KR101433826B1

KR101433826B1 - Dual-Channel Anchorable Heterocyclic Derivatives, Organic Dye Sensitizers Containing The Same for Highly Efficient Dye-sensitized Solar Cells And Dye-sensitized Solar Cells Containing The Same

Info

Publication number: KR101433826B1
Application number: KR1020110133267A
Authority: KR
Inventors: 김환규; 서강득
Original assignee: 고려대학교 산학협력단
Priority date: 2011-12-12
Filing date: 2011-12-12
Publication date: 2014-08-27
Also published as: KR20130066446A

Abstract

The present invention relates to a dual channel type heterocyclic compound derivative represented by the following formula (1), an organic dye for a dye-sensitized solar cell comprising the derivative, and a solar cell comprising the organic dye.

Description

[0001] The present invention relates to a dual-channel type heterocyclic compound derivative, an organic dye for a high-efficiency dye-sensitized solar cell and a dye-sensitized solar cell comprising the same. BACKGROUND ART -sensitized Solar Cells Containing The Same}

The present invention relates to a novel double channel type heterocyclic compound derivative and an organic dye for a high efficiency dye-sensitized solar cell comprising the same. More specifically, the present invention relates to a dual channel type heterocyclic compound derivative And a novel high-efficiency dye-sensitized solar cell having improved long-term stability and energy conversion efficiency, and a dye-sensitized solar cell comprising the organic dye.

In recent years, various researches have been carried out to replace existing fossil dyes in order to reduce the amount of carbon dioxide emission, which is regarded as a main cause of global warming, and to solve the energy problem faced. Extensive research to utilize natural energy sources such as wind power, nuclear power, and solar power has been conducted to replace petroleum resources that will be depleted in the near future. Among them, solar cells using solar energy are the most environmentally friendly, Unlike other energy sources, our resources are infinite if we develop the right method. Since the solar cell using selenium (Se) was developed in 1983, the silicon solar cell is in the spotlight in recent years, but it is very expensive in terms of production cost, so there is a limit in practical use and battery efficiency is still insufficient. A dye-sensitized solar cell instead of the electric energy used in the driving mechanism of an organic electroluminescent display (OLED) is a mechanism for generating an electron-hole pair by absorbing light energy of a visible light ray. The present invention relates to a photoelectrochemical solar cell using a transition metal oxide as a main constituent material. A dye-sensitized solar cell using titanium oxide nanoparticles developed by the research team of Michael Graetzel of the Swiss Federal Institute of Technology (Lausanne) (EPFL) in 1991 is a representative example of conventional dye-sensitized solar cells. The dye-sensitized solar cell using the ruthenium-based complex as a dye has advantages in that it can be applied to a glass window of a building or a glass greenhouse due to a transparent electrode. The manufacturing cost is lower than that of a conventional silicon solar cell, Has attracted considerable attention from academia due to its energy conversion efficiency, but it has a disadvantage in that it has low photoelectric conversion efficiency and low stability, which is the biggest problem of a complex dye, and has yet to be commercialized due to the limit of manufacturing cost. Therefore, in this field, research for replacing organic dyes with photoelectric conversion efficiency with much lower cost is being actively carried out.

For example, Korean Patent Laid-Open No. 10-2010-0136931 discloses a dye-sensitized solar cell (DSSC) which is used as a dye-sensitized photoelectric conversion element and has an improved molar extinction coefficient, Jsc Density) and photoelectric conversion efficiency, thereby greatly improving the efficiency of the solar cell.

However, the above conventional techniques have a problem in long-term stability of the dye, and when the organic metal dye is used as a photosensor, the solar cell can not exhibit sufficient power conversion efficiency.

KR 2010-0136931 A

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel double-channel type organic dye having excellent light-conversion efficiency as well as long-term stability. It is another object of the present invention to provide a novel dye for solar cells having improved long-term stability and energy conversion efficiency including the dye. Still another object of the present invention is to provide a solar cell element using the dye.

In order to achieve the above object, the present invention provides a double channel type heterocyclic compound derivative represented by the following general formula (1).

[Chemical Formula 1]

In this formula,

Z is O or S;

R ₁ is hydrogen, C ₁ -C 20 alkyl, C ₁ -C 20 alkoxy, aryl substituted with C 1 -C 20 alkoxy, or

;

R ₂ is

, or

;

R ₃ is hydrogen,

, or

;

R ₄ is

,

,

, or

;

X is hydrogen, C1-C20 alkyl, C1-C20 alkoxy or aryl substituted with C1-C20 alkoxy;

X1 is hydrogen, C1-C20 alkyl, aryl or C1-C20 alkoxy, or

Lt;

n is an integer of 1 to 10;

The present invention also provides an organic dye for a high-efficiency dye-sensitized solar cell comprising the double-channel type heterocyclic compound derivative represented by the above formula (1).

The present invention also provides a dye-sensitized solar cell comprising the organic dye for the high-efficiency dye-sensitized solar cell.

The organic dye for a high-efficiency dye-sensitized solar cell comprising the double channel type heterocyclic compound derivative represented by the formula (1) of the present invention not only has excellent light conversion efficiency, but also has excellent long-term stability. Therefore, a dye-sensitized solar cell device with high efficiency can be manufactured by using such a dye.

The present invention provides a double channel type heterocyclic compound derivative represented by the following general formula (1).

[Chemical Formula 1]

In this formula,

Z is O or S;

;

R ₂ is

, or

;

R ₃ is hydrogen,

, or

;

R ₄ is

,

,

, or

;

X1 is hydrogen, C1-C20 alkyl, aryl or C1-C20 alkoxy, or

Lt;

n is an integer of 1 to 10;

The present invention provides a double channel type heterocyclic compound derivative represented by the above formula (1), which not only has excellent light conversion efficiency but also has long-term stability. It has excellent long-term stability by strongly adsorbing to the interface of TiO ₂ by introducing two acrylic acid into one dye and has excellent photo-conversion efficiency by introducing a strong electron donor having a high molar extinction coefficient.

Hereinafter, specific examples of the novel compounds of the present invention and preparation methods thereof will be described by way of example.

Specific examples of the compound of Formula 1 include compounds of Formula 2 below.

[Formula 2]

The compound of formula (2) is characterized by containing a heterocyclic structure in the form of a double channel. Since the compound includes two electron donors and a binding group in the structure, the compound exhibits excellent light conversion efficiency and long-term stability.

The compound of Formula 2 may be prepared by the following Reaction Scheme 1. Further details are described in Example 1 below.

[Reaction Scheme 1]

The double-channel type heterocyclic compound derivative represented by Formula 1 may be useful as a dye for a dye-sensitized solar cell. Accordingly, the present invention provides a dye for a dye-sensitized solar cell comprising the double-channel type heterocyclic compound derivative represented by Formula 1 above.

The present invention also provides a dye-sensitized solar cell comprising the dye for the dye-sensitized solar cell.

In the present invention, the dye-sensitized solar cell may have the following configuration, but not limited thereto:

A first electrode comprising a conductive transparent substrate;

A light absorbing layer formed on one surface of the first electrode;

A second electrode disposed opposite to the first electrode on which the light absorbing layer is formed; And

Wherein the electrolyte is located in a space between the first electrode and the second electrode.

The materials constituting the solar cell will be described as follows.

The first electrode comprising the conductive transparent substrate is a glass substrate comprising a transparent electrode formed of at least one material selected from the group consisting of indium tin oxide, fluorine tin oxide, ZnO-Ga2O3, ZnO-Al2O3 and tin oxide It may be a plastic substrate.

The light absorbing layer includes semiconductor fine particles, a dye, a compound having hole conduction characteristics, and the like. The semiconductor fine particles may include, but are not limited to, titanium dioxide (TiO 2), tin dioxide (SnO 2), zinc oxide Nanoparticle < / RTI > oxide. The dye adsorbed on the semiconductor fine particles may be used without limitation as long as it absorbs light in the visible light region, forms a strong chemical bond with the surface of the nano-oxide, and has heat and optical stability. As a representative example, a ruthenium-based organometallic compound can be mentioned. The conjugate having the hole conduction characteristic absorbs light to fill the hole formed in the dye that receives the electron, and the hole again becomes the hole, and the hole is filled with the electrolyte again.

The second electrode may be the same as the first electrode, or a conductive layer formed of platinum or the like on the light-transmitting electrode of the first electrode may be used.

Hereinafter, the present invention will be described in detail by way of examples. However, these embodiments are provided to explain the present invention more clearly and not to limit the scope of the present invention. The scope of the present invention will be determined by the technical idea of the following claims.

Examples.

Reagents used

(Diphenylphosphino) ferrocene, palladium acetate, sodium tart butoxide, 1,4-dibromobenzene, 2,2-bithiophene-5-carboxy Aldehyde, dichlorobis (triphenylphosphine) palladium, ethylene glycol, cyanoacetic acid, anhydrous benzene, anhydrous toluene, and anhydrous tetrahydrofuran were used.

The above reagents were used without further purification.

Identification of synthesized compounds

All new compounds were identified by ¹ H-NMR, ¹³ C-NMR and FT-IR. ¹ H-NMR was recorded using a Varian 300 spectrometer and all chemical mobilities were recorded in ppm for tetramethylsilane, an internal standard. IR spectra were measured with KBr pellet using a Perkin-Elmer Spectrometer.

Example 1: Synthesis of (E) -3- (5- (4 - ((7 - ((4- (5 '- Phenyl) amino) - 10-hexyl-10H-phenothiazin-3-yl) (4- (hexyloxy) phenyl) amino) -2,3'-bithiophen-5'-yl) -2-cyanoacrylic acid

1-1: Synthesis of 10-hexyl-10H-phenosyanazine

Phenothiazine (10.0 g, 50.2 mmol), 1-bromohexane (9.94 g, 60.2 mmol) and sodium hydride (1.32 g, 55.0 mmol) were placed in a 500 ml flask, 200 ml of anhydrous tetrahydrofuran was added, Followed by refluxing and stirring at 80 DEG C for 12 hours. When the reaction was completed, distilled water was added thereto, and the mixture was extracted with ethyl acetate and washed several times with distilled water. The organic layer was dried with magnesium sulfate, and then the solvent was removed under reduced pressure. This was purified by silica column chromatography (hexane) to obtain the product. The yield was 83%. ^{1 H NMR (300 MHz, Acetone} -d 6) δ (TMS, ppm): 0.82-0.87 (3H, m, -CH 3), 1.25-1.31 (4H, m, -CH 2 -), 1.39-1.49 ( _{2H, m, -CH 2 -)} , 1.72-1.82 (2H, m, -CH 2 -), 3.92 (2H, t, -CH 2 N-), 6.92 (2H, dt, Ar-H), 7.00 ( 2H, dd, Ar-H), 7.11-7.15 (2H, m, Ar-H), 7.18 (2H, ddd, Ar-H).

1-2: Synthesis of 3,7-dibromo-10-hexyl-10H-phenothiazine

10-hexyl-10H-phenosyanazine (9.27 g, 32.7 mmol) was dissolved in 50 ml of tetrahydrofuran, and then n-bromosuccinimide (12.8 g, 71.9 mmol) was dissolved in tetrahydrofuran The mixture was stirred while being added dropwise at 0 占 폚. After the reaction was completed after 6 hours, the solvent was removed under reduced pressure and the product was purified by silica column chromatography (hexane) to obtain the product. The yield was 91%. ^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm): 0.88 (3H, t, -CH 3), 1.27-1.31 (4H, m, -CH 2 -), 1.75 (2H, m, -CH _{2 -), 1.41 (2H,} m, -CH 2 -), 3.75 (2H, t, -CH 2 N-), 6.68 (2H, d, Ar-H), 7.21-7.27 (4H, m, Ar- H).

1-3: Synthesis of 10-hexyl-N ³ , N ⁷ -bis (4- (hexyloxy) phenyl) -10H-phenothiazine-3,7-diamine

(5.00 g, 14.4 mmol), 4-hexyloxyaniline (8.32 g, 43.0 mmol), palladium acetate (0.15 g, 0.67 mmol), 1,1-hexyl-10H-phenothiazine 40 ml of toluene was added to a 100 ml Schlenk flask containing bis (diphenylphosphino) ferrocene (0.80 g, 1.44 mmol) and sodium tert-butoxide (2.44 g, 25.4 mmol) and refluxed at 110 ° C for 24 hours , And stirred.

When the reaction is completed, a saturated aqueous solution of ammonium chloride is added, and the mixture is extracted with methylene chloride and washed several times with distilled water. The organic layer was dried with magnesium sulfate, and then the solvent was removed under reduced pressure. This was purified by silica column chromatography (methylene chloride-hexane = 1: 4) to obtain the product. The yield was 61%.

^{1 H NMR (300 MHz, DMSO} -d 6) δ (TMS, ppm): 0.83 (9H, m, -CH 3), 1.24-1.36 (20H, m, -CH 2 -), 1.64 (4H, m, _{-CH 2 -), 3.69 (2H} , t, -NCH 2 -), 3.84 (4H, t, -OCH 2 -), 6.67-6.92 (14H, m, Ar-H), 7.61 (2H, s, - NH-).

1-4: N ³ , N ⁷ -bis (4-bromophenyl) -10-hexyl-N ³ , N ⁷ -bis (4- (hexyloxy) phenyl) -10H-phenothiazine- - Synthesis of diamine

Diaminobenzene (5.64 g, 8.47 mmol), 1,4-dibromobenzene (prepared in Example 1), 10-hexyl-N ³ , N ⁷ -bis (Diphenylphosphino) ferrocene (0.39 g, 0.70 mmol) and sodium tert-butoxide (2.45 g, 25.5 mmol) in DMF (20.0 g, 84.8 mmol) 100 ml of anhydrous toluene was placed in a 250 ml Schlenk flask, and the mixture was refluxed and stirred for 24 hours. When the reaction was completed, an aqueous saturated ammonium chloride solution was added thereto, followed by extraction with methylene chloride and washing with distilled water several times. The organic layer was dried with magnesium sulfate, and then the solvent was removed under reduced pressure. This was purified by silica column chromatography (methylene chloride-hexane = 1: 4) to obtain the product. The yield was 30%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm): 0.84 (9H, m, -CH 3), 1.28-1.45 (20H, m, -CH 2 -), 2.03 (4H, m, -CH _{2 -), 3.75 (2H,} t, -NCH 2 -), 3.91 (4H, t, -OCH 2 -), 6.73-6.98 (18H, m, Ar-H), 7.23 (4H, d, Ar-H ).

1-5: 5- (4 - ((7 - ((4- (5'-formyl-2,2'-bithiophen- Amino) phenyl) -2,3'-bithiophene-5'-carbaldehyde Synthesis of (4-hydroxyphenyl) -2,3'-bithiophene-

N ^3, N ⁷ - bis (4-bromophenyl) -10-cyclohexyl -N ^3, N ⁷ - bis (4- (hexyloxy) phenyl) -10H- page nosayi-triazine-3,7-diamine ( 0.50 g, 0.51 mmol), (5'- (1,3-dioxolan-2-yl) -2,2'- 50 ml of anhydrous tetrahydrofuran, in which chlorobis (triphenylphosphine) palladium (0.03 g, 0.04 mmol) was dissolved, was refluxed and stirred at 80 DEG C for 24 hours. After completion of the reaction, 5 ml of hydrochloric acid was added, and the mixture was stirred at room temperature. The solvent was then removed under reduced pressure, dissolved in methylene chloride, extracted with saturated aqueous sodium bicarbonate solution, and washed several times with water. After drying over anhydrous magnesium sulfate, the solvent was removed under reduced pressure. This was purified by silica column chromatography (methylene chloride) to obtain the product. The yield was 20%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm): 0.87 (9H, m, -CH 3), 1.32-1.51 (20H, m, -CH 2 -), 2.11 (4H, m, -CH _{2 -), 3.80 (2H,} t, -NCH 2 -), 3.84 (4H, t, -OCH 2 -), 6.82-7.11 (18H, m, Ar-H), 7.45 (2H, d, Ar-H ). 9.87 (2H, s, O = CH).

1-6 Preparation of (E) -3- (5- (4 - ((7 - ((4- (5 '- ((E) -2-carboxy- Phenyl) amino) - 10-hexyl-10H-phenothiazin-3-yl) (4- (hexyloxy) phenyl) amino) -2,3'-bithiophen-5'-yl) -2-cyanoacrylic acid

Phenyl) (4- (hexyloxy) phenyl) amino) -10-hexyl (4- (5 - (3-ethoxyphenyl) -2,3'-bithiophene-5'-carbaldehyde (0.20 g, 0.17 mmol), cyano Acetic acid (0.04 g, 0.50 mmol) and piperidine (0.02 ml) were dissolved in 20 ml of acetonitrile and chloroform (1: 1) and refluxed for 6 hours and stirred. After the reaction was completed, the solvent was removed under reduced pressure, and the residue was dissolved in methylene chloride. The solution was extracted with a saturated aqueous 1M hydrochloric acid solution and washed several times with water. After drying over anhydrous sodium sulfate, the solvent was removed under reduced pressure. This was purified by silica column chromatography (methanol-methylene chloride = 1: 4) to obtain the product. The yield was 30%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm): 0.84 (9H, m, -CH 3), 1.29-1.51 (20H, m, -CH 2 -), 2.09 (4H, m, -CH _{2 -), 3.71 (2H,} t, -NCH 2 -), 3.82 (4H, t, -OCH 2 -), 6.79-7.02 (18H, m, Ar-H), 7.35 (2H, d, Ar-H ). 8.09 (2H, s, C = CH).

Claims

A dual channel type heterocyclic compound derivative represented by the following formula (1):
[Chemical Formula 1]

In this formula,
Z is O or S;
In the above formula
R ₁ is hydrogen, C ₁ -C 20 alkyl, C ₁ -C 20 alkoxy, aryl substituted with C 1 -C 20 alkoxy, or

;
R ₂ is

, or

;
R ₃ is hydrogen,

, or

;
R ₄ is

,

,

, or

;
X is hydrogen, C1-C20 alkyl, C1-C20 alkoxy or aryl substituted with C1-C20 alkoxy;
X1 is hydrogen, C1-C20 alkyl, aryl or C1-C20 alkoxy, or

Lt;
n is an integer of 1 to 10;

The compound according to claim 1, wherein the double-channeled heterocyclic compound derivative represented by Formula 1 is a compound represented by Formula 2:
(2)

An organic dye for a dye-sensitized solar cell comprising the double-channel type heterocyclic compound derivative represented by the general formula (1) of claim 1.

A dye-sensitized solar cell comprising the organic dye for a dye-sensitized solar cell according to claim 3.

[5] The dye-sensitized solar cell of claim 4,
A first electrode comprising a conductive transparent substrate;
A light absorbing layer formed on one surface of the first electrode;
A second electrode disposed opposite to the first electrode on which the light absorbing layer is formed; And
And an electrolyte located in a space between the first electrode and the second electrode.