KR100451440B1 - Tin-based electroluminescent polymer - Google Patents
Tin-based electroluminescent polymer Download PDFInfo
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- KR100451440B1 KR100451440B1 KR10-2002-0022881A KR20020022881A KR100451440B1 KR 100451440 B1 KR100451440 B1 KR 100451440B1 KR 20020022881 A KR20020022881 A KR 20020022881A KR 100451440 B1 KR100451440 B1 KR 100451440B1
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- South Korea
- Prior art keywords
- polymer
- formula
- tin
- light emitting
- copolymer
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- 229920000642 polymer Polymers 0.000 title claims abstract description 39
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 6
- 125000005566 carbazolylene group Chemical group 0.000 claims abstract description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 9
- 229920005603 alternating copolymer Polymers 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 229920000265 Polyparaphenylene Polymers 0.000 description 7
- -1 poly (p-phenylene) Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000005424 photoluminescence Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910020813 Sn-C Inorganic materials 0.000 description 3
- 229910018732 Sn—C Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 1
- ZDFZWZGIGKUBRA-UHFFFAOYSA-N 3,6-dibromo-9-(2-ethylhexyl)carbazole Chemical compound BrC1=CC=C2N(CC(CC)CCCC)C3=CC=C(Br)C=C3C2=C1 ZDFZWZGIGKUBRA-UHFFFAOYSA-N 0.000 description 1
- LQQKFGSPUYTIRB-UHFFFAOYSA-N 9,9-dihexylfluorene Chemical compound C1=CC=C2C(CCCCCC)(CCCCCC)C3=CC=CC=C3C2=C1 LQQKFGSPUYTIRB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ISXUHJXWYNONDI-UHFFFAOYSA-L dichloro(diphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](Cl)(Cl)C1=CC=CC=C1 ISXUHJXWYNONDI-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229920000267 ladder-type polyparaphenylene Polymers 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/917—Electroluminescent
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
본 발명은 청색발광 재료로서 유용한 주석계 전기발광 고분자에 관한 것으로서, 본 발명에 의한 고분자는 하기 화학식의 반복단위를 갖는 것을 특징으로 한다:The present invention relates to a tin-based electroluminescent polymer useful as a blue light emitting material, wherein the polymer according to the present invention has a repeating unit of the formula
상기 식에서, X는 치환 또는 비치환 페닐렌, 플로레닐렌 또는 카바졸릴렌이고, n은 양의 정수이다.Wherein X is substituted or unsubstituted phenylene, florenylene or carbazolylene, and n is a positive integer.
Description
본 발명은 신규한 주석계 고분자, 보다 상세하게는 청색발광 재료로서 유용한 주석계 전기발광 고분자에 관한 것이다.The present invention relates to novel tin-based polymers, and more particularly to tin-based electroluminescent polymers useful as blue light emitting materials.
최근, π-결합 고분자 박막을 이용한 전기발광(electroluminescent; EL) 소자는 학술적인 연구 및 대면적 평판표시소자 및 발광 다이오드와 같은 다양한 용도에 있어서 잠재적 용도로 인하여 관심의 대상이 되고 있다. 저분자 규모의(small molecule-based) 풀칼라 EL 소자가 이제 출현되기 시작하는데 반하여, 대면적 평판 표시소자의 거대한 잠재 시장으로 인하여 π-결합 전자발광 고분자에 대한 과학적, 상업적 관심이 증대되고 있다.Recently, electroluminescent (EL) devices using π-bonded polymer thin films are of interest due to their potential for use in academic research and various applications such as large area flat panel display devices and light emitting diodes. While small molecule-based full-color EL devices are now beginning to emerge, the enormous potential market for large area flat panel display devices is increasing the scientific and commercial interest for π-bonded electroluminescent polymers.
EL 고분자 재료는 무기계 EL 재료 및 유기염료 분자에 비하여, 분자구조의 조작을 통한 π-π* 에너지 갭 조절에 의한 R/G/B 삼원색, 빠른 응답시간, 고품질 표시 및 반도체 기술을 이용한 소자의 가공 용이성과 같은 수많은 장점을 제공한다.Compared with inorganic EL materials and organic dye molecules, the EL polymer material has R / G / B three primary colors, fast response time, high quality display, and semiconductor technology by controlling the π-π * energy gap through the manipulation of the molecular structure. It offers numerous advantages such as ease of use.
천연색 디스플레이의 실현을 위해서는 적, 녹, 청의 삼원색에서 발광하는 재료가 요구된다. 장수명 안정성 및 소자 성능이 우수한 적색 및 녹색 발광체는 이미 개발되었지만, 적합한 청색 발광체는 여전히 요구된다. 따라서, 상업적으로 유용한 발광 다이오드를 얻기 위한 필수적인 요건인 장수명 안정성, 높은 효율성 및 비교적 저전압에서 밝은 청색 발광을 구비하는 재료를 얻고자 하는 노력은 계속되고 있다. 특히, 청색 LED 소자에 사용될 수 있는 보다 우수한 폴리머 재료에 대한연구는 이 분야에서 주된 관심사이다.In order to realize a color display, a material emitting light in three primary colors of red, green, and blue is required. Although red and green emitters with good long life stability and device performance have already been developed, suitable blue emitters are still required. Thus, there is an ongoing effort to obtain a material having long lifetime stability, high efficiency and light blue light emission at a relatively low voltage, which are essential requirements for obtaining a commercially useful light emitting diode. In particular, the search for better polymer materials that can be used in blue LED devices is a major concern in this field.
현재 청색 발광체를 제조하는데 주로 사용되는 합성법은 4가지가 있다. 첫 번째 방법은 가시광선 스펙트럼의 청색 빛을 발할 수 있을 뿐 아니라 에너지 전달 과정을 통해 발광 파장을 변화시킬 수 있는 폴리(p-페닐렌), 폴리(알킬플로렌), 사다리형 폴리(p-페닐렌) (LPPP)과 같은 큰 밴드갭을 갖는 일반적인 폴리(p-페닐렌) 유도체를 개발하는 것이다. 이들 폴리머를 사용하는 청색 LED의 실현과 관련된 두 가지 중요한 문제는, 고체 상태에서 π-π 상호작용을 통해 응집체/엑시머를 형성하는 경향 때문에 장파장 영역에서 부가적인 발광밴드를 갖는다는 것과 전기발광(EL) 양자효과의 부수적인 강하가 나타난다는 것이다.At present, there are four synthetic methods mainly used to prepare blue light emitters. The first method is poly (p-phenylene), poly (alkylfluorene), ladder poly (p-phenyl) which can not only emit blue light in the visible spectrum but also change the emission wavelength through energy transfer process. It is to develop a general poly (p-phenylene) derivative having a large band gap, such as ethylene) (LPPP). Two important problems associated with the realization of blue LEDs using these polymers are the additional luminescence bands in the long wavelength region due to the tendency to form aggregates / eximers through π-π interactions in the solid state and electroluminescence (EL). An incidental drop in quantum effects.
두 번째 방법은, 공액 길이를 조절하는 것이다. 예를 들어, PPV- 또는 폴리(알킬플로렌)계 폴리머에m-결합을 도입하여 전자의 비편재화를 방해할 수 있다.The second method is to adjust the conjugate length. For example, m -bonds may be introduced into a PPV- or poly (alkylfluorene) -based polymer to hinder delocalization of electrons.
세 번째 방법은, π-콘쥬게이트 전기 발광 폴리머 내에 명확하게 콘쥬게이트된 발색단(chromophore)를 도입하는 것이다. 후자의 경우 발색단의 공액길이는 π-콘쥬게이트 시스템에 콘쥬게이트 되지 않은 유연한 단편을 도입함으로써 조절될 수 있다. 그러나, 이러한 유연한 단편을 리지드한 콘쥬게이트 폴리머 주쇄 내에 도입하는 것은 견고성(stiffness)을 감소시키며, 따라서, 폴리머의 미세한 분자 질서에 영향을 미칠 뿐 아니라 개시 및 작동 전압을 상승시키게 된다.The third method is to introduce chromophores that are specifically conjugated into the π-conjugated electroluminescent polymer. In the latter case the conjugate length of the chromophore can be controlled by introducing a non-conjugated flexible fragment into the π-conjugate system. However, introducing such flexible fragments into a rigid conjugated polymer backbone reduces the stiffness, thus increasing the onset and operating voltages as well as affecting the fine molecular order of the polymer.
네 번째 방법은 본 발명자들의 실험실에서 개발된 것으로서, 방향족 또는 지방족 그룹을 가진 유기실리콘 단위를, 소위 실리콘계 교대 공중합체라는 π-콘쥬게이트 시스템에 도입하여 공액 길이를 제한하는 것이다. 이들은 청색 발광 다이오드로 사용할 수 있다[Kim, H. K. et al.,Macromolecules30, 1236(1997), Kim, H. K. et al.,Macromolecules31, 1114 (1998), Kim, K. D. et al.,Macromolecules31, 7267 (1998), Jung, S. H. et al.,Macromolecules33,9277 (2000), Baek, N. S. et al., Synth. Met. 121, 1743 (2001)].The fourth method, developed in our laboratory, is to introduce organosilicon units having aromatic or aliphatic groups into a π-conjugate system called a silicon-based alternating copolymer to limit the conjugate length. They can be used as blue light emitting diodes [Kim, HK et al., Macromolecules 30, 1236 (1997), Kim, HK et al., Macromolecules 31, 1114 (1998), Kim, KD et al., Macromolecules 31, 7267 (1998), Jung, SH et al., Macromolecules 33,9277 (2000), Baek, NS et al., Synth. Met. 121, 1743 (2001).
실리콘계 공중합체는 발광 다이오드로서 다음과 같은 장점을 갖고 있다. 첫째, 가공성이 우수하고, 실리콘 원자에 방향족 또는 지방족 기를 갖고 있는 유기실리콘 단위를 π-콘쥬게이트 시스템에 도입함으로써 전기발광(EL) 컬러의 조정이 용이하다. 둘째, 이들을 이용한 EL소자는 실리콘 원자의 d-오비탈 참여와 환원 LUMO 레벨로 인하여 10 V 미만의 낮은 전압에서도 비교적 높은 발광효율을 나타낸다.Silicone-based copolymers have the following advantages as light emitting diodes. First, it is easy to adjust the electroluminescence (EL) color by introducing an organosilicon unit having excellent processability and having an aromatic or aliphatic group in a silicon atom to a π-conjugate system. Second, EL devices using these devices exhibit relatively high luminous efficiency even at low voltages of less than 10 V due to d-orbital participation of silicon atoms and reduced LUMO levels.
또한, 최근에는, 주입된 정공-전자 전하의 균형과 양자효율 향상을 위하여, 옥사디아졸 및 카바졸 또는 플로렌 단위를 다양한 비율로 함유하는 실리콘계 EL 공중합체를 개발한 바 있다[Paik, K. L. et al.,ACS Polymer Preprints43(1), 77 (2002)].In recent years, silicone EL copolymers containing oxadiazole and carbazole or florene units in various ratios have been developed to balance the injected hole-electron charge and improve the quantum efficiency [Paik, KL et. al., ACS Polymer Preprints 43 (1), 77 (2002)].
따라서, 본 발명의 기술적 과제는 가공성이 우수하고 EL 컬러의 조정이 용이할 뿐 아니라 낮은 구동전압에서 높은 발광효율을 나타낼 수 있는 신규한 전기발광 고분자를 제공하는 것이다.Therefore, the technical problem of the present invention is to provide a novel electroluminescent polymer which is excellent in processability, easy to adjust EL color, and can exhibit high luminous efficiency at low driving voltage.
도 1은 본 발명에 의한 주석계 공중합체의 UV-가시광선 흡수 스펙트럼을 나타낸다.1 shows the UV-visible light absorption spectrum of the tin copolymer according to the present invention.
도 2는 본 발명에 의한 주석계 공중합체의 광발광(PL) 스펙트럼이다.2 is a photoluminescence (PL) spectrum of the tin-based copolymer according to the present invention.
도 3은 본 발명에 의한 주석계 공중합체의 가열특성을 나타내는 그래프이다.3 is a graph showing the heating characteristics of the tin-based copolymer according to the present invention.
도 4 및 도 5는 각각 본 발명의 실시예 4 및 6에서 제작한 발광 다이오드의 인가전압에 따른 전기발광 스펙트럼이다.4 and 5 are electroluminescence spectra according to applied voltages of light emitting diodes manufactured in Examples 4 and 6, respectively.
도 6은 실시예 4 내지 7에서 제작한 발광 다이오드의 인가전압에 따른 전류 밀도를 나타내는 그래프이다.6 is a graph showing current density according to an applied voltage of light emitting diodes manufactured in Examples 4 to 7. FIG.
도 7은 본 발명에 의한 주석계 공중합체의 에너지 다이어그램이다.7 is an energy diagram of a tin-based copolymer according to the present invention.
도 8은 실시예 4 내지 7에서 제작한 발광 다이오드의 전류밀도에 따른 휘도 변화를 나타내는 그래프이다.FIG. 8 is a graph showing a change in luminance according to current density of light emitting diodes manufactured in Examples 4 to 7. FIG.
도 9는 실시예 4 내지 7의 발광 다이오드에 대한 C.I.E. 1931 색도 좌표이다.9 shows C.I.E. light-emitting diodes of Examples 4-7. 1931 chromaticity coordinates.
본 발명은 상기 기술적 과제를 달성하기 위하여, 페닐 그룹을 가지는 유기주석(organotin) 단위를 π-콘쥬게이트 시스템에 도입한, 하기 화학식 1의 반복단위를 포함하는 주석계 고분자를 제공한다.The present invention provides a tin-based polymer comprising a repeating unit represented by the following Formula 1, in which an organotin unit having a phenyl group is introduced into a π-conjugate system.
상기 식에서, X는 치환 또는 비치환 페닐렌, 플로레닐렌 또는 카바졸릴렌 이고, n은 양의 정수이다.Wherein X is substituted or unsubstituted phenylene, florenylene or carbazolylene, and n is a positive integer.
본 발명의 바람직한 실시예에 의하면, 하기 화학식 2의 반복단위를 갖는 주석계 공중합체가 제공된다.According to a preferred embodiment of the present invention, there is provided a tin-based copolymer having a repeating unit of the formula (2).
본 발명의 바람직한 실시예에 의하면, 하기 화학식 3의 반복단위를 갖는 주석계 공중합체가 제공된다.According to a preferred embodiment of the present invention, there is provided a tin-based copolymer having a repeating unit of the formula (3).
본 발명의 바람직한 실시예에 의하면, 하기 화학식 4의 반복단위를 갖는 주석계 공중합체가 제공된다.According to a preferred embodiment of the present invention, there is provided a tin-based copolymer having a repeating unit of the formula (4).
바람직하게는, 본 발명에 의한 주석계 공중합체는 교대 공중합체 형태를 가질 수 있으며, 수평균 분자량은 1×103- 5×103일 수 있다.Preferably, the tin-based copolymer according to the present invention may have an alternating copolymer form, and the number average molecular weight may be 1 × 10 3 -5 × 10 3 .
이하 본 발명을 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명자들은 극히 낮은 구동전압에서 청색 발광을 얻을 수 있는 주석계 공중합체를 개발하였으며, 이 공중합체는 주쇄내에 유기주석 단위를 함유하는 주석계 교대 공중합체이다.The inventors have developed a tin-based copolymer capable of obtaining blue light emission at an extremely low driving voltage, and this copolymer is a tin-based alternating copolymer containing an organotin unit in the main chain.
본 발명자들은 유기주석 단위를 함유하는 EL 공중합체를 하기 반응식 1과 같은 Heck 반응(Heck reaction)에 의해 합성하였다.The present inventors synthesize | combined the EL copolymer containing an organotin unit by the Heck reaction like the following Reaction Formula 1.
상기 식에서, X는 전술한 화학식 1과 같고, Pd(OAC)2는 팔라듐(II) 아세테이트[palladium(II)acetate], TOP는 트리스(2-메틸페닐)포스핀[tris(2-methylphenyl) phosphine], NBu3는 트리부틸아민(tributylamine), DMF는 N,N-디메틸포름아미드 (N,N-dimethylformamide)이다.Wherein X is the same as in Formula 1, Pd (OA C ) 2 is palladium (II) acetate, TOP is tris (2-methylphenyl) phosphine ], NBu 3 is tributylamine, DMF is N, N-dimethylformamide.
즉, 본 발명에 의한 주석계 고분자는 화학식 5의 단량체와 일반식 Br-X-Br (X는 치환 또는 비치환 페닐렌, 플로레닐렌 또는 카바졸릴렌)로 표기되는 화합물을 Heck 반응시켜 얻을 수 있다.That is, the tin-based polymer according to the present invention can be obtained by Heck reaction of a monomer represented by the general formula (5) with a compound represented by the general formula Br-X-Br (X is substituted or unsubstituted phenylene, florenylene or carbazolylene). .
리지드(rigid)한 π-콘쥬게이트 폴리머는 일반적인 유기 용매에 용해되지 않지만, Sn-C 결합길이가 긴(δSn-C= 217 pm) 유기주석 단위를 리지드 콘쥬게이트 폴리머 주쇄에 도입하게 되면 폴리머 주쇄내의 Sn-C 결합의 회전 장벽이 저하되어 견고성이 감소된다. 그 결과, 주석계 교호 공중합체의 용해도가 향상되어 일반적인 유기 용매에도 용해될 수 있고, 이들의 용액을 스핀 코팅함으로써 고품질의 박막을 얻을 수 있다. π-콘쥬게이트 시스템이 유기주석 단위에 의해 조절됨으로써, 공중합체의 UV-가시광선 흡수 스펙트럼은 클로로포름 용액 및 필름 형태일 때 350∼394 nm의 파장에서 나타난다.Rigid π-conjugate polymers are not soluble in common organic solvents, but the introduction of organotin units with long Sn-C bonds (δ Sn-C = 217 pm) into the rigid conjugate polymer backbone The rotational barrier of Sn-C bonds in the interior is lowered, thereby reducing the robustness. As a result, the solubility of the tin-based alternating copolymer is improved and can be dissolved in a general organic solvent, and a high quality thin film can be obtained by spin coating these solutions. By controlling the π-conjugate system by organotin units, the UV-visible absorption spectrum of the copolymer appears at a wavelength of 350-394 nm when in the form of chloroform solution and film.
이하 실시예를 들어 본 발명을 보다 구체적으로 설명하나, 본 발명의 범위가 이들에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited thereto.
제조예 1: 디스티릴디페닐스테인(distyryldiphenylstannane: 화학식 5)의 합성Preparation Example 1 Synthesis of Distyryldiphenylstannane (Formula 5)
질소대기하에서 건조 THF(20 ml)에 4-브로모스티렌(500㎕, 1.9 mmol) 및 마그네슘 터닝(92.4 mg, 3.8 mmol)을 부가하여 30℃에서 교반하였다. 건조 THF (10 ml)내 디페닐틴디클로라이드(326.6 mg, 0.95 mmol)를 적가한 후 동일한 온도에서 5시간 동안 교반하였다. 반응혼합물을 에틸아세테이트로 추출한 후 염수로 세척하였다. 유기층을 무수황산마그네슘으로 건조한 후 여과한 다음 농축시켰다. 조생성물을 컬럼크로마토그래피(실리카겔, 용리액: 헥산/에틸아세테이트(15:1))로 정제하여, 백색 고체를 얻었다(159 mg, 35%, 융점 95-96℃). 반응식은 다음과 같다.To broth THF (20 ml) under nitrogen atmosphere was added 4-bromostyrene (500 μl, 1.9 mmol) and magnesium turning (92.4 mg, 3.8 mmol) and stirred at 30 ° C. Diphenyltindichloride (326.6 mg, 0.95 mmol) in dry THF (10 ml) was added dropwise and stirred at the same temperature for 5 hours. The reaction mixture was extracted with ethyl acetate and washed with brine. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated. The crude product was purified by column chromatography (silica gel, eluent: hexane / ethyl acetate (15: 1)) to give a white solid (159 mg, 35%, melting point 95-96 ° C.). The scheme is as follows.
1H-NMR(300 MHZ, CDCl3):δ 5.25(d, 2H, J=10.9 Hz), 5.77(d, 2H, J=17.6 Hz), 6.70(dd, 2H, J=17.6 Hz & 10.9 Hz), 7.24-7.46 (m, 10H), 7.54-7.60 (m, 8H) 1 H-NMR (300 MHZ, CDCl 3 ): δ 5.25 (d, 2H, J = 10.9 Hz), 5.77 (d, 2H, J = 17.6 Hz), 6.70 (dd, 2H, J = 17.6 Hz & 10.9 Hz ), 7.24-7.46 (m, 10H), 7.54-7.60 (m, 8H)
13C-NMR (75 MHz, CDCl3): δ 138.5, 138.0, 137.6, 137.4, 137.0, 129.4, 128.9, 126.5, 114.7 13 C-NMR (75 MHz, CDCl 3 ): δ 138.5, 138.0, 137.6, 137.4, 137.0, 129.4, 128.9, 126.5, 114.7
FT-IR (NaCl, cm-1): 3060, 2987, 2958, 1628, 1588, 1492, 1429, 1300, 1260, 1185, 1159, 1013, 995, 913FT-IR (NaCl, cm -1 ): 3060, 2987, 2958, 1628, 1588, 1492, 1429, 1300, 1260, 1185, 1159, 1013, 995, 913
HRMS(M+) C28H24Sn 에 대한 계산치: 480.0900, 실험치:480.0906HRMS (M + ) calcd for C 28 H 24 Sn: 480.0900, found: 480.0906
C28H24Sn에 대한 원소분석 계산치: C 70.18, H 5.05, 실험치: C 69.90, H 5.32Elemental Analysis Calcd for C 28 H 24 Sn: C 70.18, H 5.05, Experimental Value: C 69.90, H 5.32
제조예 2: 2,7-디브로모-9,9'-디헥실플로렌(화학식 7)의 합성Preparation Example 2 Synthesis of 2,7-Dibromo-9,9'-dihexylflorene (Formula 7)
질소 대기하에서 9,9-디헥실플로렌 (15 g, 44.84 mmol)을 0 ℃ 클로로포름 120 ml에 녹이고 용액에 염화제이철(112 mg, 0.688 mmol)과 브롬 (4.83 ml, 93.98 mmol)을 첨가한다. 알킬사슬의 브롬화를 막기 위해 반응용기를 빛으로 보호한다. 온도를 상온으로 올리고 3시간동안 교반시킨다. 반응 종결 후 반응물을 물에 붓고 적색이 사라질 때까지 티오황산나트륨으로 세척하고 유기층을 분리하고 컬럼크로마토그래피(실리카겔, 용리액: 헥산)로 정제하여, 백색 고체를 얻었다. 반응식은 다음과 같다.Dissolve 9,9-dihexylfluorene (15 g, 44.84 mmol) in 120 ml of 0 ° C. chloroform under nitrogen atmosphere and add ferric chloride (112 mg, 0.688 mmol) and bromine (4.83 ml, 93.98 mmol) to the solution. The reaction vessel is protected with light to prevent bromination of the alkyl chain. The temperature is raised to room temperature and stirred for 3 hours. After completion of the reaction, the reaction was poured into water, washed with sodium thiosulfate until the red color disappeared, the organic layer was separated and purified by column chromatography (silica gel, eluent: hexane) to obtain a white solid. The scheme is as follows.
1H-NMR(300 MHZ, CDCl3):δ 0.58(m, 4H), 0.82-1.25(m, 18H), 1.90 (m, 4H), 7.44 (d, 2H), 7.46 (d, 2H), 7.53 (d, 2H). 1 H-NMR (300 MHZ, CDCl 3 ): δ 0.58 (m, 4H), 0.82-1.25 (m, 18H), 1.90 (m, 4H), 7.44 (d, 2H), 7.46 (d, 2H), 7.53 (d, 2 H).
제조예 3: 3,6-디브로모-9-(2-에틸헥실)카바졸(화학식 6)의 합성Preparation Example 3 Synthesis of 3,6-Dibromo-9- (2-ethylhexyl) carbazole (Formula 6)
질소대기하에서 적가깔대기가 설치된 플라스크에 3,6-디브로모카바졸 (2 g, 6.15 mmol), THF (30 ml)와 NaH (177 mg, 7.38 mmol)을 넣고 상온에서 2 시간동안 교반시킨 후 2-에틸헥실브로마이드 (1.78 g, 9.22 mmol)를 천천히 적가한다. 이 혼합물에 서서히 열을 가하여 110 ℃에서 60시간 환류시킨다. 반응이 끝난 후 온도를 상온으로 내리고 차가운 물을 (150 ml) 넣은 다음 디에틸에테르로 유기물을 추출한다. 추출 된 유기물을 염수로 세척 후 무수황산마그네슘을 넣어 건조시킨 다음 농축시켜 컬럼크로마토그래피(실리카겔, 용리액: 헥산/에틸아세테이트(3:1))로 정제하여, 노란색의 용액을 얻었다. 반응식은 다음과 같다.3,6-dibromocarbazole (2 g, 6.15 mmol), THF (30 ml) and NaH (177 mg, 7.38 mmol) were added to a flask equipped with a dropping funnel under nitrogen atmosphere, and stirred at room temperature for 2 hours. -Ethylhexylbromide (1.78 g, 9.22 mmol) is slowly added dropwise. The mixture is slowly heated to reflux at 110 ° C. for 60 hours. After the reaction, the temperature was lowered to room temperature, cold water (150 ml) was added, and the organics were extracted with diethyl ether. The extracted organics were washed with brine, dried over anhydrous magnesium sulfate, and then concentrated and purified by column chromatography (silica gel, eluent: hexane / ethyl acetate (3: 1)) to obtain a yellow solution. The scheme is as follows.
1H-NMR(300 MHZ, CDCl3): δ 0.82-0.89 (m, 6H), 1.21-1.31 (m, 8H), 2.02(m, 1H),4.07 (d, 2H), 7.2-8.1 (m, 6H) 1 H-NMR (300 MHZ, CDCl 3 ): δ 0.82-0.89 (m, 6H), 1.21-1.31 (m, 8H), 2.02 (m, 1H), 4.07 (d, 2H), 7.2-8.1 (m , 6H)
13C-NMR (75 MHz, CDCl3): δ 139.53, 128.79, 123.21, 123.03, 111.78, 110.52, 47.59, 39.32, 30.96, 28.78, 24.37, 23.06, 14.10, 10.95 13 C-NMR (75 MHz, CDCl 3 ): δ 139.53, 128.79, 123.21, 123.03, 111.78, 110.52, 47.59, 39.32, 30.96, 28.78, 24.37, 23.06, 14.10, 10.95
실시예 1: SnPhPPV(화학식 2의 중합체)의 제조Example 1 Preparation of SnPhPPV (Polymer of Formula 2)
제조예 1의 단량체와 1,4-디브로모벤젠을 사용하여 다음과 같이 중합반응을 실시하였다.The polymerization reaction was carried out using the monomer of Preparation Example 1 and 1,4-dibromobenzene as follows.
질소기류하에서 1,4-디브로모벤젠(246 mg, 1.04 mmol)을 10 ml DMF에 녹인 후 Pd(OAc)2(24 mg, 0.11 mmol)와 트리스(o-톨릴)포스핀(95 mg, 0.313 mmol)을 넣고 50 ℃에서 한시간 동안 교반시킨다. 이 용액에 단량체인 디스트릴디페닐스테인 (0.5 g, 1.04 mmol)와 트리부틸아민(2.36 ml, 12.52 011mmol)을 첨가하고 온도를 100 ℃로 올린 후 24 시간동안 교반시킨 후, 반응물의 온도를 상온으로 내리고 메탄올에 침전시켜 1 시간동안 교반시킨다. 이 침전물을 뜨거운 클로로포름으로 녹인 후 미세필터(0.45 ㎛)로 남은 촉매를 제거하고, 메탄올에 재침전을 시킨다. 생성물을 진공오븐속에서 50 ℃에서 하루동안 건조시킨다.Under nitrogen stream, 1,4-dibromobenzene (246 mg, 1.04 mmol) was dissolved in 10 ml DMF, followed by Pd (OAc) 2 (24 mg, 0.11 mmol) and tris (o-tolyl) phosphine (95 mg, 0.313 mmol) and stirred at 50 ° C. for one hour. To this solution, monomeric distridyl diphenylsteine (0.5 g, 1.04 mmol) and tributylamine (2.36 ml, 12.52 011 mmol) were added and the temperature was raised to 100 ° C. and stirred for 24 hours. Down to precipitate in methanol and stirred for 1 hour. After dissolving the precipitate with hot chloroform, the remaining catalyst was removed with a fine filter (0.45 μm), and methanol was reprecipitated. The product is dried in a vacuum oven at 50 ° C. for one day.
실시예 2: SnPhFPV(화학식 3의 중합체)의 제조Example 2: Preparation of SnPhFPV (Polymer of Formula 3)
1,4-디브로모벤젠 대신 제조예 2의 단량체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 중합반응을 실시하였다The polymerization was carried out in the same manner as in Example 1, except that the monomer of Preparation Example 2 was used instead of 1,4-dibromobenzene.
실시예 3: SnPhPVK(화학식 4의 중합체)의 제조Example 3: Preparation of SnPhPVK (Polymer of Formula 4)
1,4-디브로모벤젠 대신 제조예 3의 단량체를 사용한 것을 제외하고는 실시예1과 동일한 방법으로 중합반응을 실시하였다.The polymerization was carried out in the same manner as in Example 1, except that the monomer of Preparation Example 3 was used instead of 1,4-dibromobenzene.
실시예 1-3에서 제조한 공중합체의 물성 및 특성은 다음 표 1과 같다.Physical properties and properties of the copolymer prepared in Example 1-3 are shown in Table 1 below.
실시예 1 내지 3에서 제조한 공중합체의 화학적 구조는 FR-IR,1H-NMR,13C-NMR 및 UV-가시광선 분광분석법에 의해 확인하였다. 주석계 공중합체의 일반적인 FT-IR 스펙트럼은 단량체 내의 비닐결합(C=C)이 1600 cm-1에서 희미한 흡수피크를 보이는 반면, 폴리머내의 트랜스 비닐렌 그룹의 비평면 벤딩모드는 960cm-1에서 약하지만 날카로운 새로운 피크를 나타내었다. 이것은 트랜스 이중결합을 보유한 주석계 교대 공중합체가 형성되었음을 의미한다.1H-NMR 연구에 의하면, 중합이 진행될수록 5.2-5.7 ppm에 존재하는 단량체의 말단 피크가 사라지고, 폴리머내의 비닐 수소 피크가 새롭게 나타나 7.0-7.5 ppm의 방향족 수소 피크와 중첩된다. 또한, 주석원자와 카바졸 단위내의 질소원자에 인접한 알킬 수소에 해당하는 브로드한 피크가 0.2-2.0 ppm에 걸쳐 나타났다. 4.1 ppm 부근의 브로드한 피크는 카바졸 단위내의 질소원자에 인접한 α-메틸렌 프로톤에 해당한다. 이러한 결과는 디스티릴디페닐스테인 단량체 내의 말단 비닐 수소 피크가 사라지면서 비교적 높은 분자량의 폴리머가 형성됨을 의미한다. 결과적으로 얻어진 공중합체의 수평균 분자량(Mn)은, 폴리스티렌 표준을 사용하여 겔투과 크로마토그래피로(GPC) 측정한 결과, 2.5×103- 4.6×103이었다(표 1 참조). 공중합체는 THF, CHCl3, CH2Cl2, DMF 등과 같은 유기용매에 매우 잘 용해되어 스핀 코팅법에 의해 고품질의 박막을 얻을 수 있었다.Chemical structures of the copolymers prepared in Examples 1 to 3 were confirmed by FR-IR, 1 H-NMR, 13 C-NMR and UV-Vis spectroscopy. Typical FT-IR spectra of tin-based copolymers show a faint absorption peak of vinyl bonds (C = C) in the monomer at 1600 cm −1 , while the non-planar bending mode of the transvinylene group in the polymer is about 960 cm −1 . But it showed a sharp new peak. This means that tin-based alternating copolymers with trans double bonds were formed. According to the 1 H-NMR study, as the polymerization proceeds, the terminal peaks of the monomers present at 5.2-5.7 ppm disappear, and the vinyl hydrogen peaks in the polymer newly appear and overlap with the aromatic hydrogen peaks of 7.0-7.5 ppm. In addition, broad peaks corresponding to the alkyl hydrogens adjacent to the tin atoms and the nitrogen atoms in the carbazole units appeared over 0.2-2.0 ppm. Broad peaks around 4.1 ppm correspond to α-methylene protons adjacent to the nitrogen atom in the carbazole unit. This result means that a relatively high molecular weight polymer is formed as the terminal vinyl hydrogen peak in the distyryldiphenylsteine monomer disappears. The number average molecular weight (Mn) of the resulting copolymer was 2.5 × 10 3 to 4.6 × 10 3 as measured by gel permeation chromatography (GPC) using a polystyrene standard (see Table 1). The copolymer was very well dissolved in organic solvents such as THF, CHCl 3 , CH 2 Cl 2 , DMF and the like to obtain a high quality thin film by spin coating.
도 1은 실시예 1 내지 3에서 제조한 주석계 공중합체의 UV-가시광선 흡수 스펙트럼을 나타낸다. 도 1을 참조하면, 본 발명에 의한 주석계 공중합체의 흡수스펙트럼(클로로포름 용액) 350-394 nm에서 나타나는 것을 알 수 있는데, 이는 π-콘쥬게이션 시스템이 유기주석 단위에 의해 조절되기 때문이다. SnPhFPV는 SnPhPVK 보다 흡수 파장이 긴 것으로 나타났다. 이는 카바졸 단위보다 플로렌 단위의 콘쥬게이션 특성이 양호하기 때문인 것으로 판단된다.Figure 1 shows the UV-visible absorption spectrum of the tin copolymer prepared in Examples 1 to 3. Referring to Figure 1, it can be seen that the absorption spectrum (chloroform solution) of the tin-based copolymer according to the invention appear at 350-394 nm, because the π-conjugation system is controlled by organotin units. SnPhFPV showed longer absorption wavelength than SnPhPVK. This is considered to be because the conjugation property of the florene unit is better than the carbazole unit.
도 2는 크세논 램프의 350 nm의 자외선 파장으로 광여기시 광발광(PL) 스펙트럼으로서, 470∼502 nm의 청색발광을 나타내는 것을 알 수 있다.FIG. 2 shows a photoluminescence (PL) spectrum when excited at 350 nm ultraviolet wavelength of a xenon lamp, showing blue emission of 470 to 502 nm.
실시예 2 및 3에서 제조한 주석계 공중합체의 열 특성은 질소 대기하에서 DSC 및 TGA로 분석하였다. 공중합체의 녹는점은 명확하지 않았으며, 이는 공중합체가 비정질일 수 있다는 것을 의미한다. 또한, 넓은 X-선 회절 패턴 역시 이를 뒷받침해주었다. 공중합체의 Tg는 81℃ 부근이었다. 공중합체는 질소 대기하에서300∼314℃에서 소량(1% 미만)의 중량 손실만을 나타내는 등 열안정성이 우수하였다(도 3 참조).The thermal properties of the tin copolymers prepared in Examples 2 and 3 were analyzed by DSC and TGA under nitrogen atmosphere. The melting point of the copolymer was not clear, which means that the copolymer can be amorphous. In addition, a wide X-ray diffraction pattern also supported this. T g of the copolymer was around 81 ° C. The copolymer was excellent in thermal stability such as showing only a small amount (less than 1%) of weight loss at 300 to 314 ° C. under a nitrogen atmosphere (see FIG. 3).
실시예 4: 발광다이오드의 제작Example 4 Fabrication of Light Emitting Diode
ITO/PEDOT (50nm)/폴리머(80nm)/Ca (50nm)/Al (200nm)의 다층 발광 다이오드를 다음과 같이 제작하였다. PEDOT (Polyethylenedioxythiophene)는 정공전달층(HTL)으로 사용되었다. 실시예 2에서 제조한 주석계 공중합체 ShPhFPV를 클로로벤젠 용액 형태로 HTL 상에 스핀캐스팅하였다. 두께 약 80nm의 핀홀이 없는 박막을 얻었다. 칼슘은 폴리머 층상에 50 nm 두께로 증착시켰고, 알루미늄 보호층을 200 nm 두께로 형성하여 이층구조의 발광 다이오드를 완성하였다.A multilayer light emitting diode of ITO / PEDOT (50 nm) / polymer (80 nm) / Ca (50 nm) / Al (200 nm) was produced as follows. Polyethylenedioxythiophene (PEDOT) was used as the hole transport layer (HTL). The tin-based copolymer ShPhFPV prepared in Example 2 was spincast on HTL in the form of a chlorobenzene solution. A thin film without pinholes having a thickness of about 80 nm was obtained. Calcium was deposited to a thickness of 50 nm on the polymer layer, and an aluminum protective layer was formed to a thickness of 200 nm to complete a two-layered light emitting diode.
실시예 5: 발광 다이오드의 제작Example 5: Fabrication of Light Emitting Diode
폴리머 층으로서 실시예 3에서 제조한 주석계 공중합체 ShPhPVK를 사용한 것을 제외하고는 실시예 4와 동일한 방법으로 발광다이오드를 제작하였다.A light emitting diode was manufactured in the same manner as in Example 4, except that the tin copolymer ShPhPVK prepared in Example 3 was used as the polymer layer.
실시예 6: 발광 다이오드의 제작Example 6 Fabrication of Light Emitting Diode
폴리머 층으로서 ShPhFPV:PVK[폴리(9-비닐카바졸)] 8: 2 블렌드를 사용한 것을 제외하고는 실시예 4와 동일한 방법으로 발광다이오드를 제작하였다.A light emitting diode was manufactured in the same manner as in Example 4, except that ShPhFPV: PVK [poly (9-vinylcarbazole)] 8: 2 blend was used as the polymer layer.
실시예 7: 발광 다이오드의 제작Example 7: Fabrication of Light Emitting Diode
폴리머 층으로서 ShPhPVK:PVK 8: 2 블렌드를 사용한 것을 제외하고는 실시예 4와 동일한 방법으로 발광다이오드를 제작하였다.A light emitting diode was manufactured in the same manner as in Example 4, except that the ShPhPVK: PVK 8: 2 blend was used as the polymer layer.
실시예 4 내지 7에서 제작한 발광 다이오드의 특성을 평가한 결과는 다음 표 2와 같다.The results of evaluating the characteristics of the light emitting diodes manufactured in Examples 4 to 7 are shown in Table 2 below.
실시예 4 및 6에서 제작한 발광 다이오드에 대하여 인가전압에 따른 전기발광 스펙트럼은 각각 도 4 및 도 5와 같다. 도 4 및 도 5를 참조하면, 실시예 4 및 실시예 6의 발광 다이오드는 각각 청색영역인 470 nm와 464 nm에서 발광하는 것을 확인할 수 있다. 또한, EL 강도는 인가 전압이 증가할수록 증가한다는 것도 알 수 있다.For the light emitting diodes fabricated in Examples 4 and 6, electroluminescence spectra according to applied voltages are shown in FIGS. 4 and 5, respectively. 4 and 5, it can be seen that the light emitting diodes of Examples 4 and 6 emit light at 470 nm and 464 nm, which are blue regions, respectively. It can also be seen that the EL intensity increases as the applied voltage increases.
도 6은 실시예 4 내지 7의 발광 다이오드에 대하여, 인가전압에 따른 전류 밀도를 측정한 결과를 나타낸다. 실시예 4 내지 7의 발광 다이오드 모두 4V 미만으로 매우 낮은 작동개시 전압을 갖는 것을 알 수 있다.6 shows the results of measuring current densities according to applied voltages for the light emitting diodes of Examples 4 to 7. FIG. It can be seen that the light emitting diodes of Examples 4 to 7 all have very low starting voltages of less than 4V.
이러한 결과가 나타나는 원인을 파악하기 위하여, ShPhFPV 및 ShPhPVK의 전자 친화력(LUMO 레벨)과 이온포텐샬(HOMO 레벨)을 순환 전압 전류법 (cyclic voltametry) 연구와 광학 데이터로부터 평가하였다. 도 7은 본 발명에 의한 주석계 공중합체의 에너지 준위를 나타낸다. SnPhFPV와 SnPhPVK의 LUMO 준위는 각각 3.21 eV와 2.93 eV이며, 이온포텐샬에너지(HOMO 준위)는 각각 5.89 eV 및 5.64 eV 이다. PPP, 사다리형 PPP 및 PAF와 같은 폴리(p-페닐렌) 유도체와 비교하여 낮아진 LUMO 레벨은 전자주입에 대한 에너지장벽을 낮추며, 따라서, 폴리(시아노테레프탈리덴)과 같은 폴리머 LED의 구동전압이 감소되는 것이다. 폴리(p-페닐렌) 유도체와 비교하여 상대적으로 높은 전류밀도는 본 발명에 의한 주석계 공중합체가 폴리(p-페닐렌) 유도체보다 금속특성을 갖기 때문인 것으로 판단된다.To understand the cause of this result, the electron affinity (LUMO level) and ion potential (HOMO level) of ShPhFPV and ShPhPVK were evaluated from cyclic voltametry studies and optical data. Figure 7 shows the energy level of the tin-based copolymer according to the present invention. The LUMO levels of SnPhFPV and SnPhPVK are 3.21 eV and 2.93 eV, respectively, and the ion potential energy (HOMO level) is 5.89 eV and 5.64 eV, respectively. Lower LUMO levels compared to poly (p-phenylene) derivatives such as PPP, ladder PPP and PAF lower the energy barrier to electron injection, thus driving voltage of polymer LEDs such as poly (cyanoterephthalidene) Will be reduced. The relatively high current density compared to the poly (p-phenylene) derivative is considered to be because the tin-based copolymer according to the present invention has a metal characteristic than the poly (p-phenylene) derivative.
도 8은 실시예 4 내지 7의 발광 다이오드에 있어서 전류밀도에 따른 휘도를 측정한 결과이다. 실시예 4 및 5에 비하여, 실시예 6 및 7의 경우 파워 및 전기발광 효율이 각각 2-4배 및 3-6배 향상되었다(표 2 참조). 표 2로부터, 블렌드 시스템인 실시예 6 및 7의 경우 전기발광효율이 0.1-0.3 lm/W가 향상되는 것을 확인할 수 있다.8 is a result of measuring the luminance according to the current density in the light emitting diodes of Examples 4 to 7. Compared to Examples 4 and 5, the power and electroluminescent efficiencies were improved 2-4 times and 3-6 times for Examples 6 and 7, respectively (see Table 2). From Table 2, it can be seen that in the case of Examples 6 and 7, which are blend systems, the electroluminescence efficiency is improved by 0.1-0.3 lm / W.
도 9는 실시예 4 내지 7의 발광 다이오드에 대한 C.I.E. 1931 색도 좌표이다. 도 9로부터 블렌드 시스템의 경우 청색 순도 또한 향상되는 것을 확인할 수 있다. 이상과 같은 결과는, EL 폴리머를 PVK로 희석함에 따라 엑시머 형성 및 분자간 구속이 억제되기 때문인 것으로 판단된다. 대표적으로, 실시예 6의 발광 다이오드는 11V에서 휘도가 2047 cd/m2이고 광세기 효율이 0.3 cd/A 인 것으로 나타났다.9 is CIE 1931 chromaticity coordinates for the light emitting diodes of Examples 4-7. From the blend system from Figure 9 it can be seen that the blue purity is also improved. The above result is considered to be because excimer formation and intermolecular restraint are suppressed by diluting EL polymer with PVK. Typically, the light emitting diode of Example 6 was found to have a luminance of 2047 cd / m 2 and a light intensity efficiency of 0.3 cd / A at 11V.
본 발명에 의한 주석계 고분자는 일반적인 유기 용매에 대한 용해도가 우수하여 스핀코팅에 의해 고품질의 박막을 얻을 수 있고, 4V 이하의 매우 낮은 구동전압에서 청색발광이 가능하여, 새로운 소재의 전기발광 고분자로써 대형 평판표시소자와 같은 정보표시소자 산업에 활용도가 클 것으로 기대된다.The tin-based polymer according to the present invention has excellent solubility in general organic solvents, so that a high quality thin film can be obtained by spin coating, and blue light can be emitted at a very low driving voltage of 4V or less. It is expected to be of great use in the information display device industry such as large flat panel display devices.
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