KR102416108B1 - Organic-inorganic complex solar cell and method for manufacturing same - Google Patents

Abstract

The present specification includes a first electrode; a first common layer including metal oxide nanoparticles provided on the first electrode; a second common layer including a fullerene derivative provided on the first common layer; a light absorption layer including a compound having a perovskite structure provided on the second common layer; a third common layer provided on the light absorption layer; And it relates to an organic-inorganic composite solar cell including a second electrode provided on the third common layer.

Description

Organic-inorganic composite solar cell and organic-inorganic composite solar cell manufacturing method

The present specification relates to an organic-inorganic composite solar cell and an organic-inorganic composite solar cell manufacturing method.

In order to solve the global environmental problems caused by the depletion of fossil energy and its use, research on renewable and clean alternative energy sources such as solar energy, wind power, and hydroelectric power is being actively conducted. Among them, interest in solar cells that directly change electrical energy from sunlight is increasing. Here, the solar cell refers to a cell that generates current-voltage using the photovoltaic effect of absorbing light energy from sunlight to generate electrons and holes.

Organic-inorganic composite perovskite materials have recently been spotlighted as light-absorbing materials for organic-inorganic composite solar cells because of their high extinction coefficient and their properties that they can be easily synthesized through a solution process.

However, in the case of an organic-inorganic composite solar cell to which a conventional perovskite material is applied, there is a problem in that it is difficult to secure reliability such as heat resistance and light resistance. In order to overcome this, research is being conducted to apply a metal oxide-based common layer together with an organic-based common layer.

Conventionally, among metal oxides, organic-inorganic composite solar cells to which Ti oxide is applied have been mainly studied. However, in the case of Ti oxide, when applied as a common layer, driving stability is deteriorated due to surface defects, and to form a TiO ₂ layer, There is a problem in that the precursor solution must be heat-treated at a high temperature of 400° C. or higher. Therefore, it is necessary to study a common layer to replace Ti oxide.

Korean Patent Publication No. 2015-0143010

The present specification provides an organic-inorganic composite solar cell and an organic-inorganic composite solar cell manufacturing method having excellent stability and energy conversion efficiency.

The present specification provides a method for manufacturing an organic-inorganic composite solar cell with a simple manufacturing process.

An exemplary embodiment of the present specification includes a first electrode;

a first common layer including metal oxide nanoparticles provided on the first electrode;

a second common layer including a fullerene derivative provided on the first common layer;

a light absorption layer including a compound having a perovskite structure provided on the second common layer;

a third common layer provided on the light absorption layer; and

It provides an organic-inorganic composite solar cell including a second electrode provided on the third common layer.

Another embodiment of the present specification comprises the steps of preparing a first electrode;

forming a first common layer including metal oxide nanoparticles on the first electrode;

forming a second common layer including a fullerene derivative on the first common layer;

forming a light absorption layer including a compound having a perovskite structure on the second common layer;

forming a third common layer on the light absorption layer; and

It provides an organic-inorganic composite solar cell manufacturing method comprising the step of forming a second electrode on the third common layer.

The organic-inorganic composite solar cell according to an exemplary embodiment of the present specification has an effect of improving the stability of the device.

In addition, the organic-inorganic composite solar cell according to an exemplary embodiment of the present specification can absorb a wide light spectrum, thereby reducing light energy loss and increasing energy conversion efficiency.

The organic-inorganic composite solar cell manufacturing method according to an exemplary embodiment of the present specification has an effect of improving fairness and bonding strength between the first common layer and the second common layer by using the nanoparticle dispersion.

1 illustrates the structure of an organic-inorganic composite solar cell according to an embodiment of the present specification.
Figure 2 is an organic-inorganic composite solar cell according to an exemplary embodiment of the present specification, stability evaluation results at room temperature conditions.
3 is an organic-inorganic composite solar cell according to an exemplary embodiment of the present specification, and is a result of stability evaluation at 60°C.
4 is a view showing a hysteresis measurement result of the device manufactured in Example 1. Referring to FIG.
5 is a view showing a scanning electron microscope (SEM) image of the surface of the device prepared in Experimental Example 5-1.
6 is a view showing a scanning electron microscope (SEM) image of the surface of the device prepared in Experimental Example 5-2.

Hereinafter, the present specification will be described in detail.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

In the present specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

The organic-inorganic composite solar cell according to the present specification includes a first electrode;

a first common layer including metal oxide nanoparticles provided on the first electrode;

a second common layer including a fullerene derivative provided on the first common layer;

a light absorption layer including a compound having a perovskite structure provided on the second common layer;

a third common layer provided on the light absorption layer; and

and a second electrode provided on the third common layer.

1 illustrates the structure of an organic-inorganic composite solar cell according to an exemplary embodiment of the present specification. Specifically, FIG. 1 shows that the first electrode 101, the first common layer 102, the second common layer 103, the light absorption layer 104, the third common layer 105, and the second electrode 106 are sequentially formed. The structure of the organic-inorganic composite solar cell stacked with

The organic-inorganic composite solar cell according to the present specification is not limited to the stacked structure of FIG. 1 , and additional members may be further included.

In the exemplary embodiment of the present specification, the metal oxide nanoparticles include at least one of Ni oxide, Cu oxide, and Sn oxide. Specifically, it may include Sn oxide, more specifically SnO ₂ .

When Ni oxide, Cu oxide, and Sn oxide are applied as the metal oxide nanoparticles, stability is better than when other metal oxides (eg, Ti oxide) are applied.

As used herein, “fullerene derivative” refers to a material having one or more spherical shell structures in which molecules are formed of carbon. For example, fullerene as a spherical shell-shaped molecule; a fullerene derivative having an inorganic group or an organic group bonded to the carbon constituent fullerene; and fullerene derivatives in which fullerene or a spherical shell structure constituting the fullerene derivative is bonded directly or through one or more elements.

In an exemplary embodiment of the present specification, the fullerene derivative is C ₆₀ fullerene, C ₆₁ fullerene, C ₇₁ fullerene, ICBA (1′,1′′,4′,4′′-Tetrahydro-di[1,4]methanonaphthaleno [1,2:2′,3′,56,60:2′′,3′′][5,6]fullerene-C ₆₀ ) and phenyl-C ₆₁ -butyric acid methyl ester (Phenyl-C ₆₁ - butyric acid methyl ester, PC ₆₁ BM). Specifically, in one embodiment of the present specification, the fullerene derivative may be PC ₆₁ BM.

In the present specification, the first common layer, the second common layer, and the third common layer mean an electron transport layer or a hole transport layer, respectively.

In the present specification, the first common layer may be a first electron transport layer, the second common layer may be a second electron transport layer, and the third common layer may be a hole transport layer.

In the present specification, the thickness of the first common layer may be 5 nm to 50 nm. In the present specification, the thickness of the first common layer means a width between the surface of the first common layer in contact with the first electrode and the surface of the first common layer in contact with the second common layer.

In the present specification, the thickness of the second common layer may be 5 nm to 50 nm. In the present specification, the thickness of the second common layer means a width between the surface of the second common layer in contact with the first common layer and the surface of the second common layer in contact with the light absorption layer.

In the present specification, the thickness of the third common layer may be 30 nm to 200 nm. In the present specification, the thickness of the third common layer means a width between the surface of the third common layer in contact with the light absorption layer and the surface of the third common layer in contact with the second electrode.

When the first common layer, the second common layer, and the third common layer satisfy the above thickness, the short circuit current Isc and the filling factor FF increase due to a decrease in the internal electrical resistance of the device.

In an exemplary embodiment of the present specification, the light absorption layer includes a compound of a perovskite structure represented by any one of the following Chemical Formulas 1 to 3.

[Formula 1]

R1M1X1 ₃

[Formula 2]

R2 _a R3 _(1-a) M2X2 _z X3 _(3-z)

[Formula 3]

R4 _b R5 _c R6 _d M3X4 _z' X5 _(3-z')

In Formulas 1 to 3,

R2 and R3 are different from each other,

R4, R5 and R6 are different from each other,

R1 to R6 are each 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 ⁺ is a monovalent cation selected from,

M1 to M3 are the same as or different from each other, ^and each independently Cu ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ^{2+ ,} Pd ^{2+ , Cd 2+ , Ge 2+ , Sn 2 +} , Bi ^{2 +} , Pb ^{2 +} and Yb ^{2 +} is a divalent metal ion selected from,

X1 to X5 are the same as or different from each other, each independently a halogen ion,

n is an integer from 1 to 9,

a is a real number 0<a<1,

b is a real number 0<b<1,

c is a real number 0 < c < 1,

d is a real number 0<d<1,

b+c+d is 1,

z is a real number 0<z<3,

z' is a real number 0<z'<3.

In one embodiment of the present specification, the compound of the perovskite structure of the light absorption layer may include a single cation. In the present specification, a single cation means that one type of monovalent cation is used. That is, in Formula 1, it means that only one type of monovalent cation is selected as R1. For example, R1 in Formula 1 may be C _n H _{2n + 1} NH ₃ ⁺ , and n may be an integer of 1 to 9.

In one embodiment of the present specification, the compound of the perovskite structure of the light absorption layer may include a complex cation. In the present specification, the complex cation means that two or more types of monovalent cations are used. That is, in Formula 2, monovalent cations in which R2 and R3 are different from each other are selected, and in Formula 3, monovalent cations in which R4 to R6 are each different from each other are selected. For example, in Formula 2, R2 may be C _n H _2n+1 NH ₃ ⁺ , and R3 may be HC(NH ₂ ) ₂ ⁺ . In addition, in Formula 3, R4 may be C _n H _{2n + 1} NH ₃ ⁺ , R5 may be HC(NH ₂ ) ₂ ⁺ , and R6 may be Cs ⁺ .

In an exemplary embodiment of the present specification, the compound of the perovskite structure is represented by Formula 1.

In an exemplary embodiment of the present specification, the compound of the perovskite structure is represented by Chemical Formula 2.

In an exemplary embodiment of the present specification, the compound of the perovskite structure is represented by Formula 3.

In an exemplary embodiment of the present specification, R1 to R6 are each C _n H _{2n + 1} NH ₃ ⁺ , HC(NH ₂ ) ₂ ⁺ or Cs ⁺ . In this case, R2 and R3 are different from each other, and R4 to R6 are different from each other.

In an exemplary embodiment of the present specification, R1 is CH ₃ NH ₃ ⁺ , HC(NH ₂ ) ₂ ⁺ or Cs ⁺ .

In an exemplary embodiment of the present specification, R2 and R4 are each CH ₃ NH ₃ ⁺ .

In an exemplary embodiment of the present specification, R3 and R5 are each HC(NH ₂ ) ₂ ⁺ .

In the exemplary embodiment of the present specification, R6 is Cs ⁺ .

In the exemplary embodiment of the present specification, M1 to M3 are each Pb ^{2 +} .

In an exemplary embodiment of the present specification, X2 and X3 are different from each other.

In an exemplary embodiment of the present specification, X4 and X5 are different from each other.

In an exemplary embodiment of the present specification, X1 to X5 are each F or Br.

In the exemplary embodiment of the present specification, in order for the sum of R2 and R3 to be 1, a is a real number of 0<a<1. In addition, in order for the sum of R4 to R6 to be 1, b is a real number of 0<b<1, c is a real number of 0<c<1, d is a real number of 0<d<1, b+c +d is 1.

In the exemplary embodiment of the present specification, in order for the sum of X2 and X3 to be 3, z is a real number of 0<z<3. Also, in order for the sum of X4 and X5 to be 3, z' is a real number of 0<z'<3.

In one embodiment of the present specification, the compound of the perovskite structure is CH ₃ NH ₃ PbI ₃ , HC(NH ₂ ) ₂ PbI _{3 ,} CH ₃ NH ₃ PbBr ₃ , HC(NH ₂ ) ₂ PbBr ₃ , (CH ₃ NH ₃ ) _a (HC(NH ₂ ) ₂ ) _(1-a) PbI _z Br _(3-z) or (CH ₃ NH ₃ ) _b (HC(NH ₂ ) ₂ ) _c Cs _d PbI _z′ Br _(3-z′) , a is a real number 0<a<1, and b is 0<b<1 real number, c is a real number 0<c<1, d is a real number 0<d<1, b+c+d is 1, z is a real number 0<z<3, z' is 0< It can be a real number of z'<3.

In the present specification, the thickness of the light absorption layer may be 200 nm to 1,500 nm.

Another embodiment of the present specification comprises the steps of preparing a first electrode;

forming a first common layer including metal oxide nanoparticles on the first electrode;

forming a second common layer including a fullerene derivative on the first common layer;

forming a light absorption layer including a compound having a perovskite structure on the second common layer;

forming a third common layer on the light absorption layer; and

It provides an organic-inorganic composite solar cell manufacturing method comprising the step of forming a second electrode on the third common layer.

In the present specification, the forming of the first common layer may include coating a solution containing metal oxide nanoparticles and a dispersant on the first electrode; and

and drying the coated solution at 70°C to 150°C.

In general, after coating using a metal precursor as a method for applying a metal oxide to the common layer, a high-temperature process of 400° C. or more is performed to form a crystal. On the other hand, in the manufacturing method according to an exemplary embodiment of the present specification, the formation of the first common layer to which the metal nanoparticles are applied is completed through the steps of applying the metal nanoparticles to the dispersion and drying at 150° C. or less, thus improving the fairness. . In addition, when the first common layer is formed through the above method, bonding strength with the second common layer including the fullerene derivative is increased.

In one embodiment of the present specification, the solution containing the metal oxide nanoparticles and the dispersing agent is the first solution.

In one embodiment of the present specification, the metal oxide nanoparticles in the first solution are the same as described above in the organic-inorganic composite solar cell. Specifically, the metal oxide nanoparticles include at least one of Ni oxide, Cu oxide, and Sn oxide.

In one embodiment of the present specification, the step of coating the first solution including the metal oxide nanoparticles and the dispersant on the first electrode is spin coating, slit coating, dip coating, inkjet printing, gravure printing, spray coating, Doctor blade, bar coating, brush painting or thermal evaporation method can be performed.

In one embodiment of the present specification, the solvent of the first solution is water, methanol, ethanol, isopropyl alcohol, butanol, benzyl alcohol ), alcohols such as phenol, oleyl alcohol, and 2-propoxy-propanol (PnP); glycol ethers such as propylene glycol monomethyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), and ethylene glycol butyl ether (EGBE); toluene; ethyl lactate (EL); acetonitrile; acetone; THF (tetrahydrofuran); Cyclic ketones and mixtures thereof may be used, but the present invention is not limited thereto.

In one embodiment of the present specification, the dispersant is organosilane, organocarboxylic acids, 4-vinylpridine, a-methylstyrene, butyl acryl butyl acrylate, polyethylene glycol, polypropylene glycol, alkyl ether phosphate ester (RO—(C ₂ H ₄ O) _m (C ₃ H ₆ O) _n —H , R is an alkyl group having 1 to 10 carbon atoms, m and n are each independently an integer of 2 to 60), a block copolymer of a phosphate ester (RO(C ₂ H ₄ O) _o (PES) _p —H, R is An alkyl group having 1 to 10 carbon atoms, PES is a polyester derived from a cyclic lactone, o is an integer from 5 to 60, p is an integer from 2 to 30, RO(C ₂ H ₄ O) Molecular weight of _o > (PES) _p of molecular weight), mixtures thereof, or polymers thereof.

In an exemplary embodiment of the present specification, the first solution contains 0.01 wt% to 10 wt% of the dispersing agent compared to the metal nanoparticles. When the dispersant satisfies the above range, there is an effect of increasing device efficiency due to a decrease in electrical resistance.

In one embodiment of the present specification, the forming of the second common layer comprises: coating a second solution containing a fullerene derivative on the first common layer; and

and drying the coated second solution at 70°C to 150°C.

In one embodiment of the present specification, the fullerene derivative in the second solution is the same as described above.

In an exemplary embodiment of the present specification, the solvent of the second solution is not limited as long as it is a solvent capable of dissolving the fullerene derivative, but may be, for example, chlorobenzene, dichlorobenzene, or chloroform.

In one embodiment of the present specification, the content of the fullerene derivative in the second solution may be 15 mg to 25 mg per 1 ml of the solution. If the content of the fullerene derivative is out of the above range, there is a problem in that the coating is not uniformly achieved.

In one embodiment of the present specification, the second common layer may be formed through spin coating, slit coating, dip coating, inkjet printing, gravure printing, spray coating, doctor blade, bar coating, brush painting, or thermal evaporation method. have.

In one embodiment of the present specification, the third common layer is introduced through a method such as spin coating, dip coating, inkjet printing, gravure printing, spray coating, doctor blade, bar coating, gravure coating, brush painting, thermal evaporation, etc. can be

In one embodiment of the present specification, the light absorption layer may be formed through spin coating, slit coating, dip coating, inkjet printing, gravure printing, spray coating, doctor blade, bar coating, brush painting, or thermal evaporation method.

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

In one embodiment of the present specification, the substrate may be a substrate excellent in transparency, surface smoothness, handling and waterproofing properties. Specifically, a glass substrate, a thin glass substrate, or a plastic substrate may be used. The plastic substrate may include a film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone and polyimide in the form of a single layer or multiple layers. can However, the substrate is not limited thereto, and a substrate commonly used in organic-inorganic composite solar cells may be used.

In the exemplary embodiment of the present specification, the first electrode may be an anode, and the second electrode may be a cathode. In addition, the first electrode may be a cathode, and the second electrode may be an anode.

In the exemplary embodiment of the present specification, the first electrode may be a transparent electrode, and the solar cell may absorb light via the first electrode.

In the exemplary embodiment of the present specification, when the first electrode is a transparent electrode, the first electrode is polyethylene terephthalate (PET), polyethylene naphthelate (PEN), poly Propylene (polyperopylene, PP), polyimide (PI), polycarbonate (polycarbornate, PC), polystyrene (polystylene, PS), polyoxyethlene (POM), AS resin (acrylonitrile styrene copolymer), ABS resin ( A material in which a conductive material is doped on a flexible and transparent material such as plastic including acrylonitrile butadiene styrene copolymer), triacetyl cellulose (TAC) and polyarylate (PAR) may be used. Specifically, the first electrode is indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum doped zinc oxide (aluminium doped zink oxide, AZO), IZO (indium) zinc oxide), ZnO-Ga ₂ O ₃ , ZnOAl ₂ O ₃ , and antimony tin oxide (ATO), and more specifically, the first electrode may be ITO.

In the exemplary embodiment of the present specification, the first electrode may be a semi-transparent electrode. When the first electrode is a translucent electrode, it may be made of a metal such as silver (Ag), gold (Au), magnesium (Mg), or an alloy thereof.

In the exemplary embodiment of the present specification, the second electrode may be a metal electrode. Specifically, the metal electrode is silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), palladium (Pd) ), magnesium (Mg), chromium (Cr), calcium (Ca), and may include one or two or more selected from the group consisting of samarium (Sm).

In an exemplary embodiment of the present specification, the organic-inorganic composite solar cell may have an n-i-p structure.

When the organic-inorganic composite solar cell according to the present specification has a nip structure, the second electrode may be a metal electrode, an oxide/metal composite electrode, or a carbon electrode. Specifically, the second metal is 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, V ₂ O ₅ /Al, WO ₃ /Au, WO ₃ /Ag or WO ₃ /Al.

In the present specification, the n-i-p structure refers to a structure in which a first electrode, a first electron transport layer, a second electron transport layer, a light absorption layer, a hole transport layer, and a second electrode are sequentially stacked.

In an exemplary embodiment of the present specification, the organic-inorganic composite solar cell may have a p-i-n structure. When the organic-inorganic composite solar cell according to the present specification has a p-i-n structure, the second electrode may be a metal electrode.

In the present specification, the p-i-n structure refers to a structure in which a first electrode, a hole transport layer, a light absorption layer, a first electron transport layer, a second electron transport layer, and a second electrode are sequentially stacked.

In one embodiment of the present specification, the hole transport layer material is tertiary butyl pyridine (TBP), lithium bis (trifluoromethanesulfonyl) imide (Lithium Bis (Trifluoro methanesulfonyl) Imide, LiTFSI) , poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate)(PEDOT:PSS), 2,2',7,7'-tetrakis(N,N-di-p-methoxy Phenylamine)-9,9'-spirobifluorene (2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene, Spiro-OMeTAD) It can be used, but is not limited thereto.

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art.

Example 1.

On an alkali-free glass substrate sputtered with indium tin oxide (ITO), 1 wt% of tin dioxide (SnO ₂ ) and 1 wt% of a dispersant compared to tin dioxide in ethanol (ethanol) was spin-coated at 2,000 rpm and then spin-coated 150 It was dried at ℃ for 30 minutes. Thereafter, a solution of PC ₆₁ BM dissolved in chlorobenzene at a concentration of 20 mg/ml was spin-coated at 5,000 rpm and dried at 120° C. for 10 minutes. Then the perovskite precursor ((HC(NH ₂ ) ₂ ) _x (CH ₃ NH ₃ ) _y Cs _{1 -x- y} PbI _z Br _{3 -z} (0<x<1, 0<y<1, 0.8 A solution of <x+y<1, 0<z<3) in dimethylformamide was spin-coated at 5,000 rpm, and then heated at 100° C. for 30 minutes to form a light absorption layer. After dissolving 7,7'-tetrakis (N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-OMeTAD) in chlorobenzene, tert-butylpyridine ( tBP) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were spin-coated, and finally, Au was vacuum deposited to complete an organic-inorganic composite solar cell.

Comparative Example 1.

On an alkali-free glass substrate sputtered with indium tin oxide (ITO), 2 wt% of titanium dioxide (TiO ₂ ) and a solution containing 1 wt% of dispersant in isopropyl alcohol compared to titanium dioxide was spin coated at 2,000 rpm Then, it was heated at 150° C. for 30 minutes. Then the perovskite precursor((HC(NH ₂ ) ₂ ) _x (CH ₃ NH ₃ ) _y Cs _1-xy PbI _z Br _3-z (0<x<1, 0<y<1, 0.8<x A solution of +y<1, 0<z<3)) in dimethylformamide was spin-coated and heated at 100° C. for 30 minutes to form a light absorption layer. After dissolving Spiro-OMeTAD in chlorobenzene, a solution containing tBP and LiTFSI was spin-coated. Finally, an organic-inorganic composite solar cell was completed by vacuum deposition of Au.

Comparative Example 2.

After dissolving PC ₆₁ BM in chlorobenzene at a concentration of 20 mg/ml on an alkali-free glass substrate sputtered with indium tin oxide (ITO), spin-coated at 5,000 rpm, and dried at 120° C. for 10 minutes. Then 1wt% SnO ₂ and SnO ₂ A solution containing 1 wt% of a dispersant in ethanol was spin-coated at 2,000 rpm and then heated at 150° C. for 30 minutes. Then the perovskite precursor((HC(NH ₂ ) ₂ ) _x (CH ₃ NH ₃ ) _y Cs _1-xy PbI _z Br _3-z (0<x<1, 0<y<1, 0.8<x A solution of +y<1, 0<z<3)) in dimethylformamide was spin-coated at 5,000 rpm, and then dried at 100° C. for 30 minutes to form a light absorption layer. After dissolving Spiro-OMeTAD in chlorobenzene, a solution containing tBP and LiTFSI was spin-coated. Finally, Au was vacuum-deposited to complete an organic-inorganic composite solar cell.

Comparative Example 3

After dissolving PC ₆₁ BM in chlorobenzene at a concentration of 20 mg/ml on an alkali-free glass substrate sputtered with indium tin oxide (ITO), spin-coated at 5,000 rpm, and dried at 120° C. for 10 minutes. Then the perovskite precursor ((HC(NH ₂ ) ₂ ) _x (CH ₃ NH ₃ ) _y Cs _{1 -x- y} PbI _z Br _{3 -z} (0<x<1, 0<y<1, 0.8 A solution of <x+y<1, 0<z<3)) in dimethylformamide was spin-coated at 5,000 rpm, and then heated at 100° C. for 30 minutes to form a light absorption layer. After dissolving Spiro-OMeTAD in chlorobenzene, a solution containing tBP and LiTFSI was spin-coated. Finally, Au was vacuum-deposited to complete an organic-inorganic composite solar cell.

Experimental Example 1.

Table 1 shows the results of measuring the devices prepared in Example 1 and Comparative Examples 1 to 3 under white LED light (101 μW/cm ² ) of 400 lux illuminance.

PCE
(%) J _sc
(μA/cm ² ) V _oc
(V) FF
(%) Example 1 23.3 40.7 0.752 76.8 Comparative Example 1 25.8 44 0.811 72.2 Comparative Example 2 20.8 38.7 0.714 76.0 Comparative Example 3 16.5 34.8 0.709 66.9

In Table 1, V _oc denotes an open circuit voltage, J _sc denotes a short-circuit current, FF denotes a fill factor, and PCE denotes 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, and the higher these two values, the higher the efficiency of the solar cell is. Also, the fill factor is the value obtained by dividing the maximum area of a rectangle that can be drawn inside the curve by the product of the short-circuit current and the open-circuit voltage. By dividing these three values by the intensity of the irradiated light, energy conversion efficiency can be obtained, and a higher value is preferable.

From the results in Table 1, it can be confirmed that Comparative Examples 2 and 3 have lower efficiency than Example 1. That is, it can be seen that when the order of the materials applied to the first common layer and the second common layer is changed (Comparative Example 2) and when only one common layer is applied between the electrode and the photoactive layer (Comparative Example 3), the efficiency is reduced. .

Experimental Example 2.

While the devices prepared in Example 1 and Comparative Example 1 were stored at room temperature, the efficiency was measured under white LED light (101 μW/cm ² ) of 400 lux illuminance every predetermined time, and the results are shown in FIG. 2 .

That is, FIG. 2 shows the evaluation results of stability when the organic-inorganic composite solar cells manufactured in Example 1 and Comparative Example 1 are driven at room temperature. In the case of the organic-inorganic composite solar cell prepared in Comparative Example 1 in which TiO ₂ was applied to the first common layer, the efficiency decreased after 200 hours, and the device was not driven after 600 hours. On the other hand, in the case of the organic-inorganic composite solar cell prepared in Example 1 in which SnO ₂ is applied to the first common layer, it can be seen that the initial efficiency is maintained for 1,000 hours or more.

Experimental Example 3.

While the devices prepared in Example 1 and Comparative Example 1 were stored in a vacuum oven at 60° C., the efficiency was measured under white LED light (101 μW/cm ² ) of 400 lux illuminance every predetermined time, and the results are shown in FIG. 3 .

That is, FIG. 3 shows the stability evaluation results when the organic-inorganic composite solar cells prepared in Example 1 and Comparative Example 1 were driven at 60°C. In the case of the organic-inorganic composite solar cell prepared in Comparative Example 1 in which TiO ₂ was applied to the first common layer, the device efficiency was reduced to 70% or less within 2 hours. On the other hand, in the case of the organic-inorganic composite solar cell prepared in Example 1 in which SnO ₂ is applied to the first common layer, it can be seen that the initial efficiency is maintained for 250 hours or more.

Experimental Example 4.

The hysteresis of the device manufactured in Example 1 was measured and shown in FIG. 4 .

Hysteresis refers to the occurrence of a difference in efficiency (PCE) depending on the scan direction. In FIG. 4, REV (reverse scan) is a measurement of current while changing from a voltage greater than V _oc to 0V, and FWD (forward scan) measures the current while changing it from 0V to a voltage greater than Voc. 4 shows the measurement results of REV scan from 1V to 0V and FWD scan from 0V to 1V.

Experimental Example 5-1.

On an alkali-free glass substrate sputtered with indium tin oxide (ITO), a solution containing 1 wt% of tin dioxide (SnO ₂ ) in ethanol was spin-coated at 2,000 rpm, and then dried at 150° C. for 30 minutes. Thereafter, a solution of PC ₆₁ BM dissolved in chlorobenzene at a concentration of 20 mg/ml was spin-coated at 5,000 rpm and dried at 120° C. for 10 minutes.

5 shows a scanning electron microscope (SEM) image of the surface of the device prepared in Experimental Example 5-1, it can be confirmed that the surface of the PC ₆₁ BM layer (second common layer) is uniformly formed.

Experimental Example 5-2.

A solution containing 1 wt% of tin dioxide (SnO ₂ ) in ethanol (ethnaol) was spin-coated at 2,000 rpm on an alkali-free glass substrate sputtered with indium tin oxide (ITO), and then dried at 150° C. for 30 minutes. Then, a solution of PC ₆₁ BM dissolved in chlorobenzene at a concentration of 10 mg/ml was spin-coated at 5,000 rpm and dried at 120° C. for 10 minutes.

6 shows a scanning electron microscope (SEM) image of the surface of the device prepared in Experimental Example 5-2, it can be confirmed that the surface of the PC ₆₁ BM layer (second common layer) is not uniformly formed.

5 and 6, when the content of the fullerene derivative in the solution satisfies 15 mg to 25 mg per 1 ml of the solution when the second common layer is formed, it can be confirmed that the fullerene derivative layer (the second common layer) is uniformly formed.

101: first electrode
102: first common layer
103: second common layer
104: light absorption layer
105: third common layer
106: second electrode

Claims (6)

a first electrode;
a first common layer including metal oxide nanoparticles provided on the first electrode;
a second common layer including a fullerene derivative provided on the first common layer;
a light absorption layer including a compound having a perovskite structure provided on the second common layer;
a third common layer provided on the light absorption layer; and
a second electrode provided on the third common layer;
The metal oxide nanoparticles may include at least one of Ni oxide, Cu oxide, and Sn oxide. An organic-inorganic composite solar cell. The method according to claim 1,
The light absorption layer is an organic-inorganic composite solar cell comprising a compound of a perovskite structure represented by any one of the following Chemical Formulas 1 to 3:
[Formula 1]
R1M1X1 ₃
[Formula 2]
R2 _a R3 _(1-a) M2X2 _z X3 _(3-z)
[Formula 3]
R4 _b R5 _c R6 _d M3X4 _z' X5 _(3-z')
In Formulas 1 to 3,
R2 and R3 are different from each other,
R4, R5 and R6 are different from each other,
R1 to R6 are each 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 ⁺ is a monovalent cation selected from,
M1 to M3 are the same as or different from each other, ^and each independently Cu ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ^{2+ ,} Pd ^{2+ , Cd 2+ , Ge 2+ , Sn 2 +} , Bi ^{2 +} , Pb ^{2 +} and Yb ^{2 +} is a divalent metal ion selected from,
X1 to X5 are the same as or different from each other, each independently a halogen ion,
n is an integer from 1 to 9,
a is a real number 0<a<1,
b is a real number 0<b<1,
c is a real number 0 < c < 1,
d is a real number 0<d<1,
b+c+d is 1,
z is a real number 0<z<3,
z' is a real number 0<z'<3. delete preparing a first electrode;
forming a first common layer including metal oxide nanoparticles on the first electrode;
forming a second common layer including a fullerene derivative on the first common layer;
forming a light absorption layer including a compound having a perovskite structure on the second common layer;
forming a third common layer on the light absorption layer; and
forming a second electrode on the third common layer;
The metal oxide nanoparticles are organic-inorganic composite solar cell manufacturing method comprising at least one of Ni oxide, Cu oxide, and Sn oxide. 5. The method according to claim 4,
The forming of the first common layer may include: coating a solution containing metal oxide nanoparticles and a dispersant on the first electrode; and
An organic-inorganic composite solar cell manufacturing method comprising the step of drying the coated solution at 70 °C to 150 °C. 6. The method of claim 5,
The solution is an organic-inorganic composite solar cell manufacturing method comprising 0.01 wt% to 10 wt% of the dispersing agent compared to the metal oxide nanoparticles.

Images