KR101908472B1 - Method of manufacturing of CZTS-based absorber layer using metal and compound thin film - Google Patents
Method of manufacturing of CZTS-based absorber layer using metal and compound thin film 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
- H01L31/0256—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
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
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- H01L31/02—Details
- H01L31/0216—Coatings
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Abstract
본 발명은 금속 및 화합물 박막 전구체를 이용한 CZTS계 광흡수층을 제작하고, 화합물 박막에 포함되어 있는 황(S)의 양에 따라 밴드갭 변화 특성을 갖는 광흡수층을 형성하는 공정 방법에 관한 것이다. 본 발명은 금속 전구체 형성 및 황-셀렌화 열처리를 통한 CZTS계 박막 태양전지의 일반적인 제조 방법의 개선 효과를 보이는 것으로, 금속 물질을 대체하는 황화금속 물질을 이용하여 전구체를 제작하고 셀렌화 열처리함으로써 밴드갭 제어가 용이하고, 균일한 광흡수층 형성하는 CZTSSe 박막 태양전지를 구현할 수 있다. 또한, 본 발명은 셀렌화 열처리를 통한 CZTS계 박막 태양전지, 그 제조 방법에 대한 것으로, 상세하게는 황화금속 물질의 대체 정도에 따라 광흡수층의 밴드갭 에너지를 효과적으로 제어하기 위함이다.The present invention relates to a process for producing a CZTS light absorbing layer using metal and compound thin film precursors and forming a light absorbing layer having a bandgap change characteristic according to the amount of sulfur (S) contained in the compound thin film. The present invention demonstrates the effect of improving the general manufacturing method of a CZTS thin film solar cell through the formation of a metal precursor and a sulfur-selenifying heat treatment. A precursor is prepared using a sulfide metal material replacing a metal material, It is possible to realize a CZTSSe thin film solar cell which can easily control the gap and form a uniform light absorption layer. In addition, the present invention relates to a CZTS thin film solar cell through a selenization heat treatment, and a method for manufacturing the same. More specifically, the present invention is to effectively control the band gap energy of the light absorption layer according to the substitution degree of the sulfide metal material.
Description
본 발명은 금속 및 화합물 박막 전구체를 이용한 CZTS계 광흡수층을 제작하고, 화합물 박막에 포함되어 있는 황(S)의 양에 따라 밴드갭 변화 특성을 갖는 광흡수층을 형성하는 공정 방법에 관한 것이다.The present invention relates to a process for producing a CZTS light absorbing layer using metal and compound thin film precursors and forming a light absorbing layer having a bandgap change characteristic according to the amount of sulfur (S) contained in the compound thin film.
박막 태양전지 소자 물질에서 CIGS(Cu(In,Ga)Se2)로 대표되는 찰코파이라이트(chalcopyrite) 기반의 화합물을 이용한 광흡수층은 직접 천이형 물질로 흡수계수가 높아 얇은 박막으로도 고효율의 태양전지를 제조할 수 있으며 열적 안정성이 뛰어나 많은 연구가 이루어지고 있다. 또한, 구성 원소의 조성조절을 통해 결정격자 상수 뿐만 아니라 1.0~2.0eV 까지의 에너지 밴드갭의 조절이 가능하다. 이러한 CIGS계 화합물 반도체는 전기 및 광학적으로 안정성이 우수하여 태양전지의 광흡수층 구현에 유리하다. 독일의 태양에너지수소연구센터(ZSW)에서는 유리기판을 이용한 태양전지에서 21.7% 효율을 달성하였고, 스위스의 재료시험연구원(EMPA)에서는 poly-imide 유연기판을 이용하여 20.4%의 변환 효율을 달성한 바가 있다.The light absorption layer using a chalcopyrite based compound represented by CIGS (Cu (In, Ga) Se 2 ) in a thin film solar cell element material is a direct transition type material and has a high absorption coefficient. Therefore, A battery can be manufactured, and thermal stability is excellent, and many studies have been made. In addition, it is possible to control the energy band gap from 1.0 to 2.0 eV as well as the crystal lattice constant by controlling the composition of the constituent elements. Such CIGS compound semiconductors are excellent in electrical and optical stability and are advantageous for realizing a light absorption layer of a solar cell. At the Solar Energy Hydrogen Research Center (ZSW) in Germany, 21.7% efficiency was achieved in solar cells using glass substrates. In Switzerland, the Materials Testing Laboratory (EMPA) achieved a conversion efficiency of 20.4% using a poly-imide flexible substrate There is a bar.
그러나 현재 태양전지 기술 개발은 고효율인 동시에 저가 생산을 목표로 하여 연구가 진행되는 추세이다. CIGS계의 화합물 반도체는 In, Ga 등의 유해성과 가격 경쟁력에 대한 문제점을 보이는 한편, 그 보완으로 희소금속이 아닌 Zn, Sn으로 대체한 CZTS계 소재를 이용한 연구 개발도 진행되고 있다. 이는 자연적으로 매장량이 풍부한 원소를 이용하여 저가 생산이 가능하고, 유해성이 낮아 친환경적인 물질로 평가받는 장점을 가지고 있다.However, the current development of solar cell technology is progressing with high efficiency and low price production. CIGS-based compound semiconductors have problems in terms of harmfulness and price competitiveness of In and Ga, and research and development using CZTS-based materials that are replaced with Zn and Sn instead of rare metals are underway. This is advantageous in that it can be produced at low cost naturally by using abundantly available elements and is evaluated as an environmentally friendly material due to low harmfulness.
CIGS계 물질을 대체할 kesterite 기반의 CZTS(Cu2ZnSnS4), CZTSe(Cu2ZnSnSe4), CZTSSe(Cu2ZnSn(S,Se)4) 화합물 반도체는 104cm-1 이상의 높은 광흡수계수를 가지며, 1.0~1.5eV의 밴드갭 에너지 조절이 가능한 직접 천이형 물질 특성을 보인다. CZTS계 광흡수층은 Zn/Sn비가 1이상, Cu/(Zn+Sn)비가 1미만인 화학량론 조성비에서 우수한 태양전지 특성을 보이고 있다. IBM에서 발표한 최고 효율의 CZTS계 태양전지는 Zn/Sn=1.1, Cu/(Zn+Sn)=0.8의 조성비를 가진 흡수층으로 광전효율 12.6%, 개방전압 513.4mV, 단락전류 35.2mA/cm2, 충진율 69.8%의 특성을 보였다. 그리고 광흡수층의 에너지 밴드갭은 1.13eV로 CZTSSe 흡수층 특성을 나타내었다.Of kesterite based alternative to CIGS-based material CZTS (Cu 2 ZnSnS 4), CZTSe (Cu 2 ZnSnSe 4), CZTSSe (Cu 2 ZnSn (S, Se) 4) compound semiconductor is more than 10 4 cm -1 high light absorption coefficient, And has a direct-transition type material characteristic capable of adjusting the band gap energy of 1.0 to 1.5 eV. The CZTS light absorbing layer exhibits excellent solar cell characteristics at a stoichiometric composition ratio of Zn / Sn ratio of 1 or more and Cu / (Zn + Sn) ratio of less than 1. The most efficient CZTS solar cell announced by IBM is an absorption layer with a composition ratio of Zn / Sn = 1.1 and Cu / (Zn + Sn) = 0.8. It has a photoelectric efficiency of 12.6%, an open voltage of 513.4mV, short circuit current of 35.2mA / cm 2 , And the filling rate was 69.8%. The energy bandgap of the light absorption layer was 1.13 eV, indicating the characteristics of the CZTSSe absorption layer.
하지만, 비슷한 에너지 밴드갭을 가진 CIGSe계나 SQ(Shockley-Queisser) limit 이론과 비교해 볼 때, 다른 태양전지 특성인자 보다 개방전압 부분에서 그 감소가 두드러진다. 이를 해결하기 위한 인듐(In), 게르마늄(Ge) 등의 도핑기술을 이용하여 CZTS계 태양전지의 개방전압의 증가를 위한 많은 연구가 진행되고 있다. 또한, 효율과 단락전류의 감소를 최소화하면서 개방전압을 최대한 증가시키기 위한 연구 중에 하나가 황(S) 함유량을 조절하여 최적화된 CZTSSe 광흡수층을 제작하는 것이다. However, when compared with the CIGSe or Shockley-Queisser (SQ) limit theory with similar energy band gaps, the decrease in open-circuit voltage is more noticeable than other solar cell characteristics. To solve this problem, many studies have been made for increasing the open-circuit voltage of CZTS-type solar cells by using a doping technique such as indium (In) and germanium (Ge). In addition, one of the studies to maximize the open-circuit voltage while minimizing the reduction of efficiency and short-circuit current is to fabricate an optimized CZTSSe light absorption layer by controlling the sulfur content.
이에 본 발명자는 황(S)을 포함하는 CZTSSe 광흡수층 제작을 위한 최적화된 공정 기술 개발을 위하여, 적층구조의 금속 및 황화금속 전구체를 제작하고, 고온 셀렌화 열처리 공정을 통해 황-셀렌화하는 CZTS계 광흡수층을 형성하는 제조 방법을 확립하였다.Accordingly, the inventors of the present invention prepared a metal and a metal sulfide precursor of a laminated structure and developed a CZTSSe light-absorbing layer containing a sulfur-selenized CZTS A method of forming a light absorbing layer was established.
따라서 본 발명의 목적은 광흡수층의 밴드갭 에너지를 제어할 수 있는 박막 태양전지의 광흡수층 제조방법을 제공하는 것이다.It is therefore an object of the present invention to provide a method of manufacturing a light absorbing layer of a thin film solar cell capable of controlling the band gap energy of the light absorbing layer.
본 발명의 또 다른 목적은 광흡수층의 밴드갭 에너지를 제어할 수 있는 박막 태양전지의 제조방법을 제공하는 것이다.It is still another object of the present invention to provide a method of manufacturing a thin film solar cell capable of controlling the band gap energy of a light absorption layer.
상기와 같은 목적을 달성하기 위해서, 본 발명은 금속 및 화합물을 함유하는 전구체층을 형성한 후 셀렌화 처리 공정을 수행하는 단계를 포함하는, 박막 태양전지의 광흡수층 제조방법을 제공한다.In order to achieve the above object, the present invention provides a method of manufacturing a light absorbing layer of a thin film solar cell, which comprises the step of forming a precursor layer containing a metal and a compound and then carrying out a selenization process.
본 발명의 일실시예에 있어서, 상기 전구체층은 Cu 층, Zn 층, Sn 층, CuS 층, Cu2S 층, SnS 층 및 ZnS 층으로 이루어진 군으로부터 선택된 1종 이상의 층이 적층된 구조로 형성될 수 있다.In one embodiment of the present invention, the precursor layer is formed by stacking at least one layer selected from the group consisting of a Cu layer, a Zn layer, a Sn layer, a CuS layer, a Cu 2 S layer, a SnS layer and a ZnS layer .
본 발명의 일실시예에 있어서, 상기 전구체층은 Zn/Sn/Cu/ZnS, Zn/Cu/Sn/ZnS, Zn/Sn/ZnS/Cu, Zn/Cu/ZnS/Sn, Zn/ZnS/Sn/Cu 및 Zn/ZnS/Cu/Sn로 이루어진 군으로부터 선택된 적층 구조를 가질 수 있다.In one embodiment of the present invention, the precursor layer may include at least one of Zn / Sn / Cu / ZnS, Zn / Cu / Sn / ZnS, Zn / Sn / ZnS / Cu, Zn / Cu / ZnS / / Cu and Zn / ZnS / Cu / Sn.
본 발명의 일실시예에 있어서, 상기 Sn 금속은 SnS로 대체되거나 Cu 금속은 Cu2S로 대체됨으로써 전구체층의 황(S) 함유량을 증대시킬 수 있다.In one embodiment of the present invention, the Sn metal may be replaced by SnS, or the Cu metal may be replaced by Cu 2 S, thereby increasing the sulfur content of the precursor layer.
본 발명의 일실시예에 있어서, 상기 전구체층 형성은 스퍼터링법(sputtering), 동시증발증착법(evaporation), CVD법(Chemical vapor deposition), 유기금속화학기상증착(MOCVD), 근접승화법(Close-spaced sublimation, CSS), 스프레이 피롤리시스(Spray pyrolysis), 화학 스프레이법(Chemical spraying), 스크린프린팅법(Screeen printing), 비진공 액상성막법, CBD법(Chemical bath deposition), VTD법(Vapor transport deposition) 및 전착법(electrodeposition) 중에서 어느 하나의 방법에 의하여 형성될 수 있다.In one embodiment of the present invention, the precursor layer may be formed by a sputtering method, a simultaneous evaporation method, a CVD (Chemical Vapor Deposition) method, an MOCVD (Metal Organic Chemical Vapor Deposition) Spray pyrolysis, chemical spraying, screen printing, non-vacuum liquid-phase deposition, CBD (chemical bath deposition), VTD (vapor transport) deposition, and electrodeposition. [0031] As shown in FIG.
본 발명의 일실시예에 있어서, 상기 셀렌화 처리 공정은 밀폐된 챔버 내의 불활성 기체 분위기하에서 열처리를 통해 수행될 수 있다.In one embodiment of the present invention, the selenization process may be performed through heat treatment in an inert gas atmosphere in a closed chamber.
본 발명의 일실시예에 있어서, 상기 불활성 기체는 아르곤(Ar)일 수 있다.In one embodiment of the present invention, the inert gas may be argon (Ar).
본 발명의 일실시예에 있어서, 상기 열처리는 450~550℃의 최종 온도에서 10 ~ 30분 동안 진행될 수 있다.In one embodiment of the present invention, the heat treatment may be performed at a final temperature of 450 to 550 ° C for 10 to 30 minutes.
본 발명의 일실시예에 있어서, 상기 셀렌화 처리 공정시 황(S) 가스를 동시에 주입하는 과정을 통해 황(S) 함유량을 증대시킬 수 있다.In one embodiment of the present invention, sulfur (S) content can be increased through simultaneous injection of sulfur (S) gas during the selenization process.
또한, 본 발명은 a) 기판 상에 후면전극을 형성하는 단계; 및 b) 상기 후면전극 상에 금속 및 화합물을 함유하는 전구체층을 형성한 후 셀렌화 처리 공정을 거쳐 광흡수층을 형성하는 단계를 포함하는, 박막 태양전지의 제조방법을 제공한다.The present invention also provides a method of manufacturing a plasma display panel, comprising the steps of: a) forming a back electrode on a substrate; And b) forming a precursor layer containing a metal and a compound on the rear electrode, and then forming a light absorption layer through a selenization process.
본 발명은 금속 전구체 형성 및 황-셀렌화 열처리를 통한 CZTS계 박막 태양전지의 일반적인 제조 방법의 개선 효과를 보이는 것으로, 금속 물질을 대체하는 황화금속 물질을 이용하여 전구체를 제작하고 셀렌화 열처리함으로써 밴드갭 제어가 용이하고, 균일한 광흡수층 형성하는 CZTSSe 박막 태양전지를 구현할 수 있다.The present invention demonstrates the effect of improving the general manufacturing method of a CZTS thin film solar cell through the formation of a metal precursor and a sulfur-selenifying heat treatment. A precursor is prepared using a sulfide metal material replacing a metal material, It is possible to realize a CZTSSe thin film solar cell which can easily control the gap and form a uniform light absorption layer.
도 1은 금속 및 황화금속 물질로 이루어진 전구체 적층구조를 나타낸 것이다.
도 2는 제작된 CZTS계 태양전지 소자의 EQE 분석을 통한 밴드갭 에너지 변화를 나타낸 것이다.
도 3은 제작된 CZTS계 광흡수층의 XRD 분석을 통한 (112) 피크의 변화를 나타낸 것이다.
도 4는 제작된 CZTS계 태양전지 소자의 황화금속 물질의 대체 정도에 따른 I-V 특성을 나타낸 것이다.1 shows a precursor laminate structure made of a metal and a metal sulfide material.
FIG. 2 shows the band gap energy change by EQE analysis of the fabricated CZTS solar cell device.
3 shows the change of the peak (112) through the XRD analysis of the CZTS-type optical absorption layer.
FIG. 4 shows the IV characteristics of the manufactured CZTS-based solar cell device according to the substitution degree of the sulfide metal material.
본 발명의 실시예들은 여러 가지 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들에 한정되는 것은 아니다. 본 발명의 실시예들은 본 발명을 보다 완전하게 설명하기 위하여 제공되는 것이다. 본 명세서에서 어떤 막(또는 층)이 다른 막(또는 층) 또는 기판의 “위(또는 상)”에 있다고 기재된 경우, 상기 어떤 막(또는 층)이 상기 다른 막(또는 층) 위에 직접 존재할 수 있고, 그 사이에 제3의 다른 막(또는 층)이 개재될 수 있다.The embodiments of the present invention can be modified in various forms, and the scope of the present invention is not limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention. It is to be understood that any film (or layer) may be directly present on the other film (or layer) if it is described herein as being "on (or over) And a third other film (or layer) may be interposed therebetween.
이하, 첨부된 도면을 참조하여 본 발명의 일 실시예에 따른 태양전지 제조방법에 대하여 상세히 설명한다. 명세서 전체에 걸쳐 동일 참조 부호는 동일 구성 요소를 지칭한다.Hereinafter, a method of manufacturing a solar cell according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. Like reference numerals refer to like elements throughout the specification.
도 1은 본 발명에서 제조한 CZTS계 전구체의 단면도를 나타낸 것으로, 후면전극(101)인 Mo층이 증착된 기판(100)에 Zn(102), Sn(103), Cu(104), ZnS(105) 등의 금속 및 황화금속으로 이루어진 전구체를 형성되어 있는 구조를 보여준다.FIG. 1 is a cross-sectional view of a CZTS-based precursor according to the present invention. Referring to FIG. 1, Zn (102), Sn (103), Cu (104), ZnS 105), and a precursor composed of a metal sulfide are formed.
본 발명에서는 금속 및 황화금속 물질을 이용하여 전구체를 제작하고, 셀렌화 열처리 공정을 진행하였다. 그리고 황(S)이 함유된 정도에 따른 광흡수층의 밴드갭 조절을 유도할 수 있는 방법을 규명하였다.In the present invention, a precursor was prepared using metal and metal sulfide materials, and a selenization heat treatment process was performed. And the method of inducing the bandgap control of the light absorbing layer according to the degree of sulfur (S) contained therein.
따라서 본 발명은 금속 및 화합물을 함유하는 전구체층을 형성한 후 셀렌화 처리 공정을 수행하는 단계를 포함하는, 박막 태양전지의 광흡수층 제조방법을 제공한다.Accordingly, the present invention provides a method of manufacturing a light absorbing layer of a thin film solar cell, which comprises forming a precursor layer containing a metal and a compound, and then carrying out a selenization treatment process.
본 발명의 일 구체예에서, 상기 전구체층은 Cu 층, Zn 층, Sn 층, CuS 층, Cu2S 층, SnS 층 및 ZnS 층으로 이루어진 군으로부터 선택된 1종 이상의 층이 적층된 구조로 형성될 수 있으며, 자세하게는, Zn/Sn/Cu/ZnS, Zn/Cu/Sn/ZnS, Zn/Sn/ZnS/Cu, Zn/Cu/ZnS/Sn, Zn/ZnS/Sn/Cu 및 Zn/ZnS/Cu/Sn로 이루어진 군으로부터 선택된 적층 구조를 가질 수 있다. 한편, 후면전극인 Mo층 다음으로 ZnS 박막을 증착하는 것은 후면전극과의 계면에 이차상 형성이 우려되므로 이를 제한하는 것이 바람직하다.In one embodiment of the present invention, the precursor layer is formed by stacking at least one layer selected from the group consisting of a Cu layer, a Zn layer, a Sn layer, a CuS layer, a Cu 2 S layer, a SnS layer and a ZnS layer Zn / Sn / Cu / ZnS / ZnS / Cu / ZnS / Cu / ZnS / Cu / ZnS / Cu / Sn, and the like. On the other hand, it is preferable to deposit the ZnS thin film next to the Mo layer, which is the rear electrode, because it is likely to form a secondary phase at the interface with the rear electrode.
상기 전구체를 이루는 각 박막은 스퍼터링법(sputtering), 동시증발증착법(evaporation), CVD법(Chemical vapor deposition), 유기금속화학기상증착(MOCVD), 근접승화법(Close-spaced sublimation, CSS), 스프레이 피롤리시스(Spray pyrolysis), 화학 스프레이법(Chemical spraying), 스크린프린팅법(Screeen printing), 비진공 액상성막법, CBD법(Chemical bath deposition), VTD법(Vapor transport deposition) 및 전착법(electrodeposition) 중에서 어느 하나의 방법에 의하여 수행될 수 있고, 이에 제한되지는 않지만, 스퍼터링 공정 방법이 바람직하다. 스퍼터링(sputtering) 공정으로 제작된 박막은 재현성이 우수하고 대면적에 유리한 장점이 있다.Each of the thin films forming the precursor may be formed by a sputtering method, a simultaneous evaporation method, a CVD method, an MOCVD method, a close-spaced sublimation method (CSS) A chemical vapor deposition method, a chemical vapor deposition method, a chemical vapor deposition method, a screen printing method, a non-vacuum liquid phase film forming method, a CBD method (chemical bath deposition), a VTD method (vapor transport deposition), and an electrodeposition ), And a sputtering process method is preferable, although not limited thereto. The thin film produced by the sputtering process is excellent in reproducibility and advantageous in large area.
전구체층을 형성하는 금속-화합물 박막은 후면전극 상에, Zn, Sn, Cu, ZnS 등의 타겟을 이용한 스퍼터링 방법을 이용한 증착할 수 있는데, 본 발명의 일실시예에서는 Mo/Zn/Sn/Cu/ZnS 순으로 진행하였다. 이때 압력은 1~3mTorr, 아르곤(Ar) 15~20sccm의 가스분위기에서 상온 증착할 수 있다.The metal-compound thin film forming the precursor layer can be deposited on the rear electrode using a sputtering method using a target such as Zn, Sn, Cu, or ZnS. In one embodiment of the present invention, Mo / Zn / Sn / Cu / ZnS in that order. At this time, the pressure can be deposited at room temperature in a gas atmosphere of 1 to 3 mTorr and argon (Ar) of 15 to 20 sccm.
본 발명의 다른 구체예에서, 박막 태양전지의 광흡수층 제조방법은 Sn은 SnS로 대체되거나 Cu은 Cu2S로 대체됨으로써 전구체층의 황(S) 함유량을 증대시킬 수 있다.In another embodiment of the invention, a light absorbing layer manufacturing method of the thin film solar cell, or Sn is replaced with Cu SnS it is possible to increase the sulfur (S) content of the precursor layer by being replaced with a Cu 2 S.
본 발명의 또 다른 구체예에서, 박막 태양전지의 광흡수층 제조방법은 셀렌화 처리 공정시 황(S) 가스를 동시에 주입하는 과정을 통해서 황(S) 함유량을 증대시킬 수 있다.In another embodiment of the present invention, the method of manufacturing a light absorbing layer of a thin film solar cell can increase sulfur (S) content by simultaneously injecting sulfur (S) gas during the selenization process.
이후, 셀렌화 열처리를 통해 광흡수층을 형성할 수 있다.Thereafter, the light absorbing layer can be formed through the selenization heat treatment.
셀렌화 열처리 공정은 RTP 장비를 이용한, 밀폐된 챔버 내에서 불활성 기체 분위기하에서 수행할 수 있고, 밀폐된 챔버의 사용은 셀레늄(Se) 소스의 기화 공급을 효과적으로 진행할 수 있다. 상기 불활성 기체는 아르곤(Ar)을 사용할 수 있다.The selenization heat treatment process can be performed in an inert gas atmosphere in an enclosed chamber using RTP equipment, and the use of a sealed chamber can effectively promote vaporization supply of a selenium (Se) source. The inert gas may be argon (Ar).
상기 열처리 공정시, 아르곤(Ar)과 더불어 황화수소(H2S) 가스를 동시에 주입하거나 황화수소 가스를 이용한 후열처리 공정을 이용하여 광흡수층의 황(S) 함유량을 추가로 조절할 수 있다.During the heat treatment process, the sulfur (S) content of the photoabsorption layer can be further controlled by simultaneously injecting hydrogen sulfide (H 2 S) gas in addition to argon (Ar) or by post heat treatment using hydrogen sulfide gas.
셀렌화 열처리 공정은 셀레늄(Se) 소스를 기화시켜 전구체 내로 침투시키는데, 셀레늄(Se) 소스는 펠렛 및 파우더 형태의 셀레늄(Se) 등이 사용가능하고, 불활성 기체를 이용한 상압 이상 분위기에서 450~550℃의 반응온도로 열처리할 수 있다.In the selenization heat treatment process, the selenium (Se) source is vaporized and permeated into the precursor. As the selenium (Se) source, pellets and selenium (Se) in the form of powder can be used. In the atmosphere above atmospheric pressure using an inert gas, Lt; 0 > C.
또한, 본 발명은 a) 기판 상에 후면전극을 형성하는 단계; 및 b) 상기 후면전극 상에 금속 및 화합물을 함유하는 전구체층을 형성한 후 셀렌화 처리 공정을 거쳐 광흡수층을 형성하는 단계를 포함하는, 박막 태양전지의 제조방법을 제공한다.The present invention also provides a method of manufacturing a plasma display panel, comprising the steps of: a) forming a back electrode on a substrate; And b) forming a precursor layer containing a metal and a compound on the rear electrode, and then forming a light absorption layer through a selenization process.
본 발명은 상기 a) 단계 이전에 기판을 준비하는 단계를 포함할 수 있다.The present invention may include a step of preparing the substrate before the step a).
기판(100)은 단단한(hard) 재질의 기판 또는 유연성(flexible) 재질의 기판을 사용한다. 예를 들어, 기판으로 단단한 재질의 기판을 사용하는 경우, 유리 플레이트, 석영 플레이트, 실리콘 플레이트, 합성수지 플레이트, 금속 플레이트 등을 포함할 수 있다. 상기 유리 플레이트는 소다 라임 유리(soda lime glass), 보로실리케이트 유리(borosilicate glass) 및 무알칼리 유리(alkali free glass) 등이 사용될 수 있다. 상기 합성수지 플레이트는 폴리에틸렌나프탈레이트, 폴리에틸렌테레프탈레이트, 폴리카보네이트, 폴리비닐알코올, 폴리아크릴레이트, 폴리이미드, 폴리노르보넨, 폴리에테르설폰 등이 사용될 수 있다. 상기 금속 플레이트로는 알루미늄 호일 등이 사용될 수 있다.The
본 발명이 일 구체예에서는 기판 준비 단계로 일반적으로 많이 사용되는 SLG(소다 라임 유리)를 준비하였다. 세척은 아세톤, 메탄올로 각각 초음파 10분 세척 후 증류수(D.I. water)로 충분히 세척하여 준비하였다.In one embodiment of the present invention, SLG (soda lime glass), which is generally used as a substrate preparation step, is prepared. Washing was done by washing with acetone and methanol for 10 minutes, respectively, followed by thorough washing with distilled water (D.I. water).
본 발명의 a) 단계는 기판 상에 후면전극을 형성하는 단계이다.The step a) of the present invention is a step of forming a back electrode on a substrate.
상기 후면전극은 몰리브덴(Mo), 구리(Cu), 알루미늄(Al), 니켈(Ni), 텅스텐(W), 코발트(Co), 티탄(Ti), 구리(Cu), 금(Au) 또는 이들의 합금 중에서 선택되는 1종 이상을 사용할 수 있으나, 특별히 그 종류를 제한하는 것은 아니다. 몰리브덴(Mo)은 높은 전기전도성과 CZTS계 광흡수층과의 오믹 접합이 가능하고 내열특성 및 계면 접착력이 우수한바, 본 발명의 하기 실시예에서는 몰리브덴 전극을 사용하였다. 후면전극 두께는 0.2μm ~ 1μm일 수 있으나, 특별히 그 범위를 한정하는 것은 아니다. 일반적으로 후면전극은 높은 전기전도도가 요구되고 고온 안정성을 가져야 하며, 종래에는 이러한 요건을 충족시킬 수 있는 몰리브덴(Mo)이 주로 사용된다.The rear electrode may be formed of one selected from the group consisting of Mo, Cu, Al, Ni, W, Co, Ti, Cu, Au, , But it is not particularly limited to these types. Molybdenum (Mo) has high electrical conductivity and is capable of ohmic bonding with a CZTS-based light absorbing layer, and is excellent in heat resistance and interfacial adhesion. Molybdenum electrodes are used in the following embodiments of the present invention. The thickness of the rear electrode may be 0.2 탆 to 1 탆, but the range is not particularly limited. In general, the back electrode must have high electrical conductivity and high temperature stability, and molybdenum (Mo), which can meet these requirements in the past, is mainly used.
후면전극은 스퍼터링법(sputtering), 증발법(evaporation), CVD법(Chemical vapor deposition), 유기금속화학기상증착(MOCVD), 근접승화법(Close-spaced sublimation, CSS), 스프레이 피롤리시스(Spray pyrolysis), 화학 스프레이법(Chemical spraying), 스크린프린팅법(Screeen printing), 비진공 액상성막법, CBD법(Chemical bath deposition), VTD법(Vapor transport deposition), 및 전착법(electrodeposition) 중에서 선택된 어느 하나의 방법으로 형성될 수 있다.The rear electrode may be formed by sputtering, evaporation, chemical vapor deposition (MOCVD), close-spaced sublimation (CSS), spraying a chemical vapor deposition (CVD) method, a vapor deposition (VTD) method, and an electrodeposition method, which are selected from the group consisting of pyrolysis, chemical spraying, screen printing, non-vacuum liquid phase film forming, CBD Can be formed in one method.
본 발명이 일 구체예에서는 SLG 기판 위에 광흡수층과의 오믹(ohmic)접합 및 고온의 열처리에서 우수한 안정성을 갖는 몰리브덴(Mo)층을 후면전극으로서 DC 스퍼터링(직류 스퍼터링) 공정으로 0.6 마이크로미터 두께로 형성시켰다. 그러나 마이크로미터의 두께는 일 구현예로 기재되는 것일 뿐이며, 사용자의 박막 제조 공정에 따라서 더 얇거나 두꺼울 수 있다.In one embodiment of the present invention, a molybdenum (Mo) layer having excellent stability in an ohmic junction with a light absorption layer and a high-temperature heat treatment on a SLG substrate is formed as a back electrode by a DC sputtering (DC sputtering) process to a thickness of 0.6 micrometers / RTI > However, the thickness of the micrometer is only described in one embodiment, and may be thinner or thicker depending on the thin film manufacturing process of the user.
본 발명의 b) 단계는 상기 후면전극 상에 금속 및 화합물을 함유하는 전구체층을 형성한 후 셀렌화 처리 공정을 거쳐 광흡수층을 형성하는 단계이다.In the step b) of the present invention, a precursor layer containing a metal and a compound is formed on the rear electrode, and then a light absorbing layer is formed through a selenization process.
후면전극층 상에 증착되는 전구체층은 Cu 층, Zn 층, Sn 층, CuS 층, Cu2S 층, SnS 층 및 ZnS 층으로 이루어진 군으로부터 선택된 1종 이상의 층이 적층된 구조로 형성될 수 있다.The precursor layer deposited on the rear electrode layer may be formed by stacking at least one layer selected from the group consisting of a Cu layer, a Zn layer, a Sn layer, a CuS layer, a Cu 2 S layer, a SnS layer and a ZnS layer.
금속 전구체층의 형성은 스퍼터링법(sputtering), 동시증발증착법(evaporation), CVD법(Chemical vapor deposition), 유기금속화학기상증착(MOCVD), 근접승화법(Close-spaced sublimation, CSS), 스프레이 피롤리시스(Spray pyrolysis), 화학 스프레이법(Chemical spraying), 스크린프린팅법(Screeen printing), 비진공 액상성막법, CBD법(Chemical bath deposition), VTD법(Vapor transport deposition), 및 전착법(electrodeposition) 중에서 어느 하나의 방법에 의하여 증착될 수 있으며, 바람직하게는 스퍼터링 공정으로 수행될 수 있다. 스퍼터링 공정으로 증착하는 경우에, 재현성이 우수한 대면적의 박막 태양전지의 제조가 가능하다. The metal precursor layer may be formed by sputtering, evaporation, chemical vapor deposition (MOCVD), close-spaced sublimation (CSS) A chemical vapor deposition method, a chemical vapor deposition method, a chemical vapor deposition method, a screen printing method, a non-vacuum liquid phase film forming method, a CBD method (chemical bath deposition), a VTD method (vapor transport deposition), and an electrodeposition ), And can be preferably performed by a sputtering process. In the case of depositing by a sputtering process, it is possible to manufacture a thin film solar cell with a large area and excellent reproducibility.
금속-화합물 박막은 후면전극 상에, Zn, Sn, Cu, ZnS 등의 타겟을 이용한 스퍼터링 방법을 이용한 증착할 수 있는데, 본 발명의 일실시예에서는 Mo/Zn/Sn/Cu/ZnS 순으로 진행하였다. 이때 압력은 1 내지 3mTorr, 아르곤(Ar) 15 내지 20sccm의 가스분위기에서 상온 증착한다.The metal-compound thin film can be deposited on the rear electrode by a sputtering method using a target such as Zn, Sn, Cu, ZnS. In one embodiment of the present invention, Mo / Zn / Sn / Cu / Respectively. At this time, the pressure is evaporated at room temperature in a gas atmosphere of 1 to 3 mTorr and argon (Ar) of 15 to 20 sccm.
또한, 상기 전구체 박막 증착 순서는 Zn/Cu/Sn/ZnS, Zn/Sn/ZnS/Cu, Zn/Cu/ZnS/Sn, Zn/ZnS/Sn/Cu, Zn/ZnS/Cu/Sn 등의 순서로 수행할 수 있다. 후면전극인 Mo층 다음으로 ZnS 박막을 증착하는 것은 후면전극과의 계면에 이차상 형성이 우려되어 제한하기로 한다. 그리고 광흡수층의 황(S) 함유를 더 증가시키기 위해서, Sn과 Cu 박막의 일부 대신 SnS, Cu2S, CuS 등의 화합물 타겟을 이용하여 전구체를 제작할 수 있다.The order of deposition of the precursor thin film is the order of Zn / Cu / Sn / ZnS, Zn / Sn / ZnS / Cu, Zn / Cu / ZnS / Sn, Zn / ZnS / Sn / . ≪ / RTI > Deposition of the ZnS thin film next to the Mo layer as the rear electrode is limited due to the possibility of forming a secondary phase at the interface with the rear electrode. In order to further increase the content of sulfur (S) in the light absorption layer, a precursor can be prepared by using a compound target such as SnS, Cu 2 S, CuS instead of Sn and a part of the Cu thin film.
이후, 셀렌화 열처리를 통해 광흡수층을 형성할 수 있다.Thereafter, the light absorbing layer can be formed through the selenization heat treatment.
셀렌화 열처리 공정은 RTP 장비를 이용한, 밀폐된 챔버 내에서 불활성 기체 분위기하에서 수행할 수 있고, 밀폐된 챔버의 사용은 셀레늄(Se) 소스의 기화 공급을 효과적으로 진행할 수 있다. 상기 불활성 기체는 아르곤(Ar)을 사용할 수 있다. 셀렌화 열처리 공정은 셀레늄(Se) 소스를 기화시켜 전구체 내로 침투시키는데, 셀레늄(Se) 소스는 펠렛 및 파우더 형태의 셀레늄(Se) 등이 사용가능하고, 불활성 기체를 이용한 상압 이상 분위기에서 450~550℃의 반응온도로 열처리한다.The selenization heat treatment process can be performed in an inert gas atmosphere in an enclosed chamber using RTP equipment, and the use of a sealed chamber can effectively promote vaporization supply of a selenium (Se) source. The inert gas may be argon (Ar). In the selenization heat treatment process, the selenium (Se) source is vaporized and permeated into the precursor. As the selenium (Se) source, pellets and selenium (Se) in the form of powder can be used. In the atmosphere above atmospheric pressure using an inert gas, Lt; RTI ID = 0.0 > C. ≪ / RTI >
광흡수층 형성을 위한 셀렌화 처리 공정은 셀레늄 소스와 더불어 밴드갭 조절을 위한 황(S) 가스를 동시에 주입시킬 수 있다. The selenization process for forming the light absorbing layer can simultaneously inject selenium source and sulfur (S) gas for controlling the bandgap.
상기와 같이 광흡수층 형성이 완료되면 후속 공정으로 버퍼층과 전면전극층, 그리고 그리드 전극을 증착하여 CZTS계 태양전지 소자를 제작할 수 있다.After the formation of the light absorbing layer as described above, a buffer layer, a front electrode layer, and a grid electrode are deposited in a subsequent step to fabricate a CZTS solar cell device.
광흡수층 위에 형성되는 버퍼층은 CdS, ZnS, Zn(O,S), CdZnS 및 ZnSe로 이루어지는 군으로부터 선택되는 1종 이상일 수 있다. The buffer layer formed on the light absorption layer may be at least one selected from the group consisting of CdS, ZnS, Zn (O, S), CdZnS and ZnSe.
버퍼층은 상기 광흡수층 상에 적어도 하나 이상의 층으로 형성될 수 있고, 바람직하게는 황화 카드뮴(CdS)이 적층되어 형성될 수 있다. 이때, 상기 버퍼층은 n형 반도체 층이고, 상기 광흡수층은 P형 반도체 층이다. 따라서, 상기 광흡수층 및 버퍼층은 pn접합을 형성할 수 있다.The buffer layer may be formed of at least one layer on the light absorption layer, and may be formed by stacking cadmium sulfide (CdS). At this time, the buffer layer is an n-type semiconductor layer, and the light absorbing layer is a p-type semiconductor layer. Therefore, the light absorbing layer and the buffer layer can form a pn junction.
상기 버퍼층 위에 윈도우층을 더 형성할 수도 있다. 스퍼터링 공정을 진행하여 상기 황화 카드뮴을(CdS) 상에 ITO, ZnO, i-ZnO, ZnO:Al, ZnO/Al:ZnO, ZnO:AZO, ZnO:B(BZO) 및 ZnO:Ga(GZO)로 이루어지는 군으로부터 어느 하나의 윈도우층이 형성될 수 있으며, 광투과율이 높고, 전기전도도가 좋은 것을 사용한다.A window layer may be further formed on the buffer layer. ZnO, Al: ZnO, ZnO: AZO, ZnO: B (BZO), and ZnO: Ga (GZO) on the surface of CdS by sputtering. Any one of the window layers may be formed from the group consisting of a material having a high light transmittance and a high electrical conductivity.
상기 윈도우층은 스퍼터링, 진공공정, 열 증착공정 및 화학적 용액 성장법(Chemical Bath Deposition) 등의 방법으로 형성될 수 있으나, 상기 윈도우층의 형성방법이 이에 제한되는 것은 아니다.The window layer may be formed by a method such as a sputtering, a vacuum process, a thermal deposition process, or a chemical solution deposition (Chemical Bath Deposition) method, but the method of forming the window layer is not limited thereto.
버퍼층 또는 윈도우층 위에 전면전극을 형성할 수 있다. 상기 전면전극은 태양전지의 표면에서 전류 수집을 위한 기능을 한다. 상기 전극은 알루미늄(Al), 알루미나(Al2O3), 마그네슘(Mg), 갈륨(Ga) 등의 불순물을 포함하는 아연계 산화물 또는 ITO(Indium Tin Oxide)로 형성되는 투명전극일 수 있다. 본 발명의 일 구체예에서, 윈도우층 상에 열증발기(Thermal Evaporator)를 이용하여 알루미늄(Al) 그리드 전극을 형성할 수 있다.The front electrode may be formed on the buffer layer or the window layer. The front electrode functions to collect current from the surface of the solar cell. The electrode may be a transparent electrode formed of aluminum (Al), alumina (Al 2 O 3), magnesium (Mg), gallium zinc oxide, or ITO (Indium Tin Oxide) which includes impurities such as (Ga). In one embodiment of the present invention, an aluminum (Al) grid electrode may be formed on a window layer using a thermal evaporator.
하기 실시예에서, 본원발명의 광흡수층 및 태양전지 소자의 특성에 있어 황(S) 함유에 의한 특성 변화를 확인하기 위한 대조군으로, 황(S)이 포함되지 않은 CZTSe 태양전지 소자 및 광흡수층(비교예)을 사용하였다. 황(S) 함유량에 따른 특성 변화를 확인하기 위해, 태양전지 소자를 EQE(External Quantum Efficiency) 분석을 통하여 밴드갭 에너지 변화를 관찰하였는데, 도 2에 나타난 바와 같이, 황화금속 박막의 양이 늘어날수록 광흡수층의 밴드갭 에너지 값이 약 1.01eV에서 약 1.11eV까지 증가한 것을 확인할 수 있었다. 황화금속 박막은 실시예 1, 실시예 2, 실시예 3 순으로 대체 증가시켜 전구체를 제작하였다.In the following examples, a CZTSe solar cell element without a sulfur (S) and a light absorption layer (not shown) as a control group for confirming the change in characteristics due to the sulfur (S) content in the characteristics of the light absorption layer and the solar cell element of the present invention Comparative Example) was used. In order to confirm the change of the characteristic according to the sulfur content, the band gap energy change was observed through the EQE (External Quantum Efficiency) analysis of the solar cell element. As shown in FIG. 2, It was confirmed that the band gap energy value of the light absorption layer was increased from about 1.01 eV to about 1.11 eV. The metal sulfide thin film was alternately increased in the order of Example 1, Example 2, and Example 3 to prepare a precursor.
그리고 제작된 각 광흡수층의 XRD(X-ray Diffraction) 특성을 나타내는 도 3에서도, 비교예인 CZTSe (112) 피크에서 황(S)의 함유량이 증가할수록 CZTS (112) 피크 쪽으로 이동하는 CZTSSe 특성을 보여주는 것으로 볼 때, 황화금속 물질이 포함된 전구체를 셀렌화 열처리하는 것으로 S/Se 비 제어가 가능함을 보여주고 있다.3 showing XRD (X-ray Diffraction) characteristics of each manufactured light absorbing layer, CZTSe (112) peaks show CZTSSe characteristics moving toward CZTS (112) peaks as the sulfur content increases , It is shown that S / Se ratio control can be achieved by subjecting a precursor containing a metal sulfide substance to selenization heat treatment.
또한, 각 광흡수층을 이용하여 제작된 태양전지 소자의 전기적 특성을 분석하였다. 그 결과, 도 4에 나타낸 바와 같이, 비교예의 소자에서부터 실시예 1, 2, 3의 소자 순으로 개방전압이 402, 418, 441, 456mV로 증가하는 경향을 보인다. 이도 역시, S/Se 비가 증가함에 따라 태양전지 소자의 특성이 CZTSe에서 CZTSSe 광흡수층으로 변하고 있음을 보여준다.In addition, the electrical characteristics of the solar cell devices fabricated using the respective light absorbing layers were analyzed. As a result, as shown in Fig. 4, the open-circuit voltage tends to increase to 402, 418, 441 and 456 mV in the order of the elements of the first, second and third embodiments from the element of the comparative example. It also shows that as the S / Se ratio increases, the solar cell characteristics change from CZTSe to CZTSSe light absorbing layer.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명하고자 한다. 이들 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for further illustrating the present invention, and the scope of the present invention is not limited to these examples.
<< 비교예Comparative Example >>
황(S)이 포함되지 않은 Sulfur (S) -free CZTSeCZTSe 태양전지 소자 제조 Photovoltaic device manufacturing
SLG(Soda Lime Glass, 소다 라임 유리) 기판을 아세톤, 메탄올로 각각 초음파 10분 세척 후 증류수(D.I. water)로 충분히 세척하여 준비하였다. 상기 SLG 기판에 후면전극으로서 Mo층을 DC 스퍼터링(직류 스퍼터링) 공정으로 0.6 마이크로미터 두께로 형성시켰다. 전극층 상에 DC 스퍼터링 공정을 이용한 Zn, Sn, Cu 금속 박막을 증착하였다. 이때, Zn/Sn 비 1.0~1.2, Cu/(Zn+Sn) 비 0.6~0.7 조성비를 가진 광흡수층 형성하였다. 박막증착 시 챔버 내부 압력은 1 ~ 3mTorr, Ar 15 ~ 20sccm의 가스 분위기에서 진행하였다. 이어 광흡수층 형성을 위한 셀렌화 열처리 공정은 상압 이상의 아르곤(Ar) 분위기에서 450~480℃의 최종온도로 20분간 열처리되었다. 열처리 공정에 사용된 셀레늄(Se) 소스는 펠렛 형태의 5N 순도를 가진 소스를 이용하였다. 그리고 CZTS계 광흡수층 상에 화학적 용액성장법(CBD : Chemical Bath Deposition)을 이용하여 65℃의 온도에서 40~50 nm 두께의 CdS 버퍼층을 형성하였다. 윈도우층으로는 RF 스퍼터링 공정을 이용한 ZnO/Al:ZnO 박막을 형성하였고, 윈도우층 상에 열증발기(Thermal Evaporator)를 이용하여 알루미늄(Al) 그리드 전극을 형성하여 CZTS계 태양전지 소자를 제작하였다.SLG (Soda Lime Glass) substrates were washed with acetone and methanol for 10 minutes, respectively, and washed thoroughly with distilled water (D.I. water). A Mo layer as a back electrode was formed on the SLG substrate to a thickness of 0.6 micrometers by a DC sputtering (direct current sputtering) process. Zn, Sn and Cu metal thin films were deposited on the electrode layer by DC sputtering process. At this time, a light absorption layer having a Zn / Sn ratio of 1.0 to 1.2 and a Cu / (Zn + Sn) ratio of 0.6 to 0.7 was formed. The pressure inside the chamber was 1 ~ 3 mTorr and the Ar atmosphere was 15 ~ 20 sccm. The selenization heat treatment process for forming the light absorbing layer was then heat-treated at a final temperature of 450 to 480 ° C. for 20 minutes in argon (Ar) atmosphere above normal pressure. The source of selenium (Se) used in the heat treatment process was a pellet-shaped source having a purity of 5N. Then, a CdS buffer layer having a thickness of 40 to 50 nm was formed on the CZTS light absorbing layer at a temperature of 65 ° C by chemical solution deposition (CBD). A ZnO / Al: ZnO thin film was formed by RF sputtering for the window layer, and an aluminum (Al) grid electrode was formed on the window layer by using a thermal evaporator to fabricate a CZTS solar cell device.
<< 실시예Example >>
황(S)을 포함하는 Containing sulfur (S) CZTSSeCZTSSe 태양전지 소자 Solar cell element
본 실험에서는 화합물 박막에 황(S) 함유량 증대에 따른 CZTSSe 태양전지 소자를 제조하였다.In this experiment, CZTSSe solar cell devices were fabricated by increasing sulfur (S) content in compound thin films.
<< 실시예Example 1> 1>
상기 <비교예>와 비교하여 후면전극 상에 증착되는 전구체로 Zn, Sn, Cu, ZnS 금속 및 화합물 타켓을 이용해 증착한 것을 제외하고 다른 조건은 모두 동일하게 진행하여 태양전지를 제조하였다. 전극층 상에 DC 스퍼터링 공정을 이용한 Zn, Sn, Cu 금속 박막을 증착한 후, RF 스퍼터링 공정을 이용하여 ZnS 황화금속 박막을 형성하였다. Zn 금속 박막 증착은 <비교예>의 15/20 두께로 형성하고, 부족한 Zn 함유량은 ZnS 황화금속 박막의 증착으로 조성비를 조절하였다. Sn, Cu 금속 박막의 공정은 비교예와 동일하게 진행하였다.As compared with the above <Comparative Example>, the other conditions were all the same except that the precursor was deposited using Zn, Sn, Cu, ZnS metal and compound target as a precursor to be deposited on the rear electrode. Zn, Sn and Cu thin films were deposited on the electrode layer by DC sputtering process and RF sputtering process was used to form ZnS thin films. The Zn metal thin film deposition was formed to a thickness of 15/20 of the comparative example, and the Zn content was adjusted by deposition of the ZnS metal sulfide thin film. The process of the Sn and Cu metal thin films proceeded in the same manner as the comparative example.
<< 실시예Example 2> 2>
상기 <비교예>와 비교하여 후면전극 상에 증착되는 전구체로 Zn, Sn, Cu, ZnS 금속 및 화합물 타켓을 이용해 증착한 것을 제외하고 다른 조건은 모두 동일하게 진행하여 태양전지를 제조하였다. 전극층 상에 DC 스퍼터링 공정을 이용한 Zn, Sn, Cu 금속 박막을 증착한 후, RF 스퍼터링 공정을 이용하여 ZnS 황화금속 박막을 형성하였다. Zn 금속 박막 증착은 <비교예>의 12/20 두께로 형성하고, 부족한 Zn 함유량은 ZnS 황화금속 박막의 증착으로 조성비를 조절하였다. Sn, Cu 금속 박막의 공정은 비교예와 동일하게 진행하였다.As compared with the above <Comparative Example>, the other conditions were all the same except that the precursor was deposited using Zn, Sn, Cu, ZnS metal and compound target as a precursor to be deposited on the rear electrode. Zn, Sn and Cu thin films were deposited on the electrode layer by DC sputtering process and RF sputtering process was used to form ZnS thin films. The deposition of the Zn metal thin film was formed in a thickness of 12/20 of the comparative example, and the Zn content of the Zn metal thin film was controlled by the deposition of the ZnS metal sulfide thin film. The process of the Sn and Cu metal thin films proceeded in the same manner as the comparative example.
<< 실시예Example 3> 3>
상기 <비교예>와 비교하여 후면전극 상에 증착되는 전구체로 Zn, Sn, Cu, ZnS 금속 및 화합물 타켓을 이용해 증착한 것을 제외하고 다른 조건은 모두 동일하게 진행하여 태양전지를 제조하였다. 전극층 상에 DC 스퍼터링 공정을 이용한 Zn, Sn, Cu 금속 박막을 증착한 후, RF 스퍼터링 공정을 이용하여 ZnS 황화금속 박막을 형성하였다. Zn 금속 박막 증착은 <비교예>의 9/20 두께로 형성하고, 부족한 Zn 함유량은 ZnS 황화금속 박막의 증착으로 조성비를 조절하였다. Sn, Cu 금속 박막의 공정은 비교예와 동일하게 진행하였다. As compared with the above <Comparative Example>, the other conditions were all the same except that the precursor was deposited using Zn, Sn, Cu, ZnS metal and compound target as a precursor to be deposited on the rear electrode. Zn, Sn and Cu thin films were deposited on the electrode layer by DC sputtering process and RF sputtering process was used to form ZnS thin films. The deposition of the Zn metal thin film was formed to a thickness of 9/20 of the comparative example, and the compositional ratio of the Zn content was adjusted by deposition of the ZnS metal sulfide thin film. The process of the Sn and Cu metal thin films proceeded in the same manner as the comparative example.
<< 실험예Experimental Example 1> 1>
광흡수층의The light- 밴드갭Band gap 측정 Measure
상기 비교예 및 실시예 1, 2, 3에서 제조한 박막 태양전지의 광흡수층의 밴드갭을 측정하였다. 밴드갭은 SR830 DSP lock-in amplifier system (McScience사)을 사용하여 외부 양자 효율(External Quantum Efficiency, EQE) 측정값으로부터 측정되었다.The band gaps of the light absorbing layers of the thin film solar cells prepared in the above Comparative Examples and Examples 1, 2 and 3 were measured. The bandgap was measured from the External Quantum Efficiency (EQE) measurements using the SR830 DSP lock-in amplifier system (McScience).
그 결과 도 2에서 나타낸 바와 같이, 황화금속 박막의 양이 늘어날수록 광흡수층의 밴드갭 에너지 값이 약 1.01eV에서 약 1.11eV까지 증가한 것을 확인할 수 있었다. As a result, as shown in FIG. 2, it was confirmed that the band gap energy value of the light absorption layer increased from about 1.01 eV to about 1.11 eV as the amount of the metal sulfide thin film increased.
<< 실험예Experimental Example 2> 2>
광흡수층의The light- XRDXRD 분석 analysis
상기 비교예 및 실시예 1, 2, 3에서 제조한 박막 태양전지의 광흡수층의 XRD(X-ray Diffraction) 특성을 분석하였다.The XRD (X-ray diffraction) characteristics of the light absorbing layer of the thin film solar cell prepared in the above Comparative Examples and Examples 1, 2 and 3 were analyzed.
그 결과 도 3에서 나타낸 바와 같이, 비교예인 CZTSe 피크에서 황(S)의 함유량이 증가할수록 CZTS 피크 쪽으로 이동하는 CZTSSe 특성을 보여주는 것으로 볼 때, 황화금속 물질이 포함된 전구체를 셀렌화 열처리하는 것으로 S/Se 비 제어가 가능함을 보여주었다.As a result, as shown in FIG. 3, the CZTSe peak shifted toward the CZTS peak as the sulfur (S) content increased in the comparative CZTSe peak, indicating that the precursor containing the sulfide metal substance was heat- / Se ratio control is possible.
<< 실험예Experimental Example 3> 3>
광흡수층의The light- 황(S) 함유량 증대에 따른 태양전지 소자의 효율 특성 분석 Analysis of efficiency characteristics of solar cell devices with increasing sulfur (S) content
상기 비교예 및 실시예 1, 2, 3에서 제조한 박막 태양전지의 광흡수층의 XRD(X-ray Diffraction) 특성을 분석하였다.The XRD (X-ray diffraction) characteristics of the light absorbing layer of the thin film solar cell prepared in the above Comparative Examples and Examples 1, 2 and 3 were analyzed.
비교예 및 실시예 1, 2, 3에서 제조된 CZTS 박막 태양전지의 효율을 측정하기 위해, 솔라 시뮬레이터(solar simulator) 측정 기기로 에어매스 1.5 글로벌(air mass 1.5 global(AM 1.5G))의 조건에서, 효율, 개방전압, 단락전류 및 충진율을 측정했다. 결과는 하기 표 1 및 도 4에서 나타내었다.In order to measure the efficiency of the CZTS thin film solar cell manufactured in Comparative Examples and Examples 1, 2 and 3, the conditions of the air mass 1.5 global (AM 1.5G) as a solar simulator measuring instrument Efficiency, open-circuit voltage, short-circuit current and filling rate were measured. The results are shown in Table 1 and FIG.
그 결과, 비교예의 소자에서부터 실시예 1, 2, 3의 소자 순으로 개방전압이 약 0.40, 0.42, 0.44, 0.46V로 증가하는 경향을 보인다. 이도 역시, S/Se 비가 증가함에 따라 태양전지 소자의 특성이 CZTSe에서 CZTSSe 광흡수층으로 변하고 있음을 보여준다.As a result, the open-circuit voltage tends to increase to about 0.40, 0.42, 0.44, and 0.46 V in the order of the elements of Examples 1, 2, and 3 from the device of the comparative example. It also shows that as the S / Se ratio increases, the solar cell characteristics change from CZTSe to CZTSSe light absorbing layer.
100: 기판
101: 후면전극
102: Zn 금속박막층
103: Sn 금속박막층
104: Cu 금속박막층
105: ZnS 화합물박막층100: substrate
101: Rear electrode
102: Zn metal thin film layer
103: Sn metal thin film layer
104: Cu metal thin film layer
105: ZnS compound thin film layer
Claims (10)
상기 방법은 a) 기판 상에 후면전극을 형성하는 단계; 및
b) 상기 후면전극 상에 금속 및 화합물을 함유하는 전구체층을 형성한 후 셀렌화 처리 공정을 거쳐 광흡수층을 형성하는 단계를 포함하며,
상기 전구체층은 Zn/Sn/Cu/ZnS, Zn/Cu/Sn/ZnS, Zn/Sn/ZnS/Cu, Zn/Cu/ZnS/Sn, Zn/ZnS/Sn/Cu 및 Zn/ZnS/Cu/Sn로 이루어진 군으로부터 선택된 적층 구조를 갖는 것을 특징으로 하는, 박막 태양전지의 제조방법.1. A method of manufacturing a thin film solar cell,
The method comprising: a) forming a back electrode on a substrate; And
b) forming a precursor layer containing a metal and a compound on the rear electrode, and then forming a light absorbing layer through a selenization process,
The precursor layer may include at least one of Zn / Sn / Cu / ZnS, Zn / Cu / Sn / ZnS, Zn / Sn / ZnS / Cu, Zn / Cu / ZnS / Sn, Zn / ZnS / Sn / Cu, And Sn. The method of manufacturing a thin film solar cell according to claim 1,
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| WO2012172999A1 (en) | 2011-06-16 | 2012-12-20 | 昭和シェル石油株式会社 | Czts thin film solar cell and manufacturing method thereof |
| KR101407161B1 (en) | 2013-08-12 | 2014-06-16 | 영남대학교 산학협력단 | Manufacturing method of CZTS-based thin film solar cell light absorber |
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| WO2012172999A1 (en) | 2011-06-16 | 2012-12-20 | 昭和シェル石油株式会社 | Czts thin film solar cell and manufacturing method thereof |
| KR101407161B1 (en) | 2013-08-12 | 2014-06-16 | 영남대학교 산학협력단 | Manufacturing method of CZTS-based thin film solar cell light absorber |
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| CN110137687A (en) * | 2019-05-29 | 2019-08-16 | 兰州大学 | A method of preparing flexible Meta Materials |
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