JPS6179767A - Formation of film - Google Patents

Abstract

PURPOSE:To form easily a film deposited by evaporation with high quality in the stage of depositing the film of nitride or carbide by evaporation on the surface of a substrate by a high-frequency bias ion plating method, etc. by providing an electron emitter between the substrate and a vapor deposition source and adjusting plasma density by said emitter. CONSTITUTION:The substrate 1 to be subjected to vapor deposition such as glass or ceramics is held by a holder 8 provided with an electrode 2 in a vacuum vessel 9. Metallic Ti is put into a crucible 3 in the bottom of the vessel 9 and is heated and evaporated by an electron beam 5. The inside of the vessel 9 is evaporated through a discharge valve 11 and gaseous N2 is preliminarily introduced through a supply valve 10 into the vessel. A high-frequency voltage is impressed by a high-frequency power source 7 to the electrode 2 to generate electric discharge near the substrate 1 and to form N2 plasma, thereby forming Ti and TiN and depositing TiN on the surface of the substrate 1. The electron emitter 12 having a W filament 14 is disposed between the substrate 1 and the material 4 for vapor deposition to adjust the quantity of the thermoelectrons (e) directed toward an anode 13 and to control the plasma density so that the dense film having high hardness and high quality deposited by evaporation is formed on the substrate 1.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method of forming a film by an improved high frequency bias ion plating method or high frequency bias sputtering method.

[Prior Art and Problems Therewith] Since Mattox announced the DC bipolar ion brating method in 1963, various ion brating methods have been developed. The high-frequency bias ion brating method is one of them, and in 1969, Matt
Published by ox. When an insulating film is formed by an ion blating method, an acceleration effect due to the application of a DC voltage cannot be expected due to charge-up, and dielectric breakdown of the film may occur. In this case, it has been found that applying a high frequency to the substrate is effective. According to this method, the substrate is negatively biased due to the difference in moving speed between ions and electrons in the high-frequency plasma, creating a potential difference between the substrate and the plasma, and the ions are accelerated by the electric field and incident on the substrate. Researchers have found that this method is very effective for forming oxide films such as TiQ□ and 5iQ2, and uses a lower pressure than conventional methods.
It has been found that a hard, dense, and high-quality film can be obtained at a 0-' Torr level.

However, although it is sufficiently effective for the above-mentioned oxide films, when it is applied to nitride films and carbide films, it has been found that it is insufficient as it is. This is because when synthesizing a compound thin film using the reactive ion blating method, the degree of ionization or activation required and its energy depend on the type of compound, starting materials,
This varies depending on the introduced gas, the X-plate, etc., but in the high-frequency bias ion plating method, the ion density or plasma density and its kinetic energy cannot be independently controlled because both depend on the input high-frequency power. In addition, the conventional high frequency /<
Exactly the same thing can be said about the Iasbatta method.

[Objective and Summary of the Invention] In view of the above-mentioned points, the present invention provides a method of forming a film using a high frequency bias ion plating method or a high frequency bias smentor method that can control plasma density without changing high frequency power. It was invented as a result of research with the aim of providing a method, and its gist is to generate evaporated particles by heating an evaporation source in a vacuum chamber, or to generate sputtered particles by sputtering a target,
A film is formed by a high frequency bias ion plating method or a high frequency bias sputtering method in which gas plasma is formed by providing high frequency power to the substrate, and evaporated particles or sputtered particles ionized by the gas plasma are deposited on the substrate. An improved high frequency bias ion plating method characterized in that an electron emitter is provided between the substrate and the skin source or target, and the plasma density is controlled by the amount of electron current of the electron emitter. Alternatively, the present invention relates to a method of forming a film by high frequency bias sputtering.

[Structure of the invention]

Hereinafter, the present invention will be explained in detail with reference to the drawings.

Figure 3 shows a principle diagram of a high frequency bias ion plating device that combines electron beam heating with a power supply.
FIG. 1.2 shows a principle diagram of the high frequency bias ion plating apparatus with an electron emitter of the present invention.

In the figure, l is a substrate, 2 is an electrode for inducing high-frequency discharge, 3 is a crucible for a vapor deposition source, 4 is a vapor deposition source material, 5 is an electron beam, 6 is a shutter, 7 is a high-frequency power source, 8 is a holder for a substrate, 9 is a vacuum chamber, IO is a main valve, 11 is a leak valve, 12 is an electron emitter, 13 is a 7 node, and 14 is a filament.

The apparatus according to one embodiment of the present invention is shown in FIG.

It is a three-pole type device in which an electron emitter 12 made of a tungsten filament and a 77-dead 13 made of copper are arranged facing each other.
This is the case using an annular electron emitter 12 with nodes 13. In either case, the electrons emitted from the electron emitter 12 are ionized by colliding with the detonating particles.

Activation is performed, and the ion density is controlled by the amount of electron current. The amount of electron current is determined by the amount of electrons flowing through the filament and the voltage, and the energy of the electrons is mainly determined by the upper k between the 7th node and the filament.

When forming a film using such a high-frequency bias ion plating apparatus, first, a predetermined substrate 1 selected from various materials such as glass, plastic, and ceramics is placed in a substrate holder 8 in a vacuum chamber 9 and placed in a vacuum chamber. After reducing the pressure inside the vacuum chamber 9, a predetermined plasma generating gas (for example, 07.N7.Ar, etc.) is introduced into the vacuum chamber 9 at a predetermined rate.
-1 High frequency power is applied to the electrode 2 to induce a high frequency discharge near the base 1.

The source material 4 for forming a predetermined film is heated by the electron beam 5, the electron emitter 12 is activated, and after various conditions are adjusted 1-, the shank 6 is opened to deposit it on the substrate 1 surface. .

Although Figures 1 to 3 show examples in which electron beam heating is used as the evaporation source, other thermal evaporation methods, magnetron sputtering, plasma sputtering, and ion heating can also be used. A sputtering method such as the Muspanter method can be used in combination with a high frequency bias and an electron emitter. The outline of the apparatus for such a high frequency bias sputtering method can basically be considered to be that the Shigeru source in FIG. 1.2 is replaced with a target.

According to the present invention, the electron emitter 12 is provided between the substrate l and the evaporator [4], and by adjusting the amount of electron current to the emitter 12, the interlocking energy of the evaporator particles can be independently adjusted to the ionized evaporator particles. The plasma density or ion density can be controlled. Similarly, an electron emitter is provided between the substrate and the target, and
By adjusting the amount of electron current to the E emitter 12, the kinetic energy of the Svanter particles can be independently controlled, and the plasma density or ion density of the ionized Svanter particles can be controlled. The method of the present invention makes it possible to widen the discharge pressure range of discharge by applying high-frequency power and, in particular, to lower the discharge pressure.

A film of higher quality can be obtained compared to conventional high frequency bias ion plating methods or high frequency bias sputtering methods. Furthermore, when applying the ion blating method, the optimum ion kinetic energy and ion density or plasma density required depend on the membrane material and substrate.

Since they differ depending on the starting material, introduced gas, etc., being able to independently control the ion kinetic energy and ion density or plasma density is an effective means for obtaining a high-quality film.

In particular, the present invention is effective for reactive high frequency bias ion plating methods for forming films such as 1m thick films, nitride films, and carbide films.

[Example] Next, an uninvented embodiment will be described.

Example 1: A TiN film was formed on a substrate by the method shown below using a high frequency bias ion plating apparatus with an electron emitter shown in FIG. First, one dimension is 30cm
30cm square soda lime glass substrate (thickness: 2
(2) was washed with a neutral detergent, thoroughly rinsed with water, washed with ethanol, and dried with N2 gas.Then, this glass substrate i was placed in a substrate holder 8 in a vacuum chamber 9. ,
As a source material, a plate-shaped metal Ti was placed in the crucible 3 and ignited. Next, the inside of the vacuum chamber 9 was pumped 2×10− by an exhaust pump (diffusion pump with liquid N2 trap).
After exhausting to 150' Torr, N2 gas was introduced from the N2 gas introduction valve to 5 x 10-' Torr, and the electrode 2 was aimed at the glass plate 1 using the high frequency power source 7.
A high frequency power of W is applied to start discharging I near the substrate, a N plasma is formed and the matsunog is Jfi, and then the high frequency input is set to 20 h, while metal T as an evaporation source is applied.
i is heated by an electron beam, while 7 nodes 12
Applying a current 2 of 150 mA, the electron emitter 12 is activated, and the pressure in the vacuum chamber 9 is further increased to 3 X 10-' Ta
After adjusting the temperature to rt, the shutter 6 was opened and a TiN film (1 body m) was reactively deposited on the glass substrate (room temperature) at a predetermined deposition rate.

In this way, TiNll5J was prepared in combination with a t-emitter in a 3 to 5 x 10-' nitrogen atmosphere.
teeth.

It was golden in color and had sufficient adhesion and hardness. On the other hand, a TiN film produced using only the high-frequency bias ion blating method according to the method of Example 2, but without prior use of electronic engineering E = t, is TiNff! The color was reddish, not the golden color typical of 2, and the hardness was not sufficient.

Example 2 SiJ, 1
A film was formed. First, a square sortalime glass substrate (thickness: 2 zm) with dimensions of 30 cll x 30 cm was washed with a neutral detergent, thoroughly rinsed with water, washed with ethanol, and dried with N2 gas. The substrate 1 was set in a substrate holder 8 in a vacuum chamber 9. As a vapor deposition source material, granular 81 was placed in the crucible 3 and prepared. Next, after evacuating the inside of the vacuum chamber 9 to 2XIO-GTorr with an exhaust pump (diffusion pump with liquid N2 tramp), N2 gas is introduced into the tank 5X1 from the N2 gas introduction valve.
A high frequency power of 150 W is applied to the glass plate 1 through the electrode 8 by the high frequency power source 7 to start a discharge near the substrate to form N2 plasma and adjust the matching, and then the high frequency input is increased to 200 W. Meanwhile, metal Si as ffJ was heated with an electron beam. The pressure inside the vacuum chamber 9 is further increased by 3 to 5 x 10
-' Tarr, open the shunter 6 and deposit the 513N4 film (at room temperature) on the glass substrate (room temperature) at the prescribed deposition rate.
100OA) was reactively deposited.

In this way, in order to improve the reactivity of Si and H and obtain a higher quality Si3N4 film, the 5i
3Na film is transparent, and Si3N has sufficient adhesion and hardness.
There were 4 films. On the other hand, 5i3N was formed on a glass substrate according to the method of Example 2, but only by high frequency bias ion plating method without using an electron emitter.
The o film was transparent, but had insufficient hardness and density. Moreover, even if Si is used as a starting material and deposited on a substrate at room temperature in a nitrogen atmosphere using a normal vapor deposition method, transparent S! 3+
A 10 film was not obtained, and only a reddish-brown mixed film of Si and SiQ□ films was obtained.

[Effects of the present invention] As described above, according to the present invention, by providing an electron emitter between the substrate and the evaporation source, the ion density or plasma density can be adjusted independently of the kinetic energy of the ions of the Moba particles. This makes it possible to expand the discharge pressure range and obtain high-quality membranes.

In particular, when an insulating substrate such as glass or ceramics is used as the base, 1 When C acceleration, such as in normal ion blating, is used, the surface of the substrate is charged just before the start of evaporation, which has an accelerating effect on the evaporated particles forming the first layer. Can't you expect that?
In this case, a high frequency bias is effective, and the degree of ionization or activation can be increased by using an electron emitter as in the present invention, thereby making it possible to obtain a film with high adhesive strength and hardness.

[Brief explanation of drawings]

FIG. 1.2 is a schematic diagram of a high frequency bias ion plating device with an electron emitter according to the present invention, and FIG. 3 is a schematic diagram of a conventional high frequency bias ion plating device. 1: Substrate, 2: Electrode, 3: Nil acupuncture point. 4. Raw materials in advance, 5. electron beam. 6 shunter, 7: high frequency power supply. 8: Holter for substrate, 9: Vacuum chamber.

Claims (1)

[Claims] In a vacuum chamber, an evaporation source is heated to generate evaporated particles, or a target is sputtered to generate sputtered particles, and high-frequency power is supplied to a substrate to form a gas plasma. In a method of forming a film by high-frequency bias ion plating or high-frequency bias sputtering, in which evaporated particles or sputtered particles ionized in plasma are deposited on a substrate, there is a gap between the substrate and the evaporation source or target. Equipped with an electron emitter,
A method of forming a film by an improved high frequency bias ion plating method or a high frequency bias sputtering method, characterized in that the plasma density is controlled by the amount of electron current of the electron emitter.