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  • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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  • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
  • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells

Definitions

• the p-i-n PSCs have several advantages over the more popular n-i-p architecture. First, the high temperature annealing required for TiO 2 formation is avoided.
• the present invention is concerned with uniformly-formed layers on TCOs of minimal thickness hole-transporting due to a hole-conductive material configured for self-assembly on the corresponding surface.
• minimal parasitic absorption, reduced material consumption and the avoidance of doping processes are problems to be solved, especially with regard to
• the present invention seeks to provide HTMs that are relatively tolerant of perovskite processing and any patterned surface such as pyramidal structured silicon with a height of several microns that can be formed by wet chemical etching, such as in solar cells is common, have been processed, can conformally cover.
• one aspect of the present invention is to provide a compound comprising at least one molecule of formula (I) that functions as HTM: where F is a linking fragment, A is an anchor group, and HTF (hole transporting fragment) is a hole-conducting fragment selected from one of the following formulas II or III, a polycycle
• ZDZ (II) wherein Z and D are homocyclic or at least one of Z or D comprises a heteroatom selected from the group consisting of N, S, O, Si and Z is a Cs or C ⁇ substituted or unsubstituted aromatic group D is N or a C 8 or C 8 aromatic group wherein two carbon atoms of the aromatic group D are each bonded to one of the two aromatic Z groups, a tricycloundecane
• Tricyclotridecane or a tricyclotetradecane derivative Tricyclotridecane or a tricyclotetradecane derivative
• R is a substituent
• the compound of the invention functions as a hole-conducting material due to electron localization.
• D is preferably an aromatic fragment and / or an electron pushing element in association with the fragments Z.
• Particularly preferred are symmetrical structures, ie, compounds that can be mirrored along an axis. Reflection refers to the schematic structure and not necessarily to the actual steric appearance. It is advantageous that the mirror axis passes through the component D, so that the two Z components are the same or inverse.
• the molecule of formula (I) may be mixed with other molecules, the so-called “filler molecules” (FM).
• FM is generally a molecule or mixture of molecules selected from an anchor group (e.g.
• the FMs act as a passivating agent that reduces pad carrier recombination between the TCO and the perovskite, as well as a means of modifying the wettability of the TCO.
• a preparation without FMs is always possible and for selected proportions HTF, F and A without any disadvantage.
• the proportion x of HTM in the mixture is in the range of 0.02 to 1.
• n is preferably 1 or 2.
• D is a Cs or C6 heteroaromatic group, wherein the heteroatom is N, Si, S and / or O.
• the hole-conducting fragment is selected from any one of those given in formulas IV to XIX.
• the groups R are independently selected from the group consisting of H; Ci- to Cio-alkyl; C2 to Cio alkenyl; C 3 to C 20 cycloalkyl; C 3 to C 8 heterocycloalkyl, alkoxy, aryloxy, alkylthio, arylthio, amino, amido, ester, carboxylic acid, dialkoxydiphenylamine, carbamate, urea, ketone, aldehyde, cyano, nitro, halogen; (Cycloalkyl) alkyl and (heterocycloalkyl) alkyl.
• the groups R are independently selected from hydrogen
• the linking fragment L is one that is selected from Ci to C 9 - alkylene, C 4 - to C2o-arylene, C 4 - to C2o-heteroarylene, C 4 - to C2o-alkylarylene, C 4 - to C2o-heteroalkylarylene, wherein the heteroatoms are selected from O, N, S, Se, Si and wherein said alkylenes, arylenes, heteroarylenes, alkylarylenes, heteroalkylarylenes, heteroalkylarylenes, if they comprise three or more carbon atoms, can be linear, branched or cyclic , in particular selected from one of
• dashed lines represent the bond connecting L to the HTF of Formula II or III.
• the anchor group A (head group) is selected from phosphonic acid, phosphoric acid, sulfuric acid, sulfonic acid, carboxylic acid, siloxanes, in particular selected from one of
• dashed lines represent the bond by which A is joined to L according to any one of the preceding claims and R 'is preferably aliphatic.
• Another aspect of the invention is the provision of a hole-conducting material comprising the inventive compound.
• Yet another aspect of the present invention relates to an opto-electrical and / or photoelectric device comprising the inventive compound according to one of the aforementioned embodiments.
• the optoelectrical and / or photoelectric device comprises a hole-conducting material, wherein the hole-conducting material comprises the compound of formula II or III.
• the optoelectronic and / or photoelectrochemical component is preferably a photovoltaic solid-state device which is a solid-state solar cell which contains an organic-inorganic perovskite as a sensitizing molecule in the form of
• perovskite in the sense of this description refers to the "perovskite structure” and not specifically to the perovskite material CaTiCb.
• perovskite includes any material and preferably refers to any material having the same crystal structure type as calcium titanium oxide and to materials wherein the divalent cation is replaced by two separate monovalent cations.
• the perovskite structure has the general stoichiometry AMX 3 , where "A” and “M” are cations and "X” is an anion. The cations "A” and "M” can
• the perovskite formulas include structures having one (1), two (2), three (3) or four (4) cations, which may be the same or different, and / or one or two (2) anions and / or metal atoms carrying two or three positive charges according to the formulas given elsewhere in this specification.
• organic-inorganic perovskite layer material of the optoelectronic and / or photoelectrochemical component has a perovskite structure of one of the following formulas:
• a 1 , A 2 , A 3 , A 4 are either organic monovalent cations or mixtures thereof, which are independently selected from primary, secondary, tertiary or
• quaternary organic ammonium compounds including N-containing fletero rings and ring systems, wherein A and A 'are independently 1 to 60 carbon atoms and 1 to 20 fletero atoms (such as methyl ammonium or ammonium amininium) or inorganic cations (such as Na, K, Rb, Cs) exhibit.
• B is an organic divalent cation selected from primary, secondary, tertiary or quaternary organic ammonium compounds having 1 to 60 carbon atoms and 2 to 20 heteroatoms and having two positively charged nitrogen atoms;
• - M is a divalent metal cation selected from the group consisting of Cu 2+ , Ni 2+ , Co 2+ , Fe 2+ , Mn 2+ , Cr, Pd 2+ , Cd 2+ , Ge 2+ , Sn 2 + , Pb 2+ , Eu 2+ or Yb 2+ ;
• - N is selected from the group of Bi 3+ and Sb 3+ ;
• - X is independently selected from Cf, Br, G, NCS, CN and NCO ⁇ X may also be a mixture of the listed halides / anions.
• the compound of the invention for forming a SAM is characterized as follows.
• the anchor group A is made of a
• the hole-conducting fragment HTF is selected from the formula (II) (Z-D-Z) wherein D is N and Z is a C6-cyclic aromatic group substituted with a methoxy group. Another preferred
• Embodiment corresponds to the previously described, wherein Z is not with a
• Methoxy group is substituted. Both embodiments have in common that they can be prepared without filler molecules (FM), and without losses in their characterizing properties and stability.
• FM filler molecules
• Another aspect of the present invention is the use of the inventive compound as a hole-conducting material in an optoelectronic and / or
• the method for forming the inventive compound as SAM on a TCO for use in inverted architecture perovskite solar cells is to be realized by two methods, one method comprising the steps:
• L is a linking fragment
• A is an anchor group
• HTF is a hole-conducting
• Tricyclotridecane or a tricyclotetradecane derivative Tricyclotridecane or a tricyclotetradecane derivative
• R is a substituent, where the FM is generally a molecule or mixture of molecules selected from an anchor group (eg, phosphonic acid, phosphoric acid, sulfuric acid, sulfonic acid,
• an anchor group eg, phosphonic acid, phosphoric acid, sulfuric acid, sulfonic acid
• Examples of an FM are ethyl or
• Butylphosphonic acid (“C2" or “C4") or (aminomethyl) phosphonic acid.
• the solvent for the solution any liquid capable of dissolving the compound and guaranteeing the immersion of a surface can be selected.
• the concentration of the compound in the solution is preferably in the range of 0.01 to 100 mM per liter.
• the time for immersing the surface to form the SAM should be at least sufficient for the molecules to bind to the oxide surface and is preferably in the
• the substrate is then thermally baked and / or washed.
• the compounds according to the invention, with and without FM are spin-coated in a solution (for example, by rotary evaporation). The optimal procedure for the selected HTM and possible substrates should be determined experimentally if necessary.
• FIG. 2 A) UV / VIS absorption spectra for 10-4M THF solution of VI 036 and PTAA (polytriarylamine)); B) UV / Vis absorption spectra of bare ITO substrate, ITO with PTAA and ITO with 100% V1036 SAM.
• FIG. 5 A) FTIR absorption spectra of monolayers on Si / ITO substrate prepared from (a)
• Fig. 6 A) contact angle dependence on percentage of V1036 in the SAM composition; B) equilibrium contact angle of perovskite solution to 100% C4 SAM; PTAA; 100% V1036 SAM.
• Fig. 7 J-V characteristic of the most powerful PSCs with PTAA and SAM HTMs.
• Figure 8 JV characteristic of forward and backward scanning of the most powerful PSC with PTAA and 10% V1036 90% C4 SAM HTMs.
• B EQE and integrated Jsc of the most powerful PSC with PTAA and 10% V1036 90% C4 SA-HTMs. The inset shows the statistical distribution of the Jsc.
• Fig. 9. REMs of PTAA and 10% V1036 90% C4, above and in cross section.
• Phosphonic acid (V1036), synthesized.
• the dimethoxydiphenylamine substituted carbazole fragment can be found in several efficient HTMs for regular perovskite solar cells, and active hydrogen in the ninth position of the carbazole can be further used for functionalization with phosphonic acid anchor groups (head group).
• the synthesis was carried out in a 4-stage synthesis process (see FIG. 1) starting from commercially available materials.
• 3 6-dibromocarbazole was alkylated with 1, 2-dibromoethane to give Intermediate 1.
• the aliphatic bromide was converted to ethyl phosphonate 2 by the Arbuzov reaction.
• dimethoxydiphenylamine fragments were introduced by means of the palladium catalyzed Buchwaid-Hartwig amination reaction to obtain the compound 3.
• phosphonic acid V1036 was obtained by cleavage of the ester
• the spruce In the inverted PSC, the spruce first passes through the HTM layer, and accordingly it is important to minimize the parasitic absorption of this layer.
• the base material V1036 without FM has a 95% weight loss at a temperature (Tdec) of 343 ° C, which is suitable for practical use in optoelectronic devices.
• V olecular vibrations of CN bonds are visible as intense bands near 1238 cm 4 .
• Two average intensity bands near 1438 to 1442 and 1461 to 1466 cm 4 contain a high proportion of symmetric and asymmetric CFb deformation vibrations of the methoxy group.
• Absorbance intensity of the band near 1503 cm 4 was determined to be 0 for the SAM prepared from methanolic solution with 0.1 mM V1036 and 0.9 mM C4 as FM (10% V1036 90% C4). 62, which indicates a decrease in surface coverage by the V1036 compound as compared to the 100% V1036 SAM (relative intensity 1.00). Obviously, the decline is the
• Fig. 5 we show sum frequency spectrums (VSFG) of HTM SAMs (VI 036 with and without filler molecule) on Si / ITO substrate in the spectral range of 1150 to 1300 cm 4 (A) and in the spectral range of 1400 to 1600 cm 4 (B).
• the Si / ITO substrate provides a substantial non-resonant SFG signal, which interferes with the resonance signal and results in the spectral distortions, as can be seen at GL S1. Because of this interference, the shape of the resonance centered at -1490 cm 1 resembles the asymmetric Fano-like resonance and also appears to be shifted in frequency compared to the FTIR spectra (-1503 cm 1 ).
• contact angle measurements were made using triple cation perovskite solution as the assay liquid.
• the contact angles for PTAA, 100% V1036 SAM, and 100% C4 SAM are 42.6 °, 26.3 ° and 60.5 °, respectively.
• the contact angle gradually changes, confirming the presence of the two species on the surface of the ITO. Differences in contact angles correlate with the polarity of the material and give larger angle values for nonpolar aliphatic 100% C4 SAM and lowest values for 100% V1036 SAM with methoxy functional groups.
• Control device with PTAA showed a slightly higher efficiency of 18.4% PCE.
• Table 3 Average PSC performance parameters extracted from the J / V scans, including standard errors and performance parameters of the best devices (in Klammem). The statistic is based on 9 to 20 cells on different substrates for different HTMs.
• C2 ethylphosphone
• C6 n-hexylphosphonic
• Elemental analyzer model 440 C / H / N / performed.
• the thermogravimetric analysis was performed on a thermogravimetric analyzer Q50 (TA Instruments) at a scan rate of 10 K min 1 in the nitrogen atmosphere.
• electrothermal MEL-TEMP capillary melters were used. UV / VIS spectra were recorded with the Shimadzu UV-3600 spectrometer.
• the contact angle measurement was carried out using the drop contour analysis system DSA25 from Kruss.
• ITO was deposited on Si substrate and further functionalized with SAMs according to the above-mentioned method.
• Monolayer FTIR spectra were recorded in transmission mode using the FTIR spectrometer Vertex 80v (Bruker, Inc., Germany) equipped with a liquid nitrogen cooled MCT narrow band detector. The spectra were recorded from 512 interferogram s cans with a resolution of 4 cm 1 ; the final spectrum was determined by averaging two spectra.
• the reference sample used was a bare Si substrate with a 30 nm thick ITO layer.
• the infrared spectrum of the Vl036 ground substance sample was recorded in transmission mode on an AFPHA FTIR spectrometer (Bruker, Inc., Germany) equipped with a DFATGS room temperature detector. The spectral resolution was set to 4 cm 1 . The spectrum was obtained from 124 interferogram scans. The sample was dispersed in KBr-T settle.
• Nd YAG laser generates pulses at 1064 nm with a pulse length of ⁇ 28 ps and 20 kHz repetition rate. Part of the laser power is used to pump an optical parametric generator (EKSPLA PG401 VIR / DF G) to generate infrared pulses (COIR) that are tuned in the range between 1000 cm 1 and 4000 cm 1 with the typical energies of 60 to 200 pj can be.
• EKSPLA PG401 VIR / DF G optical parametric generator
• COIR infrared pulses
• the second harmonic of the laser power (532 nm) is called visible beam (VIS) used for sum frequency generation (COSF).
• VIS visible beam
• Sum frequency is generated when infrared and visible pulses overlap in time and space on the sample surface. All spectra in this work were recorded with a polarization combination ssp (s - SPG, s - VIS, p - IR). The intensity of the visible beam has been attenuated to avoid damaging the samples ( ⁇ 30 m ⁇ ). The generated sum frequency light is filtered with a monochromator and detected with a photomultiplier tube (PMT).
• PMT photomultiplier tube
• the measured VSFG intensity is proportional to where A NR is the non-resonant amplitude, A Rq is the resonant amplitude of the q-th
• f is the phase between resonant and non-resonant contributions.
• coq and G q are the frequency and the width of the q-th vibration, respectively.
• the solid state ionization potential (7p) of Y1036, PTAA on ITO and SA-HTMs on ITO was measured by the method of electron photoemission in air [l4-l6] 14 16 l
• the sample for the ionization potential measurement of V1036 ground substance was prepared by dissolving material in THF and applied to an Al plate precoated with a ⁇ 0.5 m2 thick methylmethacrylate and methacrylic acid copolymer adhesive layer. The layer thickness was ⁇ 0.5 to 1 square meter.
• the PTAA layer on ITO was performed in a manner similar to that used for PSC formation
• the SA-HTMs were formed by the above method.
• the investigated organic materials are stable enough to oxygen and the measurements can be carried out in air.
• the samples were illuminated with monochromatic light from the quartz monochromator with deuterium lamp.
• the power of the incident light beam was (2 to 5) 10 8 W.
• the negative voltage of -300 V was supplied to the sample substrate.
• the counter electrode with the 4.5 x 15 mm 2 slit for illumination was placed 8 mm away from the sample surface.
• the counter electrode was connected to the input of the BK2-16 electrometer connected in the open input mode for photocurrent measurement.
• the 10 15 to 10 12 A strong photocurrent flowed during the lighting in the circuit.
• the photocurrent / is strong of the incident
• ITO glass substrates 25x25 mm, 15 W sq-l, samples from Automatic Research GmbH
• ITO indium-tin oxide
• the samples were dried with a nitrogen gun and immediately prior to HTM deposition, the substrates were treated in a UV ozone cleaner (FHR Anlagenbau) for 15 minutes.
• FHR Anlagenbau UV ozone cleaner
• the HTM SAMs were obtained by immersing UV ozone-treated ITO substrates in a 1 mM / L solution of the corresponding phosphonic acid molecules dissolved in isopropanol for 20 hours, followed by annealing at 100 ° C for 1 hour, followed by washing with isopropanol and chlorobenzene.
• mixtures of V1036 and n-butylphosphonic acid (C4) with different ratios were investigated in addition to the pure V1036 SAM.
• PTAA Sigma Aldrich
• a triple cation- Cso.o5 (MAo.i7FAo. 83 ) o. 95 Pb (Io.83Bro.i7) 3 Perovskite film was formed according to a slightly modified, recently published procedure. First, PbBn and Pbb were dissolved in DMF: DMSO (4: 1 by volume) to the nominal 1.5 M concentration by shaking overnight at 60 ° C. Subsequently, the PbBn and Pbb stock solutions were added to MABr and FAI powders, respectively, to obtain MAPbBn and FAPbE solutions with a final concentration of 1.24M. The molar ratio between lead and the respective cations was 1.09: 1.00 (9% lead excess) for both solutions.
• MAPbEtA and FAPbL solutions were then mixed in a 1: 5 volume ratio. Finally, the cesium cation was added from a 1.5 M Csl solution in DMSO in a 5:95 volume ratio. This final perovskite solution was slightly diluted by the addition of DMF: DMSO (4: 1) in a 5:95 volume ratio for substrates with suboptimal wettability properties.
• the precursor solution is run using the following program
• the perovskite coated sample is annealed for 60 minutes on a hot plate at 100 ° C.
• R ' hydrogen, Cl- to C9-alkyl group
• R "' hydrogen, alkyl (Cl to C12)
• V1036 and mixed V1036 and n-butylphosphonic acid (C4) SAMs were prepared by immersing UV ozone-treated ITO substrates in a 1 mM solution of
• the V1193 in a solution was photographed on ITO substrates and then annealed at 100 C for 10 minutes. Washing is optional in this case.
• the VI 193 shows the VI 036 improved properties, as can be seen from FIG.
• HTM SAMs according to the invention, V1036, VI 193, VI 194 and for comparison also to PTAA, in a diagram.
• the data comes from a component analysis.
• the measured parameters were determined at a light intensity equivalent to a sun (AM 1.5 g standard).
• the bars show the largest measured photoluminescent lifetimes.
• the area between the curved solid lines indicates the maximum and minimum QFLS values that were measured (from 3 Vl036 samples, 8 VI 193 samples and 9 VI l94 samples). Error bars for open circuit voltage Voc and efficiencies indicate standard deviation, from measurements on 38 Vl036 cells, 56 PTAA cells, 42VI 193 cells and 40Vl94 cells. A clear correlation between efficiency, Voc, photoluminescence (PL) lifetimes and QFLS can be seen.
• the SAMs VI 193 and VI 194 outperform PTAA, the current standard in highly efficient inverted perovskite solar cells, in PL lifetime, QFLS, and device performance.
• the values for VI 036 approximate those of PTAA.
• the dashed line indicates the PL lifetime on glass as a reference.
• the HTM SAMs according to the invention are distinct from PTAA
• the new HTM may possibly be extended to serve as a model system for substrate-based perovskite nucleation and passivation control.

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