JP5134040B2 - ZnS powder for sputtering target and sputtering target - Google Patents
ZnS powder for sputtering target and sputtering target Download PDFInfo
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- 238000005477 sputtering target Methods 0.000 title claims description 30
- 239000000843 powder Substances 0.000 title claims description 25
- 229910052783 alkali metal Inorganic materials 0.000 claims description 19
- 150000001340 alkali metals Chemical class 0.000 claims description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- 238000005452 bending Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 8
- 238000013001 point bending Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000010408 film Substances 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 238000004544 sputter deposition Methods 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000005083 Zinc sulfide Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008642 heat stress Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- Physical Vapour Deposition (AREA)
Description
本発明は、焼結性に優れたスパッタリングターゲット用ＺｎＳ粉末及びスパッタリングによって膜を形成する際に、アーキングやノジュールを低減でき、且つ高強度、高密度で品質のばらつきが少なく量産性を向上させることのできる、ＺｎＳを主成分とするスパッタリングターゲットに関する。 The present invention is capable of reducing arcing and nodules when forming a film by sputtering with a ZnS powder for sputtering target having excellent sinterability, and improving mass productivity with high strength and high density with little quality variation. The present invention relates to a sputtering target mainly composed of ZnS.
近年、磁気ヘッドを必要とせずに書き換え可能な高密度光情報記録媒体である高密度記録光ディスク技術が開発され、急速に商品化されている。特に、ＣＤ−ＲＷは、書き換え可能なＣＤとして１９７７年に登場し現在、最も普及している相変化光ディスクである。このＣＤ−ＲＷの書き換え回数は１０００回程度である。
また、ＤＶＤ用としてＤＶＤ−ＲＷが開発され商品化されているが、このディスクの層構造は基本的にＣＤ−ＲＷと同じものである。この書き換え回数は１０００〜１００００回程度である。
In recent years, high-density recording optical disc technology, which is a rewritable high-density optical information recording medium without requiring a magnetic head, has been developed and rapidly commercialized. In particular, the CD-RW is a phase change optical disk that appeared in 1977 as a rewritable CD and is currently most popular. The CD-RW is rewritten about 1000 times.
Moreover, although DVD-RW has been developed and commercialized for DVD, the layer structure of this disc is basically the same as that of CD-RW. The number of rewrites is about 1000 to 10000 times.
一般に、ＣＤ−ＲＷ又はＤＶＤ−ＲＷ等に使用される相変化光ディスクは、Ａｇ−Ｉｎ−Ｓｂ−Ｔｅ系又はＧｅ−Ｓｂ−Ｔｅ系等の記録薄膜層の両側を、ＺｎＳ−ケイ酸化物（ＺｎＳ・ＳｉＯ２）系の高融点誘電体の保護層で挟み、さらにアルミニウム合金反射膜を設けた四層構造となっている。また、繰返し回数を高めるために、必要に応じてメモリ層と保護層の間に界面層を加えることなどが行われている。
反射層と保護層は、記録層のアモルファス部と結晶部との反射率の差を増大させる光学的機能が要求されるほか、記録薄膜の耐湿性や熱による変形の防止機能、さらには記録の際の熱的条件制御という機能が要求される（非特許文献１参照）。
In general, a phase change optical disk used for a CD-RW or a DVD-RW is formed on both sides of a recording thin film layer such as an Ag-In-Sb-Te system or a Ge-Sb-Te system by using ZnS-silicate (ZnS). -It has a four-layer structure sandwiched between protective layers of SiO 2 ) high melting point dielectric and further provided with an aluminum alloy reflective film. In order to increase the number of repetitions, an interface layer is added between the memory layer and the protective layer as necessary.
The reflective layer and the protective layer are required to have an optical function to increase the difference in reflectance between the amorphous portion and the crystalline portion of the recording layer, and also have a moisture resistance of the recording thin film and a function to prevent deformation due to heat. A function called thermal condition control is required (see Non-Patent Document 1).
このように、高融点誘電体の保護層は昇温と冷却による熱の繰返しストレスに対して耐性をもち、さらにこれらの熱影響が反射膜や他の箇所に影響を及ぼさないようにし、かつそれ自体も薄く、低反射率でかつ変質しない強靭さが必要である。この意味において誘電体保護層は重要な役割を有する。
上記誘電体保護層は、通常スパッタリング法によって形成されている。このスパッタリング法は正の電極と負の電極とからなる基板とターゲットを対向させ、不活性ガス雰囲気下でこれらの基板とターゲットの間に高電圧を印加して電場を発生させるものであり、この時電離した電子と不活性ガスが衝突してプラズマが形成され、このプラズマ中の陽イオンがターゲット（負の電極）表面に衝突してターゲット構成原子を叩きだし、この飛び出した原子が対向する基板表面に付着して膜が形成されるという原理を用いたものである。
In this way, the protective layer of the high melting point dielectric is resistant to the repeated heat stress caused by heating and cooling, and further prevents these thermal effects from affecting the reflective film and other parts. The film itself must be thin, have low reflectivity, and do not deteriorate. In this sense, the dielectric protective layer has an important role.
The dielectric protective layer is usually formed by a sputtering method. In this sputtering method, a substrate composed of a positive electrode and a negative electrode is opposed to a target, and an electric field is generated by applying a high voltage between the substrate and the target in an inert gas atmosphere. Electrons that have been ionized and an inert gas collide to form a plasma. The cations in the plasma collide with the target (negative electrode) surface and knock out target constituent atoms, and the substrate that the ejected atoms face. This is based on the principle that a film is formed on the surface.
従来、相変化光ディスク用保護層は可視光域での透過性や耐熱性等を要求されるため、ＺｎＳ−ＳｉＯ２等のセラミックスターゲットを用いてスパッタリングし、１００〜１０００Å程度の薄膜が形成されている。
上記ＺｎＳ−ケイ酸化物（ＺｎＳ−ＳｉＯ２）ターゲットに使用されるＳｉＯ２は、通常４Ｎ以上の高純度で平均粒径が０．１〜２０μｍのものが使用されており、７００〜１２００°Ｃで焼結して製造されている。
Conventionally, since a protective layer for a phase change optical disk is required to have transparency in the visible light range, heat resistance, and the like, a thin film of about 100 to 1000 mm is formed by sputtering using a ceramic target such as ZnS-SiO 2. Yes.
SiO 2 used for the ZnS- silicon oxide (ZnS-SiO 2) target, an average particle size in a conventional 4N or more high purity are used those 0.1 to 20 [mu] m, 700 to 1200 ° C It is manufactured by sintering.
しかし、このような温度範囲ではＳｉＯ２自体の変形等は発生せず、ＺｎＳとの反応も殆んど起こらないため、ＺｎＳとＳｉＯ２の間に空隙を生じ易く、またＳｉＯ２を微細にするほど、それが顕著となり、ＺｎＳの緻密化も阻害されるため、ターゲット密度が低下するという問題があった。
ターゲット焼結の際の密度低下は、特に重要な問題であり、スパッタリングによって膜を形成する際にアーキングを発生し易く、それが起因となってスパッタ時に発生するパーティクル（発塵）やノジュールが発生し、成膜の均一性及び品質が低下するだけでなく、生産性が劣るという問題があった。また、ターゲット強度が低下し、割れ易いという問題もあった。
However, in such a temperature range, the deformation of SiO 2 itself does not occur and the reaction with ZnS hardly occurs, so that voids are easily generated between ZnS and SiO 2 and SiO 2 is made finer. As it becomes so remarkable, the densification of ZnS is also inhibited, so that there is a problem that the target density is lowered.
Density reduction during target sintering is a particularly important problem, and it tends to cause arcing when forming a film by sputtering, which causes particles (dust generation) and nodules generated during sputtering. However, there is a problem that not only the uniformity and quality of film formation are deteriorated, but also productivity is inferior. Moreover, there existed a problem that target strength fell and it was easy to break.
従来の光ディスク保護膜形成用ターゲットとしては、硫酸根の含有量を２００ｐｐｍ以下に制限した硫化亜鉛を主成分とする焼結体からなる光記録媒体誘電保護膜形成用スパッタリングターゲット及びそのために硫酸根の含有量を９００ｐｐｍ以下に制限した硫化亜鉛粉末（例えば、特許文献１参照）、添加物としてＮａ、Ｋ又はこれらの酸化物から選択した１種以上を０．００１〜５ｗｔ％含有するＺｎＳ−ＳｉＯ２からなる光ディスク保護膜形成用スパッタリングターゲット（例えば、特許文献２参照）、ＺｎＳ−ＳｉＯ２系の焼結体ターゲット材において、焼結密度が３．４〜３．７ｇ／ｃｃであり、かつ最大気孔径が２〜４μｍ、熱膨張係数が３×１０−６〜５×１０−６／°Ｃである記録保護膜形成用焼結体ターゲットが開示されている（例えば、特許文献３参照）。
本発明は、スパッタ時に発生するパーティクル（発塵）やノジュールを低減し、品質のばらつきが少なく量産性を向上させることができ、かつターゲットの結晶粒が微細であり、密度が９７％以上、さらには９９％以上の高密度を備え、平均曲げ強度２５ＭＰａ以上の高い強度を有し、かつ均質なＺｎＳを主成分とするスパッタリングターゲット及び焼結性に優れた該スパッタリングターゲット製造用ＺｎＳを得ることを目的とする。 The present invention reduces particles (dust generation) and nodules generated at the time of sputtering, can improve the mass productivity with little variation in quality, has a fine target crystal grain, and has a density of 97% or more. Has a high density of 99% or higher, an average bending strength of 25 MPa or higher, a homogeneous sputtering target with ZnS as a main component, and ZnS for producing the sputtering target excellent in sinterability. Objective.
上記の課題を解決するために、本発明者らは鋭意研究を行った結果、焼結性を高めるためには、微量のアルカリ金属を添加することが極めて有効であり、また保護膜としての特性も損なわず、さらにスパッタ時に発生するパーティクルやノジュールを低減させることが可能であり、さらに密度及び強度を向上させ、かつ均質な材料を得ることができるとの知見を得た。 In order to solve the above problems, the present inventors have conducted intensive research. As a result, it is extremely effective to add a trace amount of an alkali metal in order to improve the sinterability, and the properties as a protective film. It was found that particles and nodules generated during sputtering can be further reduced, density and strength can be further improved, and a homogeneous material can be obtained.
本発明はこの知見に基づき、１）アルカリ金属０．５〜１０ｗｔｐｐｍを含有することを特徴とする焼結性に優れたスパッタリングターゲット用ＺｎＳ粉末、２）アルカリ金属がＮａ又はＫであることを特徴とする上記１記載のスパッタリングターゲット用ＺｎＳ粉末、３）アルカリ金属０．５〜１０ｗｔｐｐｍを含有するＺｎＳ粉末を主成分とする粉末を焼結して形成されたスパッタリングターゲット、４）アルカリ金属がＮａ又はＫであることを特徴とする上記３記載のスパッタリングターゲット、５）アルカリ金属が０．５〜１０ｗｔｐｐｍ以下、相対密度９７％以上及びターゲットに含有されるＳｉＯ２の平均結晶粒径が１０μｍ以下であることを特徴とする上記３又は４記載のスパッタリングターゲット、６）スパッタリングターゲット内より少なくとも１０個サンプルを採取し、３点曲げ強度を測定（ＪＩＳ Ｒ１６０１による）及び解析（ＪＩＳ Ｒ１６２５による）したとき、その平均曲げ強度が２５ＭＰａ以上、形状母数が１５以上であることを特徴とする上記３〜５のいずれかに記載のスパッタリングターゲットを提供する。 Based on this finding, the present invention is characterized in that 1) ZnS powder for sputtering target having excellent sinterability characterized by containing 0.5-10 wtppm of alkali metal, and 2) the alkali metal is Na or K. 3. ZnS powder for sputtering target according to 1 above, 3) Sputtering target formed by sintering a powder mainly composed of ZnS powder containing 0.5 to 10 wtppm of alkali metal, 4) Alkali metal is Na or 4. The sputtering target according to 3 above, wherein the sputtering target is K, 5) the alkali metal is 0.5 to 10 wtppm or less, the relative density is 97% or more, and the average crystal grain size of SiO 2 contained in the target is 10 μm or less. 6. The sputtering target according to 3 or 4 above, wherein the sputtering target is characterized in that When at least 10 samples are taken from the inside of the rack and the three-point bending strength is measured (according to JIS R1601) and analyzed (according to JIS R1625), the average bending strength is 25 MPa or more and the shape parameter is 15 or more. The sputtering target according to any one of the above 3 to 5, which is characterized in that
本発明は、焼結性が著しく改善され、ターゲットの密度が９７％以上、さらには９９％以上の高密度を備え、平均曲げ強度が２５ＭＰａ以上、形状母数が１５以上の、強度が高くかつ均質性が良好であるＺｎＳを主成分とするスパッタリングターゲットを得ることが可能となる。これによって、該ターゲットを使用してＺｎＳを主成分とする相変化型光ディスク保護膜を形成する際に、スパッタ時に発生するパーティクル（発塵）やノジュールを低減し、品質のばらつきが少なく量産性を向上させることができる。 In the present invention, the sinterability is remarkably improved, the density of the target is 97% or more, further high density of 99% or more, the average bending strength is 25 MPa or more, the shape parameter is 15 or more, and the strength is high. It becomes possible to obtain a sputtering target whose main component is ZnS with good homogeneity. This makes it possible to reduce particles (dust generation) and nodules generated during sputtering when forming a phase change type optical disk protective film mainly composed of ZnS using the target, thereby reducing mass variation and mass productivity. Can be improved.
本発明のＺｎＳ（硫化亜鉛）粉末は、アルカリ金属０．５〜１０ｗｔｐｐｍを含有する。これによって焼結性が一段と優れたＺｎＳ粉末が得られる。焼結原料となるＺｎＳ粉末に微量のアルカリ金属（０．５〜１０ｗｔｐｐｍ）を含有することは、後述する実施例に示すように、焼結性を上げる上で極めて有効である。
０．５ｗｔｐｐｍ未満では、焼結性の改善効果は小さい。また１０ｗｔｐｐｍを超えると、焼結体ターゲットが変色する問題がある。したがって、０．５〜１０ｗｔｐｐｍの範囲で添加することが望ましい。
The ZnS (zinc sulfide) powder of the present invention contains 0.5 to 10 wtppm of alkali metal. As a result, a ZnS powder having a further excellent sinterability can be obtained. Inclusion of a trace amount of alkali metal (0.5 to 10 wtppm) in the ZnS powder as a sintering raw material is extremely effective in increasing the sinterability as shown in the examples described later.
If it is less than 0.5 wtppm, the effect of improving the sinterability is small. Moreover, when it exceeds 10 wtppm, there exists a problem which a sintered compact target discolors. Therefore, it is desirable to add in the range of 0.5 to 10 wtppm.
さらに、アルカリ金属が５ｗｔｐｐｍ以下、相対密度９７％以上、ターゲットに含有されるＳｉＯ２の平均結晶粒径が１０μｍ以下であることが望ましい。通常使用するアルカリ金属としては、ナトリウム及びカリウムが推奨される。
これによって、相対密度が９７％以上、さらには９９％以上の高密度及び平均曲げ強度が２５ＭＰａ以上、形状母数が１５以上であるターゲットを容易に得ることができる。さらに、スパッタリングの際にパーティクル（発塵）やノジュールをより低減させ、品質のばらつきが少なく量産性を向上させることができる。
形状母数は高いほど、すなわち強度の分布が小さいほど、そのバルク体が均質であることを意味するが、形状母数１５以上とすることが望ましい。
Furthermore, it is desirable that the alkali metal is 5 wtppm or less, the relative density is 97% or more, and the average crystal grain size of SiO 2 contained in the target is 10 μm or less. Sodium and potassium are recommended as commonly used alkali metals.
Thus, a target having a relative density of 97% or more, further 99% or more, an average bending strength of 25 MPa or more, and a shape parameter of 15 or more can be easily obtained. Furthermore, particles (dust generation) and nodules can be further reduced during sputtering, and quality variation can be reduced and mass productivity can be improved.
The higher the shape parameter, that is, the smaller the intensity distribution, the more homogeneous the bulk body, but it is desirable that the shape parameter be 15 or more.
本発明のアルカリ金属を含有するＺｎＳ粉末の製造は、例えば次の工程によって行う。予め硫酸亜鉛溶液に硫化水素を吹き込み反応沈殿させる等の方法で作製したＺｎＳ粉末に、ＮａＣｌ又はＫＣｌ等を微量添加し、さらに攪拌混合した後乾燥し、Ｎａ又はＫ等のアルカリ金属が均一に分散したＺｎＳ粉末を得る。
本発明のスパッタリングターゲットの製造方法に際しては、上記のＺｎＳ及び所定量のＳｉＯ２等の原料粉末を均一に混合し、ホットプレス又は熱間静水圧プレスにより、温度８００〜１３００°Ｃに加熱し、面圧１００ｋｇ／ｃｍ２以上の条件で焼結する。これによって、焼結体の相対密度９７％以上であるＺｎＳを主成分とするスパッタリングターゲットを製造することができる。
また、このようにして製造したスパッタリングターゲット内から、１０個以上のサンプルを採取し、３点曲げ強度を測定（ＪＩＳ Ｒ１６０１による）し、ワイブル統計解析法（ＪＩＳ Ｒ１６２５による）で解析した場合、下記実施例に示すように、平均曲げ強度が２５ＭＰａ以上、形状母数が１５以上を達成することができる。強度及び均質性が向上し、ターゲットの取扱において割れが発生することなく、安全は操作が可能となる。
Manufacture of the ZnS powder containing the alkali metal of this invention is performed by the following process, for example. Add a small amount of NaCl or KCl, etc. to ZnS powder prepared by a method such as blowing hydrogen sulfide into a zinc sulfate solution in advance, then stirring and mixing, and drying to uniformly disperse alkali metals such as Na or K ZnS powder is obtained.
In the manufacturing method of the sputtering target of the present invention, the above raw materials powder such as ZnS and a predetermined amount of SiO 2 are uniformly mixed and heated to a temperature of 800 to 1300 ° C. by hot pressing or hot isostatic pressing, Sintering is performed at a surface pressure of 100 kg / cm 2 or more. Thereby, it is possible to manufacture a sputtering target whose main component is ZnS whose sintered body has a relative density of 97% or more.
Further, when 10 or more samples are collected from the sputtering target thus manufactured, the three-point bending strength is measured (according to JIS R1601), and analyzed by the Weibull statistical analysis method (according to JIS R1625), As shown in the Examples, the average bending strength can be 25 MPa or more and the shape parameter can be 15 or more. Strength and homogeneity are improved, and safety can be operated without cracks in handling the target.
本発明のＺｎＳを主成分とするスパッタリングターゲットの著しい密度及び強度と均質性の向上は、主としてアルカリ金属の含有による。
このアルカリ金属の添加によって密度、強度及びは均質性が向上する原因は、必ずしも理論的に解明された訳ではないが、ＺｎＳ粉末に吸着されたアルカリ金属が粒子表面に欠陥を生成させ、均一に焼結を促進させるという効果をもたらすためと考えられる。
そして、これは後述するデータによって、アルカリ金属の添加と密度、強度及び均質性向上の関係から確認できた。
本発明のターゲットは上記密度、強度及び均質性の向上と共に、空孔を減少させ、ターゲットのスパッタ面を均一かつ平滑にすることができるので、スパッタリング時のパーティクルやノジュールを一段と低減させ、さらにターゲットライフも長くすることができるという著しい効果を有する。
The remarkable improvement in density, strength and homogeneity of the sputtering target mainly composed of ZnS of the present invention is mainly due to the inclusion of alkali metal.
The reason why the density, strength and homogeneity are improved by the addition of the alkali metal is not necessarily theoretically elucidated, but the alkali metal adsorbed on the ZnS powder generates defects on the particle surface and makes it uniform. This is considered to bring about the effect of promoting the sintering.
This can be confirmed from the relationship between the addition of alkali metal and the density, strength, and homogeneity improvement by the data described later.
The target of the present invention can improve the above-mentioned density, strength and homogeneity, reduce vacancies, and make the sputtering surface of the target uniform and smooth, further reducing particles and nodules during sputtering, and further reducing the target. It has a remarkable effect that the life can be lengthened.
以下、実施例および比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例によって何ら制限されるものではない。すなわち、本発明は特許請求の範囲によってのみ制限されるものであり、本発明に含まれる実施例以外の種々の変形を包含するものである。 Hereinafter, description will be made based on Examples and Comparative Examples. In addition, a present Example is an example to the last, and is not restrict | limited at all by this example. In other words, the present invention is limited only by the scope of the claims, and includes various modifications other than the examples included in the present invention.
（実施例１−３）
２．０ｗｔｐｐｍのＮａ金属（実施例１）、６ｗｔｐｐｍのＮａ金属（実施例２）、８ｗｔｐｐｍのＫ金属（実施例３）を含有する平均粒径５μｍの純度４Ｎ（９９．９９％）であるＺｎＳ粉に、純度４Ｎ（９９．９９％）の平均粒径５μｍの酸化ケイ素（ＳｉＯ２）粉を２０ｍｏｌ％添加し均一に混合した。
この混合粉をグラファイトダイスに充填し、真空雰囲気中、面圧２００ｋｇｆ／ｃｍ２、温度１０００°Ｃの条件でホットプレスを行った。
このようにして製造したスパッタリングターゲット内から、１０個のサンプルを採取し、３点曲げ強度（ＪＩＳ Ｒ１６０１による）及び密度を測定した。これらの結果の一覧を、表１に示す。
表１に示すように、実施例１については、平均曲げ強度が３８ＭＰａ、形状母数が３０、バルク体の相対密度が９８％であった。
実施例２については、平均曲げ強度が３９ＭＰａ、形状母数が５２、バルク体の相対密度が９９．５％であった。
実施例３については、平均曲げ強度が３７ＭＰａ、形状母数が４９、バルク体の相対密度が９９．０％であった。
以上に示すとおり、実施例１−３のいずれの条件も、十分な平均曲げ強度、形状母数及び密度向上が達成できた。
(Example 1-3)
ZnS of 2.0 wtppm Na metal (Example 1), 6 wtppm Na metal (Example 2), 8 wtppm K metal (Example 3) and having an average particle size of 5 μm and a purity of 4N (99.99%) 20 mol% of silicon oxide (SiO 2 ) powder having a purity of 4N (99.99%) and an average particle diameter of 5 μm was added to the powder and mixed uniformly.
This mixed powder was filled in a graphite die and hot pressed in a vacuum atmosphere under conditions of a surface pressure of 200 kgf / cm 2 and a temperature of 1000 ° C.
Ten samples were collected from the thus produced sputtering target, and the three-point bending strength (according to JIS R1601) and density were measured. A list of these results is shown in Table 1.
As shown in Table 1, in Example 1, the average bending strength was 38 MPa, the shape parameter was 30, and the relative density of the bulk body was 98%.
In Example 2, the average bending strength was 39 MPa, the shape parameter was 52, and the relative density of the bulk body was 99.5%.
In Example 3, the average bending strength was 37 MPa, the shape parameter was 49, and the relative density of the bulk body was 99.0%.
As shown above, in any of the conditions of Example 1-3, sufficient average bending strength, shape parameter, and density improvement could be achieved.
（比較例１）
０．１ｗｔｐｐｍのＮａ金属を含有する純度４Ｎ（９９．９９％）であるＺｎＳ粉に、平均粒径５μｍの酸化ケイ素（ＳｉＯ２）粉を２０ｍｏｌ％添加し、均一に混合した。
この混合粉をグラファイトダイスに充填し、真空雰囲気中、面圧２００ｋｇｆ／ｃｍ２、温度１０００°Ｃの条件でホットプレスを行った。
これを実施例と同様に、製造したスパッタリングターゲット内から、１０個のサンプルを採取し、３点曲げ強度（ＪＩＳ Ｒ１６０１による）及び密度を測定した。これらの結果の一覧を、表１に示す。
表１に示すように、比較例１については、平均曲げ強度が３０ＭＰａ、形状母数が９、バルク体の相対密度が９６％であった。
これによって得られたバルク体は、平均曲げ強度は良いが、形状母数、相対密度が悪く、また均質性が不十分であった。
(Comparative Example 1)
20 mol% of silicon oxide (SiO 2 ) powder having an average particle diameter of 5 μm was added to ZnS powder having a purity of 4N (99.99%) containing 0.1 wtppm of Na metal and mixed uniformly.
This mixed powder was filled in a graphite die and hot pressed in a vacuum atmosphere under conditions of a surface pressure of 200 kgf / cm 2 and a temperature of 1000 ° C.
In the same manner as in Examples, 10 samples were collected from the produced sputtering target, and the three-point bending strength (according to JIS R1601) and density were measured. A list of these results is shown in Table 1.
As shown in Table 1, in Comparative Example 1, the average bending strength was 30 MPa, the shape parameter was 9, and the relative density of the bulk body was 96%.
The bulk body thus obtained had good average bending strength, but had poor shape parameters and relative density, and was insufficient in homogeneity.
（比較例２）
０．１ｗｔｐｐｍのＫ金属を含有する純度４Ｎ（９９．９９％）であるＺｎＳ粉に、平均粒径５μｍの酸化ケイ素（ＳｉＯ２）粉を２０ｍｏｌ％添加し、均一に混合した。
この混合粉をグラファイトダイスに充填し、真空雰囲気中、面圧２００ｋｇｆ／ｃｍ２、温度１０００°Ｃの条件でホットプレスを行った。
これを実施例と同様に、製造したスパッタリングターゲット内から、１０個のサンプルを採取し、３点曲げ強度（ＪＩＳ Ｒ１６０１による）及び密度を測定した。これらの結果の一覧を、表１に示す。
表１に示すように、比較例２については、平均曲げ強度が２３ＭＰａ、形状母数が７、バルク体の相対密度が９５％であった。
これによって得られたバルク体は、平均曲げ強度、形状母数、相対密度も悪く十分な特性が得られなかった。
(Comparative Example 2)
20 mol% of silicon oxide (SiO 2 ) powder having an average particle diameter of 5 μm was added to ZnS powder having a purity of 4N (99.99%) containing 0.1 wtppm of K metal and mixed uniformly.
This mixed powder was filled in a graphite die and hot pressed in a vacuum atmosphere under conditions of a surface pressure of 200 kgf / cm 2 and a temperature of 1000 ° C.
In the same manner as in Examples, 10 samples were collected from the produced sputtering target, and the three-point bending strength (according to JIS R1601) and density were measured. A list of these results is shown in Table 1.
As shown in Table 1, in Comparative Example 2, the average bending strength was 23 MPa, the shape parameter was 7, and the relative density of the bulk body was 95%.
The bulk body thus obtained was poor in average bending strength, shape parameter, and relative density, and sufficient characteristics could not be obtained.
図１に、Ｎａ添加量が、それぞれＮａ：０．１ｗｔｐｐｍ、Ｎａ：２ｗｔｐｐｍ、Ｎａ：６ｗｔｐｐｍである場合のワイブルプロットにおける強度分布の指標を示す。
図１において、形状母数が高いほど、すなわち強度の分布が小さいほど、そのバルク体が均質であることを意味する。
図１において、直線状に立っている方が形状母数が高く均質であるが、Ｎａ：０．１ｗｔｐｐｍに比べ、Ｎａ添加量：２ｗｔｐｐｍ、６ｗｔｐｐｍの方が垂直に近くなり、より均質になっていることが分かる。
FIG. 1 shows an index of intensity distribution in the Weibull plot when the amount of Na added is Na: 0.1 wtppm, Na: 2 wtppm, and Na: 6 wtppm, respectively.
In FIG. 1, the higher the shape parameter, that is, the smaller the intensity distribution, the more homogeneous the bulk body.
In FIG. 1, the shape parameter is more uniform when standing in a straight line, but Na addition amount: 2 wtppm and 6 wtppm are closer to vertical and more homogeneous than Na: 0.1 wtppm. I understand that.
本発明は、相対密度９７％以上、さらには相対密度９９％以上の高密度及び平均曲げ強度２５ＭＰａ以上、形状母数１５以上の高強度のＺｎＳを主成分とするターゲットを製造することができるので、スパッタ時に発生するパーティクル（発塵）やノジュールを低減し、品質のばらつきが少なく量産性を向上させることができるという優れた効果を有し、このターゲットを使用してＺｎＳを主成分とする相変化型光ディスク保護膜を形成することができる。 Since the present invention can produce a target mainly composed of ZnS having a relative density of 97% or more, further a high density of 99% or more, an average bending strength of 25 MPa or more, and a high strength ZnS having a shape parameter of 15 or more. It has the excellent effect of reducing particles (dust generation) and nodules generated during sputtering, improving quality with little variation in quality, and using this target as a main component of ZnS A changeable optical disc protective film can be formed.
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