KR101194257B1 - Transparent substrate for solar cell having a broadband anti-reflective multilayered coating thereon and method for preparing the same - Google Patents
Transparent substrate for solar cell having a broadband anti-reflective multilayered coating thereon and method for preparing the same Download PDFInfo
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- KR101194257B1 KR101194257B1 KR1020110104288A KR20110104288A KR101194257B1 KR 101194257 B1 KR101194257 B1 KR 101194257B1 KR 1020110104288 A KR1020110104288 A KR 1020110104288A KR 20110104288 A KR20110104288 A KR 20110104288A KR 101194257 B1 KR101194257 B1 KR 101194257B1
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- 239000000758 substrate Substances 0.000 title claims abstract description 57
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title claims abstract description 37
- 230000003667 anti-reflective effect Effects 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 9
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000002834 transmittance Methods 0.000 claims description 23
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- 239000010409 thin film Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
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- 239000010703 silicon Substances 0.000 claims description 7
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 229910004613 CdTe Inorganic materials 0.000 claims description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 78
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
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- 229910052742 iron Inorganic materials 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910021426 porous silicon Inorganic materials 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 3
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- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
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- 239000002356 single layer Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
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- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
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- 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
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- General Physics & Mathematics (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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- Surface Treatment Of Glass (AREA)
Abstract
Description
본 발명은 광대역 반사방지 다층코팅을 갖는 태양전지용 투명 기판 및 그 제조방법에 관한 것으로, 보다 상세하게는, 태양전지의 최외각면(태양빛을 받아들이는 면)에 적용 가능한 투명 기판으로서 그 표면상에 고굴절률 물질층과 저굴절률 물질층이 교대하여 순차적으로 적층되어 형성되는 4층의 다층코팅을 가짐으로써 광대역(380~1,100nm) 반사방지 기능을 발휘하여 가시광선뿐만 아니라 근적외선 영역의 투과율을 향상시키는 한편 태양전지 발전에 기여하지 못하고 태양전지 모듈의 열화를 일으키는 적외선 영역은 투과율을 떨어뜨려 태양전지의 효율 향상에 기여할 수 있는 광대역 (380~1,100nm) 반사방지성 태양전지용 투명 기판 및 그 제조방법에 관한 것이다.The present invention relates to a transparent substrate for a solar cell having a broadband antireflection multilayer coating and a method of manufacturing the same. More particularly, the present invention relates to a transparent substrate applicable to the outermost surface of the solar cell (surface to receive sunlight). It has four layers of multi-layer coating formed by alternately stacking high and low refractive index material layers in order to achieve broadband (380 ~ 1,100nm) antireflection to improve transmittance not only in visible light but also in near infrared. In addition, the infrared region, which does not contribute to solar cell power generation and causes deterioration of the solar cell module, can reduce the transmittance, thereby contributing to the improvement of the solar cell efficiency. It is about.
반사방지 코팅은 본래 액자, 렌즈, 디스플레이 장치 등의 용도에서 기술이 시작되어 발전된 것으로, 가시광 영역 즉, 380~780nm까지의 투과율을 높이기 위한 코팅 기술이다. 이러한 반사방지 코팅은 통상적으로 기판의 굴절률(유리일 경우 통상 1.5)과 공기의 굴절률(1.0) 사이의 굴절률을 갖는 물질의 막으로 이루어진다. Anti-reflective coating is a technology that has been developed since the beginning in the use of the frame, lens, display device, etc., is a coating technology for increasing the transmittance in the visible light region, that is, 380 ~ 780nm. Such antireflective coatings typically consist of a film of material having a refractive index between the refractive index of the substrate (typically 1.5 for glass) and the refractive index (1.0) of air.
태양전지용 투명 기판, 예컨대 태양전지 커버 유리에서는 가시광 영역뿐만 아니라, 근적외선 영역 (~1,100nm) 까지의 투과도를 증가시킬 필요가 있는데, 이는 태양전지가 흡수하는 빛의 파장대역이 가시광 영역보다 넓기 때문이다. 따라서 태양전지의 변환 효율을 증가시키기 위해서는 태양전지의 최외각 투명 기판을 통과하는 태양 빛의 투과율을 광대역(380~1,100nm) 영역에서 개선해야 한다. In solar cell transparent substrates such as solar cell cover glass, it is necessary to increase the transmittance not only in the visible region but also in the near infrared region (~ 1,100 nm) because the wavelength band of light absorbed by the solar cell is wider than the visible region. . Therefore, in order to increase the conversion efficiency of the solar cell, the transmittance of solar light passing through the outermost transparent substrate of the solar cell should be improved in the broadband (380-1,100 nm) region.
이러한 광대역 영역의 태양광 투과율을 개선하기 위해 종래에는, 태양전지용 최외각 유리의 외부 표면에 다공성 규소 산화물의 단일층으로 만들어진 반사방지 코팅을 성막하였다. 이 다공성 규소 산화물에 의해 제공되는 기공은 규소 산화물의 굴절률을 낮춰주는 역할을 한다. 하지만, 이러한 단일층 코팅은 수분에 대한 내구성이 불충분하다. 또한 이러한 다공성 규소 산화물 코팅층은 통상적으로 졸-겔(Sol-gel) 법을 사용하여 형성되며, 스프레이나 침지(Dipping) 코팅법으로 제조하는 경우에는 균일한 박막을 얻기가 힘들다는 단점이 있다.In order to improve the solar transmittance in this broadband region, an antireflective coating made of a single layer of porous silicon oxide is conventionally formed on the outer surface of the outermost glass for solar cells. The pores provided by the porous silicon oxide lower the refractive index of the silicon oxide. However, such monolayer coatings have insufficient durability against moisture. In addition, such a porous silicon oxide coating layer is typically formed using a sol-gel method, it is difficult to obtain a uniform thin film when manufactured by a spray or dipping coating method.
다르게는, 유리의 외부면을 불산 등의 화학약품으로 식각하여, 다공질의 규소 산화물을 유리 위에 얇게 형성하는 방법이 알려져 있다. 그러나 이러한 방법은 식각하는데 시간이 오래 걸려 생산성이 크게 떨어지고, 유리 표면이 불균일하며, 또한 불산을 사용함에 따른 환경적인 문제가 있다. Alternatively, a method is known in which an outer surface of glass is etched with a chemical such as hydrofluoric acid to form a porous silicon oxide thinly on glass. However, this method takes a long time to etch, greatly reducing the productivity, uneven glass surface, and there is an environmental problem by using hydrofluoric acid.
대한민국 공개특허 제10-2008-0089351호에서는 다층 코팅에 의한 반사 방지막을 개시하고 있다. 그러나 이 특허 문헌에 개시된 다층코팅을 구성하는 고굴절율 물질의 총두께는 100~150nm에 이를 정도로 두꺼워서 제품 생산 속도가 느린 단점이 있으며, 이를 극복하기 위해서는 보다 빠른 증착을 수행하기 위한 장비가 요구되는바 투자 비용이 증가하고, 결과적으로 제품의 원가가 상승하는 단점이 발생한다. 또한, 이 대한민국 공개특허에 개시된 고굴절율 제3층의 경우 그 두께가 140~160nm으로 두껍고 이에 따라 민감성(sensitivity)이 지나치게 높아져 품질 공정 관리가 매우 어렵게 된다.Korean Patent Laid-Open No. 10-2008-0089351 discloses an anti-reflection film by multilayer coating. However, the total thickness of the high refractive index material constituting the multi-layer coating disclosed in this patent document is thick enough to reach 100 ~ 150nm, there is a disadvantage that the product production speed is slow, to overcome this need equipment for performing faster deposition The cost of investment increases, and as a result, the cost of the product rises. In addition, in the case of the high refractive index third layer disclosed in the Korean Patent Publication, the thickness thereof is 140 to 160 nm, and thus the sensitivity is too high, making quality process management very difficult.
본 발명은 상기 종래기술의 문제점들을 해결하고자 한 것으로서, 태양전지의 최외각면에 적용되는 투명 기판으로서 가시광선 및 근적외선 영역의 투과율을 향상시키는 한편 태양전지 발전에 기여하지 못하고 태양전지 모듈의 열화를 일으키는 적외선 영역의 투과율은 떨어뜨려 태양전지의 효율 향상에 기여할 수 있는 광대역(380~1,100nm) 반사방지성 태양전지용 투명 기판 및 그 제조방법을 제공하는 것을 기술적 과제로 한다.The present invention is to solve the problems of the prior art, a transparent substrate that is applied to the outermost surface of the solar cell to improve the transmittance of the visible light and near infrared region while not contributing to the development of the solar cell without deterioration of the solar cell module It is a technical object of the present invention to provide a transparent substrate for a broadband (380-1,100 nm) antireflective solar cell and a method of manufacturing the same, which can reduce the transmittance of the resulting infrared ray and contribute to the improvement of solar cell efficiency.
상기한 기술적 과제를 해결하고자 본 발명은, 표면으로부터 순차적으로 형성된 (1) 1.9 ~ 2.5의 굴절률을 갖는 제1 고-굴절층; (2) 1.3 ~ 1.6의 굴절률을 갖는 제1 저-굴절층; (3) 1.9 ~ 2.5의 굴절률을 갖는 제2 고-굴절층; 및 (4) 1.3 ~ 1.6의 굴절률을 갖는 제2 저-굴절층;의 4층 코팅을 포함하는 광대역 반사방지성 태양전지용 투명 기판을 제공한다.In order to solve the above technical problem, the present invention, the first high-refractive layer having a refractive index of 1.9 ~ 2.5 formed sequentially from the surface; (2) a first low refractive index layer having a refractive index of 1.3 to 1.6; (3) a second high-refractive layer having a refractive index of 1.9 to 2.5; And (4) a second low-refractive layer having a refractive index of 1.3 to 1.6; and providing a four-layer coating of a transparent anti-reflection solar cell substrate.
본 발명의 다른 측면에 따르면, (1) 투명 기판 상에 1.9 ~ 2.5의 굴절률을 갖는 제1 고-굴절층을 형성하는 단계, (2) 상기 제1 고-굴절층 상에 1.3 ~ 1.6의 굴절률을 갖는 제1 저-굴절층을 형성하는 단계, (3) 상기 제1 저-굴절층 상에 1.9 ~ 2.5의 굴절률을 갖는 제2 고-굴절층을 형성하는 단계, (4) 상기 제2 고-굴절층 상에 1.3 ~ 1.6의 굴절률을 갖는 제2 저-굴절층을 형성하는 단계를 포함하는, 광대역 반사방지성 태양전지용 투명 기판의 제조방법이 제공된다.According to another aspect of the invention, (1) forming a first high-refractive layer having a refractive index of 1.9 to 2.5 on the transparent substrate, (2) a refractive index of 1.3 to 1.6 on the first high-refractive layer Forming a first low-refractive layer having a refractive index, (3) forming a second high-refractive layer having a refractive index of 1.9 to 2.5 on the first low-refractive layer, and (4) the second high refractive index layer A method of manufacturing a transparent substrate for a broadband antireflection solar cell is provided, comprising forming a second low-refractive layer having a refractive index of 1.3 to 1.6 on the refractive layer.
본 발명의 또 다른 측면에 따르면, 본 발명의 광대역 반사방지성 태양전지용 투명 기판을 최외각에 설치한 것을 특징으로 하는 태양전지 모듈이 제공된다.According to another aspect of the invention, there is provided a solar cell module characterized in that the transparent substrate for a wideband antireflection solar cell of the present invention is installed on the outermost.
본 발명에 따르면, 가시광선-근적외선 파장(380nm~1,100nm) 범위와 원적외선을 포함하는 장파장 범위 사이에서 선택적인 투과특성을 나타내어 태양전지에 적용시 가시광선 및 근적외선 영역의 투과율이 높아져 태양에너지 흡수량이 증가하여 셀의 효율을 높일 수 있는 광대역 반사방지성 투명 기판을 우수한 생산성 및 절감된 원가로 제조할 수 있다.According to the present invention, it exhibits selective transmission between visible-near-infrared wavelength (380nm ~ 1,100nm) range and long-wavelength range including far-infrared rays, so that the transmittance of visible and near-infrared region increases when applied to solar cells, so that the amount of solar energy absorption is increased. Broadband antireflective transparent substrates that can increase cell efficiency can be manufactured at high productivity and reduced cost.
도 1은 본 발명의 일 구체예에 따라 4층의 반사방지성 다층코팅을 그 표면상에 가지는 유리의 층 구성에 대한 개략도이다.
도 2는 본 발명의 실시예 및 비교예에서 제조된 반사방지성 코팅 유리들의, 파장에 따른 투과율을 나타낸 그래프이다.
도 3은 대한민국 공개특허 제10-2008-0089351호에 개시된 바와 같은 두께 및 굴절율의 4층코팅에 대해 각 코팅층별로 상대적 민감성(relative sensitivity)을 나타낸 박막 시뮬레이션 결과 그래프이다.
도 4는 본 발명에 따른 4층코팅의 각 코팅층별 상대적 광학 민감성(sensitivity)을 나타낸 박막 시뮬레이션 결과 그래프이다.1 is a schematic diagram of a layer configuration of glass having four layers of antireflective multilayer coatings on its surface according to one embodiment of the invention.
Figure 2 is a graph showing the transmittance according to the wavelength of the antireflective coating glass prepared in Examples and Comparative Examples of the present invention.
3 is a graph showing a thin film simulation result showing relative sensitivity for each coating layer for the four-layer coating of thickness and refractive index as disclosed in Korean Patent Laid-Open Publication No. 10-2008-0089351.
4 is a thin film simulation result graph showing the relative optical sensitivity (sensitivity) for each coating layer of the four-layer coating according to the present invention.
이하에서 본 발명에 대해 상세히 설명한다.Hereinafter, the present invention will be described in detail.
(1) 투명 기판(1) transparent substrate
본 발명에 따른 반사방지성 다층코팅이 형성될 수 있는 투명 기판으로는 유리 기판 및 투명 플라스틱 기판(예컨대 폴리카보네이트(PC), 폴리메틸메타크릴레이트(PMMA) 소재 투명 기판)과 같이 투명한 재질로서 그 표면 상에 본 발명에 따른 반사방지성 다층코팅이 형성될 수 있는 것이면 제한 없이 사용가능하며, 바람직하게는 유리 기판이 사용된다. The transparent substrate on which the antireflective multilayer coating according to the present invention may be formed may be formed of a transparent material such as a glass substrate and a transparent plastic substrate (eg, a transparent substrate made of polycarbonate (PC) or polymethyl methacrylate (PMMA)). Any anti-reflective multilayer coating according to the invention on the surface can be used without limitation, preferably a glass substrate is used.
유리 기판의 경우 예컨대, 건축용 혹은 자동차용 소다라임 유리와 같은 통상의 유리와 태양전지용 저철분 무늬유리(low-iron patterned glass), 저철분 판유리( low-iron float glass), 투명전도막(Transparent Conductive Oxide, TCO) 유리 등을 제한 없이 사용할 수 있다. 또한, 필요에 따라 표면 결처리 (surface texture treatment) 되거나 강화 또는 부분강화된 유리를 사용할 수도 있다. In the case of glass substrates, for example, conventional glass such as architectural or automotive soda-lime glass, low-iron patterned glass for solar cells, low-iron float glass, and transparent conductive film Oxide, TCO) glass and the like can be used without limitation. In addition, it is also possible to use a surface texture treated, tempered or partially tempered glass as needed.
투명 기판의 두께에는 특별한 제한이 없으며, 사용목적에 따라 1mm ~ 8mm의 두께의 범위 내에서 자유롭게 선택될 수 있다 The thickness of the transparent substrate is not particularly limited, and may be freely selected within a range of 1 mm to 8 mm depending on the purpose of use.
(2) 고-굴절층(2) high-refractive layers
본 발명에 따른 반사방지성 다층코팅에 포함되는 고-굴절층은 1.9 ~ 2.5의 굴절률을 갖는다. 고-굴절층은 아연 산화물, 주석 산화물, 지르코늄 산화물, 아연-주석 산화물, 티타늄 산화물, 니오븀 산화물로부터 선택된 하나 이상의 금속 산화물을 포함할 수 있다. 또한, 고-굴절층은 규소 질화물 및 알루미늄 질화물로부터 선택된 하나 이상의 질화물을 추가로 포함할 수 있다. The high refractive index layer included in the antireflective multilayer coating according to the present invention has a refractive index of 1.9 to 2.5. The high-refractive layer may comprise one or more metal oxides selected from zinc oxide, tin oxide, zirconium oxide, zinc-tin oxide, titanium oxide, niobium oxide. In addition, the high-refractive layer may further comprise one or more nitrides selected from silicon nitride and aluminum nitride.
본 발명에 따른 반사방지성 다층코팅에 포함되는 각 고-굴절층의 두께는 5 ~ 40nm 범위 내에서 적절히 선택될 수 있다. 본 발명의 일 구체예인 4층 구성의 다층코팅에 있어서, 기판으로부터 순차적으로, 제1 고-굴절층의 두께는 바람직하게 5 ~ 40nm, 보다 바람직하게 10 ~ 30nm이고; 제2 고-굴절층의 두께는 바람직하게 5 ~ 40nm, 보다 바람직하게 10 ~ 30nm이다. 각 고-굴절층의 두께가 상기 범위를 만족시키면, 가시광 파장 범위뿐만 아니라 보다 넓은 적외선 영역까지 기판 투과도의 실질적인 증가와 함께 광대역(broadband) 반사방지 효과를 얻을 수 있고, 이에 따라 380nm ~ 1,100nm까지의 파장 범위에 걸쳐 고성능 반사방지 다층코팅을 얻을 수 있어 바람직하다.The thickness of each high-refractive layer included in the antireflective multilayer coating according to the present invention may be appropriately selected within the range of 5-40 nm. In the multi-layer coating of the four-layer constitution which is one embodiment of the present invention, the thickness of the first high-refractive layer is sequentially from the substrate, preferably 5 to 40 nm, more preferably 10 to 30 nm; The thickness of the second high-refractive layer is preferably 5-40 nm, more preferably 10-30 nm. If the thickness of each high-refractive layer satisfies the above range, broadband antireflection effect can be obtained with a substantial increase in substrate transmittance not only in the visible wavelength range but also in the wider infrared region, thus up to 380 nm to 1,100 nm. It is preferable to obtain a high performance antireflection multilayer coating over a wavelength range of.
(3) 저-굴절층(3) low refractive index layer
본 발명에 따른 반사방지성 다층코팅에 포함되는 저-굴절층은 1.3 ~ 1.6의 굴절률을 갖는다. 저-굴절층은 규소 산화물, 규소 옥시질화물, 규소 옥시탄화물 및 규소-알루미늄 혼합 산화물로부터 선택된 하나 이상의 산화물을 포함할 수 있다. 혼합 산화물의 경우 순수 규소 산화물(SiO2)에 비하여 내구성, 특히 내화학적인 특성을 향상시킬 수 있는 장점이 있으며, 규소와 알루미늄의 각각의 비율은 층의 굴절률을 지나치게 증가시키지 않으면서 내구성을 기대만큼 향상시키기 위해 적절히 조절될 수 있다.The low refractive index layer included in the antireflective multilayer coating according to the present invention has a refractive index of 1.3 to 1.6. The low-refractive layer may comprise one or more oxides selected from silicon oxides, silicon oxynitrides, silicon oxycarbide and silicon-aluminum mixed oxides. Mixed oxides have the advantage of improving durability, especially chemical resistance, compared to pure silicon oxide (SiO 2 ), and the ratio of silicon and aluminum is as high as expected for durability without excessively increasing the refractive index of the layer. It can be adjusted appropriately to improve.
본 발명에 따른 반사방지성 다층코팅에 포함되는 각 저-굴절층의 두께는 30 ~ 150nm 범위 내에서 적절히 선택될 수 있다. 본 발명의 일 구체예인 4층 구성의 다층코팅에 있어서, 기판으로부터 순차적으로, 제1 저-굴절층의 두께는 바람직하게 30 ~ 80nm, 보다 바람직하게 40 ~ 70nm이고; 제2 저-굴절층의 두께는 바람직하게 70 ~ 150nm, 보다 바람직하게 100 ~ 140nm이다. 각 저-굴절층의 두께가 상기 범위를 만족시키면, 가시광 파장 범위뿐만 아니라 보다 넓은 적외선 영역까지 기판 투과도의 실질적인 증가와 함께 광대역(broadband) 반사방지 효과를 얻을 수 있고, 이에 따라 380nm ~ 1,100nm까지의 파장 범위에 걸쳐 고성능 반사방지 다층코팅을 얻을 수 있어 바람직하다. The thickness of each of the low refractive index layers included in the antireflective multilayer coating according to the present invention may be appropriately selected within the range of 30 to 150 nm. In the multi-layer coating of the four-layer constitution, which is one embodiment of the present invention, the thickness of the first low-refractive layer is preferably from 30 to 80 nm, more preferably from 40 to 70 nm, sequentially from the substrate; The thickness of the second low-refractive layer is preferably 70 to 150 nm, more preferably 100 to 140 nm. If the thickness of each low-refractive layer satisfies the above range, a broadband antireflection effect can be obtained with a substantial increase in substrate transmittance not only in the visible wavelength range but also in the wider infrared region, and thus up to 380 nm to 1,100 nm. It is preferable to obtain a high performance antireflection multilayer coating over a wavelength range of.
(4) 다층코팅(4) multilayer coating
본 발명에 따르면, 상기한 바와 같은 투명 기판 상에 상기 고-굴절층 및 상기 저-굴절층을 교대하며 순차적으로 적층하여 4층의 반사방지성 다층코팅이 형성된다. According to the present invention, four layers of anti-reflective multilayer coatings are formed by alternately stacking the high-refractive layer and the low-refractive layer on the transparent substrate as described above.
본 발명의 바람직한 일 구체예에 따르면, 광대역에서 투과율을 높이기 위해 하기와 같은 층 구성을 연속적으로 갖는 반사방지성 다층코팅이 투명 기판 상에 순차적으로 형성된다:According to a preferred embodiment of the present invention, an antireflective multilayer coating having a layer structure as follows is sequentially formed on the transparent substrate in order to increase the transmittance at the broadband:
5 ~ 40nm 의 두께 및 1.9 ~ 2.5의 굴절률을 갖는 제1 고-굴절층First high-refractive layer having a thickness of 5-40 nm and a refractive index of 1.9-2.5
30 ~ 80nm 의 두께 및 1.3 ~ 1.6의 굴절률을 갖는 제1 저-굴절층First low-refractive layer having a thickness of 30 to 80 nm and a refractive index of 1.3 to 1.6
5 ~ 40nm 의 두께 및 1.9 ~ 2.5의 굴절률을 갖는 제2 고-굴절층Second high-refractive layer having a thickness of 5-40 nm and a refractive index of 1.9-2.5
70 ~ 150nm 의 두께 및 1.3 ~ 1.6의 굴절률을 갖는 제2 저-굴절층Second low-refractive layer having a thickness of 70 to 150 nm and a refractive index of 1.3 to 1.6
또한, 상기와 같은 4층구조의 다층코팅은 바람직하게는 다음과 같은 층 구성 물질들을 포함한다:In addition, the multilayer coating of the above four-layer structure preferably includes the following layered materials:
기판으로부터 순차적으로 Sequentially from the substrate
- 티타늄산화물/규소산화물/ 티타늄산화물/규소산화물, 또는Titanium oxide / silicon oxide / titanium oxide / silicon oxide, or
- 티타늄산화물/규소알루미늄산화물/티타늄산화물/규소알루미늄산화물 -Titanium oxide / silicon aluminum oxide / titanium oxide / silicon aluminum oxide
(여기서 규소알루미늄산화물은 알루미늄-규소 혼합 산화물에 해당하며, 이 때 알루미늄 대 규소의 사용비에는 특별한 제한이 없으며, 예컨대 알루미늄-규소 혼합 산화물 내 알루미늄 함량 1~20중량%의 범위 내에서 적절히 선택될 수 있다.) (Here, silicon aluminum oxide corresponds to aluminum-silicon mixed oxide, and there is no particular limitation on the use ratio of aluminum to silicon, for example, it may be appropriately selected within the range of 1 to 20% by weight of aluminum in the aluminum-silicon mixed oxide. Can be.)
종래의 다층 코팅 반사 방지막은 고굴절율 물질의 총두께가 100~150nm에 이를 정도로 두꺼워서 제품 생산 속도가 느리고, 제품의 원가가 상승하는 단점이 있었지만, 본 발명에서는 고굴절율 물질의 총 두께를 80nm 이하로 감소시키면서도 우수한 반사방지 성능을 나타낼 수 있어서, 생산성을 증대시키고 원가를 낮출 수 있다. 또한, 대한민국 공개특허 제10-2008-0089351호에 개시된 제3층과 같이 두께가 140~160nm으로 두꺼우면 민감성(sensitivity)이 지나치게 높아져 품질 공정 관리가 매우 어렵게 된다. 이에 대한 참고로서 대한민국 공개특허 제10-2008-0089351호에 개시된 바와 같은 두께 및 굴절율의 4층코팅에 대해 각 코팅층별로 상대적 민감성(relative sensitivity)을 나타낸 박막 시뮬레이션 결과 그래프를 도 3에 나타내었다. 여기서 상대적 민감성이란 막두께의 변화에 따라 코팅유리의 광학 물성이 얼마나 영향을 받는지를 상대적으로 나타내주는 척도로서 그 값이 낮을수록 코팅유리의 광학 물성에 미치는 영향이 적다. 도 3을 참고하면, 제3층의 상대적 민감성이 800 이상으로 너무 높아 코팅유리의 광학 물성에 미치는 영향이 지나치게 커지고, 이는 코팅 유리 생산시 품질 및 공정 관리가 지극히 어려움을 의미한다. 반면 도 4는 본 발명에 따른 4층코팅의 각 코팅층별 상대적 광학 민감성(sensitivity)을 나타낸 박막 시뮬레이션 결과 그래프로서, 이에 따르면 제3층의 상대적 민감성이 12 이하로 낮음을 알 수 있다. 이는, 본 발명의 4층코팅을 적용한 유리는 생산시 품질 및 공정 관리가 상기 종래 기술 대비 지극히 용이함을 의미한다. 즉, 본 발명은 고굴절층-저굴절층-고굴절층-저굴절층의 4층코팅에 있어서 제3층의 두께가 종래와 같이 두꺼우면 상대적 민감성이 너무 높아지는 문제점을 발견하여, 이를 해결하고자 굴절률이 1.9~2.5인 고굴절율층을 얇은 두께(예컨대 5 ~ 40nm)로 하여 제3층으로 배치함으로써 목적하는 광학 물성을 달성하면서 동시에 상대적 민감성을 12 이하로 크게 낮출 수 있는 것이다.Conventional multilayer coating antireflection film has a disadvantage that the product thickness is slow and the cost of the product is increased because the total thickness of the high refractive index material reaches 100 ~ 150nm, but in the present invention, the total thickness of the high refractive index material to 80nm or less Excellent anti-reflective performance can be achieved while reducing, thereby increasing productivity and lowering cost. In addition, as the third layer disclosed in Korean Patent Laid-Open No. 10-2008-0089351, when the thickness is 140 to 160 nm thick, the sensitivity is too high, making quality process management very difficult. As a reference, a thin film simulation result graph showing relative sensitivity for each coating layer for the four-layer coating of thickness and refractive index as disclosed in Korean Patent Laid-Open Publication No. 10-2008-0089351 is shown in FIG. 3. Here, the relative sensitivity is a measure of relative influence of the optical properties of the coated glass according to the change in film thickness. The lower the value, the less the influence on the optical properties of the coated glass. Referring to FIG. 3, the relative sensitivity of the third layer is so high as 800 or more that the influence on the optical properties of the coated glass becomes too large, which means that the quality and process control of the coated glass is extremely difficult. On the other hand, Figure 4 is a thin film simulation result graph showing the relative optical sensitivity (sensitivity) for each coating layer of the four-layer coating according to the present invention, it can be seen that the relative sensitivity of the third layer is less than 12. This means that the glass to which the four-layer coating of the present invention is applied is extremely easy in production and process control compared to the prior art. That is, the present invention, in the four-layer coating of the high refractive layer-low refractive layer-high refractive layer-low refractive layer finds a problem that the relative sensitivity becomes too high if the thickness of the third layer is thick as conventional, and the refractive index is to solve this problem By arranging the high refractive index layer of 1.9 to 2.5 as the third layer with a thin thickness (for example, 5 to 40 nm), it is possible to achieve the desired optical properties while significantly lowering the relative sensitivity to 12 or less.
본 발명에 따른 반사방지성 다층코팅을 표면상에 갖는 투명 기판은, 바람직하게는 8mm까지의 두께에 대하여, 380~1,100 nm에서 바람직하게 92% 이상의 평균 투과율을 나타낸다. 또한, 바람직하게는 380~1,100nm 범위의 파장에서는 다층코팅 형성전 기판보다 투과율이 높고, 1,100nm ~2,500nm 범위의 파장에서는 다층코팅 형성전 기판보다 투과율이 낮은 선택적 투과특성을 나타낸다.The transparent substrate having the antireflective multilayer coating according to the present invention on the surface preferably exhibits an average transmittance of 92% or more at 380 to 1,100 nm, with a thickness of preferably up to 8 mm. In addition, preferably in the wavelength range of 380 ~ 1,100nm, the transmittance is higher than the substrate before forming the multilayer coating, and in the wavelength range of 1,100nm ~ 2,500nm, the transmittance is lower than that of the substrate before forming the multilayer coating.
(5) 다층코팅 투명 기판 제조방법 (5) Multi-layer coating transparent substrate manufacturing method
본 발명의 다른 측면에 따르면, (1) 투명 기판 상에 1.9 ~ 2.5의 굴절률을 갖는 제1 고-굴절층을 형성하는 단계, (2) 상기 제1 고-굴절층 상에 1.3 ~ 1.6의 굴절률을 갖는 제1 저-굴절층을 형성하는 단계, (3) 상기 제1 저-굴절층 상에 1.9 ~ 2.5의 굴절률을 갖는 제2 고-굴절층을 형성하는 단계, (4) 상기 제2 고-굴절층 상에 1.3 ~ 1.6의 굴절률을 갖는 제2 저-굴절층을 형성하는 단계를 포함하는, 광대역 반사방지성 태양전지용 투명 기판의 제조방법이 제공된다.According to another aspect of the invention, (1) forming a first high-refractive layer having a refractive index of 1.9 to 2.5 on the transparent substrate, (2) a refractive index of 1.3 to 1.6 on the first high-refractive layer Forming a first low-refractive layer having a refractive index, (3) forming a second high-refractive layer having a refractive index of 1.9 to 2.5 on the first low-refractive layer, and (4) the second high refractive index layer A method of manufacturing a transparent substrate for a broadband antireflection solar cell is provided, comprising forming a second low-refractive layer having a refractive index of 1.3 to 1.6 on the refractive layer.
투명 기판 상에 상기 각 층을 순차적으로 형성하는 방법에는 특별한 제한이 없으며, 물리적 기상 증착법(Physical Vapor Deposition, PVD), 화학적 기상 증착법(Chemical Vapor Deposition, CVD), 졸-겔(sol-gel) 법을 비롯하여 통상 알려진 박막코팅법을 활용할 수 있다. 본 발명의 바람직한 일 구체예에 따르면, 마그네트론 스퍼터링 방식에 의해 연속적으로 모든 층을 증착할 수 있다. 이 방식은 특히 대형 기판의 제품에 대해 적합하며, 여기에서는, 산소의 존재 하에 해당 금속의 반응 스퍼터링에 의해 산화물 층을 증착하고, 질소의 존재 하에 질화물 층을 증착할 수 있다. 또한 SiO2 또는 Si3N4층을 형성하고자 타겟에 전도성을 충분하게 해주기 위해서 알루미늄과 같은 금속으로 미량 도핑된 규소 타깃을 사용하여 증착할 수도 있다.There is no particular limitation on the method of sequentially forming each of the layers on the transparent substrate, and physical vapor deposition (PVD), chemical vapor deposition (CVD), and sol-gel method In addition, it is possible to utilize a commonly known thin film coating method. According to one preferred embodiment of the present invention, all layers can be deposited continuously by a magnetron sputtering method. This approach is particularly suitable for products of large substrates, where the oxide layer can be deposited by the reactive sputtering of the metal in the presence of oxygen and the nitride layer in the presence of nitrogen. It may also be deposited using a silicon target that is microdoped with a metal such as aluminum to provide sufficient conductivity to the target to form a SiO 2 or Si 3 N 4 layer.
(6) 태양전지 모듈(6) solar cell module
본 발명의 또 다른 측면에 따르면, 본 발명의 광대역 반사방지성 태양전지용 투명 기판을 최외각에 설치한 것을 특징으로 하는 태양전지 모듈이 제공된다.According to another aspect of the invention, there is provided a solar cell module characterized in that the transparent substrate for a wideband antireflection solar cell of the present invention is installed on the outermost.
본 발명의 광대역 반사방지성 태양전지용 투명 기판이 적용가능한 태양전지 모듈의 종류에는 특별한 제한이 없으며, 결정질 실리콘, 비정질 실리콘 박막, 염료감응형 태양전지 (Dye Sensitized Solar Cell, DSSC), CIGS(CuInGaSe) 형, CdTe 형, GaAs 형 및 III-V족 화합물 반도체 형 등의 태양전지에 모두 적용 가능하다.There is no particular limitation on the type of solar cell module to which the transparent substrate for the broadband antireflection solar cell of the present invention is applicable, and the crystalline silicon, amorphous silicon thin film, dye-sensitized solar cell (DSSC), CIGS (CuInGaSe) Applicable to all solar cells such as the type, the CdTe type, the GaAs type and the III-V compound semiconductor type.
본 발명의 일 구체예에 따르면, 본 발명의 광대역 반사방지성 태양전지용 투명 기판이 적용된 태양전지 모듈은 그 적용 전에 비하여 적어도 2~5%의 효율의 증가를 나타낸다. According to one embodiment of the present invention, the solar cell module to which the transparent substrate for wideband antireflection solar cell of the present invention is applied exhibits an increase in efficiency of at least 2 to 5% compared to before application thereof.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 이 실시예에 의하여 본 발명의 보호범위가 제한되는 것은 결코 아니다.Hereinafter, the present invention will be described in more detail by way of examples. However, the scope of the present invention is not limited by this embodiment.
[실시예][Example]
실시예 1Example 1
3.2mm 두께의 저철분 판유리 위에 하기 표 1에 나타낸 구성의 4층 반사방지코팅을 형성하였다. 각 코팅층의 형성은 마그네트론 스퍼터링 설비를 사용하여 수행되었다. A four-layer antireflective coating of the configuration shown in Table 1 was formed on the 3.2 mm thick low iron plate glass. The formation of each coating layer was performed using a magnetron sputtering facility.
증착 조건은 분위기 압력 3 내지 5 mtorr, 파워 1kw 에서 Ti 메탈 타겟과 SiAl 타겟을 사용하여 실시하였다. Deposition conditions were carried out using a Ti metal target and a SiAl target at an atmospheric pressure of 3 to 5 mtorr and a power of 1 kw.
제조된 다층코팅 유리에 대해 380~1,100nm까지의 투과율을 분광투과율 측정기(모델명 Lambda 950, Perkin Elmer社)로 측정하였고, 그 결과값에 ISO 9050 규격에 따라 AM1.5에 해당하는 중가 계수(weighting function)를 곱한 평균값을 하기 표 3에 나타내었다. The transmittance from 380 to 1100 nm was measured with a spectrophotometer (Model Lambda 950, Perkin Elmer) for the manufactured multilayer coated glass, and the weighting factor (weighting) corresponding to AM1.5 according to the ISO 9050 standard was measured. The average value multiplied by the function) is shown in Table 3 below.
실시예 2Example 2
3.2mm 두께의 저철분 판유리 위에 하기 표 2에 나타낸 구성의 4층 반사방지코팅을 형성하였다. 각 코팅층의 형성은 마그네트론 스퍼터링 설비를 사용하여 수행되었다. A four-layer antireflective coating of the configuration shown in Table 2 was formed on the 3.2 mm thick low iron plate glass. The formation of each coating layer was performed using a magnetron sputtering facility.
증착 조건은 분위기 압력 3 내지 5 mtorr, 파워 1kw 에서 NbOx 세라믹 타겟과 SiAl 타겟을 사용하여 실시하였다. Deposition conditions were carried out using an NbOx ceramic target and a SiAl target at an atmospheric pressure of 3 to 5 mtorr and a power of 1 kw.
제조된 다층코팅 유리에 대해 380~1,100nm까지의 투과율을 분광투과율 측정기(모델명 Lambda 950, Perkin Elmer社)로 측정하였고, 그 결과값에 ISO 9050 규격에 따라 AM1.5에 해당하는 중가 계수(weighting function)를 곱한 평균값을 하기 표 3에 나타내었다. The transmittance from 380 to 1100 nm was measured with a spectrophotometer (Model Lambda 950, Perkin Elmer) for the manufactured multilayer coated glass, and the weighting factor (weighting) corresponding to AM1.5 according to the ISO 9050 standard was measured. The average value multiplied by the function) is shown in Table 3 below.
비교예Comparative example
실시예에서 사용된, 코팅되지 않은 (즉, 반사방지 다층코팅이 없는) 3.2mm 두께의 저철분 판유리에 대해 380~1,100nm까지의 투과율을 분광투과율 측정기(모델명 Lambda 950, Perkin Elmer社)로 측정하였고, 그 결과값에 ISO 9050 규격에 따라 AM1.5에 해당하는 중가 계수를 곱한 평균값을 하기 표 3에 나타내었다.
The transmittance from 380 to 1,100 nm was measured with a spectrophotometer (Model Lambda 950, Perkin Elmer) for the 3.2 mm thick low iron plate glass uncoated (ie without antireflective multilayer coating) used in the examples. The average value obtained by multiplying the resultant weight coefficient corresponding to AM1.5 according to ISO 9050 is shown in Table 3 below.
[표 1][Table 1]
※ 굴절률 값은 @550nm 기준
※ Refractive index value is based on @ 550nm
[표 2][Table 2]
※ 굴절률 값은 @550nm 기준
※ Refractive index value is based on @ 550nm
[표 3] [Table 3]
또한, 실시예 1, 2및 비교예 유리의 파장대별 투과율을 도 2에 나타내었다.In addition, the transmittance | permeability by wavelength band of Example 1, 2, and the comparative example glass is shown in FIG.
Claims (12)
5 ~ 40nm 의 두께 및 1.9 ~ 2.5의 굴절률을 갖는 제1 고-굴절층;
30 ~ 80nm 의 두께 및 1.3 ~ 1.6의 굴절률을 갖는 제1 저-굴절층;
5 ~ 40nm 의 두께 및 1.9 ~ 2.5의 굴절률을 갖는 제2 고-굴절층; 및
70 ~ 150nm 의 두께 및 1.3 ~ 1.6의 굴절률을 갖는 제2 저-굴절층.The transparent substrate for a broadband antireflection solar cell according to claim 1, having the following multilayer coating formed sequentially from the surface:
A first high-refractive layer having a thickness of 5-40 nm and a refractive index of 1.9-2.5;
A first low-refractive layer having a thickness of 30 to 80 nm and a refractive index of 1.3 to 1.6;
A second high-refractive layer having a thickness of 5-40 nm and a refractive index of 1.9-2.5; And
A second low refractive index layer having a thickness of 70 to 150 nm and a refractive index of 1.3 to 1.6.
(2) 상기 제1 고-굴절층 상에 1.3 ~ 1.6의 굴절률을 갖는 제1 저-굴절층을 형성하는 단계,
(3) 상기 제1 저-굴절층 상에 1.9 ~ 2.5의 굴절률을 갖는 제2 고-굴절층을 형성하는 단계 및
(4) 상기 제2 고-굴절층 상에 1.3 ~ 1.6의 굴절률을 갖는 제2 저-굴절층을 형성하는 단계를 포함하는,
광대역 반사방지성 태양전지용 투명 기판의 제조방법.(1) forming a first high-refractive layer having a refractive index of 1.9 to 2.5 on the transparent substrate,
(2) forming a first low refractive index layer having a refractive index of 1.3 to 1.6 on the first high refractive index layer,
(3) forming a second high refractive index layer having a refractive index of 1.9 to 2.5 on the first low refractive index layer;
(4) forming a second low-refractive layer having a refractive index of 1.3 to 1.6 on the second high-refractive layer,
Method of manufacturing a transparent substrate for a broadband antireflection solar cell.
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