 Organic materials for transport of holes for opto-electronic devices (Machine-translation by Google
专利摘要:
The present invention relates to new hole transport materials (Hole Transporting Materials, HTMs) and optoelectronic and/or electrochemical devices comprising the new hole transporting materials. In some aspects, HTMs comprise a nucleus based on thienothiophene, dithienothiophene or benzothiazolo (piazthiol). The center is preferably conjugated via π with the part of triarylamine, carbazolo or diindolocarbazolo, and the latter can be substituted by alkoxy groups. The HTMs thus obtained constitute an alternative to the Spiro-OMeTAD. The synthesis of the latter is complex and expensive. (Machine-translation by Google Translate, not legally binding) 公开号:ES2659663A1 申请号:ES201631098 申请日:2016-08-16 公开日:2018-03-16 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:
2 Description Organic void transport materials for opto-electronic devices Technical field 5 The present invention relates to new compounds for use as void transport materials (Hole Transporting Materials, HTMs) in optoelectronic and / or electrochemical devices and in cells solar comprising the compounds of the invention. 10 State of the art and problems solved by the invention The first solid state cell sensitized by a dye, manufactured using Spiro-OMeTAD as a hollow transport material (HTM), showed a power conversion efficiency (PCE) of 0. 74% After decades of optimization of these devices, an efficiency of 7 was reached. 2%, using cobalt complexes as a p-type dopant. Recent advances in the application of lead organo-halide perovskite for the manufacture of thin-layer solar cells have led to a remarkable level of power conversion efficiency of more than 22%, placing these cells among the 20-layer photovoltaic technology thin more emerging. The potential of perovskites as a light absorber was first revealed in 2009 for solar cells sensitized by a dye (dye sensitized solar cells, DSSCs) with a liquid electrolyte, with a mere efficiency of 3. 8% Currently, a power conversion efficiency (PCE) measured more than six times in a solid state configuration has been reached. This incredible increase in the efficiency of power conversion of the solar cells based on perovskite, has motivated researchers to focus their studies on new configurations and on the optimization of crystalline formation. In all these developed configurations, Spiro-OMeTAD is the obvious choice as a hollow transport material (HTM). Recently, some articles show new organic semiconductors that can be used as HTM, although these materials present difficulties and difficult synthesis methods, and their use is therefore limited to manufacturing on the laboratory scale. The classic Spiro-OMeTAD3 shows the best results both in perovskite cell and in DSSCs in their doped state. However, Spiro-OMeTAD suffers from a multi-step synthesis and complex purification, which moves away from its commercial viability. In addition, it works efficiently only when dopants are added as metal complexes and / or other additives. The use of dopants / additives of Spiro-OMeTAD induces the instability of the devices and also its oxidized state of Spiro-OMeTAD acts as a filter in the visible region at 520 nm due to absorption. Therefore, different inorganic polymers, small organic molecules and conjugated polymers have been developed as HTMs in the manufacture of perovskite solar cells. The 10 best efficiencies were obtained with materials such as CuSCN (12.4%), carbazole derivative molecule (14.6%) and polytriarylamine [PTAA] (16.2%). Narrow energy band separation polymers have also been used as HTMs similar to their energy bandwidth separation counterparts using perovskite as a light collector, and the highest PCE reached was 9.2%. 15 An important limitation in the performance of perovskite solar cells may be the discrepancy between series resistance and drift resistance. In general, a thick layer of HTM is required to avoid short circuits but this also increases the resistance in series. Therefore, it is very important to find a cost-effective HTM that has desirable conductivity and high load mobility to reduce series resistance and at the same time create a thin layer free of defects. An efficient HTM must have good thermal stability, high hole mobility, high conductivity and a higher occupied molecular orbital level (HOMO) above the valence band of the perovskite to achieve efficient hole transport. Of course, such HTMs must be obtainable by simple synthetic procedures. The object of the invention is to provide a novel void transport material that can be used in optoelectronic devices, such as organic light emitting diodes (OLED) and solar cells based on a light collector, such as dye-sensitized solar cells. or solar cells based on perovskite. Ideally, HTMs should avoid the disadvantages of Spiro-OMeTAD but also allow high power conversion efficiency. 4 The present invention addresses the problems described above. Summary of the Invention In one aspect, the present invention provides new compounds comprising the structure of any one of formulas (I), (II) and / or (III): SSSR1R2 (I) SSR2R1 (II) NSNR2R1 (III ) 10 where R1 and R2 are independently selected from the substituents of formulas (1), (2) or (3) below: NR1R5R4R3R8R2R10R9R6R7NR3R4R1R5R7R2R8R9R17R16R15NNNR3R4R1R5R7R8R2R9 (single line) on the single line multiple links by which the substituent of formula (1), (2) or (3), respectively, is connected directly or in a manner conjugated to the structure of formulas (I), (II) or (III);5 where from R1 to R10, to the extent present, is independently selected from H, halogen, -R19, -O-R20, -S-R20, and -NR20R21; where R19, R20 and R21 are independently selected from C1-C30 and / or C4-C30 aliphatic substituents, which can, independently, be totally or partially halogenated and can, independently, be further substituted by additional substituents, and in which R20 and R21 can also be selected from H; wherein R15, R16, and R17 are independently selected from H and C1-C30 and / or C4-C30 aliphatic substituents, which may, independently, be totally or partially halogenated and may, independently, be further substituted by additional substituents; 10 wherein said additional substituents of said C1-C30 aliphatic and / or C4-C30 aromatic substituents can be independently selected from -R24, -O-R22, -S-R22, and -NR22R23, wherein R22, R23 and R24 they are independently selected from C1-C20 aliphatic and / or C4-C20 aromatic substituents, where R22 and R23 can also independently be selected from H, and where said C1-C20 aliphatic and / or C4-C20 aromatic substituents can independently be totally or partially halogenated. In one aspect, the present invention provides new compounds comprising a nucleus selected from a thienothiophene, dithienetiophene and benzothiazolo (piatzolo), a nucleus that is preferably pi-conjugated to one independently selected from a triarylamine, a carbazolo, and a diinodolocarbazolo. The latter may be substituted, for example with alkoxy groups. In one aspect, the present invention provides the use of the compounds of the invention as hollow transport material (HTM), preferably an organic HTM. In one aspect, the present invention provides an optoelectronic and / or electrochemical device, comprising one or more compounds according to the invention's invention. In one aspect, the invention provides an optoelectronic and / or electrochemical device comprising a void transport layer, the void transport layer comprising one or more compounds according to the invention. In one aspect, the invention provides a solar cell comprising one or more compounds of the invention. In one aspect, the invention provides a solar cell sensitized by a light collector comprising one or more compounds of the invention. In one aspect, the invention provides organic-inorganic perovskite-based solar cells comprising one or more compounds according to the invention's invention. In one aspect, the invention provides a method for producing an optoelectronic 10 and / or electrochemical device wherein the method comprises the step of providing a device comprising a void transport layer, said void transport layer comprising one or more compounds of The present invention. Other preferred aspects and embodiments of the present invention are provided in the detailed description below and in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the synthetic route used for the preparation of 4,4 '- (dithiene [3,2-b: 2, 3'-20 d] thiophene-2,6-diyl) bis (N , N-diphenylaniline) (DTT-TPA2, compound 100), a void transport material of an embodiment of the present invention. Figure 2 shows the optical absorption spectrum of DTT-TPA2 in a dichloromethane solution. 25 Figure 3 shows the J-V curve (left) and the efficiency of conversion of incident photons into electrons (IPCE) (right) for solar cells based on DTT-TPA2 as HTM. Figure 4 shows the synthetic route used for the preparation of thieno [3,2-b] thiophene-2,5-30 diyl) bis (N, N-diphenylaniline) (TT-TPA2, compound 101), a transport material of gaps of an embodiment of the present invention. 7 Figure 5 shows the optical absorption spectrum of TT-TPA2 in a dichloromethane solution. Figure 6 shows the J-V curve for solar cells based on the HTM TT-TPA2. 5 Figure 7 shows the synthetic route used for the preparation of 4,4 '- (benzo [c] [1,2,5] thiadiazol-4,7-diyl) bis (N, N-diphenylaniline) (BDT-TPA2 , compound 102), as a void transport material of an embodiment of the present invention. Figure 8 shows the optical absorption spectrum of BDT-TPA2 (Fig. 7) in a solution of dichloromethane. Figure 9 shows the synthetic route used for the preparation of 2,6-di (9H-carbazol-9-yl) dithiene [3,2-b: 2 ', 3'-d] thiophene (DTT-CB2, compound 103 ), as a void transport material of an embodiment of the present invention. 15 Figure 10 shows the optical absorption spectrum of DDT-CB2 (Fig. 9) in a dichloromethane solution. Figure 11 shows the DTT-CB2 cyclovoltamogram (Fig. 9), measured in a 0.1 20 M solution of tetra-n-butylammonium hexafluorophosphate in a dichloromethane solution using a carbon electrode as a working electrode, as a reference electrode and as a Pt electrode with Fc electrode / Fc + as internal standard. Figure 12 shows the J-V curve for solar cells based on the HTM DTT-CB2 HTM. Figures 13 A and B show the synthetic route used for the preparation of 4,4 '- (dithiene [3,2-b: 2', 3'-d] thiophene-2,6-diyl) bis (N, N-bis (4-methoxyphenyl) aniline) (DTT-OMeTPA2, compound 104, Fig. 13, part B), a void transport material of an embodiment of the present invention. 30 Figure 14 shows the optical absorption spectrum of DTT-OMeTPA2 (Fig. 13 B). 8 Figure 15 shows the DTT-OMeTPA2 cyclovoltamogram (Fig. 13 B) measured as described with respect to fig. eleven. Figure 16 shows the J-V curve for doping and non-doping DTT-OMeTPA2 solar cells. 5 Figure 17 shows the IPCE of solar cells containing different concentrations of doped and undoped DTT-OMeTPA2 (Fig. 13B). Figure 18 shows the synthetic route used for the preparation of 2,6-bis (3,6-dimethoxy-9H-10 carbazol-9-yl) dithiene [3,2-b: 2 ', 3'-d] thiophene (DTT-OMeCB2, compound 106), a void transport material of an embodiment of the present invention. Figure 19 shows the optical absorption spectrum of DTT-OMeCB2 (Fig. 18). 15 Figure 20 shows the J-V curve for solar cells containing different concentrations of doped and undoped DTT-OMeCB2. Figure 21 shows the synthetic route used for the preparation of 2,6-bis (5,10,15-tris (2-ethylhexyl) -10,15-diidro-5H-diindolo [3,2-a: 3 ', 2'-c] carbazol-3-yl) dithiene [3,2-b: 2 ', 3'-d] thiophene (DTT-20 EHDI2, compound 107), a hollow transport material of an embodiment of the present invention. Figure 22 shows the optical absorption spectrum of DTT-EHDI2 (Fig. twenty-one). 25 Figure 23 shows the J-V curve for solar cells containing doped DTT-EHDI2. Figure 24 shows the IPCE of solar cells containing different concentrations of doped DTT-EHDI2. Figure 25 shows the synthetic route used for the preparation of 2,5-di (9H-carbazol-9-yl) thieno [3,2-b] thiophene (TT-CB2, compound 108), a transport material of gaps of an embodiment of the present invention. 9 Figure 26 shows the optical absorption spectrum of TT-CB2 (Fig. 25, compound 108). Figure 27 shows the TT-CB2 cyclovoltamogram, measured as described with respect to fig. eleven. 5 Figure 28 shows the J-V curve for solar cells containing doped and undoped TT-CB2. Figure 29 shows the IPCE for solar cells containing doped TT-CB2 and not doped. Figure 30 shows the synthetic route used for the preparation of 2,5-bis (3,6-dimethoxy-9H-carbazol-9-yl) thieno [3,2-b] thiophene (TT-OMeCB2, compound 109), as a hollow transport material of an embodiment of the present invention. 15 Figure 31 shows the optical absorption spectrum of TT-OMeCB2 (Fig. 30, compound 109). Figure 32 shows the J-V curve for solar cells containing doped TT-OMeCB2. 20 Figure 33 shows the IPCE of solar cells containing different concentrations of doped TT-OMeCB2. Figure 34 is a schematic representation of a perovskite-based solar cell according to an embodiment of the invention. Figure 35 is a schematic representation of a solar cell based on perovskite according to another embodiment of the invention. 30 Detailed description of preferred embodimentsThe present invention provides one or more compounds selected from compounds comprising the structure of any one of formulas (I), (II) and / or (III): SSSR1R2 (I) SSR2R1 (II) NSNR2R1 (III) . For the purpose of the present invention, the term "comprising" means "includes, among others." It is not intended to mean "consists only of". In one embodiment, said structures of formulas (I), (II) or (III) are selected from the structures of formulas (Ia), (IIa) and (IIIa), respectively: SSSR1R2 (Ia) SSR1R2 (IIa) NSNR1R2 (IIIa). In a preferred embodiment, the compound of the present invention is selected from a compound consisting of the structure of any one of formulas (I), (II) or (III), or of compounds comprising or consisting of formulas (Ia), (IIa), (IIIa), (IV), (V), (VI), (VII), (VII), (VIII), (IX), (X), (XI), ( XII), and of (13) - (21), as set forth below. In the compounds of formulas (I), (Ia), (II), (IIa), (III) and (IIIa), R1 and R2 are preferably independently selected from the substituents of formulas (1), (2) or (3) below: 2011 NR1R5R4R3R8R2R10R9R6R7NR3R4R1R5R7R2R8R9R17R16R15NNNR3R4R1R5R7R8R2R9 (1) (2) (3) where the dotted line represents a single CC link or multiple links by which the substituent of either formula (1), directly (3), of (1) 5 conjugated to the structure of formulas (I), (II) or (III); where from R1 to R10, to the extent herein, is independently selected from H, halogen, -R19, -O-R20, -S-R20, and -NR20R21; where R19, R20 and R21 are independently selected from C1-C30 10 and / or C4-C30 aliphatic substituents, which can, independently, be totally or partially halogenated and can, independently, be further substituted by additional substituents, and in which R20 and R21 can also be selected from H; wherein R15, R16, and R17 are independently selected from H and C1-C30 and / or C4-C30 aliphatic substituents, which can, independently, be totally or partially halogenated and can, independently, be further substituted by additional substituents; wherein said additional substituents of said C1-C30 aliphatic and / or C4-C30 aromatic substituents can be independently selected from -R24, -O-R22, -S-R22, and -NR22R23, wherein R22, R23 and R24 are independently select from aliphatic substituents C1-C20 and / or aromatic C4-C20, where R22 and R23 can also independently be selected from H, and where said aliphatic substituents C1-C20 and / or aromatic C4-C20 can, independently, be halogenated totally or partially. 12 Preferably, said C1-C30 aliphatic and / or C4-C30 aromatic substituents from which R19, R20, R21, R15, R16, and R17 are preferably selected from C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkenyl, alkynyl, C5-C30 aryl (C6-C30 or aryl), C4-C30 heteroaryl, wherein said alkyl, alkenyl, and alkynyl can be independently linear, branched or cyclic. On the other hand, said alkyl, alkenyl, alkynyl, aryl and heteroaryl can be, independently, partially or totally halogenated. In one embodiment, R15, R16, and R17 are different from H. For the purpose of the present specification, the halogens are selected from Cl, Br, I and F. In one embodiment, said halogen is independently selected from F and Cl. Said C1-C20 aliphatic and / or C4-C20 aromatic substituents are preferably independently selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C20 aryl (or C6-C20 aryl), C4-C20 heteroaryl, wherein said alkyl, alkenyl, and alkynyl may be, independently, linear, branched or cyclic. In addition, said alkyl, alkenyl, alkynyl, aryl and heteroaryl may, independently, be partially or totally halogenated. In one embodiment, R19, R20, R21, R15, R16, and R17 are independently selected from C1-C20 and / or C4-C20 aliphatic substituents, preferably as defined above, wherein said aliphatic C1-C20 alkyl and / or C4-C20 aromatic substituents can be, independently, totally or partially halogenated and can, independently, be more substituted. R20, R21, R15, R16, and R17 can also be selected from H. Additional optional substituents can be independently selected from -R24, -O-R22, -S-R22, -NR22R23, in which R22, R23 and R24 can, independently, be selected from C1-C15 and / or aromatic aliphatic substituents C4-C15, preferably as defined below, and in which R22 and R23 can also independently be selected from H, and wherein said C1-C15 aliphatic and / or aromatic C4-C15 substituents can be, independently, totally or partially halogenated . Preferably, R15-R17 are different from H. Said C1-C15 aliphatic and / or C4-C15 aromatic substituents are preferably independently selected from C1-C15 alkyl, C2-C15 alkenyl, C2-C15 alkynyl, C5-C15 aryl (or13 C6-C15 aryl), C4-C15 heteroaryl, wherein said alkyl, alkenyl, and alkynyl can be, independently, linear, branched or cyclic. In addition, said alkyl, alkenyl, alkynyl, aryl and heteroaryl may, independently, be partially or totally halogenated. In one embodiment, R19, R20, R21, R15, R16, and R17 are independently selected from the 5 C1-C15 aliphatic and / or C4-C15 aromatic substituents, preferably as defined above, wherein said C1-C15 aliphatic substituents s and / or aromatic C4-C15 can be, independently, totally or partially halogenated and can, independently, be more substituted. R20, R21, R15, R16, and R17 can also be selected from H. Additional optional substituents can be independently selected from -10 R24, -O-R22, -S-R22, -NR22R23, in which R22, R23 and R24 independently are selected from C1-C10 and / or aromatic C4-C12 aliphatic substituents, preferably as defined below, in which R22 and R23 can also independently be selected from H, and in which said C1-C10 and / or aromatic C4-C12 aliphatic substituents can, independently, be totally or partially halogenated. Said C1-C10 aliphatic and / or C4-C12 aromatic substituents are preferably independently selected from C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C5-C12 aryl (or C6-C12 aryl), C4-C12 heteroaryl , wherein said alkyl, alkenyl, and alkynyl can be, independently, linear, branched or cyclic. On the other hand, said alkyl, alkenyl, alkynyl, aryl and heteroaryl can be, independently, partially or totally halogenated. In one embodiment, R19, R20, R21, R15, R16, and R17 are independently selected from C1-C10 and / or C4-C12 aliphatic substituents, preferably as defined above, wherein said C1-C10 aliphatic substituents and / or C4-C12 aromatics can be, independently, totally or partially halogenated and can, independently, be more substituted. R20, R21, R15, R16, and R17 can also be selected from H. Additional optional substituents can be independently selected from -R24, -O-R22, -S-R22, -NR22R23, in which R22, R23 and R24 can independently be selected from C1-C5 and / or aromatic C4-C12 aliphatic substituents , preferably as defined below, and in which R22 and R23 can also independently be selected from H, and wherein said C1-C5 aliphatic and / or C4-C12 aromatic substituents14 may, independently, be totally or partially halogenated. In one embodiment, R15, R16, and R17 are different from H. Said C1-C5 aliphatic and / or C4-C12 aromatic substituents are preferably independently selected from C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkenyl, alkynyl, C5-C12 aryl 5 (or C6-C12 aryl), C4- C12 heteroaryl, wherein said alkyl, alkenyl, and alkynyl can be, independently, linear, branched or cyclic. In addition, said alkyl, alkenyl, alkynyl, aryl and heteroaryl may, independently, be partially or totally halogenated. In one embodiment, R19, R20, R21, R15, R16, and R17 are independently selected from the 10 C1-C5 aliphatic and / or C4-C12 aromatic substituents, preferably as defined above, wherein said C1-C5 aliphatic substituents and / or C4-C12 aromatics can be, independently, totally or partially halogenated and can, independently, be more substituted. R20, R21, R15, R16, and R17 can also be selected from H. Additional optional substituents can be independently selected from -R24, -O-R22, -S-R22, -NR22R23, in which R22, R23 and R24 can independently be independently selected from C1-C4 and / or aromatic aliphatic substituents C4-C6, preferably as defined below, in which R22 and R23 can also independently be selected from H, and wherein said C1-C4 aliphatic and / or C4-C6 aromatic substituents can, independently, be wholly or partially 20 halogenated. In one embodiment, R15, R16, and R17 are different from H. Said C1-C4 aliphatic and / or C4-C6 aromatic substituents are preferably independently selected from C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C5-C6 (or C6-aryl) aryl, C4-C6 heteroaryl, wherein said alkyl, alkenyl, and alkynyl can be, independently, linear, branched or cyclic. On the other hand, said alkyl, alkenyl, alkynyl, aryl and heteroaryl can be, independently, partially or totally halogenated. In one embodiment, R19, R20 and R21 are independently selected from C1-C4 aliphatic and / or C4-C6 aromatic substituents, preferably as defined above, in which R20 and R21 are also independently selected from H; wherein R15, R16, and R17 are independently selected from C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkenyl,Alkynyl, C6-C12 aryl, C4-C10 heteroaryl, and H, wherein said alkyl, alkenyl, and alkynyl may be independently linear, branched or cyclic. On the other hand, said alkyl, alkenyl, alkynyl, aryl and heteroaryl can be, independently, partially or totally halogenated. In one embodiment, R15, R16, and R17 are different from H. 5 In one embodiment, R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10, to the extent currently, are all H. In a preferred embodiment, in formulas (I), (Ia), (II), (IIa), (III) and (IIIa), one or more of the group consisting of R1 and R3-R6 (or R3-R5 as applicable) and one of the group consisting of R2 and R7-10 R10 (or R7-R9 as the case may be) is different from H, the others are H. In these embodiments, said one (or more) of the group consisting of R1 and R3-R6 (or R3-R5 as appropriate) and one (or more) of the group consisting of R2 and R7-R10 (or R7-R9 as applicable) which is different from H is preferably selected from substituents as defined above. For example, said substituent other than H can be selected from -R19, -O-R20, -S-R20, and -NR20R21, wherein R19, R20, and R21, are independently selected from C1-C30 aliphatic substituents and / or C4-C30 aromatics, preferably as defined above, wherein R20 and R21 may, independently, also be H, wherein said C1-C30 aliphatic and / or C4-C30 aromatic substituents may, independently, be substituted. additionally by -R24, -O -R22, -S-R22, -NR22R23, wherein R22, R23 and R24 are independently selected from C1-C20 and / or aromatic C4-C20 aliphatic substituents, preferably as defined above, and in which R22 and R23 are more can be selected from H. Other embodiments set forth above, for example, where R19, R20 and R21 are aromatic C1-C20 and / or C4-C20 aliphatic substituents (R20 and R21 may, independently, also be H), which may be further substituted, also apply in the indicated terms. Preferably, said one or more different from H are independently selected from R19 and from O-R20, the others being H. In a preferred embodiment, in the formula (I), (Ia), (II), (IIa), (III) 30 and (IIIa), R1 and R2 are different from H, the others (R3-R10 or R3- R9 as applicable) being H. In a preferred embodiment, the substituents of the group consisting of R1 and R3-R6 (or R3-R5 as the case may be) and of the group consisting of R2 and R7-R10 (or R7-R9 as the case may be) that are different from H are identical. For example, they are -O-R22, as defined in this specification. In a preferred embodiment, in formulas (I), (Ia), (II), (IIa), (III) and (IIIa), R3-R10 (or R3-R5 and R7-R9 as the case may be) are H, and, R1 and R2 are independently selected from -R19, -O-R20 and H, preferably from -O-R20 and -R19. In one embodiment of the compounds of formulas (I), (Ia), (II), (IIa), (III) and (IIIa), R1 and R2 are selected from the substituents of formulas (1) and (2 ), preferably (1). In a preferred embodiment, R1 to R10, to the extent currently, are independently selected from H, -O-R20 and -R19 as defined above. R15, R16, and R17 as far as present, are independently selected from -R19 as defined above. In one embodiment, the compound of the invention is selected from the following compounds of formulas (IV), (V) and (VI): NNSSSR6R5R1R4R7R8R2R10R9R3R4R1R5R6R7R8R2R10R9R3 (IV)17 NSSSNR3R4R1R5R9R8R2R7R9R8R2R7R3R4R1R5 (V) R17R16R15NNNSSSR17R16R15NNNR9R2R8R7R5R1R4R3R3R4R1R5R7R8R2R9 (VI). R1 to R10, (or R1 to R9, as appropriate), R15, R16 and R17 are preferably as defined above with respect to formulas (I), (Ia), (II), (IIa), (III) and (IIIa), or in this specification 5 elsewhere. In one embodiment, the compound of the invention is selected from the compounds of formulas (VII), (VIII) and (IX) below:18 NR6R5R1R4R7R8R2R10R9R3SSNR3R4R1R5R6R7R8R2R10R9 (VII) SSNR3R4R1R5R9R8R2R7NR9R8R2R7R3R4R1R5 (VIII) R17R16R15NNNR3R4R2R3R1R9R2R3R1R9R3R1R9R2 R1 to R10, (or R1 to R9, as appropriate), R15, R16 and R17 are preferably as defined above with respect to formulas (I), (Ia), (II), (IIa), (III) and (IIIa), or in this specification 5 elsewhere. In a preferred embodiment, in the compound of formula (VII) above, R1 and R2 are19 preferably different between alkoxy, in particular, different from methoxy. In a preferred embodiment, R1 and R2 are independently selected from H, alkyl and S-alkyl. In one embodiment, these embodiments apply not only to R1 and R2, but through R1 R10 of compound (VII) in general. In a preferred embodiment, the compound of the invention is selected from the following compounds of formulas (X), (XI) and (XII): NR6R5R1R4R7R8R2R10R9R3NSNNR3R4R1R5R6R7R8R2R10R9 (X) NSNNR3R4R1R5R9R8R2R4R9R8R3R4R5R5R5R5R5R520 R17R16R15NNNR9R2R8R7R5R1R4R3NSNR17R16R15NNNR3R4R1R5R7R8R2R9 (XII) In the compounds of formulas (IV) - (XII), R1 -R10 (or R1 -R5 and R7- R9 as the case may be), and R15 currently measured, they are preferably as defined above with respect to formulas (I), (Ia), (II), (IIa), (III) and (IIIa), or in this specification elsewhere. In one embodiment, in the compounds of formulas (IV) - (XII), R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10, to the extent currently, are selected independently of H, halogen, -R19, -O-R20, -S-R20, -NR20R21, wherein R19, R20 and R21 are independently selected from C1-C30 and / or aromatic C4-C30 aliphatic substituents, preferably 10 as defined above, and in which R20 and R21 can also be independently selected from H, wherein said C1-C30 and / or C4-C30 aliphatic substituents can, independently, be totally or partially halogenated and can, independently, be also substituted by other substituents. R15, R16, and R17 are independently selected from H and C1-C30 aliphatic and / or C4-C30 aromatic substituents, 15 preferably as defined above, which can be, independently, totally or partially halogenated and can, independently, be further substituted for additional substituents. Said additional substituents of said C1-C30 aliphatic and / or C4-C30 aromatic substituents may be independently selected from -R24, -O-R22, -S-R22, and -NR22R23, wherein R22, R23 and R24 are independently selected from C1-C20 aliphatic and / or C4-C20 aromatic substituents, preferably as defined above, in which R22 and R23 can also be21 independently selected from H, and wherein said C1-C20 and / or C4-C20 aliphatic substituents can be, independently, totally or partially halogenated. Preferably, and to the extent applicable, the indications and preferred embodiments made above with respect to (I), (Ia), (II), (IIa), (III) and (IIIa) also apply. to the compounds of formulas (IV) - (XII). Preferably, said C1-C30 and / or C4-C30 aliphatic substituents are those defined above. In particular, in an embodiment of the compounds of formulas (IV) - (XII), R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10, to the extent currently, are selected independently of H, halogen, -R19, -O-R20, -S-R20, -NR20R21; wherein R19, R20, R21, R15, R16, and R17 are independently selected from C1-C20 and / or C4-C20 aliphatic substituents, preferably as defined above, wherein said C1-C20 aliphatic substituents and / or C4-C20 aromatics may, independently, be totally or partially halogenated and may, independently, be further substituted. R20, R21, R15, R16, and R17 can also be selected from H. Additional optional substituents can be independently selected from -R24, -O-R22, -S-R22, -NR22R23, in which R22, R23 and R24 can independently be selected from C1-C15 and / or C4 aromatic substituents -C15, preferably as defined above, and in which R22 and R23 can also independently be selected from H, and wherein said C1-C15 and / or aromatic C4-C15 aliphatic substituents can be, independently, totally or partially halogenated. Preferably, R15-R17 are different from H. In an embodiment of the compounds of formulas (IV) - (XII), R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10, to the extent currently, are independently selected from H , halogen, -R19, -O-R20, -S-R20, -NR20R21; wherein R19, R20, R21, R15, R16, and R17 are independently selected from C1-C15 and / or C4-C15 aliphatic substituents, preferably as defined above, wherein said C1-C15 and / or aliphatic C4-C15 aromatic substituents may be, independently, totally or partially halogenated and may, independently, be further substituted. R20, R21, R15, R16, and R17 can also be selected from H. Optional additional substituents may22 independently selected from -R24, -O-R22, -S-R22, -NR22R23, in which R22, R23 and R24 can independently be selected from C1-C10 and / or C4-C12 aliphatic substituents, preferably as defined above, wherein R22 and R23 can also independently be selected from H, and wherein said C1-C10 and / or aromatic C4-C12 aliphatic substituents can, independently, be totally or partially halogenated. In one embodiment of the compounds of formulas (IV) - (XII), R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10, to the extent currently, are independently selected from H, halogen, -R19, -O-R20, -S-R20, -NR20R21; wherein R19, R20, R21, R15, R16, and R17 are independently selected from C1-C5 and / or C4-C12 aliphatic substituents, preferably as defined above, wherein said C1-C5 aliphatic substituents and / or C4-C12 aromatics may be, independently, totally or partially halogenated and may, independently, be further substituted. R20, R21, R15, R16, and R17 can also be selected by H. Additional optional substituents 15 can be independently selected -R24, -O-R22, -S-R22, -NR22R23, wherein R22, R23 and R24 can independently be independently selected from the C1-C4 aliphatic and / or C4 aromatic substituents C6, preferably as defined above, in which R22 and R23 can also independently be selected by H, and wherein said C1-C4 aliphatic and / or C4-C6 aromatic substituents can be, independently, totally 20 or partially halogenated. In one embodiment, R15, R16, and R17 are different from H. In one embodiment of the compounds of formulas (IV) - (XII), R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10, to the extent currently, are independently selected from H, halogen, -R19, -O-R20, -S-R20, -NR20R21; wherein R19, R20 and R21 are independently selected from the C1-C4 and / or C4-C6 aliphatic substituents, preferably as defined above, wherein said C1-C4 and / or C4-C6 aliphatic substituents can be , independently, totally or partially halogenated, and in which R20 and R21 are also independently selected from H; wherein R15, R16, and R17 are independently selected from C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkenyl, alkynyl, C6 -30 C12 aryl, C4-C10 heteroaryl, and H, wherein said alkyl, alkenyl, and alkynyl can be, independently, linear, branched or cyclic. On the other hand, said alkyl, alkenyl,Alkynyl, aryl and heteroaryl may be independently partially or totally halogenated. In one embodiment, R15, R16, and R17 are different from H. In one embodiment of the compounds of formulas (IV) - (XII), R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10, to the extent currently, are independently selected from H, halogen, -5 R19, -OR20, -SR20, -NR20R21; wherein R19, R20 and R21 are independently selected from the C1-C4 and / or C4-C6 aliphatic substituents, preferably as defined above, wherein said C1-C4 and / or C4-C6 aromatic substituents may be, independently, totally or partially halogenated, and in which R20 and R21 are also independently selected from H; wherein R15, R16, and R17 are independently selected from C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkenyl, alkynyl, C6-C12 aryl, C4-C10 heteroaryl, and H, wherein said alkyl, alkenyl, and alkynyl can be, independently, linear, branched or cyclic. On the other hand, said alkyl, alkenyl, alkynyl, aryl and heteroaryl can be, independently, partially or totally halogenated. In one embodiment, R15, R16, and R17 are different from H. In an embodiment of the compounds of formulas (IV) - (XII), R1 -R10, to the extent currently, are independently selected from H, -O -R20 and -R19, in which R20 and R19 are independently as defined above. R15, R16, and R17 are preferably independently selected from -R19 as defined above. In a preferred embodiment, the substituents of formula (1), (2) or (3) are selected from substituents of the formulas (1a), (2a) and (3a) below: NR2R1NR1R2R17R16R15NNNR1R2 (1a) (2a) ( 3a). 2524 Preferably, in the substituents (1a), (2a) and (3a), R1, R2, R15, R16 and R17 are as defined above with respect to formulas (I), (Ia), (II), ( IIa), (III), (IIIa), and (IV) - (XII) or in this specification elsewhere. Preferably, R1, R2, R15, R16 and R17 are different from H but otherwise as defined above or elsewhere in this specification. In one embodiment, R1 and R2 are selected from H, -O -R20 and -R19, in which R20 and R19 are independently as defined above. R15, R16, and R17 are preferably independently selected from -R19 as defined above. In a preferred embodiment, the compound of the invention is selected from among the 10 compounds of formulas from (13) to (21) below: NNSSSR1R2R2R1 (13) NSSSNR1R2R1R2 (14) R17R16R15NNNSSSR17R16R15NNNR1R2R1R2 (15) NSSNR1R2R1R2R1R2R1R2R1R1R2SSR17R16R15NNNR17R16R15NNNR2R1R1R2 (18) NNSNNR1R2R1R2 (19) NNSNNR1R2R1R2 (20) R17R16R15NNNNSNR17R16R15NNNR1R2R1R2 (21). Preferably, in compounds (13) - (21), R1, R2, R15, R16 and R17, to the extent present, they are as defined above with respect to formulas (I), (Ia), ( II), (IIa), (III), (IIIa) and (IV) - (XII), or in this specification elsewhere. Preferably, R15, R16 and R17 are different from H but otherwise as defined above. In the compound of formula (16) R1 and R2 are preferably different from alkoxy, in particular, different from methoxy. In a preferred embodiment, R1 and R2 are independently selected from H and alkyl. In one embodiment, the indications and preferred embodiments made above with respect to (I), (Ia), (II), (IIa), (III), (IIIa) and (IV) - (XII) are they also apply to the compounds of the formulas (13) - (21) and to the substituents (1a), (2a) and (3a). In one embodiment, in the compounds of formulas (13) - (21), R1, R2 are independently selected from H, halogen, -R19, -O-R20, -S-R20, -NR20R21; where R19, R20 and R21 are26 independently select from among the C4-C30 aromatic substituents (preferably as defined above), which can be, independently, totally or partially halogenated and can, independently, be further substituted by other C1-C30 aliphatic substituents and / or and which R20 and R21 can also be selected from H. R15, R16, and R17 are independently selected from H and C4-C30 aromatic substituents (preferably as defined above) C1-C30 aliphatic and / or, which may be, independently, totally or partially halogenated and may, independently, be additionally substituted by other substituents; wherein said additional substituents of said C1-C30 aliphatic and / or C4-C30 aromatic can be independently selected from -R24, -O-R22, -S-R22, and -NR22R23, wherein R22, R2310 and R24 they are independently selected from C1-C20 aliphatic and / or C4-C20 aromatic substituents, preferably as defined above, in which R22 and R23 can also independently be selected from H, and wherein said aliphatic C1-C20 substituents and / or C4-C20 aromatics can be, independently, totally or partially halogenated. Preferably, R15, R16, and R17 are different from H. In particular, in one embodiment of the compounds of formulas (13) - (21), R1, R2 are independently selected from H, halogen, -R19, -O-R20, -S-R20, -NR20R21; wherein R19, R20, R21, R24, R15, R16, and R17 are independently selected from the C1-C20 aliphatic and / or C4-C20 aromatic substituents, preferably as defined above, wherein said C1- aliphatic substituents C20 and / or aromatic C4-C20 can be, independently, totally or partially halogenated and can, independently, be more substituted. R20, R21, R15, R16, and R17 can also be selected from H. Additional optional substituents can be independently selected from -R24, -O-R22, -S-R22, -NR22R23, in which R22, R23 and R24 can, independently, be selected from the C1-25 C15 aliphatic and / or aromatic substituents C4-C15, preferably as defined above, and in which R22 and R23 can also independently be selected from H, and wherein said C1-C15 aliphatic and / or aromatic C4-C15 substituents can be, independently, totally or partially halogenated. Preferably, R15-R17 are different from H. In one embodiment of the compounds of formulas (13) - (21), R1, R2 are independently selected from H, halogen, -R19, -O-R20, -S-R20, -NR20R21; wherein R19, R20, R21, R15, R16, and R17 are independently selected from the C1-C15 and / or aliphatic substituents27 C4-C15 aromatics, preferably as defined above, wherein said C1-C15 aliphatic and / or C4-C15 aromatic substituents may, independently, be totally or partially halogenated and may, independently, be further substituted. R20, R21, R15, R16, and R17 can also be selected from H. Additional optional substituents can be independently selected from -R24, -O-R22, -S-R22, and -NR22R23, in which R22, R23 and R24 can independently be selected from C1-C10 and / or C4 aromatic substituents. C12, preferably as defined above, in which R22 and R23 can also independently be selected from H, and wherein said C1-C10 and / or aromatic C4-C12 aliphatic substituents can, independently, be totally or partially halogenated. In an embodiment of the compounds of formulas (13) - (21), R1, R2 are independently selected from H, halogen, -R19, -O-R20, -S-R20, -NR20R21; wherein R19, R20, R21, R15, R16, and R17 are independently selected from C1-C5 and / or C4-C12 aliphatic substituents, preferably as defined above, wherein said C1-C5 aliphatic substituents and / or C4-C12 aromatics may, independently, be totally or partially halogenated and may, independently, be further substituted. R20, R21, R15, R16, and R17 can also be selected from H. Additional optional substituents can be independently selected from -R24, -O-R22, -S-R22, and -NR22R23, in which R22, R23 and R24 can independently be independently selected from the 20 aliphatic substituents C1-C4 and / or C4-C6 aromatics, preferably as defined above, in which R22 and R23 can also independently be selected from H, and wherein said C1-C4 aliphatic and / or C4-C6 aromatic substituents can, independently, be wholly or partially halogenated In one embodiment, R15, R16, and R17 are different from H. In one embodiment of the compounds of formulas R1, R2 are independently selected from H, halogen, -R19, -O-R20, -S-R20, -NR20R21; wherein R19, R20, R21, are independently selected from the C1-C4 and / or C4-C6 aliphatic substituents, preferably as defined above, wherein said C1-C4 30 and / or C4-C6 aromatic substituents can be, independently, totally or partially halogenated and may, independently, be further substituted, and in which R20 and R21 can also be independently selected from H; wherein R15, R16, and R17 are selected28 independently of C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkenyl, alkynyl, C6-C12 aryl, C4-C10 heteroaryl, and H, wherein said alkyl, alkenyl, and alkynyl may be, independently, linear, branched or cyclic. On the other hand, said alkyl, alkenyl, alkynyl, aryl and heteroaryl can be, independently, partially or totally halogenated. In one embodiment, R15, R16, and R17 are different from H. In an embodiment of the compounds of formulas R1, R2 are independently selected from H, halogen, -R19, -OR20, -SR20, -NR20R21; wherein R19, R20 and R21 are independently selected from the C1-C4 and / or C4-C6 aliphatic substituents, preferably as defined above, wherein said C1-C4 10 and / or C4-C6 aliphatic substituents can be , independently, totally or partially halogenated and can, independently, be further substituted, and in which R20 and R21 can also be independently selected from H; wherein R15, R16, and R17 are independently selected from C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkenyl, alkynyl, C6-C12 aryl, C4-C10 heteroaryl, and H, wherein said alkyl, alkenyl , and alkynyl can be, independently, linear, branched or cyclic. On the other hand, said alkyl, alkenyl, alkynyl, aryl and heteroaryl can be, independently, partially or totally halogenated. In one embodiment, R15, R16, and R17 are different from H. In a preferred embodiment, R1, R2 are selected from H and -O-R20, -S-R20, and -R19, with R19 and 20 R20 which can be independently a linear, branched or cyclic C1-C20 alkyl , alkenyl or alkynyl and in which R15, R16, and R17, to the extent herein, is selected from branched, linear or cyclic C1-C20 alkyl, alkenyl or alkynyl, and R3-R10, to the extent herein , are H. In a preferred embodiment, R1, R2 are selected from H and -O-R20, -S-R20, and -R19, with R19 and R20 which can be a linear alkyl, branched or cyclic C1-C15 alkyl, preferably a C1-C10 alkyl, and more preferably a C1-C5 alkyl. In one embodiment, R15, R16, and R17, to the extent currently, are selected from branched, linear or cyclic C1-C20 alkyl, alkenyl or alkynyl. In a preferred embodiment, R15, R16, and R17, to the extent currently, are selected from branched, linear or cyclic C1-C15 alkyl, alkenyl or alkynyl, C1-C12 alkyl, preferably branched. 29 In one embodiment, R15, R16, and R17, to the extent currently, are selected from branched, linear or cyclic C1-C20 alkyl, alkenyl or alkynyl. In a preferred embodiment, R15, R16, and R17, to the extent currently, are selected from branched, linear or cyclic C1-C15 alkyl, alkenyl or alkynyl, C1-C12 alkyl, preferably branched. In a preferred embodiment of the compound of structures (I) - (III), (Ia), (IIa), (IIIa), (IV) - (XII), (13) - (21) and the substituents of the formulas (1) - (3) and (1a) - (3a), R1 and R2 are identical. For example, they are identical substituents that are different from H. In one embodiment of the invention, the compounds are selected from the compounds (100), (101), (102), (103), (104), (106), (107), (108), (109) . In one embodiment of the invention, the compounds are selected from: 4,4 '- (dithiene [3,2-b: 2', 3'-d] thiophene-2,6-diyl) bis (N, N-diphenylaniline ) (DTT-TPA2), 15 4.4 '- (thieno [3,2-b] thiophene-2,5-diyl) bis (N, N-diphenylaniline) (TT-TPA2), 4,4' - ( benzo [c] [1,2,5] thiadiazol-4,7-diyl) bis (N, N-diphenylaniline) (BDT-TPA2), 2,6-di (9H-carbazol-9-yl) dithiene [3 , 2-b: 2 ', 3'-d] thiophene (DTT-CB2), 4,4' - (dithiene [3,2-b: 2 ', 3'-d] thiophene-2,6-diyl) bis (N, N-bis (4-methoxyphenyl) aniline) (DTT-OMeTPA2), 2,6-bis (-9-yl-3,6-dimethoxy-9H-carbazole) dithiene [3,2-b: 2 ', 3'-d] thiophene (DTT-OMeCB2), 2,6-bis (5,10,15-tris (2-ethylexyl) -10,15-diidro-5H-diindolo [3,2-a: 3 ', 2'-c] carbazol-3-yl) dithiene [3,2-b: 2', 3'-d] thiophene (DTT-EHDI2), 2,5-di (9H-carbazol-9-yl) thieno [3,2-b] thiophene (TT-CB2), 2,5-bis (3,6-dimethoxy-9H-carbazol-9-yl) thieno [3,2-b] thiophene (TT-OMeCB2), and combinations of two 25 or more of the above. In one embodiment, the compound of the invention is not a polymer and / or does not comprise a polymer. Preferably, the compound of the invention is a "small molecule." In one embodiment, the molecular weight of the compound of the invention is 3. 500 g / mol, preferably 30 2. 500 g / mol, preferably 2. 000 g / mol, more preferably 1. 700 g / mol, even more preferably 1. 600 g / mol, more preferably 1. 000 g / mol In another embodiment, the weight of the compound of the invention is 2. 000 g / mol, preferably 1. 800 g / mol, more preferably 1. 700 g / mol, even more preferably 1. 500 g / mol, more preferably 1. 100 g / mol The present invention encompasses optoelectronic and / or electrochemical devices comprising a void transport layer comprising the void transport composition of the invention. Devices for example are solar cells, such as sensitized solar cells, for example dye sensitized or perovskite sensitized solar cells. In one embodiment, the solar cell is a solar cell based on organic-inorganic perovskite or perovskite oxides. Preferably, the sensitized solar cells 10 are solid state devices and / or without electrolyte, in particular, a liquid electrolyte comprising a redox pair. In one embodiment, the solar cell is a solid state hybrid solar cell. Figures 34 and 35 schematically illustrate the solar cells by way of example 1 of 15 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 34 comprises a current collector layer 5, a semiconductor layer of type n 2, a light collecting or sensitizing material 3, a gap transport layer 4 and a layer that provides the realization of current 6 , wherein the 20-hole transport layer 4 is provided between said light-collecting layer 3 and said current provided by layer 6, said hole-carrying layer comprises a cargo transport composition of the invention. In solar cells sensitized by a dye or by a light collecting material in the present invention, the light collecting material layer is preferably an organic-inorganic perovskite. Such light collectors are described, for example, in WO2014 / 020499 and WO2014 / 0180789. In another embodiment, the invention provides a solar cell 1, as illustrated in Figure 35, 30 comprising a surface increase of structure 9. The remaining reference numbers correspond to those described with respect to Figure 34. The surface augmentation structure 9 can be a nanoporous and / or mesoscopic structure, which can be made to31 starting from nanoparticles, for example. The surface augmentation structure 9 can be an insulating oxide, for example, alumina (Al2O3), zirconium oxide, silica (SiO2), etc. , or of type n semiconductor and / or may comprise the same material as layer 2. TiO2 or other metal oxide semiconductor materials can be used for layers 2 and / or 9, for example. The light collecting layer 3 is preferably provided between the surface increasing layer 9 and the gap transport layer 4 comprising the compounds of the invention. The hollow layer or transport material of the device herein may comprise one (1) hollow transport compound of the present invention, a mixture 10 comprising two or more structurally different hollow transport compounds of the invention, or a mixture comprising two or more structurally different void transport compounds, of which at least one is preferably selected from the compounds of the invention. In a preferred embodiment, the hole transport layer may comprise one or more additives in addition to the organic material transported from holes of the invention, such additives may be selected, for example, from the group consisting of lithium salt bis (trifluoromethylsulfonyl) amine (LiTFSI), tert-buthylpyridine (t-PA), tris (2- (1H-pyrazol-1-yl) -4-tert-butylpyridine) cobalt (III) tri [bis (trifluoromethane) sulfonimide ] (FK209) and combinations of two or more of the above, are preferably used as doping agents. Examples Example 1 below describes the general procedure that was used for the preparation of perovskite-based solar cells containing the various HTMs the synthesis of which is described in Examples 2-10. Example 1: Preparation and characterization of perovskite-based solar cells Perovskite (PSC) solar cells were manufactured on FTO 30 coated glass (TEC, Pilkington) laser-labeled. Before any deposition, the substrates were cleaned using a Hellmanex solution and rinsed with deionized water and ethanol. After this, they were ultrasonicized in acetone, rinsed with ethanol and 2-propanol and32 dried through compressed air. A compact TiO2 layer was deposited by pyrolysis spray at 450 ° C using 1 ml of a solution of titanium diisopropoxide bis (acetyl acetonate) (75% in 2-propanol, Sigma Aldrich) in 19 ml of pure ethanol using O2 as carrier gas. After deposition of the blocking layer (TiO2 compact layer), the substrates were maintained for an additional 30 minutes at 450 ° C for anatase phase formation. Once the samples 5 reached room temperature, they were treated with 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. Then, the samples were washed with deionized water, burned to 500 ° C for 10 minutes and cooled to room temperature. After this, a mesoporous layer of TiO2 (Dyesol, 30NRD) was deposited by coating by centrifugation 10 (4. 000 rpm for 30 s) and the samples were annealed by heating progressively to 450 ° C for 2 hours. On top of this, a mixed perovskite layer of organic cation and halide ((FAPbI3) 0.85 (MAPbBr3) 0. 15) was deposited by a one step method. A mixture of 1.4 M of lead iodide (PbI2), lead bromide (PbBr2) and a mixture of 15 formamidinium iodide (FAI) and methyl ammonium bromide (MABr) were mixed in a mixture of N solvents, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The solution was prepared inside a glove box in an argon atmosphere under conditions of humidity and controlled oxygen (H2O level: <1 ppm and the level of O2: <10 ppm) and kept under stirring at 80 ° C overnight in order to completely dissolve PbI2. Deposition 20 of the perovskite was carried out by a one-step method with solvent engineering. In this method, the perovskite precursor solution was deposited by rotation coating on top of the mesoporous layer at 1,000 rpm for 10 seconds and then 6000 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 samples were transferred to a hot plate and tempered at 100 ° C for 60 minutes. The HTM was dissolved in 1 ml of chlorobenzene. Then, 35 µl of each HTM solution was administered on the perovskite substrates of the solar cell samples described above and a 4,000 rpm rotation coating was applied to the samples for 30 seconds.33 After that, approximately 80 nm of metal cathode (gold or silver) was thermally evaporated on top of HTM under a vacuum level between 110-6 and 110-5 torr. Characterization: Current-voltage density curves were recorded with a Keithley 5 2400 measuring device under AM 1.5 G, 100 mWcm2 with illumination of a certified AAA Class, 450 W solar simulator (Oriel 94023 A). The light power was calibrated using a solar cell certified monocrystalline silicon cell. A black metal mask (0.16 cm2) was used as an active area of the square solar cells (0.5 cm2) during the measurement to reduce the influence of scattered light. 10 IPCE measurements were made using a 150W Newport Xenon lamp coupled to a motorized Oriel Cornerstone 260 ¼ m mono-Chromator as a light source, and a 2936-R Energy Meter to measure the short-circuit current. Example 2: 4,4 '- (dithiene [3,2-b: 2', 3'-d] thiophene-2,6-diyl) bis (N, N-diphenylaniline) (DTT-TPA2) DTT-TPA2 (compound 100) is prepared according to the scheme shown in Fig. 1. First, 2,6-dibromoditiene [3,2-b: 2 ', 3'-d] thiophene (0.1 g ; 0.28 mmol), (4- (diphenylamino) phenyl) boronic acid (0.2 g; 0.7 mmol), K2CO3 (2 M, 4 ml) and Pd (PPh3) 4 (35 mg, 0.03 mmol) were dissolved in THF (20 ml). The reaction mixture was stirred at reflux in the dark for 12 h, then allowed to cool and poured into water. The organic layer was dried over 20 MgSO4, concentrated and the residue mixture was purified by column chromatography on silica gel with CH2Cl2 / hexane = 4: 1 as eluent to obtain the product as a bright yellow solid. 1 H NMR (400 MHz, CD 2 Cl 2) = 7.57-7.54 (m; 4H, PhH); 7.49 (s, 2H, thiophene); 7.35-7.31 (m, 8H, PhH); 7.18 to 7.9 (m, 16H, PhH). Molecular weight: 682.16 g / mol. Figure 2 shows the optical absorption spectrum of DTT-TPA2 in dichloromethane solvent. 25 Figure 3 shows the J-V curve (left) and IPCE (right) for solar cells using DTT-TPA2 as HTM. Example 3: 4,4 '- (thieno [3,2-b] thiophene-2,5-diyl) bis (N, N-diphenylaniline) (TT-TPA2) TT-TPA2 (compound 101) is prepared according to The scheme shown in Fig. 4. In brief 2,5-dibromothiene [3,2-b] thiophene, (0.1 g; 0.336 mmol), (4- (diphenylamino) phenyl) boronic acid (0.2 g; 0.7 mmol), K2CO3 (2 M, 4 ml) and Pd (PPh3) 4 (35 mg, 0.03 mmol) were dissolved in THF (20 ml). The reaction mixture was stirred at reflux in the dark for 12 h, then left34 cool and poured into water. The organic layer was dried over MgSO4, concentrated and the residue mixture was purified by column chromatography on silica gel with CH2Cl2 / hexane = 4: 1 as eluent to obtain the product as a bright yellow solid. 1 H NMR (400 MHz, CD 2 Cl 2) = 7.95-7.93 (m, 4H, PhH); 7.81 (s, 2H, thiophene); 7.35-7.31 (m, 8H, PhH); 7.18 to 7.09 (m, 16H, PhH). Molecular weight: 626.19 g / mol. Figure 5 shows the optical absorption spectrum of TT-TPA2 in dichloromethane. Since the molecules do not have a high absorption in the UV part of electromagnetic spectra, they are expected to have good stability. Example 4: 4,4 '- (benzo [c] [1,2,5] thiadiazol-4,7-diyl) bis (N, N-diphenylaniline) (BDT-TPA2) 10 BDT-TPA2 (compound 102) prepared according to the scheme shown in Fig. 7. In summary, 4,7-dibromobenzo [c] [1,2,5] thiadiazole (0.1 g; 0.34 mmol), boronic acid (4- (diphenylamino) phenyl) boronic (0.25 g; 0.85 mmol), K2CO3 (2M, 4 ml) and Pd (PPh3) 4, (35 mg, 0.03 mmol) were dissolved in THF (20 ml). The reaction mixture was stirred at reflux in the dark for 12 h, then allowed to cool and poured into water. The organic layer was dried over MgSO4, concentrated and the residue mixture was purified by column chromatography on silica gel with CH2Cl2 / hexane = 3: 1 as eluent to obtain the product as an orange solid (203 mg, Y = 96%) 1 H NMR (400 MHz, CD 2 Cl 2) = 7.95-7.93 (m; 4H, PhH); 7.81 (s, 2H, benzodithiazole); 7.37-7.33 (m, 8H, PhH); 7.23 to 7.12 (m, 16H, PhH). MS (MALDI-TOF): m / z calculated for C42H30N4S: 622.219; Found: 622.210. As with TT-TPA2, the absorption of BDT-TPA2 in the UV part of electromagnetic spectra (Fig. 8) indicates the high stability of the molecules. Example 5: 2,6-di (9H-carbazol-9-yl) dithiene [3,2-b: 2 ', 3'-d] thiophene (DTT-CB2) DTT-CB2 (compound 103) is prepared according with the scheme shown in Fig. 9. 25 In summary, 2,6-dibromoditiene [3,2-b: 2 ', 3'-d] thiophene (150 mg; 0.423 mmol), carbazolo (156 mg; 0.932 mmol), Pd (dba) 2 (39 mg, 0.04 mmol), X-Phos (40 mg, 0.084) and NaOtBu (244 mg, 2.54 mmol) were dissolved in dry toluene (50 ml). The reaction mixture was then stirred at reflux in the dark for two days under N2 atmosphere. Then, the reaction mixture was allowed to cool, filtered through celite®, washed with water twice and extracted with CH2Cl2. The organic layer was dried over MgSO4, concentrated and the residue mixture was purified by column chromatography on silica gel with hexane / CH2Cl2 = 70:30 as eluent to obtain the product as a light brown solid (100 mg, Y = 45%) 1 H NMR (400 MHz,CD2Cl2) = 8.20 to 8.18 (d; J = 8 Hz, 4H, carbazole); 7.65-7.63 (d, J = 8 Hz, 4H, carbazole); 7.61 (s, 2H, thiophene); 7.55-7.51 (dd, J = 16 Hz, 8 Hz; 4H, carbazole); 7.41-7.37 (dd, J = 16 Hz, 8 Hz, 4H, carbazole). MS (MALDI-TOF): m / z calculated for C32H18N2S3: 526.063; Found: 526.132. As with TT-TPA2 and BDT-TPA2, the relatively low absorption of DTT-CB2 in the UV part of electromagnetic spectra (Fig. 10) indicates the high stability of the molecules. The 5 HOMO level calculated for DTT-CB2 is estimated around -5.6 eV (Fig. 11). Example 6: 4,4 '- (dithiene [3,2-b: 2', 3'-d] thiophene-2,6-diyl) bis (N, N-bis (4-methoxyphenyl) aniline) (DTT- OMeTPA2) DTT-OMeTPA2 (compound 104) is prepared according to the schemes shown in Figures 13A and 13B. First, precursor LC8 (4-methoxy-N- (4-methoxyphenyl) -N- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) aniline )) is prepared in steps 1.1 and 1.2. 1.1: 4-bromo-N, N-bis (4-methoxyphenyl) aniline: 4-bromoaniline (10 g, 0.058 mol), 4-iodoanisole (34 g, 0.145 mol), 1.10-phenanthroline (522 mg, 0 , 0279 mol), CuCl (287 mg, 0.029 mol) and KOH (42 15 g, 0.756 mol) are dissolved in 150 ml of toluene. The solution was stirred at 100 ° C for two days under N2 atmosphere. Then, the reaction mixture was allowed to cool, filtered through celite®, washed with water twice and extracted with CH2Cl2. The organic layer was dried over MgSO4, concentrated and the residue mixture was purified by column chromatography on silica gel with CH2Cl2 / hexane = 70:30 as eluent to obtain the product as a light yellow solid (20 g, Y = 90%) 1H NMR (400 MHz, CD2Cl2) = 7.28 to 7.26 (d; J = 8 Hz, 2H, PhH); 7.07 to 7.05 (d, J = 8 Hz, 4H, PhH); 6.88-6.86 (d, J = 8 Hz, 4H, PhH); 6.81-6.79 (d, J = 8 Hz, 2H, PhH); 3.81 (s, 6H, OMe). 1,2: 4-methoxy-N- (4-methoxyphenyl) -N- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) aniline 25 (LC8 ): 4-Bromo-N, N-bis (4-methoxyphenyl) aniline (7.34 g, 0.019 mol), bis (pinacolato) diboro (7.28 g, 0.028 mol), KOAc (5.62 g, 0.057 mol) and Pd (dppf) Cl2 were dissolved in DMF (100 ml). The solution was stirred at 80 ° C for two days under N2 atmosphere. Then, the reaction mixture was allowed to cool, filtered through celite®, washed with water twice and extracted with CH2Cl2. The organic layer was dried over MgSO4, concentrated and the residue mixture was purified by column chromatography on silica gel with CH2Cl2 / hexane = 60:40 as eluent to obtain the product as a light yellow solid (7.25 g , Y = 88%). 1 H NMR (400 MHz,36 CD2Cl2) = 7.63-7.61 (d; J = 8 Hz, 2H, PhH); 7.10-7.00 (m, 4H, PhH); 6.88-6.84 (m, 6H, PhH); 3.81 (s, 6H, OMe), 1.37-1.27 (m, 12 H, Pinh). DTT-OMeTPA2, is prepared as follows: 2,6-dibromodithiene [3,2-b: 2 ', 3'-d] thiophene, (150 mg; 0.28 mmol), 4-methoxy-N- (4- methoxyphenyl) N- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) aniline (402 mg; 0.93 mmol), K2CO3 (2 M, 5 ml ) and Pd (PPh3) 4 (49 mg, 0.04 mmol) were dissolved in THF (25 ml). The reaction mixture was stirred at reflux in the dark for 12 h, then allowed to cool and poured into water. The organic layer was dried over MgSO4, concentrated and the residue mixture was purified by column chromatography on silica gel with CH2Cl2 / hexane = 90:10 as eluent to obtain the product as a bright orange solid (310 mg, Y = 91%). 1 H NMR (400 MHz, CD 2 Cl 2) = 7.48-7.41 (d, J = 4 Hz; 4H, PhH); 10 7.41 (s, 2H, thiophene); 7.14 to 7.10 (d, 8H, PhH); 6.95-6.89 (m, 12H, PhH) 3.83 (s, 12H, OMe). MS (MALDI-TOF): m / z calculated for C48H38N2O4S3: 802.1992; Found: 802.1993. As with the previous compounds, DTT-OMeTPA2 does not show very high absorption in the UV part of the electromagnetic spectrum (Fig. 14), which indicates the high stability of the molecules. The HOMO level calculated for DTT-OMeTPA2 is estimated at around -5.30 eV (Fig. 15). Example 7: 2,6-bis (3,6-dimethoxy-9H-carbazol-9-yl) dithiene [3,2-b: 2 ', 3'-d] thiophene (DTT-OMeCB2) DTT-OMeCB2 ( compound 106) is prepared according to the scheme shown in Fig. 18. In summary, 2,6-dibromoditiene [3,2-b: 2 ', 3'-d] thiophene (150 mg; 0.424 mmol) , 3.6-20 dimethoxy-9H-carbazole (212 mg; 0.932 mmol), Pd (dba) 2 (39 mg, 0.04 mmol), X-Phos (40 mg, 0.084) and NaOtBu (244 mg, 2 , 54 mmol) were dissolved in dry toluene (50 ml). The reaction mixture was then stirred at reflux in the dark for 24 h under N2 atmosphere. Then, the reaction mixture was allowed to cool, filtered through celite, washed with water twice and extracted with CH2Cl2. The organic layer was dried over MgSO4, concentrated and the residue mixture was purified by column chromatography on silica gel with CH2Cl2 / hexane = 80:20 as eluent to obtain the product as a light brown solid (126 mg, Y = 46%). 1 H NMR (400 MHz, CD 2 Cl 2) = 7.56 (s, 4 H, carbazole); 7.53 (s, 2H, thiophene); 7.50-7.48 (d, 4H, carbazole); 7.12 to 7.10 (d, J = 8 Hz; 4H, carbazole); 3.99 (s, 12H, OMe). MS (MALDI-TOF): m / z calculated for C36H26N2O4S3: 646,1055; Found: 646,1050. DTT-OMeCB230 shows a higher absorption in the UV part of the electromagnetic spectrum (Fig. 19), compared to the compounds of Examples 2-6.37 Example 8: 2,6-bis (5,10,15-tris (2-ethylexyl) -10,15-diidro-5H-diindolo [3,2-a: 3 ', 2'-c] carbazol-3 -yl) dithieno [3,2-b: 2 ', 3'-d] thiophene (TDT-EHDI2) DTT-EHDI2 (compound 107) is prepared according to the scheme shown in Fig. 21. In summary , 2,6-dibromoditiene [3,2-b: 2 ', 3'-d] thiophene (80 mg; 0.226 mmol), N-tris (2-ethylhexyl) triazatruxene boronic ester (402 mg; 0.497 mmol), K2CO3 (2 M, 3 ml) and Pd (PPh3) 4 (26 mg, 0.02 mmol) were dissolved in THF (20 ml). The reaction mixture was stirred at reflux in the dark for 12 h, then allowed to cool and poured into water. The organic layer was dried over MgSO4, concentrated and the residue mixture was purified by column chromatography on silica gel with CH2Cl2 / hexane = 3: 2 as eluent to obtain the product as a solid dark orange (345 mg, Y = 98%) 1H NMR (400 MHz, CD2Cl2) = 8.5 to 8.30 (m, 6H, PhH); 10 7.88 (s, 2H, thiophene); 7.70-7.48 (m, 8H, PhH); 7.50-7.30 (m, 10H, PhH) 5.10 to 4.8 (m, 12H, N-CH) 1.7-1.0 (m, 90 H). MS (MALDI-TOF): m / z calculated for C104H126N6S3: 1555.9191; Found: 1555.9238. Molecular weight: 1555.92 g / mol. DTT-EHDI2 shows high absorption in the UV part, as well as in the visible part of the electromagnetic spectrum (Fig. 22). Example 9: 2,5-di (9H-carbazol-9-yl) thieno [3,2-b] thiophene (TT-CB2) TT-CB2 (compound 108) is prepared according to the scheme shown in Fig. 25. In summary, 2,5-dibromothiene [3,2-b] thiophene (200 mg; 0.671 mmol), carbazole (247 mg; 1.47 mmol), Pd (dba) 2 (61 mg, 0 , 07 mmol), X-Phos (64 mg, 0.1 mmol) and NaOtBu (387 mg, 3.02 mmol) were dissolved in dry toluene (60 ml). The reaction mixture was then stirred at reflux in the dark for two days under N2 atmosphere. Then, the reaction mixture was allowed to cool, filtered through celite, washed with water twice and extracted with CH2Cl2. The organic layer was dried over MgSO4, concentrated and the residue mixture was purified by column chromatography on silica gel with hexane / CH2Cl2 = 4: 1 as eluent to obtain the product as a light brown solid (240 mg, Y = 76%) 1 H NMR (400 MHz, 25 CD 2 Cl 2) = 8.21 to 8.19 (d; J = 8 Hz, 4H, carbazole); 7.66-7.64 (d, J = 8 Hz, 4H, carbazole); 7.59 (s, 2H, thiophene); 7.56-7.52 (dd, J = 16 Hz, 8 Hz; 4H, carbazole); 7.42-7.38 (dd, J = 16 Hz, 8 Hz, 4H, carbazole). Molecular weight: 470.09 g / mol. TT-CB2 exhibits poor absorption in the UV part of the electromagnetic spectrum (Fig. 26). Example 10: 2,5-bis (3,6-dimethoxy-9H-carbazol-9-yl) thieno [3,2-b] thiophene (TT-OMeCB2) TT-OMeCB2 (compound 109) is prepared according to the scheme shown in Fig. 30. In summary, 2,5-dibromothiene [3,2-b] thiophene (200 mg; 0.671 mmol), carbazole (247 mg; 1.4738 mmol), Pd (dba) 2 (61 mg, 0.07 mmol), X-Phos (64 mg, 0.1 mmol) and NaOtBu (387 mg, 3.02 mmol) were dissolved in dry toluene (60 ml ). The reaction mixture was then stirred at reflux in the dark for two days under N2 atmosphere. Then, the reaction mixture was allowed to cool, filtered through celite®, washed with water twice and extracted with CH2Cl2. The organic layer was dried over MgSO4, concentrated and the residue mixture was purified by column chromatography on silica gel with CH2Cl2 / hexane = 3: 1 as eluent to obtain the product as a light brown solid (200 mg, Y = 68%). 1H NMR (400 MHz, CD2Cl2) = 7.57 (s; 4H, carbazole); 7.25-7.50 (d, J = 8 Hz, 4H, carbazole); 7.45 (s, 2H, thiophene); 7.29 (s, 2H, carbazole); 07.13 to 07.11 (d, J = 8 Hz, 4H, carbazole) 3.99 (s, 12 H, OMe). Molecular weight: 590.13 g / mol. TT-OMeCB2 exhibits absorption in the UV part of electromagnetic spectra 10 (Fig. 31). Example 11: Solar cells using HTMs In this example, the characteristics of perovskite-based solar cells containing exemplary HTMs of the invention are compared with each other and with cells containing the prior art Spiro-OMeTAD HTM. The cells were prepared according to the general process described in Example 1 above, and the structure as shown in Table 1 below. 20 Table 1: Structure and characteristics of solar cells. "Bl" and "mp" correspond respectively to the compact TiO2 layer and the TiO2 mesoporous structure. No Cell structure Voc (V) Jsc (mA / cm2) FF (%) 1 FTO / bl-TiO2 / mp-TiO2 / Perovskita / DTT-TPA230mM + LiTFSI + t-BP / Au 0.87 19.50 56.039.51 2 FTO / bl-TiO2 / mp-TiO2 / Perovskita / DTT-TPA2 30mM without dopants / Au 0.54 15.45 29.882.50 3 FTO / bl-TiO2 / mp-TiO2 / Perovskita / TT-TPA230mM + LiTFSI + t-BP / Au 0.87 16.18 49.186 .95 4 FTO / bl-TiO2 / mp-TiO2 / Perovskita / TT-TPA2 30mM without 0.83 19.12 36.155.7739 dopants / Au 5 FTO / bl-TiO2 / mp-TiO2 / Perovskita / TT-TPA270mM + LiTFSI + t-BP / Au 0.84 18.74 53.338.41 6 FTO / bl-TiO2 / mp-TiO2 / Perovskita / TT-TPA2 30mM without dopants / Au 0.94 15.93 49.227.35 7 FTO / bl-TiO2 / mp-TiO2 / Perovskita / DTT-CB230mM + LiTFSI + t-BP / Au 0.82 19.48 52.798.48 8 FTO / bl-TiO2 / mp-TiO2 / Perovskita / DTT-CB2 30mM without dopants / Au 0.63 18.51 30.213.54 9 FTO / bl-TiO2 / mp-TiO2 / Perovskita / DTT-OMeTPA2 30mM + LiTFSI + t-BP + FK209 / Au 0.96 21.21 69.3614.1810FTO / bl-TiO2 / mp-TiO2 / Perovskita / DTT-OMeTPA2 30mM + LiTFSI + t-BP / Au 0.94 21.20 68.7813.7311FTO / bl-TiO2 / mp-TiO2 / Perovskita / DTT-OMeTPA2 50mM + LiTFSI + t-BP / Au 0.88 19.95 49.118 .57 12FTO / bl-TiO2 / mp-TiO2 / Perovskita / DTT-OMeTPA2 60mM + LiTFSI + t-BP + FK209 / Au 0.98 21.39 74.1015.5013FTO / bl-TiO2 / mp-TiO2 / Perovskita / DTT-OMeTPA2 70mM + LiTFSI + t-BP / Au 0.87 21.57 70.9713.3614FTO / bl-TiO2 / mp-TiO2 / Perovskita / DTT-OMeTPA2 70mM + (70%) LiTFSI + t-BP / Au 0.97 21.34 72.8715.0415FTO / bl-TiO2 / mp- TiO2 / Perovskita / DTT-OMeCB230mM + LiTFSI + t-BP / Au 0.97 18.96 52.799.68 16FTO / bl-TiO2 / mp- TiO2 / Perovskita / DTT-OMeCB2 30mM without dopants / Au 0.85 18.35 30.404.74 17FTO / bl-TiO2 / mp-TiO2 / Perovskita / DTT-EHDI2 + LiTFSI + t-BP + FK209 / Au- 1.03 21.97 70.8416.0718FTO / -TiO2 / mp-TiO2 / Perovskita / DTT-EHDI2 + LiTFSI + t-BP / Au 1.05 21.50 70.0515.7419FTO / bl-TiO2 / mp-TiO2 / Perovskita / TT-CB230mM + LiTFSI + t-BP / Au 0.78 19.71 47.707 .2940 20FTO / bl-TiO2 / mp-TiO2 / Perovskita / TT-CB2 30mM / Au 0.86 9.77 48.624.10 21FTO / bl-TiO2 / mp-TiO2 / Perovskita / TT-OMeCB2 + LiTFSI + t-BP + FK209 / Au 0.86 15.24 71.539.43 22FTO / bl-TiO2 / mp-TiO2 / Perovskita / TT-OMeCB2 + LiTFSI + t-BP / Au 0.83 20.64 58.719.98 23FTO / bl-TiO2 / mp-TiO2 / Perovskita / Spiro-OMeTAD 60mM + LiTFSI + t-BP + FK209 / Au 1.02 21.06 72.4515.58 Figures 3 (left), 6, 12, 16, 20, 23, 28 and 32 show the JV current-voltage density curve of the DTT-TPA2, TT molecules -TPA2, DTT-CB2, DTT-OMeTPA2, DTT-OMeCB2, DTT-EHDI2, TT-CB2 and TT-OMeCB2, respectively. Figures 3 (right), 17, 24, 29 and 33 show the IPCE of the DTT-TPA2, DTT-OMeTPA2, DTT-EHDI2, TT-CB2 and TT-OMeCB2, 5 respectively. DTT-TPA2 30 mM is used in its form without additives and with the addition of LiTFSI and t-BP as dopants and additives. It can be seen in Table 1, no. 2 and 1, respectively, that there is an improvement in the photovoltaic properties with the use of a dopant and the additive, with the obtaining of a PCE of 9.51%. Two different concentrations of TT-TPA230 mM and 70 mM have been used. It can be seen that with 70 mM of TT-TPA2 HTM, the 10 power conversion efficiency (PCE) can reach up to 8.41% using doping LiTFSI and t-BP additive, while in the 30 mM configuration with doping agents it achieves only 6.95%, and 5.77% without any dopant (Table 1, nº 5, 3 and 4, respectively). DTT-CB2 was also used in the concentration of 30 mM both without dopants and with the addition of LiTFSI and t-BP (Table 1 No. 8 and 7 respectively). In the case of dopant configuration there is an improvement in the photovoltaic properties that lead to a PCE of 8.48%. Similarly, DTT-OMeCB2 and TT-CB2 were used in the concentration of 30 mM in its undoped form and with the addition of LiTFSI and t-BP as a dopant (Table 1, No. 16, 17 and 20, 19 respectively) . Even in this case, the best results were obtained with the addition of the additives; in the case of DTT-OMeCB2 the value of FF increased from 30.40% to 52.79%, while for TT-CB2 there is an improvement in the short-circuit current density (Jsc) of 9.77 mA / cm2 to 19.71 mA / cm2 for TT-CB2 in the configuration without dopants and with dopants respectively. Notable results were obtained with the use of DTT-OMeTPA2 (Table 1, No. 9-14), where four different concentrations, 30 mM, 50 mM, 60 mM and 70 mM have been used. The best 2541 results were obtained with a concentration of 60 mM DTT-OMeTPA2, with the addition of LiTFSI, FK209 and t-BP as dopants and additives (Table 1, No. 12), obtaining a PCE value that is comparable with that obtained with the commercial Spiro-OMeTAD (Table 1, no. 23). The short-circuit current density (Jsc) and the fill factor value (FF) increased to 21.39 mA / cm2 and 74.10% with respect to 21.06 mA / cm2 and 72.45% of the Spiro-OMeTAD, 5 respectively. However, the open circuit voltage (Voc) was slightly lower (0.98 V) in the case of DTT-OMeTPA2, compared to 1.02 V of Spiro-OMeTAD due to the high series resistance of HTM. Almost the same 70 mM use value of DTT-OMeTPA2 was obtained without the use of the FK209 dopant (Table 1, No. 14). Figure 17 shows the IPCE of all devices with the different configurations of the DTT-OMeTPA2 compared to 10 Spiro-OMeTAD. The highest IPCE was observed up to 90% in the case of 70 mM DTT-OMeTPA2 HTM using a dopant that is even higher than the commercial Spiro-OMeTAD. In this case it turned out that more than 80% of the photons are successfully converted to electricity in the entire spectral range 300-800 nm. The best results were obtained with the use of the DTT-EHDI2 molecule as HTM (Table 1, No. 17-18), using all three LiTFSI, t-BP and 15 FK209 or simply LiTFSI and t-BP (Table 1, no. 17 and 18, respectively). In the first configuration, with the use of LiTFSI, t-BP and FK209, a PCE of 16.07% is obtained, which is a higher value than the reference cell with commercial Spiro-OMeTAD (Table 1, No. 23) . The short-circuit current density (Jsc) and the open circuit voltage (Voc) were increased to 21.97 mA / cm2 and 1.03 V with respect to Spiro-OMeTAD, 21.06 mA / cm2 and 1.02 V, 20 respectively. In the case of the configuration containing DTT-EHDI2 doped with only LiTFSI and t-BP (Table 1, No. 18), an even higher Voc value, 1.05 V, was obtained, leading to an overall efficiency of 15, 74%, which is comparable to the efficiency obtained with the commercial standard Spiro-OMeTAD (Table 1, no. 23). Figure 24 shows the IPCE of all devices with the different configurations of DTT-EHDI2 compared to Spiro-25 OMeTAD. The highest IPCE was observed up to 85% in the case of DTT-EHDI2 with LiTFSI and t-BP as a dopant that is even higher than with commercial Spiro-OMeTAD. In this case, more than 80% of the photons can be successfully converted to electricity in the entire 300-800 nm spectral range. 30
权利要求:
Claims (15) [1] 42 CLAIMS 1. A compound comprising the structure of any one of formulas (I), (II) and / or (III): SSSR1R2 (I) SSR2R1 (II) NSNR2R1 (III) wherein R1 and R2 are independently selected of the substituents of formulas (1), (2) or (3) below: NR1R5R4R3R8R2R10R9R6R7NR3R4R1R5R7R2R8R9R17R16R15NNNR3R4R1R5R7R8R2R9 (1) (2) or the multi-point substituent where the single line CC represents 10 where the substituent CC formula (1), (2) or (3), respectively, is connected in a pi-conjugated manner to the structure of formulas (I), (II) or (III); where R1 to R10, as present, are independently selected from H, halogen, -R19, -O-R20, -S-R20, and -NR20R21; Wherein R19, R20 and R21 are independently selected from C1-C30 aliphatic and / or C4-C30 aromatic substituents, which may be, independently, fully or partially halogenated and may, independently, be further substituted by other substituents, and in the that R20 and R21 can also be selected from H;43 wherein R15, R16, and R17 are independently selected from H and C1-C30 aliphatic and / or C4-C30 aromatic substituents, which may, independently, be fully or partially halogenated and may, independently, be further substituted by substituents additional; wherein said additional substituents of said C1-C30 aliphatic and / or C4-C30 aromatic substituents can be independently selected from -R24, -O-R22, -S-R22, and -NR22R23, wherein R22, R23 and R24 are independently selected from C1-C20 aliphatic and / or C4-C20 aromatic substituents, wherein R22 and R23 may also independently be selected from H, and wherein said C1-C20 aliphatic and / or C4-C20 aromatic substituents may, independently, be fully or partially halogenated. [2] 2. The compound of claim 1, wherein said structures of formulas (I), (II) or (III) are selected from the structures of formulas (Ia), (IIa) and (IIIa), respectively: SSSR1R2 (Ia) SSR1R2 (IIa) NSNR1R2 (IIIa) 15 [3] 3. The compound of any one of claims 1 or 2, which is selected from the compounds of formulas (IV), (V) and (VI) below: NNSSSR6R5R1R4R7R8R2R10R9R3R4R1R5R6R7R8R2R10R9R3 (IV)44 NSSSNR3R4R1R5R9R8R2R7R9R8R2R7R3R4R1R5 (V) R17R16R15NNNSSSR17R16R15NNNR9R2R8R7R5R1R4R3R3R4R1R5R7R8R2R9 (VI) [4] 4. The compound of any one of claims 1 or 2, which is selected from the 5 compounds of formulas (VII), (VIII) and (IX) below: NR6R5R1R4R7R8R2R10R9R3SSNR3R4R1R5R6R7R8R2R10R9 (VII)45 SSNR3R4R1R5R9R8R2R7NR9R8R2R7R3R4R1R5 (VIII) R17R16R15NNNR3R4R1R5R7R8R2R9R17R16R15NNNR9R2R8R7R5R1R4R3SS (IX) [5] 5. The compound of any one of claims 1 or 2, which is selected from the 5 compounds of formulas (X), (XI) and (XII) below: NR6R5R1R4R7R8R2R10R9R3NSNNR3R4R1R5R6R7R8R2R10R9 (X)46 NSNNR3R4R1R5R9R8R2R7NR9R8R2R7R3R4R1R5 (XI) R17R16R15NNNR9R2R8R7R5R1R4R3NSNR17R16R15NNNR3R4R1R5R7R8R2R9 (XII) 5 [6] 6. The compound of any one of the preceding claims, wherein the substituents of formula (1), (2) or (3) are selected from formulas (1a), (2a) and (3a) below:47 NR2R1NR1R2R17R16R15NNNR1R2 (1a) (2a) (3a) [7] 7. The compound of any of the preceding claims, which is selected from the compounds of formula comprised of (13) to (21) below: NNSSSR1R2R2R1 NSSSNR1R2R1R25 (13) (14) R17R16R15NNNSSSR17R16R15NNNR1R2R1R2 (15) 17R SSNNR1R2R1R2 (15) 17R SSNNR148 SSR17R16R15NNNR17R16R15NNNR2R1R1R2 (18) NNSNNR1R2R1R2 (19) NNSNNR1R2R1R2 (20) R17R16R15NNNNSNR17R16R15NNNR1R2R1R2 (21) [8] 8. The compound of any one of the preceding claims, wherein R1 and R2 are selected from H and -R19, -O-R20, -S-R20, and -R20, with R19 and R20 independently being, a linear, branched, or cyclic C1-C20 alkyl, alkenyl, or alkynyl, and wherein R15, R16, and R17, to the extent present, are selected from branched, linear, or cyclic C1-C20 alkyl, alkenyl, or alkynyl , and R3-R10, as far as they are present, are H. 10 [9] 9. The compound of any one of the preceding claims, wherein R1 and R2 are selected from H and -O-R20, with R20 - being linear, branched, or cyclic C1-C20 alkyl, preferably C1-C10 alkyl, and more preferably a C1-C5 alkyl. [10] The compound of any one of the preceding claims, wherein R15, R16, and R17, to the extent present, is selected from branched, linear or cyclic C1-C15 alkyl, alkenyl or alkynyl, preferably branched alkyl C1-C12.49 [11] 11. Use of the compounds of any one of claims 1-10 as a hole transport material (HTM), preferably an organic HTM. [12] 12. An optoelectronic and / or electrochemical device, comprising the compound of any one of claims 1-10. [13] The optoelectronic and / or electrochemical device of claim 12, comprising a hole transport layer, the hole transport layer comprising the compound of any one of claims 1-10. 10 [14] The optoelectronic and / or electrochemical device of claim 12 or 13, which is of the light absorbing solar cell or dye type. [15] 15. The optoelectronic and / or electrochemical device of any one of claims 12 to 14, which is an organic-inorganic perovskite-based solar cell.
类似技术:
公开号 | 公开日 | 专利标题 Rakstys et al.2017|Molecular engineering of face-on oriented dopant-free hole transporting material for perovskite solar cells with 19% PCE ES2887212T3|2021-12-22|Processable molecular chromophores in inert solution for organic electronic devices ES2641860B1|2018-09-11|Organic materials for transporting holes containing an ionic liquid Zhang et al.2013|The synthesis and photovoltaic properties of A–D–A-type small molecules containing diketopyrrolopyrrole terminal units ES2659663B1|2019-01-28|Organic materials for transport of holes for opto-electronic devices KR101607594B1|2016-03-30|organic-inorganic hybride solar cells having organinc semiconductor compound and manufacturing method thereof ES2575511B1|2017-04-05|New compound and its use as hollow transport material Lu et al.2017|New benzoselenadiazole-based D–A–π–A type triarylamine sensitizers for highly efficient dye-sensitized solar cells Li et al.2020|Fluorinated D1 |–A–D2 |–A model terpolymer: Ultrafast charge separation kinetics and electron transfer at the fluorinated D/A interface for power conversion Liu et al.2016|Diketopyrrolopyrrole or benzodithiophene-arylamine small-molecule hole transporting materials for stable perovskite solar cells Zhang et al.2017|Two dimethoxyphenylamine-substituted carbazole derivatives as hole-transporting materials for efficient inorganic-organic hybrid perovskite solar cells EP3080206B1|2020-01-08|Porphyrin based sensitizer for dye-sensitized solar cell Li et al.2020|Facile donor |-π-D triphenylamine-based hole transporting materials with different π-linker for perovskite solar cells Xue et al.2016|Influence of aromatic heterocycle of conjugated side chains on photovoltaic performance of benzodithiophene-based wide-bandgap polymers Caliò et al.2018|Design of cyclopentadithiophene-based small organic molecules as hole selective layers for perovskite solar cells Park et al.2015|A comparison of the optical and photovoltaic properties of novel double branched organic dyes in dye sensitized solar cells Park et al.2019|Effect of regioisomeric substitution patterns on the performance of quinoxaline-based dye-sensitized solar cells Wu et al.2017|Simple and low-cost thiophene and benzene-conjugated triaryamines as hole-transporting materials for perovskite solar cells Jia et al.2017|New D–π–A dyes incorporating dithieno [3, 2-b: 2′, 3′-d] pyrrole |-based π-spacers for efficient dye-sensitized solar cells JP2017206479A|2017-11-24|Organic material and photoelectric conversion element Hemavathi et al.2019|New 2-methoxy-4, 6-bis | phenyl) nicotinonitrile: Synthesis, characterization and DSSC study Shang et al.2017|Indenothiophene-based asymmetric small molecules for organic solar cells Wang et al.2016|Phenothiazine organic dyes with the cone-shaped structural: Broad photoresponse and limitations on short-circuit photocurrent density in dye-sensitized solar cells Xia et al.2015|Engineering of the electron donor of triarylamine sensitizers for high-performance dye-sensitized solar cells Wang et al.2020|Synergy effect of electronic characteristics and spatial configurations of electron donors on photovoltaic performance of organic dyes
同族专利:
公开号 | 公开日 WO2018033654A1|2018-02-22| ES2659663B1|2019-01-28|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 ITMI20121672A1|2012-10-05|2014-04-06|Eni Spa|ORGANIC COLORING FOR A SOLAR SENSITIZED COLORING CELL| EP3806176A1|2012-10-31|2021-04-14|Merck Patent GmbH|Electronic device| CN103232472B|2013-04-10|2015-09-23|中节能万润股份有限公司|Also three thiophene derivants and the application thereof of a kind of bipolarity| CN103880849A|2014-03-05|2014-06-25|南京邮电大学|Narrow-band gap conjugated molecule as well as preparation method and application thereof| CN104017571B|2014-06-11|2016-02-17|郑州大学|Electroluminescent organic material and application thereof| CN106432265B|2016-10-17|2018-06-01|中国科学院长春应用化学研究所|Thiophenes, its preparation method and application, perovskite solar cell|CN108727405B|2018-07-27|2022-02-01|武汉天马微电子有限公司|Aromatic heterocyclic compound and organic light-emitting display device| CN111533757B|2020-04-30|2021-08-10|华南理工大学|Dithienobenzimidazole-based undoped hole transport material, preparation method thereof and application thereof in perovskite solar cell| CN111777627B|2020-08-05|2021-06-08|中国科学院重庆绿色智能技术研究院|Small molecule photovoltaic material based on halogenated two-dimensional BDT core unit and preparation and application thereof|
法律状态:
2019-01-28| FG2A| Definitive protection|Ref document number: 2659663 Country of ref document: ES Kind code of ref document: B1 Effective date: 20190128 | 2019-09-12| FA2A| Application withdrawn|Effective date: 20190906 |
优先权:
[返回顶部]
申请号 | 申请日 | 专利标题 ES201631098A|ES2659663B1|2016-08-16|2016-08-16|Organic materials for transport of holes for opto-electronic devices|ES201631098A| ES2659663B1|2016-08-16|2016-08-16|Organic materials for transport of holes for opto-electronic devices| PCT/ES2017/070531| WO2018033654A1|2016-08-16|2017-07-21|Organic hole-transporting materials for optoelectronic devices| 相关专利
Sulfonates, polymers, resist compositions and patterning process
Washing machine
Washing machine
Device for fixture finishing and tension adjusting of membrane
Structure for Equipping Band in a Plane Cathode Ray Tube
Process for preparation of 7 alpha-carboxyl 9, 11-epoxy steroids and intermediates useful therein an
国家/地区
|