KR20160146100A - Photovoltaic efficiency and mechanical stability improved conducting polymer for all-polymer solar cells - Google Patents
Photovoltaic efficiency and mechanical stability improved conducting polymer for all-polymer solar cells Download PDFInfo
- Publication number
- KR20160146100A KR20160146100A KR1020150082746A KR20150082746A KR20160146100A KR 20160146100 A KR20160146100 A KR 20160146100A KR 1020150082746 A KR1020150082746 A KR 1020150082746A KR 20150082746 A KR20150082746 A KR 20150082746A KR 20160146100 A KR20160146100 A KR 20160146100A
- Authority
- KR
- South Korea
- Prior art keywords
- pbdtttpd
- polymer
- pscs
- ndi2hd
- blend
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims description 58
- 229920001940 conductive polymer Polymers 0.000 title claims description 11
- 239000002322 conducting polymer Substances 0.000 title 1
- -1 5- (2-ethylhexyl) thiophen-2-yl Chemical group 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims description 55
- 239000000758 substrate Substances 0.000 claims description 22
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 15
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002959 polymer blend Polymers 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- WLLGXSLBOPFWQV-UHFFFAOYSA-N MGK 264 Chemical compound C1=CC2CC1C1C2C(=O)N(CC(CC)CCCC)C1=O WLLGXSLBOPFWQV-UHFFFAOYSA-N 0.000 abstract description 5
- 125000005605 benzo group Chemical group 0.000 abstract description 5
- 238000010494 dissociation reaction Methods 0.000 abstract description 5
- 230000005593 dissociations Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000000370 acceptor Substances 0.000 description 36
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 26
- 239000010408 film Substances 0.000 description 26
- 239000012528 membrane Substances 0.000 description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000005259 measurement Methods 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 13
- 229910003472 fullerene Inorganic materials 0.000 description 13
- 238000005452 bending Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000000523 sample Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229920002521 macromolecule Polymers 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000004630 atomic force microscopy Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001654 grazing-incidence X-ray scattering Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical compound ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 230000000877 morphologic effect Effects 0.000 description 3
- 238000001894 space-charge-limited current method Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- URMVZUQDPPDABD-UHFFFAOYSA-N thieno[2,3-f][1]benzothiole Chemical compound C1=C2SC=CC2=CC2=C1C=CS2 URMVZUQDPPDABD-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- 241000248771 Amphiops mater Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000333 X-ray scattering Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BODUWJSFPLUDMP-UHFFFAOYSA-N benzo[lmn][3,8]phenanthroline-1,3,6,8(2h,7h)-tetrone Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=C2C(=O)NC(=O)C1=C32 BODUWJSFPLUDMP-UHFFFAOYSA-N 0.000 description 1
- 229930008407 benzylideneacetone Natural products 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002036 chloroform fraction Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-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
- CCRMAATUKBYMPA-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C.C[Sn](C)C CCRMAATUKBYMPA-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 230000037303 wrinkles Effects 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
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
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- 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
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- 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
- C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
-
- 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
- C08G2261/91—Photovoltaic 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Crystallography & Structural Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The present invention relates to a process for the preparation of poly [4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2- b: 4,5- b '] dithiophen- 3,4-c] pyrrole-4,6 (5H) -dione] (PBDTTTPD) as an electron donor, N, N'-bis (2-hexyldecyl) -naphthalene-1,4,5,8-bis (dicarboximide) -2,6-diyl] ] (P (NDI2HD) -T) as an electron acceptor.
According to the present invention, all-PSC having excellent mechanical elasticity and efficiency can be produced. Specifically, polymer blends with favorable exciton dissociation were synthesized with small domain size and good mixing degree, and they were applied to solar cells. As a result, the polymer blend prevented the decrease of electrical characteristics, and the performance of the organic solar cell such as high PCE and V oc value was improved, the elongation at break was improved, and the mechanical endurance was also improved.
Description
The present invention relates to a conductive polymer for an all-polymer solar cell enhanced in photoconductivity and mechanical stability. More specifically, conductive polymers and all-polymer solar cells (all-PSCs), which can be applied to flexible electronic products, have improved mechanical properties and cell performance compared to conventional fullerene-based polymer solar cells. .
The emergence of flexible and wearable devices such as smart glasses, electronic textiles, mobile devices and curved organic light emitting diode (OLED) TV has enabled research into alternative power generators for such devices. Electronic components of next-generation ubiquitous platforms including generators must have portability and flexibility to survive in new work environments (Rogers, JA et al ., Science 327, 1603-1607 (2010); Kim, D.-H. . et al, Nat Mater 9, 511-517 (2010);.... Kaltenbrunner, M. et al, Nature Commun 3, 770 (2012)). As a result, organic solar cells (OSCs) are currently considered promising solar technologies due to their low cost, light weight and flexibility (Thompson, BC et al ., Angew. Chem. Int . (2008); Shrotriya, V. Nature Photon . 3, 447-449 (2009)), the power conversion efficiency (PCE) of fullerene-based OSCs for commercial use exceeded 10% Numerous studies have been carried out as an effort to improve this. However, the development of additional donor materials in fullerene-based OSCs will not further improve efficiency. In addition, commercialization of OPVs is limited to the inability of the fullerene-based active layer due to strong mechanical forces (e.g., bending and stretching) and thermal stresses.
Thus, the present inventors have studied to design a novel bifluorene acceptor for highly efficient and flexible OSCs. To meet this need, several alternative acceptors have been proposed and evaluated, such as quantum dots, small molecules and polymers (Huynh, WU et al ., Science 295, 2425-2427 (2002); Anthony, JE Chem. Mater ., 23, 583-590 (2011)). Among these attempts, all-polymer solar cells (all-PSCs) made of polymeric donors and polymeric acceptors have the advantage of being highly flexible and capable of chemically and energy-tunable polymeric acceptors Can be a powerful solution to overcome these shortcomings and can be a promising candidate for independent generators of flexible devices (Hwang, Y.-J. et al ., Macromolecules 45, 9056-9062 (2012); Facchetti , A. Mater Today 16, 123-132 ( 2013);.... Zhou, E. et al, Adv Mater 25, 6991-6996 (2013)).
Simultaneous adjustment of the energy levels of the polymer donor and polymer acceptor increases the optical absorption range of the active layer and increases the value of the open-circuit voltage (V OC ), resulting in better performance than fullerene PSCs (PCBM-PSCs) makes it possible to provide a (Mori, D. et al, Science 7, 2939-2943 (2014);...... Earmme, T. et al, J. Am Chem Soc 135, 14960-14963 (2013) ). In addition, all-PSCs have excellent mechanical and thermal properties. Polymer / phenyl -C 61 - acid methyl ester (Polymer / phenyl-C 61 -butyric acid methyl ester; PCBM) blends has a relatively low flexibility and stretchability due to the well to break the crystalline characteristics of the fullerene (Lipomi, DJ et al ., Solar Cells 107, 355-365 (2012); Savagatrup, S. et al ., Energy Environ.
Accordingly, the present inventors have completed the present invention based on experiments to develop all-PSCs having enhanced mechanical characteristics and superior performance than conventional PCBM-PSCs to be applied to flexible and portable electronic products.
Accordingly, the present invention provides an all-polymer solar cell having enhanced photovoltaic and mechanical properties by synthesizing a conductive polymer for an all-polymer solar cell containing an optimal electron donor material and an electron acceptor material in an appropriate ratio .
In order to accomplish the above object, the present invention provides a conductive polymer in the form of a blend containing a compound represented by the following formula (1) as an electron donor and containing a compound represented by the following formula (2) as an electron acceptor.
Wherein R 1 is 2-ethylhexyl and R 2 is n-octyl.
In the present invention, the above-mentioned formula (1) is a poly [4,8-bis (5- (2-ethylhexyl) thiophen- 4H-thieno [3,4-c] pyrrole-4,6 (5H) -dione] (poly [4 , 8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2- b: 4,5- b '] dithiophene- (2-hexyldecyl) -4Hthieno [3,4-c] pyrrole-4,6 (5H) -dione], also referred to as PBDTTTPD, Hexyldecyl) -naphthalene-1,4,5,8-bis (dicarboximide) -2,6-diyl] -alte-5,5'-thiophen] (poly [[N, N'- bis 2-hexyldecyl) -naphthalene-1,4,5,8-bis (dicarboximide) -2,6-diyl] -alt-5,5'-thiophene]) is also referred to as P (NDI2HD) -T.
In the present invention, the conductive polymer is generally a polymer having a conductivity of 10 -7 Scm -1 or more, and includes an electron acceptor and an electron donor. Polymers such as plastics, which are widely used in real life, have been known as insulators because they are light and elastic. However, starting with the discovery of the first conductive polymer, polyacetylene, polymer materials with high electrical conductivity such as polyethylene, polypyrrole and polythiophene Found. Polyacetylene is a semiconductor in itself, but if it is treated with iodine, it has electrical conductivity comparable to that of metal.
In the present invention, the electron donor is a substance that donates electrons well to a portion lacking an electron pair, and is also referred to as an electron donor or an electron donor. The ion includes OH - , CN - , OR - , NH 2 - and the like , and particularly includes an alkyl group of an organic metal compound, that is, a carbanion. As the molecule having a non-covalent electron pair, there are many molecules containing nitrogen, oxygen, and sulfur atoms, and examples thereof include ammonia, amines, and ethers. As the atom, there is one which acts as a reducing agent such as an alkali metal or iron (II).
In the present invention, the electron acceptor is a material which accepts electrons from other particles well, and is also called an electron acceptor or an electron acceptor. A halogen, a nitro group, a cyano group, a compound having a carbonyl group and the like, and a metal ion such as Ag + .
In the present invention, the blend refers to a polymer blend in which two or more polymers are mixed, and is used to obtain a polymer having better properties than when a polymer is used alone. Specifically, the present invention refers to a structure in which an electron donor polymer and an electron acceptor polymer are mixed, and is also referred to as a bulk heterojunction (BHJ). Simultaneous adjustment of the energy levels of the donor and acceptor polymers can increase the optical absorption range of the active layer and increase the open-circuit voltage (V OC ) to provide better performance than PCBM-PSCs (Mori, D. et al ., Science , 7, 2939-2943 (2014); Earmme, T. et al ., J. Am. Chem. Soc ., 135, 14960-14963 (2013)).
In one embodiment of the present invention, the electron donor and the electron acceptor may be included in a ratio of 1: 1-2: 1 (w: w), but preferably in a ratio of 1.3: 1 (w / .
In one embodiment of the present invention, the polymer may have a band gap of 1.50-2.50 eV.
The efficiency of the solar cell is determined by V oc , I sc, and FF. Among these, the open circuit voltage V oc is determined by the bandgap of the semiconductor. Therefore, when a material having a large band gap is used, a generally high V oc value is obtained . On the other hand, the smaller the bandgap, the wider the wavelength range of the absorbable light. In such a case, the V oc value also decreases. Therefore, it is important to set the band gap to an appropriate value.
The present invention also provides a polymer solar cell comprising a substrate, an organic thin film, an active layer, and an electrode, wherein the active layer contains the compound represented by
In the present invention, the all-polymer solar cell refers to a solar cell in which both an electron donor and an electron acceptor are made of a polymer, and has advantages such as high flexibility and chemical characteristics of a polymer, Easy to apply
In one embodiment of the present invention, the substrate may be a glass substrate coated with indium thin oxide (ITO).
In one embodiment of the present invention, the organic thin film may include poly- (3,4-ethylenedioxythiophene): poly- (3,4-ethylenedioxythiophene): poly (styrenesulfonate) PSS).
In the present invention, the PEDOT: PSS is a polymer in which two ionomers are mixed, and is a transparent conductive polymer having high flexibility. Dispersed as gelled particles in water, and dispersed in a substrate such as glass in the same manner as spin coating.
In one embodiment of the present invention, the electrode may be deposited with lithium fluoride (LiF) and aluminum (Al).
According to the present invention, all-PSC having excellent mechanical elasticity and efficiency can be produced. Specifically, polymer blends with favorable exciton dissociation were synthesized with small domain size and good mixing degree, and they were applied to solar cells. As a result, the polymer blend prevented the decrease of the electrical characteristics, so that the performance such as high PCE and V oc value was improved, the elongation at break was improved, and the mechanical durability was also improved.
Figure 1 shows the chemical structure, energy level, and ultraviolet-visible absorption spectra of PBDTTTPD (black line), PC 61 BM (red line) and P (NDI2HD) -T (blue line).
Figure 2 relates to JV and EQE characteristics for PCBM-PSC and all-PSC. Figure 2 (a) shows the current density-voltage curves of a typical single cell device under an AM 1.5 G-simulated daylight illumination (100 mW cm -2 ), showing PBDTTTPD: PC 61 BM (black line), PBDTTTPD: P ) -T (red line). Fig. 2 (b) shows the measurement results for the PBDTTTPD: PC 61 BM (black line) and PBDTTTPD: P (NDI2HD) -T (red line), respectively,
3 is a graph showing UV-Vis absorption characteristics of PBDTTTPD: PCBM and PBDTTTPD: P (NDISHD) -TBHJ blend films.
Figure 4 shows the results of GIXS measurements in and out-of-plane (not shown). (NDISHD) -T new thin film (FIG. 4A) and PBDTTTPD: PCBM and PBDTTTPD: P (NDISHD) -T blend film (FIG.
5 is an AFM image. 5A is an image at optimized device conditions of PBDTTTPD: PCBM (RMS roughness is 6.4 nm) and FIG. 5B is PBDTTTPD: P (NDISHD) -T (RMS roughness 3.1 nm) blend film.
Figure 5c is a graph of the RSoXS profile results of the PBDTTTPD: PCBM and PBDTTTPD: P (NDISHD) -T blend membranes (285.4 eV photon energy was used for maximum scatter contrast between the membranes).
FIG. 6 is an image obtained by measuring the contact angle in PBDTTTPD, PCBM and P (NDISHD) -T films using water and glycerol.
Figure 7 shows the results of measurements of the space charge limited JV characteristics of the PBDTTTPD: PCBM and PBDTTTPD: P (NDISHD) -T blends using only devices with a major (Figure 7a) and only an electron (Figure 7b) Graph.
FIG. 8 shows the tensile modulus test results of PBDTTTPD: PCBM and PBDTTTPD: P (NDI2HD) -T blend films. Shows the toughness (1: 1.5 and 1: 0.5) of the stress strain curves (Fig. 8A), PBDTTTPD: PCBM and PBDTTTPD: P (NDI2HD) -T (Fig. 8A is a photograph of a BHJ blend membrane floating on the water surface. Samples were captured by PDMS-coated Al grips and the films were prepared under optimized device conditions. FIG. 8C is an optical microscope image of PBDTTTPD: PCBM and PBDTTTPD: P (NDI2HD) -T blend films with and without cracks, respectively.
Fig. 9 shows the results of bending test of PBDTTTPD: PC 61 BM and PBDTTTPD: P (NDI2HD) -T blend films. 9 (a) is a photograph of a BHJ blend film deposited on a PI substrate under mechanical bending, and Fig. 9 (b) is a photograph of a BHJ blend film deposited on a PI substrate with various R values of PBDTTTPD: PC 61 BM and PBDTTTPD: P (NDI2HD) Lt; / RTI > (IV) of the PBDTTTPD: PC 61 BM and (e) PBDTTTPD: P (
10 is an SEM image of the PBDTTTPD: PCBM and PBDTTTPD: P (NDISHD) -T blend films bent at R = 1.0 mm.
Hereinafter, the present invention will be described in detail with reference to examples. However, these examples are intended to further illustrate the present invention, and the scope of the present invention is not limited to these examples.
Experimental Example Materials and Methods
Experimental material
The PBDTTPD donor was synthesized by a microwave-assisted steel coupling reaction. (2,6-bis (trimethylthyne) -4,8-bis- (5-ethylhexyl-2-thienyl) benzo [1,2- b : 4,5- b '] dithiophene bis (trimethyltin) -4,8-bis- (5-ethylhexyl-2-thienyl) benzo [1,2- b : 4,5- b '] dithiophene; BDTT, 1.0 eq.) and 1,3- 3-dibromo-5-octylthieno [3,4-c] pyrrole-4,6-dione; TPD, 1.0 Equivalent) was added to a microwave vial equipped with an electronic stirrer. Pd 2 (dba) 3 (3 mol%) and p ( o- toluyl) 3 (12 mol%) were added and then sealed with a lid. The mixture was degassed three times and degassed chlorobenzene was added. The vials were stirred in a microwave reactor at 180 < 0 > C for 8 hours. After cooling to room temperature, the polymer was precipitated with methanol and filtered through a Soxhlet thimble. The precipitate was successively purified by Soxhlet extraction using methanol, hexane, acetone, dichloromethane and chloroform (if necessary). The dichloromethane or chloroform polymer was concentrated under reduced pressure and precipitated with cold methanol. The polymer was dried under vacuum for 24 hours.
P (NDI2HD) -T acceptor was also synthesized through condensation in microwave-assisted steel. 4,9- dibromo-2,7-bis (2R) benzo [lmn] [3,8] Pena troll line -1,3,6,8 (2 H, 7 H) - tetrahydro-one (4,9 -dibromo-2,7-bis (2R) benzo [lmn] [3,8] phenanthroline-1,3,6,8 (2 H, 7 H) -tetraone, 150mg, 1 eq.) and 2,5-bis (Trimethylstannyl) thiophene (62.5 mg, 1 equivalent) was added to a microwave vial equipped with an electromagnetic stirrer. Dry toluene (1.2 mL) and dimethylformamide (0.12 mL) were injected and the solution was degassed with N 3 for 20 min. A catalyst of tri ( o- toyl) phosphine (3.7 mg, 8 mol%) and tri (benzylideneacetone) dipalladium (1.4 mg, 2 mol%) was added and the mixture was then degassed for an additional 20 minutes. The reaction was terminated by reacting in a microwave reactor at 150 < 0 > C for 1 hour. After cooling to room temperature, the resulting gel was diluted with chloroform and precipitated in a methanol / hydrochloric acid co-solvent. The polymer was continuously purified by Soxhlet extraction using methanol, acetone, hexane and chloroform. The acceptor from the chloroform fraction was precipitated in methanol and dried in vacuo for 24 h. PCBM was purchased from Nano-C. The DIO additive was purchased from Aldrich and used as is.
Preparation of active layer solution
The PBDTTTPD: PCBM (1: 1.5, w / w) blended solution was dissolved in chloroform / 1,8-diiodooctane (97% to 3%) and in a glovebox at 45 ° C until the active substances were completely dissolved Hr. The total concentration of the polymeric donor in the solution was 10 mg / ml. The solution was passed through a 0.45 μm polytetrafluoroethylene (PTFE) syringe filter before it was subsequently used.
The PBDTTTPd: P (NDI2HD) -T (1.3: 1 w / w) blend solution was dissolved in chloroform / 1,8-diiodooctane (99% to 1%) and when the active materials were completely dissolved in the glovebox at 45 ° C Lt; / RTI > for 24 hours. The total concentration of D + A in the solution was 12.5 mg / ml. The solution was passed through a 0.45 μm polytetrafluoroethylene (PTFE) syringe filter before it was subsequently used.
Surface tension calculation
The surface tensions of PBDTTTPd, PCBM and P (NDI2HD) -T were calculated by surface angle measurements. The contact angles of two different solvents, water and glycerol, were measured on PBDTTTPD, PCBM and P (NDI2HD) T membranes. The surface tension of each of the pellets was calculated by the Wu model and the following equations (1) to (3).
gamma total is the total surface tension of PBDTTTPD, PCBM and P (NDI2HD) -T; γ d and γ p are the dispersion and polarity factors of γ total , respectively. gamma i is the total surface tension of the I material (i = water or glycerol); ri d and ri p are the dispersion and polarity components of γ i, respectively. θ is the contact angle on PBDTTTPD, PCBM and P (NDI2HD) -T membranes of water or glycerol droplets.
In addition, the interfacial tension between PBDTTTPD and PCBM and PBDTTTPD and P (NDI2HD) -T was calculated using the following equation (4) to explain the relationship between the miscibility and performance of PSCs.
? 12 is the interfacial tension between PBDTTTPD (1) and PCBM (2) (or PBDTTTPD (1) and P (NDI2HD) -T (2)). γi is the surface tension of the j material ( j = 1 or 2), and the dispersion and polarity components of γi are denoted by ri d and ri p . The contact angles on PBDTTTPD, PCBM and P (NDI2HD) -T membranes of water and glycerol droplets Lt; / RTI >
Example 1 Preparation of PBDTTTPD: P (NDI2HD) -Tall-PSCs
1.1 Manufacture of PSCs
Conventional polymer solar cells and all-polymer solar cells (all-PSCs) are indium tin oxide (ITO) / poly (3,4-ethylenedioxythiophene): poly (styrene sulfonate) (PEDOT: PSS) / PBDTTTPD: PC 61 BM or PBDTTTPD: P (NDI2HD) -T) / LiF / Al.
The ITO-coated glass substrate was sonicated in acetone and then extensively washed with deionized water. This was sonicated in isopropyl alcohol. Thereafter, the substrate was dried in an oven at 80 캜 for several hours. The ITO substrate was treated with UV-ozone prior to PEDOT: PSS deposition. The filtered PEDOT: PSS dispersion in water (PH 500) was applied by spin coating at 3,000 rpm for 40 seconds and heated in air at 150 ° C for 20 minutes. After the application of the PEDOT: PSS layer, all subsequent procedures were performed under an N 2 atmosphere in a glove box. Each active bending solution was then spin-cast on an ITO / PEDOT: PSS substrate for 60 seconds at 1,000 rpm (or 3,000 rpm for 40 seconds)
Subsequently, the substrate was placed in a deposition chamber and maintained under a high vacuum (less than 10 -6 Torr) for more than 1 hour before depositing approximately 0.7 nm (or 0.9 nm) of LiF and 100 nm of Al. The shape of the shadow mask produced four independent devices on each substrate. The active area of the fabricated device was 0.09 cm < 2 & gt ;.
The power conversion efficiency of the device was characterized by an air mass (AM) 1.5G filter using a solar simulator (Newport Oriel Solar Simulators). The intensity of the solar simulator was carefully tuned using an AIST-certified silicon photodiode. The current-voltage behavior was measured using a Keithley 2400 SMU.
1.2 Preparation of PBDTTTPD: P (NDI2HD) -T all-PSCs
All-PSCs prepared in accordance with Example 1.1 above were prepared by reacting poly [4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [ 2-b: 4,5-b '] dithiophene-alt-1,3-bis (thiophen-2-yl) -5- (2-hexyldecyl) -4Hthieno [3,4- -4,6 (5H) -dione (poly [4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2- b: 4,5- b '] dithiophene- -1,3-bis (thiophen-2- yl) -5- (2-hexyldecyl) -4Hthieno [3,4-c] pyrrole-4,6 (5H) -dione]; PBDTTTPD) (Kang, TE et al ( Macromolecules 46, 6806-6813 (2013); Yuan, J. et al ., Adv. Funct. Mater . 23, 885-892 (2013)) and as an electron acceptor poly [[N, N'-bis 2-hexyldecyl) -naphthalene-1,4,5,8-bis (dicarboximide) -2,6-diyl] -alta-5,5'-thiophene] (poly [[N, N'- bis (2-hexyldecyl) -naphthalene-1,4,5,8-bis (dicarboximide) -2,6-diyl] -alt-5,5'-thiophene] et al ., Adv. Mater ., DOI: 10.1002 / adma.201405226 (2015)).
As shown in Fig. 1, a PBDTTTPD polymer having a band gap of 2.02 eV (number average molecular weight, Mn = 22 kg / mol, Table 1) was synthesized and used as an electron donor in the all-PSC system. UV-Vis absorption spectra were measured at room temperature using a UV-1800 spectrophotometer (Shimadzu Scientific Instruments) and absorbed light at a wavelength of 400-650 nm. P (NDI2HD) -T (Mn = 48 kg / mol, Table 1) was used as the electron acceptor in all-PSCs. This acceptor polymer has 1) a higher LUMO level than PCBM and 2) a higher electron mobility (Kang, H. et al ., ACS Macro Lett . 3, 1009-1014 (2014); Yan, H. et al ., Nature 457, 679-686 (2009)).
Table 1 above shows the characteristics of PBDTTTPD and P (NDI2HD) -T. polydispersity index (PDI) of the molecular weight of the polymer and a were determined by GPC using o-DCB. b LUMO was measured with cyclic voltammetry and c optical bandgap was determined to initiate UV-vis absorption in the polymer film.
≪ Example 2 >
2.1 PSC Device Optimization
All PSC devices were fabricated with the general device structure of ITO / PEDOT: PSS / active layer / LiF / Al as in Example 1.1 above, but the optimized conditions for PBDTTTPD: PC 61 BM and PBDTTTPD: P (NDI2HD) Respectively.
First, in a PBDTTTPD: PC 61 BM system, a chloroform-based solution having a donor: acceptor blend ratio of 1: 1.5 (w / w) and a solution concentration of 10 mg / ml was used, and 1,8-diiodooctane , 3 vol%) were added to optimize PCBM-PSCs. On the other hand, a blend of PBDTTTPD: P (NDI2HD) -T (1.3: 1, w / w) was dissolved in chloroform with a solution concentration of 12.5 mg / ml and 1 volume% DIO added.
Figure 2 shows the current density versus voltage (JV) curve and the external quantum efficiency (EQE) spectrum of the optimized PCBM-PSC. The EQE spectrum was measured by a spectroscopic measurement system (K3100 IQX, McScience Inc.) with a light source (300-W Xenon arc lamp), a monochromator (Newport) and an optical chopper (MC 2000 Thorlabs) .
2.2 Measurement of Battery Performance Ⅰ
To investigate the possibility of PBDTTTPD and P (NDI2HD) -T blends on the efficiency of all-PSCs, PSCs were prepared according to Example 1 above and optimized according to Example 2.1 and then PBDTTTPD: P (NDI2HD) -T all -PSCs (all-PSCs) and the conventional PSCs PBDTTTPD: PC 61 BM (PCBM-PSCs). Table 2 below summarizes the solar cell characteristics produced.
Table 2 relates to organic solar cell characteristics and hole and electron mobility of BDTTTPD: PC 61 BM and PBDTTTPD: P (NDI2HD) -T systems, where a is the AM 1.5 G-simulated daylight intensity (100 mW cm -2 ), And b represents the integrated value obtained from the EQE spectrum. c , d The mean PCEs from at least 8 devices were 6.08% for the PC 61 BM system and 6.60% for the P (
As shown in Table 1, the best PCE value of PCBM-PSC was 6.12% (V OC = 0.96 V; J SC = 11.17 mA cm -2 ; fill factor = 0.57). PBDTTTPD: This efficiency based on the PC 61 BM system was in agreement with or higher than the PCE values of 4-6% reported in the literature (Kang, TE et al ., Macromolecules 46, 6806-6813 (2013); Yuan , J. et al ., Adv. Funct. Mater ., 23, 885-892 (2013)).
On the other hand, when the P (NDI2HD) -T polymer according to the present invention was used as an electron acceptor instead of PC 61 BM, the best PCE value was 6.64%, much higher and V OC was 1.06 V, The highest PCE and V OC reported so far are shown.
2.3 Measurement of battery performance Ⅱ
The apparatus was also optimized by varying the additive volume fraction, as shown in Table 3 and Table 4 below.
Table 3 above gives detailed photovoltaic parameter values according to various volume ratios in PBDTTTPD: PCBM based general type PSC devices.
Table 4 above gives detailed photoelectrochemical parameter values according to various volume ratios in PBDTTTPD: P (NDI2HD) -T based general type PSC devices.
The performance of higher all-PSCs was mainly due to the improved V OC value due to P (NDI2HD) -T with higher LUMO energy levels compared to PC 61 BM. In order to obtain a deeper insight into the performance of PCBM- and all-PSCs, we measured the EQE spectra for optimized PSCs. The J SC value matched well with the integrated J SC value obtained from the EQE spectrum (error within 3%) (Figure 2b, Table 2). The EQE values of all-PSC were higher than those of PCBM-PSC at wavelengths of 550-640 and 660-700 nm, mainly due to absorption of P (NDI2HD) -T (see FIG. However, introduction of the polymer acceptor slightly lowered the EQE in the range of 350-500 nm, resulting in a comparable value of J SC .
≪ Example 3 > Electrical and morphological characteristics investigation
To obtain insight into photovoltaic operation, we investigated the electrical and morphological characteristics of PBDTTTPD: P (NDI2HD) -T and PBDTTTPD: PC 61 BM blends.
3.1 Investigation of Electrical Characteristics
First, the hole mobility (μ h ) and the electron mobility (μ e ) of PBDTTTPD: P (NDI2HD) -T and PBDTTTPD: PC 61 BM are shown as ITO / PEDOT: PSS / polymer blend / Au and ITO / ZnO / (See Table 2 and Figure 4) using a Blend / LiF / Al device, as described below, by the space charge limited current (SCLC) method.
The current-voltage measurements were performed in the range of 0 - 8 V, and the results were applied to the space-charge-limiting function. SCLC is expressed as: < RTI ID = 0.0 >
Where ε 0 is the dielectric constant of free space (8.85 ㅧ 10 14 F / cm), ε is the relative dielectric constant of the active layer (3.2 for PBDTTTPD and P (NDI2HD) -T and 3.9 for fullerene) V is the potential across the device (V = V applied - V bi - V r ), and L is the thickness of the active layer. The voltage induced was measured using a: (PSS / Au and ITO / ZnO / LiF / Al, respectively ITO / PEDOT), by the resistance (V r), an empty device-series and contact resistance (25 Ω 15) of the device The drop was excluded from the applied voltage.
As a result, the μ h values of the PCBM and all-polymer blends were 2.52 ㅧ 10 -5 and 2.84 ㅧ 10 -5 cm 2 / (V s), respectively, and the μ h of the blend was approximately 10 -5 cm 2 / V s and that the μ h values of PCBM-PSCs are consistent with those reported previously (Kang, TE et al ., Macromolecules 46, 6806-6813 (2013)). For μ e values, both blends had the same order of 10 -5 cm 2 / V s, but the μ e value of PBDTTTPD: PC 61 BM was relatively larger. The results are due to the fact that PC 61 BM has a higher μ e than the polymer acceptor (Kang, H. et al ., ACS Macro Lett . 3, 1009-1014 (2014); Schubert, M. et al ., Adv . Funct . , 24, 4068-4081 (2014)).
3.2 Survey of morphological characteristics
The blend form of the PBDTTTPD: PC 61 BM and PBDTTTPD: P (
Table 5 above gives detailed photoelectrochemical parameter values according to various volume ratios in PBDTTTPD: PC 71 BM based general type PSC devices.
First, in order to understand the interfacial interaction between the donor and the acceptor, which are key factors in determining the mixing behavior and macroscopic blend morphology, we measured the contact angle between PBDTTTPD and PC 61 BM and PBDTTTPD and P (NDI2HD) - T were compared with each other. The contact angle was measured with a contact angle analyzer (
AFM measurements were performed in a tapping mode using a Veeco Dimension 3100 instrument. Samples were prepared by spin coating on PEDOT: PSS / ITO glass. As a result, compared to all-polymer blends (3.1 nm), the fullerene-based blend has a coarse domain with much greater surface roughness (root-mean-square (RMS) of 6.4 nm) Was observed; This suggests that the domain size of the all-PSC blend is more advantageous for exciton dissociation.
RSoXS measurements were then performed using a series of photon energies at BL 11.0.1.2 in an Advanced Light Source (USA), and the data obtained at 284.2, 285.4 and 287 eV were used to determine the maximum scattering contrast between donor and acceptor Lt; / RTI > RSoXS samples were prepared on PEDOT: PSS / glass substrates under the same optimized active layer conditions. The active layer was then floated in water and transferred to a 1.0 mm x 1.0 mm, 100 nm thick Si 3 N 4 film supported by a 5 mm x 5 mm, 200 μm thick Si frame (Norcada Inc.). As a result, it was shown that the scattering peak of the all-polymer blend film had a larger q value (0.0097 Å -1 ) and was weaker and wider than the fullerene-based blend film (q = 0.0083 Å -1 and 0.0036 Å -1 ) : P (NDI2HD) -T blend has a smaller domain size and a much better degree of intermixing.
In other words, the trend of RSoXs measurement was consistent with the results of AFM measurements. Thus, even though the μ e value of PCBM-PSC was relatively larger than that of all-PSCs, efficient exciton dissociation at a larger area of all-PSCs prevented its electrical properties from decreasing and that PCBM-PSC and all- Resulting in similar J SC and FF trends.
Example 4 Microstructure measurement
For further characterization, we evaluated the microstructure of PBDTTTPD: PC 61 BM and PBDTTTPD: P (NDI2HD) -T blends via GIXS measurements (see FIG. 7). The GIXS measurement was performed at the Beamline 3C of the Pohang Accelerator Laboratory (Korea). The GIXS sample was prepared by spin coating on a PEDOT: PSS / Si substrate, and an X-ray having a wavelength of 1.1179 A was used. The incident angle (~ 0.12 °) was chosen so that the X-ray completely penetrated into the film.
As a result, PBDTTTPD and P (p) in the in-plane direction with a lamellar domain interval of 24.1 Å (q in = 0.26 Å -1 ) and 22.5 Å (q in = 0.28 Å -1 ) (NDI2HD) -T pure membrane had a (100) scattering peak, confirming that this characteristic of the original membrane was well preserved in the blend membrane (see Fig. 7 (b)). Also noticeable (010) peaks of the PBDTTTPD: PC 61 BM and PBDTTTPD: P (
As a result, the all-PSC system has excellent characteristics comparable to the PCBM-PSC system in terms of macroscopic phase separation, microstructure and electrical characteristics, but has much better performance due to higher V OC values.
Example 5: Measurement of mechanical properties
The strength of all-PSCs affects mechanical stability in terms of optimizing both mechanical and photocell performance to accommodate portable device applications (Printz, AD et al ., RSC Adv . 4, 13635-13643 (2014) ; Savagatrup, S. et al ., Macromolecules 47, 1981-1992 (2014)).
In fullerene-PSCs, the sharp and weak interface between the polymer / fullerene junctions leads to mechanical vulnerability of the BHJ active layer with relatively low cohesion and ductility (Lipomi, DJ et al ., Solar Cells 107, 355-365 (2012); Brand, V. et al ., Solar Cells 99, 182-189 (2012)). In addition, the small molecule fullerene in the blend film tends to crystallize strongly, making the membrane harder and more fragile through higher tensile modulus, lower cohesive energy, and a weaker interface with other polymer domains (Savagatrup , S. et al ., Energy Environ. Sci . 8, 55-80 (2015)). On the other hand, the mechanical properties of all-PSCs can be significantly improved due to the intrinsic flexibility of the polymer acceptor compared to well-fractured fullerenes, and the donor / acceptor interface can be enhanced by the entanglement of the polymer chains. In this regard, we first measured the tensile modulus of PBDTTTPD: PC 61 BM and PBDTTTPD: P (NDI2HD) -T blend membranes to compare the mechanical elasticity between the two membranes (see FIG. 8).
5.1 Semi-independent tensile test
We have conducted a "pseudo free-standing tensile test ", wherein no substrate-free blend film can be obtained on the water surface without any noticeable sample damage or sample wrinkles. Thus, the intrinsic mechanical properties of membranes, including tensile moduli, have been measured directly without any substrate effects, complicated calculations or assumptions (Kim, HJ et al .,
The test was carried out as follows. For the tensile test on the sample, the active layer was spin-coated onto the PEDOT: PSS / glass substrate. The active layer samples were prepared using a cutting plotter (GCC Jaguar IV-61, USA). In order to float the sample on the water surface, water is penetrated into the PEDOT: PSS layer. Then, the PEDOT: PSS is dissolved and the active layer is delaminated from the glass substrate. By performing this process on the check surface, a floating active layer sample can be obtained. Sample gripping is accomplished by bonding PDMS-coated Al grips to the sample capture surface using van der Waals adhesion forces. The tensile test is performed by a linear stage at a strain rate of 0.06 x 10 < -3 > / s. During the tensile test, stress and strain data are obtained through the load cell and the DIC device, respectively.
As a result, independent PBDTTTPD: PC 61 BM and PBDTTTPD: P (
These remarkably improved mechanical properties of PBDTTTPD: P (NDI2HD) -T blend membranes are largely due to (1) enhanced flexibility by use of polymeric acceptors and (2) the presence of mixed phases of polymeric donors and acceptors and polymeric entanglement (Nam, S. et al ., Adv. Funct. Mater . 21, 4527-4534 (2011)) between the donor and the acceptor. The present inventors speculated that the low interfacial tension between the PBDTTTPD and P (NDI2HD) -T domains also contributed to the enhancement of mechanical strength by providing better interfacial adhesion than the polymer / fullerene blend (Pracella, M. Macromol. Chem. Phys . 208, 233-233 (2007)). The excellent mechanical properties of the all-PSC membrane can improve ductility and durability against mechanical deformation by effectively reducing the stress without mechanical failure, which is an important requirement for flexible PSCs (Savagatrup, S. et al ., Macromolecules 47, Savagatrup, S. et al ., Adv. Funct. Mater . 24, 1169-1181 (2014)).
5.2 Bending test
For a closer study to analyze the possibility of all-PSCs in flexible devices, we also measured the bending properties of PBDTTTPD: PC 61 BM and PBDTTTPD: P (
In contrast, the current of the all-PSC film did not change even at a very low R = 1.0 mm. 9 (d) and (e), we also found that PBDTTTPD: PC 61 BM and PBDTTTPD: after a number of bending cycles (N = 0, 50, 100 and 150) The IV characteristics of the P (NDI2HD) -T membrane were measured with a four-point probe (CMT-SR1000N and MCP-T610). As N increased, the PBDTTTPD: PC 61 BM blend film exhibited a significant reduction in current. However, the IV characteristics of the all-PSC membrane were very stable and showed only negligible change in some measurement conditions. The tendency of the bending test was in perfect agreement with the result of the tensile modulus test and the mechanical stability test consistently derived the same result that all-PSCs were much better in terms of mechanical durability than fullerene-PSCs.
That is, the present inventors have experimentally proved that all-PSCs are superior to both PCBM-PSCs in mechanical elasticity and device efficiency. Specifically, PBDTTTPD all-PSCs (PCE = 6.7%) showed the best performance reported for all-PSCs, which outperformed the corresponding fullerene-PSCs (PCE = 6.1%) and all-PSCs 0.0 > V OC < / RTI > (1.06 V) (see Examples 2.2 and 2.3). We also observed favorable interfacial interactions between PBDTTTPD and P (NDI2HD) -T producing a relatively well mixed BHJ domain with a large interface (see Example 3.2), indicating that it is effective for all-PSCs Accelerated exciton dissociation and charge transfer. More importantly, all-PSCs were much better in terms of mechanical durability. For example, the elongation at break of all-PSCs was 70-fold higher than that of fullerene-PSCs (see Example 5.1). In addition, bending tests have shown that the use of polymeric acceptors effectively improves the mechanical stability of the active layer in PSCs (see Example 5.2). Thus, these results provide guidelines for material design of all-PSC systems and demonstrate the potential for future use as a portable and wearable device requiring both high performance and mechanical stability.
The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.
Claims (7)
(Formula 1)
Wherein R 1 is 2-ethylhexyl and R 2 is n-octyl.
(2)
The active layer is an all-polymer solar cell (all-polymer solar cell) comprising a compound represented by Formula 1 as an electron donor and a compound represented by Formula 2 as an electron acceptor, polymer solar cell; all-PSCs).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150082746A KR101743909B1 (en) | 2015-06-11 | 2015-06-11 | Photovoltaic efficiency and mechanical stability improved conducting polymer for all-polymer solar cells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150082746A KR101743909B1 (en) | 2015-06-11 | 2015-06-11 | Photovoltaic efficiency and mechanical stability improved conducting polymer for all-polymer solar cells |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20160146100A true KR20160146100A (en) | 2016-12-21 |
| KR101743909B1 KR101743909B1 (en) | 2017-06-08 |
Family
ID=57734557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150082746A KR101743909B1 (en) | 2015-06-11 | 2015-06-11 | Photovoltaic efficiency and mechanical stability improved conducting polymer for all-polymer solar cells |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101743909B1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210066605A (en) * | 2019-11-28 | 2021-06-07 | 한국과학기술원 | Composition for organic electronic device having excellent mechanical properties and organic electronic device comprising the same |
| US11283033B2 (en) | 2018-03-09 | 2022-03-22 | Lg Chem, Ltd. | Composition for organic layer of organic solar cell and organic solar cell |
| US11690282B2 (en) | 2017-06-23 | 2023-06-27 | Lg Chem, Ltd. | Organic solar cell |
| US11711966B2 (en) | 2018-03-12 | 2023-07-25 | Lg Chem, Ltd. | Polymer and organic solar cell comprising same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102315399B1 (en) | 2017-09-28 | 2021-10-20 | 주식회사 엘지화학 | Polymer material for lithium secondary battery and manufacturing methods thereof |
-
2015
- 2015-06-11 KR KR1020150082746A patent/KR101743909B1/en active IP Right Grant
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11690282B2 (en) | 2017-06-23 | 2023-06-27 | Lg Chem, Ltd. | Organic solar cell |
| US11283033B2 (en) | 2018-03-09 | 2022-03-22 | Lg Chem, Ltd. | Composition for organic layer of organic solar cell and organic solar cell |
| US11711966B2 (en) | 2018-03-12 | 2023-07-25 | Lg Chem, Ltd. | Polymer and organic solar cell comprising same |
| KR20210066605A (en) * | 2019-11-28 | 2021-06-07 | 한국과학기술원 | Composition for organic electronic device having excellent mechanical properties and organic electronic device comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101743909B1 (en) | 2017-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fan et al. | Mechanically robust all-polymer solar cells from narrow band gap acceptors with hetero-bridging atoms | |
| Li et al. | A sulfur-rich small molecule as a bifunctional interfacial layer for stable perovskite solar cells with efficiencies exceeding 22% | |
| Inganäs et al. | Low bandgap alternating polyfluorene copolymers in plastic photodiodes and solar cells | |
| Zhang et al. | Hole-transporting layer based on a conjugated polyelectrolyte with organic cations enables efficient inverted perovskite solar cells | |
| Kim et al. | Optimization and analysis of conjugated polymer side chains for high‐performance organic photovoltaic cells | |
| Liao et al. | In-situ growing CdS single-crystal nanorods via P3HT polymer as a soft template for enhancing photovoltaic performance | |
| Park et al. | Recently Advanced Polymer Materials Containing Dithieno [3, 2‐b: 2′, 3′‐d] phosphole Oxide for Efficient Charge Transfer in High‐Performance Solar Cells | |
| KR101743909B1 (en) | Photovoltaic efficiency and mechanical stability improved conducting polymer for all-polymer solar cells | |
| Jung et al. | The effect of different chalcogenophenes in isoindigo-based conjugated copolymers on photovoltaic properties | |
| Bi et al. | An obvious improvement in the performance of ternary organic solar cells with “guest” donor present at the “host” donor/acceptor interface | |
| Melenbrink et al. | Influence of acceptor side-chain length and conjugation-break spacer content on the mechanical and electronic properties of semi-random polymers | |
| Wu et al. | Poly (3‐hexylthiophene)‐b‐poly (3‐cyclohexylthiophene): synthesis, microphase separation, thin film transistors, and photovoltaic applications | |
| Cai et al. | Cross-linkable and alcohol-soluble pyridine-incorporated polyfluorene derivative as a cathode interface layer for high-efficiency and stable organic solar cells | |
| Huang et al. | Simultaneouly enhanced durability and performance by employing dopamine copolymerized PEDOT with high work function and water-proofness for inverted perovskite solar cells | |
| Waters et al. | Organic photovoltaics based on a crosslinkable PCPDTBT analogue; synthesis, morphological studies, solar cell performance and enhanced lifetime | |
| Bini et al. | Alcohol-soluble conjugated polymers as cathode interlayers for all-polymer solar cells | |
| Yuan et al. | Dual structure modifications to realize efficient polymer solar cells with low fullerene content | |
| Cho et al. | Understanding of fluorination dependence on electron mobility and stability of naphthalenediimide-based polymer transistors in environment with 100% relative humidity | |
| Lu et al. | Stable perovskite solar cells with efficiency of 22.6% via quinoxaline-based polymeric hole transport material | |
| Beaupré et al. | Random D–A 1–D–A 2 terpolymers based on benzodithiophene, thiadiazole [3, 4-e] isoindole-5, 7-dione and thieno [3, 4-c] pyrrole-4, 6-dione for efficient polymer solar cells | |
| Liu et al. | Impact of chemical design on the molecular orientation of conjugated donor–acceptor polymers for field-effect transistors | |
| Li et al. | High performance quinacridone-based polymers in film transistors and photovoltaics: effects of vinylene linkage on crystallinity and morphology | |
| Fan et al. | Enhancing the photovoltaic properties of low bandgap terpolymers based on benzodithiophene and phenanthrophenazine by introducing different second acceptor units | |
| Geng et al. | A facile route for preparation of conjugated polymer functionalized inorganic semiconductors and direct application in hybrid photovoltaic devices | |
| Salikhov et al. | New organic polymers for solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right |