CN103443948B

CN103443948B - Photovoltaic element

Info

Publication number: CN103443948B
Application number: CN201280014885.XA
Authority: CN
Inventors: A·库恩; I·布鲁德; R·森斯; N·G·普希雷尔; P·埃尔克
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2011-02-01
Filing date: 2012-01-24
Publication date: 2016-05-04
Anticipated expiration: 2032-01-24
Also published as: KR20140007416A; AU2012213134A1; AU2012213134B2; CN103443948A; ZA201306535B; EP2671271A1; JP6150732B2; JP2014509048A; EP2671271A4; WO2012104742A1

Abstract

Propose a kind of for electromagnetic radiation being changed into the photovoltaic element (110) of electric energy, more especially dye solar cell (112). Photovoltaic element (110) has at least one first electrode (116), at least one n-semiconduction metal oxide (120), at least one absorption of electromagnetic radiation dyestuff (122), at least one SOLID ORGANIC p-semiconductor (126) and at least one the second electrode (132). This p-semiconductor (126) comprises the silver that is oxidised form.

Description

Photovoltaic element

Invention is described

Invention field

The present invention relates to photovoltaic element, a kind of production is for there being the SOLID ORGANIC p-semiconductor of thermomechanical components Method, a kind of and method of producing photovoltaic element. This class photovoltaic element and method are used for electromagnetism Radiation, especially daylight changes into electric energy. More particularly, the present invention can be applicable to dye solar electricity Pond.

Prior art

In solar cell solar energy directly change into the general based semiconductor material of electric energy what is called " in Luminous effect ", by absorbing, photon closes with at p-n junction or schottky junctions touches down and separates negative, positive current-carrying Son and produce electron-hole pair. Like this, produce photovoltage, it can cause photoelectric current in external circuit, Solar cell discharges its power by described photoelectric current. Semiconductor conventionally only energy-absorbing be greater than it Those photons of band gap. Therefore the size of semiconductor band gap determines to change into the daylight of electric energy conventionally Ratio.

Solar cell based on silicon metal produces as far back as 1850s. Technology is at that time logical Cross the use support in space satellite. Even if silica-based solar cell is dominant now in world markets Gesture, but this technology remains costliness. Therefore, attempt the more not expensive variation route of exploitation. These roads Some in line are described in hereinafter, and it forms basis of the present invention.

The important route of developing new solar cell is organic solar batteries, and comprising at least one has The solar cell of machine semi-conducting material, or replace solid inorganic semiconductor, comprise other material, outstanding It is organic dyestuff or even liquid electrolyte and semi-conductive solar cell. The solar-electricity of innovation Concrete condition in pond is dye solar cell. Dye solar cell (DSC) is the most effective so far One of replacement solar battery technology. In the liquid scheme of this technology, realize at present at the most 11% Efficiency (for example referring toDeng, J.Photochem.Photobio.C, 2003,4,145; Chiba etc., JapaneseJournalofAppl.Phys., 2006,45,638-640 is capable).

, there are several modification in dye solar cell, conventionally has two electrodes, wherein at least at present One is transparent. According to their function, two electrodes are called as " working electrode " (also referred to as " sun The utmost point ", produce electronics) and " to electrode " (also referred to as " negative electrode "). On working electrode or attached at it Closely, conventionally apply n-conductive metal oxide, especially as porous, for example nano porous layer, For example thickness is the nano porous titanium dioxide (TiO of about 10-20 μ m₂) layer. At n-conductive metal oxygen Between compound layer and working electrode, also can provide at least one barrier layer, for example metal oxide as TiO₂Impermeable barrier. N-conductive metal oxide has the light-sensitive coloring agent adding conventionally. For example, light Quick dyestuff (for example ruthenium complex) individual layer is adsorbable on the surface of n-conductive metal oxide, and it can Absorption by light changes into excitation state. To electrode place or thereon, be generally several micron thick Catalytic Layer, for example platinum. Area in conventional dye solar cell between two electrodes is filled with conventionally Redox electrolytes matter, for example iodine (I₂) and/or the solution of KI (KI).

The function of dye solar cell is absorbed by dyestuff based on light. Electronics is transferred to dyestuff from being excited In n-semiconduction metal-oxide semiconductor (MOS), also migrate to anode thereon, and electrolyte is by negative electrode Guarantee charge balance. Therefore n-semiconduction metal oxide, dyestuff and electrolyte are dye solar The necessary component of battery.

But, with liquid electrolyte produce dye solar cell meet with in many cases non-the best Sealing, this can cause stability problem. Liquid oxidation also original electrolyte especially can be by solid p-semiconductor Replace. This class solid dye solar cell is also referred to as sDSC (solid DSC). Dye solar electricity The efficiency of the solid modification in pond is about 4.6-4.7% (Snaith, H., Angew.Chem.Int. at present Ed.，2005，44，6413-6417)。

Various inorganic p-semiconductors replace oxygen at present as CuI, CuBr 〃 3 (S (C4H9) 2) or CuSCN Change and go back original electrolyte for dye solar cell. For example also can apply from photosynthetic discovery Thing. In fact, it is also Cu (I) enzyme plastocyanin, its in photosystem I again by oxidation leaf Green plain dimer reduction. This class p-semiconductor can be by least three kinds of diverse ways processing, by molten Liquid, by electro-deposition or pass through laser deposition.

Organic polymer is also as solid p-semiconductor. The example comprises polypyrrole, poly-(the sub-second of 3,4- Base dioxy thiophene), carbazolyl polymers, polyaniline, poly-(4-undecyl-2,2 '-bithiophene), poly-(3- Octyl group thiophene), poly-(triphenyl diamine) and gather (N-VCz). In the feelings of poly-(N-VCz) Under condition, efficiency propagation to 2%. The PEDOT (poly-(3,4-ethylidene dioxy thiophene)) of in-situ polymerization is also aobvious Show 0.53% efficiency. Polymer described herein is conventionally with pure form, but uses with additive.

Inorganic-organic mixed system has also replaced redox electrolytes matter for dye solar cell. For example CuI is used for sDSC (ZhangJ. as hole conductor together with PEDOT:PSS Photochem：Photobio.，2007，189，329)。

Also can use the organic p-semiconductor of low-molecular-weight, non-polymeric, for example monomer or oligomeric organic P-semiconductor. Low-molecular-weight p-semiconductor in the use first of solid dye solar cell with triphenylamine (TPD) vapor deposited layers replaces liquid electrolyte. Organic compound 2,2 ', 7,7 '-tetra-(N, N-bis--to first Oxygen base phenyl amine)-9, the use report of 9 '-spiral shell, two fluorenes (spiro-MeOTAD) in dye solar cell In 1998. It can be introduced and be had relatively high glass transition temperature by solution, and this prevents from not thinking The crystallization of wanting with contact with the bad of dyestuff. Methoxyl group regulates the oxidation potential of spiro-MeOTAD, Ru complex can be regenerated effectively. Be used alone as the semi-conductive feelings of p-at spiro-MeOTAD Under condition, find 5% maximum IPCE (incident photon-current efficiency, outer photon transformation efficiency). When being also used as the N (PhBr) of adulterant₃SbCl₆And Li[CF₃SO₂)₂N] time, IPCE rises to 33%, and efficiency is 0.74%. Tert .-butylpyridine is used as solid p-semiconductor at about 1.07cm²Work Under property area with the open-circuit voltage (V of about 910mV_oc) and the short circuit current I of about 5mA_SCEfficiency is carried High to 2.56% (referring to Kr ü ger etc., Appl.Phys.Lett., 2001,79,2085). Realize more Good TiO₂Layer cover and have the good wet on spiro-MeOTAD dyestuff show be greater than 4% efficiency. In the time that ruthenium complex has oxygen ethylene lateral chain, report that even better efficiency (approximately 4.6%)。

L.Schmidt-Mende etc., Adv.Mater.17,813-815 page (2005) proposes to be used for Wherein spiral shell two fluorenes are as the indoline dyestuff of the dye solar cell of amorphous organic p-conductor. Tool Have more aobvious in solid dye solar cell than this organic dyestuff of the extinction coefficient of high 4 times of ruthenium complex High efficiency (under 1 daylight 4.1%) is shown. In addition, a conception of species is proposed, wherein by polymer p- Semiconductor is directly combined in (Peter, K., Appl.Phys.A.2004,79,65) on Ru dyestuff. Durrant etc., Adv.Munc.Mater.2006,16,1832-1838 has stated in many situations Under, photoelectric current directly depends on the yield that shift in the hole from oxidation dye to solid p-conductor. This gets Certainly in two factors: first depend on the permeability of p-semiconductor in oxide holes, next depends on Electric charge shift thermodynamic driving force (especially dyestuff and p-conductor between free enthalpy Δ G it Poor).

A shortcoming of dye solar cell is that the ratio of the light that can utilize by dyestuff is subject to used conventionally Energy distance limit between the fermi level of n-and p-conductor. Photovoltage is also subject to this distance limit conventionally. In addition,, due to required electric charge transmission, dye solar cell conventionally must relative thin (for example 1-2.5 Micron), the utilization that makes incident light is not best conventionally.

Prior art discloses silver nitrate (AgNO₃) add dye solution can cause solar cell effect Increase (J.Krueger, Thesis, EPFLLausanne, 2003 (paper No.2793), of rate 76-100 page). The silver that is not openly oxidised form as adulterant for the semi-conductive generality of p- Purposes.

In various further research, detect and there is the semi-conductive dyestuff of different low-molecular-weight p-too Electricity and the photoelectric properties of sun energy battery. An one example can be at U.Bach, paper, EPFL Lausanne, 2000 (paper No.2187) and especially wherein finding in 139-149 page. This The feature that place is detected is the low-down conductance of spiro-MeOTAD. For example,, at layer thickness In the film of approximately 2 microns, measure M Ω/cm²Resistivity. Conductance κ defines by following formula:

k＝μN_he(1)。

In the formula, e=1.6022 × 10^-19C, the elementary charge in electronics or hole. μ represents that carrier moves Move rate, and N_hRepresenting charge density, is the charge density in hole in this case. Suppose mobility Constant,, the in the situation that of p-material, conductance, because other hole adds, is adulterated at p- In situation, improve. Such result is that the activity coefficient of sDSC is not very high, in not low light intensity Like this especially under degree. Activity coefficient in photovoltaic device is often referred to solar-electricity in the time approaching peak power The business of the product of the peak power in pond and open-circuit voltage and short circuit current. In current-voltage figure, fill Coefficient can be described as the maximum rectangle of the following record of current-voltage curve and the minimum of envelope curve conventionally The Area Ratio of rectangle. Activity coefficient is without unit. Some merits that low activity coefficient ordinary representation produces Rate is because the interior resistance of battery loses. The in the situation that of above-mentioned spiro-MeOTAD, relatively low Therefore activity coefficient is especially explained by the high specific resistance of spiro-MeOTAD, is also for example described in F.Fabregat-Santiago etc., J.Am.Chem.Soc., 2009,131 (2), in 558-562, Especially true under the illumination of 1 daylight.

Prior art also discloses the semi-conductive doping of the organic p-of low-molecular-weight. For example, at U.Bach, Paper, EPFLLansanne, 2000 (paper No.2187), in 37-50 page, antimonic salt is used as The adulterant of spiro-MeOTAD. Doping operation can schematically be described below:

[N(p-C₆H₄Br)₃]+[SbCl₆]^-+spiro-MeOTAD

→[N(p-C₆H₄Br)₃]+[SbCl₆]^-+spiro-MeOTAD⁺。

With the spiro-compound of the ratio of 0.17-0.18M, use the concentration of 0.26-0.33mMSb. Even if conductance improves, hole mobility is because reduce adding of anion, and this dislikes electric charge transmission Change. In addition, the stability of this class antimonic salt in battery is problematic.

N.Rossier-Iten, paper, EPFLLausanne, 2006 (paper No.3457), especially It is the hole conductor material that 56-75 page and 91-113 page have also detected various doping. Wherein for The adulterant of the amorphous hole conductor in sDSC comprises I₂, 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone, NOBF₄And the spiral shell diradical cation (spiro-MeOTAD of doping⁺⁺[PF₆-]₂(0.1-0.7%)。 But, the decisive improvement of unrealized sDSC battery.

At Snaith etc., Appl.Phys.Lett.2006, in 89,262114-262116, finds sDSC In hole mobility by adding bis trifluoromethyl sulfimide lithium (lithium Bis (trifluoromethylsulfonyl) amine) (Li-TFSI) and greatly improve. Therefore, can will move The rate of moving is from 1.6 × 10^-4cm²/ Vs is increased to 1.6 × 10^-3cm²/ Vs, even if do not observe herein The oxidation of spiro-MeOTAD, does not have actual doping effect. Find leading of spiro-MeOTAD Electricity rate is affected by antimonic salt to lesser extent, and best sDSC battery is even with the realization of this salt, Because anion works as so-called coulomb of trap (carrier traps).

The adulterant that conventionally, need to be greater than the amount of 1 % by mole moves with the electric charge that improves amorphous p-conductor Move rate.

Organic p-adulterant, for example F4-TCNQ (tetrafluoro four cyano quino bismethane) is also with p Type organic polymer use together (for example, referring to R.Friend etc., Adv.Mater., 2008,20, 3319-3324, Zhang etc., Adv.Funct.Mater., 2009,19,1901-1905). Also report Road the so-called proton doping to polythiophene by alkyl silane (referring to Podzorov etc., Advanced FunctionalMaterials2009,19,1906-1911). But, there is the group of organic blended dose Divide and there is in many cases the relatively low life-span.

Also known SnCl₅And FeCl₃Also as p-adulterant. In addition, for example, doped with LiCF₃SO₃、 LiBF₄, LiTFSI and LiClO₄Polymer, for example PEDOT is also used as hole in sDSC Conductor. But, the in the situation that of this class component, also record 2.85% relatively low external work at the most Rate efficiency (Yanagida etc., JACS, 2008,130,1258-1263).

In addition, metal oxide is used as adulterant also by prior art, for example, by DE102007024 153A1 or DE102007023876A1 are known. Metal oxide steam is deposited on to organic layer In and therein as adulterant. The example of mentioning is that phenanthroline derivative forms matrix as complex Material, it is for example doped with rheium oxide.

In addition, about depositing by steam for organic p-transferring material of Organic Light Emitting Diode The research of inorganic compound doping is also known, such as Kim etc., and Appl.Phys.Lett.2007, 91,011113 (1-3). Herein, for example, by NPB ReO₃(8-25%) doping, this causes lower Use voltage (cut-in voltage) and higher power efficiency. The stability of OLED is improved equally. Kim Deng, Org.Elec.2008,805-808 has stated hole injection layer CuI has been adulterated. This doping also Cause higher current efficiency and energy efficiency. Kim etc., Appl.Phys.Lett.2009,94, 123306 (1-3) have compared CuI, the MoO as adulterant in Organic Light Emitting Diode (OLED)₃ And ReO₃. Find that a kind of tendency is the semi-conductive HOMO of organic p-(highest occupied molecular orbital) herein And the energy difference between the fermi level of adulterant works. In a word, find that adulterant improves transport layer In carrier density and conductance therefore, it is equal to p-doping.

Kahn etc., Chem.Mater.2010, it is that 0-3.8 rubs that 22,524-531 also discloses concentration Dithiolene (dithiolene) molybdenum (Mo (tfd) of you %₃) the various hole conductor of can adulterating. Pass through UPS Experiment (UV photoelectron spectroscopy), shows that the fermi level of hole conductor moves with the direction of HOMO, This is the instruction of p-doping.

Kowalsky etc., Org.Elec.2009,10,932-938 has reported steam deposition MoO₃ Mo₃O₉Bunch may improve, and can in doping, work. In addition, be determined at and presuppose Much lower level under fermi level (6.86eV) and electron affinity (6.7eV). Also infer (referring to Kanai etc., OrganicElectronics2010,11,188-194) MoO₃Layer can easily pass through Oxygen defect point n-doping, this cause bands of a spectrum each other relative improvement arrange.

Pure metal oxides is also described as MoO₃And V₂O₅Layer is at OLED and organic solar electricity Use in pond, to improve self-electrode/inject to the hole in electrode or hole is extracted. For example, Y.Yang etc., Appl.Phys.Lett.2006,88,073508 have detected V₂O₅、MoO₃With PEDOT:PSS is as the purposes in the intermediate layer between ITO (tin indium oxide) and p-type polymer. ? The what is called that wherein hole migrates to negative electrode (being generally in this case Ag) from p-type polymer is oppositely poly- In compound battery, VO_xLayer steam is deposited between polymer and silver, and this causes the improvement of battery performance.

In addition it is also known, preparing metal oxide buffer layer by the aqueous solution. For example, Liu SESMC, 2010,842-845, the 94th volume has been stated MoO₃Layer successfully as polymer too Cushion on anode in sun energy battery. This class layer in so-called organic serial connection solar cell also As the part of charge recombination layer (for example, referring to Kowalsky etc., Adv.Func.Mater.2010, 20，1762-1766)。

Due to typically, in the past few years in still unknown for the effective solvable of hole mobile material and Stable p-adulterant, is in fact stored in dye solar cell air (environment in many cases Condition) under. In its process, infiltrate the oxygen doping sDSC in sDSC. But battery is at environment gas In atmosphere or at controlled O₂Storage in atmosphere can not be reproduced, and for the commodity production of solar components Relatively to be a problem. In addition, can not seal in airtight mode the battery of oxygen doping, because Only with oxygen constant contact under ensure the high conductivity of whole conductor that operation is needed.

Goal of the invention

Therefore, the object of this invention is to provide and at least substantially avoid known photovoltaic element and production method The photovoltaic element of shortcoming and the method for producing photovoltaic element. More particularly, a kind of photovoltaic element is described, It has the p-semiconductor of high conductivity, as doping p-semiconductor and even get rid of oxygen stablize The method of p-adulterant produces the stable p-doping for the organic material of dye solar cell. Meanwhile, Even sealing the dye solar cell of stablizing and have high-quantum efficiency and high fill-factor under state Be desirable, but produce simple.

Disclosure of the invention content

This object realizes with the feature of independent claims by the present invention. Can be independently or real in combination The favourable scheme of executing is described in dependent claims.

In first aspect present invention, the photovoltaic element for electromagnetic radiation being changed into electric energy is proposed, more Be in particular fuel solar cell. This photovoltaic element comprises at least one first electrode, at least one n- The dyestuff of semiconduction metal oxide, at least one absorption of electromagnetic radiation, at least one SOLID ORGANIC P-semiconductor and at least one second electrode are preferably described order or suitable on the contrary (but be not must) Order, wherein p-semiconductor comprises the silver that is oxidised form.

P-semiconductor especially can be by by least one p-semiconduction organic material (128) be oxidation The silver of form is applied at least one carrier element and produces or produce by it, is wherein oxidised form Silver preferably with at least one silver (I) salt [Ag⁺]_m[A^m-] form be applied at least one carrier element, Wherein A^m-For the anion of organic acid or inorganic acid, and the m integer that is 1-3, preferably m wherein Be 1.

[A^m-] especially can be organic acid anion, preferably wherein organic acid has at least one fluorin radical -F or cyano group (CN). Now, [A^m-] more preferably there is the structure of formula (II):

Wherein R^aFor fluorin radical-F or the alkyl being replaced by fluorin radical or cyano group separately, cycloalkyl, aryl or Heteroaryl,

And wherein X be-O-or-N^--R^b，

And wherein R^bComprise fluorin radical-F or cyano group,

And wherein R^bFurther contained-S (O)₂ ^-Group.

R^aEspecially can be selected from-F ,-CF₃、-CF₂-CF₃With-CH₂-CN。

Especially can be-N of X^--R^b, and R^bEspecially can be selected from-S (O)₂-F、-S(O)₂-CF₃、 -S(O)₂-CF₂-CF₃With-S (O)₂-CH₂-CN。

[A^m-] especially can be selected from: bis trifluoromethyl sulfimide (TFSI^-), two trifluoroethyl sulfimide, Two fluorine sulfimides, trifluoromethane sulfonic acid root.

Preferably, [A^m-] be bis trifluoromethyl sulfimide (TFSI-).

In replacement preferred embodiment, [A^m-] be trifluoroacetic acid root.

In addition [A,^m-] can also be especially group NO₃ ^-。

This applies and can be undertaken by any required method. For the purpose of the present invention preferably by being sunk by liquid phase Long-pending and apply described at least one p-semiconduction organic material (128) and silver.

P-semiconductor preferably can pass through at least one p-semiconduction organic material (128) and at least silver-colored, Preferably at least one silver (I) salt [Ag⁺]_m[A^m-] be applied at least one carrier element and produce or by its Produce, wherein apply by by comprising described at least one p-semiconduction organic material and at least one Silver (I) salt [Ag⁺]_m[A^m-] liquid deposition and carry out.

Deposition also can be undertaken by any required deposition process in principle, for example by spin coating, blade coating, The combination of printing or described deposition process and/or other deposition process is carried out.

P-semiconductor especially can comprise at least one organic basis material, now by anionic compound [A^m-] and Ag⁺Sneak into matrix material or be present in matrix material, especially with dissolved form.

At least Ag⁺With preferred anionic compound [A in addition^m-] especially can substantially be uniformly distributed and be present in In matrix material.

Matrix material especially can comprise the organic p-semiconductor of at least one low-molecular-weight.

The organic p-semiconductor of low-molecular-weight especially can comprise at least one spiro-compound.

The organic p-semiconductor of low-molecular-weight especially can be selected from: spiro-compound, especially Spiro-MeOTAD; There is the compound of following structural formula:

Wherein:

A¹、A²、A³Be optional aryl or the heteroaryl replacing independently of one another,

R¹、R²、R³Be selected from independently of one another substituting group-R ,-OR ,-NR₂、-A⁴-OR and-A⁴-NR₂， Wherein R is selected from alkyl, aryl and heteroaryl, and

Wherein A⁴For aryl or heteroaryl, and

Wherein in formula I, n is 0,1,2 or 3 value independently in each case,

Condition is each n value sum is at least 2 and radicals R¹、R²And R³In at least two be-OR and/or -NR₂。

Preferably, A²And A³Identical; Therefore formula (I) compound preferably has following structure (Ia):

This photovoltaic element can further comprise at least one to be sealed, and wherein designs this and seals to protect light Volt element, especially electrode and/or p-semiconductor are in case surrounding atmosphere.

In preferred embodiments, this p-semiconductor is as mentioned above by there being at least one p-electric conductivity Machine material (128) and at least one silver (I) salt [Ag⁺]_m[A^m-] be applied at least one carrier element and produce Maybe can produce by it, wherein this apply can be by by comprising at least one p-electric conductivity organic material With at least one silver (I) salt [Ag⁺]_m[A^m-] liquid deposition and carry out, and wherein this liquid phase with 0.5-50mM/ml, more preferably the concentration of 1-20mM/ml comprises at least one silver (I) salt [Ag⁺]_m[A^m-]。

In another aspect of this invention, a kind of production has been proposed for there being the SOLID ORGANIC p-half of thermomechanical components The method of conductor, the more especially photovoltaic of one or more embodiments of photovoltaic element according to the present invention Element, the latter has described above or has not also described. In the method, at least one p-is led Electrically organic basis material and be at least the silver of oxidised form, preferably at least one silver (I) salt [Ag⁺]_m[A^m-] be applied at least one carrier element by least one liquid phase, wherein [A]-be organic acid or The anion of inorganic acid, and compound [Ag wherein⁺]_m[A^m-] be preferably AgNO₃Or bis trifluoromethyl Sulfimide silver.

Liquid phase can further comprise at least one solvent, especially organic solvent, is especially selected from ring The solvent of hexanone, chlorobenzene, benzofuran and cyclopentanone.

The method especially can be at least partially in carrying out in hypoxic atmosphere, for example, be less than comprising 500ppm oxygen, is especially less than 100ppm oxygen, is more preferably less than 50ppm oxygen, or is even less than In the atmosphere of 10ppm oxygen, carry out.

In another aspect of this invention, a kind of method of producing photovoltaic element, especially basis have been proposed The photovoltaic element of one or more configurations of photovoltaic element of the present invention, the latter is above describing or is going back Do not describe. In the method, provide at least one first electrode, at least one n-semiconduction gold Belong to oxide, at least one absorption of electromagnetic radiation dyestuff, at least one SOLID ORGANIC p-semiconductor and At least one second electrode, especially (but not must) be described order or reverse order, wherein p-half Conductor dbus is crossed according to partly leading for the production SOLID ORGANIC p-that describes above or also do not describe The method of one or more configurations of the inventive method of body is produced.

Find surprisingly for the present invention, the silver that is oxidised form can effectively be realized p-and mix Assorted, especially in dye solar cell. Especially effectively p-doping especially can be by use formula [Ag⁺]_m[A^m-] silver (I) salt realize, wherein [A^m-] be the anion of organic acid or inorganic acid, and m For the integer of 1-3. These silver (I) salt can especially pass through one or more organic solvents, preferably with p-half Conductive base material with choose any one kind of them or multiple organic salt together with apply with liquid phase. Can realize like this tool There is the photovoltaic element of high fill-factor and high long-time stability.

In above-mentioned first aspect of the present invention, the light for electromagnetic radiation being changed into electric energy is proposed thus Volt element. This photovoltaic element can especially comprise one or more photocells. Photovoltaic element can especially comprise At least one can for example put on suprabasil layer structure. Photovoltaic element can especially comprise at least one and dye Expect solar cell and/or be configured to dye solar cell.

Photovoltaic element have at least one first electrode, at least one n-semiconduction metal oxide, At least one absorption of electromagnetic radiation dyestuff, at least one SOLID ORGANIC p-semiconductor and at least one Two electrodes. Propose p-semiconductor and comprise the silver that is oxidised form.

Described element can especially provide with described order. Photovoltaic element for example can comprise and be described order At least one first electrode, at least one n-semiconduction metal oxide, at least one electromagnetic radiation Absorbability dyestuff, at least one SOLID ORGANIC p-semiconductor and at least one the second electrode. But, dye Material and n-semiconduction metal oxide also can completely or partially combine, as are usually used in dye solar In battery. For example, can by n-semiconduction metal oxide with at least one dyestuff wholly or in part Ground dipping, or mix with this dyestuff with some alternate manners. Like this and/or with some alternate manners, can Especially by the dye sensitization of n-semiconduction metal oxide, make for example dye molecule can be used as individual layer Put on n-semiconduction metal oxide particle. For example, at dye molecule and n-semiconduction metal Between oxide, can there is direct contact, make the transfer of carrier become possibility. Photovoltaic element can be outstanding It comprises at least one and optionally has the n-semiconduction metal oxide layer of dyestuff, and at least one is solid The organic p-semiconductor layer of body. This layer of structure can intercalation electrode between. In addition, photovoltaic element can comprise one Individual or multiple other layers. For example, between the first electrode and n-semiconduction metal oxide, can introduce One or more other layers, for example one or more cushions, for example metal oxide layer. Although slow Punching layer is preferably not saturating, but especially porous and/or particle of n-semiconduction metal oxide Shape. More particularly, as the n-semiconduction metal oxide of hereinafter describing in detail can be configured to nanometer Stratum granulosum. In addition also can between n-semiconduction metal oxide and SOLID ORGANIC p-semiconductor, carry, For one or more other layers, and optionally also can between p-semiconductor and the second electrode, provide one Or multiple other layers.

P-semiconductor especially can be the silver of oxidised form, preferably at least one formula [Ag⁺]_m[A^m-] silver (I) salt p-doping. This means the semi-conductive p-electric conductivity of p-by being the silver of oxidised form, preferably extremely Few a kind of formula [Ag⁺]_m[A^m-] silver (I) salt obtain or strengthen. More particularly, can arrange and be oxidised form Silver, preferably at least one formula [Ag⁺]_m[A^m-] silver (I) salt with doping p-semiconductor or this p-semiconductor The matrix material of middle existence. For example, p-semiconductor can comprise at least one organic basis material, at this In the situation of kind, the silver of oxidised form will be, preferably at least one formula [Ag⁺]_m[A^m-] silver (I) salt sneak into In matrix material. This is preferably by being the silver of oxidised form, preferably at least one formula [Ag⁺]_m[A^m-] Silver (I) salt and organic basis material be applied at least one carrier material and realize.

Therefore, the present invention preferably relates to a kind of photovoltaic element as above, and wherein p-semiconductor can lead to Cross at least one p-electric conductivity organic material (128) and the silver that is oxidised form are applied to at least one Carrier element is produced or is produced by it, and wherein this silver that is oxidised form is preferably with at least one silver (I) Salt [Ag⁺]_m[A^m-] form be applied at least one carrier element, wherein [A]^-For organic acid or inorganic acid Anion, and the m integer that is 1-3, preferably wherein m is 1.

Matrix material can be applied to together with silver or in division step to carrier material. Preferably, will Matrix material is applied to carrier material together with silver. " apply together " thus or " combine and apply " Mean preferably the mixture G that comprises matrix material at least one step, preferably a step In be applied to carrier material.

Preferably, mixture G is liquid phase. Term " liquid phase " means mixture G extremely thus Small part exists with liquid. Preferably, mixture G or preferred liquid phase are as described below comprises at least one Silver and at least one organic basis material dissolve and/or are scattered in solvent wherein. As mentioned above, this is executed Add preferably by being undertaken by liquid deposition, and deposition also can be passed through any required deposition process in principle As spin coating, blade coating, printing and as described in the combination of deposition process and/or other deposition process carry out.

The organic p-semiconductor of low-molecular-weight:

More particularly, matrix material can have the organic p-semiconductor of at least one low-molecular-weight. Low molecule Amount material should be understood to mean the material existing with monomer, non-polymeric or non-oligomeric form conventionally. This Invent the molecular weight that term used " low-molecular-weight " preferably means semiconductor and have 100-25000g/mol. Preferably, described low molecular weight substance has the molecular weight of 500-2000g/mol. These low-molecular-weights Organic p-semiconductor especially can form above-mentioned matrix material and can have inherently p-semiconductive performance. Logical Often, for the present invention, p-semiconductive performance should be understood to mean material, especially organic molecule Form hole and transmit these holes and make their performances to adjacent molecule. More particularly, these points The stable oxidation of son should be possible. In addition, the organic p-semiconductor of described low-molecular-weight especially can have π-the electron system of extension. More particularly, at least one low-molecular-weight p-semiconductor can be processed by solution. Low-molecular-weight p-semiconductor especially can comprise at least one triphenylamine. The organic p-semiconductor of low-molecular-weight bag Particularly preferred containing at least one spiro-compound. Spiro-compound should be understood to mean it and only encircles The polycyclic organic compound connecting at an atom place, described atom is also referred to as spiro-atom. More particularly, Spiro-atom can be sp³-hydridization, make the component via the interconnective spiro-compound of spiro-atom For example be arranged in relative to each other different planes.

More preferably, spiro-compound has the structure of following formula:

Wherein ary¹、ary²、ary³、ary⁴、ary⁵、ary⁶、ary⁷And ary⁸Be selected from and get independently of one another For aryl and heteroaryl, be especially selected from substituted-phenyl, wherein said aryl and heteroaryl, preferably benzene Base is substituted independently of one another, preferably in each case by one or more being selected from-O-alkyl ,-OH, -F ,-Cl ,-Br and-substituting group of I replaces, wherein alkyl is preferably methyl, ethyl, propyl group or different Propyl group. More preferably, phenyl is substituted independently of one another, in each case by one or more choosings From-O-Me ,-OH ,-F ,-Cl ,-Br and-substituting group of I replaces.

Further preferably, spiro-compound is following formula: compound:

Wherein R^r、R^s、R^t、R^u、R^v、R^w、R^xAnd R^yBe selected from independently of one another-O-alkyl ,-OH, -F ,-Cl ,-Br and-I, wherein alkyl is preferably methyl, ethyl, propyl group or isopropyl. More preferably Ground, R^r、R^s、R^t、R^u、R^v、R^w、R^xAnd R^yBe selected from independently of one another-O-Me ,-OH ,-F, -Cl ,-Br and-I.

More particularly, p-semiconductor or matrix material can comprise spiro-MeOTAD or by Spiro-MeOTAD forms, and, for example by Darmstadt, Germany MerckKGaA, Taiwan is commercial Formula (III) compound:

Alternatively or extraly, also can use other p-semiconduction compound, especially low-molecular-weight And/or oligomeric and/or polymerization p-semiconduction compound.

In replacement embodiment, the organic p-semiconductor of low-molecular-weight or matrix material comprise one or many The compound of kind of above-mentioned general formula I, reference example is as announcement the application's the priority date after for this reason PCT application number PCT/EP2010/051826.

With regard to above-mentioned spiro-compound extraly or alternatively, p-semiconductor can comprise at least one The compound of above-mentioned general formula I.

For the present invention, term used " alkyl " or " alkyl group " should be understood to common meaning Refer to replace or unsubstituted C₁-C₂₀Alkyl. Preferably C₁-C₁₀Alkyl, particularly preferably C₁-C₈Alkyl. Alkyl can be straight chain or branching. In addition, alkyl can be selected from following substituting group by one or more Replace: C₁-C₂₀Alkoxyl, halogen, preferably F, and C₆-C₃₀Aryl, described substituting group is passable again Substituted or unsubstituted. The example of suitable alkyl is methyl, ethyl, propyl group, butyl, penta Base, hexyl, heptyl and octyl group, and isopropyl, isobutyl group, isopentyl, sec-butyl, the tert-butyl group, Neopentyl, 3,3-dimethylbutyl, 2-ethylhexyl, and by C₆-C₃₀Aryl, C₁-C₂₀Alkoxyl And/or halogen, the especially derivative of the described alkyl of F replacement, for example CF₃。

For the present invention, term used " aryl " or " aromatic yl group " should be understood to mean appoint Choose the C derived from monocycle, dicyclo, three rings or polycyclic aromatic ring in generation₆-C₃₀Aryl, wherein said Aromatic ring does not comprise any ring hetero atom. Aryl preferably comprises 5 and/or 6 yuan of aromatic rings. When aryl not While being monocycle system, term " aryl " in the situation that, for the second ring, saturated form (perhydrogenate Form) or the unsaturated form of part (for example dihydro form or tetrahydro form) be also possible, condition That concrete form is known and stable. For the present invention, term " aryl " therefore for example also comprises Dicyclo or three cyclic groups that wherein two or all three groups are aromatics, and wherein only a ring be The dicyclo of aromatics or three cyclic groups, also have wherein two three cyclic groups that ring is aromatics. The example of aryl For: phenyl, naphthyl, indanyl, 1,2-dihydro naphthyl, Isosorbide-5-Nitrae-dihydro naphthyl, fluorenyl, indenyl, anthracene Base, phenanthryl or 1,2,3,4-tetralyl. Particularly preferably C₆-C₁₀Aryl, for example phenyl or naphthyl, non- Often C particularly preferably₆Aryl, for example phenyl. In addition, term " aryl " also comprises and comprising via singly-bound Or the member ring systems of two keys at least two monocycles connected to one another, dicyclo or polycyclic aromatic ring. An example To there are those of xenyl.

For the present invention, term used " heteroaryl " or " heteroaryl groups " should be understood to meaning Refer to optional 5 and/or 6 yuan of aromatic rings and the many rings replacing, for example, at least one ring, have at least one Individual heteroatomic dicyclo and tricyclic compound. For the present invention, heteroaryl preferably comprises 5-30 ring Atom. They can be monocycle, dicyclo or three rings, and some can pass through in aryl basic skeleton At least one carbon atom with hetero atom replace and derived from above-mentioned aryl. Preferred hetero atom be N, O and S. Heteroaryl more preferably has 5-13 annular atoms. The basic skeleton of heteroaryl especially preferably selects From system, as pyridine, and 5 yuan of assorted aromatic hydrocarbons are as thiophene, pyrroles, imidazoles or furans. These basic skeletons Can optionally condense with 1 or 26 yuan of aromatic group. In addition, term " heteroaryl " also comprises and comprising Via the member ring systems of singly-bound or two key at least two monocycles connected to one another, dicyclo or polycyclic aromatic ring, Wherein at least one ring comprises hetero atom. In the situation that term " heteroaryl " is at least one ring, In the time that heteroaryl is not monocycle system, saturated form (perhydrogenate form) or the unsaturated form of part are (for example Dihydro form or tetrahydro form) be also possible, as long as concrete form is known and stable. Just The present invention, term " heteroaryl " therefore for example also comprises that wherein two or all three groups are The dicyclo of aromatics or three cyclic groups, and dicyclo or three cyclic groups that ring is aromatics only wherein, also That to have wherein two rings be aromatics and at least one ring wherein, i.e. an aromatic ring or a non-aromatic ring There are heteroatomic three cyclic groups. It is suitable that to condense assorted aromatic hydrocarbons be carbazyl, benzimidazolyl, benzo Furyl, dibenzofuran group or dibenzothiophenes base. Basic skeleton can 1, more than one or All desirable subrogate to be set up be substituted, suitable substituting group with have been described in C₆-C₃₀Under the definition of aryl Identical. But heteroaryl is preferably unsubstituted. Suitable heteroaryl be for example pyridine-2-base, Pyridin-3-yl, pyridin-4-yl, thiophene-2-base, thiene-3-yl-, pyrroles-2-base, pyrroles-3-base, furan Mutter-2-base, furans-3-base and imidazoles-2-base, and corresponding benzo-fused group, especially carbazyl, Benzimidazolyl, benzofuranyl, dibenzofuran group or dibenzothiophenes base.

For the present invention, term " optional replacement " refers to that wherein alkyl, aryl or heteroaryl are extremely A few hydrogen atom is substituted the group that base is replaced. Should substituent type, preferred alkyl, For example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl and octyl group, and isopropyl, Isobutyl group, isopentyl, sec-butyl, the tert-butyl group, neopentyl, 3,3-dimethylbutyl and 2-ethyl hexyl Base, aryl is as C₆-C₁₀Aryl, especially phenyl or naphthyl, more preferably C₆Aryl, for example phenyl, And heteroaryl, for example pyridine-2-base, pyridin-3-yl, pyridin-4-yl, thiophene-2-base, thiene-3-yl-, Pyrroles-2-base, pyrroles-3-base, furans-2-base, furans-3-base and imidazoles-2-base, and corresponding benzene And condense group, especially carbazyl, benzimidazolyl, benzofuranyl, dibenzofuran group or Dibenzothiophenes base. Other example comprises following substituting group: alkenyl, alkynyl, halogen, hydroxyl.

Substitution value can be from monosubstituted to changing by substituent maximum number herein.

Preferred formula I compound used according to the invention is characterised in that radicals R¹、R²And R³In At least two be p-OR and/or-NR₂Substituting group. At least two groups can be OR base only herein Group, only NR₂Group, or at least one is that OR group and at least one are NR₂Group.

Particularly preferably formula I compound used according to the invention is characterised in that radicals R¹、R²And R³ In at least 4 be p-OR and/or-NR₂Substituting group. At least four groups can be OR only herein Group, only NR₂Group, or OR and NR₂The mixture of group.

Formula I compound very particularly preferably used according to the invention is characterised in that all groups R¹、R²And R³For p-OR and/or-NR₂Substituting group. They can be only OR group, only NR₂ Group, or OR and NR₂The mixture of group.

In all cases, NR₂Two R in group can differ from one another, but they are preferably phase With.

Preferably, A¹、A²And A³Be selected from independently of one another:

Wherein:

M is the integer of 1-18,

R⁴For alkyl, aryl or heteroaryl, wherein R4 is preferably aryl, more preferably phenyl,

R⁵、R⁶Be H, alkyl, aryl or heteroaryl independently of one another,

The aromatics of structure shown in it and heteroaromatic rings can optionally have other replacement. Aromatics and heteroaromatic herein The substitution value of ring can be from monosubstituted to changing by substituent maximum number.

In the case of other replacement of aromatics and heteroaromatic rings, preferred substituting group comprise above about 1, the substituting group that the aromatics of 2 or 3 optional replacements or heteroaromatic group have been mentioned.

The aromatics of structure preferably, and heteroaromatic rings do not have other replacement.

More preferably, A¹、A²And A³Be independently of one another

More preferably

More preferably, at least one formula (I) compound has following structure:

In replacement embodiment, matrix material is ID322, i.e. formula (IV) compound:

Compound used according to the invention can be by conventional organic synthesis well known by persons skilled in the art Method preparation. The reference of relevant (patent) document can be found in addition in the synthetic example of quoting as proof below.

At least one electrode can be transparent. For example the first electrode can be working electrode and the second electricity Very to electrode, or vice versa. One or two in these electrodes can be transparent. Photovoltaic Element especially can comprise at least one and put on suprabasil layer structure, and layer structure can in this case Comprise be described order or reverse order the first electrode, n-semiconduction metal oxide, dyestuff, There is SOLID ORGANIC p-semiconductor and at least one second electrode of metal oxide.

N-semiconduction metal oxide can be especially porous, in this case, partly leads at n- Electrically between metal oxide and the first electrode, can introduce the cushion of at least one metal oxide. Should Cushion can be for example impermeable barrier, i.e. non-particulate shape layer. For example, this cushion can pass through PVD Method applies as vapor deposition method and/or sputtering method. Replace or extraly, also can use other Method, for example CVD method and/or spray pyrolysis method. On the contrary, n-semiconduction metal oxide Preferably by paste extrusion forming method, for example by printing apply, spin coating applies or blade coating applies n- The paste of semiconduction metal oxide and applying. This paste can pass through at least one heat treatment step subsequently, For example, by being heated to be greater than 200 DEG C, be especially greater than 400 DEG C, for example 450 DEG C and sintering. This burning Knot can for example be removed the volatile component of paste, makes preferably only to retain n-semiconduction metal oxide Grain.

As mentioned above, especially dyestuff can be put on n-semiconduction metal oxide. This applies excellent Choosing is carried out by this way, makes dyestuff completely or partially infiltrate n-semiconduction metal oxide Layer, for example graininess layer, thereby for example by the one or more dye coatings that form on these particles As monolayer makes the sensitization of n-semiconduction metal oxide particle. Applying therefore of dyestuff can for example be led to Cross at least one dipping method, for example, by the sample that comprises n-semiconduction metal oxide layer is soaked Enter in dye solution and carry out. Other dipping method is also available.

As concrete advantage of the present invention, photovoltaic element especially can comprise at least one and seal. With wherein The conventional photovoltaic element phase that solid p-semiconductor is adulterated by oxygen (for example, by being stored under air) Instead, under this oxygen atmosphere, can not exist for a long time with the silver that is oxidised form, preferably at least one silver yet (I) salt [Ag⁺]_m[A^m-], the especially preferably p-semiconductor of bis trifluoromethyl sulfimideization silver doping. Cause This, can use protection photovoltaic element, and especially electrode and/or p-semiconductor are in case the sealing of surrounding environment. Like this, although by by the silver that is oxidised form, preferably at least one silver (I) salt [Ag⁺]_m[A^m-]， Especially preferably bis trifluoromethyl sulfimideization silver adulterates and has improved the semi-conductive performance of p-, can get rid of Oxygen, this protection for example one or more electrodes in case caused by oxygen and/or other ambient gas unfavorable Impact. For example, can prevent like this electrode degradation. Seal and can for example comprise by capsule fortreating AIDS element Seal, for example, there is plane or the capsule of at least one pit, it is for example applied by this way In layer structure, make its completely or partially surrounding layer structure. For example, the edge of sealing can be complete Or surrounding layer structure partly, and can for example pass through adhesive bond and/or other combination, preferred bonding knot Close and be incorporated in substrate. Replace or extraly, seal and also can comprise one or more material layers, institute State material and prevent that hostile environment from affecting as the infiltration of moisture and/or oxygen. For example can be by organic and/or nothing Organic coating puts in layer structure. Protection is in case ambiance should be understood to mean mitigation of gases conventionally And/or moisture is from surrounding atmosphere penetrating layer structure. Slow down and can for example make by this way bag Seal inside and outside concentration difference only at several hours, in preferred several days, especially even several weeks, some months extend In several years, balance out.

Dye solar cell additionally can be especially n-semiconduction metal oxide and p-semiconductor it Between there is at least one passivating material. This passivating material especially can be set to prevent at least in part n-half Electric transmission between conductive metal oxide and p-semiconductor. Passivating material especially can be selected from Al₂O₃; Silane, especially CH₃SiCl₃; Organometallic complex, especially Al³⁺Complex, 4-tert .-butylpyridine; Cetyl malonic acid.

As mentioned above, in the present invention on the other hand, propose to produce the SOLID ORGANIC for there being thermomechanical components P-method for semiconductor. This has thermomechanical components can be especially photovoltaic element, for example, be on one or more State the photovoltaic element of configuration, especially dye solar cell. But, there is other configuration of thermomechanical components Also be possible in principle, be included in the light of Organic Light Emitting Diode, heteropolar crystal pipe and other type Volt element is as the final use in organic solar batteries.

In described method, for example, by least one p-electric conductivity organic basis material, the above-mentioned type Matrix material, and be at least the silver of oxidised form, preferably at least one formula [Ag⁺]_m[A^m-] silver (I) salt Put at least one carrier element by least one liquid phase. As mentioned above, p-electric conductivity organic group Body material should be understood to mean preferably to be applied and can be transmitted by solution the organic material of positive charge. This A little positive charges can be present in matrix material and only by the p-raising of adulterating, or also can be in fact by In obtaining by the silver-colored p-doping that is oxidised form. More particularly, matrix material can be stablized and can Be oxidized contraryly and setting so that positive charge (" hole ") forwards other molecule to as adjacent point of same type On son.

Conventionally, on this point, point out that the effect of silver salt only improves based on observable p-conductance Effect. The silver that therefore, can for example be oxidised form by adding improves the current-carrying in p-semiconductor Sub-density and/or positive charge transport rate. The invention is not restricted to p-and be entrained in the side carrying out on microscopic scale Method.

As mentioned above, preferably using at least one organic basis material and as p-adulterant be oxidation shape The silver of formula, especially at least one formula [Ag⁺]_m[A^m-] silver (I) salt applied by least one liquid phase together On at least one carrier element. Carrier element can be understood as and means pure substrate, for example glass and/ Or plastics and/or laminated substrates. But, replace or extraly, carrier element also comprises other element, For example may put on suprabasil one or more electrode and/or one or more layer. For example, p- Semiconductor can be put in the layer structure partially or completely arranging, in this case for example by liquid phase One or more layers may put in substrate, then apply at least one p-semiconductor layer. For example Before p-semiconductor is applied by least one liquid phase, can be by least one first electrode, extremely Few a kind of n-semiconduction metal oxide and preferred coloring agent put on matrix, as above to photovoltaic Described in element.

Apply and conventionally can comprise for example wet-chemical process operation by liquid phase, for example spin coating, blade coating, curtain coating, The combination of printing or similarly wet chemical method or described method and/or other method. For example, can use Printing process is as ink jet printing, serigraphy, hectographic printing etc. Especially passable after being applied by liquid phase That p-is semi-conductive dry, for example with the volatile component of removing liquid phase as solvent. This is dried can be for example Under heat effect, for example, at the temperature of 30-150 DEG C, carry out. But other configuration is also in principle Possible.

As mentioned above, matrix material especially can comprise the organic p-semiconductor of at least one low-molecular-weight, example As matrix material. More particularly, can use one or more above-mentioned organic p-semiconductors. More special Not, the organic p-semiconductor of low-molecular-weight can comprise at least one triphenylamine. The organic p-of low-molecular-weight Semiconductor especially can comprise at least one spiro-compound, for example one or more above-mentioned spiro-compounds.

Except at least one matrix material and silver, especially at least one formula of being oxidised form [Ag⁺]_m[A^m-] silver (I) salt outside, liquid phase further comprise can have a kind of of different final uses or Multiple other component. For example, known to stable and/or improvement electrical property, there is at least one lithium In the solution of salt, use spiro-compound, for example spiro-MeOTAD. Conventionally, therefore liquid phase can be entered One step comprises for example at least one slaine. More particularly, this can be organic metal salt. Different salt Combination be also possible. More particularly, can use lithium salts, for example organometallic lithium salts, preferably LiN(SO₂CF₃)₂。

As mentioned above, at least one liquid phase especially can comprise at least one solvent. For the present invention, Term " solvent " for herein and no matter all, several or each component of existing of liquid phase in fact With dissolved form exist or they using other form as suspension, dispersion, emulsion or with one A little other forms exist. More particularly, be the silver of oxidised form, for example at least one silver (I) salt [Ag⁺]_m[A^m-], especially preferably bis trifluoromethyl sulfimide silver can exist with dissolved form. Example As, at least one matrix material can be to dissolve or to exist with discrete form. Be the silver of oxidised form, For example at least one silver (I) salt [Ag⁺]_m[A^m-], especially preferably bis trifluoromethyl sulfimide silver is especially Can exist with dissolved form, but in principle also can be with other form, for example, to disperse and/or to suspend Form exists.

Particularly preferably use at least one organic solvent. More particularly, can use one or more as follows Solvent: cyclohexanone, chlorobenzene, benzofuran, cyclopentanone.

Described production SOLID ORGANIC p-method for semiconductor especially can be used for production and is one or more institutes State the above-mentioned photovoltaic element of configuration. But other has thermomechanical components also can produce by the method. With it In the combination principle of its known method, be also possible, therefore, for example, ought provide multiple organic p-partly to lead When body, one or more in these p-semiconductors can be produced by the method for the invention, and conventional One or more in p-semiconductor are produced by other method.

The concrete advantage of described production SOLID ORGANIC p-method for semiconductor is with known by prior art Many method differences, must under air, not store. For example, the method especially can be at least in part Under hypoxic atmosphere, carry out. For the present invention, organic component should be understood to mean to have one conventionally Individual or multiple organic elements, the assembly of for example one or more organic layers. Can use thermomechanical components completely, For example its middle level structure-optionally except electrode-only comprise the assembly of organic layer. But, also can produce Mix assembly, for example, except one or more organic layers, also comprise the assembly of one or more inorganic layers. In the time that described method is used at multi-step production method production SOLID ORGANIC p-semiconductor, can be at hypoxemia In atmosphere, carry out one, more than one or all processing steps and have thermomechanical components to produce. More particularly, Different from above-mentioned known method, the semi-conductive processing step of production SOLID ORGANIC p-can be in hypoxic atmosphere Carry out. More particularly, liquid phase applying therefore on carrier element can be carried out in hypoxic atmosphere. Low Oxygen atmosphere should be understood to mean the atmosphere of the oxygen content compared with surrounding air with reduction conventionally. Example As, hypoxic atmosphere can have the 1000ppm of being less than, and is preferably less than 500ppm, is more preferably less than 100ppm, for example 50ppm or oxygen content still less. Also can under this hypoxic atmosphere, carry out organic Assembly, the further processing of for example dye solar cell. For example, at least executing by described method After reinforcing body p-semiconductor, until just can again interrupt hypoxic atmosphere after sealing. Whole assembly exists Processing completely in hypoxic atmosphere is also possible, and can not have any unfavorable shadow to the electrical property of assembly Ring. The particularly preferably hypoxic atmosphere of inert gas form, for example nitrogen atmosphere and/or argon gas atmosphere. Also Can use mist.

As mentioned above, in a third aspect of the present invention, propose to produce the method for photovoltaic element. This especially Can be the photovoltaic element according to one or more above-mentioned configurations, for example dye solar cell. Described The method of producing photovoltaic element especially can be used above-mentioned production SOLID ORGANIC p-method for semiconductor to carry out, In this case, with regard to the method for described production photovoltaic element, production SOLID ORGANIC p-semiconductor Method can use once or more than once. But, in the using priciple of other method, be also possible.

Described method preferably has hereinafter described processing step, and it can be preferred, but must be with described not suitable Order is carried out. Independent or several processing steps also can carry out on the time overlappingly and/or concurrently. In addition, It is also possible there is no the carrying out of the additional technical steps of describing. In described method, provide at least one Individual the first electrode, at least one n-semiconduction metal oxide, at least one absorption of electromagnetic radiation Dyestuff, at least one SOLID ORGANIC p-semiconductor and at least one the second electrode. This provide can be for example with Described order is carried out. More particularly, providing can be by for example entering according to the above generation layer structure of describing OK. This layer of structure can for example in turn be arranged in one or more substrates. In this case, also Can be by elements combination described in one or more to obtain combination layer, for example n-semiconduction metal oxide And dyestuff.

In described method, structure p-semiconductor makes it comprise the silver that is oxidised form, for example at least A kind of silver (I) salt [Ag⁺]_m[A^m-], especially preferably bis trifluoromethyl sulfimide silver. P-semiconductor is outstanding It can comprise at least one silver that is oxidised form, for example at least one silver (I) salt [Ag⁺]_m[A^m-]， Especially the preferably organic basis material of bis trifluoromethyl sulfimideization silver doping. For organic matrix material Expect and/or be the silver of oxidised form, for example at least one silver (I) salt [Ag⁺]_m[A^m-], especially preferred two three The possible configuration of methyl fluoride sulfimide silver, can be with reference to above and following description.

P-semiconductor especially can produce by the following method, wherein uses wet-chemical process operation, for example According to the above description to production SOLID ORGANIC p-method for semiconductor. At this wet-chemical process operation In, can be using at least one p-electric conductivity organic basis material with as the oxidised form that is of p-adulterant Silver, for example at least one silver (I) salt [Ag⁺]_m[A^m-], especially preferably bis trifluoromethyl sulfimide silver Put at least one carrier element by least one liquid phase together.

Further describe hereinafter appointing of particularly preferred photovoltaic element and method for the present invention Choosing can be implemented configuration. But other configuration is also possible in principle.

Photovoltaic element especially can comprise can for example put on suprabasil layer structure. In this case, For example the first electrode or the second electrode can faces substrate. At least one electrode should be transparent. At this point and Speech " transparent " electrode especially should be understood to mean in limit of visible spectrum and/or at solar spectrum (approximately 300-2000nm) in scope, have at least 50%, preferably at least 80% transmission. When substrate is transparent When substrate, it is transparent that the electrode of faces substrate especially should be.

Substrate can or comprise for example substrate of glass and/or plastic-substrates. But other material, comprises Combination of different materials is also available in principle, for example laminated material. Can be by the component of photovoltaic element Put on directly or indirectly in substrate as layer. For the present invention, term " carrier element ", " carrier " and " substrate " at least substantially synonymously uses. But, in the time that carrier element is discussed, Made, this stressed layer puts on suprabasil possibility indirectly, makes at least one other element, Especially at least other layer of one deck can be present between layer and actual base to be applied. But, directly It is also possible applying.

Photovoltaic element can be especially dye solar cell. Therefore, photovoltaic element is also united hereinafter Be called " battery ", this does not give any restriction to concrete layer structure. Battery especially can comprise at least one Individual the first electrode, n-conductive metal oxide, dyestuff, p-semiconductor and the second electrode. N-conduction Property metal oxide, dyestuff and p-semiconductor also can be described as functional layer, and it can embed between each electrode. In addition, battery can comprise one or more other layers, and it for example can be appointed as functional layer equally. One Or multiple batteries can put in substrate directly or indirectly. Photovoltaic element especially can comprise a battery Or multiple batteries. More particularly, can select single-cell structure, or many battery structures, for example serial connection electricity Pool structure, wherein multiple cell parallels and/or one are positioned at another top and are arranged in substrate.

More particularly, photovoltaic element of the present invention can be constructed in following one or more modes. Photovoltaic unit The element configuration of part can combine in substantially any mode.

The first electrode and n-semiconduction metal oxide

Can be monometallic oxidation for the n-semiconduction metal oxide of dye solar cell Thing or different hopcalite. Also can use mixed oxide. N-semiconduction metal oxide Especially can be porous and/or use with the form of Nanoparticulate oxide, nano particle at this point and It is to be less than the particle of 0.1 micron that speech should be understood to mean particle mean size. Nanoparticulate oxide is logical Normal open oversintering method puts on conductive substrates as the porous membrane with high surface area and (has work Be the carrier of the conductive layer of the first electrode).

Substrate can be rigidity or flexible. Except metal forming, suitable substrate is (hereinafter also referred to as carrying Body) particularly plastic sheet or film, especially sheet glass or glass-film. Specially suitable electrode material, outstanding It is for being conductive material according to the electrode material of the first electrode of above-mentioned preferred structure, for example transparent Electroconductive oxide (TCO), tin oxide (FTO or ITO) and/or aluminium that for example fluoro-and/or indium adulterates Zinc oxide (AZO), CNT or the metal film of doping. But, replace or extraly, also can Use the metallic film still with enough transparencies. Substrate can be covered or applies with these conductive materials. Owing to only needing single substrate in common described structure, the formation of flexible batteries is also possible. This energy Give if any, with rigid basement only can be difficult a large amount of final uses of realizing, for example use In bank card, clothes etc.

The first electrode, especially tco layer additionally can for example, by solid metal oxide cushion (thickness 10-200nm) cover or apply, with prevent p-semiconductor directly contact with tco layer (referring to Peng etc., Coord.Chem.Rev.248,1479 (2004)). But the present invention uses solid p-semiconduction Electrolyte, in this case contacting and liquid or gel form electrolyte of electrolyte and the first electrode Compare greatly and reduce, making this cushion is unessential in many cases, makes in many feelings Under condition, can save this layer, this also has current limitation effect and also can make n-semiconduction metal oxide and the The contact of one electrode is deteriorated. This has strengthened the efficiency of assembly. On the other hand, sort buffer layer again can Use so that the current component of dye solar cell and the electric current of organic solar batteries in a controlled manner Divide flux matched. In addition save therein in the situation of battery of cushion, especially at solid state battery, In, usually there is undesired carrier recombination problem. Thus, cushion in many cases In solid state battery, be particularly favourable.

As everyone knows, (n-partly leads the solid semiconductor material that thin layer of metal oxide or film are normally cheap Body), but due to large band gap, it absorbs common not in the visual field of electromagnetic spectrum, but conventionally exists In ultraviolet spectrogram district. For the use in solar cell, its metal oxide therefore conventionally as Situation in dye solar cell, must with the dye combinations as sensitising agent, described dyestuff is in day Optical wavelength range, absorbs in 300-2000nm, and under excited electronic state, electronic injection is partly led In the conduction band of body. By extra as electrolytical solid p-semiconductor in battery, it is again to electricity Utmost point place (or serial connection solar cell in the situation that at the transition position to the second sub-battery) reduction, electronics Can be recycled to sensitizer, make its regeneration.

For particularly importantly semiconductor oxide zinc, tin ash, two of the use at solar cell The mixture of titanium oxide or these metal oxides. Metal oxide can be with nanocrystal porous layer Form is used. These layers have the high surface area scribbling as the dyestuff of sensitizer, make to realize Gao Light absorption. The metal oxide layer of structure has advantage, for example higher electron mobility as nanometer rods Or dyestuff is filled the improvement in hole.

Metal-oxide semiconductor (MOS) can use separately or with the form of mixture. Also can be by burning One or more other metal oxide-coated for thing. In addition, metal oxide also can be used as coating and executes Be added on other semiconductor as on GaP, ZnP or ZnS.

Particularly preferred semiconductor is zinc oxide and the polymorphous titanium dioxide of anatase, and it is preferably to receive Rice crystal form uses.

In addition, sensitizer can advantageously be usually used in all n-half in these solar cells with discovery Conductor combination. Preferred example comprises metal oxide used in pottery, for example titanium dioxide, oxidation Zinc, tin oxide (IV), tungsten oxide (VI), tantalum oxide (V), niobium oxide (V), cerium oxide, strontium titanates, The composite oxides of zinc stannate, perovskite type are as barium titanate, and the oxide of binary and three rod iron, It also can exist with nanocrystal or amorphous form.

Due to the strong absorption that conventional organic dyestuff and phthalocyanine and porphyrin have, even n-semiconduction The thin layer of metal oxide or film are enough to absorb the dyestuff of aequum. Metal-oxide film has again not The possibility of the recombination method of wanting reduces and reduces the advantage of the interior resistance of the sub-battery of dyestuff. For n- Semiconduction metal oxide, can preferably use 100nm to 20 micron, and more preferably 500nm extremely approximately The layer thickness of 3 microns.

Dyestuff

For the present invention, as be usually used in DSC, term " dyestuff ", " sensitizer dyestuff " and " sensitizer " substantially synonymously uses and do not have any restriction of possibility configuration. For the present invention Spendable a large amount of fuel is known by prior art, therefore, for possible examples of materials, also can join Examine the above description of the Prior Art about dye solar cell. Listed and described all dyestuffs in principle Also can be used as pigment exists. DSSC based on titanium dioxide as semi-conducting material For example be described in US-A-4927721, Nature353,737-740 page (1991) and US-A-5350644, and Nature395,583-585 page (1998) and EP-A-1176646 In. Also can advantageously use in principle for the present invention the dyestuff described in these documents. These dye Material solar cell preferably comprises by acid groups and is incorporated into the transition on titanium dioxide layer as sensitizer The monomolecular film of metal complex, especially ruthenium complex.

Not just due to cost reason, the sensitizer that repeats to propose comprises metal-free organic dyestuff, It equally also can use for the present invention. Especially in solid dye solar cell, for example, use Indoline dyestuff can be realized and be greater than 4% high efficiency (for example, referring to Schmidt-Mende etc., Adv. Mater.2005,17,813). US-A-6359211 described cyanine,Piperazine, thiazine and acridine Dyestuff also enforceable purposes for the present invention, it has by the carboxyl of alkylidene bonding with solid Fix on titanium dioxide semiconductor.

Organic dyestuff is realized now in liquid cell almost 12.1% efficiency (for example, referring to P.Wang Deng, ACS.Nano2010). Also report containing pyridineDyestuff, can use also for the present invention Demonstrate efficiency likely.

In described dye solar cell, particularly preferred sensitizer dyestuff is DE102005053995 The derivative of perylene described in A1 or WO2007/054470A1, three naphthalene embedding benzene (terrylene) derivatives With four naphthalene embedding benzene (quaterrylene) derivatives. The use of these dyestuffs causes having high efficiency and same Time high stability photovoltaic element.

Naphthalene embedding benzene (rylene) demonstrates the strong absorption in day optical wavelength range, and depends on conjugated body The length of system can contain from about 400nm (DE102005053995A1 perylene derivative I) extremely approximately The scope of 900nm (four rylene derivatives of DE102005053995A1). Based on three naphthalene embedding benzene Rylene derivatives I be adsorbed in solid-state lower on titanium dioxide according to its composition approximately In the scope of 400-800nm, absorb. For realizing incident daylight filling very much from visual field near infrared region Point utilization, advantageously use the mixture of different rylene derivatives I. Also be feasiblely once in a while Also use different naphthalene embedding benzene homologues.

Rylene derivatives I can easily and in a permanent way be fixed on the burning of n-semiconduction On thing film. Carboxyl-COOH that this combination forms by acid anhydride functional group (x1) or original position or-COO-, or Undertaken by the acid groups A existing in acid imide or condensation group ((x2) or (x3)). Described in DE102005053995A1, rylene derivatives I is for the present invention at the dye sensitization sun Use in energy battery has good adaptability.

Particularly preferably dyestuff has and can make it be fixed on the anchor on n-semiconductor film in one end of molecule Group. At the other end of molecule, dyestuff preferably comprises promotion dyestuff and is discharged on n-semiconductor at electronics Regenerate later and prevent and the electron donor Y that is discharged into the electron recombination on semiconductor.

About other details that may select of suitable dye, can for example again mention DE102005053995A1. For serial connection battery described herein, especially can use ruthenium to coordinate Thing, porphyrin, other organic sensitizer and preferred naphthalene embedding benzene.

Dyestuff can with plain mode be fixed on n-semiconduction metal oxide film or within. Example As, n-semiconduction metal oxide film can be with fresh sintering (still warm) state and dyestuff suitable For example, during the solution in organic solvent or suspension contact are enough (about 0.5-24H). This can for example lead to Cross and the substrate of metal oxide-coated is immersed in dye solution and realize.

If use the combination of different dyes, they can for example comprise one or many by one or more Solution or the suspension of planting dyestuff in turn apply. Also can use separated by for example CuSCN layer two Kind dyestuff (about this theme, for example, referring to Tennakone, K.J., Phys.Chem.B.2003, 107,13758). The method of most convenient can relatively easily be determined in all cases.

In the selection of the granularity of the oxide particle of dyestuff and n-semiconduction metal oxide, can structure Make the light that solar cell makes to absorb maximum. Should construct oxide skin(coating) makes the solid p-semiconductor can Filler opening effectively. For example, less particle has larger surface area, therefore can absorb greater amount Dyestuff. On the other hand, larger particle has larger hole conventionally, and it can pass through p-better Conductor.

As mentioned above, described concept comprises the semi-conductive use of one or more solids p-. For preventing n- Electronics in semiconduction metal oxide and the restructuring of solid p-conductor, can be at n-semiconduction metal oxygen Between compound and p-semiconductor, use at least one to there is the passivation layer of passivating material. This layer should be very Thin and should as far as possible only cover the current unconverted point of n-semiconduction metal oxide. In certain situation Under, passivating material also can put on metal oxide before dyestuff. Preferred passivating material especially One or more following material: Al₂O₃; Silane, for example CH₃SiCl₃；Al³⁺; 4-tert-butyl group pyrrole Pyridine (TBP); MgO; GBA (4-guanidine radicals butyric acid) and like derivatives; Alkyl acid; Cetyl third Diacid (HDMA).

P-semiconductor

As mentioned above, with regard to photovoltaic element described herein, one or more SOLID ORGANIC p-semiconductor Use separately or with one or more other p-semiconductor combinations that are organic or inorganic in nature. As above Described, at least one SOLID ORGANIC p-semiconductor comprises the silver that is at least oxidised form. With regard to the present invention and Speech, p-semiconductor should be understood to mean material, the especially organic material of energy conduction hole conventionally. More particularly, it can be for having the organic material of extension π-electron system, and it can stably be oxidizing to Less once, for example, to form so-called radical cation. For example, p-semiconductor can comprise at least one Plant the organic basis material with described performance. More particularly, p-semiconductor can be by silver (I) p-doping. This any p-semiconductive performance that means to be present in any case in p-semiconductor or matrix material is led to Cross with silver (I) doping and strengthen or even in fact produce. More particularly, can to improve carrier close in doping Degree, especially hole density. Replace or extraly, the mobility in carrier, especially hole also Affected by doping, especially improve.

More particularly, as mentioned above, the p-semiconductor of doping can pass through at least one p-electric conductivity Organic material is applied at least one carrier element with the silver that is oxidised form and produces or give birth to by it Produce, be wherein the silver of oxidised form preferably with at least one silver (I) salt [Ag⁺]_m[A^m-] form be applied to At least one carrier element, wherein A^m-For the anion of organic acid or inorganic acid, and m is 1-3 Integer, preferably wherein m is 1.

With regard to integer m, m is preferably 1 or 2, and very preferably 1. Therefore, for p-semiconductor Production, very preferably use formula Ag⁺A^-Salt.

With regard to A^m-, this is preferably the anion of organic acid or inorganic acid.

In preferred version, [A^m-] be organic acid anion, wherein said organic acid preferably comprise to A few fluorin radical or cyano group (CN), more preferably at least one fluorin radical. Preferably, [A^m-] be each From the organic carboxyl acid, sulfonic acid, phosphonic acids or the sulfimide that preferably comprise at least one fluorin radical or cyano group Anion.

Preferably, the present invention relates to a kind of photovoltaic element as above, wherein [A^m-] there is following formula (II) Structure:

Wherein R^aFor fluorin radical-F or the alkyl being replaced by least one fluorin radical or cyano group separately, cycloalkyl, Aryl or heteroaryl,

And wherein X is-O^-Or-N^--Rb，

And wherein R^bComprise fluorin radical-F or cyano group,

And wherein R^bFurther contained-S (O)₂-group.

For the present invention, to relate to ring-type optional for term used " group of naphthene base " or " cycloalkyl " The alkyl replacing, preferably 5 or 6 rings or preferably there are many rings of 5-20 carbon atom.

Radicals R ^a ：

In a preferred embodiment of the invention, R^aFor-F or by least one fluorin radical or a cyanogen Base, the alkyl that preferably at least one fluorin radical replaces, very preferably by least one fluorin radical or one Cyano group, methyl, ethyl or propyl group that preferably fluorin radical replaces. Except fluorin radical or cyano group, institute State alkyl and can comprise at least one other substituting group. Preferably, R^aComprise at least 3 fluoro substituents or A cyano group, more preferably at least 3 fluoro substituents.

R^aEspecially be selected from-F ,-CF₃、-CF₂-CF₃With-CH₂-CN, is further preferably selected from-F ,-CF₃ With-CF₂-CF₃。

Therefore, the invention still further relates to a kind of photovoltaic element as above, wherein [A^m-] have and be selected from down The structure of formula:

And wherein X is-O^-Or-N^--Rb. More preferably, R^aFor-CF₃。

Radicals R ^b ：

As mentioned above, R^bFor comprising the group of fluorin radical-F or cyano group, wherein R^bAdditionally contained -S(O)₂-group. Preferably, R^bComprise at least one alkyl, cycloalkyl, aryl or heteroaryl, Wherein said alkyl, cycloalkyl, aryl or heteroaryl are in each case by least one fluorin radical-F Or cyano group, preferably at least one fluorin radical replaces, and R wherein^bAdditionally contained-S (O)₂-group.

Preferably, R^bThere is following formula structure:

Wherein R^bbFor-F or by least one fluorin radical or a cyano group, preferably at least one fluorin radical replaces Alkyl, the methyl very preferably being replaced by least one fluorin radical, ethyl or propyl group. Except fluorine-based Beyond group and/or cyano group, described alkyl can comprise at least one other substituting group. Preferably, R^bbBag Containing at least 3 fluoro substituents.

R^bbEspecially be selected from-F ,-CF₃、-CF₂-CF₃With-S (O)₂-CH₂-CN, is especially selected from-F ,-CF₃ With-CF₂-CF₃。

Therefore, the invention still further relates to a kind of photovoltaic element as above, wherein X Wei – N^--Rb, and And wherein R^bBe selected from-S (O)₂-F、-S(O)₂-CF₃、-S(O)₂-CF₂-CF₃With-S (O)₂-CH₂-CN， Especially be selected from-S (O)₂-F、-S(O)₂-CF₃With-S (O)₂-CF₂-CF₃。

[A^m-] therefore more preferably there is the one in following structure:

Wherein R^aEspecially be selected from-F ,-CF₃With-CF₂-CF₃. Preferably, at X be-N^--Rb and Rb tool There is structureSituation under, R^aAnd R^bbIdentical; [A^m-] therefore symmetry sulphonyl Asia more preferably Amine. In preferred embodiments, [A^m-] be therefore selected from bis trifluoromethyl sulfimide (TFSI^-), two three Fluoro ethyl sulfimide and two fluorine sulfimide.

Replacing in embodiment, the present invention relates to a kind of photovoltaic element as above, wherein [A^m-] For trifluoroacetic acid root.

In another preferred embodiment, [A^m-] be the anion of inorganic acid. In this case, [A^m-] Be preferably-NO₃ ^-(nitrate anion). Therefore, the invention still further relates to a kind of photovoltaic element, it as mentioned above can By by least one silver (I) salt [Ag⁺]_m[A^m-] introduce, especially mixing and/or dissolving at least one has Machine matrix material (128) and produce or by its produce, wherein [A^m-] be group-NO₃ ^-And wherein m=1.

Therefore, the invention still further relates to a kind of photovoltaic element as above, wherein [A^m-] be selected from two trifluoros Sulfonyloxy methyl imines (TFSI^-), two trifluoroethyl sulfimide, two fluorine sulfimide, trifluoromethyl sulphur Acid group, preferably [A wherein^m-] be bis trifluoromethyl sulfimide (TFSI^-)。

Doped with the silver that is at least oxidised form, for example at least one silver (I) salt [Ag⁺]_m[A^m-], especially Preferably the solid p-semiconductor of bis trifluoromethyl sulfimide silver can be used in photovoltaic element of the present invention, Even do not there is any large raising of cell resistance, especially when dyestuff strongly absorbs and therefore only While needing n-semiconductor lamella. More particularly, p-semiconductor should have continuous impermeable barrier substantially, with Reduction may be by n-semiconduction metal oxide (especially nanoporous form) and the second electrode and/or The undesired recombining reaction contacting between other element of photovoltaic element and produce.

Especially can the silver of oxidised form will be, for example at least one silver (I) salt [Ag⁺]_m[A^m-], especially excellent Select bis trifluoromethyl sulfimide silver to be put on carrier element by liquid phase together with matrix material. Example As, can will at least be the silver of oxidised form, for example at least one silver (I) salt [Ag⁺]_m[A^m-], especially excellent Select bis trifluoromethyl sulfimideization silver and the combination of p-semiconduction matrix material with solution, dispersion or Suspension processing. Optionally, can at least one organic salt is added in this at least one liquid phase (although also can There are several liquid phases), for example, for stable and/or improvement electrical property.

The remarkable parameter that affects the semi-conductive selection of p-is hole mobility, empty because this part ground determines Cave diffusion length (referring to Kumara, G., Langmuir, 2002,18,10493-10495). No Contrast with carrier mobility in spiro-compound can be for example at T.Saragi, Adv.Funct. Mater.2006, finds in 16,966-974.

Preferably, for the present invention, using organic semiconductor (is low molecular weight oligomeric or polymer semiconductor Or the mixture of this based semiconductor). The p-semiconductor that particularly preferably can be processed by liquid phase. Example is herein Based on polymer as polythiophene and polyarylamine, or based on amorphous, can the non-polymeric of reversible oxidation have Organic compounds is if the p-semiconductor of spiral shell two fluorenes mentioned of beginning is (for example, referring to US2006/0049397 and its Middle as the disclosed spiro-compound of p-semiconductor, it also can use for the present invention). Preferably use Low-molecular-weight organic semiconductor. Solid p-semiconductor can for example, to have the silver that is oxidised form, extremely Few a kind of silver (I) salt [Ag⁺]_m[A^m-], especially preferably bis trifluoromethyl sulfimide silver is as adulterant Doped forms use.

In addition, also can with reference to from description of the Prior Art about p-semiconduction material and adulterant Comment. May element and may structure for other of dye solar cell, also can be fully with reference to Upper description.

The second electrode

The second electrode can be the hearth electrode of faces substrate or the top electrode back to substrate. Spendable Especially metal electrode of two electrodes, it can have one or more pure forms or as mixture/alloy Metal, for example especially aluminium or silver. The use of inorganic/organic mixed electrode or multi-layered electrode is also possible , for example use LiF/Al electrode.

In addition, also can use the quantum efficiency of assembly wherein by forcing photon extremely by suitable reflection Few electrode design improving by absorbed layer for twice.

This class layer structure, also referred to as " concentrator ", is equally for example described in WO02/101838 (especially 23-24 page) in.

Accompanying drawing summary

Other details of the present invention and feature are described together with dependent claims by following preferred embodiment Learn together. Thus, specific features can carry out separately or with several in combination. The present invention does not limit In work embodiment. Work embodiment is schematically shown in figure. Identical accompanying drawing mark in each figure The element that note refers to identical element or has the element of identical function or correspond to each other in its function aspects.

Each figure shows:

The schematic layer structure of organic photovoltaic element of the present invention in the profile of Fig. 1 side-looking;

Fig. 2 arranges according to the schematic energy level in the layer structure of Fig. 1;

The current-voltage without the silver-colored control sample that is oxidised form that Fig. 3 measures after producing for 2 days Feature;

Fig. 4 has the current-voltage feature of Ag-TFSI doping.

Work embodiment

Fig. 1 shows photovoltaic element 110 with height schematic cross sectional view, and it is in this work embodiment Dye solar cell 112. Can basis according to the photovoltaic element 110 of the schematic layer structure in Fig. 1 The present invention's structure. According to the control sample of prior art in principle also corresponding to structure shown in Fig. 1, and For example only different from it aspect SOLID ORGANIC p-semiconductor. But, should point out that the present invention also can be used for In other layer of structure and/or other structure.

Photovoltaic element 110 comprises substrate 114, for example substrate of glass. Other substrate is also as mentioned above Available. In this substrate 114, apply the first electrode 116, its also referred to as working electrode and preferably as The above is transparent. Again to the barrier layer that applies optional metals oxide on this first electrode 116 118, it is preferably atresia and/or non-granular. Use dyestuff 122 sensitizations to applying on it again N-semiconduction metal oxide 120.

Matrix 114 and the layer 116-120 applying on it form carrier element 124, on it, apply at least A SOLID ORGANIC p-semiconductor layer 126, it is organic that it can especially comprise again at least one p-semiconduction Matrix material 128 and at least one are the silver 130 of oxidised form, for example at least one silver (I) salt [Ag⁺]_m[A^m-], especially preferably bis trifluoromethyl sulfimide silver. On this p-semiconductor 126, execute Add the second electrode 132, it is also referred to as to electrode. Layer shown in Fig. 1 forms layer structure 134 together, and it is logical Cross and seal 136 protections in case surrounding atmosphere, for example with protective layer structure 134 completely or partially in case Oxygen and/or moisture. As in Fig. 1 to as described in the first electrode 116, in electrode 116,132 one or Derive from sealing 136, sealing one or more contacts of 136 outsides to can provide for two Connection area.

Fig. 2 for example with height shows in schematic form display case as according to the energy level of the photovoltaic element 110 of Fig. 1 Figure. What show is the fermi level 138 of the first electrode 116 and the second electrode 132, and dyestuff (for example HOMO energy level with 5.7eV shows) and p-semiconductor 126 (also referred to as HTL, hole transmission layer) Layer 118/120 (it can comprise same material, for example TiO₂) HOMO (highest occupied molecular rail Road) 140 and LUMO (lowest unoccupied molecular orbital). For example, for the first electrode 116 and the second electrode Material described in 132 is FTO (tin oxide of fluorine doping) and silver.

Photovoltaic element additionally can optionally comprise other element. By thering is or not having the light of sealing 136 Volt element 110, carries out work embodiment hereinafter described, based on the provable the present invention of described embodiment, The effect of especially by being the silver 130 of oxidised form, p-semiconductor 126p-being adulterated.

Control sample

As the control sample of photovoltaic element, as being had without being by production known in the art in principle The semi-conductive dye solar cell of solid p-of the silver doping of oxidised form.

As base material and substrate, use and scribble the tin oxide (FTO) of fluorine doping and there is size The glass plate of 25mm × 25mm × 3mm (HartfordGlass), will as the first electrode (working electrode) It uses successively glass cleaner (RBS35), deionized water and acetone treatment (every kind of feelings in ultra sonic bath Under condition, process 5 minutes), then in isopropyl alcohol, seethe with excitement 10 minutes and be dried in nitrogen stream.

For producing optional solid TiO₂Cushion, uses spray pyrolysis method. To comprise diameter is 25nm TiO₂The TiO of particle in terpineol/ethylcellulose dispersion₂Sticking with paste (Dyesol) partly leads as n- Electrically with 4500rpm spin coating, it is upper with spin coater for metal oxide, and is dried 30 minutes at 90 DEG C. Maintain 45 minutes and after the sintering step of 30 minutes, obtain approximately at 450 DEG C being heated to 450 DEG C The TiO of 1.8 μ m₂Layer thickness.

After taking out, sample is cooled to 80 DEG C and the ID662 (example that immerses additive from drying box As obtained according to embodiment H) 5mM solution in 12 hours, immerse subsequently dyestuff at dichloro In 0.5mM solution in methane 1 hour. Dyestuff used is that dyestuff ID504 (for example can be according to reality Executing routine G obtains). From solution take out after, subsequently by sample with same solvent rinse and at nitrogen Dry in air-flow. Subsequently that the sample obtaining in this manner is dry at 40 DEG C under the pressure reducing Dry.

Then, spin coating p-semiconductor solution. For this reason, preparation 0.12Mspiro-MeOTAD (Merck) And 20mMLiN (SO₂CF₃)₂(Aldrich) chlorobenzene solution. 125 these solution of μ l are put on to sample Go up and make its effect 60 seconds. , supernatant with 2000rpm removed to 30 second, and sample is existed thereafter Store overnight in the dark in air. As mentioned above, think that this storage causes the semi-conductive oxygen doping of p-, Therefore strengthen the semi-conductive conductance of p-.

Finally, apply metal back electrode as the second electrode by thermometal evaporation under the pressure reducing. Metal used is Ag, by it at about 2*10^-6Millibar pressure under withSpeed evaporation, with To the layer thickness of about 200nm.

After producing, battery is stored to 2 days under dry air (relative air humidity is 8%).

For determination efficiency η, within latter two days, using xenon solar simulator (LOT-Oriel300WAM in production 1.5) under irradiation, measure concrete electric current/electricity with 2400 type digital sourcemeters (KeithleyInstrumentsInc.) Press feature. Carry out initial measurement with non-encapsulated battery. The electric current of the control sample of measurement two days later- Voltage characteristic is shown in Fig. 3. Control sample has feature shown in table 1.

Table 1: the feature of unadulterated control sample

	Isc[mA/cm²]	Voc[mV]	FF[%]	ETA[%]
					Without Ag-TFSI, t=2 days	9.29	860	55	4.4

Short circuit current Isc (i.e. current density under 0 load resistance) is 9.29mA/cm², open-circuit voltage V_oc(being the load that current density is down to 0 o'clock) is 860mV. Activity coefficient FF is 55%, and efficiency ETA is 4%.

Embodiment 1: doping 5mmAG-TFSI

As the first work embodiment of photovoltaic element 110 of the present invention, above-mentioned control sample is passed through will P-semiconductor 126 or 128 use bis trifluoromethyl sulfimide silver (Ag-TFSI) doping of its matrix material And improve. For this reason, by (the source: Aldrich) of the bis trifluoromethyl sulfimide silver in 5mM cyclohexanone Merck) and 20mMLiN (BO add 0.12Mspiro-MeOTAD (source:₂CF₃)₂(source: Aldrich) the p-semiconductor solution in chlorobenzene. As described in to control sample, this solution is spun on to this On sample.

Next-door neighbour is under reduced pressure evaporated and is applied metal back electrode as the second electrode by thermometal thereafter 132. Metal used is Ag, by it at about 2*10^-6Millibar pressure under withSpeed evaporation, To form the bed thickness of about 200nm.

For determination efficiency η, within latter two days, using xenon solar simulator (LOT-Oriel immediately and in production 300WAM1.5) irradiation is lower to 2400 type digital sourcemeters (KeithleyInstrumentsInc.) measurements Concrete current/voltage feature. Carry out initial measurement with non-encapsulated battery.

The current-voltage feature with 5mM bis trifluoromethyl sulfimide silver is shown in Fig. 4. The feature of control sample and embodiment 1 sample is presented in table 2.

Table 2: in the comparison of the feature of unadulterated control sample of different measuring time and embodiment 1 sample

	Isc[mA/cm²]	Voc[mV]	FF[%]	ETA[%]
					Without Ag-TFSI, t=0	4.13	760	26	0.8
Without Ag-TFSI, t=2 days	9.29	860	55	4.4
					There is Ag-TFSI, t=0	9.20	800	69	5.1
There is Ag-TFSI, t=2 days	9.80	780	66	5.0

Embodiment 2: the variation of concentration of dopant

In order to study the impact of dopant dose on photovoltaic element 110 performances, additionally use 1-20mM two Trifluoromethanesulp-onyl-onyl imide silver obtains the variant of embodiment 1. In addition, sample is similar to above-mentioned Embodiment 1 sample and producing. Feature at these samples of measuring is two days later presented in table 3. ? During these are measured, illumination value is also 100 daylight in each case, as in above measurement. Table 3: there is the comparison of the feature of embodiment 2 samples of different Ag-TFSI content

	Isc[mA/cm²]	Voc[mV]	FF[%]	ETA[%]
					1mM Ag-TFSI	-10.4	780	53	4.3
3mM Ag-TFSI	-10.1	780	62	4.8
					5mM Ag-TFSI	-9.8	780	66	5.0
10mM Ag-TFSI	-9.7	760	69	5.1
					20mM Ag-TFSI	-9.7	800	64	4.9

Measure and show with regard to efficiency, under about 10mMAg-TFSI, occur approximately 5.1% maximum. But in a word, the efficiency between 3-20mM has the curve of relatively flat, it just can form produces The advantage of technology.

Embodiment 3: the variation of matrix material

In addition,, as embodiment 3, studied the shadow of matrix material 128 to photovoltaic element 110 performances Ring. For this reason, produce sample according to above-described embodiment 1, different from matrix material 128 The different matrix material 128 that spiro-MeOTAD is had variable concentrations replaces, more especially by Matrix material in ID522 mentioned above, ID322 and ID367 type replaces. Be in order to introduce The silver 130 of oxidised form, in all samples, adulterant used is also that 10mM is two in each case Trifluoromethanesulp-onyl-onyl imide silver. The feature of the sample obtaining with which is shown in table 4. Described Concentration 160mg/ml and 200mg/ml be the concentration in liquid phase based on matrix material 128. Feature is 2 After it again record and at 100 daylight [mW/cm²] lower measurement.

Table 4: there is the comparison of the feature of embodiment 4 samples of different matrix material

Embodiment 4: the variation of adulterant

In addition, carry out the silver 130 that is wherein oxidised form to introduce matrix material by other adulterant 128 test. In addition the silver that, is Ag-TFSI form is replaced detecting doping effect by other group Whether can instead of be oxidised form by TFSI with it to the positive effect of photovoltaic element 110 features Silver 130 causes.

For this reason, in embodiment 4, produce the also each examination corresponding to above embodiment 1 except adulterant Sample. But, replace Ag-TFSI, other salt as adulterant is added with the amount of 20mM separately. The results are shown in table 5. Silver nitrate is added to p-conductor solution with solid form.

Table 5: there is the comparison of the feature of embodiment 5 samples of different dopant

Adulterant	Isc[mA/cm²]	Voc[mV]	FF[%]	ETA[%]
					Silver nitrate	-9.8	800	66	5.1
Silver trifluoromethanesulfonate	-4.4	920	43	1.8
					Trifluoroacetic acid silver	-1.2	640	35	0.3
1-ethyl-3-methyl-TFSI	-1.9	1000	39	0.7
					1-butyl-3-methyl-TFSI	-1.2	1000	26	0.3
TFMS sodium	-1.6	1000	29	0.5

Result shows that TFSI only causes high efficiency as the anion in silver salt conventionally. But, remove Outside Ag-TFSI, other silver salt also demonstrates relatively high efficiency, especially silver nitrate and fluoroform sulphur Acid silver. Conventionally can use thus and contain the silver-colored compound, the especially salt that are oxidised form, especially Formula [Ag⁺]_m[A^m-] silver (I) salt, more preferably Ag-TFSI, silver nitrate and silver trifluoromethanesulfonate are as mixing Assorted agent.

Finally, below also list the semi-conductive synthetic example of the organic p-of low-molecular-weight, its just the present invention Can be used alone or in combination and can for example meet the above formula I providing.

Synthetic example:

A) the general synthetic schemes that prepared by formula I compound:

(a) synthetic route I:

(a1) synthesis step I-R1:

Synthesizing based on following quoted bibliography in synthesis step I-R1:

a)Liu，Yunqi；Ma，Hong；Jen，AlexK-Y.；CHCOFS；Chem.Commun.； 24；1998；2747-2748，

b)Goodson，FelixE.；Hauck，Sheila；Hartwig，JohnF.；J.Am.Chem. Soc.；121；33；1999；7527-7539，

c)Shen，JiunYi；Lee，ChungYing；Huang，Tai-Hsiang；Lin，JiannT.； Tao，Yu-Tai；Chien，Chin-Hsiung；Tsai，Chiitang；J.Mater.Chem.； 15；25；2005；2455-2463，

d)Huang，Ping-Hsin；Shen，Jiun-Yi；Pu，Shin-Chien；Wen，Yuh-Sheng； Lin，JiannT.；Chou，Pi-Tai；Yeh，Ming-ChangP.；J.Mater.Chem.； 16；9；2006；850-857，

e)Hirata，Narukuni；Kroeze，JessicaE.；Park，Taiho；Jones，David； Haque，SaifA.；Holmes，AndrewB.；Durrant，JamesR.；Chem.Commun.； 5；2006；535-537。

(a2) synthesis step I-R2:

Synthesizing based on following quoted bibliography in synthesis step I-R2:

a)Huang，Qinglan；Evmenenko，Guennadi；Dutta，Pulak；Marks， TobinJ.；J.Am.Chem.Soc.；125；48；2003；14704-14705，

b)Bacher，Erwin；Bayerl，Michael；Rudati，Paula；Reckefuss，Nina； Mueller，C.David；Meerholz，Klaus；Nuyken，Oskar；Macromolecules； EN；38；5；2005；1640-1647，

c)Li，ZhongHui；Wong，ManShing；Tao，Ye；D'Iorio，Marie；J.Org. Chem.；EN；69；3；2004；921-927。

(a3) synthesis step I-R3:

Synthesizing based on following quoted bibliography in synthesis step I-R3:

J.Grazulevicius; J.ofPhotochem. and Photobio., A:Chemistry2004 162(2-3)，249-252。

Formula I compound can be standby by the sequential system of synthesis step shown in above synthetic route I. In step Suddenly (I-R1) in (I-R3), each reactant can be for example by ullmann reaction using copper as catalyst or Coupling under palladium catalysis.

(b) synthetic route II:

(b1) synthesis step II-R1:

The synthetic bibliography based on quoting under I-R2 in synthesis step II-R1.

(b2) synthesis step II-R2:

The synthetic bibliography based on quoting below in synthesis step II-R2:

a)Bacher，Erwin；Bayerl，Michael；Rudati，Paula；Reckefuss，Nina； Müller，C.David；Meerholz，Klaus；Nuyken，Oskar；Macromolecules； 38；5；2005；1640-1647，

b)Goodson，FelixE.；Hauck，Sheila；Hartwig，JohnF.；J.Am.Chem. Soc.；121；33；1999；7527-7539；Hauck，SheilaI.；Lakshmi，K.V.； Hartwig，JohnF.；Org.Lett.；1；13；1999；2057-2060。

(b3) synthesis step II-R3:

Formula I compound can be by standby at synthesis step sequential system shown in synthetic route II above. In step Suddenly (II-R1) in (II-R3), each reactant can be also as for example passed through Liv Ullmann in synthetic route I React using copper as catalyst or coupling under palladium catalysis.

(c) preparation of initial amine:

When the diaryl amine in synthesis step I-R2 and II-R1 in synthetic route I and II is not commercially available Time, their can be for example be urged using copper as catalyst or at palladium by ullmann reaction according to following reaction Change lower preparation:

Synthetic based on following listed Review literature:

The C-N coupling reaction of palladium catalysis:

a)Yang，Buchwald；J.Organomet.Chem.1999，576(1-2)，125-146，

b)Wolfe，Marcoux，Buchwald；Acc.Chem.Res.1998，31，805-818，

c)Hartwig；Angew.Chem.Int.Ed.Engl.1998，37，2046-2067。

The C-N coupling reaction of copper catalysis:

a)Goodbrand，Hu；Org.Chem.1999，64，670-674，

b)Lindley；Tetrahedron1984，40，1433-1456。

(B) synthetic (the synthetic route I) of synthetic example 1: Compound I D367

(B1) according to the synthesis step of general synthetic schemes I-R1:

By 4,4'-'-dibromobiphenyl (93.6g; 300mmol), 4-aminoanisole (133g; 1.08mol), Pd(dppf)Cl₂(Pd (two (diphenylphosphino) ferrocene of 1,1'-) Cl₂; 21.93g; 30mmol) and T-BuONa (sodium tert-butoxide; 109.06g; 1.136mol) mixture in toluene (1500ml) is at nitrogen Under atmosphere, at 110 DEG C, stir 24 hours. After cooling, mixture diluted with ether and pass through Pad (from CarlRoth) filters. By filter course ethyl acetate, the first of 1500ml separately Alcohol and washed with dichloromethane. Obtain product (36g with light brown solid; Productive rate: 30%).

¹HNMR(400MHz,DMSO):δ7.81(s,2H),7.34-7.32(m,4H), 6.99-6.97(m,4H),6.90-6.88(m,4H),6.81-6.79(m,4H),3.64(s,6H).

(B2) according to the synthesis step of general synthetic schemes I-R2:

Make nitrogen pass through dppf (two (diphenylphosphino) ferrocene of 1,1'-; 0.19g; 0.34mmol) and Pd₂(dba)₃(three (dibenzalacetone) two palladiums (0); 0.15g; 0.17mmol) in the toluene (220ml) Solution 10 minutes. Add subsequently t-BuONa (2.8g; 29mmol) and by reactant mixture stir again 15 minutes. Then add successively 4,4'-'-dibromobiphenyl (25g; 80mmol) with 4,4 '-dimethoxy hexichol Base amine (5.52g; 20mmol). Reactant mixture is heated under nitrogen atmosphere at the temperature of 100 DEG C 7 hours. After being cooled to room temperature, by reactant mixture frozen water quenching, by the solid filter of precipitation Go out and be dissolved in ethyl acetate. Organic layer is washed with water, also (wash by column chromatography through dried over sodium sulfate De-liquid: 5% ethyl acetate/hexane) purify. Obtain light yellow solid (7.58g, productive rate: 82%).

¹HNMR(300MHz,DMSO-d₆):7.60-7.49(m,6H),7.07-7.04(m,4H), 6.94-6.91(m,4H),6.83-6.80(d,2H),3.75(s,6H).

(B3) according to the synthesis step of general synthetic schemes I-R3:

By N⁴,N⁴'-bis-(4-methoxyphenyl) biphenyl-4,4'-diamines is (from the product of synthesis step I-R1; 0.4g; 1.0mmol) with from the product (1.0g of synthesis step I-R2; 2.2mmol) under nitrogen atmosphere Add t-BuONa (0.32g; In ortho-xylene (25ml) solution 3.3mmol). Subsequently by acid chloride (0.03g; 0.14mmol) and P (t-Bu)₃(tri-butyl phosphine) is at hexane (0.3ml; 0.1mmol) 10 % by weight solution adds in reactant mixture, and it is stirred 7 hours at 125 DEG C. To react thereafter Mixture 150ml dilution with toluene, passes throughFilter, and by organic layer through Na₂SO₄Dry. Remove desolventizing and crude product is precipitated 3 times from oxolane (THF)/carbinol mixture again. By solid Purifying by column chromatography (eluent: 20% ethyl acetate/hexane), is thereafter to use THF/ methanol extraction Purify with activated carbon. Except after desolventizing, obtain product (1.0g, productive rate: 86%) with light yellow solid.

¹HNMR(400MHz,DMSO-d₆):7.52-7.40(m,8H),6.88-7.10(m,32H), 6.79-6.81(d,4H),3.75(s,6H),3.73(s,12H).

(C) synthetic (the synthetic route II) of synthetic example 2: Compound I D447

(C1) according to the synthesis step of general synthetic schemes II-R2:

By P-nethoxyaniline (5.7g, 46.1mmol), t-BuONa (5.5g, 57.7mol) and P(t-Bu)₃(0.62ml, 0.31mmol) add from the product of synthesis step I-R2 (17.7g, In toluene (150ml) solution 38.4mmol). After 20 minutes, add by reactant mixture at nitrogen Enter Pd₂(dba)₃(0.35g, 0.38mmol). Gained reactant mixture is kept at room temperature at nitrogen gas Under atmosphere, stir 16 hours. Subsequently it diluted with ethyl acetate and pass throughFilter. By filtrate By water and the saturated nacl aqueous solution washed twice of 150ml separately. In organic phase through Na₂SO₄Dry And except after desolventizing, obtain black solid. This solid is passed through to column chromatography (eluent: 0-25% second Acetoacetic ester/hexane) purify. This obtains organic solid (14g, productive rate: 75%).

¹HNMR(300MHz,DMSO):7.91(s,1H),7.43-7.40(d,4H),7.08-6.81 (m,16H),3.74(s,6H),3.72(s,3H).

(C2) according to the synthesis step of general synthetic schemes II-R3:

By t-BuONa (686mg; 7.14mmol) heating at 100 DEG C under the pressure reducing, so After by reaction flask with nitrogen blowing and make it be cooled to room temperature. Then add 2,7-bis-bromo-9,9-diformazan Base fluorenes (420mg; 1.19mmol), toluene (40ml) and Pd[P (tBu) 3] 2 (20mg; 0.0714mmol), And reactant mixture is at room temperature stirred 15 minutes. Subsequently by N, N, N '-to trimethoxy triphenyl Benzidine (1.5g; 1.27mmol) add in reactant mixture, it is stirred 5 hours at 120 DEG C. Mixture is passed throughMixture filters and uses toluene wash. Crude product is passed through to post Chromatography (eluent: 30% ethyl acetate/hexane) purifies twice, precipitating two from THF/ methyl alcohol again After inferior, obtain light yellow solid (200mg, productive rate: 13%).

¹HNMR:(400MHz,DMSO-d₆):7.60-7.37(m,8H),7.02-6.99(m,16H), 6.92-6.87(m,20H),6.80-6.77(d,2H),3.73(s,6H),3.71(s,12H),1.25(s,6H)

(D) synthetic (the synthetic route I) of synthetic example 3: Compound I D453

(D1) preparation of initial amine:

Step 1:

By NaOH (78g; 4eq) add the bromo-9H-fluorenes of 2-(120g; 1eq) and BnEt₃NCl (benzyl three Ethyl ammonium chloride; 5.9g; 0.06eq) in the mixture in 580mlDMSO (methyl-sulfoxide). Will Mixture is cooling with frozen water, and slowly drips methyl iodide (MeI) (160g; 2.3eq). By reactant mixture Keep stirred overnight, be then poured into water, be extracted with ethyl acetate subsequently 3 times. Organic by what merge With saturated nacl aqueous solution washing, through Na₂SO₄Dry, and except desolventizing. Crude product is passed through Column chromatography uses silica gel (eluent: benzinum) to purify. After by methanol wash, with white solid Obtain product (2-bromo-9,9 '-dimethyl-9H-fluorenes) (102g).

¹HNMR(400MHz,CDCl3):δ1.46(s,6H),7.32(m,2H),7.43(m,2 H),7.55(m,2H),7.68(m,1H)

Step 2:

By P-nethoxyaniline (1.23g; 10.0mmol) and 2-bromo-9,9 '-dimethyl-9H-fluorenes (3.0g; 11.0mmol) under nitrogen atmosphere, add t-BuONa (1.44g; 15ml toluene (15ml) 15.0mmol) In solution. Add Pd₂(dba)₃(92mg; 0.1mmol) and P (t-Bu)₃At hexane (0.24ml; 10 % by weight solution 0.08mmol), and reactant mixture is at room temperature stirred 5 hours. With After by mixture frozen water quenching, the solid of precipitation is leached and is dissolved in ethyl acetate. By organic phase Wash with water and through Na₂SO₄Dry. Passing through column chromatography (eluent: 10% ethyl acetate/hexane) After purifying crude product, obtain light yellow solid (1.5g, productive rate: 48%).

¹HNMR(300MHz,C₆D₆):7.59-7.55(d,1H),7.53-7.50(d,1H), 7.27-7.22(t,2H),7.19(s,1H),6.99-6.95(d,2H),6.84-6.77(m,4H),4.99(s, 1H),3.35(s,3H),1.37(s,6H).

(D2) preparation of Compound I D453 used according to the invention

(D2.1): the synthesis step according to general synthetic schemes I-R2:

Will be from product (4.70g a); 10.0mmol) with 4,4 '-'-dibromobiphenyl (7.8g; 25mmol) exist Under nitrogen, add t-BuONa (1.15g; 12mmol) in the solution in 50ml toluene. Add Pd₂(dba)₃(0.64g; 0.7mmol) and DPPF (0.78g; 1.4mmol), and by reactant mixture protect Be held at 100 DEG C and stir 7 hours. After reactant mixture is used to frozen water quenching, by consolidating of precipitation Body leaches and it is dissolved in ethyl acetate. Organic phase is washed with water and through Na₂SO₄Dry. ? After column chromatography (eluent: 1% ethyl acetate/hexane) purifying crude product, obtain light yellow solid (4.5g, productive rate: 82%).

¹HNMR(400MHz,DMSO-d6):7.70-7.72(d,2H),7.54-7.58(m,6H), 7.47-7.48(d,1H),7.21-7.32(m,3H),7.09-7.12(m,2H),6.94-6.99(m,4H), 3.76(s,3H),1.36(s,6H).

(D2.2): the synthesis step according to general synthetic schemes I-R3:

By N⁴,N⁴'-bis-(4-methoxyphenyl) biphenyl-4,4'-diamines (0.60g; 1.5mmol) with from previously Product (the 1.89g of synthesis step I-R2; 3.5mmol) under nitrogen, add t-BuONa (0.48g; 5.0mmol) in the solution in 30ml ortho-xylene. Add acid chloride (0.04g; 0.18mmol) and P(t-Bu)₃At hexane (0.62ml; 10 % by weight solution 0.21mmol), and by reactant mixture At 125 DEG C, stir 6 hours. Subsequently by mixture by 100ml dilution with toluene and pass throughCross Filter. Organic phase is through Na₂SO₄Dry, and gained solid is passed through to column chromatography (eluent: 10% acetic acid Ethyl ester/hexane) purify. After this be from THF/ methyl alcohol, precipitate again to obtain light yellow solid (1.6g, Productive rate: 80%).

¹HNMR(400MHz,DMSO-d₆):7.67-7.70(d,4H),7.46-7.53(m,14H), 7.21-7.31(m,4H),7.17-7.18(d,2H),7.06-7.11(m,8H),6.91-7.01(m,22H), 3.75(s,12H),1.35(s,12H).

(E) other formula I compound used according to the invention:

Listed compounds is similar to above-mentioned synthetic obtaining below:

(E1) synthetic example 4: Compound I D320

¹HNMR(300MHz,THF-d₈):δ7.43-7.46(d,4H),7.18-7.23(t,4H), 7.00-7.08(m,16H),6.81-6.96(m,18H),3.74(s,12H)

(E2) synthetic example 5: Compound I D321

¹HNMR(300MHz,THF-d₈):δ7.37-7.50(t,8H),7.37-7.40(d,4H), 7.21-7.26(d,4H),6.96-7.12(m,22H),6.90-6.93(d,4H),6.81-6.84(d,8H), 3.74(s,12H)

(E3) synthetic example 6: Compound I D366

¹HNMR(400MHz,DMSO-d6):δ7.60-7.70(t,4H),7.40-7.55(d,2H), 7.17-7.29(m,8H),7.07-7.09(t,4H),7.06(s,2H),6.86-7.00(m,24H),3.73(s, 6H),1.31(s,12H)

(E4) synthetic example 7: Compound I D368

¹HNMR(400MHz,DMSO-d6):δ7.48-7.55(m,8H),7.42-7.46(d,4H), 7.33-7.28(d,4H),6.98-7.06(m,20H),6.88-6.94(m,8H),6.78-6.84(d,4H), 3.73(s,12H),1.27(s,18H)

(E5) synthetic example 8: Compound I D369

¹HNMR(400MHz,THF-d8):δ7.60-7.70(t,4H),7.57-7.54(d,4H), 7.48-7.51(d,4H),7.39-7.44(t,6H),7.32-7.33(d,2H),7.14-7.27(m,12H), 7.00-7.10(m,10H),6.90-6.96(m,4H),6.80-6.87(m,8H),3.75(s,12H),1.42 (s,12H)

(E6) synthetic example 9: Compound I D446

¹HNMR(400MHz,dmso-d₆):δ7.39-7.44(m,8H),7.00-7.07(m,13H), 6.89-6.94(m,19H),6.79-6.81(d,4H),3.73(s,18H)

(E7) synthetic example 10: Compound I D450

¹HNMR(400MHz,dmso-d₆):δ7.55-7.57(d,2H),7.39-7.45(m,8H), 6.99-7.04(m,15H),6.85-6.93(m,19H),6.78-6.80(d,4H),3.72(s,18H), 1.68-1.71(m,6H),1.07(m,6H),0.98-0.99(m,8H),0.58(m,6H)

(E8) synthetic example 11: Compound I D452

¹HNMR(400MHz,DMSO-d6):δ7.38-7.44(m,8H),7.16-7.19(d,4H), 6.99-7.03(m,12H),6.85-6.92(m,20H),6.77-6.79(d,4H),3.74(s,18H), 2.00-2.25(m,4H),1.25-1.50(m,6H)

(E9) synthetic example 12: Compound I D480

¹HNMR(400MHz,DMSO-d6):δ7.40-7.42(d,4H),7.02-7.05(d,4H), 6.96-6.99(m,28H),6.74-6.77(d,4H),3.73(s,6H),3.71(s,12H)

(E10) synthetic example 13: Compound I D518

¹HNMR(400MHz,DMSO-d6):7.46-7.51(m,8H),7.10-7.12(d,2H), 7.05-7.08(d,4H),6.97-7.00(d,8H),6.86-6.95(m,20H),6.69-6.72(m,2H), 3.74(s,6H),3.72(s,12H),1.24(t,12H)

(E11) synthetic example 14: Compound I D519

¹HNMR(400MHz,DMSO-d6):7.44-7.53(m,12H),6.84-7.11(m, 32H),6.74-6.77(d,2H),3.76(s,6H),3.74(s,6H),2.17(s,6H),2.13(s,6H)

(E12) synthetic example 15: Compound I D521

¹HNMR(400MHz,THF-d₆):7.36-7.42(m,12H),6.99-7.07(m,20H), 6.90-6.92(d,4H),6.81-6.84(m,8H),6.66-6.69(d,4H),3.74(s,12H), 3.36-3.38(q,8H),1.41-1.17(t,12H)

(E13) synthetic example 16: Compound I D522

¹HNMR(400MHz,DMSO-d₆):7.65(s,2H),7.52-7.56(t,2H), 7.44-7.47(t,1H),7.37-7.39(d,2H),7.20-7.22(m,10H),7.05-7.08(dd,2H), 6.86-6.94(m,8H),6.79-6.80-6.86(m,12H),6.68-6.73,(dd,8H),6.60-6.62(d, 4H),3.68(s,12H),3.62(s,6H)

(E14) synthetic example 17: Compound I D523

¹HNMR(400MHz,THF-d₈):7.54-7.56(d,2H),7.35-7.40(dd,8H), 7.18(s,2H),7.00-7.08(m,18H),6.90-6.92(d,4H),6.81-6.86(m,12H),3.75 (s,6H),3.74(s,12H),3.69(s,2H)

(E15) synthetic example 18: Compound I D565

¹HNMR(400MHz,THF-d8):7.97-8.00(d,2H),7.86-7.89(d,2H), 7.73-7.76(d,2H),7.28-7.47(m,20H),7.03-7.08(m,16H),6.78-6.90(m, 12H),3.93-3.99(q,4H),3.77(s,6H),1.32-1.36(s,6H)

(E16) synthetic example 19: Compound I D568

¹HNMR(400MHz,DMSO-d6):7.41-7.51(m,12H),6.78-7.06(m, 36H),3.82-3.84(d,4H),3.79(s,12H),1.60-1.80(m,2H),0.60-1.60(m,28H)

(E17) synthetic example 20: Compound I D569

¹HNMR(400MHz,DMSO-d6):7.40-7.70(m,10H),6.80-7.20(m, 36H),3.92-3.93(d,4H),2.81(s,12H),0.60-1.90(m,56H)

(E18) synthetic example 21: Compound I D572

¹HNMR(400MHz,THF-d8):7.39-7.47(m,12H),7.03-7.11(m,20H), 6.39-6.99(m,8H),6.83-6.90(m,8H),3.78(s,6H),3.76(s,6H),2.27(s,6H)

(E19) synthetic example 22: Compound I D573

¹HNMR(400MHz,THF-d8):7.43-7.51(m,20H),7.05-7.12(m,24H), 6.87-6.95(m,12H),3.79(s,6H),3.78(s,12H)

(E20) synthetic example 23: Compound I D575

¹HNMR(400MHz,DMSO-d6):7.35-7.55(m,8H),7.15-7.45(m,4H), 6.85-7.10(m,26H),6.75-6.85(d,4H),6.50-6.60(d,2H),3.76(s,6H),3.74(s, 12H)

(E21) synthetic example 24: Compound I D629

¹HNMR(400MHz,THF-d₈):7.50-7.56(dd,8H),7.38-7.41(dd,4H), 7.12-7.16(d,8H),7.02-7.04(dd,8H),6.91-6.93(d,4H),6.82-6.84(dd,8H), 6.65-6.68(d,4H)3.87(s,6H),3.74(s,12H)

(E22) synthetic example 25: Compound I D631

¹HNMR(400MHz,THF-d₆):7.52(d,2H),7.43-7.47(dd,2H), 7.34-7.38(m,8H),7.12-7.14(d,2H),6.99-7.03(m,12H),6.81-6.92(m,20H), 3.74(s,18H),2.10(s,6H)

(F) formula IV compound is synthetic:

(a) P-nethoxyaniline and 2-are bromo-9, the coupling of 9-dimethyl-9H-fluorenes

To 0.24ml (0.08mmol) P (t-Bu)₃And 0.1gPd (d=0.68g/ml)₂(dba)₂[=(three (two Asias Benzylacetone) two palladiums (0)] add 10-15ml toluene (anhydrous, 99.8%) in (0.1mmol), and this is mixed Compound at room temperature stirs 10 minutes. Add 1.44g (15mmol) sodium tert-butoxide (97.0%), and should Mixture at room temperature stirs 15 minutes again. Subsequently, add 2.73g (11mmol) 2-bromo-9,9-diformazan Base-9H-fluorenes, and this mixture is at room temperature stirred 15 minutes again. Finally, add 1.23g (10mmol) P-nethoxyaniline, and this mixture is stirred 4 hours at 90 DEG C.

Reactant mixture is mixed with water, and this product is precipitated by hexane. Additionally extract with ethyl acetate Water intaking phase. The solid of organic phase and the precipitation leaching is merged, and pass through at SiO₂Phase (10:1 hexane: Ethyl acetate) upper column chromatography and purifying.

Obtain 1.5g (productive rate: 47.6%) yellow solid.

¹HNMR(300MHz,C6D6):6.7-7.6(m,11H),5.00(s,1H,),3.35(s,3H), 1.37(s,6H)

(b) from the coupling of product and three (4-bromophenyl) amine of (a)

To 0.2ml (0.07mmol) P (t-Bu)₃(D=0.68g/ml) and in 0.02g (0.1mmol) acid chloride Add 25ml toluene (anhydrous), and this mixture is at room temperature stirred 10 minutes. Add 0.4g (1.2 Mmol) sodium tert-butoxide (97.0%), and this mixture is at room temperature stirred 15 minutes again. Subsequently, Add 0.63g (1.3mmol) three (4-bromophenyl) amine, and this mixture is stirred 15 minutes again. Finally, Add the product of 1.3g (1.4mmol) from (a), and this mixture is stirred 5 hours at 90 DEG C.

Reactant mixture is mixed with frozen water, and will be extracted by ethyl acetate. By this product by hexane/ The mixture precipitation of ethyl acetate, and pass through at SiO₂Phase (9:1-> 5:1 hexane: ethyl acetate gradient) on Column chromatography and purifying.

Obtain 0.7g (productive rate: 45%) yellow product.

¹HNMR(300MHz,C6D6):6.6-7.6(m,45H),3.28(s,9H),1.26(s,18H) (G) Compound I D504's is synthetic:

Start preparation (referring to Chemical by (4-bromophenyl) two (9,9-dimethyl-9H-fluorenes-2-yl) Communications, 2004,68-69), its first with 4,4,5,5,4', 4', 5', 5'-prestox-[2,2'] (step a) in two [[1,3,2] dioxy boron penta encircles] reaction. After this with 9Br-DIPP-PDCI coupling (step B). Hydrolysis obtains acid anhydride (step c), and obtain subsequently final compound with glycine reactant after this (steps d).

Step a:

By 30g (54mmol) (4-bromophenyl) two (9,9-dimethyl-9H-fluorenes-2-yl), 41g (162mmol) 4,4,5,5,4', 4', 5', 5'-prestox-[2,2'] two [[1,3,2] dioxy boron penta encircles], 1g (1.4mmol) Pd(dpf)₂Cl₂, 15.9g (162mmol) potassium acetate and 300ml bis-The mixture of alkane is heated to 80 DEG C And stir 36 hours.

After cooling, except desolventizing residue is dry in vacuum drying chamber at 50 DEG C.

Purify by filtering eluent 1:1 n-hexane for silica gel: carrene carries out. Removing reactant After, eluent is become to carrene. With red and viscous residue separated product. This passes through at RT Lower stirring methanol extraction. Leach light sediment. At 45 DEG C, in vacuum drying chamber, be dried it After, obtaining 24g light color solid, this is corresponding to 74% productive rate.

Analyze data

¹HNMR(500MHz,CD₂Cl₂,25℃):δ=7.66-7.61(m,6H);7.41-7.4(m, 2H);7.33-7.25(m,6H);7.13-7.12(m,2H);7.09-7.07(m,2H);1.40(s,12H); 1.32(s,12H)

Step b:

17.8g (32mmol) 9Br-DIPP-PDCI and 19ml (95mmol) 5MNaOH are introduced 500ml bis-In alkane. This mixture is used to argon-degassed 30 minutes. Then add 570mg (1.1mmol)Pd[P(tBu)₃]₂And 23g (38mmol) step a and by this mixture at 85 DEG C and argon gas Lower stirring 17 hours.

Purify by column chromatography eluent 4:1 carrene: toluene carries out.

Obtain 22.4 purple solids, this is corresponding to 74% productive rate.

Analyze data:

¹HNMR(500MHz,CH2Cl2,25℃):δ=8.59-8.56(m,2H);8.46-8.38 (m,4H);8.21-8.19(d,1H);7.69-7.60(m,6H);7.52-7.25(m,17H);2.79-2.77 (m,2H);1.44(s,12H);1.17-1.15(d,12H)

Step c:

22.4g (23mmol) step b and 73g (1.3mol) KOH are introduced to 200ml2-methyl-2-fourth In alcohol, and this mixture is stirred 17 hours under refluxing.

After cooling, reactant mixture is added in the concentrated acetic acid of 1L frozen water+50ml. Orange is brown Look solid filter glass material also washes with water.

Solid is dissolved in carrene and extracts with demineralized water. Acetic acid concentrated 10ml is added and had Machine mutually in, it is stirred under RT. Solvent is removed from this solution. Residue passes through at RT Methanol extraction for lower stirring 30 minutes, by frit suction strainer filter and at 55 DEG C in vacuum drying Dry in case.

This obtains 17.5g purple solid, and this is corresponding to 94% productive rate.

This product is without purifying for next step.

Steps d:

By 17.5g (22mmol) step c, 16.4g (220mmol) glycine and 4g (22mmol) zinc acetate Introduce in 350mlN-methyl pyrrolidone, and this mixture is stirred 12 hours at 130 DEG C.

After cooling, reactant mixture is added in 1L demineralized water. By sediment filter glass material, Wash with water and in vacuum drying chamber, be dried at 70 DEG C.

Purify by eluent 3:1 carrene for column chromatography: ethanol+2% triethylamine carries out. Through dividing From product by stirring and use 50% acetic acid extraction at 60 DEG C. Leach solid by frit suction strainer, Wash with water and in vacuum drying chamber, be dried at 80 DEG C.

Obtain 7.9g purple solid, this is corresponding to 42% productive rate.

Analyze data:

¹HNMR(500MHz,THF,25℃):δ=8.37-8.34(m,2H);8.25-8.18(m, 4H);8.12-8.10(d,1H);7.74-7.70(m,4H);7.59-7.53(m,4H);7.45-7.43(m, 4H);7.39-7.37(m,2H);7.32-7.22(m,6H);4.82(s,2H);1.46(s,12H)

(H) Compound I D662's is synthetic:

ID662 by make corresponding commercial hydroxamic acid [2-(4-butoxy phenyl)-N-hydroxyl acetamide] with NaOH reacts and prepares.

Reference numeral is enumerated

110 photovoltaic elements

112 dye solar cells

114 substrates

116 first electrodes

118 barrier layers

120n-semiconduction material

122 dyestuffs

124 carrier elements

126p-semiconductor

128 matrix materials

130 are the silver of oxidised form

132 second electrodes

134 layers of structure

136 seal

138 fermi levels

140HOMO

142LUMO

144 do not have the feature of the silver-colored control sample that is oxidised form, t=0

146 do not have the feature of the silver-colored control sample that is oxidised form, t=2 days

The feature of 148 embodiment 1 samples, t=0

The feature of 150 embodiment 1 samples, t=2 days

Claims

1. one kind for electromagnetic radiation being changed into the photovoltaic element (110) of electric energy, wherein said photovoltaic unit Part (110) comprises at least one first electrode (116), at least one n-semiconduction metal oxide (120), at least one absorption of electromagnetic radiation dyestuff (122), at least one SOLID ORGANIC p-semiconductor (126) and at least one second electrode (132), wherein p-semiconductor (126) comprises the silver that is oxidised form (130)。

2. according to the photovoltaic element of claim 1 (110), wherein said p-semiconductor can pass through will be at least A kind of p-electric conductivity organic material (128) and the silver that is oxidised form are applied at least one carrier element And produce or by its production.

3. according to the photovoltaic element of claim 2 (110), wherein silver is with at least one salt [Ag⁺]_m[A^m-] Form apply, wherein A^m-For organic acid anion.

4. according to the photovoltaic element of claim 3 (110), wherein [A^m-] there is the structure of formula (II):

And wherein X be-O-or-N^--R^b，

And wherein R^bComprise fluorin radical-F or cyano group,

And wherein R^bFurther contained-S (O)₂ ^-Group.

5. according to the photovoltaic element of claim 4 (110), wherein R^aBe selected from-F ,-CF₃、-CF₂-CF₃ With-CH₂-CN。

6. according to the photovoltaic element (110) of claim 4 or 5, wherein X is-N^--R^b, and wherein R^bBe selected from-S (O)₂-F、-S(O)₂-CF₃、-S(O)₂-CF₂-CF₃With-S (O)₂-CH₂-CN。

7. according to the photovoltaic element (110) of any one in claim 3-5, wherein [A^m-] be selected from two trifluoros Sulfonyloxy methyl imines, two trifluoroethyl sulfimide, two fluorine sulfimide and trifluoromethane sulfonic acid root.

8. according to the photovoltaic element of claim 3 (110), wherein [A^m-] be trifluoroacetic acid root.

9. according to the photovoltaic element of claim 3 (110), wherein [A^m-] be NO₃ ^-。

10. according to the photovoltaic element (110) of any one in claim 3-5, wherein said p-semiconductor Can pass through at least one p-electric conductivity organic material (128) and at least one salt [Ag⁺]_m[A^m-] apply Produce at least one carrier element or produce by it, wherein apply by by described in comprising at least A kind of p-electric conductivity organic material and at least one salt [Ag⁺]_m[A^m-] liquid deposition and carry out.

11. according to the photovoltaic element of claim 10 (110), and wherein said liquid phase further comprises at least A kind of solvent.

12. according to the photovoltaic element of claim 11 (110), and wherein said solvent is organic solvent.

13. according to the photovoltaic element of claim 11 (110), and wherein said solvent is selected from cyclohexanone, chlorine Benzene, benzofuran, cyclopentanone.

14. according to the photovoltaic element of claim 11 (110), wherein Ag⁺Substantially described in being uniformly distributed in In p-electric conductivity organic material (128).

15. according to the photovoltaic element (110) of claim 11 or 14, and wherein said p-electric conductivity is organic Material (128) comprises the organic p-semiconductor of at least one low-molecular-weight (126).

16. according to the photovoltaic element (110) of any one in claim 2-5, wherein said p-electric conductivity Organic material (128) comprises spiro-compound and/or has the compound of following structural formula:

Wherein:

A¹、A²、A³Be replacement or unsubstituted aryl or heteroaryl independently of one another,

Wherein A⁴For aryl or heteroaryl, and

Wherein in formula I, n is 0,1,2 or 3 value independently in each case,

17. according to the photovoltaic element of claim 16 (110), and wherein said spiro-compound is spiro-MeOTAD。

18. according to the photovoltaic element (110) of any one in claim 1-5, and it further comprises at least Seal for one, wherein design seals to protect photovoltaic element (110) in case surrounding atmosphere.

19. according to the photovoltaic element (110) of any one in claim 1-5, and it further comprises at least Seal for one, wherein design was sealed with guard electrode (116,132) and/or p-semiconductor (126) in case week Enclose atmosphere.

20. according to the photovoltaic element of claim 10 (110), and wherein said liquid phase is with 0.5-50mM/ml Concentration comprise described at least one salt [Ag⁺]_m[A^m-]。

21. according to the photovoltaic element of claim 11 (110), and wherein said liquid phase is with 0.5-50mM/ml Concentration comprise described at least one salt [Ag⁺]_m[A^m-]。

22. according to the photovoltaic element (110) of any one in claim 1-5, and it is dye solar electricity Pond (112).

23. 1 kinds of productions are used for the method for the SOLID ORGANIC p-semiconductor (126) that has thermomechanical components, wherein will At least one p-electric conductivity organic basis material (128) and the silver that is at least oxidised form are by least one Liquid phase is applied at least one carrier element, wherein [A]^-For the anion of organic acid or inorganic acid.

24. according to the method for claim 23, and wherein said to have thermomechanical components be according to claim 1-22 The photovoltaic element (110) of middle any one.

25. according to the method for claim 23, and wherein said liquid phase further comprises at least one solvent.

26. according to the method for claim 25, and wherein said solvent is organic solvent.

27. according to the method for claim 25, and wherein said solvent is selected from cyclohexanone, chlorobenzene, benzo Furans, cyclopentanone.

28. according to the method for any one in claim 23-27, and wherein said method exists at least in part In hypoxic atmosphere, carry out.

Produce the method for photovoltaic element (110), wherein, in described method, provide at least one for 29. 1 kinds Individual the first electrode (116), at least one n-semiconduction metal oxide (120), at least one electromagnetism spoke Penetrate absorbability dyestuff (122), at least one SOLID ORGANIC p-semiconductor (126) and at least one the second electrode (132), wherein said p-semiconductor (126) is by raw according to the method for any one in claim 23-28 Produce.