KR20170000422A - Method for preparing Perovskite Solar Cell using 1,8-diiodooctane - Google Patents

Method for preparing Perovskite Solar Cell using 1,8-diiodooctane Download PDF

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KR20170000422A
KR20170000422A KR1020150088940A KR20150088940A KR20170000422A KR 20170000422 A KR20170000422 A KR 20170000422A KR 1020150088940 A KR1020150088940 A KR 1020150088940A KR 20150088940 A KR20150088940 A KR 20150088940A KR 20170000422 A KR20170000422 A KR 20170000422A
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electron transport
transport layer
forming
solar cell
layer
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KR1020150088940A
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Korean (ko)
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이은철
이건봉
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가천대학교 산학협력단
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    • H01L51/4213—
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • H01L51/0026—
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L2031/0344—Organic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The present invention relates to a method for producing a high performance perovskite solar cell by improving the morphology of an electron transport layer using 1,8-diiodooctane.
The present invention improves the photovoltaic efficiency of solar cells by doping 1,8-diiodooctane into the electron transport layer to improve the interfacial morphology between the perovskite layers as well as the morphology of the electron transport layer.
The present invention can improve the short circuit current value, the open circuit voltage and the fill factor value as well as the photoelectric efficiency by suppressing the recombination of electrons and holes due to the improved morphology of the electron transport layer.
The present invention can manufacture a solar cell by a solution process, and its photoelectric efficiency is much higher than that of an organic solar cell, thereby simplifying the process and realizing high performance of the cell.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a perovskite solar cell using 1,8-diiodooctane,

The present invention relates to a process for producing a perovskite solar cell doped with 1,8-diiodooctane, and more particularly, to a process for producing a perovskite solar cell by improving the morphology of an electron transport layer by using 1,8-diiodooctane, To a method of manufacturing a robust solar cell.

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. Currently, np diode-type silicon (Si) single crystal based solar cells with a light energy conversion efficiency of more than 20% can be manufactured and used for actual solar power generation. Compound semiconductors such as gallium arsenide (GaAs) There is also solar cell using. However, since inorganic semiconductor-based solar cells require highly refined materials for high efficiency, a large amount of energy is consumed in the purification of raw materials, and expensive processes are required in the process of making single crystals or thin films using raw materials And the manufacturing cost of the solar cell can not be lowered, which has been a hindrance to a large-scale utilization.

In the case of organic solar cells using conductive polymers, the maximum is 8% (Advanced Materials, 23 (2011) 4636).

Recently, perovskite solar cells (PSCs) have attracted great attention due to their high performance, low cost and simplification of processes. In particular, the PSCs technology based on methylammonium lead halides (CH3NH3PbX3, X = Cl, Br, orI) has progressed rapidly and photoelectric conversion rates have improved dramatically from 4% to 19.3% over the years.

In order to replace inorganic silicon solar cells using perovskite having low manufacturing cost and high process efficiency, it is necessary to further increase the photoelectric efficiency of the perovskite solar cell. In order to accomplish this, the perovskite material as well as the electron transport layer It is also necessary to make improvements.

The present invention provides a method for improving the photovoltaic efficiency of a solar cell by improving the interfacial morphology between the perovskite layers as well as the morphology of the electron transport layer.

According to an embodiment of the present invention,

Forming an anode electrode on the substrate; Forming an electron transfer layer on the anode electrode; Forming a light absorbing layer including a compound of a Pervoskite structure on the hole transporting layer; Forming an electron transport layer on the light absorption layer; And forming a cathode electrode on the electron transport layer, wherein the electron transport layer formation step includes forming a solution by coating a solution containing a solvent, an electron transport organic compound, and a crystalline culture agent, followed by heat treatment Perovskite solar cell manufacturing method.

The present invention improves the photovoltaic efficiency of solar cells by doping 1,8-diiodooctane into the electron transport layer to improve the interfacial morphology between the perovskite layers as well as the morphology of the electron transport layer.

The present invention can improve the short circuit current value, the open circuit voltage and the fill factor value as well as the photoelectric efficiency by suppressing the recombination of electrons and holes due to the improved morphology of the electron transport layer.

The present invention can manufacture a solar cell by a solution process, and its photoelectric efficiency is much higher than that of an organic solar cell, thereby simplifying the process and realizing high performance of the cell.

1 shows a solar cell of the present invention.
Fig. 2 (a) shows the structure of the perovskite solar cell device manufactured in Example 1, b is a SEM image of the cross section of the device, c is an SEM image of the perovskite layer after heat treatment, d UV-vis spectrum of the perovskite layer.
FIG. 3 shows the current-voltage characteristics of the solar cell devices manufactured in Examples 1 to 3 and Comparative Example 1. FIG.
Fig. 4 shows IPCE (a) and absorption rate (b) of Example 2 and Comparative Example 1. Fig.
5 shows an AFM image of the PCBM layer of Example 2 (b) and Comparative Example 1 (a).

1 shows a solar cell of the present invention. 1, the solar cell of the present invention includes a substrate 10, an anode electrode 20, a hole transport layer 30, a light absorption layer 40, an electron transport layer 50, and a cathode electrode 60 .

A method for manufacturing a perovskite solar cell according to the present invention comprises sequentially forming an anode electrode 20, an electron transfer layer 30, a light absorption layer 40, an electron transfer layer 50, and a cathode electrode 60 on a substrate 10 . ≪ / RTI >

The present invention includes forming an anode electrode (20) on a substrate (10). As the substrate 10, any transparent material such as glass, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyamide, and polyethersulfone can be used without limitation.

The anode electrode 20 may be made of ITO (indium tin oxide), SnO 2, IZO (In 2 O 3 -ZnO), AZO (aluminum doped ZnO), or GZO (gallium doped ZnO) (INdium Tin Oxide). When ITO is processed into a spattering target and the glass plate is sputtered, a transparent conductive film can be obtained. Alternatively, a transparent electrode film can be obtained by dissolving ITO in a glass plate and spraying the glass plate or immersing the glass plate in a solution.

The present invention includes a step of forming a hole transport layer (30) on the anode electrode (20). The hole transporting layer is formed by applying a hole transporting material. The hole transporting layer is formed of poly (3,4-ethylenedioxythiophene) -polystyrenesulfonate, PEDOT-PSS, polyaniline ), Polypyrrole, copper phthalocyanine (CuPC), polythiophenylenevinylene, polyvinylcarbazole, polyphenylenevinylene, and poly (methylphenyl) silane methylphenylsilane), or a mixture thereof, but is not limited thereto. The hole transport layer may be formed by spin-coating a hole transport material.

The step of forming the light absorbing layer is a step of coating a solution of a Pervoskite precursor on the hole transporting layer. More specifically, a perovskite precursor solution is spin coated on the hole transport layer and heat treated.

The present invention can use any known perovskite precursor solution that can be used as a solar cell without limitation. For example, the perovskite precursor solution may be one in which methylammonium iodide (MAI) and lead chloride (PbCl2) are dissolved in anhydrous dimethylformamide.

The perovskite precursor solution may be a solution of a precursor capable of producing an organic-metal halide compound having a perovskite structure without limitation.

For example, the organic-metal halide compound of the perovskite structure can be represented by the following formula (1).

[Chemical Formula 1]

(R1-NH3) MX

Wherein R1 is an aryl-cycloalkyl or C6-C20 alkyl, C3-C20 of C1-C24, 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 Yb 2 + , and X is one or more selected from I - , Br - and Cl - It is a halogen ion.

The present invention includes a step of forming an electron transport layer on the light absorption layer. The electron transport layer may be formed by coating a solution containing a solvent, an electron transport organic compound, and a crystalline culture agent followed by heat treatment.

The electron transfer organics include (6,6) -phenyl-C61-butyric acid methyl ester [(6,6) -phenyl-C61-butyric acid methyl ester, PCBM], (6,6) (6,6) -phenyl-C71-butyric acid methyl ester, C70-PCBM], fullerene (C60) and (6,6) -thienyl-C61-butyric acid methyl ester [ (6,6) -thienyl-C61-butyric acid methyl ester; ThCBM].

The crystalline culture agent of the present invention can enhance the electron mobility by optimizing the morphology and degree of crystallization of the electron transport layer by controlling the boiling point, solubility or viscosity of the solvent.

A material having a boiling point of 100 占 폚, preferably 150 占 폚 higher than the boiling point of the solvent may be used as the crystalline culture medium. During the heat treatment of the electron transport layer, the crystalline culture agent inhibits rapid evaporation of the solvent, thereby reducing the surface roughness of the electron transport layer.

The crystalline culture agent may be any one selected from 1-chloronaphthalene, diiodooctane, nitrobenzene and 1,8-octanedithiol.

The solvent may be chloroform, chlorobenzene, methyl chloride, toluene, methyl isobutyl ketone, acetone, tetrahydrofuran, isopropyl ether, or the like.

The crystalline culture agent may contain 1 to 3% by volume, preferably 2% or more, in the solution. The photoelectric conversion efficiency is the most excellent when it is in the above range.

The electron transfer organics may comprise 0.5 to 5% by volume of the solution.

The present invention includes a step of forming a cathode electrode (60) on an electron transporting layer (50).

The cathode electrode 50 can be used without limitation as long as the work function is lower than that of the anode electrode 20. Metal, metal alloy, semimetal or transparent transparent oxide. Examples of the metal include an alkaline earth metal such as magnesium (Mg); Aluminum (Al); Transition metals such as silver (Ag), gold (Au), and platinum (Pt); Rare earth elements; And semi-metals such as selenium (Se). Examples of the metal alloy include a sodium-potassium alloy, a magnesium-indium alloy, and an aluminum-lithium alloy.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example  1 to 3, Comparative Example  One

PEDOT: PSS (Clevios P VP AI 4083) solution was spin-coated on ITO (Indium Tin Oxide) coated on a glass substrate at 2500 rpm for 40 seconds to form a thickness of about 40 nm. A perovskite precursor solution was prepared by dissolving methylammonium iodide (MAI) and lead chloride (PbCl2) in dimethylformamide (40 wt%) at a molar ratio of 3: 1. The perovskite precursor solution was spin-coated on the PEDOT: PSS layer to a thickness of 260 nm and heat-treated at about 100 degrees.

Subsequently, chlorobenzene solutions each containing PCBM and DIO (containing 0% - Comparative Example 1, containing 1% - Example 1, containing 2% - Example 2, containing 3% - Comparative Example 2) Layer was spin-coated at 100 nm and then heat-treated at 40 ° C for 30 minutes. A perovskite solar cell was fabricated by thermal evaporation of 0.6 nm LiF and 100 nm Al films on the PCBM layer in vacuum (<8.0 × 106 Torr).

Fig. 2 (a) shows the structure of the perovskite solar cell device manufactured in Example 1, b is a SEM image of the cross section of the device, c is an SEM image of the perovskite layer after heat treatment, d UV-vis spectrum of the perovskite layer. Observing the SEM image of FIG. 2 shows that the PEDOT: PSS layer is sufficiently covered with the pbrozacite film after the heat treatment, and that the perovskite film has a similar domain size (100300 nm). Also, according to Fig. 2 (d), ultraviolet-visible absorption spectrum of perovskite is shown to be effective for condensing.

FIG. 3 and Table 1 show the current-voltage characteristics of the solar cell devices manufactured in Examples 1 to 3 and Comparative Example 1. FIG.

Device configuration V oc [V] J sc [mA cm 2 ]       Fill factor       PCE [%] Comparative Example 1 0.951 0.005 17.13 ± 0.29 0.679 ± 0.005 11.09 + - 0.24 Example 1 0.959 ± 0.007  18.09 ± 0.26 0.683 ± 0.009 11.81 + - 0.25 Example 2 0.979 ± 0.005  18.79 ± 0.31 0.688 ± 0.006 12.73 ± 0.20 Comparative Example 2 0.968 ± 0.007  17.67 + - 0.12 0.643 + 0.014 10.93 ± 0.25

Referring to Table 1 and FIG. 3, the photoelectric conversion efficiency (PCE) of Examples 1 and 2 was higher than that of Comparative Examples 1 and 2. In particular, in Example 2, the photoelectric conversion efficiency (PCE) increased from 11.09 to 12.73 by about 14%. Referring to Table 1, there was no significant difference between the open-circuit voltage (Voc) and the fill factor (FF) of the comparative example and the embodiment, but the short-circuit current value Jsc was 17.13 (Comparative Example 1) 2). The rise of the short-circuit current value seems to induce an increase in photoelectric conversion efficiency.

In addition, when DIO is excessively added as in Comparative Example 2, separation of the PCBM layer and non-uniformity of the layer become higher, so that the photoelectric conversion efficiency is lowered.

Fig. 4 shows IPCE (a) and absorption rate (b) of Example 2 and Comparative Example 1. Fig. Fig. 4 (a) shows that the IPCE of Example 1 is improved in a wide wavelength range from 420 to 750 nm. Fig. 4 (b) shows that the total absorption of ultraviolet-visible light in Example 2 and Comparative Example 1 is approximately the same, indicating that the performance improvement of the IPCE is almost independent of the light absorption.

5 shows an AFM image of the PCBM layer of Example 2 (b) and Comparative Example 1 (a). Referring to FIG. 5, since the height distribution width of Comparative Example 1 is large, it can be seen that Comparative Example 1 has a rougher surface than Example 2. The surface roughness value of Example 2 was 3.29, which was much smaller than that of Comparative Example 1 of 1.72. This reduction in surface roughness can be explained by the addition of DIO having a boiling point much higher than the boiling point of the solvent. That is, the addition of DIO suppressed the evaporation of the solvent during the heat treatment, thereby reducing the surface roughness of the PCBM layer.

Hereinafter, specific embodiments of the present invention have been described. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (5)

Forming an anode electrode on the substrate;
Forming an electron transfer layer on the anode electrode;
Forming a light absorbing layer by coating a precursor solution of Pervoskite on the precursor transfer layer and then performing heat treatment;
Forming an electron transport layer on the light absorption layer;
And forming a cathode electrode on the electron transport layer, wherein the organic electron transport layer formation step is a step of forming a solution by coating a solution containing a solvent, an electron transport organic compound, and a crystalline culture agent, followed by heat treatment Wherein the method comprises the steps of: The perovskite solar cell according to claim 1, wherein the crystalline culture agent is any one selected from 1-chloronaphthalene, diiodooctane, nitrobenzene and 1,8-octanedithiol. Gt; 2. The method of claim 1, wherein the crystalline culture medium comprises 1-3 vol% of the solution. The organic electroluminescent device according to claim 1, wherein the hole transport layer comprises at least one selected from the group consisting of poly (3,4-ethylenedioxythiophene) -polystyrenesulfonate, PEDOT-PSS, polyaniline, polypyrrole polypyrrole, polypyrrole, copper phthalocyanine (CuPC), polythiophenylenevinylene, polyvinylcarbazole, polyphenylenevinylene and poly (methylphenylsilane). Or a mixture thereof. &Lt; Desc / Clms Page number 19 &gt; The method of claim 1, wherein the electron transporting organic compound is selected from the group consisting of (6,6) -phenyl-C61-butyric acid methyl ester [(6,6) -phenyl-C61-butyric acid methyl ester, PCBM] C71-butyric acid methyl ester, C70-PCBM], fullerene (C60), and (6,6) -thienyl-C61- Butyric acid methyl ester [(6,6) -thienyl-C61-butyric acid methyl ester; ThCBM]. &Lt; / RTI &gt;



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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107863443A (en) * 2017-10-17 2018-03-30 华中科技大学 A kind of flexible transconfiguration perovskite solar cell and preparation method thereof
KR20200138457A (en) 2019-05-29 2020-12-10 주식회사 이노카 Apparatus having functions of e-call service and electronic toll collection
CN113571643A (en) * 2021-06-15 2021-10-29 华东师范大学 Novel organic hole transport layer perovskite solar cell and preparation method thereof
KR20220095295A (en) 2020-12-29 2022-07-07 주식회사 이노카 On-board unit for vehicles having functions of e-call service and electronic toll collection

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107863443A (en) * 2017-10-17 2018-03-30 华中科技大学 A kind of flexible transconfiguration perovskite solar cell and preparation method thereof
KR20200138457A (en) 2019-05-29 2020-12-10 주식회사 이노카 Apparatus having functions of e-call service and electronic toll collection
KR20220095295A (en) 2020-12-29 2022-07-07 주식회사 이노카 On-board unit for vehicles having functions of e-call service and electronic toll collection
CN113571643A (en) * 2021-06-15 2021-10-29 华东师范大学 Novel organic hole transport layer perovskite solar cell and preparation method thereof
CN113571643B (en) * 2021-06-15 2024-04-16 华东师范大学 Novel perovskite solar cell with organic hole transport layer and preparation method thereof

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