JPH05311434A - Formation of film and surface-treated substrate for film formation - Google Patents

Abstract

PURPOSE:To attain excellent adhesion of a film to a substrate. CONSTITUTION:Ions 12 of a group IVA element are implanted into the film forming surface of a substrate 11 to form an ion implanted layer 13 in the film forming surface of the substrate 11. By this layer 13, the chemical activity of the film forming surface of the substrate 11 is increased. A desired film 15 is then formed on the film forming surface of the substrate 11 by vapor deposition and irradiation with ions. At the same time, a mixed layer 16 is formed at the interface between the substrate 11 and the film 15. Since the chemical activity of the film forming surface of the substrate 11 is increased and the mixed layer 16 is formed, excellent adhesion of the film 15 to the substrate 11 can be attained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention improves the mechanical properties and chemical stability of a substrate on which a film is formed.
Alternatively, a film forming method for forming a film on the surface of the substrate and a surface treatment suitable for forming the film may be performed for the purpose of forming a film having various semiconductor characteristics on the substrate and using it as a semiconductor element. The present invention relates to the film-formed surface-treated substrate. In the present specification, the expression "surface-treated substrate for film formation" means a substrate after a predetermined surface treatment just before forming a desired film on a film formation surface, and is simply referred to as "substrate". The expression refers to the initially prepared substrate.

[0002]

2. Description of the Related Art Conventionally, various PVD methods and CVD methods have been proposed as a method of forming a film on the surface of a substrate. Among them, the IVD method in which vapor deposition such as vacuum vapor deposition or sputtering is used in combination with ion irradiation to form a film on the surface of a substrate, a mixed layer is formed at the interface between the substrate and the film, so that excellent adhesion is obtained. Attention has been paid to the fact that the film it has has the advantage that it can be formed on the surface of the substrate by low-temperature treatment.

[0003]

The reason why the IVD method has excellent adhesion is that the irradiated ions form a mixed layer of the constituent atoms of the two at the interface between the substrate and the film. However, for example, when the substrate and the film are made of a material having a poor wettability such as a metal and a nitride ceramic, it may be difficult to obtain sufficient adhesion only by forming the mixed layer. ..

An object of the present invention is to provide a film forming method which can improve the adhesion of the film to the substrate. Another object of the present invention is to provide a film-forming surface-treated substrate capable of providing excellent film adhesion.

[0005]

According to a first aspect of the film forming method, an ion-implanted layer is formed on the film forming surface of a substrate by previously implanting ions of a group IVA element into the film forming surface of the substrate. Then, vapor deposition on the film forming surface of the substrate and ion irradiation are used together to form a desired film on the film forming surface of the substrate and a mixed layer is formed at the interface between the substrate and the desired film.

The surface-treated substrate for film formation according to claim 2 is used in a film forming method for forming a desired film on the surface, and ion implantation is performed by implanting ions of a group IVA element into the film formation surface of the substrate. Forming layers.

[0007]

According to the structure of the present invention, the IV is formed on the film forming surface of the substrate.
Since the ion-implanted layer is formed on the film forming surface of the substrate by previously implanting ions of the group A element, the chemical activity of the film forming surface of the substrate is increased by the presence of the group IVA element. As a result, the adhesion of the desired film formed on the film formation surface of the substrate becomes excellent.

[0008]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT An embodiment of the present invention will be described below with reference to FIGS.
It will be explained based on. FIG. 2 is a schematic view of a film forming apparatus for carrying out the film forming method of the present invention. In FIG. 2, 1 is a vacuum container, 2 is a substrate, and 3 is a substrate holder that holds the substrate 2. Reference numeral 4 is an evaporation source, and 5 is an evaporation material. 6 is an ion source, and 7 is an ion beam with which the substrate 2 is irradiated from the ion source 6.

Reference numeral 8 is a film thickness monitor for measuring the number of vapor-deposited substances vapor-deposited on the substrate 2 and the film thickness of a film to be formed, which is composed of, for example, a crystal oscillator. Reference numeral 9 denotes an ion current measuring device for measuring the number of ions to be irradiated, which is composed of, for example, a Faraday cup. A method for forming a film using the above film forming apparatus will be described below. First, as shown in FIG. 2, the substrate 2 is fixed to the holder 3 and housed in the vacuum container 1 to maintain a predetermined degree of vacuum. After that, ions of Group IVA element are injected from the ion source 6 into the film forming surface of the substrate 2. At this time, the acceleration energy of the ions and the implantation amount are appropriately determined according to the heat resistance of the substrate 2. The method of the ion source is not particularly limited.

After that, the evaporation material 5 evaporated from the evaporation source 4
Is vapor-deposited on the film formation surface of the substrate 2. At this time, ion irradiation from the ion source 6 is performed simultaneously or alternately or after vapor deposition. As a result, a mixed layer of the base material and the film material is formed at the interface between the base 2 and the film formed thereon. Note that the vapor deposition can also be performed by sputtering.

When a film is formed by using this vapor deposition and ion irradiation in combination, the film thickness monitor 8 and the ion current measuring device 9 are used.
Can be used to measure the film thickness of the deposit reaching the substrate 2 and the number of ions, and by setting the values arbitrarily, it is possible to form a film having a desired composition ratio to a predetermined film thickness. it can. Next, the process of film formation will be described with reference to FIG.

First, as shown in FIG. 1A, ion irradiation A is performed on the film forming surface of a substrate 11 made of various alloys, ceramics or the like.
Ti by _1, the ion 1 consisting of Group IVA element such as Zr
By implanting 2 in advance, the ion-implanted layer 13 is formed on the film formation surface of the base 11. The surface-treated substrate 14 for film formation is in the state shown in FIG. After that, FIG. 1 (b)
As shown in FIG. 3, a desired film 15 is formed on the film forming surface of the base 11 by performing vapor deposition on the film forming surface of the base 11 and also performing ion irradiation A ₂ on the film forming surface of the base 11. At the same time, the mixed layer 16 made of the base material and the film material is formed at the interface between the base 11 and the desired film 15.

The film 15 formed on the substrate 11 may be composed of only the evaporation material, or may be composed of a mixed composition of the evaporation material and the ions irradiated from the ion source. As described above, when the ions 12 composed of the group IVA element are preliminarily implanted into the film forming surface of the substrate 11 to form the ion-implanted layer 13, the chemical activity of the film forming surface of the substrate 11 is increased. As a result, when the desired film 15 is formed on the film formation surface of the substrate 11 by using both vapor deposition and ion irradiation, and the mixed layer 16 is formed at the interface between the substrate 11 and the desired film 15, the desired film for the substrate 11 is obtained. The adhesion of the film 15 becomes excellent, and the base 1
The desired film 15 formed in 1 can be hardly peeled off.

Further, even if the acceleration energy of the irradiation ions at the time of forming the mixed layer 16 is made small, the required adhesiveness can be secured, and at the time of forming the desired film 15, the substrate 11 is formed.
It is possible to reduce the thermal damage given to the.
Furthermore, by implanting ions into the film forming surface of the substrate 11, the film forming surface is often hardened, and as a result, mechanical characteristics such as wear resistance can be improved.

Here, concrete examples and comparative examples corresponding thereto will be shown. Example 1 A substrate made of cemented carbide (K10 type) is shown in FIG.
The above-described processing was performed by the film forming apparatus shown in FIG. Specifically, first, the vacuum container was kept at a vacuum degree of 5 × 10 ⁻⁷ torr or less, TiC gas was introduced to the ion source at 6.7 × 10 ⁻⁵ torr, and Ti ions were accelerated at an energy of 200 keV and 2 × 1.
It was injected into the film forming surface of the substrate under the condition of 0 ¹⁶ pieces / cm ² .

Then, titanium (Ti) having a purity of 99.9%
At the same time as evaporating the pellets using an evaporation source using an electron beam and depositing a titanium film on the film forming surface of the substrate,
Nitrogen ions were irradiated from the ion source under the condition of 2 keV.
At this time, the Ti / N transport ratio was adjusted so that the number ratio (Ti / N composition ratio) of Ti and nitrogen atoms reaching the substrate was 1. At this time, the titanium nitride film formed on the surface of the substrate had a film thickness of 1 μm.

Comparative Example 1 IV for the same substrate as in Example 1
1 μm was added to the substrate without pre-injection treatment of group A element ions.
A titanium nitride film having a thickness of m was formed. The method for forming the titanium nitride film was the same as in Example 1. The adhesion of the titanium nitride films of Example 1 and Comparative Example 1 above was measured by an automatic scratch tester with an AE sensor (a scratch test is performed to measure the load at which the film peels). The film of Comparative Example 1 was peeled off at 20 N, while the film was peeled off at 50 N.

Therefore, it is apparent that the film forming method according to the present invention has a better adhesion of the film to the substrate. As the substrate, various metals, alloys or ceramics (for example, nitride ceramics such as AlN and BN) other than the cemented carbide (K10 type) shown in the first embodiment can be considered.

For example, if the surface of a base made of metal is Al
When coating with a nitride compound thin film of N, TiN, BN, etc., ions of Ti, Zr, etc. are implanted into the film forming surface of the base,
After that, AlN, TiN, BN, etc. are deposited. Also, A
When a substrate made of a nitride ceramic such as AlN or BN is coated with a metal thin film of l, Ti, Cr, Ni or the like, ions such as Ti or Zr are implanted into the film forming surface of the substrate, and then Al or Ti. , Cr, Ni, etc. are deposited.

As the ions to be irradiated for forming the mixed layer, for example, in the case of forming a nitride film, ions containing nitrogen ions, such as nitrogen ions or a mixture of nitrogen ions and an inert gas ion, are used. Irradiation is preferable, and in the case of forming a single metal film, it is preferable to irradiate with ions containing an inert gas ion, but hydrogen ions or various metal ions may be used in combination with the above ions.

[0021]

According to the film forming method and the surface-treated substrate for film formation of the present invention, the ion-implanted layer is formed on the film forming surface of the substrate by previously implanting the ions of the group IVA element into the film forming surface of the substrate. Since it is formed, the chemical activity of the film forming surface of the substrate is increased by the presence of the Group IVA element, and the adhesion of the desired film formed on the film forming surface of the substrate can be made excellent. It is possible to make it difficult to peel off the desired film.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a film forming process by a film forming method of the present invention.

FIG. 2 is a schematic view showing the structure of a film forming apparatus used in the film forming method of the present invention.

[Explanation of symbols]

 11 Substrate 12 Ion 13 Ion Implantation Layer 14 Surface Treatment Substrate for Film Formation 15 Film 16 Mixed Layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akinori Ebe 47 Umezu Takaunecho, Ukyo-ku, Kyoto City Nissin Electric Co., Ltd.

Claims (2)

[Claims] 1. A film forming method for forming a desired film on a surface of a substrate, comprising implanting ions of a group IVA element into the film forming surface of the substrate in advance to ion-implant the film forming surface of the substrate. After forming a layer, a vapor deposition on the film forming surface of the substrate and ion irradiation are used together to form a desired film on the film forming surface of the substrate, and a mixed layer is formed at the interface between the substrate and the desired film. A method for forming a film, which comprises forming the film. 2. A surface-treated substrate for film formation used in a film forming method for forming a desired film on a surface, wherein an ion of a group IVA element is injected into a film formation surface of the substrate to form an ion-implanted layer. A surface-treated substrate for film formation, comprising: