KR101541414B1 - Bilayered transparent conductive layer and solar-cell using it and method of the same - Google Patents
Bilayered transparent conductive layer and solar-cell using it and method of the same Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 22
- 238000005530 etching Methods 0.000 claims abstract description 39
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000151 deposition Methods 0.000 claims description 37
- 230000008021 deposition Effects 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 230000003746 surface roughness Effects 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- 238000005566 electron beam evaporation Methods 0.000 claims description 2
- 238000002207 thermal evaporation Methods 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 12
- 239000011787 zinc oxide Substances 0.000 claims 6
- 230000009977 dual effect Effects 0.000 claims 4
- 238000007751 thermal spraying Methods 0.000 claims 1
- 230000006872 improvement Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 101
- 239000010408 film Substances 0.000 description 50
- 239000010409 thin film Substances 0.000 description 19
- 238000002834 transmittance Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001887 tin oxide Inorganic materials 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
본 발명은 태양전지의 투명전도막에 관한 것으로, 특히 광포획성능을 개선한 투명전도막의 개량에 관한 것이다. 본 발명은 태양전지의 전면 반사 방지막이나 전면전극 또는 후면 반사막으로 사용되는 투명전도막으로서, 광투과층(100)과; 일면은 상기 광투과층(100)에 접하고, 타면에는 표면 텍스처 구조가 형성된 광포획층(200)으로 구성되며, 상기 광투과층(100)의 전기전도도 A와 상기 광포획층(200)의 전기전도도 a는 A>a의 관계가 있고, 상기 광투과층(100)의 에칭성 B와 상기 광포획층(200)의 에칭성 b는 B<b의 관계가 있는 것에 있어서, 상기 광투과층(100)은 산화인듐주석(ITO : Indium Tin Oxide)층인 것을 특징으로 하는 이중구조 투명전도막을 제공한다. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film of a solar cell, and more particularly to an improvement of a transparent conductive film with improved light trapping performance. A transparent conductive film used as a front antireflection film, a front electrode, or a rear reflective film of a solar cell, comprising: a light-transmitting layer (100); And a light trapping layer formed on one surface of the light trapping layer and having a surface texture structure formed on the other surface of the light trapping layer. The conductivity a has a relation of A > a, and the etching property B of the light-transmitting layer 100 and the etching property b of the light-trapping layer 200 have a relation of B < b, 100) is an indium tin oxide (ITO) layer.
Description
본 발명은 태양전지의 투명전도막에 관한 것으로, 특히 광포획성능을 개선한 투명전도막의 개량에 관한 것이다.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film of a solar cell, and more particularly to an improvement of a transparent conductive film with improved light trapping performance.
박막형 태양전지의 광포획을 늘리기 위하여 텍스처링부가 형성된 유리 기판을 이용하려는 기술이나 금속 기판 표면에 텍스처 구조를 형성하는 기술이 제안되고 있으나, 유리나 금속 재질의 기판은 텍스처 구조의 형성이 어려운 단점이 있다.
In order to increase the light trapping of the thin film solar cell, a technique of using a glass substrate having a texturing portion or a technique of forming a texture structure on the surface of a metal substrate has been proposed. However, it is difficult to form a textured structure on a glass or metal substrate.
최근에는 기판 위에 증착된 투명전도막에도 텍스처 구조를 형성하려는 노력이 이루어지고 있으며, SnO2계나 ZnO계 투명전도막에 텍스처를 형성하는 기술이 제안되고 있으나, 만족할만한 광포획 효율을 나타내고 있지 못한 실정이다.
In recent years, attempts have been made to form a texture structure on a transparent conductive film deposited on a substrate. Techniques for forming a texture on a SnO 2 -type or ZnO-based transparent conductive film have been proposed, but they do not exhibit satisfactory light trapping efficiency to be.
상판형 박막 태양전지에서 유리 기판 위에 형성되는 투명전도막은 전면전극으로 사용되며, 전면전극을 통하여 투과되는 태양광을 전면전극 표면 텍스처 구조를 통하여 산란시켜줌으로써 광흡수층 내에서의 입사광 이동경로를 증가시켜 흡수율을 증가시킨다. 그리고 하판형 박막 태양전지에서 금속 기판 위에 형성되는 투명전도막은 금속 기판과 함께 입사광 중 광흡수층에서 흡수되지 않는 빛을 다시 광흡수층으로 반사시켜 입사광이 최대한 흡수될 수 있도록 하는 역할을 하는 후면반사막으로 사용되며, 후면반사막의 표면 텍스처 구조를 통하여 후면반사막의 반사광을 산란(light scattering)시켜 이동경로를 증가시키게 된다.
The transparent conductive film formed on the glass substrate in the planar thin film solar cell is used as the front electrode and scattering the sunlight transmitted through the front electrode through the texture structure of the front electrode surface increases the incident light traveling path in the light absorbing layer Increase the absorption rate. In addition, the transparent conductive film formed on a metal substrate in a bottom plate type thin film solar cell is used as a rear reflection film which serves to absorb incident light as much as possible by reflecting the light not absorbed in the light absorption layer of the incident light, And the scattered light of the back reflection film is scattered through the surface texture structure of the rear reflection film to increase the movement path.
특히, 태양전지의 총투과(total transmittance)는 선택투과(specular transmittance)와 산란투과(diffuse transmittance)로 구성되며, 전면전극에서의 산란특성을 증가시키기 위해서는 산란투과의 증가가 요구된다. 그리고 태양전지의 총반사(total reflectance)는 정반사(specular reflectance)와 산란반사(diffuse reflectance)로 구성되며, 산란특성을 증가시키기 위해서는 산란반사 증가가 요구된다. 이러한 산란투과와 산란반사는 입사광의 파장과 전면전극의 표면형상 및 표면거칠기(표면조도)와 밀접한 관계를 가지며, 일반적으로 단파장 영역의 입사광은 광흡수층 초기 영역에서 대부분 흡수되므로 가시광선 영역(500~800nm)과 장파장 영역(800~1000nm)에 대한 전면전극 또는 후면반사막의 산란 투과 또는 산란 반사 특성을 최대화하는 것이 중요하다. 가시광과 장파장에 대한 산란투과와 산란반사를 향상시키기 위해서는 파장 크기에 버금가는 표면형상 및 표면 거칠기의 변화가 요구되지만, 현재 사용 중인 대부분의 투명전도성물질은 에칭성이 낮기 때문에 에칭에 의하여 충분한 표면 거칠기를 이루어내지 못하여 광포획 효율이 높지 못하다.
In particular, the total transmittance of the solar cell is composed of specular transmittance and diffuse transmittance. In order to increase the scattering characteristics at the front electrode, it is required to increase the scattering transmittance. The total reflectance of the solar cell is composed of specular reflectance and diffuse reflectance. In order to increase the scattering characteristics, it is required to increase scatter reflection. In general, incident light in a short wavelength region is mostly absorbed in the initial region of the light absorption layer, so that the visible light region (500 to 500 nm) It is important to maximize scattering transmission or scattering reflection characteristics of the front electrode or the rear reflection film for the long wavelength region (800 to 1000 nm). In order to improve scattering transmittance and scattering reflection for visible light and long wavelength, it is required to change the surface shape and surface roughness comparable to the wavelength size. However, since most of the transparent conductive materials currently used have low etchability, The efficiency of light trapping is not high.
본 발명은 전술한 종래 기술의 문제점을 해결하기 위한 것으로서 표면의 에칭성이 좋아서 텍스처 구조의 형성을 통한 광포획성이 매우 뛰어남과 동시에, 전기적 특성과 광학적 특성이 뛰어난 투명전도막 및 그 제조방법을 제공하면서도, 증착에 필요한 재료를 절감하고 증착온도를 낮춤으로써 제조효율을 높이는데 그 목적이 있다.
Disclosure of the Invention The present invention has been made to solve the problems of the prior art described above, and provides a transparent conductive film having excellent electrical properties and optical characteristics, The purpose of the present invention is to improve the manufacturing efficiency by reducing the material required for deposition and lowering the deposition temperature.
상기 목적을 달성하기 위한 본 발명에 의한 이중구조 투명전도성막은, 태양전지의 전면 반사 방지막이나 전면전극 또는 후면 반사막으로 사용되는 투명전도막으로서, 광투과층과; 일면은 상기 광투과층에 접하고, 타면에는 표면 텍스처 구조가 형성된 광포획층으로 구성되며, 상기 광투과층의 전기전도도 A와 상기 광포획층의 전기전도도 a는 A>a의 관계가 있고, 상기 광투과층의 에칭성 B와 상기 광포획층의 에칭성 b는 B<b의 관계가 있는 것에 있어서, 상기 광투과층은 산화인듐주석(ITO : Indium Tin Oxide)층인 것을 제공한다.
According to an aspect of the present invention, there is provided a transparent conductive film for use as a front antireflection film, a front electrode, or a rear reflective film of a solar cell, the transparent conductive film comprising: a light transmitting layer; And a light trapping layer having a surface texture structure formed on the other surface, wherein the electric conductivity A of the light transmitting layer and the electric conductivity a of the light trapping layer have a relationship of A > a, The etching property B of the light-transmitting layer and the etching property b of the light-trapping layer have a relation of B < b, wherein the light-transmitting layer is an indium tin oxide (ITO) layer.
등록번호 제10-1178496호는, ZnO 박막이 에칭성이 뛰어나서 불균일한 식각에 의한 표면 텍스처 구조의 형성이 용이한 경우에는 전기적 특성이 나쁘고, 전기적 특성이 좋은 경우에는 에칭성이 나빠서 불균일 식각에 의한 표면 텍스처 구조의 형성이 어려운 특성을 가지고 있음을 확인하고 전기적 특성이 뛰어난 투명 전도 박막인 광투과층과 표면 텍스처 구조의 형성이 쉬운 ZnO계 투명전도막인 광포획층의 2중 층으로 구성되는 이중구조의 투명전도성막을 제안하였다. 그러나 이 경우, 300℃ 이상의 증착온도와 면저항 확보를 위해 1.5μm 이상을 증착하여야 했다. Registration No. 10-1178496 discloses that the ZnO thin film is excellent in the etching property, and when the surface texture structure is easily formed by the uneven etching, the electrical characteristics are poor, and when the electrical characteristics are good, the etching property is poor, It is confirmed that the surface texture structure is difficult to form, and the light transmission layer, which is a transparent conductive thin film having excellent electrical properties, and the double layer composed of a double layer of the light trapping layer, which is a ZnO transparent conductive film, Transparent conductive film of the structure. In this case, however, a deposition temperature of 300 [deg.] C or more and a deposition of 1.5 [mu] m or more were required in order to secure sheet resistance.
이에 본 발명은, 면저항을 충분히 확보하기 위해 ZnO 에 갈음하여 산화인듐주석(ITO : Indium Tin Oxide)으로 광투과층을 형성시킴으로써 증착두께와 증착온도를 낮추어 제조효율을 높이고자 한다.
Accordingly, in order to sufficiently secure the sheet resistance, the present invention aims to improve the manufacturing efficiency by lowering the deposition thickness and the deposition temperature by forming a light transmitting layer with indium tin oxide (ITO) instead of ZnO.
상술한 바와 같이 구성된 본 발명은, 태양전지에 사용되는 투명전도막을 전기적 특성과 광투과성이 뛰어난 광투과층과 표면 텍스처 형성에 뛰어난 광포획층으로 구성하고 광포획층에 표면 텍스처를 형성함으로써, 전기적 특성과 광포획 능력이 모두 뛰어난 투명전도막을 제공할 수 있는 효과가 있으며, 면저항을 충분히 확보하기 위해 ZnO 에 갈음하여 산화인듐주석(ITO : Indium Tin Oxide)으로 광투과층을 형성시킴으로써 증착두께와 증착온도를 낮추어 제조효율을 높이는 효과가 있다.
The present invention constituted as described above is characterized in that a transparent conductive film used in a solar cell is constituted by a light transmitting layer excellent in electrical characteristics and light transmittance and a light trapping layer excellent in surface texture formation and a surface texture formed in the light trapping layer, And has the effect of providing a transparent conductive film having both excellent characteristics and light trapping ability. In order to sufficiently secure the sheet resistance, the light-transmitting layer is formed of indium tin oxide (ITO) And the manufacturing efficiency is improved by lowering the temperature.
도 1은 본 발명의 투명전도막의 요부 발췌 단면도이다.
도 2는 본 발명의 투명전도막의 주사전자현미경(SEM) 사진으로서, (a)(b)는 에칭전 사진이고, (c)(d)는 에칭 후의 사진이다.
도 3은 본 발명의 투명전도막을 제조하는 방법을 설명하는 순서도이다.
도 4의 그래프는 AZO(Al Doped ZnO)막을 HCl용액으로 45초 에칭한 후의 총 투과도와 산란투과도의 변화를 나타낸 것이다.
도 5의 그래프는 AZO 박막을 HCl용액으로 에칭하는 시간에 따른 면저항 변화를 나타낸 것이다.
도 6은 단일층 AZO 박막 및 ITO 하부층 위에 증착온도에 따라 제조된 AZO/ITO 이중층의 엑스선회절(XRD) 변화를 나타낸 그래프이다. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view of a main portion of a transparent conductive film of the present invention. FIG.
2 is a scanning electron microscope (SEM) photograph of the transparent conductive film of the present invention, wherein (a), (b) are photographs before etching, and (c) and (d) are photographs after etching.
3 is a flow chart illustrating a method of manufacturing the transparent conductive film of the present invention.
The graph of FIG. 4 shows changes in total transmittance and scattered transmittance after etching the AZO (Al Doped ZnO) film with a HCl solution for 45 seconds.
The graph of FIG. 5 shows the sheet resistance change with time for etching the AZO thin film with the HCl solution.
FIG. 6 is a graph showing changes in X-ray diffraction (XRD) of the AZO / ITO bilayer prepared according to the deposition temperature on the single-layer AZO thin film and the ITO lower layer.
본 발명은 태양전지의 투명전도막에 관한 것으로, 특히 광포획성능을 개선한 투명전도막의 개량에 관한 것이다. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film of a solar cell, and more particularly to an improvement of a transparent conductive film with improved light trapping performance.
이하, 도면을 참조하여 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to the drawings.
도 1은 본 발명의 투명전도막의 요부 발췌 단면도이다. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view of a main portion of a transparent conductive film of the present invention. FIG.
본 발명은 태양전지의 전면 반사 방지막이나 전면전극 또는 후면 반사막으로 사용되는 투명전도막으로서, The present invention relates to a transparent conductive film used as a front antireflection film, a front electrode, or a rear reflective film of a solar cell,
광투과층(100)과;A light transmitting layer (100);
일면은 상기 광투과층(100)에 접하고, 타면에는 표면 텍스처 구조가 형성된 광포획층(200)으로 구성되며,And a light trapping layer (200) having a surface texture structure on the other surface, the surface being in contact with the light transmitting layer (100)
상기 광투과층(100)의 전기전도도 A와 상기 광포획층(200)의 전기전도도 a는 A>a의 관계가 있고, 상기 광투과층(100)의 에칭성 B와 상기 광포획층(200)의 에칭성 b는 B<b의 관계가 있는 것에 있어서,The electric conductivity A of the light transmitting
본 실시예의 투명전도막은 기판(300) 위에 순차적으로 형성된 광투과층(100)과 광포획층(200)으로 구성된다.The transparent conductive film of this embodiment is composed of a light-transmitting
기판(300)은 상판형 박막 태양전지의 경우에는 유리 등 투명 기판이고, 하판형 박막 태양전지의 경우 금속층이 형성된 금속 또는 폴리머 재질의 기판이다.
The
광투과층(100)은 기판(300) 위에 증착된 투명전도막으로서, 표면 텍스처 구조 형성을 위한 특성을 고려하지 않고 전기적 특성과 광투과성이 뛰어난 재질인 산화인듐주석(ITO : Indium Tin Oxide)층으로 형성시킨다. 상기 산화인듐주석(ITO)층은 두께가 50-200nm 인 것이 바람직하며, 상기 산화인듐주석(ITO)층의 비저항이 10Ω/sq 이하인 것이 바람직하다. The light transmitting
상기 광투과층(100)의 전기전도도 A와 상기 광포획층(200)의 전기전도도 a는 A>a의 관계가 있고, 상기 광투과층(100)의 에칭성 B와 상기 광포획층(200)의 에칭성 b는 B<b의 관계에 있어서, 산화인듐주석(ITO)층은 에칭성은 낮으나 전기적 특성과 광투과성이 뛰어나기 때문에 최적의 광투과층(100)으로 적용될 수 있다. ITO층의 뛰어난 전기전도도 때문에 광투과층(100)의 두께는 50-200nm로 얇게 형성시킬 수 있게 된다.
The electric conductivity A of the light transmitting
상기 광포획층(200)은 알루미늄, 갈륨 또는 붕소가 도핑된 산화아연(Al Doped ZnO : AZO, Ga Doped ZnO : GZO, B Doped ZnO : BZO), 플루오르가 도핑된 산화주석(F-doped SnO2), 탄소나노튜브(CNT) 필름, 그래핀 중 하나를 선택하여 형성시킨다. The
플루오르가 도핑된 산화주석(F-doped SnO2)는 음이온 치환형 투명 전극으로 제조 방법이 한정적이며 투과도가 높지 않은 문제점을 갖고 있어 알루미늄, 갈륨 또는 붕소가 도핑된 산화아연(Al Doped ZnO : AZO, Ga Doped ZnO : GZO, B Doped ZnO : BZO)층으로 광포획층을 형성시키는 것이 바람직하다. The fluorine-doped tin oxide (F-doped SnO2) is an anion-exchange type transparent electrode and has a limited manufacturing method and has a problem in that the transmittance is not high. Therefore, aluminum doped ZnO (AZO, Ga Doped ZnO: GZO, B-doped ZnO: BZO) layer.
상기 광포획층(200)의 두께는 500-1000nm인 것이 바람직하다. 등록번호 제10-1178496호에서의 경우에는 면저항 확보를 위해 1.5μm 이상을 증착하여야 했음에 비추어볼 때, 증착 필요량이 현저히 감소함을 알 수 있다. 이는 광투과층(100)인 ITO층이 높은 전기적 특성을 가져 면저항을 확보해주기 때문이다.
The thickness of the
도 2는 본 발명의 투명전도막의 주사전자현미경(SEM) 사진으로서, (a)(b)는 에칭전 사진이고, (c)(d)는 0.5%의 HCl 용액으로 45초 에칭한 후의 사진이다. (a)(b)와 (c)(d)는 에칭 후의 표면 거칠기가가 변하는 모습을 보여주며, (b)(d)에서 나타나듯이 ITO층은 AZO에 비해 매우 얇게 형성되어있다.2 is a scanning electron microscope (SEM) photograph of the transparent conductive film of the present invention, wherein (a) and (b) are photographs before etching, and (c) and (d) are photographs after 45 seconds etching with 0.5% HCl solution . (a), (b) and (c) (d) show the surface roughness after etching changes. As shown in (b) and (d), the ITO layer is very thin compared to AZO.
상기 광포획층(200)의 표면 텍스처 구조가 형성된 면의 표면거칠기가 10nm 이상인 것이 바람직하다.
It is preferable that the surface roughness of the surface on which the surface texture structure of the
본 발명은 이에 나아가, 태양전지의 전면 반사 방지막이나 전면전극 또는 후면 반사막으로 사용되는 투명전도막을 제조하는 방법으로서,The present invention further provides a method of manufacturing a transparent conductive film used as a front antireflection film, a front electrode, or a rear reflective film of a solar cell,
기판에 산화인듐주석(ITO : Indium Tin Oxide)의 광투과층을 형성시키는 단계(s100);Forming a light transmitting layer of indium tin oxide (ITO) on the substrate (s100);
상기 광투과층 위에 광포획층을 형성하는 단계(s200); 및 Forming a light trapping layer on the light transmitting layer (s200); And
상기 광포획층의 표면을 에칭하여 표면 텍스처 구조를 형성하는 단계(s300)를 포함하며,(S300) etching the surface of the light trapping layer to form a surface texture structure,
상기 광투과층의 전기전도도 A와 상기 광포획층의 전기전도도 a는 A>a의 관계가 있고, 상기 광투과층의 에칭성 B와 상기 광포획층의 에칭성 b는 B<b의 관계가 있는 것을 특징으로 하는 이중구조 투명전도막의 제조방법을 제공한다.
The relationship between the electrical conductivity A of the light transmitting layer and the electrical conductivity a of the light trapping layer is A> a, and the etching property B of the light transmitting layer and the etching property b of the light trapping layer satisfy the relationship of B < b The transparent conductive film having a double structure.
상기 기판에 산화인듐주석(ITO : Indium Tin Oxide)의 광투과층을 형성하는 단계(s100)는 RF 마그네트론 스퍼터링, DC 마그네트론 스퍼터링, MF 마그네트론 스퍼터링, 열증발법, 전자빔증발법, 열분무법 중 하나의 방법을 선택하여 증착시킨다.The step (s100) of forming an optically transparent layer of indium tin oxide (ITO) on the substrate may include one of RF magnetron sputtering, DC magnetron sputtering, MF magnetron sputtering, thermal evaporation, electron beam evaporation, Select the method to deposit.
상기 기판에 산화인듐주석(ITO : Indium Tin Oxide)의 광투과층을 형성하는 단계(s100)에서 상기 도핑농도는 0.1-0wt%인 것이 바람직하며, 증착시 증착압력은 0.5-5 mTorr 것이 바람직하다.
In the step (s100) of forming a light transmitting layer of indium tin oxide (ITO) on the substrate, the doping concentration is preferably 0.1-0 wt%, and the deposition pressure during deposition is preferably 0.5-5 mTorr .
상기 기판에 산화인듐주석(ITO : Indium Tin Oxide)의 광투과층을 형성하는 단계(s100)는 증착시 증착파워밀도가 0.5-10 W/cm2 로 적용하며, 증착두께는 50-200nm로 적용한다.
The step (s100) of forming a light transmitting layer of indium tin oxide (ITO) on the substrate is carried out with a deposition power density of 0.5-10 W / cm 2 and a deposition thickness of 50-200 nm do.
상기 광투과층 위에 광포획층을 형성하는 단계(s200)의 광포획층은 광투과층 위에, 알루미늄, 갈륨 또는 붕소가 도핑된 산화아연(Al Doped ZnO : AZO, Ga Doped ZnO : GZO, B Doped ZnO : BZO), 플루오르가 도핑된 산화주석(F-doped SnO2), 탄소나노튜브(CNT) 필름, 그래핀 중 하나를 선택하여 증착시키는 것이 바람직하다. The light trapping layer of step (s200) of forming the light trapping layer on the light transmitting layer is formed on the light transmitting layer by using aluminum doped ZnO (AZO), Ga Doped ZnO (GZO), B doped ZnO: BZO), fluorine-doped SnO2, carbon nanotube (CNT) film, and graphene.
광포획층(200)은 광투과층(100)의 위에 증착된 투명전도막으로서, 전기적 특성과 광투과성보다는 표면 텍스처 구조 형성을 위한 에칭성이 뛰어난 재질을 선택한다. 특히, 증착온도가 저온(150℃ 미만)에서 증착된 ZnO계 투명전도막을 사용하는 것이 바람직하다. 이러한 광포획층(200)의 일면은 에칭에 의하여 표면 텍스처 구조가 형성된다.
The
상기 광투과층(100) 위에 광포획층을 형성하는 단계(s200)의 광포획층은 증착압력 0.5-10 mTorr로 증착시키고, 150℃ 이하의 온도로 증착되어 형성되는 것이 바람직하다. 또한, 상기 광투과층 위에 광포획층을 형성하는 단계(s200)의 광포획층의 증착시 증착파워밀도는 0.5-10.0 W/cm2 로 적용하며, 증착시 증착두께는 상술한 바와 같이 500-1000nm인 것이 바람직하다.
Preferably, the light trapping layer of the step (s200) of forming the light trapping layer on the light transmitting layer (100) is formed by vapor deposition at a deposition pressure of 0.5-10 mTorr and vapor deposition at a temperature of 150 ° C or lower. In addition, the deposition power density in the deposition of the light trapping layer (s200) for forming the light trapping layer on the light transmission layer is 0.5-10.0 W / cm 2 , and the deposition thickness during deposition is 500- And more preferably 1000 nm.
도 4의 그래프는 AZO 박막을 HCl용액으로 45초 에칭한 후의 총 투과도와 산란투과도의 변화를 나타낸 것이다. 상기 그래프에 나타난 바와 같이 AZO 박막에 있어서, 50-150℃에서 산란투과도(Diffuse Transmittance)가 높게 나타나기 때문에 상기 증착온도를 150℃ 이하로 적용하는 것이다. 상기 그래프에서 총투과도(Total Transmittance)는 증착온도에 상관없이 유사한 것으로 나타났다.
The graph of FIG. 4 shows changes in total transmittance and scatter transmittance after etching the AZO thin film with a HCl solution for 45 seconds. As shown in the graph, the AZO thin film exhibits a high scattering transmittance at 50-150 DEG C, so that the deposition temperature is 150 DEG C or less. In the graph, the total transmittance was found to be similar regardless of the deposition temperature.
상기 광포획층의 표면을 에칭하여 표면 텍스처 구조를 형성하는 단계(s300)는 농도 0.1-10%의 HCl, H2C2O4 중 하나의 용액으로 에칭한다. 상기 광포획층의 표면을 에칭하여 표면 텍스처 구조를 형성하는 단계(s300)는 10-90초 동안 에칭하는 것이 바람직하다. 에칭하는 시간에 따라 도5의 그래프에 나타나듯이 AZO 박막의 면저항이 증가되기 때문에, 필요한 표면 거칠기와 면저항을 고려하여 에칭시간을 결정한다. AZO 박막의 면저항이 증가하는 이유는 에칭에 따른 두께의 감소에 기인한다.
Step (s300) of etching the surface of the light trapping layer to form a surface texture structure is performed by etching with a solution of one of HCl and H 2 C 2 O 4 at a concentration of 0.1-10%. Preferably, the step (S300) of etching the surface of the light trapping layer to form the surface texture structure is preferably performed for 10 to 90 seconds. Since the sheet resistance of the AZO thin film increases as shown in the graph of FIG. 5 depending on the etching time, the etching time is determined in consideration of the required surface roughness and sheet resistance. The reason why the sheet resistance of the AZO thin film is increased is due to the reduction of the thickness due to the etching.
상술한 바와 같이 광투과층(100)에 ITO를 적용하고 광포획층(200)에 AZO를 적용하는 경우, ITO층은 AZO층의 결정성에도 영향을 미치게 된다. 도 6은 단일층 AZO 박막 및 ITO 하부층 위에 증착온도에 따라 제조된 AZO/ITO 이중층의 엑스선회절(XRD) 변화를 나타낸 그래프이다. 박막의 재질과 증착온도에 따라 (a) AZO (250도), (b) AZO(50도)/ITO(200도), (c) AZO(100도)/ITO(200도), (d) AZO(150도)/ITO(200도), (e) AZO(250도)/ITO(200도)로 구분하였다. When ITO is applied to the light-transmitting
단일층의 AZO의 박막은 증착온도에 상관없이 강한 방향성을 갖는 피크를 나타내고, ITO 하부층 위에 증착된 AZO박막에서는 증착온도에 상관없이 방향성이 크게 감소됨을 알 수 있다. 따라서 ITO하부층이 AZO 상부층의 결정성에 영향을 미치게 됨을 알 수 있다.
The single layer of AZO thin film shows strong directional peak regardless of the deposition temperature, and the AZO thin film deposited on the ITO lower layer shows a significant decrease in orientation regardless of the deposition temperature. Therefore, it can be seen that the lower layer of ITO affects the crystallinity of the AZO upper layer.
또한 본 발명은 이에 나아가, 기판과, 상기 기판 상의 후면전극층과, 상기 광흡수층 상의 버퍼층과, 상기 버퍼층 상의 투명전도층을 포함하는 태양전지에 있어서, 상기 투명전도층이 상술한 본 발명의 이중구조 투명전도막인 것을 특징으로 하는 태양전지와 상술한 이중구조 투명전도막의 제조방법을 포함하는 태양전지의 제조방법을 제공한다.
The present invention further provides a solar cell including a substrate, a rear electrode layer on the substrate, a buffer layer on the light absorption layer, and a transparent conductive layer on the buffer layer, wherein the transparent conductive layer has a double structure Wherein the transparent conductive film is a transparent conductive film, and the method for manufacturing the double-structure transparent conductive film described above.
본 발명을 첨부된 도면과 함께 설명하였으나, 이는 본 발명의 요지를 포함하는 다양한 실시 형태 중의 하나의 실시 예에 불과하며, 당 업계에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 하는 데에 그 목적이 있는 것으로, 본 발명은 상기 설명된 실시 예에만 국한되는 것이 아님은 명확하다. 따라서, 본 발명의 보호범위는 하기의 청구범위에 의해 해석되어야 하며, 본 발명의 요지를 벗어나지 않는 범위 내에서의 변경, 치환, 대체 등에 의해 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함될 것이다. 또한, 도면의 일부 구성은 구성을 보다 명확하게 설명하기 위한 것으로 실제보다 과장되거나 축소되어 제공된 것임을 명확히 한다.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it should be understood that various changes and modifications will be apparent to those skilled in the art. It is to be understood that the present invention is not limited to the above-described embodiments. Accordingly, the scope of protection of the present invention should be construed according to the following claims, and all technical ideas which fall within the scope of equivalence by alteration, substitution, substitution, Range. In addition, it should be clarified that some configurations of the drawings are intended to explain the configuration more clearly and are provided in an exaggerated or reduced size than the actual configuration.
100. 광투과층
200. 광포획층
300. 기판100. The light-
200. Light trap layer
300. Substrate
Claims (21)
광투과층(100)과;
일면은 상기 광투과층(100)에 접하고, 타면에는 표면 텍스처 구조가 형성된 광포획층(200)으로 구성되며,
상기 광투과층(100)의 전기전도도 A와 상기 광포획층(200)의 전기전도도 a는 A>a의 관계가 있고, 상기 광투과층(100)의 에칭성 B와 상기 광포획층(200)의 에칭성 b는 B<b의 관계가 있는 것에 있어서,
상기 광투과층(100)은 두께가 50-200nm인 산화인듐주석(ITO : Indium Tin Oxide)층인 것을 특징으로 하는 이중구조 투명전도막.
A transparent conductive film used as a front antireflection film, a front electrode, or a rear reflection film of a solar cell,
A light transmitting layer (100);
And a light trapping layer (200) having a surface texture structure on the other surface, the surface being in contact with the light transmitting layer (100)
The electric conductivity A of the light transmitting layer 100 and the electric conductivity a of the light trapping layer 200 have a relationship of A> a and the etching property B of the light transmitting layer 100 and the light trapping layer 200 ) Has a relationship of B < b,
Wherein the light-transmitting layer (100) is an indium tin oxide (ITO) layer having a thickness of 50-200 nm.
The dual structure transparent conducting film according to claim 1, wherein the indium tin oxide (ITO) layer has a resistivity of 10 OMEGA / sq or less.
The dual structure transparent conducting film according to claim 1, wherein the surface of the light trapping layer (200) has a surface roughness of 10 nm or more.
The light-trapping layer (200) according to claim 4, wherein the light trapping layer (200) is made of aluminum, gallium or boron-doped zinc oxide (AZO, Ga-doped ZnO: GZO, B doped ZnO: BZO) (F-doped SnO2), a carbon nanotube (CNT) film, and a graphene.
The dual structure transparent conducting film according to claim 4, wherein the light trapping layer (200) has a thickness of 500 to 1000 nm.
기판에 50-200nm의 증착 두께로 산화인듐주석(ITO : Indium Tin Oxide)의 광투과층을 형성하는 단계(s100);
상기 광투과층 위에 광포획층을 형성하는 단계(s200); 및
상기 광포획층의 표면을 에칭하여 표면 텍스처 구조를 형성하는 단계(s300)를 포함하며,
상기 광투과층의 전기전도도 A와 상기 광포획층의 전기전도도 a는 A>a의 관계가 있고, 상기 광투과층의 에칭성 B와 상기 광포획층의 에칭성 b는 B<b의 관계가 있는 것을 특징으로 하는 이중구조 투명전도막의 제조방법.
A method for manufacturing a transparent conductive film used as a front antireflection film, a front electrode, or a rear reflection film of a solar cell,
Forming a light transmitting layer of indium tin oxide (ITO) on the substrate at a deposition thickness of 50 to 200 nm (s100);
Forming a light trapping layer on the light transmitting layer (s200); And
(S300) etching the surface of the light trapping layer to form a surface texture structure,
The relationship between the electrical conductivity A of the light transmitting layer and the electrical conductivity a of the light trapping layer is A> a, and the etching property B of the light transmitting layer and the etching property b of the light trapping layer satisfy the relationship of B < b Wherein the transparent conductive film is a transparent conductive film.
The method according to claim 7, wherein the step (s100) of forming a light transmitting layer of indium tin oxide (ITO) on the substrate comprises RF magnetron sputtering, DC magnetron sputtering, MF magnetron sputtering, thermal evaporation, electron beam evaporation, Wherein the transparent conductive film is formed by a method selected from a thermal spraying method and a vapor deposition method.
9. The method according to claim 8, wherein the doping concentration of the light-transmitting layer in step (s100) of forming a light-transmitting layer of indium tin oxide (ITO) on the substrate is 0.1-20 wt% Conductive film.
9. The method according to claim 8, wherein the deposition pressure in the step (s100) of forming a light transmitting layer of indium tin oxide (ITO) on the substrate is 0.5-5 mTorr. Gt;
The method of claim 8, wherein the indium tin oxide to the substrate: as a dual step (s100) of forming the light transmission layer of (ITO Indium Tin Oxide) is characterized in that the deposition power density during deposition of 0.5-10 W / cm 2 A method for manufacturing a transparent conductive film.
8. The method of claim 7, wherein the light trapping layer of the step (s200) of forming the light trapping layer on the light transmitting layer comprises at least one material selected from the group consisting of Al Doped ZnO (AZO), Ga Doped Wherein the transparent conductive film is formed by selectively depositing one of ZnO: GZO, B-doped ZnO: BZO, F-doped SnO2, carbon nanotube (CNT) Gt;
14. The method of claim 13, wherein the light trapping layer of the step (s200) of forming the light trapping layer on the light transmitting layer is formed by depositing at a deposition pressure of 0.5-10 mTorr.
14. The method according to claim 13, wherein the light trapping layer of the step (s200) of forming the light trapping layer on the light transmitting layer is formed by depositing at a temperature of 150 DEG C or less.
14. The method according to claim 13, wherein the deposition power density of the light trapping layer in step (s200) of forming the light trapping layer on the light transmitting layer is 0.5-10.0 W / cm 2 . Way.
The method according to claim 13, wherein the deposition thickness of the light trapping layer of the step (s200) of forming the light trapping layer on the light transmitting layer is 500-1000 nm.
According to claim 7, characterized in that the etching in step (s300) is a solution in a concentration of 0.1-10% HCl, H 2 C 2 O 4 to form a surface texture structure by etching the surface of the light trapping layer Wherein the transparent conductive film is a transparent conductive film.
19. The method of claim 18, wherein etching the surface of the light trapping layer to form a surface texture structure (s300) comprises etching for 10-90 seconds.
A manufacturing method of a solar cell, which comprises the manufacturing method of the double-structure transparent conductive film according to any one of claims 7 to 11, 13 to 19, .
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| JP2862174B2 (en) | 1987-05-22 | 1999-02-24 | グラステツク・ソーラー・インコーポレーテツド | Substrates for solar cells |
| KR101178496B1 (en) | 2011-09-28 | 2012-09-07 | 한국에너지기술연구원 | Bilayered transparent conductive film and fabrication method of the same |
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| JP2862174B2 (en) | 1987-05-22 | 1999-02-24 | グラステツク・ソーラー・インコーポレーテツド | Substrates for solar cells |
| KR101178496B1 (en) | 2011-09-28 | 2012-09-07 | 한국에너지기술연구원 | Bilayered transparent conductive film and fabrication method of the same |
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