KR20240043564A - A porous monolithic AgAu layer and Deep Metal-Assisted Chemical Etching Process for Neutral-colored Transparent Silicon - Google Patents
A porous monolithic AgAu layer and Deep Metal-Assisted Chemical Etching Process for Neutral-colored Transparent Silicon Download PDFInfo
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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
- H01L31/0248—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
- H01L31/0352—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035272—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
- H01L31/035281—Shape of the body
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
- H01L21/30608—Anisotropic liquid etching
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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
- H01L31/0248—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
- H01L31/0264—Inorganic materials
- H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic System
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
Abstract
본 발명은 습식 식각시 실리콘 기판 상에 증착되는 다공성 모놀리틱 AgAu 촉매 층, 이를 이용한 반투명 실리콘의 금속 촉매 화학 식각 방법 및 이를 포함하는 태양전지에 관한 것이다. The present invention relates to a porous monolithic AgAu catalyst layer deposited on a silicon substrate during wet etching, a metal-catalyzed chemical etching method for translucent silicon using the same, and a solar cell including the same.
Description
본 발명은 습식 식각시 실리콘 기판 상에 증착되는 다공성 모놀리틱 AgAu 촉매 층, 이를 이용한 반투명 실리콘의 금속 촉매 화학 식각 방법 및 이를 포함하는 태양전지에 관한 것이다. The present invention relates to a porous monolithic AgAu catalyst layer deposited on a silicon substrate during wet etching, a metal-catalyzed chemical etching method for translucent silicon using the same, and a solar cell including the same.
투명 태양전지(TPV)는 건물 창문 및 차량과 같은 다양한 응용 분야에 적용될 수 있는 신흥 장치이다. 현재, 다양한 유형의 TPV가 개발되었지만 대부분 낮은 전력 변환 효율(PCE) 또는 낮은 안정성으로 어려움을 겪고 있다.Transparent solar cells (TPVs) are emerging devices that can be applied to a variety of applications such as building windows and vehicles. Currently, various types of TPVs have been developed, but most suffer from low power conversion efficiency (PCE) or low stability.
최근 이러한 문제점을 극복하기 위해 12.2%의 높은 PCE(평균 가시광선 투과율 20%)와 안정성을 가지는 중성색(neutral-colored) 결정질 실리콘 기반 TPV(c-Si TPV)가 개발되었다. 상기 c-Si TPV의 경우, c-Si에 건식 식각(Dry etching) 공정인 심층 반응성 이온 에칭(deep reactive ion etching, DRIE)를 통해 마이크로 원형 홀 모양의 광투과창(LTW)을 제작하여 모든 가시 파장(350-750 nm)의 투과율을 생성할 수 있다. 또한, LTW 사이의 간격을 정밀하게 조절함으로써 사람의 눈으로 LTW 패턴을 인식하지 못하게 하여 무채색 유리처럼 보이도록 할 수 있다.Recently, to overcome these problems, a neutral-colored crystalline silicon-based TPV (c-Si TPV) with high PCE of 12.2% (average visible light transmittance of 20%) and stability was developed. In the case of the c-Si TPV, a micro circular hole-shaped light transmission window (LTW) is manufactured on c-Si through deep reactive ion etching (DRIE), a dry etching process, to provide all visible areas. Transmittance of wavelengths (350-750 nm) can be produced. Additionally, by precisely controlling the spacing between LTWs, the LTW pattern can be made unrecognizable to the human eye and appears like colorless glass.
그러나, 상기 DRIE 공정은 높은 제조 비용을 필요로 하고, 필연적으로 LTW 측벽의 플라즈마 유발 표면 손상이 발생되는 문제점이 있었고, 이는 태양전지 상용화에 문제가 되었다.However, the DRIE process requires high manufacturing costs and inevitably causes plasma-induced surface damage to the sidewall of the LTW, which poses a problem in commercialization of solar cells.
이에, 상기 DRIE 대신에 c-Si와 에칭액의 금속 촉매(예: Ag 및 Au) 사이의 계면에서 산화환원 반응을 사용하는 습식 식각(Wet etching) 공정인 금속 보조 화학 에칭(metal-assisted chemical etching, MACE)은 단순성과 비용 효율성으로 인해 큰 주목을 받고 있다. 상기 MACE는 실리콘 기판/금속 촉매/식각액(Etchant, HF+H2O2) 간의 전하전달반응을 통해 실리콘을 SiF6 -로 산화시키는 과정으로, 건식 식각 공정의 고비용 및 효율 저하 문제를 해결할 수 있는 적합한 방법이다.Therefore, instead of the DRIE, metal-assisted chemical etching, which is a wet etching process that uses a redox reaction at the interface between c-Si and the metal catalyst of the etchant (e.g. Ag and Au), is used. MACE) is attracting great attention due to its simplicity and cost-effectiveness. The MACE is a process of oxidizing silicon to SiF 6 - through a charge transfer reaction between the silicon substrate/metal catalyst/etchant (HF+H 2 O 2 ), which can solve the problems of high cost and low efficiency of the dry etching process. This is an appropriate method.
그러나, 상기 MACE는 상기 금속 촉매가 무전해 증착에 의해 나노 입자에 증착되어 무작위로 작용(즉, 불균일한 식각)되어 식각된 c-Si에 많은 결함이 발생되는 문제가 있었다. However, the MACE had a problem in that the metal catalyst was deposited on nanoparticles by electroless deposition and acted randomly (i.e., non-uniform etching), resulting in many defects in the etched c-Si.
구체적으로, 기존 입자 형태(particle-form)로 성장한 Ag 금속 촉매는 습식 식각 공정 중 불규칙적으로 이동하여, 특히 깊은 두께(200 um)의 실리콘 식각의 불균일성을 야기할 수 있고, 에천트 환경에서 화학적 안정성이 낮아 촉매 구조 붕괴가 일어날 수 있다.Specifically, the Ag metal catalyst grown in the existing particle-form moves irregularly during the wet etching process, which can cause non-uniformity in etching silicon, especially at deep thicknesses (200 um), and has poor chemical stability in the etchant environment. If this is low, catalyst structure collapse may occur.
결과적으로 식각하고자 하는 원형 홀의 균일성 저하 및 결함(Defect)를 만들어 반투명 실리콘 기판 퀄리티 및 이의 태양전지 효율 저하를 가져올 수 있다.As a result, the uniformity of the circular hole to be etched may decrease and defects may be created, which may reduce the quality of the translucent silicon substrate and its solar cell efficiency.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로, The present invention is intended to solve the problems of the prior art as described above,
본 발명의 목적은 균일한 습식 식각을 위한 다공성 모놀리틱(monolithic) AgAu 촉매를 개발하여 반투명 실리콘 기판 및 이를 포함하는 태양전지를 제공하기 위한 것이다.The purpose of the present invention is to develop a porous monolithic AgAu catalyst for uniform wet etching and to provide a translucent silicon substrate and a solar cell including the same.
한편으로, 본 발명은On the one hand, the present invention
습식 식각시 실리콘 기판 상에 증착되는 촉매에 있어서,In the catalyst deposited on the silicon substrate during wet etching,
양극성(Amphiphilic) 물질을 이용하여 Ag 전구체 용액으로부터 환원된 다공성 Ag 층; 및 Amphiphilic A porous Ag layer reduced from an Ag precursor solution using a material; and
상기 다공성 Ag 층의 외부 표면 상에 패시베이션되는 Au 층;을 포함하는 것을 특징으로 하는, 바이메탈릭 특성을 가지는 다공성 모놀리틱 AgAu 촉매 층을 제공한다.A porous monolithic AgAu catalyst layer having bimetallic properties is provided, comprising an Au layer passivated on the outer surface of the porous Ag layer.
본 발명에 따른 다공성 모놀리틱 AgAu 촉매는 식각액(에천트)의 침투를 고려함과 동시 균일한 움직임이 가능한 다공성 단일 구조체 형태로 제조되어 200 um 이상의 깊은 두께의 실리콘 기판에서 균일하고 연속적인 습식 식각을 구현할 수 있으므로 원형 홀의 균일성 저하 및 결함(Defect) 문제를 해결할 수 있다.The porous monolithic AgAu catalyst according to the present invention is manufactured in the form of a single porous structure capable of uniform movement while taking into account the penetration of the etchant, enabling uniform and continuous wet etching on a silicon substrate with a thickness of 200 um or more. Since it can be implemented, the problem of poor uniformity and defects in circular holes can be solved.
또한, 본 발명에 따른 다공성 모놀리틱 AgAu 촉매를 이용하여 불균일한 식각을 억제시켜 고품질 반투명 실리콘 기판을 제조할 수 있으며, 이는 태양전지의 효율을 향상시킬 수 있다. In addition, using the porous monolithic AgAu catalyst according to the present invention, high-quality translucent silicon substrates can be manufactured by suppressing non-uniform etching, which can improve the efficiency of solar cells.
도 1은 본 발명의 일 실시예에 따른 습식 식각을 통한 반투명 실리콘 기판 제작 과정 및 촉매에 따른 식각 균일성 개선 효과를 나타낸 도면이다.
도 2는 본 발명의 일 실시예에 따른 무전해 증착(Electroless deposition) 과정 및 각 과정에서 나타나는 특성들을 나타낸 도면이다((a) Ag 촉매의 Electroless deposition 과정. (b) Ag 촉매 성장 제어를 위한 기능적 양극성 물질 및 구조에 따른 특성. (c) 기능적 양극성 물질 도입에 따른 Ag+이온과 실리콘 표면 간의 상호작용 증가. (d) 기능적 양극성 물질 후보군 도입 후 Ag 촉매 구조체 분석).
도 3은 본 발명의 일 실시예에 따른 AN의 기능에 의한 다공성 단일체 Ag 층의 형성 결과를 나타낸 도면이다.
도 4는 본 발명의 일 실시예에 따른 다공성 모놀리틱 AgAu 촉매 층의 Galvanic replacement 반응을 통한 패시베이션(캡슐화) 공정(a) 및 다공성 모놀리틱 원소분석 결과(b-d)를 나타낸 도면이다.
도 5는 본 발명의 일 실시예에 따라 제조되는 반투명 실리콘 태양전지 및 실리콘 기판과 태양전지의 효율을 나타낸 도면이다. Figure 1 is a diagram showing the process of manufacturing a translucent silicon substrate through wet etching according to an embodiment of the present invention and the effect of improving etching uniformity according to the catalyst.
Figure 2 is a diagram showing the electroless deposition process and the characteristics appearing in each process according to an embodiment of the present invention ((a) Electroless deposition process of Ag catalyst. (b) Functional method for controlling Ag catalyst growth Characteristics according to anodic materials and structures (c) Increased interaction between Ag + ions and silicon surface due to introduction of functional anodic materials (d) Analysis of Ag catalyst structure after introduction of functional anodic material candidates)
Figure 3 is a diagram showing the results of forming a porous monolithic Ag layer by the function of AN according to an embodiment of the present invention.
Figure 4 is a diagram showing the passivation (encapsulation) process through galvanic replacement reaction of a porous monolithic AgAu catalyst layer (a) and the results of porous monolithic element analysis (bd) according to an embodiment of the present invention.
Figure 5 is a diagram showing the efficiency of a translucent silicon solar cell, silicon substrate, and solar cell manufactured according to an embodiment of the present invention.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 일 실시형태에 따른 바이메탈릭 특성을 가지는 다공성 모놀리틱 AgAu 촉매 층은, A porous monolithic AgAu catalyst layer with bimetallic properties according to an embodiment of the present invention,
습식 식각시 실리콘 기판 상에 증착되는 촉매에 있어서,In the catalyst deposited on the silicon substrate during wet etching,
양극성(Amphiphilic) 물질을 이용하여 Ag 전구체 용액으로부터 환원된 다공성 Ag 층; 및 Amphiphilic A porous Ag layer reduced from an Ag precursor solution using a material; and
상기 다공성 Ag 층의 외부 표면 상에 패시베이션되는 Au 층;을 포함하는 것을 특징으로 한다.An Au layer passivated on the outer surface of the porous Ag layer.
또한, 본 발명의 일 실시형태에 따른 반투명 실리콘의 금속 촉매 화학 식각 방법은,In addition, the metal-catalyzed chemical etching method of translucent silicon according to an embodiment of the present invention includes:
금속 촉매 화학 식각(metal-assisted chemical etching)에 의해 실리콘 기판을 식각하는 방법에 있어서,In a method of etching a silicon substrate by metal-assisted chemical etching,
실리콘 기판 상에 상기 다공성 모놀리틱 AgAu 촉매 층을 증착하는 단계; 및Depositing the porous monolithic AgAu catalyst layer on a silicon substrate; and
상기 다공성 모놀리틱 AgAu 촉매 층이 증착된 실리콘 기판에 식각액을 반응시켜 식각하는 단계;를 포함하고,A step of etching the silicon substrate on which the porous monolithic AgAu catalyst layer is deposited by reacting an etchant,
상기 다공성 모놀리틱 AgAu 촉매 층은The porous monolithic AgAu catalyst layer is
Ag 전구체 용액에 아세토니트릴(AN)을 도입하여 Ag+ 이온과 상기 실리콘의 표면 간 상호 작용을 제어되어 환원된 다공성 Ag 층에 갈바닉 교체를 통해 상기 다공성 Ag 층의 외부 표면을 Au로 패시베이션하여 제조되는 것을 특징으로 한다.It is manufactured by passivating the outer surface of the porous Ag layer with Au through galvanic replacement in the reduced porous Ag layer by controlling the interaction between Ag + ions and the surface of the silicon by introducing acetonitrile (AN) into the Ag precursor solution. It is characterized by
본 발명은 기존 입자 형태의 Ag로 인해 불균일하고 불안정한 식각 공정을 i) 구조적 개선 및 ii) 성분적 개선을 통해 균일하고 연속적인 습식 식각을 구현하고 고품질의 반투명 실리콘 기판을 제조할 수 있는 것을 특징으로 한다.The present invention is characterized by realizing uniform and continuous wet etching and manufacturing high-quality translucent silicon substrates through i) structural improvement and ii) component improvement in the non-uniform and unstable etching process due to the existing particle form of Ag. do.
구체적으로, 본 발명에 따른 다공성 모놀리식 AgAu 층은 i) 아세토니트릴(AN)을 사용하여 Ag를 무전해 증착하는 동안 Ag 이온과 c-Si 표면 사이의 상호 작용을 조절하고, ii) Au 요소를 사용한 순차적 패시베이션에 의해 제조될 수 있다.Specifically, the porous monolithic AgAu layer according to the present invention i) regulates the interaction between Ag ions and the c-Si surface during electroless deposition of Ag using acetonitrile (AN), and ii) Au elements It can be manufactured by sequential passivation using .
i) 구조적 개선i) Structural improvements
본 발명의 일 실시형태에서, 상기 Ag 이온과 결정 실리콘(c-Si) 사이의 상호 작용을 개선하고 상기 Ag의 환원을 촉진하기 위해 상기 입자 형태의 Ag에 기능적 양극성(Amphiphilic) 물질인 아세토나이트릴(Acetonitrile, AN)을 계면활성제로서 도입함으로써 다공성 Ag 층(layer) 형태로 개선하여 불균일한 식각을 억제할 수 있다.In one embodiment of the present invention, acetonitrile, a functional amphiphilic material, is added to Ag in particle form to improve the interaction between Ag ions and crystalline silicon (c-Si) and promote reduction of Ag. By introducing (Acetonitrile, AN) as a surfactant, uneven etching can be suppressed by improving the form of a porous Ag layer.
금속 촉매의 무전해 증착(Electroless deposition)은 외부 바이어스 없이 금속 촉매 이온의 화학적 환원에 의해 이루어진다. 무전해 증착을 통한 c-Si 표면의 Ag 성장은 다음과 같다.Electroless deposition of metal catalysts is achieved by chemical reduction of metal catalyst ions without external bias. Ag growth on c-Si surface through electroless deposition is as follows.
도 2의 (a)는 Ag 촉매의 무전해 증착 과정을 나타낸 것으로, Ag+이온이 실리콘의 Valence band로부터 전자를 받아 환원되어 성장이 이루어진다. 그러나. 실리콘 표면은 높은 소수성(Hydrophilic)을 띄므로, Ag 전구체 용액(Aqueous 10mM AgNO3 solution)과 친화력이 떨어지게 된다(도 2의 (c) 참조). 그 결과, Ag+이온과 실리콘 표면 간의 상호 작용을 저해하여 국부적인 Ag+의 환원만이 일어나 입자 형태(Particle-form)의 구조체 촉매가 형성되고, 이 과정에서, c-Si과의 농도차이로 인해 부산물로 H2 기포가 발생한다. 즉, Ag 입자가 개별적으로 작용하여 불균일한 식각을 유발하여 식각된 홀에 많은 결함을 유발하여 c-Si TPV의 성능을 저하시킨다.Figure 2 (a) shows the electroless deposition process of Ag catalyst, in which Ag + ions receive electrons from the valence band of silicon and are reduced to achieve growth. however. Since the silicon surface is highly hydrophobic, its affinity with the Ag precursor solution (Aqueous 10mM AgNO 3 solution) is low (see Figure 2 (c)). As a result, the interaction between Ag + ions and the silicon surface is inhibited, and only local reduction of Ag + occurs, forming a particle-form structural catalyst. In this process, the concentration difference with c-Si causes As a result, H2 bubbles are generated as a by-product. In other words, Ag particles act individually and cause uneven etching, causing many defects in the etched holes and deteriorating the performance of c-Si TPV.
이 입자 형태의 Ag는 습식 식각 반응에 필요한 에천트의 침투는 용이하나, 불균일하게 움직이기 때문에 200 um 높이의 균일한 원형 홀을 식각하기에는 부적합하다.Ag in this particle form is easily penetrated by the etchant required for a wet etching reaction, but moves unevenly, making it unsuitable for etching a uniform circular hole with a height of 200 um.
따라서, 에천트의 침투를 고려함과 동시에 균일한 움직임이 가능도록 Ag+이온과 실리콘 표면의 상호 작용을 높일 수 있는 아세토나이트릴(Acetonitrile, AN)을 Ag 전구체 용액에 도입할 수 있다(도 2의 (b) 및 (c) 참조). 상기 AN은 c-Si 표면과 AN의 소수성-소수성 상호작용을 통해 c-Si 표면 위에 존재히고, Ag+는 AN과의 배위 결합으로 인해 c-Si 표면에 유리하게 접근하여 Ag+를 효과적으로 환원시키고 다공성 모놀리식 구조를 형성한다.Therefore, acetonitrile (AN), which can increase the interaction between Ag + ions and the silicon surface to enable uniform movement while considering penetration of the etchant, can be introduced into the Ag precursor solution (see Figure 2). (see (b) and (c)). The AN exists on the c-Si surface through the hydrophobic-hydrophobic interaction between the c-Si surface and AN, and Ag + favorably approaches the c-Si surface due to the coordination bond with AN, effectively reducing Ag + and Forms a porous monolithic structure.
ii) 성분적 개선ii) Ingredient improvement
본 발명의 일 실시형태에서, 상기 다공성 Ag 층의 외부 표면을 Au로 패시베이션(passivation)하여 바이메탈 특성을 부여하는 갈바닉 교체를 통해 다공성 모놀리틱 AgAu 층 형태로 성분을 개선시킬 수 있다.In one embodiment of the present invention, the component can be improved in the form of a porous monolithic AgAu layer through galvanic replacement, which imparts bimetallic properties by passivation of the outer surface of the porous Ag layer with Au.
습식 식각 반응은 H2O2로부터 정공전하(hole)을 받은 Ag 촉매가 실리콘을 SiF6 -형태로 산화시키면서 진행된다. 그러나, Ag 또한 정공전하에 의해 이온화가 일어나 구조적 붕괴가 일어나고, 습식 식각의 연속성을 저하시킬 수 있다.The wet etching reaction proceeds as the Ag catalyst, which receives hole charges from H 2 O 2 , oxidizes silicon into SiF 6 - form. However, Ag is also ionized by positive charges, which can cause structural collapse and reduce the continuity of wet etching.
따라서, 상기 다공성 Ag의 안정성을 향상시킬 수 있도록 Galvanic replacement 반응(다공성 Ag을 Aqueous 1mM KAuCl4 solution에 침지)을 통해 화학적으로 안정한 물질인 Au로 패시베이션하여 바이메탈릭(bimetallic) 구조체를 제조하는 것을 특징으로 한다. Therefore, in order to improve the stability of the porous Ag, a bimetallic structure is manufactured by passivation with Au, a chemically stable material, through a galvanic replacement reaction (immersing the porous Ag in Aqueous 1mM KAuCl 4 solution). do.
본 발명은 20%의 중성 투명도를 나타낼 수 있고, 13.0%의 높은 전력 변환 효율을 달성 가능한 투명 결정질 실리콘 태양전지(c-Si TPV, Al/SiNx/Al2O3/BSF/Si/emitter/Al 마이크로그리드)에 관한 것이다.The present invention provides a transparent crystalline silicon solar cell (c-Si TPV, Al/ SiN Al microgrid).
본 발명에 따르면, 깊고 수직 방향의 금속 보조 화학 에칭(MACE)에 적합한 상기 다공성 모놀리식 AgAu 층을 이용하여 고성능의 중성색 투명 실리콘 광전지(c-Si TPV)를 제조할 수 있다.According to the present invention, high-performance neutral color transparent silicon photovoltaics (c-Si TPVs) can be fabricated using the porous monolithic AgAu layer suitable for deep and vertical metal-assisted chemical etching (MACE).
이하, 실시예에 의해 본 발명을 보다 구체적으로 설명하고자 한다. 이들 실시예는 오직 본 발명을 설명하기 위한 것으로, 본 발명의 범위가 이들 실시예에 국한되지 않는다는 것은 당업자에게 있어서 자명하다. Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited to these examples.
실시예 1: MACE를 통한 투명한 c-Si의 제조Example 1: Preparation of transparent c-Si via MACE
n형 Czochralski Si 웨이퍼(두께 200μm, 1-3Ω·cm)를 사용하여 투명한 c-Si를 제조하였다. 마이크로홀 어레이(투과율 20%)는 포토리소그래피 공정을 통해 AZ4330E 포토레지스트(AZ Electronic Materials)를 사용하여 주기적으로 패턴화하였다. 턴된 c-Si를 Ag 전구체(0-6% AN을 첨가하는 수성 10mM AgNO3)에 2분 동안 침지하여 Ag 촉매를 침착시켰다. MACE는 구멍이 완전히 관통될 때까지(약 6시간) 실온에서 Ag 촉매 증착된 c-Si를 에칭액(4.8M HF와 0.44M H2O2의 혼합물)에 담가 수행하였다. 포토레지스트는 아세톤으로 제거하고 Ag 촉매 잔류물은 희석된 질산과 왕수(aqua regia)로 제거하였다.Transparent c-Si was fabricated using n-type Czochralski Si wafers (200 μm thick, 1-3 Ω·cm). Microhole arrays (transmittance of 20%) were periodically patterned using AZ4330E photoresist (AZ Electronic Materials) through a photolithography process. The Ag catalyst was deposited by immersing the turned c-Si in Ag precursor (aqueous 10mM AgNO 3 with 0-6% AN) for 2 min. MACE was performed by immersing Ag catalyst-deposited c-Si in an etchant (a mixture of 4.8M HF and 0.44MH 2 O 2 ) at room temperature until the hole was completely penetrated (about 6 hours). The photoresist was removed with acetone, and the Ag catalyst residue was removed with diluted nitric acid and aqua regia.
실시예 2: c-Si TPV의 제조Example 2: Preparation of c-Si TPV
p-n 접합 및 후면 전계(BSF)는 스핀-온-도펀트 방법에 의해 투명한 c-Si 상에 형성되었다. 도핑 공정 전에, PECVD(Plasma-enhanced Chemical Deposition)를 통해 확산 장벽으로서 마이크로홀 측벽에 SiO2 층을 선택적으로 형성하였다. p-n 접합과 BSF를 형성한 후 ALD(Atomic Layer Deposition) 공정을 통해 10nm 두께의 Al2O3 층을 증착하여 표면 재결합을 최소화하였다. 또한, 표면 반사를 줄이기 위해 PECVD를 사용하여 장치 전면에 70nm 두께의 SiNx 층을 형성하였다. 전면 전극은 투과율이 95% 이상인 마이크로그리드 전극을 적용했다. 후면 전극으로 700nm 두께의 은(Ag)을 열증착법으로 증착하였다.The pn junction and back surface field (BSF) were formed on transparent c-Si by the spin-on-dopant method. Before the doping process, a SiO 2 layer was selectively formed on the sidewalls of the microholes as a diffusion barrier through plasma-enhanced chemical deposition (PECVD). After forming the pn junction and BSF, a 10 nm thick Al 2 O 3 layer was deposited through the ALD (Atomic Layer Deposition) process to minimize surface recombination. Additionally, to reduce surface reflection, a 70 nm thick SiNx layer was formed on the front of the device using PECVD. The front electrode used a microgrid electrode with a transmittance of over 95%. Silver (Ag) with a thickness of 700 nm was deposited as a back electrode using thermal evaporation.
실험예 1: Experimental Example 1:
Ag 촉매 구조가 입자 형태에서 다공성 모놀리틱 층 형태로 개선되었는지 확인하기 위하여 AN의 함량(%)을 다르게 하여 에칭 속도(Etching rate)를 확인하였다. In order to confirm whether the Ag catalyst structure was improved from a particle form to a porous monolithic layer form, the etching rate was checked by varying the AN content (%).
그 결과, 0 vol.% AN(32μm/h)에 비해 4 vol.% AN(31μm/h)의 조건에서 다공성의 효과로 에천트의 효과적 침투가 가능해 식각 속도가 잘 유지되는 것을 확인하였다(도 3d). 가장 많은 양의 AN(5 vol.% AN)의 경우, Ag 입자 사이의 과도한 네트워킹이 에칭액의 확산을 방지하기 때문에 에칭 속도(26 μm/h)를 감소시키는 것을 확인하였다. As a result, it was confirmed that effective penetration of the etchant was possible due to the effect of porosity under the condition of 4 vol.% AN (31μm/h) compared to 0 vol.% AN (32μm/h), and the etching rate was well maintained (Figure 3d). In the case of the highest amount of AN (5 vol.% AN), it was confirmed that the etching rate (26 μm/h) decreased because excessive networking between Ag particles prevented diffusion of the etchant.
또한, 식각된 Si의 노출된 표면적을 측정하고 AN의 첨가가 촉매 운동을 조절함으로써 결함 부위를 감소시킬 수 있는지 여부를 조사하기 위해 이중층 정전용량(Cdl) 측정을 수행하였다.Additionally, double-layer capacitance (C dl ) measurements were performed to measure the exposed surface area of etched Si and to investigate whether the addition of AN could reduce defect sites by controlling catalyst motion.
순환 전압 전류 곡선의 수소 흡착/탈착 영역을 얻기 위해 작업 전극으로 다른 기하학(0 및 4 vol.% AN)의 Ag 촉매를 사용하고 전해질로 0.1 M H2SO4를 사용하여 MACE를 통해 투명한 c-Si로 구성하였다. To obtain the hydrogen adsorption/desorption region of the cyclic voltammetry curve, transparent c-Si was catalyzed via MACE using Ag catalysts of different geometries (0 and 4 vol.% AN) as working electrodes and 0.1 MH 2 SO 4 as electrolyte. It was composed of.
도 3e에서 볼 수 있듯이, 모놀리틱의 효과로 균일한 움직임에 따른 습식 식각의 높은 균일성이 식각 후 실리콘 표면적으로 확인되었다. 즉, 마이크로홀 어레이의 동일한 패터닝에도 불구하고 입자 형태(검정)에 비해 다공성 모놀리틱(빨강)에서 더 작은 실리콘 표면적이 계산되었고, 이는 불균일한 식각이 억제되어 그만큼 표면적이 줄어들었다는 것을 의미한다.As can be seen in Figure 3e, high uniformity of wet etching due to uniform movement due to the monolithic effect was confirmed in the silicon surface area after etching. In other words, despite the same patterning of the microhole array, a smaller silicon surface area was calculated for the porous monolith (red) compared to the particle form (black), which means that non-uniform etching was suppressed and the surface area was reduced accordingly.
상기 AN이 다공성 모놀리틱 Ag 층의 형성에 어떻게 기여하는지 확인하기 위해 AN의 양에 따른 접촉각 측정에 의해 c-Si 표면에서 Ag 전구체의 거시적 습윤성을 관찰하였다(도 4f). 부식성이 높고 AN과의 상관 관계가 적기 때문에 Ag 전구체에서 HF를 제외하였고, 접촉각은 5% AN에서 69°까지 점차 감소하였다. Ag 전구체의 향상된 젖음성은 소수성-소수성 상호작용을 통해 수소화된 Si 표면에 메틸기가 흡착되는 AN의 배향을 의미한다. 대조적으로, cyanide 그룹은 위쪽으로 노출되어 Ag+와 결합할 수 있다. AN의 유무에 따른 Ag+의 환원전위는 Ag+가 AN의 cyanide 그룹과 결합함을 보여주었다. To determine how the AN contributes to the formation of the porous monolithic Ag layer, the macroscopic wettability of the Ag precursor on the c-Si surface was observed by measuring the contact angle depending on the amount of AN (Figure 4f). HF was excluded from the Ag precursor because it is highly corrosive and has little correlation with AN, and the contact angle gradually decreased to 69° at 5% AN. The improved wettability of the Ag precursor implies the orientation of AN, where the methyl group is adsorbed on the hydrogenated Si surface through hydrophobic-hydrophobic interactions. In contrast, the cyanide group is exposed upward and can bind Ag + . The reduction potential of Ag + in the presence or absence of AN showed that Ag + combines with the cyanide group of AN.
도 3g는 RHE에 대해 1.2V에서 0.0V로 전위를 스위핑함으로써 전해질로서의 Ag 전구체의 선형 스위프 전압전류법(LSV) 결과를 보여준다. 4% AN이 Ag 전구체에 첨가되었을 때, Ag+가 AN의 시안화물 그룹과의 배위 결합 형성에 의해 안정화되기 때문에 개시 전위가 0.6V vs. RHE로 음극으로 이동하였다. 이러한 결과는 Ag+가 수소화된 Si를 흡착하는 AN과의 배위결합을 통해 c-Si 표면에 유리하게 도달한다는 것을 의미한다. Figure 3g shows linear sweep voltammetry (LSV) results of Ag precursor as electrolyte by sweeping the potential from 1.2 V to 0.0 V with respect to RHE. When 4% AN was added to the Ag precursor, the onset potential was 0.6 V vs. It moved to the cathode with RHE. These results mean that Ag + advantageously reaches the c-Si surface through coordination with AN, which adsorbs hydrogenated Si.
밀도 함수 이론 기반의 이론적 시뮬레이션을 통해 c-Si 표면에 대한 Ag+의 열역학적으로 유리한 접근과 함께 Ag+, AN 및 c-Si 표면 사이의 예상되는 배열을 확인할 수 있다. 도 3i에서 볼 수 있듯이, Ag+가 c-Si 표면에 접근할 때 -0.53 eV의 낮은 결합 에너지(Eb)가 계산되었다. 이는 Ag+가 주로 확산을 통해 c-Si 표면에 접근함을 나타낸다. AN 추가의 경우 Ag+가 있는 c-Si 표면 위에 위치한다(도 4h). 또한, Ag+와의 높은 배위 Eb(-2.26 eV)와 AN의 c-Si 표면에 대한 흡착(-1.98 eV)이 모두 계산되었다. 이것은 Ag+와 c-Si 표면 사이의 AN 유도된 높은 상호 작용을 설명하여 다공성 모놀리식 Ag 층을 생성한다. 이러한 결과는 습윤성 및 LSV와 일치한다. Theoretical simulations based on density functional theory confirm the expected arrangement between Ag + , AN and c-Si surfaces along with the thermodynamically favorable approach of Ag + to the c-Si surface. As shown in Figure 3i, a low binding energy (Eb) of -0.53 eV was calculated when Ag + approaches the c-Si surface. This indicates that Ag + approaches the c-Si surface mainly through diffusion. In case of AN addition, Ag + is located on the c-Si surface (Figure 4h). Additionally, the high coordination Eb with Ag + (-2.26 eV) and the adsorption of AN on the c-Si surface (-1.98 eV) were both calculated. This explains the AN-induced high interaction between Ag + and c-Si surfaces, resulting in a porous monolithic Ag layer. These results are consistent with wettability and LSV.
위에서 언급한 AN의 기능과 함께, AN이 두 개의 기본 전하가 환경에서 정전기적으로 상호 작용하는 거리인 Bjerrum length(λB)를 통해 Ag+ 환원에 유리한 환경을 제공한다는 것을 확인하였다. AN은 HF 및 H2O(각각 7.0 및 7.1 Å)에 비해 약 2배 많은 λB(15.6 Å)를 나타냈다. 이는 AN이 풍부한 환경(즉, c-Si 표면 근처)에서 Ag+의 환원이 활발하게 일어난다는 것을 의미한다.In addition to the functions of AN mentioned above, it was confirmed that AN provides a favorable environment for Ag + reduction through the Bjerrum length (λB), which is the distance at which two basic charges electrostatically interact in the environment. AN exhibited approximately twice as much λB (15.6 Å) compared to HF and H 2 O (7.0 and 7.1 Å, respectively). This means that reduction of Ag + occurs actively in an AN-rich environment (i.e., near the c-Si surface).
실험예 2:Experimental Example 2:
갈바닉 교체(GR)를 수행하여 상기 다공성 모놀리틱 Ag 층을 에칭액의 강력한 요소로 알려진 Au로 부동태화하였다. 다공성 단일체 Ag 층의 외부 표면에서 Au 원소 교환은 도 4a와 같이 이들 사이의 표준 전위차에 의해 자발적으로 발생한다. 이 공정은 다공성 모놀리틱 Ag 층-증착 c-Si를 Au 전구체(수성 1mM KAuCl4 용액)에 10초 동안 침지하여 쉽게 수행되고, 결과적인 패시베이션은 에너지 분산 x-선 분광법(EDX)에 의해 확인되었다. 다공성 단일체 층의 윤곽이 관찰되었고(도 4b) Ag와 Au가 9:1의 비율로 공존하는 전체 층에서 Au 원자가 감지되었다(도 4c, d). 더불어 다공성 모놀리틱 AgAu를 이용한 습식 식각 결과 가장 낮은 실리콘 표면적(파랑)이 측정되었다. Galvanic replacement (GR) was performed to passivate the porous monolithic Ag layer with Au, which is known to be a strong element in etchants. The exchange of Au elements on the outer surface of the porous monolithic Ag layer occurs spontaneously by the standard potential difference between them, as shown in Figure 4a. This process is easily performed by immersing the porous monolithic Ag layer-deposited c-Si in Au precursor (aqueous 1mM KAuCl 4 solution) for 10 s, and the resulting passivation is confirmed by energy dispersive x-ray spectroscopy (EDX). It has been done. The outline of the porous monolithic layer was observed (Figure 4b) and Au atoms were detected in the entire layer where Ag and Au coexisted in a ratio of 9:1 (Figure 4c, d). In addition, the lowest silicon surface area (blue) was measured as a result of wet etching using porous monolithic AgAu.
이것은 외부 표면이 Au(즉, 다공성 모노리스 AgAu 층)로 덮인 바이메탈 구조에 기인하며 에칭액 환경에서 Ag의 용해, 재생성에 의한 무분별한 식각을 억제하여 표면적이 줄어들었다는 것을 의미한다. 개선된 구조의 내구성은 고품질의 투명한 c-Si를 생성하는 다공성 모노리스 AgAu 층을 기반으로 하는 MACE 기반 투명 c-Si의 가장 낮은 Cdl(도 3e)과 매끄러운 표면에 의해 입증되었다.This is due to the bimetallic structure whose outer surface is covered with Au (i.e., a porous monolithic AgAu layer), and means that the surface area is reduced by suppressing indiscriminate etching due to dissolution and regeneration of Ag in the etchant environment. The durability of the improved structure was demonstrated by the lowest C dl (Figure 3e) and smooth surface of the MACE-based transparent c-Si based on porous monolithic AgAu layer, resulting in high-quality transparent c-Si.
실험예 3:Experimental Example 3:
상기 다공성 모놀리틱 AgAu 층 기반 습식 식각으로 제작한 반투명 실리콘 기판(20% 투과도)으로 태양전지를 제작하였고, 기존 건식 공정을 거친 태양전지 효율과 비교하였다.A solar cell was manufactured using a translucent silicon substrate (20% transmittance) produced by wet etching based on the porous monolithic AgAu layer, and the efficiency was compared with the solar cell efficiency obtained through a conventional dry process.
도 5a의 개략도에서 볼 수 있듯이, 다공성 모노리스 AgAu 층(MACE-A)을 기반으로 MACE를 통해 c-Si TPV를 제조했으며, 유리와 같은 중성 색상으로 20% 투과율을 나타내었다(도 5b). 또한, c-Si TPV의 광기전 특성을 평가하기 위해 AM 1.5G 조명에서 전류 밀도-전압(J-V) 곡선을 얻었다(도 5c). MACE-A를 통한 c-Si TPV는 Ag 입자 및 다공성 단일체 Ag 층을 기반으로 한 MACE 기반 MACE와 비교하여 Voc의 점진적인 개선으로 인해 DRIE(11.5%)를 통한 PCE를 능가하는 13.0%의 PCE를 달성하였다.As shown in the schematic diagram in Figure 5a, c-Si TPV was fabricated via MACE based on a porous monolithic AgAu layer (MACE-A), and exhibited 20% transmittance with a glass-like neutral color ( Figure 5b). Additionally, to evaluate the photovoltaic properties of c-Si TPV, current density-voltage (J-V) curves were obtained under AM 1.5G illumination (Figure 5c). c-Si TPV via MACE-A achieves a PCE of 13.0%, surpassing PCE via DRIE (11.5%) due to gradual improvement in Voc compared to MACE based on Ag particles and porous monolithic Ag layer. did.
상기 MACE-A의 가장 높은 PCE를 설명하기 위해 QSSPC(quasi-steady-state photo-conductance)를 사용한 제조 기술에 따라 투명 c-Si의 소수 캐리어 수명과 내재 개방 회로 전압(iVoc)을 모두 측정하였다(도 5d). 표면 재결합을 최소화하기 위해 투명한 c-Si 위에 10nm 두께의 Al2O3 필름을 증착했다는 점은 주목할 만하다. DRIE를 통한 투명 c-Si의 소수 캐리어 수명은 61.1μs인 반면, MACE-A는 575.4μs의 캐리어 수명으로 이어지며 이는 DRIE보다 9.4배 더 길었다. 또한 MACE-A를 통한 투명 c-Si의 iVoc은 DRIE를 통한 iVoc에 비해 약 31.3mV 증가하였다. 투명 c-Si의 캐리어 재결합 영역은 MACE의 장점과 함께 다공성 단일체 AgAu 층에 의한 선택적 에칭으로 인해 효과적으로 감소되었다. 전압의 함수로서의 암전류 밀도(Jdark)는 도 5e와 같이 MACE-A를 통해 c-Si TPV의 높은 PCE를 지원한다. DRIE와 MACE-A-진행 c-Si TPV의 Jdark 값은 역 바이어스 -1V에서 주목할 만한 차이로, 위의 분석 결과에 해당하는 DRIE의 Jdark가 약 7배 더 높다. MACE-A에 의한 재조합 감소는 외부 양자 효율(EQE) 측정에 의해 뒷받침되는 Jsc의 약간의 증가에도 기여하였다(도 5f). To demonstrate the highest PCE of MACE-A, both the minority carrier lifetime and the intrinsic open circuit voltage (iVoc) of transparent c-Si were measured according to a fabrication technique using quasi-steady-state photo-conductance (QSSPC) ( Figure 5d). It is noteworthy that a 10 nm thick Al 2 O 3 film was deposited on transparent c-Si to minimize surface recombination. The minority carrier lifetime of transparent c-Si via DRIE was 61.1 μs, while MACE-A led to a carrier lifetime of 575.4 μs, which was 9.4 times longer than DRIE. Additionally, the iVoc of transparent c-Si through MACE-A increased by about 31.3 mV compared to the iVoc through DRIE. The carrier recombination area of transparent c-Si was effectively reduced due to selective etching by the porous monolithic AgAu layer with the advantage of MACE. The dark current density (Jdark) as a function of voltage supports the high PCE of c-Si TPV over MACE-A, as shown in Figure 5e. There is a notable difference between the Jdark values of DRIE and MACE-A-progress c-Si TPV at reverse bias of -1V, with the Jdark of DRIE being approximately 7 times higher, corresponding to the above analysis results. The reduction in recombination by MACE-A also contributed to a slight increase in Jsc, supported by external quantum efficiency (EQE) measurements (Figure 5f).
또한, MACE-A에 의한 성능향상과 더불어 DRIE 원가에 비해 매우 경제적인 태양전지의 제작이 가능할 것으로 기대된다. DRIE와 달리 MACE는 Deep Si Plasma Etcher와 같은 고가의 장비를 필요로 하지 않기 때문에 마이크로홀 어레이 제조 공정의 비용을 크게 줄일 수 있다. 따라서, MACE-A는 높은 PCE를 제공할 뿐만 아니라 c-Si TPV의 비용을 혁신적으로 절감할 수 있어 c-Si TPV의 상용화에 큰 도움이 될 것으로 기대된다.In addition, along with the performance improvement by MACE-A, it is expected that it will be possible to produce solar cells that are very economical compared to the DRIE cost. Unlike DRIE, MACE can significantly reduce the cost of the microhole array manufacturing process because it does not require expensive equipment such as Deep Si Plasma Etcher. Therefore, MACE-A is expected to be of great help in the commercialization of c-Si TPV by not only providing high PCE but also innovatively reducing the cost of c-Si TPV.
이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 본 발명이 속한 기술분야에서 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아님은 명백하다. 본 발명이 속한 기술분야에서 통상의 지식을 가진 자라면 상기 내용을 바탕으로 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다.As the specific parts of the present invention have been described in detail above, it is clear to those skilled in the art that these specific techniques are merely preferred embodiments and do not limit the scope of the present invention. do. Anyone skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above contents.
따라서, 본 발명의 실질적인 범위는 첨부된 특허청구범위와 그의 등가물에 의하여 정의된다고 할 것이다.Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (8)
양극성(Amphiphilic) 물질을 이용하여 Ag 전구체 용액으로부터 환원된 다공성 Ag 층; 및
상기 다공성 Ag 층의 외부 표면 상에 패시베이션되는 Au 층;을 포함하는 것을 특징으로 하는, 바이메탈릭 특성을 가지는 다공성 모놀리틱 AgAu 촉매 층.In the catalyst deposited on the silicon substrate during wet etching,
Amphiphilic A porous Ag layer reduced from an Ag precursor solution using a material; and
A porous monolithic AgAu catalyst layer with bimetallic properties, comprising: an Au layer passivated on the outer surface of the porous Ag layer.
상기 양극성 물질은 아세토니트릴(Acetonitrile)인 것을 특징으로 하는, 바이메탈릭 특성을 가지는 다공성 모놀리틱 AgAu 촉매 층.According to paragraph 1,
A porous monolithic AgAu catalyst layer with bimetallic properties, wherein the anodic material is acetonitrile.
상기 양극성 물질은 습식 식각시 식각액의 침투를 고려함과 동시에 균일한 움직임이 가능하도록 Ag+ 이온과 실리콘 표면의 상호 작용을 높일 수 있는 것을 특징으로 하는, 바이메탈릭 특성을 가지는 다공성 모놀리틱 AgAu 촉매 층.According to paragraph 1,
The anodic material is a porous monolithic AgAu catalyst layer with bimetallic properties, characterized in that it can increase the interaction between Ag + ions and the silicon surface to enable uniform movement while taking into account the penetration of the etchant during wet etching. .
실리콘 기판 상에 제1항에 따른 다공성 모놀리틱 AgAu 촉매 층을 증착하는 단계; 및
상기 다공성 모놀리틱 AgAu 촉매 층이 증착된 실리콘 기판에 식각액을 반응시켜 식각하는 단계;를 포함하고,
상기 다공성 모놀리틱 AgAu 촉매 층은
Ag 전구체 용액에 아세토니트릴(AN)을 도입하여 Ag+ 이온과 상기 실리콘의 표면 간 상호 작용을 제어되어 환원된 다공성 Ag 층에 갈바닉 교체를 통해 상기 다공성 Ag 층의 외부 표면을 Au로 패시베이션하여 제조되는 것을 특징으로 하는, 반투명 실리콘의 금속 촉매 화학 식각 방법.In a method of etching a silicon substrate by metal-assisted chemical etching,
Depositing a porous monolithic AgAu catalyst layer according to claim 1 on a silicon substrate; and
A step of etching the silicon substrate on which the porous monolithic AgAu catalyst layer is deposited by reacting an etchant,
The porous monolithic AgAu catalyst layer is
It is manufactured by passivating the outer surface of the porous Ag layer with Au through galvanic replacement in the reduced porous Ag layer by controlling the interaction between Ag + ions and the surface of the silicon by introducing acetonitrile (AN) into the Ag precursor solution. A metal-catalyzed chemical etching method of translucent silicon, characterized in that.
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