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WO2016047556A1 - Cible de pulvérisation cathodique et procédé de fabrication de celle-ci - Google Patents

Cible de pulvérisation cathodique et procédé de fabrication de celle-ci Download PDF

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Publication number
WO2016047556A1
WO2016047556A1 PCT/JP2015/076515 JP2015076515W WO2016047556A1 WO 2016047556 A1 WO2016047556 A1 WO 2016047556A1 JP 2015076515 W JP2015076515 W JP 2015076515W WO 2016047556 A1 WO2016047556 A1 WO 2016047556A1
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Prior art keywords
phase
sputtering target
alloy
raw material
material powder
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English (en)
Japanese (ja)
Inventor
啓太 梅本
張　守斌
恒太郎 浦山
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority claimed from JP2015181053A external-priority patent/JP6634750B2/ja
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Priority to US15/511,753 priority Critical patent/US20170298499A1/en
Priority to CN201580033520.5A priority patent/CN106471150B/zh
Priority to EP15845101.3A priority patent/EP3199662A4/fr
Publication of WO2016047556A1 publication Critical patent/WO2016047556A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/12—Metallic powder containing non-metallic particles
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering

Definitions

  • the present invention relates to a sputtering target used for forming a Cu—In—Ga—Se compound film (hereinafter sometimes abbreviated as CIGS film) for forming a light absorption layer of a CIGS thin film solar cell, and It relates to the manufacturing method.
  • CIGS film Cu—In—Ga—Se compound film
  • This application claims priority based on Japanese Patent Application No. 2014-192151 filed in Japan on September 22, 2014, and Japanese Patent Application No. 2015-181053 filed on September 14, 2015 in Japan. , The contents of which are incorporated herein.
  • a Mo electrode layer serving as a positive electrode is formed on a soda lime glass substrate, and a light absorption layer composed of a CIGS film is formed on the Mo electrode layer. It has a basic structure in which a buffer layer made of ZnS, CdS, or the like is formed on the light absorption layer, and a transparent electrode layer to be a negative electrode is formed on the buffer layer.
  • a sputtering method suitable for film formation on a large-area substrate has been proposed.
  • an In film is formed by sputtering using an In sputtering target.
  • a Cu—Ga binary alloy film is sputtered on the In film using a Cu—Ga binary alloy sputtering target, and then, the In film and the Cu—Ga binary alloy film thus obtained are formed.
  • a selenization method is employed as a method of forming a CIGS film by heat-treating the laminated precursor film in an Se atmosphere.
  • the order of forming the In film and the Cu—Ga binary alloy film may be reversed.
  • a Cu—Ga alloy is formed by sputtering to a thickness of about 500 nm, and a laminated film is formed on the film by sputtering an In film to a thickness of about 500 nm. Is heated in H 2 Se gas at 500 ° C., and Se is diffused into CuGaIn to form a Cu—In—Ga—Se compound film.
  • the Cu—Ga alloy sputtering target is indispensable for manufacturing a CIGS solar cell using a Cu—In—Ga—Se compound film (CIGS film) as a light absorption layer. It is.
  • the band gap changes depending on the ratio of In and Ga, and the light absorption wavelength varies. For example, when the Ga ratio increases, the light absorption wavelength shifts to the lower wavelength side. It is known. Therefore, a thin film solar cell using a Cu—Ga—Se 2 compound film not containing In is expected to be applied as a top cell in a tandem structure of a CIGS thin film solar cell. Therefore, a Cu—Ga alloy sputtering target containing a high concentration of Ga is required to form a Cu—Ga—Se 2 compound film.
  • Patent Documents 2 and 3 Various types of Cu—Ga alloy sputtering targets containing high concentrations of Ga have been proposed (see, for example, Patent Documents 2 and 3).
  • Patent Document 2 describes a Cu—Ga alloy containing a plurality of phases, containing 40 wt% or more and 60 wt% or less of Ga, with the balance being made of Cu and inevitable impurities.
  • a Cu—Ga alloy sputtering target containing a segregation phase containing 80% by weight or more is disclosed.
  • Patent Document 3 is composed of a Cu—Ga alloy material having an average composition of Ga of 32 wt% or more and 45 wt% or less, and the balance of Cu, unavoidable impurities, and unavoidable voids, and 65 wt%.
  • a Cu—Ga alloy sputtering target is disclosed in which a Cu—Ga alloy phase containing at least% gallium includes at least one of a ⁇ 1 phase, a ⁇ 2 phase, and
  • Japanese Laid-Open Patent Publication No. 10-135495 A) Japanese Unexamined Patent Publication No. 2010-280944 (A) Japanese Patent Application Laid-Open No. 2011-241452 (A)
  • the Cu—Ga alloy in the Cu—Ga alloy sputtering target disclosed in Patent Document 2 is manufactured by melting the raw material and then rapidly solidifying the molten raw material. Specifically, a melting step of heating and melting a mixture containing 40 wt% or more and 60 wt% or less of Ga and the balance of Cu and inevitable impurities in a melting furnace, cooling the molten mixture to 254 ° C. , A cooling step in which the ⁇ 3 phase of the Cu—Ga alloy is solidified in the melted mixture, followed by a temperature of 254 ° C. in the cooling step and then 200 ° C.
  • the Cu—Ga alloy sputtering target according to Patent Document 2 contains a segregation phase containing Ga: 80% by weight or more, although Ga is contained at a high concentration but relatively poor in workability.
  • a sputtering target obtained by adding an alkali metal such as Na to a Cu—Ga alloy has the same problem as described above.
  • the entire Cu—Ga alloy material having a volume in a region containing less than 47% by weight of copper is used.
  • a Cu—Ga alloy material having a volume ratio of 2% or less is proposed.
  • the portion excluding the region containing less than 47% by weight of copper becomes a region containing 32% by weight to 53% by weight or less of gallium. That is, when the gallium ratio is 32% by weight or more, the brittle ⁇ phase becomes the main phase, and thus there is a problem that cracks and chips are likely to occur during processing during the production of the sputtering target.
  • the present invention has been made in view of the above-described problems, and an object thereof is to provide a Cu—Ga alloy sputtering target that is difficult to break during processing even if it contains a high concentration of Ga, and a method for manufacturing the same. .
  • a sputtering target of one embodiment of the present invention contains 30.0 to 67.0 atomic% of Ga, with the balance being Cu and inevitable impurities.
  • the sputtering target of (1) is characterized in that the average crystal grain size of the ⁇ phase is 5.0 to 50.0 ⁇ m.
  • the sputtering target of (1) is characterized in that the average crystal grain size of the ⁇ phase is 5.0 to 100.0 ⁇ m.
  • the ⁇ phase relative to the main peak intensity of the diffraction peak attributed to the ⁇ phase obtained by the X-ray diffraction (XRD) pattern of the sputtering surface The ratio of the main peak intensity of the assigned diffraction peak is 0.01 to 10.0.
  • the Na in the sputtering target of (5) is characterized by being contained in a state of at least one Na compound among sodium fluoride, sodium sulfide, and sodium selenide.
  • Another aspect of the present invention is a method for manufacturing a sputtering target according to any one of the above (1) to (4) (hereinafter referred to as “the manufacturing method of the sputtering target of the present invention”).
  • XRD X-ray diffraction
  • the firing temperature is 254 ° C. or higher and 450 ° C. or lower, preferably 254 ° C. or higher and lower than 400 ° C., and the main peak intensity ratio is higher than 0.5.
  • the firing temperature is 254 ° C. or higher and 450 ° C. or lower, preferably 254 ° C. or higher and lower than 400 ° C., and the main peak intensity ratio is higher than 0.5.
  • the mixing ratio of the raw material powder is 35% or less, preferably 30% or less, and contains 30.0 to 42.6 atomic% of Ga, with the balance being a component composition consisting of Cu and inevitable impurities.
  • the mixed powder is sintered in a non-oxidizing atmosphere or a reducing atmosphere at a temperature of 150 to 400 ° C. to produce a sintered body.
  • the present invention has the following effects. That is, according to the sputtering target of the present invention, the sintered body containing 30.0 to 67.0 atomic% of Ga and the balance of Cu and inevitable impurities is used as the sintered body of the Cu—Ga alloy. Since the phase matrix has a structure in which the ⁇ phase of the Cu—Ga alloy is dispersed, in the sintered body of the Cu—Ga alloy, it is possible to suppress the enlargement of the ⁇ phase crystal grains, and at the time of target processing The generation of cracks can be reduced.
  • a raw material powder containing 6 atomic% Ga and mixed so that the balance is composed of Cu and inevitable impurities is sintered at a temperature of 150 to 400 ° C.
  • the ⁇ phase matrix of the Cu—Ga alloy has a structure in which the ⁇ phase of the Cu—Ga alloy is dispersed, and particularly preferably, the average particle diameter of the ⁇ phase is 5.0 to 50.
  • the ratio of the main peak intensity of the diffraction peak attributed to the ⁇ phase to the main peak intensity of the diffraction peak attributed to the ⁇ phase obtained by the X-ray diffraction (XRD) pattern ( ⁇ phase intensity / A sintered body having a ⁇ phase strength of 0.01 to 10.0 can be obtained.
  • the Cu—Ga alloy sputtering target containing high-concentration Ga which is one embodiment of the present invention, is difficult to break during processing, and the yield of target production can be improved.
  • a light absorption layer of a CIGS thin film solar cell containing a high concentration of Ga can be formed, which can contribute to improvement of photoelectric conversion efficiency in the light absorption layer, and manufacture a solar cell with high power generation efficiency. It becomes possible.
  • the sputtering target of the embodiment contains 30.0 to 67.0 atomic% of Ga, and the remainder has a component composition consisting of Cu and inevitable impurities.
  • Cu In the ⁇ phase matrix of the Cu—Ga alloy, Cu It is characterized by comprising a sintered body having a structure in which the ⁇ phase of a -Ga alloy is dispersed.
  • the structure in which the ⁇ phase is dispersed in the ⁇ phase matrix means that in the sintered body, the ⁇ phase and the ⁇ phase precipitated during sintering coexist, and among the ⁇ phase and the ⁇ phase, It refers to a state in which one phase surrounds the other phase and each phase is dispersed without being assembled into a macro.
  • the basis for setting the Ga content in the range of 30.0 to 67.0 atomic% is that when the Ga content is less than 30.0 atomic%, the ⁇ phase is almost eliminated, and the structure Is substantially a single phase of ⁇ phase, and the target processability is abruptly deteriorated.
  • the content exceeds 67.0 atomic%, the ⁇ phase exists, but pure Ga is present. This is because (melting point is 29.6 ° C.) is generated, Ga is melted by heat during target cutting, and target cracks are generated starting from the melted Ga.
  • the ⁇ phase in the present embodiment includes ⁇ and ⁇ 1 to ⁇ 3 in the state diagram shown in FIG.
  • FIG. 2 is an X-ray diffraction (XRD) pattern obtained by analyzing the above-described sputtering target by X-ray diffraction (XRD).
  • FIG. 3 is a photograph of a composition image (COMPO image) obtained by performing electron probe microanalysis (EPMA) on the above sputtering target.
  • XRD X-ray diffraction
  • the above-described sputtering target exists in a state where two phases of ⁇ phase and ⁇ phase are dispersed.
  • the whitest part shows the area
  • the dark gray area is the ⁇ phase.
  • the reason why two phases of ⁇ phase and ⁇ phase coexist in the crystal structure of the sputtering target is that the diffraction peak attributed to the ⁇ phase obtained by the X-ray diffraction (XRD) pattern of the raw material Cu—Ga alloy powder. This is because the ratio between the main peak intensity of the diffraction peak and the main peak intensity of the diffraction peak attributed to the ⁇ phase is 0.01 to 10.0.
  • the firing temperature is set to 254 ° C.
  • the raw material Cu— A second Cu—Ga alloy raw material powder containing no ⁇ phase in the Ga alloy, ie, a ⁇ phase (Cu 1 ⁇ x Ga x : x 0.295 to 0.426),
  • the raw material powder is composed of the ⁇ phase from the Cu—Ga alloy raw material powder composed of the ⁇ phase.
  • the mixing ratio of the Cu—Ga alloy raw material powder with the ⁇ phase ratio exceeding 0.5 is preferably 30% or less.
  • the mixing ratio exceeds 30%, the amount of liquid phase from the ⁇ phase is large even if Ga diffuses from the Cu—Ga alloy raw material powder consisting of the ⁇ phase to the Cu—Ga alloy raw material powder consisting of the ⁇ phase. Therefore, it is difficult to maintain the shape of the sintered body.
  • the advantage of the coexistence of two phases, ⁇ phase and ⁇ phase is that the presence of the ⁇ phase suppresses the enlargement of the crystal grains of the ⁇ phase, reduces the average crystal grain size in the target structure, and allows the sputtering target to be processed. It is difficult to break.
  • XRD X-ray diffraction
  • the main phase of the matrix is formed of a single phase of ⁇ phase, and there is no ⁇ phase containing a relatively large amount of Ga. I understand that.
  • the average crystal grain size of the ⁇ phase is 5.0 to 50.0 ⁇ m
  • the average crystal grain size of the ⁇ phase is 5.0 to 100.0 ⁇ m
  • the ratio of the main peak intensity of the diffraction peak attributed to the ⁇ phase to the main peak intensity of the diffraction peak attributed to the ⁇ phase obtained by the X-ray diffraction (XRD) pattern is A range of 0.01 to 10.0 is preferable.
  • the processing after the sputtering target is manufactured.
  • chipping breaking or chipping
  • the ⁇ phase ratio for representing the coexistence of two phases of the ⁇ phase and the ⁇ phase in the sputtering target is in the range of 0.01 to 10.0, the presence of the ⁇ phase causes the ⁇ phase to exist. Since the enlargement of the crystal grains is suppressed, it can be made difficult to break when the sputtering target is processed.
  • the sputtering target of this embodiment can be used when forming a CIGS film that becomes a light absorption layer of a solar cell
  • Na is added to the sputtering target in an amount of 0.05 to 0.05 in order to increase its photoelectric conversion efficiency.
  • the Na may be contained in an amount of 15 atomic%, and the Na may be contained in the form of at least one Na compound among sodium fluoride, sodium sulfide, and sodium selenide.
  • 0.05 to 15 atomic% of K is contained instead of Na, and the K is contained in potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium sulfide, potassium selenide, niobium. It can also be made to contain in the state of at least 1 sort (s) of K compound among potassium acid. Na and K may be added simultaneously. In this case, the total of Na and K is 0.05 to 15 atomic%.
  • the method for producing a sputtering target according to this embodiment is a method for producing the sputtering target according to the above embodiment, which contains 40.0 to 67.0 atomic% of Ga, with the balance being Cu and inevitable impurities.
  • -Ga alloy powder the ratio of the main peak intensity of the diffraction peak attributed to the ⁇ phase to the main peak intensity of the diffraction peak attributed to the ⁇ phase obtained by the X-ray diffraction (XRD) pattern ( ⁇ phase intensity / ⁇ If the ratio of the main peak intensities is 0.5 or less in a non-oxidizing atmosphere or a reducing atmosphere, the firing temperature is 254 ° C.
  • the method has a step of sintering at a firing temperature of less than 254 ° C. to produce a sintered body. That is, in this sputtering target manufacturing method, the crystal grain size in the sintered body can be easily adjusted by using Cu—Ga alloy powder.
  • the ratio of the main peak intensity of the diffraction peak attributed to the ⁇ phase to the main peak intensity of the diffraction peak attributed to the ⁇ phase obtained by the X-ray diffraction (XRD) pattern ( ⁇ phase intensity / ⁇ phase intensity) is 0
  • the sintering temperature for obtaining the sintered body related to the sputtering target was set in the range of 150 to 450 ° C., so that the ⁇ phase of the Cu—Ga alloy was used in the sintered body.
  • a structure in which the ⁇ phase of the Cu—Ga alloy is dispersed in the matrix can be formed, and the average crystal grain size of the ⁇ phase can be made 50.0 ⁇ m or less.
  • Cu—Ga is included in the ⁇ phase matrix of the Cu—Ga alloy.
  • the ⁇ phase of the alloy can be made more dispersed, and the average crystal grain size of the ⁇ phase can be made 50.0 ⁇ m or less.
  • the manufacturing procedure of the Cu—Ga binary sputtering target of the present embodiment is, for example, as an alloy powder, Cu metal lump, Ga metal lump, and these are weighed to a predetermined amount, and each is melted in a crucible,
  • the Cu—Ga alloy atomized powder as the raw material powder is filled with a Cu metal lump and a Ga metal lump in a carbon crucible at a predetermined composition ratio, and a gas atomizing method using Ar gas. It is prepared with.
  • any one of hot press, hot isostatic pressing and atmospheric sintering is used, and the holding temperature at the time of sintering is set within a range of 150 to 450 ° C. did.
  • the non-oxidizing atmosphere refers to an atmosphere containing no oxygen such as an Ar atmosphere or a vacuum atmosphere.
  • the reducing atmosphere refers to an atmosphere containing a reducing gas such as H 2 or CO.
  • the surface portion and the outer peripheral portion of the obtained sintered body are turned to produce a sputtering target having a diameter of 50 mm and a thickness of 6 mm.
  • the processed sputtering target is bonded to a backing plate made of Cu or sus (stainless steel) or other metal (for example, Mo) using In as a solder, and is used for sputtering.
  • a vacuum pack or a pack obtained by replacing the entire target with a vacuum in order to prevent oxidation and moisture absorption.
  • the thus produced sputtering target is subjected to a DC magnetron sputtering apparatus using Ar gas as a sputtering gas.
  • direct current (DC) sputtering may be performed using a pulsed DC power source to which a pulse voltage is applied or a DC power source without a pulse.
  • the ⁇ phase is dispersed in the ⁇ phase matrix in the sintered body of the Cu—Ga alloy by the above manufacturing procedure.
  • the firing temperature is set to 254 ° C. or more, so that Cu— Since a liquid phase of the ⁇ phase appears from the Ga alloy powder and so-called liquid phase sintering is performed, densification easily occurs, and a high-density sintered body can be obtained while performing powder sintering by low-temperature hot pressing. In the process of cooling the sintered body, ⁇ phase precipitation occurs at around 254 ° C.
  • the liquid phase from the ⁇ phase can be set by setting the firing temperature to less than 254 ° C. Therefore, the ⁇ phase in the raw material Cu—Ga alloy is retained. At this time, if the firing temperature is set to 254 ° C. or higher, the amount of liquid phase from the ⁇ phase is too large, and it is difficult to maintain the shape of the sintered body. According to the Cu—Ga phase diagram described in “Binary Alloy Phase Diagrams (2nd edition)” described above, this phase separation is expected to occur whenever the atomic ratio of Ga is 42.6% or more. .
  • a structure in which the ⁇ phase of the Cu—Ga alloy is dispersed in the ⁇ phase matrix of the Cu—Ga alloy and can do.
  • the advantage of the two-phase coexistence is that the presence of the ⁇ phase suppresses the enlargement of the crystal grains of the ⁇ phase, reduces the average grain size of the target structure, and makes it difficult to break during sputtering target processing.
  • a 4N (purity 99.99%) Cu metal block and a 4N (purity 99.99%) Ga metal block were prepared.
  • Raw material powder A with a Ga content adjusted by a gas atomization method using Ar gas after weighing each component composition as shown in Table 1 to a total weight of 1200 g, filling each in a carbon crucible and dissolving it And raw material powder B was produced, and these raw material powders were classified by passing through a 125 ⁇ m sieve.
  • gas atomization conditions the melting temperature was 1000 to 1200 ° C.
  • the injection gas pressure was 28 kgf / cm 2
  • the nozzle diameter was 1.5 mm.
  • a CuGa raw material powder was prepared using a raw material powder A having a structure dispersed in a ⁇ phase matrix at a ⁇ phase ratio (mixing ratio 100%).
  • the mixing conditions using the rocking mixer were a rotational speed of 72 rpm and a mixing time of 30 minutes.
  • the raw material powder A and the Na additive shown in Table 2 were weighed at the mixing ratio of the raw material powder A shown in Table 1 and the Na additive shown in Table 2, and then rocked with a rocking mixer.
  • the raw material powder was obtained by mixing. Moreover, in Examples 8 and 11, Na additive shown in Table 2 was added to the mixture obtained by weighing the raw material powder A and the raw material powder B at the mixing ratio shown in Table 1 and mixing them with a rocking mixer. Were added at a mixing ratio shown in Table 2 and then mixed with a rocking mixer to obtain a CuGa raw material powder. As the Na additive, 3N (purity 99.9%) Na compound powder was used. In Examples 14 and 19 to 23, the raw material powder A and the K additive shown in Table 2 were weighed at the mixing ratio of the raw material powder A shown in Table 1 and the mixing ratio of the K additive shown in Table 2. And mixed with a rocking mixer to obtain a raw material powder.
  • Example 17 the raw material powder A, the raw material powder B, and the K additive shown in Table 2 were mixed, the mixing ratio of the raw material powder A and the raw material powder B shown in Table 1 and the mixing of the K additive shown in Table 2 After weighing in proportion, mixing was performed with a rocking mixer to obtain a raw material powder.
  • Example 18 the raw material powder A, the Na additive and the K additive shown in Table 2, the mixing ratio of the raw material powder A shown in Table 1, and the Na additive and K additive shown in Table 2 were mixed. Weighed at a ratio and mixed with a rocking mixer to obtain a raw material powder.
  • I obs ( ⁇ phase) is the measurement peak intensity of the ⁇ phase (102) plane
  • I obs ( ⁇ phase) is the measurement of the ⁇ phase (330) plane. Assuming the peak intensity, it is obtained by I obs ( ⁇ phase) / I obs ( ⁇ phase).
  • Example 14 shows a typical example in the case of adding a K compound instead of the Na compound.
  • a K compound instead of the Na compound.
  • the CuGa obtained previously was used.
  • a raw material powder and a K compound powder (KF) having a mixing ratio shown in Table 2 were prepared and mixed.
  • Na compound powder (NaF) and K compound powder (KCl) were similarly prepared and mixed.
  • Comparative Example 1 is a hot press at a high temperature outside the temperature range in the sputtering target manufacturing method of the present invention, in which the Ga content in the raw material powder A is smaller than that in the example and the ⁇ phase ratio is low.
  • Comparative Example 2 is a case where the content of Ga in the raw material powder A is larger than that in the Example, and there is no ⁇ phase.
  • Comparative Example 3 the raw material powder A and the raw material powder Although it is a case where B is used, it is a case where the mixing rate of the raw material powder B is high and the content of Ga in the CuGa raw material powder is smaller than in the case of the example. Moreover, although the comparative example 4 is a case where the raw material powder A and the raw material powder B are used, it is a case where the mixing ratio of the raw material powder A is high.
  • the maximum circumscribed circle is drawn for 20 crystals selected arbitrarily from the ⁇ phase (or ⁇ phase) of the image obtained by displaying the ⁇ phase (or ⁇ phase) in black, and the average of the diameters is drawn. Is the average crystal grain size in this image, and the average value of the five images is the average crystal grain size.
  • the measurement results are shown in the “ ⁇ phase average crystal grain size ( ⁇ m)” column and “ ⁇ phase average crystal grain size ( ⁇ m)” column of Table 4.
  • ⁇ Ratio of ⁇ phase For the sputtering targets of Examples 1 to 23 and Comparative Examples 1 and 3, the main peak intensity of the diffraction peak attributed to the ⁇ phase obtained by the X-ray diffraction (XRD) pattern and the diffraction peak attributed to the ⁇ phase The ratio of the main peak intensity of the diffraction peak attributed to the ⁇ phase to the main peak intensity of the diffraction peak attributed to the ⁇ phase was calculated to determine the ratio of the ⁇ phase. The main peak intensity of the diffraction peak was the (102) plane in the ⁇ phase and the (330) plane peak intensity in the ⁇ phase.
  • This XRD pattern was measured after wet-polishing and drying the sputtering surface of the sputtering target with SiC-Paper (grit 180).
  • the apparatus and measurement conditions used for this analysis are shown below.
  • Ratio of ⁇ phase I obs ( ⁇ phase) / I obs ( ⁇ phase)
  • I obs ( ⁇ phase) is the measured intensity of the ⁇ phase (201) plane
  • I obs ( ⁇ phase) is the measured intensity of the ⁇ phase (330) plane.
  • composition images obtained by EPMA for the sputtering targets of Examples 1 to 23 and Comparative Examples 1 and 3, the structure in which the ⁇ phase is dispersed in the ⁇ phase is indicated as “A”, One phase is shown as “B” in the “Target organization” column of Table 4.
  • the average particle diameter of the ⁇ phase is as small as 50.0 ⁇ m or less.
  • two phases of the ⁇ phase and the ⁇ phase are present. Observed, it was confirmed that the ratio of the ⁇ phase was 10.0 or less. In these examples, good results were obtained with respect to chipping during cutting, and improvement in workability was confirmed.
  • Comparative Example 1 although the raw material powder A was used as the raw material powder, the Ga component was small and hot pressing was performed at a high temperature outside the temperature range of the sputtering target manufacturing method of the present invention. No phase was generated, the target structure became a single ⁇ phase, and chipping occurred during cutting. In Comparative Example 2, Ga was too much out of the composition range of the sputtering target and the sputtering target manufacturing method of the present invention, so that Ga was eluted during processing, and the target was cracked.
  • Comparative Example 3 since the mixing ratio of the raw material powder B composed of a single phase of ⁇ phase is large, even if the raw material powder A composed of the ⁇ phase is used, the ⁇ phase is not generated, and the target structure is a single ⁇ phase. Phase and chipping occurred during cutting. In Comparative Example 4, the sputtering of the sputtering target could not be performed because the ⁇ phase melted during sintering and could not be molded. Thus, all of the comparative examples were inferior in workability.
  • the Ga content is in the range of 30.0 to 67.0 atomic% and sintered at a temperature of 150 to 400 ° C.
  • Cu -Both the diffraction peak attributed to the ⁇ phase and the diffraction peak attributed to the ⁇ phase of the Ga alloy are observed, and the ratio of the main peak intensity of the diffraction peak attributed to the ⁇ phase to the main peak intensity of the diffraction peak attributed to the ⁇ phase
  • the (ratio of the ⁇ phase) was in the range of 0.01 to 10.0.
  • the ⁇ phase containing a relatively large amount of Ga is dispersed in the matrix of ⁇ phase. It was confirmed that it had a crystal structure. Accordingly, it has been found that the occurrence of chipping (cracking, chipping) during processing can be suppressed by dispersing the ⁇ phase in the ⁇ phase matrix in the sintered body of the Cu—Ga alloy in the sputtering target of the present invention.
  • the sputtering target of the present invention has a surface roughness of 1.5 ⁇ m or less, an electric resistance of 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, a metal impurity concentration of 0.1 atomic% or less, and a bending strength of 150 MPa or more. Preferably there is.
  • Each of the above-described embodiments satisfies these conditions.
  • the technical scope of the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention.
  • the sputtering target of the said embodiment and the said Example is a flat thing, it is good also as a cylindrical sputtering target.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Vapour Deposition (AREA)
  • Powder Metallurgy (AREA)

Abstract

　Cette cible de pulvérisation cathodique comprend un corps fritté ayant une composition contenant 30,0-67,0 % (en pourcentage atomique) de Ga, le reste étant constitué par Cu et des impuretés inévitables; et le corps fritté présente une structure présentant une phase θ d'un alliage Cu-Ga dispersée dans une matrice à phase γ de l'alliage Cu-Ga.
PCT/JP2015/076515 2014-09-22 2015-09-17 Cible de pulvérisation cathodique et procédé de fabrication de celle-ci Ceased WO2016047556A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US15/511,753 US20170298499A1 (en) 2014-09-22 2015-09-17 Sputtering target and method for manufacturing same
CN201580033520.5A CN106471150B (zh) 2014-09-22 2015-09-17 溅射靶及其制造方法
EP15845101.3A EP3199662A4 (fr) 2014-09-22 2015-09-17 Cible de pulvérisation cathodique et procédé de fabrication de celle-ci

Applications Claiming Priority (4)

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JP2014192151 2014-09-22
JP2014-192151 2014-09-22
JP2015-181053 2015-09-14
JP2015181053A JP6634750B2 (ja) 2014-09-22 2015-09-14 スパッタリングターゲット及びその製造方法

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008138232A (ja) * 2006-11-30 2008-06-19 Mitsubishi Materials Corp 高Ｇａ含有Ｃｕ−Ｇａ二元系合金スパッタリングターゲットおよびその製造方法
WO2011055537A1 (fr) * 2009-11-06 2011-05-12 三菱マテリアル株式会社 Cible de pulvérisation et son procédé de production
JP2011149039A (ja) * 2010-01-20 2011-08-04 Sanyo Special Steel Co Ltd 高強度を有するＣｕ−Ｇａ系スパッタリングターゲット材およびその製造方法
WO2012098722A1 (fr) * 2011-01-17 2012-07-26 Jx日鉱日石金属株式会社 Cible d'alliage de cuivre-gallium et procédé de fabrication de cette dernière ainsi que couche absorbant la lumière formée à partir du film d'alliage de cuivre-gallium et cellule solaire au cigs qui utilise la couche absorbant la lumière

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008138232A (ja) * 2006-11-30 2008-06-19 Mitsubishi Materials Corp 高Ｇａ含有Ｃｕ−Ｇａ二元系合金スパッタリングターゲットおよびその製造方法
WO2011055537A1 (fr) * 2009-11-06 2011-05-12 三菱マテリアル株式会社 Cible de pulvérisation et son procédé de production
JP2011149039A (ja) * 2010-01-20 2011-08-04 Sanyo Special Steel Co Ltd 高強度を有するＣｕ−Ｇａ系スパッタリングターゲット材およびその製造方法
WO2012098722A1 (fr) * 2011-01-17 2012-07-26 Jx日鉱日石金属株式会社 Cible d'alliage de cuivre-gallium et procédé de fabrication de cette dernière ainsi que couche absorbant la lumière formée à partir du film d'alliage de cuivre-gallium et cellule solaire au cigs qui utilise la couche absorbant la lumière

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