KR20150124397A - hole-transporting material for inorganic-organic hybrid perovskite solar cells - Google Patents

Abstract

The present invention relates to a hole-transporting compound having a novel structure and, more specifically, to a hole-transporting compound for an inorganic/organic hybrid perovskite-based solar cell. In the present invention, the inorganic/organic hybrid perovskite-based solar cell including a hole-transporting body has very high generating efficiency.

Description

[0001] The present invention relates to a hole-transporting material for an organic / inorganic hybrid perovskite solar cell,

TECHNICAL FIELD The present invention relates to a hole transporting compound, and more particularly, to a hole transporting compound having a novel structure applicable to a non-organic / organic hybrid perovskite solar cell.

In order to solve the global environmental problems caused by the depletion of fossil energy and its use, researches on renewable and clean alternative energy sources such as solar energy, wind power, and hydro power are being actively carried out.

Among these, there is a great interest in solar cells that change electric energy directly from sunlight. Here, a solar cell refers to a cell that generates a current-voltage by utilizing a photovoltaic effect that absorbs light energy from sunlight to generate electrons and holes.

Currently, np diode-type silicon (Si) single crystal based solar cells with a light energy conversion efficiency of more than 20% can be manufactured and used for actual solar power generation. Compound semiconductors such as gallium arsenide (GaAs) There is also solar cell using. However, since inorganic semiconductor-based solar cells require highly refined materials for high efficiency, a large amount of energy is consumed in the purification of raw materials, and expensive processes are required in the process of making single crystals or thin films using raw materials And the manufacturing cost of the solar cell can not be lowered, which has been a hindrance to a large-scale utilization.

Accordingly, in order to manufacture a solar cell at a low cost, it is necessary to drastically reduce the cost of the material or manufacturing process used as a core of the solar cell. As an alternative to the inorganic semiconductor-based solar cell, Type solar cells and organic solar cells have been actively studied.

Dye-sensitized solar cell (DSSC) was first developed by Professor Michael Gratzel of the Lausanne University of Technology in Switzerland (1991) and introduced in Nature.

In the early dye-sensitized solar cell structure, a dye that absorbs light is adsorbed on a porous photo-electrode on a transparent electrode film through which light and electricity pass, and then another conductive glass substrate is placed on top and a simple structure .

The working principle of the dye-sensitized solar cell is that when dye molecules chemically adsorbed on the porous photocathode absorb solar light, dye molecules generate electron-hole pairs and electrons are injected into the conduction band of the semiconductor oxide used as a porous photocathode And is transferred to the transparent conductive film to generate a current. The remaining holes in the dye molecules are transferred to the photocathode by hole conduction or hole-conducting polymers by the oxidation-reduction reaction of liquid or solid electrolyte, forming a complete solar cell circuit, .

Organic photovoltaics (OPV), on the other hand, consist of organic materials with electron donor (D or often hole acceptor) properties and electron acceptor (A) properties. When a solar cell made of organic molecules absorbs light, electrons and holes are formed. This is called an exciton. The exciton migrates to the D-A interface and the charge is separated, the electrons are transferred to the electron acceptor, and the holes are transferred to the electron donor to generate the photocurrent.

Since the distance that the exciton generated from the electron donor can travel normally is very short, about 10 nm, the efficiency is low due to the low light absorption because the photoactive organic material can not be stacked thickly. Recently, the so- called bulk heterojunction (BHJ) ) Concept and the development of a donor organic material having a small bandgap which is easy to absorb a wide range of solar light, efficiency has greatly increased, and organic solar cells having an efficiency of about 10% or more have been reported.

Organic solar cells can be manufactured at a low cost compared to existing solar cells because of easy processability and diversity of organic materials, and low manufacturing cost compared to conventional solar cells. However, in the organic solar cell, the structure of the BHJ is deteriorated by moisture and oxygen in the air and the efficiency thereof is rapidly deteriorated. That is, there is a problem in stability of the solar cell. As a method for solving the problem, There is a problem that the price goes up.

As a method for solving the problem of the dye-sensitized solar cell by the liquid electrolyte, Mikael Gratchel of the EPFL of Switzerland, inventor of the dye-sensitized solar cell (DSSC) Instead, the efficiency was 0.74% using Spiro-OMeTAD [2,2 ', 7,7'-tetrkis (N, N-di-p-methoxyphenylamine) All solid state dye-sensitized solar cells have been reported.

Therefore, studies have been made to achieve high efficiency by applying Spiro-OMeTAD, which is a hole conductive material, to the perovskite solar cell (J. Burschka, N. Pellet, S.-J. Moon, R. Humphry- Baker, P. Gao, MK Nazeeruddin and M. Grüzel, Nature , 2013, 499, 316-319).

However, there is still a demand for a solar cell having high efficiency that can be commercialized.

Korea Patent No. 1172534

Nature, 2013, 499, 316-319

The present invention provides a hole transport compound having a novel structure that can be used in a high-efficiency organic / organic hybrid perovskite solar cell.

The present invention can be used for an organic / organic hybrid perovskite solar cell, and is easy to synthesize and separate, and has a lowest unoccupied molecular orbital (LUMO) level compared to a conventional monomolecular hole transport compound, Hole transporting hole transporting compound of a solar cell for organic / hybrid hybrid perovskite having a novel structure which provides improved efficiency by more effectively blocking electrons that can leak from the anode.

[Chemical Formula 1]

[In the above formula (1)

Z ₁ to Z ₄ and Z ₁₁ to Z ₁₄ are independently of each other O, S or Se;

R ₁ to R ₄ and R ₁₁ to R ₁₄ independently of one another are (C 1 -C 7) alkyl]

Z ₁ to Z ₄ and Z ₁₁ to Z ₁₄ in the general formula (1) according to an embodiment of the present invention are independently O or S; R ₁ to R ₄ and R ₁₁ to R ₁₄ may independently of each other be (C 1 -C 3) alkyl.

Preferably, Z ₁ to Z ₄ in the general formula (1) are O; R ₁ to R ₄ may independently of each other be (C ₁ -C 3) alkyl.

More preferably, the formula (1) may be represented by the following formula (1-1).

[Formula 1-1]

[In the formula 1-1,

Z ₁₁ to Z ₁₄ independently of one another are O, S or Se;

R ₁₁ to R ₁₄ are each independently (C 1 -C 7) alkyl]

The present invention provides a solar cell comprising a hole transporting layer for a hole transporting compound for an organic / inorganic hybrid perovskite solar cell represented by the following formula (1).

[Chemical Formula 1]

[In the above formula (1)

Z ₁ to Z ₄ and Z ₁₁ to Z ₁₄ are independently of each other O, S or Se;

R ₁ to R ₄ and R ₁₁ to R ₁₄ independently of one another are (C 1 -C 7) alkyl]

The hole conductive layer of the solar cell according to an embodiment of the present invention may further include a phthalocyanine derivative.

The phthalocyanine derivative according to an embodiment of the present invention may be represented by the following general formula (8).

[Chemical Formula 8]

[In the formula (8)

M is copper, zinc, cobalt, lead, silver, magnesium, iron, titanyl or vanadyl;

R ₂₁ to R ₂₄ independently represent hydrogen, (C 1 -C 7) alkyl, (C 1 -C 7) alkoxy or sulfonic acid group (-SO ₃ H)

In the case of the phthalocyanine derivative according to an embodiment of the present invention, when R ₂₁ to R ₂₄ are each independently (C 1 -C 7) alkyl, solubility in a solvent is improved, and not only a deposition process but also a solution process is possible The hole transporting layer characteristics can be further improved.

The phthalocyanine derivative according to an embodiment of the present invention may be contained in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the hole transport compound for the organic / organic hybrid perovskite type solar cell.

The solar cell according to an embodiment of the present invention includes a first electrode; A composite layer on which the light absorber is embedded, the composite layer being positioned on the first electrode; A light absorbing structure disposed on the composite layer and made of a light absorbing material; A hole conduction layer disposed on the light absorbing structure; And a second electrode located above the hole conductive layer; . ≪ / RTI >

The hole transporting compound for an organic / organic hybrid perovskite solar cell represented by Formula 1 of the present invention has a LUMO level higher than that of the conventional Spiro-OMeTAD and has a remarkably improved power generation efficiency.

Further, the hole transporting compound for the organic / inorganic hybrid perovskite type solar cell represented by Formula 1 of the present invention is a single molecule and is very advantageous for commercial application since it can be prepared and separated by a simple process unlike the conventional polymer hole transport compound.

In addition, the hole transporting compound for an organic / inorganic hybrid perovskite solar cell represented by the general formula (1) of the present invention can be employed as a hole transporting compound of a non-organic / organic hybrid perovskite solar cell, An organic / organic hybrid perovskite solar cell adopts a high efficiency and high stability, and can be manufactured by a simple solution coating method, so that it can be mass-produced at a low cost in a short time, .

FIG. 1 is a scanning electron microscope (SEM) image of a cross section of a solar cell manufactured according to Example 2 of the present invention. It can be seen that the hole transfer material synthesized in the present invention is uniformly applied to the upper portion.

Hereinafter, the hole transporting compound for an organic / organic hybrid perovskite solar cell of the present invention will be described in detail. In the following description and drawings, unless otherwise indicated, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. A description of the known function and configuration that can be blurred is omitted.

The present invention provides a hole transport compound for an organic / organic hybrid perovskite solar cell represented by the following general formula (1).

[Chemical Formula 1]

[In the above formula (1)

Z ₁ to Z ₄ and Z ₁₁ to Z ₁₄ are independently of each other O, S or Se;

R ₁ to R ₄ and R ₁₁ to R ₁₄ independently of one another are (C 1 -C 7) alkyl]

The hole transporting compound for an organic / inorganic hybrid perovskite solar cell represented by Formula 1 of the present invention is a substituent of N, N-di-p-methoxyphenylamine in the Spiro-OMeTAD compound unlike the existing Spiro-OMeTAD The efficiency and efficiency of the existing Spiro-OMeTAD are remarkably higher than those of conventional Spiro-OMeTAD because the position or position of four methoxy groups in a specific position among 8 p-methoxy substituents are different from those of substituents.

More specifically, Spiro-OMeTAD, which is a conventional hole transport compound, has a structure represented by the following formula.

[Spiro-OMeTAD]

As shown in the above formula, Spiro-OMeTAD has 8 methoxy groups, and the present inventors have found that the position / position of four methoxy groups at specific positions among the eight methoxy groups are different from those of the non-organic / It has been surprisingly found that the power generation efficiency of the organic / organic hybrid perovskite solar cell is improved remarkably when applied to a hole transporting compound of a lobsquioctic solar cell, thereby completing the present invention.

In addition, the hole transporting compound for organic / organic hybrid perovskite solar cells of the present invention is a single molecule, unlike the conventional polymer hole transport compound, monodisperse synthesis is very easy and easy to separate, This has advantages of commercial application is very high.

Z ₁ to Z ₄ and Z ₁₁ to Z ₁₄ in the general formula (1) according to an embodiment of the present invention are independently O or S; R ₁ to R ₄ and R ₁₁ to R ₁₄ may independently of each other be (C 1 -C 3) alkyl.

Preferably, Z ₁ to Z ₄ in the general formula (1) are O; R ₁ to R ₄ may independently of each other be (C ₁ -C 3) alkyl.

Preferably, the formula (1) may be represented by the following formula (1-1).

[Formula 1-1]

[In the formula 1-1,

Z ₁₁ to Z ₁₄ independently of one another are O, S or Se;

R ₁₁ to R ₁₄ are each independently (C 1 -C 7) alkyl]

In view of power generation efficiency in the formula 1 according to an embodiment of the present invention, preferably, Z ₁ to Z ₄ are O; R ₁ to R ₄ may independently be (C ₁ -C 3) alkyl, more specifically, R ₁ to R ₄ may be methyl or ethyl, more preferably Z ₁ to Z ₄ are O and R ₁ to R ₄ , R ₄ may all be methyl.

The hole transport compound represented by Formula 1 of the present invention can be prepared by the following reaction scheme.

[Reaction Scheme 1]

[In the above Reaction Scheme 1, Z ₁ to Z ₄ and R ₁ to R ₄ are the same as defined in Formula 1,

X ₁ to X ₄ independently of one another are halogen.]

Reaction Scheme 1 shows the reaction scheme when the R ₁ to R _4, which corresponds to the case where R ₁ to R ₄ the same of different are possible prepared by synthetic methods that can be appreciated by those skilled in the art. FIG.

The substituents comprising " alkyl ", " alkoxy " and other " alkyl " moieties described in this invention encompass both linear and branched forms. The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.

&Quot; Cycloalkyl ", alone or as part of another group described in the present invention, refers to a fully saturated and partially unsaturated hydrocarbon ring of 3 to 9 carbon atoms, inclusive of the fused aryl or heteroaryl do.

The perovskite solar cell to which the hole transport compound represented by the formula 1 of the present invention is applied is not limited to a conventional perovskite solar cell that can be recognized by those skilled in the art, agent (Inorganic-Orgaic Hybrid perovskites) compound, CdS, CdSe, CdTe, PbS , PbSe, PbTe, Bi 2 S 3, Bi 2 Se 3, InP, InAs, InGaAs, ZnSe, ZnTe, GaN, GaP, GaAs, GaSb, InSb, Si, Ge, AlAs, AlSb, InCuS 2, In (CuGa) Se 2, Sb 2 S 3, Sb 2 Se 3, Sb 2 Te 3, SnS x (1≤x≤2), NiS, CoS, FeS _x (1≤x≤2), may be _{in 2 S 3, MoS, MoSe} , Cu 2 S, a taeang cell employing the light absorber comprises a material selected at least one or both on HgTe and MgSe.

Preferably, the absorber of the organic / organic hybrid perovskite solar cell of the present invention may be one or more materials selected from organic / organic hybrid perovskite compounds satisfying the following general formulas (2) to (3).

(2)

AMX ₃

Wherein A is a monovalent organic ammonium ion or Cs ⁺ , M is a divalent metal ion, and X is a halogen ion.

(Formula 3)

A ₂ MX ₄

Wherein A is a monovalent organic ammonium ion or Cs ⁺ , M is a divalent metal ion, and X is a halogen ion.

At this time, M is located at the center of the unit cell in the perovskite structure, X is located at the center of each surface of the unit cell, forming an octahedron structure around M, and A May be located at each corner of the unit cell.

In detail, the light absorbers may be independently selected from one or more of the compounds satisfying the following general formulas (4) to (7).

(Formula 4)

(R ₁ -NH ₃ ⁺ ) MX ₃

In the general formula 4 R ₁ is an aryl-cycloalkyl or C6-C20 alkyl, C3-C20 of C1-C24, M is ^{Cu 2+, Ni 2+, Co 2+} , Fe 2+, Mn 2+, Cr 2 ⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ and Yb ²⁺ , and X is one or two or more selected from Cl ^- , Br ^- and I ^- It is the selected halogen ion.

(Formula 5)

(R ₁ -NH ₃ ⁺ ) ₂ MX ₄

In formula 5 R ₁ is an aryl-cycloalkyl or C6-C20 alkyl, C3-C20 of C1-C24, M is ^{Cu 2+, Ni 2+, Co 2+} , Fe 2+, Mn 2+, Cr 2 ⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ and Yb ²⁺ , and X is one or two or more selected from Cl ^- , Br ^- and I ^- It is the selected halogen ion.

(Formula 6)

(R ₂ -C ₃ H ₃ N ₂ ⁺ -R ₃ ) MX ₃

R ₂ is C ₁ -C ₂₄ alkyl, C 3 -C 20 cycloalkyl or C 6 -C 20 aryl, R ₃ is hydrogen or C 1 -C ₂₄ alkyl, M is Cu ^{2 +} , Ni ^{2 +} , Co ^{2 +} , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ and Yb ²⁺ , and X is Cl ^-, Br ^- and I ^- it is a halogen ion selected from the more than one or two.

(Formula 7)

(R ₂ -C ₃ H ₃ N ₂ ⁺ -R ₃ ) ₂ MX ₄

R ₂ is C ₁ -C ₂₄ alkyl, C 3 -C 20 cycloalkyl or C 6 -C 20 aryl, R ₃ is hydrogen or C 1 -C ₂₄ alkyl, M is Cu ²⁺ , Ni ²⁺ , Co ^{2 +} , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ and Yb ²⁺ , and X is Cl ^-, Br ^- and I ^- it is a halogen ion selected from the more than one or two.

For example, the perovskite-structured compound may be AMX ^a _x X ^b _y or A ₂ MX ^a _x X ^b _y (real number 0 <x <3, real number 0 <y <3, x + y = X ^a and X ^b may be different halogen ions).

For example, a perovskite compound of the structure X AMX ^a _x ^b _y (0≤x≤3 mistake, 0≤y≤3 the real and x + y = 3, X ^a and X ^b are different from each other halogen ions ) Or A ₂ MX ^a _x X ^b _y (a real number of 0? X? 4, ^a real number of 0? Y? 4 and x + y = 4, and X ^a and X ^b are different halogen ions).

For example, in Formula 4 or Formula 5, R ₁ may be C1-C24 alkyl, preferably C1-C7 alkyl, more preferably methyl. As a specific example, the perovskite structure compound may be CH ₃ NH ₃ PbI _x Cl _y (real number 0 ≦ _x ≦ ₃ , real number 0 ≦ _y ≦ 3 and x + y = 3), CH ₃ NH ₃ PbI _x Br _y (real number of 0? X? 3, real number of 0? Y? 3 and x + y = 3), CH ₃ NH ₃ PbCl _x Br _y (real number 0? _{X? 3} , and x + y = 3), and _{CH 3 NH 3 PbI x F y} (0≤x≤3 mistake, it can be selected at least one or both on the real 0≤y≤3 and x + y = 3), also _{(CH 3 NH 3) 2 PbI} x Cl y ( 0≤x≤4 of mistakes, 0≤y≤4 real and x + y = 4), ( CH 3 NH 3) 2 PbI x Br y (0≤x ≤4 mistake, 0≤y≤4 the real and x + y = 4), CH 3 NH 3 PbCl x Br y (0≤x≤4 mistake, 0≤y≤4 the real and x + y = 4 ) and _{(CH 3 NH 3) 2 PbI} x F y (0≤x≤4 mistake, can be selected at least one or both on the real 0≤y≤4 and x + y = 4).

For example, in Formula 6 or Formula 7, R ₂ can be C ₁ -C ₂₄ alkyl and R ₃ can be hydrogen or C 1 -C ₂₄ alkyl, preferably R ₂ can be C ₁ -C 7 alkyl, and R ₃ is hydrogen Or C1-C7alkyl, more preferably R &lt; ₂ &gt; may be methyl and R &lt; ₃ &gt; may be hydrogen.

An organic / organic hybrid perovskite solar cell of the present invention comprises a first electrode; A composite layer on which the light absorber is embedded, the composite layer being positioned on the first electrode; A light absorbing structure disposed on the composite layer and made of a light absorbing material; A hole conduction layer disposed on the light absorbing structure; And a second electrode located above the hole conduction layer, wherein the hole conduction layer contains the hole transport compound for the organic / hybrid hybrid perovskite type solar cell of the present invention.

The hole transport compound for an organic / inorganic hybrid perovskite solar cell represented by Formula 1 of the present invention is a first electrode; A composite layer on which the light absorber is embedded, the composite layer being positioned on the first electrode; A light absorbing structure disposed on the composite layer and made of a light absorbing material; A hole conduction layer disposed on the light absorbing structure; And a second electrode located above the hole conductive layer. The organic electroluminescent device according to the present invention has a higher efficiency than the organic electroluminescent device in a non-organic hybrid perovskite solar cell having a structural feature.

This is because the organic / organic hybrid perovskite solar cell having the above-described structural features has a structure in which a light absorber layer having a structure including a composite layer having an electron carrier, a light absorber, and a light absorbing structure formed on the complex layer It has a double layered structure and has a structure in which an electron carrier and a hole transport compound are well combined with each other organically and has a high LUMO level so as to efficiently block leakage electrons, Organic hybrid perovskite solar cells have the synergistic effect on the power generation efficiency and have higher power generation efficiency by employing the compound of formula (1), which is the hole transfer compound for the organic / organic hybrid perovskite type solar cell of the present invention.

That is, the hole transporting compound represented by Formula 1 of the present invention has a structure in which the light absorbing body is filled with the porous electron transporting material and the light absorbing structure made of the light absorbing material is positioned on the porous electron transporting body And has a higher power generation efficiency when it is employed in a hole conduction layer of an organic / inorganic hybrid perovskite solar cell having a structure in which a light absorber covers an upper portion of a porous electron carrier.

The terms referred to in the present invention, such as a hole transport compound, a light absorber, an electron transporting material, and a hole conduction layer, are definitions that can be appreciated by those skilled in the art.

The hole transport layer of the solar cell according to an embodiment of the present invention may include a hole transport compound and a phthalocyanine derivative for the organic / hybrid hybrid perovskite type solar cell.

The phthalocyanine derivative may be doped to the hole conduction layer together with the hole transporting compound for the organic / organic hybrid perovskite type solar cell, thereby realizing a better efficiency. The phthalocyanine derivative may be a compound represented by the following general formula (8) .

[Chemical Formula 8]

[In the formula (8)

M is copper, zinc, cobalt, lead, silver, magnesium, iron, titanyl or vanadyl;

R ₂₁ to R ₂₄ independently represent hydrogen, (C 1 -C 7) alkyl, (C 1 -C 7) alkoxy or sulfonic acid group (-SO ₃ H)

In detail, when M of the phthalocyanine derivative represented by Formula 8 is copper (Cu), zinc (Zn), or cobalt (Co), the leakage current of the solar cell can be completely blocked and the electronic blocking property can be improved It is possible to provide a solar cell showing higher efficiency.

The phthalocyanine derivative represented by Formula 8 according to an embodiment of the present invention may be added in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the hole transporting compound for the organic / organic hybrid perovskite type solar cell, To 15 parts by weight, and more preferably from 2 to 10 parts by weight, of the total weight of the composition.

The present invention also relates to an organic / organic hybrid perovskite solar cell containing a hole transport compound for an organic / inorganic hybrid perovskite type solar cell represented by Formula 1 of the present invention and a solar cell module including such a solar cell to provide.

Hereinafter, the present invention will be described in detail with reference to specific examples of the present invention, but it is not intended to limit the claims of the present invention.

[Example 1]

Preparation of 2,4'-dimethoxydiphenylene amine

In 100 mL 2-necked flask under a nitrogen gas o -anisidine (2.00 g, 16.2 mmol ), 4-bromoaniline (3.34g, 17.9 mmol), sodium tert-butoxide (2.34 g, 24.4 mmol), tris (dibenzylideneacetone) dipalladium (0 ) (0.149 g, 0.162 mmol) and tri-tertbutylphosphine (0.053 g, 0.26 mmol) were added, and 23 mL of anhydrous toluene was added and the mixture was stirred at 110 ° C for 12 hours. When the reaction was completed, the reaction mixture was extracted with ethyl acetate, washed with brine, dried over MgSO ₄ to remove the solvent, and then separated and purified by column chromatography (ethyl acetate / hexane = 1/10) to obtain the title compound as a sticky solid (54%, 2.01 g).

^{1 H-NMR (CDCl3, 300} MHz) δ = 7.11 (d, 2H), 7.03 (dd, 1H), 6.75-6.90 (m, 5H), 5.98 (br s, 1H), 3.90 (s, 3H), 3.80 (s, 1 H).

N ² , N ^2' , N ⁷ , N ^{7 '} -tetrakis (2-methoxyphenyl) -N ² , N ^2' , N ⁷ , N ^{7 '} -tetrakis (4-

methoxyphenyl) -9,9'spirobi [fluorene] -2,2 ', 7,7'tetraamine (hereinafter referred to as po)

(2.00 g, 8.72 mmol), 2,2 ', 7,7'-tetrabromo-9,9'spirobi [9H-fluorene] (1.23 g, 1.94 mmol) in a 50 mL two-necked flask under nitrogen gas, tert-butylphosphine (0.025 g, 0.12 mmol) was added to a solution of sodium tert-butoxide (1.12 g, 11.6 mmol), tris (dibenzylideneacetone) dipalladium Lt; / RTI &gt; for 12 hours. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, washed with brine, dried over MgSO ₄ to remove the solvent and purified by column chromatography (ethyl acetate / hexane = 1/2) to give the title compound as a beige solid (40%, 0.95 g).

¹ H-NMR (CDCl ₃ , 500 MHz)? = 7.32 (d, 4H), 7.08 (7, 4H), 6.96 (d, 4H), 6.86 s, 4H), 3.75 (s, 12H), 3.47 (s, 12H).

¹³ C-NMR (CDCl ₃ , 125 MHz)? = 154.95, 154.55, 149.83, 146.84, 141.29, 136.08, 135.09, 128.48, 125.39, 125.59, 121.24, 120.70, 119.19, 116.52, 113.96, 113.09, 65.65, 55.70, .

m / z 1124 (M &lt; + &gt;).

[Comparative Example 1]

N ² , N ² , N ^2' , N ^2' , N ⁷ , N ⁷ , N ^{7 '} , N ^{7 '} -octakis (4-methoxyphenyl) -9,9 ' spiro [

fluorene] -2,2'7,7'tetraamine (spiro-OMeDTAD, hereinafter referred to as pp)

(2.00 g, 8.72 mmol), 2,2 ', 7,7'-tetrabromo-9,9'spirobi [9H-fluorene] (1.23 g, 1.94 mmol) in a 50 mL two-necked flask under nitrogen gas, tert-butylphosphine (0.025 g, 0.12 mmol) was added to a solution of sodium tert-butoxide (1.12 g, 11.6 mmol), tris (dibenzylideneacetone) dipalladium Lt; / RTI &gt; for 12 hours. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, washed with brine, dried over MgSO ₄ to remove the solvent and purified by column chromatography (ethyl acetate / hexane = 1/2) to give the title compound as a beige solid (45%, 1.07 g).

¹ H-NMR (CDCl ₃ , 500 MHz)? = 7.36 (d, 4H), 6.91 (d, 16H), 6.80 (br d, 4H) (s, 24 H).

¹³ C-NMR (CDCl ₃ , 125 MHz)? = 154.95, 149.93, 147.11, 141.45, 135.46, 124.96, 122.67, 119.72, 118.03, 114.31, 65.45, 55.42.

m / z 1124 (M &lt; + &gt;).

[Comparative Example 2]

Preparation of 3,4-Dimethoxydiphenyleneamine

In 100 mL 2-necked flask under a nitrogen gas m -anisidine (2.00 g, 16.2 mmol ), 4-bromoaniline (3.34g, 17.9 mmol), sodium tert-butoxide (2.34 g, 24.4 mmol), tris (dibenzylideneacetone) dipalladium (0 ) (0.149 g, 0.162 mmol) and tri-tertbutylphosphine (0.053 g, 0.26 mmol) were added, and 23 mL of anhydrous toluene was added and the mixture was stirred at 110 ° C for 12 hours. When the reaction was completed, the reaction mixture was extracted with ethyl acetate, washed with brine, dried over MgSO ₄ to remove the solvent, and then separated and purified by column chromatography (ethyl acetate / hexane = 1/10) to obtain the title compound as a sticky solid (54%, 2.01 g).

_{^{1 H-NMR (CDCl 3,}} 300 MHz) δ = 7.05-7.15 (m, 3H), 6.87 (d, 2H), 6.35-6.53 (m, 3H), 5.50 (br s, 1H), 3.80 (s, 3H), 3.76 (s, 3H).

N ² , N ^2' , N ⁷ , N ^{7 '} -tetrakis (3-methoxyphenyl) -N ² , N ^2' , N ⁷ , N ^{7 '} -tetrakis (4-

methoxyphenyl) -9,9'spirobi [fluorene] -2,2 ', 7,7'tetraamine (hereinafter referred to as pm)

(2.00 g, 8.72 mmol), 2,2 ', 7,7'-tetrabromo-9,9'spirobi [9H-fluorene] (1.23 g, 1.94 mmol) in a 50 mL two-necked flask under nitrogen gas, tert-butylphosphine (0.025 g, 0.12 mmol) was added to a solution of sodium tert-butoxide (1.12 g, 11.6 mmol), tris (dibenzylideneacetone) dipalladium Lt; / RTI &gt; for 12 hours. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, washed with brine, dried over MgSO ₄ to remove the solvent and purified by column chromatography (ethyl acetate / hexane = 1/2) to give the title compound as a beige solid (40%, 0.95 g).

_{^{1 H-NMR (CDCl 3,}} 500 MHz) δ = 7.42 (d, 4H), 7.05 (t, 4H), 6.97 (d, 8H), 6.88 (d, 4H), 6.81 (d, 8H), 6.65 ( d, 4H), 6.40-6.51 (m, 12H).

¹³ C-NMR (CDCl ₃ , 125 MHz)? = 160.17, 155.87, 129.80, 149.37, 146.583, 140.45, 136.19, 129.44, 126.80, 123.98, 120.08, 119.18, 114.52, 114.01, 107.35, 106.44, 65.51, .

m / z 1124 (M &lt; + &gt;).

[Example 2]

Porous TiO ₂  Thin Film Substrate Manufacturing

After cutting a glass substrate (FTO: F-doped SnO ₂ , 8 ohms / cm ² , Pilkington, hereinafter referred to as FTO substrate (first electrode)) coated with fluorine-containing tin oxide to a size of 25 x 25 mm, Partially removing the FTO.

A 50 nm thick TiO ₂ dense film as a metal oxide thin film was prepared by spray pyrolysis on the cut and partially etched FTO substrate. Spray pyrolysis was carried out using a solution of titanium acetylacetonate (TAA): EtOH (1: 9 v / v%), spraying for 3 seconds on the FTO substrate placed on a hot plate kept at 450 ° C and stopping for 10 seconds The thickness was adjusted by the method.

TiO ₂ powder having an average particle size (diameter) of 50 nm (prepared by hydrothermally treating titanium peroxocomplex aqueous solution of 1 wt% based on TiO ₂ dissolved therein at 250 ° C for 12 hours) was mixed with 10% by weight of ethyl cellulose acetate the ethyl cellulose solution in an alcohol, then a solution was added 5 ml per TiO ₂ powder 1g, adding the hotel pinol (terpinol) 5 g per 1 g TiO ₂ powder, and the ethanol removed by vacuum distillation TiO ₂ Paste.

Ethanol was added to the prepared TiO ₂ powder paste to prepare a TiO ₂ slurry for spin coating. The TiO ₂ thin film of the FTO substrate was coated with a TiO ₂ slurry for spin coating by a spin coating method and heat-treated at 500 ° C. for 60 minutes. Subsequently, the substrate which had been thermally treated was immersed in a 30 mM aqueous solution of TiCl ₄ at 60 ° C., , Washed with deionized water and ethanol, dried, and then heat-treated at 500 ° C for 30 minutes to prepare a porous TiO ₂ thin film (porous electron carrier).

Fabrication of light absorber solution

30 mL of hydrochloric acid (57% in water, Aldrich) and 27.86 mL of methylamine (40% in methanol, manufactured by Junsei Chemical Co., Ltd.) were reacted in a 250 mL two-necked round flask at 0 ° C for 2 hours. The reaction mixture is dissolved the precipitate was obtained by distillation under reduced pressure for 1 hour at 50 ℃ in ethanol was recrystallized using ethyl ether and dried at 60 ℃ for 24 hours to produce a NH ₃ CH ₃ I.

The obtained CH ₃ NH ₃ I was dissolved in a mixed solution of γ-butyrolactone and dimethylsulfoxide (7: 3), PbI 2 (Aldrich) was added thereto and dissolved at 60 ° C. for 12 hours to prepare a CH ₃ NH ₃ PbI 3 solution (40 wt%) .

Manufacture of perovskite light absorbers

The porous TiO ₂ thin-film substrate (mp-TiO2 / bl-TiO2 / FTO) onto the light absorbent solution prepared in (CH3NH3PbI3 solution) to 1000 rpm in 90 seconds coating and re-coated for 30 seconds at 5000 rpm during the production in the And dried at 100 ° C for 10 minutes to prepare a light absorber. Here, 1 mL of toluene was dropwise added to the substrate in the second spin-coating step.

Preparation of hole conduction layer solution for forming hole conduction layer

The (N ^2, N ² a hole conductor prepared in Example 1 to form a hole conducting layer ^{', N 7, N 7'} -tetrakis (2-methoxyphenyl) -N 2, N 2 ', N 7, N ^{7 '} -tetrakis (4-methoxyphenyl)

-9,9'spirobi [fluorene] -2,2 ', 7,7'tetraamine, po) were dissolved in toluene to prepare a hole conductor solution having a concentration of 10 mM, and 10 μl of Li-bis (trifluoromethanesulfonyl) imide The hole conduction layer solution was prepared by adding Li-TFSI / acetonitrile (170 mg / 1 ml) and 5 μl TBP (4-tert-butylpyridine).

Manufacture of organic / organic hybrid perovskite solar cells

The hole conductive layer solution prepared above was spin-coated at 3000 rpm for 30 seconds on the composite layer formed with the light absorbing structure manufactured above to form a hole conductive layer.

Thereafter, an Au electrode (second electrode) having a thickness of 70 nm was formed on the hole conduction layer by vacuum evaporation of Au with a thermal evaporator (not more than 5 × 10 ^-6 torr) using a thermal evaporator to form Au / CH 3 NH 3 PbI 3 / -TiO2 / bl-TiO2 / FTO type solar cell.

The active area of this electrode was 0.16 cm ² .

SEM photographs of cross sections of the manufactured solar cells are shown in FIG. 1, and the characteristics of the produced solar cells are shown in Table 1 below.

[Comparative Example 3]

The photovoltaic cell was manufactured in the same manner except that pp (spiro-OMeTAD) was used instead of the hole conduction layer solution. The characteristics of the produced solar cell are shown in Table 1 below.

[Comparative Example 4]

A solar cell was fabricated in the same manner except that pm was used instead of the hole conduction layer solution, and the characteristics of the produced solar cell are shown in Table 1 below.

[Comparative Example 5]

The solar cell was manufactured in the same manner except that the hole conduction layer solution was replaced with a commercially available pp instead of the po. The properties of the produced solar cell are shown in Table 1 below.

As shown in Table 1, the solar cell employing the hole transport compound of the present invention has a very high efficiency as compared with the solar cell employing the conventional hole transport compound.

[Example 3]

Porous TiO ₂  Thin Film Substrate Manufacturing

After cutting a glass substrate (FTO: F-doped SnO ₂ , 8 ohms / cm ² , Pilkington, hereinafter referred to as FTO substrate (first electrode)) coated with fluorine-containing tin oxide to a size of 25 x 25 mm, Partially removing the FTO.

A 50 nm thick TiO ₂ dense film as a metal oxide thin film was prepared by spray pyrolysis on the cut and partially etched FTO substrate. Spray pyrolysis was carried out using a 20 mM titanium diisopropoxide bis (acetylacetonate) solution (Aldrich), sprayed for 3 seconds on a FTO substrate placed on a hot plate maintained at 450 ° C, and stopped for 10 seconds. Respectively.

TiO ₂ powder having an average particle size (diameter) of 50 nm (prepared by hydrothermally treating titanium peroxocomplex aqueous solution of 1 wt% based on TiO ₂ dissolved therein at 250 ° C for 12 hours) was mixed with 10% by weight of ethyl cellulose acetate the ethyl cellulose solution in an alcohol, then a solution was added 5 ml per TiO ₂ powder 1g, adding the hotel pinol (terpinol) 5 g per 1 g TiO ₂ powder, and the ethanol removed by vacuum distillation TiO ₂ Paste.

2-methoxyethanol was added to the prepared TiO ₂ powder paste to prepare a TiO ₂ slurry for spin coating. The TiO ₂ thin film of the FTO substrate was coated with a TiO ₂ slurry for spin coating by a spin coating method and heat-treated at 500 ° C. for 60 minutes. Subsequently, the substrate which had been thermally treated was immersed in a 30 mM aqueous solution of TiCl ₄ at 60 ° C., , Washed with deionized water and ethanol, dried, and then heat-treated at 500 ° C for 30 minutes to prepare a porous TiO ₂ thin film (porous electron transporting material, thickness: 100 nm).

Fabrication of light absorber solution

NH ₂ CH = NH ₂ I (= FAI) and CH ₃ NH ₃ Br (= MABr) were added to PbI 2 and PbBr 2 dissolved in a DMF: DMSO (6: 1, v / v) mixed solution in a 250 mL two- (FAPbI ₃ ) 0.85 (MAPbBr ₃ ) 0.15 perovskite solution with a concentration of 1.05 M was prepared by mixing.

Manufacture of perovskite light absorbers

The optical absorber solution ((FAPbI ₃ ) _0.85 (MAPbBr ₃ ) _0.15 perovskite solution) prepared above was coated on the porous TiO ₂ thin film substrate (mp-TiO ₂ / bl-TiO ₂ / FTO) rpm for 5 seconds, coated again at 5000 rpm for 1 second, and dried at 100 캜 for 10 minutes to prepare a light absorber. Here, 1 mL of diethyl ether was dropwise added to the substrate in the second spin-coating step.

Preparation of hole conduction layer solution for forming hole conduction layer

The (N ^2, N ² a hole conductor prepared in Example 1 to form a hole conducting layer ^{', N 7, N 7'} -tetrakis (2-methoxyphenyl) -N 2, N 2 ', N 7, N ^{7 '} -tetrakis (4-methoxyphenyl)

-9,9'spirobi [fluorene] -2,2 ', 7,7' tetraamine, po) were dissolved in toluene to prepare a hole conductor solution having a concentration of 30 mg / ml, and 21.5 [ (4-tert-butylpyridine), and 19.8 占 퐇 of tris (2- (1H-pyrazol-1-yl) -4-tert-butoxycarbonyl) imide (Li-TFSI) / acetonitrile (170 mg / butylpyridine-cobalt (III) tris (trifluoromethylsulfonyl) imide: (FK209) / acetonitrile (150 mg / 1 ml) was added to prepare a hole conduction layer solution.

Manufacture of organic / organic hybrid perovskite solar cells

The hole conductive layer solution prepared above was spin-coated at 3000 rpm for 30 seconds on the composite layer formed with the light absorbing structure manufactured above to form a hole conductive layer.

Thereafter, an Au electrode (second electrode) having a thickness of 70 nm was formed on the hole conduction layer by vacuum evaporation of Au with a thermal evaporator (5 × 10 ^-6 torr or less) using a thermal evaporator to form Au / (FAPbI ₃ ) _0.85 (MAPbBr ₃ ) _0.15 (CuPC) / mp-TiO ₂ / bl-TiO ₂ / FTO type solar cell.

The active area of this electrode was 0.16 cm ² .

The characteristics of the produced solar cell are shown in Table 2 below.

[Example 4]

Example holes when the conductive layer forming solution for hole conduction layer made from 3, copper (II) 0.61 mg of the additive 2,9,16,23-tetra- tert -butyl-29 H , 31 H -phthalocyanine (tert -butylCuPC) was further added, and the properties thereof are shown in Table 2 below.

[Example 5]

Example holes when the conductive layer forming solution for hole conduction layer made from 3, copper (II) 1.51 mg of the additive 2,9,16,23-tetra- tert -butyl-29 H , 31 H -phthalocyanine (tert -butylCuPC) was further added, and the properties thereof are shown in Table 2 below.

[Example 6]

Example holes when the conductive layer forming solution for hole conduction layer made from 3, 3.0 mg of an additive copper (II) 2,9,16,23-tetra- tert -butyl-29 H, 31 H -phthalocyanine (tert -butylCuPC, CuPC) was further added, and the properties thereof are shown in Table 2 below.

[Comparative Example 6]

Example holes when the conductive layer forming solution for hole conduction layer made from 3, of 6.01 mg copper (II) as an additive 2,9,16,23-tetra- tert -butyl-29 H , 31 H -phthalocyanine (tert -butylCuPC, CuPC) was further added, and the properties thereof are shown in Table 2 below.

As shown in Table 2, it can be seen that CuPC, which is a compound represented by Formula 8 according to the present invention, is further added to the hole conduction layer to have an improved current detection resistance (R _shunt ).

That is, the electron blocking property is improved and a better photoelectric conversion efficiency (PCE) can be realized.

Claims (9)

A hole transport compound for a non-organic / organic hybrid perovskite solar cell represented by the following formula (1).
[Chemical Formula 1]

[In the above formula (1)
Z ₁ to Z ₄ and Z ₁₁ to Z ₁₄ are independently of each other O, S or Se;
R ₁ to R ₄ and R ₁₁ to R ₁₄ independently of one another are (C 1 -C 7) alkyl] The method according to claim 1,
Wherein Z ₁ to Z ₄ and Z ₁₁ to Z ₁₄ are independently of each other O or S;
Wherein R ₁ to R ₄ and R ₁₁ to R ₁₄ are each independently (C 1 -C 3) alkyl. 3. The method of claim 2,
Z ₁ to Z ₄ are O;
And R &_lt; ₁ &gt; to R &_lt; ₄ &_gt; independently of one another are (C1-C3) alkyl. The method according to claim 1,
The hole transporting compound for organic / inorganic hybrid perovskite type solar cells is represented by the following formula (1-1).
[Formula 1-1]

[In the formula 1-1,
Z ₁₁ to Z ₁₄ independently of one another are O, S or Se;
R ₁₁ to R ₁₄ are each independently (C 1 -C 7) alkyl] A solar cell comprising a hole transporting layer for a hole transporting compound for a non-organic / organic hybrid perovskite solar cell represented by the following formula (1).
[Chemical Formula 1]

[In the above formula (1)
Z ₁ to Z ₄ and Z ₁₁ to Z ₁₄ are independently of each other O, S or Se;
R ₁ to R ₄ and R ₁₁ to R ₁₄ independently of one another are (C 1 -C 7) alkyl] 6. The method of claim 5,
Wherein the hole conduction layer further comprises a phthalocyanine derivative. The method according to claim 6,
Wherein the phthalocyanine derivative is represented by the following general formula (8).
[Chemical Formula 8]

[In the formula (8)
M is copper, zinc, cobalt, lead, silver, magnesium, iron, titanyl or vanadyl;
R ₂₁ to R ₂₄ independently represent hydrogen, (C 1 -C 7) alkyl, (C 1 -C 7) alkoxy or sulfonic acid group (-SO ₃ H) 8. The method of claim 7,
Wherein the phthalocyanine derivative is contained in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the hole transporting compound for the organic / organic hybrid perovskite type solar cell. 6. The method of claim 5,
The solar cell includes a first electrode; A composite layer on which the light absorber is embedded, the composite layer being positioned on the first electrode; A light absorbing structure disposed on the composite layer and made of a light absorbing material; A hole conduction layer disposed on the light absorbing structure; And a second electrode located above the hole conductive layer; &Lt; / RTI &gt;

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