TW202409135A - 嵌段式共軛高分子材料及應用其之主動層材料及有機光電元件 - Google Patents
嵌段式共軛高分子材料及應用其之主動層材料及有機光電元件 Download PDFInfo
- Publication number
- TW202409135A TW202409135A TW112129395A TW112129395A TW202409135A TW 202409135 A TW202409135 A TW 202409135A TW 112129395 A TW112129395 A TW 112129395A TW 112129395 A TW112129395 A TW 112129395A TW 202409135 A TW202409135 A TW 202409135A
- Authority
- TW
- Taiwan
- Prior art keywords
- polymer
- active layer
- electrode
- group
- item
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 105
- 239000002861 polymer material Substances 0.000 title claims abstract description 25
- 230000005693 optoelectronics Effects 0.000 title claims abstract description 20
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 86
- 238000012546 transfer Methods 0.000 claims abstract description 23
- 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 claims description 13
- 229910003472 fullerene Inorganic materials 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 10
- 229920006254 polymer film Polymers 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 3
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 3
- 125000005213 alkyl heteroaryl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000006492 halo alkyl aryl group Chemical group 0.000 claims description 2
- 125000004149 thio group Chemical group *S* 0.000 claims description 2
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000862 absorption spectrum Methods 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229920005604 random copolymer Polymers 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000000944 Soxhlet extraction Methods 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 229920005603 alternating copolymer Polymers 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002800 charge carrier Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- -1 polymers) Chemical class 0.000 description 4
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000005669 field effect Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000013086 organic photovoltaic Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000126 substance 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
- 239000011787 zinc oxide Substances 0.000 description 3
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 2
- OAIASDHEWOTKFL-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(4-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=C(C)C=CC=1)C1=CC=CC=C1 OAIASDHEWOTKFL-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- PDXRPWHBHWWTIG-UHFFFAOYSA-N C(C)C(CC1=CC=CC=2C3=CC=CC=C3CC12)CCCC Chemical compound C(C)C(CC1=CC=CC=2C3=CC=CC=C3CC12)CCCC PDXRPWHBHWWTIG-UHFFFAOYSA-N 0.000 description 1
- VESBOBHLCIVURF-UHFFFAOYSA-N COC(=O)CCCC1(c2ccccc2)C23c4c5c6c7c8c9c(c%10c%11c2c2c4c4c%12c5c5c6c6c8c8c%13c%14c%15c%16c%17c%18c%19c%20c%21c%22c%23c(c%14c%14c8c9c8c%10c9c%11c%10c2c(c%20c%10c%22c9c%23c%148)c4c%19c%12c%17c5c%16c6%13)C%152C(CCCC(=O)OC)(c4ccccc4)C%18%212)C137 Chemical compound COC(=O)CCCC1(c2ccccc2)C23c4c5c6c7c8c9c(c%10c%11c2c2c4c4c%12c5c5c6c6c8c8c%13c%14c%15c%16c%17c%18c%19c%20c%21c%22c%23c(c%14c%14c8c9c8c%10c9c%11c%10c2c(c%20c%10c%22c9c%23c%148)c4c%19c%12c%17c5c%16c6%13)C%152C(CCCC(=O)OC)(c4ccccc4)C%18%212)C137 VESBOBHLCIVURF-UHFFFAOYSA-N 0.000 description 1
- 208000025721 COVID-19 Diseases 0.000 description 1
- 238000000018 DNA microarray Methods 0.000 description 1
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000002106 pulse oximetry Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012372 quality testing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- YVJYDECLDWHYHD-UHFFFAOYSA-N tri(quinolin-8-yl)alumane Chemical compound C1=CN=C2C([Al](C=3C4=NC=CC=C4C=CC=3)C=3C4=NC=CC=C4C=CC=3)=CC=CC2=C1 YVJYDECLDWHYHD-UHFFFAOYSA-N 0.000 description 1
- 210000003462 vein Anatomy 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
-
- 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
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
-
- 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
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- 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
-
- 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
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
-
- 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
- C08G2261/126—Copolymers block
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/144—Side-chains containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/146—Side-chains containing halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/149—Side-chains having heteroaromatic units
-
- 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
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—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
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing 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
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/414—Stille reactions
-
- 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
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/512—Hole transport
-
- 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
- C08G2261/94—Applications in sensors, e.g. biosensors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Electromagnetism (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Photovoltaic Devices (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
一種有機光電元件，包含第一電極、主動層以及第二電極。主動層中的主動層材料包含有式一結構之嵌段式共軛高分子材料：
Description
本發明係涉及應用於有機光電元件的一種共軛高分子材料，尤指一種嵌段式共軛高分子材料以及包含其之主動層材料及有機光電元件。
有機光感測器(organic photodetector，OPD)技術係指以有機半導體材料為光電流響應來源之感光二極體。其原理與概念十分類似有機太陽能(organic photovoltaic，OPV)之作動機制。在有機光感測器之主動層中一般存在著兩種以上能階以電子供體(electrode donor)與電子受體(electron acceptor)功能相互配對的半導體材料。當材料吸收特定具有響應範圍之光線後產生電子電洞對(electron/hole pair，亦稱exciton)，電子電洞對即會飄移至供體與受體之界面。因異質材料間的能階作用力驅使，將電子電洞對拆解為電洞與電子，並且依循著能帶傳遞至相對應之正負極，形成電流。而其中與太陽能技術不同的是，由於有機光感測器用於光感測需求，因此材料對於特定波段的感測能力，以及整體元件之訊噪比(signal/noise ratio)十分要求。因此在技術評價上，一般會參酌電壓電流曲線之第三象限
特徵，以外部量子轉換效率(external quantum efficiency，EQE)與其元件之洩漏電流(leakage current)作為依據。
影像感測器成為成長最快的半導體產品類別之一，有機光感測器屬於其中之被動元件。其應用上主要可依據感光波段進行分類，如鏡頭、光通訊、生物晶片或指紋掃描均需要仰賴可見光(visible)波段之光感測技術，而現今主流技術即為單晶矽構成之感光元件。然而，在可預見的未來，不可見光(invisible)波段之應用需求將大幅提升，舉凡靜脈掃描辨識(vein scanner)、虹膜辨識(iris sensor)，以及面部辨識(facial recognition)等生物特徵技術，以及因COVID-19疫情導致需求量增加的脈搏血氧(pulse oximetry)量測之生理生命徵象監控技術，或是現行自駕車所需求之光達(LiDAR)、Time of fight sensor等機械視覺應用。因此，在以上應用所對應之近紅外光(near infrared)或短波紅外光(shortwave infrared)的光吸收範圍中，如何提供一種具有高性能與低成本之有機光感測器是目前非常重要的課題。
有鑑於此，本發明之一範疇在於提供一種嵌段式共軛高分子材料以突破現有技術之偵測度能力。根據本發明之一實施例，嵌段式共軛高分子材料包含式一結構：
其中，第一高分子的薄膜吸收最大值的波長≦800nm，而第二高分子的薄膜吸收最大值的波長>800nm。
其中，第一高分子選自以下結構中之一者：
其中，第二高分子選自以下結構中之一者：
本發明之另一範疇在於提供一種主動層材料，其包含p型材料以及n型材料。p型材料為一種如前所述之嵌段式共軛高分子材料。n型材料包含有拉電子基團的非富勒烯材料結構或富勒烯材料結構，且該n型材料的能隙小於2.5。
其中，非富勒烯材料結構包含式二結構：Ar2-Ar1-Ar2(式二)。Ar1包含有5~40個碳原子的共軛結構，且包含有一個以上的稠環或稠雜環。Ar2包含有酮類之單環結構或酮類之稠環結構。
其中，Ar1選自以下結構中之一者：
其中，Ar2選自以下結構中之一者：
其中，富勒烯材料結構選自以下結構中之一者：
本發明再一範疇再於提供一種有機光電元件，包含第一電極、主動層以及第二電極。主動層至少包含一種如前所述之主動層材料。其中，該主動層位於該第一電極及該第二電極之間，且該第一電極和該第二電極至少一者為透明或半透明電極。
其中，更包含有一第一載子傳遞層及一第二載子傳遞層，其中該第一載子傳遞層位於該第一電極與該主動層之間、該主動層位於該第一載子傳遞層與該第二載子傳遞層之間，以及該第二載子傳遞層位於該主動層與該第二電極之間。
相較於現有技術，本發明之嵌段式共軛高分子材料係由第一
高分子及第二高分子組合而成的嵌段式聚合物。其中第一高分子為具有高能隙的p型高分子，而第二高分子為具有低能隙的p型高分子。將此嵌段式共軛高分子材料作為p型材料所形成的主動層材料，其中具有低能隙的第二高分子可以吸收光線並與主動層材料中的n型材料進行激子拆解以及載子傳遞。而具有高能隙的第一高分子可以抑制載子複合機率，進而有效降低有機光電元件之漏電流的產生。
1:有機光電元件
10:基板
11:第一電極
12:第一載子傳遞層
13:主動層
14:第二載子傳遞層
15:第二電極
M1:主動層材料
P1:第一高分子
P2:第二高分子
N1:n型材料
圖1係繪示本發明有機光電元件之一具體實施例之結構示意圖。
圖2係顯示了本發明之嵌段式共軛高分子材料之比較例RP1與實施例BP1於薄膜態的吸收光譜。
圖3係顯示了本發明之嵌段式共軛高分子材料之比較例RP1與實施例BP1於溶液態的吸收光譜。
圖4係繪示了本發明主動層材料之結構關係示意圖。
圖5係繪示了本發明主動層材料之載子傳遞作動示意圖。
圖6係顯示了本發明主動層材料之比較例RP1與實施例BP1的暗電流密度測試結果。
為了讓本發明的優點，精神與特徵可以更容易且明確地了解，後續將以實施例並參照所附圖式進行詳述與討論。值得注意的是，這些實施例僅為本發明代表性的實施例。但是其可以許多不同的形式來實現，並不限於本說明書所描述的實施例。相反地，提供這些實施例的目的
是使本發明的公開內容更加透徹且全面。
在本發明公開的各種實施例中使用的術語僅用於描述特定實施例的目的，並非在限制本發明所公開的各種實施例。如在此所使用的單數形式係也包括複數形式，除非上下文清楚地另外指示。除非另有限定，否則在本說明書中使用的所有術語(包含技術術語和科學術語)具有與本發明公開的各種實施例所屬領域普通技術人員通常理解的涵義相同的涵義。上述術語(諸如在一般使用的辭典中限定的術語)將被解釋為具有與在相同技術領域中的語境涵義相同的涵義，並且將不被解釋為具有理想化的涵義或過於正式的涵義，除非在本發明公開的各種實施例中被清楚地限定。
在本說明書的描述中，參考術語”一實施例”、”一具體實施例”等的描述意指結合該實施例描述地具體特徵、結構、材料或者特點包含於本發明的至少一個實施例中。在本說明書中，對上述術語的示意性表述不一定指的是相同的實施例。而且，描述的具體特徵、結構、材料或者特點可以在任何一個或多個實施例中以合適的方式結合。
定義：
本文所用之「供體」材料，係指一半導體材料，例如有機半導體材料，其具備電洞作為主要電流或電荷載子。於某些實施例，當p型半導體材料被沈積於一基板上，其可提供超過約10-5cm2/Vs之電洞遷移率。於場效元件的例子中，一p型半導體材料可顯示超過約10之電流開/關比。
本文所用之「受體」材料，係指一半導體材料，例如有機半導體材料，其具備電子作為主要電流或電荷載子。於某些實施例，當n型半導體材料被沈積於一基板上，其可提供超過約10-5cm2/Vs之電子遷移率。於
場效元件的例子中，一n型半導體材料可顯示超過約10之電流開/關比。
本文所用之「拉電子基」，係為拉電子能力比氫強的基團或原子，即具有拉電子誘導效應。而本文所用之「推電子基」，係為推電子能力比氫強的基團或原子，即具有推電子誘導效應。誘導效應即因分子中原子或基團極性(電負度)不同而致使成鍵電子雲在原子鍵上向某一方向移動的效應。電子雲偏向電負度較強的基團或原子移動。
本文所列的結構中的「
」或「*」代表此結構可供鍵結之位置，但並不以此為限。
本文所用之「遷移率」，係指電荷載子在電場的影響下移動穿過該材料的速率之測量，例如電荷載子在p型半導體材料中為電洞(正電荷)，在n型半導體材料中為電子(負電荷)。該參數取決於元件的架構，可利用場效元件或空間電荷限制電流量測。
本文所用之「高分子」，係指一個非常大的分子，以數千以上的共價鍵結原子組成。高分子是由許多重複單元，即單體(由一個或多個原子組成)以共價鍵方式鍵結在一起。由物性觀點而言，重複單元的數目應該大到再多加一些重複單元，其物性並不會有顯著的改變。高分子又分為共聚物及均聚物。均聚物是僅由一種單體聚合而成。共聚物是由兩種或更多單體聚合所形成的聚合物。共聚物分為交替共聚物(Alternating copolymers)、無規共聚物(Random copolymers)、嵌段共聚物(Block copolymer)以及接枝共聚物(Graft copolymers)。交替共聚物中兩結構單元A和B嚴格交替相間，兩者在共聚物中的摩爾分數均約為50%。無規共聚物中兩結構單元A和B隨機出現，其中A和B自身連續的單元數不多，一般在幾個
到十幾個。從統計上看，無規聚合物的某結構單元在聚合物鏈上的含量等於其在整個聚合物中的含量。嵌段共聚物係由較長的只有結構單元A的鏈段和較長的只有結構單元B的鏈段構成，其中每一鏈段可達到幾十到幾千結構單元。近來隨著可控自由基聚合反應的發展，出現了梯度聚合物。其A和B的結構單元的組成隨主鏈的延伸而漸變，不像無規和交替共聚物那樣基本不變，也不像接枝共聚物那樣呈現突變關係。接枝共聚物在結構上屬於支化聚合物，其不僅有主鏈，還有較長的支鏈，且主鏈和支鏈是由不同的種結構單元組成。主鏈全部是結構單元A，而支鏈全部是結構單元B。有時候，接枝聚合物的主鏈和支鏈可能都是共聚物，比如主鏈是A和B的無規共聚物，支鏈是A和B的交替共聚物，整體仍然是接枝共聚物。
本文所用之化合物被視為「環境安定」或「環境條件下安定」，係指當結合化合物作為其半導體材料之電晶體，在該化合物暴露於環境條件下，例如空氣、環境溫度及濕度一段時間後，顯示載子遷移率維持在其初始值。例如一化合物可視為環境安定，若是結合該化合物之電晶體，在暴露於包括空氣、濕度及溫度之環境條件3天、5天或10天後，顯示載子遷移率之變化不超過20%或不超過10%之初始值。
本文所用之構件(例如薄膜層)，若其包含一個或一個以上的可吸收光子而產生用以產生光電流的激子之化合物，可被視為「光活性」。
本文所用之「溶液加工」，係指化合物(例如聚合物)、材料或組成物可用於溶液態的製程，例如旋轉塗佈、印刷法(例如噴墨印刷、凹版印刷、平版印刷等)、噴塗法、電噴塗法、滴鑄法、浸塗法及刮刀塗佈法。
如本文所用之「退火」，係指在環境中或在減壓或加壓下，
對半結晶聚合物膜進行一定持續時間的沉積後熱處理，「退火溫度」，係指該退火過程中該聚合物膜或該聚合物與其他分子之混合薄膜可進行小規模分子運動及重新排列之溫度。不受任何特定理論束縛，據信退火可在可能的情況下導致聚合物膜中的結晶度增加，提升聚合物膜或該聚合物與其他分子之混合薄膜之材料載子遷移率，並形成分子交互排列而達到有效電子與電洞之獨立傳遞路徑之效果。
本文所用之暗電流(dark current，J d )，也稱無照電流，指在沒有光照射的狀態下，在光電元件中流動的電流。
本文所用之響應度(Responsibility，R)及偵測度(Detectivity，D)係根據測量有機光感測元件之暗電流及外部量子效率(EQE)，並藉由以下公式計算出來：
於一實施例中，本發明之一種嵌段式共軛高分子材料，其包含式一結構：
於實際應用中，將第一高分子視為A嵌段、將第二高分子視為B嵌段。嵌段式共軛高分子材料之結構可進一步以下結構：
於實際應用中，第一高分子的薄膜吸收最大值的波長≦800nm，而第二高分子的薄膜吸收最大值的波長>800nm。
本實施例中，第一高分子選自以下P1~P22結構中之一者：
本實施例中，第二高分子選自以下P23~P35結構中之一者：
於實際應用中，本發明之一種嵌段式共軛高分子材料可包含以下結構：
本發明之一實施例為一種主動層材料，其包含p型材料以及n型材料。其中p型材料為包含有前述之嵌段式共軛高分子材料。n型材料包含有拉電子基團的非富勒烯材料結構或富勒烯材料結構，且n型材料的能隙小於2.5。
其中，非富勒烯材料結構包含式二結構：Ar2-Ar1-Ar2(式二)；其中Ar1包含有5~40個碳原子的共軛結構，且包含有一個以上的稠環或稠雜環；以及Ar2包含有酮類之單環結構或酮類之稠環結構。
於實際應用中，Ar1選自以下結構中之一者：
詳細來說，非富勒烯材料可以包含以下實施例N1~N35：
於實際應用中，Ar2選自以下結構中之一者：
詳細來說，富勒烯材料可以包含以下實施例N36~N39、ICBA、Bis-PCBM：
請參閱圖1，圖1係繪示本發明有機光電元件1之一實施例之結構示意圖。如圖1所示，於實施例中，本發明提供一種有機光電元件1，其包含有第一電極11、第二電極15以及主動層13。主動層13位於第一電極11與第二電極15之間。其中，一實施例中主動層13包含有前述之包含有式一結構之主動層材料。有機光電元件1可為層疊結構，依序包含有基板10、第一電極11(透明或半透明電極)、第一載子傳遞層12、主動層13、第二載子傳遞層14以及第二電極15。其中，第一載子傳遞層為電子傳輸層與電洞傳輸層中之一者，而第二載子傳遞層為另一者。詳細來說，當第一載子傳遞層為電子傳輸層時，第二載子傳遞層為電洞傳輸層，其為反式堆疊結構；當第一載子傳輸層為電洞傳輸層時，第二載子傳遞層為電子傳輸層，其為正式堆疊結構。於實務中，有機光電元件1可包含有有機光伏元件、有機光感測元件、有機發光二極體。
為了更清楚的說明本發明之嵌段式共軛高分子材料，接著將以比較例RP1與本發明之實施例BP1進行以下說明，並進一步將其製備為主
動層材料，以及有機光電元件以進行材料測試及元件測試。
材料測試及元件測試的光學物理性質量測部分，UV吸收光譜量測儀器型號為Hitachi UH5700，氧化電位使用循環伏安法搭配CH Instrument 611E量測。
p型材料：比較例RP1的合成：
p型材料：實施例BP1的合成：
根據上述合成方式，可以明顯看出比較例RP1係直接將反應物D1、A1及A2直接同時加入反應中，因此合成出來的將為D1-A1和D1-A2的無規共聚物。而本發明之實施例BP1則是分開將D1、A1及D1、A2進行反應後，以分別形成第一高分子及第二高分子兩個嵌段後，再將兩個嵌段反應連接在一起，因此合成出來的將為嵌段共聚物。由上列的結構化學式可以看出兩者為不同類型的聚合物。不同類型的共聚物將會具有不同的物性及化性，因此比較兩者時，需先確認兩者的共聚物類型，而不可以一以概之。以下將說明不同類型的共聚物的比較結果。
比較例RP1與實施例BP1的材料效能測試，包含材料光學性質及電化學性質測試：
請參閱圖2、圖3及表1。圖2係顯示了本發明之嵌段式共軛高分子材料之比較例RP1與實施例BP1於薄膜態的吸收光譜，圖3係顯示了本發明之嵌段式共軛高分子材料之比較例RP1與實施例BP1於溶液態的吸收光譜，表1顯示了圖2及圖3的數據結果。
表1：圖2及圖3的數據結果
如圖2、圖3及表1所示，實施例BP1在吸收光譜上具有良好表現。實施例BP1的薄膜態吸光最大值落在770nm，吸光起始值落在1001nm。從薄膜態吸收光譜上可看到在700~1000nm有良好的吸收性質。實施例BP1的光學性質與比較例RP1吸收光譜相似，但實施例BP1的吸收峰半高寬與波段區間皆略大於比較例RP1。由吸收光譜結果顯示BP1與RP1皆具有良好的光學性質。BP1的吸收光譜波寬較RP1的寬，是由於嵌段組成方式較隨機組成方式更能將組成的片段的物理特性展現出來，因此推測嵌段式的聚合物對於暗電流抑制效果是有助益的。
有機光電元件之有機光感測元件的製備及效能測試：使用具有~15Ω/sq的薄層電阻的預圖案化的銦錫氧化物(indium tin oxide，ITO)塗覆的玻璃作為基板。依順序在含有肥皂之去離子水、去離子水、丙酮及異丙醇中超音波震盪處理，在每個步驟中清洗15分鐘。用UV-ozone清潔器進一步處理洗滌過的基材15分鐘。將摻鋁氧化鋅奈米粒子(Aluminum doped zinc oxide nanoparticle，AZO)的頂塗層，以2000rpm的旋轉速率40秒旋轉塗佈在ITO基板上，然後在空氣中在120℃下烘烤5分鐘，進而形成電子傳輸層(electron transporting layer，ETL)。在鄰二甲苯(o-xylene)中製備主動層溶液(供體材料：受體材料重量比為1：1~2)。供體材料的濃度為20mg/mL。供體材料包含前述之嵌段式共軛高分子材料。為將主動層材料完全溶解，
主動層溶液需在加熱板上以100℃下攪拌至少3小時。以PTFE濾膜過濾(孔徑0.45~1.2μm)，再將活性層溶液加熱1小時。隨後將主動層材料降至室溫進行旋轉塗佈，以塗佈轉速控制膜厚範圍於100~200nm上下。最後將塗佈完成之主動層材料形成的薄膜在100℃下熱退火5分鐘，然後傳送至熱蒸鍍機中。在3×10-6Torr的真空度下，沉積三氧化鉬(MoO3)的薄層(8nm)作為電洞傳輸層(hole transporting layer，HTL)。此實驗使用KeithleyTM 2400 source meter儀器記錄無光下之暗電流(J d ，偏壓為-0.5~-6.0V)。外部量子效率(External quantum efficiency,EQE)則使用外部量子效率量測器，量測範圍為300~1100nm(偏壓為0~-0.5V)，光源校正使用矽(300~1100nm)。
在此需要說明的是，於實際應用中，第一電極以具有良好之透光性為佳。第一電極常選用透明導電材料，較佳為選自由以下導電材料群組之一者：銦氧化物、錫氧化物、摻雜鹵素之錫氧化物衍生物(Florine Doped Tin Oxide，FTO)、或複合金屬氧化物，如銦錫氧化物(Indium Tin Oxide，ITO)和銦鋅氧化物(Indium Zinc Oxide，IZO)。第二電極之材料係選用導電金屬，較佳為選用銀或鋁，更佳為銀。電子傳輸層的合適且優選的材料包括但不限於金屬氧化物，例如ZnOx，摻鋁的ZnO(AZO)、TiOx或其奈米顆粒，鹽(例如LiF、NaF、CsF、CsCO3)，胺(例如伯胺、仲胺或叔胺)，共軛聚合物電解質(例如聚乙烯亞胺)，共軛聚合物(例如聚[3-(6-三甲基銨己基)噻吩]、聚(9,9)-雙(2-乙基己基-芴)-b-聚[3-(6-三甲基銨己基)噻吩]或聚[(9,9-雙(3'-(N,N-二甲基氨基)丙基)-2,7-芴)-alt-2,7-(9,9-二辛基芴)]，以及有機化合物(例如三(8-喹啉基)-鋁(III)(Alq3)、4,7-二苯基-1,10-菲咯啉)，或上述物質中的一或多種的組合。電洞傳輸層的合適且優選的材料包括但不限於金屬氧
化物，例如ZTO、MoOx、WOx、NiOx或其奈米顆粒，共軛聚合物電解質，例如PEDOT：PSS，聚合物酸，例如聚丙烯酸酯，共軛聚合物，例如聚三芳基胺(PTAA)，絕緣聚合物，例如納菲薄膜、聚乙烯亞胺或聚苯乙烯磺酸鹽，有機化合物，例如N,N'-二苯基-N,N'-雙(1-萘基)(1,1'-聯苯)-4,4'-二胺(NPB)、N,N'-二苯基-N,N'-(3-甲基苯基)-1,1'-聯苯-4,4'-二胺(TPD)，或上述一或多種材料的組合。
請參閱圖4及圖5，圖4係繪示了本發明主動層材料M1之結構關係示意圖，圖5係繪示了本發明主動層材料M1之載子傳遞作動示意圖。如圖4所示，本案提出一種概念，藉由具有高能隙的第一高分子P1、具有低能隙的第二高分子P2共聚之嵌段式共軛高分子作為p型材料，進而與n型材料N1進行混和成如圖4所示之主動層材料M1。利用濕式製程將主動層材料M1以塗佈或印刷方式沉積於目標基材上進行光致電子轉換的應用。其中，嵌段式共軛高分子包含兩種或兩種以上之嵌段。如圖5所示，嵌段包含有具有高能隙的第一高分子P1與具有低能隙的第二高分子P2。其中，實線框選的為第一高分子P1的能帶，一點一線所框選的為第二高分子P2的能帶，虛線框選的則為n型材料N1的能帶。實心圓的移動方向為電子流方向，空心圓的移動方向為電洞流方向。具有低能隙的第二高分子P2主要用於吸收光線並與主動層材料中相鄰近之n型材料N1進行激子拆解及拆解後之載子傳遞。過程中，具有高能隙之第一高分子P1因緊鄰第二高分子P2與n型材料N1。因為第一高分子P1增加了與第二高分子P2與n型材料N1間的能障(如圖5中之雙箭頭位置)，因此高能隙之第一高分子P1扮演了載子阻擋單元(carrier blocking unit)的角色。第一高分子P1可用於抑制載子複合機率，進而降低有
機光電元件之漏電流產生。
請參閱圖6及表2，圖6係顯示了本發明主動層材料之比較例RP1與實施例BP1的暗電流測試結果，表2係顯示了圖6的測試數據結果。
綜合上述之實驗結果，本發明之嵌段式共軛高分子材料係為一種可調節暗電流的p型材料。相較於無規共聚物，本發明所屬之嵌段共聚物可以藉由高能隙的嵌段抑制漏電流的產生，並根據前述計算公式得到較高的偵測度，而可以在有機光感測元件中具有良好的表現。
藉由以上具體實施例之詳述，係希望能更加清楚描述本發明
之特徵與精神，而並非以上述所揭露的具體實施例來對本發明之範疇加以限制。相反地，其目的是希望能涵蓋各種改變及具相等性的安排於本發明所欲申請之專利範圍的範疇內。
1:有機光電元件
10:基板
11:第一電極
12:第一載子傳遞層
13:主動層
14:第二載子傳遞層
15:第二電極
Claims (11)
- 一種嵌段式共軛高分子材料，其包含式一結構：
其中第一高分子為具有高能隙的p型高分子，且第一高分子包含有交替排列的一第一電子供體及一第一電子受體；第二高分子為具有低能隙的p型高分子，且第二高分子包含有交替排列的一第二電子供體及一第二電子受體；以及o、p>0。 - 如申請專利範圍第1項所述之嵌段式共軛高分子材料，其中第一高分子的薄膜吸收最大值的波長≦800nm，而第二高分子的薄膜吸收最大值的波長>800nm。
- 如申請專利範圍第2項所述之嵌段式共軛高分子材料，其中第一高分子選自以下結構中之一者：
其中，n為正整數。 - 如申請專利範圍第2項所述之嵌段式共軛高分子材料，其中第二高分子選自以下結構中之一者：
其中，n為正整數。 - 一種主動層材料，其包含：一p型材料，其為一種如申請專利範圍第1項所述之嵌段式共軛高分子材料；以及一n型材料，其包含有一拉電子基團的非富勒烯材料結構或富勒 烯材料結構，且該n型材料的能隙小於2.5。
- 如申請專利範圍第5項所述之主動層材料，其中非富勒烯材料結構包含式二結構：Ar2-Ar1-Ar2(式二)；其中Ar1包含有5~40個碳原子的共軛結構，且包含有一個以上的稠環或稠雜環；以及Ar2包含有酮類之單環結構或酮類之稠環結構。
- 如申請專利範圍第6項所述之主動層材料，其中Ar1選自以下結構中之一者：
其中，a=0或1；以及R1、R2與R3獨立選自下列群組及其衍生物中之一者：C1~C30的烷基、C1~C30的矽烷基、C1~C30的烷氧基、C1~C30的烷硫基、C1~C30的鹵代烷基、C2~C30的酯基、C1~C30烷基芳基、C1~C30烷基雜芳基、C1~C30矽烷基芳基、C1~C30矽烷基雜芳基、C1~C30烷氧基芳基、C1~C30烷氧基雜芳基、C1~C30烷硫基芳基、C1~C30烷硫基雜芳基、C1~C30鹵代烷基芳基、C1~C30鹵代烷基雜芳基、C1~C30酯基芳基或C1~C30酯基雜芳基。 - 如申請專利範圍第6項所述之主動層材料，其中Ar2選自以下結構中之一者：
其中，R4、R5、R6及R7係獨立選自下列群組及其衍生物中之一者：C1~C30的烷基、C1~C30的矽烷基、C1~C30的烷氧基、C1~C30的烷硫基、C1~C30的鹵代烷基、鹵素、氫原子以及氰基。 - 如申請專利範圍第5項所述之主動層材料，其中富勒烯材料結構選自以下結構中之一者：
其中，R8為C2~C30的烷基。 - 一種有機光電元件，包含：一第一電極；一主動層，至少包含一種如申請專利範圍第5項所述之主動層材料；以及一第二電極，其中該主動層位於該第一電極及該第二電極之間，且該第一電極和該第二電極至少一者為透明或半透明電極。
- 如申請專利範圍第10項所述之有機光電元件，其中更包含有一第一載子傳遞層及一第二載子傳遞層，其中該第一載子傳遞層位於該第一電極與該主動層之間、該主動層位於該第一載子傳遞層與該第二載子傳遞層之間，以及該第二載子傳遞層位於該主動層與該第二電極之間。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202263401145P | 2022-08-26 | 2022-08-26 | |
| US63/401,145 | 2022-08-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW202409135A true TW202409135A (zh) | 2024-03-01 |
Family
ID=90029290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW112129395A TW202409135A (zh) | 2022-08-26 | 2023-08-04 | 嵌段式共軛高分子材料及應用其之主動層材料及有機光電元件 |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20240099121A1 (zh) |
| CN (1) | CN117642044A (zh) |
| TW (1) | TW202409135A (zh) |
-
2023
- 2023-08-04 TW TW112129395A patent/TW202409135A/zh unknown
- 2023-08-09 CN CN202310999831.3A patent/CN117642044A/zh active Pending
- 2023-08-18 US US18/235,565 patent/US20240099121A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US20240099121A1 (en) | 2024-03-21 |
| CN117642044A (zh) | 2024-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Brus et al. | Solution‐processed semitransparent organic photovoltaics: From molecular design to device performance | |
| JP6007273B2 (ja) | タンデム型光電池 | |
| JP5965888B2 (ja) | 有機光電池を製造するための処理添加剤 | |
| Li et al. | Efficient small bandgap polymer solar cells with high fill factors for 300 nm thick films | |
| US8158881B2 (en) | Tandem photovoltaic cells | |
| CN109476679B (zh) | 杂环化合物和包含其的有机电子器件 | |
| Zhu et al. | Recent progress in polymer-based infrared photodetectors | |
| Park et al. | Visible-light-responsive high-detectivity organic photodetectors with a 1 μm thick active layer | |
| JP5573066B2 (ja) | 有機光電変換素子と、それを用いた太陽電池及び光センサアレイ | |
| Wang et al. | Indenothiophene‐Based Wide Bandgap Copolymer for Polymer Fullerene Solar Cells with 9.01% Efficiency and 1.0 V Open Circuit Voltage | |
| Lim et al. | Synthesis and photovoltaic properties of a thienylenevinylene and diketopyrrolopyrrole copolymer with high mobility | |
| KR20180030224A (ko) | 유기 반도체 조성물 및 유기 전자 디바이스 제조에서의 그 용도 | |
| KR20120130706A (ko) | 전자 공여체 고분자 및 이를 포함하는 태양 전지 | |
| WO2011148717A1 (ja) | 有機光電変換素子、太陽電池及び光センサアレイ | |
| KR101772095B1 (ko) | 광대역 감광 전-고분자 유기광전자소자 | |
| Wen et al. | Improved efficiency in dithieno [3, 2-b: 2′, 3′-d] silole-based polymer solar cells by the insertion of ZnO optical spacer | |
| Cheung et al. | Solution processed polymer near-infrared photodiode with electron and hole blockers | |
| JP2010098034A (ja) | 有機光電変換素子、太陽電池及び光センサアレイ | |
| TW202409135A (zh) | 嵌段式共軛高分子材料及應用其之主動層材料及有機光電元件 | |
| KR102206298B1 (ko) | 광에너지 상향전환층을 구비하는 태양전지 | |
| KR102531257B1 (ko) | 화합물 및 이를 포함하는 유기 전자 소자 | |
| TWI824203B (zh) | 共軛高分子材料及應用其之有機光電元件 | |
| US20150194607A1 (en) | Photovoltaic element | |
| TW202409053A (zh) | 具有乙烯基之近紅外光有機小分子及應用其之主動層材料及有機光電元件 | |
| Chasteen | Exciton dynamics in conjugated polymer photovoltaics: Steady-state and time-resolved optical spectroscopy |