WO2011144537A1 - Photoactive composition with a high mobility of the electronic holes - Google Patents
Photoactive composition with a high mobility of the electronic holes Download PDFInfo
- Publication number
- WO2011144537A1 WO2011144537A1 PCT/EP2011/057791 EP2011057791W WO2011144537A1 WO 2011144537 A1 WO2011144537 A1 WO 2011144537A1 EP 2011057791 W EP2011057791 W EP 2011057791W WO 2011144537 A1 WO2011144537 A1 WO 2011144537A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- same
- photoactive
- high mobility
- groups
- electronic holes
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 38
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- HPJFXFRNEJHDFR-UHFFFAOYSA-N 22291-04-9 Chemical compound C1=CC(C(N(CCN(C)C)C2=O)=O)=C3C2=CC=C2C(=O)N(CCN(C)C)C(=O)C1=C32 HPJFXFRNEJHDFR-UHFFFAOYSA-N 0.000 claims abstract description 26
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- 150000001502 aryl halides Chemical class 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002285 desorption chemical ionisation mass spectrometry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960003903 oxygen Drugs 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 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 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- WZQLPNKUOCSIAB-UHFFFAOYSA-N undeca-1,7-diene Chemical compound CCCC=CCCCCC=C WZQLPNKUOCSIAB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
-
- 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
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
- H10K10/488—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions the channel region comprising a layer of composite material having interpenetrating or embedded materials, e.g. a mixture of donor and acceptor moieties, that form a bulk heterojunction
-
- 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
- H10K30/50—Photovoltaic [PV] devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
-
- 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
Definitions
- the present invention relates to a photoactive com ⁇ position with a high mobility of the electronic holes.
- the present invention relates to a photoactive composition with a high mobility of the electronic holes, comprising at least one photoactive organic polymer and at least one naphthalene diimide.
- the present invention also relates to the use of said photoactive composition having a high mobility of the electronic holes in the construction of photo ⁇ voltaic devices such as, for example, photovoltaic cells, photovoltaic modules, solar cells and solar mod ⁇ ules, on both a rigid and flexible support.
- photo ⁇ voltaic devices such as, for example, photovoltaic cells, photovoltaic modules, solar cells and solar mod ⁇ ules
- the present invention also relates to the use of said photoactive composition having a high mobility of the electronic holes in the construction of organic thin film transistors (OTFT) or organic field effect transistors (OFET) .
- OFT organic thin film transistors
- OFET organic field effect transistors
- the present invention also relates to said naphtha ⁇ lene diimide.
- Photovoltaic devices are devices capable of con ⁇ verting the energy of a light radiation into electric energy.
- most photovoltaic devices which can be used for practical applications exploit the physico- chemical properties of photo-active materials of the inorganic type, in particular high-purity crystalline silicon.
- high-purity crystalline silicon As a result of the high production costs of silicon, scientific research has been orienting its ef- forts towards the development of alternative organic materials having a polymeric structure (so-called "po ⁇ lymer photovoltaic cells”) .
- organic polymers are characte ⁇ rized by a relative synthesis facility, a low produc- tion cost, a reduced weight of the relative photovol ⁇ taic device, in addition to allowing the recycling of said polymer at the end of the life-cycle of the device in which it is used.
- polymer photovoltaic cells The functioning of polymer photovoltaic cells is based on the combined use of an electron acceptor compound and an electron donor compound.
- the most widely-used electron donor and accep ⁇ tor compounds in photovoltaic devices are ⁇ -conj ugated polymers belonging to the groups of polyparaphenylene vinylenes and polythiophenes.
- the former can be used as both acceptor compounds and as donor compounds, on the basis of the electronic properties determined by the substituents of the polymer chain.
- the latter are nor ⁇ mally used as donor compounds.
- Derivatives of fullerene are most widely-used as acceptor compounds.
- the basic conversion process of light into electric current in a polymer photovoltaic cell takes place through the following steps:
- the photo-absorption process with the formation of the exciton and subsequent yielding of the electron to the acceptor compound leads to the electron excitation from the HOMO (Highest Occupied Molecular Orbital) to the LUMO (Lowest Unoccupied Molecular Orbital) of the donor compound and subsequently the passage from this to the LUMO of the acceptor compond.
- HOMO Highest Occupied Molecular Orbital
- LUMO Low Unoccupied Molecular Orbital
- the band-gap between HOMO and LUMO must not be excessively high, but at the same time not excessively low, as an excessively low band-gap would jeopardize the voltage obtained at the electrodes of the device.
- Another fundamental characteristic of the materials used for producing photovoltaic devices is the mobility of the electrons in the acceptor compound and of the electronic holes in the donor compound, which deter ⁇ mines the facility with which the electric charges, once photogenerated, reach the electrodes.
- the electronic mobility i.e. the mobility of the electrons in the acceptor compound and electronic holes in the donor compound, in addition to being an intrin- sic property of the molecules, is also strongly influ ⁇ enced by the morphology of the photoactive layer, which, in turn, depends on the reciprocal miscibility of the components and their solubility.
- polymer photo- voltaic cells are produced by introducing a thin layer (about 100 nanometres) of a mixture of the acceptor compound and donor compound (generally known as "bulk heterojunction") , between two electrodes, normally consisting of indium-tin oxide (ITO) (anode) and aluminium (Al) (cathode) .
- ITO indium-tin oxide
- Al aluminium
- a solution of the two components is generally prepared and a photoactive film is subsequently created on the anode [indium-tin oxide (ITO] starting from said solution, resorting to suitable deposition techniques such as, for example, “spin-coating”, “spray-coating” "ink-jet printing” and similar.
- the counter-electrode i.e. the aluminium cathode (Al)
- Al aluminium cathode
- other addi ⁇ tional layers capable of exerting specific functions of an electric, optical or mechanical nature, can be introduced between the anode and photoactive film.
- the donor compound which is most commonly used in the construction of polymer photovoltaic cells is re- gioregular poly (3-hexylthiophene) (P3HT) .
- This polymer has optimal electronic and optical characteristics (good HOMO and LUMO orbital values, good adsorption coefficient) , a good solubility in the solvents used in the construction of photovoltaic cells and a reasonable mobility of the electronic holes.
- polymers which can be advanta ⁇ geously used as donor compounds are: the polymer MDMO- PPV ⁇ (poly [2-methoxy-5- (3, 7-dimethyloctyloxy) -1, 4- phenylene] -alt- (vinylene) ⁇ , the polymer PCDTBT ⁇ poly [N-9"-heptade-cyl-2, 7-carbazole-alt-5, 5- (4' , 7' -di- 2-thienyl-2' , 1' , 3' -benzothiadiazole ] ⁇ , the polymer PCPDTBT ⁇ poly[2,6-(4, 4 -bis- ( 2 -ethylhexyl ) -4H- cyclopenta [2, 1-b; 3, 4-b' ] -dithiophene) -alt-4, 7- (2, 1, 3- benzothiadiazole) ] ⁇ .
- the above-mentioned donor compounds when used in combination with acceptor compounds based on fullerenes (C 6 o or C70) are generally capable of obtaining maximum conversion efficiencies of solar radiation of up to 6%.
- a film starting from an aqueous sus ⁇ pension of PEDOT:PSS poly (3, 4-ethylenedioxythiophene) sulfonated polystyrene] is generally deposited, using suitable deposition techniques such as, for example, "spin-coating", “spray-coating” "ink-jet printing” and similar.
- the counter-electrode [cathode (Al) ] is fi ⁇ nally deposited on the dried film.
- naphthaleneimide derivatives are semiconductors of the n type, i.e. the mobility of electrons is favoured in their interior, whereas they are extremely poor semiconductors of the p type, in which, on the contrary, the mobility of the electronic holes is favoured, as described for example by Singh Th. B. et al. in “Organic Electronics” (2006), Vol. 7, pages 480-489; by Yamashita Y. in “Science and Technol- ogy of Advanced Material” (2009), Vol. 10, 024313 pg. 1- 9); by Chen Z. et al . in "Journal of American Chemical Society (2009), Vol. 131, pages 8-9. Said semiconduc ⁇ tors cannot therefore be used as donor compounds for the production of polymer photovoltaic cells or tran- sistors of the p type.
- the Applicant consequently considered the problem of finding a system capable of improving the mobility of the electronic holes towards the anode through the donor compound.
- composition thus obtained can also be advantageously used in the construction of organic thin film transistors (OTFT) , or organic field effect transistors (OFET) .
- An object of the present invention therefore re ⁇ lates to a photoactive composition with a high mobility of the electronic holes comprising:
- Ri and R 2 are selected from linear or branched C 1 -C36 alkyl groups, preferably C4-C24 optionally con ⁇ taining heteroatoms such as, for example, oxy- gen, nitrogen, sulfur;
- R' i and R'2 are a hydrogen atom, or are selected from linear or branched Ci-Cio, preferably C2-C6, alkyl groups, they are preferably a hydrogen atom;
- R 11 and R20 are a hydrogen atom, or are selected from linear or branched C 1 -C16 alkyl groups, preferably C2-C 1 0;
- R16, i7, Ri8 ed Rig the same or different are a hydrogen atom, or are selected from linear or branched C 1 -C 1 6 alkyl groups, preferably C2-C 1 0; - a, b, c, d, e, f, g, and h, the same or differ ⁇ ent, are 0 or 1, on the condition that at least one is different from 0.
- said organic photoactive polymer can be selected from:
- polythiophenes such as, for example, poly (3- hexylthiophene) (P3HT) , poly (3-octylthiophene) , poly (3, 4-ethylenedioxythiophene) ; or mixtures thereof;
- polyphenylenevinylenes such as, for example, poly (2-methoxy-5- (2-ethylhexyloxy) -1,4- phenylenevinylene, poly (paraphenylenevinylene) ,
- group R is selected from alkyl groups, aryl groups, acyl groups, or thioacyl groups, said alkyl, aryl, acyl and thioacyl groups, being op ⁇ tionally substituted;
- each unit (B) is connected to at least one unit (A) in any one of the positions 4, 5, 6 or 7, preferably in positions 4 or 7;
- alternate ⁇ -conjugated polymers comprising:
- substituents X 1 -X5 are selected from hydrogen, fluorine, or from alkyl groups containing from 1 to 12 carbon atoms, preferably from 1 to 4 carbon atoms, and on the condition that at least one, preferably at least two, more preferably at least three, of the substituents X 1 -X5 is fluorine, or a -CF 2 R group, wherein R is selected from hydrogen, fluorine, or from hydrocarbon groups having from 1 to 10 carbon atoms, said hydrocarbon groups being optionally fluorinated;
- At least one electron-donor conjugated structural unit (B) connected to the unit (A) in the points indicated by the dotted lines in general formula
- copolymers based on acridonic units comprising: one monomeric unit (A) having general formula (IV) :
- X is selected from sulfur, selenium
- Y is selected from oxygen, sulfur, or from -NR' groups
- R and R' are organic sub- stituents having from 1 to 24 carbon atoms, se ⁇ lected from alkyl groups, aryl groups, said alkyl groups being optionally substituted, acyl groups, thioacyl groups;
- Z is selected from 0, S, Se, or from -NR" groups, wherein R" is an organic substituent having from 1 to 24 carbon atoms selected from alkyl groups, aryl groups, said alkyl and aryl groups be ⁇ ing optionally substituted, acyl groups, thioacyl groups; said monomeric unit (B) being connected at any available position of a side hetero-aromatic ring of the unit (A) , through one of the two posi ⁇ tions indicated by the dashed lines in general for ⁇ mula (V) ;
- said photoactive organic polymer can be selected from poly (3-hexylthiophene) (P3HT) , or polymers having the following general formulae:
- R is a linear or branched C 1 -C20 / preferably C6 _ Ci 5 , alkyl group; and n is an integer ranging from 2 to 500, preferably from 5 to 100.
- Poly (3-hexylthiophene) (P3HT) is preferred.
- the number of carbon atoms of the substituents Ri, R 2 , R3, R 4 , R5, R6, R7, Rs R9, Rio, R11, R12, Ri3, Ri4, Ri5, Ri6, Ri7, Ri8, Ri9 and R 20 can be higher than or equal to 10, preferably ranging from 12 to 50.
- - Ri and R2 are an alkyl group having 7 carbon atoms
- - R' i and R' 2 are a hydrogen atom
- R 3 , R 4 , Ri 3 , and R 1 are a hy ⁇ drogen atom
- Ri and R2 are an alkyl group having 7 carbon atoms
- R' 1 and R' 2 r are a hydrogen atom
- R3, R 4 , R 5 , R6, Ri2 / Ri3 / Ri4 and R15 are a hydrogen atom;
- R 11 and R2 0 are an alkyl group having 6 carbon atoms
- Ri and R2 are an alkyl group having 7 carbon atoms
- R' 1 and R' 2 r are a hydrogen atom
- R3, R5, R6, R 7 / R8/ RlO/ R 11/ Rl2/ Rl4/ Rl5/ Rl6/ Rl7/ Rl9/ and R2 0/ the same as each other, are a hydrogen atom;
- R 4 , Rg, Ri 3 and Ris are an al- kyl group having 6 carbon atoms;
- liner or branched alkyl groups are: methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, heptyl, octyl, decyl, tetradecyl, dodecyl, hexa- decyl, octadecyl, eicosyl, 1-ethylpropyl, 1- butylpentyl, 1-hexylheptyl, 1-octylnonyl, 1- dodecyltridecyl , 1-hexadecylheptadecyl, 1- octadecylnonadecyl 2-ethylhexyl, 2-ethyloctyl, 2- ethyldecyl, 2-ethyldodecyl, 2-butylhexyl, 2- butyldodecyl, 2-
- said naphthalene diimide having gen ⁇ eral formula (I) can be present in the photoactive com ⁇ position in a quantity ranging from 0.1% by weight to 18% by weight, preferably from 1% by weight to 15% by weight, with respect to the weight of said photoactive organic polymer.
- the naphthalene diimide having general formula (I) can be synthesized starting from the anhydride of naph- thalenecarboxydiimide according to the following Scheme 1 :
- the naphthalene diimide ring operating in accordance with what is described in litera ⁇ ture, is brominated using dibromoisocyanuric acid (AD- BIC) as brominating agent, thus obtaining dibromo naph- thalenetetracarboxylic anhydride.
- AD- BIC dibromoisocyanuric acid
- the transformation of the anhydride into diimide is subsequently effected by operating according to normal organic synthesis proce- dures. According to what is described in literature, for example in "Angewandte Chemie Int.” (1998), Vol.
- the Sonogashira reaction is a metal- catalyzed reaction (generally by complexes of palladium and copper) between an aryl halide and a terminal al- kyne to give an aryl substituted with an alkinyl chain.
- R has the same meanings in ⁇ dicated above for Ri and R2;
- R' 3 and R' 4 are selected from linear or branched Ci-Cs alkyl groups, so that, af ⁇ ter reduction of the triple bond, the groups R' 1 and R' 2 indicated above are obtained;
- R v is a Sn(R vl ) 3 group wherein R V1 is a linear or branched C 1 -C6 alkyl group, preferably a tributylstannyl group; or R v is a compound of boron having the formula: : -B(OH) 2 ; or - B(0R V11 ) 2 wherein R V11 is a linear or branched C1-C6 alkyl group; or
- R v is a compound of boron
- the reaction is preferably carried out in the presence of 1 , 2-dimethoxyethane (DME) , palladium-tetrakistri- phenylphosphine Pd [P (C 6 H 5 ) 3] 4 and sodium bicarbonate (Na- HCO3) .
- DME 2-dimethoxyethane
- Pd palladium-tetrakistri- phenylphosphine Pd [P (C 6 H 5 ) 3] 4
- sodium bicarbonate Na- HCO3
- alkyl chains can be introduced onto the naphthalene ring by the palladium-catalyzed reac ⁇ tion of dibromonaphthalene diimide with alkylboron es ⁇ ters or acids according to the following Scheme 2:
- ADBIC is dibromoisocyanuric acid
- R has the same meanings defined above for Ri and R2; R'i, R'2, R3, R4, R5, R6, R 7 / R8/ R9/ RlO/ Rll/ Rl2/ Rl3/ Rl4/ Rl5/ Rl6/ Rl7/
- Ri8, Rig and R20 / have the same meanings defined above; a, b, c, d, e, f, g and h, have the same meanings de ⁇ fined above; R 1V is a linear or branched C 1 -C6 alkyl group; Pd [P (C 6 H 5 ) 3 ] 4 is palladium-tetrakistriphenyl- phosphine; R v has the meaning defined above.
- ADBIC and DBU have the same meaning defined above;
- R has the same meanings defined above for Ri and R2;
- R' 3 and R' 4 are selected from linear or branched Ci- C8 alkyl group, so that, after reduction of the triple bond, the groups R' 1 and R' 2 defined above, are ob ⁇ tained;
- Ri5, R16, Ri7, Ri8 / Ri9 and R20 have the same meanings de- fined above; a, b, c, d, e, f, g and h, have the same meanings defined above; R v has the same meaning defined above .
- ADBIC has the same meaning defined above;
- R has the same meanings defined above for Ri and R2;
- Ri8, Rig and R20 have the same meanings defined above; a, b, c, d, e, f, g and h, have the same meanings de ⁇ fined above; R v has the same meaning defined above
- Stille reaction is generally catalyzed by PdCl 2 (PPhs) 2 , as such or prepared in situ starting from PdCl 2 and triphenylphosphine ; or palladium- tetrakistriphenylphosphine Pd [P (CeH 5 ) 3] 4 or Pd(OAc) 2 and other phosphines such as, for example, tri-ortho- tolylphosphine or tris-para-tolyl phosphine.
- Stille and Suzuki reactions can be carried out in solvents selected, for example, from ethers (for exam ⁇ ple, 1 , 2-dimethoxyethane, 1,4-dioxane, tetrahydrofu- ran) ; hydrocarbons (toluene, xylene) ; dipolar aprotic solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide) .
- the reaction temperatures generally range from 80°C to 160°C.
- reaction products are generally extracted with solvents selected, for exam- pie, from: ethers (ethyl ether, methyltertbutylether) ; chlorinated solvents (dichloromethane) ; esters (ethyl acetate) .
- solvents selected, for exam- pie, from: ethers (ethyl ether, methyltertbutylether) ; chlorinated solvents (dichloromethane) ; esters (ethyl acetate) .
- condensation products obtained after extraction are generally subsequently isolated by means of elution on a silica gel chromatographic column.
- Said photoactive composition with a high mobility of the electronic holes can be advantageously used in the construction of photovoltaic devices such as, for example, photovoltaic cells, photovoltaic modules, so ⁇ lar cells, solar modules.
- a further object of the present invention therefore relates to the use of said photoactive composition with a high mobility of the electronic holes in the con ⁇ struction of photovoltaic devices such as, for example, photovoltaic cells, photovoltaic modules, solar cells, solar modules.
- a further object of the present invention also re ⁇ lates to a photovoltaic device comprising the photo ⁇ active composition with a high mobility of the elec ⁇ tronic holes described above.
- Said photoactive composition with a high mobility of the electronic holes can also be advantageously used in the construction of organic thin film transistors (OTFT) , or organic field effect transistors (OFET) .
- OFT organic thin film transistors
- OFET organic field effect transistors
- Another object of the present invention relates to the use of said photoactive composition with a high mo ⁇ bility of the electronic holes in the construction of organic thin film transistors (OTFT) , or organic field effect transistors (OFET) .
- OFT organic thin film transistors
- OFET organic field effect transistors
- Yet another object of the present invention relates to a transistor selected from organic thin film transistors (OTFT) , or from organic field effect transis ⁇ tors (OFET) , comprising said photoactive composition with a high mobility of the electronic holes.
- OTFT organic thin film transistors
- OFET organic field effect transis ⁇ tors
- a further object of the present invention also re ⁇ lates to a naphthalene diimide having general formula (I), provided that: a and h are 1 and at least one of b, c, d, e, f and g, is 1.
- Yet another object of the present invention relates to a process for the preparation of a photovoltaic de ⁇ vice comprising:
- a solution of the photo ⁇ active composition having a high mobility of the electronic holes comprising at least one photo ⁇ active organic polymer and at least one naphthalene diimide having general formula (I), in order to ob- tain a photoactive film;
- the film is subjected to a thermal treatment at a temperature ranging from 50°C to 200°C, preferably ranging from 90°C to 140 °C, for a time ranging from 5 to 90 minutes, preferably ranging from 15 minutes to 30 minutes .
- said process can comprise, before depositing said photoactive composition having a high mobility of the electronic holes on the anode, depositing on the anode, at least one anodic buffer layer comprising an organic polymer such as, for example, poly (3, 4-ethyl- enenedioxythiophene) polystyrenesulfonate (PEDOT:PSS).
- an organic polymer such as, for example, poly (3, 4-ethyl- enenedioxythiophene) polystyrenesulfonate (PEDOT:PSS).
- said process can comprise, before depositing said cathode, depositing on said photoactive film at least one cathodic buffer layer comprising a fluoride of an alkaline metal such as, for example, lithium fluoride .
- a further object of the present invention also re ⁇ lates to a process for the preparation of a photo ⁇ voltaic device comprising:
- a solution of the photo- active composition having a high mobility of the electronic holes comprising at least one photo ⁇ active organic polymer and at least one naphthalene diimide having general formula (I), in order to ob- tain a photoactive film;
- the film is subjected to a thermal treatment at a temperature ranging from 50°C to 200°C, preferably ranging from 90°C to 140 °C, for a time ranging from 5 to 90 minutes, preferably ranging from 15 minutes to 30 minutes .
- said process can comprise, before depositing said photoactive composition having a high mobility of the electronic holes on the cathode, depositing on the cathode at least one cathodic buffer layer comprising a carbonate of an alkaline metal such as, for example, cesium carbonate, or an oxide of a transition metal such as, for example, titanium dioxide.
- an alkaline metal such as, for example, cesium carbonate
- an oxide of a transition metal such as, for example, titanium dioxide.
- said process can comprise, before depositing said anode, depositing on said photoactive film at least one anodic buffer layer comprising an oxide of a transition metal such as, for example, vanadium oxide (V 2 O 5 ) , molybdenum oxide (M0O 3 ) , or a phthalocyanine of a transition metal such as, for example, copper phthalocyanine .
- a transition metal such as, for example, vanadium oxide (V 2 O 5 ) , molybdenum oxide (M0O 3 )
- a phthalocyanine of a transition metal such as, for example, copper phthalocyanine .
- the photoactive compositions object of the present invention were characterized in order to determine the mobility of the electronic holes.
- compositions were prepared, com ⁇ prising regioregular poly ( 3-hexyl ) thiophene (P3HT) (Plexcore ® OS 1200 of Plextronics Inc.) and naphthalene diimides having general formula (I), obtained as de ⁇ scribed in the following examples, at various concen ⁇ trations .
- the films were deposited by spin-coating (Spin Coater KW-4A of Chemat Technology) , operating at 600 rpm-1,100 rpm depending on the relative concentration of the two components (i.e. P3HT and naphthalene diim- ide) for 60 seconds (18 seconds per single spin- coating, repeated 3 times) , in the air, at room temperature (25°C), from solutions in chloroform, on sub- strates of ITO/PEDOT : PSS .
- the thickness of the films obtained varies from about 0.8 ⁇ to about 1.4 ⁇ (the thickness was measured with a Tencor Alpha Step 200 profilometer) .
- the characterization of the transport properties was effected at room temperature (25°C) using the tech ⁇ nique known as admittance spectroscopy.
- the second electric contact was obtained [cathode (Al) ] of the devices by means of deposition under vac ⁇ uum (basic pressure of about 4xl0 ⁇ 6 mbar) of a layer of aluminium having a thickness of at least 70 nm.
- the films were subjected to a thermal an ⁇ nealing treatment at 135°C, for 25 minutes, in an argon (Ar) atmosphere.
- the admittance spectroscopy measurements were ef ⁇ fected using a Solartron 1255 Frequency Response Ana ⁇ lyzer together with a Solartron 1294 dielectric interface.
- the amplitude of the alternating voltage is 50 mV
- the frequency sweep was within the range of 1 Hz - 10 s Hz
- the DC bias voltage (V dc ) was varied within the range of 0 V - 10 V.
- the measurements were effected under dynamic vacuum (about 2xl0 ⁇ 4 mbar) , directly po ⁇ larizing the devices [positive ITO/PEDOT : PSS contact (anode) with respect to the aluminium (Al) (cathode) ] .
- the frequency f max corresponding to the negative differential susceptance peak is linked to the transit time of the charges X tr by the following relation:
- k is an empirical coefficient
- V b ⁇ is the built-in potential given by the dif ⁇ ference in the operating function of the two electric contacts [i.e. anode (ITO) and cathode (Al) ] .
- ADBIC is dibromoisocyanuric acid and SnBu 3 is the tributylstannyl group.
- ADBIC dibromoisocyanuric acid
- the intermediate compound 2, 6-dibromo-l, 4, 5, 8- tetracarboxynaphthalenedianhydride (12) was obtained by reaction of 1, 4, 5, 8-tetracarboxynaphthalenediimide with dibromoisocyanuric acid (ADBIC) according to the fol- lowing reaction scheme:
- the intermediate compound 2 6-dibromo-N, N' - diheptyl-1, 4, 5, 8-tetracarboxynaphthalenediimide (13) was obtained starting from the intermediate compound (12) according to the following reaction scheme:
- Heptylamine H 2 C 7 H 15
- 2, 6-dibromo-l, 4, 5, 8- tetracarboxynaphthalenedianhydride (12) in acetic acid (CH 3 COOH) acetic acid
- the temperature was brought to 100 °C. After 8 hours at this temperature, the mixture was filtered and the precipitate obtained was washed various times with ethyl ether and finally with toluene.
- Tributylstannylthiophene was added, in an inert at ⁇ mosphere, to the toluene solution of 2 , 6-dibromo-N, N' - diheptyl-1, 4, 5, 8-tetracarboxynaphthalenediimide (13) . After removing the air present by means of vac ⁇ uum/nitrogen cycles, palladium- tetrakistriphenylphosphine was added. The temperature was then brought to 100°C. After 7 hours at this tem ⁇ perature, water was added and the mixture obtained was subjected various times to extraction with ethyl ether.
- ADBIC is dibromoisocyanuric acid.
- Dibromoisocyanuric acid (ABDIC) , 2,6-dibromo- 1, 4, 5, 8-tetracarboxynaphthalenedianhydride (12) and 2, 6-dibromo-N,N' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalenediimide (13) were prepared ac ⁇ cording to the procedure described in Example 1.
- ADBIC is dibromoisocyanuric acid.
- ADBIC Dibromoisocyanuric acid
- 2,6-dibromo- 1, 4, 5, 8-tetracarboxynaphthalenedianhydride (12) and 2, 6-dibromo-N,N' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalenediimide (13) were prepared ac ⁇ cording to the procedure described in Example 1.
- Composition comprising poly (3-hexylthiophene) (P3HT) and 2, 6-bis (2' -thienyl) - ⁇ , ⁇ ' -diheptyl-1, 4, 5, 8- tetracarboxy-naphthalene diimide (5%)
- the solution thus obtained was used for preparing a film having a thickness equal to 0.83 ⁇ , by means of spin coating, operating according to what is described above in the paragraph "method for measuring the mobil- ity of the electronic holes".
- Composition comprising poly (3-hexylthiophene) (P3HT) and 2, 6-bis (2' -thienyl) - ⁇ , ⁇ ' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalene diimide (10%)
- the solution thus obtained was used for preparing a film having a thickness equal to 1 ⁇ , by means of spin coating, operating according to what is described above in the paragraph "method for measuring the mobility of the electronic holes".
- Composition comprising poly (3-hexylthiophene) (P3HT) and 2, 6-bis (2' -thienyl) - ⁇ , ⁇ ' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalene diimide (15%)
- the solution thus obtained was used for preparing a film having a thickness equal to 1.2 ⁇ , by means of spin coating, operating according to what is described above in the paragraph "method for measuring the mobil- ity of the electronic holes".
- the mobility values of the electronic holes ob ⁇ tained as described above in the paragraph "method for measuring the mobility of the electronic holes” are in ⁇ dicated in Figure 3.
- Composition comprising poly (3-hexylthiophene) (P3HT) and 2, 6-bis [ 5"-hexyldithien-2 ' -yl] - ⁇ , ⁇ ' -diheptyl-
- the solution thus obtained was used for preparing a film having a thickness equal to 0.83 ⁇ , by means of spin coating, operating according to what is described above in the paragraph "method for measuring the mobil ⁇ ity of the electronic holes".
- Composition comprising poly (3-hexylthiophene) (P3HT) and 2, 6-bis [ 5"-hexyldithien-2 ' -yl] - ⁇ , ⁇ ' -diheptyl-
- Composition comprising poly (3-hexylthiophene) (P3HT) and 2, 6-bis [ 5"-hexyldithien-2 ' -yl] - ⁇ , ⁇ ' -diheptyl-
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Abstract
A photoactive composition with a high mobility of the elec tronic holes, comprising: -at least one organic photoactive polymer; -at least one naphthalene diimide having general formul (I): wherein: - R1 and R2, the same or different, preferably the same, are selected from linear or branched C1-C36 alky1 groups, preferably C4-C24, optionally containing heteroatoms such as, for example, oxygen, nitrogen, sulphur; - R'1 and R'2, the same or different, preferably the same, are a hydrogen atom, or are selected from linear or branched C1-C10 alkyl groups, preferably C2-C6; they are preferably a hydrogen atom. - R11 and R20, the same or different, preferably the same, are a hydrogen atom, or are selected from linear or branched C1-C16 alkyl groups, preferably C2-C10; - R3, R4, R5, R6, R7, R8, R9, R10, R12, R13, R14, R15, R16, R17, R18 and R19, the same or different, are a hydrogen atom, or are selected from linear or branched C1-C16 alkyl groups preferably C2-C10; - a, b, c, d, e, f, g, and h, the same or different, are 0 or 1, on the condition that at least one is different from zero. Said photoactive composition with a high mobility of the electronic holes, can be advantageously used in the construction of photovoltaic devices, such as, for example, photovoltaic cells, photovoltaic modules, solar cells, solar modules, both on rigid and flexible support.
Description
PHOTOACTIVE COMPOSITION WITH A HIGH MOBILITY OF THE ELECTRONIC HOLES
The present invention relates to a photoactive com¬ position with a high mobility of the electronic holes.
More specifically, the present invention relates to a photoactive composition with a high mobility of the electronic holes, comprising at least one photoactive organic polymer and at least one naphthalene diimide.
The present invention also relates to the use of said photoactive composition having a high mobility of the electronic holes in the construction of photo¬ voltaic devices such as, for example, photovoltaic cells, photovoltaic modules, solar cells and solar mod¬ ules, on both a rigid and flexible support.
The present invention also relates to the use of said photoactive composition having a high mobility of the electronic holes in the construction of organic thin film transistors (OTFT) or organic field effect transistors (OFET) .
The present invention also relates to said naphtha¬ lene diimide.
Photovoltaic devices are devices capable of con¬ verting the energy of a light radiation into electric energy. At present, most photovoltaic devices which can be used for practical applications exploit the physico-
chemical properties of photo-active materials of the inorganic type, in particular high-purity crystalline silicon. As a result of the high production costs of silicon, scientific research has been orienting its ef- forts towards the development of alternative organic materials having a polymeric structure (so-called "po¬ lymer photovoltaic cells") . Unlike high-purity crystal¬ line silicon, in fact, organic polymers are characte¬ rized by a relative synthesis facility, a low produc- tion cost, a reduced weight of the relative photovol¬ taic device, in addition to allowing the recycling of said polymer at the end of the life-cycle of the device in which it is used.
The functioning of polymer photovoltaic cells is based on the combined use of an electron acceptor compound and an electron donor compound. In the state of the art, the most widely-used electron donor and accep¬ tor compounds in photovoltaic devices are π-conj ugated polymers belonging to the groups of polyparaphenylene vinylenes and polythiophenes. The former can be used as both acceptor compounds and as donor compounds, on the basis of the electronic properties determined by the substituents of the polymer chain. The latter are nor¬ mally used as donor compounds. Derivatives of fullerene are most widely-used as acceptor compounds.
The basic conversion process of light into electric current in a polymer photovoltaic cell takes place through the following steps:
1. absorption of a photon on the part of the donor compound with the formation of an exciton, i.e. a pair of "electron-hole" electronic charge transporters;
2. diffusion of the exciton in a region of the donor compound in which its dissociation can take place;
3. dissociation of the exciton in the two charge transporters (electron (-) and electronic hole ( + ) ) se¬ parated;
4. transporting of the charges thus formed to the ca¬ thode (electron, through the acceptor compound) and anode (electronic hole, through the donor compound) , with the generation of an electric current in the cir¬ cuit of the device.
The photo-absorption process with the formation of the exciton and subsequent yielding of the electron to the acceptor compound leads to the electron excitation from the HOMO (Highest Occupied Molecular Orbital) to the LUMO (Lowest Unoccupied Molecular Orbital) of the donor compound and subsequently the passage from this to the LUMO of the acceptor compond.
As the efficiency of a polymer photovoltaic cell depends on the number of free electrons which are gen-
erated by dissociation of the excitons, one of the structural characteristics of donor compounds which mostly influences said efficiency is the difference in energy existing between the HOMO and LUMO orbitals of the donor compound (so-called band-gap) . From this dif¬ ference depends, in particular, the wave-length of the photons which the donor compound is capable of collect¬ ing and effectively converting into electric energy (so-called "photo harvesting" or "light-harvesting" process) . In order to obtain acceptable electric cur¬ rents, the band-gap between HOMO and LUMO must not be excessively high, but at the same time not excessively low, as an excessively low band-gap would jeopardize the voltage obtained at the electrodes of the device.
Another fundamental characteristic of the materials used for producing photovoltaic devices is the mobility of the electrons in the acceptor compound and of the electronic holes in the donor compound, which deter¬ mines the facility with which the electric charges, once photogenerated, reach the electrodes.
It is known that in high- and low-molecular weight organic materials, the charge transportation is orders of magnitude lower with respect to inorganic semicon¬ ductors as described for example, by M.C. Petty in "Mo- lecular electronics: from principle to practice" (2007)
Wiley Ed. Chapter 3.
The electronic mobility, i.e. the mobility of the electrons in the acceptor compound and electronic holes in the donor compound, in addition to being an intrin- sic property of the molecules, is also strongly influ¬ enced by the morphology of the photoactive layer, which, in turn, depends on the reciprocal miscibility of the components and their solubility.
In the simplest way of operating, polymer photo- voltaic cells are produced by introducing a thin layer (about 100 nanometres) of a mixture of the acceptor compound and donor compound (generally known as "bulk heterojunction") , between two electrodes, normally consisting of indium-tin oxide (ITO) (anode) and aluminium (Al) (cathode) . In order to produce a layer of this type, a solution of the two components is generally prepared and a photoactive film is subsequently created on the anode [indium-tin oxide (ITO] starting from said solution, resorting to suitable deposition techniques such as, for example, "spin-coating", "spray-coating" "ink-jet printing" and similar. At the end, the counter-electrode [i.e. the aluminium cathode (Al) ] is deposited on the dried film. Optionally, other addi¬ tional layers (called interlayers or buffer layers) , capable of exerting specific functions of an electric,
optical or mechanical nature, can be introduced between the anode and photoactive film.
The donor compound which is most commonly used in the construction of polymer photovoltaic cells is re- gioregular poly (3-hexylthiophene) (P3HT) .
This polymer has optimal electronic and optical characteristics (good HOMO and LUMO orbital values, good adsorption coefficient) , a good solubility in the solvents used in the construction of photovoltaic cells and a reasonable mobility of the electronic holes.
Other examples of polymers which can be advanta¬ geously used as donor compounds are: the polymer MDMO- PPV { (poly [2-methoxy-5- (3, 7-dimethyloctyloxy) -1, 4- phenylene] -alt- (vinylene) } , the polymer PCDTBT {poly [N-9"-heptade-cyl-2, 7-carbazole-alt-5, 5- (4' , 7' -di- 2-thienyl-2' , 1' , 3' -benzothiadiazole ] } , the polymer PCPDTBT {poly[2,6-(4, 4 -bis- ( 2 -ethylhexyl ) -4H- cyclopenta [2, 1-b; 3, 4-b' ] -dithiophene) -alt-4, 7- (2, 1, 3- benzothiadiazole) ] } .
The above-mentioned donor compounds, when used in combination with acceptor compounds based on fullerenes (C6o or C70) are generally capable of obtaining maximum conversion efficiencies of solar radiation of up to 6%.
In order to facilitate the electronic holes in reaching the anode [indium-tin oxide (ITO], and at the
same time block the transporting of electrons, thus im¬ proving the collection of the charges on the part of the electrode and inhibiting recombination phenomena, before creating the photoactive film starting from the mixture of the acceptor compound and donor compound as described above, a film starting from an aqueous sus¬ pension of PEDOT:PSS [poly (3, 4-ethylenedioxythiophene) sulfonated polystyrene] is generally deposited, using suitable deposition techniques such as, for example, "spin-coating", "spray-coating" "ink-jet printing" and similar. The counter-electrode [cathode (Al) ] is fi¬ nally deposited on the dried film.
It is known that the addition of molecules deriving from tetracarboxyperylene diimide [e.g. N, N' -bis (2 , 5- di-tert-butylphenyl) -3, 4, 9, 10- perylenetetracarboxydiimide ] to regioregular poly (3- hexylthiophene) causes a decrease in the mobility of the electronic holes, as specified, for example, by Saeki A. et al . in "Journal of Physical Chemistry C" (2008), Vol. 112, pages 16643-16650, due to the distur¬ bance caused on the intermolecular packing.
It is also known that naphthaleneimide derivatives are semiconductors of the n type, i.e. the mobility of electrons is favoured in their interior, whereas they are extremely poor semiconductors of the p type, in
which, on the contrary, the mobility of the electronic holes is favoured, as described for example by Singh Th. B. et al. in "Organic Electronics" (2006), Vol. 7, pages 480-489; by Yamashita Y. in "Science and Technol- ogy of Advanced Material" (2009), Vol. 10, 024313 pg. 1- 9); by Chen Z. et al . in "Journal of American Chemical Society (2009), Vol. 131, pages 8-9. Said semiconduc¬ tors cannot therefore be used as donor compounds for the production of polymer photovoltaic cells or tran- sistors of the p type.
In order to improve the efficiency of the materials to be used in photovoltaic devices, it is therefore de¬ sirable to find new systems capable of more effectively transporting the charges to the electrodes.
The Applicant consequently considered the problem of finding a system capable of improving the mobility of the electronic holes towards the anode through the donor compound.
The Applicant has now found that, contrary to what could be expected on the basis of the electronic prop¬ erties of known naphthalene diimides described in sci¬ entific literature, the addition of at least one naph¬ thalene diimide having the specific general formula in¬ dicated hereunder, to photoactive organic polymers which can be used in the construction of photovoltaic
devices, is capable of improving the mobility of the electronic holes towards the anode through the donor compound, consequently allowing better conversion effi¬ ciencies of solar radiation.
The Applicant has also found that the composition thus obtained can also be advantageously used in the construction of organic thin film transistors (OTFT) , or organic field effect transistors (OFET) .
An object of the present invention therefore re¬ lates to a photoactive composition with a high mobility of the electronic holes comprising:
at least one photoactive organic polymer;
at least one naphthalene diimide having general formula (I)
wherein :
Ri and R2 , the same or different, preferably the same, are selected from linear or branched C1-C36 alkyl groups, preferably C4-C24 optionally con¬ taining heteroatoms such as, for example, oxy-
gen, nitrogen, sulfur;
R' i and R'2, the same or different, preferably the same, are a hydrogen atom, or are selected from linear or branched Ci-Cio, preferably C2-C6, alkyl groups, they are preferably a hydrogen atom;
R11 and R20, the same or different, preferably the same, are a hydrogen atom, or are selected from linear or branched C1-C16 alkyl groups, preferably C2-C10;
R3, R4, R5, R6, R7, R8/ R9/ RlO/ Rl2/ Rl3/ Rl4/ Rl5/
R16, i7, Ri8 ed Rig the same or different, are a hydrogen atom, or are selected from linear or branched C1-C16 alkyl groups, preferably C2-C10; - a, b, c, d, e, f, g, and h, the same or differ¬ ent, are 0 or 1, on the condition that at least one is different from 0.
In accordance with a preferred embodiment of the present invention, said organic photoactive polymer can be selected from:
(a) polythiophenes such as, for example, poly (3- hexylthiophene) (P3HT) , poly (3-octylthiophene) , poly (3, 4-ethylenedioxythiophene) ; or mixtures thereof; (b) polyphenylenevinylenes such as, for example, poly (2-methoxy-5- (2-ethylhexyloxy) -1,4-
phenylenevinylene, poly (paraphenylenevinylene) ,
{ (poly [2-methoxy-5- (3, 7-dimethyloctyloxy) -1,4- phenylene] -alt- (vinylene) } (MDMO-PPV) , or mixtures thereof;
alternate or statistic conjugated copolymers, com¬ prising :
at least one benzotriazole unit (B) having general formula (la) or (lb) :
at least one structural conjugated unit (A) , wherein each unit (B) is connected to at least one unit (A) in any one of the positions 4, 5, 6 or 7, preferably in positions 4 or 7; alternate π-conjugated polymers comprising:
at least one electron-acceptor fluoroarylvi- nylidene unit (A) having general formula (III) :
(III)
wherein the substituents X1-X5, the same or dif¬ ferent, are selected from hydrogen, fluorine, or from alkyl groups containing from 1 to 12 carbon atoms, preferably from 1 to 4 carbon atoms, and on the condition that at least one, preferably at least two, more preferably at least three, of the substituents X1-X5 is fluorine, or a -CF2R group, wherein R is selected from hydrogen, fluorine, or from hydrocarbon groups having from 1 to 10 carbon atoms, said hydrocarbon groups being optionally fluorinated;
at least one electron-donor conjugated structural unit (B) , connected to the unit (A) in the points indicated by the dotted lines in general formula
( i n ) ;
copolymers based on acridonic units, comprising: one monomeric unit (A) having general formula (IV) :
(IV)
wherein X is selected from sulfur, selenium; Y is selected from oxygen, sulfur, or from -NR' groups; R and R' , the same or different, are organic sub- stituents having from 1 to 24 carbon atoms, se¬ lected from alkyl groups, aryl groups, said alkyl groups being optionally substituted, acyl groups, thioacyl groups;
at least one monomeric unit (B) having general for¬ mula (V) :
(V)
wherein Z is selected from 0, S, Se, or from -NR" groups, wherein R" is an organic substituent having from 1 to 24 carbon atoms selected from alkyl groups, aryl groups, said alkyl and aryl groups be¬ ing optionally substituted, acyl groups, thioacyl groups; said monomeric unit (B) being connected at
any available position of a side hetero-aromatic ring of the unit (A) , through one of the two posi¬ tions indicated by the dashed lines in general for¬ mula (V) ;
f) alternate conjugated copolymers comprising ben- zothiadiazole units such as PCDTBT {poly[N-9"- heptadecyl-2 , 7-carbazole-alt-5, 5- (4' , Ί ' -di-2- thienyl-2' , 1' , 3' -benzothiadiazole] } , PCPDTBT {poly- [2, 6- (4, 4 -bis- (2-ethylhexyl) -4H-cyclopenta [ 2 , 1- b; 3, 4-b' ] -dithiophene) -alt-4, 7- (2,1,3- benzothiadiazole) ] } ;
g) alternate conjugated copolymers comprising thieno [3, 4-b] pyrazidinic units;
h) alternate conjugated copolymers comprising quinoxa- line units;
i) alternate conjugated copolymers comprising mono- meric silole units such as, for example, copolymers of 9, 9-dialkyl- 9-silafluorene ;
1) alternate conjugated copolymers comprising con¬ densed thiophene units such as, for example, co¬ polymers of thieno [3, 4-b] thiophene and of benzo [ 1 , 2-b : 4 , 5-b' ] dithiophene .
For the purposes of the present invention and fol¬ lowing claims, the definitions of the numerical ranges always comprise the extremes unless otherwise speci-
fied .
Greater details relating to alternate or statistic conjugated copolymers (c) comprising at least one ben- zotriazole unit (B) and at least one structural conju- gated unit (A) and the process for their preparation can be found, for example, in Italian patent applica¬ tion MI08A001869 in the name of the Applicant.
Greater details relating to alternate π-conjugated polymers (d) comprising at least one electron-acceptor fluoroarylvinylidene unit (A) and at least one elec¬ tron-donor conjugated structural unit (B) and the proc¬ ess for their preparation can be found, for example, in Italian patent application MI09A002150 in the name of the Applicant.
Greater details relating to copolymers based on ac- ridonic units (e) comprising one monomeric unit (A) and at least one monomeric unit (B) and the process for their preparation can be found, for example, in Italian patent application MI09A002232 in the name of the Ap- plicant.
Greater details relating to alternate conjugated copolymers comprising benzothiadiazole units (f) , al¬ ternate conjugated copolymers comprising thieno[3,4- b] pyrazidinic units (g) , alternate conjugated copoly- mers comprising quinoxaline units (h) , alternate conju-
gated copolymers comprising monomeric silole units (i) , alternate conjugated copolymers comprising condensed thiophene units (1) , can be found, for example, in "Accounts of chemical research" (2009), Vol. 42, No. 11, pages 1709-1718, "Development of Novel Conjugated Donor Polymers for High-Efficiency Bulk-Heterojunction Photovoltaic Device" (Chen et al . ) .
According to a further preferred embodiment of the present invention, said photoactive organic polymer can be selected from poly (3-hexylthiophene) (P3HT) , or polymers having the following general formulae:
-17-
m/n=0,59
wherein R is a linear or branched C1-C20/ preferably C6_ Ci5, alkyl group; and n is an integer ranging from 2 to 500, preferably from 5 to 100.
Poly (3-hexylthiophene) (P3HT) is preferred.
According to a further preferred embodiment of the present invention, in said naphthalene diimide having general formula (I), the number of carbon atoms of the substituents Ri, R2, R3, R4, R5, R6, R7, Rs R9, Rio, R11, R12, Ri3, Ri4, Ri5, Ri6, Ri7, Ri8, Ri9 and R20, can be higher than or equal to 10, preferably ranging from 12 to 50.
According to a further preferred embodiment of the present invention, in said naphthalene diimide having general formula (I) :
- Ri and R2, the same as each other, are an alkyl group having 7 carbon atoms;
- R' i and R' 2, the same as each other, are a hydrogen atom;
- R3, R4, Ri3, and R12, the same as each other, are a hy¬ drogen atom;
- d and e, the same as each other, are 1;
- a, b, c, f, g and h, the same as each other, are 0.
According to a further preferred embodiment of the present invention, in said naphthalene diimide having general formula (I) :
- Ri and R2, the same as each other, are an alkyl group having 7 carbon atoms;
- R' 1 and R' 2r the same as each other, are a hydrogen atom;
R3, R4, R5, R6, Ri2/ Ri3/ Ri4 and R15, the same as each other, are a hydrogen atom;
R11 and R20, the same as each other, are an alkyl group having 6 carbon atoms;
- c, d, e and f, the same as each other, are 0;
- a, b, g and h, the same as each other, are 1.
According to a further preferred embodiment of the present invention, in said naphthalene diimide having general formula (I) :
- Ri and R2, the same as each other, are an alkyl group having 7 carbon atoms;
- R' 1 and R' 2r the same as each other, are a hydrogen
atom;
- R3, R5, R6, R7/ R8/ RlO/ R 11/ Rl2/ Rl4/ Rl5/ Rl6/ Rl7/ Rl9/ and R20/ the same as each other, are a hydrogen atom;
- R4, Rg, Ri3 and Ris, the same as each other, are an al- kyl group having 6 carbon atoms;
- a, b, c, d, e, f, g and h, the same as each other, are 1.
Examples of liner or branched alkyl groups are: methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, heptyl, octyl, decyl, tetradecyl, dodecyl, hexa- decyl, octadecyl, eicosyl, 1-ethylpropyl, 1- butylpentyl, 1-hexylheptyl, 1-octylnonyl, 1- dodecyltridecyl , 1-hexadecylheptadecyl, 1- octadecylnonadecyl 2-ethylhexyl, 2-ethyloctyl, 2- ethyldecyl, 2-ethyldodecyl, 2-butylhexyl, 2- butyldodecyl , 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-decyldodecyl, 4-butylhexyl, 4-butyloctyl, 4- butyldecyl, 4-butyldodecyl, 4-hexyldecyl .
According to a further preferred embodiment of the present invention, said naphthalene diimide having gen¬ eral formula (I) can be present in the photoactive com¬ position in a quantity ranging from 0.1% by weight to 18% by weight, preferably from 1% by weight to 15% by weight, with respect to the weight of said photoactive organic polymer.
The naphthalene diimide having general formula (I) can be synthesized starting from the anhydride of naph- thalenecarboxydiimide according to the following Scheme 1 :
In the above Scheme 1, R has the same meanings in¬ dicated above for Ri and R2; R' 3 and R' 4 are selected from linear or branched Ci-Cs alkyl groups, so that, af¬ ter reduction of the triple bond, the groups R' 1 and R' 2 indicated above are obtained; R3, R4, R5, R6, R7, Rs, R9,
Rio, R11, R12, Ri3, Ri4, Ri5, Ri6, Ri7, Ris, Rig and R20, have the same meanings defined above; a, b, c, d, e, f, g and h, have the same meanings defined above; DBU is
1 , 8-diazobicyclo [ 5.4.0 ] undecen-7-ene ; Rv is a Sn(Rvl)3 group wherein RV1 is a linear or branched C1-C6 alkyl
group, preferably a tributylstannyl group; or Rv is a compound of boron having the formula: : -B(OH)2; or - B(0RV11) 2 wherein RV11 is a linear or branched C1-C6 alkyl group; or
wherein B is boron. When Rv is a compound of boron, the reaction is preferably carried out in the presence of 1 , 2-dimethoxyethane (DME) , palladium-tetrakistri- phenylphosphine Pd [P (C6H5) 3] 4 and sodium bicarbonate (Na- HCO3) .
Alternatively, alkyl chains can be introduced onto the naphthalene ring by the palladium-catalyzed reac¬ tion of dibromonaphthalene diimide with alkylboron es¬ ters or acids according to the following Scheme 2:
wherein ADBIC is dibromoisocyanuric acid; R has the same meanings defined above for Ri and R2; R'i, R'2, R3, R4, R5, R6, R7/ R8/ R9/ RlO/ Rll/ Rl2/ Rl3/ Rl4/ Rl5/ Rl6/ Rl7/
Ri8, Rig and R20/ have the same meanings defined above; a, b, c, d, e, f, g and h, have the same meanings de¬ fined above; R1V is a linear or branched C1-C6 alkyl group; Pd [P (C6H5) 3] 4 is palladium-tetrakistriphenyl- phosphine; Rv has the meaning defined above.
Alternatively, when R3 = R12, R4 = R13, R5 = R14, R6 =
Rl5/ R7 = Rl6/ ¾ = Rl7/ R9 = Rl8/ RlO = Rl9/ R11 = i is possible to operate according to the following Scheme 3:
wherein ADBIC and DBU have the same meaning defined above; R has the same meanings defined above for Ri and R2; R' 3 and R' 4 are selected from linear or branched Ci- C8 alkyl group, so that, after reduction of the triple bond, the groups R' 1 and R' 2 defined above, are ob¬ tained; R3, R4, R5, R6, R7, R8/ R9/ RlO/ Rll/ Rl2/ Rl3/ Rl4/
Ri5, R16, Ri7, Ri8/ Ri9 and R20, have the same meanings de-
fined above; a, b, c, d, e, f, g and h, have the same meanings defined above; Rv has the same meaning defined above .
Alternatively, when R' 1 and R' 2 are a hydrogen atom, it is possible to operate according to the following Scheme 4 :
wherein ADBIC has the same meaning defined above; R has the same meanings defined above for Ri and R2; R3, R4, R5, R6, R7, R8/ R9/ RlO/ Rll/ Rl2/ Rl3/ Rl4/ Rl5/ Rl6/ Rl7/
Ri8, Rig and R20, have the same meanings defined above; a, b, c, d, e, f, g and h, have the same meanings de¬ fined above; Rv has the same meaning defined above
Operative conditions under which the above conden- sation reactions can be carried out are known in lit¬ erature, such as for example, in "Chemistry of Materials" (2006), Vol. 18, pages 3151-3161; or in "Chemical
- A European Journal" (2009), Vol. 15, pages 4906-4913.
Condensation reactions of the above type are also known as Stille reactions (when Rv = -Sn(Rvl)3, or as Suzuki reactions [when Rv = -B(OH)2, or -B(OR)2] and are generally catalyzed by palladium complexes.
Stille reaction is generally catalyzed by PdCl2 (PPhs) 2, as such or prepared in situ starting from PdCl2 and triphenylphosphine ; or palladium- tetrakistriphenylphosphine Pd [P (CeH5) 3] 4 or Pd(OAc)2 and other phosphines such as, for example, tri-ortho- tolylphosphine or tris-para-tolyl phosphine.
Stille and Suzuki reactions can be carried out in solvents selected, for example, from ethers (for exam¬ ple, 1 , 2-dimethoxyethane, 1,4-dioxane, tetrahydrofu- ran) ; hydrocarbons (toluene, xylene) ; dipolar aprotic solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide) . The reaction temperatures generally range from 80°C to 160°C.
In the case of Suzuki reaction, a saturated aqueous solution of sodium bicarbonate or potassium bicarbonate, or a saturated aqueous solution of sodium or po¬ tassium carbonate, must be added.
At the end of the above reactions, after quenching the reactions with water, the reaction products are generally extracted with solvents selected, for exam-
pie, from: ethers (ethyl ether, methyltertbutylether) ; chlorinated solvents (dichloromethane) ; esters (ethyl acetate) .
The condensation products obtained after extraction are generally subsequently isolated by means of elution on a silica gel chromatographic column.
Further details relating to the synthesis process of said naphthalene diimide having general formula (I) are provided hereunder in the following examples.
Said photoactive composition with a high mobility of the electronic holes can be advantageously used in the construction of photovoltaic devices such as, for example, photovoltaic cells, photovoltaic modules, so¬ lar cells, solar modules.
A further object of the present invention therefore relates to the use of said photoactive composition with a high mobility of the electronic holes in the con¬ struction of photovoltaic devices such as, for example, photovoltaic cells, photovoltaic modules, solar cells, solar modules.
A further object of the present invention also re¬ lates to a photovoltaic device comprising the photo¬ active composition with a high mobility of the elec¬ tronic holes described above.
Said photoactive composition with a high mobility
of the electronic holes can also be advantageously used in the construction of organic thin film transistors (OTFT) , or organic field effect transistors (OFET) .
Another object of the present invention relates to the use of said photoactive composition with a high mo¬ bility of the electronic holes in the construction of organic thin film transistors (OTFT) , or organic field effect transistors (OFET) .
Yet another object of the present invention relates to a transistor selected from organic thin film transistors (OTFT) , or from organic field effect transis¬ tors (OFET) , comprising said photoactive composition with a high mobility of the electronic holes.
A further object of the present invention also re¬ lates to a naphthalene diimide having general formula (I), provided that: a and h are 1 and at least one of b, c, d, e, f and g, is 1.
Yet another object of the present invention relates to a process for the preparation of a photovoltaic de¬ vice comprising:
depositing on the anode, a solution of the photo¬ active composition having a high mobility of the electronic holes comprising at least one photo¬ active organic polymer and at least one naphthalene diimide having general formula (I), in order to ob-
tain a photoactive film;
depositing a cathode on said photoactive film;
wherein, before or after the deposition of said cathode, the film is subjected to a thermal treatment at a temperature ranging from 50°C to 200°C, preferably ranging from 90°C to 140 °C, for a time ranging from 5 to 90 minutes, preferably ranging from 15 minutes to 30 minutes .
According to a further embodiment of the present invention, said process can comprise, before depositing said photoactive composition having a high mobility of the electronic holes on the anode, depositing on the anode, at least one anodic buffer layer comprising an organic polymer such as, for example, poly (3, 4-ethyl- enenedioxythiophene) polystyrenesulfonate (PEDOT:PSS).
According to a further embodiment of the present invention, said process can comprise, before depositing said cathode, depositing on said photoactive film at least one cathodic buffer layer comprising a fluoride of an alkaline metal such as, for example, lithium fluoride .
A further object of the present invention also re¬ lates to a process for the preparation of a photo¬ voltaic device comprising:
- depositing on the cathode, a solution of the photo-
active composition having a high mobility of the electronic holes comprising at least one photo¬ active organic polymer and at least one naphthalene diimide having general formula (I), in order to ob- tain a photoactive film;
depositing an anode on said photoactive film;
wherein, before or after the deposition of said anode, the film is subjected to a thermal treatment at a temperature ranging from 50°C to 200°C, preferably ranging from 90°C to 140 °C, for a time ranging from 5 to 90 minutes, preferably ranging from 15 minutes to 30 minutes .
According to a further embodiment of the present invention, said process can comprise, before depositing said photoactive composition having a high mobility of the electronic holes on the cathode, depositing on the cathode at least one cathodic buffer layer comprising a carbonate of an alkaline metal such as, for example, cesium carbonate, or an oxide of a transition metal such as, for example, titanium dioxide.
According to a further embodiment of the present invention, said process can comprise, before depositing said anode, depositing on said photoactive film at least one anodic buffer layer comprising an oxide of a transition metal such as, for example, vanadium oxide
(V2O5) , molybdenum oxide (M0O3) , or a phthalocyanine of a transition metal such as, for example, copper phthalocyanine .
Some illustrative and non-limiting examples are provided for a better understanding of the present invention and for its embodiment.
Method for measuring the mobility of the electronic holes
The photoactive compositions object of the present invention, were characterized in order to determine the mobility of the electronic holes.
For this purpose, compositions were prepared, com¬ prising regioregular poly ( 3-hexyl ) thiophene (P3HT) (Plexcore® OS 1200 of Plextronics Inc.) and naphthalene diimides having general formula (I), obtained as de¬ scribed in the following examples, at various concen¬ trations .
The films were deposited by spin-coating (Spin Coater KW-4A of Chemat Technology) , operating at 600 rpm-1,100 rpm depending on the relative concentration of the two components (i.e. P3HT and naphthalene diim- ide) for 60 seconds (18 seconds per single spin- coating, repeated 3 times) , in the air, at room temperature (25°C), from solutions in chloroform, on sub- strates of ITO/PEDOT : PSS . The thickness of the films
obtained varies from about 0.8 μη to about 1.4 μη (the thickness was measured with a Tencor Alpha Step 200 profilometer) .
The characterization of the transport properties was effected at room temperature (25°C) using the tech¬ nique known as admittance spectroscopy. For this pur¬ pose, the second electric contact was obtained [cathode (Al) ] of the devices by means of deposition under vac¬ uum (basic pressure of about 4xl0~6 mbar) of a layer of aluminium having a thickness of at least 70 nm.
Before the deposition of the cathode made of Al (aluminium), the films were subjected to a thermal an¬ nealing treatment at 135°C, for 25 minutes, in an argon (Ar) atmosphere.
The admittance spectroscopy measurements were ef¬ fected using a Solartron 1255 Frequency Response Ana¬ lyzer together with a Solartron 1294 dielectric interface. The amplitude of the alternating voltage is 50 mV, the frequency sweep was within the range of 1 Hz - 10s Hz and the DC bias voltage (Vdc) was varied within the range of 0 V - 10 V. The measurements were effected under dynamic vacuum (about 2xl0~4 mbar) , directly po¬ larizing the devices [positive ITO/PEDOT : PSS contact (anode) with respect to the aluminium (Al) (cathode) ] .
The transit times of the positive charges injected
from the ITO/PEDO : PSS electrode (anode) were obtained from the position of the negative differential suscep- tance peaks (-ΔΒ) as indicated by H. C. F. Martens et al . in "Applied Physics Letters (2000), Vol. 77, pages 1852-1855:
-A5 = -co(C-C8)
in relation to the frequency f, C being the capacity, Cg the geometrical capacity of the sample and CO = 2nf the angular velocity.
For each value of the DC bias, the frequency fmax corresponding to the negative differential susceptance peak is linked to the transit time of the charges Xtr by the following relation:
wherein k is an empirical coefficient.
Assuming a value of 0.54 for k, as indicated by P. W. M. Blom et al . in "Synthetic Metals" (2001), Vol. 121, pages 1621-1624, the mobility of the charges μ is obtained with the following formula:
wherein Vb± is the built-in potential given by the dif¬ ference in the operating function of the two electric contacts [i.e. anode (ITO) and cathode (Al) ] .
EXAMPLE 1
Preparation of 2, 6-bis (2' -thienyl) -Ν,Ν' -diheptyl-
1,4,5, 8-tetracarboxynaphthalenediimide
The compound 2 , 6-bis (2 ' -thienyl ) -N, N' -diheptyl- 1, 4, 5, 8-tetracarboxynaphthalenediimide having the for- mu1a :
was synthesized according to the following reaction scheme :
The dibromoisocyanuric acid (ADBIC) was synthesized according to the following reaction scheme:
by reacting 6.5 g (50.4 mmoles) of cyanuric acid, 4.3 g (104.8 mmoles) of lithium hydroxide (LiOH), 31 g (193.7 mmoles) of bromine (Br2) and 500 ml of water.
Bromine was slowly added dropwise to the aqueous solution of cyanuric acid and lithium hydroxide. After 12 hours at 4°C, the dibromoisocyanuric acid was iso¬ lated, as a white solid, by filtration. After washing the precipitate with water and drying it, 9.0 g of di¬ bromoisocyanuric acid (ADBIC) was obtained (yield = 62%) .
The intermediate compound 2, 6-dibromo-l, 4, 5, 8- tetracarboxynaphthalenedianhydride (12) was obtained by reaction of 1, 4, 5, 8-tetracarboxynaphthalenediimide with dibromoisocyanuric acid (ADBIC) according to the fol- lowing reaction scheme:
(12)
by reacting 3 g (11.2 mmoles) of 1, 4, 5, 8-tetracarboxy- naphthalenedianhydride, 6.3 g (21.9 mmoles) of dibro- moisocyanuric acid (ADBIC) and 36 ml of concentrated sulfuric acid (H2S04) (97%) .
The compound 1, 4, 5, 8-tetracarboxy-naphthalenedi- anhydride suspended in 18 ml of concentrated sulfuric acid (H2S04) (97%) was slowly added dropwise to a sus¬ pension of dibromoisocyanuric acid (ADBIC) in 18 ml of concentrated sulfuric acid (H2SO4) (97%). The tempera¬ ture of the mixture was brought to 130°C. After 10 hours at this temperature, the mixture obtained was poured into ice. The precipitate obtained was filtered and washed with water. 4.7 g of 2, 6-dibromo-l, 4, 5, 8- tetracarboxynaphthalenedianhydride (12) (quantitative yield) were obtained, after drying under vacuum.
The intermediate compound 2 , 6-dibromo-N, N' - diheptyl-1, 4, 5, 8-tetracarboxynaphthalenediimide (13) was obtained starting from the intermediate compound
(12) according to the following reaction scheme:
(13)
by reacting 4.8 g (11.2 mmoles) of 2, 6-dibromo-l, 4, 5, 8- tetracarboxynaphthalenedianhydride (12), 3.2 g (27.8 mmoles) of n-heptylamine (H2 C7H15) and 50 ml of glacial acetic acid (CH3COOH) .
Heptylamine (H2 C7H15) was added, in an inert atmos— phere, to the solution of 2, 6-dibromo-l, 4, 5, 8- tetracarboxynaphthalenedianhydride (12) in acetic acid (CH3COOH) . The temperature was brought to 100 °C. After 8 hours at this temperature, the mixture was filtered and the precipitate obtained was washed various times with ethyl ether and finally with toluene. After removing the toluene by distillation at reduced pressure, 2 g of 2, 6-dibromo-N,N' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalenediimide (13) were obtained (yield = 29%) .
The compound 2 , 6-bis (2 ' -thienyl ) -N, N' -diheptyl-
1, 4, 5, 8-tetracarboxynaphthalenediimide was finally ob¬ tained starting from the intermediate compound (13) ac¬ cording to the following reaction scheme:
by reacting 2 g (3.2 mmoles) of 2 , 6-dibromo-N, N' - diheptyl-1, 4, 5, 8-tetracarboxynaphthalenediimide (13) , 4.5 g (12.1 mmoles) of tributylstannylthiophene, 180 mg (0.16 mmoles) of palladium-tetrakistriphenylphosphine Pd [P (C6H5) 3] 4 and 120 ml of anhydrous toluene.
Tributylstannylthiophene was added, in an inert at¬ mosphere, to the toluene solution of 2 , 6-dibromo-N, N' - diheptyl-1, 4, 5, 8-tetracarboxynaphthalenediimide (13) . After removing the air present by means of vac¬ uum/nitrogen cycles, palladium- tetrakistriphenylphosphine was added. The temperature was then brought to 100°C. After 7 hours at this tem¬ perature, water was added and the mixture obtained was subjected various times to extraction with ethyl ether.
The organic extracts obtained after extraction, were washed until neutral and subsequently anhydrified on sodium sulfate and the solvent was removed by distilla¬ tion at reduced pressure. After purification by elution (eluent: heptane/dichloromethane = 20/80) on a silica gel chromatographic column, 0.5 g of 2, 6-bis (2' - thienyl) -Ν,Ν' -diheptyl-1, 4, 5, 8-tetracarboxy- naphthalenediimide (yield = 24%) and 0.5 g of 2-(2'- thienyl) -Ν,Ν' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalenediimide (yield 30%) were ob¬ tained .
The 2, 6-bis (2' -thienyl) -Ν,Ν' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalenediimide was characterized by means of 1H-NMR (200MHz; CDC13) , obtaining the following spectrum: 8.8 ppm (2H, s) ; 7.6 ppm (2H, d) ; 7.2 ppm (4H,m); 4.1 ppm (4H,t); 1.7 ppm (4H, m) ; 1.3 ppm (16H, m) ; 0.9 ppm (6H, t) .
EXAMPLE 2
Preparation of 2, 6-bis [ 5"-hexyldithien-2 ' -yl] -Ν,Ν' - diheptyl-1, 4, 5, 8-tetracarboxynaphthalenediimide
The compound 2 , 6-bis [ 5"-hexyldithien-2 ' -yl ] -N, N' - diheptyl-1, 4, 5, 8-tetracarboxynaphthalenediimide having the formula:
was synthesized according to the following reaction scheme :
Dibromoisocyanuric acid (ABDIC) , 2,6-dibromo- 1, 4, 5, 8-tetracarboxynaphthalenedianhydride (12) and 2, 6-dibromo-N,N' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalenediimide (13) were prepared ac¬ cording to the procedure described in Example 1.
The compound 2 , 6-bis [ 5"-hexyldithien-2 ' -yl ] -N, N' - diheptyl-1, 4, 5, 8-tetracarboxynaphthalenediimide was fi¬ nally obtained starting from 2 , 6-dibromo-N, N' -diheptyl- 1, 4, 5, 8-tetracarboxynaphthalenediimide (13) according to the following reaction scheme:
(13) by reacting 400 mg (0.63 mmoles) of 2 , 6-dibromo-N, N' - diheptyl-1, 4, 5, 8-tetracarboxynaphthalenediimide (13) , 30 ml of 1, 2-dimethoxyethane (DME) , 30 mg (0.02 mmoles) of palladium-tetrakistriphenylphosphine Pd [P (CeH5) 3] 4, 533 mg (1.4 mmoles) of of 5 ' -hexyl-2 , 2 ' -bithiophene-5- boronic acid pinacol ester and 806 mg (9.6 mmoles) of sodium bicarbonate (NaHCOs) .
533 mg of of 5 ' -hexyl-2 , 2 ' -bithiophene-5-boronic acid pinacol ester diluted in 10 ml of 1,2- dimethoxyethane (DME) were slowly added dropwise, in an inert atmosphere to the suspension of 400 mg of 2,6- dibromo-Ν,Ν' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalenediimide (13) and 30 mg of palla- dium-tetrakistriphenylphosphine in 30 ml of 1,2-
dimethoxyethane (DME) . 806 mg (9.6 mmoles) of sodium bicarbonate (NaHCOs) dissolved in 20 ml of distilled wa¬ ter were finally added. The temperature was brought to 90°C. After 3 hours at this temperature, water was added and the mixture obtained was subjected various times to extraction with dichloromethane . The organic extracts obtained after extraction were filtered on celite to withhold the mucilages, subsequently washed until neutral with water and anhydrified on sodium sul- fate, and the solvent was removed by distillation at reduced pressure. After purification by elution (elu- ent : hexane/ethyl acetate = 98/2) on a silica gel chro¬ matographic column and subsequent re-crystallization from dichloromethane/methanol (90/10), 250 mg of 2,6- bis [5"-hexyldithien-2' -yl] -Ν,Ν' -diheptyl-1, 4, 5, 8- tetracarboxy-naphthalenediimide (yield = 41%) were ob¬ tained, which was characterized by means of 1H-NMR (200MHz; CDCI3) , obtaining the following spectrum: 8.8 ppm (2H, s) ; 7.28 ppm (2H, d) ; 7.17 ppm (2H,d); 7.07 ppm (2H, d) ; 6.27 ppm (2H, d) ; 4.1 ppm (4H,t); 2.8 ppm (4H, t) ; 1.7 ppm (8H, m) ; 1.3 ppm (28H, m) ; 0.9 ppm (12H, t)
EXAMPLE 3
Preparation of 2 , 6-bis [ 3 ' ' ' -didodecyl-2 , 2 ' : 5 ' , 2 ' ' : 5 ' ' , 2 ' ' ' -quaterthien-5-yl] -Ν,Ν' -diheptyl-1, 4,5,8
tetracarboxynaphthalenediimide
The compound 2 , 6-bis [ 3 ' ' ' -didodecyl-
2, 2 ' : 5 ' , 2 ' ' : 5 ' ' , 2''' -quarterthien-5-yl ] -Ν,Ν' -diheptyl- 1, 4, 5, 8-tetracarboxynaphthalenediimide having the for¬ mula :
was synthesized according to the following reaction scheme :
wherein ADBIC is dibromoisocyanuric acid.
Dibromoisocyanuric acid (ADBIC), 2,6-dibromo- 1, 4, 5, 8-tetracarboxynaphthalenedianhydride (12) and
2, 6-dibromo-N,N' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalenediimide (13) were prepared ac¬ cording to the procedure described in Example 1.
The compound 2 , 6-bis [ 3 , 3 ' ' ' -didodecyl- 2,2':5',2'':5'',2''' -quarterthien-5-yl ] -Ν,Ν' -diheptyl- 1, 4, 5, 8-tetracarboxynaphthalenediimide was finally ob¬ tained starting from 2, 6-dibromo-l, 4, 5, 8- tetracarboxynaphthalenediimide (13) according to the following reaction scheme:
82 mg (0.16 mmoles) of a solution of 3,3'''-
didodecyl-2 , 2 ' : 5 ' , 2 ' ' : 5 ' ' , 2 ' ' ' -quaterthiophene-2- boronic acid pinacol ester in 5 ml 1 , 2-dimethoxyethane (DME) were slowly added dropwise, in an inert atmos¬ phere, to the solution of 50 mg (0.08 mmoles) of 2,6- dibromo-Ν,Ν' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalenediimide (13) in 5 ml of 1,2- dimethoxyethane (DME) and 5 mg of palladium- tetrakistriphenylphosphine . 100 mg (1.2 mmoles) of so¬ dium bicarbonate (NaHCOs) dissolved in 2.5 ml of dis- tilled water were finally added. The temperature was brought to 85°C. After 3 hours at this temperature, brine (saturated solution of sodium chloride) was added and the mixture obtained was subjected various times to extraction with ethyl acetate. The organic extracts ob- tained after extraction were washed until neutral and subsequently anhydrified on sodium sulfate, and the solvent was removed by distillation at reduced pres¬ sure. After purification by elution (eluent: n- heptane/ethyl acetate = 98/2) on a silica gel chroma- tographic column, 10 mg of 2 , 6-bis [ 3 , 3 ' ' ' -didodecyl-
2,2':5',2'':5'',2''' -quarterthien-5-yl ] -Ν,Ν' -diheptyl-
1, 4, 5, 8-tetracarboxynaphthalenediimide (yield = 10%) were obtained, which was characterized by means of
DCI-MS mass spectrometry: the data obtained showed the presence of a product having a molecular weight equal
to 1454.
EXAMPLE 4
Composition comprising poly (3-hexylthiophene) (P3HT) and 2, 6-bis (2' -thienyl) -Ν,Ν' -diheptyl-1, 4, 5, 8- tetracarboxy-naphthalene diimide (5%)
8.4 mg of poly (3-hexylthiophene) (P3HT) and 0.4 mg of 2, 6-bis (2' -thienyl) -Ν,Ν' -diheptyl-1, 4, 5, 8-tetracarb- oxynaphthalenediimide obtained as described in Example
1, were dissolved in 290 μΐ of chloroform. The solution was kept under stirring for 17 hours at 40°C.
The solution thus obtained was used for preparing a film having a thickness equal to 0.83 μιη, by means of spin coating, operating according to what is described above in the paragraph "method for measuring the mobil- ity of the electronic holes".
The mobility values of the electronic holes ob¬ tained as described above in the paragraph "method for measuring the mobility of the electronic holes" are in¬ dicated in Figure 1.
EXAMPLE 5
Composition comprising poly (3-hexylthiophene) (P3HT) and 2, 6-bis (2' -thienyl) -Ν,Ν' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalene diimide (10%)
8.1 mg of poly (3-hexylthiophene) (P3HT) and 0.9 mg of 2, 6-bis (2' -thienyl) -Ν,Ν' -diheptyl-1, 4, 5, 8-tetracarb- oxynaphthalene diimide obtained as described in Example
1, were dissolved in 210 μΐ of chloroform. The solution was kept under stirring for 16 hours at 40°C.
The solution thus obtained was used for preparing a film having a thickness equal to 1 μιη, by means of spin coating, operating according to what is described above in the paragraph "method for measuring the mobility of the electronic holes".
The mobility values of the electronic holes ob¬ tained as described above in the paragraph "method for measuring the mobility of the electronic holes" are in¬ dicated in Figure 2.
EXAMPLE 6
Composition comprising poly (3-hexylthiophene) (P3HT) and 2, 6-bis (2' -thienyl) -Ν,Ν' -diheptyl-1, 4, 5, 8- tetracarboxynaphthalene diimide (15%)
6.5 mg of poly (3-hexylthiophene) (P3HT) and 1.2 mg of 2, 6-bis (2' -thienyl) -Ν,Ν' -diheptyl-1, 4, 5, 8-tetracarb- oxynaphthalene diimide obtained as described in Example
1, were dissolved in 180 μΐ of chloroform. The solution was kept under stirring for 64 hours at 40°C.
The solution thus obtained was used for preparing a film having a thickness equal to 1.2 μιη, by means of spin coating, operating according to what is described above in the paragraph "method for measuring the mobil- ity of the electronic holes".
The mobility values of the electronic holes ob¬ tained as described above in the paragraph "method for measuring the mobility of the electronic holes" are in¬ dicated in Figure 3.
EXAMPLE 7
Composition comprising poly (3-hexylthiophene) (P3HT) and 2, 6-bis [ 5"-hexyldithien-2 ' -yl] -Ν,Ν' -diheptyl-
1,4,5, 8-tetracarboxynaphthalenediimide (5%)
13.3 mg of poly (3-hexylthiophene) (P3HT) and 0.7 mg of 2, 6-bis [5"-hexyldithien-2' -yl] -Ν,Ν' -diheptyl-
1, 4, 5, 8-tetracarboxynaphthalenediimide obtained as de¬ scribed in Example 2, were dissolved in 400 μΐ of chlo¬ roform. The solution was kept under stirring for 43 hours at 40°C.
The solution thus obtained was used for preparing a film having a thickness equal to 0.83 μιη, by means of spin coating, operating according to what is described above in the paragraph "method for measuring the mobil¬ ity of the electronic holes".
The mobility values of the electronic holes ob¬ tained as described above in the paragraph "method for measuring the mobility of the electronic holes" are in¬ dicated in Figure 4.
EXAMPLE 8
Composition comprising poly (3-hexylthiophene) (P3HT)
and 2, 6-bis [ 5"-hexyldithien-2 ' -yl] -Ν,Ν' -diheptyl-
1,4,5, 8-tetracarboxynaphthalenediimide (10%)
12.6 mg of poly (3-hexylthiophene) (P3HT) and 1.4 mg of 2, 6-bis [5"-hexyldithien-2' -yl] -Ν,Ν' -diheptyl- 1, 4, 5, 8-tetracarboxynaphthalenediimide obtained as de¬ scribed in Example 2, were dissolved in 330 μΐ of chlo¬ roform. The solution was kept under stirring for 72 hours at 40°C.
160 μΐ of the solution thus obtained was used for preparing a film having a thickness equal to 1.1 μιη, by means of spin coating, operating according to what is described above in the paragraph "method for measuring the mobility of the electronic holes".
The mobility values of the electronic holes ob- tained as described above in the paragraph "method for measuring the mobility of the electronic holes" are in¬ dicated in Figure 5.
EXAMPLE 9
Composition comprising poly (3-hexylthiophene) (P3HT) and 2, 6-bis [ 5"-hexyldithien-2 ' -yl] -Ν,Ν' -diheptyl-
1,4,5, 8-tetracarboxynaphthalenediimide (15%)
12.5 mg of poly (3-hexylthiophene) (P3HT) and 2.1 mg of 2, 6-bis [5"-hexyldithien-2' -yl] -Ν,Ν' -diheptyl-
1, 4, 5, 8-tetracarboxynaphthalenediimide obtained as de- scribed in Example 2, were dissolved in 340 μΐ of chlo-
roform. The solution was kept under stirring for 72 hours at 40°C.
160 μΐ of the solution thus obtained was used for preparing a film having a thickness equal to 1.3 μιη, by means of spin coating, operating according to what is described above in the paragraph "method for measuring the mobility of the electronic holes".
The mobility values of the electronic holes ob¬ tained as described above in the paragraph "method for measuring the mobility of the electronic holes" are in¬ dicated in Figure 6.
EXAMPLE 10 (comparative)
15.3 mg of poly (3-hexylthiophene) (P3HT) were dis¬ solved in 500 μΐ of chloroform. The solution was kept under stirring for 24 hours at 40°C.
160 μΐ of the solution thus obtained was used for preparing a film having a thickness equal to 0.72 μτα, by means of spin coating, operating according to what is described above in the paragraph "method for measur- ing the mobility of the electronic holes".
The mobility values of the electronic holes ob¬ tained as described above in the paragraph "method for measuring the mobility of the electronic holes" are in¬ dicated in Figure 7.
Upon comparing Figure 7 with Figures 1-6 it can be
deduced that the addition of naphthalene diimide in ac¬ cordance with the present invention causes an increase in the mobility of the electronic holes.
Claims
1. A photoactive composition with a high mobility of the electronic holes, comprising:
at least one organic photoactive polymer;
at least one naphthalene diimide having gen¬ eral formula (I) :
wherein :
Ri and R2, the same or different, are selected from linear or branched C1-C36 alkyl groups, op¬ tionally containing heteroatoms such as oxygen, nitrogen, sulphur;
R' 1 and R'2/ the same or different, are a hydro¬ gen atom, or are selected from linear or branched C1-C10 alkyl groups;
R11 and R20, the same or different, are a hydro¬ gen atom, or are selected from linear or branched C1-C16 alkyl groups;
R3, R4, R5, R6, R7, R8/ R9/ RlO/ Rl2/ Rl3/ Rl4/ Rl5/
R16, Ri7, Ri8 and R19, the same or different, are a hydrogen atom, or are selected from linear or branched C1-C16 alkyl groups;
a, b, c, d, e, f, g, and h, the same or differ¬ ent, are 0 or 1, on the condition that at least one is different from zero.
The photoactive composition with a high mobility of electronic holes according to claim 1, wherein said nic photoactive polymer is selected from:
a) polythiophenes such as poly (3-hexylthiophene)
(P3HT), poly (3-octylthiophene) , poly (3,4- ethylenedioxythiophene) ; or mixtures thereof;
b) polyphenylenevinylenes such as poly (2-methoxy-5- (2-ethylhexyloxy) -1, 4-phenylenevinylene, poly (paraphenylenevinylene) , { (poly [2-methoxy-5- (3, 7-dimethyloctyloxy) -1, 4-phenylene] -alt-
(vinylene) (MDMO-PPV) , or mixtures thereof;
c) alternate or statistic conjugated copolymers, com¬ prising :
at least one benzotriazole unit (B) having general formula (la) or (lb) :
4 4
la lb wherein the group R is selected from alkyl groups, aryl groups, acyl groups, or thioacyl groups, said alkyl, aryl, acyl and thioacyl groups, being op¬ tionally substituted;
at least one structural conjugated unit (A) , wherein each unit (B) is connected to at least one unit (A) in any one of the positions 4, 5, 6 or 7, preferably in positions 4 or 7 ; lternate π-conjugated polymers comprising:
at least one electron-acceptor fluoroarylvi- nylidene unit (A) having general formula (III) :
(III)
wherein the substituents X1-X5, the same or dif¬ ferent, are selected from hydrogen, fluorine, or from alkyl groups containing from 1 to 12 carbon atoms, and on the condition that at least one of the X1-X5 substituents is fluorine, or a -CF2R group, wherein R is selected from hydrogen, fluo¬ rine, or from hydrocarbon groups having from 1 to
10 carbon atoms, said hydrocarbon groups being op- tionally fluorinated;
at least one electron-donor conjugated struc¬ tural unit (B) , connected to the unit (A) in the points indicated by the dotted lines in general formula (III) ;
copolymers based on acridonic units, comprising: one monomeric unit (A) having general formula (IV) :
(IV)
wherein X is selected from sulfur, selenium; Y is selected from oxygen, sulfur, or from -NR' groups; R and R' , the same or different, are organic sub- stituents having from 1 to 24 carbon atoms, se¬ lected from alkyl groups, aryl groups, said alkyl groups being optionally substituted, acyl groups, thioacyl groups;
at least one monomeric unit (B) having general formula (V) : 
(V)
wherein Z is selected from 0, S, Se, or from -NR" groups, wherein R" is an organic substituent hav¬ ing from 1 to 24 carbon atoms selected from alkyl groups, aryl groups, said alkyl and aryl groups being optionally substituted, acyl groups, thioa- cyl groups; said monomeric unit (B) being con¬ nected at any available position of a side het- eroaromatic ring of the unit (A) , through one of the two positions indicated by the dotted lines in general formula (V) ;
alternate conjugated copolymers comprising ben- zothiadiazole units such as PCDTBT {poly[N-9"- hep- tadecyl-2, 7-carbazole-alt-5, 5- (4' , Ί ' -di-2-thienyl- 2' , 1' , 3' -benzothiadiazole] } , PCPDTBT {poly[2,6- (4, 4 -bis- (2-ethylhexyl) -4H-cyclopenta [ 2 , 1-b; 3, 4- b' ] -dithiophene) -alt-4, 7- (2,1,3- benzothiadiazole) ] } ;
alternate conjugated copolymers comprising thieno [3, 4-b] pyrazidinic units;
alternate conjugated copolymers comprising quinoxa- line units; 1) alternate conjugated copolymers comprising mono- meric silole units such as copolymers of 9, 9- dialchil-9-silafluorene;
1) alternate conjugated copolymers comprising con¬ densed thiophene units such as copolymers of thieno [3, 4-b] thiophene and of benzo [ 1 ,
2-b : 4 , 5- b' ] dithiophene .
3. The photoactive composition with a high mobility of the electronic holes according to claim 2, wherein said organic photoactive polymer is poly (3-hexylthiophene) (P3HT) .
4. The photoactive composition with a high mobility of the electronic holes according to claim 2, wherein said organic photoactive polymer is selected from polymers having the following general formulae:
-60-
-61-
5. The photoactive composition with a high mobility of the electronic holes according to anyone of the previ¬ ous claims, wherein in said naphthalenediimide having general formula (I), the number of carbon atoms of the substituents Ri, R2, R3, R4, R5, R6, R7, Rs R9, Rio, R11, R12, Ri3, Ri4, Ri5, Ri6, Ri7, Ri8, Ri9 and R20, is higher than or equal to 10.
6. The photoactive composition with a high mobility of the electronic holes according to claim 5, wherein in said naphthalenediimide having general formula (I), the number of carbon atoms of the substituents Ri, R2, R3,
R4, R5, R6, R7, R8 R9, RlO, Rll/ Rl2, Rl3/ l4/ l5/ l6/ l7/
Ri8, Ri9 and R20, ranges from 12 to 50.
7. The photoactive composition with a high mobility of the electronic holes according to anyone of the previ- ous claims, wherein in said naphthalenediimide having general formula (I) : - Ri and R2, the same as each other, are an alkyl group having 7 carbon atoms;
- R' i and R'2, the same as each other, are a hydrogen atom;
- R3, R4, Ri3, and R12, the same as each other, are a hy¬ drogen atom;
- d and e, the same as each other, are 1;
- a, b, c, f, g and h, the same as each other, are 0.
8. The photoactive composition with a high mobility of the electronic holes according to anyone of the claims from 1 to 6, wherein in said naphthalenediimide having general formula (I) :
- Ri and R2, the same as each other, are an alkyl group having 7 carbon atoms;
- R' 1 and R'2, the same as each other, are a hydrogen atom;
- R3, R4, R5, R6, Ri2, Ri3, Ri4 and R15, the same as each other, are a hydrogen atom;
- R11 and R20, the same as each other, are an alkyl group having 6 carbon atoms;
- c, d, e and f, the same as each other, are 0.
- a, b, g and h, the same as each other, are 1.
9. The photoactive composition with a high mobility of the electronic holes according to anyone of the claims from 1 to 6, wherein in said naphthalenediimide having general formula (I) :
- Ri and R2, the same as each other, are an alkyl group having 7 carbon atoms;
- R' i and R'2, the same as each other, are a hydrogen atom;
- R3, R5, R6, R7/ R8/ RlO/ Rll/ Rl2/ Rl4/ Rl5/ Rl6/ Rl7/ Rl9/ and R20/ the same as each other, are a hydrogen atom;
- R4, Rg, Ri3 and Ris, the same as each other, are an al¬ kyl group having 6 carbon atoms;
- a, b, c, d, e, f, g and h, the same as each other, are 1.
10. The photoactive composition with a high mobility of the electronic holes according to anyone of the previ¬ ous claims, wherein said naphthalenediimide having gen- eral formula (I) is present in a quantity ranging from 0.1% by weight to 18% by weight with respect to the weight of said photoactive organic polymer.
11. The photoactive composition with a high mobility of the electronic holes according to claim 10, wherein said naphthalenediimide having general formula (I) is present in a quantity ranging from 1% by weight to 15% by weight with respect to the weight of said photo¬ active organic polymer.
12. Use of the photoactive composition with a high mo- bility of the electronic holes according to anyone of the previous claims, in the construction of photo¬ voltaic devices, such as photovoltaic cells, photo¬ voltaic modules, solar cells, solar modules.
13. A photovoltaic device comprising the photoactive composition with a high mobility of the electronic holes according to anyone of the claims from 1 to 11.
14. Use of the photoactive composition with a high mo¬ bility of the electronic holes according to anyone of the claims from 1 to 11, in the construction of organic thin film transistors (OTFT) , or of organic field ef¬ fect transistors (OFET) .
15. A transistor selected from organic thin film transistors (OTFT) , or from organic field effect transis¬ tors (OFET) , comprising the photoactive composition with a high mobility of the electronic holes according to anyone of the claims from 1 to 11.
16. Naphthalenediimide having general formula (I):
wherein :
Ri and R2 , the same or different, are selected from linear or branched C1-C36 alkyl groups, op¬ tionally containing heteroatoms such as oxygen, nitrogen, sulfur;
R' 1 and R'2, the same or different, are a hydro- gen atom, or are selected from linear or branched C1-C10 alkyl groups;
R11 and R20, the same or different, are a hydro¬ gen atom, or are selected from linear or branched C1-C16 alkyl groups; - R3, R4, R5, R6, R7, R8/ R9/ RlO/ Rl2/ Rl3/ Rl4/ Rl5/
R16, Ri7, Ri8 and R19, the same or different, are a hydrogen atom, or are selected from linear or branched C1-C16 alkyl groups; a, b, c, d, e, f, g, and h, the same or differ- ent, are 0 or 1; on the condition that: a and h are 1 and at least one of b, c, d, e, f and g, is 1.
17. A process for the preparation of a photovoltaic de¬ vice, comprising:
- depositing on the anode a solution of the photo¬ active composition having a high mobility of the electronic holes according to anyone of the claims from 1 to 11, in order to obtain a photoactive film;
depositing a cathode on said photoactive film;
wherein, before or after the deposition of said cathode, the film is subjected to a thermal treatment at a temperature ranging from 50°C to 200°C, for a time ranging from 5 to 90 minutes.
18. The process for the preparation of a photovoltaic device according to claim 17, wherein said process comprises, before the deposition on the anode of said photoactive composition having a high mobility of the electronic holes, depositing on the anode at least one layer (anodic buffer layer) comprising an organic polymer such as poly (3, 4-ethylenedioxythiophene) polysty- rene-sulfonate (PEDOT:PSS).
19. The process for the preparation of a photovoltaic device according to claim 17 or 18, wherein said process comprises, before the deposition of said cathode, depositing on said photoactive film at least one layer (cathodic buffer layer) comprising an alkaline metal fluoride such as lithium fluoride.
20. A process for the preparation of a photovoltaic de¬ vice, comprising:
depositing on the cathode a solution of the photo¬ active composition having a high mobility of the electronic holes according to anyone of the claims from 1 to 11, in order to obtain a photoactive film;
depositing an anode on said photoactive film;
wherein, before or after the deposition of said anode, the film is subjected to a thermal treatment at a tem¬ perature ranging from 50°C to 200°C, for a time ranging from 5 to 90 minutes.
21. The process for the preparation of a photovoltaic device according to claim 20, wherein said process comprises, before the deposition of said photoactive com¬ position having a high mobility of the electronic holes on the cathode, depositing on the cathode at least one layer (cathode buffer layer) comprising an alkaline metal carbonate such as caesium carbonate, or a transi¬ tion metal oxide such as titanium dioxide.
22. The process for the preparation of a photovoltaic device according to claim 20 or 21, wherein said process comprises, before the deposition of said anode on said photoactive film, depositing at least one layer
(anode buffer layer) on said photoactive film, compris¬ ing a transition metal oxide such as vanadium oxide
(V2O5) , molybdenum oxide (M0O3) , or a phthalocyanine of a transition metal such as a copper phthalocyanine.
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| WO2014097079A1 (en) * | 2012-12-18 | 2014-06-26 | Basf Se | Semiconducting materials based on naphthalenediimide-vinylene-oligothiophene-vinylene polymers |
| US9444060B2 (en) | 2014-04-29 | 2016-09-13 | Sabic Global Technologies B.V. | Synthesis of new small molecules/oligomers with high conductivity and absorption for optoelectronic application |
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