WO2011021800A2 - Method for fabricating a physical vapor deposition target - Google Patents

Method for fabricating a physical vapor deposition target Download PDF

Info

Publication number
WO2011021800A2
WO2011021800A2 PCT/KR2010/005198 KR2010005198W WO2011021800A2 WO 2011021800 A2 WO2011021800 A2 WO 2011021800A2 KR 2010005198 W KR2010005198 W KR 2010005198W WO 2011021800 A2 WO2011021800 A2 WO 2011021800A2
Authority
WO
WIPO (PCT)
Prior art keywords
cis
target
cigs
added
molar ratio
Prior art date
Application number
PCT/KR2010/005198
Other languages
French (fr)
Korean (ko)
Other versions
WO2011021800A3 (en
Inventor
조용수
연득호
Original Assignee
연세대학교 산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 연세대학교 산학협력단 filed Critical 연세대학교 산학협력단
Publication of WO2011021800A2 publication Critical patent/WO2011021800A2/en
Publication of WO2011021800A3 publication Critical patent/WO2011021800A3/en

Links

Images

Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0623—Sulfides, selenides or tellurides
    • 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
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • 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

Definitions

  • the present invention relates to a method for manufacturing a target for physical vapor deposition (PVD), and more specifically, to a CIS target, which makes it difficult to manufacture a target for PVD due to the characteristics of the material, it is possible to manufacture a CIS target with a simple manufacturing process and low manufacturing cost. It relates to a target manufacturing method.
  • PVD physical vapor deposition
  • CIS Cu-In-Se
  • CIGS Cu-In-Ga-Se
  • a method currently used a lot is to deposit using a separate target, such as Cu, In, Ga, Se.
  • a laser or electron is bombarded to each target to separate a small amount of material from the target by the force, and the separated material is deposited on a desired substrate.
  • a problem that it is difficult to control the composition of the thin film because it uses a target of various compositions, it is difficult to produce a film of a uniform form.
  • the reason for using individual targets in the manufacture of absorbent layers is due to the intrinsic properties of CIS and CIGS materials.
  • the CIS, CIGS-based material is a compound consisting of three or more atoms, there is a problem that the high temperature and high vacuum of 1000 °C or more is required for the synthesis of the material, there is a problem in productivity, a low cost simple method is required The same method is employed.
  • the present invention is to solve the problems appearing in the prior art, the object is to provide a method for producing a CIS-based, CIGS-based target at low temperature without new equipment.
  • Another object of the present invention is to provide a CIS-based or CIGS-based target manufacturing method capable of lowering the manufacturing cost compared to the existing manufacturing method and maintaining a uniform composition until thin film deposition without generating a new phase.
  • a CIS-based target manufacturing method used for depositing a solar cell absorbing layer.
  • the method comprises the steps of (a) preparing a Cu, In, Se powder in a molar ratio of 1: 1: 2; (b) putting Cu, In, Se powder and a metal ball into a container and stirring to prepare a CIS synthetic material by this mechanical force; (c) further adding Se to the synthesized CIS material, then mixing and compressing using a ball mill to produce pellets of a shape corresponding to the target shape; (d) heat-treating the prepared pellets to produce a final CIS target.
  • step (c) Se may be further added in a ratio of about 25 to 50 wt% with respect to the CIS material synthesized in step (b), preferably about 50 wt% It may be added in proportion.
  • the heat treatment in step (d) may be performed at a temperature of about 300 °C and atmospheric pressure.
  • a CIGS-based target manufacturing method used to deposit a solar cell absorbing layer.
  • the method comprises the steps of (a) preparing Cu, In, Ga, Se powder in a molar ratio of 1: 1: 1: 2; (b) putting Cu, In, Ga, Se powder and metal balls into a container and stirring to prepare a CIGS synthetic material by this mechanical force; (c) further adding Se to the synthesized CIGS material, then mixing and compressing using a ball mill to produce pellets of a shape corresponding to the target shape; (d) heat-treating the prepared pellets to produce a final CIGS target.
  • the CIS-based or CIGS-based target manufacturing method it is possible to produce a hard CIS and CIGS target by a low temperature process compared to the prior art.
  • high pressure or high vacuum is not required, cost reduction can be expected, and the manufacturing process is also very simple.
  • Figure 1 shows the XRD pattern of the CIS material prepared through the Mechano chemical process.
  • FIG. 2 is a view showing an XRD pattern after heat-treating a material in which an excess of Se is mixed with the CIS material of FIG. 1 at about 300 ° C. for 1 hour.
  • FIG. 3 is a micrograph showing the microstructure of the mixed material of FIG.
  • FIG. 4 is a diagram showing an XRD pattern of a thin film after depositing a thin film using a target to which an excess of Se of 50 wt% is added.
  • the present inventors studied a method of forming a light absorbing layer, which is a core layer of a solar cell, of a CIS-based or CIGS-based solar cell, using a CIS-based or CIGS-based material.
  • a light absorbing layer which is a core layer of a solar cell
  • CIS-based and CIGS-based materials are difficult to be manufactured as solid targets at low temperatures and atmospheric pressures due to their own characteristics. .
  • CIS materials were synthesized using a well-known method called mechano chemical process. That is, Cu, In, Se material was prepared in accordance with a predetermined molar ratio (1: 1: 2), and then placed in a container with zirconia balls, and stirred with a strong force. By this agitation, the balls collide with each powder, energy is continuously accumulated in the material, and mechanical forces are converted into chemical energy, thereby synthesizing the CIS material. In this process, Cu, In, Se material is continuously divided by the collision with the ball, the surface area is widened, it is possible to synthesize without applying a large force. This mechano chemical process was performed at room temperature and atmospheric pressure.
  • FIG. 1 XRD pattern for the CIS material synthesized according to the above process is shown in FIG. As shown in Figure 1, it can be seen that the CIS single phase can be prepared at room temperature and atmospheric pressure.
  • the inventor produced a CIS target using the CIS material made according to the above procedure. That is, the CIS target is in the form of a hard disk, and the CIS material made according to the above process is in the form of a powder. While such CIS materials require high temperatures and high vacuum to produce hard CIS target forms, we have prepared CIS targets through a simplified method rather than this expensive manufacturing process.
  • the present inventors further added Se material among the elements constituting the CIS-based material. Specifically, an excess of Se was added to the CIS material prepared through the above process (a) 50 wt%, (b) 33 wt%, (c) 25 wt%, and (d) 0 wt%, and then each mixture was added.
  • the pellet After mixing through a ball mill (ball mill) for 2 hours and pressurized through a press to produce a pellet (pellet) form, the pellet is heat-treated in nitrogen atmosphere for 1 hour at 300 °C to produce a solid CIS target could. That is, the melting point of Se is so low that it melts at 217 ° C.
  • the heat treatment is performed at about 300 ° C. At this temperature, Se melts and has sufficient fluidity to connect the particles of the CIS material, thereby making it possible to manufacture a rigid CIS target.
  • the present inventors performed XRD analysis on the crystal structure of the CIS target produced through the above process, and the results are shown in FIG. 2. As shown in Figure 2, the peak position of the CIS did not change despite the addition of Se, which means that the added Se did not react with the CIS material, and also because the heat treatment temperature was as low as 300 ° C It can be seen that no phase was generated.
  • Figure 3 is added to the CIS material in excess of Se (a) 0wt%, (b) 25 wt%, (c) 33 wt%, (d) 50 wt%, respectively, and then pressurized to make a target form After the heat treatment for 1 hour at 300 °C is a photo observing the microstructure.
  • FIG. 3 when excess Se was not added, micropores with many pores were observed, but there were almost no pores in the microstructure of the target to which 50 wt% of Se was added. That is, when Se is added in an excess of about 50 wt%, the best CIS target for PVD can be prepared.
  • the inventors deposited the CIS thin film through the PVD process using the most dense target among Se-added targets, that is, a target added with 50 wt% Se.
  • XRD analysis was performed on the deposited thin film, and the results are shown in FIG. 4.
  • Se was detected in the XRD pattern of the target (see FIG. 2), but Se was not observed after the thin film was deposited. That is, Se has a low melting point or vaporization temperature and is sufficiently vaporized during deposition using PVD, and it is presumed that Se is not included in the thin film. Therefore, when the thin film is deposited using the CIS-based target prepared according to the present invention described above, a CIS single phase can be obtained.
  • This embodiment relates to manufacturing a CIS target.
  • the present invention can be applied to manufacturing a CIGS-based target, and in this case, it is possible to produce a CIGS-based target through the same process as manufacturing a CIS target, which is also within the scope of the present invention. That is, the present invention is not limited to the above embodiments, but may be variously modified and modified within the scope of the claims, and these are also within the scope of the present invention. Accordingly, the invention is limited only by the claims and the equivalents thereof.

Abstract

The present invention relates to a method for fabricating a CIS-based target for use in depositing an absorption layer of a solar cell. The method comprises: (a) a step of preparing a Cu, In and Se powder with a mole ratio of 1:1:2; (b) a step of stirring the Cu, In and Se powder and metal balls in a vessel to produce a synthesized CIS material by mechanical force; (c) a step of adding Se to the synthesized CIS material, and mixing and compressing the synthesized CIS material using a ball mill to produce a pellet having a shape corresponding to a target; and (d) a step of performing a heat treatment on the thus-produced pellet to produce a final CIS target.

Description

물리적 증착용 타겟 제조 방법Method for manufacturing target for physical vapor deposition
본 발명은 물리적 증착(PVD)용 타겟 제조 방법에 관한 것으로서, 보다 구체적으로는 재료가 갖고 있는 특성상 PVD용 타겟으로 제조하기가 어려운 CIS 타겟을 간단한 제조 공정 및 낮은 제조 비용으로 제조할 수 있도록 해주는 CIS 타겟 제조 방법과 관련된 것이다.The present invention relates to a method for manufacturing a target for physical vapor deposition (PVD), and more specifically, to a CIS target, which makes it difficult to manufacture a target for PVD due to the characteristics of the material, it is possible to manufacture a CIS target with a simple manufacturing process and low manufacturing cost. It relates to a target manufacturing method.
CIS(Cu-In-Se)(Cu:In:Se=1:1:2 (몰비)) 혹은 CIGS(Cu-In-Ga-Se)(Cu:In:Ga:Se=1:1-x:x:2(0<x<1)(몰비)) 계열 태양전지는 Si 태양전지에 버금가는 높은 효율과 재료에 드는 상대적으로 적은 비용 등으로 Si 태양전지를 대체할 유력한 후보로 주목받고 있다. 한편, CIS, CIGS 계열 태양전지를 구성하는 각 층 중에 빛을 흡수하는 광 흡수층이 가장 중요한 층이라 할 수 있다.CIS (Cu-In-Se) (Cu: In: Se = 1: 1: 2 (molar ratio)) or CIGS (Cu-In-Ga-Se) (Cu: In: Ga: Se = 1: 1-x: x: 2 (0 <x <1) (molar ratio) series solar cells are attracting attention as potential candidates to replace Si solar cells due to their high efficiency and the relatively low cost of materials. Meanwhile, the light absorbing layer that absorbs light is the most important layer among the layers constituting the CIS and CIGS series solar cells.
상기 태양전지의 흡수층을 제조하는 방법에는 여러 가지가 있는데, 현재 많이 사용하고 있는 방법은 Cu, In, Ga, Se라는 개별 타겟을 이용하는 증착시키는 것이다. 즉 각각의 타겟에 레이저 또는 전자를 충돌시켜 그 힘에 의해 타겟으로부터 미량의 물질을 분리하고, 분리된 물질을 원하는 기판에 증착하는 것이다. 그러나, 여러가지 조성의 타겟을 이용하기 때문에 박막의 조성 조절이 어렵고, 균일한 형태의 막을 제조하기가 어렵다는 문제점이 있다.There are a number of methods for manufacturing the absorber layer of the solar cell, a method currently used a lot is to deposit using a separate target, such as Cu, In, Ga, Se. In other words, a laser or electron is bombarded to each target to separate a small amount of material from the target by the force, and the separated material is deposited on a desired substrate. However, there is a problem that it is difficult to control the composition of the thin film because it uses a target of various compositions, it is difficult to produce a film of a uniform form.
이와 같이, 흡수층 제조시 개별 타겟을 이용하는 이유는 CIS, CIGS 물질이 갖고 있는 본질적인 특성에 기인한다. 구체적으로, CIS, CIGS계 물질은 3가지 이상의 원자로 이루어진 화합물인데, 이 물질의 합성을 위해서는 1000℃ 이상의 고온과 고진공이 필요하다는 문제점이 있고, 생산성에 문제가 있어, 저가의 단순 공법이 필요해 상기와 같은 방법이 채용된다.As such, the reason for using individual targets in the manufacture of absorbent layers is due to the intrinsic properties of CIS and CIGS materials. Specifically, the CIS, CIGS-based material is a compound consisting of three or more atoms, there is a problem that the high temperature and high vacuum of 1000 ℃ or more is required for the synthesis of the material, there is a problem in productivity, a low cost simple method is required The same method is employed.
본 발명은 상기한 종래 기술에서 나타나는 문제점을 해결하기 위한 것으로서, 그 목적은 새로운 장비 없이 저온에서 CIS계, CIGS계 타겟을 제조할 수 있는 방법을 제공하는 것이다.The present invention is to solve the problems appearing in the prior art, the object is to provide a method for producing a CIS-based, CIGS-based target at low temperature without new equipment.
본 발명의 다른 목적은 기존의 제조 방법과 비교하여 제조 단가를 낮출 수 있고, 새로운 상을 생성하지 않으면서 박막 증착시까지 균일한 조성을 유지할 수 있는 CIS계, CIGS계 타겟 제조 방법을 제공하는 것이다.Another object of the present invention is to provide a CIS-based or CIGS-based target manufacturing method capable of lowering the manufacturing cost compared to the existing manufacturing method and maintaining a uniform composition until thin film deposition without generating a new phase.
상기 목적을 달성하기 위하여, 본 발명에 따라서 태양전지 흡수층을 증착하는 데 사용되는 CIS계 타겟 제조 방법이 제공된다. 상기 방법은 (a) Cu, In, Se 파우더를 1:1:2의 몰비로 준비하는 단계와; (b) 상기 Cu, In, Se 파우더와 금속 볼을 용기 안에 넣고 교반하여, 이 기계적 힘에 의해 CIS 합성 물질을 제조하는 단계와; (c) 상기 합성된 CIS 물질에 Se을 추가로 첨가한 후, 볼밀을 이용하여 혼합하고 압축을 가해 타겟 형태에 대응하는 형상의 펠릿으로 제조하는 단계와; (d) 상기 제조된 펠릿에 대해 열처리를 하여 최종 CIS 타겟을 제조하는 단계를 포함하는 것을 특징으로 한다.In order to achieve the above object, according to the present invention there is provided a CIS-based target manufacturing method used for depositing a solar cell absorbing layer. The method comprises the steps of (a) preparing a Cu, In, Se powder in a molar ratio of 1: 1: 2; (b) putting Cu, In, Se powder and a metal ball into a container and stirring to prepare a CIS synthetic material by this mechanical force; (c) further adding Se to the synthesized CIS material, then mixing and compressing using a ball mill to produce pellets of a shape corresponding to the target shape; (d) heat-treating the prepared pellets to produce a final CIS target.
한 가지 실시예에 있어서, 상기 (c) 단계에서 Se은 상기 (b) 단계에서 합성한 CIS 물질에 대해 약 25~50 wt%의 비율로 추가 첨가될 수 있고, 바람직하게는 약 50 wt%의 비율로 추가 첨가될 수 있다.In one embodiment, in step (c) Se may be further added in a ratio of about 25 to 50 wt% with respect to the CIS material synthesized in step (b), preferably about 50 wt% It may be added in proportion.
한 가지 실시예에 있어서, 상기 (d) 단계에서 상기 열처리는 약 300℃의 온도 및 대기압 중에서 수행할 수 있다.In one embodiment, the heat treatment in step (d) may be performed at a temperature of about 300 ℃ and atmospheric pressure.
본 발명의 또 다른 실시예에 따라서, 태양전지 흡수층을 증착하는 데 사용되는 CIGS계 타겟 제조 방법도 제공된다. 상기 방법은 (a) Cu, In, Ga, Se 파우더를 1:1:1:2의 몰비로 준비하는 단계와; (b) 상기 Cu, In, Ga, Se 파우더와 금속 볼을 용기 안에 넣고 교반하여, 이 기계적 힘에 의해 CIGS 합성 물질을 제조하는 단계와; (c) 상기 합성된 CIGS 물질에 Se을 추가로 첨가한 후, 볼밀을 이용하여 혼합하고 압축을 가해 타겟 형태에 대응하는 형상의 펠릿으로 제조하는 단계와; (d) 상기 제조된 펠릿에 대해 열처리를 하여 최종 CIGS 타겟을 제조하는 단계를 포함하는 것을 특징으로 한다.According to another embodiment of the present invention, there is also provided a CIGS-based target manufacturing method used to deposit a solar cell absorbing layer. The method comprises the steps of (a) preparing Cu, In, Ga, Se powder in a molar ratio of 1: 1: 1: 2; (b) putting Cu, In, Ga, Se powder and metal balls into a container and stirring to prepare a CIGS synthetic material by this mechanical force; (c) further adding Se to the synthesized CIGS material, then mixing and compressing using a ball mill to produce pellets of a shape corresponding to the target shape; (d) heat-treating the prepared pellets to produce a final CIGS target.
본 발명에 따른 CIS계, CIGS계 타겟 제조 방법에 따르면, 종래 기술과 비교하여 저온 공정으로 경질의 CIS 및 CIGS 타겟을 제조할 수 있다. 또한, 높은 압력이나 고진공도 필요하지 않으므로 비용절감을 효과를 기대할 수 있으며, 그 제조 공정도 매우 단순하다는 이점이 있다.According to the CIS-based or CIGS-based target manufacturing method according to the present invention, it is possible to produce a hard CIS and CIGS target by a low temperature process compared to the prior art. In addition, since high pressure or high vacuum is not required, cost reduction can be expected, and the manufacturing process is also very simple.
도 1은 Mechano chemical process를 통해 제조한 CIS 물질의 XRD 패턴을 보여준다.Figure 1 shows the XRD pattern of the CIS material prepared through the Mechano chemical process.
도 2는 도 1의 CIS 물질에 과량의 Se를 혼합한 물질을 약 300℃에서 1시간 동안 열처리한 후의 XRD 패턴을 보여주는 도면이다.FIG. 2 is a view showing an XRD pattern after heat-treating a material in which an excess of Se is mixed with the CIS material of FIG. 1 at about 300 ° C. for 1 hour.
도 3은 도2의 혼합 물질의 미세구조를 보여주는 현미경 사진이다.3 is a micrograph showing the microstructure of the mixed material of FIG.
도 4는 50 wt%의 과량 Se이 첨가된 타겟을 이용하여 박막을 증착한 후 박막의 XRD 패턴을 보여주는 도면이다.4 is a diagram showing an XRD pattern of a thin film after depositing a thin film using a target to which an excess of Se of 50 wt% is added.
이하에서는 첨부 도면을 참조하여 본 발명의 바람직한 실시예를 설명한다. 이하의 설명에 있어서, 태양전지 등과 같이 일반적으로 널리 알려진 구성에 대한 설명은 생략한다. 이러한 설명을 생략하더라도, 당업자라면 이하의 설명을 통해 본 발명의 특징을 아무런 어려움 없이 이해할 수 있을 것이다.Hereinafter, with reference to the accompanying drawings will be described a preferred embodiment of the present invention. In the following description, a description of a generally known configuration such as a solar cell is omitted. Even if this description is omitted, those skilled in the art will be able to understand the features of the present invention without any difficulty through the following description.
본 발명자는 CIS계, CIGS계 태양전지를 제조하는 프로세스 중 태양전지의 핵심층인 광 흡수층을 CIS계, CIGS계 물질로 형성하는 방법에 대해 연구를 하였다. 종래 기술에서 설명한 바와 같이, CIS계, CIGS계 물질은 그 자체의 특성으로 인해 저온, 상압에서는 단단한 타겟으로 제조하기가 어려운데, 이를 해결하기 위해 독특한 조성을 고안하여 CIS계, CIGS계 타겟 제조에 성공하였다.The present inventors studied a method of forming a light absorbing layer, which is a core layer of a solar cell, of a CIS-based or CIGS-based solar cell, using a CIS-based or CIGS-based material. As described in the prior art, CIS-based and CIGS-based materials are difficult to be manufactured as solid targets at low temperatures and atmospheric pressures due to their own characteristics. .
먼저, mechano chemical process라고 하는 널리 알려진 방법을 이용하여 CIS 물질을 합성하였다. 즉 Cu, In, Se 물질을 미리 정해진 몰비(1:1:2)에 맞게 준비한 후, zirconia 볼과 함께 용기 안에 넣은 후, 강한 힘으로 교반하였다. 이러한 교반에 의해, 볼이 각 파우더와 충돌하게 되고, 물질에 에너지가 계속 쌓이게 되어, 기계적인 힘이 화학적인 에너지로 변환되어, CIS 물질이 합성된다. 이 과정에서, Cu, In, Se 물질이 상기 볼과의 충돌에 의해 계속 분할되면서, 표면적이 넓어지게 되어, 큰 힘을 들이지 않고도 합성이 가능하다. 이러한 mechano chemical process는 상온 및 상압에서 수행하였다.First, CIS materials were synthesized using a well-known method called mechano chemical process. That is, Cu, In, Se material was prepared in accordance with a predetermined molar ratio (1: 1: 2), and then placed in a container with zirconia balls, and stirred with a strong force. By this agitation, the balls collide with each powder, energy is continuously accumulated in the material, and mechanical forces are converted into chemical energy, thereby synthesizing the CIS material. In this process, Cu, In, Se material is continuously divided by the collision with the ball, the surface area is widened, it is possible to synthesize without applying a large force. This mechano chemical process was performed at room temperature and atmospheric pressure.
상기 과정에 따라 합성한 CIS 재료에 대한 XRD 패턴을 도 1에 도시하였다. 도 1에 도시한 바와 같이, CIS 단일 상이 상온, 상압 중에서 제조할 수 있다는 것을 확인할 수 있다.XRD pattern for the CIS material synthesized according to the above process is shown in FIG. As shown in Figure 1, it can be seen that the CIS single phase can be prepared at room temperature and atmospheric pressure.
본 발명자는 상기 과정에 따라 만들어진 CIS 물질을 이용하여 CIS 타겟을 제작하였다. 즉 CIS 타겟은 경질의 디스크 형태인데, 상기 과정에 따라 만들어진 CIS 물질은 파우더 형태이다. 이러한 CIS 물질은 경질의 CIS 타겟 형태로 제조하기 위해서는 높은 온도와 고진공이 필요하지만, 본 발명자는 이러한 고가의 제조 프로세스가 아닌 단순화된 방법을 통해 CIS 타겟을 제조하였다.The inventor produced a CIS target using the CIS material made according to the above procedure. That is, the CIS target is in the form of a hard disk, and the CIS material made according to the above process is in the form of a powder. While such CIS materials require high temperatures and high vacuum to produce hard CIS target forms, we have prepared CIS targets through a simplified method rather than this expensive manufacturing process.
구체적으로, 본 발명자는 CIS계 물질을 구성하는 원소 중 Se 물질을 추가로 첨가하여 보았다. 구체적으로 상기 과정을 통해 제작한 CIS 물질에 과량의 Se를 (a)50 wt%, (b)33 wt%, (c)25 wt%, (d) 0 wt%씩 첨가한 뒤, 각각의 혼합물을 2시간 동안 볼밀(ball mill)을 통해 혼합한 뒤에 프레스 기를 통해 가압하여 펠릿(pellet) 형태로 제조한 후, 이 펠릿을 300℃에서 1시간 동안 질소 분위기에서 열처리를 하여 단단한 CIS 타겟을 제조할 수 있었다. 즉 Se은 217℃에서 용융될 정도로 그 융점이 매우 낮다. 이와 관련하여, 본 발명에서는 300℃ 정도로 열처리를 수행하는데, 이 온도에서 Se이 녹아 충분한 유동성을 가져 CIS 물질의 입자들 사이를 연결시켜 주기 때문에, 단단한 CIS 타겟을 제조할 수가 있다. Specifically, the present inventors further added Se material among the elements constituting the CIS-based material. Specifically, an excess of Se was added to the CIS material prepared through the above process (a) 50 wt%, (b) 33 wt%, (c) 25 wt%, and (d) 0 wt%, and then each mixture was added. After mixing through a ball mill (ball mill) for 2 hours and pressurized through a press to produce a pellet (pellet) form, the pellet is heat-treated in nitrogen atmosphere for 1 hour at 300 ℃ to produce a solid CIS target Could. That is, the melting point of Se is so low that it melts at 217 ° C. In this regard, in the present invention, the heat treatment is performed at about 300 ° C. At this temperature, Se melts and has sufficient fluidity to connect the particles of the CIS material, thereby making it possible to manufacture a rigid CIS target.
본 발명자는 상기와 같은 과정을 통해 제작한 CIS 타겟의 결정구조에 대해 XRD 분석을 수행하였으며, 그 결과를 도 2에 나타낸다. 도 2에서 보는 바와 같이, CIS의 피크(peak) 위치는 Se의 첨가에도 불구하고 변치 않았으며, 이는 첨가한 Se가 CIS 물질과 반응하지 않았다는 것을 의미하며, 또한 열처리 온도가 300℃ 정도로 낮기 때문에 새로운 상도 생성되지 않았다는 것을 알 수 있다.The present inventors performed XRD analysis on the crystal structure of the CIS target produced through the above process, and the results are shown in FIG. 2. As shown in Figure 2, the peak position of the CIS did not change despite the addition of Se, which means that the added Se did not react with the CIS material, and also because the heat treatment temperature was as low as 300 ° C It can be seen that no phase was generated.
한편, 도 3은 CIS 물질에 과량의 Se을 각각 (a) 0wt%, (b) 25 wt%, (c) 33 wt%, (d) 50 wt%씩 첨가한 후, 가압하여 타겟 형태로 만든 후 300℃에서 1시간 동안 열처리 한 다음 그 미세구조를 관찰한 사진이다. 도 3에서 볼 수 있는 바와 같이, 과량의 Se이 첨가되지 않은 경우, 기공이 많은 미세구조가 관찰되었지만, 과량의 Se이 50 wt% 첨가된 타겟의 미세구조에는 기공이 거의 없었다. 즉 Se을 약 50 wt% 과량 첨가한 경우, 가장 양호한 PVD용 CIS계 타겟을 제조할 수 있다.On the other hand, Figure 3 is added to the CIS material in excess of Se (a) 0wt%, (b) 25 wt%, (c) 33 wt%, (d) 50 wt%, respectively, and then pressurized to make a target form After the heat treatment for 1 hour at 300 ℃ is a photo observing the microstructure. As can be seen in FIG. 3, when excess Se was not added, micropores with many pores were observed, but there were almost no pores in the microstructure of the target to which 50 wt% of Se was added. That is, when Se is added in an excess of about 50 wt%, the best CIS target for PVD can be prepared.
마지막으로, 본 발명자는 Se이 첨가된 타겟 중 가장 밀도가 좋았던 타겟, 즉 50 wt%의 Se이 과량 첨가된 타겟을 이용하여 PVD 공정을 통해 CIS 박막을 증착하였다. 그 증착된 박막에 대해 XRD 분석을 수행하였으며, 그 결과를 도 4에 나타내었다. 도 4에서 볼 수 있는 바와 같이, 타겟의 XRD 패턴에서는 Se이 검출되었으나(도 2 참조), 박막을 증착시킨 후에는 Se이 관찰되지 않았다. 즉 Se은 그 융점이나 기화 온도가 낮아 PVD를 이용하여 증착하는 동안 충분히 기화되어, 박막에 Se이 포함되지 않은 것으로 추측된다. 따라서, 상기한 본 발명에 따라 제작한 CIS계 타겟을 이용하여 박막을 증착할 경우, CIS 단일 상을 얻을 수 있다.Finally, the inventors deposited the CIS thin film through the PVD process using the most dense target among Se-added targets, that is, a target added with 50 wt% Se. XRD analysis was performed on the deposited thin film, and the results are shown in FIG. 4. As can be seen in FIG. 4, Se was detected in the XRD pattern of the target (see FIG. 2), but Se was not observed after the thin film was deposited. That is, Se has a low melting point or vaporization temperature and is sufficiently vaporized during deposition using PVD, and it is presumed that Se is not included in the thin film. Therefore, when the thin film is deposited using the CIS-based target prepared according to the present invention described above, a CIS single phase can be obtained.
상기 실시예는 CIS 타겟을 제조하는 것과 관련된 것이다. 그러나, 본 발명은 CIGS계 타겟을 제조하는 데에도 적용될 수 있으며, 이때에도 CIS 타겟 제조와 동일한 프로세스를 통해, CIGS계 타겟을 제조할 수 있으며, 이 역시 본 발명의 범위 내에 속하는 것이다. 즉 본 발명은 상기 실시예에 제한되는 것이 아니라, 특허청구범위 내에서 다양하게 변형 및 수정할 수 있으며, 이들 역시 본 발명의 범위에 속하는 것이다. 따라서, 본 발명은 특허청구범위 및 그 균등물에 의해서만 제한된다.This embodiment relates to manufacturing a CIS target. However, the present invention can be applied to manufacturing a CIGS-based target, and in this case, it is possible to produce a CIGS-based target through the same process as manufacturing a CIS target, which is also within the scope of the present invention. That is, the present invention is not limited to the above embodiments, but may be variously modified and modified within the scope of the claims, and these are also within the scope of the present invention. Accordingly, the invention is limited only by the claims and the equivalents thereof.

Claims (14)

  1. 태양전지 흡수층을 증착하는 데 사용되는 CIS계 타겟 제조 방법으로서,A CIS-based target manufacturing method used to deposit a solar cell absorbing layer,
    (a) Cu, In, Se 파우더를 1:1:2의 몰비로 준비하는 단계와;(a) preparing Cu, In, Se powder in a molar ratio of 1: 1: 2;
    (b) 상기 Cu, In, Se 파우더와 금속 볼을 용기 안에 넣고 교반하여, 이 기계적 힘에 의해 CIS 합성 물질을 제조하는 단계와;(b) putting Cu, In, Se powder and a metal ball into a container and stirring to prepare a CIS synthetic material by this mechanical force;
    (c) 상기 합성된 CIS 물질에 Se을 추가로 첨가한 후, 볼밀을 이용하여 혼합하고 압축을 가해 타겟 형태에 대응하는 형상의 펠릿으로 제조하는 단계와;(c) further adding Se to the synthesized CIS material, then mixing and compressing using a ball mill to produce pellets of a shape corresponding to the target shape;
    (d) 상기 제조된 펠릿에 대해 열처리를 하여 최종 CIS 타겟을 제조하는 단계(d) heat-treating the prepared pellets to prepare a final CIS target
    를 포함하는 것을 특징으로 하는 CIS계 타겟 제조 방법.CIS-based target manufacturing method comprising a.
  2. 청구항 1에 있어서, 상기 (c) 단계에서 Se은 상기 (b) 단계에서 합성한 CIS 물질에 대해 약 25~50 wt%의 비율로 추가 첨가되는 것을 특징으로 하는 CIS계 타겟 제조 방법.The method of claim 1, wherein in step (c), Se is added at a rate of about 25 to 50 wt% based on the CIS material synthesized in step (b).
  3. 청구항 2에 있어서, 상기 (c) 단계에서 Se은 상기 (b) 단계에서 합성한 CIS 물질에 대해 약 50 wt%의 비율로 추가 첨가되는 것을 특징으로 하는 CIS계 타겟 제조 방법.The method of claim 2, wherein in step (c), Se is added at a ratio of about 50 wt% to the CIS material synthesized in step (b).
  4. 청구항 1 내지 청구항 3 중 어느 한 항에 있어서, 상기 (d) 단계에서 상기 열처리는 약 300℃의 온도 및 대기압 중에서 수행하는 것을 특징으로 하는 CIS계 타겟 제조 방법.The method according to any one of claims 1 to 3, wherein the heat treatment in step (d) is performed at a temperature of about 300 ° C. and atmospheric pressure.
  5. 태양전지 흡수층을 증착하는 데 사용되는 CIGS계 타겟 제조 방법으로서,A CIGS-based target manufacturing method used to deposit a solar cell absorbing layer,
    (a) Cu, In, Ga, Se 파우더를 1:1-x:x:2(0<x<1)의 몰비로 준비하는 단계와;(a) preparing Cu, In, Ga, and Se powder in a molar ratio of 1: 1-x: x: 2 (0 <x <1);
    (b) 상기 Cu, In, Ga, Se 파우더와 금속 볼을 용기 안에 넣고 교반하여, 이 기계적 힘에 의해 CIGS 합성 물질을 제조하는 단계와;(b) putting Cu, In, Ga, Se powder and metal balls into a container and stirring to prepare a CIGS synthetic material by this mechanical force;
    (c) 상기 합성된 CIGS 물질에 Se을 추가로 첨가한 후, 볼밀을 이용하여 혼합하고 압축을 가해 타겟 형태에 대응하는 형상의 펠릿으로 제조하는 단계와;(c) further adding Se to the synthesized CIGS material, then mixing and compressing using a ball mill to produce pellets of a shape corresponding to the target shape;
    (d) 상기 제조된 펠릿에 대해 열처리를 하여 최종 CIGS 타겟을 제조하는 단계(d) heat-treating the prepared pellets to prepare a final CIGS target
    를 포함하는 것을 특징으로 하는 CIGS계 타겟 제조 방법.CIGS-based target manufacturing method comprising a.
  6. 청구항 5에 있어서, 상기 (c) 단계에서 Se은 상기 (b) 단계에서 합성한 CIGS 물질에 대해 약 25~50 wt%의 비율로 추가 첨가되는 것을 특징으로 하는 CIGS계 타겟 제조 방법.The method of claim 5, wherein in step (c), Se is added at a ratio of about 25 to 50 wt% based on the CIGS material synthesized in step (b).
  7. 청구항 6에 있어서, 상기 (c) 단계에서 Se은 상기 (b) 단계에서 합성한 CIGS 물질에 대해 약 50 wt%의 비율로 추가 첨가되는 것을 특징으로 하는 CIGS계 타겟 제조 방법.The method of claim 6, wherein in step (c), Se is added at a rate of about 50 wt% based on the CIGS material synthesized in step (b).
  8. 청구항 5 내지 청구항 7 중 어느 한 항에 있어서, 상기 (d) 단계에서 상기 열처리는 약 300℃의 온도 및 대기압 중에서 수행하는 것을 특징으로 하는 CIGS계 타겟 제조 방법.8. The method according to claim 5, wherein the heat treatment in step (d) is performed at a temperature of about 300 ° C. and atmospheric pressure. 9.
  9. 태양전지 흡수층을 증착하는 데 사용되는 CIS계 타겟으로서,As a CIS-based target used to deposit a solar cell absorbing layer,
    상기 CIS계 타겟은 Cu, In 및 Se의 1:1:2의 몰비를 초과하는 과량의 Se을 포함하는 것을 특징으로 하는 CIS계 타겟.The CIS-based target is a CIS-based target, characterized in that it comprises an excess of Se exceeding the molar ratio of 1: 1: 2 of Cu, In and Se.
  10. 청구항 9에 있어서, 상기 CIS계 타겟에서 Cu, In 및 Se의 1:1:2의 몰비의 CIS 물질에 대해 약 25~50 wt%의 비율로 Se이 추가 첨가되어 있는 것을 특징으로 하는 CIS계 타겟.The CIS target according to claim 9, wherein Se is added at a ratio of about 25 to 50 wt% based on a CIS material having a molar ratio of 1: 1: 2 of Cu, In, and Se in the CIS target. .
  11. 청구항 10에 있어서, 상기 CIS계 타겟에서 Cu, In 및 Se의 1:1:2의 몰비의 CIS 물질에 대해 약 50 wt%의 비율로 Se이 추가 첨가되어 있는 것을 특징으로 하는 CIS계 타겟.The CIS target according to claim 10, wherein Se is further added in the CIS target at a ratio of about 50 wt% to a CIS material having a molar ratio of 1: 1: 2 of Cu, In, and Se.
  12. 태양전지 흡수층을 증착하는 데 사용되는 CIGS계 타겟으로서,CIGS-based target used to deposit a solar cell absorbing layer,
    상기 CIGS계 타겟은 Cu, In, Ga 및 Se의 1:1-x:x:2(0<x<1)의 몰비를 초과하는 과량의 Se을 포함하는 것을 특징으로 하는 CIGS계 타겟.The CIGS-based target is CIGS-based target, characterized in that it comprises an excess of Se exceeding the molar ratio of 1: 1-x: x: 2 (0 <x <1) of Cu, In, Ga and Se.
  13. 청구항 12에 있어서, 상기 CIGS계 타겟에서 Cu, In, Ga 및 Se의 1:1-x:x:2(0<x<1)의 몰비의 CIGS 물질에 대해 약 25~50 wt%의 비율로 Se이 추가 첨가되어 있는 것을 특징으로 하는 CIGS계 타겟.The method according to claim 12, wherein the CIGS-based target in a ratio of about 25 to 50 wt% relative to the CIGS material in a molar ratio of 1: 1-x: x: 2 (0 <x <1) of Cu, In, Ga and Se. CIGS target, characterized in that the addition of Se.
  14. 청구항 13에 있어서, 상기 CIGS계 타겟에서 Cu, In, Ga 및 Se의 1:1-x:x:2(0<x<1)의 몰비의 CIGS 물질에 대해 약 50 wt%의 비율로 Se이 추가 첨가되어 있는 것을 특징으로 하는 CIGS계 타겟.The method of claim 13, wherein Se is added at a ratio of about 50 wt% to a CIGS material having a molar ratio of 1: 1-x: x: 2 (0 <x <1) of Cu, In, Ga, and Se in the CIGS-based target. CIGS system target characterized by being added.
PCT/KR2010/005198 2009-08-20 2010-08-09 Method for fabricating a physical vapor deposition target WO2011021800A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2009-0077002 2009-08-20
KR1020090077002A KR101067337B1 (en) 2009-08-20 2009-08-20 Method of manufaturing target for pvd

Publications (2)

Publication Number Publication Date
WO2011021800A2 true WO2011021800A2 (en) 2011-02-24
WO2011021800A3 WO2011021800A3 (en) 2011-05-05

Family

ID=43607440

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2010/005198 WO2011021800A2 (en) 2009-08-20 2010-08-09 Method for fabricating a physical vapor deposition target

Country Status (2)

Country Link
KR (1) KR101067337B1 (en)
WO (1) WO2011021800A2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8871143B2 (en) * 2012-01-20 2014-10-28 Leonard Nanis Amalgam method for forming a sputter target useful in the manufacture of thin-film solar photovoltaic cells

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5985691A (en) * 1997-05-16 1999-11-16 International Solar Electric Technology, Inc. Method of making compound semiconductor films and making related electronic devices
US20080121137A1 (en) * 2006-11-23 2008-05-29 Van Osten Karl-Uwe Coating material based on a copper-indium-gallium alloy, in particular for the production of sputter targets, tubular cathodes and the like
KR20090012140A (en) * 2007-07-25 2009-02-02 (주)누리셀 Method for depositing ceramic thin film by sputtering using non-conductive target and its apparatus therefor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5985691A (en) * 1997-05-16 1999-11-16 International Solar Electric Technology, Inc. Method of making compound semiconductor films and making related electronic devices
US20080121137A1 (en) * 2006-11-23 2008-05-29 Van Osten Karl-Uwe Coating material based on a copper-indium-gallium alloy, in particular for the production of sputter targets, tubular cathodes and the like
KR20090012140A (en) * 2007-07-25 2009-02-02 (주)누리셀 Method for depositing ceramic thin film by sputtering using non-conductive target and its apparatus therefor

Also Published As

Publication number Publication date
KR101067337B1 (en) 2011-09-23
KR20110019466A (en) 2011-02-28
WO2011021800A3 (en) 2011-05-05

Similar Documents

Publication Publication Date Title
KR100989077B1 (en) Fabrication of thin film for solar cells using paste and the thin film fabricated thereby
KR101075873B1 (en) Fabrication of cis or cigs thin film for solar cells using paste or ink
KR101533133B1 (en) Sodium/molybdenum composite metal poweders, products thereof and methods for producing photovoltaic cells
US9334559B2 (en) Powder, sintered body and sputtering target, each containing elements of Cu, In, Ga and Se, and method for producing the powder
Porthault et al. Synthesis of LiCoO2 thin films by sol/gel process
JP2013501381A (en) Method for photovoltaic absorbers with controlled stoichiometry
CN101613091A (en) A kind of CIGS powder, target, film and preparation method thereof
JP6330051B2 (en) Method for doping Cu (In, Ga) (S, Se) 2 nanoparticles with sodium or antimony
CN102451910A (en) Method for manufacturing Cu-Ga alloy sputtering target and Cu-Ga alloy sputtering target
CN102219523B (en) Low-temperature co-firing ceramic wave-absorbing material and preparation method thereof
Park et al. Effect of precursor structure on Cu (InGa) Se2 formation by reactive annealing
US8841160B2 (en) Methods for producing chalcopyrite compound thin films for solar cells using multi-stage paste coating
KR20110060211A (en) Fabrication of cuinxga1-xse2 thin films solar cell by selenization process with se solution
WO2011021800A2 (en) Method for fabricating a physical vapor deposition target
CN111850655B (en) Method for preparing high-adhesion nano thermite coating by electrophoretic deposition and coating thereof
KR101069576B1 (en) Method for fabricating the CI(G)S thin-film with dense microstructure using stoichiometric CI(G)S particles containing phases with low melting point
WO2010087484A1 (en) Process for producing compound semiconductor thin film, solar cell, and coating agent for use in production of compound semiconductor thin film
KR101418831B1 (en) Target for light absorption layer of thin film solar cell, method for the same and the thin film solar cell
US8535601B2 (en) Composite target material and method for producing the same
KR101395790B1 (en) Fabrication Method of Photo Active Layer for Solar Cell
CN104480352A (en) Al-Co-W alloy with alternating lamellar microstructure characteristics and preparation method thereof
KR101519829B1 (en) Manufacturing method of single phased cigs powder
WO2013154374A1 (en) Fabrication method of photo active layer for solar cell
KR101232671B1 (en) Method for manufacturing absorber film of solar cell and absorber film thereof, solar cell and solar cell module by using the same
JP2011099059A (en) Ink for producing compound semiconductor thin film, compound semiconductor thin film produced by using the same, solar cell having compound semiconductor thin film, and method of manufacturing solar cell

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10810108

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10810108

Country of ref document: EP

Kind code of ref document: A2