KR101838389B1 - Carbazole based on Novel Hole Transporting Materials for Solid State Dye-sensitized and Organic/Inorganic Hybrid Solar Cells - Google Patents

Abstract

The present invention relates to a p-type organic semiconductor compound having a carbazole-based hole transporting ability represented by the following formula (I), an electrolyte using the same, and a solid dye-sensitized and organic / inorganic hybrid solar cell comprising the same.
(I)

Description

TECHNICAL FIELD [0001] The present invention relates to a p-type organic semiconductor compound having a carbazole-based hole transporting ability, its use as an electrolyte for solid-state dye-sensitized and organic / inorganic hybrid solar cells, and solid-state dye-sensitized and organic / Hole Transporting Materials for Solid State Dye-sensitized and Organic / Inorganic Hybrid Solar Cells}

TECHNICAL FIELD The present invention relates to a p-type organic semiconductor compound having hole transport ability, more specifically, to a p-type organic semiconductor compound having a carbazole-based hole transporting ability, an electrolyte using the same and a solid type dye- Inorganic hybrid solar cell.

The dye-sensitized solar cell using a ruthenium-based complex as a dye has attracted considerable attention from academia due to its energy conversion efficiency exceeding 10%, but it has been difficult to commercialize the dye-sensitized solar cell because of its low long-term stability.

In general, dye-sensitized solar cells are composed of two electrodes (photo and counter electrodes), semiconductor nanoparticles (mainly titanium dioxide), dyes and liquid electrolytes, and n-type nanoparticle semiconductors When sunlight (visible light) is absorbed into the oxide electrode, the dye molecule generates an electron-hole pair. The electrons are injected into the conductive band of the semiconductor oxide and transferred to the transparent conductive film through the interface between the nanoparticles, The holes are operated by a circulation mechanism of electrons that are received and reduced again by the redox electrolyte.

The dual liquid electrolyte component portion is closely related to the long term stability of the device. Iodine-containing volatile electrolytes have excellent advantages in terms of energy conversion efficiency, but they also have a disadvantage in that if the electrolyte is leaked or volatilized during the use period, the stability of the device may become a serious problem. In particular, the iodine component of the electrolyte can cause the chemical decomposition of the dye molecules during long-time operation and seriously destroy the module grid of the metal component due to the action of a small amount of oxygen and moisture.

In order to solve the problems of the electrolyte solution, a lot of efforts have been made to replace the existing liquid electrolyte by using p-type organic semiconductor material. In 2013, the Gratzel group of Switzerland, Y123 organic dye (N, N-di-p-methoxyphenyl-amine) 9,9'-spiro-OMeTAD p - type organic semiconducting material, the energy conversion efficiency of 7.2% is obtained. This is the highest value of the efficiency of solid state dye-sensitized solar cell reported so far.

When the solid-state dye-sensitized solar cell is manufactured using the p-type organic semiconductor material, the reason why the energy conversion efficiency is lower than that of the dye-sensitized solar cell using the conventional liquid electrolyte is that the organic p- Because of the limited ability to penetrate into TiO ₂ perforations, a very thin TiO ₂ film of 2 μm should be used and in this case the amount of dye adsorption is reduced and the light can not be absorbed sufficiently.

On the other hand, in the case of organic / inorganic hybrid solar cells using a CH ₃ NH ₃ PbI ₃ light absorbing material having a perovskite structure and a Spiro-MeOTAD hole conductor, which have recently attracted a great deal of attention, a high efficiency of 15% This is because the perovskite material is very excellent in light absorption capability and can sufficiently absorb light even when a very thin TiO ₂ thin film (about 500 nm) is used.

The present invention is to provide a novel p-type hole transport material which can be used as a substitute for Spiro-OMeTAD which has been used in the past, and is superior in solubility to a solvent than a conventional Spiro-OMeTAD material, When used in the manufacture of solar cells, the ability to penetrate into pores of TiO ₂ is excellent during spin coating, so even if a TiO ₂ thin film of 2 μm or more is used, the inside of the pores is efficiently filled and the energy conversion efficiency is not lowered. OMeTAD material, it is possible to prevent the loss of open-circuit voltage by increasing the recombination resistance of the excitons at the dye / TiO ₂ / hole transport material interface. Therefore, when using the existing Sipro-OMeTAD material Not only high efficiency can be obtained, but also excellent hole transporting ability can be obtained and a perovskite light absorbing material With the organic / inorganic hybrid case to manufacture a solar cell and an object thereof is to provide a new hole transport materials that can obtain an excellent energy conversion efficiency as compared with the case using the conventional Spiro-OMeTAD material.

Another object of the present invention is to provide a dye-sensitized and organic / inorganic hybrid solar cell in which a photocurrent voltage and a fill factor are improved by replacing a conventional liquid electrolyte with the hole transport material.

In order to achieve the above object, the present invention provides a p-type organic semiconductor compound represented by the following formula (I).

(I)

In the above formula (I)

R ₁ is an alkyl group having 1 to 50 carbon atoms, Ar is a trivalent linking group, and is any one selected from the following Structural Formula 1.

[Structural formula 1]

The present invention also provides a solid electrolyte for a solar cell comprising the p-type organic semiconductor compound.

The present invention also provides a solar cell comprising the above solid electrolyte for a solar cell.

The P-type organic semiconductor compound of the present invention is easy to synthesize and has excellent performance compared to the Spiro-OMeTAD P-type organic semiconductor used in conventional solid dye-sensitized and organic / inorganic hybrid solar cells.

In addition, the p-type organic semiconductor compound of the present invention is superior in solubility to a solvent as compared with the existing Spiro-OMeTAD material, and therefore, when used in the production of a solid dye-sensitized solar cell, the ability to penetrate TiO ₂ pores It is effective to fill the pores efficiently even if a TiO ₂ thin film of 2 탆 or more is used so that the energy conversion efficiency does not decrease.

In addition, since the p-type organic semiconductor compound of the present invention is superior in hole transporting ability to the existing Spiro-OMeTAD material, the recombination resistance of the excited electrons at the dye / TiO ₂ / hole transporting material interface is increased, Therefore, it is possible to obtain higher efficiency when using the existing Sipro-OMeTAD material.

In addition, the p-type organic semiconductor compound of the present invention is superior in energy conversion efficiency compared to the conventional Spiro-OMeTAD material when an organic / inorganic hybrid solar cell is manufactured together with a perovskite light- Efficiency can be obtained.

1 is a schematic diagram of a novel P-type organic semiconductor material of the present invention.

Hereinafter, the present invention will be described in more detail.

The technical terms and scientific terms used in the present invention can be construed as meaning ordinary meanings understood by those of ordinary skill in the art without departing from the scope of the present invention.

The present invention relates to a p-type organic semiconductor compound represented by the following formula (I).

(I)

In the above formula (I)

R ₁ is an alkyl group having 1 to 50 carbon atoms, and may be an alkyl group having 1 to 35 carbon atoms according to a preferred embodiment, and Ar is a trivalent linking group selected from the following Structural Formula 1.

[Structural formula 1]

The alkyl group may be linear or branched. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert- At least one hydrogen atom of the alkyl group may be substituted with at least one substituent selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a cyano group, A substituted or unsubstituted amino group (-NH ₂ , -NH (R), -N (R ') (R "), a substituted or unsubstituted amino group , Wherein R, R 'and R "are each independently an alkyl group having 1 to 24 carbon atoms (in this case, referred to as" alkylamino group ")), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, An alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, An alkenyl group having 2 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 5 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 3 to 24 carbon atoms, Heteroarylalkyl groups, and the like.

The p-type organic semiconductor compound represented by the formula (I) according to the present invention has an advantage that the price can be set at a lower price than the existing expensive Spiro-OMeTAD material due to a short synthesis route. Nevertheless, The P-type organic semiconductor compound according to the present invention can be obtained by introducing a carbazole derivative having a Dimer or Trimer chemical structure into the p-type organic semiconductor compound according to the present invention. And exhibits excellent charge conductivity, and also has improved solubility due to the introduction of an alkyl group, thereby improving the interface property with the TiO ₂ photoelectrode.

According to an embodiment of the present invention, the p-type organic semiconductor compound represented by the formula (I) may be any one selected from the following formulas (1) to (3) The scope of the present invention is not limited thereto.

[Chemical Formula 1]

(2)

(3)

The p-type organic semiconductor compound according to the present invention can be produced, for example, by the following Reaction Scheme 1. More details will be described in Examples 1 to 3 below. However, the production method is not limited to the following Reaction Scheme 1, but can be synthesized by various methods using known organic reactions.

[Reaction Scheme 1]

The p-type organic semiconductor compound represented by the above formula (I) can be usefully used as a solid electrolyte for solid dye-sensitized and organic / inorganic hybrid solar cells.

Accordingly, the present invention provides a solid electrolyte for a solid dye-sensitized and organic / inorganic hybrid solar cell comprising a p-type organic semiconductor compound of the above formula (I).

The present invention also provides a solar cell comprising the above solid electrolyte for a solar cell. The solar cell may be a dye-sensitized solar cell or an organic / inorganic hybrid solar cell.

The dye-sensitized solar cell of the present invention is not limited to this, but may include the following arrangement according to an embodiment.

A first electrode including 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 having the light absorbing layer formed thereon, and a space between the first electrode and the second electrode / RTI >

The electrolyte includes a p-type organic semiconductor compound represented by Formula (I) according to the present invention.

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

Wherein the first electrode including the conductive transparent substrate is formed of at least one material selected from the group consisting of indium tin oxide, fluorine tin oxide, ZnO-Ga ₂ O ₃ , ZnO-Al ₂ O ₃ and tin oxide, A glass substrate or a plastic substrate including an electrode.

The light absorbing layer includes semiconductor fine particles, a dye, a CH ₃ NH ₃ PbI ₃ compound having a perovskite crystal structure, and the semiconductor fine particles include, but are not limited to, titanium dioxide (TiO ₂ ) Tin oxide (SnO ₂ ), zinc oxide (ZnO), or the like. 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 or a CH ₃ NH ₃ PbI ₃ compound having a perovskite crystal structure can be given.

Au, Ag, or Al may be used as the second electrode, and is deposited on the p-type organic semiconductor through a thermal deposition method.

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.

Reagents used

The reagents necessary for preparing the compounds of the present invention include zinc dust, sodium nitrite, sodium iodide, triphenylphosphine, 4-iodoanisole (4- iodoanisole, p-anisidine, sodium hydride, palladum (II) acetate, sodium tert-butoxide, 1,1 ' Bis (diphenylphosphino) ferrocene, copper powder, lithium aluminum hydride, 1,3,5-tribromobenzene, 1,1'- (1,3,5-tribromobenzene), triphenylamine (triphenylamine), Hydrogen iodide, Lithium Bis (Trifluoromethanesulfonyl) Imide, 4-tert-butylpyridine, carbazole (carbazol), N-Bromosuccinimide, methylamine (CH 3 NH 2) solution (33 wt% in absolute ethanol) and hydroiodic acid (55 wt% in water) were obtained from Aldrich and 1,3,5-tris (5-nitro-m-xylene) was synthesized by using Alfa aesar (3-bromophenyl) benzene, The product was used in the same manner as in Example 1 but using tetrahydrofuran, hexane, toluene, dichloromethane, chloroform, ethanol, acetone, para-toluenesulfonyl chloride p-toluenesulfonyl chloride), KOH and MgSO ₄ were used. Among them, THF, hexane and toluene were purified and used under sodium / benzophenone. CHCl ₃ and CH ₂ Cl ₂ were purified and used under CaH ₂ and P ₂ O ₅ . Other reagents were used without further purification. The TIO ₂ paste used was 18-NRT from Dyesol. (III) -tris (bis (triuoromethylsulfonyl) imide) was prepared according to J. Mater. Chem. A, 2013, 1, 11842 Were prepared and used according to the literature method.

Identification of synthesized compounds

The compound was identified by ¹ H NMR, MASS SPECTRASCOPY and FT-IR spectroscopy. ¹ H NMR was recorded using a Varian 300 spectrometer, and all chemical mobilities were recorded in ppm relative to the internal standard tetramethyl silane. IR spectra were measured with KBr pellet using a Perkin-Elmer spectrometer. The luminescence spectrum was measured in solid phase with Edinburgh FS920.

Synthesis of intermediates

Bis (4-methoxyphenyl) amine is described in "Organic Letters, 2003, Vol 5, No. 14, 2453." Tris (4-bromophenyl) amine) was prepared according to the method described in J. Mater. Chem., 2012, 22 (16), 7945. " 3,6-dibromo-9H-carbazole was prepared according to the method of Chem. Eur. J., 2011, 17, 11115 , 1-bromo-4- (hexyloxy) benzene) is referred to as "organic letters., 2014, 16 (5), 3978." Were prepared according to literature methods.

Example  One : SGT Synthesis of -405 (3,6)

One- 1: 3 , 6- dibromo -9- tosyl -9H- carbazole  synthesis

To a 250 ml flask was added 3,6-bromocabazole (15.2 g, 46.77 mmol), para-toluenesulfonyl chloride (13.37 g, 70.15 mmol), sodium hydride (2.81 g, 70.15 mmol) and tetrahydrofuran And the mixture was refluxed for 12 hours. When the reaction was completed, ethanol and distilled water were added, extracted with dichloromethane, and washed several times with distilled water. The organic layer was dried with MgSO ₄ and filtered. The resulting filtrate was concentrated under reduced pressure and the product was isolated by column chromatography. The yield was 90%.

^{1 H NMR (DMSO-d 6} , ppm): δ 8.27 (s, 2H, Ar-H), 7.51 (d, 2H, Ar-H), 7.41 (d, 2H, Ar-H), 7.66 (d, 2H, Ar-H), 7.64 (d, 2H, Ar-H), 7.36 (d, 2H, Ar-H).

1-2: N3, N3, N6, N6 - tetrakis (4- 메틸oxyphenyl ) -9H- carbazole -3,6- diamine  synthesis

To a 250 ml flask was added 3,6-dibromo-9-tosyl-9H-carbazole (5.12 g, 10.68 mmol), bis (4- methoxyphenyl) amine (5.02 g, 21.90 mmol), palladium acetate ), Tri-tert-butyl-phosphine (0.86 g, 4.27 mmol), sodium-tert-butoxide (12.32 g, 128.22 mmol) and toluene (25 mL) were stirred at reflux for 12 hours. When the reaction was completed, distilled water was added, extracted with ethyl acetate, and washed several times with distilled water. The organic layer was dried with MgSO ₄ and filtered. The resulting filtrate was concentrated under reduced pressure and the product was isolated by column chromatography. The yield was 80%.

^{1 H NMR (DMSO-d 6} , ppm): δ 10.6 (s, 1H, Ar-NH), 8.13 (d, 2H, Ar-H), 6.99 (d, 8H, Ar-H), 6.89 (d, 8H, Ar-H), 6.67 (s, 2H, Ar-H), 6.65 (d, 2H, Ar-H), 3.73 (s, 12H, Ar-OCH 3). FT-IR (KBr pellet, cm ^-1 ): 3400 (Ar-NH).

1-3: SGT Synthesis of -405 (3,6)

N3, N6, N6-tetrakis-9H-carbazole-3,6-diamine (1.08g, 1.74mmol), 1,3,5-tribromobenzene (0.15g, 0.47mmol) , palladium acetate _{(Pd (OAc) 2, 0.04g} , 0.17mmol), tri-tert-butyl-phosphine _{((tert-Bu) 3 P} , 0.07g, 0.08mmol), sodium-tert-butoxide (tert-BuO ^- Na ⁺ , 0.49 g, 5.09 mmol) and toluene (25 mL) were added, and the mixture was stirred under reflux for 48 hours. After the reaction was completed, distilled water was added, extracted with ethyl acetate, and washed several times with distilled water. The organic layer was dried with MgSO ₄ and filtered. The resulting filtrate was concentrated under reduced pressure and purified by column chromatography to obtain the product SGT-401. The yield was 80%.

^{1 H NMR (DMSO-d 6} , ppm): δ 8.31 (s, 3H, Ar-H), 8.13 (s, 6H, Ar-H), 6.99 (d, 24H, Ar-H), 6.89 (d, 24H, Ar-H), 6.67 (d, 6H, Ar-H), 6.65 (d, 6H, Ar-H), 3.73 (s, 36H, Ar-OCH 3).

Example  2 : SGT Synthesis of -410 (3,6)

2- 1: 4 - ( hexyloxy ) -N- (4- 메틸oxyphenyl ) Synthesis of aniline

To a 250 ml flask was added 1-bromo-4- (hexyloxy) benzene (4.8 g, 19.4 mmol), para-anisidine (1.59 g, 12.93 mmol), palladium acetate (0.22 g, 0.39 mmol) (3.73 g, 38.80 mmol) and toluene (25 mL) were added to the solution, and the mixture was refluxed for 48 hours. After the reaction was completed, distilled water was added, extracted with ethyl acetate, and washed several times with distilled water. The organic layer was dried with MgSO ₄ and filtered. The resulting filtrate was concentrated under reduced pressure and the product was isolated by column chromatography. The yield was 70%.

_{^{1 H NMR ((CD 3)}} CO-d 6, ppm): δ 6.96 (m, 4H, Ar-H), 6.81 (m, 4H, Ar-H), 3.73 (s, 3H, -OCH 3), _{3.83 (m, 2H, -OCH 2} -), 1.26 (m, 8H, -CH 2 -), 0.88 (m, 3H, -CH 3).

2-2: N3, N6 -bis (4- ( hexyloxy ) phenyl) - N3, N6 -bis (4- 메틸oxyphenyl ) -9H-carbazole-3,6-diamine

To a 250 ml flask was added 3,6-dibromo-9-tosyl-9H-carbazole (5.12 g, 10.6 mmol), 4- (hexyloxy) -N- (4-methoxyphenyl) aniline (7.0 g, 23.3 mmol), palladium acetate (0.86 g, 4.27 mmol), sodium-tert-butoxide (12.32 g, 128.22 mmol) and toluene (25 mL) were added and the mixture was refluxed with stirring for 12 hours. When the reaction was completed, distilled water was added, extracted with ethyl acetate, and washed several times with distilled water. The organic layer was dried with MgSO ₄ and filtered. The resulting filtrate was concentrated under reduced pressure and the product was isolated by column chromatography. The yield was 80%.

^{1 H NMR (DMSO-d 6} , ppm): δ 10.6 (s, 1H, Ar-NH), 8.27 (d, 2H, Ar-H), 6.99 (d, 8H, Ar-H), 6.89 (d, 8H, Ar-H), 6.67 (s, 2H, Ar-H), 6.65 (d, 2H, Ar-H), 3.73 (s, 6H, Ar-OCH 3), 6.96 (m, 8H, Ar-H ), 6.81 (m, 8H, Ar-H), 3.83 (m, 4H, -OCH 2 -), 1.26 (m, 16H, -CH 2 -), 0.88 (m, 6H, -CH 3). FT-IR (KBr pellet, cm ^-1 ): 3400 (Ar-NH).

2-3: SGT Synthesis of -410 (3,6)

N3, N6-bis (4- (hexyloxy) phenyl) -N3, N6-bis (4-methoxyphenyl) -9H-carbazole-3,6- diamine (1.08 g, 1.3 mmol) 5-tribromobenzene (0.15g, 0.47mmol) , palladium acetate _{(Pd (OAc) 2, 0.04g} , 0.17mmol), tri-tert-butyl-phosphine _{((tert-Bu) 3 P} , 0.07g, 0.08mmol), Sodium tert-butoxide (tert-BuO ^- Na ⁺ , 0.49 g, 5.09 mmol) and toluene (25 mL) were added and the mixture was refluxed for 48 hours. After the reaction was completed, distilled water was added, extracted with ethyl acetate, and washed several times with distilled water. The organic layer was dried with MgSO ₄ and filtered. The resulting filtrate was concentrated under reduced pressure and purified by column chromatography to obtain the product SGT-401. The yield was 80%.

^{1 H NMR (DMSO-d 6} , ppm): δ 8.31 (s, 3H, Ar-H), 8.13 (s, 6H, Ar-H), 6.99 (d, 24H, Ar-H), 6.89 (d, 24H, Ar-H), 6.67 (d, 6H, Ar-H), 6.65 (d, 6H, Ar-H), 3.73 (s, 36H, Ar-OCH 3), 3.83 (m, 12H, -OCH 2 -), 1.26 (m, 48H , -CH 2 -), 0.88 (m, 18H, -CH 3).

Example  3: SGT Synthesis of -411 (3,6)

SGT-406 was prepared in the same manner as in Example 2-3 except that 1,3,5-tri (4-bromophenyl) benzene was used instead of 1,3,5-tribromobenzene. The yield was 60%.

^{1 H NMR (THF-d 5} , ppm): δ 8.13 (s, 6H, Ar-H), δ 7.87 (d, 6H, Ar-H), 7.30 (d, 6H, Ar-H), 6.99 (d ArH), 6.73 (d, 6H, Ar-H), 6.87 (d, _{3), 3.83 (m, 12H} , -OCH 2 -), 1.26 (m, 48H, -CH 2 -), 0.88 (m, 18H, -CH 3).

Example  4 to Example  6 and Comparative Example  1: Preparation of spin-coating solution containing p-type organic semiconductor compound

The p-type organic semiconductor compound and other additives shown in Table 1 below were dissolved in 1 mL of chlorobenzene to prepare a spin coating solution.

Example 4 Example 5 Example 6 Comparative Example 1 p-type
abandonment
Semiconductor compound SGT-405 (3,6) 112 mg - - - SGT-410 (3,6) - 114 mg - - SGT-411 (3,6) - - 124 mg - Spiro-OMeTAD - - - 72 mg Other
additive Tris (2- (1H- pyrazol -1-yl) -4- tert-butyl pyridine) cobalt (III) (methylsulfonyl-trifluoromethyl) bis-imide (FK209) Solution ¹⁾ 21.9 μL 21.9 μL 21.9 μL 21.9 μL Lithium Bis (Trifluoromethanesulfonyl) Imide (LiTFSi) solution ^{2 )} 17.5 μL 17.5 μL 17.5 μL 17.5 μL 4-tert-butylpyridine 28.8 μL 28.8 μL 28.8 μL 28.8 μL ^{1) A solution of} 400 mg of FK209 dissolved in 1 mL of Actonitrile
^{2) A} solution prepared by dissolving 520 mg of LiTFSi in 1 mL of Actonitrile

Example  7 to Example  9 and Comparative Example  2: organic / inorganic hybrid solar cell ( Perovskiy Photovoltaic cells)

An organic / inorganic hybrid solar cell was prepared according to the following process.

1. The FTO glass substrate was immersed in a sodium hydroxide cleaning solution, ultrasonically cleaned for 1 hour, washed with distilled water and ethanol, and dried using nitrogen gas.

2. The cleaned FTO glass substrate was masked with 3M tape and the counter electrode portion was etched with a 4M HCl aqueous solution.

3. Titanium diisopropoxide bis (acetylacetonate) 1-butanol solution at a concentration of 0.15 M was used to prepare a TiO ₂ micro-thin film.

4. Next, a TiO ₂ paste (18-NRT, Dyesol) having a particle size of 20 nm was diluted in an ethanol solvent at a weight ratio of 1: 3 and coated by spin coating at 5000 rpm and dried at room temperature (25 ° C) for 2 hours .

5. The FTO glass substrate coated with TiO ₂ was dried in an oven at 80 ° C for 2 hours.

6. Then, the FTO glass substrate coated with TiO ₂ was fired at 500 ° C for 30 minutes while gradually raising the temperature using a heating furnace.

7. Subsequently, the fired FTO glass substrate was immersed in an aqueous 20 mM TiCl ₄ solution for 15 minutes, washed with distilled water and ethanol, dried using nitrogen gas, and dried in an oven at 80 ° C for 10 minutes.

Then, the dried FTO glass substrate was sintered for 30 minutes using a heating gun, and then spin-coated with PbI ₂ DMF solution (420 mg / mL) at 6500 rpm for 30 seconds, After drying for 30 minutes, it was cooled to room temperature.

9. Next, the FTO glass substrate coated with PbI ₂ was immersed in methyl ammonium iodide (MAI) 2-propanol solution (10 mg / ml) for 20 seconds and washed with 2-propanol.

10. After the perovskite crystal was formed as described above, p-type organic semiconductor electrolyte layers of Examples 4 to 6 and Comparative Example 1 were spin-coated at 5000 rpm on each of the p-type organic semiconductor solutions to produce a p-type organic semiconductor electrolyte layer .

Then, an Au layer of 80 nm in thickness was thermally deposited using a vacuum chamber to form an oil / inorganic hybrid solar cell (Example 7) containing SGT-404, an oil / gas mixture containing SGT-405 (3,6) Organic / inorganic hybrid solar cell (Example 9) containing SGT-410 (3,6), SGT-411 (3,6) and spiro-OMeTAD containing inorganic hybrid solar cell (Example 8) Inorganic hybrid solar cell (Comparative Example 2).

Test Example  1: Performance evaluation of dye-sensitized solar cell

The photocurrent-voltage was measured under 1 sun (100 mW / cm ² ) illumination conditions using the organic / inorganic hybrid solar cells prepared in Example 7, Example 8, Example 9 and Comparative Example 2, The results are shown in Table 2 below.

Solar cell p-type organic semiconductor material J _SC
(mA / cm ² ) V _oc
(V) FF η
(%) Example 7 SGT-405 (3,6) 22.49 0.97 0.68 14.95 Example 8 SGT-410 (3,6) 22.35 0.98 0.66 14.55 Example 9 SGT-411 (3,6) 21.95 0.98 0.67 14.48 Comparative Example 2 Spiro-OMeTAD 22.74 0.98 0.69 15.64

In the case of Spiro-OMeTAD (Comparative Example 2) manufactured and sold by Merck, the synthesis route is long and the price is very high. However, since the synthesis route of the novel P-type organic semiconductor materials of the present invention is short, There is an advantage that the price can be set at a low price. In spite of its low cost, it has the advantage of showing energy conversion efficiency comparable to Spiro-OMeTAD.

Claims (5)

A p-type organic semiconductor compound represented by the following formula (I):
(I)

In the above formula (I)
R ₁ is an alkyl group having 1 to 10 carbon atoms, and Ar is a trivalent linking group, and is any one selected from the following Structural Formula 1.
[Structural formula 1]

The method according to claim 1,
The p-type organic semiconductor compound represented by the above formula (I) is any one selected from the following formulas (1) to (3)
[Chemical Formula 1]

(2)

(3)

A solid electrolyte for a solar cell comprising a p-type organic semiconductor compound represented by formula (I) according to claim 1. A solid-state dye-sensitized solar cell comprising the solid electrolyte for a solar cell according to claim 3. A solid-state organic / inorganic hybrid solar cell comprising the solid electrolyte for a solar cell according to claim 3.

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