KR102526084B1 - Organic photoconductive materials and Light conversion device using the same - Google Patents

Abstract

The present invention relates to an organic photoconductive material, which can be manufactured at a low cost, can have high charge mobility to be suitable for use as a hole transport material, can have high conversion efficiency, and can provide perovskite-type solar cells with high reliability for long-term use, and a light conversion device using the same. In addition, when the organic photoconductive material is used in a sensor material, an organic light-emitting diode (OLED) device, an electrostatic recording device, or an organic semiconductor laser diode (OSLD) device, a device with excellent responsiveness can be provided.

Description

Organic photoconductive materials and light conversion device using the same

The present invention relates to an organic photoconductive material and a photoconversion device using the same.

Recently, organic photoconductive materials have been widely researched and developed, and are used as hole transport materials for various electronic devices. Among organic solar cells, which are one of photoelectric conversion devices, perovskite type solar cells that require hole transport materials are there is.

A perovskite solar cell is a solar cell using a metal halide material having a perovskite structure for a light absorption layer. This perovskite solar cell can be manufactured using solution coating, so it can be formed on a curved surface as well as lowering the manufacturing cost.

As the structure of the perovskite solar cell is schematically shown in FIG. 1, a hole transport layer 7 and an electron transport layer 5 are stacked above and below the perovskite layer 6, and the laminate is 8) has an overlapping structure. The driving principle of the perovskite solar cell is that holes and electrons are generated by light absorption in the perovskite layer 6 first. The generated holes and electrons move to the hole transport layer 7 and the electron transport layer 5, respectively, and move to the electrodes 4 and 8 through the respective layers.

The hole transport layer of this perovskite solar cell contains a hole transport compound, and Spiro-OMeTAD (Japanese Unexamined Patent Publication No. 2017-502462) is known as this hole transport compound.

Hole-Transport Material (HTM) included in these perovskite solar cells plays an important role in terms of charge extraction characteristics, hysteresis characteristics, and device stability.

Commonly used hole transport materials are spiro-OMeTAD (2,2',7,7''-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spiro-bifluorene) and its derivatives. These materials provide an appropriate energy level in consideration of hole transport characteristics and electron block characteristics, and the rigid spirobifluorene structure twisted at 90° provides high thermal stability while suppressing aggregation. However, the hole transport properties of spiro-MeTAD are relatively insufficient due to the weak electron donor property of spirobifluorene, and the cost of Spiro-OMeTAD is quite high, which increases the cost of manufacturing a solar cell and is a cheap hole transport compound. (Japanese Patent Application No. 2020-537410) is also known.

Korean Registration Patent No. 10-1853342 (Announcement date: 2018.04.30)

Since problems such as stability and reliability of solar cell devices (deterioration in performance due to long-term use) have not been sufficiently solved, organic photoconductive materials (hole transport materials) that sufficiently improve their reliability are needed to solve these problems. It is also true that there is no An object of the present invention is to provide an organic photoconductive material that sufficiently improves reliability and a perovskite solar cell, which is one of photoelectric conversion devices using the same, and for this purpose, introduction into the molecular structure for the purpose of improving hole transport performance The condensed heterocyclic structure in which the double bonds essential for the expansion of the conjugated system are contained in the heterocycle leads to the stabilization of organic molecules, thereby improving the reliability of the photoelectric conversion device.

In order to solve the above problems, the organic photoconductive material of the present invention includes an amine compound represented by Formula 1 below.

[Formula 1]

In Formula 1, Ar1 includes an unsubstituted arylene group or an arylene group having a substituent, Ar2 includes an unsubstituted condensed heterocyclic group or a condensed heterocyclic group having a substituent, and Ar3 and Ar4 are mutually As the same or different, it includes an unsubstituted aryl group, an aryl group having a substituent, an unsubstituted heterocyclic group, or a heterocyclic group having a substituent, wherein n is an integer of 2 to 4.

In addition, the present invention is to provide a composition for forming a hole transport layer of a perovskite solar cell, characterized in that it comprises the organic photoconductive material.

In addition, the present invention relates to a photoconversion device comprising the organic photoconductive material, which is an OLED (Organic Ligtt-Emitting Diode) device, an electrostatic cell device, an OSLD (Organic Semiinductor Laser Diode) device or a perovskite It is intended to provide a photoconversion device characterized in that it is a light solar cell.

The organic photoconductive material of the present invention can be manufactured at low cost and has high charge mobility, so it is suitable for use as a hole transport material, has high conversion efficiency, and provides a perovskite type solar cell with high long-term reliability can do.

In addition, when the organic photoconductive material is used as a sensor material, an OrganIc LIgtt-EmIttIng DIode (OLED) device, an electrostatic lock device, or an OrganIc SemcInductor Laser DIode (OSLD) device, a device with excellent response can be provided.

1 is a schematic cross-sectional view of a net perovskite solar cell.
2 is a schematic cross-sectional view of an inverted perovskite solar cell.

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

The organic photoconductive material of the present invention includes an amine compound represented by Formula 1 below.

[Formula 1]

In Formula 1, Ar1 includes an unsubstituted arylene group or an arylene group having a substituent, and preferably, Ar1 includes substituted or unsubstituted 1.4-phenylene, 1,3-phenylene, Arylene groups, such as 1,2-phenylene, 1.4-naphthylene, and 9,10-bis (chloromethyl) anthracene, are included.

Ar2 in Formula 1 includes an unsubstituted fused heterocyclic group or a fused heterocyclic group having a substituent, and is preferably 2,5-benzofuran, N-2,5-indole, 2,5- Condensed heterocyclic groups such as thionaphthine may be included.

Ar3 and Ar4 in Formula 1 are the same as or different from each other, and include an unsubstituted aryl group, an aryl group having a substituent, an unsubstituted heterocyclic group, or a heterocyclic group having a substituent, and preferably Ar3 and Ar4 Are the same as or different from each other, aryl groups such as p-methoxyphenyl, p-thiomethoxyphenyl, p-dimethylaminophenyl, 5-methylciprane, 5-methylthiophene, N-methyl5-methiothiophene It may include a heterocyclic group such as.

In Formula 1, n is an integer of 2 to 4.

The amine compound represented by Chemical Formula 1, which is the organic photoconductive material of the present invention, has high charge mobility. By using the organic photoconductive material of the present invention having such a high charge mobility as a hole transport material, that is, a hole transport layer forming composition, a perovskite solar cell with high conversion efficiency and long-term reliability can be realized. .

For a preferred example of the organic photoconductive material of the present invention, the amine compound represented by Chemical Formula 1 may be an amine compound represented by Chemical Formula 2 below.

[Formula 2]

In Formula 2, Y includes -O-, -S-, -NH-, or a nitrogen atom having a substituent of an allyl group or an alkyl group, and preferably Y is -O-, -S- or -NH -, more preferably -O-. And, each of Ar1, Ar3, Ar4 and n in Chemical Formula 2 is the same as defined in Chemical Formula 1.

In addition, in the organic photoconductive material including the amine compound represented by Chemical Formula 1 of the present invention, a preferred embodiment of the amine compound is as shown in Figures 1 to 8 below.

[Figure 1]

[Figure 2]

[Figure 3]

[Figure 4]

[Figure 5]

[Figure 6]

[Figure 7]

[Figure 8]

Among the exemplary compounds shown in Figures 1 to 8 (Compounds 1 to 70), Ar1 is a 1,2 phenylene group, Ar2 is a 2,5-benzofuran, and Ar3. Compounds in which Ar4 is the same p-methoxyphenyl group or p-methylthiophenyl or p-dimethylaminephenyl group are suitable, Ar1 is a 1,4-naphthylene group, Ar2 is a 2,5-benzofuran group, Ar3, More suitable are compounds in which Ar4 is the same p-methoxyphenyl group, p-methylthiophenyl group, or p-dimethylaminephenyl group, Ar1 is a 1,2,4,5-phenyl group, and Ar2 is 2,5-benzofuran. group, and a compound in which Ar3 and Ar4 are identical to each other is a p-methoxyphenyl group, a p-methylthiophenyl group, or a p-dimethylaminephenyl group.

Among the compounds 1 to 70, compound 1 is an amine compound represented by Formula 3 below.

[Formula 3]

The amine compound represented by Chemical Formula 1, which is the organic photoconductive material of the present invention, can be synthesized by the following method.

First, an etherification reaction according to the following Reaction Scheme 1 is performed with an arylene compound represented by the following Chemical Formula 4, wherein a nitro group, an aldehyde group, and a hydroxyl group are substituted, and an arylene compound represented by the following Chemical Formula 5, to obtain Ether intermediates are prepared.

[Formula 4]

[Formula 5]

Ar2 in Formula 5 is the same as defined in Formula 1, X is -Cl, -Br or -I, and n is an integer from 2 to 4.

[Formula 6]

Ar1, Ar2 and n in Formula 6 are the same as those defined in Formula 1 above.

[Scheme 1]

The etherification reaction of Scheme 1 is carried out, for example, as follows. The arylene compound (first arylene compound) represented by Chemical Formula 4 and the arylene compound (second arylene compound) represented by Chemical Formula 5 are etherified in a solvent.

At this time, when n is 2 in Formula 5, the first arylene compound and the second arylene compound are reacted in a molar ratio of 1: 2.0 to 2.4, and when n is 3 in Formula 5, the first arylene compound and the second arylene compound are reacted. The two arylene compounds are reacted in a molar ratio of 1: 3.0 to 3.6, and when n is 4 in Formula 5, the first arylene compound and the second arylene compound are reacted in a molar ratio of 1: 4.0 to 4.8.

Examples of solvents used in the ether reaction include tetrahydrofuran, 1,4-dioxic acid, ethylene glycol, methyl ether, N,N-dimethylformamide, and N,N-dimethylacetamide. In addition, as the organic amine base, triethylamine, N,N'-diisopropylethylamine, 1,5-diazabicyclo[4.3.0]-5-nonene (1,5-Diazabicyclo[4.3.0] -5-nonene), 1,8-diazabicyclo [5.4.0] undeca-7-ene, and the like.

Alternatively, the nitro compound (ether intermediate) represented by Chemical Formula 5 may be synthesized stepwise.

That is, the first arylene compound and the second arylene compound (when n is 2) are mixed in a molar ratio of 1:1 to 2.4, and the first arylene compound and the second arylene compound (when n is 3) ), in a molar ratio of 1: 1 to 3.6, the first arylene compound and the second arylene compound (when n is 4) are heated in a molar ratio of 1: 1 to 4.8, and the ether reaction according to Scheme 2 is performed. By carrying out, the nitro compound (ether intermediate) represented by Formula 6, which is an intermediate, is once isolated.

[Formula 7]

Ar1, Ar2 and n in Formula 7 are the same as those defined in Formula 1 above.

[Scheme 2]

Ar1 and Ar2 in Reaction Scheme 2 are the same as those defined in Formula 1 above.

Next, the ether represented by Formula 7 is prepared in a solvent in a molar ratio of 1: 1 to 2.4 when n is 2, and in a molar ratio of 1: 1 to 3.6 when n is 3 with respect to the organic amine base ether in a solvent. When n is 4, the nitro compound represented by Formula 7 may be synthesized by heating at a molar ratio of 1:1 to 4.8.

Next, the nitro compound represented by Formula 6 is mixed with iron of 100 to 200 mesh in a mixed solvent at a molar ratio of 1:20 to 40 when n in Formula 6 is 2, and when n in Formula 6 is 3, 1: At a molar ratio of 40 to 50, when n in Formula 6 is 4, the general amine compound represented by the following general formula (VII) can be synthesized by adding at a molar ratio of 1:60 to 70, heating, and stirring to reduce the reaction. Examples of the mixed solvent used herein include tetrahydrofuran and water, 1,4-dioxy acid and water, and the like.

[Formula 8]

Ar1, Ar2, and n in Formula 8 are the same as those defined in Formula 1 above.

[Scheme 3]

Ar1, Ar2 and n in Reaction Scheme 2 are the same as those defined in Formula 1 above.

Further, the primary amine compound represented by Formula 8 is an aryl compound which may have a substituent containing a halogen group represented by Formula 9 or Formula 10 below, or a heterocyclic compound which may have a substituent containing a halogen group when n is 2 , 1: at a molar ratio of 2.4 to 2.6, when n is 3, at a molar ratio of 1: 3.6 to 3.9, when n is 4, at a molar ratio of 1: 4.8 to 5.1, Pd coupling reaction to formula (1) The amine compound, which is the organic photoconductive material of the present invention, can be obtained in high yield (see Scheme 4 below).

[Formula 9]

Ar3 in Formula 9 is the same as defined in Formula 1 above, and X is -Cl, -Br or -I.

[Formula 10]

Ar4 in Formula 10 is the same as defined in Formula 1 above, and X is -Cl, -Br or -I.

[Scheme 4]

Ar1, Ar2, Ar3, Ar4 and n in Scheme 4 are the same as defined in Formula 1, and X is -Cl, -Br or -I.

The amine compound represented by Chemical Formula 1, which is the organic photoconductive material of the present invention, is used in the hole transport layer of the perovskite solar cell. As schematically shown in FIGS. 1 and 2 , the perovskite solar cell typically includes a substrate 3, a first electrode 4, a second electrode 8, a perovskite layer, and a hole transport layer 7. ) and the electron transport layer (5).

As shown in FIG. 1, in the perovskite solar cell, the first electrode is a negative electrode and the second electrode is a positive electrode, and the substrate 3, the first electrode 4, the electron transport layer 5, and the perovskite layer , the hole transport layer 7 and the second electrode 8 are stacked in this order (1), as shown in FIG. 2, the first electrode is a positive electrode, the second electrode is a negative electrode, Inverted type in which the substrate 3, the first electrode 4, the hole transport layer 7, the perovskite layer 6, the electron transport layer 5, and the second electrode 8 are stacked in this order ( 2) there is.

(1) Substrate (3)

As the substrate 3, there is no particular problem as long as it has a function of preserving the layers stacked on the substrate, but a transparent substrate having a total light transmittance of 50% or more is preferably selected, and the transparent substrate is not particularly limited, but glass or acrylic resin, Transparent resins such as polyolefin resins, polycarbonate resins, and polyamide resins may be selected. The substrate 3 may be replaced by the first electrode.

(2) 1st electrode 4

As the first electrode 4, a material that has conductivity and transmits light can be used, such as fluorine-doped tin oxide (FTO), antimony-doped iron oxide (ATO), zinc oxide (ZnO), Cast iron oxide SnO ₂ ), indium tin oxide (ITO), indium gallium zinc oxide (IGZO), aluminum doped zinc oxide (AZO), graphene, and the like can be used. These may be used individually by 1 type, or may be used in combination of 2 or more types. Also, depending on pattern formation, it may be used in combination with a non-transparent electrode material.

The thickness of the first electrode 4 is, for example, 200 nm to 12000 nm. It is desired to adjust the resistance value to be 5 to 15 Ω/□.

The first electrode 4 can be formed by a coating method such as deposition, sputtering, spraying, spin coating, and dip coating.

The first electrode may be subjected to cleaning, ozone treatment, or the like before laminating the next layer.

(3) Second electrode 8

As the second electrode 8, oxides such as gold, silver, aluminum, copper, platinum, rhodium, indium, titanium, iron, nickel, tin, zinc, and molybdenum, alloys containing any of these, and conductive of carbon materials and the like can be used. The electrode 8 may be a single layer or two layers using different materials. Moreover, the material used for the 1st electrode can also be used.

The thickness of the second electrode 8 is, for example, 50 nm to 100 nm.

The second electrode 8 can be formed by a coating method such as vapor deposition, sputtering and spraying, spin coating, and dip coating.

(4) Perovskite layer (6)

The perovskite layer 6 contains a compound having a perovskite structure represented by ABX ₃ . Here, A is a monovalent cation, preferably an alkali metal cation, an organic cation, more preferably a cesium cation, a francium cation, RNH ₃ ⁺ (R is an alkyl group having 1 to 10 carbon atoms), NH ₂ CHNH ₂ ⁺ , B is a divalent cation, preferably a divalent cation of a transition metal element or a group ¹³ to group 15 element, more preferably Pb ₂₊ , Sn ₂₊ ^, Ge ₂₊ , ^and X is an anion, preferably has a halide anion. As each of A, B, and X, one type alone or a combination of multiple types may be used, but one type alone is preferable. Specifically, RNH ₃ PbX ₃ , R(NH ₂ ) ₂ PbX ₃ , RNH ₃ SnX ₃ , R(NH ₂ ) ₂ SnX ₃ (R is an alkyl group having 1 to 10 carbon atoms), complexes of these with methylformamide can hear These may use one type or a combination of two or more types.

The thickness of the perovskite layer 6 is, for example, 100 nm to 600 nm.

The perovskite layer 6 can be formed by applying a solution of a component forming the perovskite layer 6 in a solvent by a spray method, a spin coating method, a dip coating method, a die coat method, or the like.

(5) hole transport layer (7)

The hole transport layer 7 is formed using a hole transport layer forming composition containing an amine compound represented by Formula 1 above.

Also, the hole transport layer 7 does not contain a dopant.

The thickness of the hole transport layer 7 is, for example, 10 nm to 500 nm, preferably 50 nm to 150 nm.

The hole transport layer 7 is coated with the hole transport layer forming composition by a spray method, a doctor blade method, a barcode method, a spin coating method, a dip coating method, a die coating method, or the like. In addition, it may be formed through printing by a screen printing method. After that, the solvent may be dried while heating as needed.

(6) electron transport layer (5)

The electron transport layer 5 contains a semiconductor. Examples of the semiconductor include an organic n-type semiconductor and an inorganic n-type semiconductor. The band gap of the semiconductor is 1.5 to 4.2 eV.

As an organic n-type semiconductor, an imide compound, a quinone compound, fullerene, and its derivative(s) are mentioned, for example.

In addition, examples of the inorganic n-type semiconductor include metal oxides and perovskite oxides. Examples of the metal element include transition metals and transition metals of groups 12 to 15, and titanium dioxide is recommended. Examples of titanium dioxide (tinania) include compact titanium and porous titanium, and these can also be treated with titanium tetrachloride.

Examples of the perovskite oxide include SrTiO ₃ and CaTiO ₃ .

The thickness of the electron transport layer 5 is, for example, 10 nm to 500 nm.

The electron transport layer 5 can be formed by a spray method, a spin coating method, or a vacuum deposition method.

(7) others

Blocking (blocking) layer, device encapsulation (packaging) with a glass substrate, etc. can also be used as long as the object of the present invention is not degraded.

In the above, the present invention has been described with a focus on embodiments, but this is only an example and does not limit the embodiments of the present invention, and those skilled in the art to which the embodiments of the present invention belong will appreciate the essential characteristics of the present invention. It will be appreciated that various modifications and applications not exemplified above are possible within a range that does not deviate.

[Example]

Hereinafter, the present invention will be described in detail by structural examples, examples and comparative examples of exemplary compounds 1 to 70 in Figures 1 to 8, but the present invention according to these structural examples (excluding comparison) and examples It is not limited.

In addition, the chemical structure, molecular weight and elemental analysis of the compounds obtained in Structural Examples were measured under the following equipment and conditions.

(1) Chemical structure

The chemical structure was measured under the equipment and conditions in Table 1 below.

*Nuclear Magnetic Resonance Device: NMR (Bruker, DPX-200)
*Sample adjustment: Approx. 4mg sample / 0.4m (CDCl ₃ )
*Measurement mode: 1H (normal), 13C (normal, DPET-135)
In particular, in the NMR measurement, "s" means SInglet, and "br" means the width of the peak.

(2) molecular weight

Molecular weight was measured by the equipment and conditions in Table 2 below.

*Molecular weight measuring device: LC-MS (Thermo FIsher, Finegang LCQDeca Mass Spectrometer System)
*LC column: GL-ScIences InertsIl ODS-3 2.1×100mm
*Column temperature: 40℃
*Eluent = methanol : water = 90:10
*Sample injection amount: 5μl
*Detector: UV254 nm and MS ESI

(3) Elemental analysis

Elemental analysis was measured with the equipment and conditions in Table 3 below.

*Elemental analyzer: PerkInelmer's Elemental AnalyzesIs 2400
*Sample amount: about 2 mg
*Gas flow rate (ml/min): He=1.5, O ₂ = 1.1, N ₂ =4.3
*Combustion tube temperature setting: 925℃
*Reduction tube temperature setting: 640℃
Elemental analysis was measured by simultaneous quantification of carbon (C), hydrogen (H) and nitrogen (N) by the differential thermal conduction method.

Preparation Example 1

Compound 1 (Formula 3) of Figure 1 was prepared as follows.

[Formula 3]

(1) synthesis of diamine intermediates

40.0 g (1.0 equivalent) of the compound represented by Formula 5-1 and 78.28 g (2.05 equivalent) of 5-NitrosalIcylaldehyde, which is a compound represented by Formula 4-1, were mixed with 1,4-dioxy 1,8-Diazabicyclo [5.4.0] -7-undecene 　 146.1 g (4.2 equivalents) in 400 ml of 1,4-Dioxane ) was added, heated (~100°C), and reacted for 2 hours. After completion of the reaction, it was cooled to room temperature, and the formed crystals were filtered and washed with cold ethanol to obtain 77.69 g (yield: 85%) of an orange powdery nitro compound represented by the following formula (6-1).

[Formula 5-1]

[Formula 4-1]

[Formula 6-1]

70.0 g (1.0 equivalent) of the obtained nitro compound was added to 250 ml of a mixed solvent (1,4-dioxane: water = 1: 1 volume ratio), and then 100 mesh activated by 0.5 ml of concentrated acid. ) was added in 195.3 g (20.0 equivalent) of iron powder, heated to reflux at about 110°C for 2 hours, and stirred. Next, completion of the reaction was confirmed by TLC (thin film chromatography), and filtered through Celite. The residue was thoroughly washed with hot 1,4-dioxane and filtered. After repeating washing and filtration 3-4 times, the filtrate was concentrated using an evaporator. After concentration, recrystallization was performed with ethanol to obtain 47.6 g of an orange powder product represented by Chemical Formula 8-1.

[Formula 8-1]

As a result of analyzing the obtained orange powder product by LC-MS, the mass spectrum of the main peak was a molecular ion [M +H] ⁺ A significant peak was observed at 341.5.

Elemental analysis of the obtained diamine intermediate was carried out using a simultaneous quantification method for carbon (C), hydrogen (H) and nitrogen (N) by differential thermal conduction method, as shown in Table 4 below, and orange powder crystals of formula 8-1 It was confirmed that it was a diamine intermediate represented by

*Theoretical value: C=77.63%, H=4.74%, N=8.23%
*Actual values: C=77.34%, H=4.48%, N=8.05%

(2) Synthesis of Compound 1 (Formula 3)

As halogen compounds, 26.37 g (9.6 equivalents) of 4-bromoanisole, 0.281 g (0.021 equivalents) of Tris (dibenzylideneacetone) dipalladium, and 16.949 g (12.006 equivalents) of tertiary butoxysodium ) was put into a two-necked flask.

Next, 0.2591 g (0.00128 equivalent) of tritert-butylphosphine, 5.00 g (1.0 equivalent) of the diamine intermediate of Formula 8-1, and toluene (200 mL) were added, and stirring was performed at 90°C for 1 hour. After the reaction, insoluble solids were separated and washed with toluene. After the filtrate was washed twice with water (50 mL) and once with saturated brine (50 mL), the organic layer was dried over magnesium sulfate.

After magnesium sulfate was separated by filtration separately, the filtrate was concentrated under reduced pressure. The obtained preparation was filtered through a silica pad using a mixed solvent of dichloromethane:hexane = 1:1. After concentrating the filtrate, it was washed with nucleic acid to obtain 9.55 g (85% yield) of a yellow solid.

As a result of analyzing the obtained yellow powdery product by LC-MS, the mass spectrum of the main peak was a molecular ion [M+H to which a proton was added to Compound 1 (theoretical value of molecular weight: 764.29) represented by Formula 3 above. ] ⁺ a significant peak was observed at 765.8.

Further, from the results of LC-MS analysis, it was found that the obtained compound 1 had a purity of 99.5%.

Elemental analysis of the obtained compound 1 was performed using a simultaneous determination of carbon (C), hydrogen (H) and nitrogen (N) by differential thermal conduction, and it was confirmed that the yellow powder crystal was a compound represented by Formula 3 (Table below). see 5).

*Theoretical values: C=78.52%, H=5.27%, N=3.66%
*Actual values: C=78.15%, H=5.02%, N=3.31%

Production Example 2 to Production Example 8

In Figures 1 to 8, Compound 2, Compound 9, Compound 13, Compound 17, Compound 25, Compound 28, Compound 40 and Compound 68 were prepared, respectively, and Preparation Examples 2 to 9 were performed. In Production Example 1, as the amine compound (diamine, triamine or tetraamine) and the halogen compound, each of the raw material compounds shown in 2 below was used, and all the same methods were carried out.

Amine compounds and halogen compounds used in the preparation of Preparation Examples 2 to 8 are shown in Table 6 below, synthesized compounds are shown in Table 7 below, and elemental analysis and LC-MS measurement results of the synthesized compounds are shown in Table 8 below. showed up

Formula 8-2 Formula 8-3

Formula 8-4 Formula 8-5

Formula 8-6 Formula 8-7

Formula 8-8

Formula 1-2 Formula 1-3

Formula 1-4 Formula 1-5

Formula 1-6 Formula 1-7

Formula 1-8

compound Raw material constitutional formula elemental analysis LC-MS amine compounds halogen compounds C(%) H(%) N(%) Preparation Example 1
(Compound 1) Formula 8-1 4-Bromoanisole Tue 1-1 theoretical value calculated value water
(%) 78.52 5.27 3.66 764.29 measured value fruit loss value
[M+H]+ 99.5 78.15 5.02 3.31 765.8 Preparation Example 2
(Compound 2) Formula 8-2 4-Bromoanisole Tue 1-2 theoretical value calculated value water
(%) 73.35 5.06 3.51 796.24 measured value fruit loss value 99.3 73.05 4.98 3.27 797.4 Preparation Example 3
(Compound 9) Formula 8-3 4-Bromoanisole Tue 1-3 theoretical value calculated value water
(%) 77.78 5.14 3.86 1451.53 measured value fruit loss value 99.1 77.39 5.01 3.51 1452.7 Production Example 4
(Compound 13) Formula 8-4 4-Bromoanisole Tue 1-4 theoretical value calculated value water
(%) 79.59 5.19 3.44 814.3 measured value fruit loss value 99.2 79.31 5.05 3.31 814.9 Preparation Example 5
(Compound 17) Formula 8-5 4-Bromoanisole Tue 1-5 theoretical value calculated value water
(%) 80.54 5.13 3.24 864.32 measured value fruit loss value 99 80.27 5.03 3.05 865.77 Preparation Example 6
(Compound 28) Formula 8-6 4-Bromoaniline Tue 1-6 theoretical value calculated value water
(%) 79.38 6.42 10.29 816.42 measured value fruit loss value 99.4 78.98 6.25 9.95 817.9 Preparation Example 7
(Compound 40) Formula 8-7 4-broco-2-methylanisole Tue 1-7 theoretical value calculated value water
(%) 79.98 5.79 3.22 870.37 measured value fruit loss value 99.1 79.61 5.49 3.03 871.8 Preparation Example 8
(Compound 68) Formula 8-8 4-broco-3-methylanisole Tue 1-8 theoretical value calculated value water
(%) 79.98 5.79 3.22 870.37 measured value fruit loss value 99.2 79.57 5.46 3.01 871.4

Experimental Example 1: Measurement of hole mobility

As a pre-treatment of an indium tin oxide (ITO) substrate (　ITO glass (Spector product, manufactured by Geomatics), 5 Ω/□), ultrasonic cleaning was performed with acetone and ethanol.

Next, as a hole injection layer, PEDOT/PSS was spin-coated and dried at 200° C. to prepare a 45 nm thin film.

Compound 1 synthesized in Preparation Example 1 was spin-coated thereon and dried at 70°C.

Finally, an 80nm Au (gold) electrode was deposited by vacuum deposition to fabricate a device for SCLC measurement.

Compound 2, Compound 9, Compound 13, Compound 17, Compound 25, Compound 28, Compound 40 and Compound 68 of Preparation Examples 2 to 8 were prepared in the same manner. and Spiro-OMeTAD (product name: SHT-263, manufactured by Merck), respectively, to fabricate the same SCLC measurement device.

Compound 2, compound 9, compound 13, compound 17, compound 25, compound 28, compound 40 and compound 68 were prepared using the SCLC measuring device. and Spiro-OMeTAD thin films of 150 to 240 nm were measured for hole mobility by space charge limited current (SCLC) method, and the results are shown in Table 9 below.

compound Hole mobility measurement (cm ² /Vs) One 2.3×10 ^-4 2 2.2×10 ^-4 9 3.5×10 ^-4 13 3.4×10 ^-4 17 2.4×10 ^-4 25 2.5×10 ^-4 28 2.1×10 ^-4 40 2.9×10 ^-4 68 2.8×10 ^-4 Spiro-OMeTAD 2.6×10 ^-4

All of the measured compounds showed the same or higher hole mobility compared to Spiro-OMeTAD. In particular, compound 9 showed the highest hole mobility.

In addition, the above compound does not require the use of expensive raw materials, and in the synthesis of compounds 1, 2, 9, 13, 17, 25, 28, 40, and 68, the price is high and it is difficult to scale up the chromatographic column. Since it does not require use, the manufacturing cost could be lowered. Specifically, compared to the cost of manufacturing Spiro-OMeTAD, the cost could be reduced by about 1/10 to 1/4.

Example 1: Preparation of perovskite solar cell

Compound 1 synthesized in Preparation Example 1 A perovskite solar cell device was prepared as follows using the hole transport layer forming composition.

As the substrate and the first electrode, a conductive glass substrate (product name: FTN1.8) having a thickness of 1.8 mm formed with a fluorine-doped tin oxide (FTO) layer was used. As a pretreatment of the FTO layer, ultrasonic cleaning was performed in the order of 1% neutral detergent aqueous solution, acetone, isopropanol and distilled water. After cleaning, the substrate surface was treated with ozone.

A film of a compact titania layer was formed on the FTO layer. Bis(2,4-pentanedionato)bis(2-propanolato)tinanium(IV) (75% isopropyl alcohol solution) mixed with 40-fold volume ratio of dehydrated ethanol and adjusted to a concentration of 1/40 volume ratio. With this solution, a film of a compact titania layer of 30 nm was formed by spray pyrolysis on a substrate heated to 450°C on a hot plate. After air cooling, the substrate was immersed in a solution of 440 μl of titanium tetrachloride added to 100 mL of distilled water for 30 minutes, and then sintered at 500° C. to produce a compact 200 nm titania layer.

Subsequently, a film of a porous titania layer was formed on the compact titania layer. A suspension was prepared by adding eight times the amount of ethanol to the titania paste (PST-18NR), spin-coated on a substrate, and then sintered at 500° C. to prepare a 150 nm porous titania layer.

This compact titania layer and the porous titania layer are electron transport layers.

Next, a perovskite layer film was formed. The PbI/MAI(1:1)-DMF complex was adjusted by adding DMSO (dimethyl sulfoxide) to a concentration of 1.4 mol/L, and spin-coated on the substrate, followed by 45°C, 5°C, 75°C, and 100°C. After drying in order, a 300 nm perovskite layer was produced.

Next, a film of a hole transport layer was formed on the perovskite layer. 40 mg of Compound 1 was dissolved in 1 mL of 1,1,2,2-tetrachloroethane to prepare a composition for forming a hole transport layer. After forming a film on the substrate by spin coating with the solution of the prepared hole transport layer forming composition, it was dried at 70° C. to prepare an 80 nm hole transport layer.

A second electrode was formed on the hole transport layer by vacuum deposition to a thickness of 80 nm.

Finally, a perovskite solar cell device was fabricated by attaching a glass substrate to cover the device.

Examples 2 to 9

Instead of Compound 1, Compound 2, Compound 9, Compound 13, Compound 17, Compound 25, Compound 28, Compound 40, and Compound 68 were used in the same composition and method as in Example 1, except that the composition for forming a hole transport layer was used. [0080] A Robskite solar cell device was prepared and subjected to Examples 2 to 9 (Compounds 2, 9, 13, 17, 25, 28, 40, and 68 were used sequentially from Example 2 to Example 9).

Comparative Example 1

A perovskite solar cell device was manufactured in the same manner as in Example 1, except that the following composition was used as the hole transport layer forming composition for forming the hole transport layer.

72 mg of Spiro-OMeTAD was dissolved in 1 mL of chlorobenzene, and as an additive (dopant), tris[4-tert-butyl-2-(1H-pyrazol-1-yl)pilizine (Tris[4-t- butyl-2-(1H-pyrazol-1-yl)pyridine]] cobalt(III) tris(trifluoromethanesulfonyl) (Tris[bis(trifluoromethylsulfonyl)] imide (13.5 mg), tris[bis(trifluoromethane) Sulfonyl (Tris[bis(trifluoromethylsulfonyl))imilithium (9.1 mg) and 4-tert-butylpyridine (27.2 µl) were added and heated at 70°C to prepare a composition for forming a hole transport layer.

Comparative Examples 2 to 3

Instead of Spiro-OMeTAD, a perovskite solar cell device in the same manner as in Comparative Example 1 except for using the hole transport layer forming composition using each of the compounds represented by the following structural formulas (TOP-HTM-α1, TOP-HTM-α2) manufactured

Each of TOP-HTM-α1 (Formula 9) and TOP-HTM-α2 (Formula 10) was purchased from Tokyo Chemical Industry Co., Ltd.

[Formula 9]

[Formula 10]

Experimental Example 2: Evaluation of Perovskite Solar Cell Device

Regarding the light conversion characteristics of the perovskite solar cells of Examples 1 to 9 and Comparative Examples 1 to 3, measurements were performed in accordance with the JIS C8913 crystalline solar cell output measurement method.

A solar simulator (OTENTO-SUNIII, spectrometer) was combined with an AM 1.5G air mass filter, and the light amount of the light source for measurement was irradiated at 100 mW/cm ² using a standard solar cell. .

In actual measurement, JV curve characteristics are measured using a source meter (type 2400, Casely Intrumen) while light is injected into a masked solar cell device so that the measurement area is 0.1 cm ² , and the short-circuit current is measured from the result. (J _sc ), open circuit voltage (V _oc ), high line factor (FF), series resistance (R _s ), and power resistance (R _sh ) were measured. Furthermore, the photoelectric conversion efficiency (PCE) was calculated by the following formula.

[Equation 1]

PCE (%) = J _sc (mA/cm ² )×V _oc (V)×FF/100 (mW/cm ² )×100

The measurement results are shown in Table 10 below. Each shows the result of the element with the maximum conversion efficiency.

Example compound type Jsc(mA/cm ² ) Voc(V) FF PEC(%) One One 18.9 0.99 0.60 11.2 2 2 18.7 0.97 0.59 10.7 3 9 20.2 1.10 0.66 14.6 4 13 19.5 1.00 0.62 12.1 5 17 19.7 1.01 0.63 12.5 6 25 18.2 0.97 0.58 10.2 7 28 19.0 0.98 0.61 11.4 8 40 19.1 0.99 0.58 10.1 9 68 18.5 0.96 0.57 10.1 Comparative Example 1 Spiro-OMeTAD 20.5 1.03 0.70 14.8 Comparative Example 2 TOP-HTM-α1 18.6 0.98 0.59 10.8 Comparative Example 3 TOP-HTM-α2 20.0 0.99 0.64 12.7

Compounds 1, 2, 9, 13, 16, 17, 25, 28, 40 and 68 Photoelectric conversion elements used in the composition for forming a hole transport layer exhibited high photoelectric conversion efficiency of 8% or more. Among them, the photoelectric exchange device using Compounds 1, 2, 8, and 88 in the composition for forming a hole transport layer exhibits a high photoelectric conversion efficiency of 14% or more, and in particular, a photoelectric exchange device using Compound 9 in a composition for forming a hole transport layer showed high photoelectric conversion efficiency comparable to that of a photoelectric exchange device having a hole transport layer with a dopant added using Spiro-OMeTAD as a hole transport layer forming composition, despite not including a dopant in the hole transport layer.

Experimental Example 3: Durability evaluation for maximum output under light irradiation

Durability evaluation of the perovskite solar cell devices prepared in Example 1, Example 3 and Comparative Example 3 under light irradiation was measured.

The durability evaluation for light irradiation is performed by irradiating light of 100 mW/cm ² under the conditions of temperature of 25°C and humidity of 30% RH or less, with voltage applied to achieve maximum output, and measuring photoelectric conversion efficiency. The durability of the skyte solar cell device under light irradiation was confirmed, and the measurement results are shown in Table 11 below.

division compound light irradiation time
(hr) Jsc
(mA/cm ² ) Voc
(V) FF PEC
(%) ΔPEC(%)
20 to 200 hours Example 1 compound 1 20 19.7 0.99 0.39 7.6 0.7 50 19.1 0.98 0.39 7.3 100 18.7 0.97 0.40 7.3 200 18.3 0.94 0.40 6.9 Example 3 compound 9 20 21.1 1.10 0.40 9.3 0.8 50 20.5 1.09 0.40 8.9 100 20.0 1.08 0.41 8.9 200 19.6 1.06 0.41 8.5 Comparative Example 3 TOP-HTM-α2 20 21.2 0.99 0.38 8.0 2.0 50 19.8 0.95 0.40 7.5 100 18.7 0.91 0.41 7.0 200 17.9 0.82 0.41 6.0

The conversion efficiency of any photoelectric exchange device tends to decrease as the irradiation time increases, but when comparing the difference in conversion efficiency after 20 hours and 200 hours after light irradiation, Exemplary Compounds 1 and 9 are less than 1.0%. Compared to that, TOP-HTM-α2 showed a large decrease at 2.0%. This result indicates that the perovskite solar cell device using the compound of the present invention in the hole transport layer forming composition has excellent durability than conventional hole transport materials under light irradiation to which the maximum output voltage is applied. will be.

Experimental Example 4: Evaluation of durability against heating

Durability evaluation against heating of the perovskite solar cell devices prepared in Example 1, Example 3 and Comparative Example 3 was measured.

In the evaluation of durability against heating, durability against heating of the perovskite solar cell device was confirmed by heating at 150° C. in a nitrogen atmosphere, and the results are shown in Table 12 below.

division compound Element No. heating time
(minute) J _sc
(mA/cm ² ) V _oc
(V) FF PEC
(%) ∆PEC
(0-60 minutes) Example 1 compound 1 One 0 18.7 0.98 0.60 11.0 0.5 60 18.6 0.97 0.58 10.5 2 0 18.8 0.99 0.59 11.0 0.6 60 18.6 0.98 0.57 10.4 3 0 18.7 0.98 0.60 11.0 0.4 60 18.6 0.97 0.59 10.6 Example 3 compound 9 One 0 20.1 1.08 0.65 14.1 0.6 60 20.0 1.07 0.63 13.5 2 0 20.2 1.07 0.64 13.8 0.4 60 20.1 1.06 0.63 13.4 3 0 20.1 1.07 0.65 14.00 0.8 60 20.0 1.05 0.63 13.2 Comparative Example 3 TOP-HTM-α2 One 0 20.1 0.99 0.64 12.7 3.1 60 19.7 0.96 0.51 9.6 2 0 20.0 0.99 0.63 12.5 2.6 60 19.6 0.97 0.52 9.9 3 0 20.1 1.00 0.63 12.7 2.8 60 19.6 0.96 0.53 9.9

Although the conversion efficiency of any photoelectric exchange device tends to decrease after heating for 30 minutes, when comparing the difference in conversion efficiency between the initial stage (heating time of 0 minutes) and the conversion efficiency after 60 minutes of heating, Exemplary Compounds No. 1 and 9 are less than 1.0%. , (0.8~0.4%), TOP-HTM-α2 tended to decrease to 3.1~2.6%.

As a result, the perovskite solar cell device using the compound of the present invention in the hole transport layer forming composition has superior durability to heating than conventional hole transport materials even under light irradiation to which the maximum output voltage is applied. to indicate that you have

1: Direct mold manufacturing element 2: Reverse mold manufacturing element
3: substrate 4: first electrode 5: electron transport layer
6: perovskite layer 7: hole transport layer 8: second electrode

Claims (10)

delete An organic photoconductive material characterized in that the amine compound represented by the following formula (2) is an amine compound represented by the following formula (2);
[Formula 2]

In Formula 2, the Ar1 is

,

or

If Y is -O-, -S-, -NH-, or a nitrogen atom having a substituent of an allyl group or an alkyl group,
The Ar1 is

,

or

If Y is -S-, -NH-, or a nitrogen atom having a substituent of an allyl group or an alkyl group,
Ar3 and Ar4 are the same as or different from each other, and include an unsubstituted aryl group, an aryl group having a substituent, an unsubstituted heterocyclic group, or a heterocyclic group having a substituent, wherein n is an integer of 2 to 4 am. The method of claim 2, wherein the Ar1

,

or

And, the organic photoconductive material, characterized in that Y is -O-. delete The method of claim 2, wherein the Ar1

,

or

And, the Ar2 is

,

,

or

An organic photoconductive material, characterized in that. The method of claim 2, wherein each of Ar3 and Ar4 in Formula 1 is independently

,

,

,

,

,

or

An organic photoconductive material, characterized in that. The organic photoconductive material according to any one of claims 2, 3, 5 and 6, which is a material for a hole transport layer of a perovskite solar cell. A composition for forming a hole transport layer of a perovskite solar cell, comprising the organic photoconductive material of any one of claims 2, 3, 5 and 6. A photoconversion device comprising the organic photoconductive material of any one of claims 2, 3, 5, and 6. The photo-conversion device according to claim 9, wherein the photo-conversion device is an Organic Ic LIgtt-EmIttIng DIode (OLED) device, an electrostatic cell device, an Organic Semiinductor Laser Diode (OSLD) device, or a perovskite solar cell.

Images