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WO2015046319A1 - In ALLOY SPUTTERING TARGET, METHOD FOR PRODUCING SAME, AND In ALLOY FILM - Google Patents

In ALLOY SPUTTERING TARGET, METHOD FOR PRODUCING SAME, AND In ALLOY FILM Download PDF

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Publication number
WO2015046319A1
WO2015046319A1 PCT/JP2014/075405 JP2014075405W WO2015046319A1 WO 2015046319 A1 WO2015046319 A1 WO 2015046319A1 JP 2014075405 W JP2014075405 W JP 2014075405W WO 2015046319 A1 WO2015046319 A1 WO 2015046319A1
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Prior art keywords
alloy
sputtering target
film
sputtering
atomic
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French (fr)
Japanese (ja)
Inventor
加藤　慎司
啓太 梅本
張　守斌
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority to JP2015539329A priority Critical patent/JP5871106B2/en
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    • 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
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • 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
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
    • 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 an In alloy sputtering target used for forming a thin film containing In as a main component by using a sputtering method, a method for manufacturing the In alloy sputtering target, and an In alloy film.
  • This application claims priority based on Japanese Patent Application No. 2013-1993367 filed in Japan on September 26, 2013 and Japanese Patent Application No. 2014-081765 filed in Japan on April 11, 2014. Is hereby incorporated by reference.
  • a method of manufacturing a thin film solar cell including a CIGS compound semiconductor includes a step of forming a Mo electrode layer on a soda lime glass substrate, and a Cu—In—Ga—Se quaternary on the Mo electrode layer.
  • a step of forming a transparent electrode layer on the buffer layer A CIGS compound thin film solar cell has such a basic structure.
  • a method for forming a light absorption layer made of the above-described Cu—In—Ga—Se quaternary alloy film a method of forming a film by vapor deposition is known.
  • the light absorption layer made of a Cu—In—Ga—Se quaternary alloy film obtained by this method has an advantage that high energy conversion efficiency can be obtained.
  • the film formation rate is slow, and the uniformity of the in-plane distribution of film thickness is insufficient when a large-area compound thin film is formed. Therefore, a method for forming a light absorption layer made of a Cu—In—Ga—Se quaternary alloy film by a selenization method has been proposed.
  • the above Cu—In—Ga—Se quaternary alloy film is formed by a selenization method by first sputtering a Cu—Ga binary alloy sputtering target onto a Mo electrode layer.
  • a laminated film made of the Cu—Ga binary alloy film and the In film obtained here, that is, a precursor film as a precursor is formed.
  • a method of forming a Cu—In—Ga—Se quaternary alloy film by heat-treating this precursor film in a Se atmosphere has been proposed (see, for example, Patent Document 1).
  • In has the physical properties of low melting point and high surface tension.
  • In grows in a granular form due to the physical properties of In.
  • Non-Patent Documents 1 and 2 Non-Patent Documents 1 and 2.
  • an In sputtering target can be produced from an In ingot obtained by a casting method, but the In crystal grain size becomes large. For this reason, abnormal discharge and particles are likely to occur during sputtering, and a uniform In film cannot be obtained. In order to reduce the abnormal discharge and the generation of particles, it is effective to reduce the In crystal grain size. However, by rolling this In ingot, even if large In crystal grains are destroyed, the In melting point is low, so that the crystal grows immediately with the processing heat of plastic working. For this reason, it was difficult to obtain an In sputtering target having a crystal grain size of 2 mm or less.
  • the In film is formed by the sputtering method
  • In is aggregated in an island shape and a discontinuous layer is formed.
  • a part covered with In and a part not covered with In are formed.
  • a portion having no In becomes Cu-rich during subsequent selenization treatment, and a low-resistance Cu—Se compound is locally generated. Become.
  • the component composition of the light absorption layer varies, and the performance of the solar cell is reduced.
  • the island-like aggregated layer does not occur and a flat film can be obtained at a relatively thin film thickness of about 50 nm.
  • the thickness of an In film used as a precursor is generally about 500 nm, this method has a problem in improving productivity because a large number of thin In films must be stacked.
  • a method of forming a precursor film by co-sputtering using a CuGa sputtering target and an In sputtering target Non-patent Documents 1 and 2, etc.
  • co-sputtering is usually performed in a batch system and is not suitable for in-line sputtering, and thus has a problem in terms of productivity.
  • the present invention relates to an In alloy sputtering target that can reduce abnormal discharge and generation of particles during sputtering, and can suppress the formation of In island-like aggregated layers when forming an In film, a method for manufacturing the same, and an In alloy film
  • the purpose is to provide.
  • the present inventors examined the In sputtering target by paying attention to the problem that abnormal discharge can be solved by refining the In crystal grains of the In sputtering target. As a result, it was found that by adding Al that does not dissolve in In, fine Al particles are dispersed in the In substrate, and growth of In crystal grains can be suppressed. Furthermore, an AlCu alloy or an AlCuIn alloy can be generated by adding Cu. It was found that these alloys facilitate the uniform dispersion of Al, suppress the growth of In crystal grains, and make In particles finer.
  • the first aspect of the In alloy sputtering target of the present invention is characterized in that Al is contained in an amount of 0.5 to 25 atomic%, and the balance is composed of In and inevitable impurities.
  • the In alloy sputtering target of (1) is characterized in that an Al phase (Al particles) is dispersed in an In substrate, and an average crystal grain size of the In substrate is 500 ⁇ m or less.
  • the In alloy sputtering target of (2) is characterized in that the average particle size of the Al phase is 350 ⁇ m or less.
  • the first aspect of the method for producing an In alloy sputtering target of the present invention includes a step of introducing Al powder into dissolved In, containing 0.5 to 25 atomic% of Al, with the balance being In. And an In alloy sputtering target having a component composition comprising inevitable impurities.
  • the first aspect of the In alloy film of the present invention is characterized in that Al is contained in an amount of 0.3 to 25 atomic% and the balance is composed of In and inevitable impurities.
  • a second aspect of the In alloy film of the present invention is characterized by being formed using the sputtering target according to any one of (1) to (3).
  • the second aspect of the In alloy sputtering target of the present invention contains 0.5 to 25 atomic% of Al, further contains 0.3 to 25 atomic% of Cu, and the balance is made of In and inevitable impurities. It has the component composition which becomes.
  • an alloy phase (alloy particles) containing at least Al and Cu is dispersed in the In substrate, and an average crystal grain size of the In substrate is 500 ⁇ m or less.
  • the In sputtering target of (8) is characterized in that an average particle size of the alloy phase is 350 ⁇ m or less.
  • a second aspect of the method for producing an In alloy sputtering target of the present invention has a step of introducing Al—Cu alloy powder into dissolved In, and contains 0.5 to 25 atomic% of Al. Furthermore, an In alloy sputtering target having a component composition containing 0.3 to 25 atomic% of Cu and the balance of In and inevitable impurities is manufactured.
  • Al is contained in an amount of 0.3 to 25 atom%
  • Cu is further contained in an amount of 0.3 to 25 atom%
  • the balance is made of In and inevitable impurities. It has the component composition.
  • a fourth aspect of the In alloy film of the present invention is characterized by being formed using the sputtering target according to any one of (7) to (9).
  • the 1st, 2nd aspect of the In alloy sputtering target of this invention is effective in formation of the light absorption layer in a CIGS type compound thin film solar cell.
  • FIG. 5 is an In distribution image measured by FE-SEM in order to explain the evaluation of flatness in a formed In alloy film.
  • A A cross-sectional photograph of a laminated film having an In film and a Cu—Ga alloy film produced using the In film, and
  • B an In—Al alloy film and Cu—Ga produced using the In—Al alloy film. It is a cross-sectional photograph of a laminated film having an alloy film.
  • the In alloy sputtering target of this embodiment has a component composition containing 0.5 to 25 atomic% of Al, with the balance being In and inevitable impurities.
  • the amount of Al is preferably 1 to 20 atomic%.
  • the amount of Al exceeds 25 atomic%, the segregation of Al in the film formed by sputtering increases, and the flatness of the obtained sputtered film deteriorates.
  • the Al content is less than 0.5 atomic%, island aggregation of the In film cannot be suppressed.
  • Al particles (Al phase) are dispersed in the In substrate of the sputtering target, and the average crystal grain size of the In substrate (In crystal grains) becomes small.
  • the average crystal grain size of the In substrate is preferably 500 ⁇ m or less, more preferably 0.1 ⁇ m or more and 400 ⁇ m or less.
  • DC direct current
  • sputtering is performed using an In sputtering target containing Al
  • coarse In crystal grains cause abnormal discharge and nodules.
  • the average grain size of the In substrate is 500 ⁇ m or less, excessive abnormal discharge does not occur.
  • the average particle diameter of the Al particles is preferably 350 ⁇ m or less, more preferably 0.1 to 350 ⁇ m, and most preferably 0.1 to 150 ⁇ m. Abnormal discharge is less likely to occur because the Al particles are not coarse.
  • the manufacturing method of the In alloy sputtering target of the present embodiment includes a step of introducing Al powder into dissolved In.
  • the sputtering target becomes a monotectic alloy, so the Al and In melt separates into two phases, and the amount of segregation of Al increases. This increases the crystal grain size of the In substrate where Al is not present.
  • the amount of Al is small, the effect of refining the crystal grains of the In substrate is reduced. Therefore, in the manufacturing method of the In sputtering target of the present embodiment, 0.5 to 25 atomic% of Al is contained, the remainder has a composition composed of In and inevitable impurities, and the average crystal grain size of the In substrate is 500 ⁇ m or less.
  • a step of producing a molten metal by melting In and Al so as to obtain an In sputtering target having an average Al particle size of 350 ⁇ m or less (a step of introducing Al powder into the dissolved In), and It has the process of casting a molten metal on a backing plate and cooling it.
  • fine Al powder having an average particle diameter of 350 ⁇ m or less is added as an Al material.
  • the average particle size of the Al powder is preferably 0.1 to 350 ⁇ m, more preferably 0.1 to 150 ⁇ m.
  • the cooling rate is preferably 5 ° C./min or more, more preferably 30 ° C./min or more.
  • the upper limit of the cooling rate is not particularly limited, and the molten metal may be cooled by water cooling.
  • the In alloy film of this embodiment contains 0.3 to 25 atomic% of Al, and the remainder has a component composition composed of In and inevitable impurities.
  • the amount of Al is preferably 3 to 23 atomic%.
  • the In alloy film of this embodiment is formed using the sputtering target of this embodiment. For this reason, the segregation of Al in the In alloy film is small and the flatness of the film is excellent. Moreover, there is almost no island-like aggregation.
  • the In alloy sputtering target of the present embodiment contains 0.5 to 25 atomic% of Al, further contains 0.3 to 25 atomic% of Cu, and the balance is composed of In and inevitable impurities.
  • the amount of Al is preferably 1 to 10 atomic%.
  • the amount of Cu is preferably 1 to 10 atomic%.
  • fine AlCu alloy particles (AlCu alloy phase) or AlCuIn alloy particles (AlCuIn alloy phase) of 350 ⁇ m or less are generated depending on the content ratio of Al and Cu.
  • the addition of Cu facilitates uniform dispersion of the added Al, suppresses segregation of Al, and facilitates the refinement of In crystal grains.
  • the amount of Cu in the sputtering target is equal to or less than the amount of Al.
  • the ratio of Cu amount to Al amount is preferably 0.1 to 0.5, more preferably 0.3 to 0.5. The reason why the amounts of Al and Cu are limited to the above-described range is the same as in the case of adding only Al (first embodiment).
  • Alloy particles (Al alloy phase) containing at least Al and Cu are dispersed in the In substrate of the In alloy sputtering target, and the average crystal grain size of the In substrate (In crystal grains) becomes small.
  • the average crystal grain size of the In substrate is preferably 500 ⁇ m or less, more preferably 0.1 ⁇ m or more and 100 ⁇ m or less. Similar to the In alloy sputtering target of the first embodiment to which only Al is added, when direct current (DC) sputtering is performed, if the crystal grain size of the In substrate is large, coarse In crystal grains may cause abnormal discharge or nodules. It becomes a factor of occurrence. If the average grain size of the In substrate is 500 ⁇ m or less, excessive abnormal discharge does not occur.
  • the average particle size of the alloy particles is preferably 350 ⁇ m or less, more preferably 0.1 to 350 ⁇ m, and most preferably 0.1 to 150 ⁇ m. Abnormal discharge is less likely to occur because the alloy particles are not coarse.
  • the manufacturing method of the In alloy sputtering target of the present embodiment includes a step of melting In, Al, and Cu to prepare a molten metal (a step of introducing Al—Cu alloy powder into the molten In), and backing the molten metal. It has the process of casting on a plate and cooling.
  • the manufacturing conditions of the present embodiment are the same as the manufacturing conditions of the first embodiment, except that in the step of producing the molten metal, Al—Cu alloy powder is used instead of Al powder as a raw material.
  • the average particle diameter of the Al—Cu alloy powder is preferably 0.1 to 350 ⁇ m, more preferably 0.1 to 150 ⁇ m.
  • the In alloy film of the present embodiment contains 0.3 to 25 atomic percent of Al, further contains 0.3 to 25 atomic percent of Cu, and the balance is composed of In and inevitable impurities.
  • the amount of Al is preferably 1 to 10 atomic%.
  • the amount of Cu is preferably 1 to 10 atomic%.
  • the In alloy film of this embodiment is formed using the sputtering target of this embodiment. For this reason, the segregation of Al in the In alloy film is small and the flatness of the film is excellent. Moreover, there is almost no island-like aggregation.
  • the In alloy sputtering target of the first and second embodiments has a component composition containing 0.5 to 25 atomic% of Al and the balance of In and inevitable impurities.
  • the average grain size of the In substrate is 500 ⁇ m or less, and the average grain size of Al particles (Al phase) or alloy particles containing Al and Cu (Al alloy phase) is 350 ⁇ m or less.
  • Sputtering using this In alloy sputtering target makes it possible to form an In alloy film having a component composition in which Al is contained in an amount of 0.3 to 25 atomic% and the balance is made of In and inevitable impurities. Since the In alloy sputtering target contains Al, the growth of In crystal grains is suppressed, and the average crystal grain size of the In substrate is 500 ⁇ m or less.
  • the In alloy sputtering target of the first and second embodiments is effective for forming a light absorption layer in a CIGS compound thin film solar cell.
  • the In molten metal MM obtained by melting Al was poured into a graphite mold MC disposed on the backing plate BP to cast an ingot.
  • a cooling method at this time one of the following three procedures was performed.
  • the cooled ingot was machined with a lathe to produce In alloy sputtering targets of Examples 1 to 9.
  • Table 1 only the amount of additive element Al (Al concentration in the raw material) (concentration: at%) is shown, but the amount of In is not shown because it is the remainder. That is, the balance in the raw material is In and inevitable impurities.
  • Comparative Example 1 For comparison with Examples corresponding to the embodiment, as shown in Table 1 below, sputtering targets of Comparative Examples 1 to 4 were prepared by the same method as in the Examples. Comparative Examples 1 and 2 are In sputtering targets made of only In without added Al. Comparative Example 3 is an In alloy sputtering target to which 0.3 at% Al is added. Comparative Example 4 is an In alloy sputtering target (Al concentration in the target: 28.4 at%) to which 30.0 at% Al is added.
  • the Al concentration in the sputtering target, the average particle diameter of the Al particles, and the average crystal grain of the In crystal grains were measured.
  • the measuring method is as follows.
  • FIG. 2 is an example of an element distribution image obtained by mapping analysis by EPMA, (a) is a reflected electron composition image (COMPO image), (b) is an image showing an Al distribution, c) is an image showing the In distribution. From one image of the obtained Al distribution image ((FIG. 2B)), the Al particle diameter was measured, and the average particle diameter of the Al particles (Al phase) was determined. It is shown in the “Al average particle diameter ( ⁇ m)” column.
  • a sputtering target was produced on a backing plate so as to have a diameter of 125 mm and a thickness of 5 mm. This sputtering target was attached to a sputtering apparatus. A sputtering test was performed using Ar as a sputtering gas, a sputtering gas pressure of 5 mTorr, and a direct current (DC) power source with a sputtering output of 200 W. Sputtering was performed continuously for 1 hour. During this time, the number of abnormal discharges caused by sputtering abnormality was counted using an arc counter attached to the power source. The measurement result is shown in the “abnormal discharge count” column of Table 1.
  • the Al concentration in the In film and In alloy film obtained under the above film formation conditions was measured. Further, on the surface of the In film and In alloy film, the occurrence of In island aggregation, that is, the flatness of the In film and In alloy film was evaluated. ⁇ Measurement of Al concentration in film>
  • the obtained In alloy film was quantitatively analyzed using an ICP emission spectroscopic analyzer, and the Al concentration (at%) was measured. The results are shown in the “Al concentration in film (at%)” column of Table 1.
  • FIG. 3 is an example of an In distribution image measured by FE-SEM.
  • the area ratio of the part where In is missing in the film that is, the part where the background is visible (the part of the ground) was obtained, and the state of the occurrence of island aggregation was evaluated. .
  • FIG. 4 shows (a) a cross-sectional photograph of a laminated film having an In film and a Cu—Ga alloy film manufactured using the In film, and (b) using an In—Al alloy film containing 5 at% Al. A cross-sectional photograph of a laminated film having the manufactured In—Al alloy film and Cu—Ga alloy film is shown.
  • the average grain size of Al particles is 350 ⁇ m or less, and the average grain size of In substrate (In crystal grains) is 500 ⁇ m or less. It was confirmed that In sputtering using the In alloy sputtering target of Examples 1 to 9, the number of abnormal discharges was 1 or less, and almost no abnormal discharge occurred. It was confirmed that the island-like aggregation of In was suppressed in any of the formed In alloy films.
  • the In sputtering target of Comparative Examples 1 and 2 is a conventional sputtering target to which Al is not added, and the average crystal grain size of the In substrate (In crystal grain) is large and the number of abnormal discharges is large. . Also, a flat In film was not obtained.
  • the In alloy sputtering target of Comparative Example 3 since the amount of Al added was small, the growth of In crystal grains could not be suppressed, and the average crystal grain size of the In substrate (In crystal grains) became large. For this reason, abnormal discharge was observed during sputtering. Moreover, a flat In film was not obtained.
  • the In alloy sputtering target according to the first embodiment can eliminate any abnormal discharge during sputtering.
  • the In alloy film formed by this In alloy sputtering target contains 0.3 to 25 atomic% of Al, and the balance is composed of In and inevitable impurities, and the film quality is improved and the film is uniform and flat. It was confirmed that.
  • the first example described above was the case of the In alloy sputtering target to which only Al was added (first embodiment), but in the second example, the In alloy sputtering target to which Al and Cu were added was used. This is the case (second embodiment).
  • In (purity 4N or higher), Al (purity 4N or higher), Cu (purity 4N or higher), and Cu (purity 4N or higher) were prepared as target manufacturing raw materials in order to manufacture an In alloy sputtering target.
  • a predetermined amount of Al and Cu raw materials were weighed so as to have the composition ratio shown in Table 2.
  • a predetermined amount of Al and Cu raw materials were melted to cast an Al—Cu alloy.
  • the Al—Cu ingot was pulverized to obtain an Al—Cu alloy raw material.
  • a predetermined amount of In was introduced into the carbon crucible MP, and In was dissolved in an induction furnace (in Ar).
  • Al concentration and Cu concentration in the sputtering target and Al alloy particles Al alloy phase
  • the average crystal grain size of In crystal grains, and the number of abnormal discharges during sputtering The measurement method is the same as in the case of the first embodiment described above, and the measurement results relating to the Al concentration average value and the Cu concentration average value are shown in the “Target composition measurement value” column of Table 2, and other measurements are performed. The results are shown in the “Al alloy phase average grain size ( ⁇ m)” column, the “In average crystal grain size ( ⁇ m)” column, and the “abnormal discharge count” column in Table 2.
  • the average particle diameter of the Al alloy particles (Al alloy phase) was 350 ⁇ m or less, and the average of the In substrate (In crystal grains) It was confirmed that the crystal grain size was 500 ⁇ m or less.
  • the number of abnormal discharges was 1 or less, and abnormal discharge was hardly generated. It was confirmed that the island-like aggregation of In was suppressed in any of the formed In alloy films.
  • FIG. 5 is an element distribution image obtained by mapping analysis by EPMA
  • (a) is a reflected electron composition image (COMPO image)
  • (b) is an image showing In distribution
  • (c) is an image showing the Al distribution
  • (d) is an image showing the Cu distribution.
  • FIG. 6 shows an X-ray diffraction (XRD) pattern.
  • the uppermost graph in FIG. 6 shows the entire diffraction peak (XRD pattern of the sputtering target).
  • the middle graph shows the diffraction peak related to In
  • the lowermost graph shows the diffraction peak related to the AlCu alloy (Al 4 Cu 9 ).
  • AlCu alloy grains are distributed in the In substrate. You can see that
  • the In alloy sputtering target of the second embodiment can eliminate any abnormal discharge during sputtering.
  • the In alloy film formed with this In alloy sputtering target contains 0.3 to 25 atomic% of Al, further contains 0.3 to 25 atomic% of Cu, and the balance is made of In and inevitable impurities. It was confirmed that it had a component composition, improved film quality, and was uniform and flat.
  • the sputtering target of this embodiment can suppress excessive abnormal discharge during sputtering and can produce a uniform and flat In alloy film. For this reason, the sputtering target of this embodiment is suitably applicable to the manufacturing process of the light absorption layer in a CIGS type compound thin film solar cell.

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Abstract

An In alloy sputtering target has a chemical composition containing 0.5 to 25 at.% of Al, with the remainder made up by In and unavoidable impurities. The In alloy sputtering target may additionally contain 0.3 to 25 at.% of Cu. An In alloy film has a chemical composition containing 0.3 to 25 at.% of Al, with the remainder made up by In and unavoidable impurities. The In alloy film may additionally contain 0.3 to 25 at.% of Cu.

Description

Ｉｎ合金スパッタリングターゲット、その製造方法及びＩｎ合金膜In alloy sputtering target, manufacturing method thereof, and In alloy film

　本発明は、スパッタリング法を用いて、Ｉｎを主成分とする薄膜を形成する際に使用されるＩｎ合金スパッタリングターゲット及びその製造方法と、Ｉｎ合金膜とに関する。
　本願は、２０１３年９月２６日に日本に出願された特願２０１３－１９９３６７号及び２０１４年４月１１日に日本に出願された特願２０１４－０８１７６５号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to an In alloy sputtering target used for forming a thin film containing In as a main component by using a sputtering method, a method for manufacturing the In alloy sputtering target, and an In alloy film.
This application claims priority based on Japanese Patent Application No. 2013-1993367 filed in Japan on September 26, 2013 and Japanese Patent Application No. 2014-081765 filed in Japan on April 11, 2014. Is hereby incorporated by reference.

　近年、Ｉｎ又はＩｎ合金からなるスパッタリングターゲットが実用に供せられている。例えば、ＣＩＧＳ化合物半導体を具備する薄膜太陽電池の製造方法は、先ず、ソーダライムガラス基板上に、Ｍｏ電極層を形成する工程と、このＭｏ電極層上に、Ｃｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜からなる光吸収層を形成する工程と、このＣｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜からなる光吸収層上に、ＺｎＳ、ＣｄＳなどからなるバッファ層を形成する工程と、さらに、このバッファ層上に、透明電極層を形成する工程を有する。ＣＩＧＳ系化合物薄膜太陽電池は、この様な基本構造を有している。 In recent years, sputtering targets made of In or In alloys have been put into practical use. For example, a method of manufacturing a thin film solar cell including a CIGS compound semiconductor includes a step of forming a Mo electrode layer on a soda lime glass substrate, and a Cu—In—Ga—Se quaternary on the Mo electrode layer. A step of forming a light absorption layer made of an alloy film, a step of forming a buffer layer made of ZnS, CdS, etc. on the light absorption layer made of this Cu—In—Ga—Se quaternary alloy film; And a step of forming a transparent electrode layer on the buffer layer. A CIGS compound thin film solar cell has such a basic structure.

　上記のＣｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜からなる光吸収層の形成方法としては、蒸着法により成膜する方法が知られている。この方法により得られたＣｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜からなる光吸収層は、高いエネルギー変換効率が得られるという利点もある。しかし、この蒸着法によると、成膜速度が遅く、大面積の化合物薄膜を成膜する場合には、膜厚の面内分布の均一性が不足している。そのために、セレン化法によって、Ｃｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜からなる光吸収層を形成する方法が提案されている。 As a method for forming a light absorption layer made of the above-described Cu—In—Ga—Se quaternary alloy film, a method of forming a film by vapor deposition is known. The light absorption layer made of a Cu—In—Ga—Se quaternary alloy film obtained by this method has an advantage that high energy conversion efficiency can be obtained. However, according to this vapor deposition method, the film formation rate is slow, and the uniformity of the in-plane distribution of film thickness is insufficient when a large-area compound thin film is formed. Therefore, a method for forming a light absorption layer made of a Cu—In—Ga—Se quaternary alloy film by a selenization method has been proposed.

　上記のＣｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜をセレン化法で成膜する方法は、先ず、Ｃｕ－Ｇａ二元系合金スパッタリングターゲットを使用してスパッタリングすることにより、Ｍｏ電極層上に、Ｃｕ－Ｇａ二元系合金膜を成膜する工程と、Ｉｎスパッタリングターゲットを使用したスパッタリングにより、Ｃｕ－Ｇａ二元系合金膜上に、Ｉｎ膜を成膜する工程を有する。ここで得られたＣｕ－Ｇａ二元系合金膜及びＩｎ膜からなる積層膜、即ち、前駆体であるプリカーサー膜が形成される。このプリカーサー膜を、Ｓｅ雰囲気中で熱処理して、Ｃｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜を形成する方法が提案されている（例えば、特許文献１を参照）。 The above Cu—In—Ga—Se quaternary alloy film is formed by a selenization method by first sputtering a Cu—Ga binary alloy sputtering target onto a Mo electrode layer. A step of forming a Cu—Ga binary alloy film, and a step of forming an In film on the Cu—Ga binary alloy film by sputtering using an In sputtering target. A laminated film made of the Cu—Ga binary alloy film and the In film obtained here, that is, a precursor film as a precursor is formed. A method of forming a Cu—In—Ga—Se quaternary alloy film by heat-treating this precursor film in a Se atmosphere has been proposed (see, for example, Patent Document 1).

　Ｉｎは低融点で表面張力が大きいという物性を有する。Ｉｎスパッタリングターゲットを使用したスパッタリングにより、Ｉｎ膜を形成する際、前記Ｉｎの物性に起因して、Ｉｎが粒状に成長してしまう。これにより、不連続に隙間を有する粗い島状のＩｎ膜が表面に生成されることが報告されている（例えば、非特許文献１、２を参照）。 In has the physical properties of low melting point and high surface tension. When an In film is formed by sputtering using an In sputtering target, In grows in a granular form due to the physical properties of In. Thereby, it has been reported that a rough island-like In film having gaps discontinuously is generated on the surface (for example, see Non-Patent Documents 1 and 2).

　一般にＩｎスパッタリングターゲットは、鋳造法により得たＩｎインゴットから作製することができるが、Ｉｎ結晶粒径が大きくなる。このため、スパッタリング時に異常放電やパーティクルが発生しやすくなり、均一なＩｎ膜が得られないという問題があった。この異常放電やパーティクルの発生を低減するには、Ｉｎ結晶粒径を小さくすることが有効である。しかし、このＩｎインゴットを圧延することにより、大きいＩｎ結晶粒を破壊しても、Ｉｎの融点が低いことから、塑性加工の加工熱で直ぐに結晶成長してしまう。このため、結晶粒径が２ｍｍ以下のＩｎスパッタリングターゲットを得ることが困難であった。 Generally, an In sputtering target can be produced from an In ingot obtained by a casting method, but the In crystal grain size becomes large. For this reason, abnormal discharge and particles are likely to occur during sputtering, and a uniform In film cannot be obtained. In order to reduce the abnormal discharge and the generation of particles, it is effective to reduce the In crystal grain size. However, by rolling this In ingot, even if large In crystal grains are destroyed, the In melting point is low, so that the crystal grows immediately with the processing heat of plastic working. For this reason, it was difficult to obtain an In sputtering target having a crystal grain size of 2 mm or less.

　一方、上述のように、Ｉｎ膜をスパッタリング法で形成すると、Ｉｎが島状に凝集して不連続層が形成されるようになる。例えば、Ｃｕ－Ｇａ合金膜上にＩｎ膜を積層する場合には、Ｉｎで覆われる部分とＩｎで覆われない部分が形成される。この様なＩｎの島状の凝集層が形成されると、その後のセレン化処理時に、Ｉｎのない箇所がＣｕリッチとなって、低抵抗のＣｕ－Ｓｅ化合物が局所的に生成されることになる。結果的に、光吸収層の成分組成にばらつきが生じ、太陽電池の性能低下をもたらす。 On the other hand, as described above, when the In film is formed by the sputtering method, In is aggregated in an island shape and a discontinuous layer is formed. For example, when an In film is stacked on a Cu—Ga alloy film, a part covered with In and a part not covered with In are formed. When such an island-like aggregated layer of In is formed, a portion having no In becomes Cu-rich during subsequent selenization treatment, and a low-resistance Cu—Se compound is locally generated. Become. As a result, the component composition of the light absorption layer varies, and the performance of the solar cell is reduced.

　この島状の凝集層のない平坦なＩｎ膜を得るためのスパッタリング条件を検討した結果、５０ｎｍ程度の比較的薄い膜厚では、この島状凝集層が発生せず、平坦な膜が得られることがわかった。しかしながら、プリカーサーとして用いられるＩｎ膜の膜厚は５００ｎｍ程度であるのが一般的であるため、この方法では薄いＩｎ膜を多数積層しなければならず、生産性の向上に問題がある。
　別の方法として、ＣｕＧａスパッタリングターゲットと、Ｉｎスパッタリングターゲットとを用い、コスパッタリングしてプリカーサー膜を成膜する方法（非特許文献１、２など）も考えられる。しかし、コスパッタリングは、通常、バッチ方式で処理が行われており、インライン方式のスパッタリングには適していないため、生産性の点で問題がある。 As a result of investigating sputtering conditions for obtaining a flat In film having no island-like aggregated layer, the island-like aggregated layer does not occur and a flat film can be obtained at a relatively thin film thickness of about 50 nm. I understood. However, since the thickness of an In film used as a precursor is generally about 500 nm, this method has a problem in improving productivity because a large number of thin In films must be stacked.
As another method, a method of forming a precursor film by co-sputtering using a CuGa sputtering target and an In sputtering target (Non-patent Documents 1 and 2, etc.) is also conceivable. However, co-sputtering is usually performed in a batch system and is not suitable for in-line sputtering, and thus has a problem in terms of productivity.

特許第３２４９４０８号公報Japanese Patent No. 3249408

Hyeonwook Park, etc., “Effect of precursor structure on Cu(InGa)Se2 formation by reactive annealing”, Thin Solid Film, Vol. 519 (2011) 7245-7249, Fig. 2(a), (c) [journal homepage: www.elesevier.com/locate/tsf]Hyeonwook Park, etc., “Effect of precursor structure on Cu (InGa) Se2 formation by reactive annealing”, ThinSolid Film, Vol. 519 (2011) 7245-7249, Fig. 2 (a), (c) [journal homepage : Www.elesevier.com/locate/tsf] S. Merdes, etc., “Influence of precursor stacking on the absorber growth in Cu(InGa)S2 based solar cells prepared by a rapid thermal process”, Thin Solid Film, Vol. 519 (2011) 7189-7192, Fig. 1(a) [journal homepage: www.elesevier.com/locate/tsf]S. Merdes, etc., “Influence of precursor stacking on the absorber growth in Cu (InGa) S2 based solar cells prepared by a rapid thermal process”, Thin Solid Film, Vol. 519 (2011) 7189 192 (a) [journal homepage: www.elesevier.com/locate/tsf]

　本発明は、スパッタリング時の異常放電やパーティクルの発生を低減でき、かつＩｎ膜を成膜するときにＩｎの島状凝集層の形成を抑制できるＩｎ合金スパッタリングターゲット及びその製造方法と、Ｉｎ合金膜とを提供することを目的とする。 The present invention relates to an In alloy sputtering target that can reduce abnormal discharge and generation of particles during sputtering, and can suppress the formation of In island-like aggregated layers when forming an In film, a method for manufacturing the same, and an In alloy film The purpose is to provide.

　本発明者らは、ＩｎスパッタリングターゲットのＩｎ結晶粒を微細化することにより、異常放電の問題を解決できることに着目し、Ｉｎスパッタリングターゲットについて検討した。その結果、Ｉｎに固溶しないＡｌを添加することで、微細なＡｌ粒子がＩｎ素地に分散し、Ｉｎの結晶粒の成長を抑えられることが判明した。さらに、Ｃｕを添加することで、ＡｌＣｕ合金又はＡｌＣｕＩｎ合金を生成できる。これらの合金により、Ａｌが均一に分散しやすくなり、Ｉｎの結晶粒の成長を抑え、Ｉｎ粒子を微細化できることが判明した。 The present inventors examined the In sputtering target by paying attention to the problem that abnormal discharge can be solved by refining the In crystal grains of the In sputtering target. As a result, it was found that by adding Al that does not dissolve in In, fine Al particles are dispersed in the In substrate, and growth of In crystal grains can be suppressed. Furthermore, an AlCu alloy or an AlCuIn alloy can be generated by adding Cu. It was found that these alloys facilitate the uniform dispersion of Al, suppress the growth of In crystal grains, and make In particles finer.

　そこで、Ｉｎを主成分とし、少量のＡｌを添加したＩｎ合金スパッタリングターゲットを種々作製した。これらのＩｎ合金スパッタリングターゲットを用いて、直流（ＤＣ）スパッタリングを行うと、異常放電やパーティクルの発生を低減できた。また、このスパッタリングターゲットを用いてＩｎ合金膜を成膜したところ、島状の凝集層は、形成され難く、面内均一性を有するＩｎ合金膜が得られることが確認された。さらに、Ｉｎを主成分とし、Ａｌ及びＣｕを添加したＩｎ合金スパッタリングターゲットを作製した。このＩｎ合金ターゲットを用いたＤＣスパッタリングにおいても、異常放電やパーティクルの発生を低減できた。このスパッタリングターゲットを用いてＩｎ合金膜を成膜したところ、島状の凝集層は、形成され難く、面内均一性を有するＩｎ合金膜が得られることが確認された。 Therefore, various In alloy sputtering targets containing In as a main component and added with a small amount of Al were prepared. When direct current (DC) sputtering was performed using these In alloy sputtering targets, abnormal discharge and generation of particles could be reduced. Further, when an In alloy film was formed using this sputtering target, it was confirmed that an island-like aggregated layer was hardly formed and an In alloy film having in-plane uniformity was obtained. Furthermore, an In alloy sputtering target containing In as a main component and added with Al and Cu was produced. Even in DC sputtering using this In alloy target, abnormal discharge and generation of particles could be reduced. When an In alloy film was formed using this sputtering target, it was confirmed that an island-shaped aggregated layer was hardly formed, and an In alloy film having in-plane uniformity was obtained.

　本発明は、上記知見から得られたものであり、前記課題を解決するために以下の要件を有する。
（１）本発明のＩｎ合金スパッタリングターゲットの第１の態様は、Ａｌを０．５～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有することを特徴とする。
（２）前記（１）のＩｎ合金スパッタリングターゲットは、Ｉｎ素地中にＡｌ相（Ａｌ粒子）が分散し、前記Ｉｎ素地の平均結晶粒径が５００μｍ以下であることを特徴とする。
（３）前記（２）のＩｎ合金スパッタリングターゲットは、前記Ａｌ相の平均粒径が、３５０μｍ以下であることを特徴とする。
（４）本発明のＩｎ合金スパッタリングターゲットの製造方法の第１の態様は、溶解したＩｎ中にＡｌ粉末を投入する工程を有し、Ａｌを０．５～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有するＩｎ合金スパッタリングターゲットを製造することを特徴とする。
（５）本発明のＩｎ合金膜の第１の態様は、Ａｌを０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有すること特徴とする。
（６）本発明のＩｎ合金膜の第２の態様は、前記（１）～（３）のいずれかに記載のスパッタリングターゲットを用いて成膜されることを特徴とする。
（７）本発明のＩｎ合金スパッタリングターゲットの第２の態様は、Ａｌを０．５～２５原子％含有し、さらに、Ｃｕを０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有することを特徴とする。
（８）前記（７）のＩｎ合金スパッタリングターゲットは、Ｉｎ素地中に、少なくともＡｌとＣｕを含む合金相（合金粒子）が分散し、前記Ｉｎ素地の平均結晶粒径が５００μｍ以下であることを特徴とする。
（９）前記（８）のＩｎスパッタリングターゲットは、前記合金相の平均粒径が、３５０μｍ以下であることを特徴とする。
（１０）本発明のＩｎ合金スパッタリングターゲットの製造方法の第２の態様は、溶解したＩｎ中にＡｌ－Ｃｕ合金粉末を投入する工程を有し、Ａｌを０．５～２５原子％含有し、さらに、Ｃｕを０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有するＩｎ合金スパッタリングターゲットを製造することを特徴とする。
（１１）本発明のＩｎ合金膜の第３の態様は、Ａｌを０．３～２５原子％含有し、さらに、Ｃｕを０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有すること特徴とする。
（１２）本発明のＩｎ合金膜の第４の態様は、前記（７）～（９）のいずれかに記載のスパッタリングターゲットを用いて成膜されることを特徴とする。 This invention is obtained from the said knowledge, and has the following requirements in order to solve the said subject.
(1) The first aspect of the In alloy sputtering target of the present invention is characterized in that Al is contained in an amount of 0.5 to 25 atomic%, and the balance is composed of In and inevitable impurities.
(2) The In alloy sputtering target of (1) is characterized in that an Al phase (Al particles) is dispersed in an In substrate, and an average crystal grain size of the In substrate is 500 μm or less.
(3) The In alloy sputtering target of (2) is characterized in that the average particle size of the Al phase is 350 μm or less.
(4) The first aspect of the method for producing an In alloy sputtering target of the present invention includes a step of introducing Al powder into dissolved In, containing 0.5 to 25 atomic% of Al, with the balance being In. And an In alloy sputtering target having a component composition comprising inevitable impurities.
(5) The first aspect of the In alloy film of the present invention is characterized in that Al is contained in an amount of 0.3 to 25 atomic% and the balance is composed of In and inevitable impurities.
(6) A second aspect of the In alloy film of the present invention is characterized by being formed using the sputtering target according to any one of (1) to (3).
(7) The second aspect of the In alloy sputtering target of the present invention contains 0.5 to 25 atomic% of Al, further contains 0.3 to 25 atomic% of Cu, and the balance is made of In and inevitable impurities. It has the component composition which becomes.
(8) In the In alloy sputtering target of (7), an alloy phase (alloy particles) containing at least Al and Cu is dispersed in the In substrate, and an average crystal grain size of the In substrate is 500 μm or less. Features.
(9) The In sputtering target of (8) is characterized in that an average particle size of the alloy phase is 350 μm or less.
(10) A second aspect of the method for producing an In alloy sputtering target of the present invention has a step of introducing Al—Cu alloy powder into dissolved In, and contains 0.5 to 25 atomic% of Al. Furthermore, an In alloy sputtering target having a component composition containing 0.3 to 25 atomic% of Cu and the balance of In and inevitable impurities is manufactured.
(11) In the third aspect of the In alloy film of the present invention, Al is contained in an amount of 0.3 to 25 atom%, Cu is further contained in an amount of 0.3 to 25 atom%, and the balance is made of In and inevitable impurities. It has the component composition.
(12) A fourth aspect of the In alloy film of the present invention is characterized by being formed using the sputtering target according to any one of (7) to (9).

　本発明のＩｎ合金スパッタリングターゲットの第１，２の態様は、Ａｌを含有するため、Ｉｎの結晶粒の成長が抑えられ、Ｉｎ素地の平均結晶粒径が５００μｍ以下である。このため、スパッタリング中における過度な異常放電を抑制することができる。これにより、スパッタリングによって形成されるＩｎ膜の膜質が改善され、均一なＩｎ膜が得られる。このため、本発明のＩｎ合金スパッタリングターゲットの第１，２の態様は、ＣＩＧＳ系化合物薄膜太陽電池における光吸収層の形成に有効である。 In the first and second aspects of the In alloy sputtering target of the present invention, since Al is contained, the growth of In crystal grains is suppressed, and the average crystal grain size of the In substrate is 500 μm or less. For this reason, excessive abnormal discharge during sputtering can be suppressed. Thereby, the film quality of the In film formed by sputtering is improved, and a uniform In film is obtained. For this reason, the 1st, 2nd aspect of the In alloy sputtering target of this invention is effective in formation of the light absorption layer in a CIGS type compound thin film solar cell.

本実施形態のＩｎ合金スパッタリングターゲットの製造方法の一例を説明するための図である。It is a figure for demonstrating an example of the manufacturing method of the In alloy sputtering target of this embodiment. 実施形態のＩｎ合金スパッタリングターゲットの一具体例について、スパッタリングターゲットの組織をＥＰＭＡにより測定して得られた各元素の元素分布像である。It is an element distribution image of each element obtained by measuring the structure | tissue of a sputtering target by EPMA about one specific example of In alloy sputtering target of embodiment. 成膜されたＩｎ合金膜における平坦性の評価を説明するために、ＦＥ－ＳＥＭにより測定されたＩｎ分布像である。FIG. 5 is an In distribution image measured by FE-SEM in order to explain the evaluation of flatness in a formed In alloy film. （ａ）Ｉｎ膜を用いて作製されたＩｎ膜とＣｕ－Ｇａ合金膜を有する積層膜の断面写真及び（ｂ）Ｉｎ－Ａｌ合金膜を用いて作製されたＩｎ－Ａｌ合金膜とＣｕ－Ｇａ合金膜を有する積層膜の断面写真である。(A) A cross-sectional photograph of a laminated film having an In film and a Cu—Ga alloy film produced using the In film, and (b) an In—Al alloy film and Cu—Ga produced using the In—Al alloy film. It is a cross-sectional photograph of a laminated film having an alloy film. 実施形態のＩｎ合金スパッタリングターゲットの他の具体例について、スパッタリングターゲットの組織をＥＰＭＡにより測定して得られた各元素の元素分布像である。It is an element distribution image of each element obtained by measuring the structure | tissue of a sputtering target by EPMA about the other specific example of In alloy sputtering target of embodiment. 実施形態のＩｎ合金スパッタリングターゲットの他の具体例のＸ線回折（ＸＲＤ）パターンを示すグラフである。It is a graph which shows the X-ray-diffraction (XRD) pattern of the other specific example of In alloy sputtering target of embodiment.

（第１の実施形態）
　本実施形態のＩｎ合金スパッタリングターゲットは、Ａｌを０．５～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有する。
　Ａｌ量は、好ましくは１～２０原子％である。
　Ａｌ量が、２５原子％を超えて多くなると、スパッタリングによって形成された膜中のＡｌの偏析が大きくなり、得られたスパッタ膜の平坦性が悪化する。一方、Ａｌ量が、０．５原子％未満であると、Ｉｎ膜の島状凝集を抑制できない。 (First embodiment)
The In alloy sputtering target of this embodiment has a component composition containing 0.5 to 25 atomic% of Al, with the balance being In and inevitable impurities.
The amount of Al is preferably 1 to 20 atomic%.
When the amount of Al exceeds 25 atomic%, the segregation of Al in the film formed by sputtering increases, and the flatness of the obtained sputtered film deteriorates. On the other hand, if the Al content is less than 0.5 atomic%, island aggregation of the In film cannot be suppressed.

　スパッタリングターゲットのＩｎ素地中にＡｌ粒子（Ａｌ相）が分散し、Ｉｎ素地（Ｉｎ結晶粒）の平均結晶粒径が小さくなる。Ｉｎ素地の平均結晶粒径は、好ましくは５００μｍ以下であり、より好ましくは０．１μｍ以上４００μｍ以下である。
　ここで、Ａｌを含むＩｎスパッタリングターゲットを用いて直流（ＤＣ）スパッタリングするとき、Ｉｎ素地の結晶粒径が大きいと、粗大なＩｎ結晶粒が、異常放電やノジュールの発生の要因となる。Ｉｎ素地の平均結晶粒径が５００μｍ以下であれば、過度な異常放電は発生しない。
　Ａｌ粒子の平均粒径は、好ましくは３５０μｍ以下であり、より好ましくは０．１～３５０μｍであり、最も好ましくは０．１～１５０μｍである。Ａｌ粒子が粗大でないことにより、異常放電が起こり難くなる。 Al particles (Al phase) are dispersed in the In substrate of the sputtering target, and the average crystal grain size of the In substrate (In crystal grains) becomes small. The average crystal grain size of the In substrate is preferably 500 μm or less, more preferably 0.1 μm or more and 400 μm or less.
Here, when direct current (DC) sputtering is performed using an In sputtering target containing Al, if the crystal grain size of the In substrate is large, coarse In crystal grains cause abnormal discharge and nodules. If the average grain size of the In substrate is 500 μm or less, excessive abnormal discharge does not occur.
The average particle diameter of the Al particles is preferably 350 μm or less, more preferably 0.1 to 350 μm, and most preferably 0.1 to 150 μm. Abnormal discharge is less likely to occur because the Al particles are not coarse.

　本実施形態のＩｎ合金スパッタリングターゲットの製造方法は、溶解したＩｎ中にＡｌ粉末を投入する工程を有する。
　Ａｌ量が多いと、スパッタリングターゲットは偏晶系合金となるため、ＡｌとＩｎの融液が２相に分離し、Ａｌの偏析量が多くなる。これにより、Ａｌが無い部分のＩｎ素地の結晶粒径が大きくなる。一方、Ａｌ量が少ないと、Ｉｎ素地の結晶粒の微細化の効果が薄くなる。そこで、本実施形態のＩｎスパッタリングターゲットの製造方法では、Ａｌを０．５～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有し、Ｉｎ素地の平均結晶粒径が５００μｍ以下であり、Ａｌの平均粒径が３５０μｍ以下であるＩｎスパッタリングターゲットが得られるように、Ｉｎ及びＡｌを溶解して溶湯を作製する工程（溶解したＩｎ中にＡｌ粉末を投入する工程）と、前記溶湯をバッキングプレート上に鋳込み、冷却する工程を有する。
　溶湯を作製する工程では、Ａｌ原料として、平均粒径が３５０μｍ以下の微細なＡｌ粉を添加する。これにより、Ｉｎの溶湯中に微細なＡｌ粒子（Ａｌ相）を均一に分散させることができ、Ａｌの偏析を抑えることができる。Ａｌ粉の平均粒径は、好ましくは０．１～３５０μｍであり、より好ましくは０．１～１５０μｍである。
　また、この溶湯を冷却する工程においては、自然冷却による放冷であっても、溶湯中に微細なＡｌ粒子が分散していることにより、Ｉｎ結晶粒の成長を抑制することができる。しかし、あまり冷却速度が遅いと、Ｉｎ結晶粒が成長する可能性があり、Ｉｎの結晶粒径が大きくなってしまう。このため、Ｉｎ結晶粒の成長を抑制し、その粗大化を防止するには、この溶湯の冷却においては、自然冷却より早い冷却速度で冷却することが好ましい。冷却速度は、好ましくは５℃／ｍｉｎ以上であり、より好ましくは３０℃／ｍｉｎ以上である。冷却速度の上限は特に制限されず、溶湯の冷却を水冷で行ってもよい。 The manufacturing method of the In alloy sputtering target of the present embodiment includes a step of introducing Al powder into dissolved In.
When the amount of Al is large, the sputtering target becomes a monotectic alloy, so the Al and In melt separates into two phases, and the amount of segregation of Al increases. This increases the crystal grain size of the In substrate where Al is not present. On the other hand, when the amount of Al is small, the effect of refining the crystal grains of the In substrate is reduced. Therefore, in the manufacturing method of the In sputtering target of the present embodiment, 0.5 to 25 atomic% of Al is contained, the remainder has a composition composed of In and inevitable impurities, and the average crystal grain size of the In substrate is 500 μm or less. And a step of producing a molten metal by melting In and Al so as to obtain an In sputtering target having an average Al particle size of 350 μm or less (a step of introducing Al powder into the dissolved In), and It has the process of casting a molten metal on a backing plate and cooling it.
In the step of producing the molten metal, fine Al powder having an average particle diameter of 350 μm or less is added as an Al material. Thereby, fine Al particles (Al phase) can be uniformly dispersed in the molten In, and segregation of Al can be suppressed. The average particle size of the Al powder is preferably 0.1 to 350 μm, more preferably 0.1 to 150 μm.
Moreover, in the process of cooling this molten metal, even if it is left to cool by natural cooling, the growth of In crystal grains can be suppressed because fine Al particles are dispersed in the molten metal. However, if the cooling rate is too slow, In crystal grains may grow, and the In crystal grain size will increase. For this reason, in order to suppress the growth of In crystal grains and prevent the coarsening, it is preferable to cool the molten metal at a cooling rate faster than natural cooling. The cooling rate is preferably 5 ° C./min or more, more preferably 30 ° C./min or more. The upper limit of the cooling rate is not particularly limited, and the molten metal may be cooled by water cooling.

　本実施形態のＩｎ合金膜は、Ａｌを０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有する。
　Ａｌ量は、好ましくは３～２３原子％である。
　本実施形態のＩｎ合金膜は、本実施形態のスパッタリングターゲットを用いて成膜される。
　このため、Ｉｎ合金膜中のＡｌの偏析が小さく、かつ膜の平坦性に優れる。また、島状凝集がほとんど無い。 The In alloy film of this embodiment contains 0.3 to 25 atomic% of Al, and the remainder has a component composition composed of In and inevitable impurities.
The amount of Al is preferably 3 to 23 atomic%.
The In alloy film of this embodiment is formed using the sputtering target of this embodiment.
For this reason, the segregation of Al in the In alloy film is small and the flatness of the film is excellent. Moreover, there is almost no island-like aggregation.

（第２の実施形態）
　本実施形態のＩｎ合金スパッタリングターゲットは、Ａｌを０．５～２５原子％含有し、さらに、Ｃｕを０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有する。
　Ａｌ量は、好ましくは１～１０原子％である。
　Ｃｕ量は、好ましくは１～１０原子％である。
　ＡｌとＣｕとが含有されると、ＡｌとＣｕとの含有量比によって、３５０μｍ以下の微細なＡｌＣｕ合金粒子（ＡｌＣｕ合金相）又はＡｌＣｕＩｎ合金粒子（ＡｌＣｕＩｎ合金相）が生成される。このＣｕの添加により、添加されたＡｌが均一に分散しやすくなり、Ａｌの偏析が抑えられ、さらには、Ｉｎ結晶粒の微細化が容易となる。そこで、スパッタリングターゲット中のＣｕ量を、Ａｌ量と同等か、それ以下とすることが好ましい。Ａｌ量に対するＣｕ量の比（Ｃｕ量／Ａｌ量）は、好ましくは０．１～０．５であり、より好ましくは０．３～０．５である。
　Ａｌ及びＣｕの量を上述した範囲に限定している理由は、Ａｌのみの添加の場合（第１の実施形態）と同様である。 (Second Embodiment)
The In alloy sputtering target of the present embodiment contains 0.5 to 25 atomic% of Al, further contains 0.3 to 25 atomic% of Cu, and the balance is composed of In and inevitable impurities.
The amount of Al is preferably 1 to 10 atomic%.
The amount of Cu is preferably 1 to 10 atomic%.
When Al and Cu are contained, fine AlCu alloy particles (AlCu alloy phase) or AlCuIn alloy particles (AlCuIn alloy phase) of 350 μm or less are generated depending on the content ratio of Al and Cu. The addition of Cu facilitates uniform dispersion of the added Al, suppresses segregation of Al, and facilitates the refinement of In crystal grains. Therefore, it is preferable that the amount of Cu in the sputtering target is equal to or less than the amount of Al. The ratio of Cu amount to Al amount (Cu amount / Al amount) is preferably 0.1 to 0.5, more preferably 0.3 to 0.5.
The reason why the amounts of Al and Cu are limited to the above-described range is the same as in the case of adding only Al (first embodiment).

　Ｉｎ合金スパッタリングターゲットのＩｎ素地中に、少なくともＡｌとＣｕを含む合金粒子（Ａｌ合金相）が分散し、Ｉｎ素地（Ｉｎ結晶粒）の平均結晶粒径が小さくなる。Ｉｎ素地の平均結晶粒径は、好ましくは５００μｍ以下であり、より好ましくは０．１μｍ以上１００μｍ以下である。
　Ａｌのみが添加された第１の実施形態のＩｎ合金スパッタリングターゲットと同様に、直流（ＤＣ）スパッタリングするとき、Ｉｎ素地の結晶粒径が大きいと、粗大なＩｎ結晶粒が、異常放電やノジュールの発生の要因となる。Ｉｎ素地の平均結晶粒径が５００μｍ以下であれば、過度な異常放電は発生しない。
　合金粒子の平均粒径は、好ましくは３５０μｍ以下であり、より好ましくは０．１～３５０μｍであり、最も好ましくは０．１～１５０μｍである。合金粒子が粗大でないことにより、異常放電が起こり難くなる。 Alloy particles (Al alloy phase) containing at least Al and Cu are dispersed in the In substrate of the In alloy sputtering target, and the average crystal grain size of the In substrate (In crystal grains) becomes small. The average crystal grain size of the In substrate is preferably 500 μm or less, more preferably 0.1 μm or more and 100 μm or less.
Similar to the In alloy sputtering target of the first embodiment to which only Al is added, when direct current (DC) sputtering is performed, if the crystal grain size of the In substrate is large, coarse In crystal grains may cause abnormal discharge or nodules. It becomes a factor of occurrence. If the average grain size of the In substrate is 500 μm or less, excessive abnormal discharge does not occur.
The average particle size of the alloy particles is preferably 350 μm or less, more preferably 0.1 to 350 μm, and most preferably 0.1 to 150 μm. Abnormal discharge is less likely to occur because the alloy particles are not coarse.

　本実施形態のＩｎ合金スパッタリングターゲットの製造方法は、Ｉｎ，Ａｌ，及びＣｕを溶解して溶湯を作製する工程（溶解したＩｎ中にＡｌ－Ｃｕ合金粉末を投入する工程）と、前記溶湯をバッキングプレート上に鋳込み、冷却する工程を有する。
　溶湯を作製する工程において、原料としてＡｌ粉の代わりにＡｌ－Ｃｕ合金粉末を用いる以外は、本実施形態の製造条件は、第１の実施形態の製造条件と同様である。
　Ａｌ－Ｃｕ合金粉末の平均粒径は、好ましくは０．１～３５０μｍであり、より好ましくは０．１～１５０μｍである。 The manufacturing method of the In alloy sputtering target of the present embodiment includes a step of melting In, Al, and Cu to prepare a molten metal (a step of introducing Al—Cu alloy powder into the molten In), and backing the molten metal. It has the process of casting on a plate and cooling.
The manufacturing conditions of the present embodiment are the same as the manufacturing conditions of the first embodiment, except that in the step of producing the molten metal, Al—Cu alloy powder is used instead of Al powder as a raw material.
The average particle diameter of the Al—Cu alloy powder is preferably 0.1 to 350 μm, more preferably 0.1 to 150 μm.

　本実施形態のＩｎ合金膜は、Ａｌを０．３～２５原子％含有し、さらに、Ｃｕを０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有する。
　Ａｌ量は、好ましくは１～１０原子％である。
　Ｃｕ量は、好ましくは１～１０原子％である。
　本実施形態のＩｎ合金膜は、本実施形態のスパッタリングターゲットを用いて成膜される。
　このため、Ｉｎ合金膜中のＡｌの偏析が小さく、かつ膜の平坦性に優れる。また、島状凝集がほとんど無い。 The In alloy film of the present embodiment contains 0.3 to 25 atomic percent of Al, further contains 0.3 to 25 atomic percent of Cu, and the balance is composed of In and inevitable impurities.
The amount of Al is preferably 1 to 10 atomic%.
The amount of Cu is preferably 1 to 10 atomic%.
The In alloy film of this embodiment is formed using the sputtering target of this embodiment.
For this reason, the segregation of Al in the In alloy film is small and the flatness of the film is excellent. Moreover, there is almost no island-like aggregation.

　第１，２の実施形態のＩｎ合金スパッタリングターゲットは、Ａｌを０．５～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有する。Ｉｎ素地の平均結晶粒径が５００μｍ以下であり、さらには、Ａｌ粒子（Ａｌ相）又はＡｌとＣｕを含む合金粒子（Ａｌ合金相）の平均粒径が３５０μｍ以下である。このＩｎ合金スパッタリングターゲットを用いてスパッタリングすれば、Ａｌが、０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有するＩｎ合金膜を成膜することができる。
　Ｉｎ合金スパッタリングターゲットはＡｌを含むため、Ｉｎの結晶粒の成長が抑えられ、Ｉｎ素地の平均結晶粒径が５００μｍ以下である。このため、スパッタリング中における過度な異常放電を抑制することができる。これにより、スパッタリングによって形成されるＩｎ膜の膜質が改善され、均一なＩｎ膜が得られる。このため、第１，２の実施形態のＩｎ合金スパッタリングターゲットは、ＣＩＧＳ系化合物薄膜太陽電池における光吸収層の形成に有効である。 The In alloy sputtering target of the first and second embodiments has a component composition containing 0.5 to 25 atomic% of Al and the balance of In and inevitable impurities. The average grain size of the In substrate is 500 μm or less, and the average grain size of Al particles (Al phase) or alloy particles containing Al and Cu (Al alloy phase) is 350 μm or less. Sputtering using this In alloy sputtering target makes it possible to form an In alloy film having a component composition in which Al is contained in an amount of 0.3 to 25 atomic% and the balance is made of In and inevitable impurities.
Since the In alloy sputtering target contains Al, the growth of In crystal grains is suppressed, and the average crystal grain size of the In substrate is 500 μm or less. For this reason, excessive abnormal discharge during sputtering can be suppressed. Thereby, the film quality of the In film formed by sputtering is improved, and a uniform In film is obtained. For this reason, the In alloy sputtering target of the first and second embodiments is effective for forming a light absorption layer in a CIGS compound thin film solar cell.

　次に、実施形態のＩｎ合金スパッタリングターゲット及びその製造方法について、以下に、実施例により具体的に説明する。 Next, the In alloy sputtering target of the embodiment and the manufacturing method thereof will be specifically described below with reference to examples.

〔第１実施例〕
　先ず、Ｉｎ合金スパッタリングターゲットを製造するために、ターゲット製造原料として、Ｉｎ（純度４Ｎ以上）と、Ａｌ（純度４Ｎ以上）とを用意した。ここで、Ａｌに関しては、平均粒径が３５０μｍ以下の微粉末を用いた。表１に示されたＡｌ濃度となるように、ＩｎとＡｌをそれぞれ秤量した。
　図１に示されたように、誘導炉ＩＦ内にカーボンるつぼＭＰを配置した。まず、カーボンるつぼＭＰに所定量のＩｎを投入し、誘導炉（Ａｒ中）にてＩｎを溶解した。Ｉｎが溶解した後に、７５０℃付近で、Ａｌ粉末を投入した。Ａｌが溶落した後に、黒鉛棒で撹拌した。
　次いで、Ａｌが溶落して得られたＩｎ溶湯ＭＭを、バッキングプレートＢＰ上に配置された黒鉛製の鋳型ＭＣに流し込み、インゴットを鋳造した。このときの冷却の仕方として、以下の３つの手順のうちいずれかを行った。（ａ）そのまま放冷する（放冷）。（ｂ）冷し金を当てて冷却する（冷し金冷却）。（ｃ）水をプレートに当てる（水冷）。
　その後、冷却されたインゴットに対して、旋盤で機械加工を施して、実施例１～９のＩｎ合金スパッタリングターゲットを作製した。
　なお、表１には、添加元素Ａｌの量（原料中のＡｌ濃度）（濃度：ａｔ％）のみが示されているが、Ｉｎの量は、その残部であるため、表示されていない。すなわち、原料中の残部は、Ｉｎ及び不可避不純物である。 [First embodiment]
First, in order to manufacture an In alloy sputtering target, In (purity 4N or more) and Al (purity 4N or more) were prepared as target production raw materials. Here, for Al, a fine powder having an average particle size of 350 μm or less was used. In and Al were weighed so that the Al concentrations shown in Table 1 were obtained.
As shown in FIG. 1, a carbon crucible MP was disposed in the induction furnace IF. First, a predetermined amount of In was introduced into the carbon crucible MP, and In was dissolved in an induction furnace (in Ar). After In was dissolved, Al powder was charged at around 750 ° C. After Al was melted down, the mixture was stirred with a graphite rod.
Next, the In molten metal MM obtained by melting Al was poured into a graphite mold MC disposed on the backing plate BP to cast an ingot. As a cooling method at this time, one of the following three procedures was performed. (A) Allow to cool as it is (cooling). (B) Apply cooling metal to cool (cooling gold cooling). (C) Apply water to the plate (water cooling).
Thereafter, the cooled ingot was machined with a lathe to produce In alloy sputtering targets of Examples 1 to 9.
In Table 1, only the amount of additive element Al (Al concentration in the raw material) (concentration: at%) is shown, but the amount of In is not shown because it is the remainder. That is, the balance in the raw material is In and inevitable impurities.

〔比較例〕
　実施形態に相当する実施例と比較するため、下記の表１に示すように、実施例の場合と同様の手法により、比較例１～４のスパッタリングターゲットを作製した。比較例１，２は、Ａｌが添加されておらずＩｎのみからなるＩｎスパッタリングターゲットである。比較例３は、０．３ａｔ％のＡｌが添加されたＩｎ合金スパッタリングターゲットである。比較例４は、３０．０ａｔ％のＡｌが添加されたＩｎ合金スパッタリングターゲット（ターゲット中のＡｌ濃度：２８．４ａｔ％）である。 [Comparative example]
For comparison with Examples corresponding to the embodiment, as shown in Table 1 below, sputtering targets of Comparative Examples 1 to 4 were prepared by the same method as in the Examples. Comparative Examples 1 and 2 are In sputtering targets made of only In without added Al. Comparative Example 3 is an In alloy sputtering target to which 0.3 at% Al is added. Comparative Example 4 is an In alloy sputtering target (Al concentration in the target: 28.4 at%) to which 30.0 at% Al is added.

　次に、作製した実施例１～９及び比較例１～４のＩｎスパッタリングターゲット及びＩｎ合金スパッタリングターゲットについて、スパッタリングターゲット中におけるＡｌ濃度と、Ａｌ粒子の平均粒径と、Ｉｎ結晶粒の平均結晶粒径と、スパッタリング時の異常放電回数とを測定した。その測定方法は、以下の様である。 Next, for the In sputtering targets and In alloy sputtering targets of Examples 1 to 9 and Comparative Examples 1 to 4 that were produced, the Al concentration in the sputtering target, the average particle diameter of the Al particles, and the average crystal grain of the In crystal grains The diameter and the number of abnormal discharges during sputtering were measured. The measuring method is as follows.

＜ターゲット中のＡｌ濃度の測定＞
　得られたＩｎ合金スパッタリングターゲットについて、任意の３箇所でＩＣＰ発光分光分析装置を用いて定量分析を行い、Ａｌ濃度（ａｔ％）を測定した。測定値の平均値が、表１の「ターゲット組成測定値、Ａｌ濃度平均値（ａｔ％）」欄に示されている。 <Measurement of Al concentration in target>
The obtained In alloy sputtering target was subjected to quantitative analysis using an ICP emission spectroscopic analyzer at arbitrary three locations, and the Al concentration (at%) was measured. The average value of the measured values is shown in the “Target composition measured value, Al concentration average value (at%)” column of Table 1.

＜Ａｌ平均粒径の測定＞
　得られたスパッタリングターゲットの表面（旋盤加工面）を王水で1分程度エッチングし、次いで純水で洗浄した。その後、表面上の任意の５箇所において、倍率２００倍で、電子線マイクロアナライザ（ＥＰＭＡ）によるマッピング分析を行った。明確な組織が確認できない場合には、王水のエッチングを追加で行った。
　図２は、ＥＰＭＡによるマッピング分析で得られた元素分布像の一例であり、（ａ）は、反射電子組成像（ＣＯＭＰＯ像）であり、（ｂ）は、Ａｌ分布を示す像であり、（ｃ）は、Ｉｎ分布を示す像である。得られたＡｌの分布像（（図２（ｂ））の１画像から、Ａｌ粒子径を測定し、Ａｌ粒子（Ａｌ相）の平均粒径を求めた。その測定結果が、表１の「Ａｌ平均粒径（μｍ）」欄に示されている。 <Measurement of Al average particle diameter>
The surface (lathe surface) of the obtained sputtering target was etched with aqua regia for about 1 minute, and then washed with pure water. Thereafter, mapping analysis using an electron beam microanalyzer (EPMA) was performed at an arbitrary five locations on the surface at a magnification of 200 times. If a clear structure could not be confirmed, etching of aqua regia was additionally performed.
FIG. 2 is an example of an element distribution image obtained by mapping analysis by EPMA, (a) is a reflected electron composition image (COMPO image), (b) is an image showing an Al distribution, c) is an image showing the In distribution. From one image of the obtained Al distribution image ((FIG. 2B)), the Al particle diameter was measured, and the average particle diameter of the Al particles (Al phase) was determined. It is shown in the “Al average particle diameter (μm)” column.

＜Ｉｎ平均結晶粒径の測定＞
　作製した実施例１～８及び比較例１～４のスパッタリングターゲットについて、耐水研磨紙にて機械研磨を行った。次いで、Ｃｒｏｓｓ　ｓｅｃｔｉｏｎ　ｐｏｌｉｓｈｅｒ（ＪＥＯＬ社製　ＳＭ－０９０１０）により仕上げ研磨を行った。そして、ＥＢＳＤ測定装置（日立ハイテク社製　ＳＵ－７０、ＴＳＬ社製　ＯＩＭ　Ｄａｔａ、Ｃｏｌｌｅｃｔｉｏｎ）と、解析ソフト（ＴＳＬ社製　ＯＩＭ　Ａｎａｌｙｓｉｓ　Ｖｅｒ．５，３１）によって、Ｉｎ素地中の結晶粒界を特定した。次いで結晶粒界の長さを測定し、結晶粒が真円であると仮定して直径を算出した。算出された直径の値の平均値を、Ｉｎ素地（Ｉｎ結晶粒）の平均結晶粒径とした。その測定結果が、表１の「Ｉｎ平均結晶粒径（μｍ）」欄に示されている。 <Measurement of In average crystal grain size>
The produced sputtering targets of Examples 1 to 8 and Comparative Examples 1 to 4 were mechanically polished with water-resistant abrasive paper. Next, finish polishing was performed using a cross section polisher (SM-09010 manufactured by JEOL). Then, the grain boundaries in the In substrate were identified by the EBSD measurement device (Hitachi High-Tech SU-70, TSL OIM Data, Collection) and analysis software (TSL OIM Analysis Ver. 5, 31). . Next, the length of the crystal grain boundary was measured, and the diameter was calculated on the assumption that the crystal grain was a perfect circle. The average value of the calculated diameter values was defined as the average crystal grain size of the In substrate (In crystal grains). The measurement results are shown in the “In average crystal grain size (μm)” column of Table 1.

＜異常放電回数の測定＞
　スパッタリングターゲットを、直径１２５ｍｍ、厚さ５ｍｍとなるように、バッキングプレート上に作製した。このスパッタリングターゲットをスパッタ装置に取り付けた。スパッタガスとしてＡｒを用い、スパッタガス圧を５ｍＴｏｒｒとし、直流（ＤＣ）電源にてスパッタ出力：２００Ｗの条件でスパッタリングテストを実施した。スパッタリングを１時間連続して行った。この間、電源に付属するアークカウンターを用いて、スパッタ異常により生じた異常放電の回数をカウントした。この測定結果が、表１の「異常放電回数」欄に示されている。 <Measurement of abnormal discharge times>
A sputtering target was produced on a backing plate so as to have a diameter of 125 mm and a thickness of 5 mm. This sputtering target was attached to a sputtering apparatus. A sputtering test was performed using Ar as a sputtering gas, a sputtering gas pressure of 5 mTorr, and a direct current (DC) power source with a sputtering output of 200 W. Sputtering was performed continuously for 1 hour. During this time, the number of abnormal discharges caused by sputtering abnormality was counted using an arc counter attached to the power source. The measurement result is shown in the “abnormal discharge count” column of Table 1.

　次に、上述した実施例１～８及び比較例１～４のスパッタリングターゲットを用いて、以下の成膜条件により、Ｉｎ膜及びＩｎ合金膜の成膜試験を行った。Ｉｎ膜及びＩｎ合金膜の目標膜厚は、３００ｎｍである。
＜成膜条件＞
・基板：ガラス基板
・基板サイズ：２０ｍｍ角
・電源：ＤＣ２００Ｗ
・全圧：０．１５Ｐａ
・スパッタリングガス：Ａｒ＝５０ｓｃｃｍ
・ターゲット－基板（ＴＳ）距離：７０ｍｍ Next, using the sputtering targets of Examples 1 to 8 and Comparative Examples 1 to 4 described above, a film formation test of an In film and an In alloy film was performed under the following film formation conditions. The target film thickness of the In film and In alloy film is 300 nm.
<Film formation conditions>
・ Substrate: Glass substrate ・ Substrate size: 20 mm square ・ Power supply: DC 200 W
・ Total pressure: 0.15Pa
Sputtering gas: Ar = 50 sccm
・ Target-substrate (TS) distance: 70mm

　上記の成膜条件で得られたＩｎ膜及びＩｎ合金膜中のＡｌ濃度を測定した。さらに、Ｉｎ膜及びＩｎ合金膜の表面について、Ｉｎの島状凝集の発生の評価、即ち、Ｉｎ膜及びＩｎ合金膜の平坦性の評価を行った。
＜膜中Ａｌ濃度の測定＞
　得られたＩｎ合金膜について、ＩＣＰ発光分光分析装置を用いて、定量分析を行い、Ａｌ濃度（ａｔ％）を測定した。その結果が、表１の「膜中Ａｌ濃度（ａｔ％）」欄に示されている。 The Al concentration in the In film and In alloy film obtained under the above film formation conditions was measured. Further, on the surface of the In film and In alloy film, the occurrence of In island aggregation, that is, the flatness of the In film and In alloy film was evaluated.
<Measurement of Al concentration in film>
The obtained In alloy film was quantitatively analyzed using an ICP emission spectroscopic analyzer, and the Al concentration (at%) was measured. The results are shown in the “Al concentration in film (at%)” column of Table 1.

＜平坦性の評価方法＞
　得られた膜の表面を取り出し、例えば、電界放出型走査電子顕微鏡（ＦＥ－ＳＥＭ）で表面を観察した。図３は、ＦＥ－ＳＥＭにより測定されたＩｎ分布像の一例である。ＦＥ－ＳＥＭで取得した画像において、膜の中でＩｎが欠損している部分、即ち、地肌の見えている部分（地の部分）の面積率を求め、島状凝集の発生の状態を評価した。ここでは、地肌の見えている部分が少ない程、膜の平坦性があるとして、以下のように評価した。
　地の部分の面積率が３０％より多い場合を、「Ｃ」（ｂａｄ）と評価した。地の部分の面積率が１５％より多く３０％以下の場合を、「Ｂ」（ｇｏｏｄ）と評価した。地の部分の面積率が１５％以下の場合を、「Ａ」（ｅｘｃｅｌｌｅｎｔ）と評価した。
　この評価結果は、表１における「平坦性」欄に示されている。
　図４は、（ａ）Ｉｎ膜を用いて作製されたＩｎ膜とＣｕ－Ｇａ合金膜を有する積層膜の断面写真、及び（ｂ）５ａｔ％のＡｌを含有するＩｎ－Ａｌ合金膜を用いて作製されたＩｎ－Ａｌ合金膜とＣｕ－Ｇａ合金膜を有する積層膜の断面写真を示す。写真（ａ）では、Ｃｕ－Ｇａ合金膜上に成膜されたＩｎ膜に島状凝集が発生しており、膜の平坦性が悪いことが確認された。一方、写真（ｂ）では、Ｃｕ－Ｇａ合金膜上に成膜されたＩｎ－Ａｌ合金膜において、島状凝集の発生が抑制されており、膜の平坦性が良好であることが確認された。 <Evaluation method of flatness>
The surface of the obtained film was taken out, and the surface was observed with, for example, a field emission scanning electron microscope (FE-SEM). FIG. 3 is an example of an In distribution image measured by FE-SEM. In the image acquired by FE-SEM, the area ratio of the part where In is missing in the film, that is, the part where the background is visible (the part of the ground) was obtained, and the state of the occurrence of island aggregation was evaluated. . Here, it was evaluated as follows, assuming that the smaller the visible portion of the background, the more flat the film.
A case where the area ratio of the ground portion was more than 30% was evaluated as “C” (bad). The case where the area ratio of the ground portion was more than 15% and 30% or less was evaluated as “B” (good). The case where the area ratio of the ground portion was 15% or less was evaluated as “A” (excellent).
The evaluation result is shown in the “flatness” column in Table 1.
FIG. 4 shows (a) a cross-sectional photograph of a laminated film having an In film and a Cu—Ga alloy film manufactured using the In film, and (b) using an In—Al alloy film containing 5 at% Al. A cross-sectional photograph of a laminated film having the manufactured In—Al alloy film and Cu—Ga alloy film is shown. In the photograph (a), it was confirmed that island-like aggregation occurred in the In film formed on the Cu—Ga alloy film and the flatness of the film was poor. On the other hand, in the photograph (b), it was confirmed that the island-like aggregation was suppressed in the In—Al alloy film formed on the Cu—Ga alloy film, and the flatness of the film was good. .

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

　以上の表１によれば、実施例１～９のＩｎ合金スパッタリングターゲットにおいて、いずれもＡｌ粒子の平均粒径が３５０μｍ以下であって、Ｉｎ素地（Ｉｎ結晶粒）の平均結晶粒径が５００μｍ以下になっていることが確認された。そして、実施例１～９のＩｎ合金スパッタリングターゲットを用いたスパッタリングでは、異常放電の回数が１回以下であり、異常放電はほぼ発生しなかった。成膜されたＩｎ合金膜のいずれにおいても、Ｉｎの島状凝集が抑制されていることが確認された。 According to Table 1 above, in each of the In alloy sputtering targets of Examples 1 to 9, the average grain size of Al particles is 350 μm or less, and the average grain size of In substrate (In crystal grains) is 500 μm or less. It was confirmed that In sputtering using the In alloy sputtering target of Examples 1 to 9, the number of abnormal discharges was 1 or less, and almost no abnormal discharge occurred. It was confirmed that the island-like aggregation of In was suppressed in any of the formed In alloy films.

　一方、比較例１、２のＩｎスパッタリングターゲットは、Ａｌが添加されていない従来技術のスパッタリングターゲットであって、Ｉｎ素地（Ｉｎ結晶粒）の平均結晶粒径が大きく、異常放電の回数も多かった。また平坦なＩｎ膜も得られなかった。
　比較例３のＩｎ合金スパッタリングターゲットでは、Ａｌの添加量が少ないため、Ｉｎ結晶粒の成長を抑制できず、Ｉｎ素地（Ｉｎ結晶粒）の平均結晶粒径が大きくなった。このため、スパッタ中に異常放電が見られた。また平坦なＩｎ膜が得られなかった。
　比較例４のＩｎ合金スパッタリングターゲットでは、Ａｌの添加量が多すぎ、しかも、Ａｌ粒子の平均粒径が大きかった。このため、Ｉｎ結晶粒の成長を十分に抑制できず、Ｉｎ素地（Ｉｎ結晶粒）の平均結晶粒径は５００μｍを超えた大きさになった。このため、スパッタ中に異常放電が見られた。また平坦なＩｎ合金膜が得られなかった。 On the other hand, the In sputtering target of Comparative Examples 1 and 2 is a conventional sputtering target to which Al is not added, and the average crystal grain size of the In substrate (In crystal grain) is large and the number of abnormal discharges is large. . Also, a flat In film was not obtained.
In the In alloy sputtering target of Comparative Example 3, since the amount of Al added was small, the growth of In crystal grains could not be suppressed, and the average crystal grain size of the In substrate (In crystal grains) became large. For this reason, abnormal discharge was observed during sputtering. Moreover, a flat In film was not obtained.
In the In alloy sputtering target of Comparative Example 4, the amount of Al added was too large, and the average particle size of the Al particles was large. For this reason, the growth of In crystal grains could not be sufficiently suppressed, and the average crystal grain size of the In substrate (In crystal grains) exceeded 500 μm. For this reason, abnormal discharge was observed during sputtering. Moreover, a flat In alloy film was not obtained.

　以上の様に、第１の実施形態のＩｎ合金スパッタリングターゲットでは、スパッタリング時の異常放電を皆無とすることができた。
　このＩｎ合金スパッタリングターゲットで成膜されたＩｎ合金膜は、Ａｌを、０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有し、膜質が改善され、均一で平坦であることを確認できた。 As described above, the In alloy sputtering target according to the first embodiment can eliminate any abnormal discharge during sputtering.
The In alloy film formed by this In alloy sputtering target contains 0.3 to 25 atomic% of Al, and the balance is composed of In and inevitable impurities, and the film quality is improved and the film is uniform and flat. It was confirmed that.

〔第２実施例〕
　上述した第１実施例は、Ａｌのみが添加されたＩｎ合金スパッタリングターゲットの場合（第１の実施形態）であったが、第２実施例では、Ａｌ及びＣｕが添加されたＩｎ合金スパッタリングターゲットの場合（第２の実施形態）である。 [Second Embodiment]
The first example described above was the case of the In alloy sputtering target to which only Al was added (first embodiment), but in the second example, the In alloy sputtering target to which Al and Cu were added was used. This is the case (second embodiment).

　先ず、Ｉｎ合金スパッタリングターゲットを製造するために、ターゲット製造原料として、Ｉｎ（純度４Ｎ以上）と、Ａｌ（純度４Ｎ以上）と、Ｃｕ（純度４Ｎ以上）とを用意した。そのうちＡｌとＣｕの原料を表２に示される組成比になるように所定量秤量した。所定量のＡｌとＣｕの原料を溶融してＡｌ－Ｃｕ合金を鋳造した。このＡｌ－Ｃｕインゴットを粉砕し、Ａｌ－Ｃｕ合金原料とした。
　まず、カーボンるつぼＭＰに所定量のＩｎを投入し、誘導炉（Ａｒ中）にてＩｎを溶解した。Ｉｎが溶解した後に、７５０℃付近で、Ａｌ－Ｃｕ合金原料をカーボンるつぼＭＰに投入した。Ａｌ－Ｃｕ合金原料が溶落した後に、黒鉛棒で撹拌した。
　得られた溶湯ＭＭを、バッキングプレートＢＰ上に配置された黒鉛製の鋳型ＭＣに流し込み、インゴットを鋳造した。このときの冷却は、冷し金を当てる手段で行った。
　その後、製造されたインゴットに対して、旋盤で機械加工を施して、実施例１０～１８のＩｎ合金スパッタリングターゲットを作製した。
　なお、表２には、添加元素のＡｌ及びＣｕの量（原料中のＡｌ濃度及びＣｕ濃度）（濃度：ａｔ％）のみが示されているが、Ｉｎの量は、その残部であるため、表示されていない。すなわち、原料中の残部は、Ｉｎ及び不可避不純物である。 First, In (purity 4N or higher), Al (purity 4N or higher), Cu (purity 4N or higher), and Cu (purity 4N or higher) were prepared as target manufacturing raw materials in order to manufacture an In alloy sputtering target. Among them, a predetermined amount of Al and Cu raw materials were weighed so as to have the composition ratio shown in Table 2. A predetermined amount of Al and Cu raw materials were melted to cast an Al—Cu alloy. The Al—Cu ingot was pulverized to obtain an Al—Cu alloy raw material.
First, a predetermined amount of In was introduced into the carbon crucible MP, and In was dissolved in an induction furnace (in Ar). After In was dissolved, an Al—Cu alloy raw material was charged into the carbon crucible MP at around 750 ° C. After the Al—Cu alloy raw material melted down, it was stirred with a graphite rod.
The obtained molten metal MM was poured into a graphite mold MC disposed on the backing plate BP to cast an ingot. The cooling at this time was performed by means of applying cooling metal.
Thereafter, the manufactured ingot was machined with a lathe to produce In alloy sputtering targets of Examples 10 to 18.
In Table 2, only the amounts of additive elements Al and Cu (Al concentration and Cu concentration in the raw material) (concentration: at%) are shown, but since the amount of In is the remainder, It is not displayed. That is, the balance in the raw material is In and inevitable impurities.

〔比較例〕
　実施形態に相当する実施例と比較するため、下記の表２に示すように、実施例の場合と同様の手法により、Ａｌ及びＣｕの添加量が実施形態の範囲外となる条件で、比較例５，６のＩｎ合金スパッタリングターゲットを作製した。 [Comparative example]
In order to compare with the example corresponding to the embodiment, as shown in Table 2 below, the same method as in the case of the example, with the conditions that the addition amount of Al and Cu is outside the range of the embodiment, the comparative example 5 and 6 In alloy sputtering targets were prepared.

　次に、作製した実施例１０～１８及び比較例５，６のＩｎ合金スパッタリングターゲットについて、スパッタリングターゲット中におけるＡｌ濃度及びＣｕ濃度と、Ａｌ合金粒子（Ａｌ合金相）（ＡｌＣｕ合金相、ＡｌＣｕＩｎ合金相）の平均粒径と、Ｉｎ結晶粒の平均結晶粒径と、スパッタリング時の異常放電回数とを測定した。その測定方法は、上述した第１実施例の場合と同様であり、Ａｌ濃度平均値及びＣｕ濃度平均値に係る測定結果が、表２の「ターゲット組成測定値」欄に示され、その他の測定結果が、表２の「Ａｌ合金相平均粒径（μｍ）」欄、「Ｉｎ平均結晶粒径（μｍ）」欄、「異常放電回数」欄に示されている。 Next, with respect to the produced In alloy sputtering targets of Examples 10 to 18 and Comparative Examples 5 and 6, Al concentration and Cu concentration in the sputtering target and Al alloy particles (Al alloy phase) (AlCu alloy phase, AlCuIn alloy phase) ), The average crystal grain size of In crystal grains, and the number of abnormal discharges during sputtering. The measurement method is the same as in the case of the first embodiment described above, and the measurement results relating to the Al concentration average value and the Cu concentration average value are shown in the “Target composition measurement value” column of Table 2, and other measurements are performed. The results are shown in the “Al alloy phase average grain size (μm)” column, the “In average crystal grain size (μm)” column, and the “abnormal discharge count” column in Table 2.

　次に、上述した実施例１０～１８及び比較例５，６のＩｎ合金スパッタリングターゲットを用いて、第１実施例で示した成膜条件により、Ｉｎ合金膜の成膜試験を行った。
　上記成膜条件で得られたＩｎ合金膜中のＡｌ濃度及びＣｕ濃度を測定した。さらに、第１実施例で述べた評価方法を用いて、Ｉｎ合金膜の表面について、Ｉｎの島状凝集の発生の評価、即ち、Ｉｎ合金膜の平坦性の評価を行った。その測定結果が、表２の「膜中Ａｌ濃度（ａｔ％）」と「膜中Ｃｕ濃度（ａｔ％）」の欄、及び「平坦性」欄に示されている。なお、平坦性の評価基準は、第１実施例の場合と同様である。 Next, using the In alloy sputtering targets of Examples 10 to 18 and Comparative Examples 5 and 6 described above, an In alloy film formation test was performed under the film formation conditions shown in the first example.
The Al concentration and Cu concentration in the In alloy film obtained under the above film formation conditions were measured. Further, using the evaluation method described in the first example, the surface of the In alloy film was evaluated for the occurrence of In island aggregation, that is, for the flatness of the In alloy film. The measurement results are shown in the columns “Al concentration in film (at%)” and “Cu concentration in film (at%)” and “Flatness” in Table 2. The evaluation criteria for flatness are the same as in the first embodiment.

Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

　以上の表２によれば、実施例１０～１８のＩｎ合金スパッタリングターゲットにおいて、いずれもＡｌ合金粒子（Ａｌ合金相）の平均粒径が３５０μｍ以下であって、Ｉｎ素地（Ｉｎ結晶粒）の平均結晶粒径が５００μｍ以下になっていることが確認された。そして、実施例１０～１８のＩｎ合金スパッタリングターゲットを用いたスパッタリングでは、異常放電の回数が１回以下であり、異常放電はほぼ発生しなかった。成膜されたＩｎ合金膜のいずれにおいても、Ｉｎの島状凝集が抑制されていることが確認された。 According to Table 2 above, in each of the In alloy sputtering targets of Examples 10 to 18, the average particle diameter of the Al alloy particles (Al alloy phase) was 350 μm or less, and the average of the In substrate (In crystal grains) It was confirmed that the crystal grain size was 500 μm or less. In sputtering using the In alloy sputtering target of Examples 10 to 18, the number of abnormal discharges was 1 or less, and abnormal discharge was hardly generated. It was confirmed that the island-like aggregation of In was suppressed in any of the formed In alloy films.

　ここで、上述したように製造された実施例１３のＩｎ合金スパッタリングターゲットを代表例として、その分析結果を図５，６に示す。
　図５は、ＥＰＭＡによるマッピング分析で得られた元素分布像であり、（ａ）は、反射電子組成像（ＣＯＭＰＯ像）であり、（ｂ）は、Ｉｎ分布を示す像であり、（ｃ）は、Ａｌ分布を示す像であり、（ｄ）は、Ｃｕ分布を示す像である。
　図６は、Ｘ線回折（ＸＲＤ）パターンを示す。図６の最上段のグラフは、全体の回折ピーク（スパッタリングターゲットのＸＲＤパターン）を示している。中段のグラフには、Ｉｎに係る回折ピークを示し、最下段のグラフは、ＡｌＣｕ合金（Ａｌ４Ｃｕ９）に係る回折ピークを示す。
　図５に示された元素分布画像における元素分布と図６のＸＲＤパターンに現れた回折ピークとを併せて考慮すると、実施例１３のＩｎ合金スパッタリングターゲットでは、Ｉｎ素地中に、ＡｌＣｕ合金粒が分布していることが分かる。 Here, using the In alloy sputtering target of Example 13 manufactured as described above as a representative example, the analysis results are shown in FIGS.
FIG. 5 is an element distribution image obtained by mapping analysis by EPMA, (a) is a reflected electron composition image (COMPO image), (b) is an image showing In distribution, (c) Is an image showing the Al distribution, and (d) is an image showing the Cu distribution.
FIG. 6 shows an X-ray diffraction (XRD) pattern. The uppermost graph in FIG. 6 shows the entire diffraction peak (XRD pattern of the sputtering target). The middle graph shows the diffraction peak related to In, and the lowermost graph shows the diffraction peak related to the AlCu alloy (Al 4 Cu 9 ).
In consideration of the element distribution in the element distribution image shown in FIG. 5 and the diffraction peak appearing in the XRD pattern of FIG. 6, in the In alloy sputtering target of Example 13, AlCu alloy grains are distributed in the In substrate. You can see that

　一方、比較例５のＩｎ合金スパッタリングターゲットでは、Ａｌ及びＣｕの添加量が多く、Ａｌの偏析を抑制できていなかった。このため、Ｉｎ素地（Ｉｎ結晶粒）の平均結晶粒径が大きく、異常放電の回数も多かった。また平坦なＩｎ合金膜も得られなかった。
　比較例６のＩｎ合金スパッタリングターゲットでは、Ａｌ及びＣｕの添加量が少ないため、Ｉｎの結晶粒の粗大化を抑制できず、異常放電回数も多かった。また平坦なＩｎ合金膜も得られなかった。 On the other hand, in the In alloy sputtering target of Comparative Example 5, the addition amount of Al and Cu was large, and segregation of Al could not be suppressed. For this reason, the average grain size of the In substrate (In crystal grains) was large, and the number of abnormal discharges was also large. Further, a flat In alloy film was not obtained.
In the In alloy sputtering target of Comparative Example 6, since the addition amounts of Al and Cu were small, coarsening of In crystal grains could not be suppressed, and the number of abnormal discharges was also large. Further, a flat In alloy film was not obtained.

　以上の様に、第２の実施形態のＩｎ合金スパッタリングターゲットでは、スパッタリング時の異常放電を皆無とすることができる。
　このＩｎ合金スパッタリングターゲットで成膜されたＩｎ合金膜は、Ａｌを、０．３～２５原子％含有し、さらに、Ｃｕを０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有し、膜質が改善され、均一で平坦であることを確認できた。 As described above, the In alloy sputtering target of the second embodiment can eliminate any abnormal discharge during sputtering.
The In alloy film formed with this In alloy sputtering target contains 0.3 to 25 atomic% of Al, further contains 0.3 to 25 atomic% of Cu, and the balance is made of In and inevitable impurities. It was confirmed that it had a component composition, improved film quality, and was uniform and flat.

　本実施形態のスパッタリングターゲットは、スパッタリング中における過度な異常放電を抑制でき、均一で平坦なＩｎ合金膜を製造できる。このため、本実施形態のスパッタリングターゲットは、ＣＩＧＳ系化合物薄膜太陽電池における光吸収層の製造工程に好適に適用できる。 The sputtering target of this embodiment can suppress excessive abnormal discharge during sputtering and can produce a uniform and flat In alloy film. For this reason, the sputtering target of this embodiment is suitably applicable to the manufacturing process of the light absorption layer in a CIGS type compound thin film solar cell.

ＢＰ　バッキングプレート
ＩＦ　誘導炉
ＭＣ　黒鉛製鋳型
ＭＭ　溶湯
ＭＰ　るつぼ BP Backing plate IF Induction furnace MC Graphite mold MM Molten metal MP Crucible

Claims (12)

　Ａｌを０．５～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有することを特徴とするＩｎ合金スパッタリングターゲット。 An In alloy sputtering target characterized in that it contains 0.5 to 25 atomic% of Al, and the remainder has a composition composed of In and inevitable impurities. 　Ｉｎ素地中にＡｌ相が分散し、前記Ｉｎ素地の平均結晶粒径が５００μｍ以下であることを特徴とする請求項１に記載のＩｎ合金スパッタリングターゲット。 The In alloy sputtering target according to claim 1, wherein an Al phase is dispersed in the In substrate, and an average crystal grain size of the In substrate is 500 μm or less. 　前記Ａｌ相の平均粒径が、３５０μｍ以下であることを特徴とする請求項２に記載のＩｎ合金スパッタリングターゲット。 3. The In alloy sputtering target according to claim 2, wherein an average particle diameter of the Al phase is 350 μm or less. 　溶解したＩｎ中にＡｌ粉末を投入する工程を有し、
　Ａｌを０．５～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有するＩｎ合金スパッタリングターゲットを製造することを特徴とするＩｎ合金スパッタリングターゲットの製造方法。 Having a step of pouring Al powder into dissolved In,
A method for producing an In alloy sputtering target, comprising producing an In alloy sputtering target having a component composition containing 0.5 to 25 atomic% of Al and the balance being In and inevitable impurities. 　Ａｌを０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有すること特徴とするＩｎ合金膜。 An In alloy film characterized in that it contains 0.3 to 25 atomic% of Al, and the remainder has a component composition composed of In and inevitable impurities. 　請求項１～３のいずれか一項に記載のスパッタリングターゲットを用いて成膜されたＩｎ合金膜。 An In alloy film formed using the sputtering target according to any one of claims 1 to 3. 　Ａｌを０．５～２５原子％含有し、さらに、Ｃｕを０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有することを特徴とするＩｎ合金スパッタリングターゲット。 An In alloy sputtering target characterized in that it contains 0.5 to 25 atomic% of Al, further contains 0.3 to 25 atomic% of Cu, and the balance is composed of In and inevitable impurities. 　Ｉｎ素地中に、少なくともＡｌとＣｕを含む合金相が分散し、前記Ｉｎ素地の平均結晶粒径が５００μｍ以下であることを特徴とする請求項７に記載のＩｎ合金スパッタリングターゲット。 The In alloy sputtering target according to claim 7, wherein an alloy phase containing at least Al and Cu is dispersed in the In substrate, and an average crystal grain size of the In substrate is 500 μm or less. 　前記合金相の平均粒径が、３５０μｍ以下であることを特徴とする請求項８に記載のＩｎ合金スパッタリングターゲット。 The In alloy sputtering target according to claim 8, wherein an average particle size of the alloy phase is 350 µm or less. 　溶解したＩｎ中にＡｌ－Ｃｕ合金粉末を投入する工程を有し、
　Ａｌを０．５～２５原子％含有し、さらに、Ｃｕを０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有するＩｎ合金スパッタリングターゲットを製造することを特徴とするＩｎ合金スパッタリングターゲットの製造方法。 A step of introducing Al—Cu alloy powder into dissolved In,
It is characterized by producing an In alloy sputtering target containing 0.5 to 25 atomic% of Al, further containing 0.3 to 25 atomic% of Cu, and the balance being composed of In and inevitable impurities. Manufacturing method of In alloy sputtering target. 　Ａｌを０．３～２５原子％含有し、さらに、Ｃｕを０．３～２５原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有すること特徴とするＩｎ合金膜。 An In alloy film characterized by containing Al in an amount of 0.3 to 25 atom%, further containing Cu in an amount of 0.3 to 25 atom%, and the balance being composed of In and inevitable impurities. 　請求項７～９のいずれか一項に記載のスパッタリングターゲットを用いて成膜されたＩｎ合金膜。 An In alloy film formed using the sputtering target according to any one of claims 7 to 9.
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