KR101633150B1 - Fluorene derivatives and salts thereof - Google Patents
Fluorene derivatives and salts thereof Download PDFInfo
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- KR101633150B1 KR101633150B1 KR1020120001932A KR20120001932A KR101633150B1 KR 101633150 B1 KR101633150 B1 KR 101633150B1 KR 1020120001932 A KR1020120001932 A KR 1020120001932A KR 20120001932 A KR20120001932 A KR 20120001932A KR 101633150 B1 KR101633150 B1 KR 101633150B1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E10/542—Dye sensitized solar cells
Abstract
The present invention relates to a fluorene derivative and a salt thereof, an electrolyte including the same, and a photoelectric conversion element. The fluorene derivative and a salt thereof can be used to produce an electrolyte used in a photoelectric conversion element.
Description
The present invention relates to a fluorene derivative and its salt, an electrolyte using the same, and a photoelectric conversion element.
The photoelectric conversion element means a device that converts a light signal into an electric signal by using a photoelectric effect. In particular, a dye-sensitized solar cell (DSSC) of a photoelectric conversion device is a dye-sensitized solar cell developed by Gratzel et al. In Switzerland, and includes dye molecules capable of absorbing visible light to generate electron-hole pairs, It is a photoelectrochemical solar cell whose main constituent material is a transition metal that transfers electrons. Therefore, it is attracting attention as a new type of solar cell different from the conventional silicon solar cell.
The electrolyte used in this dye-sensitized solar cell is composed of a redox pair such as I - / I 3 -, and in the case of a liquid type electrolyte, the redox ion moves quickly in the medium to help regenerate the dye smoothly High energy conversion efficiency is possible, but if the bonding between the electrodes is not perfect, it has leakage problem. On the other hand, when the polymer is used as a medium, there is no fear of leaking, but since the movement of the oxidation-reduction species is slowed, it may adversely affect the energy conversion efficiency, so that when the polymer electrolyte is used, the oxidation- It is necessary to design it.
As a technique for solidifying a dye-sensitized solar cell, there is a method using a hole conductor. The hole conductor is classified into an inorganic hole conductor and an organic hole conductor. Among them, the inorganic hole conductor is difficult to fill the inside of the nanoporous film, so that it is not easy to produce a solid dye-sensitized solar cell. . Since the organic hole conductor can be dissolved in various solvents, the filling can be easily performed and the bonding property can be improved in the actual photoelectric conversion element. For example, an alkoxy group can be introduced to enhance the bonding property of the hole conductor. The compound in which the alkoxy group is introduced can be both liquid or solid, and these compounds are easily soluble in an organic solvent and are useful for device and battery fabrication.
As typical organic hole conductor compounds, arylamine compounds are generally well known. In addition, there are examples using pentacene, polythiophene, polyaniline, and polypyrrole-based compounds, but it is known that the photoelectric conversion efficiency is as low as less than 1%.
An object of the present invention is to provide a fluorene derivative and its salt, an electrolyte using the same, and a photoelectric conversion element.
The present invention provides a fluorene derivative represented by the following formula (1).
[Chemical Formula 1]
R 1 is a hydrogen atom, an alkyl group, an alkoxy group, -OCOR 3, -OCONR 4 R 5, an aryl group, an aryloxy group, a heteroaryl group or a heteroaryloxy group, and each of R 3, R 4 and R 5 independently represents hydrogen, an alkyl group, a cycloalkyl group, Or a heteroaryl group, and A1, A2, A3, and A4 are each independently an alkyl group, an aryl group, an aryloxy group, a heteroaryl group or a heteroaryloxy group,
R2 is represented by the following formula (2) or (3)
(2)
(3)
In Formula 2 or Formula 3, Q is -O-, -S- or -N (A5) -, A5 is a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, L 1 and L 2 are independently R6 and R7 are each independently hydrogen, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group and are connected to each other to form a cycloalkyl group, an aryl group or a heteroaryl group R8 and R9 are each independently hydrogen, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, and may be connected to form a cycloalkyl group, an aryl group or a heteroaryl group, and each R10 independently represents hydrogen, An alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
According to an embodiment of the present invention, R 2 in Formula 1 may be a fluorene derivative represented by Formula 2. More specifically, for example, R2 may be a fluorene derivative represented by the following formula (4).
[Chemical Formula 4]
In Formula 4, A5 is hydrogen, an alkyl group or an aryl group, L 1 is an arylene group, and R 6 and R 7 are each an aryl group or may be connected to each other to form an aryl group.
In the above formulas 2 to 4, "
In the above, the direct bond means that the atom and the atom are directly connected to each other without a substituent.
In the present specification, the alkyl group may be straight chain or branched chain having 1 to 30 carbon atoms, 1 to 16 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.
In the present specification, the cycloalkyl group may have 3 to 60 carbon atoms, 3 to 30 carbon atoms, 3 to 16 carbon atoms, or 3 to 8 carbon atoms.
In the present specification, the aryl group may have 6 to 30 carbon atoms, 6 to 15 carbon atoms, or 6 to 10 carbon atoms.
In the present specification, the heteroaryl group may have 2 to 30 carbon atoms, 2 to 15 carbon atoms, and 2 to 10 carbon atoms.
In the present specification, the arylene group may have 6 to 30 carbon atoms, 6 to 15 carbon atoms, or 6 to 10 carbon atoms.
In the present specification, the heteroarylene group may have 2 to 30 carbon atoms, 2 to 15 carbon atoms, or 2 to 10 carbon atoms.
In the present specification, the alkoxy group may have 1 to 30 carbon atoms, 1 to 16 carbon atoms, or 1 to 8 carbon atoms.
In the present specification, the aryloxy group may have 6 to 30 carbon atoms, 6 to 15 carbon atoms, or 6 to 10 carbon atoms.
In the present specification, the heteroaryloxy group may have 2 to 30 carbon atoms, 2 to 15 carbon atoms, or 2 to 10 carbon atoms.
The heteroaryl, heteroarylene and heteroaryloxy groups of the functional groups mean that at least one of the carbon atoms in the aromatic ring is replaced by a heteroatom such as nitrogen, oxygen, sulfur, phosphorus, or silicon.
And the functional groups are one or more of the hydrogen bonded to the carbon atom may be substituted, the substituent is -COOR6, -OCOR7, -OCONR8R9, -CN, -NO 2, -NH 2, -OH, -F, -Cl, -Br, or -I. In the above, R6, R7, R8 and R9 may each independently be hydrogen, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
According to an embodiment of the present invention, a fluorene derivative salt prepared by reacting a compound of the formula (1) with a compound of the following formula (5) can be provided.
[Chemical Formula 5]
RX
In the above, R may be selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, and an arylalkyl group, and each functional group may be as described above.
X is a halogen atom, NO 3, N (CN) 2, BF 4, ClO 4, PF 6, (CF 3) 2 PF 4, (CF 3) 3 PF 3, (CF 3) 4 PF 2, (CF 3 ) 5 PF, (CF 3) 6 P, CF 3 SO 3, CF 3 CF 2 SO 3, (CF 3 SO 2) 2 N, (FSO 2) 2 N, CF 3 CF 2 (CF 3) 2 CO, (CF 3 SO 2) 2 CH , (SF 5) 3 C, (CF 3 SO 2) 3 C, CF 3 (CF 2) 7 SO 3, CF 3 CO 2, CH 3 CO 2, SCN and (CF 3 CF 2 SO 2) may be selected from the group consisting of N 2. In particular, when a salt of the compound of Formula 1 and the compound of Formula 5 is reacted, X may form an anion.
When the fluorene derivative salt is prepared by reacting the compound of Formula 1 and the compound of Formula 5, for example, the compound of Formula 5 may be used in an amount of 1 to 10 mol, 1 to 5 mol or 1 To 3 mols.
According to one embodiment of the present invention, an electrolyte including a fluorene derivative represented by the general formula (1) can be provided.
As described above, in the dye-sensitized solar cell using the hole conductor compound, the compound used as the hole conductor uses an arylamine group having an excellent hole-transporting ability, but the photoelectric conversion characteristics of the hole- Which is lower than the solar cell used. In addition, alkoxy groups were introduced to lower the melting point or increase the solubility of the compounds containing arylamine groups used as the hole conductors, but the characteristics of these compounds were remarkably low.
In order to overcome this problem, the compound of Formula 1 has been developed as a hole conductor and an electrolyte, preferably a solid electrolyte. As for the structure of the compound, an arylamine group having an excellent hole transporting property and a fluorene group having an excellent charge and electron transporting ability were introduced. Conversely, heteroaryl groups such as imidazole group, oxazole group and thiazole group are also introduced to facilitate electron transfer. As an example, in particular, the imidazole group not only has excellent electron transferring ability but also lowers HOMO (Highest Occupied Molecular Orbital) value, so that the open circuit light voltage (Voc) value of the solar cell can be increased. Such characteristics can also be expected from a thiazole group and the like.
The fluorene derivative of Formula 1 may be solely included in the electrolyte, and may include two or more kinds.
According to an embodiment of the present invention, there can be provided an electrolyte including a salt of a fluorene derivative prepared by reacting a fluorene derivative of the formula (1) and a compound of the formula (5).
An oxidative reducing pair (redox pair) may be added to the electrolyte containing the fluorene derivative salt, although it is not an essential component. The redox pair is preferably added when the electrolyte is applied to a dye-sensitized solar cell or the like.
Examples of the redox pair include, but are not limited to, halogen ions such as iodine ion (I - ), bromine ion (Br - ) and chlorine ion (Cl - ), and Br 3 - , I 3 - , I 5 - Containing redox pair composed of a polyhalogen ion such as 7 - , Cl 2 I - , ClI 2 - , Br 2 I - , or BrI 2 - is preferably used.
The halogen-containing redox pair can be obtained, for example, by reacting a halogen molecule with a halogen ion such as Cl - , Br - or I - .
As the halogen molecule, a single halogen molecule such as Cl 2 , Br 2 , I 2 and / or an interhalogen compound (interhalogen compound) such as ClI, BrI or BrCl can be used. Specifically, iodine / iodine ion or bromine / bromine ion can be exemplified.
The molar ratio of the halogen molecule to the halogen ion is not particularly limited, but may be 0 to 1. Addition of a halogen molecule is not particularly required, but in the presence of a polyhalogen ion, it is preferable to add a halogen molecule in that a halogen ion and a polyhalogen ion form an oxidation-reduction pair, and photoelectric conversion characteristics and the like can be improved .
As the source of the halogen ion, a lithium salt, quaternary imidazolium, tetrabutylammonium salt, etc. may be used alone or in combination.
The electrolyte of the present invention may also be gelled physically or chemically using a gelling agent.
The electrolyte of the present invention may optionally contain an organic nitrogen compound such as 4-tert-butylpyridine, 2-vinylpyridine or N-vinyl-2-pyrrolidone; An additive such as a lithium salt, a sodium salt, a magnesium salt, an iodide salt, a thiocyanate salt, or water may be added within a range that does not impair the properties or properties of the electrolyte composition. As the additive is added, for example, the current density can be increased by increasing the electron flow.
A charge transfer compound (for example, TCNQ [7,7,8,8-Tetracyanoquinodimethan]) may be added to the electrolyte of the present invention if necessary.
The compounds of formula (1) of the present invention may be used alone or in combination of two or more.
The method for producing the electrolyte of the present invention is not particularly limited. For example, there is a method of adding a compound of Chemical Formula 1 and an additive such as a redox couple to an ionic liquid and mixing them uniformly.
According to an embodiment of the present invention, there can be provided a photoelectric conversion element, for example, a dye-sensitized solar cell having an electrolyte layer comprising a fluorene derivative represented by the formula (1) or a salt thereof.
The structure of the dye-sensitized solar cell is not particularly limited, and may be a conventional structure including a dye.
As an example of the dye-sensitized solar cell in the present invention, an oxide semiconductor
In order to produce such a dye-sensitized solar cell, conventional methods for preparing a conventional dye-sensitized solar cell using a dye may be applied, except that the fluorene derivative represented by the formula (1) is used.
In the present invention, as the substrate on which the oxide semiconductor thin film is formed, the surface of the substrate is preferably conductive, and those sold in the market may be used. As a specific example, a conductive metal oxide such as indium, fluorine or antimony coated on the surface of a glass or a polymeric material having transparency such as polyethylene terephthalate or polyethersulfone or a metal thin film such as steel, May be used. In this case, the conductivity is usually 1000 Ω or less, more preferably 100 Ω or less.
As the fine particles of the oxide semiconductor, a metal oxide is preferable. Specifically, oxides such as titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum or vanadium can be used. The oxide semiconductor may be used singly, or it may be mixed or coated on the surface of a semiconductor.
The average particle diameter of the fine particles of the oxide semiconductor may be 1 to 500 nm, preferably 1 to 100 nm. The fine particles of the oxide semiconductor may be mixed with one having a large particle diameter or a particle having a small particle diameter, or may be used as a multilayer.
The oxide semiconductor thin film may be formed by a method of forming oxide semiconductor fine particles directly on a substrate by spraying spray or the like, a method of electrically depositing a semiconductor fine particle thin film using the substrate as an electrode, a method of depositing semiconductor fine particles such as slurry of semiconductor fine particles or semiconductor alkoxide A paste containing fine particles which can be obtained by hydrolyzing the precursor is applied on a substrate and then dried, cured or baked, but the present invention is not limited thereto.
The dispersion medium for dispersing the slurry is not particularly limited as long as it can disperse the semiconductor fine particles. The dispersion medium may be an alcohol such as water or ethanol, a ketone such as acetone or acetyl acetone, or a hydrocarbon such as hexane, have.
Further, a dispersion stabilizer may 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, but are not limited to, acids such as acetic acid, hydrochloric acid or nitric acid, acetylacetone, acrylic acid, polyethylene glycol or polyvinyl alcohol.
The substrate to which the slurry has been applied can be fired, and the firing temperature is not lower than 100 占 폚, preferably not lower than 200 占 폚, and the upper limit is generally not higher than the melting point (softening point) Or less. The baking time in the present invention is not particularly limited, but is preferably within 4 hours in general.
In the present invention, the thickness of the thin film on the substrate is preferably 1 to 200 mu m, and preferably 1 to 50 mu m.
Further, the oxide semiconductor thin film may be subjected to a secondary treatment. For example, the performance of a semiconductor thin film can be improved by dipping a thin film directly on a solution of the same metal alkoxide, chloride, nitrogen, or sulfide as the semiconductor and drying or re-firing the substrate.
Examples of the metal alkoxide include titanium ethoxide, titanium isopropyl epoxide, titanium t-butoxide, and n-dibutyl-diacetyltin, and alcohol solutions thereof may also be used.
Examples of the chloride include titanium tetrachloride, tin tetrachloride and zinc chloride, and aqueous solutions thereof can be used. The oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.
The method of supporting the dye on the oxide semiconductor fine particles formed by the thin film in the present invention is not particularly limited. For example, a solution obtained by dissolving a dye in a solvent capable of dissolving a dye, or a solution obtained by dispersing a dye, And then immersing the substrate on which the substrate is mounted. The concentration in the solution or dispersion can be appropriately selected depending on the dye. The immersion time is generally from room temperature to the boiling point of the solvent, and may be from 1 minute to 48 hours. Specific examples of the solvent that can be used for dissolving the dye include, but are not limited to, methanol, ethanol, acetonitrile, dimethylsulfoxide, dimethylformamide, acetone or t-butanol. The dye concentration of the solution may usually be from 1 x 10-5 M to 1 x 10-1 M.
In the present invention, the dye to be supported may be one kind or a mixture of several kinds. The dye that can be mixed may be a metal complex or an organic dye, and examples of the metal complex dye include, but not limited to, a ruthenium complex or its quaternary salt, phthalocyanine or propylene. Examples of usable organic dyes include methine-based, xanthan-based, azo-based, anthraquinone-based or perylene-based dyes such as phthalocyanine-free phthalocyanine, porphyrin or cyanine, merocyanine, oxolin, triphenylmethane- (MKNazeeruddin, 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 two or more kinds of dyes are used, the dye may be successively adsorbed to the semiconductor thin film, or mixed and dissolved to be adsorbed.
In the present invention, when a dye is supported on a thin film of oxide semiconductor fine particles, a dye may be supported in the presence of an inclusion compound in order to prevent bonding between the dyes. Examples of the inclusion compound include colic acids such as deoxycholic acid, dehydrodeoxycholic acid, chenodeoxycholic acid, cholic acid methyl ester and sodium cholate, steroid compounds, crown ether, cyclodextrin, calixarene, polyethylene oxide and the like .
After the dye is supported, the surface of the semiconductor electrode can be treated with an amine compound such as 4-tert-butylpyridine or a compound having an acidic group such as acetic acid or propionic acid. The treatment method is not particularly limited, and for example, a method of immersing a substrate provided with a semiconductor fine particle thin film carrying a dye in an ethanol solution of amine can be used.
In the dye-sensitized solar cell of the present invention, the hole conductor represented by Formula 1 may be formed into an organic layer by a solution coating method. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.
In addition, since the hole conductor material is in a solid state, unlike an ionic liquid or a solution phase which is easy to inject electrolyte into a fabricated cell, it can be melted at a high temperature and injected into a molten state at the time of injection. However, in addition to using a photoelectric conversion element by forming a hole conductor by such a melt injection method, conventional methods for manufacturing a solar cell using a conventional photoelectric conversion element can be applied. Of course, (Cathode), a counter electrode (anode), a redox electrolyte, a hole transporting material, a p-type semiconductor, or the like.
As an example of the present invention, a dye-sensitized solar cell includes a step of coating a titanium oxide paste on a conductive transparent substrate, a step of forming a titanium oxide thin film by firing a paste-coated substrate, a step of dissolving a dye- A second glass substrate on which a counter electrode is formed; a step of forming a hole through the second glass substrate and the counter electrode; Forming a thermoplastic polymer film between the counter electrode and the titanium oxide film electrode on which the dye is adsorbed and performing a heat pressing process to bond the counter electrode and the titanium oxide film electrode; Injecting an electrolyte into the thermoplastic polymer film between the electrode and the titanium oxide film electrode, It can be prepared through the step of sealing characters.
In the solar cell of the present invention, for example, a counter electrode (anode) is disposed so as to oppose to a photoelectric conversion element (cathode) on which a dye is supported on oxide semiconductor fine particles on a substrate, and a fluorene derivative or a salt thereof is interposed therebetween .
It is possible to provide a photoelectric conversion element having excellent energy conversion efficiency, stability, and lifetime by using an electrolyte including a fluorene derivative or a salt thereof.
Fig. 1 shows, as an example, the structure of a dye-sensitized solar cell.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Experimental Example 1: Measurement of spectrum
The mass spectra of the intermediate and final compounds synthesized in the preparation examples were measured with a JEOL JMS-SX102A (JEOL USA, INC.) Instrument.
Experimental Example 2: Photoelectricity Measurement of conversion characteristics
The dye-sensitized solar cell prepared in Examples and Comparative Examples was subjected to an open-circuit photovoltage at an incident light condition of 100 mW / cm 2 using a solar simulator (abbreviated as abet technology, Xe lamp, 150 W) Short-circuit photocurrent density, fill factor and photo-conversion efficiency (η) were measured. At this time, the effective area of the dye-sensitized solar cell was 0.18 cm 2 . The open circuit light voltage V oc means a potential difference formed at both ends of the solar cell when light is received in a state where the circuit is opened. The single-path photocurrent density J sc refers to the current density when the circuit is short-circuited, that is, when light is received in the absence of external resistance. The filling factor (FF) was measured by the following formula (1).
[Equation 1]
In the above equation, V max And J max mean the value of the voltage and current density measured at the maximum power point.
The photoelectric conversion efficiency (?) Was measured by the following formula (2).
&Quot; (2) "
Wherein, P is a P in in the sense of the incident light energy, Examples and Comparative Examples is 100 mW / cm 2.
Manufacturing example One: Fluorene Preparation of Derivative Compound A
(1) Preparation of the compound of formula A-1
4-Bromobenzaldehyde diethyl acetal (7.8 g, 30 mmol) was diluted with 200 mL of anhydrous tetrahydrofuran, and then maintained at -78 ° C. Then, a 2.5 M solution prepared by adding 42 mmol of normal butyl lithium in 16.8 mL of hexane was added dropwise, followed by stirring for 40 minutes. 2,7-Dibromofluorene (7.6 g, 22.5 mmol) was added and further stirred at -78 [deg.] C for 2 h. Then, iodomethane (MeI, 5.96 g, 42 mmol) was slowly added dropwise, the reaction temperature was raised to room temperature, and the mixture was stirred for 4 hours. 200 mL of NH 4 Cl aqueous solution was added to the reaction solution, and the mixture was stirred for 2 hours. The organic solvent layer was separated, dried over anhydrous magnesium sulfate, and filtered. After the separated organic layer vacuum reduced pressure, and column purification (SiO 2, ethyl acetate (EtOAc) / hexane = 1/10 (volume ratio)) to the compound of formula A-1 by using method (8.14g, 79% yield) .
MS: [M] < + & gt ; = 458
(2) Preparation of the compound of formula A-2
50 mL of toluene and 10 mL of acetic acid were added to the compound of the above formula A-1 (8.14 g, 17.8 mmol) and N-phenyl-1,2-diaminobenzene (3.61 g, 19.6 mmol) and the mixture was heated and stirred at 120 ° C for 24 hours . Then, the temperature was lowered to room temperature, and distilled water and ethyl acetate were added to separate the layers. The organic solvent layer was dried over anhydrous magnesium sulfate, filtered and the solvent was evaporated under reduced pressure to obtain 4.3 g of the compound of the above formula A-2 (SiO 2 , tetrahydrofuran: hexane = 1: 6 , Yield: 74%).
MS: [M + H] < + > = 623
(3) Preparation of the compound of formula (A)
The compound A-2 (12.58 g, 20.22 mmol) and 4,4'-bis (methoxyphenyl) amine (9.74 g, 42.5 mmol) were dissolved in 200 mL of xylene and sodium- tertiary-butoxide , 60.33 mmol) and Pd [P (t-Bu) 3 ] 2 (0.20 g, 0.40 mmol) were added thereto and refluxed in a nitrogen stream for 5 hours. Distilled water was added to the reaction solution, and the reaction was terminated and the organic layer was extracted. The column was separated with a solvent of n-hexane / ethyl acetate = 10/1 (volume ratio), stirred with petroleum ether and vacuum dried to prepare fluorene derivative compound A (14.12 g, yield 76%).
MS: [M + H] < + > = 623
Manufacturing example 2: Fluorene Preparation of derivative B
(1) Preparation of compound of formula (B-1)
A suspension of benzyl (2.1 g, 10 mmol), ammonium acetate (1.16 g, 15 mmol), aniline (4.67 g, 50 mmol) and compound A-1 (4.58 g, 10 mmol) , Stirred at 100 < 0 > C for about 6 hours, and cooled to room temperature. The mixture was diluted with water (50 mL), and the resulting solid was filtered and washed with water and ethyl ether to obtain the compound of Formula B-1 (4.49 g, 62%).
MS: [M + H] < + > = 725
(2) Preparation of compound of formula (B)
Fluorene derivative compound B was obtained in the same manner as in (3) of Production Example 1, except that Compound B-1 was used instead of Compound A-2.
MS: [M + H] < + > = 1021
Manufacturing example 3: Fluorene Preparation of Derivative Compound C
(1) Preparation of compound of formula C-1
The compound of the above formula (C-1) was reacted with the compound of the formula (C-1) in the same manner as in the production example 1 (2) except that N-methyl-1,2-benzimidazole was used instead of N- .
MS: [M + H] < + > = 561
(2) Preparation of compound of formula (C)
Fluorene derivative C was obtained in the same manner as in (3) of Production Example 1, except that Compound C-1 was used instead of Compound A-2.
MS: [M + H] < + > = 857
< Fluorene Synthesis of derivative salt >
Manufacturing example 4: Fluorene Synthesis of derivative salt D
9.19 g (10 mmol) of Compound A was added to 100 mL of chloroform and stirred. 1.42 g (10 mmol) of iodomethane was added to 20 mL of chloroform to be diluted, and then slowly added dropwise to the mixture. Subsequently, the mixture was heated at 60 to 70 DEG C for 2 hours, and then the solvent was distilled off under vacuum to remove 80 mL of chloroform. 100 mL of ethanol was added to the mixture, and the mixture was maintained at 0 ° C for 12 hours to obtain 9.02 g (85% yield) of a fluorene derivative salt D as a white solid.
Manufacturing example 5: Fluorene Synthesis of derivative salt E
The reaction was carried out in the same manner as in Production Example 4 except that 5.11 g (5 mmol) of the compound B and 0.08 g (5 mmol) of iodoethane were used instead of the compound A and iodomethane in the above Production Example 4 to obtain 4.06 g (Yield 69%) of fluorene derivative salt E was obtained.
≪ Preparation of dye-sensitized solar cell &
Example One
The particle diameters of 5 to titanium oxide particle dispersion of 30nm-sized on the conductive film of the first electrode is a tin oxide (fluorine-doped tin oxide) doped with fluorine by 1cm using a screen printing technique - applied to the second area, and 450 Lt; 0 > C for 30 minutes to prepare a 10 mu m-thick porous film.
Then, 0.5 mM Ru (4,4'-dicarboxy-thiophene- 2- carboxylate) prepared by dissolving Ru (4,4'-dicarboxy-2,2'-bipyridine) 2 (NCS) 2,2'-bipyridine) 2 (NCS) 2 dye The porous film was immersed in a small color solution, and the dye adsorption treatment was performed for 12 hours or more. Then, the dye-adsorbed porous membrane was washed with ethanol and dried in a vacuum oven at 50 ° C for 4 hours to prepare a cell.
(4,4'-dicarboxy-2,2'-bipyridine) 2 (NCS) 2
Compound A, and tert-butylpyridine and bis (trifluoromethane) sulfoneimide lithium salt (hereinafter referred to as Li-TFSI) were mixed and dissolved in a chlorobenzene solution to prepare a hole conductor solution. The thus-prepared hole conductor solution was coated on the cell by spray coating. Au was vacuum deposited on the thus fabricated device to form a counter electrode, thereby fabricating a dye-sensitized solar cell.
Example 2
A dye-sensitized solar cell was prepared in the same manner as in Example 1, except that 7,7,8,8-tetracyanoquinodimethane [hereinafter referred to as TCNQ] was used instead of tert-butylpyridine as one of the additives .
Example 3
A dye-sensitized solar cell was prepared in the same manner as in Example 1 except that Compound B was used instead of Compound A.
Example 4
A dye-sensitized solar cell was prepared in the same manner as in Example 2 except that Compound B was used instead of Compound A.
Example 5
A dye-sensitized solar cell was prepared in the same manner as in Example 1 except that Compound C was used instead of Compound A.
Example 6
A dye-sensitized solar cell was prepared in the same manner as in Example 2 except that Compound C was used instead of Compound A.
Comparative Example One
N'-diphenyl-N, N'-bis (3-methylphenyl) - (1,1'-biphenyl) -4,4'-diamine (TPD) represented by the following formula Comparative Example 1 was prepared in the same manner as in Example 1, except that it was used.
N, N'-diphenyl-N, N'-bis (3-methylphenyl) - (1,1'-biphenyl) -4,4'-
1.2 mmol [1.10 g]
0.12 mmol [0.016 mL]
0.12 mmol [0.034 g]
1.2 mmol [1.10 g]
0.12 mmol [0.025 g]
0.12 mmol [0.034 g]
1.2 mmol [1.22 g]
0.12 mmol [0.016 mL]
0.12 mmol [0.034 g]
1.2 mmol [1.22 g]
0.12 mmol [0.025 g]
0.12 mmol [0.034 g]
1.2 mmol [1.02 g]
0.12 mmol [0.016 mL]
0.12 mmol [0.034 g]
1.2 mmol [1.02 g]
0.12 mmol [0.025 g]
0.12 mmol [0.034 g]
1.2 mmol [1.02 g]
0.12 mmol [0.016 mL]
0.12 mmol [0.034 g]
The photoelectric conversion characteristics of the solar cells manufactured according to Examples 1 to 6 and Comparative Example 1 were examined and are shown in Table 2 below. Photoelectric conversion characteristics here was measured at 100mW / cm 2, the performance of the dye-sensitized solar cell was measured by the working area 0.18cm 2.
As shown in Table 2, the compounds having the structure of Formula 1 were used in the dye-sensitized solar cell, which showed high charging factors and photo-conversion efficiencies.
Example 7
The washed FTO (Pilkington, 8 Ωsq-1) glass substrate was impregnated in a 40 mM aqueous solution of TiCl 4 . TiO 2 paste (Solaronix, 13 nm anatase) a screen-printed by a thickness of 13㎛ claim 1 to prepare a TiO 2 layer and the other a paste for the light scattering (CCIC, HWP-400) in claim 2 TiO 2 scattering layer thickness of 10㎛ . The TiO 2 electrode was impregnated with the ethanol solution in which the dye compound represented by Formula 6 was dissolved, and allowed to stand at room temperature for 18 hours.
H 2 PtCl 8 solution (2 mg Pt in 1 mL of ethanol) was coated on the FTO substrate on which the TiO 2 electrode was formed to prepare a counter electrode. Then, 0.6 M fluorene derivative salt D of Production Example 4 (salt formed by reacting Compound A with iodomethane in a molar ratio of 1: 1), 0.04 MI 2 , 0.025 M LiI, and 0.05 M guanidium thiourea in acetonitrile Cyanate and 0.28M tert-butylpyridine (TBP) were dissolved in a solvent to prepare a dye-sensitized solar cell.
Example 8
Except that the fluorene derivative salt E [the salt formed by reacting the compound B with iodoethane at a molar ratio of 1: 1] of the preparation example 5 was used and lithium iodide (LiI) was used instead of Li-TFSI as one of the additives A dye-sensitized solar cell was prepared in the same manner as in Example 7.
Example 9
A dye-sensitized solar cell was prepared in the same manner as in Example 7, except that the resulting salt was prepared by reacting Compound A and iodoethane in a molar ratio of 2: 1.
Example 10
Except that lithium iodide (LiI) was used in place of Li-TFSI, which is one of the additives, and the salt produced by reacting Compound B and iodoethane in a molar ratio of 2: 1, respectively, Sensitive solar cell.
Comparative Example 2
1-hexyl-2,3-dimethylimidazolium iodide and iodine and lithium iodide and 4-tert-butylpyridine as additives were dissolved in acetonitrile to prepare a liquid electrolyte.
Then, the liquid electrolyte was injected into the solar cell and the injection port was sealed to complete the manufacture of the solar cell. Here, the solar cell was fabricated in the same manner as in Example 7.
The photoelectric conversion characteristics of the solar cells prepared according to Examples 7 to 10 and Comparative Example 2 were examined and are shown in Table 4 below. Photoelectric conversion characteristics here was measured at 100 mW / cm 2, the performance of the dye-sensitized solar cell was measured by the working area 0.18cm 2.
As shown in Table 4, it can be confirmed that the exemplary dye-sensitized solar cell of the present invention using the compounds having the structure of Formula (I) has the same performance as the dye-sensitized solar cell using the conventional liquid electrolyte.
11: a first substrate
12: Conductive thin film
13: oxide semiconductor thin film
14: counter electrode
15: second substrate
16: electrolyte layer
Claims (16)
[Chemical Formula 1]
In Formula 1,
R 1 is a hydroxy group, an alkoxy group, an aryloxy group, or a heteroaryloxy group, A 1, A 2, A 3, and A 4 are methoxyphenyl groups,
R2 is the following formula 2,
(2)
Wherein Q is -N (A5) -, A5 is a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, L 1 is an arylene group or a heteroarylene group, R 6 and R 7 are each independently An aryl group, or may be connected to each other to form an aryl group.
[Chemical Formula 4]
In Formula 4,
A5 is hydrogen, an alkyl group or an aryl group, L < 1 > is an arylene group, and R6 and R7 are each an aryl group or may be connected to each other to form an aryl group.
[Chemical Formula 5]
RX
Wherein R is selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group and an arylalkyl group,
X is a halogen atom, NO 3, N (CN) 2, BF 4, ClO 4, PF 6, (CF 3) 2 PF 4, (CF 3) 3 PF 3, (CF 3) 4 PF 2, (CF 3 ) 5 PF, (CF 3) 6 P, CF 3 SO 3, CF 3 CF 2 SO 3, (CF 3 SO 2) 2 N, (FSO 2) 2 N, CF 3 CF 2 (CF 3) 2 CO, (CF 3 SO 2) 2 CH , (SF 5) 3 C, (CF 3 SO 2) 3 C, CF 3 (CF 2) 7 SO 3, CF 3 CO 2, CH 3 CO 2, SCN and (CF 3 CF 2 SO 2) is selected from the group consisting of N 2.
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| JP2005290000A (en) | 2004-04-02 | 2005-10-20 | Samsung Sdi Co Ltd | Fluorene-based compound and organic electroluminescent device using the same |
| JP2006131782A (en) | 2004-11-08 | 2006-05-25 | Konica Minolta Holdings Inc | Material for organic electroluminescent element, organic electroluminescent element, lighting apparatus and display |
| KR100989467B1 (en) * | 2006-12-06 | 2010-10-22 | 주식회사 엘지화학 | New fluorene derivatives and organic electronic device using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005290000A (en) | 2004-04-02 | 2005-10-20 | Samsung Sdi Co Ltd | Fluorene-based compound and organic electroluminescent device using the same |
| JP2006131782A (en) | 2004-11-08 | 2006-05-25 | Konica Minolta Holdings Inc | Material for organic electroluminescent element, organic electroluminescent element, lighting apparatus and display |
| KR100989467B1 (en) * | 2006-12-06 | 2010-10-22 | 주식회사 엘지화학 | New fluorene derivatives and organic electronic device using the same |
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