WO2014081388A1 - Dopants pour cellules solaires sensibilisées par colorant à hétérojonction solide - Google Patents

Dopants pour cellules solaires sensibilisées par colorant à hétérojonction solide Download PDF

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WO2014081388A1
WO2014081388A1 PCT/SG2013/000487 SG2013000487W WO2014081388A1 WO 2014081388 A1 WO2014081388 A1 WO 2014081388A1 SG 2013000487 W SG2013000487 W SG 2013000487W WO 2014081388 A1 WO2014081388 A1 WO 2014081388A1
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complex
mole
formula
spiro
htm
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PCT/SG2013/000487
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Teck Ming KOH
Andrew Clive GRIMSDALE
Subodh G MHAISALKAR
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Nanyang Technological University
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Publication of WO2014081388A1 publication Critical patent/WO2014081388A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • Y02E10/542—Dye sensitized solar cells
    • 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 invention relates to new complexes that are useful as p-dopants.
  • the present invention further relates to the use of the new complexes as p-dopants in hole-transporting- material (HTM).
  • HTM hole-transporting- material
  • the invention further relates to HTM p-doped with the complex of the invention.
  • the invention further relates to photo-electrochemical devices such as solar cells, in particular solid state dye sensitizer solar cells (ssDSC) that comprise the new complex of the invention.
  • ssDSC solid state dye sensitizer solar cells
  • Chemical doping is an important strategy to alter the charge transport properties of both molecular and polymeric organic semiconductors, and finds application in organic electronic devices such as in solar cell.
  • ssDSC solid-state dye-sensitized solar cells
  • HTM hole transporting material
  • I ' /b electrolyte
  • the most commonly used HTM in ssDSC is still 2,2',7 ( 7'-tetrakis(/V,/V-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro- MeOTAD, Fig. 1) which was reported in the first ssDSC in 1998 2 .
  • the present invention addresses this need by providing new and improved p- dopants that improve the conductivity of HTM.
  • the present invention provides new complexes of transition metal, in particular of cobalt, nickel, manganese, chromium and iron that are useful as p-dopants.
  • the complexes are useful as p-dopants in HTM.
  • the complexes of the present invention have a high oxidation potential, which provides a high driving force for the one electron oxidation reaction in HTM, thereby improving the conductivity of the HTM.
  • M is Co, Ni, Cr, Mn and Fe preferably Co 3+ , Ni 3+ , Cr 3+ , Mn 3+ and Fe 3+ ,
  • La is independently a bi- or tri-dentate ligand selected from
  • R 1 is CF 3 or F
  • each R 2 is independently selected from H or CF3
  • X is 0 or S
  • n is an integer selected from 2 and 3
  • A is a counter ion
  • n is an integer selected from 0, 1, 2, or 3.
  • the present invention provides a p-doped HTM comprising a HTM and a complex of formula (I).
  • the HMT is 2,2',7,7'-tetrakis(A/ / /V-di-p- methoxyphenylamine)-9,9'-spirobifluorene (spiro-MeOTAD).
  • the present invention provides a photo-electrochemical device comprising a complex of formula (I).
  • the device is a solar cell, more preferably an ssDSC.
  • the present invention provides a photo-electrochemical device comprising a first and a second electrode having a layer between said first and second electrodes, said layer comprising a complex of formula (I).
  • the device is a solar cell, more preferably is an ssDSC.
  • the present invention provides a photo-electrochemical device comprising a first and a second electrode having a layer between said first and second electrodes, said layer comprising a p-doped HTM, said HTM comprising the complex of formula (I) as p-dopant.
  • the device is a solar cell, more preferably an ssDSC.
  • the present invention provides a solar cell, more preferably an ssDSC, comprising the complex of formula (I).
  • the present invention provides the use of the complex of the invention as a p-dopant agent in an electrochemical device.
  • the device is a photo- electrochemical device, more preferably, the photochemical device is a solar cell, even more preferably an ssDSC.
  • the present invention provides the use of the complex of formula (I) as p-dopant for a HTM.
  • the present invention provides a method of preparing a p-doped HTM, the method comprising the step of providing an HTM, and, adding thereto the complex of formula (I).
  • the invention provides a method for increasing the conductivity of an HTM, the method comprising the step of adding to said HTM the complex of formula (I).
  • the present invention provides a method of preparing an electrochemical device, the method comprising the steps of providing a first and a second electrode and providing, between said first and second electrode, an HTM comprising the complex of formula (I). DESCRIPTION OF THE DRAWINGS
  • Fig. 1 shows the chemical formula of the hole transporting material (HMT) Z ⁇ ' ⁇ '-tetrakisi/V ⁇ -di-p-methoxyphenylamineJ-g ⁇ '-spirobifluorene (spiro-MeOTAD).
  • HMT hole transporting material
  • Fig. 2 shows the prior art complex FK102.
  • Fig. 3 shows the cationic component (MY) of the complex of the invention.
  • Fig. 4 (a), (b), (c), (d) and (e) show the chemical structures of (a) Y123, (b) D35 and (c) C220, (d) D-205 and (e) MK-2 organic sensitizers.
  • Fig. 5 shows the synthetic route for the preparation of 2,6-dipyrazolylpyridine ligand.
  • Fig. 6 shows the results of cyclic voltammetry of complex MYl.
  • Fig. 7 shows UV-Vis absorption spectra of spiro-MeOTAD solution in chlorobenzene with MY1 doping concentration of 0% (pristine spiro) 1.6 mole%, 2.1 mole%, 2.5 mole%, 3.0 mole%, 3.5 mole% and 6.0 mole%.
  • Fig. 8 shows spiro-MeOTAD to spiro-MeOTAD + conversion yield using MY1 dopant.
  • Fig. 9 shows Current-voltage curves of non-doped, FK102 (1.6%) and MY1 (0.9%)- doped spiro-MeOTAD based devices measured under simulated AM1.5G (100 mWcnr 2 ).
  • Fig. 10 depicts a schematic drawing of the device comprising Spiro-OMeTAD.
  • HMTs such as spiro 2,2',7,7'-tetrakis(/V,/V-di-p-methoxyphenylamine)-9,9'- spirobifluorene (spiro-MeOTAD) (Fig. 1) act as charge transport medium in solid state dye sensitized solar cell (ssDSC). Due to the low conductivity of HMTs, such as spiro-MeOTAD, in their pristine form, chemical doping is necessary in order to enhance the performance of the HMT and ultimately of the solar cell.
  • ssDSC solid state dye sensitized solar cell
  • the present inventors have found new complexes that provide a driving force greater than the driving force of FK102. Due to the large driving force for doping reaction, a high spiro-MeOTAD-to-spiro-lv1eOTAD + conversion and a higher power conversion yield is achieved using an amount of p-dopant complex of formula (I) lower than the amount requires when FK102 is used.
  • the present inventors have measured the redox potential of the p-dopant of the invention " Yl" and found it to be 1.26 V vs. NHE, which is more positive of the first oxidation potential of spiro-MeOTAD (0.72 V vs. NHE) and greater than the redox potential of compound FK102 when measured under the same experimental conditions. Said difference provides a driving force of 540 mV for spiro-MeOTAD first electron oxidation reaction, which is greater than the driving force of about 350 mV of complex FK102 for spiro-MeOTAD one electro oxidation reaction. The greater driving force of the complexes of the invention results in a greater conductivity of the HTM.
  • the present invention relates to a p-dopant complex of formula (I)
  • M is Co, Ni, Cr, Mn and Fe
  • La is independently a bi- or tri- dentate ligand selected from
  • R 1 is CF 3 or F
  • each R 2 is independently selected from H or CF3;
  • X is O or S
  • n is an integer selected from 2 and 3;
  • A is a counter ion
  • n is an integer selected from 0, 1, 2, or 3.
  • M is Co 3+ , Ni 3+ , Cr 3+ , Mn 3+ , Fe 3+ ;
  • La is independently a bi- or tri- dentate ligand selected from
  • R 1 is CF 3 or F
  • each R 2 is independently selected from H or CF3;
  • X is 0 or S
  • n is an integer selected from 2 and 3;
  • A is a counter ion
  • rh is an integer selected from 0, 1, 2, or 3.
  • M is Co 3+ or Ni 3+ .
  • A is bis(trifluoromethane)sulfonimide (TFSI ), PF 6 " , BF 4 " , CI0 4 " or Trifluoromethanesulfonate (OTf ). More preferably, A is TFSI " .
  • TFSI Trifluoromethanesulfonate
  • the ligand in a complex is the same ligand (for example (Ll) 2 , (L2) 3 , (L4) 3 , (L4) 3 , (L5) 3 ).
  • the value of "m” would depend also on the counter ion A.
  • the value of m is such the net charge of the complex of formula (I) is 0.
  • the charge of the counter ion has a (one) negative charge, such as TFSI “ , PF6 “ , BF4 " , CI04,0 m is 3 to have a net 0 charge of the complex
  • m is 3.
  • A is PF6 " , TFSI " , BF4 " , CIO4 " and m is 3. More preferably, A is TFSI " and m is 3.
  • TFSI " may be chosen because it enhances solubility of the desired metal complexes, providing an additional advantage in case higher doping concentrations are required.
  • M(La) n of formula (I) is selected from:
  • a preferred complex is a complex wherein in formula (I) M(La) n is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9, MYIO, MY11, MY12, MY13, MY14, MY15 and MY16.
  • a more preferred complex is a complex wherein in formula (I) M(La) n is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9, ⁇ , ⁇ , MY12, MY13, MY14, MY15 and MY16, A is TFSI" and m is 3.
  • the complex of formula (I) is
  • the complex of formula (I) is
  • the complex of formula (I) is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoe
  • the complex of formula (I) is
  • the complex of formula (I) is
  • the complex of formula (I) is
  • the complex of formula (I) is
  • the complex of formula (I) is
  • the complex of formula (I) is
  • the complex of formula (I) is
  • the complex of formula (I) is
  • the present invention is directed to a p dopant complex of formula (I):
  • M is Co, Ni, Cr, Mn, Fe,
  • La is independently a bi- or tri- dentate ligand selected from
  • R 1 is CF3 or F
  • each R 2 is independently selected from H or CF3;
  • X is 0 or S
  • n is an integer selected from 2 and 3;
  • A is a counter ion
  • n is an integer selected from 0, 1, 2, or 3;
  • the present invention is directed to a complex of formula (I),
  • M is Co 3+ , Ni 3+ , Cr 3+ , Mn 3+ , Fe 3+ ;
  • La is independently a bi- or tri- dentate ligand selected from
  • R 1 is CF3 or F
  • each R 2 is independently selected from H or CF3;
  • X is O or S
  • n is an integer selected from 2 and 3;
  • A is a counter ion
  • n is an integer selected from 0, 1, 2, or 3;
  • the complex comprises one or more ligands, preferably two ligands or three ligands.
  • the complex is made of 2 or 3 of same ligands.
  • MY and MY1 the ways to tune the redox potential of resultant complex more positively
  • MY2 Ni metal center
  • the inventors coupled the pyrazole unit with different heterocycles instead of pyridine.
  • Pyrazine (MY3 and MY4) and pyrimidine (MY5 and MY6) are two good candidates to couple with pyrazole and provide more positive redox potential of resultant Co 3+ or Ni 3+ complexes.
  • Employing fused-ring heterocycles such as benzo-thiazole and benzoxazole moiety into ligand frameworks together with pyrazole is an additional way to tune the redox potential of the dopant (MY7 to MYIO).
  • the presence of sulfur or oxygen atoms in the metal complexes brings different effect from nitrogen atoms in pyridine-based moiety.
  • electro- withdrawing substituents such as CF3 in ortho position with respect to the "N" on the pyrazole ring have been seen to tune the redox potential leading to the complexes of the invention (MY11 to MY16).
  • the present invention is further directed to the use of the complexes as disclosed in the above embodiments as p-dopants.
  • P-dopants are molecules, in particular complexes, that confer an excess of mobile electron hole to the material to be doped.
  • the complex of the invention is preferably used as p-dopant in HTM.
  • Preferred HTM according to the present invention is 2,2' / 7,7'-tetrakis(/V / / ⁇ /-di-p-methoxyphenylamihe)-9 ( 9'-spirobifluorene (spiro- OMeTAD).
  • the present invention is further directed to p-doped HTM comprising the complex of formula (I) of the invention.
  • the HTM according to the present invention is spiro-OMeTAD.
  • More preferred concentrations range from 0.6% specifically 0.6 mole% to 2.5% specifically 2.5 mole%, even more preferred from 0.6% to 1.6%, specifically 0.6 mole% to 1.6 mole%, even further more preferred concentrations range from 0.7 to 0.9%, specifically 0.7 mole% to 0.9 mole%.
  • spiro-OMeTAD compositions comprising a complex wherein in formula (I) M(La) n is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9,MY10, MY11, MY12, MY13, MY14, MY15 and MY16, A is TFSI and m is 3 at a concentration of 0.9%, specifically 0.9 mole%, 1.6% specifically 1.6 mole%, 2.1% specifically 2.1 mole%, 2.5% specifically 2.5 mole%, 3.0% specifically 3.0 mole%, 3.5% specifically 3.5% mole%, and 6.0% specifically 6.0 mole%.
  • spiro-OMeTAD compositions comprising MY1, at a concentration of 0.9%, specifically 0.9 mole%, 1.6%, specifically 1.6 mole%, 2.1%, specifically 2.1 mole%, 2.5% specifically 2.5 mole%, 3.0% specifically 3.0 mole%, 3.5% specifically 3.5 mole%, and 6.0% specifically 6.0 mole%. More preferably the concentration is of 0.9% specifically 0.9 mole%.
  • the present complex has a high oxidative potential and provide a high driving force to the oxidation reaction in HTM. Hence, low concentration of the complex can be used and yet achieve an effective conductivity of the HTM.
  • the present invention is directed to a photo-electro chemical device comprising the complex of formula (I) of the invention.
  • the photo-electro chemical device is a solar cell, more preferably a dye sensitized solar cell (DSC), even more preferably a solid state DSC (ssDSC).
  • the complex of the invention is preferably comprised in a HTM.
  • the HTM is a p-doped HTM doped with a complex of the invention.
  • the photo-electro chemical device comprises a p-doped HTM comprising a complex of formula (I) of the invention.
  • the photochemical device comprises a p-doped HTM comprising the complex of formula (I) of the invention at a concentration ranging from 0.5% to 6.0% specifically 0.5 mole% to 6.0 mole%. More preferred concentrations range from 0.6% to 2.5% specifically 0.6 mole% to 2.5 mole%, even more preferred from 0.6% to 1.6% specifically 0.6 mole% to 1.6 mole%, and most preferred concentration ranges from 0.7 mole% to 0.9 mole%.
  • the p-doped HTM is spiro-OMeTAD and the preferred complex is a complex wherein in formula (I) M(La) n is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9 MY10, MY11, MY12, MY13, MY14, MY15 and MY16.
  • a more preferred complex is complex wherein in formula (I) M(La) n is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9, MY10, MY11, MY12, MY13, MY14, MY15 and MY16 and A is TFSI ⁇ .
  • the dopant complex is MY1.
  • the concentration of MY1 in spiro-OMeTAD is of at a concentration of 0.9%, specifically 0.9 mole%, 1.6%, specifically 1.6 mole%, 2.1%, specifically 2.1 mole%, 2.5% specifically 2.5 mole%, 3.0% specifically 3.0 mole%, 3.5% specifically 3.5 mole%, and 6.0% specifically 6.0 mole%. More preferably, the concentration is of 0.9% specifically 0.9 mole%.
  • the present invention is directed to a photo-electro chemical device comprising the complex of formula (I) of the invention.
  • the photo-electro chemical device is a solar cell, more preferably a dye sensitized solar cell (DSC), even more preferably a solid state DSC (ssDSC).
  • the complex of the invention is preferably comprised in a HTM.
  • the HTM is a p-doped HTM doped with a complex of the invention.
  • the HTM is a p-doped HTM according to the invention.
  • the photo-electro chemical device comprises a p-doped HTM comprising a complex of formula (I) of the invention.
  • the photochemical device comprises the p-doped HTM according to the invention comprising the complex of formula (I) of the invention.
  • the p-doped HTM is spiro-OMeTAD and the preferred complex is a complex wherein M(La) interven is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9, MY10, MY11, MY12, MY13, MY14, MY15 and MY16.
  • More preferred complex is a complex wherein in formula (I) M(La) n is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9 MY10, MY11, MY12, MY13, MY14, MY15 or MY16,A is TFSI " and m is 3.
  • the dopant complex is MYl.
  • the concentration of the complex of formula (I) ranges from 0.5 mole% to 6.0 mole%, more preferably ranges from 0.5 mole to 2.5 mole%; even more preferably the concentration ranges from 0.6 mole% to 1.6 mole , even further more preferably the concentration ranges from 0.7 mole % to 0.9 mole%.
  • the concentration of MYl in spiro-OMeTAD is of 0.9 mole or of 1.6 mole% or of 2.1 mole% or of 2.5 mole%.
  • the photo-electro chemical device of the invention is preferably a DSC, even more preferably the DSC is selected from ssDSC.
  • the dye/sensitizer is selected from the following dyes: triphenylamine-based organic dyes such as D35; metal free dyes such as Y123 and C220, the indoline dye D205 (2-((E)-5-(l,2,3,3a,4,8b-hexahydro-4-(4-(2.2- diphenylvinyl)phenyl)cyclopenta[b]indole-7-yl)methyl)-3-octyl-5-(3-carboxymethyl-4-oxo- thiazolidin-2-ylidene)rhodanine) and MK-2 (2-Cyano-3-[5"'-(9-ethyl-9H-carbazol-3-yl)- 3',3",3"',4-tetra-n-hexyl-[2,
  • the photo-electro chemical device of the invention comprises a first and a second electrode having a layer between said first and second electrodes, the layer comprising the complex of formula (I) as disclosed above.
  • Preferred complex is a complex wherein M(La) n is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9,MY10, MY11, MY12, MY13, MY14, MY15 and MY16.
  • More preferred complex is a complex wherein in formula (I) M(La) n is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9, MY10, MY11, MY12, MY13, MY14, MY15 and MY16 and A is TFSI " and m is 3.
  • MYl is MYl.
  • the present invention is directed to a method for improving the conductivity of a HTM comprising doping the HTM with a complex of formula (I) of the invention.
  • the HTM is spiro-OMeTAD and the complex is a complex wherein M(La) n is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9, MY10, MY11, MY12, MY13, MY14, MY15 and MY16.
  • a more preferred complex is complex wherein in formula (I) M(La) n is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9,MY10, MY11, MY12, MY13, MY14, MY15 and MY16, A is TFSI " and m is 3. Even more preferably, the doped complex is MYl.
  • the complex of formula (I) is added to the HTM to have a final concentration ranging from 0.5 mole % to 6.0 mole %; more preferably to have a final concentration ranging from 0.6 mole % to 2.5 mole%, even more preferably from 0.6 mole% to 1.6 mole%, even further more preferably from 0.7 mole% to 0.9mole%.
  • the concentration of MY1 in spiro- OMeTAD is of 0.9%, specifically 0.9 mole %, 1.6%, specifically 1.6 mole %, 2.1%, specifically 2.1 mole %, 2.5% specifically 2.5 mole %, More preferably, MY1 is added to have p-doped- spiro-OMeTAD at 0.9 % specifically 0.9 mole %.
  • the present invention is directed to a method for preparing a photochemical device comprising:
  • the HTM is spiro-OMeTAD and the complex is a complex of formula (I) wherein M(La) n is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9, MY10, MY11, MY12, MY13, MY14, MY15 and MY16.
  • M(La) n is MY, MY2, MY3, MY4, MY5, MY6, MY7, MY8, MY9, MY10, MY11, MY12, MY13, MY14, MY15 and MY16, A is TFSI " and m is 3.
  • the dopant complex is MY1.
  • the complex of formula (I) is added to have a final concentration ranging from 0.5 mole% to 6.0 mole%; more preferably to have a final concentrations ranging from 0.6 mole% to 2.5 mole%, even more preferably from 0.6 mole% to 1.6 mole%, even further more preferably from 0.7 mole% to 0.9 mole%.
  • the concentration of MY1 in spiro- OMeTAD is of 0.9%, specifically 0.9 mole %, 1.6%, specifically 1.6 mole %, 2.1%, specifically 2.1 mole %, 2.5% specifically 2.5 mole %,. More preferably, MY1 is added to have p-doped- spiro-OMeTAD at 0.9 % specifically at 0.9% mole%.
  • the present invention is further directed to a complex selected from:
  • the present invention is further directed to a molecule selected from:
  • Fluorine doped tin oxide (FTO) substrate was first immersed in 40 mM of TiCU solution for 30 min at 70°C and then rinsed with deionized water and ethanol.
  • a thin compact layer of Ti0 2 (blocking layer) was deposited by aerosol spray-pyrolysis at 450°C.
  • a 2.3 ⁇ thick mesoporous T1O2 film was screen-printed on the substrate and it was calcined at 500°C for 30 min. Then, the substrate was again immersed in 40 mM of TiCU solution for 30 min at 70 °C, followed by sintering at 500 °C for 30 min.
  • the films were dipped into ethanolic solution containing 0.2 mM D35 (Dyenamo) for 4 hours.
  • Spiro-OMeTAD (2,2',7,7'-tetrakis- (/V,/V-di-p-methoxyphenylamine)9,9'-spirobifluorene) solution was subsequently spin-coated on top of mesoporous T1O2 film loaded with D35 sensitizers.
  • Gold counter electrode was deposited using thermal evaporation method. The cross-section of the device is shown in Fig.10.
  • the redox potential of the new spiro-OMeTAD dopant (MY1) is characterized by using cyclic voltammetry.
  • the CV plot is given in Figure 6.
  • the redox potential of the MY1 was found to be 1.26 V vs. NHE which is more positive compared to the first oxidation potential (0.72 V vs. NHE) of spiro-OMeTAD.
  • oxidation of pristine spiro-OMeTAD can be investigated via optical absorption measurement of doped spiro-OMeTAD solution.
  • the UV-Vis absorption spectra of spiro- OMeTAD in chlorobenzene solution with different MY1 doping concentrations are shown in Fig. 7. With gradually increase of dopant concentrations, the appearance of absorption band at 523 nm is enhanced which is corresponded to the absorption of oxidized spiro species (spiro-OMeTAD + ).
  • non-doped spiro-OMeTAD is having an issue of low conductivity.
  • MYl dopant By using MYl dopant, spiro-OMeTAD is oxidized and radical cation of MeOTAD* is formed. These free charge carriers increase the conductivity of spiro-OMeTAD and hence exhibited better photovoltaic performances.
  • Solar cells using MYl-doped spiro-OMeTAD were fabricated together with the devices having non-doped and FK102-doped spiro-OMeTAD according to the process disclosed in Example 1 d).
  • Fig. 10 [0085] J-V curves measured under simulated AM1.5G (100 mWcm 2 ) of these devices are illustrated in Figure 9 whereas the photovoltaic parameters are summarized in Table 1.
  • FK102 has been shown its optimized performance at 1.6 mole% doping concentration 2 . From Table 2, it can be noticed that 0.9% doping concentration of MY1 performs better than FK102 (1.6% doping concentration) in which 4.9 % of power conversion efficiency is achieved by using Y1 dopant. Owing to its more positive redox potential as compared to FK102 (1.26 V vs. 1.06 V), spiro-OMeTAD-to-spiro-OMeTAD + conversion efficiency of Y1 is higher than FK102 (73% vs. 65%). Unlike the use of 1.6% doping concentration in FK102, high power conversion efficiency can also be accomplished by using lesser doping concentration (0.9% in MY1). The high spiro-OMeTAD conversion yield in MY1 allows less amount of dopant to be used in device which leads to reduced manufacturing cost.
  • MYl doping concentration With only 0.9% of MYl doping concentration, a power conversion efficiency of 4.9% has been obtained. The power conversion of the obtained with the present is higher than that of using FK102 at a higher doping concentration of 1.6%. The feasibility of using minimal amount of dopant in achieving high efficiency ssDSCs could reduce the manufacturing cost as well as enhance the device long term stability. Lastly, MYl with highly positive redox potential can be dopant for more kinds of HTMs as compared to FK102 in organic electronics and photovoltaic applications.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Hybrid Cells (AREA)

Abstract

La présente invention concerne un nouveau complexe de formule (I) qui est utile en tant que dopant p. Le nouveau complexe est un complexe de Co3+, Ni3+, Cr3+, Mn3+ou Fe3+, et contient de nouveaux ligands bi- ou tridentés. L'invention concerne en outre l'utilisation du nouveau complexe en tant que dopant p dans un matériau transporteur de trou (HTM). L'invention concerne en outre un HTM à dopage p avec le complexe de l'invention. L'invention concerne en outre un dispositif photo-électrochimique tel qu'une cellule solaire, des cellules solaires sensibilisées par colorant à hétérojonction solide (ssDSC) qui comprennent le complexe de l'invention.
PCT/SG2013/000487 2012-11-20 2013-11-15 Dopants pour cellules solaires sensibilisées par colorant à hétérojonction solide WO2014081388A1 (fr)

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JP2016046486A (ja) * 2014-08-26 2016-04-04 株式会社豊田中央研究所 金属錯体色素、配位子及び色素増感型太陽電池
WO2019181701A1 (fr) * 2018-03-19 2019-09-26 Ricoh Company, Ltd. Élément de conversion photoélectrique et module d'élément de conversion photoélectrique
JP2019176136A (ja) * 2018-03-29 2019-10-10 株式会社リコー 光電変換素子、及び光電変換素子モジュール
JP2020102602A (ja) * 2018-03-19 2020-07-02 株式会社リコー 光電変換素子、及び光電変換素子モジュール
WO2020250901A1 (fr) * 2019-06-10 2020-12-17 Ricoh Company, Ltd. Élément de conversion photoélectrique, module d'élément de conversion photoélectrique, dispositif électronique et module d'alimentation électrique
JP2021027078A (ja) * 2019-07-31 2021-02-22 株式会社リコー 光電変換素子、電子機器、及び電源モジュール

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016046486A (ja) * 2014-08-26 2016-04-04 株式会社豊田中央研究所 金属錯体色素、配位子及び色素増感型太陽電池
WO2019181701A1 (fr) * 2018-03-19 2019-09-26 Ricoh Company, Ltd. Élément de conversion photoélectrique et module d'élément de conversion photoélectrique
JP2020102602A (ja) * 2018-03-19 2020-07-02 株式会社リコー 光電変換素子、及び光電変換素子モジュール
JP2019176136A (ja) * 2018-03-29 2019-10-10 株式会社リコー 光電変換素子、及び光電変換素子モジュール
WO2020250901A1 (fr) * 2019-06-10 2020-12-17 Ricoh Company, Ltd. Élément de conversion photoélectrique, module d'élément de conversion photoélectrique, dispositif électronique et module d'alimentation électrique
JP2021027078A (ja) * 2019-07-31 2021-02-22 株式会社リコー 光電変換素子、電子機器、及び電源モジュール

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