WO2017099441A1 - Cellule solaire organique et son procédé de fabrication - Google Patents

Cellule solaire organique et son procédé de fabrication Download PDF

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Publication number
WO2017099441A1
WO2017099441A1 PCT/KR2016/014183 KR2016014183W WO2017099441A1 WO 2017099441 A1 WO2017099441 A1 WO 2017099441A1 KR 2016014183 W KR2016014183 W KR 2016014183W WO 2017099441 A1 WO2017099441 A1 WO 2017099441A1
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WIPO (PCT)
Prior art keywords
solar cell
electrode
organic solar
organic
regions
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PCT/KR2016/014183
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English (en)
Korean (ko)
Inventor
장송림
김연신
이재철
최두환
이지영
김진석
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from KR1020160163556A external-priority patent/KR102066322B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP16873306.1A priority Critical patent/EP3389102B1/fr
Priority to CN201680039503.7A priority patent/CN107851719B/zh
Priority to US15/736,216 priority patent/US11081603B2/en
Priority to JP2017563515A priority patent/JP6544544B2/ja
Publication of WO2017099441A1 publication Critical patent/WO2017099441A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • 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

Definitions

  • the present application relates to an organic solar cell and a method of manufacturing the same.
  • Organic solar cells are devices that can directly convert solar energy into electrical energy by applying the photovoltaic effect.
  • Solar cells can be divided into inorganic solar cells and organic solar cells according to the material constituting the thin film.
  • Typical solar cells are made of p-n junctions by doping crystalline silicon (Si), an inorganic semiconductor. Electrons and holes generated by absorbing light diffuse to the p-n junction and are accelerated by the electric field to move to the electrode.
  • the power conversion efficiency of this process is defined as the ratio of the power given to the external circuit and the solar power entered into the solar cell, and is currently achieved by 24% when measured under standardized virtual solar irradiation conditions.
  • organic semiconductor solar cell which is easy to process, cheap and has various functions, has been spotlighted as a long-term alternative energy source.
  • the present application is to design an organic solar cell to display a colorful color, it is intended to be able to utilize the organic solar cell in a variety of applications.
  • An exemplary embodiment of the present application is the first electrode; A second electrode provided to face the first electrode; And at least one organic material layer including a photoactive layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes at least two regions having different thicknesses.
  • the two or more regions having different thicknesses are made of the same material as each other.
  • the two or more regions having different thicknesses are different from each other at least one of the materials constituting.
  • two or more regions having different thicknesses have different absorbances for at least some of visible light.
  • Another embodiment of the present application is a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer comprising a photoactive layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers has a thickness different by a coating method. It provides a method for producing an organic solar cell, characterized in that formed to include the above region.
  • the coating method is a spray coating.
  • the organic material layer required for driving the organic solar cell by changing the thickness of the organic material layer it is possible to express two or more colors in the same layer, thereby to express a character or pattern By expressing the visual appearance of the organic solar cell can be improved. Thereby, not only the energy storage effect by the organic solar cell itself but also the disclosure of necessary information or the provision of visual beauty can be provided together. In addition, as compared with the opaque organic solar cell, it is possible to arrange the organic solar cell in a more various space or location.
  • FIG. 1 is a photograph of the appearance of an organic solar cell manufactured in Example 1.
  • FIG. 2 is a graph showing absorbance for each region of the organic solar cell manufactured in Example 1.
  • FIG. 3 is a photograph of the appearance of the organic solar cell manufactured in Example 2.
  • FIG. 4 is a graph showing absorbance for each region of the organic solar cell manufactured in Example 3.
  • 5 and 6 are examples of colors that can be represented by organic solar cells according to exemplary embodiments of the present application.
  • FIG. 7 illustrates a laminated structure of the organic solar cell module manufactured in the embodiment.
  • FIG. 8 illustrates a laminated structure of an organic solar cell module according to an exemplary embodiment of the present application.
  • An organic solar cell includes a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer including a photoactive layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes at least two regions having different thicknesses.
  • an organic solar cell capable of expressing two or more colors may be provided by forming at least one organic material layer to include two or more regions having different thicknesses.
  • the two or more areas to display a letter or a pattern, as shown in FIGS. 5 and 6, while serving as the organic solar cell itself, it is also possible to display information or provide visual beauty through the letter or pattern.
  • the difference in thickness may be determined according to the visible light absorbance to be distinguished by the difference, that is, the color.
  • the thickness of the organic material layer including two or more regions different in thickness may be 30 nm to 600 nm.
  • the thickness of the first region and the second region may be 30 nm to 600 nm, respectively.
  • the thickness difference between two or more regions having different thicknesses may be 10 nm to 570 nm.
  • the difference in thickness may be measured by measuring the thickness by using an ⁇ -step apparatus or an SEM photograph.
  • one or more layers of the organic material layer includes two or more regions having different thicknesses.
  • one or more layers of the organic material layer may include three or more regions having different thicknesses.
  • one or more layers of the organic material layer may include four or more regions having different thicknesses.
  • two or more regions having different thicknesses may have the same material. Even when the two or more regions are made of the same material, different colors may be displayed by different thicknesses.
  • At least one of the materials constituting the two or more regions having different thicknesses may be different from each other.
  • the thickness required for displaying a desired color may vary according to the type of material, at least one of the constituent materials may be different from each other, and the thicknesses of the layers may be different from each other.
  • the spray coating described later may be repeated once or twice or more.
  • the thick layer can be formed by repeating the spray coating one or more times.
  • the organic solar cell may display two or more colors by including two or more regions having different absorbances.
  • the color that can be expressed by the organic solar cell may be determined by the material of the organic material layer, the thickness of the organic material layer, the transparency of the electrode, and the like.
  • the organic material layer including two or more regions having different thicknesses is a photoactive layer.
  • the photoactive layer may include an electron donor material and an electron acceptor material.
  • the electron donor material may be selected according to the color to be displayed in the organic solar cell among the electron donor.
  • the electron donor material does not absorb at least a part of the visible light region by adjusting the thickness, and may be selected from materials having a specific color.
  • the electron donor material may be at least one of the following Chemical Formulas 1-1 to 1-6.
  • X1 to X8 are the same as or different from each other, and each independently SiRR 'or NR,
  • R, R 'and R1 to R11 are the same as or different from each other, and each independently an alkyl group
  • a, b, c, d, e, f, g and h are the same as or different from each other, each independently a real number of 0 to 1,
  • n is an integer from 1 to 10,000.
  • the material of Table 1 may be used as the electron acceptor material, but is not limited thereto.
  • Table 1 above describes colors that can be expressed from the materials, but this can be adjusted according to the thickness of the layer of the materials.
  • fullerene, fullerene derivatives, vasocuproin, semiconducting elements, semiconducting compounds, and combinations thereof may be used, but are not limited thereto.
  • fullerene, fullerene derivative PCBM ((6,6) -phenyl-C 61 -butyric acid-methylester) or PCBCR ((6,6) -phenyl-C 61 -butyric acid)
  • PCBM ((6,6) -phenyl-C 61 -butyric acid-methylester)
  • PCBCR ((6,6) -phenyl-C 61 -butyric acid)
  • One or two or more compounds selected from the group consisting of -cholesteryl ester), perylene (polybenzimidazole), and PTCBI (3,4,9,10-perylene-tetracarboxylic bis-benzimidazole) may be used.
  • the photoactive layer has an absorbance of at least a portion of the visible light region of 2 or less.
  • the absorbance of at least some of the visible light region may be 2 or less.
  • the first electrode is an anode
  • the second electrode is a cathode.
  • the first electrode is a cathode and the second electrode is an anode.
  • the organic solar cell according to the exemplary embodiment of the present specification may further include a substrate in contact with the anode side or the cathode side.
  • the organic solar cell may be arranged in the order of cathode, photoactive layer and anode, and may be arranged in order of anode, photoactive layer and cathode, but is not limited thereto.
  • the organic solar cell may be arranged in the order of an anode, a hole transport layer, a photoactive layer, an electron transport layer, and a cathode, and may be arranged in the order of a cathode, an electron transport layer, a photoactive layer, a hole transport layer, and an anode, but is not limited thereto.
  • the organic solar cell has a normal structure.
  • the normal structure may mean that an anode is formed on a substrate.
  • the first electrode formed on the substrate may be an anode.
  • the organic solar cell has an inverted structure.
  • the inverted structure may mean that a cathode is formed on a substrate.
  • the first electrode formed on the substrate may be a cathode.
  • the organic solar cell has a tandem or stack structure.
  • the organic solar cell may include two or more photoactive layers.
  • the photoactive layer may be one layer or two or more layers.
  • a buffer layer may be provided between the photoactive layer and the hole transport layer or between the photoactive layer and the electron transport layer.
  • a hole injection layer may be further provided between the anode and the hole transport layer.
  • an electron injection layer may be further provided between the cathode and the electron transport layer.
  • the substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto, and the substrate may be any substrate that is commonly used in organic solar cells. Specifically, there are glass, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC). It is not limited to this.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PP polypropylene
  • PI polyimide
  • TAC triacetyl cellulose
  • the anode electrode may be a transparent and excellent conductive material, but is not limited thereto.
  • Metals such as vanadium, chromium, copper, zinc and gold or alloys thereof;
  • Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SNO 2 : Combination of metals and oxides such as Sb;
  • Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the cathode electrode may be a metal having a small work function, but is not limited thereto.
  • metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; LiF / Al, LiO 2 / Al, LiF / Fe, Al: Li, Al: BaF 2 , Al: BaF 2
  • It may be a material of a multi-layer structure such as, but is not limited thereto.
  • the hole transport layer and / or electron transport layer material plays a role of efficiently transferring electrons and holes separated in the photoactive layer to the electrode, and the material is not particularly limited.
  • the hole transport layer material may be PEDOT: PSS (Poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid)), molybdenum oxide (MoO x ); Vanadium oxide (V 2 O 5 ); Nickel oxide (NiO); Tungsten oxide (WO x ), and the like, but is not limited thereto.
  • PSS Poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid)
  • MoO x molybdenum oxide
  • V 2 O 5 Vanadium oxide
  • NiO Nickel oxide
  • WO x Tungsten oxide
  • the electron transport layer material may be electron-extracting metal oxides, specifically, a metal complex of 8-hydroxyquinoline; Complexes including Alq 3 ; Metal complexes including Liq; LiF; Ca; Titanium oxide (TiO x ); Zinc oxide (ZnO); And cesium carbonate (Cs 2 CO 3 ), and the like, but is not limited thereto.
  • metal oxides specifically, a metal complex of 8-hydroxyquinoline; Complexes including Alq 3 ; Metal complexes including Liq; LiF; Ca; Titanium oxide (TiO x ); Zinc oxide (ZnO); And cesium carbonate (Cs 2 CO 3 ), and the like, but is not limited thereto.
  • Another embodiment of the present application is a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer comprising a photoactive layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers has a thickness different by a coating method. It provides a method for producing an organic solar cell, characterized in that formed to include the above region.
  • the coating method is a spray coating.
  • spray coating may be sequentially performed for each region by using two or more masks which are manufactured to spray-coat each region having a different thickness.
  • Spray coating may be performed using a solution in which the organic material to form the layer is dissolved in an organic solvent. If necessary, in order to control the thickness of the organic layer, the spray injection amount may be adjusted, or the coating may be repeated one or more times. It is advantageous to form the desired thickness by repeating the coating one or more times.
  • the electrode and the organic material layer may be formed using methods and materials in the art.
  • the method of forming the anode electrode is not particularly limited, but is applied to one surface of the substrate or coated in a film form using, for example, sputtering, E-beam, thermal deposition, spin coating, screen printing, inkjet printing, doctor blade or gravure printing. It can be formed by.
  • the anode electrode When the anode electrode is formed on the substrate, it may be subjected to cleaning, water removal, and hydrophilic modification.
  • the patterned ITO substrate is sequentially cleaned with a detergent, acetone, isopropyl alcohol (IPA), and then dried in a heating plate for 1 to 30 minutes at 100 to 150 ° C., preferably at 120 ° C. for 10 minutes to remove moisture.
  • IPA isopropyl alcohol
  • the surface of the substrate is modified to be hydrophilic.
  • the bonding surface potential can be maintained at a level suitable for the surface potential of the photoactive layer.
  • Pretreatment techniques for the anode electrode include a) surface oxidation using parallel plate discharge, b) oxidation of the surface through ozone generated using UV ultraviolet light in a vacuum state, and c) oxygen radicals generated by plasma. And oxidation using the same method.
  • One of the above methods can be selected depending on the state of the anode electrode or the substrate. In any case, however, it is desirable to prevent oxygen escape from the surface of the anode electrode or the substrate and to minimize the residual of moisture and organic matter in common. At this time, the substantial effect of the pretreatment can be maximized.
  • a method of oxidizing a surface through ozone generated using UV may be used.
  • the patterned ITO substrate is baked on a hot plate and dried well, then put into a chamber, and a UV lamp is activated to cause oxygen gas to react with UV light.
  • the patterned ITO substrate can be cleaned.
  • the surface modification method of the patterned ITO substrate in this specification does not need to be specifically limited, Any method may be used as long as it is a method of oxidizing a substrate.
  • the cathode electrode is 5x10 - may be formed is deposited on the internal heat evaporator showing a degree of vacuum of less than 7 torr, not limited to this method.
  • organic material layers such as hole transport layer, electron transport layer, and photoactive layer
  • the organic solar cell according to the exemplary embodiments of the present specification may display characters or patterns through two or more colors, and thus may be used for displaying specific information or designs. For example, it may be used for applications such as blinds, curtains, glass windows, sheet paper, sunroofs, signs, etc., which have the function of organic solar cells.
  • ultrasonic cleaning was sequentially performed for 20 minutes each using a detergent, acetone, and isopropanol (IPA), followed by drying to completely remove moisture. Once the cleaning of the patterned ITO substrate was completed, the surface was modified for 15 minutes in a UVO cleaner.
  • IPA isopropanol
  • a solution containing 2.5 wt% of ZnO nanoparticles (nanograde) in IPA (isopropyl alcohol) was performed by a bar coating method. Bar coating was reciprocally coated at a rate of 20 mm / sec. Subsequently, heat treatment was performed for 10 minutes in air in an oven at 150 ° C. to form an electron transport layer.
  • a solution containing the electron donor material and the electron acceptor material of Table 2 in chlorobenzene (CB) on the electron transport layer was cleanly dissolved at 80 ° C., and then spray-coated at room temperature in air to include the areas 1 to 5.
  • a photoactive layer was formed. Regions 2 or 3 exhibited different visible light transmittance (different colors) with the same material, varying the concentration of the solution or the number of coatings depending on the location.
  • the MoO 3 layer was deposited as a hole transport layer at a rate of 0.3 kW / s by a thermal evaporation method to form a thickness of 10 nm.
  • an Ag metal having a thickness of 100 nm was formed at a rate of 1 ⁇ / s by thermal evaporation to prepare an organic solar cell module having a structure as shown in FIG. 7.
  • FIG. 1 An external photograph of the organic solar cell manufactured in Example 1 is illustrated in FIG. 1. Region-specific absorbances of the organic solar cells (absorbances up to the ITO substrate / ZnO / photoactive layer) are shown in FIG. 2.
  • the solution containing the electron donor material and the electron acceptor material of Table 3 in chlorobenzene (CB) on the electron transport layer was cleanly dissolved in air at 80 ° C., and then spray-coated at room temperature in air to include the areas 1 to 4. It carried out similarly to Example 1 except having formed the photoactive layer.
  • FIG. 3 An external photograph of the organic solar cell manufactured in Example 2 is illustrated in FIG. 3. Region-specific absorbances of the organic solar cells (absorbances up to the ITO substrate / ZnO / photoactive layer) are shown in FIG. 4.

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  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne une cellule solaire organique et son procédé de fabrication, la cellule solaire organique comprenant : une première électrode ; une seconde électrode disposée de façon à être en regard de la première électrode ; et des couches de matériau organique d'une ou plusieurs couches, comprenant une couche photoactive disposée entre la première électrode et la seconde électrode, une ou plusieurs couches des couches de matériau organique comprenant au moins deux régions ayant des épaisseurs différentes.
PCT/KR2016/014183 2015-12-07 2016-12-05 Cellule solaire organique et son procédé de fabrication WO2017099441A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP16873306.1A EP3389102B1 (fr) 2015-12-07 2016-12-05 Cellule solaire organique et son procédé de fabrication
CN201680039503.7A CN107851719B (zh) 2015-12-07 2016-12-05 有机太阳能电池及其制造方法
US15/736,216 US11081603B2 (en) 2015-12-07 2016-12-05 Organic solar cell and manufacturing method therefor
JP2017563515A JP6544544B2 (ja) 2015-12-07 2016-12-05 有機太陽電池およびその製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2015-0173537 2015-12-07
KR20150173537 2015-12-07
KR10-2016-0163556 2016-12-02
KR1020160163556A KR102066322B1 (ko) 2015-12-07 2016-12-02 유기태양전지 및 이의 제조방법

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109950402A (zh) * 2019-03-26 2019-06-28 华南师范大学 叠层有机薄膜太阳能电池及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0173537B1 (en) 1995-01-31 1999-02-01 Mitsubishi Electric Corp Convergence correcting device
EP1672653A2 (fr) * 2004-12-20 2006-06-21 Konarka Technologies, Inc. Cellule photovoltaique à motifs
US20060145365A1 (en) * 2002-07-03 2006-07-06 Jonathan Halls Combined information display and information input device
KR100989285B1 (ko) * 2010-05-24 2010-10-22 (주) 비제이파워 칼라 태양 전지를 이용한 형상화된 태양 전지 모듈
KR20100115848A (ko) * 2009-04-21 2010-10-29 주식회사 유나티앤이 태양전지를 이용한 광고방법
KR20120037316A (ko) * 2010-10-11 2012-04-19 포항공과대학교 산학협력단 유기 태양 전지 및 이의 제조 방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0173537B1 (en) 1995-01-31 1999-02-01 Mitsubishi Electric Corp Convergence correcting device
US20060145365A1 (en) * 2002-07-03 2006-07-06 Jonathan Halls Combined information display and information input device
EP1672653A2 (fr) * 2004-12-20 2006-06-21 Konarka Technologies, Inc. Cellule photovoltaique à motifs
KR20100115848A (ko) * 2009-04-21 2010-10-29 주식회사 유나티앤이 태양전지를 이용한 광고방법
KR100989285B1 (ko) * 2010-05-24 2010-10-22 (주) 비제이파워 칼라 태양 전지를 이용한 형상화된 태양 전지 모듈
KR20120037316A (ko) * 2010-10-11 2012-04-19 포항공과대학교 산학협력단 유기 태양 전지 및 이의 제조 방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109950402A (zh) * 2019-03-26 2019-06-28 华南师范大学 叠层有机薄膜太阳能电池及其制备方法

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