KR102054308B1 - Perovskite solar cell and preparing method thereof - Google Patents

Abstract

A first electrode; A recombination prevention layer formed on the first electrode; A perovskite layer comprising alkali iodine and perovskite on the recombination preventing layer; A hole transport layer formed on the perovskite layer; And it relates to a perovskite solar cell comprising a second electrode formed on the hole transport layer.

Description

Perovskite solar cell and method for manufacturing same {PEROVSKITE SOLAR CELL AND PREPARING METHOD THEREOF}

The present application relates to a perovskite solar cell and a method of manufacturing the same.

Recently, research on organic-inorganic perovskite solar cells using a light absorber having an organic-inorganic perovskite structure as a next-generation solar cell has been actively conducted. Organic-inorganic composite perovskite materials have been applied to solar cells for the first time in 2009 by the Tsutomu Miyasaki Group in Japan (J. Am. Chem. Soc. 2009, 131, 6050-6051), and have a high absorption coefficient and a solution process. Due to its properties that can be easily synthesized through, it has been spotlighted as a solar cell light absorbing material.

The material having the perovskite structure (ABX3) is an inorganic metal oxide.

Such inorganic metal oxides are generally oxides, and titanium (Ti), strontium (Sr), calcium (Ca), cesium (Cs), barium (Ba), and yttrium having different sizes at A and B positions. Y), gadolinium (Gd), lanthanum (La), iron (Fe), manganese (Mn) and other metals (alkali metals, alkaline earth metals, transition metals and lanthanum groups) cations are located and oxygen (oxygen) at the X position ) Anion is located, and metal cations in position B are combined with oxygen anions in position X as a corner-sharing octahedron of 6-fold coordination. Examples thereof include strontium ferrite (SrFeO ₃ ), lanthanum manganite (LaMnO ₃ ), calcium ferrite (CaFeO ₃ ), and the like.

Inorganic metal oxide perovskite has characteristics such as superconductivity, ferroelectricity, and colossal magnetoresistance. In general, researches are being conducted using such characteristics to be applied to sensors, fuel cells, memory devices, and the like.

The organic-inorganic hybrid halide perovskite has an organic ammonium (RNH ₃ ) cation or an alkali metal cation in position A in the ABX3 structure, and a halide perovskite in which the halides (Cl, Br, I) are located in position X. The sky material will be formed.

Organic-inorganic hybrid halide perovskite (or organometallic and inorganic metal halide perovskite) has an organic plane (or an alkali metal plane) and an inorganic plane that are alternately stacked, similar to the lamellar structure and the excitons within the inorganic plane. Because of the possibility of confinement, it is essentially an ideal emitter that emits very high color purity light by the crystal structure itself rather than the size of the material.

Among organic-inorganic perovskite materials, mainly CH ₃ NH ₃ PbI ₃ and CH ₃ NH ₃ PbI _{3 - x} Cl _x are used as the photoactive layer of the solar cell. Such methylammonium lead halide perovskite exhibits excellent photoelectric performance with high charge transport properties and light absorption properties. It is also stabilized at tetragonal phase at room temperature, which has a bandgap of about 1.5 eV.

Assuming that methylammonium lead halide perovskite has no loss of incident light by reflection in the transparent conductive substrate, the theoretical maximum photocurrent density was about 27.2 mA / cm ² , and the incident photon-to-electron conversion The absorption onset wavelength, measured by efficiency (IPCE), was about 800 nm. However, it should be taken into account that about 15% to about 20% light loss will occur in an actual device, leading to about 23.1 mA / cm ² to about 21.8 mA / cm ² . Thus, a methylammonium lead halide based perovskite cell can deliver about 20% PCE when a voltage of about 1.1 V and a fill factor of about 0.8 are achieved.

However, the organic-inorganic composite perovskite material based on the methylammonium cation has a bandgap of about 1.55 eV and can absorb up to about 800 nm wavelength light, thus limiting the amount of photocurrent generated to about 21 mA / cm ² . do. In addition, in the case of the organic-inorganic hybrid perovskite solar cell based on the existing methyl ammonium cation, since there is a hysteresis phenomenon due to an external voltage, it is difficult to determine accurate photoelectric characteristics.

When hysteresis occurs, the efficiency of the solar cell is determined by the average value of the reverse and forward bias. As a result, perovskite solar cells exhibiting high hysteresis have low efficiency.

Korean Patent Publication No. 10-1666563, which is a background technology of the present application, relates to a perovskite solar cell and a method of manufacturing the same. However, this patent does not mention eliminating the hysteresis of perovskite solar cells.

The present invention is to solve the above-mentioned problems of the prior art, an object of the present invention to provide a perovskite solar cell and a manufacturing method thereof.

However, the technical problem to be achieved by the embodiments of the present application is not limited to the technical problems as described above, and other technical problems may exist.

As a technical means for achieving the above technical problem, the first side of the present application, the first electrode; A recombination prevention layer formed on the first electrode; A perovskite layer comprising alkali iodine and perovskite represented by Formula 1 on the recombination prevention layer; A hole transport layer formed on the perovskite layer; And it provides a perovskite solar cell, comprising a second electrode formed on the hole transport layer.

<Formula 1>

(RMX ₃ ) _{1-y- z} (R'MX ' ₃ ) _z (AMX'' ₃ ) _y

In Formula 1,

R and R 'are each independently a substituted or unsubstituted alkyl group, and when R and R' are substituted, the substituents are amino, hydroxyl, cyano, halogen, nitro or methoxy groups,

M is Pb, Sn, or Ge,

A is an alkali metal or alkaline earth metal,

X, X 'and X' 'are each independently F, Cl, Br, or I,

y is more than 0 and 0.2 or less, and z is 0 or more and 0.2 or less.

According to one embodiment of the present application, the alkali iodine may be included in a concentration of 0.1 mmol to 10 mmol, but is not limited thereto.

According to one embodiment of the present application, the alkali iodine may include Na, K, Rb, Cs, Fr or Li metal, but is not limited thereto.

According to an embodiment of the present disclosure, the perovskite layer is ((HC (NH ₂ ) ₂ ) MX ₃ ) _1-y (AMX '' ₃ ) _y (wherein M is Pb, Sn or Ge, and A is Alkali metal or alkaline earth metal, X and X '' are each independently F, Cl, Br, or I, and y is greater than 0 and less than or equal to 0.2), but is not limited thereto.

According to an embodiment of the present disclosure, the perovskite layer comprises ((HC (NH ₂ ) ₂ ) PbI ₃ ) _1-y (CsPbBr ₃ ) _y , wherein y is greater than 0 and less than or equal to 0.2 It may be, but is not limited thereto.

According to the exemplary embodiment of the present application, the first electrode and the second electrode each independently include a material selected from the group consisting of metals, conductive polymers, carbon materials, tin oxides, zinc oxide, and combinations thereof. It may be, but is not limited thereto.

According to the exemplary embodiment of the present application, the recombination preventing layer may include a material selected from the group consisting of an organic semiconductor, an inorganic semiconductor, and combinations thereof, but is not limited thereto.

According to the exemplary embodiment of the present application, the hole transport layer may include a material selected from the group consisting of a single molecule hole transport material, a polymer hole transport material, and combinations thereof, but is not limited thereto.

The second aspect of the present application, forming a recombination preventing layer on the first electrode; Forming a perovskite layer comprising an alkali iodine and a perovskite represented by Chemical Formula 1 below on the recombination prevention layer; Forming a hole transport layer on the perovskite layer; And it provides a method of manufacturing a perovskite solar cell comprising the step of forming a second electrode on the hole transport layer.

<Formula 1>

(RMX ₃ ) _{1-y- z} (R'MX ' ₃ ) _z (AMX'' ₃ ) _y

In Formula 1,

R and R 'are each independently a substituted or unsubstituted alkyl group, and when R and R' are substituted, the substituents are amino, hydroxyl, cyano, halogen, nitro or methoxy groups,

M is Pb, Sn, or Ge,

A is an alkali metal or alkaline earth metal,

X, X 'and X' 'are each independently F, Cl, Br, or I,

y is more than 0 and 0.2 or less, and z is 0 or more and 0.2 or less.

According to an embodiment of the present disclosure, the perovskite layer may be formed by (MX ₂ ) _1-yz , (MX ′ ₂ ) _z , (MX ″ ₂ ) _y , wherein M is Pb, Sn, or Ge, X, X 'and X''are each independently F, Cl, Br, or I, y is greater than 0 and less than or equal to 0.2 and z is greater than or equal to 0 and less than or equal to 0.2), (AX'') _y ( Wherein A is an alkali or alkaline earth metal, X '' is F, Cl, Br, or I), precursors for preparing perovskite (RX) _1-yz and (R'X) _1-yz where R and R 'are each independently a substituted or unsubstituted alkyl group, and when R and R' are substituted, the substituents are amino groups, hydroxyl groups, cyano groups, halogen groups, nitro groups or methoxy groups, and X is F , Cl, Br, or I, y is greater than 0 to 0.2 or less, z is greater than or equal to 0.2 and less than 0.2), and the alkali iodine is coated on the anti-recombination layer, but is not limited thereto. .

According to one embodiment of the present application, the alkali iodine may be included in a concentration of 0.1 mmol to 10 mmol, but is not limited thereto.

According to one embodiment of the present application, the alkali iodine may include Na, K, Rb, Cs, Fr or Li metal, but is not limited thereto.

According to one embodiment of the present application, the precursor for preparing perovskite may include (HC (NH ₂ ) ₂ ) X, wherein X is F, Cl, Br, or I, but is not limited thereto. It doesn't happen.

According to one embodiment of the present application, the precursor for preparing perovskite may be to include (HC (NH ₂ ) ₂ ) I, but is not limited thereto.

According to the exemplary embodiment of the present application, the (MX ₂ ) _1-yz , (MX ′ ₂ ) _z , (MX ″ ₂ ) _y , (AX ″) _y , (RX) _1-yz on the recombination prevention layer And (R'X) _1-yz , and alkali iodine coating method is spin coating method, cast method, Liangmuir-Blodgett (LB) method, inkjet printing method, nozzle printing method, slot die coating method Dr. blade coating method, screen printing method, dip coating method, gravure printing method, reverse off-sensing printing method, physical transfer method, spray coating method, chemical vapor deposition method, thermal deposition method, vacuum deposition method and combinations thereof It may be performed by a coating selected from, but is not limited thereto.

The above-mentioned means for solving the problems are merely exemplary and should not be construed as limiting the present application. In addition to the above-described exemplary embodiments, additional embodiments may exist in the drawings and detailed description of the invention.

According to the above-described problem solving means of the present application, the perovskite solar cell according to the present application can remove the hysteresis phenomenon by adding alkali iodine on the existing perovskite layer. The efficiency of the solar cell at the time of hysteresis is determined by the average of the resulting values in the reverse and forward directions. As a result, the perovskite solar cell exhibiting a large hysteresis exhibits low efficiency. By removing the hysteresis, the average of the reverse and forward biases increases, thereby developing a solar cell having a high efficiency of 18.4%.

1 is a structure of a perovskite solar cell according to an embodiment of the present application.
2 is a flow chart of a method of manufacturing a perovskite solar cell according to an embodiment of the present application.
FIG. 3 shows the voltage (V) of a perovskite solar cell in which 0 mmol, 2 mmol, 4 mmol, 6 mmol, 8 mmol, and 10 mmol of KI are added to the perovskite layer according to an embodiment of the present invention. ) Is a graph showing the current density (mA / cm ² ) according to.
FIG. 4 shows KI of a perovskite solar cell in which 0 mmol, 2 mmol, 4 mmol, 6 mmol, 8 mmol, and 10 mmol of KI were added to the perovskite layer according to an embodiment of the present invention. It is a graph showing the photoelectric conversion efficiency (PCE), the filling factor (FF), the voltage (V) and the short circuit current density (J _sc ) according to the concentration.
5 is a graph showing trap density, dielectric constant, and V _TFL according to the concentration of KI of a perovskite solar cell according to an embodiment of the present invention.
6 is a graph showing energy (tail energy, Eu) according to the concentration of KI in a perovskite solar cell according to an embodiment of the present invention.
FIG. 7 illustrates that KI is added on a perovskite layer and that KI is added on a triple and perovskite layer is not added (FAPbI ₃ ) _0.85 (MAPbBr ₃ ) according to an embodiment of the present invention. _It is a graph showing the current density according to the voltage of _0.15 .

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure.

 As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a part is "connected" to another part, this includes not only "directly connected" but also "electrically connected" with another element in between. do.

Throughout this specification, when a member is said to be located on another member "on", "upper", "top", "bottom", "bottom", "bottom", this means that any member This includes not only the contact but also the presence of another member between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise.

As used herein, the terms "about", "substantially", and the like, are used at the numerical values of, or in the vicinity of, numerical values when manufacturing and material tolerances inherent in the meanings indicated are provided to aid the understanding herein. In order to prevent the unfair use of unscrupulous infringers. In addition, throughout this specification, "step to" or "step of" does not mean "step for."

Throughout this specification, the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.

 Throughout this specification, description of "A and / or B" means "A, B, or A and B."

Hereinafter, a perovskite solar cell of the present application and a method for manufacturing the same will be described in detail with reference to embodiments, examples, and drawings. However, the present application is not limited to these embodiments, examples and drawings.

The first side of the present application, the first electrode; A recombination prevention layer formed on the first electrode; A perovskite layer comprising alkali iodine and perovskite represented by Formula 1 on the recombination prevention layer; A hole transport layer formed on the perovskite layer; And it relates to a perovskite solar cell comprising a second electrode formed on the hole transport layer.

<Formula 1>

(RMX ₃ ) _{1-y- z} (R'MX ' ₃ ) _z (AMX'' ₃ ) _y

In Formula 1,

R and R 'are each independently a substituted or unsubstituted alkyl group, and when R and R' are substituted, the substituents are amino, hydroxyl, cyano, halogen, nitro or methoxy groups,

M is Pb, Sn, or Ge,

A is an alkali metal or alkaline earth metal,

X, X 'and X' 'are each independently F, Cl, Br, or I, y is greater than 0 to 0.2 or less, and z is 0 or more and 0.2 or less.

1 is a structure of a perovskite solar cell according to an embodiment of the present application.

Referring to FIG. 1, the perovskite solar cell includes a first electrode 110, a recombination preventing layer 120 formed on the first electrode 110, and a perovskite layer formed on the recombination preventing layer 120. 130, a hole transport layer 140 formed on the perovskite layer 130, and a second electrode 150 formed on the hole transport layer 140.

The perovskite solar cell may include, but is not limited to, a sensitive structure, a mesoscopic structure, or a heterojunction structure.

The perovskite solar cell may have a sandwich structure in which two electrodes, that is, the first electrode 110 and the second electrode 150 are bonded to each other, but are not limited thereto. For example, the first electrode 110 may be represented as a working electrode or a semiconductor electrode, and the second electrode 150 may be represented as a counter electrode, but is not limited thereto. It is not.

Since the alkaline iodine is included in the perovskite layer, hysteresis of the perovskite solar cell including the perovskite layer may be removed. The efficiency of the solar cell at the time of hysteresis is determined by the average of the resulting values in the reverse and forward directions. As a result, the perovskite solar cell, which exhibits a large hysteresis, has low efficiency. By removing the hysteresis, the average of the reverse and forward biases is increased, thereby increasing the efficiency of the solar cell.

According to one embodiment of the present application, the alkali iodine may be included in a concentration of 0.1 mmol to 10 mmol, but is not limited thereto.

According to one embodiment of the present application, the alkali iodine may include Na, K, Rb, Cs, Fr or Li metal, but is not limited thereto.

The alkali iodine may include, for example, a material selected from the group consisting of KI, NaI, RbI, CsI, FrI, LiI, and combinations thereof, but is not limited thereto.

In Formula 1, R and R 'may each independently include a linear or branched alkali group having 1 to 20 carbon atoms, but is not limited thereto. For example, R and R 'may be, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, or isomers thereof.

When R and R 'are each independently substituted, it may be an alkyl group having one or more of the above substituents. Where R and R 'are each independently substituted alkyl group may be substituted by one or more amino groups (-NH ₂ ), for example, one, two, or three amino groups May be, but is not limited thereto.

In Formula 1, R, R ', M and A may be present in a cation form, and X may be present in an anion form, but is not limited thereto. For example, in Formula 1, R and R 'may each independently be a monovalent organic cation, M may be a + divalent cation, A may be present in the form of a + monovalent cation, and X May be one in which -1 is present in anionic form.

In Formula 1, R and R 'each independently have (R ¹ R ² R ³ R ⁴ N) ⁺ , and R ¹ is hydrogen, unsubstituted or substituted C _1-20 alkyl, or unsubstituted Or substituted aryl; R ² is hydrogen, unsubstituted or substituted C _1-20 alkyl, or unsubstituted or substituted aryl; R ³ is hydrogen, unsubstituted or substituted C _1-20 alkyl, or unsubstituted or substituted aryl; And R ⁴ may be hydrogen, unsubstituted or substituted C _1-20 alkyl, or unsubstituted or substituted aryl, but is not limited thereto.

R and R 'in Formula 1 each independently have (R ⁵ R ⁶ N = CH-NR ⁷ R ⁸ ) ⁺ , and R ⁵ is hydrogen, unsubstituted or substituted C _1-20 alkyl, or unsubstituted Substituted aryl; R ⁶ is hydrogen, unsubstituted or substituted C _1-20 alkyl, or unsubstituted or substituted aryl; R ⁷ is hydrogen, unsubstituted or substituted C _1-20 alkyl, or unsubstituted or substituted aryl; And R ⁸ may be hydrogen, unsubstituted or substituted C _1-20 alkyl, or unsubstituted or substituted aryl, but is not limited thereto.

Alkyl groups used throughout this specification may be substituted or unsubstituted, may be linear or branched chain saturated radicals, and may be unsubstituted linear chain saturated radicals. C _1-20 alkyl groups are substituted or unsubstituted, linear or branched chain saturated hydrocarbon radicals. Usually C _1-10 alkyl is for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, or C ₁ -C ₄ alkyl, for example methyl, ethyl, i- Propyl, n-propyl, t-butyl, s-butyl or n-butyl.

When an alkyl group is substituted, it usually has one or more substituents selected from: substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted aryl, cyano, amino, C ₁ -C ₁₀ alkylamino, di (C ₁ -C ₁₀ ) alkylamino, arylamino, diarylamino, arylalkylamino, amide, acylamide, hydroxyl group, oxo, halogen, carboxy, ester, acyl, acyloxy, C ₁ -C ₂₀ alkoxy, aryloxy, halogenalkyl, sulfonic acid, sulfonic group, C ₁ -C ₁₀ alkylthio, arylthio, sulfonyl group, phosphoric acid, phosphate ester, phosphonic acid and phosphonate ester.

Examples of substituted alkyl groups include halogenalkyl, alkyl hydroxy, aminoalkyl, alkoxyalkyl and alkaryl groups. The term alkalyl as used herein belongs to a C ₁ -C ₂₀ alkyl group in which at least one hydrogen atom is substituted with an aryl group. Examples of each group may include, but are not limited to, benzyl, benzhydryl, triphenylmethyl, phenethyl, styryl, and cinnamil.

The substituted alkyl group may have one, two or three, for example one or two substituents, but is not limited thereto.

The aryl group is a substituted or unsubstituted single ring or double ring aromatic group, which may be from 6 to 14 carbon atoms, preferably from 6 to 10 carbon atoms in the ring portion However, the present invention is not limited thereto. Examples include phenyl, naphthyl, indenyl, and indanyl groups. Ali groups are unsubstituted or substituted. When the aryl group defined above is substituted, one or more of the following substituents are substituted: unsubstituted C ₁ -C ₆ alkyl, unsubstituted aryl, cyano, amino, C ₁ -C ₁₀ Alkylamino, di (C ₁ -C ₁₀ ) alkylamino, arylamino, diarylamino, arylalkylamino, amide, acylamide, hydroxyl group, oxo, halogen, carboxy, ester, acyl, acyloxy, C ₁ -C ₂₀ Alkoxy, aryloxy, halogenalkyl, sulfonic acid, sulfonic group, C ₁ -C ₁₀ alkylthio, arylthio, sulfonyl group, phosphoric acid, phosphate ester, phosphonic acid and phosphonate ester.

Substituted aryl groups are taken together with a single C ₁ -C ₆ alkylene group or with the formula -X- (C ₁ -C ₆ ) alkylene, or -X- (C ₁ -C ₆ ) alkylene-X- It may be substituted at two positions with the bidentate group represented, in which case X is selected from O, S and NR, and R is H, aryl or C ₁ -C ₆ alkyl. The substituted aryl group may thus be a cycloalkyl group or an aryl group fused with a heterocyclyl group. Ring atoms of an aryl group may include one or more heteroatoms. Such aryl groups are substituted or unsubstituted single or double cyclic heterocyclic aromatic groups, which can include 6 to 10 atoms in a ring portion comprising one or more heteroatoms. A 5- or 6-parted ring and may comprise at least one hetero atom selected from O, S, N, P, Se and Si. For example, it may contain 1, 2 or 3 hetero atoms. Heteroaryl groups are, for example, pyridyl, pyrazinyl, pyrimidinyl, paridazinyl, furanyl, thienyl, pyrazolidinyl, pyrrolyl, oxazolyl, oxadiazolyl, isoxazolyl, thiadiazolyl , Thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, quinolyl, isoquinoli, and combinations thereof, but is not limited thereto. Heteroaryl groups may be unsubstituted or substituted, for example, as defined for aryl above.

According to an embodiment of the present disclosure, the perovskite layer is ((HC (NH ₂ ) ₂ ) MX ₃ ) _1-y (AMX '' ₃ ) _y , wherein M is Pb, Sn, or Ge, A Is an alkali metal or alkaline earth metal, X and X '' are each independently F, Cl, Br, or I, y is greater than 0 to less than 0.2), but is not limited thereto.

According to an embodiment of the present disclosure, the perovskite layer comprises ((HC (NH ₂ ) ₂ ) PbI ₃ ) _1-y (CsPbBr ₃ ) _y , wherein y is greater than 0 and less than or equal to 0.2 It may be, but is not limited thereto.

According to the exemplary embodiment of the present application, the first electrode and the second electrode each independently include a material selected from the group consisting of metals, conductive polymers, carbon materials, tin oxides, zinc oxide, and combinations thereof. It may be, but is not limited thereto.

The first electrode 110 includes a material selected from the group consisting of indium tin oxide (ITO), fluorine tin oxide (FTO), ZnO-Ga ₂ O ₃ , ZnO-Al ₂ O _3, and combinations thereof. It may be, but is not limited to such.

The metal is Cu, Ni, Sc, Ti, V, Cr, Mn, Fe, Co, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re , Os, Ir, Pt, Au, Hg, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Cn and may include a metal selected from the group consisting of, but is not limited thereto. It is not.

The conductive polymer may be poly (3,4-ethylenedioxythiophene) (PEDOT), poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS), polyacetylene, polypyrrole, polythiophene, The polyaniline, polyphenylene, polyphenylene sulfide, poly fullerene and the combination may be to include a material selected from the group consisting of, but is not limited thereto.

The carbon material may include, but is not limited to, a carbon material selected from the group consisting of carbon nanotubes, graphene, fullerenes, carbon nanofibers, and combinations thereof.

According to the exemplary embodiment of the present application, the recombination preventing layer may include a material selected from the group consisting of an organic semiconductor, an inorganic semiconductor, and combinations thereof, but is not limited thereto.

The recombination prevention layer may include, for example, a metal oxide selected from the group consisting of TiO ₂ , SnO ₂ , ZnO, WO ₃ , NB ₂ O ₅ , TiSrO _3, and combinations thereof, but is not limited thereto. It is not.

According to the exemplary embodiment of the present application, the hole transport layer may include a material selected from the group consisting of a single molecule hole transport material, a polymer hole transport material, and combinations thereof, but is not limited thereto.

The hole transport layer 140 may be formed of, for example, spiro-MeOTAD (2, 2 ', 7, 7'-tetrakis (N, Np-dimethoxy-phenylamino) -9,9'-spirobifluorene), P3HT ( poly (3-hexylthiophene)), PTAA (polytriarylamine), PEDOT: PSS (poly (3,4-ethylenedioxythiophene) polystyrene sulfonate) and combinations thereof, but may include a material selected from the group It is not.

The second aspect of the present application, forming a recombination preventing layer on the first electrode; Forming a perovskite layer comprising an alkali iodine and a perovskite represented by Chemical Formula 1 below on the recombination prevention layer; Forming a hole transport layer on the perovskite layer; And it relates to a method of manufacturing a perovskite solar cell comprising the step of forming a second electrode on the hole transport layer.

<Formula 1>

(RMX ₃ ) _{1-y- z} (R'MX ' ₃ ) _z (AMX'' ₃ ) _y

In Formula 1,

R and R 'are each independently a substituted or unsubstituted alkyl group, and when R and R' are substituted, the substituents are amino, hydroxyl, cyano, halogen, nitro or methoxy groups,

M is Pb, Sn, or Ge,

A is an alkali metal or alkaline earth metal,

X, X 'and X' 'are each independently F, Cl, Br, or I,

y is more than 0 and 0.2 or less, and z is 0 or more and 0.2 or less.

2 is a flow chart of a method of manufacturing a perovskite solar cell according to an embodiment of the present application.

First, to form a recombination prevention layer on the first electrode (S100).

The recombination preventing layer may include, but is not limited to, a material selected from the group consisting of organic semiconductors, inorganic semiconductors, and combinations thereof.

The recombination prevention layer may include, for example, a metal oxide selected from the group consisting of TiO ₂ , SnO ₂ , ZnO, WO ₃ , NB ₂ O ₅ , TiSrO _3, and combinations thereof, but is not limited thereto. It is not.

Subsequently, a perovskite layer including alkali iodine and perovskite represented by Chemical Formula 1 is formed on the recombination prevention layer (S200).

According to an embodiment of the present disclosure, the perovskite layer may be formed by (MX ₂ ) _1-yz , (MX ′ ₂ ) _z , (MX ″ ₂ ) _y , wherein M is Pb, Sn, or Ge, X, X 'and X''are each independently F, Cl, Br or I, y is greater than 0 and less than or equal to 0.2 and z is greater than or equal to 0 and less than or equal to 0.2), (AX'') _y (where , A is an alkali metal or alkaline earth metal, X '' is F, Cl, Br, or I), precursors for preparing perovskite (RX) _1-yz and (R'X) _1-yz where R And R 'are each independently a substituted or unsubstituted alkyl group, and when R and R' are substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group or a methoxy group, and X is F, One selected from the group consisting of Cl, Br, I and combinations thereof, y is greater than 0 and less than or equal to 0.2 and z is greater than or equal to 0 and less than or equal to 0.2), and by coating the alkali iodine on the anti-recombination layer But that would be a line, but is not limited thereto.

According to one embodiment of the present application, the alkali iodine may be included in a concentration of 0.1 mmol to 10 mmol, but is not limited thereto.

According to one embodiment of the present application, the alkali iodine may include Na, K, Rb, Cs, Fr, or Li metal, but is not limited thereto.

According to one embodiment of the present application, the precursor for preparing perovskite may include (HC (NH ₂ ) ₂ ) X, wherein X is F, Cl, Br, or I, but is not limited thereto. It doesn't happen.

According to one embodiment of the present application, the precursor for preparing perovskite may be to include (HC (NH ₂ ) ₂ ) I, but is not limited thereto.

The perovskite layer may include ((HC (NH ₂ ) ₂ ) PbI ₃ ) _{1- y} (CsPbBr ₃ ) _y (where y is greater than 0 and less than 0.2), but is not limited thereto. no.

According to the exemplary embodiment of the present application, the (MX ₂ ) _1-yz , (MX ′ ₂ ) _z , (MX ″ ₂ ) _y , (AX ″) _y , (RX) _1-yz on the recombination prevention layer And (R'X) _1-yz , and alkali iodine coating method is spin coating method, cast method, Liangmuir-Blodgett (LB) method, inkjet printing method, nozzle printing method, slot die coating method Dr. blade coating method, screen printing method, dip coating method, gravure printing method, reverse off-sensing printing method, physical transfer method, spray coating method, chemical vapor deposition method, thermal deposition method, vacuum deposition method and combinations thereof It may be performed by a coating selected from, but is not limited thereto.

The perovskite layer may be formed on the recombination preventing layer, and may further include heat treatment at 50 ° C. to 200 ° C., but is not limited thereto.

Subsequently, a hole transport layer is formed on the perovskite layer (S300).

The hole transport layer may include, but is not limited to, a material selected from the group consisting of a single molecule hole transport material, a polymer hole transport material, and combinations thereof.

The hole transport layer 140 is, for example, spiro-MeOTAD (2,2 ', 7, 7'-tetrakis (N, Np-dimethoxy-phenylamino) -9,9'-spirobifluorene), P3HT ( poly (3-hexylthiophene)), PTAA (polytriarylamine), PEDOT: PSS (poly (3,4-ethylenedioxythiophene) polystyrene sulfonate) and combinations thereof, but may include a material selected from the group It is not.

Subsequently, a second electrode is formed on the hole transport layer (S400).

For example, the second electrode may improve the long-term stability of the perovskite solar cell of the present application by using gold (Au), which is a highly stable metal, but is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present application.

Example 1

HC (NH ₂ ) ₂ I (FAI) was reacted by reaction of 30 mL hydrogen iodide (57 wt% in water, Sigma-Aldrich, HI) with 15 g of formaminium acetate (99%, Aldrich) at 0 ° C. Synthesized. After stirring for 2 hours, the dark yellow precipitate was recovered by evaporating the solvent at 60 ° C. using a rotary evaporator. The precipitate was washed with diethyl ether (SAMCHUN, 99.0%) for about 2 hours to remove the unreacted HI and formamidenium acetate. When the precipitate turns yellow, it is obtained by recrystallization with ethanol. The resulting white precipitate was dried under vacuum at 60 ^° C. for 24 hours and stored in a glove box filled with Ar.

Fluorine-doped tin oxide (FTO) glass substrates (Pilkington, TEC-8, 8Ω / sq) were washed with detergent and subjected to UV-ozone treatment by sonication in ethanol bath for 15 minutes.

About 60 nm thick dense TiO 2 layer was deposited on the FTO substrate by spin-coating a 0.15 M 1-butanol (Aldrich, 99.8%), titanium diisopropoxide bis (acetylacetonate) solution once. Between each coating, the substrate was dried on a hot plate at 125 ° C. for 5 minutes and finally annealed at 50 ° C. for 30 minutes after spin-coating the TiO ₂ nanoparticles.

The dense TiO ₂ -coated FTO glass was treated with UV-ozone for 10 minutes before spin-coating the perovskite solution.

The perovskite solution is prepared by mixing PbI ₂ , FAI, CsBr, PbBr ₂ in N, N-dimethylformamide (DMF) (Sigma-Aldrich, 99.8%) and dimethyl sulfoxide (DMSO) in an equivalent weight. It was. The solution was filtered by a syringe filter (Whatman) with a 0.45 μm pore size.

25 μL of the perovskite solution was spin-coated at 4,000 rpm for 30 seconds and dropped after 10 seconds on a substrate on which 400 μL of diethyl ether (SAMCHUN, 99.0%) was spun.

2 mmol, 4 mmol, 6 mmol, 8 mmol, and 10 mmol of KI were added onto the substrate coated with the perovskite solution, respectively.

The substrate was heat treated at 50 ° C. for 3 minutes and at 15 ° C. for 5 minutes.

spiro-MeOTAD was deposited by dropping 20 μL of the spiro-MeOTAD solution onto a substrate rotating at 3,000 rpm.

For the counter electrode, Au was thermally evaporated at a deposition rate of 0.3 kW / s for about 110 minutes to produce perovskite solar cells.

Example 2

CsI 0.05 mol, MABr 0.1 mmol, FAI 0.85 mmol, PbBr 2 0.1 mmol, and PbI ₂ was added to DMSO 1 mmol on a 0.9 mmol, was stirred for one hour in a 0.5 mL DMF solution was prepared in the perovskite solution .

The perovskite solar cell was manufactured by the method of Example 1 using the perovskite solution, and this was called triple.

Example 3

A perovskite solution was prepared by stirring FAI, PbI ₂ 0.85 mmol, MABr, PbBr ₂ 0.15 mmol and DMSO 1 mmol in 0.5 mL DMF solution for 1 hour.

The perovskite solar cell was manufactured by the method of Example 1 using the perovskite solution, and this was called (FAPbI ₃ ) _0.85 (MAPbBr ₃ ) _0.15 .

Experimental Example

The properties of the perovskite solar cell manufactured in the above embodiment was confirmed, and the results are shown as FIGS. 3 to 6.

Specifically, the current density-voltage curve is one solar light simulated by a solar simulator (Oriel Sol 3A classAAA) equipped with a 450 W Xenon lamp (Newport 6280NS) (AM 1.5G, 100 mW / cm ² ) The measurements were taken using a Keithley 2400 source meter. Light intensity was adjusted by NREL-corrected Si solar cells equipped with KG-2 filters. During the measurement, the device was covered with a metal aperture mask with an active area of 0.125 cm ² .

3 is a current density (mA / mA) according to the voltage (V) of the perovskite solar cell in which 0 mmol, 2 mmol, 4 mmol, 6 mmol, 8 mmol, and 10 mmol of KI is added to the perovskite layer, respectively. cm ² ).

According to the results shown in FIG. 3, the IV data of the perovskite solar cell without adding KI showed hysteresis (hysteresis), and the difference between the values in the reverse and forward directions was large, whereas the perovskite with KI was added. The IV data of the SKY solar cell showed a significant decrease in hysteresis, so that the values in the reverse and forward directions were almost identical.

4 is a photoelectric conversion efficiency (PCE) according to the concentration of KI in a perovskite solar cell in which 0 mmol, 2 mmol, 4 mmol, 6 mmol, 8 mmol, and 10 mmol of KI are added to the perovskite layer, respectively. , Graph of filling factor (FF), voltage (V) and short-circuit current density (J _sc ).

According to the results shown in FIG. 4, the photoelectric conversion efficiency (PCE), the filling factor (FF), the voltage (V), and the short-circuit current density (J _sc ) are decreased in the reverse and forward directions as the concentration of KI increases. The value tends to increase. This means that by adding KI, the hysteresis of the perovskite solar cell can be reduced and the efficiency of the perovskite solar cell can be improved.

5 is a graph showing trap density, dielectric constant, and V _TFL according to the concentration of KI in a perovskite solar cell.

6 is a graph showing the energy (tail energy, Eu) according to the concentration of KI of the perovskite solar cell.

5 and 6 are graphs showing that the defects in perovskite decrease with the concentration of KI. When the KI is doped to a concentration of [KI] / [PbI ₂ ] = 0.001 to 0.01, the KI enters into the perovskite lattice during the formation of the perovskite layer. This allows passivation of interstitial sites or schottky defects within the perovskite bulk to reduce defects.

The characteristics of (CsPbI ₃ ) _0.05 (FAPbI ₃ ) _0.85 (MAPbBr ₃ ) _0.10 Triple and (FAPbI ₃ ) _0.85 (MAPbBr ₃ ) _0.15 prepared in Examples 2 and 3 were confirmed, and the results are shown in FIG. 7. .

FIG. 7 shows the current density according to the voltage of KI added to perovskite layer with and without KI added to triple and perovskite layer with and without (FAPbI ₃ ) _0.85 (MAPbBr ₃ ) _0.15 The graph shown.

According to the results shown in FIG. 7, triple and (FAPbI ₃ ) _0.85 (MAPbBr ₃ ) solar cells of _0.15 were also confirmed that the hysteresis of the perovskite solar cell was reduced by adding KI.

The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application.

110: first electrode
120: recombination prevention layer
130: perovskite layer
140: hole transport layer
150: second electrode

Claims (15)

A first electrode;
A recombination prevention layer formed on the first electrode;
A perovskite layer comprising KI and a perovskite represented by Formula 1 on the recombination prevention layer;
A hole transport layer formed on the perovskite layer; And;
It comprises a second electrode formed on the hole transport layer;
As perovskite solar cell,
The hysteresis of the perovskite solar cell is removed by the KI,
The KI is to enter the lattice of the perovskite,
Perovskite Solar Cells:
<Formula 1>
(RMX ₃ ) _1-yz (R'MX ' ₃ ) _z (AMX'' ₃ ) _y
In Formula 1,
R and R 'are each independently a substituted or unsubstituted alkyl group, and when R and R' are substituted, the substituents are amino, hydroxyl, cyano, halogen, nitro or methoxy groups,
M is Pb, Sn, or Ge,
A is an alkali metal or alkaline earth metal,
X, X 'and X''are each independently F, Cl, Br, or I,
y is more than 0 and 0.2 or less, and z is 0 or more and 0.2 or less.
The method of claim 1,
The KI is included in a concentration of 0.1 mmol to 10 mmol, perovskite solar cell.
delete The method of claim 1,
The perovskite layer is ((HC (NH ₂ ) ₂ ) MX ₃ ) _{1- y} (AMX '' ₃ ) _y (where M is Pb, Sn, or Ge, A is an alkali metal or an alkaline earth metal, X and X '' are each independently F, Cl, Br, or I, y is greater than 0 to 0.2 or less), perovskite solar cell.
The method of claim 1,
The perovskite layer is a perovskite solar cell comprising ((HC (NH ₂ ) ₂ ) PbI ₃ ) _{1- y} (CsPbBr ₃ ) _y (where y is greater than 0 and less than 0.2) .
The method of claim 1,
The first electrode and the second electrode each independently include a material selected from the group consisting of metal, conductive polymer, carbon material, tin oxide, zinc oxide and combinations thereof, perovskite solar cell .
The method of claim 1,
The recombination preventing layer is a perovskite solar cell comprising a material selected from the group consisting of organic semiconductors, inorganic semiconductors, and combinations thereof.
The method of claim 1,
The hole transport layer is a perovskite solar cell comprising a material selected from the group consisting of a single molecule hole transport material, a polymer hole transport material and combinations thereof.
Forming a recombination preventing layer on the first electrode;
Forming a perovskite layer including KI and a perovskite represented by Formula 1 on the recombination prevention layer;
Forming a hole transport layer on the perovskite layer; And
Forming a second electrode on the hole transport layer,
As a manufacturing method of a perovskite solar cell,
The hysteresis of the perovskite solar cell is removed by the KI,
The KI is to enter the lattice of the perovskite,
Method of making perovskite solar cells:
<Formula 1>
(RMX ₃ ) _1-yz (R'MX ' ₃ ) _z (AMX'' ₃ ) _y
In Formula 1,
R and R 'are each independently a substituted or unsubstituted alkyl group, and when R and R' are substituted, the substituents are amino, hydroxyl, cyano, halogen, nitro or methoxy groups,
M is Pb, Sn, or Ge,
A is an alkali metal or alkaline earth metal,
X, X 'and X''are each independently F, Cl, Br, or I,
y is more than 0 and 0.2 or less, and z is 0 or more and 0.2 or less.
The method of claim 9,
The perovskite layer may be formed by (MX ₂ ) _1-yz , (MX ′ ₂ ) _z , (MX ″ ₂ ) _y (wherein M is Pb, Sn, or Ge, and X, X ′ and X '' are each independently F, Cl, Br, or I, y is greater than 0 and less than or equal to 0.2, z is greater than or equal to 0.2 and less than or equal to 0, and (AX '') _y (where A is an alkali metal or alkali) Earth metal, X '' is F, Cl, Br, or I), precursors for preparing perovskite (RX) _1-yz and (R'X) _1-yz where R and R 'are each independently A substituted or unsubstituted alkyl group, where R and R 'are substituted, the substituent is an amino group, hydroxyl group, cyano group, halogen group, nitro group or methoxy group, X is F, Cl, Br, or I , y is greater than 0 and less than or equal to 0.2 and z is greater than or equal to 0.2 and less than or equal to 0.2), and the KI is coated on the anti-recombination layer.
The method of claim 9,
Wherein KI is included in a concentration of 0.1 mmol to 10 mmol, a perovskite solar cell manufacturing method.
delete The method of claim 10,
The precursor for preparing perovskite is (HC (NH ₂ ) ₂ ) X (where X is F, Cl, Br or I), the method for producing a perovskite solar cell.
The method of claim 10,
Wherein the precursor for producing perovskite is (HC (NH ₂ ) ₂ ) I containing a method of manufacturing a perovskite solar cell.
The method of claim 10,
The (MX ₂ ) _1-yz , (MX ' ₂ ) _z , (MX'' ₂ ) _y , (AX'') _y , (RX) _1-yz and (R'X) _1- on the recombination prevention layer. _yz and the KI coating method include spin coating method, cast method, Liangmuir-Blodgett (LB) method, inkjet printing method, nozzle printing method, slot die coating method, doctor blade coating method, and screen printing method. Performed by a coating selected from the group consisting of a method, a dip coating method, a gravure printing method, a reverse off-sensing method, a physical transfer method, a spray coating method, a chemical vapor deposition method, a thermal vapor deposition method, a vacuum deposition method and combinations thereof Method for producing phosphorous and perovskite solar cells.

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