TW201114844A - Novel organic dye and preparation thereof - Google Patents

Abstract

The present invention relates to a novel organic dye for a dye-sensitized photoelectric conversion device, and a preparation method thereof. The organic dye according to the present invention is used as a dye-sensitized photoelectric conversion device in a dye-sensitized solar cell (DSSC) and provides improved molar absorptivity, Jsc (short circuit photocurrent density) and photoelectric conversion efficiency when compared with known dyes, thereby being capable of remarkably improving the efficiency of the solar cell.

Description

201114844 VI. Description of the Invention: [Technical Field] The present invention relates to an organic organic device for increasing or decreasing photoelectric conversion elements used in dye-sensitized solar cells (DSSC). Dyes and preparation methods thereof. BACKGROUND OF THE INVENTION Since the development of the dye-sensitized nanoparticle oxidized solar cell by the Michael Gratzel research team at the Swiss National Lausanne Institute of Advanced Technology (EPFL) in 1991, many studies have been conducted in this field. Because it is more efficient and the manufacturing unit price is significantly lower than the original lanthanide solar cell's dye-sensing solar cell, it is expected to replace the original amorphous 太阳能 solar electric field. Unlike Shishi solar cells, dye-sensing solar cells are photoelectrochemical solar cells that use a dye that absorbs visible light to generate electron holes and a transition metal oxide that transports the generated electrons. Composition material. As a conventional dye-sensing solar cell, a base metal complex exhibiting high photoelectric conversion efficiency has been widely used in the past. However, the base metal complex has a drawback that it is very expensive. Recently, an organic dye containing no metal which exhibits excellent physical properties in terms of light absorption efficiency 'redox reaction stability and intramolecular charge-transfer (CT) absorption has been found, and dyes for solar cells using dyes can be used. Instead of the expensive metal complexes, weighed 201114844 to conduct research on organic dyes that do not contain metals. In general, an organic dye has a structure in which an electron donor-electron acceptor residue which is connected through a π bond unit is formed in most organic dyes and amine derivatives. The task of the electron donor, and the 2-cyanoacrylic or rhondanine residue fulfills the task of the electron acceptor, and the two sites are transmitted through, for example, amethine (〇16 to 111 magic unit or thiophene). The π bond system of the chain is linked. Usually, the electronic characteristics of the absorption spectrum, which has been shifted to the blue side, are changed by the change in the configuration of the electron donor, that is, the amine unit, and passed. The change in the length of the 7Γ bond can adjust the absorption spectrum and the redox potential. However, most organic dyes that have been known in the past exhibit low conversion efficiency and low drive stability compared to the base metal complex. Sexuality, the actual situation is to develop a molar absorption coefficient that is significantly improved compared to the previous organic dye by changing the type of such electron donor and acceptor or the length of the π bond ( The effort of the novel extinction coefficient and the novel dyes exhibiting high photoelectric conversion efficiency is continuously carried out. C SUMMARY OF THE INVENTION: SUMMARY OF THE INVENTION Problem to be Solved The object of the present invention is to provide a dye which is comparable to the prior metal complex dyes. An organic dye for increasing or decreasing the efficiency of a dye-sensing solar cell, which is capable of greatly improving the efficiency of a dye-sensing solar cell, without increasing the optical absorption coefficient and the photoelectric conversion efficiency. 4 201114844 A further object of the present invention is to provide a method for preparing the aforementioned organic dye. Another object of the present invention is to provide a dye-increasing/degrading photoelectric conversion element which exhibits a remarkable improvement in photoelectric conversion efficiency, and which has excellent Jsc (short-circuit photo current density) and molar absorption coefficient, and contains the aforementioned organic dye. And a solar cell having a significantly improved efficiency. The means for solving the problem is based on the above object, and the present invention provides an organic dye for dye addition and subtraction of a photoelectric conversion element represented by Chemical Formula 1 or 2. [Chemical Formula 1]

In the above formula, 201114844, at this time, eight^ to eight!·?? are independently substituted or unsubstituted c6-c50 aryl groups, or at least two or more of eight to eight! N together form a heterocyclic ring,

COOH

The An lines are each independently selected from COOH

, 0 I

Si-0

and

The group consisting of, *, the bonding sites, 0 and P are each independently 0 or 1, and R1 and R2 are each independently an alkyl group of CM2, a substituted or unsubstituted C6-3Q aryl group. And substituted or unsubstituted heteroaryl groups of C6^) or linked to each other to form a heterocyclic ring containing a hetero atom selected from the group consisting of N, 0 and S, 201114844 R4

Sp lines are each independently selected from \R3 R4

The group consisting of NR9, R3 and R4 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted CM2 alkyl, substituted or unsubstituted, fluorenyl, and substituted or unsubstituted Cwo heteroaryl. The above or the other may be linked to each other to form a ring, and each of R5 to R9 is independently hydrogen or a substituted or unsubstituted (^-12 alkyl group, η is an integer of 1 to 1 。. Further, the present invention provides A method for producing the above organic dye, comprising the steps of: (1) a step of producing a compound of Chemical Formula 5 by coupling a compound of the following Chemical Formula 3 with a compound of the following Chemical Formula 4; (2) a compound of the above Chemical Formula 5; After reacting with n-bromosuccinimide in an organic solvent to produce a compound of formula 6, it is reacted with BuLi in 1-mercaptopiperidine or the compound of formula 5 is organically a step of reacting with BuLi in a solvent to produce a compound of Chemical Formula 7; and (3) a step of reacting a compound of the above Chemical Formula 7 with a compound providing a docking group in the presence of CHKN.

[Chemical Formula 3]

A-W [Chemical Formula 4]

[Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] In the above formula, 0 II /—P(〇Et) 2 w is *—B(〇H) 2 or /

8 8 201114844 Y series Br or *, CH〇 A, RI, R 2 , Sp, 〇 and p are as defined above. According to the present invention, the present invention provides a dye-increasing and dimming-changing type which contains an oxide semi-conductive particle; and the aforementioned organic dye which is supported by a prior art. According to another aspect of the invention, the present invention provides a dye-sensing 7 battery which is used as an ageing material. EFFECTS OF THE INVENTION The dye compound of the present invention is used in a dye-sensing solar cell, a ΜτMoule absorption coefficient, a Μ short-circuit photocurrent density, and a photoelectric efficiency, which can greatly improve the efficiency of a solar battery. MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The term "hospital" as used throughout this specification means a linear or branched saturated Cl to Q (tetra) radical chain. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, and hexyl group, but are not limited thereto. . In this book, θ θ i. The aryl group of hydrazine is a ring system formed by arbitrarily substituted benzene rings or one or more optional substituents. Examples of the substituent which may be any substituent include a substituted filament, a substituted CM dilute group, a substituted c2.3 alkynyl group, a heteroaryl group, a heterocyclic group, an aryl group, with or without 1 to 3 The base of the Wei substituent, the dilute propoxy group, the aryloxy group 201114844 (aralkoxy), the fluorenyl group, the aryl fluorenyl group, the heteroaryl aryl milk; and the aryl oxoxide, the aforementioned ring or ring system can be arbitrarily fused to have or An aromatic ring (including a benzene ring) having no oxime & oxime group, a carbocyclic or heterocyclic ring. Examples of the "4" or more of the square base J include a phenyl group, a naphthyl group, a tetrahydronaphthyl group, a biphenyl group, an anthracyl group, an anthracyl group, a phenanthryl group, and the like. However, the "heteroaryl group" in this specification is a single-membered 5-member to 6-membered aromatic ring having a hetero atom such as oxygen, sulfur or nitrogen in the ring. It means an aromatic ring (for example, a bicyclic or tricyclic ring system) which is fused to one or more rings such as a heterocyclic ring, an aromatic ring, a heterocyclic ring or a carbocyclic ring. Examples of the heteroaryl group include a t group, a scaly group, an anthrace group, a decyl group, a hetero group, a fluorenyl group, a furanyl group, a thiophenyl group, a benzofuran $, a benzothiophene group. , carbazolyl, imidazolyl 'thiazolyl' isoxazolyl (iS〇xaz〇iyi), pyrazolyl, isothiazolyl, quinolyl, isoquinolinyl, hydrazine, pyrimidinyl, pyrene Base (these may be substituted or unsubstituted), etc., but is not limited by this. In the present specification, "substituted" or "substituted" means that at least one hydrogen of a compound or an active group is selected from the group consisting of dentate 'alkyl, alkenyl, alkynyl, aryl, alkoxycarbonyl, and nitrate. Substituents substituted by a group consisting of a group, an alkyl group, an amine group, an alkylcarbamate group, a cycloalkyl group, a cyano group, and a thiol group. The "*" in the entire specification means the bonding portion. The organic dye according to the present invention has a structure of the following Chemical Formula 1 or 2, which is characterized in that when a dye-sensing solar cell (DSSC) is used as a dye-increasing/decreasing photoelectric conversion element, it exhibits an elevated Mob absorption coefficient, Jsc (short circuit). Photocurrent density) and photoelectric conversion efficiency: 8 10 201114844 [Chemical Formula 1]

In the above formula

Ar2

-Ar Factory N

Ar3 Α 此时 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 ring,

The An series of anchoring groups are each independently selected from

201114844

Here, the *-bonding moiety, 0 and p are each independently 〇 or 1, and the heart and the 尺 2 are each independently an alkyl group of CM2, an aryl group of a substituted or unsubstituted Cho, and a substituted or unsubstituted group. a heteroaryl group, or a heterocyclic group containing a hetero atom selected from the group consisting of N, 0, and S, and a spacer group, each independently selected from

One or more of the group consisting of the 'L series are each independently selected from the group consisting of ruthenium, s ' cr5r6, SiR7R8, and NR9, and each of R3 and R4 is independently selected from hydrogen, substituted or unsubstituted CM2. One or more groups of a group consisting of a fluorenyl group, a substituted or unsubstituted fluorene group, a 6-3 aryl group, and a substituted c6-20 heteroaryl group, and light B 5 is not. Attacks*"^ can also form a ring with each other, and R5 to R9 are independently hydrogen or accommodating

Cm2 yard base, η is an integer from 1 to 10. "" Take the generation of 12 201114844 is preferably in the aforementioned chemical formula 1 or 2, the aforementioned A system

In this case, Ar1 to Ar3 are each independently an aryl aryl group or an alkyl group-substituted C6_C5 aryl group, and a phenyl group/methyl fluorenyl group is more preferable.

0 and p are each independently 〇 or 1, and the phenylthio groups R1 and R2 are simultaneously hydrogen, or are linked to each other and to the neighbors.

#同形成基

13 201114844 In groups. Specific examples of the organic dye of the present invention include compounds having the following chemical formula. [Chemical Formula 8]

8 14 201114844 [Chemical Formula 10]

[Chemical Formula 11]

15 201114844 [Chemical Formula 12]

[Chemical Formula 13]

201114844 [Chemical Formula 14]

[Chemical Formula 15]

17 201114844 [Chemical Formula 16]

8 18 201114844 [Chemical Formula 18]

[Chemical Formula 19]

19 201114844 [Chemical Formula 20]

[Chemical Formula 21]

8 20 201114844 [Chemical Formula 22]

[Chemical Formula 23] 201114844 [Chemical Formula 24]

[Chemical Formula 25]

8 22 201114844 [Chemical Formula 26]

[Chemical Formula 27]

23 201114844 [Chemical Formula 28]

[Chemical Formula 29]

[Chemical Formula 30]

8 24 201114844 [Chemical Formula 31]

[Chemical Formula 32]

[Chemical Formula 33]

25 201114844 [Chemical Formula 34]

[Chemical Formula 35]

[Chemical Formula 36]

8 201114844 [Chemical Formula 37]

[Chemical Formula 38]

27 201114844 [Chemical Formula 39]

[Chemical Formula 40]

[Chemical Formula 41]

28 201114844 [Chemical Formula 42]

[Chemical Formula 43]

[Chemical Formula 44]

29 201114844 [Chemical Formula 45]

[Chemical Formula 46]

8 30 201114844 [Chemical Formula 47]

[Chemical Formula 48]

31 201114844 [Chemical Formula 49]

[Chemical Formula 50]

The organic dye of the present invention is produced by a production method comprising the following steps. (1) a step of producing a compound of Chemical Formula 5 by coupling a compound of the following Chemical Formula 3 with a compound of the following Chemical Formula 4; (2) Compound of the above Chemical Formula 5 in an organic solvent with N-bromosuccinimide After reacting to produce a compound of Chemical Formula 6, it is reacted with BuLi in 1-formylpiperidine or the compound of Chemical Formula 5 in an organic solvent with 8 32 201114844

a step of reacting a BuLi reaction to produce a compound of the formula 7; and (3) a step of reacting the compound of the above formula 7 with a compound which provides a docking group in the presence of CH3CN and piperidine. [Chemical Formula 3]

A——W [Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

[Chemical Formula 7]

In the above formula, 33 201114844 W series b(〇h)2 or Ο II /P(〇Et)2

Y series Br or * - CHO, A, R1, R2, Sp, 〇 and p are as defined above. Specifically, first, a compound of the above Chemical Formula 3 is coupled with a compound of the above Chemical Formula 4 to produce a compound of Chemical Formula 5. The coupling reaction is in the chemical formula 3, and when the substituent W is B(OH)2, it is in the presence of a catalyst such as Pd(PPh3)4 or a base such as K2C03, such as dimethylformamide (DMF). It is preferred to carry out the reaction with Y, which is a compound of the formula 4, in the organic solvent, etc., and in the chemical formula 3, the substituent W is 0.

When II /~P(QEt)2, in the presence of a catalyst such as t-Bu〇-K+, it is reacted with a compound of the formula 4 in the organic solvent such as tetrahydrofuran (THF) and Y is *-CH0. It is better to implement it. In this case, the compounds of Chemical Formulas 3 and 4 used as starting materials can be produced by a usual method or commercially. Specific examples of the above Chemical Formula 3 include

BfOHiz or 34 201114844

In the case of the coupling reaction, the compound of the above Chemical Formula 3 is preferably used in an amount of from 2 to 2.5 mols per mol of the compound of the formula 4 . After the dimethylformamide is used, the compound of the chemical formula 5, (DMF) or the like is reacted with an N-bromosuccinimide to produce a compound of the chemical formula 6 ^ The compound of the formula 7 is produced by reacting it with BuLi in the formylpiperidine. At this time, the compound of the chemical formula 5 is preferably used in the range of 〇4 to 〇.5 mol relative to the 丨Molar NBS, and the compound of the chemical formula 6 formed by the reaction is used in the range of 0.4 to 0.5 with respect to the 丨Moole BuU. Further, as another method, the compound of Chemical Formula 5 prepared in the above step (1) is reacted with BuU in an organic solvent such as DMF to produce a compound of Chemical Formula 7. In this case, the compound of Chemical Formula 5 is preferably used in the range of 〇·4 to 0'5 mol with respect to 1 mol of BuLi. The organic dye of the present invention can be produced by providing the compound of the chemical formula 7 obtained in the presence of a bite in CH3CN at the bottom of the CH3CN to provide a compound bond with the anchoring group of cyanoacetic acid or the like. The compound of Chemical Formula 7 provides a compound relative to a 1 molar anchoring group, preferably from 0.4 to 0.5 moles. Specifically, the organic dye of the present invention can be produced by the methods described in the following Reaction Formula 1 to Reaction Formula 4, but this is merely an example, and the present invention is not limited thereto. [Reaction formula 1]

36 201114844 [Reaction formula 2]

[Reaction formula 3]

37 201114844 [Reaction 4]

The organic dye of the present invention produced according to the aforementioned manufacturing method is used as a dye-sensitized solar cell (DSSC) as a dye-increasing/decreasing photoelectric conversion element, and exhibits a molar absorption coefficient, a Jsc (short-circuit photocurrent density), and a photoelectric conversion efficiency. The dye is improved to greatly improve the efficiency of the solar cell. Accordingly, the present invention provides a dye up-and-down photoelectric conversion element comprising the aforementioned organic dye. Specifically, the dye-increasing/decreasing photoelectric conversion device according to the present invention is characterized in that it contains oxide semiconductor fine particles and the organic dye supported by the oxide semiconductor fine particles. Of course, the dye addition-reduction photoelectric conversion element of the present invention can employ a method of producing a dye-enhanced photoelectric conversion element using a usual dye in addition to the use of the above-mentioned organic dye, and it is preferable to increase or decrease the photoelectric conversion of the dye of the present invention.

(S 38 201114844 The replacement element is capable of producing a thin film of an oxide semiconductor on a substrate by using the oxide semiconductor fine particles, and then the film is produced by supporting the organic dye according to the present invention. At this time, as a film forming an oxide semiconductor The substrate may preferably be electrically conductive on the surface thereof, and may be commercially available. As a specific example, it is possible to use transparency in glass, or polyethylene terephthalate, or sputum. The surface of the molecular material is formed by a thin film of a conductive metal oxide such as tin oxide coated with indium, I or bismuth, or a metal thin film such as copper, silver or gold. In this case, the conductivity is usually 1000 Ω. The following is preferable, and it is particularly preferably 100 Ω or less. As the oxide semiconductor fine particles, a metal oxide is preferable, and specific examples thereof include titanium, tin, zinc, tungsten, lanthanum, potassium, indium, ruthenium, iridium, An oxide such as a button or vanadium. Among these, an oxide such as titanium 'tin, rhenium, energy, or indium is preferred. 'Titanium oxide, zinc telluride, and tin oxide are more preferred, and titanium oxide is preferred. The oxide semiconductor may be used singly or after being mixed and applied to the surface of the semiconductor. The particle diameter of the vaporized semiconductor fine particles is preferably from 1 to 10 nm, and preferably from 1 to 10 Å. Further, the fine particles of the oxide semiconductor may be used by mixing a large particle size with a small particle size and forming a plurality of layers. The oxide semiconductor film can be produced by the following method: A method of forming a thin film directly on a substrate by atomization of an oxide semiconductor fine particle or the like; a method of using the substrate as an electrode to electrically deposit a thin film of the semiconductor fine particle; and agglomerating the semiconductor fine particle or semiconductor; A method in which a fine particle-containing paste prepared by hydrolyzing a precursor of a semiconductor fine particle is coated on a substrate, dried, hardened or calcined, etc., wherein a method of applying a paste to a substrate is preferred. In the method of slurry of semiconductor fine particles, the slurry can be used by agglomerating oxide semiconductor fine particles twice The dispersion method is obtained by dispersing the average primary particle diameter of 1 to 2 〇〇 ηηη in a dispersion medium. The dispersion medium for dispersing the slurry is not particularly limited as long as it can disperse the semiconductor fine particles. It is possible to use an alcohol such as water 'ethanol; a ketone such as acetone or acetalacetone; or a hydrocarbon such as hexane; or a mixture of δ 玄, etc., in which the viscosity of the slurry is reduced. In addition, it is preferable to use water as a dispersion medium, and a dispersion stabilizer can be used for the purpose of stabilizing the dispersion state of the oxide semiconductor fine particles. Specific examples of the dispersion stabilizer that can be used include acetic acid. Acid, hydrochloric acid, nitric acid, etc.; acetal acetone; acrylic acid; polyethylene glycol; polyvinyl alcohol, etc. Subsequently, when calcined after coating the slurry, the calcination temperature is loot: or more, preferably 200 C or more, and The upper limit is substantially the melting point (softening point) of the substrate. Hereinafter, the upper limit is usually 9 Å, preferably 600 t or less. In the present invention, the calcination time is not particularly limited, and is preferably about 4 hours. In the present invention, the thickness of the edge film of the oxide semiconductor fine particles formed on the substrate is preferably from 1 to 20 μm, more preferably from 1 to 2. Further, a part of the film of the oxide semiconductor fine particles is fused during calcination, but such a fusion does not particularly affect the present invention. 8 40 201114844 The above oxide semiconductor film can be subjected to two treatments. As an example, (4) by φ directly according to the county (four) color and semiconductor of the same metal oxide, chloride, nitride, sulfide and other solutions and dry, or again: to improve the performance of the semiconductor film. Examples of the metal-burning oxygen include titanium ethoxide, titanium isopropoxide, and octa-butyl oxidized, and butyl ethyl-tin ruthenium. In this case, an alcohol can be used as a solvent to form an alcohol. Use it for money. As the vapor, for example, (vaporized, tin chloride, zinc chloride, etc.) can be used as a solvent, and water can be used as an aqueous solution. The oxide semiconductor thin film thus obtained is made of an oxide. In the present invention, the oxide semiconductor fine particles formed in the form of a film are not particularly limited, and a specific example thereof is a solvent which is sufficiently cold-decomposable using a month b. A solution produced by cold-dissolving an organic dye represented by (1) and (9), or a method of immersing a substrate provided with the oxide semiconductor thin film in a scission liquid produced by dispersing the organic dye. The concentration of the organic dye in the dispersion can be appropriately determined according to the dye. The dye concentration is preferably 1×HT6MJUM, and is preferably 1χ1 (Τ5μ to lxlO^Vl is more preferable. The temperature of the /Beibei is substantially normal temperature to solvent. The temperature and the immersion time are from about 1 minute to about 48 hours. Specific examples of the solvent which can be used for dissolving the dye include decyl alcohol, acetonitrile, and dimercaptoarylene. Dimercaptoamine, propanil, tert-butanol, etc. 41 201114844 Further, the organic dye to be used may be one type or a mixture of several types. The organic dye of the present invention and other organic dyes or metals may be mixed during mixing. The complex compound is mixed together. The metal complex dye which can be mixed is not particularly limited, and is preferably a ruthenium complex or a 4-grade salt thereof, a phthalocyanine or a guanidine, and the other organic dyes may be metal-free. Chitin (such as phthalocyanine, porphyrin or anthocyanin, melocyanine, oxonphthalium, triphenylnonane, acrylic dyes disclosed in WO2002/011213 ( Methine) is a dye, or xanthene, azo, enamel, perylene, etc. (Ref. K. Nazeeruddin, A. Kay, I. Rodicio, R Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos. M_Gratzel, J. Am. Chem. Soc., Vol. 115, p. 6382 (1993)]. When using more than two dyes, The dye is adsorbed to the semiconductor film in order, and it can also be mixed and dissolved to adsorb it. In the case where the film of the oxide semiconductor fine particles is supported by the dye, it is preferred to carry the dye in the presence of the inclusion compound in order to prevent the bonding between the dyes. As the above-mentioned inclusion compound, deoxycholic acid, deaza deoxygenation can be used. Cholic acid such as cholic acid, chodeoxycholic acid, methyl cholate, sodium cholate; steroid compounds such as polyethylene oxide and cholic acid; crown ether; cyclodextrin; calixarene ( Calixarene); polyethylene oxide and the like. Further, after the dye is applied, a substrate provided with a semiconductor fine particle film can be treated with an amine compound such as 4-tert-butyl group or a compound having an acidic group such as acetic acid or propionic acid. The treatment method can be carried out by, for example, impregnating a semiconductor fine particle film provided with a dye in an ethanol solution of an amine.

(Method of substrate of S 42 201114844, etc. In this way, it is possible to obtain a dye addition and subtraction photoelectric conversion element having oxide semiconductor fine particles on a thin film which is increased or decreased by using a dye. The present invention provides a dye induction solar cell, which is characterized by The dye-sensitized solar cell is a photoelectric conversion element electrode (negative electrode), a counter electrode (positive electrode), a redox electrolyte, and an electric charge, which are obtained by using an oxide semiconductor fine particle to hold a dye. The dye-inducing solar cell is used in addition to the use of a dye-enhanced photoelectric conversion 7L (which is obtained by using an oxide semiconductor fine particle containing the organic dye). The photoelectric conversion element is used to manufacture the usual square of the solar cell. As a specific example, the dye-sensing solar cell of the present invention can be manufactured by the steps of: coating a titanium oxide paste on a conductive transparent substrate; calcining Coating the substrate of the paste to form a thin step of titanium oxide a step of immersing a substrate on which a titanium oxide film is formed in a mixed solution obtained by dissolving organic turns to form a gettering material, and a second glass having a counter electrode formed on the upper portion thereof a step of forming a hole through the holes of the second glass substrate and the counter electrode; and a thermoplastic polymer film disposed between the counter electrode and the titanium oxide film formed by adsorbing the dye, and performing a heating pressure a step of bonding to the electrode of the purified titanium electrode; a step of inserting the thermoplastic polymer film A between the counter electrode and the electrode of the titanium oxide film into the electrolyte through the hole; and a step of sealing the heat polymer 43 201114844 It can be used in the form of 'solid (gel and gel), solid, etc. when it can be used in liquid form such as the original electrolysis f, the hole transporting material, and the p-type semiconductor. When used, it can be exemplified by redox The electro-transporting material, the p-type semi-turning station, the fresh soli-electric π-loss tt, etc. are each dissolved in a solvent or dissolved in a normal temperature, etc., when the solidified body (shock gel and gel-like) can be cited as a polymer matrix or low Molecular gel The chemical agent ^ contains these ingredients. When used in a solid form, it can be used.

The solid oxidation also replies to f^ A bismuth electrolysis shell, dissolved salt, hole transport material, and the like.

...with the same material, it is possible to use a well-known hole transporting material 'as a specific example' to use an amine derivative or a conductive polymer such as polyethylidene, polyaniline or polythiophene; or a triacylene system A liquid crystal phase such as a compound or the like. In addition, as a (four) semiconductor, CUI, CUSCN, etc. can be used in multiple sentences. It is preferable that the counter electrode ' is electrically conductive and that the reduction reaction of the redox electrolyte is generated. (4) For example, if the glass or polymer film is vapor-deposited, carbon, money, bismuth, or the like, or the conductive particles are coated as the redox electrolyte, the elemental compound 1 may be used as the counter ion. a metal-transfer-based electrolyte composed of a metal-substituted redox-based electrolyte; a ferrous lactic acid _ ferrous citrate or a ferrocene ferrocene ion, a sulphonate, or the like; An organic redox-based electrolyte such as a thiol thiol-alkyl disulfide or a redox dye, gas, or the like, is preferably a halogen redox-based electrolysis f. The dentate redox electrolyte composed of the dentate compound-i molecule is preferably a moth molecule as a dentate molecule. Further, LiI, 譲'Ki, Cai2, Mgi2 can be used as the "compound" of the sulphate ion as a pair of 44 201114844

Cui et al., a metallized metal salt, or a four-burning base. Meter. Sitting on the rust,. It is more than the organic salt of halogen such as biting rust, or 12. Further, when the redox system is configured in the form of a solution containing the same, it can be used as a solvent in which the electrochemical property is inert. Specific examples thereof include acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, decyloxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butyrolactone, Dimethoxyethane, diphenyl carbonate, u_dioxolane (-o(tetra), methyl f0rmate, 2_mercaptotetrahydrofuran, 3methoxy·cinazole-2 - ketone, cyclobutyl hydrazine, tetrahydrofuran, water, etc., with B guess, propylene carbonate, ethylene carbonate 1, 3 曱 methoxy propionitrile, ethylene glycol 3 曱 今 炫 炫 炫 _2 The solvent may be used in combination or in combination. When the gel electrolyte is used, it is possible to use an electrolyte or an electrolyte solution in a matrix such as an oligomer or a polymer. Alternatively, the low molecular gelling agent or the like may be contained in the same manner as the electrolyte or the electrolyte. The concentration of the redox electrolyte is preferably 0.01 to 99% by weight, more preferably 0.1 to 30% by weight. a solar cell capable of supporting an S-electric conversion element (negative electrode) by using an oxide semiconductor fine particle on a substrate The counter electrode (positive electrode) is disposed in such a manner as to be filled with a solution containing a redox electrolyte therebetween. [Examples] The present invention will be more specifically described below based on the examples. However, the examples are merely Examples of the invention, the invention is not limited by the examples. 45 201114844 Example 1: Synthesis of Chemical Formula 18 1) Synthesis of Intermediate (18a) 4-(Bis(9,9-dimercapto-9H-) -2-yl)amino)phenylboronic acid, 3,4-bis(7-bromo-2,3-dihydrothiophene[3,4-b][l,4]dioxin _5_ group) thiophene 'Pd(PPh1) 2 and 3M ICO1 aqueous solution were mixed in dimethyl decylamine (DMF) and refluxed for 12 hours. The reaction solution obtained as a result was cooled, and water (30 ml) and brine were added, and the organic layer was separated and purified to obtain an intermediate (18a) having the following chemical structural formula. [Intermediate 18a]

46 1 The obtained solid was dissolved in THF, dried over anhydrous magnesium sulfate and 2 solvent THF was removed under reduced pressure to give intermediate (18b) 〇 3 ) intermediate (18b) of the following chemical formula. Synthesis of the solution prepared by adding the above-mentioned (18a) to DMF and stirring to add 'NBS and stirring at 5 (TC for 2 hours. After the resulting reactant was injected into the water and stirred, the resulting solid was formed. Filtration. By making the result 201114844 [intermediate 18b]

3) Synthesis of Intermediate (18c) After the above-prepared (18b) was added to THF, n-BuLi was added under argon while maintaining the temperature at -78 °C. After 30 minutes, 1-carbenylpiperidine was added to the reaction product obtained under the argon atmosphere, and then reacted for 12 hours to obtain an intermediate (18c) of the following chemical formula. [Intermediate 18c]

4) Synthesis of Chemical Formula 18 The above-obtained intermediate (18c) and cyanoacetic acid were mixed, and the obtained mixture was dried under vacuum, and then mixed with MeCN and piperidine and refluxed for 6 hours. After the resulting reaction solution was cooled, the organic layer was removed under vacuum, and the obtained solid matter was subjected to gelatin chromatography to obtain a compound of the following chemical formula. 47 201114844 Elemental Analysis: C, 76.57; Η, 4.82; N, 3 72 ; 〇 . 8.50 ; S ' 6.39 [Chemical Formula 18]

Example 2: Synthesis of Chemical Formula 27 1) Synthesis of Intermediate (27a) Diethyl 4-(bis(9,9-dimethyl-9H--2-yl)amino)phosphonic acid vinegar And 7,7'-(喽 _3,4_diyl) bis(2,3-dihydrothiophene [3,4-b][l,4]dioxin-5-acid), in the third In the presence of potassium butoxide and subjecting it to a Witting reaction in a TFF solution, an intermediate (27a) of the following chemical formula is obtained [Intermediate 27a]

48 201114844 2) Synthesis of the intermediate (27b) In the same manner as in the above-mentioned Example 1, except that the intermediate (27a) produced as described above was used instead of the intermediate (18a), the following chemical structural formula was obtained. Body (27b). [Intermediate 27b]

3) Synthesis of Intermediate (27c) An intermediate of the following chemical formula was obtained by using the same procedure as in Example 1 except that the intermediate (27a) produced above was used instead of the intermediate (18b). 27c). [Intermediate 27c]

4) Synthesis of Chemical Formula 27 The same procedure as in Example 1 above was used except that the intermediate (18c) produced as described above was used instead of the medium 49 201114844 of Example 1, and the same procedure as in the above Example 1 was carried out to the following chemical structure. A compound of formula 27. Elemental analysis: C, 77.10; S, 6.17 Η ' 4.92 ; Ν ^ 3.60 ; 〇 8.22 ; [Chemical Formula 27]

Example 3: Synthesis of Chemical Formula 37 In Example 1 'In addition to the use of 4,4,-bis(7.bromo-2,3-dihydroseptene [3,4-1][1,4]dioxin -5-yl)-2,2'-diphene in place of 3,4-bis(7-bromo-2 3-dihydrothiophene [3,4-b;|[l,4]dioxin-5- The compound of the following chemical structural formula 37 was obtained in the same manner as in the above Example 1 except for the thiophene. Elemental analysis: C, 75.64; Η, 4.70; N, 3.53; 0, 8.06; S, 8.08 50 201114844 [Chemical Formula 37]

Example 4: Synthesis of Chemical Formula 49 except that 7,7'-(2,2'-dithiophene-4,4'-diyl)bis(2,3-dihydrothiophene [3,4-13][1 , 4] Dioxin-5-aldehyde) instead of 7,7'-(thiophene-3,4-diyl)bis(2,3-dihydrothiophene [3,4-b][l,4]dioxene The compound of the following chemical structural formula 49 was obtained in the same manner as in the above Example 1 except for the case of the indole-5-aldehyde. Elemental analysis: C, 76.16; Η, 4.79; N, 3.42; Ο, 7.80; S, 7.82 [Chem. 49]

51 201114844 Manufacture of Dye Induction Solar Cell In order to evaluate the current-voltage characteristic of the dye of the present invention, a dye-sensing solar cell was fabricated using a 13+10 μm TiO 2 transparent layer. Specifically, the washed FTO (Pilkington, 8Qsq_1) glass substrate was immersed in a 40 Mm TiCl4 aqueous solution. A Ti02 paste (Solaronix, 13 nm anatase type) was screen-printed to produce a first Ti02 layer having a thickness of 13 μm. For the light scattering, a thickness of ΙΟμιη was produced using another paste (CCIC, HWP-400). 2 Ti〇2 layer. The manufactured TiO 2 electrode was immersed in the dye solution of the present invention in an ethanol containing 3 mM of 3a, 7a-dihydroxy-5b-cholic acid to make each of the compounds produced in the foregoing Examples 1-4 After being dissolved in 0.3 mM, it was allowed to stand at room temperature for 18 hours. A counter electrode was fabricated by coating a H2PtCl6 solution (containing 2 mg of Pt in 1 mL of ethanol) on an FTO substrate. Subsequently, 0.6 M 3-hexyl-1,2-dimercaptoimidazole iodine, 0.04 M 12, 〇·〇25Μ Lil, 0.05 M guanidinium thiocyanate and 0.28 M tributyl group were placed in acetonitrile. ratio. The dissolved electrolyte is injected into the battery to manufacture a dye-sensing solar cell. The photocell performance of the dye-sensing solar cell was measured using a 1000 w 光源 light source. The results are shown in Table 1. [Table 1] Differentiating efficiency (η) (%) Differentiating efficiency (η) (%) Compound 1 4.8 Compound 3 5.5 Compound 2 5.2 Compound 4 6.2 As shown in Table 1 above, it was found that the dye system of the present invention showed excellent efficiency. The present invention has been described in relation to the specific embodiments, but it is within the scope of the invention defined by the appended claims. And changes. I: Simple description of the figure 3 (none) [Explanation of main component symbols] (none) 53

Claims (1)

201114844 VII. Scope of application for patent: It is based on chemical formula 1. A dye is used to increase or decrease the photoelectric conversion element with organic dye 1 or 2, [Chemical Formula 1] [Chemical Formula 2] A is a substituted or unsubstituted square group independently of Ai*| to Αι*3, or at least two or more of Ar丨 to At"3 may be linked to each other to form a heterocyclic ring with N, An Individually selected from CN COOH 54 201114844 The group consisting of, *, the bonding sites, 0 and P are each independently 0 or 1, and R1 and R2 are each independently an alkyl group of CM2, a substituted or unsubstituted C6_30 aryl group, and a substituted or unsubstituted heteroaryl group of C6_2〇, or linked to each other to form a heterocyclic ring containing a hetero atom selected from the group consisting of N, fluorene and S, 55 201114844 In this case, the L series are each independently selected from the group consisting of ruthenium, S, CR5R6, SiR7R8, and NR9, and each of R3 and R4 is independently selected from hydrogen, substituted or unsubstituted C丨_丨2 alkyl, substituted or An unsubstituted C6_3G aryl group, and a substituted or unsubstituted C6_2 anthracene aryl group, or may be bonded to each other to form a ring, and R5 to R9 are each independently hydrogen or a substituted or unsubstituted alkyl group. , η is an integer from 1 to 10. 2. The organic dye according to claim 1, wherein Af2 Άη-Ν Af3 is an aryl group of c6-c5〇 or an aryl group of c6-c5〇 substituted by an alkyl group. 〇 and ρ are each independently 0 or 1, and R1 and R2 are simultaneously hydrogen, or are linked to each other and form together with adjacent phenylthio groups. Base 56 201114844 3. The organic dye according to claim 1, wherein the organic dye is selected from the group consisting of compounds represented by the following Chemical Formulas 8 to 50, 57 201114844 [Chemical Formula 8] [Chemical Formula 9] 58 201114844 [Chemical Formula 11] 59 201114844 [Chemical Formula 12] 201114844 [Chemical Formula 14] [Chemical Formula 15] 61 201114844 [Chemical Formula 16] 8 62 201114844 [Chemical Formula 18] [Chemical Formula 19] 63 201114844 [Chemical Formula 20] [Chemical Formula 21] 8 64 201114844 [Chemical Formula 22] 65 201114844 [Chemical Formula 24] [Chemical Formula 25] 66 201114844 [Chemical Formula 26] [Chemical Formula 27] 67 201114844 [Chemical Formula 28] [Chemical Formula 29] [Chemical Formula 30] 8 68 201114844 [Chemical Formula 31] [Chemical Formula 32] [Chemical Formula 33] 69 201114844 [Chemical Formula 34] [Chemical Formula 35] [Chemical Formula 36] 8 201114844 [Chemical Formula 37] [Chemical Formula 38] 71 201114844 [Chemical Formula 39] [Chemical Formula 40] [Chemical Formula 41] 8 72 201114844 [Chemical Formula 42] [Chemical Formula 43] [Chemical Formula 44] 73 201114844 [Chemical Formula 45] [Chemical Formula 46] 8 74 201114844 [Chemical Formula 47] H00C (jj NC C00H Λ [Chemical Formula 48] 75 201114844 [Chemical Formula 49] [Chemical Formula 50] 4. A preparation method, which is the preparation method of the patent scope of the present invention, comprising the steps of: (1) an organic dye (1), wherein a compound of the following chemical formula 3 is coupled with a compound of the following chemical formula 4 to produce a compound of the chemical formula 5; Step (2) reacting the compound of the above Chemical Formula 5 with N-bromosuccinimide in an organic solvent to prepare a compound of Chemical Formula 6, reacting it with BuLi in 1-methylpyridylpiperidine, or a step of reacting a compound of Chemical Formula 5 with BuLi in an organic solvent to produce a compound of Chemical Formula 7; 8 76 201114844 and (3) a compound of the above Chemical Formula 7 in CH3CN and in the presence of piperidine with a compound providing a docking group The step of the bond reaction. [Chemical Formula 3] A—W [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] In the above formula, W system *-8 (0 is called 2 or 0II -P(OEt)2 77 201114844 Y-based Br or *-CHO, A, R1, R2, Sp, o, and p are as defined in the first item of the patent application. A dye-increasing/decreasing photoelectric conversion element characterized by containing oxide semiconductor fine particles; and an organic dye as claimed in the first aspect of the patent application of the above-mentioned oxide semiconductor fine particles. 6. The dye up-and-down photoelectric conversion element according to claim 5, wherein the organic dye is supported by the oxide semiconductor fine particles in the presence of the inclusion compound. 7. The dye addition and subtraction photoelectric conversion element according to claim 5, wherein the oxide semiconductor fine particles contain titanium oxide. 8. The dye addition and subtraction photoelectric conversion element according to claim 5, wherein the oxide semiconductor fine particles have an average particle diameter of from 1 to 500 nm. A dye-sensing solar cell characterized by comprising a dye-increasing/decreasing photoelectric conversion element according to item 5 of the patent application as an electrode. 8 78 201114844 IV. Designated representative map: (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: