CN102959660A - Photoelectric conversion device comprising hydroxamic acid derivative or salt thereof as additive and process for producing same - Google Patents

Photoelectric conversion device comprising hydroxamic acid derivative or salt thereof as additive and process for producing same Download PDF

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CN102959660A
CN102959660A CN2011800309999A CN201180030999A CN102959660A CN 102959660 A CN102959660 A CN 102959660A CN 2011800309999 A CN2011800309999 A CN 2011800309999A CN 201180030999 A CN201180030999 A CN 201180030999A CN 102959660 A CN102959660 A CN 102959660A
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alkyl
aryl
base
alkoxyl
heteroaryl
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CN102959660B (en
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N·G·普希雷尔
F·艾克迈尔
J·舍恩布姆
R·森斯
P·埃尔克
H·赖歇尔特
H·博格曼
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BASF SE
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • 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
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K99/00—Subject matter not provided for in other groups of this subclass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • 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

Abstract

Disclosed is a process for producing a photoelectric conversion device comprising a dye-sensitized metal oxide semiconductor, which is treated with an essentially transparent hydroxamic acid derivative or a salt thereof. Also disclosed are the photoelectric conversion device obtained by the said process and the use of the essentially transparent hydroxamic acid derivative for enhancing the energy conversion efficiency eta of dye-sensitized photoelectric conversion device.

Description

Comprise hydroxamic acid derivs or its salt as photoelectric conversion device of additive and preparation method thereof
The present invention relates to a kind of method for preparing the photovoltaic converter that comprises the dye sensitization metal-oxide semiconductor (MOS) of processing with its salt of the hydroxamic acid of substantially transparent or substantially transparent.The invention still further relates to a kind of photoelectric conversion device that can obtain by the inventive method, also relate to a kind of photocell that comprises described photoelectric conversion device, especially solar cell.In addition, the invention still further relates to the purposes of its salt in the energy conversion efficiency η that improves the dye sensitization photovoltaic converter of hydroxamic acid or the substantially transparent of substantially transparent.
Background of invention
Use for example is disclosed in United States Patent (USP) 4 by the photoelectric conversion device (hereinafter referred to as " dye sensitization photoelectric conversion device ") of the metal oxide semiconductor of dye sensitization and material thereof and preparation method, 927,721,5,350,644,6,245,988, in WO 2007/054470 and WO 2009/013258.Because it can use for its cheap metal oxide semiconductor as titanium dioxide and without purifying to high-purity, the dye sensitization photoelectric conversion device can be to compare the cost preparation of reduction with silica-based battery.
For example, photoelectric conversion device overall performance for () solar cell is characterised in that some parameters, as open circuit voltage (V oc), short circuit current (I sc), fill factor, curve factor (FF) and the energy conversion efficiency (η) (referring to for example Jenny Nelson, " The Physics of Solar Cells " (2003), Imperial College Press) that caused by it.
Because traditional dye sensitization photoelectric conversion device not necessarily has sufficiently high electricity conversion, many trials have been carried out further to improve these devices.
For this reason, EP 1473745 has proposed to make the compound with hydrophobic part and anchoring group to be adsorbed to altogether together with dyestuff on metal oxide semiconductor, and it has been described this and has caused open circuit voltage V ocraising.
US 6,586, and 670 have reported a kind of dye sensitization photoelectric conversion device that uses the metal oxide semiconductor of processing with specific carbamide compound, and it has excellent energy conversion efficiency η.
The dyestuff that use comprises the hydroxamate structure division is for example known by WO 99/03868, WO 2008/029523 and WO 2006/010290 to prepare photoelectric conversion device as anchoring group.Yet, with regard to photoelectric conversion, not yet report up to now the hydroxamic acid salt compound for any other purpose except in conjunction with catching photoinitiator dye.
Still continue further to improve performance, especially its energy conversion efficiency η of dye sensitization photoelectric conversion device.
Therefore, the purpose of this invention is to provide a kind of photoelectric conversion device with energy conversion efficiency η of improvement, comprise solar cell of described device and preparation method thereof.
Described purpose realizes by the method and the device that hereinafter describe in detail.
The present invention relates to a kind of method for preparing the dye sensitization photoelectric conversion device, described device comprises the photosensitive layer that the metal oxide semiconductor of at least one chromonic material is arranged containing absorption at least one its, wherein said metal oxide semiconductor is used in 400-1000nm, and preferably in the electromagnetic wavelength scope of 400-800nm, at least one hydroxamic acid of substantially transparent or at least one its salt are processed.
Surprisingly, add this class hydroxamic acid/hydroxamic acid salt additives and cause device performance significantly to improve in dye sensitization photoelectric conversion device and the solar cell that comprises this device, even in the situation that to have extinction dyestuff still less in battery be also like this.
The invention still further relates to and a kind ofly can obtain and there is the dye sensitization photoelectric conversion device of following feature and the photocell that comprises this class device by the inventive method, preferably solar cell.Described photocell comprises the dye sensitization photoelectric conversion device and is the part of circuit.In addition, the invention still further relates to above and hereinafter defined hydroxamic acid and/or its salt at the photocell that improves the dye sensitization photoelectric conversion device and comprise described device, the purposes in the energy conversion efficiency η of solar cell especially.
Hereinafter the description of the inventive method also is applicable to dye sensitization photoelectric conversion device of the present invention and photocell.
In the context of the invention, " substantially transparent " means hydroxamic acid or its salt does not absorb substantially, and does not preferably also substantially reflect 400-1000nm, preferably the electromagnetic radiation in the 400-800nm wave-length coverage.
" substantially do not absorb, and preferably substantially do not reflect yet " in described wave-length coverage mean hydroxamic acid or its salt have in carrene, record at 400-1000nm, preferably in 400-800nm electromagnetic wavelength scope lower than 10 3lmol -1cm -1, preferably lower than 10 2lmol -1cm -1extinction coefficient.
If use TiO 2as metal oxide semiconductor, hydroxamic acid or its salt can have and TiO 2absorb overlapping electric charge transfer absorbed band.The extinction coefficient of these charge-transfer bands is at 400nm place<1000L/ (molcm), and in fact the photoelectric current of photovoltaic cell do not contributed.
The inventive method and device have some advantages.For example, the inventive method allows cheap and easily prepares and have the feature of excellent energy conversion efficiency η and be highly suitable for the durable photoelectric conversion device in solar cell.
In the context of the present invention, term used is defined as follows usually:
Term " cation equivalent " refer to can in and hydroxamic acid anion (R 1-C (O)-NR 2-O -) cationic equivalent.For example, Ca 2+ion can be in conjunction with 2 hydroxamic acid roots, i.e. M in formula (I') +corresponding to 1/2Ca 2+, now cation equivalent is the calcium ion equivalent.
Except as otherwise noted, term " alkyl ", " alkoxyl ", " alkylthio group ", " haloalkyl ", " halogenated alkoxy ", " halogenated alkylthio ", " alkenyl ", " alkadienyl ", " alkatriene base ", " alkynyl ", " alkylidene " and derivative group comprises respectively not " alkyl ", " alkoxyl ", " alkylthio group ", " haloalkyl ", " halogenated alkoxy ", " halogenated alkylthio ", " alkenyl ", " alkadienyl ", " alkatriene base ", " alkynyl " and " alkylidene " of branching and branching all the time by it.
Prefix C n-C mmean the corresponding carbon number in the hydrocarbon unit.Except as otherwise noted, the halo substituting group preferably has 1-5 identical or different halogen atom, especially fluorine atom or chlorine atom.In the context of the present specification, except as otherwise noted, C 0alkylidene or (CH 2) 0or similar wording refers to singly-bound.
Term " halogen " refers to fluorine, bromine, chlorine or iodine in each case, refers in particular to fluorine, chlorine or bromine.
For example, alkyl structure part in alkyl and () alkoxyl, alkylthio group, aralkyl, heteroarylalkyl, cycloalkyl-alkyl or alkoxyalkyl: there is one or more C atoms, for example 1-4 is individual, 1-6 is individual, 1-8 is individual, 1-10 is individual, 1-12 is individual or saturated straight chain or the branched hydrocarbyl radical of 1-18 carbon atom, for example C 1-C 4alkyl is as methyl, ethyl, propyl group, 1-Methylethyl (isopropyl), butyl, 1-methyl-propyl (sec-butyl), 2-methyl-propyl (isobutyl group) or 1,1-dimethyl ethyl (tert-butyl group), C 1-C 6alkyl is as methyl, ethyl, propyl group, the 1-Methylethyl, butyl, the 1-methyl-propyl, the 2-methyl-propyl, 1, the 1-dimethyl ethyl, amyl group, the 1-methyl butyl, the 2-methyl butyl, the 3-methyl butyl, 2, the 2-dimethyl propyl, the 1-ethyl propyl, hexyl, 1, the 1-dimethyl propyl, 1, the 2-dimethyl propyl, the 1-methyl amyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 1-dimethylbutyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 2, the 3-dimethylbutyl, 3, the 3-dimethylbutyl, the 1-ethyl-butyl, the 2-ethyl-butyl, 1, 1, 2-trimethyl propyl group, 1, 2, 2-trimethyl propyl group, 1-ethyl-1-methyl-propyl or 1-Ethyl-2-Methyl propyl group, C 1-C 8alkyl is as above to C 1-C 6the described group of alkyl, also have heptyl, 2-methyl hexyl, octyl group or 2,4-diethylhexyl and position isomer thereof in addition, C 1-C 10alkyl is as above to C 1-C 8the described group of alkyl, also have nonyl, decyl, 2,4-dimethyl octyl group and position isomer thereof in addition, C 1-C 12alkyl is as above to C 1-C 10the described group of alkyl, also have undecyl, dodecyl, 5,7-dimethyl decyl, 3-methyl undecyl and position isomer thereof in addition, and C 1-C 18alkyl is as above to C 1-C 12the described group of alkyl, also have tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl and position isomer thereof in addition.
C 3-C 10alkyl is saturated straight chain or the branched hydrocarbyl radical with 3-10 carbon atom.The example is propyl group, 1-Methylethyl (isopropyl), butyl, 1-methyl-propyl (sec-butyl), 2-methyl-propyl (isobutyl group), 1, 1-dimethyl ethyl (tert-butyl group), amyl group, the 1-methyl butyl, the 2-methyl butyl, the 3-methyl butyl, 2, the 2-dimethyl propyl, the 1-ethyl propyl, hexyl, 1, the 1-dimethyl propyl, 1, the 2-dimethyl propyl, the 1-methyl amyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 1-dimethylbutyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 2, the 3-dimethylbutyl, 3, the 3-dimethylbutyl, the 1-ethyl-butyl, the 2-ethyl-butyl, 1, 1, 2-trimethyl propyl group, 1, 2, 2-trimethyl propyl group, 1-ethyl-1-methyl-propyl, 1-Ethyl-2-Methyl propyl group, heptyl, 2-methyl hexyl, octyl group, 2, the 4-diethylhexyl, nonyl, decyl, 2, 4-dimethyl octyl group and position isomer thereof.
C 3-C 12alkyl is saturated straight chain or the branched hydrocarbyl radical with 3-12 carbon atom.The example removes above to C 3-C 10alkyl is described outside those, also has undecyl, dodecyl, 5,7-dimethyl decyl, 3-methyl undecyl and position isomer thereof.
Haloalkyl: its hydrogen atom by halogen atom as fluorine, chlorine, what bromine and/or iodine partially or completely replaced has 1-4 usually, 1-6, 1-8, 1-10, the abovementioned alkyl of 1-12 or 1-18 carbon atom, for example chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, the chlorine methyl fluoride, dichlorofluoromethyl, chlorodifluoramethyl-, the 2-fluoro ethyl, the 2-chloroethyl, the 2-bromoethyl, 2-iodine ethyl, 2,2-, bis-fluoro ethyls, 2,2,2-trifluoroethyl, the chloro-2-fluoro ethyl of 2-, 2-is chloro-2,2-bis-fluoro ethyls, the chloro-2-fluoro ethyl of 2,2-bis-, 2,2,2-, tri-chloroethyls, pentafluoroethyl group, the 2-fluoropropyl, the 3-fluoropropyl, 2,2-, bis-fluoropropyls, 2,3-, bis-fluoropropyls, the 2-chloropropyl, the 3-chloropropyl, 2,3-, bis-chloropropyls, the 2-bromopropyl, the 3-bromopropyl, 3,3,3-trifluoro propyl, 3,3,3-, tri-chloropropyls, 2,2,3,3,3-, five fluoropropyls, seven fluoropropyls, 1-(methyl fluoride)-2-fluoro ethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorine butyl, the 4-chlorobutyl, the 4-brombutyl, nine fluorine butyl, 3-chlorine amyl group, 2-(methyl fluoride) hexyl, 4-bromine heptyl, 1-(chloromethyl)-5-chlorine octyl group, 2,3-difluoro nonyl, 10-bromine decyl, 2,3,6-trifluoro undecyl, 2-chlorododecane base.
Cycloalkyl and (for example) cycloalkyloxy or cycloalkyl C 1-C 6cycloalkyl structure division in alkyl: have 3 or more C atom, for example 3-7 carbocyclic ring member is as 3,4,5,6 or 7 carbocyclic ring members' monocyclic saturated hydrocarbon group base, as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl or suberyl.
Alkenyl and (for example) aryl C 2-C 6alkenyl structure part in alkenyl: have 2 or more C atom, for example 2-4 is individual, 2-6 is individual or 2-12 carbon atom and cholesterol straight chain or the branched hydrocarbyl radical that is positioned at two keys of optional position, for example a C 2-C 6alkenyl is as vinyl, the 1-acrylic, the 2-acrylic, the 1-methyl ethylene, the 1-cyclobutenyl, the 2-cyclobutenyl, the 3-cyclobutenyl, 1-methyl-1-propylene base, 2-methyl-1-propylene base, 1-methyl-2-acrylic, 2-methyl-2-acrylic, the 1-pentenyl, the 2-pentenyl, the 3-pentenyl, the 4-pentenyl, 1-methyl isophthalic acid-cyclobutenyl, the 2-methyl-1-butene thiazolinyl, the 3-methyl-1-butene base, 1-methyl-2-butene base, 2-methyl-2-butene base, 3-methyl-2-butene base, 1-methyl-3-cyclobutenyl, 2-methyl-3-cyclobutenyl, 3-methyl-3-cyclobutenyl, 1,1-dimethyl-2-acrylic, 1,2-dimethyl-1-acrylic, 1,2-dimethyl-2-acrylic, 1-ethyl-1-acrylic, 1-ethyl-2-acrylic, the 1-hexenyl, the 2-hexenyl, the 3-hexenyl, the 4-hexenyl, the 5-hexenyl, 1-methyl-1-pentene thiazolinyl, 2-methyl-1-pentene thiazolinyl, 3-methyl-1-pentene thiazolinyl, the 4-methyl-1-pentene base, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, the 1-methyl-3-pentenyl, the 2-methyl-3-pentenyl, the 3-methyl-3-pentenyl, the 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-cyclobutenyl, 1,1-dimethyl-3-cyclobutenyl, 1,2-dimethyl-1-cyclobutenyl, 1,2-dimethyl-2-cyclobutenyl, 1,2-dimethyl-3-cyclobutenyl, 1,3-dimethyl-1-cyclobutenyl, 1,3-dimethyl-2-cyclobutenyl, 1,3-dimethyl-3-cyclobutenyl, 2,2-dimethyl-3-cyclobutenyl, 2,3-dimethyl-1-cyclobutenyl, 2,3-dimethyl-2-cyclobutenyl, 2,3-dimethyl-3-cyclobutenyl, 3,3-dimethyl-1-cyclobutenyl, 3,3-dimethyl-2-cyclobutenyl, 1-ethyl-1-cyclobutenyl, 1-ethyl-2-cyclobutenyl, 1-ethyl-3-cyclobutenyl, 2-ethyl-1-cyclobutenyl, 2-ethyl-2-cyclobutenyl, 2-ethyl-3-cyclobutenyl, 1,1,2-trimethyl-2-acrylic, 1-ethyl-1-methyl-2-acrylic, 1-Ethyl-2-Methyl-1-acrylic, 1-Ethyl-2-Methyl-2-acrylic.
Alkynyl: have 2 or more C atom, for example 2-4,2-6 or 2-12 carbon atom and 1 or 2 are positioned at any position but straight chain or the branched hydrocarbyl radical of non-conterminous triple bond, for example C 2-C 6alkynyl is as acetenyl, the 1-propinyl, 2-propynyl, the 1-butynyl, the 2-butynyl, the 3-butynyl, 1-methyl-2-propynyl, the 1-pentynyl, the valerylene base, the 3-pentynyl, the 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl isophthalic acid-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexin base, 2-hexin base, 3-hexin base, 4-hexin base, 5-hexin base, 1-methyl-valerylene base, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentene alkynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentene alkynyl, 4-methyl-valerylene base, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl.
Alkadienyl: there is 4 or more carbon atom, for example 4-6, 4-10 or 4-12 carbon atom and two are positioned at optional position but straight chain or the branched hydrocarbyl radical of non-conterminous pair of key, as 2, the 4-butadienyl, 2, the 4-pentadienyl, 2-methyl-2, the 4-pentadienyl, 2, the 4-hexadienyl, 2, 4-heptadiene base, 2, the 4-octadienyl, 2, 4-nonadiene base, 2, 4-decadinene base, 1, the 3-butadienyl, 1, the 3-pentadienyl, the 2-methyl isophthalic acid, the 3-pentadienyl, 1, the 3-hexadienyl, 1, 3-heptadiene base, 1, the 3-octadienyl, 1, 3-nonadiene base, 1, 3-decadinene base etc.
Alkatriene base: there is 6 or more carbon atom, for example 6-8, 6-10 or 6-12 carbon atom and three are positioned at optional position but straight chain or the branched hydrocarbyl radical of non-conterminous pair of key, as 2, 4, 6-hexatriene base, 2, 4, 6-heptantriene base, 2-methyl-2, 4, 6-heptantriene base, 2, 4, 6-sarohornene base, 2, 4, 6-trialkenyl in the ninth of the ten Heavenly Stems, 2, 4, 6-trialkenyl in the last of the ten Heavenly stems, 2, 4, 6-11 carbon trialkenyl, 2, 4, 6-12 carbon trialkenyl, 1, 3, 5-hexatriene base, 1, 3, 5-heptantriene base, the 2-methyl isophthalic acid, 3, 5-heptantriene base, 1, 3, 5-sarohornene base, 1, 3, 5-trialkenyl in the ninth of the ten Heavenly Stems, 1, 3, 5-trialkenyl in the last of the ten Heavenly stems, 1, 3, 5-11 carbon trialkenyl, 1, 3, 5-12 carbon trialkenyl etc.
CH wherein 2group is referred to wherein one or more non-conterminous-CH by the group of O, NH or S replacement 2-group independently of one another by-O-,-NH-or-alkyl that S-replaces.The example of this class group is-CH 2-CH 2-O-CH 3,-CH 2-CH 2-O-CH 2-CH 2-O-CH 3,-CH 2-CH 2-O-CH 2-CH 2-NH-CH 3,-CH 2=CH 2-CH 2-O-CH 3,-CH 2-CH 2-S-CH 3deng.
For example, alkoxyl structure division in alkoxyl or () alkoxyalkyl:
As hereinbefore defined, it preferably has 1-4 to alkyl, 1-6 or 1-12 C atom, it is via the former sub-connection of O: methoxyl group for example, ethyoxyl, positive propoxy, the 1-methyl ethoxy, butoxy, 1-methyl propoxyl group, 2-methyl propoxyl group or 1,1-dimethyl ethyoxyl, amoxy, 1-methyl butoxy, 2-methyl butoxy, 3-methyl butoxy, 1,1-dimethyl propoxyl group, 1,2-dimethyl propoxyl group, 2,2-dimethyl propoxyl group, 1-ethyl propoxyl group, own oxygen base, 1-methyl amoxy, 2-methyl amoxy, 3-methyl amoxy, 4-methyl amoxy, 1,1-dimethyl butoxy, 1,2-dimethyl butoxy, 1,3-dimethyl butoxy, 2,2-dimethyl butoxy, 2,3-dimethyl butoxy, 3,3-dimethyl butoxy, 1-ethyl butoxy, 2-ethyl butoxy, 1,1,2-trimethyl propoxyl group, 1,2,2-trimethyl propoxyl group, 1-ethyl-1-methyl propoxyl group or 1-Ethyl-2-Methyl propoxyl group, amoxy, own oxygen base, heptan the oxygen base, the own oxygen base of 2-methyl, 4-propyl group oxygen in heptan base, octyloxy, 2,4-diethyl octyloxy, the ninth of the ten Heavenly Stems oxygen base, 3,4-dimethyl oxygen in ninth of the ten Heavenly Stems base, the last of the ten Heavenly stems oxygen base, 3-ethyl oxygen in last of the ten Heavenly stems base.
C 3-C 10alkoxyl is saturated straight chain or the branched hydrocarbyl radical with 3-10 carbon atom.The example is propoxyl group, 1-methyl ethoxy (isopropoxy), butoxy, 1-methyl propoxyl group (sec-butoxy), 2-methyl propoxyl group (isobutoxy), 1,1-dimethyl ethyoxyl (tert-butoxy), amoxy, 1-methyl butoxy, 2-methyl butoxy, 3-methyl butoxy, 2,2-dimethyl propoxyl group, 1-ethyl propoxyl group, own oxygen base, 1,1-dimethyl propoxyl group, 1,2-dimethyl propoxyl group, 1-methyl amoxy, 2-methyl amoxy, 3-methyl amoxy, 4-methyl amoxy, 1,1-dimethyl butoxy, 1,2-dimethyl butoxy, 1,3-dimethyl butoxy, 2,2-dimethyl butoxy, 2,3-dimethyl butoxy, 3,3-dimethyl butoxy, 1-ethyl butoxy, 2-ethyl butoxy, 1,1,2-trimethyl propoxyl group, 1,2,2-trimethyl propoxyl group, 1-ethyl-1-methyl propoxyl group, 1-Ethyl-2-Methyl propoxyl group, heptan the oxygen base, the own oxygen base of 2-methyl, octyloxy, the own oxygen base of 2,4-diethyl, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, 2,4-dimethyl octyloxy and position isomer thereof.
C 3-C 12alkoxyl is saturated straight chain or the branched hydrocarbyl radical with 3-12 carbon atom.The example is except above to C 3-C 10alkoxyl is described outside those, also has hendecane oxygen base, dodecyloxy, 5,7-dimethyl oxygen in last of the ten Heavenly stems base, 3-methyl hendecane oxygen base and position isomer thereof.
Halogenated alkoxy: above-mentioned alkoxyl, wherein the hydrogen atom of these groups is replaced wholly or in part by halogen atom, that is, and C for example 1-C 6halogenated alkoxy is as the chlorine methoxyl group, the dichloro methoxyl group, the trichlorine methoxyl group, the fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group, dichloro fluorine methoxyl group, the chlorine difluoro-methoxy, 2-fluorine ethyoxyl, the 2-chloroethoxy, the 2-bromine oxethyl, 2-iodine ethyoxyl, 2,2-difluoroethoxy, 2,2,2-trifluoro ethoxy, the chloro-2-fluorine of 2-ethyoxyl, 2-is chloro-2, the 2-difluoroethoxy, the chloro-2-fluorine of 2,2-bis-ethyoxyl, 2,2,2-, tri-chloroethoxies, five fluorine ethyoxyls, 2-fluorine propoxyl group, 3-fluorine propoxyl group, 2,2-difluoro propoxyl group, 2,3-difluoro propoxyl group, 2-chlorine propoxyl group, 3-chlorine propoxyl group, 2,3-dichloro propoxyl group, 2-bromine propoxyl group, 3-bromine propoxyl group, 3,3,3-trifluoro propoxyl group, 3,3,3-trichlorine propoxyl group, 2,2,3,3,3-, five fluorine propoxyl group, seven fluorine propoxyl group, 1-(methyl fluoride)-2-fluorine ethyoxyl, 1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromine oxethyl, 4-fluorine butoxy, 4-chlorine butoxy, 4-bromine butoxy, nine fluorine butoxy, the fluoro-1-amoxy of 5-, the chloro-1-amoxy of 5-, the bromo-1-amoxy of 5-, the iodo-1-amoxy of 5-, the chloro-1-amoxy of 5,5,5-tri-, 11 fluorine amoxys, the own oxygen base of the fluoro-1-of 6-, the own oxygen base of the chloro-1-of 6-, the own oxygen base of the bromo-1-of 6-, the own oxygen base of the iodo-1-of 6-, the own oxygen base of the chloro-1-of 6,6,6-tri-or the own oxygen base of ten difluoros are especially the chlorine methoxyl group, the fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, 2-fluorine ethyoxyl, 2-chloroethoxy or 2,2,2-trifluoro ethoxy.
Alkoxyalkyl: one of them hydrogen atom is had the alkyl that alkoxyl replaced of 1-6 or 1-4 C atom usually.The example is CH 2-OCH 3, CH 2-OC 2h 5, n-propoxymethyl, CH 2-OCH (CH 3) 2, n-butoxy methyl, (1-methyl propoxyl group) methyl, (2-methyl propoxyl group) methyl, CH 2-OC (CH 3) 3, 2-(methoxyl group) ethyl, 2-(ethyoxyl) ethyl, 2-(positive propoxy) ethyl, 2-(1-methyl ethoxy) ethyl, 2-(n-butoxy) ethyl, 2-(1-methyl propoxyl group) ethyl, 2-(2-methyl propoxyl group) ethyl, 2-(1,1-dimethyl ethyoxyl) ethyl, 2-(methoxyl group) propyl group, 2-(ethyoxyl) propyl group, 2-(positive propoxy) propyl group, 2-(1-methyl ethoxy) propyl group, 2-(n-butoxy) propyl group, 2-(1-methyl propoxyl group) propyl group, 2-(2-methyl propoxyl group) propyl group, 2-(1,1-dimethyl ethyoxyl) propyl group, 3-(methoxyl group) propyl group, 3-(ethyoxyl) propyl group, 3-(positive propoxy) propyl group, 3-(1-methyl ethoxy) propyl group, 3-(n-butoxy) propyl group, 3-(1-methyl propoxyl group) propyl group, 3-(2-methyl propoxyl group) propyl group, 3-(1,1-dimethyl ethyoxyl) propyl group, 2-(methoxyl group) butyl, 2-(ethyoxyl) butyl, 2-(positive propoxy) butyl, 2-(1-methyl ethoxy) butyl, 2-(n-butoxy) butyl, 2-(1-methyl propoxyl group) butyl, 2-(2-methyl propoxyl group) butyl, 2-(1,1-dimethyl ethyoxyl) butyl, 3-(methoxyl group) butyl, 3-(ethyoxyl) butyl, 3-(positive propoxy) butyl, 3-(1-methyl ethoxy) butyl, 3-(n-butoxy) butyl, 3-(1-methyl propoxyl group) butyl, 3-(2-methyl propoxyl group) butyl, 3-(1,1-dimethyl ethyoxyl) butyl, 4-(methoxyl group) butyl, 4-(ethyoxyl) butyl, 4-(positive propoxy) butyl, 4-(1-methyl ethoxy) butyl, 4-(n-butoxy) butyl, 4-(1-methyl propoxyl group) butyl, 4-(2-methyl propoxyl group) butyl, 4-(1,1-dimethyl ethyoxyl) butyl etc.
Alkylthio group: preferably have the above defined alkyl of 1-6 or 1-4 C atom, it is via the former sub-connection of S, such as methyl mercapto, ethylmercapto group, rosickyite base etc. just.
Halogenated alkylthio: the above defined haloalkyl that preferably there is 1-6 or 1-4 C atom, it is via the former sub-connection of S, for example fluorine methyl mercapto, difluoro methyl mercapto, trifluoromethylthio, 2-fluorine ethylmercapto group, 2,2-difluoro ethylmercapto group, 2,2,2-trifluoro ethylmercapto group, five fluorine ethylmercapto groups, 2-fluorine rosickyite base, 3-fluorine rosickyite base, 2,2-difluoro rosickyite base, 2,3-difluoro rosickyite base and seven fluorine rosickyite bases.
Aryl: monocycle, dicyclo or thrcylic aromatic hydrocarbon group be as phenyl or naphthyl, especially phenyl.
Heterocyclic radical: can be saturated (" Heterocyclylalkyl ") or part is undersaturated and usually have the heterocyclic radical of 3,4,5,6,7 or 8 annular atomses, wherein except the carbon atom as ring members, common 1,2,3 or 4, especially 1,2 or 3 annular atoms is that hetero-atom is as N, S or O.
The example of saturated heterocyclyl is especially:
Heterocyclylalkyl:, usually have the saturated heterocyclyl of 3,4,5,6 or 7 annular atomses, wherein, except the carbon atom as ring members, common 1,2 or 3 annular atoms is that hetero-atom is as N, S or O.These for example comprise:
3-4 person's saturated rings of C-keyed jointing, as: 2-Oxyranyle, 2-oxetanyl, 3-oxetanyl, 2-aziridinyl, 3-Thietane base (thiethanyl), 1-azetidinyl, 2-azetidinyl;
5-person's saturated rings of C-keyed jointing, as different as: oxolane-2-base, oxolane-3-base, thiophane-2-base, thiophane-3-base, nafoxidine-2-base (pyrrolidin-2-yl), nafoxidine-3-base (pyrrolidin-3-yl), tetrahydro-pyrazole-3-base (pyrazolidine-3-yl), tetrahydro-pyrazole-4-base (pyrazolidine-4-yl), tetrahydrochysene
Figure BDA00002636077400091
azoles-3-base is (different azoles alkane-3-yl), tetrahydrochysene is different
Figure BDA00002636077400093
azoles-4-base is (different
Figure BDA00002636077400094
azoles alkane-4-yl), tetrahydrochysene is different
Figure BDA00002636077400095
azoles-5-base is (different
Figure BDA00002636077400096
azoles alkane-5-yl), 1,2-oxa-thia penta ring (oxathiolan)-3-base, 1,2-oxa-thia penta ring-4-base, 1,2-oxa-thia penta ring-5-base, tetrahydrochysene isothiazole-3-base (isothiazolidine-3-yl), tetrahydrochysene isothiazole-4-base (isothiazolidine-4-yl), tetrahydrochysene isothiazole-5-base (isothiazolidine-5-yl), 1,2-dithiolane-3-base, 1,2-dithiolane-4-base, imidazolidine-2-base (imidazolidine-2-yl), imidazolidine-4-base (imidazolidine-4-yl), tetrahydrochysene
Figure BDA00002636077400097
azoles-2-base (
Figure BDA00002636077400098
azoles alkane-2-yl), tetrahydrochysene azoles-4-base (
Figure BDA000026360774000910
azoles alkane-4-yl), tetrahydrochysene
Figure BDA000026360774000911
azoles-5-base (
Figure BDA000026360774000912
azoles alkane-5-yl), tetrahydro-thiazoles-2-base (thiazolidine-2-yl), tetrahydro-thiazoles-4-base (thiazolidine-4-yl), tetrahydro-thiazoles-5-base (thiazolidine-5-yl), [1,2,3] triazolidine-4-base, [1,2,4] triazolidine-3-base, 1,3-dioxolanes-2-base, 1,3-dioxolanes-4-base, 1,3-oxa-thia penta ring-2-base, 1,3-oxa-thia penta ring-4-base, 1,3-oxa-thia penta ring-5-base, 1,3-dithiolane-2-base, 1,3-dithiolane-4-base, 1,3,2-dioxa thia penta ring-4-base;
6 Yuans saturated rings of C-keyed jointing, as: oxinane-2-base, tetrahydropyran-3-base, tetrahydropyran-4-base, piperidin-2-yl, piperidines-3-base, piperidin-4-yl, tetrahydric thiapyran-2-base, tetrahydric thiapyran-3-group, tetrahydric thiapyran-4-group, 1,3-bis-
Figure BDA000026360774000913
alkane-2-base, 1,3-bis-
Figure BDA000026360774000914
alkane-4-base, 1,3-bis-
Figure BDA000026360774000915
alkane-5-base, Isosorbide-5-Nitrae-bis-
Figure BDA000026360774000916
alkane-2-base, 1,3-dithiane-2-base, 1,3-dithiane-4-base, 1,3-dithiane-5-base, 1,4-dithiane-2-base, 1,3-thioxane-2-base, 1,3-thioxane-4-base, 1,3-thioxane-5-base, 1,3-thioxane-6-base, Isosorbide-5-Nitrae-thioxane-2-base, 1,4-thioxane-3-base, 1,2-dithiane-3-base, 1,2-dithiane-4-base, hexahydropyrimidine-2-base, hexahydropyrimidine-4-base, hexahydropyrimidine-5-base, piperazine-2-base, hexahydro-pyridazine-3-base, hexahydro-pyridazine-4-base, tetrahydrochysene-1,3-
Figure BDA00002636077400101
piperazine-2-base, tetrahydrochysene-1,3-
Figure BDA00002636077400102
piperazine-4-base, tetrahydrochysene-1,3- piperazine-5-base, tetrahydrochysene-1,3-
Figure BDA00002636077400104
piperazine-6-base, tetrahydrochysene-1,3-thiazine-2-base, tetrahydrochysene-1,3-thiazine-4-base, tetrahydrochysene-1,3-thiazine-5-base, tetrahydrochysene-1,3-thiazine-6-base, tetrahydrochysene-Isosorbide-5-Nitrae-thiazine-2-base, tetrahydrochysene-1,4-thiazine-3-base, morpholine-2-Ji, morpholine-3-base, tetrahydrochysene-1,2-
Figure BDA00002636077400105
piperazine-3-base, tetrahydrochysene-1,2-
Figure BDA00002636077400106
piperazine-4-base, tetrahydrochysene-1,2-
Figure BDA00002636077400107
piperazine-5-base, tetrahydrochysene-1,2-
Figure BDA00002636077400108
piperazine-6-base;
5 Yuans saturated rings of N-keyed jointing, as different as: nafoxidine-1-base (pyrrolidin-1-yl), tetrahydro-pyrazole-1-base (pyrazolidine-1-yl), tetrahydrochysene
Figure BDA00002636077400109
azoles-2-base is (different
Figure BDA000026360774001010
azoles alkane-2-yl), tetrahydrochysene isothiazole-2-base (isothiazolidine-2-yl), imidazolidine-1-base (imidazolidine-1-yl), tetrahydrochysene
Figure BDA000026360774001011
azoles-3-base (
Figure BDA000026360774001012
azoles alkane-3-yl), tetrahydro-thiazoles-3-base (thiazolidine-3-yl);
6 Yuans saturated rings of N-keyed jointing, as: piperidin-1-yl, hexahydropyrimidine-1-base, hexahydropyrazine-1-base (piperazine-1-yl), hexahydro-pyridazine-1-base, tetrahydrochysene-1,3-
Figure BDA000026360774001013
piperazine-3-base, tetrahydrochysene-1,3-thiazine-3-base, tetrahydrochysene-Isosorbide-5-Nitrae-thiazine-4-base, tetrahydrochysene-Isosorbide-5-Nitrae-
Figure BDA000026360774001014
piperazine-4-base (morpholine-4-yl), tetrahydrochysene-1,2-
Figure BDA000026360774001015
piperazine-2-base.
Usually the undersaturated heterocyclic group of part that has 4,5,6 or 7 annular atomses, wherein, except the carbon atom as ring members, common 1,2 or 3 annular atoms is that hetero-atom is as N, S or O.These comprise, for example:
5 Yuans unsaturated rings of part of C-keyed jointing, as: DHF-2-base, DHF-3-base, DHF-2-base, DHF-3-base, 4,5-dihydrofuran-2-base, 4,5-dihydrofuran-3-base, 2,3-dihydro-thiophene-2-base, 2,3-dihydro-thiophene-3-base, 2,5-dihydro-thiophene-2-base, 2,5-dihydro-thiophene-3-base, 4,5-dihydro-thiophene-2-base, 4,5-dihydro-thiophene-3-base, 2,3-dihydro-1H-pyrroles-2-base, 2,3-dihydro-1H-pyrroles-3-base, 2,5-dihydro-1H-pyrroles-2-base, 2,5-dihydro-1H-pyrroles-3-base, 4,5-dihydro-1H-pyrroles-2-base, 4,5-dihydro-1H-pyrroles-3-base, 3,4-dihydro-2 h-pyrrole-2-base, 3,4-dihydro-2 h-pyrrole-3-base, 3,4-dihydro-5H-pyrroles-2-base, 3,4-dihydro-5H-pyrroles-3-base, 4,5-dihydro-1 h-pyrazole-3-base, 4,5-dihydro-1 h-pyrazole-4-base, 4,5-dihydro-1 h-pyrazole-5-base, 2,5-dihydro-1 h-pyrazole-3-base, 2,5-dihydro-1 h-pyrazole-4-base, 2,5-dihydro-1 h-pyrazole-5-base, 4,5-dihydro is different
Figure BDA000026360774001016
azoles-3-base, 4, the 5-dihydro is different
Figure BDA000026360774001017
azoles-4-base, 4, the 5-dihydro is different
Figure BDA000026360774001018
azoles-5-base, 2, the 5-dihydro is different
Figure BDA000026360774001019
azoles-3-base, 2, the 5-dihydro is different
Figure BDA000026360774001020
azoles-4-base, 2, the 5-dihydro is different azoles-5-base, 2, the 3-dihydro is different azoles-3-base, 2, the 3-dihydro is different
Figure BDA000026360774001023
azoles-4-base, 2, the 3-dihydro is different
Figure BDA000026360774001024
azoles-5-base, 4, 5-dihydro isothiazole-3-base, 4, 5-dihydro isothiazole-4-base, 4, 5-dihydro isothiazole-5-base, 2, 5-dihydro isothiazole-3-base, 2, 5-dihydro isothiazole-4-base, 2, 5-dihydro isothiazole-5-base, 2, 3-dihydro isothiazole-3-base, 2, 3-dihydro isothiazole-4-base, 2, 3-dihydro isothiazole-5-base, 4, 5-dihydro-1H-imidazoles-2-base, 4, 5-dihydro-1H-imidazol-4 yl, 4, 5-dihydro-1H-imidazoles-5-base, 2, 5-dihydro-1H-imidazoles-2-base, 2, 5-dihydro-1H-imidazol-4 yl, 2, 5-dihydro-1H-imidazoles-5-base, 2, 3-dihydro-1H-imidazoles-2-base, 2, 3-dihydro-1H-imidazol-4 yl, 4, the 5-dihydro
Figure BDA00002636077400111
azoles-2-base, 4, the 5-dihydro
Figure BDA00002636077400112
azoles-4-base, 4, the 5-dihydro
Figure BDA00002636077400113
azoles-5-base, 2, the 5-dihydro
Figure BDA00002636077400114
azoles-2-base, 2, the 5-dihydro
Figure BDA00002636077400115
azoles-4-base, 2, the 5-dihydro
Figure BDA00002636077400116
azoles-5-base, 2, the 3-dihydro
Figure BDA00002636077400117
azoles-2-base, 2, the 3-dihydro
Figure BDA00002636077400118
azoles-4-base, 2, the 3-dihydro
Figure BDA00002636077400119
azoles-5-base, 4, 5-thiazoline-2-base, 4, 5-thiazoline-4-base, 4, 5-thiazoline-5-base, 2, 5-thiazoline-2-base, 2, 5-thiazoline-4-base, 2, 5-thiazoline-5-base, 2, 3-thiazoline-2-base, 2, 3-thiazoline-4-base, 2, 3-thiazoline-5-base, 1, 3-dioxole-2-base, 1, 3-dioxole-4-base, 1, 3-dithiole-2-base, 1, 3-dithiole-4-base, 1, 3-oxa-dithiole (oxathiol)-2-base, 1, 3-oxa-dithiole-4-base, 1, 3-oxa-dithiole-5-base,
6 Yuans unsaturated rings of part of C-keyed jointing, as: 2H-3,4-dihydropyran-6-base, 2H-3,4-dihydropyran-5-base, 2H-3,4-dihydropyran-4-base, 2H-3,4-dihydropyran-3-base, 2H-3,4-dihydropyran-2-base, 2H-3,4-dihydro thiapyran-6-base, 2H-3,4-dihydro thiapyran-5-base, 2H-3,4-dihydro thiapyran-4-base, 2H-3,4-dihydro thiapyran-3-base, 2H-3,4-dihydro thiapyran-2-base, 1,2,3,4-tetrahydropyridine-6-base, 1,2,3,4-tetrahydropyridine-5-base, 1,2,3,4-tetrahydropyridine-4-base, 1,2,3,4-tetrahydropyridine-3-base, 1,2,3,4-tetrahydropyridine-2-base, 2H-5,6-dihydropyran-2-base, 2H-5,6-dihydropyran-3-base, 2H-5,6-dihydropyran-4-base, 2H-5,6-dihydropyran-5-base, 2H-5,6-dihydropyran-6-base, 2H-5,6-dihydro thiapyran-2-base, 2H-5,6-dihydro thiapyran-3-base, 2H-5,6-dihydro thiapyran-4-base, 2H-5,6-dihydro thiapyran-5-base, 2H-5,6-dihydro thiapyran-6-base, 1,2,5,6-tetrahydropyridine-2-base, 1,2,5,6-tetrahydropyridine-3-base, 1,2,5,6-tetrahydropyridine-4-base, 1,2,5,6-tetrahydropyridine-5-base, 1,2,5,6-tetrahydropyridine-6-base, 2,3,4,5-tetrahydropyridine-2-base, 2,3,4,5-tetrahydropyridine-3-base, 2,3,4,5-tetrahydropyridine-4-base, 2,3,4,5-tetrahydropyridine-5-base, 2,3,4,5-tetrahydropyridine-6-base, 4H-pyrans-2-base, 4H-pyrans-3-base, 4H-pyrans-4-base, 4H-thiapyran-2-base, 4H-thiapyran-3-base, 4H-thiapyran-4-base, Isosorbide-5-Nitrae-dihydropyridine-2-base, Isosorbide-5-Nitrae-dihydropyridine-3-base, Isosorbide-5-Nitrae-dihydropyridine-4-base, 2H-pyrans-2-base, 2H-pyrans-3-base, 2H-pyrans-4-base, 2H-pyrans-5-base, 2H-pyrans-6-base, 2H-thiapyran-2-base, 2H-thiapyran-3-base, 2H-thiapyran-4-base, 2H-thiapyran-5-base, 2H-thiapyran-6-base, 1,2-dihydropyridine-2-base, 1,2-dihydropyridine-3-base, 1,2-dihydropyridine-4-base, 1,2-dihydropyridine-5-base, 1,2-dihydropyridine-6-base, 3,4-dihydropyridine-2-base, 3,4-dihydropyridine-3-base, 3,4-dihydropyridine-4-base, 3,4-dihydropyridine-5-base, 3,4-dihydropyridine-6-base, 2,5-dihydropyridine-2-base, 2,5-dihydropyridine-3-base, 2,5-dihydropyridine-4-base, 2,5-dihydropyridine-5-base, 2,5-dihydropyridine-6-base, 2,3-dihydropyridine-2-base, 2,3-dihydropyridine-3-base, 2,3-dihydropyridine-4-base, 2,3-dihydropyridine-5-base, 2,3-dihydropyridine-6-base, 2H-5,6-dihydro-1,2-
Figure BDA00002636077400121
piperazine-3-base, 2H-5,6-dihydro-1,2-
Figure BDA00002636077400122
piperazine-4-base, 2H-5,6-dihydro-1,2-
Figure BDA00002636077400123
piperazine-5-base, 2H-5,6-dihydro-1,2-
Figure BDA00002636077400124
piperazine-6-base, 2H-5,6-dihydro-1,2-thiazines-3-base, 2H-5,6-dihydro-1,2-thiazines-4-base, 2H-5,6-dihydro-1,2-thiazines-5-base, 2H-5,6-dihydro-1,2-thiazines-6-base, 4H-5,6-dihydro-1,2-
Figure BDA00002636077400125
piperazine-3-base, 4H-5,6-dihydro-1,2-
Figure BDA00002636077400126
piperazine-4-base, 4H-5,6-dihydro-1,2-
Figure BDA00002636077400127
piperazine-5-base, 4H-5,6-dihydro-1,2-
Figure BDA00002636077400128
piperazine-6-base, 4H-5,6-dihydro-1,2-thiazines-3-base, 4H-5,6-dihydro-1,2-thiazines-4-base, 4H-5,6-dihydro-1,2-thiazines-5-base, 4H-5,6-dihydro-1,2-thiazines-6-base, 2H-3,6-dihydro-1,2-
Figure BDA00002636077400129
piperazine-3-base, 2H-3,6-dihydro-1,2-
Figure BDA000026360774001210
piperazine-4-base, 2H-3,6-dihydro-1,2-
Figure BDA000026360774001211
piperazine-5-base, 2H-3,6-dihydro-1,2- piperazine-6-base, 2H-3,6-dihydro-1,2-thiazines-3-base, 2H-3,6-dihydro-1,2-thiazines-4-base, 2H-3,6-dihydro-1,2-thiazines-5-base, 2H-3,6-dihydro-1,2-thiazines-6-base, 2H-3,4-dihydro-1,2-
Figure BDA000026360774001213
piperazine-3-base, 2H-3,4-dihydro-1,2-
Figure BDA000026360774001214
piperazine-4-base, 2H-3,4-dihydro-1,2-
Figure BDA000026360774001215
piperazine-5-base, 2H-3,4-dihydro-1,2-
Figure BDA000026360774001216
piperazine-6-base, 2H-3, 4-dihydro-1, 2-thiazine-3-base, 2H-3, 4-dihydro-1, 2-thiazine-4-base, 2H-3, 4-dihydro-1, 2-thiazine-5-base, 2H-3, 4-dihydro-1, 2-thiazine-6-base, 2, 3, 4, 5-tetrahydro pyridazine-3-base, 2, 3, 4, 5-tetrahydro pyridazine-4-base, 2, 3, 4, 5-tetrahydro pyridazine-5-base, 2, 3, 4, 5-tetrahydro pyridazine-6-base, 3, 4, 5, 6-tetrahydro pyridazine-3-base, 3, 4, 5, 6-tetrahydro pyridazine-4-base, 1, 2, 5, 6-tetrahydro pyridazine-3-base, 1, 2, 5, 6-tetrahydro pyridazine-4-base, 1, 2, 5, 6-tetrahydro pyridazine-5-base, 1, 2, 5, 6-tetrahydro pyridazine-6-base, 1, 2, 3, 6-tetrahydro pyridazine-3-base, 1, 2, 3, 6-tetrahydro pyridazine-4-base, 4H-5, 6-dihydro-1, 3-
Figure BDA000026360774001217
piperazine-2-base, 4H-5,6-dihydro-1,3-
Figure BDA000026360774001218
piperazine-4-base, 4H-5,6-dihydro-1,3-
Figure BDA000026360774001219
piperazine-5-base, 4H-5,6-dihydro-1,3-
Figure BDA000026360774001220
piperazine-6-base, 4H-5, 6-dihydro-1, 3-thiazine-2-base, 4H-5, 6-dihydro-1, 3-thiazine-4-base, 4H-5, 6-dihydro-1, 3-thiazine-5-base, 4H-5, 6-dihydro-1, 3-thiazine-6-base, 3, 4, 5-6-tetrahydropyrimidine--2-base, 3, 4, 5, 6-tetrahydropyrimidine-4-base, 3, 4, 5, 6-tetrahydropyrimidine-5-base, 3, 4, 5, 6-tetrahydropyrimidine-6-base, 1, 2, 3, 4-tetrahydrochysene pyrazine-2-base, 1, 2, 3, 4-tetrahydrochysene pyrazine-5-base, 1, 2, 3, 4-tetrahydropyrimidine-2-base, 1, 2, 3, 4-tetrahydropyrimidine-4-base, 1, 2, 3, 4-tetrahydropyrimidine-5-base, 1, 2, 3, 4-tetrahydropyrimidine-6-base, 2, 3-dihydro-1, 4-thiazine-2-base, 2, 3-dihydro-1, 4-thiazine-3-base, 2, 3-dihydro-1, 4-thiazine-5-base, 2, 3-dihydro-1, 4-thiazine-6-base, 2H-1, 3-
Figure BDA000026360774001221
piperazine-2-base, 2H-1,3-
Figure BDA000026360774001222
piperazine-4-base, 2H-1,3-
Figure BDA000026360774001223
piperazine-5-base, 2H-1,3-
Figure BDA00002636077400131
piperazine-6-base, 2H-1,3-thiazine-2-base, 2H-1,3-thiazine-4-base, 2H-1,3-thiazine-5-base, 2H-1,3-thiazine-6-base, 4H-1,3-
Figure BDA00002636077400132
piperazine-2-base, 4H-1,3-
Figure BDA00002636077400133
piperazine-4-base, 4H-1,3-
Figure BDA00002636077400134
piperazine-5-base, 4H-1,3-
Figure BDA00002636077400135
piperazine-6-base, 4H-1,3-thiazine-2-base, 4H-1,3-thiazine-4-base, 4H-1,3-thiazine-5-base, 4H-1,3-thiazine-6-base, 6H-1,3- piperazine-2-base, 6H-1,3- piperazine-4-base, 6H-1,3-
Figure BDA00002636077400138
piperazine-5-base, 6H-1,3-
Figure BDA00002636077400139
piperazine-6-base, 6H-1,3-thiazine-2-base, 6H-1,3-
Figure BDA000026360774001310
piperazine-4-base, 6H-1,3-
Figure BDA000026360774001311
piperazine-5-base, 6H-1,3-thiazine-6-base, 2H-1,4-
Figure BDA000026360774001312
piperazine-2-base, 2H-1,4-
Figure BDA000026360774001313
piperazine-3-base, 2H-1,4- piperazine-5-base, 2H-1,4-
Figure BDA000026360774001315
piperazine-6-base, 2H-1,4-thiazine-2-base, 2H-1,4-thiazine-3-base, 2H-1,4-thiazine-5-base, 2H-1,4-thiazine-6-base, 4H-1,4-
Figure BDA000026360774001316
piperazine-2-base, 4H-1,4-
Figure BDA000026360774001317
piperazine-3-base, 4H-1, 4-thiazine-2-base, 4H-1, 4-thiazine-3-base, 1, 4-dihydrogen dazin-3-base, 1, 4-dihydrogen dazin-4-base, 1, 4-dihydrogen dazin-5-base, 1, 4-dihydrogen dazin-6-base, 1, 4-dihydro pyrazine-2-base, 1, 2-dihydro pyrazine-2-base, 1, 2-dihydro pyrazine-3-base, 1, 2-dihydro pyrazine-5-base, 1, 2-dihydro pyrazine-6-base, 1, 4-dihydro-pyrimidin-2-base, 1, 4-dihydro-pyrimidin-4-base, 1, 4-dihydro-pyrimidin-5-base, 1, 4-dihydro-pyrimidin-6-base, 3, 4-dihydro-pyrimidin-2-base, 3, 4-dihydro-pyrimidin-4-base, 3, 4-dihydro-pyrimidin-5-base or 3, 4-dihydro-pyrimidin-6-base,
5 Yuans unsaturated rings of part of N-keyed jointing, as: 2,3-dihydro-1H-pyrroles-1-base, 2,5-dihydro-1H-pyrroles-1-base, 4,5-dihydro-1 h-pyrazole-1-base, 2,5-dihydro-1 h-pyrazole-1-base, 2,3-dihydro-1 h-pyrazole-1-base, 2, the 5-dihydro is different
Figure BDA000026360774001318
azoles-2-base, 2, the 3-dihydro is different
Figure BDA000026360774001319
azoles-2-base, 2,5-dihydro isothiazole-2-base, 2, the 3-dihydro is different
Figure BDA000026360774001320
azoles-2-base, 4,5-dihydro-1H-imidazoles-1-base, 2,5-dihydro-1H-imidazoles-1-base, 2,3-dihydro-1H-imidazoles-1-base, 2,3-dihydro
Figure BDA000026360774001321
azoles-3-base, 2,3-thiazoline-3-base;
6 Yuans unsaturated rings of part of N-keyed jointing, as: 1,2,3,4-tetrahydropyridine-1-base, 1,2,5,6-tetrahydropyridine-1-base, Isosorbide-5-Nitrae-dihydropyridine-1-base, 1,2-dihydropyridine-1-base, 2H-5,6-dihydro-1,2-
Figure BDA000026360774001322
piperazine-2-base, 2H-5,6-dihydro-1,2-thiazines-2-base, 2H-3,6-dihydro-1,2-
Figure BDA000026360774001323
piperazine-2-base, 2H-3,6-dihydro-1,2-thiazines-2-base, 2H-3,4-dihydro-1,2-
Figure BDA000026360774001324
piperazine-2-base, 2H-3,4-dihydro-1,2-thiazines-2-base, 2,3,4,5-tetrahydro pyridazine-2-base, 1,2,5,6-tetrahydro pyridazine-1-base, 1,2,5,6-tetrahydro pyridazine-2-base, 1,2,3,6-tetrahydro pyridazine-1-base, 3,4,5,6-tetrahydropyrimidine-3-base, 1,2,3,4-tetrahydrochysene pyrazine-1-base, 1,2,3,4-tetrahydropyrimidine-1-base, 1,2,3,4-tetrahydropyrimidine-3-base, 2,3-dihydro-Isosorbide-5-Nitrae-thiazine-4-base, 2H-1,2- piperazine-2-base, 2H-1,2-thiazine-2-base, 4H-1,4- piperazine-4-base, 4H-1,4-thiazine-4-base, Isosorbide-5-Nitrae-dihydrogen dazin-1-base, Isosorbide-5-Nitrae-dihydro pyrazine-1-base, 1,2-dihydro pyrazine-1-base, Isosorbide-5-Nitrae-dihydro-pyrimidin-1-base or 3,4-dihydro-pyrimidin-3-base.
Heteroaryl: usually there is 1,2,3 or 4 nitrogen-atoms or be selected from oxygen and the hetero-atom of sulphur and suitable, there are the 5 or 6 Yuan aromatic heterocyclic groups of 1,2 or 3 nitrogen-atoms as ring members except carbon atom, for example:
There is 1,2,3 or 4 nitrogen-atoms or be selected from oxygen and the hetero-atom of sulphur and suitable words have the 5 Yuan heteroaromatic group of 1,2 or 3 nitrogen-atoms as the C-keyed jointing of ring members, as: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrroles-2-base, pyrroles-3-base, pyrazole-3-yl, pyrazoles-4-base, different
Figure BDA00002636077400141
azoles-3-base, different azoles-4-base, different azoles-5-base, isothiazole-3-base, isothiazole-4-base, isothiazole-5-base, imidazoles-2-base, imidazol-4 yl,
Figure BDA00002636077400144
azoles-2-base,
Figure BDA00002636077400145
azoles-4-base,
Figure BDA00002636077400146
azoles-5-base, thiazol-2-yl, thiazole-4-yl, thiazole-5-base, 1,2,3-
Figure BDA00002636077400147
diazole-4-base, 1,2,3-
Figure BDA00002636077400148
diazole-5-base, 1,2,4-
Figure BDA00002636077400149
diazole-3-base, 1,2,4 ,-
Figure BDA000026360774001410
diazole-5-base, 1,3,4-
Figure BDA000026360774001411
diazole-2-base, 1,2,3-thiadiazoles-4-base, 1,2,3-thiadiazoles-5-base, 1,2,4-thiadiazoles-3-base, 1,2,4-thiadiazoles-5-base, 1,3,4-thiadiazoles-2-base, 1,2,3-triazoles-4-base, 1,2,4-triazole-3-base, tetrazolium-5-base;
There are the 6 Yuan heteroaromatic group of 1,2,3 or 4 nitrogen-atoms as the C-keyed jointing of ring members, as: pyridine-2-base, pyridin-3-yl, pyridin-4-yl, pyridazine-3-base, pyridazine-4-base, pyrimidine-2-base, pyrimidine-4-yl, pyrimidine-5-base, pyrazine-2-base, 1,3,5-triazine-2-base, 1,2,4-triazine-3-base, 1,2,4-triazine-5-base, 1,2,4-triazine-6-base, 1,2,4,5-tetrazine-3-base;
There are the 5 Yuan heteroaromatic group of 1,2,3 or 4 nitrogen-atoms as the C-keyed jointing of ring members, as: pyrroles-1-base, pyrazol-1-yl, imidazoles-1-base, 1,2,3-triazoles-1-base, 1,2,4-triazol-1-yl, tetrazolium-1-base.
Heterocyclic radical also comprises for example, bicyclic heterocyclic radical with one above-mentioned 5 or 6 element heterocycle rings and another saturated, unsaturated or aromatic carbocyclic condensed with it (benzene, cyclohexane, cyclohexene or cyclohexadiene ring) or another 5 or 6 element heterocycle rings that condense with it (wherein the latter can be saturated, unsaturated or aromatics equally).These comprise, for example quinolyl, isoquinolyl, indyl, indolizine base (indolizynyl), isoindolyl, indazolyl, benzofuranyl, benzothienyl, benzo [b] thiazolyl, benzo
Figure BDA000026360774001412
azoles base, benzothiazolyl and benzimidazolyl.The example of the 5-6 person's heteroaromatics that comprises fused benzene rings comprises: indolinyl, dihydro indolizine base, dihydro-iso indolyl, dihydroquinoline base, dihydro-isoquinoline base, benzopyranyl and chromanyl.
Aralkyl: via alkylidene, connect, especially via methylene, 1, the above defined aryl that 1-ethylidene or 1,2-ethylidene connect, as benzyl, 1-phenethyl and 2-phenethyl.
Aromatic yl alkenyl: via alkylene group, connect, especially via 1,1-vinyl, 1, the aryl as hereinbefore defined that 2-vinyl or 1,3-acrylic connect, as 2-phenyl ethene-1-base and 1-phenyl ethene-1-base.
Cycloalkyloxy: the above defined cycloalkyl connected via oxygen atom, for example encircle propoxyl group, cyclobutoxy group, cyclopentyloxy or cyclohexyloxy.
Cycloalkyl-alkyl: via alkylidene, connect, especially via methylene, 1, the above defined cycloalkyl that 1-ethylidene or 1,2-ethylidene connect, for example cyclopropyl methyl, cyclobutylmethyl, cyclopentyl-methyl or cyclohexyl methyl.
Heterocyclic radical alkyl and heteroaryl alkyl: via alkylidene, be connected, especially via methylene, 1, above defined heterocyclic radical or heteroaryl that 1-ethylidene or 1,2-ethylidene connect.
In the context of the invention, wording " optional replacement " means the corresponding construction part by 1,2 or 3, especially selects the substituting group replacement of following group or has 1,2 or 3 for 1, especially 1 substituting group of selecting following group: halogen, C 1-C 4alkyl, OH, SH, CN, CF 3, O-CF 3, COOH, O-CH 2-COOH, C 1-C 6alkoxyl, C 1-C 6alkylthio group, C 3-C 7cycloalkyl, COO-C 1-C 6alkyl, CONH 2, CONH-C 1-C 6alkyl, SO 2nH-C 1-C 6alkyl, CON-(C 1-C 6alkyl) 2, SO 2n-(C 1-C 6alkyl) 2, NH-SO 2-C 1-C 6alkyl, NH-CO-C 1-C 6alkyl, SO 2-C 1-C 6alkyl, O-phenyl, O-CH 2-phenyl (benzyloxy), CONH-phenyl, SO 2nH-phenyl, CONH-heteroaryl, SO 2nH-heteroaryl, SO 2-phenyl, NH-SO 2-phenyl, NH-CO-phenyl, NH-SO 2-heteroaryl and NH-CO-heteroaryl, the phenyl in wherein said rear 11 groups and heteroaryl are not substituted maybe can have 1,2 or 3 substituting group that is selected from following group: halogen, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl and C 1-C 4halogenated alkoxy.
Hereinafter with regard to the preferred embodiment of the inventive method and device, the description of especially doing with regard to the preferred meaning of the modification of the reaction condition of differential responses thing and product and described method is applicable separately, or more particularly, applicable with any combination with one another of imagining.
The compound (free acid) that preferred hydroxamic acid and salt (hydroxamate) thereof are general formula (I) and the compound (salt) of general formula (I'):
Figure BDA00002636077400151
Wherein:
M +for alkali metal cation, the alkaline earth metal cation equivalent; Or NR' 4cation, wherein R' is independently from each other hydrogen, C 1-C 6alkyl, phenyl and benzyl; Pyridine
Figure BDA00002636077400161
cation or imidazoles
Figure BDA00002636077400162
cation, the heteroaromatic structure division in wherein said rear 2 cations can not be substituted or is selected from C by 1,2 or 3 1-C 4the substituting group of alkyl and phenyl replaces;
R 1for C 1-C 18alkyl, C 2-C 12alkenyl, C 4-C 12alkadienyl, C 6-C 12alkatriene base, C 2-C 12alkynyl; 1-4 CH in wherein said rear 5 groups 2group can be replaced by O, NH or S and/or the partially or completely halogenation and/or have 1,2 or 3 substituent R of wherein said rear 5 groups 1a; C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclic radical, C 3-C 7heterocyclic radical-C 1-C 4alkyl, cycloalkyl and heterocyclic radical in wherein said rear 4 groups can have 1,2,3 or 4 radicals R 1b;
Aryl, heteroaryl, aryl-C 1-C 6alkyl, aryl-C 2-C 6alkenyl, heteroaryl-C 1-C 4alkyl or heteroaryl-C 2-C 6alkenyl, aryl and heteroaryl in wherein said rear 6 groups can not be substituted or have 1,2,3 or 4 identical or different radicals R 1c; Wherein:
R 1abe independently from each other OH, SH, NO 2, COOH, CHO, NR a1r a2, CN, OCH 2cOOH, CO-NH-OH, CO-NH-O -m +, C 1-C 12alkoxyl, C 1-C 12halogenated alkoxy, C 3-C 7cycloalkyloxy, C 1-C 12alkylthio group, C 1-C 12halogenated alkylthio, CO-C 1-C 12alkyl, CO-O-C 1-C 12alkyl, CONR a3r a4, aryl, heteroaryl, aryl-C 1-C 6alkoxyl or heteroaryl-C 1-C 4alkoxyl, aryl and heteroaryl in wherein said rear 4 groups can not be substituted or have 1,2,3 or 4 identical or different radicals R 1c;
R 1bbe independently from each other OH, SH, NO 2, COOH, CHO, NR b1r b2, CN, OCH 2cOOH, halogen,
Aryl, aryl-C 1-C 6alkyl, aryl-C 1-C 6alkoxyl, the aryl in wherein said rear 3 groups can not be substituted or have 1,2,3 or 4 identical or different radicals R 1c, C 1-C 6alkyl, C 1-C 6alkoxyl, C 1-C 6alkylthio group, the partially or completely halogenation and/or there is 1,2 or 3 substituent R of alkyl structure in wherein said rear 3 substituting groups part d1, CO-C 1-C 6alkyl, CO-O-C 1-C 6alkyl or CONR b3r b4;
R 1cbe independently from each other OH, SH, halogen, NO 2, NR c1r c2, CN, COOH, OCH 2cOOH, C 1-C 12alkyl, C 1-C 12alkoxyl, C 1-C 12alkoxy-C 1-C 6alkyl, C 1-C 12alkylthio group, the partially or completely halogenation and/or there is 1,2 or 3 substituent R of alkyl structure in wherein said rear 4 substituting groups part d1;
C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7cycloalkyloxy, C 3-C 7heterocyclic radical, C 3-C 7heterocyclic radical-C 1-C 4alkyl, C 3-C 7heterocyclic oxy group, cycloalkyl and heterocyclic radical in wherein said rear 6 groups can have 1,2,3 or 4 radicals R d2,
Aryl, heteroaryl, O-aryl, O-CH 2-aryl, wherein said rear 3 groups are not substituted in the aryl structure division maybe can have 1,2,3 or 4 radicals R 1d,
CO-C 1-C 6alkyl, CO-O-C 1-C 6alkyl, CONR c3r c4,
Perhaps be bonded to two radicals R on the adjacent C atom 1bor two radicals R 1ctogether with the C of its keyed jointing atom, form 4,5,6 or 7 Yuans optional carbocyclic rings that replace or optional replace there is the heterocycle of 1,2 or 3 identical or different hetero-atom that is selected from O, N and S as ring members;
R 1dbe selected from halogen, OH, SH, NO 2, COOH, C (O) NH 2, CHO, CN, NH 2, OCH 2cOOH, C 1-C 6alkyl, C 1-C 6haloalkyl, C 1-C 6alkoxyl, C 1-C 6halogenated alkoxy, C 1-C 6alkylthio group, C 1-C 6halogenated alkylthio, CO-C 1-C 6alkyl, CO-O-C 1-C 6alkyl, NH-C 1-C 6alkyl, NHCHO, NH-C (O) C 1-C 6alkyl and SO 2-C 1-C 6alkyl;
R a1, R b1and R c1be H, C independently of one another 1-C 6alkyl, C 1-C 6alkoxyl, C 1-C 6haloalkyl, there is 1,2 or 3 substituent R b1c 1-C 6alkyl, C 2-C 6alkenyl, C 2-C 6alkynyl, C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclylalkyl-C 1-C 4alkyl, C 1-C 6alkoxy-C 1-C 4alkyl, CO-C 1-C 6alkyl, aryl, heteroaryl, O-aryl, OCH 2-aryl, aryl-C 1-C 4alkyl, heteroaryl-C 1-C 4alkyl, CO-aryl, CO-heteroaryl, the aryl in wherein said rear 8 groups and heteroaryl are not substituted or have 1,2 or 3 substituent R 1d;
R a2, R b2and R c2be H, C independently of one another 1-C 6alkyl, C 1-C 6haloalkyl, there is 1,2 or 3 substituent R b1c 1-C 6alkyl, C 2-C 6alkenyl, C 2-C 6alkynyl, C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclylalkyl-C 1-C 4alkyl, C 1-C 6alkoxy-C 1-C 4alkyl, aryl, aryl-C 1-C 4alkyl, heteroaryl or heteroaryl-C 1-C 4alkyl, the aryl in wherein said rear 4 groups and heteroaryl are not substituted or have 1,2 or 3 substituent R 1d; Perhaps
Two radicals R a1with R a2, or R b1with R b2, or R c1with R c2form the optional replacement of 3-7 person and can optionally there is the azacyclo-of 1,2 or 3 identical or different other hetero-atom that are selected from O, N and S as ring members together with the N atom;
R a3, R b3and R c3be H, C independently of one another 1-C 6alkyl, C 1-C 6haloalkyl, there is 1,2 or 3 substituent R b1c 1-C 6alkyl, C 2-C 6alkenyl, C 2-C 6alkynyl, C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclylalkyl-C 1-C 4alkyl, C 1-C 6alkoxy-C 1-C 4alkyl, aryl, aryl-C 1-C 4alkyl, heteroaryl or heteroaryl-C 1-C 4alkyl, the aryl in wherein said rear 4 groups and heteroaryl are not substituted or have 1,2 or 3 substituent R 1d; And
R a4, R b4and R c4be H, C independently of one another 1-C 6alkyl, C 1-C 6haloalkyl, there is 1,2 or 3 substituent R b1c 1-C 6alkyl, C 2-C 6alkenyl, C 2-C 6alkynyl, C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclylalkyl-C 1-C 4alkyl, C 1-C 6alkoxy-C 1-C 4alkyl, aryl, aryl-C 1-C 4alkyl, heteroaryl or heteroaryl-C 1-C 4alkyl; Aryl in wherein said rear 4 groups and heteroaryl are not substituted or have 1,2 or 3 substituent R 1d, or two radicals R a3with R a4, or R b3with R b4, or R c3with R c4form the optional replacement of 3-7 person and can optionally there is the azacyclo-of 1,2 or 3 identical or different other hetero-atom that are selected from O, N and S as ring members together with the N atom;
R d1be independently from each other OH, SH, NO 2, COOH, CHO, NR a1r a2, CN, OCH 2cOOH, C 1-C 12alkoxyl, C 1-C 12halogenated alkoxy, C 3-C 7cycloalkyloxy, CO-C 1-C 12alkyl, CO-O-C 1-C 12alkyl, CONR a3r a4, aryl, heteroaryl, aryl-C 1-C 6alkoxyl and heteroaryl-C 1-C 4alkoxyl, aryl and heteroaryl in wherein said rear 4 groups can not be substituted or have 1,2,3 or 4 identical or different radicals R 1d;
R d2be independently from each other OH, SH, NO 2, COOH, CHO, NR b1r b2, CN, OCH 2cOOH, halogen; Aryl, aryl-C 1-C 6alkyl, aryl-C 1-C 6alkoxyl, the aryl in wherein said rear 3 groups can not be substituted or have 1,2,3 or 4 identical or different radicals R 1d; C 1-C 6alkyl, C 1-C 6alkoxyl, C 1-C 6alkylthio group, the partially or completely halogenation and/or there is 1,2 or 3 substituent R of alkyl structure in wherein said rear 3 substituting groups part d1; And
R 2for H, C 1-C 6alkyl, C 3-C 7cycloalkyl or phenyl.
At R 2in situation for hydrogen, the structure of described hydroxamate also can be expressed as formula I " dynamic isomer:
Figure BDA00002636077400191
Yet the practical structures of hydroxamate is unimportant for the purpose of the present invention.Therefore, hereinafter, all possible structure of the representation hydroxamate of formula I'.
In formula (I') compound, ion M +be preferably lithium ion; Sodium ion; Potassium ion; Cesium ion; Rubidium ion; Magnesium ion equivalent (1/2Mg 2+); Calcium ion equivalent (1/2Ca 2+); Or NR' 4ion, wherein R' is independently from each other hydrogen, C 1-C 6alkyl and benzyl; Pyridine
Figure BDA00002636077400192
ion or imidazoles
Figure BDA00002636077400193
ion.
More preferably M +for lithium ion, sodium ion, potassium ion, cesium ion or NR' 4ion, wherein R' is independently from each other hydrogen and C 1-C 4alkyl.
Even more preferably M +for lithium ion, sodium ion, potassium ion, cesium ion or N (normal-butyl) 4ion.
Radicals R at Compound I and I' 1in, when existing, radicals R 1apreferably be independently from each other NO 2, CN, CO-NH-OH, CO-NH-O -m +, C 1-C 12alkoxyl, C 1-C 12halogenated alkoxy, aryl, heteroaryl, aryl-C 1-C 6alkoxyl and heteroaryl-C 1-C 4alkoxyl, aryl and heteroaryl in wherein said rear 4 groups can not be substituted or have 1,2 or 3 identical or different radicals R 1c.
More preferably when existing, radicals R 1abe independently from each other CO-NH-OH, CO-NH-O -m +, C 1-C 6alkoxyl, phenyl and phenyl-C 1-C 6alkoxyl, the phenyl in wherein said rear 2 groups can not be substituted or have 1,2 or 3 identical or different radicals R 1c.
Even more preferably when existing, R 1abe independently from each other CO-NH-OH, CO-NH-O -m +, phenyl and phenyl-C 1-C 3alkoxyl, the phenyl in wherein said rear 2 groups can not be substituted or have 1 or 2 identical or different C that is selected from 3-C 12alkyl, C 3-C 12the group of alkoxyl and benzyloxy.
Particularly, when existing, R 1abe independently from each other CO-NH-OH, CO-NH-O -m +and phenyl, wherein phenyl can not be substituted or have 1 or 2, preferably 1 identical or different C that is selected from 3-C 12the group of alkoxyl and benzyloxy.If phenyl has 1 group, this preferably is connected to contraposition, with respect to described phenyl ring, via it, is bonded to radicals R 11 be 4.
Radicals R at Compound I and I' 1in, when existing, radicals R 1bpreferably be independently from each other NO 2; CN; Halogen; Aryl, aryl-C 1-C 6alkyl, aryl-C 1-C 6alkoxyl, the aryl in wherein said rear 3 groups can not be substituted or have 1,2 or 3 identical or different radicals R 1c; C 1-C 6alkyl and C 1-C 6alkoxyl, the partially or completely halogenation and/or there is 1 or 2 substituent R of alkyl structure in wherein said rear 2 substituting groups part d1.
More preferably when existing, radicals R 1bbe independently from each other halogen; Phenyl, phenyl-C 1-C 6alkyl, phenyl-C 1-C 6alkoxyl, the phenyl in wherein said rear 3 groups can not be substituted or have 1 or 2 identical or different C that is selected from 1-C 12alkyl, C 1-C 12alkoxyl and O-CH 2the group of-aryl; C 1-C 6alkyl and C 1-C 6alkoxyl, the partially or completely halogenation and/or there is 1 or 2 substituent R of alkyl structure in wherein said rear 2 substituting groups part d1.
Even more preferably when existing, R 1bbe independently from each other phenyl, phenyl-C 1-C 3alkyl, phenyl-C 1-C 3alkoxyl, the phenyl in wherein said rear 3 groups can not be substituted or have the C of being selected from 3-C 12alkyl, C 3-C 12the group of alkoxyl and benzyloxy; C 1-C 6alkyl and C 1-C 6alkoxyl, the alkyl structure part in wherein said rear 2 substituting groups can not be substituted or have the C of being selected from 3-C 12the group of alkoxyl and benzyloxy.
Radicals R at Compound I and I' 1, R 1aand R 1bin, when existing, radicals R 1cpreferably be independently from each other halogen, NO 2, CN; C 1-C 12alkyl, C 1-C 12alkoxyl, C 1-C 12alkoxy-C 1-C 4alkyl, the partially or completely halogenation and/or there is 1 or 2 substituent R of alkyl structure in wherein said rear 3 substituting groups part d1; C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 6heterocyclic radical, C 3-C 6heterocyclic radical-C 1-C 4alkyl, cycloalkyl or heterocyclic radical in wherein said rear 4 groups can have 1,2 or 3 R d2group; Aryl, O-aryl and O-CH 2-aryl, wherein said rear 3 groups are not substituted in the aryl structure division maybe can have 1,2 or 3 and be selected from independently of one another halogen, NO 2, CN, NH 2, C 1-C 6alkyl, C 1-C 6haloalkyl, C 1-C 6alkoxyl and C 1-C 6the group of halogenated alkoxy.
More preferably when existing, R 1cbe independently from each other halogen; C 1-C 12alkyl, C 1-C 12alkoxyl, the partially or completely halogenation and/or there is substituent R of alkyl structure in wherein said rear 2 substituting groups part d1; C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, the cycloalkyl structure division of wherein said rear 2 groups can have substituent R d2; Aryl and O-CH 2-aryl, wherein said rear 2 groups are not substituted in the aryl structure division maybe can have 1 or 2 and be independently from each other halogen, NO 2, C 1-C 6alkyl, C 1-C 6haloalkyl and C 1-C 6the group of alkoxyl.
Even more preferably when existing, R 1cbe independently from each other halogen; C 1-C 12alkyl, C 1-C 12alkoxyl, the partially or completely halogenation and/or there is the C of being selected from of alkyl structure in wherein said rear 2 substituting groups part 3-C 12the substituting group of alkoxyl, phenyl and benzyloxy; C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, the cycloalkyl structure division of wherein said rear 2 groups can have the phenyl of being selected from, phenyl-C 1-C 3alkyl, benzyloxy, C 1-C 6alkyl and C 1-C 6the substituting group of alkoxyl; Aryl and O-CH 2-aryl, wherein said rear 2 groups are not substituted maybe and can have the halogen of being selected from, C in the aryl structure division 1-C 6alkyl, C 1-C 6haloalkyl and C 1-C 6the substituting group of alkoxyl.
Particularly, when existing, R 1cbe independently from each other C 1-C 12alkoxyl and O-CH 2-aryl, more specifically be selected from C 3-C 12alkoxyl and benzyloxy.
Radicals R at Compound I and I' 1band R 1cin, when existing, radicals R d1preferably be independently from each other OH, NO 2, COOH, CN, C 1-C 12alkoxyl, C 1-C 12halogenated alkoxy, CO-C 1-C 12alkyl, CO-O-C 1-C 12alkyl, aryl and aryl-C 1-C 6alkoxyl, the aryl in wherein said rear 2 groups can not be substituted maybe can have 1,2 or 3 and be independently from each other halogen, NO 2, CN, NH 2, C 1-C 6alkyl, C 1-C 6haloalkyl, C 1-C 6alkoxyl and C 1-C 6the group of halogenated alkoxy.
More preferably when existing, R d1be independently from each other NO 2, CN, C 1-C 12alkoxyl, C 1-C 12halogenated alkoxy, aryl and aryl-C 1-C 6alkoxyl, the aryl in wherein said rear 2 groups can not be substituted maybe can have 1 or 2 and be independently from each other halogen, NO 2, CN, C 1-C 6alkyl, C 1-C 6haloalkyl, C 1-C 6alkoxyl and C 1-C 6the group of halogenated alkoxy.
Even more preferably when existing, R d1be independently from each other C 1-C 12alkoxyl, phenyl and benzyloxy, the phenyl in wherein said rear 2 groups can not be substituted or can have 1 or 2 and is independently from each other halogen, C 1-C 6alkyl, C 1-C 6haloalkyl and C 1-C 6the group of alkoxyl.
Radicals R at Compound I and I' 1band R 1cin, when existing, radicals R d2preferably be independently from each other OH, NO 2, COOH, CN, halogen; Aryl, aryl-C 1-C 6alkyl, aryl-C 1-C 6alkoxyl, the aryl in wherein said rear 3 groups can not be substituted or have 1,2 or 3 and is independently from each other halogen, NO 2, CN, NH 2, C 1-C 6alkyl, C 1-C 6haloalkyl, C 1-C 6alkoxyl and C 1-C 6the group of halogenated alkoxy; C 1-C 6alkyl and C 1-C 6alkoxyl, the partially or completely halogenation and/or there is 1,2 or 3 and be independently from each other C of alkyl structure in wherein said rear 2 substituting groups part 1-C 12alkoxyl, aryl and aryl-C 1-C 6the substituting group of alkoxyl.
More preferably when existing, R d2be independently from each other NO 2, CN, halogen; Aryl, aryl-C 1-C 6alkyl, aryl-C 1-C 6alkoxyl, the aryl in wherein said rear 3 groups can not be substituted or have 1 or 2 and is independently from each other halogen, C 1-C 6alkyl, C 1-C 6haloalkyl, C 1-C 6alkoxyl and C 1-C 6the group of halogenated alkoxy; C 1-C 6alkyl and C 1-C 6alkoxyl, the partially or completely halogenation and/or there is 1 or 2 and be independently from each other C of alkyl structure in wherein said rear 2 substituting groups part 1-C 12alkoxyl, aryl and aryl-C 1-C 6the substituting group of alkoxyl.
Even more preferably when existing, R d2be independently from each other halogen; Phenyl, benzyl, benzyloxy, the phenyl in wherein said rear 3 groups can not be substituted or have 1 or 2 and is independently from each other halogen, C 1-C 6alkyl, C 1-C 6haloalkyl and C 1-C 6the group of alkoxyl; C 1-C 6alkyl and C 1-C 6alkoxyl, the partially or completely halogenation and/or there is 1 or 2 and be independently from each other C of alkyl structure in wherein said rear 2 substituting groups part 3-C 12the substituting group of alkoxyl, phenyl and benzyloxy.
In formula (I) and compound (I'), radicals R 1be preferably:
C 1-C 10alkyl, C 2-C 10alkenyl, C 4-C 10alkadienyl, the partially or completely halogenation and/or there is 1,2 or 3 substituent R of wherein said rear 3 groups 1a, R wherein 1athere is one of General Definition mentioned above or there is especially one of preferred meaning mentioned above;
C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclic radical, C 3-C 7heterocyclic radical-C 1-C 4alkyl, cycloalkyl and heterocyclic radical in wherein said rear 4 groups can have 1,2 or 3 radicals R 1b, R wherein 1bthere is one of General Definition mentioned above or there is especially one of preferred meaning mentioned above;
Aryl, heteroaryl, aryl-C 1-C 6alkyl or heteroaryl-C 1-C 4alkyl, aryl and heteroaryl in wherein said rear 4 groups can not be substituted or have 1,2 or 3 identical or different radicals R 1c, R wherein 1cthere is one of General Definition mentioned above or there is especially one of preferred meaning mentioned above.
R 1c more preferably 1-C 10alkyl, C 2-C 10alkenyl or C 4-C 10alkadienyl, wherein said rear 3 groups can not be substituted or are independently from each other CO-NH-OH, CO-NH-O by 1,2 or 3 -m +, C 1-C 6alkoxyl, phenyl and phenyl-C 1-C 6the substituting group of alkoxyl replaces, and the phenyl in wherein said rear 2 groups can not be substituted or is independently from each other C by 1,2 or 3 3-C 12alkyl, C 3-C 12alkoxyl, C 3-C 12alkoxy-C 1-C 4alkyl and phenyl-C 1-C 6the substituting group of alkoxyl replaces.
Even more preferably R 1for C 1-C 10alkyl, C 2-C 10alkenyl or C 4-C 10alkadienyl, wherein said rear 3 groups can not be substituted or are independently from each other CO-NH-OH, CO-NH-O by 1,2 or 3 -m +, C 1-C 6alkoxyl, phenyl and phenyl-C 1-C 6the substituting group of alkoxyl replaces, and the phenyl in wherein said rear 2 groups can not be substituted or is independently from each other C by 1 or 2 3-C 12alkyl, C 3-C 12the substituting group of alkoxyl and benzyloxy replaces.
R particularly preferably 1for C 1-C 10alkyl or C 4-C 10alkadienyl, wherein said rear 2 groups can not be substituted or are selected from CO-NH-OH, CO-NH-O by 1 -m +with can not be substituted or by C 3-C 12the substituting group of the phenyl that alkoxyl or benzyloxy replace replaces.
Especially, R 1for not being substituted or thering is CO-NH-OH, CO-NH-O -m +the C of group 3-C 10alkyl or be C 4-C 10alkadienyl or be selected from C for thering is 1 3-C 12alkoxyl and benzyloxy, be preferably selected from C 3-C 6the substituent benzyl of alkoxyl and benzyloxy.Preferably benzyl has in contraposition (4), with respect to the benzyl ring of wherein said benzyl structure part, is bonded to the CH of this benzyl structure part 21 of group in 4.
In formula (I) and compound (I'), radicals R 2be preferably hydrogen, C 1-C 4alkyl, cyclohexyl or phenyl.
R 2more preferably hydrogen or methyl.
Even more preferably R 2for hydrogen.
The common commercially available acquisition of hydroxamic acid that the present invention is used or can prepare according to methods known in the art.The also commercially available acquisition or can be prepared by corresponding hydroxamic acid by known method of described hydroxamate, for example, by making hydroxamic acid and alkali reaction, described alkali is as alkali metal or alkaline earth metal hydroxide, for example lithium hydroxide, NaOH, potassium hydroxide, cesium hydroxide, rubidium hydroxide, magnesium hydroxide or calcium hydroxide; Alkali metal or alkaline earth metal carbonate, as lithium carbonate, sodium carbonate, potash, magnesium carbonate or calcium carbonate; Ammonia; Amine, as methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, propylamine, di-n-propylamine, tripropyl amine (TPA), butylamine, dibutyl amine, tri-n-butylamine, monoethanolamine, diethanol amine, triethanolamine etc.
In the method for preparation dye sensitization photoelectric conversion device of the present invention, with at least one, at 400-1000nm, preferably in 400-800nm electromagnetic wavelength scope, the hydroxamic acid of substantially transparent or its salt are processed metal oxide semiconductor.Therefore, described at least one hydroxamic acid or its salt do not absorb or only with low degree, absorb the solar irradiation in described range of wavelengths.Therefore, it obviously is different from and is suitable for the sensitized semiconductor metal oxide and has in described wave-length coverage surpassing 10 3lmol -1cm -1, be generally 15,000-150,000Lmol -1cm -1, be more typically 20,000-80,000Lmol -1cm -1the chromonic material of much higher extinction coefficient.Described at least one hydroxamic acid of the present invention or its salt preferably are respectively general formula (I) and compound (I'), are that this paper is one of described as preferred version especially.
Before term " with at least one hydroxamic acid or its salt processing metal oxide semiconductor " means the next step in the preparation of implementing photoelectric conversion device, for example, before applying charge transfer layer as described in more detail below, make described metal oxide semiconductor contact and reach the scheduled period with one or more hydroxamic acid or its salt.Do not wish to be bound by theory, after this is processed, described metal oxide semiconductor comprises described at least one hydroxamic acid or its salt that is absorpting form by inference, and its amount is usually less than amount used by inference.
Although in can any step in described photoelectric conversion device preparation process, process described metal oxide semiconductor with one or more hydroxamic acid or its salt, but preferably after the layer of semiconductor metal oxide is provided, preferably in stop-layer deposition (seeing below) afterwards, perhaps more preferably only the deposition described metal oxide semiconductor layer after, with described one or more hydroxamic acid or its salt, processed.Yet, the processing that is applicable to the processing of any type of metal oxide semiconductor and is the metal oxide semiconductor of metal oxide semiconductor layer form is hereinafter described.Preferred described description is applicable to the processing of metal oxide semiconductor layer.
Preferably use by described one or more hydroxamic acid or its salt are dissolved in to the solution (hereinafter referred to as " Treatment Solution ") prepared in solvent and process described metal oxide semiconductor, or use by described one or more hydroxamic acid or its salt are scattered in to the dispersion (hereinafter referred to as " processing dispersion ") prepared in solvent and process described metal oxide semiconductor.If described at least one hydroxamic acid or its salt are liquid, also can be in solvent-free lower use.Yet, preferably use described Treatment Solution or dispersion, more preferably by described Treatment Solution, process metal oxide semiconductor.
In the situation that process metal oxide semiconductor with surpassing a kind of hydroxamic acid or its salt, available surpass a kind of contain separately be less than be intended to for the treatment of hydroxamic acid or the Treatment Solution of its salt total amount or process dispersion and process successively.Yet, preferably with comprise be intended to for the treatment of all hydroxamic acid or a kind of Treatment Solution or a kind of processing dispersion of its salt process described metal oxide semiconductor.
Solvent for described Treatment Solution or processing dispersion is preferably organic solvent.Described organic solvent can suitably be selected according to the dissolubility of described one or more hydroxamic acid or its salt.The example of described organic solvent comprises: alcoholic solvent, as methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, the tert-butyl alcohol, ethylene glycol and benzylalcohol; The nitrile solvent, as acetonitrile, propionitrile and 3-methoxypropionitrile; Nitromethane; Halogenated hydrocarbons, as carrene, dichloroethanes, chloroform and chlorobenzene; Ether solvents, as diethyl ether, methyl tertiary butyl ether(MTBE), methyl-isobutyl ether, two
Figure BDA00002636077400241
alkane and oxolane; Methyl-sulfoxide; Amide solvent, as DMF and DMA; 1-METHYLPYRROLIDONE; 1,3-dimethyl-imidazolinone; The 3-methyl
Figure BDA00002636077400251
oxazolidone; Ester solvent, as ethyl acetate, propyl acetate, ethyl propionate and butyl acetate; Carbonate solvent, as diethyl carbonate, ethylene carbonate and propylene carbonate; Ketone solvent, as acetone, 2-butanone and cyclohexanone; Hydrocarbon solvent, as hexane, benzinum, cyclohexane, benzene and toluene; And composition thereof.Wherein, particularly preferably above-mentioned alcoholic solvent, nitrile solvent and amide solvent.
Can process metal oxide semiconductor with described at least one hydroxamic acid or its salt by the following method:
(a) Dye Adsorption thereon after, carry out processing method with described at least one hydroxamic acid or its salt, hereinafter referred to as " post-processing approach ";
(b) when Dye Adsorption is thereon, the method for processing with described at least one hydroxamic acid or its salt, hereinafter referred to as " processing method simultaneously "; Or
(c) Dye Adsorption thereon before, the method for processing with described at least one hydroxamic acid or its salt, hereinafter referred to as " pre-treating method ".
In these methods, preferred post-processing approach and pre-treating method, particularly preferably pre-treating method.
Perhaps, but these method combinations with one another use.This means and can repeatedly process metal oxide semiconductor with one or more hydroxamic acid or its salt successively or progressively.For example, can use the two step processing methods that comprise pre-treating method and while processing method.In situation about repeatedly processing with one or more hydroxamic acid or its salt therein, can be identical or different for described one or more hydroxamic acid or its salt of each processing.
In the situation that use Treatment Solution or process dispersion (wherein the two all is called " treatment fluid " hereinafter), can use described treatment fluid to process metal oxide semiconductor by distinct methods, as dip-coating, immersion, spraying, coating or flushing/rinsing.Preferably for dip-coating or immersion treatment method, described treatment fluid is processed metal oxide semiconductor, wherein by described metal oxide semiconductor submergence or be soaked in described treatment fluid.In addition, also can use described treatment fluid to process metal oxide semiconductor by spraying process for treating, wherein with pre-treating method or post-processing approach, described treatment fluid is sprayed on metal oxide semiconductor.
In dip-coating or immersion treatment method, although the temperature for the treatment of fluid and processing time can change in wide region, by temperature, be preferably 0-100 ° of C, preferably the liquid handling of 15-80 ° of C reached for 1 second to 24 hour, more preferably reached for 1 second to 3 hour.
After processing, especially, after dip-coating or immersion treatment, preferably use the described metal oxide semiconductor of solvent wash.Described solvent is preferably with identical for those of described treatment fluid, and polar solvent as described above more preferably, as nitrile solvent, alcoholic solvent or amide solvent.
Described at least one hydroxamic acid or its salt concentration in treatment fluid (I) is preferably 1 * 10 -6-2mol/L, more preferably 1 * 10 -5-1mol/L, be in particular 1 * 10 -4-5 * 10 -1mol/L is especially 5 * 10 -4-1 * 10 -2mol/L.
The photoelectric conversion device of dye sensitization comprises following element usually: conductive layer (for the part of work electrode or anode or form work electrode or oxygen base), photosensitive layer, charge transfer layer and another conductive layer (for the part to electrode or negative electrode or form electrode or negative electrode) that usually comprise metal oxide semiconductor and light-sensitive coloring agent.
Therefore, photoelectric conversion device of the present invention preferably comprises as follows hereinafter element in greater detail: conductive layer; Comprise the photosensitive layer by dyestuff (chromonic material) sensitization and the metal oxide semiconductor processed with one or more hydroxamic acid or its salt; Charge transfer layer; With to conductive layer, usually with this, sequentially process.Can be provided with priming coat between described conductive layer and photosensitive layer.
In the context of the invention, " layer " might not mean that each layer and other layer of strict physics separate.In fact, layer can infiltrate each other.For example, the material that forms charge transfer layer usually infiltrate in photosensitive layer and with described metal oxide semiconductor and dyestuff close contact, thereby but make the fast transfer electric charge.
Therefore, the invention still further relates to a kind of method for preparing the dye sensitization photoelectric conversion device, it comprises the steps:
I) provide conductive layer;
Ii) optional deposition of primer layer thereon;
Iii) available from step I) conductive layer or the words of existence available from step I i) priming coat on deposit photosensitive layer, wherein said photosensitive layer comprises by chromonic material sensitization and the metal oxide semiconductor processed with at least one hydroxamic acid or at least one its salt;
Iv) available from step I ii) photosensitive layer on the deposited charge transfer layer; With
V) available from step I v) charge transfer layer on deposition to conductive layer.
Can go up depositing conducting layer and/or the intensity with the raising photoelectric conversion device to conductive layer at substrate (also referred to as supporter or carrier).The layer that will consist of the substrate that deposits this conductive layer on conductive layer and its in the present invention, is called conductive substrates.Will be by being called electrode optionally depositing the layer that this substrate to conductive layer forms on conductive layer and its.Preferably conductive layer and the substrate that optionally deposits conductive layer on it are transparent.Described can be also transparent on conductive layer and its, also optionally depositing this substrate to conductive layer, but this is unimportant.
Hereinafter will elaborate each layer comprised in the photoelectric conversion device obtained by the inventive method.
(A) conductive layer [step (i)]
Conductive layer or enough stable to support remainder layer, otherwise the electric conducting material that will form described conductive layer is deposited on substrate (also referred to as supporter or carrier).The electric conducting material that preferably will form described conductive layer is deposited on substrate.Be deposited into be combined in hereinafter referred to as " conductive substrates " of electric conducting material on substrate.
In the first situation, conductive layer is preferably made by the material that has sufficient intensity and can fully seal described photoelectric conversion device, the alloy that for example metal forms as platinum, gold, silver, copper, zinc, titanium, aluminium and their.
In the second situation, the conductive layer that comprises electric conducting material on substrate usually and photosensitive layer relatively deposit, thereby make conductive layer directly contact with photosensitive layer.
The preferred embodiment of electric conducting material comprises: metal is as the alloy of platinum, gold, silver, copper, zinc, titanium, aluminium, indium and their formations; Carbon, especially be the carbon nano-tube form; And conducting metal oxide, especially transparent conductive oxide (TCO), as indium-Xi composite oxides, the tin-oxide of fluorine, antimony or indium doping and the zinc oxide of aluminium doping.In the situation that metal, these use with form of film usually, thereby make it form fully transparent layer.More preferably described electric conducting material is selected from transparent conductive oxide (TCO).In these materials, tin-oxide or indium-tin-oxide (ITO) that preferably fluorine, antimony or indium adulterate; The tin-oxide that more preferably fluorine, antimony or indium adulterate; Especially preferably the tin-oxide that fluorine adulterates.Particularly, tin-oxide is SnO 2.
Conductive layer preferably has 0.02-10 μ m, the more preferably thickness of 0.1-1 μ m.
Light irradiates (not from the conductive layer side is irradiated) by the conductive layer side usually.Therefore, as mentioned above, preferably substrate and the preferred conductive substrates with conductive layer is substantially transparent as a whole.Herein, to mean visible ray to the light transmittance of the light (400-1000nm) of near infrared region be 50% or higher to term " substantially transparent ".Light transmittance is preferably 60% or higher, and more preferably 70% or higher, be 80% or higher especially.Conductive substrates particularly preferably has the light that photosensitive layer is had to sensitiveness to it and has high transmission rate.
Described substrate can be made by glass, as has the low-cost soda-lime glass of excellent in strength and be not subject to the de-alkali-free glass affected of alkali cleaning.Perhaps, can be by transparent polymer film as substrate.Can be tetraacethyl cellulose (TAC), PETG (PET), PEN (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), Merlon (PC), polyarylate (PAr), polysulfones (PSF), polyether sulfone (PES), polyimides (PI), Polyetherimide (PEI), cyclic polyolefin, bromination phenoxy resin etc. as polymeric film material.
Conductive substrates is preferably by being placed in electric conducting material on substrate and preparing by for example coating or vapour deposition.
Treat the amount that is deposited into the electric conducting material on substrate and selected, to guarantee the thering is sufficient transparency.Suitable amount depends on electric conducting material used and substrate, and each situation is determined separately.For example, in the situation that use TCO as electric conducting material and use glass as substrate, this amount can be the every 1m of 0.01-100g 2.
Preferably use metal lead wire to reduce the resistance of conductive substrates.Metal lead wire is preferably made as platinum, gold, nickel, titanium, aluminium, copper, silver etc. by metal.Preferably by vapour deposition process, sputtering method etc. by metal lead wire provide to substrate with and on the conductive layer that deposited.The reduction of the incident light quantity caused due to metal lead wire is restricted to preferably 10% or lower, more preferably 1-5% or lower.
(B) priming coat (" resilient coating ") [optional step (ii)]
Available resilient coating is coated in the layer obtained in step (i).Its objective is and avoid charge transfer layer directly to contact with conductive layer, and therefore prevent short circuit, particularly in the situation that charge transfer layer is solid-state hole mobile material.
Be somebody's turn to do " priming coat " or cushioning layer material and be preferably metal oxide.Described metal oxide is preferably selected from titanium, tin, zinc, iron, tungsten, vanadium or niobium oxide, as TiO 2, SnO 2, Fe 2o 3, WO 3, ZnO, V 2o 5or Nb 2o 5, TiO more preferably 2.
Described priming coat for example can apply by spraying-pyrolysismethod, for example, as Electrochim.Acta, 40,643-652 page (1995) is described, or sputtering method, for example, as Thin Solid Films 445,251-258 page (2003), Suf.Coat.Technol.200,967-971 page (2005) or Coord.Chem.Rev.248 (2004), the 1479th page is described.
The thickness of priming coat is preferably 5-1000nm, and more preferably 10-500nm, be in particular 10-200nm.
Will be based on I -/ I 3 -liquid electrolyte as in the situation of charge transfer layer material, short-circuit risks is quite low, so priming coat is unnecessary in principle and can omits.In this class battery, do not exist this optional layer can improve the efficiency of photoelectric conversion device, this is because priming coat has the effect that reduces electric current, and also can damage contacting between photosensitive layer and conductive layer.Yet on the other hand, priming coat helps avoid the problem of undesirable charge recombination process, thereby make the application of this coating there are some advantages, especially in the situation that the solid charge transfer layer.
(C) photosensitive layer [step (iii)]
Described photosensitive layer comprises the metal oxide semiconductor with chromonic material (also referred to as dyestuff or light-sensitive coloring agent) sensitization.The metal oxide semiconductor of described dye sensitization plays photoactive substance, to absorb light and to carry out separation of charge, produces thus electronics.Just as is known, the thin layer of metal oxide or film can be used as solid semiconductor material (N-shaped semiconductor).Yet, due to its large band gap, it does not absorb in the visible-range of electromagnetic spectrum, but absorbs at ultraviolet region.Therefore, in the photoelectric conversion device used for solar cell, must be used in the systemic dyestuff of about 300-2000nm scope it is carried out to sensitization.In photosensitive layer, dye molecule absorbs the photon with enough energy of incident (immersive) light.This causes the excitation state of dye molecule, and it is by the conduction band of electronic injection metal oxide semiconductor.Described metal oxide semiconductor is accepted electronics and is transmitted it in conductive layer, and transfers to work electrode thus (vide infra).
(1) metal oxide semiconductor
Preferably the N-shaped semiconductor is used for to the present invention, wherein conduction band electron plays the work of charge carrier in order to produce anode current under the optical excitation condition.
Suitable metal oxide semiconductor is the known all metal oxides that can be used on organic solar batteries.It comprises: the oxide of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, caesium, niobium or tantalum.In addition, composite semiconductor is as M 1 xm 2 yo zalso can be used in the present invention, wherein M, M 1and M 2mean independently metallic atom, O means oxygen atom, and x, y and z mean that combination with one another is to form the number of neutral molecule.The example is TiO 2, SnO 2, Fe 2o 3, WO 3, ZnO, Nb 2o 5, SrTiO 3, Ta 2o 5, Cs 2o, zinc, Perowskit type composite oxides are as barium titanate, and binary (binary) and ternary (ternary) ferriferous oxide.
The preferred semiconductor metal oxide is selected from TiO 2, SnO 2, Fe 2o 3, WO 3, ZnO, Nb 2o 5, and SrTiO 3.In these semiconductors, more preferably TiO 2, SnO 2, ZnO and composition thereof.Even more preferably TiO 2, ZnO and composition thereof, particularly preferably TiO 2.
Described metal oxide preferably exists with amorphous or nanocrystal form.More preferably it exists with nanocrystal porous layer form.This layer has high surface area, on it, can absorb a large amount of dye molecules, causes thus the absorption of high incident light.Described metal oxide layer also can exist with structured form, as nanometer rods.Nanometer rods provides the advantage with the dyestuff filling pore of high electron mobility and improvement.
Surpass a kind of metal oxide if use, two or more metal oxides can be applied with form of mixtures when forming photosensitive layer.Perhaps, available one or more metal oxide-coated metal oxide layers different from it.
Described metal oxide also can be used as layer and is present in the semiconductor different from it as on GaP, ZnP or ZnS.
The TiO that the present invention is used 2preferably be the anatase crystal structure with ZnO, it is preferably again nanocrystal.
Described semiconductor can comprise or can not comprise the dopant that improves its electron conductivity.Preferred dopant is metallic compound, as metal, slaine and metal chalcogenide element compound.
In photosensitive layer, described metal oxide semiconductor layer is preferably porous, be particularly preferably nanoporous, is especially mesopore.
Porous material is characterised in that the rough surface of porous.Porosity is the measurement index in space, material mesopore, and it is pore volume and the ratio of cumulative volume.It is the hole in nanometer range that nano-porous materials has diameter, i.e. about 0.2-1000nm, preferably 0.2-100nm.Mesopore material is the particular form with the nano-porous materials in the hole that diameter is 2-50nm.In the context of the invention, " diameter " is the maximum gauge of finger-hole.The diameter in hole can be measured by some porosimetries, as optical method, inhalation, water evaporation, mercury are invaded porosimetry or gas expansion method.
Granularity for the preparation of the metal oxide semiconductor of metal oxide semiconductor layer is generally nanoscale to micron order.The average-size of elementary semiconductor grain (being obtained by the diameter of a circle that is equivalent to its outburst area) is preferably 200nm or less, for example 5-200nm, more preferably 100nm or less, for example 5-100nm or 8-100nm.
In the preparation process of described photosensitive layer, two or more can be there is to the metal oxide semiconductor mixing that different grain size distributes.Now, more short grained particle mean size is preferably 25nm or less, more preferably 10nm or less.For improve described photoelectric conversion device to the scattered beam of incident light the light rate of catching, can there is the metal oxide semiconductor of coarsegrain (for example, diameter is about 100-300nm) for photosensitive layer.
The method for preparing described metal oxide semiconductor preferably has: for example, as Materia, and the 35th the 9th phase of volume, the described sol-gel process of 1012-1018 page (1996).Also preferably by the method for Degussa company exploitation, it comprises by pyrohydrolysis chloride under the existence at hydrogen-oxygen salt and prepares oxide.
In the situation that use titanium dioxide as metal oxide semiconductor, preferably use above-mentioned sol-gel process, gel-sol method, pyrohydrolytic method.As sol-gel process, preferred Barb é etc. also, Journal of American Ceramic Society, the 80th the 12nd phase of volume, 3157-3171 page (1997) and Burnside etc., Chemistry of Materials, the 10th the 9th phase of volume, 2419-2425 page (1998) described those.
Can by the following method metal oxide semiconductor be applied in step (i) if or the layer of implementing to obtain in step (ii) upper: with the dispersion that comprises described particle or colloidal solution be coated in step (i) or (ii) in acquisition layer method; Above-mentioned sol-gel process etc.For a large amount of manufactures of photoelectric conversion device, the wet type stratification is comparatively favourable, its can improve the performance of metal oxide semiconductor dispersion and improve in step (i) or (ii) in, obtain layer adaptability etc.The representative instance of this class wet type stratification has cladding process, print process, strike and electro-deposition techniques.In addition, deposited semiconductor metal oxide layer by the following method: make burning; Make metallic solution carry out LPD method (liquid deposition) of ligand exchange etc.; Sputtering method; Vapour deposition process; CVD (chemical vapour deposition (CVD)) method; Perhaps thermal decomposition type metal oxide precursor is sprayed on the substrate of heating to produce SPD (spray pyrolysis deposition) method of metal oxide.
Can prepare by the dispersion that comprises metal oxide semiconductor: above-mentioned sol-gel process by the following method; Described semiconductor is pulverized in mortar; When being ground in grinder, semiconductor is disperseed; Synthesize in solvent and precipitate metal oxide semiconductor etc.
As dispersion solvent, can make water or organic solvent as methyl alcohol, ethanol, isopropyl alcohol, citronellol, terpineol, carrene, acetone, acetonitrile, ethyl acetate etc., the mixture of one or more and water in its mixture and these organic solvents.If required, can use polymer as polyethylene glycol, hydroxyethylcellulose and carboxymethyl cellulose, surfactant, acid, chelating agent etc. as dispersant.Especially, polyethylene glycol can be added in described dispersion, this is because can regulate the viscosity of described dispersion and the porosity of metal oxide semiconductor layer by the molecular weight that changes polyethylene glycol, and the metal oxide semiconductor layer that comprises polyethylene glycol is difficult to peel off.
Preferred painting method comprises, rolling method and the dip coating for applying metal oxide semiconductor for example, and for example for the air knife method of revising this layer with scrape the skill in using a kitchen knife in cookery.In addition, the method that preferably wherein can be applied simultaneously and revise is wired-rod (wire-bar) method, for example, as US 2,761,791 described slide plate-distributing device (slide-hopper) methods, extrusion molding, curtain coating method etc.In addition, also can use spin-coating method and spraying process.As for the wet type print process, preferably letterpress, hectographic printing, intaglio printing, intaglio printing, offset printing, silk screen printing etc.Preferred stratification can be selected from these methods according to viscosity and the required wet-film thickness of dispersion.
Just as described, described semiconductor alloy layer is not limited to individual layer.Available each self-contained dispersion with varigrained metal oxide semiconductor is carried out multiple coating.In addition, also the dispersion of available each self-contained different types of metal oxide semiconductor, adhesive or additive is carried out multiple coating.In the situation that the thickness in monolayer deficiency also adopts the multiple coating method effectively.
Usually, along with metal oxide semiconductor layer thickness (it equal'ss the thickness of photosensitive layer) increase, the amount of mixing dyestuff on the outstanding area of per unit increases, thereby causes the higher light rate of catching.Yet, because the diffusion length of produced electronics also increases, the proportion of goods damageds that expection causes due to charge recombination are also higher.In addition, usually dyestuff used has high-absorbility as phthalocyanines and porphyrin, thus make the thin layer of metal oxide semiconductor or film just enough.Therefore, the thickness of metal oxide semiconductor layer is preferably 0.1-100 μ m, 0.1-50 μ m more preferably, and even more preferably 0.1-30 μ m, be 0.1-20 μ m especially, is especially 0.5-3 μ m.
Every 1m 2metal oxide semiconductor coating amount on substrate is preferably 0.5-100g, more preferably 3-50g.
After the layer that metal oxide semiconductor is applied in step (i) or obtains (ii), preferably products therefrom is heat-treated to (sintering step) so that described metal oxide particle be electrical contact with each other and improve strength of coating and with the adhesiveness of lower floor.Heat treatment temperature is preferably 40-700 ° of C, more preferably 100-600 ° of C.Heat treatment time is preferably 10 minutes to 10 hours.
Yet, comprise the thermo-sensitive material with low melting point or softening point at conductive layer, in the situation as polymer film, preferably the product obtained is not carried out to high-temperature process after applying described metal oxide semiconductor, because this may destroy this substrate.In this case, heat treatment, preferably in alap temperature, is for example carried out under 50-350 ° of C.In this case, described metal oxide semiconductor be preferably have more short grained those, especially there is 5nm or less particle mean size.Perhaps, can under this low temperature, to inorganic acid or metal oxide precursor, heat-treat.
In addition, heat treatment can be carried out when metal oxide semiconductor is applied to ultra-violet radiation, infrared radiation, microwave, electric field, ultrasonic wave etc., thereby reduces heating-up temperature.In order to remove non-essential organic compound etc., heat treatment preferably with vacuumize, oxygen plasma treatment, carry out with combinations such as pure water, solvent or purge of gas.
If required, can, before with dyestuff, the semiconductor alloy oxide skin(coating) being carried out to sensitization, form barrier layer on this layer, to improve the performance of described metal oxide semiconductor layer.Introduce usually after above-mentioned heat treatment on this barrier layer.The example that forms barrier layer be by described metal oxide semiconductor layer immersion metal alkoxide as titanium ethanolate, isopropyl titanate or butanols titanium, chloride is as titanium chloride, stannic chloride or zinc chloride, in the solution of nitride or sulfide, the described substrate of drying or sintering then.Described barrier layer for example by metal oxide as TiO 2, SiO 2, Al 2o 3, ZrO 2, MgO, SnO 2, ZnO, Eu 2o 3, Nb 2o 5or its combination, TiCl 4, or polymer is made as gathered (phenylate-copolymerization-2-pi-allyl phenylate) or polymethyl siloxane.The preparation details of this layer for example is described in Electrochimica Acta 40,643,1995; J.Am.Chem.Soc 125,475, and 2003; Chem.Lett.35,252,2006; J.Phys.Chem.B, in 110,1991,2006.Preferably use TiCl 4.Barrier layer is normally closely knit and fine and close, and usually thin than described metal oxide semiconductor layer.
As described in, preferred described metal oxide semiconductor layer has high surface area to adsorb a large amount of dye molecules.The surface area of described metal oxide semiconductor layer is preferably high 10 times or more than its outstanding area, more preferably high 100 times or more.
(2) dyestuff
Dyestuff as the chromonic material of photosensitive layer has no particular limits, as long as it can absorb light, particularly in visible region and/or near infrared region (especially about 300-2000nm) absorb light, but and the described metal oxide semiconductor of sensitization.The example be metal complex dye (for example, referring to US4,927,721, US 5,350,644, EP-A-1176646; Nature 353,1991,737-740; Nature 395,1998,583-585; US 5,463,057, US 5,525,440, US 6,245,988, WO 98/50393), indoline dyestuff (for example, referring to Adv.Mater.2005,17,813), piperazine dyestuff (for example, referring to US 6,359,211), thiazine dye are (for example, referring to US 6,359,211), (preferably polymethin dye is as in cyanine dye, merocyanine dyes, square acid for acridine dye (for example, referring to US 6,359,211), porphyrin dye, methine dyes
Figure BDA00002636077400332
(squalilium) dyestuff etc.; For example, referring to US 6,359,211, EP 892411, EP 911841, EP 991092, WO 2009/109499) and naphthalene embedding benzene (rylene) dyestuff (for example, referring to JP-A-10-189065, JP 2000-243463, JP 2001-093589, JP2000-100484, JP 10-334954, New J.Chem.26,2002,1155-1160, especially DE-A-102005053995 and WO 2007/054470).
Described dyestuff is preferably selected from metal complex dye, porphyrin dye, merocyanine dyes and naphthalene embedding benzene dyestuff; More preferably be selected from ruthenium complex dyestuff and naphthalene embedding benzene dyestuff; Particularly preferably be selected from naphthalene embedding benzene dyestuff (especially those described in DE-A-102005053995 and WO 2007/054470).
For the photoelectric conversion wave-length coverage that enlarges described photoelectric conversion device and improve electricity conversion, can use two or more dyestuffs with the form of mixture or its combination.In the situation that use two or more dyestuffs, the kind of dyestuff and ratio can be selected according to the intensity distributions of wave-length coverage and light source.
For example, the scope of conjugated system is depended in the absorption of naphthalene embedding benzene dyestuff.The rylene derivatives of DE-A-102005053995 absorbs 400nm (perrylene derivative I) to 900nm (four rylene derivatives I).Three naphthalene embedding phenyl dyestuffs absorb about 400-800nm.Therefore, in order in the electromagnetic wave scope large as far as possible, to obtain and to absorb, advantageously use and there are the different mixtures that absorb peaked naphthalene embedding benzene dyestuff.
Described dyestuff preferably have can with interlocking or the anchoring group of described metal oxide semiconductor surface interaction or absorption.Preferred interlocking group comprise acid groups as-COOH ,-OH ,-SO 3h ,-P (O) is (OH) 2with-OP (O) is (OH) 2, and π-conductivity chelation group is as oximido, two oximidos, oxyquinoline group, salicylic acid ester group and α-one enolate (ketoenolate) group.Suitable also have anhydride group, because itself and hydroxy-acid group reaction in-situ.Wherein, the preferred acid group, particularly preferably-COOH ,-P (O) is (OH) 2with-OP (O) is (OH) 2.The interlocking group can form salt or form molecule inner salt with alkali metal etc.In the situation that polymethin dye, acid groups is as in square acid
Figure BDA00002636077400341
cyclic group or crocic acid (croconium) cyclic group formed by methine chain can play the interlocking group.
(preferred described dyestuff has the far-end of being positioned at, the dye molecule end relative with anchoring group) one or more electron donating groups, it contributes to regeneration and any also preventing and the electron recombination provided of dyestuff after by electronics, giving metal oxide semiconductor.
The naphthalene embedding benzene dyestuff can be used in the present invention is for example JP 3968819, JP 4211120, JP10189065 and described Ge Zhong perylene-3 for semiconductor solar cell of JP 2000/100484,4:9,10-tetra carboxylic acid derivatives.These dyestuffs are especially: have carboxyalkyl, carboxyl aryl or carboxyl aryl alkyl and/or used the perylene carboxylic acid amides of para diaminobenzene derivative (wherein the nitrogen-atoms of bit amino is replaced by two other phenyl or be the part of heteroaromatic three-ring system) imidizate on imide nitrogen atom; There is above-mentioned group or alkyl or aryl and not further functionalized perylene-3 on imide nitrogen atom, 4:9,10-tetracarboxylic acid list acid anhydride list acid imide; Huo person's perylene-3,4:9, half condensation product of 10-tetracarboxylic acid dianhydride and 1,2-diaminobenzene or 1,8-diaminonaphthalene, it is by further reacting and change into corresponding imidodicarbonic diamide or two condensation products with primary amine; With carboxyl or aminofunctional perylene-3,4:9, the condensation product of 10-tetracarboxylic acid dianhydride and 1,2-diaminobenzene; With use aliphatic series or aromatic diamine imidizate perylene-3,4:9,10-tetracarboxylic acid acid imide.
Other naphthalene embedding benzene dyestuffs that can be used in the present invention are New J.Chem.26,1155-1160 page (2002) Suo Shu perylene-3,4-dicarboxylic acid derivatives.Specifically mention 9-bis-Wan base An Ji perylene-3,4-dicarboxylic acid anhydride and replaced and have 2,5-di-tert-butyl-phenyl perylene-3,4-dicarboximide by dialkyl amido or carboxyl methylamino at 9 on imide nitrogen atom.
Be particularly useful for naphthalene embedding benzene dyestuff in the present invention and be those described in US 2008/0269482, especially acid anhydrides, the amino perylene-3 that replaces of 9-, corresponding three rylene derivatives of 4-dioctyl phthalate and formula (II):
Figure BDA00002636077400351
Wherein
X is O, NH, N-phenyl-COOH or N-(CH 2) m-COOH, the integer that wherein m is 1-4;
N is 0 or 1;
R afor hydrogen, aryloxy group, arylthio or ammonia diaryl base, the aryl in wherein said rear 3 groups can not be substituted or replaced by 1-3 group that is preferably selected from alkyl, alkoxyl and aryl;
R a' define as R a, and be preferably hydrogen when n=0, when n=1 preferably with R aidentical;
R bfor the aryl that can not be substituted or replaced by the individual group that is preferably selected from alkyl, alkoxyl, dialkyl amido, aryl and heteroaryl of 1-3;
R b' define as R b, and preferred and R bidentical, or
R band R b' form heterocycle with together with the nitrogen-atoms of its keyed jointing.
In the context of the invention, particularly preferably wherein n be 0 and X be N-phenyl-COOH or N-CH 2the formula of-COOH (II) dyestuff.Especially preferably U.B.Cappel etc., J.Phys.Chem.C, 113,33,14595-14597,2009 Gong Kai perylene dyestuffs " ID176 ", it is N-CH for X wherein 2-COOH, n is 0, R aand R a' be hydrogen and R band R b' formula (II) compound of the 4-that respectively does for oneself (1,1,3,3-tetramethyl butyl) phenyl.
Described dyestuff can be by being adsorbed on described metal oxide semiconductor by these component bridge joints to contact with each other, for example by the product that will obtain after applying the metal oxide semiconductor layer, be soaked in Dye Adsorption solution, or by Dye Adsorption solution is applied on the metal oxide semiconductor layer.In the former case, can use infusion method, infusion process, rolling method, air knife method etc.In immersion process.Dyestuff can at room temperature or as described in JP 7249790 adsorb in heating under refluxing.As the applying method in a rear situation, can use slide plate-distributing device method, extrusion molding, curtain coating method, spin-coating method, spraying process etc.In addition, can described dyestuff be applied on the metal oxide semiconductor layer and be applied on pattern by ink-jet method, the surface of the photoelectric conversion with this pattern form is provided thus.Process described metal oxide semiconductor with at least one hydroxamic acid or its salt in the situation that make Dye Adsorption on metal oxide semiconductor and simultaneously, also can use these methods, therefore, described Dye Adsorption solution can comprise one or more hydroxamic acid or its salt.Preferably, when it is new sintering, be still when hot, the dyestuff that makes (for example) be suspension or solution form contacts with metal oxide semiconductor.Answer long enough time of contact, so that Dye Adsorption is to metal oxide surface.Be generally 0.5-24 hour time of contact.
Surpass a kind of dyestuff if apply, can apply two or more dyestuffs simultaneously, for example, by using the mixture of two or more dyestuffs, or one after the other apply successively each other dyestuff.
Described dyestuff also can apply with the form of mixtures with at least one hydroxamic acid or its salt.In addition or extraly, described dyestuff can apply with the charge transport material combination.
Be not adsorbed to dyestuff on the metal oxide semiconductor layer preferably by after described Dye Adsorption technique, cleaning and remove immediately.Clean preferably by having polar solvent, especially polar organic solvent carries out as the wet type cleaner bath of acetonitrile or alcoholic solvent.
The amount of dye of adsorbing on metal oxide semiconductor is preferably the every 1g metal oxide semiconductor of 0.01-1mmol.The adsorbance of this dyestuff makes the abundant sensitization of described semiconductor usually.Too small amount of dye causes inadequate sensitization effect.On the other hand, not the dyestuff floatability of absorption on metal oxide semiconductor, thereby cause the sensitization effect to reduce.
In order to improve the adsorbance of dyestuff, can Dye Adsorption thereon before, the semiconductor alloy oxide skin(coating) is heat-treated.After heat treatment, preferably make on the dyestuff metal oxide semiconductor layer that quick adsorption to temperature is 60-150 ° of C before this layer is cooled to room temperature, to prevent water, be adsorbed on described metal oxide semiconductor layer.
(3) hydroxamic acid and salt thereof
Referring to mentioned above.
(4) passivating material
Compound with charge transfer layer in metal oxide semiconductor in order to prevent electronics, passivation layer can be provided on metal oxide semiconductor.Passivation layer can provide before dyestuff and hydroxamic acid or the absorption of its salt, or provided after processing in Dye Adsorption technique with hydroxamic acid or its salt.Suitable deactivation matter is aluminium salt, Al 2o 3, silane is as CH 3siCl 3, metal organic complex, especially Al 3+complex, 4-tert .-butylpyridine class, MgO, 4-guanidine radicals butyric acid and cetyl malonic acid.
Described passivation layer is preferably very thin.
(D) charge transfer layer [step (iv)]
Charge transfer layer is that oxide layer is supplemented electronics.Charge transfer layer can be by (i) ion-conductive electrolyte composition or (ii) is utilized the charge transport materials of the electric charge transmission of free carrier mediation to form.The example of ion-conductive electrolyte composition (i) comprising: the molten salt electrolyte composition that comprises the redox pairing; Wherein the redox pairing is dissolved in the electrolytic solution in solvent; So-called gel electrolyte composition, the solution that wherein comprises the redox pairing infiltrates in polymeric matrix; Solid electrolyte composition etc.The example of charge transport materials (ii) comprises charge transport materials and hole mobile material.These materials can be used in combination with each other.
Charge transfer layer for the present invention is preferably solid, preferably by hole mobile material, forms (solid p-type semiconductor).
(1) molten salt electrolyte composition
Can be by the molten salt electrolyte composition for wherein pursuing the charge transfer layer of the photoelectric conversion device that has enough durability and good energy conversion efficiency η concurrently.Described molten salt electrolyte composition comprises the molten salt electrolyte with low melting point.With regard to regard to the present invention, can select the salt of wide region as described molten salt electrolyte.The useful example of this class salt is for example pyridine
Figure BDA00002636077400371
salt, imidazoles
Figure BDA00002636077400372
salt and triazole
Figure BDA00002636077400381
salt, it for example is disclosed in WO 95/18456 and EP 0718288.Described molten salt electrolyte preferably has 100 ° of C or lower fusing point, is at room temperature particularly preferably liquid.
Although described molten salt electrolyte composition can comprise solvent hereinafter described, particularly preferably do not comprise solvent.The content of described molten salt electrolyte is preferably 50 % by weight or higher, 90 % by weight or higher particularly preferably, the total composition based on described charge transfer layer.The salt compounded of iodine weight ratio preferably be contained in described molten salt electrolyte composition is preferably 50 % by weight or higher, the whole salt based on wherein contained.
Described molten salt electrolyte composition preferably comprises iodine.Content of iodine is preferably the 0.1-20 % by weight, and 0.5-5 % by weight more preferably, based on whole compositions.
Described molten salt electrolyte composition also can comprise alkali compounds, as tert .-butylpyridine, 2-picoline, 2, and 6-lutidine etc., as J.Am.Ceram.Soc., the 80 (12), the 3157-3171 page (1997) is described.The concentration of alkali compounds wherein is preferably 0.05-2M.
(2) electrolytic solution
Electrolytic solution for the present invention preferably consists of electrolyte, solvent and optional additive.Described electrolyte can be: I 2with iodide, (metal iodide is as LiI, NaI, KI, CsI and CaI 2, quaternary ammonium iodide is as tetra-allkylammonium iodide, pyridine
Figure BDA00002636077400382
iodide and imidazoles
Figure BDA00002636077400383
iodide etc.) combination; Br 2with bromide, (metal bromide is as LiBr, NaBr, KBr, CsBr and CaBr 2, quaternary ammonium bromides is as tetraalkyl ammonium bromide and pyridine
Figure BDA00002636077400384
bromide etc.) combination; Metal complex is as ferrocyanide-ferricyanide and ferrocene-ferricinum ion; Sulphur compound is as sodium polysulfide and alkylthio group disulphide; The purpurine dyestuff; Quinhydrones-quinone etc.Wherein, preferred I 2combination with LiI or quaternary ammonium iodide.Also can use several electrolytical mixtures.
Electrolyte concentration in electrolytic solution is preferably 0.1-10M, more preferably 0.2-4M.In addition, described electrolytic solution can comprise iodine, and iodine concentration wherein is preferably 0.01-0.5M.
The solvent that is used for described electrolytic solution is preferably to have low viscosity and has the macroion mobility, therefore has the solvent of good ionic conductance.The example of organic solvent comprises: carbonic ester, as ethylene carbonate and propylene carbonate; Heterocyclic compound, as 3-methyl-2-
Figure BDA00002636077400385
oxazolidone; Ether, as two alkane and diethyl ether; Chain ether, as glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether and polypropylene glycol dialkyl ether; Alcohol, as methyl alcohol, ethanol, ethylene glycol monoalkyl ether, propylene-glycol monoalky lether, polyalkylene glycol monoalkyl ether and polypropylene glycol monoalky lether; Glycol, as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol and glycerine; Nitrile compound, as acetonitrile, glutaronitrile (glutarodinitrile), methoxyacetonitrile, propionitrile and benzonitrile; Methyl-sulfoxide (DMSO) and sulfolane; Water etc.But these solvent combinations with one another are used.
Described electrolytic solution also can comprise alkali compounds, as tert .-butylpyridine, 2-picoline, 2, and 6-lutidine etc., as J.Am.Ceram.Soc., the 80 (12), the 3157-3171 page (1997) is described.The concentration of alkali compounds wherein is preferably 0.05-2M.
(3) gel electrolyte composition
Can be by gellings or curing to prepare the gel electrolyte composition such as molten salt electrolyte composition mentioned above, electrolytic solutions.Gelling can realize by the following method: add polymer; Add oil-gelling agent; Aggregate packet is containing the monomer of polyfunctional monomer; The cross-linking reaction of polymer etc.
In the situation that prepare described gel electrolyte composition by adding polymer, can use " Polymer Electrolyte Reviews 1and 2 ", J.R.MacC allum and C.A.Vincent edit, Elsevier, the compound described in London (1987 and 1989) is as described polymer.In these compounds, optimization polypropylene nitrile and polyvinylidene fluoride.
In the situation that prepare described gel electrolyte composition by adding oil-gelling agent, can use J.Am.Chem.Soc., 111,5542 (1989); J.Chem.Soc., Chem.Commun., 390 (1993); Angew.Chem.Int.Ed.Engl., 35,1949 (1996); Chem.Lett., 885 (1996), J.Chem.Soc., Chem.Commun., the compound described in 545 (1997) etc. is as oil-gelling agent.In these compounds, preferably there are those of amide structure.
In the situation that prepare described gel electrolyte composition by the cross-linking reaction of polymer, preferably with crosslinking agent, be used in combination the polymer that comprises the group with cross-linking reaction.The described group with cross-linking reaction is preferably amino or nitrogen heterocyclic ring group, as pyridine radicals, imidazole radicals, thiazolyl,
Figure BDA00002636077400391
azoles base, triazolyl, morpholinyl (morpholyl), piperidyl, piperazinyl (piperazyl) etc.Crosslinking agent be preferably have a plurality of can be by the electrophilic reagent of the functional group of the nitrogen-atoms attack of amino or above-mentioned heterocyclic radical; for example multifunctional alkyl halide, aralkyl halogen, sulphonic acid ester, acid anhydrides, acyl chlorides, isocyanates, α; β-unsaturated sulfonyl compound, α; beta-unsaturated carbonyl compound, α, alpha, beta-unsaturated nitriles compound etc.
(4) hole mobile material
In the present invention, can be by inoganic solids hole mobile material, organic solid hole mobile material or its combination for charge transfer layer.
(a) inorganic hole mobile material
Inorganic hole mobile material can be the p-type inorganic compound semiconductor, and it is preferably the compound that comprises monovalent copper, as CuI, CuSCN, CuInSe 2, Cu (In, Ga) Se 2, CuGaSe 2, Cu 2o, CuS, CuGaS 2, CuInS 2, CuAlSe 2deng.Wherein, preferred CuI and CuSCN, most preferably CuI.Also can use GaP, NiO, CoO, FeO, Bi 2o 3, MoO 2, Cr 2o 3deng as the p-type inorganic compound semiconductor.
(b) organic hole transferring material
The example that can be used for the organic hole transferring material in the present invention comprises polymer, as polypyrrole (such as K.Murakoshi etc., Chem.Lett., 471,1997 is disclosed); Be disclosed in " Handbookof Organic Conductive Molecules and Polymers ", the 1-4 volume, H.S.Nalwa edits, and Wiley publishes polyacetylene, polyparaphenylene, poly-(to phenylene vinylidene), polythiophenevinylenand, polythiophene, polyaniline, polymethyl benzene amine and the derivative thereof in (1997); With poly-(3,4-ethylidene dioxy thiophene), poly-(4-undecyl-2,2'-bithiophene), poly-(3-octyl group thiophene), poly-(triphenyl diamine) and carbazolyl polymers as poly-(just vinylcarbazole).
Can be used for low-molecular-weight organic hole transferring material in the present invention and comprise and be disclosed in for example Nature, the 395th volume, on August 8th, 1198, the 583-585 page, WO 97/10617, US 4,923,774 and US 6,084,176 in aromatic amine; Be disclosed in the benzophenanthrene in JP 11176489 for example; Be disclosed in for example Adv.Mater., 9, the 7 phases, 557,1997, Angew.Chem.Int.Ed.Engl., 34,3,303-307 page, 1995, J.Am.Chem.Soc., the 120th volume, 4, the 664-672 pages, the oligothiophene compounds in 1998; Hydrazone compound, be disclosed in for example US 4, silicon nitrogen silane compound in 950,950, silicon amine (silanamine) derivative, phosphamidon (phosphamine) derivative, quinacridone compound, stilbene compounds stilbene as amino as the 4-di-p-tolyl and 4-bis-p-totuidine base-4'-[4-(two p-totuidine bases) styryl] Stilbene, triazole derivative,
Figure BDA00002636077400401
the chalcone derivative of oxadiazole derivative, imdazole derivatives, polyaryl chain alkane derivatives, pyrazoline derivative, pyrazolone derivative, amino replacement,
Figure BDA00002636077400402
zole derivatives, styryl anthracene derivant, fluorenone derivatives and polysilane derivative.These compounds can be used alone or use with the form of mixtures of two or more.
The organic hole transferring material be preferred in the present invention is spiro-bisfluorene class (for example, referring to US2006/0049397).Particularly preferred spiro-bisfluorene is 2,2', 7,7'-tetra-(N, N-di-p-methoxy phenyl amine) 9, and 9'-spiro-bisfluorene (" OMeTAD "), it is such as being disclosed in U.Bach etc., and Nature 395, and 583-585, in 1998.
Also described in this citing document in described organic hole transferring material and can add dopant as N (PhBr) 3sbCl 6in this hole mobile material, by oxidation, to introduce free carrier, and salt is as Li[CF 3sO 2) N to be to realize control of Electric potentials on the titanium oxide semiconductor surface.
As described in, described charge transfer layer is preferably solid, more preferably comprises the solid hole mobile material, even more preferably comprises the SOLID ORGANIC hole mobile material, especially comprises the spiro-bisfluorene derivative as the organic hole transferring material.
The particularly preferred embodiment according to the present invention, described charge transfer layer comprises OMeTAD and Li[CF 3sO 2) N.
(5) form the method for charge transfer layer
Described charge transfer layer can be for example by following two kinds of methods, any provides.A kind of for wherein adhering on photosensitive layer in advance electrode, and the method in the charge transfer layer material infiltration gap therebetween that makes to be in a liquid state.Another kind of for wherein charge transfer layer directly being placed on photosensitive layer, then deposit the method to electrode thereon.
In last method, conventional pressure method that can be by utilizing capillary effect or described charge transport material is infiltrated in gap by the decompression method.
In the situation that provide wet charge transfer layer by a rear method, the charge transfer layer that will wet is applied on photosensitive layer, under not being dried, will, to electrode deposition on described wet charge transfer layer, if required, to its edge, be processed to prevent fluid seepage.In the situation that provide gel charged transfer layer by a rear method, can be by described charge transport material with liquid-applied and by gellings such as polymerizations.Now, can be before or after drying fixed charge transfer layer, will be to electrode deposition to charge transfer layer.
Can for example pass through rolling method, dip coating, air knife method, extrusion molding, slide plate-distributing device method, line-excellent method, spin-coating method, spraying process, the tape casting, various printing process, be similar to formation metal oxide semiconductor layer mentioned above or by Dye Adsorption to the situation on semiconductor, the charge transfer layer deposition that will be formed by electrolytic solution, wet organic hole transferring material, gel electrolyte composition etc.
The charge transfer layer consisted of solid electrolyte, solid hole mobile material etc. can form by the dry film forming method, as vacuum deposition method and CVD method, deposits electrode thereon subsequently.Combination that can be by vacuum deposition method, the tape casting, cladding process, spin-coating method, infusion method, electrolysis polymerization method, light polymerization method, these methods etc. is infiltrated in photosensitive layer the organic hole transferring material.Can inorganic hole mobile material be infiltrated in photosensitive layer by the tape casting, cladding process, spin-coating method, infusion method, strike, electroless deposition processes etc.
(E) to electrode [step (v)]
As described in, described to electrode be optionally by defined substrate supports above to conductive layer.For the electric conducting material example to conductive layer, comprise: metal, as platinum, gold, silver, copper, aluminium, magnesium and indium; Its mixture and alloy, especially aluminium and silver-colored mixture and alloy; Carbon; Conducting metal oxide, as the tin-oxide of indium-Xi composite oxides and fluorine doping.Wherein, preferably platinum, gold, silver, copper, aluminium and magnesium, particularly preferably silver-colored or golden.Especially, use silver.In addition, suitable electrode is for mixing inorganic/organic electrode and multi-layered electrode, as the LiF/Al electrode.Suitable electrode for example is described in WO 02/101838 (especially 18-20 page).
Substrate to electrode is preferably standby by glass or the plastics of to be coated or vapour deposition electric conducting material.The thickness that conductive layer is preferably there is to 3nm to 10 μ m, however thickness has no particular limits.
Light can be from the conductive layer that provides step (i) and irradiating the either side in electrode or both sides of providing in step (v), and therefore, in them, at least one answers substantially transparent so that light arrives photosensitive layer.With regard to the angle of improving generating efficiency, the conductive layer preferably provided in step (i) is substantially transparent to incident light.In this case, electrode is preferably had to light reflective properties.This can be by having vapor deposited metal layer or conductive oxide layer to electrode, or the glass of metallic film or plastics form.Such device (also referred to as " concentrator ") is described in WO 02/101838 (especially 23-24 page).
Can be by electric conducting material direct metal plating or vapour deposition (physical vapour deposition (PVD) (PVD), CVD etc.) be arranged to charge transfer layer to electrode.Be similar to conductive substrates, preferably use metal lead wire to reduce the resistance to electrode.Metal lead wire is particularly preferred for transparent in electrode.Identical for those of the preferred embodiment to the metal lead wire of electrode and the above-mentioned metal lead wire for conductive layer.
(F) other
Can be provided with functional layer as protective layer and anti-reflection layer at described conductive layer or on to electrode one or both of.Functional layer can be used for the method setting that its material is selected by basis, as cladding process, vapour deposition process and adhesion method.
(G) internal structure of photoelectric conversion device
As mentioned above, described photoelectric conversion device can have different internal structure according to required final use.Described structure is divided into two kinds of principal modes, allows light from the structure of two sides incident and allows light only from the structure of one side incident.In the first situation, by photosensitive layer, charge transfer layer and other optional exist be placed on transparency conducting layer and transparent between conductive layer.This structure allows the two sides incident of light from described device.In the second situation, transparency conducting layer and transparent to one of conductive layer, be transparent, another is opaque.Certainly, if be transparent to conductive layer, light enters from the conductive layer side; And in the situation that be transparent to conductive layer, light is from entering the electrode side.
The invention further relates to a kind of photoelectric conversion device that can obtain by the inventive method.
Therefore, photoelectric conversion device of the present invention comprise comprise at least one its on absorption have the photosensitive layer of the metal oxide semiconductor of at least one chromonic material, wherein said metal oxide semiconductor to be used in 400-1000nm electromagnetic wavelength scope to be at least one hydroxamic acid and/or at least one its salt of substantially transparent to process.With regard to suitable and preferred metal oxide semiconductor, hydroxamic acid and salt thereof and device assembly, referring to mentioned above those.
More preferably, photoelectric conversion device of the present invention comprises:
I) conductive layer;
II) optional priming coat;
III) photosensitive layer, wherein said photosensitive layer comprises by chromonic material sensitization and the metal oxide semiconductor processed with its salt of the hydroxamic acid of at least one substantially transparent and/or at least one substantially transparent;
IV) charge transfer layer; With
V) to conductive layer.
With regard to each layer and component of forming photoelectric conversion device of the present invention, referring to content mentioned above.Just as described, in the context of the invention, term " layer " might not mean that each layer and other layer of strict physics separate.In fact, each layer can infiltrate each other.For example, the material that forms charge transfer layer can infiltrate in photosensitive layer and with described metal oxide semiconductor and dyestuff close contact, thereby but make the fast transfer electric charge.
In previously described photoelectric conversion device, in the situation that use the N-shaped metal oxide semiconductor, enter the optical excitation dyestuff of photosensitive layer, and the high energy electron that will wherein excite transfers in the conduction band of metal oxide semiconductor, therein, electrons spread reach conductive layer.Now, dyestuff is oxidised form.In comprising the photocell of described photoelectric conversion device (seeing below), outside during circuit working, the electronics in conductive layer is via conductive layer and charge transfer layer are returned to the dyestuff of oxidation, thereby makes dyestuff regeneration.Photosensitive layer plays negative electrode or light anode usually, and to the conductive layer effect of its positive electrode usually.On the border of each layer, as the border between the border between conductive layer and photosensitive layer, photosensitive layer and charge transfer layer, charge transfer layer and, in border between conductive layer etc., the component of each layer can spread and mix.
Do not wish to be bound by theory, it is believed that processing with one or more hydroxamic acid or its salt the energy conversion efficiency η that causes photoelectric conversion device of the present invention improves, this is because the photon change in concentration on metal oxide surface, make conduction band shift to the electromotive force of corrigendum (in the situation that hydroxamic acid), promote that thus electronics injects from dyestuff; Perhaps make conduction shift to more negative electromotive force (in the situation that hydroxamate), improve thus open circuit voltage.In addition, think these additives, especially but not hydroxamate only, contributing to reduce dyestuff assembles, simultaneously between dye molecule, the filling in space causes better metal oxide surface to cover, and reduces thus the undesirable compound of electronics in metal oxide and the hole in charge transfer layer.As if also can find out, by using this class additive, reduce the dependence of solid-state dye sensitized solar cell to the priming coat quality.Finally, this class additive often has positive influences to device stability.
These suppositions have obtained the support of the following fact, depend on dyestuff used, and the application of hydroxamic acid especially causes short circuit current I usually scraising, and in processing method or pre-treating method, use hydroxamate usually especially to cause open circuit voltage V at the same time ocraising.
Photocell
The invention still further relates to a kind of photocell, preferred solar cell, it comprises photoelectric conversion device mentioned above.
Photocell is constructed in the following way: by photoelectric conversion device be connected in external circuit with electricity work or in external circuit generation current.The photocell that this class has the charge transfer layer consisted of the ionic conductivity material is called light-electrochemical cell.The photocell that uses sunlight to produce electric energy is called solar cell.
Therefore, photocell of the present invention is constructed in the following way: by photoelectric conversion device of the present invention be connected in external circuit with electricity work or in external circuit generation current.The preferred light battery is solar cell, uses sunlight to produce the battery of electric energy.
Described photronic side is preferably by sealings such as polymer or adhesive, to prevent the deteriorated and volatilization of composition in battery.By external circuit via lead-in wire and conductivity substrate with electrode is connected.Can use in the present invention various known circuit.
In the situation that photoelectric conversion device of the present invention is used for to solar cell, the internal structure of described solar cell can be basically identical with the structure of above-mentioned photoelectric conversion device.The solar cell that comprises photoelectric conversion device of the present invention can have known modular construction.In known solar module structure, battery is placed on the substrate of metal, pottery etc., and, with coverings such as coating resin, protectiveness glass, makes thus light introduce from the offside of substrate.Solar module can have following structure: battery is placed on the substrate of transparent material as toughened glass, from the transparent substrates side, to introduce light.Particularly, known solar module structure has super straight (super-straight) type modular construction, substrate-type modular construction, embedding type modular construction, is generally used for substrate integrated-type modular construction in amorphous si solar cells etc.The solar cell that comprises photoelectric conversion device of the present invention can have that for example suitably be selected from can be according to the corresponding requirements of concrete application and the modular construction of the said structure of adaptive change.
Solar cell of the present invention can be used with the form of laminated cell.Therefore, the invention still further relates to a kind of laminated cell, it comprises DSSC of the present invention and organic solar batteries.
Laminated cell is known in principle, and for example is described in WO 2009/013282.Laminated cell of the present invention can, as those preparations as described in WO 2009/013282, still replace the DSSC described in this citing document with solar cell of the present invention.
The invention still further relates to above defined hydroxamic acid and/or the purposes of its salt in improving the dye sensitization photoelectric conversion device energy conversion efficiency η of (certainly also comprising the photocell that comprises described device, especially photocell).
Embodiment
Set forth in more detail the present invention by embodiment hereinafter, described embodiment limits the scope of the invention absolutely not.
The general preparation of solar cell:
Whether be suitable for as the additive in solar cell the solar cell for preparing as described below in order to test formula I compound.
Basic material used is for being coated with the glass plate of fluorine doped tin oxide (FTO) and size 25mm * 15mm * 3mm (Hartford TEC 15), it uses glass cleaner, fully softening water and acetone treatment successively, in ultra sonic bath 5 minutes in each case, then in isopropyl alcohol, seethe with excitement 10 minutes, and dry in nitrogen stream.
Use Electrochim.Acta, the described spraying-pyrolysismethod of 40, the 643-652 page (1995) deposits by solid TiO on FTO 2the priming coat formed.At the top of this priming coat, distribution TiO 2(Dyesol, 18NR-T) stick with paste and under 450 ° of C sintering 1 hour, take the TiO of thickness as 3 μ m is provided 2mesoporous layer.
Then as M.
Figure BDA00002636077400461
deng, Adv.Mater.18,1202 (2006) the described TiCl that use 4process the intermediate products of preparation in this way.By after this sample sintering, it is cooled to 60-80 ° of C.
In the situation that with hydroxamic acid or its salt pre-treatment, described sample is soaked in the 5mM hydroxamic acid or the solution of its salt in ethanol for the treatment of fluid, in bathing, cleans by straight alcohol, of short duration drying in nitrogen stream, subsequently in 0.5mM perylene dyestuff ID176 (Cappel etc., J.Phys.Chem.Lett.C, 2009,113,14595-14597) in the solution in carrene, flood 12 hours.Subsequently, use the carrene washed samples, and dry in nitrogen stream.Hydroxamic acid for this pre-treating method is listed in table 2, and lists in table 3 for the hydroxamate of this pre-treating method.
In the situation that carry out reprocessing with hydroxamic acid or its salt, at first sample is flooded 12 hours in the solution of 0.5mM perylene dyestuff ID176 in carrene.Then, clean this sample dry in nitrogen stream with carrene.Subsequently, this sample is soaked in the 5mM hydroxamic acid or the solution of its salt in methyl alcohol for the treatment of fluid, cleans in straight alcohol is bathed, and in nitrogen stream of short duration drying.Hydroxamic acid or its salt for this post-processing approach are listed in table 4.
According to pre-treatment or post-processing approach, will be applied on photosensitive layer as the hole mobile material of electronics transfer layer.For this reason, OMeTAD (Merck group) solution of preparation in chlorobenzene, and with 0.3LiN (SO 2cF 3) 2(Sigma-Aldrich group) solution in cyclohexanone mixes.This liquid deposition of 75 μ l, on described sample, and was soaked for 30 seconds.Subsequently, remove supernatant and in surrounding air dry 3 hours by centrifugal under 2000rpm.
Electrode is applied by thermometal vapour deposition process in a vacuum.For this reason, on described sample the equipment mask with deposit 4 separate there is about 5mm * 4mm size rectangle to electrode, the contact area via 3mm * 2mm contacts with charge transfer layer separately.Metal used is silver, and its speed with 0.1nm/s is used 5 * 10 -5the pressure evaporating of millibar, thus the thick layer of 200nm formed.
In order to measure energy conversion efficiency η, irradiate at the xenon lamp that is used as the sunlight simulator (LOT Orielgroup) under (using AM1.5 filter (LOT Oriel group)), with 2400 type source tables (Keithley Instruments Inc.), measure concrete current/voltage characteristic.
Hydroxamic acid or its salt as the additive test are listed in table 1.Hydroxamic acid 1-5 is commercially available; By hydroxamic acid 5 is reacted with NaOH, KOH, LiOH, CsOH or TBAH, by hydroxamic acid 5, prepared by hydroxamate 6-10.The test result of using these additives (using with pre-treatment or post-processing approach) to obtain be described in table 2,3 and 4 and Fig. 1 in.
Table 1: for solar cell to measure the additive of its energy conversion efficiency η
Table 2: the representative value of being derived by the current/voltage characteristic of the solar cell irradiated with the sunlight simulator, the described hydroxamic acid pre-treatment of table 1 for the photosensitive layer of wherein said battery.
? I sc[mA/cm 2] V oc[mV] FF[%] η[%]
1 -11.0 600 33 2.2
2 -10.7 620 35 2.3
5 -10.2 640 49 3.1
11 -8.8 660 36 2.1
Additive-free -5.1 580 55 1.6
Table 3: the representative value of being derived by the current/voltage characteristic of the solar cell irradiated with the sunlight simulator, the described hydroxamate pre-treatment of table 1 for the photosensitive layer of wherein said battery.
? I sc[mA/cm 2] V oc[mV] FF[%] η[%]
6 -9.4 800 49 3.7
7 -5.5 860 65 3.1
8 -6.5 820 69 3.7
9 -4.5 820 60 2.4
10 -11.2 700 41 3.2
Table 4: the representative value of being derived by the current/voltage characteristic of the solar cell irradiated with the sunlight simulator, the described hydroxamic acid reprocessing of table 1 for the photosensitive layer of wherein said battery.
? I sc[mA/cm 2] V oc[mV] FF[%] η[%]
1 -10.2 600 40 2.4
2 -11.2 580 41 2.6
3 -7.8 640 44 2.2
4 -8.2 540 39 1.7
5 -9.1 600 56 3.0
11 -8.7 620 48 2.6
Additive-free -5.1 580 55 1.6
Fig. 1 has shown the mesopore TiO with dyestuff ID176 processes and thickness is 3 μ m 2two Spectral Extinctions of layer (for the described battery of table 2).Top collection of illustrative plates (" not carrying out pre-treatment ") is by only processing described TiO with ID176 2the layer and obtain.Below collection of illustrative plates (" use 5 pre-treatments "), then adsorbs ID176 as described above and obtains with the hydroxamic acid of embodiment 5 processing (in Table 1) by first.Clearly, obtain similar electric current, but (used 5 pre-treatments) in the second situation, TiO 2the dyestuff adsorbed in layer will be less than the first situation (not carrying out pre-treatment).
Can be known and be found out by these results, the blank value that the efficiency eta of the solar cell that comprises additive of the present invention provides with the battery that does not contain additive is compared and is improved.This is mainly due to short circuit current (I sc) due to raising.This is a surprising discovery, because when except dyestuff, while also comprising a kind of test interpolation in photosensitive layer, originally infers that the light absorption meeting in the 400-700nm wave-length coverage descended.In a word, additive of the present invention causes the obvious raising of quantum efficiency.

Claims (35)

1. a method for preparing the dye sensitization photoelectric conversion device, wherein said device comprises the photosensitive layer that the metal oxide semiconductor of at least one chromonic material is arranged containing absorption at least one its, and wherein said metal oxide semiconductor is used at least one hydroxamic acid and/or at least one its salt of substantially transparent in 400-1000nm electromagnetic wavelength scope and processes.
2. method as claimed in claim 1, the compound that wherein said at least one hydroxamic acid is general formula (I), and described at least one its salt compound that is general formula (I'):
Wherein:
M +for alkali metal cation, the alkaline earth metal cation equivalent; Or NR' 4cation, wherein R' is independently from each other hydrogen, C 1-C 6alkyl, phenyl and benzyl; Pyridine
Figure FDA00002636077300012
cation or imidazoles
Figure FDA00002636077300013
cation, the heteroaromatic structure division in wherein said rear 2 cations can not be substituted or is selected from C by 1,2 or 3 1-C 4the substituting group of alkyl and phenyl replaces;
R 1for C 1-C 18alkyl, C 2-C 12alkenyl, C 4-C 12alkadienyl, C 6-C 12alkatriene base, C 2-C 12alkynyl; 1-4 CH in wherein said rear 5 groups 2group can be replaced by O, NH or S and/or the partially or completely halogenation and/or have 1,2 or 3 substituent R of wherein said rear 5 groups 1a; C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclic radical, C 3-C 7heterocyclic radical-C 1-C 4alkyl, cycloalkyl and heterocyclic radical in wherein said rear 4 groups can have 1,2,3 or 4 radicals R 1b;
Aryl, heteroaryl, aryl-C 1-C 6alkyl, aryl-C 2-C 6alkenyl, heteroaryl-C 1-C 4alkyl or heteroaryl-C 2-C 6alkenyl, aryl and heteroaryl in wherein said rear 6 groups can not be substituted or have 1,2,3 or 4 identical or different radicals R 1c; Wherein:
R 1abe independently from each other OH, SH, NO 2, COOH, CHO, NR a1r a2, CN, OCH 2cOOH, CO-NH-OH, CO-NH-O -m +, C 1-C 12alkoxyl, C 1-C 12halogenated alkoxy, C 3-C 7cycloalkyloxy, C 1-C 12alkylthio group, C 1-C 12halogenated alkylthio, CO-C 1-C 12alkyl, CO-O-C 1-C 12alkyl, CONR a3r a4, aryl, heteroaryl, aryl-C 1-C 6alkoxyl or heteroaryl-C 1-C 4alkoxyl, aryl and heteroaryl in wherein said rear 4 groups can not be substituted or have 1,2,3 or 4 identical or different radicals R 1c;
R 1bbe independently from each other OH, SH, NO 2, COOH, CHO, NR b1r b2, CN, OCH 2cOOH, halogen,
Aryl, aryl-C 1-C 6alkyl, aryl-C 1-C 6alkoxyl, the aryl in wherein said rear 3 groups can not be substituted or have 1,2,3 or 4 identical or different radicals R 1c, C 1-C 6alkyl, C 1-C 6alkoxyl, C 1-C 6alkylthio group, the partially or completely halogenation and/or there is 1,2 or 3 substituent R of alkyl structure in wherein said rear 3 substituting groups part d1, CO-C 1-C 6alkyl, CO-O-C 1-C 6alkyl or CONR b3r b4;
R 1cbe independently from each other OH, SH, halogen, NO 2, NR c1r c2, CN, COOH, OCH 2cOOH, C 1-C 12alkyl, C 1-C 12alkoxyl, C 1-C 12alkoxy-C 1-C 6alkyl, C 1-C 12alkylthio group, the partially or completely halogenation and/or there is 1,2 or 3 substituent R of alkyl structure in wherein said rear 4 substituting groups part d1;
C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7cycloalkyloxy, C 3-C 7heterocyclic radical, C 3-C 7heterocyclic radical-C 1-C 4alkyl, C 3-C 7heterocyclic oxy group, cycloalkyl and heterocyclic radical in wherein said rear 6 groups can have 1,2,3 or 4 radicals R d2,
Aryl, heteroaryl, O-aryl, O-CH 2-aryl, wherein said rear 3 groups are not substituted in the aryl structure division maybe can have 1,2,3 or 4 radicals R 1d,
CO-C 1-C 6alkyl, CO-O-C 1-C 6alkyl, CONR c3r c4,
Perhaps be bonded to two radicals R on the adjacent C atom 1bor two radicals R 1ctogether with the C of its keyed jointing atom, form 4,5,6 or 7 Yuans optional carbocyclic rings that replace or optional replace there is the heterocycle of 1,2 or 3 identical or different hetero-atom that is selected from O, N and S as ring members;
R 1dbe selected from halogen, OH, SH, NO 2, COOH, C (O) NH 2, CHO, CN, NH 2, OCH 2cOOH, C 1-C 6alkyl, C 1-C 6haloalkyl, C 1-C 6alkoxyl, C 1-C 6halogenated alkoxy, C 1-C 6alkylthio group, C 1-C 6halogenated alkylthio, CO-C 1-C 6alkyl, CO-O-C 1-C 6alkyl, NH-C 1-C 6alkyl, NHCHO, NH-C (O) C 1-C 6alkyl and SO 2-C 1-C 6alkyl;
R a1, R b1and R c1be H, C independently of one another 1-C 6alkyl, C 1-C 6alkoxyl, C 1-C 6haloalkyl, there is 1,2 or 3 substituent R b1c 1-C 6alkyl, C 2-C 6alkenyl, C 2-C 6alkynyl, C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclylalkyl-C 1-C 4alkyl, C 1-C 6alkoxy-C 1-C 4alkyl, CO-C 1-C 6alkyl, aryl, heteroaryl, O-aryl, OCH 2-aryl, aryl-C 1-C 4alkyl, heteroaryl-C 1-C 4alkyl, CO-aryl, CO-heteroaryl, the aryl in wherein said rear 8 groups and heteroaryl are not substituted or have 1,2 or 3 substituent R 1d;
R a2, R b2and R c2be H, C independently of one another 1-C 6alkyl, C 1-C 6haloalkyl, there is 1,2 or 3 substituent R b1c 1-C 6alkyl, C 2-C 6alkenyl, C 2-C 6alkynyl, C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclylalkyl-C 1-C 4alkyl, C 1-C 6alkoxy-C 1-C 4alkyl, aryl, aryl-C 1-C 4alkyl, heteroaryl or heteroaryl-C 1-C 4alkyl, the aryl in wherein said rear 4 groups and heteroaryl are not substituted or have 1,2 or 3 substituent R 1d; Perhaps
Two radicals R a1with R a2, or R b1with R b2, or R c1with R c2form the optional replacement of 3-7 person and can optionally there is the azacyclo-of 1,2 or 3 identical or different other hetero-atom that are selected from O, N and S as ring members together with the N atom;
R a3, R b3and R c3be H, C independently of one another 1-C 6alkyl, C 1-C 6haloalkyl, there is 1,2 or 3 substituent R b1c 1-C 6alkyl, C 2-C 6alkenyl, C 2-C 6alkynyl, C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclylalkyl-C 1-C 4alkyl, C 1-C 6alkoxy-C 1-C 4alkyl, aryl, aryl-C 1-C 4alkyl, heteroaryl or heteroaryl-C 1-C 4alkyl, the aryl in wherein said rear 4 groups and heteroaryl are not substituted or have 1,2 or 3 substituent R 1d; And
R a4, R b4and R c4be H, C independently of one another 1-C 6alkyl, C 1-C 6haloalkyl, there is 1,2 or 3 substituent R b1c 1-C 6alkyl, C 2-C 6alkenyl, C 2-C 6alkynyl, C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclylalkyl-C 1-C 4alkyl, C 1-C 6alkoxy-C 1-C 4alkyl, aryl, aryl-C 1-C 4alkyl, heteroaryl or heteroaryl-C 1-C 4alkyl; Aryl in wherein said rear 4 groups and heteroaryl are not substituted or have 1,2 or 3 substituent R 1d, or two radicals R a3with R a4, or R b3with R b4, or R c3with R c4form the optional replacement of 3-7 person and can optionally there is the azacyclo-of 1,2 or 3 identical or different other hetero-atom that are selected from O, N and S as ring members together with the N atom;
R d1be independently from each other OH, SH, NO 2, COOH, CHO, NR a1r a2, CN, OCH 2cOOH, C 1-C 12alkoxyl, C 1-C 12halogenated alkoxy, C 3-C 7cycloalkyloxy, CO-C 1-C 12alkyl, CO-O-C 1-C 12alkyl, CONR a3r a4, aryl, heteroaryl, aryl-C 1-C 6alkoxyl and heteroaryl-C 1-C 4alkoxyl, aryl and heteroaryl in wherein said rear 4 groups can not be substituted or have 1,2,3 or 4 identical or different radicals R 1d;
R d2be independently from each other OH, SH, NO 2, COOH, CHO, NR b1r b2, CN, OCH 2cOOH, halogen; Aryl, aryl-C 1-C 6alkyl, aryl-C 1-C 6alkoxyl, the aryl in wherein said rear 3 groups can not be substituted or have 1,2,3 or 4 identical or different radicals R 1d; C 1-C 6alkyl, C 1-C 6alkoxyl, C 1-C 6alkylthio group, the partially or completely halogenation and/or there is 1,2 or 3 substituent R of alkyl structure in wherein said rear 3 substituting groups part d1; And
R 2for H, C 1-C 6alkyl, C 3-C 7cycloalkyl or phenyl.
3. method as claimed in claim 2, wherein M +for lithium ion, sodium ion, potassium ion, cesium ion or NR' 4ion, wherein R' is independently from each other hydrogen, C 1-C 4alkyl and benzyl.
4. as the method for claim 2 or 3, R wherein 2for H, C 1-C 4alkyl, cyclohexyl or phenyl.
5. method as claimed in claim 4, wherein R 2for H or methyl.
6. method as claimed in claim 5, wherein R 2for H.
7. method as described as any one in claim 2-6, wherein:
R 1for C 1-C 10alkyl, C 2-C 10alkenyl, C 4-C 10alkadienyl, the partially or completely halogenation and/or there is 1,2 or 3 substituent R of wherein said rear 3 groups 1a;
C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclic radical, C 3-C 7heterocyclic radical-C 1-C 4alkyl, cycloalkyl and heterocyclic radical in wherein said rear 4 groups can have 1,2 or 3 radicals R 1b; Aryl, heteroaryl, aryl-C 1-C 6alkyl or heteroaryl-C 1-C 4alkyl, aryl and heteroaryl in wherein said rear 4 groups can not be substituted or have 1,2 or 3 identical or different radicals R 1c; Wherein:
R 1abe independently from each other NO 2, CN, CO-NH-OH, CO-NH-O -m +, C 1-C 12alkoxyl, C 1-C 12halogenated alkoxy, aryl, heteroaryl, aryl-C 1-C 6alkoxyl or heteroaryl-C 1-C 4alkoxyl, aryl and heteroaryl in wherein said rear 4 groups can not be substituted or have 1,2 or 3 identical or different radicals R 1c;
R 1bbe independently from each other NO 2, CN, halogen,
Aryl, aryl-C 1-C 6alkyl, aryl-C 1-C 6alkoxyl, the aryl in wherein said rear 3 groups can not be substituted or have 1,2 or 3 identical or different radicals R 1c,
C 1-C 6alkyl or C 1-C 6alkoxyl, the partially or completely halogenation and/or there is 1 or 2 substituent R of alkyl structure in wherein said rear 2 substituting groups part d1;
R 1cbe independently from each other halogen, NO 2, CN, C 1-C 12alkyl, C 1-C 12alkoxyl, C 1-C 12alkoxy-C 1-C 4alkyl, the partially or completely halogenation and/or there is 1 or 2 substituent R of alkyl structure in wherein said rear 3 substituting groups part d1;
C 3-C 7cycloalkyl, C 3-C 7cycloalkyl-C 1-C 4alkyl, C 3-C 7heterocyclic radical, C 3-C 7heterocyclic radical-C 1-C 4alkyl, cycloalkyl and heterocyclic radical in wherein said rear 4 groups can have 1,2 or 3 radicals R d2,
Aryl, O-aryl or O-CH 2-aryl, wherein said rear 3 groups are not substituted in the aryl structure division maybe can have 1,2 or 3 radicals R 1d, and
R 1dbe selected from halogen, NO 2, CN, NH 2, C 1-C 6alkyl, C 1-C 6haloalkyl, C 1-C 6alkoxyl and C 1-C 6halogenated alkoxy.
8. method as claimed in claim 7, wherein: R 1for C 1-C 10alkyl, C 2-C 10alkenyl or C 4-C 10alkadienyl, wherein said rear 3 groups can be replaced by 1,2 or 3 substituting group that is independently from each other following group: CO-NH-OH, CO-NH-O -m +, C 1-C 6alkoxyl, phenyl and phenyl-C 1-C 6alkoxyl, the phenyl in wherein said rear 2 groups can not be substituted or is independently from each other C by 1,2 or 3 3-C 12alkyl, C 3-C 12alkoxyl, C 3-C 12alkoxy-C 1-C 4alkyl and phenyl-C 1-C 6the substituting group of alkoxyl replaces.
9. method as claimed in claim 8, wherein R 1for can be by a group CO-NH-OH or CO-NH-O -m +the C replaced 3-C 10alkyl, or be C 4-C 10alkadienyl.
10. according to the method for claim 7, R wherein 1be selected from C for thering is one 3-C 12the substituent benzyl of alkoxyl and benzyloxy.
11., as the method for claim 10, wherein said substituting group is connected on 4 of benzyl.
12., as the method for any one in aforementioned claim, wherein, after described chromonic material is adsorbed on metal oxide semiconductor, processed with described at least one hydroxamic acid or the described metal oxide semiconductor of its salt pair.
13., as the method for any one in claim 1-11, wherein, when described chromonic material is adsorbed on metal oxide semiconductor, processed with described at least one hydroxamic acid or the described metal oxide semiconductor of its salt pair.
14., as the method for any one in claim 1-11, wherein, before described chromonic material is adsorbed on metal oxide semiconductor, processed with described at least one hydroxamic acid or the described metal oxide semiconductor of its salt pair.
15., as the method for any one in aforementioned claim, wherein said chromonic material is selected from metal complex dye, porphyrin dye, merocyanine dyes and naphthalene embedding benzene dyestuff.
16., as the method for claim 15, wherein said chromonic material is selected from ruthenium complex dyestuff and naphthalene embedding benzene dyestuff.
17., as the method for any one in aforementioned claim, the halfbody metal oxide comprised in wherein said photosensitive layer is nanoporous TiO 2.
18. the method as any one in aforementioned claim, comprise the steps:
I) provide conductive layer;
Ii) optional deposition of primer layer thereon;
Iii) deposit photosensitive layer on the priming coat of the words of described conductive layer or existence, wherein said photosensitive layer comprises by chromonic material sensitization as defined as any one in claim 1,15 or 16 and the metal oxide semiconductor as defined as any one in claim 1-17 processed with at least one hydroxamic acid as defined as any one in claim 1-11 or its salt;
Iv) deposited charge transfer layer on described photosensitive layer; With
V) on described charge transfer layer, deposit conductive layer.
19. as the method for claim 18, wherein said conductive layer and be substantial transparent to conductive layer one or both of.
20., as the method for any one in claim 18 or 19, wherein said conductive layer comprises conducting metal oxide.
21. as the method for claim 20, the tin-oxide that wherein said conducting metal oxide is fluorine, antimony or indium doping.
22. as the method for any one in claim 18-21, the metal oxide semiconductor that wherein priming coat comprises optional doping.
23., as the method for claim 22, wherein said metal oxide semiconductor is TiO 2.
24., as the method for any one in claim 18-23, wherein said chromonic material is adsorbed on the metal oxide semiconductor of described photosensitive layer.
25., as the method for any one in aforementioned claim, wherein said at least one hydroxamic acid or its salt are adsorbed on the metal oxide semiconductor of described photosensitive layer.
26., as the method for any one in aforementioned claim 14-21, wherein said charge transfer layer comprises ion-conductive electrolyte composition or hole mobile material.
27., as the method for claim 26, wherein said charge transfer layer is solid.
28., as the method for claim 26 or 27, wherein said charge transfer layer comprises the spiro-bisfluorene derivative as hole mobile material.
29., as the method for claim 28, wherein said charge transfer layer also comprises salt.
30., as the method for claim 29, wherein said salt is Li[CF 3sO 2) N].
31., as the method for any one in claim 18-30, wherein said conductive layer is comprised to metal.
32., as the method for claim 31, wherein said metal is silver or golden.
33. the photoelectric conversion device of a dye sensitization, it can obtain by the method as any one in claim 1-32.
34. a solar cell, it comprises the photoelectric conversion device as claim 33.
35. hydroxamic acid as defined as any one in claim 1-11 and/or its salt purposes in the energy conversion efficiency η that improves the dye sensitization photoelectric conversion device.
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