WO2012146672A2 - Use of fluorinated subphthalocyanine fused dimers as electron acceptors for solar cells - Google Patents
Use of fluorinated subphthalocyanine fused dimers as electron acceptors for solar cells Download PDFInfo
- Publication number
- WO2012146672A2 WO2012146672A2 PCT/EP2012/057684 EP2012057684W WO2012146672A2 WO 2012146672 A2 WO2012146672 A2 WO 2012146672A2 EP 2012057684 W EP2012057684 W EP 2012057684W WO 2012146672 A2 WO2012146672 A2 WO 2012146672A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dimer
- subphthalocyanine
- use according
- fused
- anyone
- Prior art date
Links
- PMJMHCXAGMRGBZ-UHFFFAOYSA-N subphthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(=N3)N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C3=N1 PMJMHCXAGMRGBZ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000000539 dimer Substances 0.000 title claims abstract description 42
- 239000000370 acceptor Substances 0.000 title description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 43
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 13
- 229910010272 inorganic material Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 12
- 239000011368 organic material Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000000975 dye Substances 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 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 9
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 9
- 229910003472 fullerene Inorganic materials 0.000 claims description 9
- 239000011147 inorganic material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 claims description 6
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003384 small molecules Chemical class 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000002484 inorganic compounds Chemical class 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- -1 polyphenylenvinylene Polymers 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 210000004027 cell Anatomy 0.000 description 16
- 229910015711 MoOx Inorganic materials 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229920003240 metallophthalocyanine polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical group C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 206010012422 Derealisation Diseases 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000004754 hybrid cell Anatomy 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002979 perylenes Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S20/00—Supporting structures for PV modules
-
- 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
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/045—Special non-pigmentary uses, e.g. catalyst, photosensitisers of phthalocyanine dyes or pigments
-
- 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
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
-
- 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
- H10K85/30—Coordination compounds
- H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- High Energy & Nuclear Physics (AREA)
- Electromagnetism (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present disclosure relates to the use of fluorinated subphthalocyanine dimers as photo- and electroactive compounds for the preparation of photovoltaic devices, in particular, of organic and hybrid solar cells, as well as to the devices and solar cells themselves which comprise said dimers.
Description
USE OF FLUORINATED SUBPHTHALOCYANINE FUSED DIMERS AS ELECTRON ACCEPTORS FOR SOLAR CELLS
Technical Field
The present disclosure relates to the use of fluorinated subphthalocyanine fused dimers as electron acceptors in the manufacture of organic or hybrid solar cells and/or as photoactive dyes for photovoltaic devices. Background art
Subphthalocyanines (SubPcs) are the lower homologues of phthalocyanines, well-known two-dimensional aromatic systems, whose 1 8 π- electrons and planar structure impart them with unusual electrical and optical properties [Chem. Rev. 2002, 102, 835; Angew. Chem. Int. Ed. 2006, 45, 2834; Chem. Commun., 2007, 2000]. Subphthalocyanines are composed of three diiminoisoindole rings bound through the nitrogen atoms to a boron core. The 14 π-electron delocalized in their cone-shaped structure, as determined by X- ray crystallography, make them attractive compounds due both to their chemical and physical properties.
Subphthalocyanines are having a profound impact in many technological fields such as optical data storage or nonlinear optics. Also are very interesting their photophysical and optoelectronic properties in order to employ them as new components in photovoltaic materials.
The development and optimization of new synthetic methodologies for SubPc preparation has led to the efficient synthesis of fused subphthalocyanine dimers and the separation of their syn and ani/' topoisomers [Angew. Chem. Int. Ed. 2002, 41 , 2561 ].
The curved aromatic system presented by these macrocycles converts them into remarkable structures. Despite this, litte attention has been paid to these nonplanar aromatic systems. SubPc dimers were found to present very different features from those of their corresponding SubPc monomers in terms of optical properties. These fused dimers usually present characteristic absorption peaks between 550 and 700 nm with an absorption coefficient
ranging from 5 to 1 0 x 104 M"1 cm"1. These values may be modulated by introducing different peripheral substituents.
Recent photovoltaic conversion efficiency advancements [Prog. Photovolt: Res. Appl. 2010; 1 8, 346] have transformed organic solar cells (OPVCs) into promising candidates as low-cost, renewable energy generators. This progress is partly related to the improvement of architecture of these devices, with the introduction of donor/acceptor (D/A) interfaces, bulk or block heterojunctions, and tandem structures. These improvements, although preliminary, are due in turn, to the development of improved donor materials that absorb at a wide range of the solar irradiance spectrum with energy levels that enable higher open-circuit voltages ( V∞). On the contrary, in spite of the wide variety of donor materials, acceptor materials preferably used belong to the family of fullerenes. Compared to many other organic molecules, fullerenes present, on the one hand, high electron mobility and, on the other hand, high exciton diffusion length. However, as fullerenes absorb only at wavelengths below 560 nm, their overall contribution to the photocurrent is limited. The contribution of other alternative acceptor materials such as perylenes, CdSe, ZnO, or TiO2, is also limited. Metallophthalocyanines (MPcs) are well-known donor materials in the field of organic solar cells. Also, peripherally fluorinated metallophthalocyanines have shown the ability to act as acceptor molecules. The incorporation of fluorine atoms increases the ionization potential with minimal changes to the optical bandgap. Subphthalocyanines (SubPc), have also shown power conversion efficiencies higher than 3% when paired with C6o as an acceptor material, due to the high of at least 0.9 V. Recently, we achieved comparable Voc by pairing SubPc with their fluorinated homologue (FSubPc) [Adv. Funct. Mater. 2007, 17, 2653; Adv. Funct. Mater. 2009, 19, 3435]. However, the overlapping of the absorption bands in the absorption spectre of SubPc and FSubPc ultimately limits the short-circuit current density (Jsc) of this D/A pair.
From this and other related literature, and especially from the typical drawbacks in the application of subphthalocyanines in the preparation of photovoltaic cells, can be deduced the importance and interest of preparing analogues with more suitable properties.
Summary of the disclosure
It is an aim of the present disclosure to propose acceptor molecules with improved optical properties and stability as well as improved processability, for use as active elements in photovoltaic devices, and more specifically in organic and hybrid solar cells. The inventors have found that subphthalocyanine fused dimers gather many of the desired features, such as optical and chemical stability, efficient solar light absorption, low aggregation and evaporation and anchoring to polymeric or inorganic substrates capabilities, which allow their application to the fabrication of these photovoltaic devices.
Thus, in a first aspect the present disclosure relates to the use of at least a fused subphthalocyanine dimer of structural formula I:
wherein
Ri and R2, equal or different, represent an halogen atom selected from fluorine, chlorine, bromine and iodine; a cyano group; an azido group; a carboxylic group; an ester group; a COH group; a nitro group; an alkyl group, lineal or branched, from 1 to 1 6 carbon atoms; a OR3 group; a SR3 group or a N(R3)2 group, wherein R3 is an alkyl group, lineal or branched, from 1 to 16 carbon atoms; a phenyl group, a phenoxy group, or a thiophenoxy group, optionally substituted in any one of their positions with one or two halogen atoms selected from fluorine, chlorine, bromine and iodine, one or two alkyl groups R3, one or two OR3 groups, one or two SR3 groups, or one or two N(R3)2 groups, wherein R3 has the same meaning indicated above,
as a photo- and electroactive compound for the preparation of photovoltaic devices.
A second aspect of the present disclosure relates to a photovoltaic device comprising at least a fused subphthalocyanine dimer of formula I as has been previously defined.
Likewise, the disclosure relates to an organic or hybrid solar cell comprising at least a fused subphthalocyanine dimer of formula I as has been previously defined.
The present disclosure also relates to a method for preparing a photovoltaic device. This may be achieved by
• Providing a cathode,
• Providing an anode, and
• Providing a photoactive region including an electron donor material and an electron acceptor material, between said cathode and said anode, wherein said electron acceptor material comprises at least a fused subphthalocyanine dimer as defined in any embodiment of the first aspect.
The present disclosure also relates to a photoactive material including an electron donor material and an electron acceptor material, wherein said electron acceptor material comprises at least a fused subphthalocyanine dimer as defined in any embodiment of the first aspect.
Detailed description of preferred embodiments
The present disclosure will be described with respect to particular embodiments but the disclosure is not limited thereto but only by the claims.
Furthermore, the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. The terms are interchangeable under appropriate circumstances and the embodiments of the disclosure can operate in other sequences than described or illustrated herein.
Moreover, the terms top, bottom, over, under and the like in the description and the claims are used for descriptive purposes and not necessarily for describing relative positions. The terms so used are
interchangeable under appropriate circumstances and the embodiments of the disclosure described herein can operate in other orientations than described or illustrated herein.
Furthermore, the various embodiments, although referred to as "preferred" are to be construed as exemplary manners in which the disclosure may be implemented rather than as limiting the scope of the disclosure.
The term "comprising", used in the claims, should not be interpreted as being restricted to the elements or steps listed thereafter; it does not exclude other elements or steps. It needs to be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more other features, integers, steps or components, or groups thereof. Thus, the scope of the expression "a device comprising A and B" should not be limited to devices consisting only of components A and B, rather with respect to the present disclosure, the only enumerated components of the device are A and B, and further the claim should be interpreted as including equivalents of those components.
The compounds employed in the present disclosure correspond to fluorinated subphthalocyanine fused dimers. The stereochemistry of these dimers provides two types of topoisomers, syn topoisomer of formula la and anti topoisomer of formula lb:
la (syn topoisomer) lb (anti topoisomer)
As can be appreciated, syn topoisomer represents the structure in which the two substituents (Ri and R2) of the boron atom in axial position are located pointing to the same side with respect to the aromatic skeleton of the molecule. In turn, anti topoisomer represents the structure in which the two substituents
(Ri and R2) of the boron atom in axial position are located pointing to opposite sides with respect to the aromatic skeleton of the molecule.
The following nomenclature will be used hereinafter to designate the compounds of general formula la:
Syn [R1 ,R2][hexadecafluoro]subphthalocyanine dimer
The following nomenclature will be used hereinafter to designate the compounds of general formula lb:
Anti [Ri ,R2][hexadecafluoro]subphthalocyanine dimer
In a particular embodiment of the present disclosure, the compound of formula I is a combination of any two or more compounds with syn or anti stereochemistry, in any ratio among them.
Preferably, the compound of formula I is a combination of at least a syn topoisomer of formula la and at least an anti topoisomer of formula lb. More preferably, both topoisomers have the same chemical composition. An advantage of using an appropriate combination of syn/anti topoisomers is the possibility of improving in a very simple way the morphology of the active layers and as a consequence the efficiency of the device.
In a preferred embodiment, Ri and R2, equal or different, represent an halogen atom selected from fluorine, chlorine, bromine and iodine. More preferably, Ri and R2, equal or different, represent a fluorine or chlorine atom.
Still more preferably, the dimer is selected from:
- Syn-[CI,CI][hexadecafluoro]subphthalocyanine dimer
- Anti-[CI,CI][hexadecafluoro]subphthalocyanine dimer
- Syn-[F,F][hexadecafluoro]subphthalocyanine dimer
- Anti-[F,F][hexadecafluoro]subphthalocyanine dimer
and mixtures thereof.
In a preferred embodiment, the dimer of formula (I) is a combination of the syn-[CI,CI][hexadecafluoro]subphthalocyanine dimer and the anti- [CI,CI][hexadecafluoro]subphthalocyanine dimer in any ratio among them.
In another preferred embodiment, the dimer of formula (I) is a combination of the syn-[F,F][hexadecafluoro]subphthalocyanine dimer and the anti[F,F][hexadecafluoro]subphthalocyanine dimer in any ratio among them.
The syn-[CI,CI][hexadecafluoro]subphthalocyanine and anti- [CI,CI][hexadecafluoro]subphthalocyanine dimers employed in the present disclosure can be obtained by chromatographic separation starting from a mixture of both of them, as is described in Angew. Chem. Int., Ed., 2002, 41 , 2561 .
The topoisomers of general formula la and lb can be obtained from syn- [CI,CI][hexadecafluoro]subphthalocyanine dimer or anti-
[F,F][hexadecafluoro]subphthalocyanine dimer respectively, or from a mixture of both of them, through a procedure of substitution in axial position well-known in the state of the art, reported in scientific literature both for subphthalocyanine dimers and for single subphthalocyanines [Chem. Rev. 2002, 1 02, 835; Angew. Chem. Int. Ed. 2002, 41 , 2561 ; Chem. Commun. 2005, 21 1 3; C. R. Chimie 2006, 9, 1094; Angew. Chem. Int. Ed. 201 1 , 50, 3506].
The derealization of π-electrons in the aromatic structure of these compounds, as well as the spatial disposition thereof, impart to these dimers photophysical and optoelectronic properties which make them very suitable for their incorporation in photovoltaic devices.
By "photovoltaic device" it should be understood a device capable of generating electricity from the light incident on it.
These photovoltaic devices usually incorporate, besides a cathode and an anode, a photoactive region disposed between both electrodes, which includes an electron donor material and an electron acceptor material. This photoactive region absorbs the electromagnetic radiation from the light causing the electron transfer from the donor to the acceptor, thus generating an electric current.
The dimer employed in the present disclosure can act as electron acceptor material and, therefore, this dimer can be used in combination with an electron donor material.
In a particular embodiment, the dimer employed in the disclosure is used in combination with one or more dyes or an organic or inorganic material. Combining the intrinsic properties of the dimers with specific properties of the dye or the organic or inorganic material is particularly advantageous, for example when these are electronically active materials. For example,
combining the dimer with p-type or n-type materials can be particularly advantageous. As a dye or organic material, a chelating agent, a polymer, an oligomer or an organic copolymer can be employed. Using an appropriate chelating agent can be advantageous for improving the stability of the dimers. Incorporating the dimer as a blend with a polymer can improve the processability of the dimers.
In a preferred embodiment, the organic or inorganic material is an electronically active material. Preferably, the electronically active material is a p- type electron donor material selected from phthalocyanine, subphthalocyanine and pentacene. Also preferably, the electronically active material is an n-type electron donor material selected from fullerene, carbon nanotubes and graphene.
In a particular embodiment, the dimer employed in the disclosure is covalently bound to the backbone of a polymer, oligomer or copolymer. This is particularly advantageous as it improves the processability of the dimers while simultaneously combining the intrinsic properties of the dimers with the specific properties of the polymer, oligomer or copolymer. Furthermore, such covalent binding prevents phase separation between the dimer and the polymer, oligomer or copolymer, thereby improving the stability of the mixture. Preferably, said polymer is polyphenylenvinylene, polythiophene or derivatives thereof.
In a preferred embodiment, the photovoltaic device is an organic or hybrid solar cell. In a general manner, organic solar cell designates those in which the photo- and electroactive material consists only of materials of organic origin, and hybrid cell designates those in which materials of inorganic origin are also involved.
In particular, the dimers of the disclosure are useful in the manufacture of evaporated or solution-deposited small molecule solar cells, and in this type of devices they are usually in combination with other organic or inorganic compounds. Preferably, they are in combination with other organic compounds. More preferably, these organic compounds are p-type electron donor compounds, such as for example phthalocyanine, subphthalocyanine or pentacene. Nevertheless, they could also be in combination with n-type
electron donor compounds, such as for example, fullerenes, carbon nanotubes and graphene.
In an additional aspect, the present disclosure relates to a photovoltaic device comprising at least a fused subphthalocyanine dimer as previously described.
Additionally, these photovoltaic devices can be used in combination with one or more photovoltaic devices, equal or different, in order to form tandem photovoltaic devices. Therefore, an additional aspect of the present disclosure consists of a tandem photovoltaic device comprising the combination of two or more photovoltaic devices as previously described.
Likewise, the disclosure relates to an organic or hybrid solar cell comprising at least a fused subphthalocyanine dimer as previously described.
In a particular embodiment, said solar cell is a small molecule solar cell obtainable by evaporation or solution deposition, in which said cell comprises at least a dimer as previously described in combination with a dye or an organic or inorganic material. This embodiment is advantageous because small molecules are available with improved purity when compared to polymers/
Preferably, the dimer is used in combination with an organic or inorganic electronically active material. More preferably, the electronically active material is a p-type material selected from phthalocyanine, subphthalocyanine and pentacene. Likewise, an n-type material selected from fullerene, carbon nanotubes and graphene can be employed.
In another preferred embodiment, the fused subphthalocyanine dimer is covalently bound to the backbone of a polymer, oligomer or copolymer. Said polymer can for instance be polyphenylenvinylene, polythiophene or derivatives thereof.
In another preferred embodiment, the fused subphthalocyanine dimer is adsorbed in a nanocrystalline semiconductor. This is advantageous as it permits the developing of new photosensitizers for dye sensitized solar cells with improved absorption in the visible and near infra-red (NI R).
As used herein and unless provided otherwise, a nanocrystalline semiconductor is a semiconducting nanomaterial with at least one dimension < "l OOnm and that is singlecrystalline.
A further aspect of the present disclosure relates to a method for preparing a photovoltaic device, said method comprising:
• Providing a cathode,
• Providing an anode, and
· Providing a photoactive region including an electron donor material and an electron acceptor material, between said cathode and said anode, wherein said electron acceptor material comprises at least a fused subphthalocyanine dimer as defined in any embodiment of the first aspect of the present disclosure.
In an embodiment, said photovoltaic device may be a small molecule solar cell and providing said photoactive region may comprise evaporating or depositing from solution said at least a fused subphthalocyanine dimer as defined in any embodiment of the first aspect, wherein the dimer is, optionally, deposited in combination with one or more organic or inorganic compounds.
A further aspect of the present disclosure relates to a photoactive material including an electron donor material and an electron acceptor material, wherein said electron acceptor material comprises at least a fused subphthalocyanine dimer as defined in any embodiment of the first aspect. Examples
Preparation of samples for molecular photovoltaic devices processed by evaporation
Thin films of [CI,CI][hexadecafluoro]subphthalocyanine dimer (mixture of syn and anti topoisomers) (thickness 1 1 nm) were deposited by thermal evaporation on Si/Si02 substrates. Atomic force microscopy (Pico LE from Agilent) measurements conducted in the tapping mode reveal these films to have a smooth surface with root-mean-square roughness of 6.1 A. Such a closeness of the layers eases the fabrication of multilayer devices, and prevents shunting between layers
Planar heterojunction devices with an area of 13.4 mm2 were fabricated by vacuum thermal evaporation on an 85-nm-thick indium tin oxide (ITO) layer coated on glass substrates. As a reference device, we consider the device formed by molybdenum oxide (MoOx, 1 0nm)/ axially chlorine-functionalized
subphthalocyanine (16 nm)/C6o (35 nm)/ bathocuproine (BCP, 10 nm)/Ag (150 nm). This device reaches an efficiency of 3.3%, where its most prominent feature is a high Voc of 1090 mV (Table 1 a).
First, the C6o was replaced with [CI,CI][hexadecafluoro] subphthalocyanine dimer (mixture of syn and anti topoisomers) in a similar device, MoOx (2 nm)/SubPc (13 nm)/ [CI,CI][hexadecafluoro]subphthalocyanine dimer (mixture of syn and anti topoisomers) (30 nm)/ C6o (20 nm)/ BCP (10 nm)/Ag (150 nm). A similar current was observed and only slightly decreased Voc of 960 mV was produced (Table 1 b). However, the fill factor (FF) dropped from 0.63 to 0.24. This lower FF is related to an s-shaped JV-curve with a high resistance, which in a planar heterojunction device can often be explained by bad charge extraction. To check how much the FF can be improved by using other cathodes, an inverted device with structure of spin-coated titanium oxide (TiOx)/ [CI,CI][hexadecafluoro]subphthalocyanine dimer (mixture of syn and anti topoisomers) (20 nm)/ axially chlorine-substituted subphthalocyanine (20 nm)/ Μοθχ (5 nm) /Ag (150 nm), was fabricated (Table 1 c). Changing the electrodes had a clear impact on the s-shape, indicating that this s-shape is (at least partially) contact-related. With the improved contacting, a fill factor of 48% and an efficiency of 2.5% were obtained. We tried to improve the behavior of these devices by incorporating a C6o layer acting as an electron transport layer (ETL) in between the [CI,CI][hexadecafluoro]subphthalocyanine dimer (mixture of syn and anti topoisomers) and BCP: MoOx (2nm)/ axially chlorine-functionalized subphthalocyanine (13 nm)/ [CI,CI][hexadecafluoro]subphthalocyanine dimer (mixture of syn and anti topoisomers) (30 nm)/ C6o (20 nm)/ BCP (10 nm)/Ag (150 nm) (Table 1 d). This architecture improved the FF to 54%, while Jsc increased to 7.8 mA cm"2. The resulting 4% efficiency outperformed the one obtained in the reference device which contained the axially chlorine- functionalized subphthalocyanine.
Structure JEQE 2 Voc V FF % η %
mA cm" mA cm
a) MoOx/ axially chlorine-functionalized 4.9 4.7 1 .09 61 3.3 subphthalocyanine / C60 / BCP
b) MoOx/ axially chlorine-functionalized 5.1 4.5 0.96 24 1 .2 subphthalocyanine /
[CI,CI][hexadecafluoro]subphthalocyanine
dimer / BCP
c) TiOx/ 5.8 5.6 0.89 48 2.5
[CI,CI][hexadecafluoro]subphthalocyanine
dimer / axially chlorine-functionalized
subphthalocyanine / MoOx
d) MoOx/ axially chlorine-functionalized 7.8 7.3 0.95 54 4.0 subphthalocyanine /
[CI,CI][hexadecafluoro]subphthalocyanine
dimer / C60/ BCP
Table 1. Jsc, Voc, FF and efficiency η measurements for 100 mW cm"2 AM1 .5G simulated solar illumination. JEQE is the current density as calculated by integration of the EQE over the AM1 .5G solar spectrum.
Preparation of a polymer, oligomer or copolymer covalently bound to a fused subphthalocyanine dimer as defined in any aspect of the present disclosure.
A fused subphthalocyanine dimer is covalently bound to the backbone chain of an oligomer, polymer or copolymer, as a pendant group, by nucleophilic substitution of the fluorine or chlorine axial ligand of the corresponding dimer by an oligomer, polymer or copolymer containing nucleophilic groups in its structure. This is made via methods well known to the person skilled in the art. Preparation of a nanocrystalline semiconductor on which a fused subphthalocyanine dimer as defined in any aspect of the present disclosure is adsorbed.
A fused subphthalocyanine dimer is adsorbed onto a nanocrystalline semiconductor, like titanium oxide for example, by introducing first on the axial position of the dimer an appropriate anchoring group, for example a carboxyl substituent. This can be made easily by substituting the fluorine or chlorine axial ligand of the corresponding dimer by an appropriate nucleophile containing a carboxylic function, for example p-hydroxybenzoic acid. It is well known, that carboxylic groups are easily absorbed onto the surface of the nanocrystalline semiconductor.
Claims
1 . Use of at least a fused subphthalocyanine dimer of structural formula I:
I wherein
Ri and R2, equal or different, represent an halogen atom selected from fluorine, chlorine, bromine and iodine; a cyano group; an azido group; a carboxylic group; an ester group; a COH group; a nitro group; an alkyl group, lineal or branched, from 1 to 1 6 carbon atoms; a OR3 group, a SR3 group or a N(R3)2 group, wherein R3 is an alkyl group, lineal or branched, from 1 to 16 carbon atoms; a phenyl group, a phenoxy group, or a thiophenoxy group, optionally substituted in any one of their positions with one or two halogen atoms selected from fluorine, chlorine, bromine and iodine, one or two alkyl groups R3, one or two OR3 groups, one or two SR3 groups, or one or two N(R3)2 groups, wherein R3 has the same meaning indicated above,
as a photo- and electroactive compound for the preparation of photovoltaic devices.
2. Use according to claim 1 , wherein the dimer of formula (I) is a combination of any two or more compounds with syn stereochemistry of formula (la) or anti stereochemistry of formula (lb):
(la) (lb)
3. Use according to claim 2, comprising the employment of a combination of at least a syn topoisomer of formula (la) and at least an anf/' topoisomer of formula
(lb).
4. Use according to anyone of claims 1 to 3, wherein F and R2, equal or different, represent an halogen atom selected from fluorine, chlorine, bromine and iodine.
5. Use according to claim 4, wherein F and R2, equal or different, represent a fluorine or chlorine atom.
6. Use according to anyone of claims 1 to 5, wherein the dimer is selected from:
- Syn-[CI,CI][hexadecafluoro]subphthalocyanine dimer
- Ani/'-[CI,CI][hexadecafluoro]subphthalocyanine dimer
- Syn-[F,F][hexadecafluoro]subphthalocyanine dimer
- /4nf/'-[F,F][hexadecafluoro]subphthalocyanine dimer
or mixtures thereof.
7. Use according to anyone of claims 1 to 6, comprising the employment of a combination of the syn-[CI,CI][hexadecafluoro]subphthalocyanine dimer and the anf/'-[CI,CI][hexadecafluoro]subphthalocyanine dimer in any ratio among them.
8. Use according to anyone of claims 1 to 6, comprising the employment of a combination of the syn-[F,F][hexadecafluoro]subphthalocyanine dimer and the anf/'-[F,F][hexadecafluoro]subphthalocyanine dimer in any ratio among them.
9. Use according to anyone of claims 1 to 8, wherein the dimer of formula (I) is used in combination with one or more dyes or an organic or inorganic material.
10. Use according to claim 9, wherein the dye or the organic material is a chelating agent, a polymer, an oligomer or an organic copolymer.
1 1 . Use according to claim 9 or 10, wherein the organic or inorganic material is an electronically active material.
12. Use according to claim 1 1 , wherein the electronically active material is a p- type electron donor material selected from phthalocyanine, subphthalocyanine and pentacene.
13. Use according to claim 1 1 , wherein the electronically active material is an n- type electron donor material selected from fullerene, carbon nanotubes and graphene.
14. Use according to claim 9, wherein the fused subphthalocyanine dimer is covalently bound to the backbone of a polymer, oligomer or copolymer.
15. Use according to claim 14, wherein the polymer, oligomer or copolymer is polyphenylenvinylene, polythiophene or derivatives thereof.
16. Use according to anyone of claims 1 to 15, wherein the photovoltaic device is an organic or hybrid solar cell.
17. Use of at least a fused subphthalocyanine dimer as defined in anyone of claims 1 to 8 in the manufacture of small molecule solar cells through evaporation or solution deposition, wherein the dimer is, optionally, in combination with one or more organic or inorganic compounds.
18. Use according to claim 1 7, wherein the organic compound is a p-type electron donor.
19. Use according to claim 1 8, wherein the p-type donor organic compound is selected from phthalocyanine, subphthalocyanine, pentacene and derivatives thereof.
20. Use according to claim 17, wherein the dimer is in combination with one or more n-type electron donor compounds.
21 . Use according to claim 20, wherein the n-type electron donor compounds are selected from fullerenes, carbon nanotubes and graphene.
22. Photovoltaic device comprising at least a fused subphthalocyanine dimer as defined in anyone of claims 1 to 8.
23. Tandem photovoltaic device comprising the combination of two or more photovoltaic devices as defined in claim 22.
24. Organic or hybrid solar cell comprising at least a fused subphthalocyanine dimer as defined in anyone of claims 1 to 8.
25. Organic solar cell according to claim 24, obtainable through evaporation or solution deposition, wherein said cell comprises at least a dimer as defined in anyone of claims 1 to 8 in combination with a dye or organic or inorganic material.
26. Hybrid solar cell according to claim 24, comprising the combination of a fused subphthalocyanine dimer as defined in anyone of claims 1 to 8 with a dye or organic or inorganic material.
27. Solar cell according to claims 25 or 26, wherein the organic or inorganic material is an electronically active material.
28. Solar cell according to claim 27, wherein the electronically active material is a p-type electron donor material selected from phthalocyanine, subphthalocyanine and pentacene.
29. Solar cell according to claim 27, wherein the electronically active material is an n-type electron donor material selected from fullerene, carbon nanotubes and graphene.
30. Solar cell according to claim 24, wherein the fused subphthalocyanine dimer is covalently bound to the backbone of a polymer, oligomer or copolymer.
31 . Hybrid solar cell according to claim 24, wherein the fused subphthalocyanine dimer is adsorbed in a nanocrystalline semiconductor.
32. A method for preparing a photovoltaic device, said method comprising:
• Providing a cathode,
• Providing an anode, and
• Providing a photoactive region including an electron donor material and an electron acceptor material, between said cathode and said anode, wherein said electron acceptor material comprises at least a fused subphthalocyanine dimer as defined in anyone of claims 1 to 8.
33. A method according to claim 32 wherein said photovoltaic device is a small molecule solar cell and wherein providing said photoactive region comprises evaporating or depositing from folution said at least a fused subphthalocyanine dimer as defined in anyone of claims 1 to 8, wherein the dimer is, optionally, deposited in combination with one or more organic or inorganic compounds.
34. A photoactive material including an electron donor material and an electron acceptor material, wherein said electron acceptor material comprises at least a fused subphthalocyanine dimer as defined in anyone of claims 1 to 8.
35. A polymer, oligomer or copolymer covalently bound to a fused subphthalocyanine dimer as defined in anyone of claims 1 to 8.
36. A nanocrystalline semiconductor on which a fused subphthalocyanine dimer as defined in anyone of claims 1 to 8 is adsorbed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES201130667A ES2391191B1 (en) | 2011-04-28 | 2011-04-28 | USE OF FUSED DIMMERS OF FLUORATED SUBFTALOCIANINS AS ELECTRONIC ACCEPTORS FOR SOLAR CELLS |
| ESP201130667 | 2011-04-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2012146672A2 true WO2012146672A2 (en) | 2012-11-01 |
| WO2012146672A3 WO2012146672A3 (en) | 2013-01-03 |
Family
ID=46172768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2012/057684 WO2012146672A2 (en) | 2011-04-28 | 2012-04-26 | Use of fluorinated subphthalocyanine fused dimers as electron acceptors for solar cells |
Country Status (2)
| Country | Link |
|---|---|
| ES (1) | ES2391191B1 (en) |
| WO (1) | WO2012146672A2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070272918A1 (en) * | 2006-05-25 | 2007-11-29 | Barry Rand | Organic photosensitive devices using subphthalocyanine compounds |
-
2011
- 2011-04-28 ES ES201130667A patent/ES2391191B1/en not_active Expired - Fee Related
-
2012
- 2012-04-26 WO PCT/EP2012/057684 patent/WO2012146672A2/en active Application Filing
Non-Patent Citations (11)
| Title |
|---|
| ADV. FUNCT. MATER., vol. 17, 2007, pages 2653 |
| ADV. FUNCT. MATER., vol. 19, 2009, pages 3435 |
| ANGEW. CHEM. INT. ED., vol. 41, 2002, pages 2561 |
| ANGEW. CHEM. INT. ED., vol. 45, 2006, pages 2834 |
| ANGEW. CHEM. INT. ED., vol. 50, 2011, pages 3506 |
| ANGEW. CHEM. INT., vol. 41, 2002, pages 2561 |
| C. R. CHIMIE, vol. 9, 2006, pages 1094 |
| CHEM. COMMUN., 2005, pages 2113 |
| CHEM. COMMUN., 2007, pages 2000 |
| CHEM. REV., vol. 102, 2002, pages 835 |
| PROG. PHOTOVOLT: RES. APPL., vol. 18, 2010, pages 346 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2391191A1 (en) | 2012-11-22 |
| WO2012146672A3 (en) | 2013-01-03 |
| ES2391191B1 (en) | 2013-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ganesamoorthy et al. | Fullerene based acceptors for efficient bulk heterojunction organic solar cell applications | |
| TWI485154B (en) | Hybrid organic solar cell with perovskite structure as absorption material and manufacturing method thereof | |
| Li et al. | Graphdiyne-doped P3CT-K as an efficient hole-transport layer for MAPbI3 perovskite solar cells | |
| TWI553887B (en) | Organic photovoltaic cell incorporating electron conducting exciton blocking layers | |
| KR101464798B1 (en) | Mixtures for producing photoactive layers for organic solar cells and organic photodetectors | |
| Chen et al. | A visible-near-infrared absorbing A–π 2–D–π 1–D–π 2–A type dimeric-porphyrin donor for high-performance organic solar cells | |
| KR20110060956A (en) | Organic tandem solar cells | |
| CN112542546B (en) | Photoactive layer based on ultraviolet absorber addition and ternary organic solar cell | |
| Khandelwal et al. | Semitransparent organic solar cells: from molecular design to structure–performance relationships | |
| Zhao et al. | Self-Doped and Crown-Ether Functionalized Fullerene as Cathode Buffer Layer for Highly-Efficient Inverted Polymer Solar Cells. | |
| WO2014022580A1 (en) | Organic optoelectronics with electrode buffer layers | |
| Chen et al. | Fluorinated heptacyclic carbazole-based ladder-type acceptors with aliphatic side chains for efficient fullerene-free organic solar cells | |
| US11744089B2 (en) | Multijunction organic photovoltaics incorporating solution and vacuum deposited active layers | |
| KR20150120330A (en) | Polymer photovoltaics employing a squaraine donor additive | |
| JP5888691B2 (en) | Organic thin film solar cell | |
| CN113193121A (en) | Interface dipolar molecule modification-based perovskite solar cell and preparation method thereof | |
| WO2013102985A1 (en) | Organic photoelectric conversion element and organic thin-film solar battery module | |
| JP2013128045A (en) | Organic thin-film solar cell | |
| KR102113329B1 (en) | Electron transport layer for organic photoelectric device comprising alcohol-soluble conjugated polymer based on polyfluorene and carbon nanotube, organic solar cell comprising the same and preparation method thereof | |
| WO2012146672A2 (en) | Use of fluorinated subphthalocyanine fused dimers as electron acceptors for solar cells | |
| JP2011155104A (en) | Organic photoelectric conversion element, solar cell, and optical sensor array | |
| RU2786055C2 (en) | Photovoltaic device with electron-selective layer based on tungsten oxide and method for manufacture of this device | |
| Pucci | AIE-active materials for photovoltaics | |
| Meng et al. | Fullerene-Based Transparent Solar Cells with Average Visible Transmission Exceeding 80% | |
| US9847487B2 (en) | Use of inverse quasi-epitaxy to modify order during post-deposition processing of organic photovoltaics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 12723838 Country of ref document: EP Kind code of ref document: A2 |