TWI453294B - Sputtering target and its manufacturing method - Google Patents
Sputtering target and its manufacturing method Download PDFInfo
- Publication number
- TWI453294B TWI453294B TW101114522A TW101114522A TWI453294B TW I453294 B TWI453294 B TW I453294B TW 101114522 A TW101114522 A TW 101114522A TW 101114522 A TW101114522 A TW 101114522A TW I453294 B TWI453294 B TW I453294B
- Authority
- TW
- Taiwan
- Prior art keywords
- sputtering
- sintered body
- film
- target
- purity
- Prior art date
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- 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
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
-
- 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
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
- G11B5/851—Coating a support with a magnetic layer by sputtering
-
- 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
- H01J37/3488—Constructional details of particle beam apparatus not otherwise provided for, e.g. arrangement, mounting, housing, environment; special provisions for cleaning or maintenance of the apparatus
- H01J37/3491—Manufacturing of targets
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
- C04B2235/662—Annealing after sintering
- C04B2235/663—Oxidative annealing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/785—Submicron sized grains, i.e. from 0,1 to 1 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/963—Surface properties, e.g. surface roughness
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B11/00—Recording on or reproducing from the same record carrier wherein for these two operations the methods are covered by different main groups of groups G11B3/00 - G11B7/00 or by different subgroups of group G11B9/00; Record carriers therefor
- G11B11/10—Recording on or reproducing from the same record carrier wherein for these two operations the methods are covered by different main groups of groups G11B3/00 - G11B7/00 or by different subgroups of group G11B9/00; Record carriers therefor using recording by magnetic means or other means for magnetisation or demagnetisation of a record carrier, e.g. light induced spin magnetisation; Demagnetisation by thermal or stress means in the presence or not of an orienting magnetic field
- G11B11/105—Recording on or reproducing from the same record carrier wherein for these two operations the methods are covered by different main groups of groups G11B3/00 - G11B7/00 or by different subgroups of group G11B9/00; Record carriers therefor using recording by magnetic means or other means for magnetisation or demagnetisation of a record carrier, e.g. light induced spin magnetisation; Demagnetisation by thermal or stress means in the presence or not of an orienting magnetic field using a beam of light or a magnetic field for recording by change of magnetisation and a beam of light for reproducing, i.e. magneto-optical, e.g. light-induced thermomagnetic recording, spin magnetisation recording, Kerr or Faraday effect reproducing
- G11B11/10582—Record carriers characterised by the selection of the material or by the structure or form
- G11B11/10586—Record carriers characterised by the selection of the material or by the structure or form characterised by the selection of the material
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/127—Structure or manufacture of heads, e.g. inductive
- G11B5/31—Structure or manufacture of heads, e.g. inductive using thin films
- G11B5/3103—Structure or manufacture of integrated heads or heads mechanically assembled and electrically connected to a support or housing
- G11B5/3106—Structure or manufacture of integrated heads or heads mechanically assembled and electrically connected to a support or housing where the integrated or assembled structure comprises means for conditioning against physical detrimental influence, e.g. wear, contamination
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/32—Processing objects by plasma generation
- H01J2237/33—Processing objects by plasma generation characterised by the type of processing
- H01J2237/332—Coating
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Analytical Chemistry (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
本發明係有關濺鍍靶材及其製造方法。
一般來說,濺鍍是使用輝光放電,令受加速之離子撞擊濺鍍靶材,使藉由動能而從靶材彈出之材料於基板上成膜的方法。作為在半導體、液晶、太陽能電池等領域中製作薄膜元件等構造之工具,係廣泛使用。其中,使用氧化鋁燒結體之靶材(以下亦稱為「氧化鋁靶材」),在形成磁頭、磁光碟等之保護膜或絕緣膜時,係作為膜材料的供應源之用。亦用於在超硬工具上形成耐磨損膜等。
氧化鋁靶材通常為絕緣材料,故氧化鋁的濺鍍膜之形成,係使用高頻濺鍍裝置。該裝置中,係將氧化鋁靶材與電極接合,於該電極之對極上配置基板,在減壓下處於氬等氣氛當中令其濺鍍放電,藉此,使氧化鋁在基板上堆積。
專利文獻1中揭示之氧化鋁濺鍍靶材,使用了平均結晶粒徑在5μm以上20μm以下、氣孔率在0.3%以上1.5%以下之氧化鋁燒結體。特別是該申請專利範圍第2項中,記載其使用純度99.9%以上之氧化鋁燒結體(一般稱為「three nine」,寫成「3N」)。而其實施例亦揭示了使用3N之氧化鋁粉末的例子。
[專利文獻1]日本特開2000-64034號公報
專利文獻1之氧化鋁濺鍍靶材,其性質被認為是即使施以高電力,或是異常放電、飛弧(arcing)等情形發生,也不容易產生很大的龜裂或破裂等破損。
然而近年來,隨著元件的複雜化、微細化,要求濺鍍膜愈來愈薄、對薄膜的物性面要求亦愈來愈嚴苛。為了賦予濺鍍膜良好的絕緣耐性及均質性,僅僅不讓濺鍍時之電力使靶材產生龜裂破裂等破損是不夠的。此外,若要減低濺鍍膜之雜質,提高靶材材料的純度是有效的方法。特別是,專利文獻1中所探討的僅有純度99.9%以上(3N)之氧化鋁燒結體,若要獲得更高的物性,有其極限。
另一方面,要使絕緣膜更薄,除了膜材料本身要高絕緣耐壓且可靠度高之外,如果濺鍍膜的膜厚分布等及膜質不夠均一,那麼便難以設計出高性能元件。然而,過去卻並未檢討過該等技術事項。
本發明之目的在於提供一種濺鍍靶材及其製造方法,針對由濺鍍而形成之濺鍍膜,能賦予其優良的絕緣耐性及均質性。
本發明團隊為解決上述課題,反覆研究用來作為各種
元件之絕緣層的氧化鋁薄膜之物性,特別是由濺鍍所形成之濺鍍膜的絕緣耐性及均質性。結果發現,靶材原料之氧化鋁燒結體必須更加高純度化,其純度需達99.99%以上(4N)、甚至99.999%以上(5N);另外,亦發現提高高純度氧化鋁燒結體之相對密度及結晶粒徑亦有效果,從而完成本發明。
本發明係以下述(1)~(5)及(7)之濺鍍靶材,以及下述(6)之濺鍍靶材之製造方法為要旨。
(1)一種濺鍍靶材,其使用氧化鋁燒結體,該氧化鋁燒結體在質量%下之純度為99.99%以上,相對密度為98%以上,且平均結晶粒徑未滿5μm。
(2)一種濺鍍靶材,其使用氧化鋁燒結體,該氧化鋁燒結體在質量%下之純度為99.999%以上,且相對密度為98%以上。
(3)如上述(2)之濺鍍靶材,其中,平均結晶粒徑未滿5μm。
(4)如上述(1)~(3)任一項之濺鍍靶材,其中,相對密度在99%以上。
(5)如上述(1)~(3)任一項之濺鍍靶材,其中,平均結晶粒徑未滿2μm。
(6)如上述(4)之濺鍍靶材,其中,平均結晶粒徑未滿2μm。
(7)一種濺鍍靶材之製造方法,該濺鍍靶材使用質量%下之純度為99.99%以上之氧化鋁燒結體,該濺鍍靶材
之製造方法,其特徵為:實施1250~1350℃之熱壓燒結而獲得燒結體後,在大氣中實施1300~1700℃、30~600分鐘之退火處理。
(8)藉由上述(7)之製造方法而得之濺鍍靶材。
本發明之濺鍍靶材,能夠讓使用其來濺鍍而形成之濺鍍膜具有優良之絕緣耐性、表面粗糙度小、均質性優良。像這樣,具有優良絕緣耐性及優良均質性的濺鍍膜,即使為極薄膜亦能具有穩定之電性與介電率。
本發明之濺鍍靶材中,需使用質量%下之純度達99.99%以上(4N)之氧化鋁燒結體。純度為99.9%以上(3N)之氧化鋁燒結體,即使如後文說明般實施熱壓燒結及退火處理等各種應對方法,然而以其為靶材所得之濺鍍膜,仍無法被賦予優良之絕緣耐壓或良好之表面粗糙度。相較於此,若使用純度達99.99%以上(4N)之氧化鋁燒結體,則即使不實施該等特殊熱處理,仍可成為具有良好相對密度及平均結晶粒徑之燒結體。以此燒結體作為靶材而濺鍍,可賦予所得之濺鍍膜優良之絕緣耐壓與良好的表面粗糙度。特別是不含鹼金屬及鹵素者為佳。
本發明之濺鍍靶材,亦可使用質量%下之純度達99.999%以上(5N)之氧化鋁燒結體。不過,使用了5N
之氧化鋁燒結體的濺鍍靶材,如同使用了4N之氧化鋁燒結體的濺鍍靶材般,相較於3N之氧化鋁燒結體的濺鍍靶材,能夠得到物性優良許多的濺鍍膜。
氧化鋁燒結體,係將具有與目的純度同等水準之純度的原料粉末燒成而得。在此,4N氧化鋁燒結體,一般是對4N以上的原料粉末進行粉碎、分級、造粒等前處理後,經成形、燒結而製造出來。另一方面,在製造5N氧化鋁燒結體的情形時,係使用純度達5N以上之原料粉末,採用同樣的製程。然而粉碎、分級、造粒等製程因對粉體直接處理,這些製程比較容易混入來自設備的雜質,當原料粉末純度為4N時尚無問題,但要維持5N純度(=雜質未滿10ppm),以一般的生產設備而言,在成形製程以後不易確保5N純度。
另一方面,若不對氧化鋁原料粉末進行粒徑控制,而直接成形及燒結,純度的維持會比較容易。但因粉體的粒度分布未受控制,故成形性或燒結性較差,不易得到緻密的燒結體。如果採行在非常清潔的環境下使用專用的粒徑調製設備,於粒徑調製後再追加原料粉的精製製程等因應方式,則確實能夠以純度達5N以上之原料粉末進行常壓緻密燒結,但包括設備投資在內,會增加莫大的製造成本。故,在5N氧化鋁燒結體的情形下,不以一般通常大氣爐進行常壓燒結,而是以後文所說明般實施熱壓燒結為佳。作為將常壓燒結體於完成後將其緻密化的手段,習知有HIP(熱均壓)法,但在HIP處理中結晶粒會成長,要將
平均結晶粒徑控制在未滿5μm有其難度。
氧化鋁燒結體中的氣孔較多時,最大的夾雜物會是空氣成分氣體及水,即使是高純度的氧化鋁燒結體,在其相對密度低的情形下,夾雜物會引發經濺鍍而得之濺鍍膜的低密度化及異常成長,使得絕緣耐壓降低。一旦濺鍍靶材的相對密度(實測密度除以理論密度之值以百分比表示之值)低,那麼使用該靶材經濺鍍而得之濺鍍膜,其表面粗糙度會變大,會對薄膜的均質化帶來不良影響。此外,基礎材料中之氣孔也會變多,使得基礎材料內吸附了微量水分,導致濺鍍製程中放出水,亦會對濺鍍膜的特性帶來不良影響。因此,相對密度需在98%以上。前提條件是能將燒結過程的結晶粒成長抑制在後述平均結晶粒徑範圍內,但以99%以上較佳,99.5%以上更佳。
若濺鍍靶材的平均結晶粒徑較大,則使用該靶材經濺鍍而得之濺鍍膜,其表面粗糙度會變大,會對薄膜的均質化帶來不良影響。因此,使平均結晶粒徑盡可能小為佳。尤其使其在10μm以下為佳。平均結晶粒徑使其在未滿5μ
m較佳,尤其使其在2μm以下更佳。但,純度4N之氧化鋁燒結體,必須使其平均結晶粒徑未滿5μm。
另,根據本發明團隊之研究,濺鍍靶材的純度從3N
提高至4N,甚至提高至5N,會對濺鍍膜的物性帶來正面影響。但如前述般,關於5N之氧化鋁燒結體,目前仍未建立一套在大氣爐常壓燒結下以低成本製造緻密燒結體之技術,故以熱壓燒結製造較為有效。有關這一點,若是4N之氧化鋁燒結體,即使在大氣爐下以常壓燒成,仍可獲得緻密之燒結體(亦即可使平均結晶粒徑未滿5μm),故可用較5N之氧化鋁燒結體更低的成本,製得高性能之靶材。
本發明之濺鍍靶材之製造方法並無特別限制,可在大氣爐內藉由燒結來製造。大氣爐之燒結,是在令與目的純度具有同等程度之原料粉體成形後,例如可藉由在1250~1700℃的大氣爐內保持30~600分鐘來進行。成形可採CIP(冷間均壓成形)或模具沖壓成形等手法,亦可在成形前適當實施粒度調製,或添加黏結劑來造粒。大氣爐的溫度若未滿1250℃,則無法獲得緻密之燒結體,濺鍍膜的均質性及絕緣耐壓會惡化。此外,像這樣在低溫下燒結之燒結體,其為多孔質且強度差,故在濺鍍製程時可能因異常放電等而使靶材有破損之虞,靶材的基礎材料本身可能會作為微粒而飛散,導致濺鍍膜產生缺陷。
另,成形前的原料粉末之粒度調製及造粒等製程可能會招致純度降低,要維持原料的純度,必須特別留意。此外,燒結體的最表層部分容易被來自燒成爐材料等之雜質
元素所污染,故預先全面研磨除去為佳。
另一方面,若大氣爐的溫度超過1700℃,那麼結晶粒成長會過剩,產生不均一之粗大粒子,使得濺鍍膜厚之均質性惡化。此外,一旦靶材中存在有不均一之粗大結晶粒,那麼隨著濺鍍的進行,大粒子在處理室內可能會作為異物而脫落。當脫落發生,靶材表面變得粗糙,亦可能使濺鍍膜的均質性惡化。若保持時間未滿30分鐘,則素材全體無法到達目的密度及結晶粒徑,會導致同一基礎材料內之物性不均。另一方面,若保持時間超過600分鐘,同樣會產生不均一之粗大粒子,可能招致濺鍍膜質惡化。
本發明之濺鍍靶材亦可如下製造而得:將氧化鋁燒結體以1250~1350℃實施熱壓燒結後,於大氣中實施1300~1700℃之退火處理而得。使用熱壓燒結時,一般來說是將與目的燒結體同等純度之粉末原料裝填至碳製之模型內,在真空或氮、氬等非氧化性氣氛中,於單軸方向加壓燒結。
當熱壓燒結之溫度未滿1250℃時,無法充份確保燒結體的密度,會招致濺鍍膜的均質性及絕緣耐壓惡化。另一方面,當溫度超過1350℃,雖可得到接近理論密度之緻密燒結體,但燒結體內會產生多數氧缺陷,氧缺陷愈增加,燒結體的呈色會從白色變化成灰色至黑色。若將這種缺乏氧的燒結體用作濺鍍靶材,則濺鍍膜同樣會成為缺乏氧的狀態,招致絕緣耐壓等膜的物性惡化。即使實施後述之退火製程,除去氧缺陷也僅限於表層,除去內層部的氧缺陷
係為困難。
另,熱壓溫度在1350℃以下時亦會發生氧缺陷,但其藉由後述大氣退火製程是可以除去的。
另一方面,亦可於濺鍍中在處理氣體中添加氧,使得靶材中欠缺之氧在膜堆積時補足。然而,來自靶材之氧原子在被濺鍍的瞬間會到達超過10000K的超高溫區域,相較於此,從外部作為處理氣體而被供應之氧原子係為低溫,故難以進入濺鍍膜中。結果,濺鍍膜中會帶有微小缺陷(空孔)等,膜質不穩定,絕緣耐壓可能會極端地惡化。且添加氧氣之濺鍍,必須要降低成膜速度,對良率也有不良影響;此外,亦容易伴隨膜質之歷時變化。是故,帶有氧缺陷之靶材,不適合用來形成極薄且具可靠性之絕緣膜。
熱壓燒結例如可在30~600分鐘的範圍內進行。若加壓時間未滿30分鐘,則熱傳導及燒結未達穩定狀態,整體性的緻密化不足,或是僅外周緻密化而蓄積殘留應力,可能因濺鍍的衝撃導致靶材基礎材料破損。另一方面,若加壓時間超過600分鐘,則燒結體的結晶粒成長及氧缺陷會增大,作為靶材時難以得到良質之濺鍍膜。
熱壓燒結加壓壓力在10MPa以上為佳。若加壓壓力未滿10MPa,可能因加壓力不足而導致密度降低或基礎材料中產生局部密度不均。加壓壓力的上限係為設備能力的容許範圍內,並無特別限制。
大氣退火處理,若不予實施,或是雖在熱壓燒結後實施但其溫度未滿1300℃時,無法充份除去燒結體中之氧缺
陷,故如前述般濺鍍膜的特性會降低。另一方面,若退火溫度超過1700℃,那麼結晶粒成長會過剩,產生不均一之粗大粒子,使得濺鍍膜厚之均質性惡化。此外,一旦靶材中存在有不均一之粗大結晶粒,那麼隨著濺鍍的進行,大粒子在處理室內可能會作為異物而脫落。當脫落發生,靶材表面變得粗糙,亦可能使濺鍍膜的均質性惡化。
大氣退火處理例如可在30~600分鐘的範圍內進行。若退火時間未滿30分鐘,則素材全體無法到達目的密度及結晶粒徑,會導致同一基礎材料內之物性不均。另一方面,若退火時間超過600分鐘,會產生不均一之粗大粒子,可能會招致濺鍍膜質惡化的問題。
特別是以前述熱壓條件將燒結體之相對密度調製成90~98%,以大氣退火製程進行燒結,做成相對密度98%以上,更佳為99%以上,藉此,可同時進行氧缺陷的除去,以及密度和結晶粒的控制。像這樣得到的濺鍍靶材,會成為緻密質、微結晶且幾乎不含氧缺陷者。此外,氧缺陷的除去可從燒結體的白色化來確認。
燒結體之加工,可藉由使用一般含鑽石砥粒的砥石之濕式研磨加工來進行。若有必要,亦可加上精磨(lapping)等研磨處理及/或噴砂等粗糙化處理。研磨加工後,將附著於表層之研磨液及研磨屑以藥液洗淨、純水超音波洗淨等手法來充分除去亦為有效。
為確認本發明之效果,準備了具有如表1所示之純度的氧化鋁,以各種製造條件下製作出靶材(直徑75mm、厚度5mm之圓板)。
依據JIS R 1634,以阿基米德法量測視密度(apparent density),並以3.987g/cm3
作為氧化鋁之理論密度,求出相對於此之相對密度(%)。
從燒結體之內層部切割出經鏡面研磨至Ra(表面粗糙度)未滿0.05μm之實驗片,以熱濃磷酸實施化學蝕刻處理,直到晶粒露出。其後,以掃描式電子顯微鏡(SEM)實施結晶粒之相片攝影,依據JIS R 1670,在確保N=100之任意視野內,將相當粒徑(equivalent circle diameter)作圖並加總結晶粒徑後,算出平均結晶粒徑(μm)。
對燒結體實施鹼熔等前處理使其成為溶液後,藉由感應耦合電漿原子發射光譜分析(ICP-AES)及火焰分光光度儀(以Li,Na,K為對象),對Mg、Si、Fe、Cu、Ca、Cr、Ti、Ni、Mo、W、Co、Y、Zn、Mn、Li、Na及K等17個元素實施定量分析,將檢測出來的元素之定量值
換算為氧化物,從100%扣除,以求得氧化鋁燒結體之純度。
另,所求得之燒結體純度在99.9%以上未滿99.99%者稱為3N、99.99%以上未滿99.999%者稱為4N、99.999%以上者稱為5N。
以使用#400號砥石之研磨加工對腐蝕面實施最終加工,使各靶材之研磨面的中心線平均粗糙度(Ra)落在0.2~0.8μm之範圍。
進行如下實驗:將上述各種靶材裝入超高真空高頻濺鍍裝置之傳送腔室(load-lock chamber)內,成膜,量測所得之濺鍍膜的物性值,進行評估。其結果併予記載於表1。
另,成膜係使用99.9995%之Ar氣體作為放電氣體,流量為10sccm、放電壓力為0.4Pa來進行。此外,將成膜時之到達壓力設為2.0×10-4
Pa。施加電力為150W。基板係使用50mm見方之硼矽酸玻璃與附摻錫氧化銦(Indium Tin Oxide/ITO)膜之玻璃,兩端5mm寬度之ITO上具有銀電極者,令氧化鋁濺鍍膜堆積成膜厚400nm。絕緣耐壓量測用樣本中,係在氧化鋁濺鍍膜上以濺鍍法形成直徑3mm、膜厚100 nm之Cu電極計9處。另,下述之量測,係針對靶材施加電力到達4.5kWh後所堆積之薄膜來進行。
濺鍍膜之表面粗糙度Ra(nm),係藉由掃描探針顯微鏡(AFM)在激發電壓1.36V、掃描範圍1000nm、懸臂長125μm、探針高度10μm之條件下進行量測。
使用Electrochemical Analyzer(電化學分析儀),在量測電位0~5V、掃描速度0.01V/S的條件下,量測設有Cu上部電極部分9處之絕緣耐壓值,求得9點之平均值,以作為濺鍍膜之絕緣耐壓。
如表1所示,No.1之純度雖為4N,但燒結溫度為較低的1200℃,故相對密度低,燒結體成為多孔質。其結果,使用其為靶材經濺鍍而得之濺鍍膜中會殘留空孔,絕緣耐壓極端地惡化,膜之均質性亦不良。No.2及3的純度皆為4N,相對密度、平均結晶粒徑亦良好,使用其為靶材經濺鍍而得之濺鍍膜,絕緣耐壓、均質性皆良好。
No.4的相對密度、平均結晶粒徑皆良好,但因純度為3N,故使用其為靶材經濺鍍而得之濺鍍膜,絕緣耐壓停留在中等程度、均質性差。No.5的純度為4N,相對密度、平均結晶粒徑皆良好,使用其為靶材經濺鍍而得之濺鍍膜,絕緣耐壓、均質性皆良好。但,因其以較高溫進行燒結,故不及No.3。
No.6的純度雖為4N,但因其在保持地過度高溫之大氣爐內進行常壓燒結,故平均結晶粒徑變大,使用其為靶材經濺鍍而得之濺鍍膜,絕緣耐壓、均質性皆劣化。No.7的純度雖為5N,但因其在熱壓燒結後未進行退火處理,故相對密度不足,使用其為靶材經濺鍍而得之濺鍍膜,絕緣耐壓劣化。
No.8~10的純度為5N,相對密度、平均結晶粒徑皆良好,使用其為靶材經濺鍍而得之濺鍍膜,絕緣耐壓、均質性皆良好。No.11的純度為4N,相對密度、平均結晶粒徑皆良好,使用其為靶材經濺鍍而得之濺鍍膜,絕緣耐壓、均質性皆良好。No.12的純度雖為5N,但因熱壓溫度過
高,導致在包含許多氧缺陷的狀態下緻密化,其後之大氣退火仍無法消除氧缺陷而產生問題,使用其為靶材經濺鍍而得之濺鍍膜,絕緣耐壓、均質性皆劣化。No.13的純度為3N,相對密度、平均結晶粒徑皆良好,但使用其為靶材經濺鍍而得之濺鍍膜,均質性差。
本發明之濺鍍靶材,能夠讓使用其來濺鍍而形成之濺鍍膜具有優良之絕緣耐性、表面粗糙度小、均質性優良。像這樣,具有優良絕緣耐性及優良均質性的濺鍍膜,即使為極薄膜亦能具有穩定之電性與介電率。
Claims (8)
- 一種濺鍍靶材,其特徵為:使用氧化鋁燒結體,該氧化鋁燒結體在質量%下之純度為99.99%以上,相對密度為98%以上,且平均結晶粒徑未滿5μm。
- 一種濺鍍靶材,其特徵為:使用氧化鋁燒結體,該氧化鋁燒結體在質量%下之純度為99.999%以上,且相對密度為98%以上。
- 如申請專利範圍第2項之濺鍍靶材,其中,平均結晶粒徑未滿5μm。
- 如申請專利範圍第1至3項任一項之濺鍍靶材,其中,相對密度為99%以上。
- 如申請專利範圍第1至3項任一項之濺鍍靶材,其中,平均結晶粒徑未滿2μm。
- 如申請專利範圍第4項之濺鍍靶材,其中,平均結晶粒徑未滿2μm。
- 一種濺鍍靶材之製造方法,該濺鍍靶材使用質量%下之純度為99.99%以上之氧化鋁燒結體,該濺鍍靶材之製造方法,其特徵為:實施1250~1350℃之熱壓燒結而獲得燒結體後,在大氣中實施1300~1700℃、30~600分鐘之退火處理。
- 一種濺鍍靶材,其特徵為:以申請專利範圍第7項之製造方法而得。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011242540 | 2011-11-04 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201319286A TW201319286A (zh) | 2013-05-16 |
TWI453294B true TWI453294B (zh) | 2014-09-21 |
Family
ID=48191706
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW101114522A TWI453294B (zh) | 2011-11-04 | 2012-04-24 | Sputtering target and its manufacturing method |
Country Status (6)
Country | Link |
---|---|
US (1) | US10504706B2 (zh) |
JP (1) | JP5969493B2 (zh) |
KR (1) | KR101955746B1 (zh) |
CN (1) | CN103917688B (zh) |
TW (1) | TWI453294B (zh) |
WO (1) | WO2013065337A1 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6117425B2 (ja) * | 2014-03-26 | 2017-04-19 | Jx金属株式会社 | 炭化タングステン又は炭化チタンからなるスパッタリングターゲット |
CN105331939B (zh) * | 2014-08-15 | 2018-05-11 | 安泰科技股份有限公司 | 一种含硅合金靶材及其制备方法 |
CN106222618B (zh) * | 2016-08-29 | 2018-12-18 | 基迈克材料科技(苏州)有限公司 | SnO2掺杂ZnO溅射靶材的制备方法 |
CN106191777A (zh) * | 2016-08-29 | 2016-12-07 | 基迈克材料科技(苏州)有限公司 | 一种氧化铝溅射靶材的制备方法 |
CN110073029A (zh) * | 2017-03-15 | 2019-07-30 | 捷客斯金属株式会社 | Al2O3溅射靶及其制造方法 |
DE102019102657A1 (de) | 2019-02-04 | 2020-08-06 | Bayerische Motoren Werke Aktiengesellschaft | Hochfrequenzdurchlässiges Bauteil und Verfahren zur Herstellung desselben |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201026629A (en) * | 2008-08-18 | 2010-07-16 | Tosoh Corp | Composite oxide sinter, method for producing composite oxide sinter, sputtering target and method for producing thin film |
CN101985735A (zh) * | 2009-07-29 | 2011-03-16 | 中国科学院福建物质结构研究所 | 一种氧化铝靶材和该靶材制备的透明导电薄膜 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4004452A (en) * | 1974-04-23 | 1977-01-25 | Ford Motor Company | Air/fuel ratio sensor for air/fuel ratios in excess of stoichiometry |
JPS60181270A (ja) * | 1984-02-27 | 1985-09-14 | Matsushita Electric Ind Co Ltd | スパツタ−用タ−ゲツトの製造方法 |
JPH06299347A (ja) * | 1993-04-08 | 1994-10-25 | Nippon Steel Corp | 電気絶縁性板状材料の製造方法 |
JPH0995773A (ja) * | 1995-10-03 | 1997-04-08 | Kobe Steel Ltd | 真空装置用窓材の製造方法 |
JPH11241160A (ja) * | 1998-02-26 | 1999-09-07 | Sony Corp | 絶縁膜の成膜方法及び薄膜磁気ヘッドの製造方法 |
JPH11240720A (ja) * | 1998-02-27 | 1999-09-07 | Mitsubishi Research Institute Inc | 強誘電性酸化物の緻密質焼結体およびその製造法 |
JP2000064034A (ja) * | 1998-08-19 | 2000-02-29 | Toshiba Ceramics Co Ltd | アルミナ・スパッタリング・ターゲット及びその製造方法並びに高周波スパッタリング装置 |
JP2001064426A (ja) * | 1999-06-25 | 2001-03-13 | Japan Polyolefins Co Ltd | 多孔質フィルムおよびその製法 |
JP2001348265A (ja) * | 2000-05-31 | 2001-12-18 | Ngk Spark Plug Co Ltd | アルミナ質焼結体及びその製造方法並びにこのアルミナ質焼結体を用いたセラミックヒータ、ガスセンサ素子及びこれを備えるガスセンサ |
JP2001064424A (ja) * | 2000-07-05 | 2001-03-13 | Toyobo Co Ltd | 透明ガスバリアフィルム |
WO2003029669A1 (fr) * | 2001-09-28 | 2003-04-10 | Nsk Ltd. | Unite de roulement |
US20030098102A1 (en) * | 2001-11-13 | 2003-05-29 | Perry Andrew C. | High-purity aluminum sputter targets and method of manufacture |
KR20060043427A (ko) | 2004-03-05 | 2006-05-15 | 토소가부시키가이샤 | 원통형 스퍼터링 타겟, 세라믹 소결체와 그 제조방법 |
JP4961672B2 (ja) * | 2004-03-05 | 2012-06-27 | 東ソー株式会社 | 円筒形スパッタリングターゲット並びにセラミックス焼結体及びその製造方法 |
JP2006205558A (ja) * | 2005-01-28 | 2006-08-10 | Gunma Prefecture | アルミナコーティング構造体およびその製造方法 |
JP5197975B2 (ja) * | 2006-03-24 | 2013-05-15 | 日本碍子株式会社 | 焼結体、発光管及びその製造方法 |
WO2007111380A1 (en) | 2006-03-24 | 2007-10-04 | Ngk Insulators, Ltd. | Method for producing sintered body, and sintered body |
WO2010018707A1 (ja) * | 2008-08-11 | 2010-02-18 | 出光興産株式会社 | 酸化ガリウム-酸化スズ系酸化物焼結体及び酸化物膜 |
JP2010087293A (ja) * | 2008-09-30 | 2010-04-15 | Toshiba Corp | 磁気抵抗効果素子の製造方法 |
JP5488970B2 (ja) * | 2009-12-16 | 2014-05-14 | 三菱マテリアル株式会社 | 透明導電膜、この透明導電膜を用いた太陽電池および透明導電膜を形成するためのスパッタリングターゲット |
-
2012
- 2012-04-10 JP JP2013541646A patent/JP5969493B2/ja active Active
- 2012-04-10 KR KR1020147012231A patent/KR101955746B1/ko active IP Right Grant
- 2012-04-10 CN CN201280054163.7A patent/CN103917688B/zh active Active
- 2012-04-10 WO PCT/JP2012/059795 patent/WO2013065337A1/ja active Application Filing
- 2012-04-10 US US14/355,959 patent/US10504706B2/en active Active
- 2012-04-24 TW TW101114522A patent/TWI453294B/zh active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201026629A (en) * | 2008-08-18 | 2010-07-16 | Tosoh Corp | Composite oxide sinter, method for producing composite oxide sinter, sputtering target and method for producing thin film |
CN101985735A (zh) * | 2009-07-29 | 2011-03-16 | 中国科学院福建物质结构研究所 | 一种氧化铝靶材和该靶材制备的透明导电薄膜 |
Also Published As
Publication number | Publication date |
---|---|
KR20140073570A (ko) | 2014-06-16 |
CN103917688A (zh) | 2014-07-09 |
US10504706B2 (en) | 2019-12-10 |
TW201319286A (zh) | 2013-05-16 |
JPWO2013065337A1 (ja) | 2015-04-02 |
US20150122642A1 (en) | 2015-05-07 |
JP5969493B2 (ja) | 2016-08-17 |
KR101955746B1 (ko) | 2019-03-07 |
CN103917688B (zh) | 2016-06-29 |
WO2013065337A1 (ja) | 2013-05-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI498438B (zh) | Sputtering target and its manufacturing method | |
TWI453294B (zh) | Sputtering target and its manufacturing method | |
TWI464133B (zh) | Polycrystalline MgO sintered body and its manufacturing method and MgO target for sputtering | |
JP5426173B2 (ja) | Mo系スパッタリングターゲット板,および,その製造方法 | |
KR101892761B1 (ko) | 산화물 소결체, 그것으로 이루어지는 타겟 및 산화물 반도체 박막 | |
WO2010125801A1 (ja) | ZnO-Ga2O3系スパッタリングターゲット用焼結体及びその製造方法 | |
JP6231924B2 (ja) | 酸化物焼結体及びスパッタリングターゲット | |
KR101648656B1 (ko) | Li 함유 인산염 화합물 소결체 및 스퍼터링 타깃, 및 그 제조 방법 | |
JPWO2016136611A1 (ja) | 酸化物焼結体及び該酸化物焼結体からなるスパッタリングターゲット | |
WO2007069415A1 (ja) | 真空蒸着用焼結体 | |
JP7456992B2 (ja) | 酸化物焼結体、スパッタリングターゲット及びスパッタリングターゲットの製造方法 | |
JP6158129B2 (ja) | 酸化物焼結体及びスパッタリングターゲット | |
JP5947413B1 (ja) | スパッタリングターゲット及びその製造方法 | |
KR20160067490A (ko) | 텅스텐 폐타겟의 재생방법 및 이로부터 제조된 배선 및 전극 형성을 위한 재활용 텅스텐 타겟 | |
KR20150070608A (ko) | 반도체용 텅스텐 스퍼터링 타겟의 제조방법 및 이로부터 제조된 텅스텐 스퍼터링 타겟 | |
JP4843883B2 (ja) | スパッタリングターゲット | |
JP2000313655A (ja) | 高密度酸化マグネシウム質焼結体及びその製造方法、並びにプラズマ処理装置用部材 | |
TW201716353A (zh) | 含有LiCoO2的燒結體及含有LiCoO2的濺鍍靶材以及含有LiCoO2的燒結體的製造方法 | |
JP2017150089A (ja) | スパッタリングターゲット及びその製造方法 | |
JP2016153540A (ja) | スパッタリングターゲット及びその製造方法 | |
JPH11302834A (ja) | スパッタリング方法 | |
JP2016154178A (ja) | 静電チャック用部材及びその製造方法 |