WO2012108157A1 - 太陽電池用透明膜形成用スパッタリングターゲットおよびその製造方法 - Google Patents

太陽電池用透明膜形成用スパッタリングターゲットおよびその製造方法 Download PDF

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WO2012108157A1
WO2012108157A1 PCT/JP2012/000734 JP2012000734W WO2012108157A1 WO 2012108157 A1 WO2012108157 A1 WO 2012108157A1 JP 2012000734 W JP2012000734 W JP 2012000734W WO 2012108157 A1 WO2012108157 A1 WO 2012108157A1
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sputtering target
sio
transparent film
zno
powder
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PCT/JP2012/000734
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English (en)
French (fr)
Japanese (ja)
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山口　剛
張　守斌
佑一 近藤
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三菱マテリアル株式会社
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Priority to JP2012556782A priority Critical patent/JP5747922B2/ja
Priority to KR1020177004547A priority patent/KR20170024124A/ko
Priority to CN201280004316.7A priority patent/CN103270191B/zh
Priority to KR1020137019490A priority patent/KR20140004147A/ko
Publication of WO2012108157A1 publication Critical patent/WO2012108157A1/ja

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    • 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
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Definitions

  • the present invention relates to a sputtering target for forming a transparent film for solar cells suitable for forming a ZnO—SiO 2 —Al 2 O 3 film, which is a transparent film having a low refractive index for thin film solar cells, and a method for producing the same. .
  • a transparent electrode layer such as AZO (Al-Zn-O: Aluminum-doped Zinc-Oxide) is formed, and the transparent electrode layer is transparent with a low refractive index to prevent reflection. It has a basic structure on which a film is formed. *
  • the low refractive index transparent film is provided on the upper side of the transparent conductive film so as to moderate the change in the refractive index with the atmosphere and prevent reflection.
  • a low refractive index transparent film on a transparent conductive layer is formed of MgF 2 or the like.
  • Patent Document 2 in order to continuously increase the refractive index in order to suppress the difference in refractive index of each layer, to suppress reflection at the interface, and to increase the amount of light reaching the light receiving surface.
  • a multilayer antireflection film is formed.
  • an MgF 2 film having a refractive index of 1.37 for light having a wavelength of 550 nm
  • AZO which is a transparent conductive layer under the MgF 2 film
  • the refractive index of the film is 1.8 (for light having a wavelength of 550 nm)
  • a transparent film having a refractive index lower than that of the AZO film and having a refractive index close to that of the MgF 2 film is interposed between the two to change the refractive index step by step to suppress light reflection.
  • a sputtering target capable of forming such a transparent film for solar cells by DC (direct current) sputtering excellent in productivity is a demand for a sputtering target capable of forming such a transparent film for solar cells by DC (direct current) sputtering excellent in productivity.
  • the present invention has been made in view of the above-described problems, and a sputtering target for forming a transparent film for a solar cell capable of DC sputtering a ZnO—SiO 2 —Al 2 O 3 film having a refractive index lower than that of an AZO film and its production It aims to provide a method.
  • the present inventors have to manufacture a sputtering target capable of forming a ZnO—SiO 2 —Al 2 O 3 film as a transparent film for solar cells.
  • a sputtering target is produced by firing a mixed powder of Al 2 O 3 powder, SiO 2 powder and ZnO powder in the air or in a nitrogen atmosphere, SiO 2 and ZnO react to form a composite oxide, The resistance increased to 1 ⁇ 10 6 ⁇ / cm 2 or more and abnormal discharge occurred, causing a problem that DC sputtering could not be performed.
  • a low-resistance sputtering target can be obtained even by the above-described manufacturing method.
  • a low refractive index required as a transparent film for solar cells can be obtained.
  • the present inventors have advanced the above research, and by performing hot pressing while controlling the component composition within a predetermined range, a sputtering target capable of good DC sputtering with low resistance is obtained, and the sputtering target is used. It was found that a ZnO—SiO 2 —Al 2 O 3 film having a low refractive index can be obtained by sputtering film formation.
  • the present invention has been obtained from the above findings, and the following configuration has been adopted in order to solve the above problems. That is, the sputtering target of the present invention contains Al: 0.3 to 4.0 wt%, Si: 6.0 to 14.5 wt% with respect to the total amount of metal components, and the balance is composed of Zn and inevitable impurities. It consists of an oxide sintered body having a composition, and the composite oxides Zn 2 SiO 4 and ZnO exist in the structure of the sintered body.
  • This sputtering target for forming a transparent film for a solar cell contains Al: 0.3 to 4.0 wt%, Si: 6.0 to 14.5 wt% with respect to the total amount of metal components, with the balance being Zn and inevitable impurities Since the composite oxides Zn 2 SiO 4 and ZnO exist in the structure of the sintered body, the composite oxides Zn 2 SiO 4 and ZnO are structured.
  • the ZnO—SiO 2 —Al 2 O 3 film which is suitable for a transparent film for solar cells with a lower refractive index than that of an AZO film, can be obtained by providing coexistence in the film, and providing good DC sputtering. It is done.
  • the reason why the content of Al is 0.3 to 4.0 wt% is that if it is less than 0.3 wt%, sufficient conductivity cannot be obtained, abnormal discharge occurs, and DC sputtering cannot be performed. If it exceeds 4.0 wt%, abnormal discharge due to the generated composite oxide of Al 2 O 3 and ZnO ZnAl 2 O 4 occurs, and DC sputtering cannot be performed.
  • the reason why the Si content is 6.0 to 14.5 wt% is that if it is less than 6.0 wt%, a sufficient effect of lowering the refractive index cannot be obtained. This is because sufficient conductivity cannot be obtained, abnormal discharge occurs, and DC sputtering cannot be performed.
  • the sputtering target for forming a transparent film for a solar cell of the present invention is characterized in that the density of the sintered body is 100 to 108% in terms of a theoretical density ratio.
  • the density of the sintered body is 100 to 108% of the theoretical density, so that DC sputtering is possible and target cracking can be suppressed.
  • the reason why the density of the sintered body is set to 100 to 108% in terms of the theoretical density ratio is that if it is less than 100%, problems such as the target cracking occur. This is because the oxide Zn 2 SiO 4 structure is formed and discharge by DC sputtering cannot be performed.
  • calculation of the theoretical density ratio was performed using ZnO of 5.61 g / cm 3 , SiO 2 of 2.20 g / cm 3 , and Al 2 O 3 of 3.99 g / cm 3 .
  • the sputtering target for forming a transparent film for a solar cell of the present invention has a bulk resistance value of 1 ⁇ ⁇ cm or less. That is, in this sputtering target for forming a transparent film for a solar cell, since the bulk resistance value is 1 ⁇ ⁇ cm or less, stable and good DC sputtering is possible.
  • Method for manufacturing a solar cell transparent film-forming sputtering target of the present invention is a method of making a transparent film-forming sputtering targets for the solar cell, the Al 2 O 3 powder and SiO 2 powder and ZnO powder, Al 2 O 3 : 0.5 to 5.0 wt%, SiO 2 : 10 to 22 wt%, balance: ZnO and inevitable impurities are mixed to form a mixed powder, and the mixed powder is heated in vacuum And a step of sintering with a press.
  • Al 2 O 3 powder, SiO 2 powder, and ZnO powder are mixed in the above range to obtain a mixed powder; Since sintering is performed by hot pressing in vacuum, stable DC sputtering is possible, and a sputtering target capable of forming a low refractive index transparent film can be produced.
  • the present invention has the following effects. That is, according to the sputtering target for forming a transparent film for solar cells according to the present invention, Al: 0.3 to 4.0 wt%, Si: 6.0 to 14.5 wt% with respect to the total amount of metal components. Since the balance is made of an oxide sintered body having a component composition consisting of Zn and inevitable impurities, and the composite oxides Zn 2 SiO 4 and ZnO are present in the structure of the sintered body, good DC sputtering is achieved. In addition, a ZnO—SiO 2 —Al 2 O 3 film suitable for a solar cell transparent film can be obtained with a lower refractive index than that of an AZO film.
  • the Al 2 O 3 powder and SiO 2 powder and ZnO powder, the mixed powder were mixed in the above range, sintering by a hot press in vacuo
  • the sputtering target can be manufactured. Therefore, in the transparent film for solar cells formed by DC sputtering using the sputtering target of the present invention, the required low antireflection transparent film to be formed on the AZO film (transparent electrode layer) of the thin film solar cell.
  • a thin film solar cell having a refractive index, low cost and good conversion efficiency can be produced.
  • XRD X-ray diffraction
  • the sputtering target for forming a transparent film for a solar cell of the present embodiment contains Al: 0.3 to 4.0 wt%, Si: 6.0 to 14.5 wt% with respect to the total amount of metal components, with the balance being Zn. And a target in which a composite oxide Zn 2 SiO 4 and ZnO exist in the structure of the oxide sintered body having a component composition composed of inevitable impurities. Further, in this sputtering target, the density of the sintered body is 100 to 108% of the theoretical density. Furthermore, this sputtering target has a bulk resistance value of 1 ⁇ ⁇ cm or less.
  • a method for producing a sputtering target for forming a transparent film for a solar cell comprises Al 2 O 3 powder, SiO 2 powder, and ZnO powder, Al 2 O 3 : 0.5 to 5.0 wt%, SiO 2. : 10 to 22 wt%, balance: ZnO and inevitable impurities are mixed to form a mixed powder, and this mixed powder is sintered in a vacuum by hot pressing.
  • the Al 2 O 3 powder and SiO 2 powder and ZnO powder were weighed so that the content range, pulverized by a wet ball mill, Mix to make a mixed powder.
  • each powder obtained by weighing and zirconia balls are placed in a poly container (polyethylene pot) and wet-mixed for a predetermined time in a ball mill apparatus to obtain a mixed powder.
  • alcohol is used as the solvent.
  • the obtained mixed powder is dried and then granulated through, for example, a sieve having a mesh opening of 250 ⁇ m, and further vacuum dried, and then hot-pressed in vacuum at a pressure of 200 kgf / cm 2 at 1200 ° C. for 5 hours, for example.
  • a sintered body preferably in the range of 1100 to 1250 ° C., and the pressure is preferably in the range of 150 to 350 kgf / cm 2 .
  • the hot-pressed sintered body is usually machined to a target shape using electrical discharge machining, cutting or grinding, and the processed target is In or soldered to Cu or SUS (stainless steel) or others. Bonding to a backing plate made of metal (for example, Mo) and subjecting to sputtering.
  • pulverization and mixing by the wet ball mill of the above manufacturing method is performed using a ball mill apparatus having an internal volume of 300 L with pure water as a solvent, and then dried and granulated by spray drying.
  • a method of crushed with a dry ball mill and hot pressing the crushed powder in the same manner as described above may be used.
  • omitted the crushing process by the said dry-type ball mill may be used.
  • the transparent film for a solar cell that is DC-sputtered using the sputtering target of this embodiment contains Al 2 O 3 : 0.5 to 5.0 wt%, SiO 2 : 10 to 22 wt%, and the balance is ZnO and unavoidable. It has a component composition consisting of impurities.
  • a thin film solar cell employing this solar cell transparent film has a Mo back electrode 2, a CIGS absorption layer 3, and an n-type semiconductor layer of ZnO, ZnS, ZnOH on a soda lime glass substrate 1.
  • the antireflection film 7a between the antireflection film 7b, which is a film, and the AZO electrode 6 is the transparent film for solar cells of this embodiment.
  • the sputtering target for forming a transparent film for solar cells of the present embodiment Al: 0.3 to 4.0 wt%, Si: 6.0 to 14.5 wt% with respect to the total metal component amount,
  • the balance is composed of an oxide sintered body having a composition composed of Zn and inevitable impurities, and the composite oxides Zn 2 SiO 4 and ZnO are present in the structure of the sintered body, so that the composite oxide Zn 2 SiO 4 and ZnO coexist in the structure, conductivity is obtained, good DC sputtering is possible, and ZnO—SiO 2 —Al suitable for a transparent film for solar cells with a lower refractive index than an AZO film. A 2 O 3 film is obtained.
  • the density of the sintered body of the solar cell transparent film forming sputtering target is 100 to 108% of the theoretical density, it is possible to perform DC sputtering and to suppress cracking of the target. Furthermore, since the bulk resistance value of the sputtering target for forming a transparent film for solar cells is 1 ⁇ ⁇ cm or less, stable and good DC sputtering is possible.
  • the Al 2 O 3 powder and SiO 2 powder and ZnO powder, a step of the mixed powder were mixed in the above range, the Since the mixed powder is sintered in a vacuum by hot pressing, the above sputtering target capable of stably performing good DC sputtering and forming a low refractive index transparent film can be produced.
  • the antireflection transparent film obtained by DC sputtering using this sputtering target contains Al 2 O 3 and SiO in the above content range, and the balance has a component composition consisting of ZnO and inevitable impurities.
  • the required low refractive index is obtained as the antireflection transparent film formed on the transparent electrode layer of the thin film solar cell. By adopting this film, high conversion efficiency can be obtained as a solar cell.
  • the manufacture of this example was performed under the following conditions. First, Al 2 O 3 powder, SiO 2 powder, and ZnO powder were weighed in the proportions shown in Table 1, and the obtained powder and four times (weight ratio) zirconia balls (balls having a diameter of 5 mm and diameters). A 10 mm ball and a half are put into a 10 L plastic container (polyethylene pot) and wet-mixed for 48 hours in a ball mill apparatus to obtain a mixed powder. For example, alcohol was used as the solvent.
  • the obtained mixed powder is dried, then granulated through, for example, a sieve having an opening of 250 ⁇ m, vacuum dried, vacuum hot pressed at 1200 ° C. for 5 hours at a pressure of 200 kgf / cm 2 , and sintered.
  • the body The sintered body thus hot-pressed is machined into a target shape (diameter 125 mm, thickness 10 mm), and the processed product is bonded to a backing plate made of oxygen-free copper to form the sputtering target of this example.
  • Comparative Examples 1 to 11 Al 2 O 3 powder, SiO 2 powder, and ZnO powder were weighed at the respective ratios shown in Table 1, and the obtained powders were mixed together at 0.6 t / cm 2 . Then, it was molded at 175 MPa by CIP (Cold Isostatic Press), and it was fired in the atmosphere at 1400 ° C. to produce a sputtering target. Further, as Comparative Examples 12 to 14, a sputtering target was prepared by weighing in the proportions shown in Table 1 outside the range of the composition of the present invention and vacuum hot pressing under the same conditions as in this example.
  • these sputtering targets were set in a magnetron sputtering apparatus, and the conditions were as follows: power source: DC, input power: 200 W, ultimate vacuum: 1 ⁇ 10 ⁇ 4 Pa, sputtering gas: Ar, sputtering pressure: 0.67 Pa An attempt was made to form a transparent film having a thickness of 300 nm on a glass substrate heated to 200 ° C. (Corning 1737 # length: 20 ⁇ width: 20, thickness: 0.7 mm).
  • Example and comparative example of this invention which were produced in this way, the density (theoretical density ratio) of the sintered body, the diffraction peaks of ZnO (101) and Zn 2 SiO 4 (410) by X-ray diffraction (XRD) Presence / absence, DC sputtering availability, bulk resistance value, number of abnormal discharges during DC sputtering for 60 minutes, and refractive index (for light with wavelengths of 380 nm, 550 nm, and 750 nm) of the DC-sputtered transparent film were measured and evaluated. The results are shown in Table 1.
  • Comparative Examples 1 and 2 in which the content of Al 2 O 3 is small and SiO 2 is not included among the comparative examples using atmospheric firing, the number of abnormal discharges is large and stable DC sputtering cannot be performed.
  • Comparative Examples 3 to 5 that have a certain amount of Al 2 O 3 but do not contain SiO 2 , a low refractive index is not obtained.
  • Comparative Examples 6 and 7 in which the content of Al 2 O 3 is large and does not contain SiO 2 among the comparative examples using atmospheric firing, stable DC sputtering cannot be performed with a large number of abnormal discharges, and Al 2 O 3 and In Comparative Examples 8 to 11 containing SiO 2 , the number of abnormal discharges was large, or the target was not conductive and DC sputtering could not be performed. In all of Comparative Examples 1 to 7, the density was less than 100% of the theoretical density.
  • FIG. 3 shows the result of observation by X-ray diffraction (XRD) for Example 3 (SiO 2 : 20 wt%) shown in Table 1.
  • XRD X-ray diffraction
  • SYMBOLS 1 Soda lime glass substrate, 2 ... Mo back surface electrode, 3 ... CIGS absorption layer, 4 ... Buffer layer, 5 ... i-ZnO buffer layer, 6 ... AZO electrode, 7a ... Antireflection film (transparent film for solar cells), 7b: Antireflection film (MgF 2 film), 8 ... Surface electrode

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WO2014148189A1 (ja) * 2013-03-19 2014-09-25 住友金属鉱山株式会社 酸化亜鉛系焼結体とその製造方法およびスパッタリングターゲットと透明導電膜
WO2021079947A1 (ja) * 2019-10-23 2021-04-29 三菱マテリアル株式会社 酸化物スパッタリングターゲット

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KR102000856B1 (ko) * 2015-02-27 2019-07-16 제이엑스금속주식회사 산화물 소결체, 산화물 스퍼터링 타깃 및 산화물 박막
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