JP2012036433A - BiTi BASED OXIDE SPUTTERING TARGET AND METHOD FOR PRODUCING THE SAME - Google Patents
BiTi BASED OXIDE SPUTTERING TARGET AND METHOD FOR PRODUCING THE SAME Download PDFInfo
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 35
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052796 boron Inorganic materials 0.000 claims abstract description 28
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 14
- 239000011812 mixed powder Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 238000010298 pulverizing process Methods 0.000 claims abstract description 3
- 238000004544 sputter deposition Methods 0.000 abstract description 15
- 239000010936 titanium Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000000391 spectroscopic ellipsometry Methods 0.000 description 1
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- 238000009827 uniform distribution Methods 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
本発明は、ＢｉＴｉ系酸化物スパッタリングターゲットおよびその製造方法に関するものである。 The present invention relates to a BiTi-based oxide sputtering target and a method for producing the same.
近年、写真や動画の高画質化に伴い、光記録媒体等へ記録する際のデジタルデータが増大し、記録媒体の高容量化が求められ、既に、高記録容量の光記録媒体として二層記録方式により５０ＧＢの容量を有したＢｌｕ−ｒａｙ Ｄｉｓｃ（登録商標）が販売されている。このＢｌｕ−ｒａｙ Ｄｉｓｃ（登録商標）は、今後もさらなる高容量化が望まれており、記録層の多層化による高容量化の研究が盛んに行われている。 In recent years, with the improvement of the picture quality of photographs and moving images, digital data when recording on an optical recording medium or the like has increased, and there has been a demand for an increase in the capacity of the recording medium. Blu-ray Disc (registered trademark) having a capacity of 50 GB depending on the system is on the market. The Blu-ray Disc (registered trademark) is desired to have a higher capacity in the future, and research on increasing the capacity by increasing the number of recording layers has been actively conducted.
このような複数の記録層を積層した光記録媒体の実現には、全ての記録層にレーザ光を到達させるため、記録層や反射層の半透明化が必要とされる。一方、多層光記録媒体において複数の記録層の各層との間に４０５ｎｍの波長の光に対する屈折率が高く、消衰係数の小さい光学調整層が要望され、このような膜が成膜できる材料として、ＴｉＯ２、Ｂｉ２Ｏ３、Ｎｂ２Ｏ５、Ｔａ２Ｏ５等が知られている。例えば、ＴｉＯ２とＢｉ２Ｏ３の混合物の膜を設けることが報告されている（特許文献１参照）。 In order to realize such an optical recording medium in which a plurality of recording layers are laminated, it is necessary to make the recording layer and the reflective layer translucent in order to allow the laser light to reach all the recording layers. On the other hand, in a multilayer optical recording medium, an optical adjustment layer having a high refractive index for light having a wavelength of 405 nm and a small extinction coefficient is desired between each of a plurality of recording layers. TiO 2 , Bi 2 O 3 , Nb 2 O 5 , Ta 2 O 5 and the like are known. For example, it has been reported that a film of a mixture of TiO 2 and Bi 2 O 3 is provided (see Patent Document 1).
一方、強誘電体メモリ用の誘電体膜としてＢｉ４Ｔｉ３Ｏ１２膜が知られている。このＢｉ４Ｔｉ３Ｏ１２膜をスパッタ法により成膜するためのスパッタリングターゲットとしては、例えば特許文献２に、Ｂｉ２Ｏ３粉末とＴｉＯ２粉末とＴｉ粉末との混合粉末を真空中で、１３００℃で２時間焼成して作製するスパッタリングターゲットが提案されている。 On the other hand, a Bi 4 Ti 3 O 12 film is known as a dielectric film for a ferroelectric memory. As a sputtering target for forming this Bi 4 Ti 3 O 12 film by sputtering, for example, Patent Document 2 discloses a mixed powder of Bi 2 O 3 powder, TiO 2 powder and Ti powder in vacuum of 1300. There has been proposed a sputtering target produced by baking at 2 ° C. for 2 hours.
上記従来の技術には、以下の課題が残されている。
すなわち、上記材料のうち、ＴｉＯ２、Ｂｉ２Ｏ３、Ｎｂ２Ｏ５、Ｔａ２Ｏ５は、４０５ｎｍの波長の光に対する屈折率が２．４〜２．７と十分ではない。また、Ｂｉ４Ｔｉ３Ｏ１２は、４０５ｎｍの波長の光に対する屈折率が２．８と高いものの、高電力にて長時間のスパッタを行うとスパッタリングターゲットが割れ、異常放電が発生するという問題点がある。
The following problems remain in the conventional technology.
That is, among the above materials, TiO 2 , Bi 2 O 3 , Nb 2 O 5 , and Ta 2 O 5 have an insufficient refractive index of 2.4 to 2.7 with respect to light having a wavelength of 405 nm. Bi 4 Ti 3 O 12 has a high refractive index of 2.8 with respect to light having a wavelength of 405 nm. However, when sputtering is performed at a high power for a long time, the sputtering target breaks and abnormal discharge occurs. There is.
本発明は、前述の課題に鑑みてなされたもので、高い出力でも安定してスパッタリング可能で、割れの少ないＢｉＴｉ系酸化物スパッタリングターゲットおよびその製造方法を提供することを目的とする。 The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a BiTi-based oxide sputtering target that can be stably sputtered even at a high output and has few cracks, and a method for producing the same.
本発明者らは、ＢｉＴｉ系酸化物スパッタリングターゲットについて研究を進めたところ、原料に酸化硼素を添加することにより硼素（Ｂ）が組織に分散若しくは拡散し、従来得られなかった高い熱伝導率が実現され、高い耐熱衝撃性や応力緩和効果を得ることができることを見出した。 As a result of research on the BiTi-based oxide sputtering target, the present inventors have found that boron (B) is dispersed or diffused in the structure by adding boron oxide to the raw material, resulting in a high thermal conductivity that could not be obtained conventionally. It has been realized that high thermal shock resistance and stress relaxation effects can be obtained.
したがって、本発明は、上記知見から得られたものであり、前記課題を解決するために以下の構成を採用した。すなわち、本発明のＢｉＴｉ系酸化物スパッタリングターゲットは、ＢｉとＴｉとを含む金属酸化物相を含み、熱伝導率が、１．４Ｗ／ｍ・Ｋ以上であることを特徴とする。
このＢｉＴｉ系酸化物スパッタリングターゲットでは、熱伝導率が１．４Ｗ／ｍ・Ｋ以上と高いため、高い出力でスパッタしても割れが発生し難く、異常放電の発生を抑制することができる。
Therefore, the present invention has been obtained from the above findings, and the following configuration has been adopted in order to solve the above problems. That is, the BiTi-based oxide sputtering target of the present invention includes a metal oxide phase containing Bi and Ti, and has a thermal conductivity of 1.4 W / m · K or more.
Since this BiTi-based oxide sputtering target has a high thermal conductivity of 1.4 W / m · K or higher, cracks are hardly generated even when sputtering is performed at a high output, and the occurrence of abnormal discharge can be suppressed.
また、本発明のＢｉＴｉ系酸化物スパッタリングターゲットは、硼素を含有することを特徴とする。
すなわち、このＢｉＴｉ系酸化物スパッタリングターゲットでは、硼素を含有するので、上記のような高い熱伝導率が得られる。これは、Ｔｉサイトに硼素が置換されることで形成されたキャリアであるホールが熱伝導の担い手となるためと考えられる。
Moreover, the BiTi-based oxide sputtering target of the present invention is characterized by containing boron.
That is, since this BiTi-based oxide sputtering target contains boron, the high thermal conductivity as described above can be obtained. This is presumably because holes, which are carriers formed by substitution of boron at the Ti site, are responsible for heat conduction.
さらに、本発明のＢｉＴｉ系酸化物スパッタリングターゲットは、硼素の含有量が、０．４〜３．６ａｔ％であることを特徴とする。
すなわち、このＢｉＴｉ系酸化物スパッタリングターゲットでは、硼素の含有量が、０．４〜３．６ａｔ％であるので、熱伝導率向上の十分な効果が得られると共に高記録容量の光記録媒体の記録層間に設ける透明な膜として必要な高屈折率を得ることができる。なお、硼素の含有量が、０．４ａｔ％未満であると、上記のような十分な添加効果を得ることができないと共に、３．６ａｔ％を超えると、膜の屈折率が２．７未満となり、高記録容量の光記録媒体の記録層間に設ける膜として十分ではないためである。
Furthermore, the BiTi-based oxide sputtering target of the present invention is characterized in that the boron content is 0.4 to 3.6 at%.
That is, in this BiTi-based oxide sputtering target, the boron content is 0.4 to 3.6 at%, so that a sufficient effect of improving the thermal conductivity can be obtained and recording on an optical recording medium having a high recording capacity is possible. A high refractive index required as a transparent film provided between the layers can be obtained. When the boron content is less than 0.4 at%, the above-described sufficient addition effect cannot be obtained, and when it exceeds 3.6 at%, the refractive index of the film becomes less than 2.7. This is because the film provided between the recording layers of the optical recording medium having a high recording capacity is not sufficient.
本発明のＢｉＴｉ系酸化物スパッタリングターゲットの製造方法は、上記本発明のＢｉＴｉ系酸化物スパッタリングターゲットを作製する方法であって、Ｂｉの酸化物とＴｉの酸化物とを粉砕混合して混合粉末を作製する工程と、該混合粉末を仮焼して仮焼粉とする工程と、該仮焼粉に酸化硼素を１〜９ｍｏｌ％（硼素換算で０．４〜３．６ａｔ％）添加したものを解砕しながら混合して添加仮焼粉とする工程と、該添加仮焼粉を真空または不活性ガス雰囲気中で圧力を加えながら加熱して焼結させる工程と、を有していることを特徴とする。
すなわち、このＢｉＴｉ系酸化物スパッタリングターゲットの製造方法では、仮焼粉に酸化硼素を１〜９ｍｏｌ％（硼素換算で０．４〜３．６ａｔ％）添加したものを解砕しながら混合し、これをホットプレス等で加圧焼結するので、硼素が組織に分散若しくは拡散して添加され、高い熱伝導率で安定したスパッタリングが可能であると共に、高屈折率の膜を成膜可能なスパッタリングターゲットを得ることができる。
なお、本発明で添加する酸化硼素（Ｂ２Ｏ３）の融点は４６０℃であるため、焼結助剤として機能するため、スパッタリングターゲットの密度を高めると共に、硼素が分散若しくは拡散しやすくなり、スパッタによってスパッタリングターゲットに掛かる応力を和らげる効果も発揮すると考えられる。
The manufacturing method of the BiTi-based oxide sputtering target according to the present invention is a method for producing the BiTi-based oxide sputtering target according to the present invention, wherein a mixed powder is obtained by grinding and mixing Bi oxide and Ti oxide. A step of preparing, a step of calcining the mixed powder to obtain a calcined powder, and a product obtained by adding 1 to 9 mol% of boron oxide (0.4 to 3.6 at% in terms of boron) to the calcined powder. Mixing the mixture while crushing to make an additive calcined powder, and heating and sintering the additive calcined powder while applying pressure in a vacuum or an inert gas atmosphere. Features.
That is, in this method of manufacturing a BiTi-based oxide sputtering target, a mixture obtained by adding 1 to 9 mol% of boron oxide to calcined powder (0.4 to 3.6 at% in terms of boron) is mixed while being crushed. Is sintered by hot pressing or the like, so that boron is dispersed or diffused in the structure and added, so that stable sputtering with high thermal conductivity is possible and a sputtering target capable of forming a film with a high refractive index. Can be obtained.
Since the melting point of boron oxide (B 2 O 3 ) added in the present invention is 460 ° C., it functions as a sintering aid, so that the density of the sputtering target is increased, and boron is easily dispersed or diffused. It is considered that the effect of reducing the stress applied to the sputtering target by sputtering is also exhibited.
本発明によれば、以下の効果を奏する。
すなわち、本発明に係るＢｉＴｉ系酸化物スパッタリングターゲットによれば、熱伝導率が１．４Ｗ／ｍ・Ｋ以上と高いため、高い出力でスパッタしても割れが発生し難く、異常放電の発生を抑制することができる。また、このＢｉＴｉ系酸化物スパッタリングターゲットを作製する本発明の製造方法では、酸化硼素を１〜９ｍｏｌ％（硼素換算で０．４〜３．６ａｔ％）添加したものをホットプレス等で加圧焼結するので、高い熱伝導率が得られ、高い出力でも異常放電の発生を抑制して安定したスパッタリングが可能であると共に、高屈折率の膜を成膜可能なスパッタリングターゲットを得ることができる。
したがって、本発明のＢｉＴｉ系酸化物スパッタリングターゲットを用いてスパッタリングによりＢｉＴｉ系酸化物膜を成膜することで、高記録容量の光記録媒体の構成層として設ける透明な高屈折率膜に適した膜を得ることができる。
The present invention has the following effects.
That is, according to the BiTi-based oxide sputtering target according to the present invention, since the thermal conductivity is as high as 1.4 W / m · K or more, cracking hardly occurs even if sputtering is performed at a high output, and abnormal discharge occurs. Can be suppressed. In the production method of the present invention for producing this BiTi-based oxide sputtering target, boron oxide added in an amount of 1 to 9 mol% (0.4 to 3.6 at% in terms of boron) is subjected to pressure firing using a hot press or the like. As a result, a high thermal conductivity can be obtained, a sputtering target capable of forming a film having a high refractive index can be obtained while suppressing the occurrence of abnormal discharge even at a high output and enabling stable sputtering.
Therefore, a film suitable for a transparent high refractive index film provided as a constituent layer of an optical recording medium having a high recording capacity by forming a BiTi oxide film by sputtering using the BiTi oxide sputtering target of the present invention. Can be obtained.
以下、本発明に係るＢｉＴｉ系酸化物スパッタリングターゲットおよびその製造方法の一実施形態を説明する。 Hereinafter, an embodiment of a BiTi-based oxide sputtering target and a manufacturing method thereof according to the present invention will be described.
本実施形態のＢｉＴｉ系酸化物スパッタリングターゲットは、ＢｉとＴｉとを含む金属酸化物相を含み、熱伝導率が、１．４Ｗ／ｍ・Ｋ以上であって、硼素を含有している。なお、この熱伝導率は、後述する条件設定でレーザーフラッシュ法により測定されたものである。
また、上記硼素の含有量は、０．４〜３．６ａｔ％に設定されている。
なお、このＢｉＴｉ系酸化物スパッタリングターゲットは、スパッタリングターゲットを構成する金属成分のＢｉとＴｉを、Ｂｉ：Ｔｉ＝６：ｘ（３＜ｘ＜７）となる原子比で含有し、例えばＢｉ４Ｔｉ３Ｏ１２相からなる、あるいはＢｉ４Ｔｉ３Ｏ１２相を主相として含む酸化物からなるものである。
The BiTi-based oxide sputtering target of the present embodiment includes a metal oxide phase containing Bi and Ti, has a thermal conductivity of 1.4 W / m · K or more, and contains boron. This thermal conductivity is measured by the laser flash method under the condition setting described later.
The boron content is set to 0.4 to 3.6 at%.
This BiTi-based oxide sputtering target contains Bi and Ti as metal components constituting the sputtering target in an atomic ratio of Bi: Ti = 6: x (3 <x <7), for example, Bi 4 Ti. consisting 3 O 12 phase, or made of a Bi 4 Ti 3 O 12 phase an oxide containing as a main phase.
このＢｉＴｉ系酸化物スパッタリングターゲットの製造方法は、スパッタリングターゲットを構成する金属成分としてのＢｉとＴｉとをＢｉ：Ｔｉ＝６：ｘ（３＜ｘ＜７）となる原子比で秤量したＢｉの酸化物とＴｉの酸化物とを粉砕混合して混合粉末を作製する工程と、該混合粉末を仮焼して仮焼粉とする工程と、該仮焼粉に酸化硼素（Ｂ２Ｏ３）を１〜９ｍｏｌ％（硼素換算で０．４〜３．６ａｔ％）添加したものを解砕混合して添加仮焼粉とする工程と、該添加仮焼粉を真空または不活性ガス雰囲気中で圧力を加えながら加熱して焼結させる工程と、を有している。 In this BiTi-based oxide sputtering target manufacturing method, Bi and Ti as metal components constituting the sputtering target are weighed at an atomic ratio of Bi: Ti = 6: x (3 <x <7). Pulverizing and mixing the product and Ti oxide, producing a mixed powder, calcining the mixed powder into a calcined powder, and boron oxide (B 2 O 3 ) on the calcined powder A step of adding 1 to 9 mol% (0.4 to 3.6 at% in terms of boron) to pulverize and mix to make an added calcined powder, and pressure the added calcined powder in a vacuum or an inert gas atmosphere Heating and sintering while adding.
上記製法の一例について詳述すれば、例えば、まず酸化ビスマス、酸化チタンの各粉末を、含有金属の比率がＢｉ：Ｔｉ＝６：ｘ（３＜ｘ＜７）になるように秤量する。次に、秤量した粉末をボールミル装置などを用いて混合し、混合粉末を作製する。なお、混合に用いる溶媒としては、例えばアルコールが挙げられる。
次に、得られた混合粉末を乾燥後、大気中で焼成（仮焼）し仮焼粉を作製する。仮焼の条件としては、例えば、６００〜８００℃、３〜１０時間である。
続いて、所定量の酸化硼素を添加し、ボールミル装置などを用いて解砕し、解砕粉を得る。なお、解砕に用いる溶媒としては、例えばヘキサンが挙げられる。得られた解砕粉を黒鉛モールドに充填し、ホットプレスすることで本発明のスパッタリングターゲットが得られる。なお、このホットプレスの条件としては、５５０〜１１５０℃にて１〜１０時間、１００〜６００ｋｇｆ／ｃｍ２の圧力にて真空または不活性ガス雰囲気中で行うことが好ましい。
If an example of the said manufacturing method is explained in full detail, for example, each powder of a bismuth oxide and a titanium oxide will be first weighed so that the ratio of a containing metal may become Bi: Ti = 6: x (3 <x <7). Next, the weighed powder is mixed using a ball mill apparatus or the like to produce a mixed powder. In addition, as a solvent used for mixing, alcohol is mentioned, for example.
Next, the obtained mixed powder is dried and then fired (calcined) in the air to prepare a calcined powder. As conditions of calcination, it is 600-800 degreeC and 3 to 10 hours, for example.
Subsequently, a predetermined amount of boron oxide is added and pulverized using a ball mill or the like to obtain pulverized powder. In addition, as a solvent used for crushing, hexane is mentioned, for example. The obtained pulverized powder is filled into a graphite mold and hot pressed to obtain the sputtering target of the present invention. The hot pressing is preferably performed at 550 to 1150 ° C. for 1 to 10 hours at a pressure of 100 to 600 kgf / cm 2 in a vacuum or an inert gas atmosphere.
このように作製した本実施形態のＢｉＴｉ系酸化物スパッタリングターゲットでは、熱伝導率が１．４Ｗ／ｍ・Ｋ以上と高いため、高い出力でスパッタしても割れが発生し難く、異常放電の発生を抑制することができる。
このＢｉＴｉ系酸化物スパッタリングターゲットでは、硼素を含有することにより、上記のような高い熱伝導率が得られる。特に、硼素の含有量が、０．４〜３．６ａｔ％であるので、熱伝導率向上の十分な効果が得られると共に高記録容量の光記録媒体の記録層間に設ける透明な膜として必要な高屈折率を得ることができる。
In the BiTi-based oxide sputtering target of this embodiment manufactured in this way, the thermal conductivity is as high as 1.4 W / m · K or higher, so that cracking hardly occurs even when sputtering is performed at a high output, and abnormal discharge occurs. Can be suppressed.
In this BiTi-based oxide sputtering target, the high thermal conductivity as described above can be obtained by containing boron. In particular, since the boron content is 0.4 to 3.6 at%, a sufficient effect of improving the thermal conductivity can be obtained, and it is necessary as a transparent film provided between recording layers of an optical recording medium having a high recording capacity. A high refractive index can be obtained.
また、本実施形態のＢｉＴｉ系酸化物スパッタリングターゲットの製造方法では、仮焼粉に酸化硼素を１〜９ｍｏｌ％（硼素換算で０．４〜３．６ａｔ％）添加したものを解砕混合して添加仮焼粉とし、これをホットプレス等で加圧焼結するので、硼素が組織に分散若しくは拡散して添加され、高い熱伝導率で安定したスパッタリングが可能であると共に、高屈折率の膜を成膜可能なスパッタリングターゲットを得ることができる。
なお、本実施形態で添加する酸化硼素（Ｂ２Ｏ３）の融点は４６０℃であるため、焼結助剤として機能するため、スパッタリングターゲットの密度を高めると共に、硼素が分散若しくは拡散しやすくなり、スパッタによってスパッタリングターゲットに掛かる応力を和らげる効果も発揮すると考えられる。
Moreover, in the manufacturing method of the BiTi-type oxide sputtering target of this embodiment, what added 1-9 mol% (0.4-3.6at% in conversion of boron) boron oxide to calcining powder is pulverized and mixed. Additive calcined powder is pressed and sintered with a hot press or the like, so boron is dispersed or diffused in the structure, and stable sputtering with high thermal conductivity is possible and a film with a high refractive index. Can be obtained.
Since the melting point of boron oxide (B 2 O 3 ) added in this embodiment is 460 ° C., it functions as a sintering aid, so that the density of the sputtering target is increased and boron is easily dispersed or diffused. It is considered that the effect of reducing the stress applied to the sputtering target by sputtering is also exhibited.
上記本実施形態に基づいて実際に作製したＢｉＴｉ系酸化物スパッタリングターゲットの実施例について、評価を行った結果を以下に示す。 The result of having evaluated about the Example of the BiTi-type oxide sputtering target actually produced based on the said this embodiment is shown below.
［実施例１］
酸化ビスマス（化学式：Ｂｉ２Ｏ３、純度：３Ｎ、平均粒径：２１μｍ）、酸化チタン（化学式：ＴｉＯ２、純度：３Ｎ、平均粒径：３μｍ）の各粉末を、含有金属の比率がＢｉ：Ｔｉ＝６：４．５になるように秤量する。
次に、秤量した粉末とその３倍量（重量比）のジルコニアボール（直径５ｍｍ）とをポリ容器に入れ、ボールミル装置にて１８時間湿式混合して混合粉末を作製する。なお、この際の溶媒には、アルコールを用いた。
次に、得られた混合粉末を乾燥後、目開き５００μｍの篩にかけ、７００℃にて５時間、大気中で焼成し仮焼粉を作製する。
[Example 1]
Each powder of bismuth oxide (chemical formula: Bi 2 O 3 , purity: 3N, average particle size: 21 μm), titanium oxide (chemical formula: TiO 2 , purity: 3N, average particle size: 3 μm), and the ratio of contained metal is Bi : Weigh so that Ti = 6: 4.5.
Next, the weighed powder and 3 times its amount (weight ratio) zirconia balls (diameter 5 mm) are put in a plastic container and wet mixed in a ball mill apparatus for 18 hours to produce a mixed powder. In addition, alcohol was used for the solvent in this case.
Next, the obtained mixed powder is dried, passed through a sieve having an opening of 500 μm, and calcined in the atmosphere at 700 ° C. for 5 hours to prepare a calcined powder.
この仮焼粉を目開き５００μｍの篩にかける。酸化ビスマスと酸化チタンが全て反応しＢｉ４Ｔｉ３Ｏ１２となっているとし、全体の１ｍｏｌ％（硼素換算で０．４ａｔ％）となるように酸化硼素（化学式：Ｂ２Ｏ３、純度：３Ｎ、粒径：２５０μｍ以下）を添加する。さらに、その５倍量（重量比）のジルコニアボール（直径５ｍｍ）と共にポリ容器に入れ、ボールミル装置にて２４時間解砕し、解砕粉を得る。なお、この際の溶媒には、ヘキサンを用いた。
得られた解砕粉を乾燥後、目の開き５００μｍの篩にかけ、ジルコニアボールを除去する。その後、上記解砕粉を黒鉛モールドに充填し、８５０℃にて３時間、３５０ｋｇｆ／ｃｍ２の圧力で真空ホットプレスし、実施例１のスパッタリングターゲットを得た。
The calcined powder is passed through a sieve having an opening of 500 μm. Assuming that bismuth oxide and titanium oxide all react to form Bi 4 Ti 3 O 12 , boron oxide (chemical formula: B 2 O 3 , purity: 1 mol% (0.4 at% in terms of boron) as a whole) 3N, particle size: 250 μm or less). Further, the zirconia balls (5 mm in diameter) of 5 times the weight (diameter 5 mm) are put in a plastic container and crushed for 24 hours with a ball mill device to obtain crushed powder. In this case, hexane was used as the solvent.
The obtained crushed powder is dried and then passed through a sieve having an opening of 500 μm to remove zirconia balls. Thereafter, the pulverized powder was filled into a graphite mold, and vacuum hot-pressed at 850 ° C. for 3 hours at a pressure of 350 kgf / cm 2 to obtain the sputtering target of Example 1.
［実施例１〜５、比較例１］
酸化硼素の添加量を変更した以外は実施例１と同様にして、実施例１〜５、比較例１のスパッタリングターゲットを作製した。
［比較例２〜４］
酸化硼素に代えて、ＳｉＯ２、ＴｉＯ２、Ｎｂ２Ｏ５を添加した以外は実施例１と同様にして、比較例２〜４のスパッタリングターゲットを作製した。
[Examples 1 to 5, Comparative Example 1]
Sputtering targets of Examples 1 to 5 and Comparative Example 1 were produced in the same manner as in Example 1 except that the amount of boron oxide added was changed.
[Comparative Examples 2 to 4]
Sputtering targets of Comparative Examples 2 to 4 were produced in the same manner as in Example 1 except that SiO 2 , TiO 2 , and Nb 2 O 5 were added instead of boron oxide.
［評価］
上述の各実施例・比較例のスパッタリングターゲットについて、下記の条件で各種の評価を実施した。
[Evaluation]
Various evaluation was implemented on the following conditions about the sputtering target of each above-mentioned Example and comparative example.
［屈折率］
分光エリプソメトリー法にて、４０５ｎｍの波長に対する屈折率を測定した。
・分析装置：J.A. Woollam社製 多入射角回転補償子型高速分光エリプソメーター M-2000U
・測定範囲：２４５〜１０００ｎｍ
［熱伝導率］
下記条件のレーザーフラッシュ法により行った。
・分析装置：ＮＥＴＺＳＣＨ−ＧｅｒａｔｅｂａｕＧｍｂＨ製 Ｘｅフラッシュアナライザー
・試料サイズ：１０×１０×２ｔ ｍｍ
・測定温度：２５℃
・標準比較試料：ＳＵＳ３１０
・パルス幅：０．２ｍｓ
・チャージレベル：２７０Ｖ
（測定は同じ試料にて三回行い、平均値を求めた。）
[Refractive index]
The refractive index for a wavelength of 405 nm was measured by spectroscopic ellipsometry.
・ Analyzer: Multi-angle incidence rotation compensator type high-speed spectroscopic ellipsometer made by JA Woollam M-2000U
Measurement range: 245 to 1000 nm
[Thermal conductivity]
The laser flash method was performed under the following conditions.
・ Analyzer: Xe flash analyzer manufactured by NETZSCH-Geratebau GmbH ・ Sample size: 10 × 10 × 2 t mm
・ Measurement temperature: 25 ℃
Standard comparison sample: SUS310
・ Pulse width: 0.2 ms
・ Charge level: 270V
(Measurement was performed three times on the same sample, and the average value was obtained.)
［スパッタ評価］
直径１２５ｍｍに加工した実施例および比較例のスパッタリングターゲットを銅製のバッキングプレートにインジウムを用いて接合してスパッタ試験を行った。
このスパッタの際は、アルゴンガスを５０ｓｃｃｍと酸素ガス１．５ｓｃｃｍとを一定の流量で供給し、ガスの全圧を１Ｐａとし、高周波電源を用いて８００Ｗの電力を投入して、スパッタリングターゲットに割れが発生するまでの時間を計測した。
[Sputtering evaluation]
The sputtering targets of Examples and Comparative Examples processed to a diameter of 125 mm were joined to a copper backing plate using indium, and a sputtering test was performed.
In this sputtering, 50 sccm of argon gas and 1.5 sccm of oxygen gas are supplied at a constant flow rate, the total pressure of the gas is set to 1 Pa, power of 800 W is applied using a high frequency power source, and the sputtering target is cracked. The time until the occurrence of was measured.
一連の評価の結果を表１に、熱伝導率を測定した結果を図５に示す。また、実施例２のスパッタリングターゲットの断面をＥＰＭＡにて元素マッピングした画像を図１に、比較例２〜４のものを図２〜４に示す。 The results of a series of evaluations are shown in Table 1, and the results of measuring the thermal conductivity are shown in FIG. Moreover, the image which carried out the element mapping of the cross section of the sputtering target of Example 2 by EPMA is shown in FIG. 1, and the thing of Comparative Examples 2-4 is shown in FIGS.
＜屈折率＞
表１から、酸化硼素の添加量が９ｍｏｌ％（硼素換算で３．６ａｔ％）より多いと膜の屈折率が２．７未満となるため、青色レーザを用いた高記録容量の光記録媒体の記録層間に設ける透明な膜として不十分であることがわかる。
＜熱伝導率＞
表１および図５より、密度の値に因らず、酸化硼素を添加することで熱伝導率が向上した。これは、Ｔｉサイトに硼素が置換されることで形成されたキャリアであるホールが熱伝導の担い手となるためと考えられる。
<Refractive index>
From Table 1, since the refractive index of the film is less than 2.7 when the amount of boron oxide added is more than 9 mol% (3.6 at% in terms of boron), the optical recording medium having a high recording capacity using a blue laser is used. It can be seen that the transparent film provided between the recording layers is insufficient.
<Thermal conductivity>
From Table 1 and FIG. 5, the thermal conductivity was improved by adding boron oxide regardless of the density value. This is presumably because holes, which are carriers formed by substitution of boron at the Ti site, are responsible for heat conduction.
＜ＥＰＭＡ測定＞
図２〜４より、酸化珪素、酸化チタン、酸化ニオブをそれぞれ添加した比較例２〜４のスパッタリングターゲットでは、数μｍの大きさの添加した酸化物が観察された。一方、図１より、実施例２のスパッタリングターゲットは、非常に均一に硼素が分散若しくは拡散していることがわかる。このように硼素が非常に均一に分布することで、スパッタリングターゲットに加わる熱衝撃を緩和していると考えられる。
<EPMA measurement>
2 to 4, in the sputtering targets of Comparative Examples 2 to 4 to which silicon oxide, titanium oxide, and niobium oxide were added, oxides having a size of several μm were observed. On the other hand, FIG. 1 shows that boron is dispersed or diffused very uniformly in the sputtering target of Example 2. Thus, it is considered that the thermal shock applied to the sputtering target is alleviated by the very uniform distribution of boron.
これらの結果から、酸化硼素を添加した本実施例のスパッタリングターゲットは、割れが発生するまでの時間が長く、また割れが小さいため、その後も異常放電が多発することはなかった。 From these results, the sputtering target of this example to which boron oxide was added had a long time until cracking occurred and the cracking was small, so that abnormal discharge did not occur frequently thereafter.
なお、本発明の技術範囲は上記実施形態および上記実施例に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。
例えば、上記実施形態および上記実施例では、仮焼粉をホットプレスして焼結させているが、他の焼結方法としてＨＩＰ法（熱間等方加圧式焼結法）等を採用しても構わない。
The technical scope of the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention.
For example, in the above embodiment and the above examples, the calcined powder is hot-pressed and sintered. However, as another sintering method, the HIP method (hot isostatic pressing method) is adopted. It doesn't matter.
Claims (4)
熱伝導率が、１．４Ｗ／ｍｋ以上であることを特徴とするＢｉＴｉ系酸化物スパッタリングターゲット。 Comprising a metal oxide phase comprising Bi and Ti;
A BiTi-based oxide sputtering target having a thermal conductivity of 1.4 W / mk or more.
硼素を含有することを特徴とするＢｉＴｉ系酸化物スパッタリングターゲット。 In the BiTi-based oxide sputtering target according to claim 1,
A BiTi-based oxide sputtering target containing boron.
硼素の含有量が、０．４〜３．６ａｔ％であることを特徴とするＢｉＴｉ系酸化物スパッタリングターゲット。 In the BiTi-based oxide sputtering target according to claim 2,
A BiTi-based oxide sputtering target having a boron content of 0.4 to 3.6 at%.
Ｂｉの酸化物とＴｉの酸化物とを粉砕混合して混合粉末を作製する工程と、
該混合粉末を仮焼して仮焼粉とする工程と、
該仮焼粉に酸化硼素を１〜９ｍｏｌ％添加したものを解砕しながら混合して添加仮焼粉とする工程と、
該添加仮焼粉を真空または不活性ガス雰囲気中で圧力を加えながら加熱して焼結させる工程と、を有していることを特徴とするＢｉＴｉ系酸化物スパッタリングターゲットの製造方法。 A method for producing a BiTi-based oxide sputtering target according to any one of claims 1 to 3,
A step of pulverizing and mixing Bi oxide and Ti oxide to produce a mixed powder;
A step of calcining the mixed powder into a calcined powder;
A step of adding 1 to 9 mol% of boron oxide to the calcined powder and mixing it while crushing to obtain an added calcined powder;
And a step of heating and sintering the added calcined powder while applying pressure in a vacuum or an inert gas atmosphere, and a method for producing a BiTi-based oxide sputtering target.
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