JPH0611910B2 - Method for forming hard alumina thin film - Google Patents
Method for forming hard alumina thin filmInfo
- Publication number
- JPH0611910B2 JPH0611910B2 JP21580190A JP21580190A JPH0611910B2 JP H0611910 B2 JPH0611910 B2 JP H0611910B2 JP 21580190 A JP21580190 A JP 21580190A JP 21580190 A JP21580190 A JP 21580190A JP H0611910 B2 JPH0611910 B2 JP H0611910B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- alumina thin
- vacuum container
- hard alumina
- 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.)
- Expired - Lifetime
Links
- 239000010409 thin film Substances 0.000 title claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 16
- 239000000758 substrate Substances 0.000 claims description 32
- 230000001133 acceleration Effects 0.000 claims description 11
- 239000010408 film Substances 0.000 claims description 11
- 238000007740 vapor deposition Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、硬質アルミナ薄膜の形成方法に関し、特にイ
オン照射と蒸着とを併用するダイナミックミキシング法
による硬質アルミナ薄膜の形成方法の改良に係わる。Description: TECHNICAL FIELD The present invention relates to a method for forming a hard alumina thin film, and more particularly to improvement of a method for forming a hard alumina thin film by a dynamic mixing method that uses ion irradiation and vapor deposition in combination.
［従来の技術及び課題］ 従来より真空容器内で基板を膜質の均質化のために回転
させながら、その表面にイオン照射と蒸着とを併用する
ダイナミックミキシング法によりアルミナ薄膜を形成す
る方法が行なわれている。このアルミナコーティングを
実用化するには、該アルミナ薄膜自体の強度では不十分
である場合、圧縮応力を付与して機械的特性を向上する
ことが試みられている。[Prior Art and Problem] Conventionally, a method of forming an alumina thin film on the surface of a substrate by rotating the substrate in a vacuum container for homogenization of film quality by a dynamic mixing method using both ion irradiation and vapor deposition has been performed. ing. In order to put this alumina coating into practical use, if the strength of the alumina thin film itself is insufficient, it has been attempted to apply a compressive stress to improve the mechanical properties.
上述した圧縮応力を付与する方法としては、基板と被覆
するアルミナ薄膜との熱膨張差を利用した、いわゆるバ
イメタル効果や、アルミナ薄膜の相転位を利用して薄膜
内部に圧縮応力を発生させてその強度を向上する方法が
知られている。As a method of applying the above-mentioned compressive stress, the so-called bimetal effect utilizing the difference in thermal expansion between the substrate and the alumina thin film covering the substrate, or the phase transition of the alumina thin film is used to generate the compressive stress inside the thin film. Methods for improving strength are known.
しかしながら、かかる方法では必ずしも十分に硬質のア
ルミナ薄膜を形成することが困難であった。However, it has been difficult to form a sufficiently hard alumina thin film by such a method.
本発明、上記従来の問題点を解決するためになされたも
ので、圧縮応力が向上され、硬質で平滑なアルミナ薄膜
の形成方法を提供しようとするものである。The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to provide a method for forming a hard and smooth alumina thin film having improved compressive stress.
［課題を解決するための手段］ 本発明は、真空容器内で基板表面にイオン照射と蒸着と
を併用して硬質アルミナ薄膜を形成するに際し、前記基
板を静止すると共に、加速エネルギーを20ｋｅＶ以上、
温度200℃以上でイオン照射と蒸着とを行なうことを特
徴とする硬質アルミナ薄膜の形成方法に関するものであ
る。[Means for Solving the Problems] The present invention, when forming a hard alumina thin film by using ion irradiation and vapor deposition on the substrate surface in a vacuum container together with the substrate being stationary, an acceleration energy of 20 keV or more,
The present invention relates to a method for forming a hard alumina thin film, which comprises performing ion irradiation and vapor deposition at a temperature of 200 ° C. or higher.
上記基板としては、例えばＮｉ、Ｎｉ基合金、Ｔｉ、Ｔ
ｉ基合金、ＳＵＳなどの各種の金属、ガラス等を用いる
ことができる。Examples of the substrate include Ni, Ni-based alloys, Ti, T
An i-based alloy, various metals such as SUS, glass, etc. can be used.
上記イオンの加速エネルギーを限定した理由は、その加
速エネルギーを20ｋｅＶ未満にすると内部に圧縮応力を
十分付与できず、硬質のアルミナ薄膜を形成できなくな
るからである。The reason why the acceleration energy of the ions is limited is that if the acceleration energy is less than 20 keV, a compressive stress cannot be sufficiently applied to the inside, and a hard alumina thin film cannot be formed.
上記膜形成時の温度を限定した理由は、その温度を200
℃未満にすると、内部に圧縮応力を十分付与できず、硬
質のアルミナ薄膜を形成できなくなるからである。The reason for limiting the temperature during film formation is that the temperature is 200
This is because if the temperature is lower than 0 ° C., sufficient compressive stress cannot be applied to the inside and a hard alumina thin film cannot be formed.
［作用］ 本発明によれば、真空容器内で基板表面にイオン照射と
蒸着とを併用して硬質アルミナ薄膜を形成するに際し、
前記基板を静止すると共に、加速エネルギーを20ｋｅＶ
以上、温度200℃以上でイオン照射と蒸着とを行なうこ
とによって、圧縮応力が向上され、硬質で平滑なアルミ
ナ薄膜を形成することができる。こうした硬質化効果
は、以下に説明する現象によるものと推定される。[Operation] According to the present invention, when a hard alumina thin film is formed on a substrate surface in a vacuum container by using both ion irradiation and vapor deposition,
The substrate is stationary and the acceleration energy is 20 keV.
As described above, by performing ion irradiation and vapor deposition at a temperature of 200 ° C. or higher, the compressive stress is improved, and a hard and smooth alumina thin film can be formed. It is presumed that such a hardening effect is due to the phenomenon described below.
即ち、イオン照射と蒸着とを併用したダイナミックミキ
シング法は、非平衡プロセスであり、基板表面への成膜
中にイオン照射を行なうことで、加速イオンや中性粒子
がアルミナ薄膜表面に衝突し、表面原子を叩き込む、い
わゆるアトミックピーニング（ａｔｏｍｉｃ ｐｅｅｎ
ｉｎｇ）現象を引き起こし、自らも薄膜中に不純物とし
て捕獲される。その結果、薄膜の結晶内部に空孔や格子
間原子を多数生成させるため、アルミナ薄膜の体積膨張
を引き起こし、圧縮応力を発生させる。この場合、従来
のように薄膜の均質化のために基板を回転させると、原
子のマイグレーションを促進し、格子欠陥を減少させ、
結果的には圧縮応力を緩和する方向に作用する。That is, the dynamic mixing method using both ion irradiation and vapor deposition is a non-equilibrium process, and by performing ion irradiation during film formation on the substrate surface, accelerated ions and neutral particles collide with the alumina thin film surface, So-called atomic peening, which strikes surface atoms
ing) phenomenon, and is itself trapped as an impurity in the thin film. As a result, a large number of vacancies and interstitial atoms are generated inside the crystal of the thin film, causing volume expansion of the alumina thin film and generating compressive stress. In this case, if the substrate is rotated for homogenization of the thin film as in the conventional case, migration of atoms is promoted, lattice defects are reduced,
As a result, it acts in the direction of relaxing the compressive stress.
このようなことから、成膜中での基板の回転を停止し、
更に加速エネルギー及び成膜温度を規定することによっ
て、前記薄膜内部への圧縮応力が効果的に付与される。From this, the rotation of the substrate during film formation was stopped,
Further, by defining the acceleration energy and the film forming temperature, the compressive stress inside the thin film is effectively given.
また、平滑性の向上も、前記圧縮応力の増大により密度
が高くなることに関係しているものと推定される。It is also presumed that the improvement in smoothness is related to the increase in density due to the increase in the compressive stress.
［実施例］ 以下、本発明の実施例を第１図を参照して詳細に説明す
る。[Embodiment] An embodiment of the present invention will be described in detail below with reference to FIG.
第１図は、本実施例に用いる膜形成装置を示す概略図で
ある。図中の１は、真空容器であり、この容器１には該
容器１内を所定の真空度するための真空ポンプ２が連結
されている。前記真空容器１内には、蒸着用の電子ビー
ム加熱蒸発器３が設けられている。前記容器内には、該
容器１に設けられたイオン源４からのＡｒイオンビーム
により蒸着物がスパッタリングされるターゲット５が配
置されている。前記真空容器１内には、加熱機構を備え
た基板ホルダ６が配置されている。前記真空容器１内に
は、前記基板ホルダ６に保持された基板付近にガスを供
給するための導入管７が設けられている。また、前記真
空容器１内には前記基板ホルダ６に保持された基板付近
にイオンを照射するためのイオン源８が設けられてい
る。更に、図中の９は高加速電圧でイオンを照射するた
めのイオン源である。このイオン源９は、質量分離マグ
ネット10、加速管11及び作動排気用真空ポンプ12を介し
て前記真空容器１に連結されている。FIG. 1 is a schematic view showing a film forming apparatus used in this embodiment. Reference numeral 1 in the figure is a vacuum container, and a vacuum pump 2 for connecting the container 1 to a predetermined degree of vacuum is connected to the container 1. An electron beam heating evaporator 3 for vapor deposition is provided in the vacuum container 1. Inside the container, a target 5 on which a deposit is sputtered by an Ar ion beam from an ion source 4 provided in the container 1 is arranged. A substrate holder 6 having a heating mechanism is arranged in the vacuum container 1. In the vacuum container 1, an introduction pipe 7 for supplying gas near the substrate held by the substrate holder 6 is provided. An ion source 8 for irradiating the vicinity of the substrate held by the substrate holder 6 with ions is provided in the vacuum container 1. Further, 9 in the figure is an ion source for irradiating ions with a high acceleration voltage. The ion source 9 is connected to the vacuum container 1 through a mass separation magnet 10, an acceleration tube 11 and a vacuum pump 12 for operating and exhausting.
実施例１、２及び比較例１〜７ まず、前述した膜形成装置の真空容器１に配置された基
板ホルダ６にチタン基板13を保持した後、真空ポンプ２
を作動して真空容器１内を例えば１×10-6torr程度まで
排気した。つづいて、電子ビーム加熱蒸発器３よりアル
ミニウム（Ａｌ）を２Å／secの速度で蒸着を行うと同
時に、酸素イオン源８から酸素イオンを加速エネルギー
15〜40ｋｅＶ、電流密度340μＡ／cm2の条件で前記Ａｌ
堆積中の基板13表面に照射して厚さ２μｍのアルミナ
（Ａｌ2Ｏ3）薄膜を形成した。なお、基板回転を実施す
る場合は回転速度を2rpmとし、基板温度は140℃、220℃
とした。Examples 1 and 2 and Comparative Examples 1 to 7 First, after holding the titanium substrate 13 in the substrate holder 6 arranged in the vacuum container 1 of the film forming apparatus described above, the vacuum pump 2
Was operated to evacuate the inside of the vacuum container 1 to, for example, about 1 × 10 −6 torr. Subsequently, aluminum (Al) is vapor-deposited from the electron beam heating evaporator 3 at a rate of 2Å / sec, and at the same time, oxygen ions are accelerated from the oxygen ion source 8 by acceleration energy.
The above Al under the conditions of 15 to 40 keV and current density of 340 μA / cm 2.
The surface of the substrate 13 being deposited was irradiated to form a 2 μm thick alumina (Al 2 O 3 ) thin film. When rotating the substrate, set the rotation speed to 2 rpm and the substrate temperature to 140 ° C and 220 ° C.
And
本実施例１、２及び比較例１〜７により形成されたアル
ミナ薄膜について、それらの硬さを測定すると共に、表
面性状をレプリカ法を使用した透過型電子顕微鏡により
観察した。その結果を下記第１表に示した。The hardness of the alumina thin films formed in Examples 1 and 2 and Comparative Examples 1 to 7 was measured, and the surface texture was observed by a transmission electron microscope using a replica method. The results are shown in Table 1 below.
実施例３〜５及び比較例８〜13 まず、前述した膜形成装置の真空容器１に配置された基
板ホルダ６にガラス（コーニンググラス社製商品名；コ
ーニング7059）からなる基板13を保持した後、真空ポン
プ２を作動して真空容器１内を例えば１×10-6torr程度
まで排気した。つづいて、ターゲット５をＡｌとし、イ
オン源４からＡｒイオンビームを照射してＡｌを２Å／
secの条件でスパッタリングした。これと同時に、ガス
導入管７から酸素ガスを1.4×10-4torrの分圧で供給す
ると共に、イオン源９からＡｒの１価イオン又は４価イ
オンを加速エネルギー120〜800ｋｅＶ、電流密度３〜10
μＡ／cm2の条件で前記基板13表面に照射して厚さ２μ
ｍのアルミナ（Ａｌ2Ｏ3）薄膜を形成した。なお、基板
回転を実施する場合は回転速度を2rpmとし、基板温度は
160℃、230℃、300℃とした。 Examples 3 to 5 and Comparative Examples 8 to 13 First, after the substrate 13 made of glass (Corning Glass Co., Ltd .; trade name: Corning 7059) is held in the substrate holder 6 arranged in the vacuum container 1 of the film forming apparatus described above. The vacuum pump 2 was operated to evacuate the inside of the vacuum container 1 to, for example, about 1 × 10 −6 torr. Subsequently, the target 5 is Al, and the Ar ion beam is irradiated from the ion source 4 so that Al becomes 2Å /
Sputtering was performed under the condition of sec. At the same time, oxygen gas is supplied from the gas introduction pipe 7 at a partial pressure of 1.4 × 10 −4 torr, and monovalent ions or tetravalent ions of Ar are accelerated from the ion source 9 at an acceleration energy of 120 to 800 keV and a current density of 3 to Ten
Irradiating the surface of the substrate 13 under conditions of μA / cm 2 to a thickness of 2μ
m alumina (Al 2 O 3 ) thin film was formed. When performing substrate rotation, the rotation speed is 2 rpm and the substrate temperature is
The temperature was 160 ° C, 230 ° C, and 300 ° C.
本実施例３〜５及び比較例８〜13により形成されたアル
ミナ薄膜について、それらの硬さを測定すると共に、表
面性状をレプリカ法を使用した透過型電子顕微鏡により
観察した。その結果を下記第２表に示した。The hardness of the alumina thin films formed in Examples 3 to 5 and Comparative Examples 8 to 13 was measured, and the surface texture was observed by a transmission electron microscope using the replica method. The results are shown in Table 2 below.
上記第１表、第２表から明らかなように本実施例１〜５
のように基板を停止し、かつ加速エネルギーを20ｋｅＶ
以上、成膜温度を200℃以上とすることによって2300Ｈ
ｖ以上の硬さを有し、表面平滑性が優れたアルミナ薄膜
を形成できることがわかる。 As is clear from Tables 1 and 2 above, Examples 1 to 5
The substrate is stopped and the acceleration energy is 20 keV.
As described above, by setting the film forming temperature to 200 ° C or higher, 2300H
It can be seen that an alumina thin film having a hardness of v or more and excellent surface smoothness can be formed.
［発明の効果］ 以上詳述した如く、本発明によれば内部圧縮応力が向上
され、硬質で平滑なアルミナ薄膜を形成でき、ひいては
各種の構造部品のコーティングに有効に利用できる等顕
著な効果を奏する。[Effects of the Invention] As described in detail above, according to the present invention, remarkable effects such as improved internal compressive stress, formation of a hard and smooth alumina thin film, and effective use for coating various structural parts can be obtained. Play.
第１図は本発明の実施例で用いた膜形成装置を示す概略
図である。 １……真空容器、３……電子ビーム蒸発器、４，９、８
……イオン源、５……ターゲット、６……基板ホルダ、
７……ガス導入管、13……基板。FIG. 1 is a schematic view showing a film forming apparatus used in an example of the present invention. 1 ... vacuum container, 3 ... electron beam evaporator, 4, 9, 8
…… Ion source, 5 …… Target, 6 …… Substrate holder,
7 ... Gas inlet tube, 13 ... Substrate.
Claims (1)
とを併用して硬質アルミナ薄膜を形成するに際し、前記
基板を静止すると共に、加速エネルギーを20ｋｅＶ以
上、膜形成温度を200℃以上でイオン照射と蒸着とを行
なうことを特徴とする硬質アルミナ薄膜の形成方法。1. When a hard alumina thin film is formed on a substrate surface by using both ion irradiation and vapor deposition in a vacuum container, the substrate is kept stationary, the acceleration energy is 20 keV or more, and the film forming temperature is 200 ° C. or more. A method for forming a hard alumina thin film, which comprises performing ion irradiation and vapor deposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21580190A JPH0611910B2 (en) | 1990-08-17 | 1990-08-17 | Method for forming hard alumina thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21580190A JPH0611910B2 (en) | 1990-08-17 | 1990-08-17 | Method for forming hard alumina thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0499862A JPH0499862A (en) | 1992-03-31 |
| JPH0611910B2 true JPH0611910B2 (en) | 1994-02-16 |
Family
ID=16678479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21580190A Expired - Lifetime JPH0611910B2 (en) | 1990-08-17 | 1990-08-17 | Method for forming hard alumina thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611910B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2024225362A1 (en) * | 2023-04-27 | 2024-10-31 |
-
1990
- 1990-08-17 JP JP21580190A patent/JPH0611910B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0499862A (en) | 1992-03-31 |
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