgap conjugated polymers | |
| KR102560214B1 (ko) | Cyclopentadithiophene 기반의 유기트랜지스터(organic field-effect transistors OFETs)에 적용 가능한 전도성 고분자 제조방법 | |
| KR20220022731A (ko) | 고분자 화합물 및 이를 포함하는 유기 광전소자 및 이의 제조방법 | |
| CN104744666B (zh) | 含多节共轭链段型聚合物材料及其制备方法和应用 | |
| CN113831509A (zh) | 可溶液处理的共价有机框架材料及其制备方法和用途 | |
| Madathil et al. | Synthesis and characterization of cyclopentadithiophene and thienothiophene-based polymers for organic thin-film transistors and solar cells | |
| CN114621251B (zh) | 基于喹喔啉衍生物的稠环单元、含该单元的小分子、聚合物及制备方法与应用 | |
| Wu et al. | Biaxially extended thiophene–isoindigo donor–acceptor conjugated polymers for high-performance flexible field-effect transistors | |
| JP4225820B2 (ja) | ウレタン含有側基を有するアルキレンジオキシチオフェン及びポリ（アルキレンジオキシチオフェン）、該チオフェンの製造のための方法及び出発化合物、該チオフェンを用いて得られる架橋生成物並びに新規化合物及び架橋生成物の使用 | |
| KR101739259B1 (ko) | 신규 피롤 단량체 및 그 제조방법, 피롤 단량체로부터 합성된 고분자 또는 화합물 및 그 제조방법 | |
| Lanzi et al. | A new photocrosslinkable oligothiophene for organic solar cells with enhanced stability | |
| Gedefaw et al. | An alternating copolymer of fluorene donor and quinoxaline acceptor versus a terpolymer consisting of fluorene, quinoxaline and benzothiadiazole building units: synthesis and characterization | |
| Santos et al. | Synthesis of novel low bandgap random and block terpolymers with improved performance in organic solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |