JPH04280957A - Thin film and its production - Google Patents
Thin film and its productionInfo
- Publication number
- JPH04280957A JPH04280957A JP6785191A JP6785191A JPH04280957A JP H04280957 A JPH04280957 A JP H04280957A JP 6785191 A JP6785191 A JP 6785191A JP 6785191 A JP6785191 A JP 6785191A JP H04280957 A JPH04280957 A JP H04280957A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- film
- target
- value
- refractive index
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 229910004533 TaB2 Inorganic materials 0.000 claims abstract description 5
- 229910004217 TaSi2 Inorganic materials 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 23
- 238000005546 reactive sputtering Methods 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 abstract description 23
- 229910003468 tantalcarbide Inorganic materials 0.000 abstract description 9
- 229910004166 TaN Inorganic materials 0.000 abstract 2
- 239000010408 film Substances 0.000 description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 28
- 239000002253 acid Substances 0.000 description 18
- 239000003513 alkali Substances 0.000 description 18
- 230000003287 optical effect Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- 238000005299 abrasion Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 235000012239 silicon dioxide Nutrition 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000031700 light absorption Effects 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 238000010891 electric arc Methods 0.000 description 6
- 239000005329 float glass Substances 0.000 description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 230000002159 abnormal effect Effects 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 229910018106 Ni—C Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- SZMZREIADCOWQA-UHFFFAOYSA-N chromium cobalt nickel Chemical compound [Cr].[Co].[Ni] SZMZREIADCOWQA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000007651 thermal printing Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は機械的強度と化学的安定
性を兼ね備えた薄膜及びその薄膜の製造方法に関する。
さらに詳しくは、外気に触れるような厳しい環境下で使
用される薄膜被覆物品とりわけ機械的強度と化学的安定
性を兼ね備えていることが要求される薄膜被覆物品の保
護膜として好適な薄膜や、光学特性を基板に付与するの
に低屈折率層として用いるのに好適な薄膜とその製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin film having both mechanical strength and chemical stability, and a method for producing the thin film. More specifically, we will focus on thin films suitable as protective films for thin film coated products that are used in harsh environments where they are exposed to the outside air, especially those that require both mechanical strength and chemical stability, and optical The present invention relates to a thin film suitable for use as a low refractive index layer to impart properties to a substrate, and a method for manufacturing the same.
【０００２】0002
【従来の技術】基板に薄膜を被覆した製品としては、エ
レクトロニクス、特に情報処理の分野では種々の製品が
知られており、その一つに薄膜記録媒体がある。例えば
、ポリカーボネートのようなプラスチック、ガラス、ア
ルミニウムのような基板上に、ＣｏＮｉＣｒのような磁
気膜、ＴｂＦｅＣｏのような光磁気膜、レーザー読み取
り用のアルミニウム反射膜などを形成した媒体が挙げら
れる。また熱印字記録の分野では、主として薄膜発熱抵
抗体が形成されたサーマルヘッドとよばれる部品が広く
用いられている。2. Description of the Related Art Various products in which a substrate is coated with a thin film are known in the field of electronics, particularly information processing, and one of them is a thin film recording medium. Examples include media in which a magnetic film such as CoNiCr, a magneto-optical film such as TbFeCo, an aluminum reflective film for laser reading, etc. are formed on a substrate made of plastic such as polycarbonate, glass, or aluminum. Furthermore, in the field of thermal printing and recording, a component called a thermal head, in which a thin film heating resistor is mainly formed, is widely used.
【０００３】また、プラスチック材料の実用的な用途を
広げるために、表面にハードコートを施すということが
行われている。また、ガラスやプラスチックのような透
明基板上に薄膜を被覆して、種々の光学特性を付与した
多くの透明物品が知られている。可視光線の反射率を低
減させディスプレー等を見やすくするための反射防止膜
や、任意の波長の透過率や反射率を選択的に高めたり低
めたりしたエッジフィルター、バンドパスフィルターの
ような光学干渉フィルター、さらには高反射ミラーなど
が例示できる。これらの製品で必要とする光学特性を得
るために、ある特定の波長の光を強めあったり弱めあっ
たりするように、各層の膜の厚みと屈折率を調整して光
学干渉作用を利用することがおこなわれる。この場合、
基本的な特性は、その干渉作用を発現させるために用い
られる高い屈折率膜の材料と低い屈折率膜の材料の屈折
率の比によって決まり、その比が大きいほど得られる光
学特性は優れており、例えば選択された波長域での反射
率や透過率はより高くなる。従って、より高い屈折率の
材料とより低い屈折率の材料の組合せを選ぶことが基本
的に重要となる。上記製品の薄膜の製造に際しては、薄
膜の厚みを厳密に制御する必要があることから、真空蒸
着やスパッタリングのような真空成膜法で被覆される場
合が多い。[0003] Furthermore, in order to expand the practical uses of plastic materials, hard coating has been applied to the surface of the plastic materials. Furthermore, many transparent articles are known in which a transparent substrate such as glass or plastic is coated with a thin film to provide various optical properties. Optical interference filters such as anti-reflection coatings that reduce the reflectance of visible light to make displays etc. easier to see, edge filters that selectively increase or decrease the transmittance or reflectance of arbitrary wavelengths, and bandpass filters. , and further include a high reflection mirror. In order to obtain the optical properties required by these products, we utilize optical interference by adjusting the film thickness and refractive index of each layer to strengthen or weaken each other's light at a specific wavelength. is carried out. in this case,
The basic characteristics are determined by the ratio of the refractive index of the material of the high refractive index film and the material of the low refractive index film used to create the interference effect, and the larger the ratio, the better the optical properties obtained. For example, the reflectance and transmittance in the selected wavelength range become higher. Therefore, it is of fundamental importance to choose a combination of a material with a higher refractive index and a material with a lower refractive index. When manufacturing the thin film of the above-mentioned products, it is necessary to strictly control the thickness of the thin film, so coating is often performed using a vacuum film forming method such as vacuum evaporation or sputtering.
【０００４】0004
【発明が解決しようとする課題】従来の薄膜被覆物品の
最大の問題点は、直接外部環境に曝されるような使用環
境での、機械的化学的耐久性が不足していたことである
。とりわけ、真空中で成膜された被膜ではこの問題が深
刻であった。すなわち実用的見地から耐摩耗や耐スクラ
ッチなど機械的に強く、かつ、酸、アルカリの両方に対
して化学的に安定な薄膜は得られていなかった。すなわ
ち、酸化チタン、酸化ジルコニウム、酸化タンタルなど
は、比較的優れた化学的耐久性を示すが、機械的耐久性
、特に耐摩耗性の点で不十分である。逆に、酸化シリコ
ンは、優れた機械的耐久性を示すが、耐アルカリ性に極
めて劣る。このように、優れた化学的耐久性と機械的耐
久性をあわせもった薄膜は、特に真空成膜法で成膜され
る膜の中には実質上存在しないのが実状であり、このこ
とがこれら薄膜被覆物品の普及を著しく阻害する要因に
なっていた。The biggest problem with conventional thin-film coated articles is that they lack mechanical and chemical durability in use environments where they are directly exposed to the external environment. This problem is especially serious for films formed in a vacuum. That is, from a practical standpoint, a thin film that is mechanically strong with wear resistance and scratch resistance, and chemically stable against both acids and alkalis has not been obtained. That is, titanium oxide, zirconium oxide, tantalum oxide, and the like exhibit relatively excellent chemical durability, but are insufficient in mechanical durability, particularly wear resistance. Conversely, silicon oxide exhibits excellent mechanical durability but extremely poor alkali resistance. In this way, the reality is that thin films with both excellent chemical and mechanical durability do not exist, especially in films formed by vacuum film forming methods. This has become a factor that significantly inhibits the spread of these thin film coated articles.
【０００５】また、薄膜を基板に被覆して光学物品とす
るには、低屈折率の薄膜を得ることが重要であるが、真
空成膜法では得られる低屈折率材料が非常に限られてい
た。すなわち、真空蒸着法の場合は、フッ化マグネシウ
ム（ＭｇＦ２）を始めとする各種フッ化物や二酸化ケイ
素（ＳｉＯ２ ）が知られているが、スパッタリング法
の場合にはＳｉＯ２ だけに限られていた。[0005] Furthermore, in order to coat a substrate with a thin film and make it into an optical article, it is important to obtain a thin film with a low refractive index, but the low refractive index material that can be obtained using the vacuum deposition method is extremely limited. Ta. That is, in the case of the vacuum evaporation method, various fluorides including magnesium fluoride (MgF2) and silicon dioxide (SiO2) are known, but in the case of the sputtering method, it is limited to only SiO2.
【０００６】しかしながら、真空蒸着法では、装置の大
きさの制約から大きな面積の基体に成膜することは必ず
しも適当でなく、光学部品や眼鏡のような小さな面積の
基板にもっぱら応用されている。さらに大きな面積の基
板に対して精度よく厚みを制御して成膜する手段として
はスパッタリング法に限られている。その場合は、上述
したように低屈折率材料としては二酸化ケイ素だけしか
用いられないという問題がある。さらに、その二酸化ケ
イ素膜は金属シリコンをターゲットにして酸素を含む雰
囲気中で直流反応性スパッタリング法により成膜する場
合、時間の経過とともにシリコンターゲットの表面が極
めて絶縁性の高いＳｉＯ２ 膜で覆われるため、直流ス
パッタ放電を持続することが困難になるという重大な課
題が残されている。従って、成膜プロセスが極めて不安
定となるため、工業レベルはもちろん実験室レベルでも
、二酸化ケイ素膜を直流反応性スパッタリングにより形
成することは行われていない。つまり、現状では低屈折
率材料であるＳｉＯ２ 膜を比較的大きな面積の基板に
安定的に成膜しようとする場合ＳｉＯ２ からなるター
ゲット（例えば石英ガラス）を用いて、高周波スパッタ
リングによって行われるのが唯一の方法である。However, with the vacuum evaporation method, it is not necessarily appropriate to form a film on a large area substrate due to restrictions on the size of the apparatus, and the method is mainly applied to small area substrates such as optical parts and eyeglasses. Furthermore, sputtering is the only method that can be used to form a film on a large-area substrate with precise thickness control. In that case, as mentioned above, there is a problem in that only silicon dioxide can be used as the low refractive index material. Furthermore, when the silicon dioxide film is formed using a direct current reactive sputtering method in an oxygen-containing atmosphere using metallic silicon as a target, the surface of the silicon target becomes covered with an extremely highly insulating SiO2 film over time. However, a serious problem remains that it becomes difficult to sustain DC sputter discharge. Therefore, since the film formation process becomes extremely unstable, silicon dioxide films are not formed by direct current reactive sputtering not only at the industrial level but also at the laboratory level. In other words, currently, when attempting to stably form a SiO2 film, which is a low refractive index material, on a relatively large substrate, the only way to do so is by high-frequency sputtering using a target made of SiO2 (for example, quartz glass). This is the method.
【０００７】しかしながら、この高周波スパッタリング
法で大きな面積の基板にＳｉＯ２ 薄膜を成膜しようと
した場合、ターゲットの面積を大きくしなければならず
、大きなターゲットに効率的に高周波電力を投入する電
源がないという問題があった。さらには、成膜中に時間
の経過とともに装置の内壁に絶縁性のＳｉＯ２ 膜が形
成されることによって装置の電気インピーダンスが変化
し、高周波電力の投入のマッチングをとることが困難に
なるという問題が生じていたため、大きな面積の基板に
低屈折率であるＳｉＯ２ 膜を成膜するには、依然とし
て未解決の課題が数多く残されていた。However, when attempting to form a SiO2 thin film on a large-area substrate using this high-frequency sputtering method, the area of the target must be increased, and there is no power source that can efficiently apply high-frequency power to the large target. There was a problem. Furthermore, as time passes during film formation, an insulating SiO2 film is formed on the inner wall of the device, which changes the electrical impedance of the device, making it difficult to match the input of high-frequency power. Therefore, there were still many unresolved problems in forming a low refractive index SiO2 film on a large area substrate.
【０００８】本発明は上記の問題点を解決するためにな
されたものであって、薄膜被覆物品とりわけ大きな面積
、たとえば１ｍ×１ｍ以上の大きな面積を有する薄膜被
覆物品を製造するのにも適する機械的強度と化学的安定
性を兼ね備えた薄膜とその製造方法を提供するものであ
る。The present invention has been made to solve the above-mentioned problems, and provides a machine suitable for manufacturing thin-film coated articles, particularly thin-film coated articles having a large area, for example, 1 m x 1 m or more. The purpose of this invention is to provide a thin film that has both physical strength and chemical stability, and a method for manufacturing the same.
【０００９】[0009]
【課題を解決するための手段】本発明は、シリコン、タ
ンタル、炭素、窒素、酸素からなり、化学式ＳｉＴａｊ
Ｃｋ Ｎｍ Ｏｎ で表される組成を有する薄膜であ
って、前記ｊの値が０．２以上０．６以下であって、前
記ｋの値が０．３以上１．０以下であって、前記ｍの値
が０．１以上１．０以下であって、前記ｎの値が１．０
以上である薄膜である。[Means for Solving the Problems] The present invention consists of silicon, tantalum, carbon, nitrogen, and oxygen, and has the chemical formula SiTaj.
A thin film having a composition represented by CkNmOn, wherein the value of j is 0.2 or more and 0.6 or less, the value of k is 0.3 or more and 1.0 or less, The value of m is 0.1 or more and 1.0 or less, and the value of n is 1.0.
This is the thin film described above.
【００１０】本発明の薄膜がアルカリと酸の両方に対す
る化学的耐久性と耐摩耗性等の機械的耐久性とをあわせ
もった膜であるためには、ｊの値は０．２〜０．６の範
囲でなければならない。ｊの値が０．２より小さいと十
分な化学的耐久性を有する膜とならない。ｊの値が０．
６より大きいと機械的耐久性が低下する。また、ｋの値
が１．０以上、あるいはｍの値が１．０以上、あるいは
ｎの値が１．０以下であると、機械的耐久性と、特に耐
アルカリ性が低下してしまう。一方ｋの値が０．３以下
、あるいはｍの値が０．１以下、あるいはｎの値が１．
０以上である場合は、化学的耐久性、機械的耐久性とも
低下する。In order for the thin film of the present invention to have both chemical durability against both alkalis and acids and mechanical durability such as abrasion resistance, the value of j should be 0.2 to 0. Must be in the range of 6. If the value of j is less than 0.2, the film will not have sufficient chemical durability. The value of j is 0.
When it is larger than 6, mechanical durability decreases. Moreover, if the value of k is 1.0 or more, the value of m is 1.0 or more, or the value of n is 1.0 or less, mechanical durability and especially alkali resistance will deteriorate. On the other hand, the value of k is 0.3 or less, or the value of m is 0.1 or less, or the value of n is 1.
When it is 0 or more, both chemical durability and mechanical durability decrease.
【００１１】さらに本発明の薄膜を、実用的な機械的強
度と化学的安定性を有する上に、可視光線の領域で屈折
率が１．７以下で、かつ、実質的に光の吸収がない膜と
するためには、前記ｊの値を０．２以上０．５以下、前
記ｋの値を０．３以上０．８以下、前記ｍの値を０．２
以上１．０以下、前記ｎの値が１．５以上とするのが好
ましい。Furthermore, the thin film of the present invention has practical mechanical strength and chemical stability, has a refractive index of 1.7 or less in the visible light region, and has substantially no absorption of light. In order to form a film, the value of j should be 0.2 or more and 0.5 or less, the value of k should be 0.3 or more and 0.8 or less, and the value of m should be 0.2.
It is preferable that the value of n be 1.0 or more, and 1.5 or more.
【００１２】ｊの値が０．６より大きいと屈折率が２．
０より大きくなってしまい、また光吸収を生じやすくな
る。屈折率を１．７以下程度に小さくするには、ｊの値
は０．５以下であるのが望ましい。ｋの値とｍの値の下
限値は厳密には定めにくいが、ターゲットが少なくとも
５０容積％以上のＳｉＣを含み、直流反応性スパッタリ
ングを安定的に行うこと、そして得られる膜が光学薄膜
として実用性を発揮するのに十分な機械的・化学的耐久
性を有するためには、ｋの値は０．３以上、ｍの値は０
．２以上であることが好ましい。ｋとｍの値の上限値は
、屈折率を１．７以下程度にし、実質的にほとんど光吸
収をなくすためには、ｋの値を０．８以下、ｍの値を１
．０以下とすることが好ましい。ｎの値の下限値も同様
の理由から１．５以上とすることが望ましい。ｎの値の
上限値は反応性スパッタリングの雰囲気ガスを酸素１０
０％の雰囲気内でおこなっても、約３．０以下の値とな
る。[0012] When the value of j is larger than 0.6, the refractive index is 2.
It becomes larger than 0, and light absorption tends to occur. In order to reduce the refractive index to about 1.7 or less, the value of j is preferably 0.5 or less. Although it is difficult to strictly determine the lower limits of the values of k and m, it is important that the target contains at least 50% by volume of SiC, that DC reactive sputtering is performed stably, and that the resulting film is put to practical use as an optical thin film. In order to have sufficient mechanical and chemical durability to exhibit properties, the value of k should be 0.3 or more, and the value of m should be 0.
．． It is preferable that it is 2 or more. The upper limits of the values of k and m are such that the refractive index is about 1.7 or less, and in order to virtually eliminate light absorption, the value of k should be 0.8 or less, and the value of m should be 1.
．． It is preferable to set it to 0 or less. For the same reason, it is desirable that the lower limit of the value of n be 1.5 or more. The upper limit of the value of n is that the atmospheric gas for reactive sputtering is oxygen 10
Even when carried out in a 0% atmosphere, the value is approximately 3.0 or less.
【００１３】本発明の薄膜を薄膜被覆物品の最上層に被
覆して保護膜として用いるときは、前記物品の実用的な
化学的安定性および機械的耐久性を確保するためには、
１０ｎｍ以上、さらに好ましくは２０ｎｍ以上の厚みに
被覆するのがよい。一方１００ｎｍ以上に厚く被覆して
も、化学的・機械的耐久性がさらに向上するわけではな
く、被覆に時間がかかる上に、膜の剥離を生じることが
あるので好ましくない。本発明の薄膜を多層光学薄膜を
構成する低屈折率膜として用いるときは、必要とする光
学特性と光学干渉理論とから膜の構成が定められる。When the thin film of the present invention is used as a protective film by coating the top layer of a thin film-coated article, in order to ensure practical chemical stability and mechanical durability of the article,
It is preferable to coat with a thickness of 10 nm or more, more preferably 20 nm or more. On the other hand, even if the film is coated thickly to a thickness of 100 nm or more, the chemical and mechanical durability will not be further improved, the coating will take time, and the film may peel off, which is not preferable. When the thin film of the present invention is used as a low refractive index film constituting a multilayer optical thin film, the structure of the film is determined based on required optical properties and optical interference theory.
【００１４】本発明の第２は、ＳｉＣ（炭化ケイ素）と
ＴａＣ（炭化タンタル）、ＴａＮ（窒化タンタル）、Ｔ
ａＢ２ （硼化タンタル）、ＴａＳｉ２ （珪化タンタ
ル）、ＴａＨ２ （水素化タンタル）の群から選ばれた
少なくとも一種以上のＴａ化合物とを主成分とした焼結
体からなるターゲットを用いて、少なくとも酸素と窒素
とを含む減圧された雰囲気内でおこなう直流反応性スパ
ッタリング法により、基体の上に化学式ＳｉＴａｊ Ｃ
ｋ Ｎｍ Ｏｎ で表される組成を有する薄膜を製造す
る方法である。The second aspect of the present invention is that SiC (silicon carbide), TaC (tantalum carbide), TaN (tantalum nitride), T
At least oxygen and The chemical formula SiTaj C was deposited on the substrate by direct current reactive sputtering in a reduced pressure atmosphere containing nitrogen.
This is a method for manufacturing a thin film having a composition expressed by k Nm On.
【００１５】ターゲット中のＴａ化合物の混合割合は、
得られる膜の化学的耐久性と機械的耐久性の両方が十分
に高くなるように、また少なくとも酸素と窒素とを含む
減圧された雰囲気中で、安定した反応性スパッタリング
が可能となるように定められる。そのためにターゲット
中のＴａＣ、ＴａＮ、ＴａＢ２ 、ＴａＳｉ２ 、Ｔａ
Ｈ２ の群から選ばれた少なくとも一種以上の含有量を
１０〜５０容積％とすることが好ましい。これにより前
記化学式中のｊの値は、０．２以上０．６以下の範囲に
なり、優れた化学的・機械的耐久性を有する膜となる。The mixing ratio of Ta compounds in the target is:
The method is designed so that both the chemical durability and the mechanical durability of the resulting film are sufficiently high, and that stable reactive sputtering is possible in a reduced pressure atmosphere containing at least oxygen and nitrogen. It will be done. Therefore, TaC, TaN, TaB2, TaSi2, Ta in the target
The content of at least one selected from the group H2 is preferably 10 to 50% by volume. As a result, the value of j in the chemical formula falls within the range of 0.2 or more and 0.6 or less, resulting in a film having excellent chemical and mechanical durability.
【００１６】ターゲット中に混合させるＴａ化合物の混
合割合が、１０容積％以下であると反応性スパッタリン
グが極めて不安定になるので好ましくない。ターゲット
中でＴａ化合物が連続的な構造となり、電気抵抗を低下
させ成膜プロセスを安定化させるためには、Ｔａ化合物
の混合割合は２５容積％以上であることがさらに好まし
い。一方５０容積％より多いと、得られる薄膜の屈折率
が高くなり、また光吸収が生じやすくなるので好ましく
ない。If the mixing ratio of the Ta compound mixed into the target is less than 10% by volume, reactive sputtering becomes extremely unstable, which is not preferable. In order for the Ta compound to form a continuous structure in the target, thereby lowering the electrical resistance and stabilizing the film forming process, the mixing ratio of the Ta compound is more preferably 25% by volume or more. On the other hand, if it is more than 50% by volume, the refractive index of the obtained thin film becomes high and light absorption tends to occur, which is not preferable.
【００１７】また、反応性スパッタリングを行う際の雰
囲気のガス組成を変えることによって、本発明の薄膜の
組成を調整することができる。少なくとも酸素と窒素と
を含む雰囲気で反応性スパッタリングを行う場合には、
アルゴンやネオンのような不活性ガスの量が多すぎるの
は好ましくなく、窒素の量が少なくとも０．２Ｐａ以上
の分圧を有し、かつ、全圧の４０％以上を占めるように
雰囲気のガス組成を調整するのが好ましい。これにより
得られる薄膜の光吸収が少なくなり、直流反応性スパッ
タリングの安定性も増す。さらに重要なのは雰囲気中の
酸素ガスの割合であって、屈折率が１．７程度以下に小
さくかつ光吸収がなく、十分な機械的強度と化学的耐久
性をもった膜とするには、酸素の分圧は全圧の１０％以
上とすることが好ましい。Furthermore, the composition of the thin film of the present invention can be adjusted by changing the gas composition of the atmosphere during reactive sputtering. When performing reactive sputtering in an atmosphere containing at least oxygen and nitrogen,
It is undesirable to have too much of an inert gas such as argon or neon, and the atmosphere should be made so that the amount of nitrogen has a partial pressure of at least 0.2 Pa or more and accounts for 40% or more of the total pressure. Preferably, the composition is adjusted. This reduces the light absorption of the resulting thin film and increases the stability of DC reactive sputtering. What is even more important is the proportion of oxygen gas in the atmosphere, and in order to obtain a film with a small refractive index of about 1.7 or less, no light absorption, and sufficient mechanical strength and chemical durability, oxygen gas is required. It is preferable that the partial pressure is 10% or more of the total pressure.
【００１８】本発明の薄膜を含む薄膜被覆物品を製造す
るに際しては、本発明の薄膜以外の膜の成膜法は特に限
定されるものではなく、真空蒸着法、イオンプレーティ
ング法、スパッタリング法などが用いられる。必要とす
る薄膜を連続して効率よく成する上からは、スパッタリ
ング法が好ましい。When producing a thin film-coated article containing the thin film of the present invention, the method of forming a film other than the thin film of the present invention is not particularly limited, and may include vacuum evaporation, ion plating, sputtering, etc. is used. The sputtering method is preferable from the viewpoint of continuously and efficiently forming the required thin film.
【００１９】[0019]
【作用】本発明のＳｉ−Ｔａ−Ｃ−Ｎ−Ｏ系の薄膜中の
炭素、窒素、酸素は、シリコン、タンタルと結合して化
合物を形成し、またそれらの膜中の含有量が限定される
ことにより、薄膜に大きな機械的強度と優れた化学安定
性を付与する。さらに薄膜を可視光線の波長域で透明で
かつ低屈折率にする。[Operation] Carbon, nitrogen, and oxygen in the Si-Ta-C-N-O thin film of the present invention combine with silicon and tantalum to form a compound, and their contents in the film are limited. This gives the thin film great mechanical strength and excellent chemical stability. Furthermore, the thin film is made transparent in the visible light wavelength range and has a low refractive index.
【００２０】本発明の薄膜を直流反応性スパッタリング
により製造するに際しては、ターゲット中に混合された
Ｔａ化合物は、ターゲットの電気抵抗を低下させ、また
ターゲット表面上に形成される被膜やスパッタリング装
置の内壁に形成される被膜の電気抵抗を低下させる。こ
れにより成膜プロセスの安定性が向上する。When producing the thin film of the present invention by DC reactive sputtering, the Ta compound mixed in the target lowers the electrical resistance of the target and also reduces the coating formed on the target surface and the inner wall of the sputtering device. lowers the electrical resistance of the coating formed on the This improves the stability of the film forming process.
【００２１】[0021]
【実施例】以下に実施例に基づき、本発明をさらに詳細
に説明する。図１（ａ）、（ｂ）は、本発明の薄膜を用
いた薄膜被覆物品の一実施例の一部断面図である。図１
（ａ）では、ガラス基板３の上に磁気記録膜２が被覆さ
れ、磁気記録膜２の上に本発明の薄膜１が保護膜として
被覆されている。本発明の薄膜を用いた薄膜被覆物品と
しては、基板１としてプラスチックス、アルミニウムな
どの金属板、セラミックス板を用いることができ、磁気
記録膜の他に、透明誘電体膜、電気抵抗膜無反射多層膜
などを用いることが出来る。図１（ｂ）は本発明の薄膜
を低屈折率層、本発明の膜よりも高い屈折率を有する膜
を高屈折率層とする光学多層膜を被覆した物品の一実施
例であり、本発明の薄膜１と高屈折率膜４が交互に被覆
されている。EXAMPLES The present invention will be explained in more detail below based on examples. FIGS. 1(a) and 1(b) are partial cross-sectional views of an example of a thin film-coated article using the thin film of the present invention. Figure 1
In (a), a glass substrate 3 is coated with a magnetic recording film 2, and the magnetic recording film 2 is coated with the thin film 1 of the present invention as a protective film. As a thin film-coated article using the thin film of the present invention, a plastic plate, a metal plate such as aluminum, or a ceramic plate can be used as the substrate 1, and in addition to a magnetic recording film, a transparent dielectric film, an electrically resistive film, a non-reflective film, etc. A multilayer film or the like can be used. FIG. 1(b) is an example of an article coated with an optical multilayer film in which the thin film of the present invention is used as a low refractive index layer, and the film having a higher refractive index than the film of the present invention is used as a high refractive index layer. The thin film 1 of the invention and the high refractive index film 4 are alternately coated.
【００２２】実施例１
スパッタリングターゲットとして、６５容積％（３２重
量％）のＳｉＣと３０容積％（６６重量％）のＴａＣと
焼結助剤（残分）とからなるものを用いた。清浄にされ
た２．１ｍｍ厚のフロートガラスをスパッタ装置に入れ
、上記ターゲットを設置した真空槽を約５×１０−４Ｐ
ａまで排気し、その後窒素と酸素の合計流量で１００ｓ
ｃｃｍのガスをスパッタ装置に導入して、真空槽内の圧
力を０．４Ｐａに調節した。そして、直流電源からター
ゲットに電力を投入して放電を開始し、４Ａの電流値で
約７５ｎｍの厚みの被膜をガラス基板上に成膜した。真
空槽に導入する窒素と酸素のガス流量の比を変えて、同
様の手順を繰り返し、５種類のサンプル１〜５を作成し
た。得られたサンプル１〜５の薄膜の屈折率と化学組成
を表１Example 1 A sputtering target consisting of 65% by volume (32% by weight) of SiC, 30% by volume (66% by weight) of TaC, and a sintering aid (residue) was used. A cleaned 2.1 mm thick float glass was placed in a sputtering device, and the vacuum chamber in which the target was installed was heated to approximately 5×10-4P.
Evacuate to a, then 100 s at the total flow rate of nitrogen and oxygen.
ccm of gas was introduced into the sputtering apparatus, and the pressure in the vacuum chamber was adjusted to 0.4 Pa. Then, electric power was applied to the target from a DC power source to start discharging, and a film with a thickness of about 75 nm was formed on the glass substrate at a current value of 4 A. Five types of samples 1 to 5 were created by repeating the same procedure by changing the ratio of the gas flow rates of nitrogen and oxygen introduced into the vacuum chamber. Table 1 shows the refractive index and chemical composition of the obtained thin films of Samples 1 to 5.
【００２３】[0023]
【表１】[Table 1]
【００２４】にまとめて示す。屈折率はエリプソメータ
ーを用いて、６３２．８ｎｍの波長での屈折率ｎと消衰
係数ｋを測定した。化学組成はＥＳＣＡを用いて測定し
た。
実施例２
ターゲット中に含有するＴａ化合物の種類と含有割合を
変えて成膜し、成膜時の直流反応性スパッタリングの安
定性を観察すると共に、得られた薄膜の屈折率と化学組
成を分析した結果を、[0024] The refractive index was determined by measuring the refractive index n and extinction coefficient k at a wavelength of 632.8 nm using an ellipsometer. Chemical composition was measured using ESCA. Example 2 Films were formed by changing the type and content ratio of Ta compounds contained in the target, and the stability of DC reactive sputtering during film formation was observed, and the refractive index and chemical composition of the obtained thin films were analyzed. The result is
【００２５】[0025]
【表２】[Table 2]
【００２６】表２に示す。サンプル６〜１１の作成は、
それぞれのターゲットをスパッタ装置に設置し、清浄に
された２．１ｍｍ厚のフロートガラス板を真空槽にセッ
トした後、約５×１０−４Ｐａまで排気し、その後、窒
素７０ｓｃｃｍと酸素３０ｓｃｃｍの混合ガスをスパッ
タ装置に導入して、真空槽内の圧力を０．４Ｐａに調節
した。そして、直流電源からターゲットに電力を投入し
スパッタ放電を開始し、４Ａの電流値で約７５ｎｍの膜
厚の被膜をガラス基板上に形成するようにした。[0026] It is shown in Table 2. To create samples 6 to 11,
After installing each target in a sputtering device and setting a cleaned 2.1 mm thick float glass plate in a vacuum chamber, it was evacuated to about 5 x 10-4 Pa, and then a mixed gas of 70 sccm of nitrogen and 30 sccm of oxygen was applied. was introduced into the sputtering apparatus, and the pressure in the vacuum chamber was adjusted to 0.4 Pa. Then, power was applied to the target from a DC power source to start sputtering discharge, and a film with a thickness of about 75 nm was formed on the glass substrate at a current value of 4 A.
【００２７】サンプル６の作成において、同じ条件で約
６時間継続してスパッタリングを行ったが、異常アーク
放電の発生によってプロセスが不安定になるということ
はなかった。スパッタ放電開始直後の放電電圧は約５６
０Ｖであり、６時間経過後の放電電圧は約５８０Ｖであ
り、電圧上昇は約４％程度と極めて安定していた。In preparing Sample 6, sputtering was continued for about 6 hours under the same conditions, but the process did not become unstable due to the occurrence of abnormal arc discharge. The discharge voltage immediately after the start of sputter discharge is approximately 56
0V, and the discharge voltage after 6 hours was about 580V, and the voltage increase was about 4%, which was extremely stable.
【００２８】サンプル７の作成に用いたターゲットは、
サンプル６のターゲットに比べてＴａＣの含有量が１０
容積％少ないため、ターゲットの導電性がやや低い。そ
のため、スパッタ放電がやや不安定になる現象が観察さ
れた。すなわち、放電開始後約１時間までは、安定に連
続放電していたが、その後異常アーク放電が発生するよ
うになり、約３時間後には、１時間当り数回は電源が停
止し、再放電させる必要があった。しかし、同じターゲ
ットを用いても、反応性スパッタの際の雰囲気中の酸素
の流量比が３０％以下の場合には、３時間以上の連続放
電でもプロセスは安定していた。サンプル８は、ターゲ
ット中のＴａ化合物の含有量は３０容積％であるが、Ｔ
ａＣからＴａＮに変更して行った実施例であって、放電
安定性の点では、ＴａＣを用いた場合よりもやや悪くな
る傾向が認められ、放電開始３時間後くらいから異常ア
ーク放電が散発的に発生するようになった。[0028] The target used to create sample 7 was:
Compared to the target of sample 6, the TaC content is 10
Since the volume % is small, the conductivity of the target is slightly low. Therefore, a phenomenon was observed in which sputter discharge became somewhat unstable. In other words, the discharge was stable and continuous for about an hour after the discharge started, but then abnormal arc discharge started to occur, and after about 3 hours, the power supply stopped several times per hour and the discharge started again. I needed to do it. However, even if the same target was used, if the flow rate ratio of oxygen in the atmosphere during reactive sputtering was 30% or less, the process was stable even with continuous discharge for 3 hours or more. In sample 8, the content of Ta compound in the target is 30% by volume, but T
This is an example in which TaN was used instead of aC, and in terms of discharge stability, it was observed that the discharge stability tended to be slightly worse than when TaC was used, and abnormal arc discharge occurred sporadically from about 3 hours after the start of discharge. started to occur.
【００２９】サンプル９〜１１は、ターゲット中のＴａ
化合物の量が４０〜５０容積％と多い例である。サンプ
ル９の作成においては、サンプル６に比べて、放電安定
性に向上はみられなかった。また、屈折率がやや高くな
りまた若干の光吸収が生じていた。サンプル１０，１１
においては、成膜中の放電安定性はサンプル６と同程度
に優れており、異常なアーク放電が発生するということ
は少なくとも６時間以内には起こらなかった。但し、両
方のサンプルとも薄膜の屈折率が１．８以上にまで高く
なってしまい光吸収が認められた。Samples 9 to 11 contain Ta in the target.
This is an example in which the amount of the compound is as large as 40 to 50% by volume. In the preparation of Sample 9, no improvement in discharge stability was observed compared to Sample 6. In addition, the refractive index became slightly high and some light absorption occurred. Samples 10 and 11
The discharge stability during film formation was as good as Sample 6, and abnormal arc discharge did not occur within at least 6 hours. However, in both samples, the refractive index of the thin film increased to 1.8 or higher, and light absorption was observed.
【００３０】実施例３
３つのカソードが設置できるマグネトロンスパッタ装置
の第１のカソードに金属クロムを、第２のカソードに金
属チタンを、第３のカソードに６５容積％（３２重量％
）のＳｉＣと３０容積％（６６重量％）のＴａＣと焼結
助剤（残分）とからなるターゲットをそれぞれセットと
した。清浄にされた３ｍｍ厚のフロートガラス板を真空
装置内に入れ、真空ポンプで約５×１０−４Ｐａまで排
気した。次いで、１００ｓｃｃｍの流量のアルゴン（Ａ
ｒ）ガスを真空槽に導入し０．４Ｐａの圧力に調整した
のち、第１のカソードに電力を投入してスパッタ放電を
開始し５Ａの電流値に維持した。第１のカソードの上を
所定の速度でガラス基板を通過させることにより、約６
０ｎｍのクロム膜を形成した。再び約５×１０−４Ｐａ
まで排気した後、Ａｒガスを５０ｓｃｃｍ、酸素ガスを
５０ｓｃｃｍの流量で真空槽内に導入し圧力を０．４Ｐ
ａに調整した。第２のカソードに電力を投入しスパッタ
放電を開始し５Ａの電流値に維持した。そして、第２の
カソード上を所定の速度でガラス基板を通過させること
により、クロム膜の上に７０ｎｍの酸化チタン膜を形成
した。再び約５×１０−４Ｐａまで排気した後、窒素ガ
スを７０ｓｃｃｍ、酸素ガスを３０ｓｃｃｍの流量で真
空槽内に導入し圧力を０．４Ｐａに調整した。第３のカ
ソードに電力を投入しスパッタ放電を開始し３Ａの電流
値に維持した。そして、第３のカソードの上を所定の速
度でガラス基板を通過させることにより、酸化チタン膜
の上に約１５ｎｍの厚みのＳｉ、Ｔａ、Ｃ、Ｎ、Ｏから
なる薄膜を形成した。Example 3 In a magnetron sputtering apparatus capable of installing three cathodes, the first cathode was filled with metallic chromium, the second cathode was filled with metallic titanium, and the third cathode was filled with 65% by volume (32% by weight).
) of SiC, 30% by volume (66% by weight) of TaC, and a sintering aid (residue) were each set. A cleaned float glass plate with a thickness of 3 mm was placed in a vacuum device, and the pressure was evacuated to about 5×10 −4 Pa using a vacuum pump. Then, argon (A
r) After introducing gas into the vacuum chamber and adjusting the pressure to 0.4 Pa, power was applied to the first cathode to start sputter discharge and maintain the current value at 5 A. By passing the glass substrate over the first cathode at a predetermined speed, about 6
A chromium film with a thickness of 0 nm was formed. Again about 5×10-4Pa
After evacuating the chamber to 50 sccm, Ar gas was introduced into the vacuum chamber at a flow rate of 50 sccm, and oxygen gas was introduced at a flow rate of 50 sccm to a pressure of 0.4 P.
Adjusted to a. Power was applied to the second cathode to start sputtering discharge, and the current value was maintained at 5A. A 70 nm titanium oxide film was then formed on the chromium film by passing the glass substrate over the second cathode at a predetermined speed. After evacuating to about 5×10 −4 Pa again, nitrogen gas was introduced into the vacuum chamber at a flow rate of 70 sccm and oxygen gas was introduced at a flow rate of 30 sccm to adjust the pressure to 0.4 Pa. Power was applied to the third cathode to start sputtering discharge, and the current value was maintained at 3A. Then, by passing the glass substrate over the third cathode at a predetermined speed, a thin film made of Si, Ta, C, N, and O with a thickness of about 15 nm was formed on the titanium oxide film.
【００３１】このようにして得られたサンプル１２は、
波長４５０ｎｍでの反射率が約５５％で、青色の反射色
を示す自動車用の車外用ミラーとして好適な光学特性を
示していた。このサンプルの耐摩耗性、耐酸性、耐アル
カリ性を評価した。耐摩耗性は市販のテーバー摩耗試験
機を用いて、Ｎｏ．ＣＳ１０Ｆの２つの摩耗輪に各５０
０ｇの荷重をかけ６０ｒｐｍの回転数で５００回転の摩
耗を被膜に加えた後のヘイズ率で評価した。ヘイズ率は
２．１％と低く優れた耐摩耗性を示した。耐酸性と耐ア
ルカリ性はそれぞれ０．１ＮのＨ２ ＳＯ４ 中、Ｎａ
ＯＨ中に６時間浸漬した後の透過率の変化とヘイズ率を
測定することにより評価した。耐酸性テストでは、透過
率変化が２．５％、ヘイズ率も０．８％と低く優れた耐
酸性を示した。耐アルカリ性テストでも透過率変化が１
．８％、ヘイズ率も０．６％と低く優れた耐アルカリ性
を示した。最上層の膜の組成をＥＳＣＡにより測定した
ところ、ＳｉＴａ０．４５Ｃ０．６５Ｎ０．４１Ｏ２．
５５という原子組成比で表されることがわかった。Sample 12 thus obtained is:
The reflectance at a wavelength of 450 nm was approximately 55%, and it exhibited optical properties suitable for use as an exterior mirror for automobiles, exhibiting a blue reflected color. The abrasion resistance, acid resistance, and alkali resistance of this sample were evaluated. Abrasion resistance was measured using a commercially available Taber abrasion tester. 50 each for the two wear wheels of CS10F
The haze rate after applying a load of 0 g and abrasion of 500 rotations at a rotation speed of 60 rpm to the coating was evaluated. The haze rate was as low as 2.1%, indicating excellent wear resistance. Acid resistance and alkali resistance are measured in 0.1N H2SO4 and Na
Evaluation was made by measuring the change in transmittance and haze rate after being immersed in OH for 6 hours. In the acid resistance test, the transmittance change was as low as 2.5% and the haze rate was as low as 0.8%, indicating excellent acid resistance. Even in the alkali resistance test, the transmittance change was 1
．． 8%, and the haze rate was as low as 0.6%, showing excellent alkali resistance. When the composition of the top layer film was measured by ESCA, it was found to be SiTa0.45C0.65N0.41O2.
It was found that it is expressed by an atomic composition ratio of 55.
【００３２】実施例４
スパッタリングターゲットとして、実施例３で用いた第
３のターゲットと同じものを用いた。基板として、１０
ｃｍ×１０ｃｍ×６ｍｍ厚の有機プラスチック（ＣＲ３
９）を市販のオルガノシロキサン塗布液で浸漬塗布し、
空気中で硬化させさらに８５℃のオーブンで熱的硬化さ
せたハードコート層を有するものを用いた。この基板を
清浄にした後、スパッタ装置に入れ、上記ターゲットを
設置した真空槽を約５×１０−４Ｐａまで排気し、その
後窒素ガスを７０ｓｃｃｍ、酸素ガスを３０ｓｃｃｍの
流量でスパッタ装置に導入して、真空槽内の圧力を０．
４Ｐａに調節した。そして、直流電源からターゲットに
電力を投入して２Ａの電流で放電を維持し、このターゲ
ット上を繰り返し、基板を通過させることにより約８０
ｎｍの厚みの被膜を基板上に形成した。Example 4 The same sputtering target as the third target used in Example 3 was used. As a substrate, 10
cm x 10 cm x 6 mm thick organic plastic (CR3
9) with a commercially available organosiloxane coating solution,
A hard coat layer was used which was cured in air and then thermally cured in an oven at 85°C. After cleaning this substrate, it was placed in a sputtering device, and the vacuum chamber in which the target was installed was evacuated to about 5 × 10-4 Pa, and then nitrogen gas was introduced into the sputtering device at a flow rate of 70 sccm and oxygen gas was introduced into the sputtering device at a flow rate of 30 sccm. , the pressure inside the vacuum chamber is set to 0.
It was adjusted to 4Pa. Then, power is applied to the target from a DC power supply to maintain a discharge with a current of 2A, and the target is repeatedly passed over and passed through the substrate for about 80 minutes.
A film with a thickness of nm was formed on the substrate.
【００３３】得られたサンプル１３の耐摩耗性、耐酸性
、耐アルカリ性を評価した。耐摩耗性は市販のテーパー
摩耗試験機を用いて、Ｎｏ．ＣＳ１０Ｆの２つの摩耗輪
に各２５０ｇの荷重をかけ、６０ｒｐｍの回転数で５０
０回転の摩耗を被膜に加えた後のヘイズ率で評価した。
ヘイズ率は０．５％という優れた値を示した。加えて、
＃００００のスチールウールで約５ｋｇの荷重で被膜面
をこすり、傷のつき具合いを判定したところ、わずかに
傷あとが認められる程度であった。耐酸性と耐アルカリ
性はそれぞれ０．１ＮのＨ２ ＳＯ４ 中、ＮａＯＨ中
に２４時間浸漬した後のヘイズ率を測定することにより
評価した。耐酸性テストではヘイズ率は０．３％、耐ア
ルカリ性テストではヘイズ率は０．５％という優れた化
学的耐久性を示した。The abrasion resistance, acid resistance, and alkali resistance of the sample 13 obtained were evaluated. Abrasion resistance was measured using a commercially available taper abrasion tester. A load of 250 g is applied to each of the two wear wheels of CS10F, and the rotation speed is 50 rpm at 60 rpm.
The haze rate after applying 0-rotation abrasion to the coating was evaluated. The haze rate showed an excellent value of 0.5%. In addition,
When the coated surface was rubbed with #0000 steel wool under a load of approximately 5 kg and the extent of scratches was determined, only slight scratches were observed. Acid resistance and alkali resistance were evaluated by measuring the haze rate after immersion in 0.1N H2SO4 and NaOH for 24 hours, respectively. It showed excellent chemical durability, with a haze rate of 0.3% in the acid resistance test and a haze rate of 0.5% in the alkali resistance test.
【００３４】実施例５
実施例３、４で用いたのと同様のスパッタ装置の第１の
カソードに金属磁性層として用いられるコバルト−ニッ
ケル−クロム合金ターゲットを、第２のカソードにＳｉ
Ｃ７０容積％とＴａＮ３０容積％を微量の焼結助剤で焼
結させたものをターゲットとして設置した。実施例３と
同様の手順を用いて、２ｍｍ厚フロートガラス基板上に
約５０ｎｍの厚さのＣｏ−Ｎｉ−Ｃｒ合金からなる第１
層と、約３０ｎｍの厚さのＳｉ−Ｔａ−Ｃ−Ｎ−Ｏから
なる第２層を形成した。Example 5 A cobalt-nickel-chromium alloy target used as a metal magnetic layer was placed on the first cathode of a sputtering apparatus similar to that used in Examples 3 and 4, and a Si was placed on the second cathode.
A target made by sintering 70% by volume of C and 30% by volume of TaN with a small amount of sintering aid was set up. Using the same procedure as in Example 3, a first layer of Co-Ni-Cr alloy with a thickness of about 50 nm was deposited on a 2 mm thick float glass substrate.
A second layer of Si-Ta-C-N-O with a thickness of about 30 nm was formed.
【００３５】実施例３と同じ方法で耐摩耗性、耐酸性、
耐アルカリ性を評価したところ、ヘイズ率は１．８％と
低く優れた耐摩耗性を示した。耐酸性テストでは、透過
率変化が２．２％、ヘイズ率も０．７％と低く優れた耐
酸性を示した。耐アルカリ性テストでも透過率変化が２
．０％、ヘイズ率も０．５％と低く優れた耐アルカリ性
を示した。最上層の膜の組成をＥＳＣＡにより測定した
ところ、ＳｉＴａ０．４４Ｃ０．３５Ｎ０．６０Ｏ２．
２８という原子組成比で表されることがわかった。Abrasion resistance, acid resistance,
When the alkali resistance was evaluated, the haze rate was as low as 1.8%, indicating excellent wear resistance. In the acid resistance test, the transmittance change was as low as 2.2% and the haze rate was as low as 0.7%, indicating excellent acid resistance. Even in the alkali resistance test, the transmittance change was 2.
．． 0%, and the haze rate was as low as 0.5%, showing excellent alkali resistance. The composition of the top layer film was measured by ESCA and was found to be SiTa0.44C0.35N0.60O2.
It was found that it is expressed by an atomic composition ratio of 28.
【００３６】比較例１
実施例１のサンプル１〜５を成膜したときとは異なるガ
ス流量を用いて、同様の手順でガラス基板上に被膜を成
膜し、比較サンプル１および２を作成した。得られた比
較サンプル１および２の屈折率と化学組成を表１に示す
。Comparative Example 1 Comparative Samples 1 and 2 were formed by forming a film on a glass substrate in the same manner as in Example 1, using a different gas flow rate from that used for forming Samples 1 to 5. . Table 1 shows the refractive index and chemical composition of Comparative Samples 1 and 2 obtained.
【００３７】比較例２
リンをドープすることによって比抵抗を０．００１２Ω
・ｃｍに低下させたシリコンターゲットを用いて、実施
例１〜１１と同じ装置で、直流反応性スパッタリングに
よるＳｉＯ２ 膜の成膜を行った。清浄にされた２．１
ｍｍ厚のフロートガラス板を真空槽にセットした後、約
５×１０−４Ｐａまで排気し、その後、窒素９０ｓｃｃ
ｍと酸素１０ｓｃｃｍの混合ガスをスパッタ装置に導入
して、真空槽内の圧力を０．４Ｐａに調節した。そして
、直流電源からターゲットに電力を投入してスパッタ放
電を開始し、１Ａの電流値にセットした。約１０分経過
後からすでに異常アーク放電が発生し始め、約２０分後
にはスパッタ放電を維持することが困難になり、実験を
中止した。Comparative Example 2 The specific resistance was reduced to 0.0012Ω by doping with phosphorus.
A SiO2 film was formed by direct current reactive sputtering using the same apparatus as in Examples 1 to 11 using a silicon target lowered to cm. Cleaned 2.1
After setting a mm-thick float glass plate in a vacuum chamber, it was evacuated to about 5 x 10-4 Pa, and then nitrogen was heated at 90 scc.
A mixed gas of m and oxygen at 10 sccm was introduced into the sputtering apparatus, and the pressure in the vacuum chamber was adjusted to 0.4 Pa. Then, power was applied to the target from a DC power supply to start sputtering discharge, and the current value was set to 1A. After about 10 minutes, abnormal arc discharge began to occur, and after about 20 minutes, it became difficult to maintain sputter discharge, and the experiment was discontinued.
【００３８】比較例３
市販されている、反応焼結法により製造されたＳｉＣス
パッタリングターゲットを用いて、比較例２と同一の条
件で反応性スパッタリングを行ったところ、放電開始後
３０分くらいから異常なアーク放電が発生し始めた。放
電電圧は初期には約４４０Ｖであったのに対して、３０
分後には約５５０Ｖ程度まで上昇していた。そして、約
４５分後には放電を維持し膜を形成することが困難にな
り実験を中止した。Comparative Example 3 When reactive sputtering was performed under the same conditions as Comparative Example 2 using a commercially available SiC sputtering target manufactured by the reactive sintering method, an abnormality occurred about 30 minutes after the start of discharge. Arc discharge started to occur. The discharge voltage was about 440V at the beginning, but it increased to 30V.
Minutes later, the voltage had risen to about 550V. After about 45 minutes, it became difficult to maintain the discharge and form a film, so the experiment was stopped.
【００３９】比較例４
実施例３と比較するサンプルとして、本発明の薄膜を最
上層に保護膜として被覆しない薄膜被覆物品を作成した
。実施例３に記述したのと同様の方法で、３ｍｍ厚フロ
ートガラス基板上に、約６０ｎｍの厚みのクロム膜と、
約７５ｎｍの厚みの酸化チタン膜を形成し比較サンプル
４を得た。この比較サンプル４は実施例３と同様の光学
特性を有した青色反射ミラーであった。実施例３で述べ
たのと同様の方法で耐摩耗性、耐酸性、耐アルカリ性を
評価した。耐摩耗性テストでのヘイズ率は４．３％であ
り、耐酸性テストでの透過率変化は２．９％、ヘイズ率
は１．２％、耐アルカリ性テストでの透過率変化は２．
４％、ヘイズ率は０．９％と、いずれのテストにおいて
も、実施例３で得られたサンプルより劣ることがわかっ
た。Comparative Example 4 As a sample for comparison with Example 3, a thin film-coated article was prepared in which the thin film of the present invention was not coated as the top layer as a protective film. In the same manner as described in Example 3, a chromium film with a thickness of about 60 nm was formed on a 3 mm thick float glass substrate.
Comparative sample 4 was obtained by forming a titanium oxide film with a thickness of about 75 nm. Comparative Sample 4 was a blue reflecting mirror having optical characteristics similar to those of Example 3. Abrasion resistance, acid resistance, and alkali resistance were evaluated in the same manner as described in Example 3. The haze rate in the abrasion resistance test was 4.3%, the change in transmittance in the acid resistance test was 2.9%, the haze rate was 1.2%, and the change in transmittance in the alkali resistance test was 2.9%.
4%, and the haze rate was 0.9%, which was found to be inferior to the sample obtained in Example 3 in all tests.
【００４０】比較例５
実施例４と比較するサンプルとして、プラスチック基板
上に本発明の薄膜を最上層に保護膜として被覆しない薄
膜被覆物品を作成した。実施例４で用いたのと同じハー
ドコート層を有する有機プラスチック（ＣＲ−３９）を
比較サンプル５として評価した。実施例４と同じ方法で
耐摩耗性、耐酸性、耐アルカリ性を評価した。テーバー
摩耗試験でのヘイズ率は４．８％、耐酸性テストでのヘ
イズ率は０．９％、耐アルカリ性テストでのヘイズ率は
１．４％と、いずれのテストにおいても、比較サンプル
５は実施例４で得られたサンプル１３より劣ることがわ
かった。また、＃００００のスチールウールによる傷つ
き性も劣ることがわかった。Comparative Example 5 As a sample for comparison with Example 4, a thin film-coated article was prepared on a plastic substrate without coating the thin film of the present invention as the uppermost layer as a protective film. An organic plastic (CR-39) having the same hard coat layer as used in Example 4 was evaluated as Comparative Sample 5. Abrasion resistance, acid resistance, and alkali resistance were evaluated in the same manner as in Example 4. The haze rate in the Taber abrasion test was 4.8%, the haze rate in the acid resistance test was 0.9%, and the haze rate in the alkali resistance test was 1.4%. It was found to be inferior to Sample 13 obtained in Example 4. It was also found that the scratch resistance caused by #0000 steel wool was poor.
【００４１】比較例６
実施例５と同様の方法でガラス基板上にＣｏ−Ｎｉ−Ｃ
ｒ磁性層を形成したのち、現在磁性層の保護膜として最
もよく用いられているカーボン膜を４０ｎｍの厚みで形
成し、比較サンプル６とした。実施例５と同じ方法で耐
摩耗性、耐酸性、耐アルカリ性を評価したところ、ヘイ
ズ率は２．５％であった。耐酸性テストでは、透過率変
化が２．９％、ヘイズ率が１．２％、耐アルカリ性テス
トでは、透過率変化が３．４％、ヘイズ率が０．９％と
いう値を示した。これらの結果から、本発明に基づく最
上層の膜が、磁気ディスクの耐久性を向上させることが
わかった。Comparative Example 6 Co-Ni-C was deposited on a glass substrate in the same manner as in Example 5.
After forming the r magnetic layer, a carbon film, which is currently most commonly used as a protective film for the magnetic layer, was formed to a thickness of 40 nm, and a comparative sample 6 was prepared. When the wear resistance, acid resistance, and alkali resistance were evaluated in the same manner as in Example 5, the haze rate was 2.5%. In the acid resistance test, the change in transmittance was 2.9% and the haze rate was 1.2%, and in the alkali resistance test, the change in transmittance was 3.4% and the haze rate was 0.9%. From these results, it was found that the top layer film based on the present invention improves the durability of the magnetic disk.
【００４２】[0042]
【発明の効果】本発明の薄膜を、薄膜被覆物品の最上層
に保護膜として用いることにより、化学的耐久性と機械
的耐久性の両方に優れた物品とすることが出来る。これ
により外部環境に触れる状態で使用される薄膜被覆物品
の被膜の耐久性が大幅に向上する。本発明の方法によれ
ば、このような優れた耐久性を有する被膜を、直流の反
応性スパッタリングにより形成することを可能にするの
で、薄膜付物品を真空成膜法により製造する場合に極め
て有利であり、また大きな面積の基板に安定に被覆する
ことができるので、量産性を向上させコストを低下させ
ることに寄与する。本発明の薄膜は屈折率が低いので、
光学干渉作用を利用した光学フィルターなどの光学膜の
低屈折率層として用いると、機械的強度が大きくかつ化
学的安定性が優れた光学薄膜被覆物品が得られる。また
、本発明の薄膜の製造方法は、とりわけ大面積の基板に
安定したグロー放電を長時間維持して成膜することが出
来、操業安定性、量産性が優れている。Effects of the Invention By using the thin film of the present invention as a protective film on the top layer of a thin film-coated article, the article can be made to have excellent both chemical durability and mechanical durability. This greatly improves the durability of the coating of thin-film coated articles that are used in contact with the external environment. According to the method of the present invention, it is possible to form a film having such excellent durability by direct current reactive sputtering, which is extremely advantageous when manufacturing thin film-coated articles by vacuum film forming. Moreover, since it is possible to stably coat a large area of a substrate, it contributes to improving mass productivity and reducing costs. Since the thin film of the present invention has a low refractive index,
When used as a low refractive index layer of an optical film such as an optical filter that utilizes optical interference, an optical thin film coated article with high mechanical strength and excellent chemical stability can be obtained. In addition, the method for producing a thin film of the present invention can particularly form a film on a large-area substrate while maintaining stable glow discharge for a long time, and is excellent in operational stability and mass productivity.
【図１】本発明の薄膜を用いた薄膜被覆物品の一部断面
図FIG. 1: Partial cross-sectional view of a thin film-coated article using the thin film of the present invention.
１ Ｓｉ、Ｔａ、Ｃ、Ｎ、Ｏからなる薄膜２
磁気記録膜
３ ガラス基板
４ 高屈折率膜1 Thin film 2 made of Si, Ta, C, N, and O
Magnetic recording film 3 Glass substrate 4 High refractive index film
Claims (3)
素からなり化学式ＳｉＴａｊ Ｃｋ Ｎｍ Ｏｎ で表
される組成を有する薄膜であって、前記ｊの値が０．２
以上０．６以下であって、前記ｋの値が０．３以上１．
０以下であって、前記ｍの値が０．１以上１．０以下で
あって、前記ｎの値が１．０以上である薄膜。1. A thin film comprising silicon, tantalum, carbon, nitrogen, and oxygen and having a composition represented by the chemical formula SiTaj Ck Nm On , wherein the value of j is 0.2.
0.6 or less, and the value of k is 0.3 or more and 1.
0 or less, the value of m is 0.1 or more and 1.0 or less, and the value of n is 1.0 or more.
、ＴａＳｉ２、ＴａＨ２ の群から選ばれた少なくとも
一種以上のＴａ化合物とを主成分とした焼結体からなる
ターゲットを用い、少なくとも酸素と窒素とを含む減圧
された雰囲気内でおこなう直流反応性スパッタリング法
により、基板の上に化学式ＳｉＴａｊ Ｃｋ Ｎｍ Ｏ
ｎ で表される組成を有する薄膜を製造する方法。[Claim 2] SiC and TaC, TaN, TaB2
A direct current reactive sputtering method using a target made of a sintered body mainly containing at least one Ta compound selected from the group of , TaSi2, and TaH2 in a reduced pressure atmosphere containing at least oxygen and nitrogen. The chemical formula SiTaj Ck Nm O is deposited on the substrate by
A method for producing a thin film having a composition represented by n.
ＴａＢ２ 、ＴａＳｉ２ 、ＴａＨ２ の群から選ばれ
た少なくとも一種以上の含有量を１０〜５０体積％とし
たことを特徴とする請求項２に記載の方法。3. TaC, TaN,
The method according to claim 2, characterized in that the content of at least one selected from the group of TaB2, TaSi2, and TaH2 is 10 to 50% by volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03067851A JP3121851B2 (en) | 1991-03-07 | 1991-03-07 | Thin film and manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03067851A JP3121851B2 (en) | 1991-03-07 | 1991-03-07 | Thin film and manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04280957A true JPH04280957A (en) | 1992-10-06 |
| JP3121851B2 JP3121851B2 (en) | 2001-01-09 |
Family
ID=13356878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03067851A Expired - Fee Related JP3121851B2 (en) | 1991-03-07 | 1991-03-07 | Thin film and manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3121851B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020173333A (en) * | 2019-04-10 | 2020-10-22 | デクセリアルズ株式会社 | Thin film for optical element and manufacturing method thereof, inorganic polarizer and manufacturing method thereof, and optical element and optical apparatus |
-
1991
- 1991-03-07 JP JP03067851A patent/JP3121851B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020173333A (en) * | 2019-04-10 | 2020-10-22 | デクセリアルズ株式会社 | Thin film for optical element and manufacturing method thereof, inorganic polarizer and manufacturing method thereof, and optical element and optical apparatus |
| CN111812764A (en) * | 2019-04-10 | 2020-10-23 | 迪睿合株式会社 | Film for optical element and method for producing same, inorganic polarizing plate and method for producing same, optical element and optical instrument |
| CN111812764B (en) * | 2019-04-10 | 2024-02-06 | 迪睿合株式会社 | Film for optical element and method for producing same, inorganic polarizing plate and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3121851B2 (en) | 2001-01-09 |
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