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WO2016111623A1 - Molécule d'azométhine à transport de trous - Google Patents

Molécule d'azométhine à transport de trous Download PDF

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WO2016111623A1
WO2016111623A1 PCT/NL2016/050007 NL2016050007W WO2016111623A1 WO 2016111623 A1 WO2016111623 A1 WO 2016111623A1 NL 2016050007 W NL2016050007 W NL 2016050007W WO 2016111623 A1 WO2016111623 A1 WO 2016111623A1
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layer
photovoltaic device
perovskite
molecule
hole transport
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Michiel Leonardus PETRUS
Theodorus Jacobus Dingemans
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Technische Universiteit Delft
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention is in the field of a azomethine molecule having photovoltaic characteristics and applicable as a hole transporter, in a photovoltaic device, the device further comprising a light absorbing material, such as a perovskite based device, and a solar cell comprising said molecule as a hole transporter or said device.
  • the present invention is in the field of cost effective solar cells. These cells can be processed from a liquid solution comprising a photovoltaic material, hence the possibility of a simple roll-to-roll printing process, potentially leading to in ⁇ expensive, large scale production. In addition, these cells could be beneficial for applications where mechanical flexibility and disposability are important.
  • Current flexible solar cell efficiencies have a low power conversion efficiency (PCE) of 8- 10%) , compared to inorganic based cells, and practical devices are essentially non-existent. On top of that, costs of organic materials used therein are very high, at least partly due to process costs.
  • perovskites may be used.
  • Perovskites have a general formula of ABC 3 .
  • A may be an alkaline earth element, a rare earth element, or an organic molecule, such as an amine, such as formamidinum, an ammonium, such as methylammoni- urn.
  • B may be a 3d, 4d, and 5d transition metal element, such as Pb, Sn, Ti.
  • C may be a halide, such as C1-, Br " , I ⁇ , and F ⁇ , and oxygen.
  • a perovskite solar cell is a type of solar cell which includes a perovskite light absorber.
  • Perovskite absorber materials are cheap to produce and simple to manufacture. Solar cell efficiencies of devices using these ma ⁇ terials have recently increased by a factor.
  • architectures of perovskite solar cells may vary .
  • perovskite materials can also act as highly efficient, ambipolar charge-conductor. After light absorption and the subsequent charge-generation, both negative and positive charge carrier are transported through the perovskite to charge selective contacts (typically anode and cathode) .
  • PCE Power conversion efficiency
  • a thin layer of perovskite on e.g. mesoporous 1O 2 as electron-collector was in the order of 5%, which is considerably less than e.g. silicon based solar cells.
  • efficiencies of almost 10% were achievable using a T1O 2 architecture.
  • New tech- nigues achieved more than 20% efficiency.
  • the power-conversion efficiency of a solar cell is usu ⁇ ally determined by characterizing its current-voltage (JV) behaviour under simulated solar illumination.
  • JV current-voltage
  • perovskite solar cells show a hysteretic behaviour: there is a discrepancy between the scan from forward-bias to short-circuit (FB-SC) and the scan from short-circuit to forward bias ⁇ SC-FB.
  • FB-SC forward-bias to short-circuit
  • ⁇ SC-FB short-circuit
  • perovskite systems are prone to deterioration due to water.
  • Hybrid solar cells are supposed to combine advantages of both organic and inorganic semiconductors, wherein one may act as hole transporter and the other as electron transporter.
  • Hybrid photovoltaics typically have organic materials that consist of e.g. conjugated polymers that absorb light as the donor and transport holes. Inorganic materials in hybrid cells are used as the acceptor and electron transporter in the structure.
  • the hybrid photovoltaic devices have various advantages .
  • perovskite-based solar cells As indicated above, the efficiency of perovskite-based solar cells has increased rapidly in the last five years making this one of the most promising photovoltaic technologies and al- most being competitive with current silicon-based technologies.
  • the perovskite material itself is relatively inexpensive, the best devices prepared to date use an expensive organic hole-conducting material, called spiro-OMeTAD ( ⁇ $700/gram, see Solaronix: spiro-OMeTAD) .
  • This material is expensive to produce because the synthesis requires expensive monomers, transition metal catalysts, inert reaction conditions and extensive product purificatio .
  • azomethines in organic photovoltaics
  • Petrus et al in "Small-molecule azomethines: organic photovoltaics via Schiff base condensation chemistry", J. Mater. Chem. A, 2014, 2, p. 9474-9477. They report use of azomethines as electron transport molecules (donor) in bulk hetero junction systems.
  • a HOMO energy level of about -5.3 eV which is compara ⁇ ble to the -5.6 eV of the above spiro-OMeTAD
  • the efficiencies reported are still considered poor (table 2, 0.6-1.2 %).
  • the article also recites the use of relative large amounts PCBM in combination with the azomethine.
  • PCBM' s are relatively expensive and are therefore not preferred.
  • polymer type azomethines also perform poorly (e.g. 0.2%). Such would be a demoti- vator to use the azomethines .
  • the HOMO energy is at best one characteristic that may need to be taken into account.
  • Other items could be transport mobility, LUMO energy, presence of unreacted functional groups, protonation of a bond, such as an azomethine bond, and a morphology of a layer.
  • Doping of layers may be considered.
  • Kaya et al. in Synthetic Metals 156 (2006), p. 1123-1132 recites an oligomer-metal complex compound comprising 2- [ (4-morpholin-4-yl- phenyl ) imino] methylphenol (2-MPIMP) obtained by an oxidative pol- ycondensation reaction using various oxidants.
  • Iodine (I 2 ) was claimed to be used as doping agent in order to increase a conductivity, which is considered different from hole/electron mobilities; in addition iodine has a tendency to sublime out of a material, which makes it unsuited.
  • the compounds and structures do not relate to small molecules, but to ologimers or polymers, the materials are not well defined as a conseguence, e.g. in terms of molecular mass, and the conductivities indicate that effectively the materials are insulators ⁇ see fig. 9, at the best giving a value of 10 ⁇ 6 S/cm ⁇ making them not very suited for PV-cells and also requiring doping.
  • the present invention therefore relates to use of an azomethine comprising molecule having photovoltaic characteristics as a hole transport layer in a photovoltaic device, and a solar cell comprising said hole transport layer, which solve one or more of the above problems and drawbacks of the prior art, providing reliable results, without jeopardizing functionality and advantages.
  • the present invention relates to a photovoltaic device comprising a hole transporting molecule and optionally at least one hole mobility improver in a hole transport layer, and further a light absorbing material layer, wherein the hole transporting molecule comprises an azomethine molecule according to figure 3, and a solar cell comprising said device according to claim 14.
  • the present inventors have developed azomethine-based hole-transport materials as a cheap alternative, because they are found to be easily synthesized in a one-step condensation reaction (upon loosing water as only by-product a conjugated chemical bond is formed) , do not require expensive catalysts and do not require extensive workup.
  • the estimated price of the present material is some 5$/gram. So far azomethines have not been used as charge transport layer, such as in perovskite-based pho- tovoltaics.
  • the azomethine molecules have hole transport capabilities ⁇ ties, but these are typically insufficient for the intended ap ⁇ plication in a photovoltaic device.
  • at least one hole mobility improver is therefore preferably provided to the hole transport layer.
  • the hole mobility improver is typically of p-type .
  • a typical amount of the first hole mobility improver is 0.1-100 mole %, relative to the azomethine molecule, preferably 0.5-50 mole %, more preferably 1-30 mole %, even more preferably 2-20 mole %, such as 3- 5 mole%.
  • the hole mobility improver may be considered as a dopant to the hole transport material; it is noted that the concentration of the hole mobility improver is typically much higher than e.g. dopants in semiconductor devices.
  • the hole mobility improver is typically capable of oxi- dizing the hole transport material, and/or promote oxidative reaction thereof; in this respect the hole mobility improver may be considered as an oxidant. In principle any such oxidant could be applied in the present invention. Likewise so-called ionic liquids may be used.
  • Hole mobility improvers may be selected from earth alkali metal, monovalent salts, hydrogen salts (or acids), N,N- dimethyl- pyrrolidinium, and N-methyl-N-propylpyrrolidi-nium salts of bis (tris-fluoromethylsulfonyl) imide (TFSI) , such as LiTFSI, AgTFSI, HTFSI, and N, N-dimethyl-pyrrolidinium iodide.
  • TFSI bis (tris-fluoromethylsulfonyl) imide
  • LiTFSI Lithium bis (trifluoromethanesulfonyl) imide
  • monovalent salt equivalents thereof e.g. Ag+
  • additives such as N ( PhBr) 3 SbCl 6 , F4TCNQ and cobalt dopants
  • additives for passivating a surface can be used.
  • these additives are combined with the first and/or second hole mobility improver, typically in a concentration of 10-1000 mole%, such as 100 mole%.
  • 4-tert- butylpyridine (TBP) is used; also pyridine and iodopentafluoro- benzene (IPFB) have shown to improve the device performance, like pyridine, 2, 6-lutidine, and 4-methylpyridine .
  • a series of small-molecule azomethines has been synthesized for further investigation.
  • the synthesis typically results in small-molecules with a very narrow molecular mass distribution, and typically mostly one specific type of molecule is formed in an amount of >90%, such as >95% or even >99%; i.e. conversion and selectivity are high.
  • Perovskite based solar cells using these azomethines or likewise a (co-) polymer com ⁇ prising said molecule as hole transport layer, in combination with the hole mobility improver, have been prepared and measured, showing record efficiencies of around 11% (for sake of comparison, under the same processing conditions Spiro-OMeTAD shows efficiencies up to 12%) .
  • the present azomethine molecules as hole transport material can relate to both small molecules and polymers comprising said azomethine molecules, but preferably well-defined small-molecules .
  • the present azomethine molecules are considered to relate to small, well-defined molecules having well defined properties, such as relatively excellent photovoltaic properties, a molecular mass of 300-3000, preferably 400-1500, more preferably 500-1000, such as 600-750, good film forming properties, low costs, etc.
  • the present aromatic entity A is non- heterocyclic, i.e. only comprising carbon atoms in the aromatic ring.
  • Entity B is connected to at least one entity A, or to more than one A entities, such as in a tree like structure, in a chain like structure, and combinations thereof.
  • the aromatic entity A preferably has a molecular mass of 64-1250, preferably 64-700, such as 64-500, whereas, independently, the aromatic (optionally heterocycle) bridging entity B preferably has a molecular mass of 65-1500, preferably 65- 1000, such as 64-750.
  • the aromatic entity A preferably has 1-4 aromatic ring structures, more preferably 1-3, such as 2, where ⁇ as, independently, the aromatic (optionally heterocycle) bridging entity B preferably has 1-8 aromatic ring structures, more preferably 1-5, such as 2-4.
  • the present azomethine molecules and polymeric equivalents thereof find application as a hole transport material in the present photovoltaic device.
  • the present invention relates in a first aspect to a photovoltaic device according to claim 1.
  • the present molecules have excellent properties. For instance a glass transition temperature (T g ) of about 100 °C is obtained, melting points of about 200 °C, a thermal decomposition temperature (Td, 5%) of about 400 °C, and a crystallization temperature T c of about 150 °C. Such makes the present molecules particularly suited for applications such as hybrid photovoltaic devices that function reliable under ambient conditions.
  • the molecules exhibit absorbance of light over a range of about 280 nm- about 600 nm, with a max of about 500 nm, and an onset wavelength ⁇ onse t of about 600 nm.
  • the band-gap is in the order of 2.0 eV. These absorbance properties can be improved for the present mol- ecules. Further, a maximum s al3S of 30, 000-60,000 (M _1 cm _1 ) is found .
  • Eoxi of about 1 V (versus Ag/Ag + )
  • HOMO voltage below vacuum
  • LUMO of about -3 eV
  • the molecules provide a good solubility and good film forming properties.
  • the molecule has an (A-B) n -A structure (fig. 3c) or (B-A ⁇ n -B structure, wherein ne[l-5], preferably n ⁇ [2-3], or wherein the molecule has an A m -B structure (fig. 3d), wherein me [1-5], preferably me [2-3], or wherein the molecule has a B r -A structure (fig. 3e ⁇ , wherein re [1-5], preferably re [2-3] , or combinations thereof.
  • A-B-A-B-A type molecules are preferred.
  • the aromatic (optionally heterocycle) bridging entity comprises one or more of S, N, P, Si, Se and 0, preferably one or more of S, Se and Si, such as a pyrrolidine, a pyrrole, a tetrahydrofuran, a furan, a thiolane, a thiophene, a phopholane, a phosphole, a sililane, a silole, an azole, such as an imidazolidine, a pyra- zolidine, an imidazolem a pyrazole, an ( is ) oxazolidine, an
  • the aromatic ring preferably has 5-6 ring members, such as 5-6 ring members. It is further preferred that in the at least one aromatic (optionally heterocycle) entity B at least two, and preferably at least two different, het- eroatoms are present, one of which preferably is S.
  • the present azomethine molecule comprises at least one 4-aminotriphenylamine (TPA) according to figure 2. This TPA is readily available.
  • the bridging entity is selected from 2 , 5-thiophenedicarbaldehyde (Th) , 2, 3-dihydrothieno [3, 4-b] [1, ] dioxine-5, 7-dicarbaldehyde (EDOT) , 2, 2' -bithiazole-5, 5' -dicarbaldehyde (BTz) , 4,7-bis(5- formylthiophen-2-yl ) -2 , 1 r 3-benzothiadiazole (TBT) , and combinations thereof.
  • the R is independently selected from H, -CN, OAlk, Alk, and combinations thereof, and Alk is selected from alkanes, such as Ci-Ci 8 , preferably C 1 -C12, such as Me, Et, and combinations thereof.
  • the method further comprises one or more steps selected from before spin coating the condensate, thereby forming a solution, wherein the solution is spin coated on a substrate, removing the solvent, and annealing the condensate.
  • the present product can be applied directly, e.g. to a substrate, without a further intermediate step, which is a big advantage .
  • the device preparation has not been optimized yet. Optimizing the layer thickness, dopants and solvent/co-solvent will further increase the efficiency.
  • a p-type dopant is added to the hole transporting material before spin coating.
  • An oxidant for example lithium bis-trifluoromethanesulfonimide (LiTFSI).
  • an additive like 4-tert-butylpyridine (TBP) , is added, in order to passivate the surface.
  • the hole transport layer comprises a second hole transport improver in an amount of 0.1-15 mole % relative to the azomethine molecule, preferably 0.5-10 mole %, such as 1-5 mole%. Generally it is combined with one of the first hole mobility improver.
  • Exam- pies of second hole transport improver materials are tris(2-(lH- pyrazol-l-yl ⁇ pyridine ) cobalt (III) bis- (hexafluorophosphate ) (FK102) , Tris (2- ( IH-pyrazol-l-yl ) -4-tert-butylpyridine) - cobalt (III) ris (bis (trifluoromethylsulfonyl) imide) ) (FK209), SnCl 4 , LiC10 4 , 2 , 3 , 5 , 6-Tetrafluoro-7 , 7 , 8 , 8- tetracyanoquinodimethane (F4-TCNQ) , N (PhBr) 3 SbCl 6 , N0BF 4 (exposing to vapour) , WO3 (evaporating a thin layer on top) , and combinations thereof.
  • further hole transport improvers may be added; typically 2-5 improver
  • At least one first hole mobility improver may be selected, optionally in combination with at least one second hole mobility improver, and so on.
  • the present photovoltaic device comprises a stack, the stack comprising a substrate, a first optically transparent electrode layer, a second electrode layer, and between the electrode layers, (i) a perovskite layer as light absorbing layer, (ii) the present hole transport layer, and (iii) an intermediate layer.
  • the above sequence of layers is considered an almost minimal set of layers in view of performance, Further (intermediate and protecting) layers may be added, e.g. in order to improve performance.
  • the substrate 11 therein is typically glass.
  • the anode 21 is an optically transparent electrode, such as FTO, in contact with the substrate.
  • the present hole transport layer 41 In contact with the anode and the perovskite 31 is the present hole transport layer 41.
  • a metal layer 22 (such as Al) acts as second electrode.
  • an intermediate layer 51 such as a fuller- ene, is present between the cathode and perovskite.
  • the perovskite may be CH 3 NH 3 Pbl3, CH 3 NH 3 PbBr 3 , a mixed halide, such as
  • the present perovskites having the general formula of ABC 3 , preferably relate to A being an alkaline earth element, a rare earth element, such as Na, K, Li, Ca, g, Ce, or an organic molecule, such as an amine, such as formamidinum, and an ammonium, such as methylammonium CH 3 NH 3 , and ethylammonium C 2 H 5 NH 3 , to B being a 3d, 4d, and 5d transition metal element, such as Pb, Sn, Bi, Mn, Ni, Co, Fe, and Ti, C being a halide, such as C1-, Br-, I-, and F- , and oxygen, as well as mixed minerals thereof.
  • A being an alkaline earth element, a rare earth element, such as Na, K, Li, Ca, g, Ce, or an organic molecule, such as an amine, such as formamidinum, and an ammonium, such as methylammonium CH 3 NH 3 , and eth
  • Exam ⁇ ples are lead halogenides, such as CH 3 NH 3 PbI 3 , tin halogenides, such as CH 3 NH 3 Snl 3 , titanates such as CaTi0 3 .
  • the band gap of the perovskite is preferably from 1.4-2.5 eV, such as 1.5-2.3 eV.
  • first electrode and second electrode in the above two stacks of layers change function, from anode to cathode, and vice versa. Also the nature of the intermediate layer changes. On the other hand the functions of the perovskite layer and hole transport layer remain the same.
  • the substrate is selected from glass, silicon, steel, aluminium, silicon oxide, polymers, and combinations thereof, preferably glass .
  • the first electrode layer is selected from optically transparent and electrically conducting materials, such as tin doped indium oxide (ITO), graphene, and fluorine doped tin oxide (FTO), preferably ITO.
  • ITO tin doped indium oxide
  • FTO fluorine doped tin oxide
  • the second electrode layer is selected from metals, such as Al, Cu, Mg, Ba, ZnO, Au, Ag, and Ca, preferably Au or Al, respectively.
  • Au has better properties in view of hole transport
  • Al has better properties in view of electron transport.
  • the perovskite is highly crystalline, such as > 90% crystalline, preferably > 95% crystalline, more preferably > 99% crystalline, such as may be confirmed by X-ray diffraction experiments.
  • the present photovoltaic device comprises an intermediate layer, typically for electron transport, which layer is preferably selected from fullerenes and Ti0 2 , respectively.
  • the layer may have a thickness of 10-500 nm, preferably 20-300 nm, more preferably 50-200 nm, such as 100-150 nm.
  • the present photovoltaic device has a se- quence of layers comprising one or more of an 20-1000 nm thick first electrode layer, preferably 100-750 nm, more preferably 200-500 nm, such as 300-400 nm, such as ITO, a 10-1000 nm thick light absorbing layer, preferably 20-800 nm, more preferably 50- 500 nm, such as 200-400 nm, an 10-300 nra thick hole transport layer, preferably 20-200 nm, such as 50-100 nm, such as an azo- methine according to the invention and an 10-500 nm thick electron transport layer, preferably 20-400 nm, such as 50-300 nm, and a 20-200 nm thick second electrode layer, preferably 30-100 nm, such as 50-75 nm, such as Au.
  • an 20-1000 nm thick first electrode layer preferably 100-750 nm, more preferably 200-500 nm, such as 300-400
  • the hole transport layer is preferably not too thin, as holes in the layer may occur and coverage of in particular the perovskite layer may be insufficient.
  • the hole transport layer is preferably not too thick, as it may act as a semi-insulator. In general the hole transport layer can be somewhat thinner than comparable materials.
  • a further intermediate layer between e.g. hole transport layer and second electrode may be present.
  • the present invention relates to a solar cell according to claim 11.
  • the small molecules were obtained in good yields (>80%) and characterized using 1 H and 13 C NMR, FTIR, and mass spectrometry where possible.
  • the thermal properties of the new molecules were assessed using thermogravi- metric analysis (TGA) and differential scanning calorimetry (DSC) . All small molecules show excellent thermal stabilities with degradation temperatures (T d 5% ) above 350 °C. Comparing TPA- Th-TPA to its vinyl analogue, inventors found that the degrada- tion temperature is approximately 40 °C higher, confirming the superior thermal stability of the present azomethines. DSC experiments showed a glass transition temperature (T g ) in the range of 86 to 113 °C.
  • TPA-Th-TPA and TPA-EDOT- TPA also showed a cold crystallization exotherm during the second heating at 143 °C and 171 °C, respectively. All small molecules melt above 200 °C and form isotropic melts, as was con- firmed by hot-stage optical microscopy.
  • the highest occupied molecular orbital (HOMO) energy levels of the small molecules were estimated by using the oxidation onset of the first oxidation and were found in the range of -5.2- -5.5 eV below vacuum.
  • the relatively deep HOMO energy levels are expected to give a good energy alignment with the perovskite.
  • the lowest unoccupied molecular orbital (LUMO) energy levels were estimated by combining the op- tical band-gap with the obtained HOMO energy level.
  • the azome- thine moiety was found to slightly deepen the HOMO energy level compared to the vinyl and fully aromatic analogues, which are about 0.1-0.3 eV
  • Planar perovskite based photovoltaics with the azome- thine as hole transporting layer show power conversion efficiencies (PCE) exceeding 10% (Table 2). This efficiency is only slightly lower compared state of the art materials, whereas optimisation of the chemical structure and processing conditions is found to further increase the PCE.
  • PCE power conversion efficiencies
  • azomethines can be prepared in a simple and clean condensation reaction under near ambient conditions we believe this approach offers a cost effective route towards hole transporting materials.
  • FTO glass was etched with zinc powder and HC1 (2M) and cleaned afterwards.
  • a compact 50 nm layer of T1O2 was deposited by spin-coating a titanium isopropyl solution. It was heated to 500 °C for 45 minutes. After cooling down the substrate were transferred to a nitrogen filled glove-box.
  • a so- lution of 1M Pb ⁇ 2 and 1M methylammoniumiodide was spin coated dynamically (at 5000 rpm, total 15 sec) onto the substrate. After 5 seconds 100 ⁇ , of chlorobenzene was added on top of the spinning substrate. Thereafter the substrate was placed on a hotplate at 100 °C for 10 minutes. After cooling to ambient temper- ature the present hole transporter was spin-coated on top.
  • TPA (OMe) 2 -ED0T-TPA (OMe) 2 (10 mg mL -1 ) , and Spiro-OMeTAD (75 mg mlf 1 ) were dissolved in chlorobenzene .
  • Lithium bis (tris- fluoromethylsulfonyl ) imide (Li-TFSI; 10 ⁇ L mL -1 of a 170 mg mL -1 acetonitrile solution) and Tert-butylpyridine (TBP; 30 pL mL -1 ) were added to the hole transport material solutions.
  • Li-TFSI tris- fluoromethylsulfonyl ) imide
  • TBP Tert-butylpyridine
  • Co- dopant tris (2- ( lH-pyrazol-l-yl ) pyridine) cobalt (III)
  • FK102 bis (hexafluorophosphate )
  • acetonitrile was pre-dissolved in acetonitrile and added to the hole transport material solution at a ra- tio of 0-15 mole%.
  • the thickness of the hole transport layer was found to be 20nm for TPA (OMe) 2-EDOT-TP (OMe) 2 and ⁇ 250nm for Spiro-OMeTAD. Thereafter a top electrode was deposited by thermal evaporation of gold under vacuum (at 10 ⁇ 5 mbar) , with a thickness of 40 nm.
  • Azomethine-based low molar mass molecules show good performance as hole-transporting material in perovskite photovoltaic devices.
  • a single molecule conductance of a 3-ring, con- jugated azomethine using a mechanically controlled break junction (MCBJ) is found to be fine.
  • MMBJ mechanically controlled break junction
  • the azomethine model compound exhibits transport properties comparable to vinyl-based analogues.
  • the conductance of 0PV3 with thiol anchoring groups lies between 1*10-4 GO and 2 ⁇ 10-4 GO for MCBJ setups. Comparing the conduct ⁇ ance values of both TYPI and OPV3 shows that a thiophene ring with azomethine linkers has a comparable charge transport effi- ciency as a benzene ring with vinyl linking. It is found that the HOMO' s of all molecules have a pi character and closely resemble each other, both in shape and in energy. They extend from one sulphur atom to the other and hybridize well with the gold atoms, as can be seen by the finite density around the gold- sulphur bond and their extension throughout the entire gold electrodes.
  • the similar electronic structure is further supported by the transmission calculations, which show similar broadening of the HOMO'S indicating comparable hybridization of the molecules with the gold electrodes. Furthermore, the HOMO-LUMO gap is of comparable size, 3.2 eV for TYPI, 3.4 eV for OPV3 and 3.4 eV for OPA3.
  • 5-Thiophenedicarboxaldehyde was purified by vacuum sublima- tion, prior to use.
  • Fig. 1 shows a synthesis route and molecular structures of the present small-molecule azomethines.
  • Fig. 2 shows a TPA molecule with an optional group R.
  • Fig. 3a-e show basic configurations of the present azomethine molecules .
  • Fig. 4a-b relate to a so-called inverted perovskite device and standard perovskite device, respectively.
  • TPA-Th-TPA 306 467 314 463 565 2.19 0.45 5.55 3.36
  • Table 2 J-V characteristics of the photovoltaic devices with different HTMs .

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Abstract

La présente invention concerne une molécule d'azométhine présentant des caractéristiques de conduction de trous et trouvant une application en tant quetransporteur de trous, dans un dispositif photovoltaïque, le dispositif comprenant en outre un matériau photo-absorbant, tel qu'un dispositif à base de pérovskite, et une cellule solaire comprenant ladite molécule en tant que transporteur de trous ou ledit dispositif.
PCT/NL2016/050007 2015-01-08 2016-01-07 Molécule d'azométhine à transport de trous Ceased WO2016111623A1 (fr)

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CN107275487A (zh) * 2017-06-08 2017-10-20 华东师范大学 一种高效稳定的钙钛矿太阳能电池及其制备方法
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CN108054279A (zh) * 2017-12-07 2018-05-18 暨南大学 Fk102配体修饰的钙钛矿型太阳能电池及其钙钛矿层的制备方法
CN108682747A (zh) * 2018-05-16 2018-10-19 西安电子科技大学 一种双异质结钙钛矿光电器件及其制备方法
CN115440889A (zh) * 2022-09-06 2022-12-06 华中科技大学鄂州工业技术研究院 一种提高钙钛矿太阳能电池效率和稳定性的方法及钙钛矿太阳能电池
US11976228B2 (en) 2018-11-30 2024-05-07 Nichia Corporation Method for producing ceramic sintered body, ceramic sintered body, and light emitting device

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107275487A (zh) * 2017-06-08 2017-10-20 华东师范大学 一种高效稳定的钙钛矿太阳能电池及其制备方法
CN107785487A (zh) * 2017-10-31 2018-03-09 南京旭羽睿材料科技有限公司 一种石墨烯薄膜太阳能电池及其制备方法
CN108054279A (zh) * 2017-12-07 2018-05-18 暨南大学 Fk102配体修饰的钙钛矿型太阳能电池及其钙钛矿层的制备方法
CN108054279B (zh) * 2017-12-07 2021-06-11 暨南大学 Fk102配体修饰的钙钛矿型太阳能电池及其钙钛矿层的制备方法
CN108682747A (zh) * 2018-05-16 2018-10-19 西安电子科技大学 一种双异质结钙钛矿光电器件及其制备方法
US11976228B2 (en) 2018-11-30 2024-05-07 Nichia Corporation Method for producing ceramic sintered body, ceramic sintered body, and light emitting device
CN115440889A (zh) * 2022-09-06 2022-12-06 华中科技大学鄂州工业技术研究院 一种提高钙钛矿太阳能电池效率和稳定性的方法及钙钛矿太阳能电池

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