KR102392492B1 - Manufacturing method for perovskite powder for optoelectronic device and perovskite film, perovskite optoelectronic device including the same - Google Patents

Abstract

The present invention discloses a powder for a perovskite optoelectronic device, a method for manufacturing a perovskite film, and a perovskite optoelectronic device including the same. The method of manufacturing a powder for a perovskite optoelectronic device according to an embodiment of the present invention is obtained by mixing a metal compound containing a divalent metal cation and a monovalent anion and dimethyl sulfoxide (DMSO) to the following Chemical Formula 1 preparing the indicated precursor; extracting the dimethyl sulfoxide from the precursor by mixing the precursor and an extraction solvent; and drying the precursor from which the dimethyl sulfoxide is extracted to prepare a powder for a perovskite photoelectric device.
[Formula 1]
MX ₂ (DMSO) ₂
(Here, M is the divalent metal cation, and X is the monovalent anion.)

Description

POWDER FOR PEROVSKITE OPTOELECTRONIC DEVICE AND PEROVSKITE FILM, PEROVSKITE OPTOELECTRONIC DEVICE INCLUDING THE SAME

The present invention relates to a powder for a perovskite optoelectronic device, a method for manufacturing a perovskite film, and a perovskite optoelectronic device comprising the same.

Recently, metal halide perovskite solar cells (MHP SCs) have been shown to have high absorption rates due to direct bandgap, large diffusion lengths of charge carriers, small exciton binding energies, convenient bandgap tunability, and solution processability due to their unique properties. is attracting attention

For efficient MHP SC, it is very important to form a uniform perovskite thin film without pinholes on a specific substrate.

Pinhole-free perovskite thin films can be formed by semi-solvent drip crystallization and evaporation-controlled crystallization for spin coating processes.

Jeon et al. reported that pinhole-free peroves by toluene half-solvent dripping onto a wet film of perovskite compound/butyrolactone/DMSO solution during spin coating process due to the formation of an intermediate between the perovskite compound and DMSO. It has been reported that a skyte thin film can be formed.

Also, according to Yang et al., high-performance FMAbI ₃ based MHP SC having a PCE of 20% or more can be prepared by an intramolecular exchange process, among which PbI ₂ (DMSO) ₂ composite powder was vacuumed at 60° C. for 24 hours. After drying, a PbI ₂ (DMSO) complex was synthesized.

However, in order to find commercial applications of MHP SC, the development of a technology capable of producing a stoichiometrically uniform PbI ₂ (DMSO) composite powder in large quantities has not yet been made.

Korean Patent Application Laid-Open No. 10-2018-0105087, "Porous metal halide film, manufacturing method thereof, and manufacturing method of organometal halide of perovskite structure using the same" Korean Patent Application Laid-Open No. 10-2015-0073821, "High-efficiency non/organic hybrid solar cell precursor"

In an embodiment of the present invention, DMSO can be uniformly extracted from the precursor by using a solvent extraction method, and a method for producing a powder for a perovskite optoelectronic device capable of producing a uniform perovskite photoelectric device powder in large quantities would like to provide

In an embodiment of the present invention, DMSO can be uniformly extracted from a precursor by using a solvent extraction method, so that a powder for a perovskite optoelectronic device with improved storage durability can be prepared. would like to provide

An embodiment of the present invention uses a powder for a perovskite optoelectronic device containing a metal compound and DMSO, a dense and uniform substitution reaction between the perovskite precursor and the powder for a perovskite photoelectric device through an intramolecular substitution reaction An object of the present invention is to provide a method for manufacturing a perovskite film having crystals.

An embodiment of the present invention is to provide a perovskite photoelectric device that can have excellent efficiency by forming a photoactive layer including a uniform and dense perovskite film.

The method for producing a powder for a perovskite optoelectronic device according to the present invention is represented by the following formula 1 by mixing a metal compound containing a divalent metal cation and a monovalent anion and dimethyl sulfoxide (DMSO). preparing a precursor;

[Formula 1]

MX ₂ (DMSO) ₂

(Here, M is the divalent metal cation, and X is the monovalent anion.)

extracting the dimethyl sulfoxide from the precursor by mixing the precursor and an extraction solvent; and drying the precursor from which the dimethyl sulfoxide is extracted to prepare a powder for a perovskite photoelectric device.

According to the method for producing a powder for a perovskite optoelectronic device according to an embodiment of the present invention, the powder for the perovskite optoelectronic device includes the metal compound and the dimethyl sulfoxide in a molar ratio of 1:0.1 to 1:1.2. can be included as

According to the manufacturing method of the powder for a perovskite optoelectronic device according to an embodiment of the present invention, the difference between the dissolution parameter of the dimethyl sulfoxide and the dissolution parameter of the extraction solvent may be 0.5 MPa ^1/2 to 8 MPa ^1/2 there is.

According to the method for producing a powder for a perovskite optoelectronic device according to an embodiment of the present invention, the precursor and the extraction solvent may be mixed in a molar ratio of 1:50 to 1:200.

According to the method for producing a powder for a perovskite optoelectronic device according to an embodiment of the present invention, the extraction solvent is propanol, butanol, pentanol, hexanol, and isomers thereof may include any one of them.

A method of manufacturing a perovskite film according to the present invention comprises the steps of: preparing a first precursor solution containing a powder for a perovskite optoelectronic device; preparing a second precursor solution in which a precursor powder including a monovalent cation and a monovalent anion is dispersed; applying the first precursor solution on a target surface; and forming a perovskite film by applying the second precursor solution on the target surface to which the first precursor solution is applied.

According to the method for manufacturing a perovskite film according to an embodiment of the present invention, the perovskite photoelectric device powder includes a metal compound and dimethyl sulfoxide, and the monovalent cation included in the precursor powder is the dimethyl It may be substituted with a sulfoxide.

According to the method for manufacturing a perovskite film according to an embodiment of the present invention, the perovskite film may be represented by the following formula (2).

[Formula 2]

A _a B _b X _c

(Here, A is the monovalent cation, B is a divalent metal cation, X is the monovalent anion, and a+2b=c.)

A perovskite photoelectric device according to the present invention, a first electrode; an electron transport layer formed on the first electrode; a photoactive layer including a perovskite film represented by Formula 2 below on the electron transport layer; a hole transport layer formed on the photoactive layer; and a second electrode formed on the hole transport layer.

[Formula 2]

A _a B _b X _c

(Here, A is a monovalent cation, B is a divalent metal cation, X is a monovalent anion, and a+2b=c.)

According to the perovskite optoelectronic device according to an embodiment of the present invention, the current density of the perovskite optoelectronic device is 10mA/cm ² to 40mA/cm ² It may be.

According to the perovskite optoelectronic device according to the embodiment of the present invention, the power conversion efficiency (PCE) of the perovskite photoelectric device may be 10% to 35%.

According to an embodiment of the present invention, it is possible to uniformly extract DMSO from the precursor by using a solvent extraction method, so that a uniform powder for a perovskite optoelectronic device can be produced in large quantities.

According to an embodiment of the present invention, it is possible to uniformly extract DMSO from the precursor by using a solvent extraction method, thereby manufacturing a powder for a perovskite optoelectronic device with improved storage durability.

According to an embodiment of the present invention, by using a powder for a perovskite optoelectronic device containing a metal compound and DMSO, it is dense through an intramolecular substitution reaction between the perovskite precursor and the powder for a perovskite photoelectric device. A perovskite film having a uniform crystal can be prepared.

According to an embodiment of the present invention, the perovskite photoelectric device may have excellent efficiency by forming a photoactive layer including a uniform and dense perovskite film.

1 is a flowchart illustrating a method of manufacturing a powder for a perovskite optoelectronic device according to an embodiment of the present invention.
2 is a cross-sectional view showing a specific state of a perovskite photoelectric device according to an embodiment of the present invention.
Figure 3a is a graph showing the XRD (X-ray diffraction) pattern of the powder for a perovskite optoelectronic device for a comparative example, Figure 3b is a XRD (X- It is a graph showing the ray diffraction) pattern.
4 is a graph showing the mole ratio of DMSO to PbI ₂ for Examples and Comparative Examples.
Figures 5a to 5d are SEM (scanning electron microcropy) images showing the state of the perovskite photoelectric device powder according to the extraction solvent molar ratio of the embodiment.
6 is a graph showing a thermogravimetric analysis (TGA) spectrum according to a molar ratio of an extraction solvent of a powder for a perovskite optoelectronic device for Example.
7 is a graph showing the TGA spectrum of the powder for a perovskite optoelectronic device of the example synthesized in large capacity.
8A and 8B are graphs showing TGA spectra immediately after and 4 weeks after preparing the powder for a perovskite optoelectronic device of Example.
9A and 9B are SEM images showing the surface of the perovskite film for Comparative Examples and Examples.
10A and 10B are graphs showing current density versus voltage of a perovskite optoelectronic device for Comparative Examples and Examples.
11 is a graph illustrating power conversion efficiency (PCE) of perovskite optoelectronic devices for Comparative Examples and Examples.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings and contents described in the accompanying drawings, but the present invention is not limited or limited by the embodiments.

The terminology used herein is for the purpose of describing the embodiments and is not intended to limit the present invention. In this specification, the singular also includes the plural unless specifically stated otherwise in the phrase. As used herein, "comprises" and/or "comprising" does not exclude the presence or addition of one or more other elements, steps, or elements mentioned.

As used herein, “embodiment”, “example”, “aspect”, “exemplary”, etc. are to be construed as advantageous in any aspect or design described as being preferred or advantageous over other aspects or designs. is not doing

Also, the term 'or' means 'inclusive or' rather than 'exclusive or'. That is, unless stated otherwise or clear from context, the expression 'x employs a or b' means any of natural inclusive permutations.

Also, as used herein and in the claims, the singular expression "a" or "an" generally means "one or more," unless stated otherwise or clear from the context that it relates to the singular form. should be interpreted as

The terms used in the description below have been selected as general and universal in the related technical field, but there may be other terms depending on the development and/or change of technology, customs, preferences of technicians, and the like. Therefore, the terms used in the description below should not be construed as limiting the technical idea, but as illustrative terms for describing the embodiments.

In addition, in a specific case, there is a term arbitrarily selected by the applicant, and in this case, the meaning will be described in detail in the corresponding description. Therefore, the terms used in the description below should be understood based on the meaning of the term and the content throughout the specification, rather than the simple name of the term.

Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used with the meaning commonly understood by those of ordinary skill in the art to which the present invention belongs. In addition, terms defined in a commonly used dictionary are not to be interpreted ideally or excessively unless clearly defined in particular.

Meanwhile, in the description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. In addition, the terms used in this specification are terms used to properly express the embodiment of the present invention, which may vary according to the intention of a user or operator or customs in the field to which the present invention belongs. Accordingly, definitions of these terms should be made based on the content throughout this specification.

1 is a flowchart illustrating a method of manufacturing a powder for a perovskite optoelectronic device according to an embodiment of the present invention.

Referring to FIG. 1 , in the method of manufacturing a powder for a perovskite optoelectronic device according to an embodiment of the present invention, a metal compound including a divalent metal cation and a monovalent anion and dimethyl sulfoxide (DMSO) are mixed. to prepare a precursor (S110), extracting the dimethyl sulfoxide from the precursor by mixing the precursor and an extraction solvent (S120), and drying the precursor from which the dimethyl sulfoxide is extracted to make a perovskite photoelectric device It includes a step (S130) of preparing a powder for use.

In step S110, a precursor represented by the following formula may be prepared by mixing a metal compound including a divalent metal cation and a monovalent anion and DMSO.

[Formula 1]

MX ₂ (DMSO) ₂

Here, M is the divalent metal cation, and X is the monovalent anion.

According to Formula 1, the precursor may include the metal compound and the DMSO covalently bonded.

The metal compound is a material serving as a material for the precursor represented by Formula 1, and may include a divalent metal cation and a monovalent anion.

The divalent metal cation includes any one of Pb ²⁺ , Sn ²⁺ , Ge ²⁺ , Cu ²⁺ , Co ²⁺ , Ni ²⁺ , Ti ²⁺ , Zr ²⁺ , Hf ²⁺ and Rf ²⁺ and may include Pb ²⁺ depending on the embodiment.

The monovalent anion may include any one of a halogen anion including F ⁻ , Cl ⁻ , Br ⁻ and I , BF ₄ ⁻ , PF ₆ ⁻ and SCN ⁻ , ^and in some embodiments, including I ⁻ can do.

The metal compound including the divalent metal cation and the monovalent anion may be represented by a formula such as MX ₂ (where M is the divalent metal cation and X is the monovalent anion).

That is, in the precursor represented by Formula 1, M and X may be a divalent metal cation and a monovalent anion included in the metal compound.

For example, when the divalent metal cation is Pb ²⁺ and the monovalent anion is I ⁻ , the metal compound is PbI ₂ , and thus the precursor may be PbI ₂ (DMSO) ₂

In steps S120 and S130, the dimethyl sulfoxide (DMSO) is extracted from the precursor using a solvent extraction method and then dried to prepare a powder for a perovskite photoelectric device represented by MX ₂ (DMSO).

The MX ₂ (DMSO) as an active ingredient for a perovskite photoelectric device powder is known as a material capable of making a high-quality perovskite thin film.

Conventionally, a material represented by MX ₂ (DMSO) was prepared by extracting DMSO contained in the precursor using a vacuum drying method. However, the vacuum drying method did not uniformly extract DMSO in the precursor, so that the powder for a perovskite photoelectric device was uniformly used. could not be manufactured.

In addition, the conventional vacuum drying method can produce a small amount of powder for a perovskite optoelectronic device, it was not possible to produce a uniform perovskite powder for an optoelectronic device in large quantities.

The DMSO forms an intermediate phase between MX ₂ and the perovskite compound in the crystallization process of the perovskite material, and the grain morphology of the perovskite compound varies depending on the composition of DMSO. .

That is, the perovskite photoelectric device powder prepared using the conventional vacuum drying method is non-uniformly extracted from DMSO, and as the perovskite compound prepared using this powder is non-uniformly crystallized, the perovskite film quality There was a problem with this falling.

However, the method for producing a powder for a perovskite optoelectronic device according to an embodiment of the present invention uses a solvent extraction method of extracting DMSO from a precursor by mixing and stirring a precursor and an extraction solvent, MX ₂ (DMSO) as an active ingredient It is possible to synthesize a uniform perovskite photoelectric device powder in large quantities.

In the solvent extraction method, when the precursor containing a large amount of DMSO and the extraction solvent not containing DMSO are mixed, the DMSO is extracted from the precursor by the difference in the concentration of DMSO and the affinity between the DMSO and the extraction solvent at the same time. can be extracted toward

In the solvent extraction method, the metal compound and the dimethyl sulfoxide are 1:0.1 to 1:1.2 in the powder for a perovskite photoelectric device according to an embodiment of the present invention using an extraction solvent having high affinity with the DMSO. DMSO may be selectively extracted from the precursor so as to be included in a molar ratio. For example, when a solvent with strong polarity such as ethanol or methanol is used as the extraction solvent, or when an excess of IPA is used, DMSO may be extracted from the precursor so that the metal compound and dimethyl sulfoxide are included in a molar ratio of 1:0.1.

The type of the extraction solvent may be selected based on a difference between a solubility parameter of the DMSO and a solubility parameter of the extraction solvent.

Specifically, the difference between the dissolution parameter of the DMSO and the dissolution parameter of the extraction solvent may be 0.5 MPa ^1/2 to 8 MPa ^1/2 , and the type of the extraction solvent using the difference in the dissolution parameter between the DMSO and the extraction solvent can be selected. When the difference between the dissolution parameter of the DMSO and the dissolution parameter of the extraction solvent is less than 0.5 MPa ^1/2 , the affinity with DMSO is too strong and all DMSO escapes, and the dissolution parameter of the DMSO and the extraction solvent If the difference in the dissolution parameters is greater than 8 MPa ^1/2 , the affinity with DMSO is too small, and DMSO may not escape.

The extraction solvent may include alcohol, and as the chain length of the alkyl group included in the alcohol is longer, more DMSO may be extracted from the precursor.

Specifically, the extraction solvent may include any one of propanol, butanol, pentanol, hexanol, and isomers thereof, and the extraction solvent is methylcellosolve ( It may be an extraction solvent such as methyl cellosolve), ethyl cellosolve, butyl cellosolve, diacetone alcohol, alcohol-based, furan-based, and ketone-based, more specifically As the extraction solvent may include any one of IPA (isopropyl alcohol), 1-butanol (1-butanol), 1-pentanol (1-pentanol) and 1-hexanol (1-hexanol), preferably may include IPA having good affinity with the DMSO and good volatility.

In step S120, the molar ratio of the metal compound to the DMSO may be adjusted after the DMSO is extracted by adjusting the mixing molar ratio of the precursor and the extraction solvent.

Specifically, in step S120, the mole of DMSO extracted from the precursor may increase as the mole (mol) of the extraction solvent is greater than that of the precursor.

More specifically, in step S120, the precursor and the extraction solvent may be mixed in a molar ratio of 1:50 to 1:200.

When the molar ratio of the precursor and the extraction solvent is less than 1:50, DMSO is not sufficiently extracted from the precursor, so that a uniform powder for a perovskite optoelectronic device cannot be prepared. Specifically, when the molar ratio of the precursor and the extraction solvent is less than 1:50, a phenomenon in which the mixture of PbI ₂ (DMSO) ₂ and the extraction solvent becomes too sticky occurs, and this causes the mixture to stick to the container wall There is a problem in that it becomes difficult to uniformly mix and the yield is also reduced.

When the molar ratio of the precursor and the extraction solvent exceeds 1:200, all of the DMSO escapes, and PbI ₂ instead of PbI ₂ (DMSO) _x may be obtained.

The method for producing a powder for a perovskite optoelectronic device according to an embodiment of the present invention can uniformly extract DMSO from a precursor using a solvent extraction method, so that a uniform powder for a perovskite optoelectronic device can be produced in large quantities. there is.

Hereinafter, a method for manufacturing a perovskite film prepared using the powder for a perovskite optoelectronic device according to an embodiment of the present invention will be described.

The method of manufacturing a perovskite film according to an embodiment of the present invention comprises the steps of preparing a first precursor solution containing a powder for a perovskite photoelectric device (S210), a precursor powder containing a monovalent cation and a monovalent anion Preparing the dispersed second precursor solution (S220), applying the first precursor solution on a target surface (S230), and applying the second precursor solution on the electron transport layer coated with the first precursor solution and forming a perovskite film by coating (S240).

In step S210, a first precursor solution may be prepared by mixing the above-described powder for a perovskite optoelectronic device and a solvent.

The powder for the perovskite optoelectronic device may be represented by the chemical formula of MX ₂ (DMSO), and specifically may include a metal compound (MX ₂ ) and DMSO in a molar ratio of 1:0.1 to 1:1.2.

Since the method of manufacturing the powder for the perovskite optoelectronic device has been described with reference to FIG. 1 above, redundant description will be omitted.

The solvent included in the first precursor solution is to disperse the powder for the perovskite optoelectronic device, and may be, for example, dimethylformamide (DMF).

In step S220, a second precursor solution may be prepared by mixing the precursor powder including the monovalent cation and the monovalent anion with a solvent.

The precursor powder may be a precursor of the perovskite film produced in step S240 to be described later.

The monovalent cation contained in the precursor powder is a C _1-24 straight or branched chain alkyl, amine group (-NH ₃ ), hydroxyl group (-OH), cyano group (-CN), halogen group, nitro group (-NO) , a methoxy group (-OCH ₃ ) or an imidazolium group may be a monovalent organic cation containing C _{1 to 24} straight or branched alkyl or a combination thereof, specifically MA (methyl ammonium) or FA (formamidinium) ) can be

In addition, the monovalent cations contained in the precursor powder are Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Fr ⁺ , Cu(I) ⁺ , Ag(I) ⁺ , Au(I) ⁺ or their It may be a combination of monovalent inorganic cations.

The monovalent anion contained in the precursor powder may include any one of F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- and SCN ^- .

For example, the precursor powder may be FAI, including FA as a monovalent cation and I as a monovalent anion.

According to an embodiment, the second precursor solution may include monovalent cations different from each other and monovalent anions different from each other.

For example, the precursor powder may include monovalent cations MA and FA, monovalent anions I and Br, and may include MABr and FAI.

The solvent included in the second precursor solution is to disperse the precursor powder, and may be, for example, isopropyl alcohol (IPA).

In step S230, the first precursor solution may be applied on the target surface.

The target surface means a working target surface on which the first precursor solution is applied.

When the perovskite film is included in the photoelectric device, the perovskite film may be a photoactive layer, and thus the target surface may be an electron transport layer or a hole transport layer.

The method of applying the first precursor solution to the target surface is spin coating, spray coating, ultra-spray coating, electrospinning coating, slot die coating, Gravure coating, bar coating, roll coating, dip coating, shear coating, screen printing, inkjet printing or nozzle Any one of nozzle printing may be used, and the method is not limited thereto.

In step S240, the perovskite film represented by the following Chemical Formula 2 may be formed by applying the second precursor solution on the target surface to which the first precursor solution is applied.

[Formula 2]

A _a B _b X _c

Here, A is a monovalent cation contained in the precursor powder, B is a divalent metal cation contained in the powder for perovskite optoelectronic device, C is a monovalent anion contained in the precursor powder, a+2b= c.

In the steps S230 and S240, the powder for a perovskite photoelectric device included in the first precursor solution applied on the target surface and the precursor powder included in the second precursor solution are intramolecular exchange (intramolecular exchange) The perovskite film represented by Chemical Formula 2 may be formed by the reaction.

Specifically, when the second precursor solution is applied on the first thin film formed of the powder for the perovskite optoelectronic device, DMSO contained in the powder for the perovskite optoelectronic device is a monovalent cation contained in the second precursor solution. and a compound of a monovalent anion may be substituted. At this time, the molecular size of the compound contained in the second precursor solution is similar to that of DMSO, and the interaction with PbI ₂ can be strongly bound by an ionic bond, so it is easy to substitute 1:1 for DMSO and a dense and uniformly crystallized perov A skye thin film can be produced.

For example, when the powder for the perovskite optoelectronic device is PbI ₂ (DMSO) and the precursor powder is FAI, a perovskite film of FAPBI ₃ may be formed by an intramolecular substitution reaction between DMSO and FA. .

According to an embodiment, when different precursor powders are included in the second precursor solution, the perovskite film may include different monovalent cations and different monovalent anions.

For example, when the powder for the perovskite optoelectronic device is PbI ₂ (DMSO), and the precursor powder is FAI and MABr, DMSO is intramolecularly substituted with FA and MA to FA _1-x MA _x PBI _3-y A perovskite film of Br _y (0<x<1, 0<y<3) can be formed.

The method of applying the second precursor solution is spin coating, spray coating, ultra-spray coating, electrospinning coating, slot die coating, gravure coating ( gravure coating, bar coating, roll coating, dip coating, shear coating, screen printing, inkjet printing or nozzle printing printing) may be used, and the method is not limited thereto.

The method for manufacturing a perovskite film according to an embodiment of the present invention uses a powder for a perovskite photoelectric device containing a metal compound and DMSO, and a molecule between a perovskite precursor and a powder for a perovskite photoelectric device It is possible to prepare a perovskite film having a dense and uniform crystal through the substitution reaction.

Hereinafter, a perovskite photoelectric device including a perovskite film manufactured by the method for manufacturing a perovskite film according to an embodiment of the present invention will be described together with FIG. 2 .

2 is a cross-sectional view showing a specific state of a perovskite photoelectric device according to an embodiment of the present invention.

Referring to FIG. 2 , a perovskite photoelectric device 100 according to an embodiment of the present invention includes a first electrode 110 formed on a substrate (not shown), and an electron transport layer formed on the first electrode 110 ( 120), the photoactive layer 130 including the above-described perovskite film on the electron transport layer 120, the hole transport layer 140 formed on the photoactive layer 130, and the second electrode formed on the hole transport layer 140 (150).

In this case, the perovskite photoelectric device 100 according to the embodiment of the present invention may be used as a light emitting device or a solar cell, and if the photoelectric device can be applied, the application field is not limited.

The substrate may be a substrate including an inorganic material or an organic material.

The inorganic substrate may include glass, quartz, Al ₂ O ₃ , SiC, Si, GaAs, or InP, but is not limited thereto.

The organic substrate is Kepton foil, polyimide (PI), polyethersulfone (PES), polyacrylate (PAR), polyetherimide (PEI), polyethylene naphthalate (PEN) ), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyarylate, polycarbonate (PC), cellulose triacetate (CTA) and cellulose acetate It may be selected from propionate (cellulose acetate propionate, CAP), but is not limited thereto.

It is more preferable that the inorganic substrate and the organic substrate are made of a transparent material through which light is transmitted, and in general, the substrate can be used as long as it can be positioned on the front electrode. When the organic substrate is introduced, the flexibility of the electrode can be increased.

The first electrode 110 is formed on a substrate, and when the perovskite photoelectric device 100 has an inverted structure, it may serve as an anode.

For example, the first electrode 110 may include fluorine-doped tin oxide (FTO), indium-doped tin oxide (ITO), or aluminum-containing zinc oxide (Al-doped Zinc Oxide, AZO). , may be selected from the group consisting of indium doped zinc oxide (IZO) or a mixture thereof, but is not limited thereto.

Preferably, the first electrode 110 includes ITO, which is a transparent electrode with a large work function to facilitate injection of holes into the highest occupied molecular orbital (HOMO) level of the photoactive layer 130 . can

The first electrode 110 is formed on a substrate by thermal evaporation, e-beam evaporation, radio frequency sputtering, magnetron sputtering, vacuum deposition, or chemical method. It may be formed by any one method of deposition (chemical vapor deposition).

Also, the first electrode 110 may include a transparent conductive electrode having an OMO (O=organic, metal oxide, M=metal) structure.

According to an embodiment, the first electrode 110 may have a sheet resistance of 1Ω/cm ² to 1000Ω/cm ² , and a transmittance of 80% to 99.9%.

When the sheet resistance of the first electrode 110 is less than 1Ω/cm ² , the transmittance is lowered, making it difficult to use as a transparent electrode, and when it exceeds 1000Ω/cm ² , the sheet resistance is high, so the performance of the perovskite photoelectric device 100 is poor. There is a downside.

In addition, when the transmittance of the first electrode 110 is less than 80%, light extraction or light transmission is low, so that the performance of the perovskite photoelectric device 100 is deteriorated.

The electron transport layer 120 is formed between the first electrode 110 and the photoactive layer 130 , and can easily transfer electrons between the photoactive layer 130 and the first electrode 110 .

When the perovskite photoelectric device 100 is used as a light emitting device, the electron transport layer 120 may move electrons injected from the second electrode 150 to the photoactive layer 130 , and the perovskite photoelectric device When the device 100 is used as a solar cell, electrons generated in the photoactive layer 130 may be easily transferred to the first electrode 110 .

According to an embodiment, the electron transport layer 120 is fullerene (fullerene, C60), a fullerene derivative, perylene, TPBi(2,2′,2″-(1,3,5-benzinetriyl)-tris(1) -phenyl-1-H-benzimidazole)), PBI (polybenzimidazole) and PTCBI (3,4,9,10-perylene-tetracarboxylic bis-benzimidazole), NDI (Naphthalene diimide) and their derivatives, TiO ₂ , SnO ₂ , ZnO, ZnSnO ₃ , 2,4,6-Tris(3-(pyrimidin-5-yl)phenyl)-1,3,5-triazine, 8-Hydroxyquinolinolato-lithium, 1,3,5-Tris(1-phenyl) -1Hbenzimidazol- 2-yl)benzene, 6,6'-Bis[5-(biphenyl-4-yl)-1,3,4-oxadiazo-2-yl]-2,2'-bipyridyl, 4,4' -Bis(4,6-diphenyl-1,3,5-triazin-2-yl)biphenyl(BTB), Rb ₂ CO ₃ (Rubidium carbonate), ReO ₃ (Rhenium (VI) oxide) contains at least one can do.

The fullerene derivative may be PCBM ((6,6)-phenyl-C61-butyric acid-methylester) or PCBCR ((6,6)-phenyl-C61-butyric acid cholesteryl ester). not.

According to an embodiment, when the perovskite photoelectric device 100 has an inverted structure, a TiO ₂ based or Al ₂ O ₃ based porous material may be mainly used as the electron transport layer 120 .

The photoactive layer 130 includes the above-described perovskite film, and may be represented by Chemical Formula 2 below.

[Formula 2]

A _a B _b X _c

Here, A is a monovalent cation, B is a divalent metal cation, X is a monovalent anion, and a+2b=c.

Since the perovskite film included in the photoactive layer 130 has been described through the manufacturing method of the perovskite film, redundant description will be omitted.

The hole transport layer 140 is formed on the photoactive layer 130 , and when the perovskite photoelectric device 100 is used as a light emitting device, holes injected from the second electrode 150 are transferred to the photoactive layer 130 . It serves to move, and when the perovskite photoelectric device 100 is used as a solar cell, holes generated in the photoactive layer 130 can be easily transferred to the second electrode 150 .

For example, the hole transport layer 140 may include P3HT (poly[3-hexylthiophene]), MDMO-PPV (poly[2-methoxy-5-(3',7'-dimethyloctyloxyl)]-1,4-phenylene vinylene) , MEH-PPV (poly[2-methoxy-5-(2''-ethylhexyloxy)-p-phenylene vinylene]), P3OT (poly(3-octyl thiophene)), POT( poly(octyl thiophene)), P3DT ( poly(3-decyl thiophene)), P3DDT (poly(3-dodecyl thiophene), PPV (poly(p-phenylene vinylene)), TFB (poly(9,9'-dioctylfluorene-co-N-(4-butylphenyl) diphenyl amine), Polyaniline, Spiro-MeOTAD ([2,22′,7,77′-tetrkis (N,N-dipmethoxyphenylamine)-9,9,9′-spirobi fluorine]), CuSCN, CuI, MoO _x , VO _x , NiO _x , CuO _x , PCPDTBT (Poly[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl-4H-cyclopenta[2,1-b:3,4- b']dithiophene-2,6-diyl]], Si-PCPDTBT (poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)- 2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl]), PBDTTPD (poly((4,8-diethylhexyloxyl) benzo([1,2-b:4,5- b']dithiophene)-2,6-diyl)-alt-((5-octylthieno[3,4-c]pyrrole-4,6-dione)-1,3-diyl)), PFDTBT (poly[2, 7-(9-(2-ethylhexyl)-9-hexyl-fluo rene)-alt-5,5-(4', 7,-di-2-thienyl-2',1', 3'-benzothiadiazole)]), PFO-DBT (poly[2,7-.9,9 -(dioctyl-fluorene)-alt-5,5-(4',7'-di-2-.thienyl-2', 1', 3'-benzothiadiazole)]), PSiFDTBT (poly[(2,7- dioctylsilafluorene)-2,7-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5′-diyl]), PSBTBT (poly[(4,4′) -bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl] ), PCDTBT (Poly [[9-(1-octylnonyl)-9H-carbazole-2,7-diyl]-2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5- thiophenediyl]), PFB (poly(9,9′-dioctylfluorene-co-bis(N,N′-(4,butylphenyl))bis(N,N′-phenyl-1,4-phenylene)diamine), F8BT ( poly(9,9'-dioctylfluorene-cobenzothiadiazole), PEDOT (poly(3,4-ethylenedioxythiophene)), PEDOT:PSS, poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), PTAA (poly(triarylamine)), poly (4-butylphenyldiphenyl-amine), 4,4'-bis[N-(1-naphtyl)-N-phenylamino]-biphenyl (NPD), PEDOT:PSSbis(N-(1) mixed with perfluorinated ionomer (PFI) -naphthyl-n-phenyl))benzidine (α-NPD), N,N'-di(naphthalen-1-yl)-N,N'-diphenyl-bene Zidine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-diphenyl-4,4'-diamine (TPD), copper phthalocyanine (CuPc), 4 ,4',4"-tris(3-methylphenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris(3-methylphenylamino)phenoxybenzene (m-MTDAPB), starburst ( starburst) type amines 4,4',4"-tri(N-carbazolyl)triphenylamine (TCTA), 4,4',4"-tris(N-(2-naphthyl)-N-phenylamino )-triphenylamine (2-TNATA) and at least one may be selected from copolymers thereof, but is not limited thereto.

The second electrode 150 is formed on the hole transport layer 140 and may serve as a cathode when the perovskite photoelectric device 100 has an inverted structure.

For example, the second electrode 150 may include lithium fluoride/aluminum (LiF/Al), gold (Au), silver (Ag), platinum (Pt), palladium (Pd), copper (Cu), and aluminum (Al). ), carbon (C), cobalt sulfide (CoS), copper sulfide (CuS), nickel oxide (NiO), or a mixture thereof, but is not limited thereto.

Since the second electrode 150 may be formed in the same manner as the method described for the first electrode 110 , a redundant description thereof will be omitted.

The second electrode 150 has a low work function to facilitate the injection of holes into the highest occupied molecular orbital (HOMO) level of the photoactive layer 130 , and a metal electrode having excellent internal reflectance may be used.

The perovskite photoelectric device 100 according to the embodiment of the present invention is formed with the photoactive layer 130 including a uniform and dense perovskite film, and thus can have excellent efficiency.

Specifically, the perovskite photoelectric device 100 according to an embodiment of the present invention may have a current density of 10mA/cm ² to 40mA/cm ² .

In addition, the perovskite optoelectronic device 100 according to the embodiment of the present invention may have a power conversion efficiency (PCE) of 10% to 35%.

Hereinafter, a powder for a perovskite optoelectronic device and a perovskite optoelectronic device were prepared through Examples and Comparative Examples, and then the properties of the powder for a perovskite optoelectronic device and the perovskite optoelectronic device were evaluated.

production example

1. Preparation of powder for perovskite optoelectronic devices

[Example 1]

50 g of PbI ₂ , a metal compound, was dissolved in 150 mL of DMSO at 60° C., and 350 mL of toluene was slowly added to precipitate it.

The precipitate product was then infiltrated and dried at room temperature for 3 hours to prepare Pb ₂ (DMSO) ₂ powder.

In the reaction batch, 0.5 g of Pb ₂ (DMSO) ₂ powder and the molar ratio of IPA, an extraction solvent, are mixed so that the molar ratio is 1:75, stirred for 3 hours, filtered and dried for 6 hours to prepare pale yellow PbI ₂ (DMSO) powder did

[Example 2]

A PbI ₂ (DMSO) powder was prepared in the same manner as in [Example 1], except that 1.5 g of Pb ₂ (DMSO) ₂ powder was used.

[Example 3]

A PbI ₂ (DMSO) powder was prepared in the same manner as in [Example 1], except that 4.5 g of Pb ₂ (DMSO) ₂ powder was used.

[Example 4]

A PbI ₂ (DMSO) powder was prepared in the same manner as in [Example 1], except that 45 g of Pb ₂ (DMSO) ₂ powder was used.

[Comparative Example 1]

0.5 g of Pb ₂ (DMSO) ₂ powder prepared in [Example 1] was dried in an oven at 60° C. for 24 hours to prepare PbI ₂ (DMSO) powder.

[Comparative Example 2]

A PbI ₂ (DMSO) powder was prepared in the same manner as in [Comparative Example 1], except that 1.5 g of Pb ₂ (DMSO) ₂ powder was used.

[Comparative Example 3]

A PbI ₂ (DMSO) powder was prepared in the same manner as in [Comparative Example 1], except that 4.5 g of Pb ₂ (DMSO) ₂ powder was used.

[Example 4]

After mixing the Pb ₂ (DMSO) ₂ powder prepared in [Example 1] so that the molar ratio of IPA as the extraction solvent is 1:50, the mixture was stirred for 3 hours, filtered and dried for 6 hours, followed by pale yellow PbI ₂ (DMSO) ) powder was prepared.

[Example 5]

PbI ₂ (DMSO) powder was prepared in the same manner as in [Example 4], except that the Pb ₂ (DMSO) ₂ powder and the extraction solvent, IPA, were mixed in a molar ratio of 1:75.

[Example 6]

PbI ₂ (DMSO) powder was prepared in the same manner as in [Example 4], except that the Pb ₂ (DMSO) ₂ powder and the extraction solvent, IPA, were mixed in a molar ratio of 1:100.

[Example 7]

PbI ₂ (DMSO) powder was prepared in the same manner as in [Example 4], except that the Pb ₂ (DMSO) ₂ powder and the extraction solvent, IPA, were mixed in a molar ratio of 1:150.

2. Fabrication of perovskite optoelectronic devices

TiO ₂ (bl-TiO ₂ ) with a thickness of ~50 nm was deposited on a patterned FTO substrate (Pilkington, TEC-8) through spray pyrolysis deposition using 20 mM thioacetamide (TAA) solution at 500 °C.

Then, ~400 nm thick mesoporous TiO ₂ (m-TiO ₂ , Share-Chem) was spin-coated on a bl-TiO ₂ /FTO substrate at 5000 rpm for 30 seconds and calcined at 500° C. in an air atmosphere for 1 hour. Organic components were removed.

Thereafter, the m-TiO ₂ /bl-TiO ₂ /FTO substrate was plasma-treated in an argon atmosphere under atmospheric pressure.

[Example 1] to [Example 3] and [Comparative Example 1] to [Comparative Example 3] PbI ₂ (DMSO) / DMF solution 1.5M for 30 seconds at 3000rpm m-TiO ₂ /bl-TiO ₂ / After spin coating on the FTO substrate, 0.465M of a FAI/MABr (7:3 molar ratio) solution dispersed in IPA was spin-coated at 5000 rpm for 30 seconds to prepare a perovskite film (P).

Thereafter, the P/m-TiO ₂ /bl-TiO ₂ /FTO substrate was heat-treated on a hot plate in an N ₂ atmosphere at 200° C. for 5 minutes.

The PTAA hole transport layer was formed by adding PTAA/toluene (15 mg/1 mL) to which 7.5 μL of Li-TFSI/acetonitrile (170 mg/1 mL) and 7.5 μL of t-BP/acetonitrile (1 mL/1 mL) were added at 5000 rpm for 30 seconds. It was formed by spin coating.

Finally, Au electrodes were formed by thermal evaporation.

Examples 1 to 8 and Comparative Examples 1 to 3 are summarized in the following table according to the DMSO extraction method, the amount of PbI2(DMSO)2 used, and the mixed molar ratio of PbI2(DMSO)2:IPA.

[graph]

characterization

Figure 3a is a graph showing an XRD (X-ray diffraction) pattern of the powder for a perovskite optoelectronic device for a comparative example, Figure 3b is an XRD (X- It is a graph showing the ray diffraction) pattern.

First, referring to FIG. 3a , the XRD of Pb ₂ (DMSO) at 2θ=9.4° and 9.9° as the amount of Pb ₂ (DMSO) ₂ powder used in the reaction batch increased for Comparative Examples 1 to 3 using the vacuum drying method While the peak is decreased, it can be seen that the XRD peak of the Pb ₂ (DMSO) ₂ powder at 2θ = 10.3° is enhanced.

Referring to FIG. 3b , XRD peaks of Pb ₂ (DMSO) at 2θ = 9.4° and 9.9° regardless of the amount of Pb ₂ (DMSO) ₂ powder used in the reaction batch for Examples 1 to 3 using the solvent extraction method It can be confirmed that only

Therefore, in the present invention, a uniform Pb ₂ (DMSO) powder can be prepared by uniformly extracting DMSO using a solvent extraction method.

4 is a graph showing the mole ratio of DMSO to PbI ₂ for Examples and Comparative Examples.

4, in the case of Examples 1 to 3, the mole ratio of DMSO to PbI ₂ is 1:0.99, 1:0.97, and 1:0.98, respectively, PbI ₂ irrespective of the amount of Pb ₂ (DMSO) ₂ powder used It can be seen that the relative DMSO molar ratio is almost constant.

On the other hand, in Comparative Examples 1 to 3, the molar ratio of DMSO to PbI ₂ was 1:0.98, 1:1.13 and 1:1.45, respectively, and as the amount of Pb ₂ (DMSO) ₂ powder used increased, the molar ratio of DMSO to PbI ₂ was increased. It can be seen that this increases.

Therefore, in the present invention, a uniform Pb ₂ (DMSO) powder can be prepared by uniformly extracting DMSO using a solvent extraction method.

5a to 5d are scanning electron microcropy (SEM) images showing the appearance of the powder for perovskite photoelectric devices according to the molar ratio of the extraction solvent of the embodiment.

5a to 5d sequentially show the state of the powder for the perovskite optoelectronic device of Example 4, Example 5, Example 6, Example 7.

Referring to FIGS. 5A to 5D , it can be seen that a uniform perovskite powder for an optoelectronic device was prepared even when the molar ratio of IPA to the Pb ₂ (DMSO) ₂ powder increased.

6 is a graph showing a thermogravimetric analysis (TGA) spectrum according to a molar ratio of an extraction solvent of a powder for a perovskite optoelectronic device for Example.

Referring to FIG. 6 , it can be seen that the PbI ₂ :DMSO molar ratios of Examples 4 to 7 are 1:1.07, 1:0.99, 1:0.91, and 1:0.84, respectively.

Therefore, according to the present invention, a powder for a perovskite optoelectronic device having a uniform PbI ₂ :DMSO molar ratio of almost 1:1 can be prepared by using a solvent extraction method.

7 is a graph showing the TGA spectrum of the powder for a perovskite optoelectronic device of the example synthesized in large capacity.

Referring to FIG. 7 , it can be seen that the PbI ₂ :DMSO molar ratio of Example 4 using 45 g of PbI ₂ (DMSO) ₂ powder is 1:0.98.

Therefore, in the present invention, even if the PbI ₂ (DMSO) ₂ powder is used in a large amount, DMSO is uniformly extracted to prepare a uniform perovskite photoelectric device powder.

8A and 8B are graphs showing TGA spectra immediately after and 4 weeks after preparing the powder for a perovskite optoelectronic device of Example.

8A and 8B , immediately after preparing Example 4, the molar ratio of PbI ₂ :DMSO was 1:0.98, but after 4 weeks of preparing Example 4, the molar ratio of PbI ₂ :DMSO was 1:0.984. can be seen to be almost constant.

Therefore, the present invention can prepare a powder for a perovskite optoelectronic device with excellent storage stability by uniformly extracting DMSO using a solvent extraction method.

9A and 9B are SEM images showing the surface of the perovskite film for Comparative Examples and Examples.

9A and 9B, the crystal size of the perovskite film prepared using Comparative Example 1 is not uniform, but the crystal size of the perovskite film prepared using Example 1 is the same as the comparative example. It can be seen that it is uniform compared to 1.

Therefore, in the present invention, DMSO can be uniformly extracted from the precursor than the conventional vacuum drying method, and a perovskite film having uniform crystals can be prepared.

10A and 10B are graphs showing current density versus voltage of a perovskite optoelectronic device for Comparative Examples and Examples.

Referring to FIGS. 10A and 10B , it can be seen that the perovskite photoelectric device manufactured using Comparative Example 1 does not have the same voltage versus current density value.

On the other hand, it can be seen that the perovskite photoelectric device manufactured using Example 1 has no significant difference in the same voltage versus current density value compared to Comparative Example 1.

Therefore, the present invention can manufacture a perovskite optoelectronic device with improved device performance through a uniform perovskite photoelectric device powder prepared using a solvent extraction method.

11 is a graph illustrating power conversion efficiency (PCE) of perovskite optoelectronic devices for Comparative Examples and Examples.

Referring to FIG. 11 , the PCE of the perovskite optoelectronic device manufactured using Examples 1 to 3 is higher than the PCE of the perovskite optoelectronic device manufactured using Comparative Examples 1 to 3. You can see the big one.

In addition, it can be confirmed that the perovskite photoelectric device manufactured using Examples 1 to 3 has a smaller width of PCE value than the perovskite photoelectric device manufactured using Comparative Examples 1 to 3 can

Therefore, the present invention can manufacture a perovskite optoelectronic device with improved device performance through a uniform perovskite photoelectric device powder prepared using a solvent extraction method.

As described above, although the present invention has been described with reference to limited embodiments and drawings, the present invention is not limited to the above embodiments, and various modifications and variations from these descriptions are provided by those skilled in the art to which the present invention pertains. This is possible. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the following claims as well as the claims and equivalents.

100: perovskite optoelectronic device
110: first electrode
120: electron transport layer
130: photoactive layer
140: hole transport layer
150: second electrode

Claims (11)

preparing a precursor powder represented by the following Chemical Formula 1 by mixing a metal compound containing a divalent metal cation and a monovalent anion and dimethyl sulfoxide (DMSO);
[Formula 1]
MX ₂ (DMSO) ₂
(Here, M is the divalent metal cation, and X is the monovalent anion.)
extracting the dimethyl sulfoxide from the precursor powder by adding the precursor powder and the extraction solvent to a reactor and stirring; and
Preparing a powder for a perovskite photoelectric device represented by MX ₂ (DMSO) by drying the precursor from which the dimethyl sulfoxide is extracted
A method for producing a powder for a perovskite optoelectronic device comprising a. According to claim 1,
The perovskite photoelectric device powder is a method for producing a perovskite photoelectric device powder, characterized in that it comprises the metal compound and the dimethyl sulfoxide in a molar ratio of 1:0.1 to 1:1.2. According to claim 1,
The difference between the dissolution parameter of the dimethyl sulfoxide and the dissolution parameter of the extraction solvent is 0.5 MPa ^1/2 to 8 MPa ^1/2 . According to claim 1,
The method for producing a powder for a perovskite photoelectric device, characterized in that the precursor and the extraction solvent are mixed in a molar ratio of 1:50 to 1:200. According to claim 1,
The extraction solvent is propanol (propanol), butanol (butanol), pentanol (pentanol), hexanol (hexanol) and a method for producing a powder for a perovskite photoelectric device, characterized in that it comprises any one of their isomers . Preparing a first precursor solution comprising a powder for a perovskite optoelectronic device prepared according to any one of claims 1 to 5;
preparing a second precursor solution in which a precursor powder including a monovalent cation and a monovalent anion is dispersed;
applying the first precursor solution on a target surface; and
Forming a perovskite film by applying the second precursor solution on the target surface to which the first precursor solution is applied
A method for producing a perovskite membrane comprising a. 7. The method of claim 6,
The perovskite photoelectric device powder includes a metal compound and dimethyl sulfoxide,
The method for producing a perovskite film, characterized in that the monovalent cation contained in the precursor powder is substituted with the dimethyl sulfoxide. 7. The method of claim 6,
The perovskite film is a method for producing a perovskite film, characterized in that represented by the following formula (2).
[Formula 2]
A _a B _b X _c
(Here, A is the monovalent cation, B is a divalent metal cation, X is the monovalent anion, and a+2b=c.) a first electrode;
an electron transport layer formed on the first electrode;
A photoactive layer comprising a perovskite film prepared according to any one of claims 6 to 8 represented by the following Chemical Formula 2 on the electron transport layer;
a hole transport layer formed on the photoactive layer; and
a second electrode formed on the hole transport layer
Perovskite photoelectric device comprising a.
[Formula 2]
A _a B _b X _c
(Here, A is a monovalent cation, B is a divalent metal cation, X is a monovalent anion, and a+2b=c.) 10. The method of claim 9,
A current density of the perovskite photoelectric device is 10mA/cm ² to 40mA/cm ² A perovskite photoelectric device, characterized in that it is. 10. The method of claim 9,
The perovskite photoelectric device has a power conversion efficiency (PCE) of 10% to 35%.

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