KR20170132567A - Method of manufacturing the optical absorber layer for organic-inorganic complex solar cell, and method of manufacturing organic-inorganic complex solar cell using thereof - Google Patents

Abstract

The present specification relates to a method for manufacturing a light absorbing layer of an organic-inorganic complex solar cell, which includes the steps of: coating an electrode with a droplet with a radius of 100 nm to 500 nm including a first perovskite precursor solution including metal halide; and coating the coated metal halide with a droplet with a radius of 100 nm to 500 nm including a second perovskite precursor solution including organic halide, and a method for manufacturing an organic-inorganic complex solar cell using the same. Accordingly, the present invention can simplify a manufacturing process and form a crystal with high purity.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a light absorbing layer of an organic / inorganic hybrid solar cell, and a method of manufacturing an organic / inorganic hybrid solar cell using the same. BACKGROUND ART [0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a light absorbing layer of an organic-inorganic hybrid solar cell and a manufacturing method of a organic-inorganic hybrid solar cell using the same.

Research on renewable and clean alternative energy sources such as solar energy, wind power, and hydro power is actively being conducted to solve the global environmental problems caused by depletion of fossil energy and its use. Among these, there is a great interest in solar cells that change electric energy directly from sunlight. Here, a solar cell refers to a cell that generates a current-voltage by utilizing a photovoltaic effect that absorbs light energy from sunlight to generate electrons and holes.

The organic-inorganic composite perovskite material has recently attracted attention as a light absorbing material for organic / inorganic hybrid solar cells due to its high extinction coefficient and its ability to be easily synthesized through a solution process.

In general, an absorption layer structure used in an organic-inorganic hybrid solar cell is composed of a single cation, a metal ion, and a halogen ion with a basic structure of an AMX ₃ component. Such an absorbing layer is absorbed in each case or once at a time by dissolving it and applying it on a substrate to induce thinning and crystallization. However, spin coating, slit coating, and bar coating methods, which are conventionally used as a coating method, can not simultaneously perform thinning and crystallization. Therefore, there is a problem that additional processing is required to induce crystallization. Particularly, in the case of spin coating, it is difficult to secure a high-crystalline absorption layer due to the influence of the environment and rapid crystal growth during the progress of crystallization.

Therefore, in order to solve such a problem, it is necessary to carry out a research to make the thinning and crystallization processes separate or sequentially proceed rapidly. However, the method of increasing the solid content of the solution is limited by the saturation solubility of the solution, and it is difficult to thin the solution at a high concentration in the process. .

Adv. Mater. 2014, 26, 4991-4998

The present invention provides a method for manufacturing a light absorbing layer of a organic-inorganic hybrid solar cell, and a method for manufacturing a organic-inorganic hybrid solar cell using the same, wherein a process is simple and high purity crystals are formed.

One embodiment of the present disclosure is directed to a method of forming an electrode, comprising: coating a droplet having a radius of 100 nm to 500 nm comprising a first perovskite precursor solution comprising a metal halide on the electrode; And

Wherein the step of coating is performed using a droplet having a radius of 100 nm to 500 nm and containing a second perovskite precursor solution containing an organic halide on the coated metal halide. A method for manufacturing a light absorbing layer for a battery is provided.

According to another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a first electrode;

Forming an electron transporting layer or a hole transporting layer on the first electrode;

Forming a light absorbing layer on the electron transporting layer or the hole transporting layer by the light absorbing layer manufacturing method;

Forming an electron transporting layer or a hole transporting layer on the light absorbing layer; And

And forming a second electrode on the electron transporting layer or the hole transporting layer formed on the light absorbing layer.

According to one embodiment of the present invention, a method of manufacturing a light absorbing layer of a hybrid organic / inorganic hybrid solar cell has a simple and high-purity crystalline structure because a solvent extraction process and a crystallization process are not required.

According to one embodiment of the present invention, a method for manufacturing a hybrid organic-inorganic hybrid solar cell has an effect of manufacturing an organic-inorganic hybrid solar cell having improved energy conversion efficiency.

1 shows XRD (X-Ray Diffraction) measurement results of a light absorption layer according to an embodiment of the present invention.
2 shows the results of absorbance measurement of the light absorbing layer according to the embodiment of the present invention.
3 shows a scanning electron microscope (SEM) image of the light absorbing layer prepared in Example 1 of this specification.
4 is a scanning electron microscope (SEM) image of the light absorbing layer prepared in Comparative Example 1 of this specification.
5 is a scanning electron microscope (SEM) image of the light absorbing layer prepared in Comparative Example 2 of this specification.
6 is a graph showing a current density according to a voltage of the organic-inorganic hybrid solar cell manufactured in the embodiment of the present invention.

Hereinafter, the present specification will be described in detail.

In this specification, when a part is referred to as "including " an element, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In this specification, when a member is located on another member, it includes not only when a member is in contact with another member but also when there is another member between the two members.

According to an embodiment of the present invention, there is provided a method of manufacturing a light absorbing layer for an organic-inorganic hybrid solar battery, comprising: forming a droplet having a radius of 100 nm to 500 nm and containing a first perovskite precursor solution containing a metal halide on the electrode; Coating; And

Coating with a droplet having a radius of 100 nm to 500 nm comprising a second perovskite precursor solution containing an organic halide on the coated metal halide.

In this specification, the droplet sizes of the first perovskite precursor solution and the second perovskite precursor solution realized through the electric field spray coating were calculated using Ganna-Calvo scaling law (1997) .

[Formula 1]

In Equation 1, Q is the flow of the solution. In the present specification, the flow of the solution was measured using an experimental method using the pressure difference across the capillary nozzle using the liquid supply device as the capillary nozzle.

Specifically, the liquid to be sprayed is placed in one of the capillary nozzles, and a capillary is connected to generate a pressure with carbon dioxide as a carrier. Then, the accumulated amount of the fluid passing through the capillary is checked by the pressure difference at both ends. The flow rate corresponding to the pressure difference of the flow rate was calculated. In the present specification, it is applied in the range of about 0.1 ml / s to 0.5 ml / s.

In Equation (1), rho is the density of the solution. In this specification, the density of the solution was measured using a densitometer DC-50 meter.

Specifically, the concentration of the metal halide in the first perovskite precursor solution and the concentration of the organic halide in the second perovskite precursor solution were each divided into 0.1 wt% to 0.5 wt%, and a DC-50 density meter The density of the solution corresponding to each concentration was measured.

In Equation 1,? ₀ is the dielectric constant of the liquid in vacuum. As used herein, the dielectric constant of a liquid in a vacuum refers to the level at which the liquid is charged in the electric field. The dielectric constant of the liquid was measured using a M-I871 permittivity meter from Niho-Rufto.

In the above formula 1,? Is the surface tension coefficient. In this specification, the surface tension coefficient was calculated by capillary rise measurement method and force equations.

Generally, the surface tension coefficient of a liquid in which a solid is dissolved forms an equilibrium of gravity and force corresponding to the liquid column in the capillary. The equilibrium equation of force is shown in Equation 2 below.

[Formula 2]

In the formula 2, γ ₁ is the surface tension coefficient, r is the radius, h is the height of liquid in the capillaries of the liquid column, ρ is the density of the solution, g is the gravitational acceleration.

In Equation (1), K is an electric conductivity coefficient. In the present specification, the electrical conductivity refers to the degree of electric current flow in a solution, and a circuit such as a method of measuring a resistance of a conductor that has a cross-sectional area and a length is measured.

Specifically, a liquid to be measured is filled in a Teflon tube having a length L and an inner radius r, a voltage is applied to both ends of the tube, and the current flowing through the tube is measured. The resistance R of the liquid is calculated by the Ohm's law. The electric conductivity coefficient can be confirmed by determining the reciprocal of the resistivity value by the length and the cross-sectional area of the conductor. The formulas are as shown in Equations 3 and 4 below.

[Formula 3]

[Formula 4]

In the equations (3) and (4), R denotes a resistance, r denotes a resistivity, S denotes a cross-sectional area, L denotes a length of a conductor, and K denotes an electric conduction coefficient.

In the present specification, the electrical conductivity coefficient is about 0.01 S / m to 0.04 S / m.

In Equation (1), d ₀ represents the droplet diameter.

In general, the droplet size that can be achieved through spray coating is from a few microns to a few thousand microns, while the first perovskite precursor solution and the second perovskite precursor solution implemented through the electric field spray coating of the present disclosure The droplet size has a radius of 100 nm to 500 nm. Specifically, the droplet size of the first perovskite precursor solution and the second perovskite precursor solution may be 100 nm to 250 nm.

According to the present specification, by realizing the small droplet size as described above, it is advantageous that crystal formation of perovskite used as a light absorbing layer is advantageous, and crystal size is evenly distributed.

When the radius of the droplet size is more than 500 nm, the surface roughness of the formed light absorbing layer is not uniform, and when the droplet size is less than 100 nm, the crystal size is small and voids are generated in the thin layer.

As used herein, the term low-electric-field spray coating refers to an electric field spray coating method according to the embodiment of the present invention in which the droplet size radius is 100 nm to 500 nm as described above.

As used herein, the term " precursor " refers to a substance at a stage before a substance is metabolized or reacted in a certain reaction. That is, in the present specification, the perovskite precursor means a material before the perovskite material is formed.

In the present specification, the precursor solution means a solution containing a precursor. That is, in the present specification, the perovskite precursor solution means a solution containing the substance before the perovskite substance.

In this specification, the precursor solution is prepared by dissolving dimethylformamide (DMF), isopropyl alcohol alcohol (IPA), gamma-butyrolactone, dimethyl sulfoxide, And N-methylpyrrolidone (N-methylpyrrolidone).

In one embodiment of the present invention, the metal halide is a compound represented by the general formula (1).

[Chemical Formula 1]

MX ₂

In Formula 1,

M is ^{Cu 2 +, Ni 2 +,} Co 2 +, Fe 2 +, Mn 2 +, Cr 2 +, Pd 2 +, Cd 2 +, Ge 2 +, Sn 2 +, Pb 2 + , and from Yb ^{2 +} Is a divalent metal ion to be selected,

X is a halogen ion.

In one embodiment of the present invention, the organic halide is a compound represented by the following formula (2).

(2)

AX

In Formula 2,

A is _{C n H 2n + 1 NH 3} +, HC (NH 2) 2 +, NH 4 +, CS +, NF 4 +, NCl 4 +, PF 4 +, PCl 4 +, CH 3 PH 3 +, CH ₃ AsH ₃ ⁺ , CH ₃ SbH ₃ ⁺ , PH ₄ ⁺ , AsH ₄ ⁺ and SbH ₄ ⁺

X is a halogen ion,

n is an integer of 1 to 9;

In one embodiment of the present disclosure, the concentration of the metal halide in the first perovskite precursor solution is 0.1 wt% to 5 wt%. When the concentration of the metal halide in the first perovskite precursor solution satisfies the above range, droplets of uniform size can be formed, the processability is improved, and the formation of the perovskite structure is easy.

In one embodiment of the present disclosure, the concentration of the organic halide in the second perovskite precursor solution is 0.1 wt% to 5 wt%. When the concentration of the metal halide in the second perovskite precursor solution satisfies the above range, droplets of uniform size can be formed, the processability is improved, and the formation of the perovskite structure is easy.

In this specification, a droplet of uniform size means that the droplet radius is 100 nm to 500 nm.

In the present specification, the above formula (1) is C _n H _{2n +1} I, and n may be an integer of 1 to 9.

In the present specification, the formula (2) may be PbI ₂ .

In one embodiment of the present disclosure, the coating may be performed by a spray coating method. Specifically, in one embodiment of the present disclosure, the coating may be performed by an electric field spray coating method.

In general, the structure of the light absorption layer used in the organic-inorganic hybrid solar cell is composed of a single cation, a metal ion, and a halogen ion as the basic structure of the AMX ₃ component. Such a light absorbing layer is required to be thinned and crystallized after each of the constituent materials is dissolved or dissolved at one time on a substrate to exhibit absorbency. However, spin coating, slit coating, and bar coating methods, which are conventionally used as a coating method, can not simultaneously perform thinning and crystallization. Therefore, there is a problem that additional processing is required to induce crystallization. Particularly, in the case of spin coating, it is difficult to secure a high-crystalline absorption layer due to the influence of the environment and rapid crystal growth during the progress of crystallization.

On the other hand, when the solid content of the solution is large, it is advantageous for crystal nucleus formation, but there is a limit due to the saturation solubility of the solution, and it is difficult to thin the solution at a high concentration in the process.

According to the present specification, by coating the light absorbing layer on the substrate using an electric field spraying method, it is possible to spray the solution at a concentration generally the same as the concentration used for spin coating, and the solvent extraction process or the crystallization process There is an advantage that a high-purity perovskite crystal is formed even if it is not used.

According to an embodiment of the present invention, a method of fabricating a hybrid organic-inorganic hybrid solar cell includes: forming a first electrode;

Forming an electron transporting layer or a hole transporting layer on the first electrode;

Forming a light absorbing layer on the electron transporting layer or the hole transporting layer by the light absorbing layer manufacturing method;

Forming an electron transporting layer or a hole transporting layer on the light absorbing layer; And

And forming a second electrode on the electron transporting layer or the hole transporting layer formed on the light absorbing layer.

In one embodiment of the present invention, the light absorbing layer comprises a perovskite material represented by the following formula (3).

(3)

AMX ₃

In Formula 3,

A is _{C n H 2n + 1 NH 3} +, NH 4 +, HC (NH 2) 2 +, CS +, NF 4 +, NCl 4 +, PF 4 +, PCl 4 +, CH 3 PH 3 +, CH ₃ AsH ₃ ⁺ , CH ₃ SbH ₃ ⁺ , PH ₄ ⁺ , AsH ₄ ⁺ and SbH ₄ ⁺

M is ^{Cu 2 +, Ni 2 +,} Co 2 +, Fe 2 +, Mn 2 +, Cr 2 +, Pd 2 +, Cd 2 +, Ge 2 +, Sn 2 +, Pb 2 + , and from Yb ^{2 +} Is a divalent metal ion to be selected,

X is a halogen ion,

n is an integer of 1 to 9;

In the present specification, the perovskite material may be C _n H _{2n + 1} NH ₃ PbI ₃ and n may be an integer of 1 to 9.

In the present specification, the perovskite material may be a _{CH 3 NH 3 PbI 3 (methylammonium} lead iodide, MAPbI 3).

In this specification, when an electron transporting layer is formed on the first electrode, a hole transporting layer may be formed on the light absorbing layer.

In this specification, when a hole transporting layer is formed on the first electrode, an electron transporting layer may be formed on the light absorbing layer.

In this specification, the organic-inorganic hybrid solar cell may further include a substrate. Specifically, the substrate may be provided under the first electrode.

In this specification, the substrate may be a substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness. Specifically, a glass substrate, a thin film glass substrate, or a plastic substrate can be used. The plastic substrate may include films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone, and polyimide in the form of a single layer or a multilayer . However, the substrate is not limited thereto, and a substrate commonly used in an organic-inorganic hybrid solar cell may be used.

In this specification, the first electrode may be an anode, and the second electrode may be a cathode. The first electrode may be a cathode, and the second electrode may be an anode.

In this specification, the first electrode is a transparent electrode, and the organic-inorganic hybrid solar cell absorbs light via the first electrode.

In the present invention, when the first electrode is a transparent electrode, the electrode may be formed of a material selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP) Polyimide (PI), polycarbornate (PC), polystyrene (PS), polyoxyethylene (POM), acrylonitrile styrene copolymer, ABS resin, acrylonitrile butadiene styrene copolymer, A material having conductivity may be doped on a flexible transparent material such as plastic including triacetyl cellulose (TAC) and polyarylate (PAR) or the like.

More specifically, indium tin oxide (ITO), fluorine doped tin oxide (FTO), aluminum doped zinc oxide (AZO), indium zinc oxide (IZO), and zinc oxide -Ga ₂ O ₃ , ZnOAl ₂ O ₃ and ATO (antimony tin oxide), and more specifically ITO.

Furthermore, the first electrode may be a translucent electrode. When the first electrode is a translucent electrode, the first electrode may be made of a translucent metal such as Ag, Au, Mg, or an alloy thereof. When a semitransparent metal is used as the first electrode, the produced organic-inorganic hybrid solar cell may have a microcavity structure.

In this specification, the second electrode may be a metal electrode. Specifically, the metal electrode may be formed of a metal such as silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni) Pd), and the like.

In this specification, the organic-inorganic hybrid solar cell can be manufactured with an inverted structure. When the organic-inorganic hybrid solar cell manufactured according to the present invention has an inverted structure, the second electrode may be a metal electrode. Specifically, when the organic-inorganic hybrid solar cell according to an embodiment of the present invention has an inverted structure, the second electrode may be formed of gold (Au), silver (Ag), aluminum (Al), MoO ₃ / Au, MoO ₃ / Ag MoO ₃ / Al, V ₂ O ₅ / Au, V ₂ O ₅ / Ag, or V ₂ O ₅ / Al.

In this specification, the organic-inorganic hybrid solar cell can be manufactured in a normal structure. When the organic-inorganic hybrid solar cell according to the present invention has a normal structure, the second electrode may be a metal electrode.

In this specification, the organic-inorganic hybrid solar cell may further include an additional layer provided between the first electrode and the second electrode. Specifically, according to one embodiment of the present specification, the additional layer may include at least one selected from the group consisting of a hole injection layer, a hole transporting layer, an electron blocking layer, an electron transporting layer, and an electron injecting layer.

In this specification, the hole transporting layer and / or the electron transporting layer material may be a material for increasing the probability that the charge generated by efficiently transferring electrons and holes to the light absorbing layer moves to the electrode, but is not particularly limited.

In the present specification, the electron transporting layer may include a metal oxide. Specific examples of the metal oxide include Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Zr oxide, Sr oxide, Yr oxide, La oxide, V oxide, , A Sc oxide, a Sm oxide, a Ga oxide, an In oxide, a SrTi oxide, and a combination thereof may be used, but is not limited thereto.

In this specification, the electron transporting layer can improve the characteristics of electric charge by using doping, and the surface can be modified by using a fullerene derivative or the like.

In this specification, the electron transport layer may be formed on one side of the first electrode or coated in film form using sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing .

In this specification, the hole transport layer may be an anode buffer layer.

A hole transport layer may be introduced onto the second light-absorbing layer through spin coating, dip coating, inkjet printing, gravure printing, spray coating, doctor blade, bar coating, gravure coating, brush painting or thermal deposition.

The hole transport layer may include at least one of tertiary butyl pyridine (TBP), lithium bis (trifluoromethanesulfonyl) imide, LiTFSI, poly (3,4-ethylenedioxythiophene ): Poly (4-styrenesulfonate) [PEDOT: PSS], and the like.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

Example  One

An organic substrate coated with indium tin oxide (ITO) (40 Ω / sq) was ultrasonically cleaned in ethanol for 20 minutes. A first electrode including a conductive transparent substrate was prepared by spin-coating a solution containing zinc oxide (ZnO) on the ITO substrate.

The first electrode was annealed at 150 ° C for about 15 minutes to produce an ITO substrate coated with a ZnO film (hereinafter, electron transport layer).

To form the light absorbing layer, a dimethylformamide (DMF) solution containing about 1 wt% of PbI ₂ dissolved therein was applied by electric field spray coating on the electron transport layer, and the resultant was stored in an argon (Ar) atmosphere for 10 minutes. Then, an isopropyl alcohol (IPA) solution containing 1 wt% CH ₃ NH ₃ I (MAI) dissolved therein was applied by electric field spray coating and then heat-treated at 60 ° C. for 3 minutes to form a light absorbing layer. The electric field spray coating was made up of a nozzle unit, a substrate unit, and a high voltage generator. The electric field spray coating was performed under the condition that the diameter of the nozzle discharge port was 0.1 mm to 0.3 mm, the applied voltage was 2 kV to 5 kV, and the spraying distance was 5 mm to 10 mm. At this time, a conical meniscus formed at the tip of the nozzle was formed, and the droplet was broken from the end of the meniscus, and it was confirmed that the uniform droplet was formed.

On the light absorption layer, 0.17 M of spiro-MeOTAD, 0.198 M of tertiary butyl pyridine (TBP), 64 mM of lithium bis (trifluoromethanesulfonyl) imide , Li-TFSI) was spin-coated to form a hole transport layer. At this time, the Li-TFSI was dissolved in acetonitrile at a concentration of 0.1977 g / mL and added in a solution state.

Inorganic hybrid solar cell was completed by depositing silver (Ag) on the hole transport layer at a thickness of about 120 nm to 150 nm at a pressure of 10 ^-8 torr or less to form a second electrode.

Comparative Example  One

An organic substrate coated with indium tin oxide (ITO) (40 Ω / sq) was ultrasonically cleaned in ethanol for 20 minutes. A first electrode including a conductive transparent substrate was prepared by spin-coating a solution containing zinc oxide (ZnO) on the ITO substrate.

The first electrode was annealed at 150 ° C for about 15 minutes to produce an ITO substrate coated with a ZnO film (hereinafter, electron transport layer).

In order to form a light absorbing layer, a dimethylformamide (DMF) solution having a concentration of about 40 wt% of PbI ₂ was spin-coated on the electron transport layer and heat-treated at 100 ° C for 10 minutes. Then, an isopropyl alcohol (IPA) solution in which 5 wt% CH ₃ NH ₃ I (MAI) was dissolved was spin-coated and heat-treated at 80 ° C for 10 minutes to form a light absorbing layer.

On the light absorption layer, 0.17 M of spiro-MeOTAD, 0.198 M of tertiary butyl pyridine (TBP), 64 mM of lithium bis (trifluoromethanesulfonyl) imide , Li-TFSI) was spin-coated to form a hole transport layer. At this time, the Li-TFSI was dissolved in acetonitrile at a concentration of 0.1977 g / mL and added in a solution state.

Inorganic hybrid solar cell was completed by depositing silver (Ag) on the hole transport layer at a thickness of about 120 nm to 150 nm at a pressure of 10 ^-8 torr or less to form a second electrode.

Comparative Example  2

An organic substrate coated with indium tin oxide (ITO) (40 Ω / sq) was ultrasonically cleaned in ethanol for 20 minutes. A first electrode including a conductive transparent substrate was prepared by spin-coating a solution containing zinc oxide (ZnO) on the ITO substrate.

The first electrode was annealed at 150 ° C for about 15 minutes to produce an ITO substrate coated with a ZnO film (hereinafter, electron transport layer).

To form the light absorbing layer, a dimethylformamide (DMF) solution containing about 1 wt% of PbI ₂ dissolved therein was spray-coated on the electron transport layer and heat-treated at 100 ° C for 2 minutes. Then, an isopropyl alcohol (IPA) solution in which 1 wt% of CH ₃ NH ₃ I (MAI) was dissolved was spray-coated and then heat-treated at 80 ° C. for 2 minutes to form a light absorbing layer. The spray coating was made up of a nozzle unit, a substrate unit, and a pressing unit. The spray coating was performed under the conditions that the diameter of the nozzle discharge port was 0.5 mm to 1 mm, the argon (Ar) gas pressure was 0.2 MPa to 0.5 MPa, and the spray distance was 5 cm to 10 cm.

On the light absorption layer, 0.17 M of spiro-MeOTAD, 0.198 M of tertiary butyl pyridine (TBP), 64 mM of lithium bis (trifluoromethanesulfonyl) imide , Li-TFSI) was spin-coated to form a hole transport layer. At this time, the Li-TFSI was dissolved in acetonitrile at a concentration of 0.1977 g / mL and added in a solution state.

Inorganic hybrid solar cell was completed by depositing silver (Ag) on the hole transport layer at a thickness of about 120 nm to 150 nm at a pressure of 10 ^-8 torr or less to form a second electrode.

1 shows XRD (X-Ray Diffraction) measurement results of a light absorption layer according to an embodiment of the present invention. In the case of the embodiment prepared by the low electric field spray coating, although there is no difference between the main peaks and Comparative Example 1 in which the heat treatment and the crystallization induction process proceeded after the spin coating process, Can be confirmed. Therefore, in the case of the low-electric-field spray coating method according to one embodiment of the present invention, the MAI particles uniformly penetrate the entire PbI ₂ film to cause reaction and crystallization, so that the residual PbI ₂ peak does not appear. On the other hand, in the case of Comparative Example 2 in which general spray coating was performed, it can be confirmed that a PbI ₂ peak appears.

Fig. 2 shows the results of absorbance measurement of the light absorbing layer according to the embodiment of the present invention. In the case of the example of the low-electric-field spray coating, it can be confirmed that although the separate curing and crystallization treatment process was not performed, the same absorbance as that of Comparative Example 1 in which the heat treatment and the crystallization induction process proceeded after the spin coating process was confirmed.

FIG. 3 is a scanning electron microscope (SEM) image of the light absorbing layer manufactured in the embodiment of the present invention, FIG. 4 is a scanning electron microscope (SEM) image of the light absorbing layer prepared in Comparative Example 1 of this specification, A scanning electron microscope (SEM) image of the light absorbing layer prepared in Comparative Example 2 of this specification is shown. In the case of the example of the low-electric-field spray coating, it is confirmed that the crystals are uniformly formed and the surface roughness is good, similarly to Comparative Example 1, although the separate curing and crystallization treatment steps are not performed. On the other hand, in the case of Comparative Example 2 in which general spray coating was performed, it was confirmed that the crystals were unevenly formed and the surface roughness was uneven.

Table 1 shows the performance of the organic-inorganic hybrid solar cell according to the embodiments of the present invention, and FIG. 6 shows the current density according to the voltage of the organic-inorganic hybrid solar cell manufactured in the present embodiment.

PCE (%) J _sc (mA / cm ² ) V _oc (V) FF (%) Example 1 10.2 18.1 1.05 53.9 Comparative Example 1 11.6 18.2 1.06 60.6 Comparative Example 2 5.8 15.9 0.964 38.1

In Table 1, Voc is the open-circuit voltage, Jsc is the short-circuit current, FF is the fill factor, and PCE is the energy conversion efficiency. The open-circuit voltage and the short-circuit current are the X-axis and Y-axis intercepts in the fourth quadrant of the voltage-current density curve, respectively. The higher the two values, the higher the efficiency of the solar cell. The fill factor is a value obtained by dividing the width of the rectangle which can be drawn inside the curve by the product of the short-circuit current and the open-circuit voltage. The energy conversion efficiency can be obtained by dividing these three values by the intensity of the irradiated light, and a higher value is preferable.

In the case of the organic-inorganic hybrid solar cell manufactured through Example 1, the performance was confirmed to be equivalent to that of the organic-inorganic hybrid solar cell of Comparative Example 1 prepared by the conventional spin coating. In particular, J _sc (short-circuit current) appeared to have a similar value, and it was confirmed that although the heat treatment and the separate crystallization process were not performed in the case of the example made by the low-electric-field spray coating, .

Claims (9)

Coating with a droplet having a radius of 100 nm to 500 nm comprising a first perovskite precursor solution containing a metal halide on the electrode; And
Wherein the step of coating is performed using a droplet having a radius of 100 nm to 500 nm and containing a second perovskite precursor solution containing an organic halide on the coated metal halide. A method for manufacturing a light absorbing layer for a battery. The method according to claim 1,
Wherein the coating is performed by spray coating. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
Wherein the coating is performed by an electric field spray coating. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
Wherein the metal halide is a compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
MX ₂
In Formula 1,
M is ^{Cu 2 +, Ni 2 +,} Co 2 +, Fe 2 +, Mn 2 +, Cr 2 +, Pd 2 +, Cd 2 +, Ge 2 +, Sn 2 +, Pb 2 + , and from Yb ^{2 +} Is a divalent metal ion to be selected,
X is a halogen ion. The method according to claim 1,
Wherein the organic halide is a compound represented by the following formula (2): < EMI ID =
(2)
AX
In Formula 2,
A is _{C n H 2n + 1 NH 3} +, HC (NH 2) 2 +, NH 4 +, CS +, NF 4 +, NCl 4 +, PF 4 +, PCl 4 +, CH 3 PH 3 +, CH ₃ AsH ₃ ⁺ , CH ₃ SbH ₃ ⁺ , PH ₄ ⁺ , AsH ₄ ⁺ and SbH ₄ ⁺
X is a halogen ion,
n is an integer of 1 to 9; The method according to claim 1,
Wherein the concentration of the metal halide in the first perovskite precursor solution is 0.1 wt% to 5 wt%. The method according to claim 1,
Wherein the concentration of the organic halide in the second perovskite precursor solution is 0.1 wt% to 5 wt%. Forming a first electrode;
Forming an electron transporting layer or a hole transporting layer on the first electrode;
Forming a light absorbing layer made by the method of manufacturing a light absorbing layer according to any one of claims 1 to 7 on the electron transporting layer or the hole transporting layer;
Forming an electron transporting layer or a hole transporting layer on the light absorbing layer; And
And forming a second electrode on the electron transporting layer or the hole transporting layer formed on the light absorbing layer. The method of claim 8,
Wherein the light absorbing layer comprises a perovskite material represented by the following formula (3).
(3)
AMX ₃
In Formula 3,
A is _{C n H 2n + 1 NH 3} +, NH 4 +, HC (NH 2) 2 +, CS +, NF 4 +, NCl 4 +, PF 4 +, PCl 4 +, CH 3 PH 3 +, CH ₃ AsH ₃ ⁺ , CH ₃ SbH ₃ ⁺ , PH ₄ ⁺ , AsH ₄ ⁺ and SbH ₄ ⁺
M is ^{Cu 2 +, Ni 2 +,} Co 2 +, Fe 2 +, Mn 2 +, Cr 2 +, Pd 2 +, Cd 2 +, Ge 2 +, Sn 2 +, Pb 2 + , and from Yb ^{2 +} Is a divalent metal ion to be selected,
X is a halogen ion,
n is an integer of 1 to 9;

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