• 专利附录
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    • 专利摘要:
    The present invention relates to void transport compositions containing an organic carrier material and a salt containing an organic cation. Preferably, the void transport composition comprises an ionic liquid. The ionic liquid effectively dopes the organic material of cargo transport. In a particular embodiment, the ionic liquid 1-butyl-1-methylpyridin-1-io bis (trifluoromethylsulfonyl) imide (bmp tfsi) was used as a dopant or additive. The invention further relates to optoelectronic and/or electrochemical devices that contain the void transport composition, in particular, solar cells based on perovskite. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2641860A1
    申请号:ES201630446
    申请日:2016-04-11
    公开日:2017-11-14
    发明作者:Shahzada Ahmad；Samrana KAZIM；Laura CALIÒ；Manuel SALADO MANZORRO
    申请人:Abengoa Research SL；
    IPC主号:
    专利说明:

    Organic materials for transporting holes containing an ionic liquid
    Technical field
    The present invention relates to hollow transport compositions, electrochemical and / or optoelectronic devices, solar cells and the use of an ionic liquid as an additive and / or dopant of a cargo transport material.
    State of the art
    Recently, perovskite-based hybrid organo-lead solar cells have shown the best performance among solid-state hybrid solar cells. The hollow transport layer in the solar organ-lead halide perovskite cells represents one of the key components for achieving high power conversion efficiency (PCE). Currently, for the best solid state devices, the doped Spiro-OMeTAD (2,2 ', 7,7'-tetrakis (N, N-di-p-methoxyphenyl amine) -9,9-spirobifluorene) has been used as hole transport material (HTM) for transporting the holes from the perovskite to the metal counter electrode. J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao, M. K. Nazeeruddin, M. Grätzel, Nature, 2013, 499, 316-319.
    However, Spiro-OMeTAD in its pure form is not very effective and leads to very low power conversion efficiencies (PCE), due to its low conductivity and mobility of the gaps, as recorded in U. Bach, D. Lupo , P. Comt, JE Mose, F. Weissortel, J. Salbeck, H. Sprietzer, M. Grätzel, Nature, 1998, 395, 583. To overcome this obstacle, lithium bis (trifluoromethane) sulfonimide salts (LiTFSI) were used , and / or cobalt complexes as p-dopants to increase the concentration of voids. In addition, 4-tert-butylpyridine (t-BP) was used as an additive to suppress charge recombination, as described in J. H. Noh, N. J. Jeon, Y. C. Choi, M.K. Nazeeruddin, M. Grätzel, S. I. Seok, J. Mater. Chem. A, 2013, 1, 11842-11847. See also J. Burschka, A. Dualeh, F. Kessler, E. Baranoff, N. -L. Cevey-Ha, C. Yi, M. K. Nazeeruddin, M. Grätzel, J. A.m. Chem. Soc. 2011, 133, 18042-18045. The addition of highly hygroscopic lithium salts is considered an intermediate solution because on the one hand it improves the photovoltaic properties of the device, while on the other hand it decreases its stability.


    The present invention attempts to provide other and / or different additives, which are effective in doping the organic void transport material used in these devices, but which do not have the disadvantages of LiTFSI, t-BP and cobalt complexes. It is therefore an objective to complement or dop the hollow transport material with
    5 compounds that do not have the drawbacks mentioned above. In particular, it is an objectiveavoid the harmful effect of lithium salt on the stability of solar cells.
    The present invention addresses the problems described above.
    SUMMARY OF THE INVENTION The present invention relates to new ionic liquids that allow for efficient doping of cargo transport materials and, when used as an additive and / or dopant to an organic hollow transport material (HTM), improve efficiently load characteristics of the material, while not affecting or even
    15 increase the stability of optoelectronic devices, in particular sensitized solar cells.
    In one aspect, the present invention provides a void transport composition comprising an organic cargo transport material and an ionic liquid that
    20 comprises an A + cation, in which A + is a 5- or 6-membered substituted or unsubstituted heterocyclic ring having 1-3 heteroatoms that are independently selected from N, S and O, with the proviso that at least one of the Heteroatoms is a quaternary nitrogen atom.
    In one aspect, the present invention provides an optoelectronic and / or electrochemical device, comprising the void transport composition of the invention.
    In one aspect, the present invention provides the use of an ionic liquid as a dopant and / or additive to a cargo transport material and / or a perovskite.
    In one aspect, the present invention provides the use of an ionic liquid as a dopant and / or additive to a cargo transport material for one or more selected from the group: - doping a cargo transport material; - Increase in cargo mobility of a cargo transport material;
    35 - Increase in the conductivity of a cargo transport material; I


    - Increased stability of cargo transport materials,and in particular materials for transporting holes (HTMs) and / or a deviceoptoelectronic and / or electrochemical comprising a load transport layer.
    In one aspect, the present invention provides a solar cell, in particular a cellsolar sensitized by dye and / or based on perovskite, which comprises the compositionfor transporting holes of the invention. In one aspect, the present invention providesa solar cell based on perovskite oxide. In one embodiment, the solar cell is asolid state solar cell, preferably a hybrid solid state solar cell.
    Brief description of the drawings:
    Figure 1 shows the J-V curves of illuminated solar cells, in accordance with the preferred embodiments of the invention compared to conventional devices. All devices contain Spiro-OMeTAD as HTM and different
    15 concentrations of BMP TFSI ionic liquid as a dopant, or the conventional LiTFSI salt and t-BP additive. One of the devices contains only the HTM and no additive.
    Figure 2 shows the efficiency of conversion of incident photons into electrons (IPCE) of the same devices as cited in Figure 1, with the exception of the device that
    20 does not contain any additives.
    Figure 3 shows the J-V curves of solar cells according to other embodiments of the invention. In these devices, BMIM TFSI ionic liquid was compared as an additive with combinations of different ionic liquids in the void transport layer.
    25 Figure 4 shows the conversion efficiency curves of electron-incident photons (IPCE) for one of the devices cited in Figure 3.
    Figure 5 shows the J-V curve of a solar cell according to an embodiment of the invention, which contains BMIM TFSI ionic liquid as a dopant.
    Figure 6 shows the normalized stability, measured for devices containing Spiro-OMeTAD as HTM and, or different concentrations of BMP TFSI ionic liquid as a dopant, or of the conventional LiTFSI salt and t-BP additive. The devices are
    35 kept at room temperature outside the glove box, with a humidity of


    Four. Five%. Devices containing ionic liquid (IL) are clearly more stable than the device containing conventional LiTFSI salt and t-BP additive.
    Figure 7 is a schematic representation of a solar cell according to a5 embodiment of the invention.
    Figure 8 is a schematic representation of a solar cell according to another embodiment of the invention.
    DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to additives and / or dopants of cargo transport materials and especially organic cargo transport materials. Preferably, the invention provides compositions and / or void transport materials. The invention relates to void transport compositions comprising organic materials.
    15 cargo transport and additives. The additives are preferably ionic liquids and / or molten salts. Preferably, molten salts and ionic liquids have hydrophobic properties.
    According to the invention, the ionic liquid comprises an A + cation, where A + is a ring
    20 substituted or unsubstituted 5 or 6 membered heterocyclic, having 1-3 heteroatoms, which are independently selected from N, S and O, with the proviso that at least one of the heteroatoms is a quaternary nitrogen atom. Said 5 or 6 membered heterocyclic ring may be further substituted by one or more substituents possibly present in said quaternary nitrogen atom.
    In one embodiment, said 5 or 6 member ring comprises a substituted nitrogen atom and optionally substituents on the carbon atoms.
    In one embodiment, the A + cation is selected from the compounds of formulas (1) - (4) to 30 below:


    R1-R10
    5 where, R1 and R2, as long as they are present, are independently selected from substituents comprising 1-30 carbon atoms and 0-20 heteroatoms provided that, in R1 and R2, said substituents are connected to the nitrogen atom by means of a simple CN link. R1-R10 and R2 in formula (2) can also be selected from H. In addition or in addition to said 0-20 heteroatoms, any
    The substituent may be independently partially or totally halogenated (Cl, Br, I, F), preferably fluorinated.
    The term "independently", in this context, means that any one or more of a group of substituents, such as R1-R10, R1 and R2, may be partially or totally
    15 halogenated, regardless of whether other substituents of the same group are halogenated or not.
    Heteroatoms are preferably selected from N, P, S, O, Se, Te, B, and Si. Preferably, said substituents comprise 1-30 carbon atoms and 0-20
    20 heteroatoms are substituents comprising 1-20 carbon atoms and 0-10 heteroatoms, more preferably they are substituents comprising 1-15 carbon atoms and 0-5 heteroatoms, more preferably 1-10 carbon atoms and 0 heteroatoms. Optional halogens are not included in that number of 0-10 or 0-5 heteroatoms.
    In one embodiment, R1-R10, R1 and R2, as long as they are present, are independently selected from C1-C30 hydrocarbons, which may be partially and / or fully halogenated, and which may be substituted by one or more selected from the alkoxy, thioalkyl, -CN and / or -NO2 groups, and where R1-R10 and optionally R2 in the formula
    30 (2) may be selected in addition to H. In one embodiment, said C1-C30 hydrocarbons are partially or fully fluorinated.
    In one embodiment, R1-R10, R1 and R2, as long as they are present, are independently selected from C1-C20 substituents, preferably aromatic and / or aliphatic C1-C12, which may be totally or partially halogenated, preferably


    fluorinated, and where R1-R10 and optionally R2 in formula (2) can be selected in addition to H.
    If a substituent is aromatic, it preferably has at least 6 carbons or 4-5 carbons and5 one or two heteroatoms of N, O and / or S.
    In one embodiment, R1 and R2, as long as they are present, are independently selected from alkyl, alkenyl, alkynyl or aryl which are substituted or unsubstituted, where said alkyl, alkenyl, alkynyl or aryl may be,
    10 independently, partially or totally halogenated, for example fluorinated. R2 in formula (2) can also be selected from H. R1 to R10, as long as they are present, they are independently selected from H and from alkyl, alkenyl, alkynyl or aryl which are substituted or unsubstituted, wherein said alkyl, alkenyl, alkynyl or aryl may be, independently, partially or totally halogenated.
    In one embodiment, the compounds with formulas (1) - (4) comprise at least one alkyl in one of R1-R10 which are present in the compound, while the others of said R1-R10, as long as are present, are H. Said alkyl may be partially or totally halogenated.
    In one embodiment, R1-R10, as long as they are present, are all H, or in the compound (1) at least one of R1-R5 is alkyl, while the others are H. Said alkyl may be partially or totally halogenated.
    In one embodiment, R1 and R2, as long as they are present, are independently R2
    selected from C1-C10 alkyl. in formula (2) it is possible to select additionally from H. Said C1-C10 alkyls may be partially or totally halogenated.
    In a preferred embodiment, R1-R10, as long as they are present, are all H, or at least one is alkyl and all others are H, and R1 and R2, as long as they are present, are independently selected. between C1-C10 alkyl. Some or more of one of said alkyls may be partially or totally halogenated. R2 in formula (2) can also be selected from H. In particular, in the pyridinium compound
    35 (1), at least one of R1-R5 is selected from H and a hydrocarbon other than H,


    preferably an alkyl (optionally partially or fully halogenated), the others being H. In one embodiment, A + is selected from the group of the pyridinium, imidazolium and / or pyrrolidinium compounds. Preferably, A + is selected from the group of pyridinium compounds and / or of
    5 imidazolium.
    In one embodiment, said pyridinium, imidazolium and / or pyrrolidinium compound, is a pyridine, imidazole and pyrrolidine ring, respectively, which is substituted on nitrogen, and which may comprise other substituents. In the case of imidazolium, one or preferably
    Both of the ring nitrogen atoms may be substituted.
    In a preferred embodiment, A + is selected from the compounds of formulas (I) and (II), respectively,
    R NR
    N R R1
    R2one
    R2
    R
    1 +
    2 4
    +
    R1 R 15 (I) (II)
    where:
    R1 and R2, as long as they are present, are independently selected from
    Substituted or unsubstituted alkyl, alkenyl, alkynyl or aryl, which, independently, may be totally or partially halogenated; R1 to R5, as long as they are present, are independently selected from H and substituted or unsubstituted alkyl, alkenyl, alkynyl or aryl, which, independently, can be totally or partially halogenated.
    In a preferred embodiment, in formulas (I) - (II), R1 to R5, as long as they are present, are H. In the structure of formula (I), at least one of R1 to R5 is selected from H and alkyl, preferably at least one of R1 to R5 is an alkyl. Preferably R4 in formula (I) is an alkyl. Said alkyl can be totally or partially
    30 halogenated.


    In a preferred embodiment, in formulas (I) - (II), R1 and R2, as long as they are present, are independently selected from alkyl, alkenyl, and substituted or unsubstituted alkynyl. Said alkyl, alkenyl and alkynyl may be,
    5 independently, totally or partially halogenated. Preferably, R1 to R5, as long as they are present, are H or alkyl. Said alkyl may be totally or partially halogenated.
    Preferably, R1 to R5, R1 and R2, as long as they are present, is selected
    10 independently of C1-C15 alkyl, C2-C15 alkenyl, C2-C15 alkynyl and C6-C15 aryl, alkyl, alkenyl, alkynyl and / or aryl, which may be partially or totally halogenated, and R1 to R8, in addition it may be selected from an H. Preferably, said alkyl, alkenyl, alkynyl or aryl is selected from C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl and C6-C12 aryl. More preferably, R1 and R2 are selected from
    C1-C10 alkyl, R4 in formula (I) is selected from C1-C10 alkyl and H, and R1 to R3 and R5 are H.
    In a preferred embodiment, A + is selected from the compounds of formulas (5) to (7), respectively, 4
    +
    N R1
    +
    2
    R2 NR1 R1
    N+
    20 (5) (6) (7)
    where:R1 and R2, as long as they are present, are independently selected fromsubstituted or unsubstituted alkyl, alkenyl, alkynyl or aryl, wherein said alkyl, alkenyl,
    Alkynyl or aryl may be, independently, partially or totally halogenated, and R4 is selected from alkyl and H, wherein said alkyl may be partially or totally halogenated. Preferably, said alkyl, alkenyl, alkynyl or aryl is selected from C1-C15 alkyl, C2-C15 alkenyl, C2-C15 alkynyl and C6-C15 aryl. Preferably, said alkyl, alkenyl, alkynyl or aryl is selected from C1-C10 alkyl, C2-C10 alkenyl, C2 alkynyl
    30 C10 and aryl C6-C12. Most preferably, R1 and R2 and are selected from C1-C10 alkyl and R4 is selected from C1-C10 alkyl and H.


    In a preferred embodiment, in any one of said pyridinium, imidazolium and / or pyrrolidinium compounds, for example, of structures (1) - (7) or (I) - (II), R1 and R2, as long as they are present, they are independently selected from C1-C10 alkyl, where one or both of said C1-C10 alkyl can be, independently, partially or
    R10
    R1
    5 fully halogenated. In these embodiments, as long as they arepresent, they are preferably H or alkyl. If any one or more of R1 to R10 is alkyl,any one or more of said alkyls may be totally or partially halogenated.
    In one embodiment, said A + cation is a di-alkyl imidazolium, where one or both of said alkyl groups can be, independently, totally or partially halogenated.
    In one embodiment, said A + cation is a methyl alkyl imidazolium, wherein said alkyl may be totally or partially halogenated. For example, said alkyl may be a C1-C10 alkyl, which may be totally or partially halogenated, for example fluorinated.
    In a preferred embodiment, said A + cation is selected from 1-butyl-3-methyl-pyridinium, 1-butyl3-methyl-imidazolium and 1-methyl-3- (3,3,4,4,5,5,6 , 6,6-nonafluorohexyl) -1H-imidazol-3-io (MFHI +), in particular 1-butyl-3-methylpyridin-1-io and 1-butyl-3-methyl-1H-imidazol-3-io . Preferably, the anion in this case can be TFSI (Bis (trifluoromethylsulfonyl) imide) ((CF3SO2) 2N-) and / or
    20 iodide, for example.
    The MFHI + cation mentioned above is an example of an A + cation comprising an alkyl substituent, which is partially fluorinated. In this case, the alkyl substituent is -CH2-CH2- (CF2) 4-CF3. The applicant noted that the presence of MFHI + iodide improves the
    Stability of the devices of the invention.
    The ionic liquid may comprise any suitable anion. For the purpose of illustration, a few structures are provided, from which the anions can be selected. In one embodiment, said ionic liquid comprises an anion selected from
    30 halides, such as chloride, bromide, fluoride, iodide and (CF3SO2) 2N-, (CF3CO2) 2N-, BF4 -,
    PF6, NO3, CH3CO2, CF3SO3, (CF3SO2) 2C -, (CF3CO2) 2C-, and N (CN) 2. Preferred anions
    they are TFSI 15 and / or iodide.
    In one embodiment, the void transport composition of the invention comprises a combination of two or more different ionic liquids. The two or more ionic liquids


    they preferably comprise A + cations that have different structures. The anions can be the same or different.
    In one embodiment, the composition of the invention comprises two ionic liquids.5 different, comprising A1 + and A2 + cations, where A1 + and A2 + are selectedA +
    independently from cations as defined elsewhere in this specification.
    In a preferred embodiment, one of the different ionic liquids comprises a
    Pyridinium compound and the other comprises an imidazolium compound. Preferably, A1 + is selected from pyridinium compounds and A2 + is selected from imidazolium compounds as defined herein.
    In a preferred embodiment, the void transport composition comprises a
    Compound (A1 +) of formula (1) and a compound (A2 +) of formula (2) as defined above. Preferably, the void transport composition comprises a compound (A1 +) of formula (I) and a compound (A2 +) of formula (II) as defined above. Preferably, the void transport composition comprises a compound (A1 +) of formula (5) and a compound (A2 +) of formula (6) as defined
    20 previously.
    In a preferred embodiment, the void transport composition comprises 1-butyl-1-methylpyridinium and 1-butyl-3-methyl-imidazolium.
    For the purposes of this specification, the total weight percentages (100% by weight%) are formed by the total of the organic cargo transport materials, the one or more ionic liquids present in the composition and compounds or additional additives optional. Preferably, the void transport composition is considered free of any solvent, and any residual solvent is not included in the percentages.
    30 provided in this specification.
    It is not excluded that the composition comprises several structurally different organic cargo transport materials. In a preferred embodiment, the composition comprises only a structurally defined organic cargo transport material, which is preferably a small molecule or a particularly characterized polymer, such as


    It is discussed in this specification elsewhere. In a preferred embodiment, the void transport composition is free of other additives in addition to the cargo transport material and one or more ionic liquids, or comprises less than 5% by weight or less than 10% molar of other additives, in addition to the Organic cargo transport material and the one or more ionic liquids.
    In a preferred embodiment, the void transport composition comprises 0.1% to 50% by weight of the ionic liquids and 50% to 99.9% by weight of the organic cargo transport material.
    In a preferred embodiment, the void transport composition comprises from 0.3% to 30% by weight of ionic liquids and from 70% to 99.7% by weight of the organic cargo transport material and optionally other additives. The other optional additives are therefore included in the percentage of organic cargo transport material (60 to 99.9% by weight).
    Preferably, the void transport composition comprises from 0.5% to 20% by weight of ionic liquids and from 80% to 99.5% by weight of organic cargo transport material and optionally other additives.
    In one embodiment, the void transport composition comprises from 1.0% to 15% by weight of ionic liquids and from 85% to 99.0% by weight of the organic cargo transport material and optionally other additives.
    In one embodiment, the void transport composition comprises from 1.25% to 10% by weight of ionic liquids and from 90% to 98.75% by weight of the organic cargo transport material and optionally other additives.
    In one embodiment, the void transport composition comprises 1.5% to 8% by weight of ionic liquids and 92% to 98.5% by weight of the organic cargo transport material and optionally other additives, preferably from 1.8% to 5% by weight of the ionic liquids and from 95% to 98.2% by weight of the organic cargo transport material and optionally other additives.


    In one embodiment, the void transport composition comprises 0.05% to 6.0% by weight of ionic liquids, preferably less than 5% by weight, and most preferably less than 1.0% to 5% by weight. of ionic liquids.
    5 In a preferred embodiment, the void transport composition is free of others.dopants or additives. Preferably, the void transport composition is free of4-tert-butylpyridine (t-BP) and / or lithium. Preferably, the transport composition ofgaps comprise less than 4% by weight, more preferably less than 2% by weight,even more preferably less than 1% by weight and most preferably less than 0.5%
    10 by weight of any one of the group selected between lithium and t-BP. A low amount or the absence of lithium ions is particularly preferred.
    If the organic void transport material is a small molecule (as opposed to a polymer), the molar concentrations of the ionic liquids compared to the
    15 organic cargo transport material can also be significant.
    In one embodiment, the void transport composition comprises 0.5% to 50% molar of the ionic liquids and 50% to 99.5% molar of the organic cargo transport material and optionally other additives. The other optional additives are included
    20 in the percentage of organic cargo transport material (50 to 99.9% molar). Preferably, the void transport composition comprises 1.0% to 40% molar of the ionic liquids and 60% to 99.0% molar of the organic cargo transport material and, optionally, other additives.
    In one embodiment, the void transport composition comprises 2.5% to 30% molar of the ionic liquids and 70% to 97.5% molar of the organic cargo transport material and optionally other additives.
    In one embodiment, the void transport composition comprises from 3% to 25%.
    30 molar of ionic liquids and 75% up to 97% molar of the organic cargo transport material and optionally other additives.
    In one embodiment, the void transport composition comprises from 4.5% to 20% molar of the ionic liquids and from 80% to 95.5% molar of the organic material of
    35 cargo transport and optionally other additives, preferably from 5% to 15% molar of


    ionic and 85% to 95% molar liquids of the organic cargo transport material and, optionally, other additives.
    As indicated above, the void transport composition is preferably substantially free of other dopants or additives. Preferably, the void transport composition comprises less than 4 molar%, more preferably less than 2.5 molar, even more preferably less than 1 molar and most preferably less than 0.5 molar of any one of the selected group between lithium and t-BP. Preferably, lithium ions are absent or present in low concentrations, as indicated.
    The void transport composition preferably comprises an ionic liquid. According to the generally used definition of the term, an "ionic liquid" is a salt that is liquid at 100 ° C. In one embodiment, the ionic liquid of the invention is liquid at 50 ° C, preferably at 40 ° C.
    A material is considered liquid, if it has measurable liquid properties, in particular, if it has the property of a fluid (as opposed to a solid body) and any measurable viscosity. According to a preferred embodiment, a material is considered as liquid, if it has a viscosity of 20,000 cps (centipoise) or less, preferably 15,000 cps or less, more preferably 10,000 cps or less, most preferably 5,000 cps or less. The terms "molten" or "co-molten" also refer to "liquid" as defined herein. The term liquid does not refer to the gaseous state.
    According to a preferred embodiment, the ionic liquid used in the present invention is liquid at room temperature or higher. The term "room temperature" refers to the temperature of 25 ° C.
    The void transport composition comprises a cargo transport material, preferably a void transport material (HTM). The cargo transport material is preferably an organic cargo transport material, such as an organic HTM. An organic charge transport material is characterized in that the electric charges, in particular the holes and electrons, move by means of electronic movement through the material. Charges are generally not transported by diffusion of molecules, as would be the case in liquid electrolytes, for example. In


    consequently, the organic cargo transport composition and / or the cargo transport material of the present invention is preferably not an electrolyte.
    In a preferred embodiment, the cargo transport material is Spiro-OMeTAD (2.2 ',
    7,7'-tetrakis (N, N-di-p-methoxyphenylamino) -9,9-spirobifluorene). However, the present invention is not limited to a particular HTM, and HTMs other than Spiro-OMeTAD can be doped or supplemented with one or more ionic liquids in accordance with the present invention.
    WO 2007/107961 discloses an organic cargo transport material, such as tris (pmethoxyethoxyphenyl) amine (TMPA) and other compounds. A particularity of these compounds is that they can be in liquid form at least during the processing of optoelectronic devices. These compounds can be used as cargo transport materials according to the present invention.
    15 Abate et al, Energy Environ. Sci., 2015,8, 2946-2953, describe triphenylamines linked by silolothiophene as transport materials for stable holes for solar cells based on perovskite with high efficiency. These cargo transport materials can also be used for the purpose of the present invention.
    FJ Ramos et al, RSC Adv., 2015.5, 53426-53432, and R. Kasparas et al, “Triazatruxenebased Hole Transporting Materials for Highly Efficient Perovskite Solar Cells, Journal of the American Chemical Society, 2015, 137 (51), 16172-16178 discloses 5,10,15-trihexyl3,8,13-trimethoxy-10-15-dihydro-5H-diindolo [3,2-a: 3 ', 2'-c] carbazole (HMDI) or 5 , 10.15-tris (4
    25 (hexyloxy) phenyl) -10,15-dihydro-5H-diindolo [3,2-a: 3 ', 2'-c] carbazole (HPDI) and other cargo transport materials based on a triazatruxene core.
    In one embodiment, the organic cargo transport material is selected from spirofluorenes, such as spiro-OMeTAD (2,2 ', 7,7'-tetrakis (N, N-di-p-methoxyphenyl amine)
    30 9,9-spirobifluorene) and derivatives of this and other spirofluorenes, carbazole and its derivatives, triazatruxen and derivatives thereof, compounds comprising the thiophene core and derivatives thereof, triphenylamine and its derivatives, acene and derivatives thereof. same, and 2 ', 7'-bis (4-methoxyphenyl) amino) spiro [cyclopenta [2,1-b: 3,4-b'] dithiophene-4,9'-fluorene and derivatives thereof.


    In one embodiment, the organic cargo transport material is 2 ', 7'-bis (4-methoxyphenyl) amino) spiro [cyclopenta [2,1-b: 3,4-b'] dithiophene-4,9'-fluorene (FDT) This compound showed interesting properties as organic cargo transport materials, in particular, when combined with the ionic liquid additive according to the invention.
    In a preferred embodiment, the organic cargo transport material is a non-polymeric compound and / or a small molecule. For the purpose of this specification, a small molecule is a compound that has a molecular weight (or molecular mass) of ≤ 5,000, preferably ≤ 4,000, more preferably ≤ 3,000 and most preferably ≤
    2,000 (dalton).
    In an alternative embodiment, the organic cargo transport material may be a polymeric compound. Examples of organic cargo transport materials are poly3,4-ethylenedioxythiophene (PEDOT), in particular PEDOT: PSS, polytriarylamines, such as (PTAA) and its derivatives containing fluorene and indenofluorene, called PF8-TAA, and PIF8-TAA, polyfluorene derivatives (PFO, TFB and PFB), polyaniline (PANI), poly (p-phenylene) (PPP), polythiophene (PT) and their derivatives, such as thiophene poly3-hexyl thiophene (P3HT) and poly (4.4 'bis (N-carbazolyl) -1,1'-biphenyl) (PPN).
    In one embodiment, the organic cargo transport material comprises one or more selected from the group of: PTAA (poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine]), P3HT (poly (3 -hexylthiophene-2,5-diyl)), PEDOT: PSS (poly (3,4-ethylenedioxythiophene): polystyrene sulfonate), PF8-TAA (poly [[(2,4-dimethylphenyl) imino] -1,4-phenylene (9,9-dioctyl-9H-fluorene-2,7diyl) -1,4phenylene]), PIF8-TAA (poly [[(2,4-dimethylphenyl) imino] -1,4-phenylene (6,12-dihydro6 , 6,12,12-tetraoctylindene [1,2-b] fluorene-2,8-diyl) -1,4-phenylene]), PFO (poly (9,9-diioctylfluorenyl-2,7-diyl), TFB (poly [(9,9-dioctyl fluorenyl-2,7-diyl) -co- (4,4 '- (N- (4-secbutylphenyl) diphenylamine)]), PFB (poly (9,9-dioctylfluorene-co-bis -N, N- (4-butylphenyl) -bis-N, N-phenyl1,4-phenylenediamine)), PANI (polyaniline), PPP (poly (p-phenylene)), PT (polythiophene), PPN (poly (4 , 4'-bis (N-carbazolyl) -1,1'-biphenyl)), S197 (triarylamine oligomer substituted with (2,4-dimethoxy-phenyl), PCPDTBT (poly- [2,1,3-benzothiadiazol-4, 7-diyl [4,4-bis (2-ethylhexyl) 4Hcyclop enta [2,1-b: 3,4b '] dithiophene-2,6-diyl]]), PCDTBT (poly - [[9- (1-octylnonyl) -9H-carbazol-2,7diyl] -2.5 -thiophenediyl-2,1,3-benzothiadiazol-4,7-diyl-2,5-thiophenediyl]), PCBTDPP (Poly [N-90heptadecanyl-2,7carbazol-alt-3,6-bis (thiophene-5-yl ) -2,5-dioctyl-2,5-dihydropyrrolo [3,4] pyrrol-1,4dione]), PDPPDBTE (poly [2,5-bis (2-decyldodecyl) pyrrolo [3,4-c] pyrrole- 1.4 (2H, 5H) -dione- (E) -1.2


    di (2,2-bitiophene-5-yl) ethene]), PTB7-Th (poly [[2,6'-4,8-di (5-ethylhexylthienyl) benzo [1,2-b; 3,3b] dithiophene] [3-fluoro-2 [(2-ethylhexyl) carbonyl] tien [3,4-b] thiophenediyl]]), PBDTTT-C (poly [(4,8-bis (2-ethylhexyloxy) benzo [1, 2-b; 4,5-b '] dithiophene) -2,6-diyl-alt- (4- (2-ethylhexanoyl) -thieno [3,4b] thiophene) -2,6-diyl]), PDPP3T ( poly [{2,5-bis (2-hexyldecyl) -2,3,5,6-tetrahydro-3,6-dioxopyrrolo [3,4-c] pyrrol-1,4-diyl} -alt - {[2 , 2 ': 5', 2 '' - tectiophene] -5.5 '' -diyl}]), and derivatives of one or more of the aforementioned.
    The non-polymeric cargo transport materials and polymers mentioned above are examples of organic materials that can be doped by the addition of an ionic liquid according to the present invention.
    The present invention encompasses optoelectronic and / or electrochemical devices comprising a void transport layer comprising the void transport composition of the invention. Examples of devices are solar cells, such as sensitized solar cells, for example dye-sensitized solar cells or perovskite-sensitized solar cells. In one embodiment, the solar cell is a solar cell of an organic-inorganic perovskite or one based on perovskite oxides. Preferably, the sensitized solar cells are solid state devices and / or lack an electrolyte, in particular, a liquid electrolyte comprising a redox pair. In one embodiment, the solar cell is a solid-state hybrid solar cell.
    Figures 7 and 8 schematically illustrate the solar cells 1 prepared according to the invention. The solar cells of the invention are generally flat and / or layered devices, comprising two opposite sides 7 and 8. The device of Figure 7 comprises a current collecting conductive layer 5, a semiconductor layer 2 of type n, a light collector or sensitized layer 3, a gap transport layer 4 and a conductive layer 6 that provides current, where the gap transport layer 4 is between said light collection layer 3 and said layer 6 to provide current , said hollow conveyor layer comprising a cargo transport composition of the invention.
    In another embodiment, the invention provides a solar cell 1, as illustrated in Figure 8, comprising a surface augmentation structure 9. The remaining reference numbers are as disclosed with respect to Figure 7. The structure surface augmentation 9 can be a nanoporous, mesoscopic structure, which can be made to


    starting from nanoparticles, for example. The surface augmentation structure 9 may be an insulating oxide, for example, alumina (Al2O3), zirconia, silicon oxide (SiO2), etc., or a semiconductor type-n material and / or may comprise the same material as the layer 2. Titanium dioxide (TiO2) or other metal oxide semiconductor materials can be used for layers 2 and / or 9, for example. The light collection layer 3 is preferably provided between the surface augmentation structure 9 and the gap transport layer 4 comprising the composition of the invention.
    Examples 1-4 and Comparative Examples 5-6 Material and methods
    The chemicals were purchased from Sigma Aldrich or Agros and were used as is. Spiro-OMeTAD represents 2,2 ', 7,7'-tetrakis (N, N-di-p-methoxyphenylamine) -9,9 spirobifluorene (Spiro-MeOTAD) was purchased from Merck KGaA, while methylamine iodide, CH3NH3I (IMA ), was synthesized according to the known bibliography.
    Device manufacturing: Perovskite (CSP) solar cell devices were manufactured in FTO-coated glass (TEC, Pilkington) patterned using laser engraving. Before any deposition, the substrates were cleaned using a Hellmanex® solution and rinsed with deionized water and ethanol. After this, they were sonicated in acetone, rinsed with ethanol and 2-propanol and dried through compressed air. A compact layer of TiO2 was deposited by spray pyrolysis at 450 ° C using 1 ml of titanium bis diisopropoxide (acetyl acetonate) as a precursor solution (75% in 2-propanol, Sigma Aldrich) in 19 ml of pure ethanol using O2 as a gas carrier. After deposition of the blocking layer (compact TiO2 layer), the substrates were maintained for an additional 30 minutes at 450 ° C for anatase phase formation. Once the samples reached room temperature, they were treated with titanium tetrachloride (TiCl4) (immersion in a 0.02M solution of TiCl4 in deionized water at 70 ° C for 30 minutes) in order to obtain a homogeneous layer. The samples were then washed with deionized water, heated at 500 ° C for 10 minutes and cooled to room temperature. After this, a mesoporous layer of TiO2 (Dyesol, 30NRD) was deposited by centrifugation coating (4,000 rpm for 30 s with an acceleration of 2,000 rpm seconds-1) and the samples were annealed by heating them progressively to 450 ° C for 2 hours. Over


    of this, a mixed cation and halide perovskite ((FAPbI3) 0.85 (MAPbBr3) 0.15) was deposited by a one-step method.
    A 1.4 M mixture of lead iodide (PbI2), lead bromide (PbBr2) and a mixture of formamidinium iodide (FAI) and methylammonium bromide (MABR) were mixed in a solvent mixture of N, N-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). The solution was prepared inside an argon glove box under controlled humidity and oxygen conditions (H2O level: <1 ppm and O2 level: <10 ppm) and kept under stirring at 80 ° C overnight with the in order to completely dissolve the PbI2. Deposition of perovskite was carried out by a one-step method with solvent engineering. In this method, the perovskite precursor solution was deposited by centrifugation over the top of the mesoporous layer at 1,000 rpm for 10 seconds and then 6,000 rpm for 30 seconds. During the second step, chlorobenzene dripped into the center of the substrate in the last 15 seconds. After solvent treatment, the films were transferred to a hot plate and annealed at 100 ° C for 60 minutes.
    HTM Preparation:For the void transport material, 72.3 mg of Spiro-MeOTAD was dissolved in 1 mlof chlorobenzene. 1-Butyl-1-methylpyridin-1-io bis (trifluoromethylsulfonyl) imide ionic liquid(BMP TFSI) was used as a dopant / additive for Spiro-MeOTAD.
    The stock solution of ionic liquid was prepared by adding 35 mg of 1-butyl-1-methylpyridin-1-io bis (trifluoromethylsulfonyl) imide (BMP TFSI) in 1 ml of acetonitrile. Then, the solutions of the void transport layer were prepared by adding different amounts of this stock solution of ionic liquid in the solution of 72.3 mg / ml Spiro-MeOTAD to obtain 0 mM, 3.2 mM, 4.7 mM , 6.1 mM and 7.5 mM concentration of BMP TFSI respectively. For comparison, the standard Spiro-MeOTAD doped solution was prepared by dissolving 72.3 mg of Spiro-MeOTAD in 1 ml of chlorobenzene, and adding as standard additives 17.5 µl of a stock solution of bis- (trifluoromethylsulfonyl) imide lithium (LiTFSI) (520 mg of LiTFSI in 1 ml of acetonitrile), 21.9 µl of a stock solution of FK209 (Tris (2- (1H-pyrazol-1-yl) -4-tert-butylpyridine) -cobalt (III) Tris (bis (trifluoromethylsulfonyl) imide))) (400 mg in 1 ml of acetonitrile) and 28.8 µl of 4-tert-butylpyridine (t-BP).


    Next, 35 µl of each HTM solution was dripped onto the perovskite substrates of the solar cell samples described above, and the samples were coated by centrifugation at 4,000 rpm for 30 seconds.
    5 Next, 80 nm of gold was used as a cathode which was thermally evaporated on theHTM under a vacuum between 1 · 10-6 and 1 · 10-5 torr, such as to obtain solar cells from theexamples.
    Characterization:
    10 Current-voltage density curves were recorded with a Keithley 2,400 measuring device under AM 1.5 G, 100 mW · cm2 illumination of a 450 W solar simulator (Oriel 94023 A) with certified AAA Class certificate, 450 W. The light power was calibrated using a calibrated certified monocrystalline silicon solar cell. A black metal mask (0.16 cm2) was used on the active area of the square solar cell (0.5
    15 cm 2) to reduce the influence of scattered light.
    IPCE measurements were made using a 150W Newport Xenon lamp coupled to a motorized Oriel Cornerstone 260 monochromator as a light source, and a 2936-R Energy Meter to measure the short-circuit current.
    20 Results and discussion: The photovoltaic performance of the devices prepared is shown in Figures 1 and 2 and in Table 1 below.
    Table 1: Photovoltaic properties of devices prepared using different concentrations of BMP TFSI ionic liquid and comparison with Spiro-OMeTAD using FK209 as a dopant, LiTFSI salt and t-BP additives.
    Example HTM compositionJSC (mA · cm-2)VOC (V)FF (%)PCE (%)
    one Spiro + BMP (3.2 mM)21.690.9958.6812.60
    2 Spiro + BMP (4.7 mM)21.171.0265.1214.06
    3 Spiro + BMP (6.1 mM)21.121.0057.9112.24
    4 Spiro + BMP (7.5 mM)20.741.0058.9012.19
    5 Standard Spiro + LiTFSI + t-BP + FK20921.370.9573.4514.96


    6 Spiro alone18.380.5732.533.45
    All HTM with BMP TFSI showed at least good or better performance than HTM 6 containing only Spiro-OMeTAD. The cell of Example 2 showed the best performance of all devices, and, in particular, a higher yield than the cell of Example 3 and 4, 5 which had a higher concentration of BMP. In the case of the solar cell of Example 6 (comparative) containing pure Spiro-OMeTAD, the open circuit voltage (Voc) and the short-circuit current density (Jsc) were about 0.57 V and 18.38 mA .cm-2, respectively. While in the case of the solar cell of Example 2, the Voc and Jsc values have been greatly improved to 1.02 V and 21.17 mA.cm-2, respectively. Filling factor 10 (FF), which reveals intrinsic resistance and the degree of charge recombination, also increased from approximately 32.5% to 65.1%. Apparently, the devices of Example 2 exhibit the optimal BMP TFSI ionic liquid concentration for HTM Spiro-OMeTAD and showed the best performance when achieving an energy conversion efficiency (PCE) of 14.06%. This PCE value is very close to that of solar cells
    Conventional based on HTM spiro-OMeTAD containing FK209 as a dopant, and additives LiTFSI and t-BP (PCE = 14.96%, Comparative Example 5).
    These results show that ionic liquids are promising candidates for doping organic cargo transport materials.
    20 Figure 2 further reveals that in all examples 1-4, a broad plateau was observed over the entire visible spectral range and up to 85% of the photons can be successfully converted to electricity in the case of the optimized concentration used in Examples 1-4. The highest IPCE was observed in the cell of Example 2. These results
    25 were in agreement with the J-V measurements.
    Table 2 shows the amounts in weight percent and mole percent of HTM and ionic liquid in the void transport compositions of Examples 1-4.
    Table 2: Molar and weight percentages of HTM and LI (ionic liquid) in the hollow transport compositions of the invention.
    Example Molar Ratio (LI / HTM)Mol (% HTM)Mol (% LI)Weight ratio (LI / HTM)Weight (% HTM)Weight (% LI)PCE (%)


    one 0.056294.75.30.019498.11.912.60
    2 0.084392.27.80.029097.22.814.06
    3 0,112489.910.10.038796.33.712.24
    4 0,140487.712.30.048495.44.612.19
    5 0.00.014.96
    6 0.0000100.00.00.0100.00.03.45
    The values of power conversion efficiencies (PCE) in Table 2 were taken from Table 1. The highest values were for the devices of Examples 1-4, but began to decrease slightly in Example 3. Consequently, were achieved
    5 especially good results when the void transport compositions (100% = HTM + LI) contained approximately 5.3% to 12.3% molar ionic liquid (87.7-94.7 mol% organic HTM) and 1.9% to 4.6% by weight of ionic liquid (98.1% to 95.4% by weight of HTM), respectively.
    10 Examples 7-12: BMIM ionic liquid combinations Solar cells were prepared as described above for Examples 1-6, using 1-butyl-3-methyl-1H-imidazol-3-io bis ((trifluoromethyl) sulfonyl) imide (BMIM TFSI) (Example 7) and combinations of BMIM TFSI with 1-butyl-3-methylpyridin-1-io bis ((trifluoromethyl) sulfonyl) imide (BMP TFSI).
    In Examples 7-12, the amount and molar concentrations of the ionic liquid (Example 7) or the combination of ionic liquids (Examples 8-12) was kept constant at the values corresponding to Example 2 above (4.7 mM) . It is observed that the molecular weight of BMIM TFSI and BMP TFSI are very similar, so that the ratios indicated in the
    20 Table 3 reflects relationships in weight, as well as molar relationships of the two cations (P.M. (BMP TFSI) = 430.05; P.M. (BMIM TFSI) = 419.36).
    Table 3: Power conversion efficiencies in solar cells based on BMIM TFSI ionic liquid and ionic liquid combinations.
    Example HTM compositionVoc (V)Jsc (mA · cm-2)FF (%)PCE (%)
    7 BMIM (4.7 mM)1.0117.6151.249.09


    8 BMIM: BMP 3: 2 (4.7 mM)0.9815.7549.757.66
    9 BMIM: BMP 2: 3 4.7 mM)0.9915.5349.517.64
    10 BMIM: 1: 1 BMP (4.7 mM)0.9519.4746.778.63
    eleven BMIM: BMP 2: 1 (4.7 mM)0.8715.0932.084.21
    12 BMIM: BMP 1: 2 (4.7 mM)0.8819.5340.086.87
    In Examples 7-12, solar cells containing void transport compositions containing combinations of different ionic liquids in organic void transport materials did not achieve power conversion efficiencies as high as cells containing a single ionic liquid such as dopant / additive. On the other hand, the combinations provide additional advantages over the stability of solar cells.

    权利要求:
    Claims (13)
    [1]
    1. A hollow transport composition comprising an organic cargo transport material and an ionic liquid comprising an A + cation, where A + is a ring
    5 substituted or unsubstituted 5 or 6-membered heterocyclic having 1-3 heteroatoms, which are independently selected from N, S and O, with the proviso that at least one of the heteroatoms is a quaternary nitrogen atom.
    [2]
    2. The void transport composition of claim 1, wherein said ring of
    10 or 6 members comprises a substituted nitrogen atom and optionally substituents on the carbon atoms.
    [3]
    3. The void transport composition of any of the preceding claims,
    wherein said 5 or 6 member ring comprises a substituent on the 15 carbon atoms.
    [4]
    4. The void transport composition of claim 1, wherein A + is selected from the group of pyridinium, imidazolium and / or pyrrolidinium compounds.
    The void transport composition of claim 4, wherein said pyridinium, imidazolium and / or pyrrolidinium compound is a pyridine, imidazole and pyrrolidine ring, respectively, which is substituted on nitrogen, and which may comprise Other substituents
    The void transport composition of any of the preceding claims,
    where A + is selected from the compounds of formulas (1) to (4),3
    R5
    RR
    3 6
    2 4
    1 R
    2 RR3 R8
    R
    RR 45
    R
    R R4
    RR
    8 10
    R
    R
    fifteen
    R
    R NR
    + 7 9
    R1 2N
    R
    R 2R
    R R1 (1) R (2) R2R1 (3) R2 R1 (4)
    where:

    R1 and R2, as long as they are present, are independently selected from substituted or unsubstituted alkyl, alkenyl, alkynyl or aryl, wherein said alkyl, alkenyl, alkynyl
    or aryl can, independently, be partially or totally halogenated;R1 to R10, as long as they are present, are independently selected from H and from
    5 alkyl, alkenyl, alkynyl or substituted or unsubstituted aryl, wherein said alkyl, alkenyl, alkynyl or aryl may be, independently, partially or totally halogenated.
    [7]
    7. The void transport composition of any of the preceding claims,
    wherein A + is selected from the compounds of formulas (5) to (7),4
    R
    R2+
    R1
    +
    N
    N
    +
    R2N NR1 R1
     10 (5) (6) (7)
    where:R1 and R2, as long as they are present, are independently selected from alkyl,substituted or unsubstituted alkenyl, alkynyl or aryl, wherein said alkyl, alkenyl, alkynyl
    15 or aryl can be, independently, partially or totally halogenated, and R4, as long as it is present, is selected from alkyl and from H, where said alkyl can be partially or totally halogenated.
    [8]
    8. The void transport composition of any of claims 6 and 7, in the
    20 that, in said pyridinium, imidazolium and / or pyrrolidinium compounds, R1 and R2, as long as they are present, are independently selected from C1-C10 alkyl, R4 is selected from H and C1-C10 alkyl, where any one or both of said C1-C10 alkyl may be, independently, partially or totally halogenated.
    The void transport composition of any of the preceding claims, wherein A + is selected from 1-butyl-1-methylpyridinium, 1-butyl-3-methyl-imidazolium, and 1-methyl-3 (3, 3,4,4,5,5,6,6,6-nonafluorohexyl) -1 H-imidazol-3-io.
    [10]
    10. The void transport composition of any one of the preceding claims, wherein said ionic liquid comprises an anion selected from halides, such

    as chloride, bromide, fluoride, iodide and of (CF3SO2) 2N-, (CF3CO2) 2N-, BF4-, PF6-, NO3-,
    CH3CO2-, CF3SO3-, (CF3SO2) 2C -, (CF3CO2) 2C-, and N (CN) 2-.
    [11]
    11. The hollow transport composition of any of the claims
    5 above, which comprises from 0.1% to 50% by weight of ionic liquids and from 50% to 99.9% by weight of the organic cargo transport material.
    [12]
    12. The void transport composition of any of the preceding claims, wherein said organic cargo transport material is selected from 10 spirofluorenes, such as spiro-OMeTAD (2,2 ', 7,7'-tetrakis (N , N-di-p-methoxyphenyl amine) -9,9-spirobifluorene), derivatives of this and other spirofluorenes, carbazole and its derivatives, triaza-truxen and its derivatives, compounds comprising the thiophene core and its derivatives, triphenylamine and derivatives thereof, acene and its derivatives, 2 ', 7'-bis (4-methoxyphenyl) amino) spiro [cyclopenta [2,1-b: 3,4-b'] dithiophene-4,9'-fluorene and derivatives of the
    15 same.
    [13]
    13. An optoelectronic and / or electrochemical device, comprising the void transport composition of any of claims 1-12.
    The optoelectronic and / or electrochemical device of claim 13, comprising a void transport layer, the void transport layer comprising the void transport composition of any one of claims 1-13.
    [15]
    15. The optoelectronic and / or electrochemical device of claim 13 or 14, which is a solar cell sensitized by dye or by light collection.
    [16]
    16. The optoelectronic and / or electrochemical device of any of claims 13 to 15, which is a solar cell based on organic-inorganic perovskite or perovskite oxides.
    [17]
    17. The use of the hollow transport composition of any of claims 1 to 12 as a dopant and / or additive to a perovskite solar cell.



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    同族专利:
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    CN108559014B|2018-03-29|2020-09-08|南方科技大学|Organic polymer, hole transport material comprising same, solar cell, and light-emitting electronic device|
    CN109309161A|2018-09-13|2019-02-05|华南师范大学|A kind of application of ionic liquid, solar cell device and preparation method thereof|
    GB201819380D0|2018-11-28|2019-01-09|Univ Oxford Innovation Ltd|Long-term stable optoelectronic device|
    WO2020113094A1|2018-11-30|2020-06-04|Nuvation Bio Inc.|Pyrrole and pyrazole compounds and methods of use thereof|
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