KR101465454B1 - Photosensitizer for photovoltaic cell, and photovoltaic cell including same - Google Patents

Photosensitizer for photovoltaic cell, and photovoltaic cell including same Download PDF

Info

Publication number
KR101465454B1
KR101465454B1 KR1020120128400A KR20120128400A KR101465454B1 KR 101465454 B1 KR101465454 B1 KR 101465454B1 KR 1020120128400 A KR1020120128400 A KR 1020120128400A KR 20120128400 A KR20120128400 A KR 20120128400A KR 101465454 B1 KR101465454 B1 KR 101465454B1
Authority
KR
South Korea
Prior art keywords
group
dye
formula
electrode
substituted
Prior art date
Application number
KR1020120128400A
Other languages
Korean (ko)
Other versions
KR20140061623A (en
Inventor
이윤구
김하영
김대환
심교승
Original Assignee
재단법인대구경북과학기술원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 재단법인대구경북과학기술원 filed Critical 재단법인대구경북과학기술원
Priority to KR1020120128400A priority Critical patent/KR101465454B1/en
Publication of KR20140061623A publication Critical patent/KR20140061623A/en
Application granted granted Critical
Publication of KR101465454B1 publication Critical patent/KR101465454B1/en

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Hybrid Cells (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)

Abstract

The present invention relates to organic dyes for dye-sensitized solar cells represented by the following general formula (1).
[Chemical Formula 1]

Figure 112012093356991-pat00027

(In the formula 1,
Each of A 1 and A 2 is independently selected from the group consisting of a substituted or unsubstituted C5-C20 aromatic hydrocarbon group, a substituted or unsubstituted C3-C20 aromatic heterocyclic group, and combinations thereof,
R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C 5 -C 20 aromatic hydrocarbon group, a substituted or unsubstituted C 3 -C 20 aromatic heterocyclic group, And a combination thereof,
B 1 is an acidic functional group,
X is S, N, O or - (CH = CH) -,
and n is an integer of 0 to 5.)

Description

TECHNICAL FIELD [0001] The present invention relates to an organic dye for a dye-sensitized solar cell and a dye-sensitized solar cell comprising the same. BACKGROUND ART [0002]

The present invention relates to an organic dye for a dye-sensitized solar cell and a dye-sensitized solar cell comprising the same.

Recently, various researches have been carried out to replace existing fossil fuels in order to solve the energy problems faced. Extensive research is underway to utilize natural energy such as wind, nuclear, and solar power to replace petroleum resources that will be depleted within decades. Among these solar cells, unlike other energy sources, the resources are infinite and environmentally friendly. Since the development of Se solar cells in 1983, recently, silicon solar cells have been spotlighted.

However, such a silicon solar cell is difficult to be put to practical use because the production cost is extremely high, and it is also difficult to improve the cell efficiency. In order to overcome these problems, development of a dye-sensitized solar cell having a remarkably low production cost has been actively studied.

Unlike silicon solar cells, dye-sensitized solar cells are mainly composed of photosensitive dye molecules capable of absorbing visible light to generate electron-hole pairs, and transition metal oxides transferring generated electrons as main constituent materials Photovoltaic solar cells. Such a dye-sensitized solar cell has advantages in that it can be applied to a glass window of a building or a glass greenhouse due to a transparent electrode because the manufacturing cost is lower than that of a conventional silicon solar cell, but the photoelectric conversion efficiency is low and there is a limitation in practical application .

Meanwhile, the photosensitive dye used in the dye-sensitized solar cell can be divided into an organic metal dye and a dye. These dyes absorb how much sunlight is absorbed in the visible light region reaching the surface and how effectively the electrons emitted by the absorbed sunlight are efficiently injected into the conduction band of the nano- It affects efficiency.

Currently, dyes are less efficient than organometallic dyes. However, since they do not use metals, they have no resource constraints. They have high absorption efficiency (π → π * transition in the molecule) and can absorb light well. Because it is easy to design, it is possible to control the wavelength of absorption and it is possible to synthesize at much lower cost than metal dyes. Therefore, organic dyes compounds having an improved photoelectric conversion efficiency which can replace organic metal dyes are needed.

One embodiment of the present invention is to provide a novel organic dye compound having excellent photoelectric conversion efficiency and a dye-sensitized solar cell comprising the organic dye compound.

One embodiment of the present invention provides an organic dye for a dye-sensitized solar cell represented by the following formula (1).

[Chemical Formula 1]

Figure 112012093356991-pat00001

(Wherein A 1 and A 2 are each independently selected from the group consisting of a substituted or unsubstituted C 5 -C 20 aromatic hydrocarbon group, a substituted or unsubstituted C 3 -C 20 aromatic heterocyclic group, and a combination thereof; , R 1 and R 2 each independently represent a hydrogen atom, a substituted or unsubstituted C1-C30 aliphatic hydrocarbon group, a substituted or unsubstituted C5-C20 aromatic hydrocarbon group, a substituted or unsubstituted C3-C20 aromatic heterocyclic group and is selected from the group consisting of, B 1 is an acidic functional group, X is S, N, O, or - (CH = CH) -, and, n is an integer from 0 to 5).

In one embodiment of the present invention, A 1 and A 2 each independently represent a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 arylalkyl group, a substituted or unsubstituted C6-C30 aryl A substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C2-C30 heteroarylalkyl group, a substituted or unsubstituted C2-C30 heteroaryloxy group, a substituted or unsubstituted C6-C30 aryl ester A substituted or unsubstituted C2-C30 heteroaryl ester group, and combinations thereof.

In one embodiment of the present invention, R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C2-C12 alkenyl group, a substituted or unsubstituted C2- A substituted or unsubstituted C6-C30 cycloalkyl group, a substituted or unsubstituted C6-C20 cycloalkenyl group, a substituted or unsubstituted C6-C30 aryl group , A substituted or unsubstituted C6-C30 arylalkyl group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C2-C30 heteroarylalkyl group, and combinations thereof.

In one embodiment of the present invention, B 1 is a carboxyl group, a phosphorous acid group, a sulfonic acid group, a phosphinic acid group, a hydroxyl group, an oxycarboxylic acid group, an acid amide group, a boric acid group, a substituted or unsubstituted C 1 -C 20 alkyl group, A substituted or unsubstituted C1-C20 alkenyl group, a substituted or unsubstituted C1-C20 alkenylene group, and combinations thereof.

In an embodiment of the present invention, B 1 may be * - (CH 2 ) m CH = C (COOH) CN (where m is an integer of 0 to 10).

In one embodiment of the present invention, the formula (1) may be represented by the following formula (2).

(2)

Figure 112012093356991-pat00002

Wherein R 1 , R 2 , X, B 1 and n are the same as defined in the above formula (1).

In one embodiment of the present invention, the formula (1) may be represented by the following formula (3).

 (3)

Figure 112012093356991-pat00003

(Wherein R 1 , R 2 , X, B 1, and n are as defined in Formula 1).

In one embodiment of the present invention, the formula (2) may be represented by the following formula (4).

[Chemical Formula 4]

Figure 112012093356991-pat00004

(Wherein R 1 and R 2 are -OC 12 H 25 , and X and n are as defined in Formula 1.)

In one embodiment of the present invention, the formula (3) may be represented by the following formula (5).

 [Chemical Formula 5]

Figure 112012093356991-pat00005

Wherein R 1 and R 2 are -OC 12 H 25 , and X and n are as defined in the above formula (1).

Another embodiment of the present invention is a liquid crystal display comprising: a first electrode; 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 an electrolyte positioned between the first electrode and the second electrode, wherein the light absorbing layer comprises at least one of the above-described organic dyes.

The present invention provides a dye having excellent photoelectric conversion efficiency and a dye-sensitized solar cell comprising the same.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows absorption spectra in the chloroform solution of the dyes according to Production Examples 6 and 10 used in the present invention. Fig.
2 is a graph of current density-voltage of a solar cell in Examples 1 and 2. Fig.
FIGS. 3 and 4 show a stacked structure of a dye-sensitized solar cell according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1-C20 alkoxy group, a nitro group, a cyano group, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamyl group, A cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, a cycloalkynyl group having 3 to 20 carbon atoms, Substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C30 heteroaryl group, or a combination thereof.

Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S and P is included in the ring group.

The present invention provides a novel organic dye for a dye-sensitized solar cell. The dye has a structure that simultaneously contains a functional group or a unit that functions as an electron-donor and an electron-acceptor. The present invention provides a dye-sensitized solar cell having improved photoelectric conversion efficiency by using the novel dye.

In one embodiment of the present invention, the organic dye for a dye-sensitized solar cell is represented by the following formula (1).

[Chemical Formula 1]

Figure 112012093356991-pat00006

(In the formula 1,

Each of A 1 and A 2 is independently selected from the group consisting of a substituted or unsubstituted C5-C20 aromatic hydrocarbon group, a substituted or unsubstituted C3-C20 aromatic heterocyclic group, and combinations thereof,

R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C 5 -C 20 aromatic hydrocarbon group, a substituted or unsubstituted C 3 -C 20 aromatic heterocyclic group, And a combination thereof,

B 1 is an acidic functional group,

X is S, N, O or - (CH = CH) -,

and n is an integer of 0 to 5.)

In one embodiment of the present invention, the above-mentioned formula (1) is a compound wherein A 1 and A 2 each independently represent a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 arylalkyl group, C30 aryloxy group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C2-C30 heteroarylalkyl group, a substituted or unsubstituted C2-C30 heteroaryloxy group, a substituted or unsubstituted C6 C30 aryl ester groups, substituted or unsubstituted C2-C30 heteroaryl ester groups, and combinations thereof.

Wherein R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 12 alkyl group, a substituted or unsubstituted C 2 -C 12 alkenyl group, a substituted or unsubstituted C 1 -C 12 alkyl group, A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 cycloalkenyl group, a substituted or unsubstituted C6 C30 aryl group, a substituted or unsubstituted C6-C30 arylalkyl group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C2-C30 heteroarylalkyl group, and combinations thereof have.

Specifically, R 1 and R 2 may independently be a C 1 -C 30 alkoxy group, and more specifically, R 1 and R 2 may be -OC 12 H 25 .

In one embodiment of the present invention, B 1 in Formula 1 is an acidic functional group and contains at least one hydrogen atom capable of hydrogen bonding. Preferably, B 1 includes an electron-withdrawing group, B 1 itself may be an electron withdrawing group, or B 1 may include an electron withdrawing group as a substituent.

More specifically, B 1 is selected from the group consisting of a carboxyl group, a phosphorous acid group, a sulfonic acid group, a phosphinic acid group, a hydroxyl group, an oxycarboxylic acid group, an acid amide group, a boric acid group, a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 An alkenyl group, a substituted or unsubstituted C1-C20 alkenylene group, and combinations thereof. For example, B 1 represents a group selected from the group consisting of a hydroxy group, a halogen group, a cyano group, an acyl group, a carboxyl group, a sulfonyl group, an alkyl group, a cycloalkyl group, a haloalkyl group, an alkylsulfonyl group, an aminosulfonyl group, an alkylthio group, A C 1 -C 20 alkenyl group having at least one electron withdrawing group selected from the group consisting of an alkoxycarbonyl group, an aryl group, an aryloxyl group, an aryloxycarbonyl group, an alkenyl group, an alkynyl group, an aralkyl group and a heterocyclic group, alkynyl -C20 alkylene may group, more specifically, B 1 is * - (CH 2) m CH = C (COOH) CN ( At this time, m may be an integer from 0 to 10.

In one embodiment of the present invention, the formula (1) may be represented by the following formula (2).

(2)

Figure 112012093356991-pat00007

Wherein R 1 , R 2 , X, B 1 and n are the same as defined in the above formula (1).

In one embodiment of the present invention, the formula (1) may be represented by the following formula (3).

(3)

Figure 112012093356991-pat00008

(Wherein R 1 , R 2 , X, B 1, and n are as defined in Formula 1).

In one embodiment of the present invention, the formula (2) may be represented by the following formula (4).

[Chemical Formula 4]

Figure 112012093356991-pat00009

In one embodiment of the present invention, the formula (3) may be represented by the following formula (5).

 [Chemical Formula 5]

Figure 112012093356991-pat00010

Wherein R 1 and R 2 are -OC 12 H 25 , and X and n are the same as defined in the above formula (1).

3 is a view illustrating a layered structure of a dye-sensitized solar cell according to an embodiment of the present invention.

The dye-sensitized solar cell includes a first electrode 101, a light absorbing layer 102 formed on one surface of the first electrode 101, and a first electrode 101 formed with a light absorbing layer 102 A second electrode 104, and an electrolyte 103 interposed in a space between the first electrode 101 and the second electrode 104.

The first electrode 101 is one of the two electrodes of the solar cell, and may be a conductive substrate. The surface of the conductive substrate 101 may have conductivity. The conductive substrate 101 may be formed of a conductive metal oxide such as tin oxide coated with indium, fluorine or antimony, or a thin metal film of steel, silver or gold formed on the surface of a glass or transparent polymer material.

The light absorption layer 102 includes a porous oxide semiconductor particulate film to be produced on the conductive substrate 101 and an organic dye adsorbed on the oxide semiconductor particulate film.

The porous oxide semiconductor particulate film is formed on the conductive substrate 101 as fine particles of an oxide semiconductor and the oxide semiconductor particulate film specifically includes oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, Can be used. The porous oxide semiconductor particulate film may be used alone, or may be mixed or coated on the surface of a semiconductor. The porous oxide semiconductor particle film may be formed by applying a paste containing semiconductor fine particles onto the conductive substrate 101, followed by drying, curing and firing. In this method, a paste containing a semiconductor is dispersed in various solvents such as water and ethanol to form a slurry and applied onto a substrate.

One or more sensitive organic dyes selected from the above formulas (1) to (5) are adsorbed on the formed semiconductor particulate film. The method of adsorbing one or more sensitive organic dyes selected from Chemical Formulas 1 to 5 to the semiconductor particulate film is not particularly limited, but specifically, a solution obtained by dissolving the compound selected from Chemical Formulas 1 to 5 in a solvent capable of dissolving , Or a method in which the oxide semiconductor particulate film is supported on a dispersion obtained by dispersing a dye to adsorb the dye.

The second electrode 104 is formed opposite to the first electrode 101 and includes a conductive layer and a conductive electrode which are the same as or similar to the first electrode 101. The conductive layer may be made of carbon black, a carbon material such as carbon nanotubes, or platinum. One or both of the first electrode 101 and the second electrode 104 may be transparent.

The electrolyte layer 103 is sealed by the partition wall interposed between the first electrode 101 and the second electrode 104. [ Examples of the redox electrolyte used in the electrolyte layer 103 include a halogen oxidizing / reducing agent electrolyte composed of a halogen compound and a halogen molecule having a halogen ion as a counter ion, a metal complex such as ferrocenate, ferrocene-ferricinium ion, and cobalt complex An organic redox electrolyte such as a metal oxide redox electrolyte, an alkylthiol-alkyl disulfide, a viologen dye, or a hydroquinone-quinone, or a halogen redox electrolyte. It may also be an iodine molecule. In addition, the LiI, NaI, KI, CaI 2, a halogenated metal or a tetraalkylammonium iodide, such as CuI, imidazolium iodine, the organic ammonium salt of halogen such as flutes Stadium iodine, or I 2 as the halogen compound to a halogen ion as a counter ion Can be used.

4 is a view showing a laminated structure of a dye-sensitized solar cell according to another embodiment.

4, a dye-sensitized solar cell 200 according to another embodiment includes a first substrate 202, a first electrode (transparent electrode) 204, a recombination barrier layer 206, a semiconductor layer 208, Layer 210, electrolyte 212, counter electrode 214, second electrode 216, second substrate 218, and barrier ribs 220. The first substrate 202 and the second substrate 218 may be glass, but are not limited thereto. The first electrode and the second electrode may be FTO (F-doped tin oxide) having excellent heat resistance, but are not limited thereto.

The dye-sensitized solar cell 200 according to another embodiment includes a semiconductor layer 208 including a nano-sized semiconductor compound adsorbed on one or more organic dyes selected from Chemical Formulas 1 to 5, for example, titanium dioxide (TiO 2) And an electrolyte layer 212 filled between the first electrode 202 and the second electrode 218 and between the semiconductor layer 208 and the counter electrode 214 such as an iodine can do.

Here, the dye molecule absorbs visible light to generate electron-hole pairs, and the semiconductor compound (mainly titanium dioxide) serves to transfer generated electrons.

The operation principle of the dye-sensitized solar cell 200 according to another embodiment is as follows. The dyes excited by the sun light inject electrons into the conduction band of a semiconductor compound of the semiconductor layer 208, for example titanium dioxide. The injected electrons pass through the semiconductor compound to reach the first electrode 204 and are transferred to an external circuit. Here, electrons which can not be transferred to an external circuit due to the contact state between the semiconductor compound (titanium dioxide) nano-particles constituting the semiconductor layer 208 and the first electrode 204 are generated. That is, some of the electrons transferred from the semiconductor compound to the vicinity of the first electrode 204 are not electrically connected to the first electrode 204 through the portion exposed to the electrolyte layer or the electrolyte solution 212, And disappear again. This phenomenon is referred to as recombination, which causes a decrease in photoelectric conversion efficiency. In order to minimize the recombination phenomenon, the recombination barrier layer 206 may be formed as shown in FIG. 2, but may not be formed.

The external sunlight reaches the semiconductor layer 208 through the first substrate 202, the first electrode 204 and the recombination blocking layer 206. The dye existing in the semiconductor layer 208 causes the solar light Is absorbed. However, the sunlight arriving from the outside is not completely absorbed by the semiconductor layer 208, and there is light that passes through the semiconductor layer 208, which causes a decrease in photoelectric conversion efficiency. In order to block light passing through the semiconductor layer 208, a scattering layer 210 is formed to induce light scattering, and scattered light is absorbed into the semiconductor layer 208 again. The scattering layer 210 may or may not be formed in order to block light passing through the semiconductor layer 208.

As mentioned above, the dye absorbing sunlight forms an electron-hole pair, and the electrons are transferred to the first electrode 204 through a semiconductor compound (titanium dioxide). On the other hand, the holes are transferred to the counter electrode 214 through the redox reaction of the electrolyte layer 212 and to the external circuit through the second electrode 216. The counter electrode 214 and the second electrode 216 may be separately formed, but may not be separately formed. For example, the second electrode 216 may serve as an opposing electrode.

Hereinafter, embodiments of the organic dye and the dye-sensitized solar cell including the same according to the embodiments will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the following embodiments no.

Manufacturing example  1: Preparation of dye

This compound was prepared according to the procedure shown in Scheme 1 below to give 3- (4,8-bis-dodecyloxy-6-thiophen-2-yl-1,5-dithia- ) -2-cyano-acrylic acid (10).

[Reaction Scheme 1]

Figure 112012093356991-pat00011

Step  1: 4,8- Bis - Dodecyloxy -1,5- Dythia -s- Indaken -2-carbaldehyde (1)

4-b '] dithiophene (1 g, 1.8 mmol) obtained in 1 in a round bottom flask under nitrogen and tetrahydrofuran (25 mL ). n-butyllithium (1.79 mL, 2.86 mmol) was added at -78 < 0 > C and then stirred at -78 < 0 > C for 15 min. After the temperature was raised to room temperature, the mixture was stirred for 1 hour, DME (1.13 mL, 0.014 mmol) was added at -78 ° C, and the mixture was stirred for 15 minutes. The mixture was stirred at room temperature for 3.5 hours. After the reaction mixture was extracted with diethyl ether, the organic solvent layer was washed with water using magnesium sulfate anhydride and dried in vacuo. The product was purified using methylene chloride / hexane (1: 4) and then 0.62 g of 4,8-bis-dodecyloxy-l, 5-dithia-s-indacene- (59%). 1 HNMR (CDCl 3, 400MHz) , δ (ppm): 10.06 (s, 1H), 8.14 (s, 1H), 7.45 (s, 2H), 4.33 (t, 2H), 4.23 (t, 2H), 1.87 (m, 5H), 1.55 (m, 5H), 1.26 (m, 28H), 0.87

Figure 112012093356991-pat00012

Step  2: 6- Bromo -4,7- Bis - Dodecyloxy -1,5- Dythia -s-indacene-2- Calbaaldehyde  (2)

The 4,8-bis-dodecyloxy-1,5-dithia-s-indacene-2-carbaldehyde obtained in the reaction 1 was dissolved in 22 mL of methylene chloride, and then bromine (0.23 g, 1.43 mmol) was slowly added to the reaction. The reaction was stirred at room temperature for 12 hours and then washed with sodium hydroxide and distilled water. The organic layer was dried over sodium sulfate anhydride. The product was purified using methylene chloride / hexane (1: 2) and then 0.46 g of 6-bromo-4,7-bis-dodecyloxy-1,5-dithia- 2-carbaldehyde (58%). 1 HNMR (CDCl 3, 400MHz) , δ (ppm): 10.08 (s, 1H), 8.14 (s, 1H), 7.46 (s, 1H), 4.32 (t, 2H), 4.22 (t, 2H), 1.87 (m, 5H), 1.55 (m, 5H), 1.26 (m, 28H), 0.87

Figure 112012093356991-pat00013

Step  3: Diphenyl - Thiophene 2-yl-amine (3)

2-bromo-thiophene (3 g, 0.018 mol) and diphenylamine (3.11 g, 0.018 mol) and sodium - t - butoxide (1.49 g, 0.02 mol) was put in a toluene (15 mL). Butylphosphinium tetrafluoroborate (0.11 g, 0.69 mol) was dispersed in toluene (15 ml), and then 10 (10 g, 0.18 mol) of tri Lt; / RTI > The dispersed catalyst solution was added to the reaction mixture and stirred at 105 DEG C for 12 hours. After removal of the solvent, the product was purified using methylene chloride / hexane (1: 4) to give 1.55 g of diphenyl-thiophen-2-yl-amine (33%). 1 H NMR (CDCl 3, 400MHz ), δ (ppm): 7.25 (m, 4H), 7.12 (m, 4H), 7.02 (m, 3H), 6.88 (m, 1H), 6.71 (m, 1H)

Figure 112012093356991-pat00014

Step  4 : Diphenyl - (5- Trimethylstannyl - Thiophene 2-yl) -amine < / RTI > (4)

To a round bottom flask under nitrogen was added diphenyl-thiophen-2-yl-amine (1 g, 3.98 mmol) obtained in 3 and tetrahydrofuran (25 mL). n-butyllithium (3.7 mL, 5.97 mmol) was added at -78 < 0 > C and then stirred at -78 < 0 > C for 15 min. After the temperature was raised to room temperature, the mixture was stirred for 2 hours, trimethylthin chloride (5.97 mL, 5.97 mL) was added thereto at -78 ° C, and the mixture was stirred for 15 minutes. The mixture was stirred at room temperature for 2 hours. After the reaction mixture was extracted with diethyl ether, the organic solvent layer was washed with water using magnesium sulfate anhydride and dried in vacuo. 1.5 g of diphenyl- (5-trimethylstannyl-thiophen-2-yl) -amine (91%) was obtained. 1 H NMR (CDCl 3, 400MHz ), δ (ppm): 7.25 (m, 4H), 7.12 (m, 4H), 7.00 (t, 2H), 6.95 (d, 1H), 6.79 (d, 1H), 0.33 (m, 9H)

Figure 112012093356991-pat00015

Step  5: 6- (5- Diphenylamino - Thiophene 2-yl) -4,8- Bis - Dodecyloxy -1,5- Dythia -2- Indaken -2- Calbaaldehyde  (5)

(5-trimethylstannyl-thiophen-2-yl) -amine (0.25 g, 0.3 mmol) obtained in Example 4 and 6-bromo-4,7-bis-dodecyloxy- 5-dithia-s-indacene-2-carbaldehyde (0.2, 0.3 mmol) was added to toluene (20 mL). The reaction mixture was flushed for 10 min, gave a catalyst of tetrakis (trimethyl phosphine) palladium (Pd (PPH 3) 4) Put 4 mol%. The mixed reaction was flushed for 20 minutes and then slowly warmed to 110 < 0 > C. The mixture was stirred for 24 hours. After removal of the solvent, the aqueous phase was extracted with 0.15 g of 6- (5-diphenylamino-thiophen-2-yl) -4,8-bis-dodecane using methylene chloride / hexane (1: Siloxy-1,5-dithia-2-indacene-2-carbaldehyde (60%). 1 H NMR (CDCl 3 , 400 MHz) ,? (Ppm): 10.07 (s, IH), 8.13 (s, IH), 7.31 (m, 5H), 7.22 2H), 1.87 (m, 5H), 1.55 (m, 2H), 1.26 (m,

Figure 112012093356991-pat00016

Step  6: 2- Siano -3- [6- (5- Diphenylamino - Thiophene 2-yl) -4,8- Bis - Dodecyloxy -

1,5- Dythia -s- Indaken 2-yl] -acrylic acid (6)

5-dicyano-2-indacene-2-carbaldehyde (0.14 g, 0.36 mmol) obtained in Example 5 , 0.16 mmol) and cyanoacetic acid (0.063 g, 0.74 mmol) were added to acetonitrile (10 mL) and chloroform (10 mL). Piperidine (88 μm) was added to the reaction mixture, which was then heated and stirred for 4 hours. The temperature of the reaction was lowered to room temperature, and then the solvent was removed. After the addition of methylene chloride, the organic layer was extracted with distilled water. The organic layer was washed with water using magnesium sulfate anhydride and dried in vacuo. The product was isolated using 0.13 g of 2-thieno-3- [6- (5-diphenylamino-thiophen-2-yl) -4,8-bis-dodecane Siloxy-1,5-dithia-s-indacen-2-yl] -acrylic acid (86%). 1 H NMR (DMSO, 400 MHz) ,? (Ppm): 8.39 (s, IH), 8.26 (m, IH), 7.37 (m, 4H), 7.15 m, 2H), 4.22 (m, 2H), 1.77 (m, 7H), 1.49 (m, 9H)

Figure 112012093356991-pat00017

Step  7: 9- Thiophene 2-yl-9H- Carbazole  (7)

The carbazole (2 g, 12 mmol) and idothiophene (3 g, 14 mmol) were added to nitrobenzene (10 ml). To the reaction mixture was added copper powder (2.23 g, 345 mmol) and potassium carbonate (4.94 g, 35 mmol), and the reaction was stirred at 180 ° C for 24 hours. The reaction mixture was cooled to room temperature, purified through a filter, and then the solvent was distilled off. The product was purified using ethyl acetate / hexane (1:30) to give 1.5 g of 9-thiophen-2-yl-9H-carbazole (51%). 1 H NMR (CDCl 3, 400MHz ), δ (ppm): 8.08 (d, 2H), 7.42 (m, 4H), 7.31 (d, 1H), 7.27 (m, 2H), 7.15 (m, 2H)

Figure 112012093356991-pat00018

Step  8: 9- (5- Trimethylstannyl - Thiophene 2-yl) -9H- Carbazole  (8)

To a tetrahydrofuran (50 mL) of a flask under nitrogen was added 9-thiophen-2-yl-9H-carbazole (1.53 g, 6.13 mmol) obtained in 7. n-butyllithium (5.75 mL, 9.02 mmol) was added at -78 < 0 > C and then stirred at -78 < 0 > C for 15 min. After the temperature was raised to room temperature, the mixture was stirred for 2 hours, trimethylthin chloride (9.02 mL, 9.02 mL) was added thereto at -78 ° C, and the mixture was stirred for 15 minutes. The mixture was stirred at room temperature for 2 hours. After the reaction mixture was extracted with diethyl ether, the organic solvent layer was washed with water using magnesium sulfate anhydride and dried in vacuo. 2.3 g of 9- (5-trimethylstannyl-thiophen-2-yl) -9H-carbazole (92%) was obtained. 1 HNMR (CDCl 3, 400MHz) , δ (ppm): 8.10 (d, 2H), 7.44 (d, 2H), 7.40 (t, 2H), 7.30 (m, 3H), 7.24 (m, 1H)

Figure 112012093356991-pat00019

Step  9: 4,8- Bis - Dodecyloxy -6- Thiophene 2-yl-1,5- Dythia -s- Indaken -2- Calbaaldehyde  (9)

(5-trimethylstannyl-thiophen-2-yl) -9H-carbazole (0.20 g, 0.48 mmol) obtained in Reference Example 8 and 6-bromo-4,7-bis-dodecyloxy- 1,5-Dithia-s-indacene-2-carbaldehyde (0.25 g, 0.37 mmol) was added to toluene (20 mL). The reaction mixture was flushed for 10 min, gave a catalyst of tetrakis (trimethyl phosphine) palladium (Pd (PPH 3) 4) Put 4 mol%. The mixed reaction was flushed for 20 minutes and then slowly warmed to 110 < 0 > C. The mixture was stirred for 24 hours. After removal of the solvent, the vigor was treated with methylene chloride / hexane (1: 1) to yield 0.25 g of 4,8-bis-dodecyloxy-6-thiophen- Thia-indacene-2-carbaldehyde (78%). 1 H NMR (CDCl 3 , 400 MHz) ,? (Ppm): 10.10 (s, 1 H), 8.17 (s, 1 H), 8.13 (d, 2H), 7.57 (m, 3H), 7.47 (m, 2H), 7.21 (d, 1H), 4.39 (t, 2H), 4.29 (t, 2H), 1.91 (m, 4H) m, 8H)

Figure 112012093356991-pat00020

Step  10: 3- (4,8- Bis - Dodecyloxy -6- Thiophene 2-yl-1,5- Dythia -s- Indaken 2-yl) -2- Siano - Acrylic acid  (10)

6-thiophen-2-yl-1,5-dithia-s -indacene-2-carbaldehyde (0.25 g, 0.29 mmol) obtained in Example 9 and cyanoacetic acid (0.11 g, 1.3 mmol) were added to acetonitrile (15 mL) and chloroform (15 mL). Piperidine (156 μm) was added to the reaction mixture, which was then heated and stirred for 4 hours. The temperature of the reaction was lowered to room temperature, and then the solvent was removed. After the addition of methylene chloride, the organic layer was extracted with distilled water. The organic layer was washed with water using magnesium sulfate anhydride and dried in vacuo. The product was purified using methylene chloride / methanol (10: 1). 0.08 g of 3- (4,8-bis-dodecyloxy-6-thiophen-2-yl-1,5-dithia-s-indacen-2-yl) 30%). 1 H NMR (DMSO, 400 MHz) ,? (Ppm): 8.23 (m, 3H), 8.17 (s, IH), 7.75 (s, IH), 7.69 (m, 3H), 7.32 (m, 2H), 7.30 (t, 2H), 4.25 (t, 2H), 1.76 , 7H)

Figure 112012093356991-pat00021

Example  1: Preparation of dye-sensitized solar cell using compound (6)

A conductive glass substrate (FTO; TEC8, Pilkington, 8 Ω / ㎠, Thickness of 2.3 mm) was cleaned in ethanol using ultrasonic waves. A commercially available TiO 2 paste (20 nm, solarnonix) was prepared, and the prepared glass substrate was coated with a prepared TiO 2 paste using a doctor blade and baked at 500 ° C for 30 minutes. The thickness of the fired TiO 2 paste layer was measured by Alpha-step IQ surface profiler (KLA Tencor). In order to use another TiO 2 paste as a scattering layer, the calcined layer was re-coated with TiO 2 particles having a size of 250 nm and then calcined at 500 ° C for 30 minutes. The prepared TiO 2 film was immersed in 0.04 M TiCl 4 aqueous solution at 70 ° C for 30 minutes. For the adsorption of the dye of the compound (6) prepared in Preparation Example 6, the annealed TiO 2 electrode was immersed in the dye solution of 0.3 mM Compound (6) at 50 ° C for 3 hours. A Pt counter electrode was prepared by thermally reducing the thin film formed from a 0.7 mM H 2 PtCl 6 solution dissolved in 2-propanol at 400 ° C for 20 minutes. The dye-adsorbed TiO 2 electrode and the Pt counter electrode were assembled using 60 μm-thick Surlyn (Dupont 1702) as a binder. A liquid electrolyte was introduced through the perforation holes on the opposite electrode. Electrolyte was prepared by dissolving 3-propyl-1-methyl-imidazolium iodide (PMII, 0.7M), lithium iodide (LiI, 0.2M), iodine dissolved in acetonitrile / valeronitrile (85:15) (I 2 , 0.05M) and t-butylpyridine (TBP, 0.5M).

Example  2: Preparation of dye-sensitized solar cell using compound (10)

A dye-sensitized solar cell was prepared in the same manner as in Example 1, except that the compound (10) prepared in Preparation Example 10 was used instead of the compound (6).

Experimental Example  1: Evaluation of absorbance of dye

The absorption spectra and molar absorptivities of the dyes prepared in Preparations 6 and 10 were measured in a chloroform solution, and the results are shown in Table 1.

dyes ε max / M -1 cm -1 λ max nm
Soln. Example 1 21700 370 Example 2 25200 394

Electrolyte: 3-propyl-1-methyl-imidazolyl iodide (PMII, 0.7M) dissolved in acetonitrile / valeronitrile (85:15)

Experimental Example  2: Dye-sensitized solar cell Photoelectricity  Evaluation of conversion efficiency

The current density-voltage of the dye-sensitized solar cell prepared in Examples 1 and 2 was measured and shown in FIG. From the measured graph of FIG. 2, short-circuit photocurrent density (Jsc), open circuit voltage (Voc), and fill factor (FF) The conversion efficiency (?) Was evaluated and the results are shown in Table 2 below.

The solar condition (AM 1.5) of the xenon lamp was measured using a standard solar cell (Frunhofer Institute Solare Engeriessysteme, Certificate No. C-ISE369, Type of Material: Mono -Si + KG filter).

The charge factor (FF) is a value obtained by dividing a product of a current density at a maximum power point and a voltage value (Vmp x Jmp) by a product of Voc and Jsc, and a photoelectric conversion efficiency Is calculated as a ratio of electric energy (current x voltage x charge factor) generated by the battery to energy (Pinc) incident per unit area as shown in Equation (1) below. At this time, the performance of the dye-sensitized solar cell was measured with a working area of 0.23 cm 2 .

[ Equation  One]

? = (Voc · Jsc · FF) / (P inc )

The P inc represents 100 mW / cm 2 (1 sun).

J sc / mA · cm -2 V oc / V FF η /% Example 1 4.744 0.407 70.30 1.52 Example 2 5.542 0.509 67.70 1.91

In the dye-sensitized solar cell according to Examples 1 and 2, the organic dye for the dye-sensitized solar cell of the present invention exhibits excellent single-photocurrent density (Jsc) and photoelectric conversion efficiency (η) It is possible to obtain a photoelectric conversion efficiency superior to that of a carbazole dye.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation in the embodiment in which said invention is directed. It will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the appended claims.

101: first electrode 102: light absorbing layer 103: electrolyte layer 104: second electrode
200: solar cell 202: first substrate 204: first electrode 206: recombination barrier layer
208: semiconductor layer 210: scattering layer 212: electrolyte 214: opposing electrode
216: second electrode 218: second substrate 220: partition wall

Claims (10)

An organic dye for a dye-sensitized solar cell, which is represented by the following formula (1).
[Chemical Formula 1]
Figure 112014069951964-pat00022

(In the formula 1,
A 1 and A 2 are each independently selected from the group consisting of a C5-C20 aromatic hydrocarbon group, a C3-C20 aromatic heterocyclic group, and combinations thereof,
R 1 and R 2 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 30 aliphatic hydrocarbon group, a C 5 -C 20 aromatic hydrocarbon group, a C 3 -C 20 aromatic heterocyclic group,
B 1 is an acidic functional group,
X is S, N, O or - (CH = CH) -,
and n is an integer of 0 to 5.) The method according to claim 1,
A 1 and A 2 each independently represent a C 6 -C 30 aryl group, a C 6 -C 30 arylalkyl group, a C 6 -C 30 aryloxy group, a C 2 -C 30 heteroaryl group, a C 2 -C 30 heteroarylalkyl group, a C 2 -C 30 heteroaryloxy group , A C6-C30 aryl ester group, a C2-C30 heteroaryl ester group, and combinations thereof. The method according to claim 1,
R 1 and R 2 are each independently a hydrogen atom, a C 1 -C 12 alkyl group, a C 2 -C 12 alkenyl group, a C 2-12 alkynyl group, a C 1 -C 30 alkoxy group, a C 6 -C 20 cycloalkyl group, a C 6 -C 20 cycloalkenyl group , C6-C30 aryl group, C6-C30 arylalkyl group, C2-C30 heteroaryl group, C2-C30 heteroarylalkyl group, and combinations thereof. The method according to claim 1,
Wherein B 1 is selected from the group consisting of a carboxyl group, a phosphorous acid group, a sulfonic acid group, a phosphinic acid group, a hydroxyl group, an oxycarboxylic acid group, an acid amide group, a boric acid group, a C 1 -C 20 alkyl group, a C 1 -C 20 alkenyl group, Organic dye for dye-sensitized solar cells. 5. The method of claim 4,
Wherein B 1 is * - (CH 2 ) m CH = C (COOH) CN (wherein m is an integer from 0 to 10), organic dye for dye-sensitized solar cells. The method according to claim 1,
The organic dye for dye-sensitized solar cells according to claim 1, wherein the formula (1) is represented by the following formula (2).
(2)
Figure 112012093356991-pat00023

(In the formula (2)
R 1 , R 2 , X, B 1 and n are as defined in claim 1. The method according to claim 1,
The organic dye for a dye-sensitized solar cell according to claim 1, wherein the formula (1) is represented by the following formula (3).
(3)
Figure 112012093356991-pat00024

(3)
R 1 , R 2 , X, B 1 and n are as defined in claim 1. The method according to claim 6,
Wherein the formula (2) is represented by the following formula (4).
[Chemical Formula 4]
Figure 112012093356991-pat00025

(In the formula 4,
R 1 and R 2 are -OC 12 H 25 , and X and n are as defined in claim 1. 8. The method of claim 7,
The organic dye for a dye-sensitized solar cell according to claim 1, wherein the formula (3) is represented by the following formula (5).
[Chemical Formula 5]
Figure 112012093356991-pat00026

(In the above formula (5)
R 1 and R 2 are -OC 12 H 25 , and X and n are as defined in claim 1. A first electrode; 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 an electrolyte positioned between the first electrode and the second electrode, wherein the light absorbing layer comprises at least one dye according to any one of claims 1 to 9.
KR1020120128400A 2012-11-13 2012-11-13 Photosensitizer for photovoltaic cell, and photovoltaic cell including same KR101465454B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020120128400A KR101465454B1 (en) 2012-11-13 2012-11-13 Photosensitizer for photovoltaic cell, and photovoltaic cell including same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020120128400A KR101465454B1 (en) 2012-11-13 2012-11-13 Photosensitizer for photovoltaic cell, and photovoltaic cell including same

Publications (2)

Publication Number Publication Date
KR20140061623A KR20140061623A (en) 2014-05-22
KR101465454B1 true KR101465454B1 (en) 2014-12-02

Family

ID=50890400

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020120128400A KR101465454B1 (en) 2012-11-13 2012-11-13 Photosensitizer for photovoltaic cell, and photovoltaic cell including same

Country Status (1)

Country Link
KR (1) KR101465454B1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180064883A (en) 2016-12-06 2018-06-15 주식회사 포스코 Rope for slinging work

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080103680A (en) * 2007-05-25 2008-11-28 고려대학교 산학협력단 Novel organic dye containing n-arylcarbazole moiety and preparation thereof
WO2012107488A2 (en) * 2011-02-08 2012-08-16 Universita' Degli Studi Di Milano Metal-free photosensitizers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080103680A (en) * 2007-05-25 2008-11-28 고려대학교 산학협력단 Novel organic dye containing n-arylcarbazole moiety and preparation thereof
WO2012107488A2 (en) * 2011-02-08 2012-08-16 Universita' Degli Studi Di Milano Metal-free photosensitizers

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Novel Benzo[1,2-b:4,5-b']dithiophene-Benzothiadiazole Derivatives with Variable Side Chains for High-Performance Solar Cells, ADVANCED MATERIALS (2011.10.18) *
Novel Benzo[1,2-b:4,5-b′]dithiophene-Benzothiadiazole Derivatives with Variable Side Chains for High-Performance Solar Cells, ADVANCED MATERIALS (2011.10.18)
Organic Dyes Incorporating the Benzo[1,2-b:4,5-b']dithiophene Moiety for Efficient Dye-Sensitized Solar Cells, ORGANIC LETTERS (2011.09.29) *
Organic Dyes Incorporating the Benzo[1,2-b:4,5-b′]dithiophene Moiety for Efficient Dye-Sensitized Solar Cells, ORGANIC LETTERS (2011.09.29)

Also Published As

Publication number Publication date
KR20140061623A (en) 2014-05-22

Similar Documents

Publication Publication Date Title
JP5576298B2 (en) Organic sensitizer
KR100918049B1 (en) Photosensitizer for photovoltaic cell, and photovoltaic cell including same
KR101718198B1 (en) Metal complex dye, photoelectric conversion element, dye-sensitized solar cell, dye adsorption liquid composition for dye-sensitized solar cell, semiconductor electrode for dye-sensitized solar cell, and method for producing dye-sensitized solar cell
EP3080206B1 (en) Porphyrin based sensitizer for dye-sensitized solar cell
Zhu et al. D–A–π–A featured sensitizers containing an auxiliary acceptor of benzoxadiazole: molecular engineering and co-sensitization
WO2010100930A1 (en) Photoelectric conversion element and method for manufacturing the same, optical sensor and solar battery
Shi et al. New efficient dyes containing tert-butyl in donor for dye-sensitized solar cells
WO2013121835A1 (en) Spirobifluorene derivative, dye for photoelectric conversion elements, semiconductor electrode using same, photoelectric conversion element, and photoelectrochemical cell
KR101107069B1 (en) Dye for dye-sensitized solar cell and dye-sensitized solar cell prepared using the same
Jia et al. New D–π–A dyes incorporating dithieno [3, 2-b: 2′, 3′-d] pyrrole (DTP)-based π-spacers for efficient dye-sensitized solar cells
Fang et al. Molecular engineering of efficient organic sensitizers containing diyne-bridge for dye-sensitized solar cells
WO2013042699A1 (en) Spirobifluorene compound, colorant for photoelectric transducer, and photoelectric transducer using same
KR101255541B1 (en) Novel Dye for Photoelectronic Device, Photoanode Comprising the Dye And Photoelectronic Device Employing the Photoanode
JP5233318B2 (en) Photoelectric conversion element and solar cell
KR101264082B1 (en) Photosensitizer containing benzothiazole for photovoltaic cell, and photovoltaic cell including the same
KR101465454B1 (en) Photosensitizer for photovoltaic cell, and photovoltaic cell including same
Shan et al. Ethoxy‐substituted Oligo‐phenylenevinylene‐Bridged Organic Dyes for Efficient Dye‐Sensitized Solar Cells
Joseph et al. Output current enhancement of hexylthiophene functionalized D–π-extended–A triphenylamine in dye sensitized solar cells
JP2014186995A (en) Transparent dye-sensitized solar cell and dye-sensitized solar cell module
KR101587829B1 (en) Dye sensitized sola cell and dye compond used therefin
JP6591691B2 (en) Photoelectric conversion element, dye-sensitized solar cell, and dipyrromethene complex compound
KR20130007287A (en) Dye for dye-sensitized solarcell, preparation method of the same and dye-sensitized solar cell comprising the same
CN101497745B (en) Organic dye and dye-sensitized solar cell prepared thereby
KR20100128096A (en) Novel ruthenium-based dye and preparation thereof
WO2018047498A1 (en) Photoelectric conversion element, dye-sensitized solar cell and dipyrromethene complex compound

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20170918

Year of fee payment: 4

FPAY Annual fee payment

Payment date: 20180918

Year of fee payment: 5