JPH0288762A - Production of thin film of high-valence copper oxide - Google Patents
Production of thin film of high-valence copper oxideInfo
- Publication number
- JPH0288762A JPH0288762A JP24015388A JP24015388A JPH0288762A JP H0288762 A JPH0288762 A JP H0288762A JP 24015388 A JP24015388 A JP 24015388A JP 24015388 A JP24015388 A JP 24015388A JP H0288762 A JPH0288762 A JP H0288762A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- copper
- substrate
- oxide
- temp
- 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.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 38
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 5
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- -1 oxygen ions Chemical class 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004544 sputter deposition Methods 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010884 ion-beam technique Methods 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000001133 acceleration Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000005546 reactive sputtering Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、金属材料またはセラミックス材料等の基板表
面に高原子価の銅の酸化物を形成する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for forming a high valence copper oxide on the surface of a substrate such as a metal material or a ceramic material.
基板上に銅酸化物薄膜を形成させる方法としては、反応
性イオンブレーティング法、反応性スパッタリング法等
が知られている。Reactive ion blasting, reactive sputtering, and the like are known as methods for forming a copper oxide thin film on a substrate.
反応性イオンブレーティング法は、ｏ２ガスを直流放電
もしくは高周波によってイオン化し、その中で所定の金
属を蒸発させることにより、金属酸化物を得、当該金属
酸化物を基板上に形成させる方法であるが、比較的高温
で安定な酸化物を形成させるには、非常に有効な方法で
ある。The reactive ion blating method is a method in which O2 gas is ionized by direct current discharge or high frequency, a predetermined metal is evaporated therein to obtain a metal oxide, and the metal oxide is formed on a substrate. However, it is a very effective method for forming oxides that are stable at relatively high temperatures.
また反応性スパッタリング法は、酸化物や金属をＡｒや
酸素もしくはその混合ガスでスパツタリングを行い、さ
らに基板上に形成された薄膜に酸素ガスや酸素イオンを
接触させるか、もしくは加速電圧を印加して照射し、所
定の酸化物を得ようとするものである。In the reactive sputtering method, oxides and metals are sputtered with Ar, oxygen, or a mixture thereof, and then the thin film formed on the substrate is brought into contact with oxygen gas or oxygen ions, or an accelerating voltage is applied. The purpose is to obtain a desired oxide by irradiation.
特に、高温超電導セラミックス薄膜の形成には主にスパ
ッタリング法を用いて所定の酸化物の薄膜を形成し、そ
の後熱処理を行う方法が一般的である。In particular, a common method for forming high-temperature superconducting ceramic thin films is to form a thin film of a predetermined oxide mainly by sputtering, and then heat-treat the film.
しかし上記従来技術には次の難点があった。 However, the above conventional technology has the following drawbacks.
上記イオンブレーティング法やスパッタリング法では熱
的に不安定なＣｕＯ等の高原子価酸化物は形成されない
。In the above-mentioned ion blasting method and sputtering method, thermally unstable high-valent oxides such as CuO are not formed.
またスパッタリング法ではＣｕ”はＣｕにまで還元され
てしまうことが多く、後熱処理でもその超電導温度を十
分に高くするだけの量の酸素を含ませることが困難であ
る。Further, in the sputtering method, Cu'' is often reduced to Cu, and even in post-heat treatment, it is difficult to contain enough oxygen to raise the superconducting temperature sufficiently.
そこで本発明の目的は、高温超電導を示すに十分な量の
銅の高原子価酸化物を容易に形成させることのできる方
法を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method that can easily form a high-valent oxide of copper in an amount sufficient to exhibit high-temperature superconductivity.
上記課題を解決するための本発明は、基板表面に銅の高
原子価酸化物を含む酸化物薄膜を形成させるに際し、銅
または銅を含む物質の薄膜形成途上もしくは形成後の薄
膜表面に、基板温度が室温以下の状態で、加速電圧３ｋ
Ｖ以下で酸素イオンを照射することを特徴とするもので
ある。In order to solve the above problems, the present invention, when forming an oxide thin film containing a high-valent oxide of copper on the surface of a substrate, applies a film to the surface of the thin film during or after the formation of a thin film of copper or a substance containing copper. When the temperature is below room temperature, the acceleration voltage is 3k.
This method is characterized by irradiating oxygen ions at V or less.
ここで室温とは２５℃をいう。Here, room temperature means 25°C.
一般に、薄膜に良好な高温超電導性を付与するには、可
能な限り過剰な酸素が薄膜に含まれることが必要である
。この場合全ての銅は高原子価酸化物すなわちＣｕＯに
まで酸化させる必要があり、さらに過剰の酸素も薄膜上
に存在させる必要がある。Generally, in order to impart good high temperature superconductivity to a thin film, it is necessary that the thin film contains as much excess oxygen as possible. In this case, all of the copper must be oxidized to a high valence oxide, CuO, and excess oxygen must also be present on the thin film.
本発明では、銅を蒸着させた薄膜上に、上記条件で酸素
イオン照射するものであるから、金属状態の銅を完全に
ＣｕＯにまで酸化させることができるほか、過剰の酸素
を存在させることも可能であり、良好な超電導性を得る
ことができる。In the present invention, oxygen ions are irradiated onto a thin film on which copper is vapor-deposited under the above conditions, so that not only can metallic copper be completely oxidized to CuO, but also the presence of excess oxygen can be avoided. It is possible to obtain good superconductivity.
以下本発明をさらに詳説する。 The present invention will be explained in more detail below.
本発明者は、銅を基板として、２５℃の基板上に酸素イ
オンを加速電圧を変えて照射したときのＸＰＳ Ｃｕ２
ｐｓｙ□スペクトルを調べたところ、第１図の結果を得
た。ここでスペクトルの分析は、ＸＰＳ（Ｘ線光電子分
光装置）を用い、分析条件は、Ｘ線源Ａｊ！ Ｋｏｔ
（ｈ ｖ ＝１４８６．６ｅＶ ）である。この結果に
よると、加速電圧が低いはどＣｕＯの生成量が多くなる
ことが判る。また、基板として銅を用い、酸素イオンの
加速電圧を３ｋＶとして、基板温度を変化させたときの
スペクトルを調べたところ、第２図の結果を得た。この
結果によると、基板温度が低いときＣｕＯが生成される
ことが判る。さらに、第３図には、基板温度を変化させ
たとき、薄膜中の過剰の酸素（０）のＯ−あるいは０２
−としての存在を、ＣＰＳ （紫外線光電子分光装置
）で分析した結果を示す。この結果によると、基板温度
が低いとき、過剰の０が存在することとが判る。The present inventor used XPS Cu2 as a substrate when oxygen ions were irradiated onto the substrate at 25° C. while changing the acceleration voltage.
When the psy□ spectrum was examined, the results shown in FIG. 1 were obtained. Here, the spectrum analysis is performed using XPS (X-ray photoelectron spectrometer), and the analysis conditions are as follows: X-ray source Aj! Kot
(h v =1486.6eV). According to this result, it can be seen that the lower the accelerating voltage, the more CuO is produced. Further, when copper was used as the substrate, the oxygen ion acceleration voltage was set to 3 kV, and the substrate temperature was varied, the spectrum was investigated, and the results shown in FIG. 2 were obtained. This result shows that CuO is produced when the substrate temperature is low. Furthermore, FIG. 3 shows that when the substrate temperature is changed, the excess oxygen (0) in the thin film is reduced to O- or 02.
The results of analyzing the presence of - using a CPS (ultraviolet photoelectron spectrometer) are shown. According to this result, it can be seen that when the substrate temperature is low, an excess of 0 exists.
かかる結果および後記実施例などの結果によって、銅ま
たは銅を含む物質の薄膜形成途上または形成後の薄膜表
面に、基板温度２５℃以下、加速電圧３ｋＶ以下で酸素
イオンを照射すると、ＣｕＯが容易に生成することを知
見した。According to these results and the results of Examples described later, CuO can be easily formed by irradiating the surface of a thin film of copper or a copper-containing substance during or after formation with oxygen ions at a substrate temperature of 25° C. or less and an acceleration voltage of 3 kV or less. It was discovered that it is generated.
すなわち、ＣｕＯ生成条件を実測したものを図示すると
、第４図のようになり、斜線を施した部分が本発明範囲
となる。That is, if the CuO production conditions were actually measured, they would be as shown in FIG. 4, and the shaded area is the scope of the present invention.
本発明において、薄膜形成および酸素イオンを照射する
場合は、たとえば第５図の製造・装置を用いることがで
きる。図中１は５ｉＯｚ等の基板、２はＹＢａ２Ｃｕｚ
（Ｊｒ−ｘ等のターゲット、３はＡｒイオンビーム、４
はヒーター、５は液体窒素、６は酸素イオンビームであ
る。In the present invention, when forming a thin film and irradiating oxygen ions, for example, the manufacturing apparatus shown in FIG. 5 can be used. In the figure, 1 is a substrate such as 5iOz, and 2 is YBa2Cuz.
(Target such as Jr-x, 3 is Ar ion beam, 4
5 is a heater, 5 is liquid nitrogen, and 6 is an oxygen ion beam.
かかる製造装置の下で、まずターゲット２からの銅を含
む化合物を基板１上にスパッタ蒸着する。Under such a manufacturing apparatus, a copper-containing compound from target 2 is first sputter-deposited onto substrate 1 .
次いで、基板１をヒータ４または液体窒素５により本発
明に規定する所定の温度に保持した状態で、スパッタ蒸
着過程またはスバ・７タ蒸着終了後、酸素イオンビーム
６を、加速電圧１０ｋＶ以下の条件で照射する。この場
合、スパッタ蒸着と酸素イオンビームの照射とは、同一
装置で行ってもよく、別の装置で行ってもよい。Next, while the substrate 1 is maintained at a predetermined temperature specified in the present invention by the heater 4 or liquid nitrogen 5, after the sputter deposition process or the sputter deposition process is completed, the oxygen ion beam 6 is heated at an acceleration voltage of 10 kV or less. Irradiate with In this case, sputter deposition and oxygen ion beam irradiation may be performed using the same device or may be performed using separate devices.
一方、薄膜形成途上で酸素イオンを照射する場合、基板
上へスパッタ蒸着される薄膜厚さが、酸素イオンにより
スパッタされる厚さより厚くなければならない。On the other hand, when irradiating oxygen ions during the formation of a thin film, the thickness of the thin film sputter-deposited onto the substrate must be thicker than the thickness sputtered with oxygen ions.
たとえば、Ａｒは１０ｋＶの加速電圧、０□は５ｋＶ以
下の加速電圧で実施し、また試料電流は計では数ｍＡ／
ｃ＋ａ１０ｚでは数１０１ ／ｃＩＡ以下で、特に１ｋ
Ｖ以下では１０μ八以下であれば問題は生じない。For example, Ar is carried out at an accelerating voltage of 10 kV, 0□ is carried out at an accelerating voltage of 5 kV or less, and the sample current is several mA/
c+a10z is less than several 101/cIA, especially 1k
If it is below V, no problem will occur if it is below 10μ8.
本発明において、基板としては、金属、プラスチック、
セラミックス等適宜のものが使用される。In the present invention, the substrate may include metal, plastic,
An appropriate material such as ceramics is used.
その基板表面に銅または銅を含む酸化物の薄膜を形成さ
せる方法としては、真空蒸着法、反応性スパッタリング
法、イオンブレーティング法などを挙げることができる
。その際の基板表面温度としいては、ＣｕＯを生成させ
る目的で酸素イオンを照射させる時に２５℃以下であり
さえすればよい。Examples of methods for forming a thin film of copper or an oxide containing copper on the surface of the substrate include a vacuum evaporation method, a reactive sputtering method, and an ion blating method. The substrate surface temperature at this time only needs to be 25° C. or lower when irradiating oxygen ions for the purpose of producing CuO.
次ぎに実施例を説明する。 Next, an example will be explained.
基板をＳｉｎ□とし、ターゲットにＹＢａ２Ｃｕ２Ｏ７
−、を用いたスパッタ法（スパッタガス； Ａｒ）でＩ
ＩＩを形成させるにあたり、所定の基板温度で、薄膜形
成時に酸素イオンを薄膜に照射した。このときのＣｕＯ
の生成をＸＰＳで分析し、さらに過剰のＯの０としての
存在をＵＰＳで分析した。その分析条件は、ｘｐｓ、
Ｘ線源Ａ７！Ｋ ａｃｈｖ ＝１４８６．６ｅＶ）、Ｕ
ＰＳ 、紫外線源： ＨｅＩ （ｈシー２１．２ｅＶ）
である。The substrate is Sin□, and the target is YBa2Cu2O7.
- I by sputtering method using (sputter gas; Ar)
In forming II, the thin film was irradiated with oxygen ions at a predetermined substrate temperature during thin film formation. CuO at this time
The formation of was analyzed by XPS, and the presence of excess O as 0 was analyzed by UPS. The analysis conditions are xps,
X-ray source A7! K achv =1486.6eV), U
PS, UV source: HeI (hC 21.2eV)
It is.
結果を第１表に示す。この表中、評価は、ＣｕＯのみが
存在する場合を０、ＣｕＯとＯ−が存在する場合を◎、
他を×とした。The results are shown in Table 1. In this table, the evaluation is 0 when only CuO is present, ◎ when CuO and O- are present, and ◎ when CuO and O- are present.
Others were marked as ×.
第１表より、本発明法を適用することで酸化物中に酸素
が十分に供給され、結晶化後も酸素の過剰な薄膜となり
、超電導性が得られることが明らかとなった。From Table 1, it is clear that by applying the method of the present invention, oxygen is sufficiently supplied into the oxide, and even after crystallization, a thin film containing excess oxygen is formed, resulting in superconductivity.
また、本発明ではターゲットに必ずしも所定の超電導酸
化物を用いておく必要はなく、特に本実施例の場合、Ｙ
Ｂａ２Ｃｕ２Ｏ７，５前後で熱処理をせず、銅が金属状
態で存在するような粗製ターゲットでも、薄膜としては
良好な酸素濃度を持つものが得られる利点がある。Furthermore, in the present invention, it is not necessary to use a predetermined superconducting oxide for the target, and in particular, in the case of this example, Y
Even a crude target in which copper exists in a metallic state without heat treatment around Ba2Cu2O7,5 has the advantage that a thin film with a good oxygen concentration can be obtained.
以上の通り、本発明によれば、薄膜に対し良好な超電導
性を容易に付与することができる。As described above, according to the present invention, good superconductivity can be easily imparted to a thin film.
第１図は銅基板（２５℃）に酸素イオンの加速電圧を変
化させて照射させたときのＸＰＳ Ｃｕ２ｐ：＋ｚ□ス
ペクトル、第２図はスパッタリング薄膜（Ｙ−ＢａＣｕ
−０）の作製条件によるＸＰＳ Ｃｕ２ｐ３ｚｚスペク
トル、第３図はスパッタリング薄膜の作製条件によるＵ
ＰＳスペクトル、第４図はＣｕＯの生成条件を示す図、
第５図は薄膜形成および酸素イオン照射を行う装置の概
略説明図である。
（ΔＮ）フ）哀叫／−社ギ専
Ｗ豐／１（−ｔ？＆Ｘ ％ｄ２ ｒｌ）賜
）俣屹／ＸＣ七Ｃジ’ＸＳｄ口
η１（（〜γそｄどｎ○Figure 1 shows the XPS Cu2p: +z□ spectrum when a copper substrate (25°C) is irradiated with oxygen ions at varying acceleration voltages, and Figure 2 shows the sputtered thin film (Y-BaCu
Figure 3 shows the XPS Cu2p3zz spectrum under the manufacturing conditions of -0), and the U spectrum under the sputtering thin film manufacturing conditions.
PS spectrum, Figure 4 is a diagram showing the conditions for producing CuO,
FIG. 5 is a schematic explanatory diagram of an apparatus for forming a thin film and irradiating oxygen ions. (ΔN) F) Sorrow/-Shagisen W 豐/1 (-t? &
Claims (1)
を形成させるに際し、銅または銅を含む物質の薄膜形成
途上もしくは形成後の薄膜表面に、基板温度が室温以下
の状態で、加速電圧３ｋＶ以下で酸素イオンを照射する
ことを特徴とする高原子価銅酸化物薄膜の製造方法。(1) When forming an oxide thin film containing a high-valent oxide of copper on the surface of a substrate, the thin film of copper or a substance containing copper is formed on the surface of the thin film during or after formation, while the substrate temperature is below room temperature. A method for producing a high-valent copper oxide thin film, which comprises irradiating oxygen ions at an accelerating voltage of 3 kV or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24015388A JPH0288762A (en) | 1988-09-26 | 1988-09-26 | Production of thin film of high-valence copper oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24015388A JPH0288762A (en) | 1988-09-26 | 1988-09-26 | Production of thin film of high-valence copper oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0288762A true JPH0288762A (en) | 1990-03-28 |
Family
ID=17055285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24015388A Pending JPH0288762A (en) | 1988-09-26 | 1988-09-26 | Production of thin film of high-valence copper oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0288762A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6440276B2 (en) * | 1999-02-09 | 2002-08-27 | Tong Yang Moolsan Co., Ltd. | Process for producing thin film gas sensors with dual ion beam sputtering |
-
1988
- 1988-09-26 JP JP24015388A patent/JPH0288762A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6440276B2 (en) * | 1999-02-09 | 2002-08-27 | Tong Yang Moolsan Co., Ltd. | Process for producing thin film gas sensors with dual ion beam sputtering |
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