WO2015042622A1 - Kupfer-gallium sputtering target - Google Patents
Kupfer-gallium sputtering target Download PDFInfo
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- WO2015042622A1 WO2015042622A1 PCT/AT2014/000174 AT2014000174W WO2015042622A1 WO 2015042622 A1 WO2015042622 A1 WO 2015042622A1 AT 2014000174 W AT2014000174 W AT 2014000174W WO 2015042622 A1 WO2015042622 A1 WO 2015042622A1
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- sputtering target
- cuga
- phase
- sputtering
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 96
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 title description 2
- 229910052802 copper Inorganic materials 0.000 claims abstract description 38
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims description 75
- 238000000034 method Methods 0.000 claims description 66
- 239000002245 particle Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 34
- 229910052783 alkali metal Inorganic materials 0.000 claims description 19
- 150000001340 alkali metals Chemical class 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- 238000007373 indentation Methods 0.000 claims description 8
- 230000005684 electric field Effects 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 abstract description 23
- 238000002490 spark plasma sintering Methods 0.000 abstract description 9
- 239000007921 spray Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 103
- 239000007789 gas Substances 0.000 description 36
- 239000000463 material Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 150000001339 alkali metal compounds Chemical class 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010587 phase diagram Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000005204 segregation Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005056 compaction Methods 0.000 description 4
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- 238000001513 hot isostatic pressing Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
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- 238000007731 hot pressing Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000010062 adhesion mechanism Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009838 combustion analysis Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- 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
-
- 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
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/115—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by spraying molten metal, i.e. spray sintering, spray casting
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- 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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
- C22C1/0441—Alloys based on intermetallic compounds of the type rare earth - Co, Ni
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0483—Alloys based on the low melting point metals Zn, Pb, Sn, Cd, In or Ga
-
- 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
- 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
- C23C14/06—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
- H01J37/3411—Constructional aspects of the reactor
- H01J37/3414—Targets
- H01J37/3423—Shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
- H01J37/3411—Constructional aspects of the reactor
- H01J37/3414—Targets
- H01J37/3426—Material
- H01J37/3429—Plural materials
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/05—Light metals
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/10—Copper
-
- 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 invention relates to a sputtering target with a gallium (Ga) content of 30 to 68 At%, which comprises a Ga and copper (Cu) -containing phase.
- the invention further relates to a method for its production.
- the invention relates to the use of a sputtering target.
- Cu-Ga sputtering targets are used, for example, for the production of
- Copper-indium-gallium diselenide (Cu (ln, Ga) (Se, S) 2 , abbreviated CIGS)
- CIGS thin films have a high
- the band gap energy can be adjusted by varying the Ga concentration and ranges from about 1 eV of the ternary CuInSe 2 to about 1.7 eV of the ternary CuGaS 2 .
- Zudotieren of alkali metals a
- Cu-Ga sputtering targets can basically be produced by melting or powder metallurgy.
- Sputtering targets with a high Ga content are for example in the
- CuGa2 which is also the theta phase, would form as dominant Cu-Ga phase at Ga contents above 55 At%
- the Cu-Ga phase understood, which has the highest proportion of all Cu-Ga phases.
- the term CuGa 2 is used throughout the ⁇ phase.
- CuGa 2 and Cu 9 Ga 4 are intermetallic phases.
- intermetallic phases In contrast to alloys, intermetallic phases have lattice structures which differ from those of the constituent metals. Usually there is a mixed bond with metallic bond fraction and lower atomic bonding or
- the CuGa 2 phase formation takes place on cooling of temperatures> 254 ° C via a peritectic conversion (CugGa 4 + melt (Ga content of
- Imbalance phase (often referred to as the segregation or segregation phase) surrounds the Cu 9 Ga 4 grains.
- the proportion of CugGa4 phase is significantly higher than would be expected under equilibrium conditions.
- the Ga-rich disequilibrium phase can lead to localized melting in the
- CGS cold gas spraying
- the coating material is typically accelerated to a speed of 300 to 1200 m / s.
- Ga content is also used in CGS as coating material a powder in which Ga is present mainly as CugGa 4 .
- the object of the invention is therefore to provide a sputtering target which does not have the aforementioned disadvantages.
- the invention should include a use of the sputtering target, in which the aforementioned properties of the sputtering target can be used particularly advantageously.
- the sputtering target has a Ga content of from 30 to 68 at%, preferably from 40 to 68 at%.
- the inventive task is solved by the following two alternatives:
- the sputtering target contains as Cu- and Ga-containing intermetallic
- the volume fraction CuGa 2 is greater than the volume fraction CugGa 4 .
- the sputtering target exhibits areas containing Ga and Cu
- intermetallic phase has an average microhardness of ⁇ 500 HV0.01.
- the sputtering target has both the features of alternative 1 and 2.
- volume ratio CuGa 2 to Cu g Ga4> 2, more preferably> 5, is preferred.
- the proportions of CuGa 2 and CugGa 4 phase are determined on a cross-section by means of SEM-RE (SEM) scanning electron microscope,
- RE ... backscattered electrons at 1000x magnification (reference size is the Polaroid 545 format).
- the chemical phase discrimination is done first by EDX.
- the image analysis is limited to CuGa 2 and Cu 9 Ga 4 phase. All other structural components (Cu grains, Cu solid solution grains, pores, ...) are cut out.
- binarization is carried out by the threshold value method. This makes it possible to determine the area proportions CugGa 4 or CuGa 2 .
- Phase fraction determination is repeated at two additional points and the mean value is formed. Thereafter, the identical measurement is repeated on a further transverse section, which is rotated by 90 ° to the first sample series
- the dominant intermetallic phase is CuGa 2 .
- CuGa 2 is a thermodynamically very stable intermetallic compound, which is at 254 ° C incongruent melts.
- the phase diagram Cu-Ga see FIG. 1
- the CuGa 2 phase has a homogeneity region. It follows that the CuGa 2 phase can have both a lower and a higher content of Cu or Ga than corresponds to the stoichiometric compound CuGa 2 .
- Intermetallic phases typically have a very high hardness, strength and brittleness, as is the case with CugGa 4 (microhardness approx.
- the advantages of the invention are preferably also achieved when in areas with Ga and Cu-containing intermetallic phase, the
- the mean is
- the mean microhardness is determined as follows. First, a cut is made and the microhardness is determined on the polished ground surface. The phase assignment is made optional by optical discrimination
- microhardness of the Cu-Ga-containing intermetallic phase is measured according to ISO 6507-1: 2005.
- the hardness value preferably refers to samples which do not require any additional aftertreatment, such as, for example, annealing
- Intermetallic Cu-Ga phase in each case 3 impressions set and the average determined.
- At least 90% of the Ga present in the sputtering target is present as CuGa 2 phase. ⁇ 10% can thus also in another form (Cu-Ga
- the Sputtering Targets determined by chemical analysis of 5 samples using ICP-OES and averaging. Thereafter, the volume fraction CuGa 2 by means of REM-RE determined according to the previously described measurement sequence. From the volume fraction CuGa 2 , the Ga content is calculated, which is present as CuGa 2 . This content is related to the total content of Ga in the sputtering target and thus calculates the proportion of Ga present as CuGa 2 . If the Ga content of the sputtering target lies in the homogeneity range of the CuGa 2 phase (about 64 to about 68 at%), then the entire Cu and Ga is preferably present as CuGa 2 . If the Ga content is below about 64 at%, then this contains
- Sputtering target in addition to CuGa 2 advantageously a Cu-rich phase having a Cu content> 80 at%, preferably> 90 at% and especially
- the Cu-rich phase is preferred
- Ga-containing Cu mixed crystal or pure Cu The best results could be achieved when the Cu-rich phase is pure Cu.
- pure Cu Cu is understood to mean conventional impurities. Taking into account the phases containing only Ga and Cu, the following preferred options arise for the phase structure of the sputtering target:
- the sputtering target has> 30% by volume
- Cu-Ga phases in particular Cu 9 Ga 4 ⁇ 15% by volume, preferably ⁇ 10% by volume and particularly preferably ⁇ 5% by volume.
- sputtering targets in which no Cu 9 Ga 4 can be detected with the aid of REM-RE.
- Cu and Ga-containing intermetallic phase with the largest proportion is very homogeneous sputtering properties.
- the sputtering targets according to the invention can be produced simply, inexpensively and reliably, as will be explained in detail in the examples.
- the sputtering targets are free of pores and cracks, avoiding local arcing at defects during sputtering.
- There is no segregation phase (Ga content> about 75 At%), which can lead to local melting during sputtering.
- CuGa 2 is very soft, sputtering targets can already be compacted at comparatively low temperatures. As a result, grain boundary segregations can be reliably avoided.
- the sputtering targets are characterized by a very good mechanical workability, which in turn favorable to the
- the recycling of the sputtering targets can be done in a simple manner by melting.
- the Ga concentration of the melt is preferably set by adding pure Ga to the corresponding desired value.
- a Ga content of 64 to 68 At% is selected.
- CuGa 2 powder can be produced by a customary atomization process, which in turn can be used for the production of new sputtering targets.
- the sputtering target may also contain 0.01 to 5 At% of at least one element of the group of alkali metals. In the presence of several alkali metals 0.01 to 5 At% represent the Summengehalt.
- Preferred alkali metals are Li, Na and K. As already mentioned, alkali metals have a favorable effect on the
- the sputtering target consists of 30 to 68 At% Ga, preferably 40 to 68 At% Ga, optionally one or more alkali metal (s) or one or more alkali metal compound (s), wherein the alkali metal content of the sputtering target is from 0.01 to 5 at%, balance Cu and usual impurities.
- sputtering target an alkali metal compound, it contains in addition to the alkali metal and the other elements of the compound, such as S, Cl and / or O.
- Typical O contents in the Cu or Cu-Ga powder are about 500 to 1500 pg / g.
- Sputtering targets according to the invention have a very high density.
- CuGa 2 has an average particle size of ⁇ 50 ⁇ m, measured in transverse section, of preferably ⁇ 90 ⁇ m, particularly preferably ⁇ 30 ⁇ m. Because the
- the size and shape of the CuGa 2 grains is mainly determined by the particle size and shape of the CuGa 2 powder used. Since spherical powder is preferably used, the grains in the transverse section preferably have a round shape.
- the size and shape of the Cu-rich phase can be controlled by the particle size of the pure-Cu or Cu mixed crystal powder used, wherein the mean grain size of the pure-Cu or Cu mixed crystal phase in
- Sputtering target is preferably ⁇ 150 pm, particularly preferably ⁇ 100 pm. With very fine starting material can also be a very advantageous grain size of ⁇ 50 pm set. Since the Cu powder preferably has a spherical shape, the Cu grains are preferably round. Shape and size of the CuGa 2 grains and / or the pure Cu or Cu solid solution grains have a favorable effect on the machinability of the sputtering target. Preferably, the pure Cu or Cu solid solution grains are embedded in a matrix of intermetallic Cu-Ga phase.
- the sputtering target is preferably present as a flat or tube target, the latter representing a particularly favorable embodiment of the subject invention.
- the inventive task is also fulfilled by a method for producing sputtering targets having a Ga content of 30 to 68 at%, preferably 40 to 68 at%. This method is particularly advantageous for producing the sputtering targets according to the invention.
- the method has at least the following steps
- the quantitative phase analysis is carried out by means of XRD with internal standard.
- the method preferably has at least one feature from the following list:
- the powder mixture contains pure Cu and / or Cu mixed crystal particles.
- the powder mixture contains alkali metal-containing particles.
- the CuGa 2- containing particles have a maximum or several maxima of a hardness distribution in areas with intermetallic Cu-Ga phase, wherein at least one maximum lies at an indentation hardness Hrr ⁇ 4.5 GPa.
- the CuGa 2- containing particles contain only CuGa 2 or the volume fraction CuGa 2 is greater than the volume fraction CugGa.
- the compacting is done by sintering under at least temporary
- the powder mixture is' to a sintering temperature of 150 to 250 ° C
- the time in the temperature range> 50 ° C is ⁇ 60 minutes.
- ⁇ Compacting is done by cold gas spraying.
- Cold gas spraying involves a process gas with a pressure> 10 bar in
- the substrate is designed such that the compact body
- Tube target forms, wherein the substrate performs the function of a support tube.
- the determination of the penetration hardness HIT is made as follows.
- the penetration hardness is measured according to ISO 14577 (2002 edition) with a Berkovich indenter and the evaluation method according to Oliver and Pharr.
- the hardness value refers to samples which were preferably not subjected to any additional aftertreatment such as, for example, annealing. Since the intermetallic Cu-Ga phase (white to light gray color) clearly differs from pure Cu or Cu mixed crystal (each bronze-colored) even under light microscopy, the hardness impressions can only be placed in the intermetallic Cu-Ga phase.
- the determination of the average indentation hardness takes place under the following
- a hardening grid is set in each case. If the intermetallic Cu-Ga phase regions have a sufficient size, the length and width of the grid are 10 ⁇ m.
- the distance between the impressions is 2 in, so 25 impressions per grid are set. This approach is taken in total
- the regions with intermetallic Cu-Ga phase preferably have a maximum or several maxima of the hardness distribution, wherein at least one maximum at an indentation hardness H
- at least one maximum is at an indentation hardness Hrr at ⁇ 4 GPa, more preferably at ⁇ 3 GPa.
- the grid size is reduced accordingly. The distance between the impressions is left at 2 m.
- the number of measured intermetallic Cu-Ga phase regions is chosen such that the sum of the indentation hardness values is again 250.
- the method according to the invention comprises compacting the powder mixture.
- the compaction takes place under conditions in which the least possible diffusion can take place. This avoids that at a
- Alloy composition which would contain according to phase diagram in equilibrium CugGa 4 , starting for example from a mixture of CuGa2 and Cu powder, the phase corresponding to the equilibrium can form to an unduly high degree.
- phase diagram in equilibrium CugGa 4 starting for example from a mixture of CuGa2 and Cu powder
- Kompaktierungstechniken are the spark plasma sintering and the
- SPS Spark Plasma Sintering
- FAST Field-Activated Sintering
- DC-Current Sintering DC-Current Sintering
- the pressure is advantageously 5 to 400 MPa, preferably 10 to 200 MPa, more preferably 15 to 100 MPa.
- the powder mixture is preferably filled into a graphite crucible and compressed via two graphite punches. Due to the action of the electric field, direct current is also advantageously conducted through the graphite crucible and the graphite stamp, as a result of which Joule's heating also occurs in the graphite.
- the low hardness of the powder makes it possible, at comparatively low
- Temperature and time is determined according to the Arrhenius relationship, longer times (> 60 minutes) are advantageous when the sintering temperature required for the compression is low, which is the case for example at a high pressure.
- Another very advantageous compaction method is cold gas spraying
- CGS cold gas spraying
- a plurality of layer layers is deposited on a substrate.
- the substrate may be removed after the deposition of the layer or else, which is a preferred embodiment of the invention, acting as a backplate or as a support tube of the sputtering target.
- preferred substrate materials are in particular Cu and
- a process gas for example, N 2 , air, He, or mixtures thereof
- a typical nozzle shape is the Laval nozzle.
- the process gas preferably has a pressure of greater than 10 bar, advantageously at least 20 bar and particularly preferably at least 30 bar.
- Advantageous ranges are 10 to 100 bar, preferably 20 to 80 bar and particularly preferably 30 to 60 bar.
- the upper limit for the pressure range results in part from the currently available systems. In the future, if plants are available that allow higher gas pressure, the limit may shift to higher pressure. Depending on the used
- Process gas gas speeds of, for example, 900 m / s (at N) to 2500 m / s (He) can be achieved.
- the coating material is typically accelerated to a speed of 300 to 1200 m / s. Heating the gas in front of the convergent-divergent nozzle increases the flow velocity of the gas as the gas expands in the nozzle, and thus also the gas flow rate
- Adhesion of the coating material to the substrate material and the cohesion between the particles of the coating material crucial.
- the adhesion both in the region of the coating material / substrate interface and between the particles of the coating material is understood to be an interaction of a number of physical and chemical adhesion mechanisms and in some cases not yet comprehensively understood.
- Grain boundary strength are met by different coating materials to varying degrees.
- Arcing tend to have no areas with a Ga content> 75 at% (no local smoldering during sputtering) and can be machined very well. Further advantages are the small ones
- Layer quality has not yet been understood in detail. However, it can be assumed that an interaction of several mechanisms plays a role, such as the reduction of the yield stress, the promotion of microplastic flow processes, a lower solidification or an improved particle propagation on impact.
- Coating material kept very small and / or He used as a process gas because only so the necessary particle adhesion for adhesion could be achieved.
- very fine powders have a high O content, which can adversely affect the efficiency of CIGS solar cells.
- fine powders can lead to clogging of the powder conveying systems, since their flow behavior is poor.
- the particle binding is worse on impact on the substrate with powder with very small particle size than with coarser powder.
- the sputtering targets according to the invention can not only with the process gas He, which as already mentioned to a higher
- N content is advantageously> 50% by volume, preferably> 90% by volume. It is particularly preferred for the process gas N to be used without the addition of other gases. The use of N enables an economical implementation of the invention.
- the process gas can advantageously be passed before the convergent-divergent nozzle by at least one heater.
- the gas velocity and thus also the particle velocity can be further increased, which in turn has an advantageous effect on the properties of the compacted body.
- alkali metals or alkali-metal-containing compounds can be incorporated in the sputtering target in a very finely distributed manner using the process according to the invention.
- Na is to be emphasized as particularly preferred alkali metal, as a particularly advantageous Na-containing compound Na 2 SO 4 and NaCl. Due to the short process time or low process temperature unwanted reactions between the alkali metal / the alkali-containing compound and Cu or Ga are avoided.
- a tube target can be produced in a simple manner.
- cold gas spraying is particularly suitable.
- a tube is preferably used for this purpose.
- the tubular substrate already represents the carrier tube of the sputtering target. In this way tube targets can be produced in a simple manner, which are connected to the carrier tube.
- an annealing can also take place in order to reduce any internal stresses.
- the annealing is carried out before the mechanical processing.
- Sputtering Target on at least one of the following properties.
- the volume fraction CuGa 2 is greater than the volume fraction CugGa 4 .
- the average microhardness is in areas with Ga- and Cu-containing
- the Ga content is 40 to 68 At%.
- the sputtering target contains a Cu-rich phase with a Cu content> 80 At%, selected from the group consisting of
- the Cu-rich phase is pure-Cu.
- the sputtering target contains ⁇ 15% by volume, advantageously ⁇ 10% by volume,
- the sputtering target contains> 30% by volume CuGa 2 , preferably> 60% by volume, more preferably> 90% by volume.
- the volume ratio CuGa 2 / Cu g Ga 4 is> 2, preferably> 5.
- CuGa 2 is in cross section in the form of round grains with a mean particle size ⁇ 150 ⁇ ago.
- the Cu-rich phase is in the transverse section in the form of round grains with a mean grain size ⁇ 150 pm, which are embedded in a Cu-Ga matrix.
- the sputtering target contains 0.01 to 5 at% of alkali metal, preferably Na. _
- the sputtering target consists of:
- ⁇ optionally one or more alkali metal (s) or one or more
- the sputtering targets according to the invention are suitable for producing a thin layer of a solar cell.
- CuGa 2 can also be detected in the layer deposited by sputtering.
- the mode of action of how CuGa 2 is incorporated into the layer is not yet understood. It is possible that CuGa 2 is sputtered as a molecule and also incorporated as a molecule in the layer. However, it is also possible that although Cu and Ga are sputtered atomically, they nevertheless combine again during the deposition to form the thermodynamically stable CuGa 2 .
- the invention will now be described by way of example.
- FIG. 1 shows the phase diagram Cu-Ga (source: Subramanian P.R., Laughlin D.E .: ASM Alloy Phase Diagrams Center, P. Villars, editor-in-chief, H. Okamoto and K. Cenzual, section editors).
- FIG. 2 shows a scanning electron micrograph of
- Cu-Ga powder according to the invention with a Ga content of 66 at%, balance Cu.
- FIG. 3 shows the result of the XRD measurement on Cu-Ga powder according to the invention with a Ga content of 66 at%, balance Cu (concentration in the figure in% by mass).
- FIG. 4 shows a photomicrograph of a Cu-Ga sputtering target according to the invention with a Ga content of 58 at%, balance Cu.
- Cu-Ga38 Cu-Ga powder with 60 Ma% Cu and 40 Ma% Ga (60 Ma% Cu corresponds to 62.20 At%, 40 Ma% Ga corresponds to 37.80 At%, the powder is referred to below as Cu62Ga38):
- Cu-Ga50 for the preparation of the samples according to the invention
- Cu-Ga powder with 32 Ma% Cu and 68 Ma% Ga 32 Ma% Cu corresponds to 34.05 At%, 68 Ma% Ga corresponds to 65.95 At%, the powder is referred to as Cu34Ga66 in the following text):
- the powders were prepared by atomizing a melt with Ar. Of the powders, the bulk density, tap density, flowability, particle size were Fisher (FSSS) and the measured by laser diffraction particle size (do, io, d 0, 5o, do.go) determined. The measured values are shown in Table 1. All powders are formed spherically due to the manufacturing process (Cu 34 Ga66 powder see Figure 2). GDMS analyzes were performed to determine the trace elements. The gas or C contents were determined by means of
- Hot extraction or combustion analysis determined.
- impurities oxygen Cu 6 2Ga 3 8: 1 86 pg / g, Cu 5 oGa 5 o 1064 pg / g and Cu 3 Ga 6 6 1266 pg / g
- the C content of the samples was between 8 and 18 pg / g, the H content between 41 and 59 pg / g. All other impurities had values below 50 pg / g.
- On powder grind the penetration hardness Hu was determined. The measurement was carried out according to ISO 14577 (2002 edition) with a
- Cu 62 Ga 38 has only a maximum indentation hardness at 7.7 GPa.
- CusoGaso has two maxima at 3 GPa and 7.5 GPa, respectively.
- Cu 34 Ga 6 6 shows a maximum at 2.8 GPa.
- microhardness HV 0 For large particles in the upper range of the particle size distribution, it is possible to measure the microhardness HV 0 , oi.
- oi For Cu62Ga 3 e a value of 719 HV 0 , oi was determined for Cu 5 oGa 50 of 469 HV 0 , oi and for Cu 34 Ga 6 6 of 142 HV 0 , oi.
- the phases were determined by XRD as detailed in the description. For the Cu62Ga38 powder only Cu 9 Ga 4 phase could be detected. The Cu50Ga50 powder had 48 vol% Cu 9 Ga 4 phase and 52 vol% CuGa 2 phase. For the Cu34Ga66 powder only the CuGa 2 phase could be determined. The measurement result for Cu34Ga66 is shown in FIG. To investigate any phase transformations, DSC measurements were performed. The Cu34Ga66 powder showed at around 260 ° C one
- a non-inventive sample was prepared by using Cu62Ga38 powder by HIP.
- the powder was placed in a steel can and hot isostatically compressed at 500 ° C.
- the heating rate was 5 K / min, the holding time at 500 ° C 2 h and the pressure 100 MPa.
- the compressed sample was cooled.
- the attempt to separate the compacted material by wire cutting led to cracks and material break-out.
- the densified body had a density of 8.2 g / cm 3 (> 99% of theoretical density).
- the microhardness was, as in the
- a non-inventive sample was prepared by using Cu62Ga38 powder by SPS.
- the powder was filled into a graphite tool.
- the Sinter ride was temperature-controlled, the
- Temperature measurement was carried out by means of a thermocouple.
- the sample was sintered by applying a DC voltage which resulted in Joule heat generation in the sample.
- the sintered at 300 ° C sample had a relative density of 81%, at 450 ° C sintered sample of 99.3%. Both samples were mechanical do not work. With the one shown in the description
- Phase determination method was detected only CugGa 4 phase.
- the powder batches listed in Table 2 were densified by SPS.
- the process parameters are listed in Table 3.
- the determinations of relative density, CuGa2 to Cu 9 Ga 4 ratio, Ga present as CuGa 2, and microhardness were made as described in the specification
- sputtering wherein the sputtering test is explained in detail below for the sample C.
- a sputtering target with a diameter of 105 mm was used.
- the coating rate was comparable to samples having lower and higher Ga content, respectively.
- the coating rate was about 100 nm / min at a power of 200 W, about 260 nm / min at 400 W and about 325 nm / min at 600 W.
- sputtered layers Ar pressure of 2.5 ⁇ 10 -3 mbar, 5 ⁇ 10 -3 mbar, or
- 7.5 x 10 "3 mbar had low compressive stresses of ⁇ 25 MPa, with 600 W sputtered layers (Ar pressure of 2.5 ⁇ 10 -3 mbar, 5 ⁇ 10 -3 mbar, or 7.5 ⁇ 10 "3 mbar) had low tensile stresses of ⁇ 25 MPa.
- the XRD measurement was
- the layers have a fine-grained microstructure, with
- Cu62Ga38 particle was incorporated into the layer (Ga content of the layer only 9 At%). It is assumed that the rest of the substrate or
- Carrier tube can take over.
- the surface of the sputtering target was free of defects.
- the Ga content of the sputtering targets thus prepared corresponded to the Ga content of the powders used.
- the phase proportions in the sputtering target corresponded to the phase proportions in the powder.
Abstract
Description
Claims
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