WO2023282457A1 - 페로브스카이트 층을 형성하기 위한 방법 - Google Patents
페로브스카이트 층을 형성하기 위한 방법 Download PDFInfo
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- WO2023282457A1 WO2023282457A1 PCT/KR2022/006953 KR2022006953W WO2023282457A1 WO 2023282457 A1 WO2023282457 A1 WO 2023282457A1 KR 2022006953 W KR2022006953 W KR 2022006953W WO 2023282457 A1 WO2023282457 A1 WO 2023282457A1
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- inorganic
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- perovskite
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- organic
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000010410 layer Substances 0.000 claims abstract description 123
- 150000002366 halogen compounds Chemical class 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000151 deposition Methods 0.000 claims abstract description 19
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000012044 organic layer Substances 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 238000005019 vapor deposition process Methods 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 19
- 239000011147 inorganic material Substances 0.000 claims description 15
- 229910010272 inorganic material Inorganic materials 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 12
- -1 halogen anions Chemical class 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000011368 organic material Substances 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- 239000011669 selenium Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 150000001450 anions Chemical group 0.000 claims description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052699 polonium Inorganic materials 0.000 claims description 4
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 claims description 3
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 9
- 150000007529 inorganic bases Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000004528 spin coating Methods 0.000 description 6
- 238000002207 thermal evaporation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 229960004592 isopropanol Drugs 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 238000003380 quartz crystal microbalance Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- NCCSSGKUIKYAJD-UHFFFAOYSA-N rubidium(1+) Chemical compound [Rb+] NCCSSGKUIKYAJD-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical group SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/16—Halides
-
- 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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
-
- 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 invention relates to a method for forming a photoreceptor layer made of a perovskite material included in a tandem solar cell.
- a solar cell is an assembly that converts solar energy into electricity, and has been studied for a long time as it is attracting attention as a next-generation energy, and high photoelectric efficiencies based on various materials such as silicon, CIGS, and perovskite have been reported.
- the commercialized and most used solar cell is a silicon-based solar cell, which accounts for more than 90% of the solar cell market.
- the silicon solar cell includes a crystalline silicon solar cell and an amorphous silicon solar cell
- the crystalline silicon solar cell has a disadvantage of high manufacturing cost, but is widely commercialized due to its high energy efficiency.
- process technology is difficult, equipment dependence is high, and most of all, the efficiency is low, so development is not currently progressing.
- the silicon solar cell is classified as the first generation, there is a perovskite-based solar cell as a representative of the third generation solar cell, which is currently being actively researched worldwide as an environmentally friendly future promising item.
- Perovskite solar cells utilize materials that have a perovskite crystal structure by combining inorganic and organic materials.
- Perovskite has a very special structure that shows superconductivity as well as insulator, semiconductor, and conductor properties.
- the perovskite light absorption layer used in the perovskite solar cell has the structure of ABX 3 (where A is a monovalent organic ammonium cation or metal cation, B is a divalent metal cation, and X is a halogen anion) It is made of perovskite material.
- A represents methylammonium (CH 3 NH 3 + ) or ethylammonium (CH 3 CH 2 NH 3 + ), B represents Pb or Sn, and X represents I, Br or Cl) It may include lobesite, but is not limited thereto.
- the perovskite compound is, for example, CH 3 NH 3 PbI 3 , CH 3 NH 3 PbI x Cl 3-x , MAPbI 3 , CH 3 NH 3 PbI x Br 3-x , CH 3 NH 3 PbCl x Br 3-x , HC(NH 2 ) 2 PbI 3 , HC(NH 2 ) 2 PbI x Cl 3-x , HC(NH 2 ) 2 PbI x Br 3-x , HC(NH 2 ) 2 PbCl x Br 3-x , CH 3 NH 3 )(HC(NH 2 ) 2 ) 1-y PbI 3 , (CH 3 NH 3 )(HC(NH 2 ) 2 ) 1-y PbI x Cl 3-x , (CH 3 NH 3 )( HC(NH 2 ) 2 ) 1-y PbI x Cl 3-x , (CH 3 NH 3 )( HC(NH 2 ) 2 ) 1-y Pb
- Perovskite has the characteristics of strong solar absorption, low non-radiative carrier recombination rate, high carrier mobility, and defects that cause non-radiative carrier recombination have a band gap. It is known to increase the conversion efficiency due to the property of not being formed within or at a deep level.
- organic-inorganic hybrid perovskite solar cells are currently in the limelight as next-generation thin-film solar cells because they are inexpensive to manufacture and can be fabricated through a solution process.
- Perovskite-based solar cells are rapidly increasing in efficiency in the first decade of research, and high photovoltaic efficiencies have been reported.
- perovskite-silicon tandem solar cells have a small band gap and a large band gap, respectively, so they are advantageous for photooperation, and research is active.
- the silicon surface consists of a series of pyramidal structures that confine light and prevent light reflection, but the pyramidal surface of silicon makes it difficult to coat a uniform film of perovskite.
- perovskite When perovskite is coated in a liquid form, it usually accumulates in the valleys between the pyramidal structures of the silicon surface and exposes the peaks, resulting in a problem that the perovskite is not properly coated.
- perovskite is sometimes coated on flat silicon without pyramids, but recently, in order to maximize the efficiency gain due to light reflection, vapor deposition methods such as vacuum thermal evaporation are first used to coat perovskite.
- a tandem solar cell is manufactured by completely covering the pyramidal structure of the silicon surface with an inorganic base layer and then coating an organic layer on top of the inorganic base layer using a solution deposition technique such as spin-coating. It is being used.
- the inorganic base layer of perovskite changes over time, since the inorganic base layer is unstable, it is not known in what state the organic material layer is coated, and eventually the perovskite layer formed on top of the silicon layer is also unstable. There is a problem of non-uniformity.
- the time for forming the inorganic layer for each part/batch may vary, and as a result, the final perovskite after coating the organic material layer for each part/batch Since the characteristics of the layer may vary, it may be a bigger problem in terms of yield when mass production technology is introduced.
- the present invention has been made to solve the above problems, and in a tandem solar cell, a large-area page with high uniformity is prevented from changing over time in the inorganic halide-based layer, which is a precursor of a perovskite layer.
- An object of the present invention is to provide an apparatus and method for forming a perovskite layer capable of producing a roveskite light absorption layer.
- the present invention is a method for forming a perovskite layer on top of a silicon layer, comprising: depositing an inorganic perovskite layer on top of the silicon layer by a vapor deposition process; and coating an organic perovskite layer on top of the inorganic layer by a solution process, wherein the inorganic layer is formed by sequentially or simultaneously depositing three or more inorganic halogen compounds containing different halogen elements. It provides a method for forming a perovskite layer, characterized in that.
- the inorganic material layer may include at least one divalent metal cation and three or more halogen anions.
- the inorganic material layer may further include at least one monovalent metal cation.
- the monovalent metal cation may be one or two or more selected from alkali metal ions composed of Li + , Na + , K + , Rb + , and Cs + .
- the inorganic material layer is composed of at least a first inorganic halogen compound, a second inorganic halogen compound, and a third inorganic halogen compound, and the first inorganic halogen compound and the second inorganic halogen compound have a chemical structure of BX 2 , and mutually Composed of different types of compounds, the B is lead (Pb 2+ ), tin (Sn 2+ ), tungsten (W 2+ ), copper (Cu 2+ ), zinc (Zn 2+ ), gallium (Ga 2+ ) + ), germanium (Ge 2+ ), arsenic (As 2+ ), selenium (Se 2+ ), rhodium (Rh 2+ ), palladium (Pd 2+ ), silver (Ag 2+ ), cadmium (Cd 2+ ) ), Indium (In 2+ ), Antimony (Sb 2+ ), Osmium (Os 2+ ), Iridium (Ir 2+
- the inorganic material layer may be formed by depositing PbI 2 to a thickness of 240 nm, depositing PbBr 2 to a thickness of 80 nm, and depositing CsCl to a thickness of 20 nm.
- the phase of the inorganic halide-based layer which is the precursor of the perovskite layer, is prevented from changing over time, thereby improving uniformity.
- the phase of the inorganic halide-based layer which is the precursor of the perovskite layer
- 1 is a graph showing the change in absorbance over time of an inorganic base layer of perovskite produced according to the prior art.
- FIG. 2 is a flowchart of a method of forming a perovskite layer according to an embodiment of the present invention.
- FIG 3 is a graph showing a change in absorbance over time of an inorganic base layer of perovskite produced according to an embodiment of the present invention.
- FIG. 2 is a flowchart of a method of forming a perovskite layer according to an embodiment of the present invention
- FIG. 3 is an absorbance over time of an inorganic base layer of perovskite produced according to an embodiment of the present invention.
- a graph showing the change is a graph showing the change.
- the method of forming a perovskite layer includes vapor-depositing an inorganic layer of perovskite (S10), forming an organic layer of perovskite into a solution It may include a step of coating (S20), a step of waiting for a predetermined time (S30), and a step of heat treatment (S40).
- Vapor deposition of the inorganic perovskite layer (S10) is a step of depositing an inorganic halogen compound on top of the silicon layer constituting the tandem solar cell by a vapor deposition process.
- a vacuum thermal evaporation process may be used as the vapor deposition process.
- the vacuum thermal evaporation process may be performed, for example, through a chamber maintained in an ultra-high vacuum state and an evaporator installed inside the chamber.
- a holder to which a silicon layer can be fixed may be disposed on the ceiling of the chamber, and an evaporator may be disposed below the chamber to evaporate the inorganic halogen compound and deposit the inorganic halogen compound to a predetermined thickness on the silicon layer fixed to the holder.
- a residual gas analyzer or a quartz crystal microbalance (QCM) sensor may be installed in the chamber.
- the inorganic perovskite layer deposited on the silicon layer in the vapor deposition step (S10) includes three or more different halogen elements.
- three or more kinds of inorganic halogen compounds containing different halogen elements may be sequentially or simultaneously deposited to form the inorganic perovskite layer of the present invention.
- the inorganic perovskite layer includes a first inorganic halogen compound 100, a second inorganic halogen compound 200, and a third inorganic halogen compound 300 sequentially by a vacuum thermal evaporation process.
- it may be deposited and formed on the silicon layer at the same time, and the halogen elements included in the first inorganic halogen compound 100, the second inorganic halogen compound 200, and the third inorganic halogen compound 300 are different from each other. made up of
- the first inorganic halogen compound 100 may have a chemical structure of BX 2 (B is a divalent metal metal cation and X is a halogen anion).
- B is lead (Pb 2+ ), tin (Sn 2+ ), tungsten (W 2+ ), copper (Cu 2+ ), zinc (Zn 2+ ), gallium (Ga 2+ ), germanium (Ge 2+ ) , arsenic (As 2+ ), selenium (Se 2+ ), rhodium (Rh 2+ ), palladium (Pd 2+ ), silver (Ag 2+ ), cadmium (Cd 2+ ), indium (In 2+ ), Antimony (Sb 2+ ), Osmium (Os 2+ ), Iridium (Ir 2+ ), Platinum (Pt 2+ ), Gold (Au 2+ ), Mercury (Hg 2+ ), Thallium (Tl 2+ ), Bismuth (Bi 2+ ),
- the first inorganic halogen compound 100 used in one embodiment of the present invention may be PbI 2 .
- the second inorganic halogen compound 200 is different from the first inorganic halogen compound 100, but like the first inorganic halogen compound, the chemical structure of BX 2 (B is a divalent metal metal cation and X is a halogen anion) can have B is lead (Pb 2+ ), tin (Sn 2+ ), tungsten (W 2+ ), copper (Cu 2+ ), zinc (Zn 2+ ), gallium (Ga 2+ ), germanium (Ge 2+ ) , arsenic (As 2+ ), selenium (Se 2+ ), rhodium (Rh 2+ ), palladium (Pd 2+ ), silver (Ag 2+ ), cadmium (Cd 2+ ), indium (In 2+ ), Antimony (Sb 2+ ), Osmium (Os 2+ ), Iridium (Ir 2+ ), Platinum (Pt 2+ ), Gold (Au 2+ ), Mercury (Hg 2
- the second inorganic halogen compound 200 used in one embodiment of the present invention may be PbBr 2 .
- the cation may be a monovalent alkali metal ion selected from the group consisting of Li + , Na + , K + , Rb + , and Cs +
- the halogen anion may be chlorine (Cl - )
- It may be any one anion selected from bromine (Br - ) and iodine (I - ).
- the third inorganic halogen compound 300 used in one embodiment of the present invention may be CsCl.
- the first inorganic halogen compound 100 (PbI 2 ) is deposited to a thickness of 240 nm and the second inorganic halogen compound 200 (PbBr 2 ) is deposited to a thickness of 80 nm by a vacuum thermal evaporation process, ,
- a third inorganic halogen compound 300 (CsCl) is deposited to a thickness of 20 nm to form a perovskite inorganic material layer on top of the silicon layer.
- the absorbance of the inorganic layer was first deposited on the silicon layer (as -deposited) showed little change in absorbance.
- the image of the inorganic layer at the time of one hour (1 hour) from the time of depositing the inorganic perovskite layer on the silicon layer shown by the absorbance measurement shown in FIG. 3 and the inorganic perovskite layer on the silicon layer The phase of the inorganic layer at 24 hours (overnight) from the time of deposition is maintained almost the same as the phase (as-deposited) of the inorganic layer at the time of depositing the first perovskite inorganic layer on the silicon layer. Able to know.
- the perovskite inorganic layer (PbI 2 +CsBr) formed by the conventional method shown in FIG. 1 has a wavelength of 450 nm to 650 nm. Although the absorbance is significantly reduced with time in the range, the perovskite inorganic layer (PbI 2 +PbBr 2 +CsCl) formed by the method of the present invention is measured over time in the entire wavelength range (450 nm to 800 nm). ), it can be seen that the absorbance is maintained almost the same.
- the inorganic perovskite organic layer is formed in a state in which the phase of the inorganic layer is accurately identified. It can be coated on top of the layer. Therefore, the organic-inorganic perovskite layer formed by the reaction of the organic material layer and the inorganic material layer can be stably and uniformly formed.
- inorganic halogen compounds having different halogen elements are deposited to form a perovskite inorganic layer, but it is not limited thereto, PbI 2 +CsBr+PbCl 2 , PbI 2 +CsBr+CsCl +PbBr 2 It is possible to form an inorganic material layer through various combinations of 3, 4, 5 or more precursors such as .
- a step (S20) of coating an organic perovskite layer by a solution process is performed on the inorganic perovskite layer thus formed.
- a heat treatment process may be added before the step of coating the organic material layer (S20).
- the solution process has an advantage in that it is easy to form a perovskite thin film having a constant element ratio (Stoichiometry).
- a spin coating process may be performed as the solution process.
- the precursor solution of the perovskite organic layer is dropped onto the inorganic perovskite layer formed on the substrate, and then the substrate is rotated to discard the excess perovskite organic layer precursor solution by centrifugal force. It is a method to form a uniform wet film on the inorganic material layer.
- the organic halide compound forming the organic material layer may have a chemical structure of AX (where A is a monovalent organic ammonium cation or metal cation and X is a halogen anion).
- A is a cation of cesium (Cs+), rubidium (Rb+), potassium (K+), an amido group, an amidino group, or an alkali group
- X is chlorine (Cl-), bromine (Br-), iodine ( I-), thiocyanic acid group (NCS-), cyan group (CN-), and oxycyanate (NCO-).
- an organic perovskite layer may be formed by dissolving FAI and FABr, which are organic halogen compounds, in iso-propanol (IPA), and then performing a spin coating process with the solution.
- FAI and FABr organic halogen compounds
- IPA iso-propanol
- the waiting time to form the organic-inorganic perovskite thin film is also called quenching time, and in one or multiple embodiments, the quenching time may be approximately 5 to 20 seconds. However, it is not limited thereto, and quenching may not be performed depending on the penetrating power of the solvent used.
- an organic-inorganic perovskite layer is formed by heat-treating the organic-inorganic perovskite thin film at a predetermined temperature for a predetermined time to harden the organic-inorganic perovskite thin film (S40).
- the organic-inorganic perovskite thin film may be heat-treated at a temperature of 100 to 150° C. for 10 to 30 minutes.
- the present invention can be used in the field of manufacturing solar cells.
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Abstract
Description
Claims (8)
- 실리콘층 상부에 페로브스카이트층을 형성하기 위한 방법에 있어서,기상 증착 공정에 의해 상기 실리콘층 상부에 페로브스카이트 무기물층을 증착하는 단계; 및용액 공정에 의해 상기 무기물층 상부에 페로브스카이트 유기물층을 코팅하는 단계;를 포함하고,상기 무기물층은 서로 다른 할로겐 원소를 포함하는 3종 이상의 무기할로겐화합물들이 순차로 또는 동시에 증착되어 형성되는 것을 특징으로 하는 페로브스카이트층을 형성하기 위한 방법.
- 제1항에 있어서,상기 코팅하는 단계 이후에 상기 무기물층과 상기 유기물층이 반응하여 유-무기 페로브스카이트 박막을 형성도록 소정 시간을 대기하는 단계; 및상기 대기하는 단계 이후에 상기 유-무기 페로브스카이트 박막을 소정 시간 동안 소정 온도로 열처리하는 단계;를 더 포함하는 것을 특징으로 하는 페로브스카이트층을 형성하기 위한 방법.
- 제1항에 있어서,상기 무기물층은 적어도 하나 이상의 2가의 금속 양이온과 3종 이상의 할로겐 음이온을 포함하는 것을 특징으로 하는 페로브스카이트층을 형성하기 위한 방법.
- 제3항에 있어서,상기 무기물층은 적어도 하나 이상의 1가의 금속 양이온을 더 포함하는 것을 특징으로 하는 페로브스카이트층을 형성하기 위한 방법.
- 제4항에 있어서,상기 1가의 금속 양이온은 Li+, Na+, K+, Rb+, 및 Cs+으로 이루어진 알칼리 금속 이온 중에서 하나 또는 둘 이상 선택되는 것을 특징으로 하는 페로브스카이트층을 형성하기 위한 방법.
- 제1항에 있어서,상기 무기물층은 적어도 제1 무기할로겐화합물과 제2 무기할로겐화합물 및 제3 무기할로겐화합물로 구성되며,상기 제1 무기할로겐화합물과 상기 제2 무기할로겐화합물은 BX2의 화학식 구조를 가지되, 서로 다른 종류의 화합물로 이루어지고,상기 B는 납(Pb2+), 주석(Sn2+), 텅스텐(W2+), 구리(Cu2+), 아연(Zn2+), 갈륨(Ga2+), 게르마늄(Ge2+), 비소(As2+), 셀레늄(Se2+), 로듐(Rh2+), 팔라듐(Pd2+), 은(Ag2+), 카드뮴(Cd2+), 인듐(In2+), 안티몬(Sb2+), 오스뮴(Os2+), 이리듐(Ir2+), 백금(Pt2+), 금(Au2+), 수은(Hg2+), 탈륨 (Tl2+), 비스무트(Bi2+), 폴로늄(Po2+) 중 어느 하나의 양이온이고, 상기 X는 염소(Cl-), 브롬(Br-), 요오드(I-) 중 어느 하나의 음이온이며,상기 제3 무기할로겐화합물은 양이온은 Li+, Na+, K+, Rb+, 및 Cs+으로 이루어진 군에서 선택되는 어느 하나의 1가의 알칼리 금속 이온이고, 할로겐 음이온은 염소(Cl-), 브롬(Br-), 요오드(I-) 중에서 선택되는 어느 하나의 음이온으로 이루어지는 것을 특징으로 하는 페로브스카이트층을 형성하기 위한 방법.
- 제6항에 있어서,상기 무기물층은 PbI2를 240nm 두께로 증착하고, PbBr2을 80nm 두께로 증착하며, CsCl을 20nm 두께로 증착하여 형성되는 것을 특징으로 하는 페로브스카이트층을 형성하기 위한 방법.
- 제1항에 있어서,상기 유기물층을 형성하는 유기할로겐화합물은 MACl, MABr, 및 MAI으로 이루어지는 군에서 선택되는 어느 하나의 메틸암모늄(MA=CH3NH3+) 화합물이거나 또는 FACl, FABr, 및 FAI로 이루어지는 군에서 선택되는 어느 하나의 포름아미디늄 (FA=HC(NH2)2+) 화합물인 것을 특징으로 하는 페로브스카이트층을 형성하기 위한 방법.
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KR101172374B1 (ko) | 2011-02-14 | 2012-08-08 | 성균관대학교산학협력단 | 페로브스카이트계 염료를 이용한 염료감응 태양 전지 및 이의 제조방법 |
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WO2020210399A1 (en) * | 2019-04-09 | 2020-10-15 | Swift Solar Inc. | Vapor phase transport system and method for depositing perovskite semiconductors |
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