JPH03134160A - Method and apparatus for producing compound - Google Patents

Abstract

PURPOSE:To produce the compd. of an exactly controlled compsn. at a low temp. and high speed by applying the respectively independently controlled kinetic energies to respective ionized raw materials and bringing the ions into collision against a substrate, thereby forming the reaction product onto the substrate. CONSTITUTION:The 1st raw material 2 (for example, Si) is heated to evaporate by a heating means 3a and the vapor 2a thereof is excited by an ionizing means 4 to ionize at least a part of the evaporated particles, then the ions are accelerated by an electric field and are brought into collision against the substrate 6 in a hermetic type vessel 1 subjected to a pressure reduction. On the other hand, the 2nd raw material 8d (for example, hydrogen) is excited by an ion gun 8 existing in the position corresponding to the ionizing means 4 to ionize at least a part of the raw material. The ions are accelerated by using the electric field and are brought into collision against the substrate 6. The respectively independently controlled kinetic energies are applied to these raw materials 2, 8d in this way. The two raw materials 2, 8d arrive at the substrate 6 and react without colliding with each other. The compd. having the prescribed compsn. is thus formed on the substrate 6 with the high adhesive strength, density and throwing power.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method and an apparatus for producing a compound, and in particular to a method and apparatus for producing a compound, in particular a method for independently controlled movement of first and second raw materials, each of which is at least partially ionized. This invention relates to novel improvements for the rapid production at low temperatures of precisely controlled compositions of compounds with high adhesion, high density, and high coverage by energized bombardment with substrates to form the compounds.

[Prior Art] There are various methods and apparatuses for producing this type of compound that have been used in the past, and among them, representative ones are described, for example, Proc, 11th Symp.

(Brosy Deindus, 11th Symposium).

on l5IAT'87. Reactive ion beam control technology and Japanese Journal of Appli disclosed on page 317 of Tokyo (198))
ed Physics (Japanese Journal
of Applied Physics), vol 23. N
O, 3, March 1984, pages 273 to 276
The ion-assisted vapor deposition method disclosed on page 2 can be mentioned.

That is, in the former conventional example, a type of raw material is heated by a heating means, and is configured to be attached to a heated substrate by an ionization filament and an accelerating electrode.

Furthermore, the latter conventional example discloses reactive vapor deposition of a-3i:H, in which high-purity H2 gas is ionized and supplied into the chamber in a state in which Si is vaporized.

[Problems to be Solved by the Invention] Since the conventional compound manufacturing method and apparatus are configured as described above, the following problems have existed.

In other words, in the sputtering method and ion blating method, the second raw material is inevitably excited during the ionization process of the first raw material, but the collision energy is independently controlled and the second raw material is excited to the substrate. It has been impossible to variably control the kinetic energy of the collision to control the adhesion force, density, etc. of the compound formed by adhering to the substrate.

In addition, in the reactive vapor deposition method, the first raw material is not excited and collides with the substrate, the excited second raw material does not accelerate and collide, and the vapor velocity of the raw material colliding with the substrate cannot be controlled. It was impossible.

Furthermore, in ion-assisted deposition, the first source material could not be accelerated by excitation.

Here, the general drawbacks of each method when amorphous silicon is produced by vapor deposition using the conventional method described above are summarized as follows.

(1) Disadvantages of the sputtering method are that the film formation rate is low and Ar gas remains. Furthermore, the target material is very expensive.

(2) The disadvantages of ion-assisted vapor deposition are as follows:
It has weak adhesion to the substrate and low density.

(3) Disadvantages of the ion blating method The present invention has been made to solve the above-mentioned problems. In particular, the first and second raw materials, which are at least partially ionized, are each independently treated. A compound that allows controlled kinetic energy to collide with a substrate to form a compound, thereby producing a compound with a precisely controlled composition at low temperature and high speed due to its high adhesion, high density, and high coverage. The purpose of the present invention is to provide a manufacturing method and apparatus for.

[Means for Solving the Problems] The method for producing a compound according to the present invention includes evaporating a first raw material as vapor in a reduced pressure container, and then exciting at least a portion of the vapor to cause it to collide with a substrate. In this method, a second raw material that is excited separately from the first coolant collides with the substrate, and reaction products of each of the raw materials are deposited on the substrate.

Further, the compound manufacturing apparatus according to the present invention is such that at least a part of the vapor of the first raw material evaporated by the heating means is attached to the substrate provided in the reduced pressure container to generate particles. This configuration includes ionization means provided above the heating means, and an ion gun provided in the container for exciting and accelerating at least a portion of the second raw material and causing it to collide with the substrate.

Furthermore, in the compound manufacturing apparatus according to another aspect of the present invention, at least a part of the vapor of the first raw material evaporated by a heating means is caused to collide with the substrate provided in a reduced pressure container, thereby: In the apparatus for attaching evaporated particles to the substrate, the ionization means is provided above the heating means, and the ionization means provided in the container excites and accelerates at least a part of the vapor of the second raw material. This configuration includes an ion accelerator for collision, and a second raw material heating means provided in the ion accelerator for heating the second raw material.

[Function] In the method and apparatus for producing a compound according to the present invention, the first raw material is evaporated by resistance heating, discharge heating, electron beam heating, etc., and vaporized by the ionization means, which is an excitation device disposed above the evaporation device. excite. Excitation methods include discharge and thermionic emission. The excitation causes at least some of the evaporated particles to become ionized. The ions thus formed are accelerated by the electric field between them and the substrate and collide with the substrate. The evaporated particles that have not been ionized are deposited on the substrate without being accelerated. The degree of acceleration (kinetic energy of particles) can be adjusted arbitrarily by controlling the strength of the electric field. The strength of the electric field can be changed depending on the purpose, and can also be changed during the process of compound production. For example, the electric field strength can be initially increased so that the ions collide strongly with the substrate to increase adhesion, and then the electric field strength can be lowered to reduce internal stress. Due to the ion collision effect, dense compounds without voids or cavities can be produced.

Separately from this, the second raw material is excited by discharge or thermionic irradiation, and the at least partially ionized second raw material is accelerated using an electric field and made to collide with the substrate. As a result, most of the second raw material collides with the substrate and reacts without colliding with the first raw material, but some of the collided raw materials mutually excite each other and collide with the substrate as well. The collision energy of this second raw material can be arbitrarily controlled by adjusting the electric field strength.

In this way, by imparting independently controlled kinetic energy to at least a portion of both raw materials and causing them to collide with the substrate and form a compound, high adhesion, density, and high coverage that cannot be obtained with conventional methods. can be obtained, and compounds with accurately controlled compositions can be produced rapidly at low temperatures.

[Example] Hereinafter, preferred examples of the method and apparatus for producing a compound according to the present invention will be described in detail with reference to the drawings.

1 and 2 are for showing the method and apparatus for producing a compound according to the present invention, FIG. 1 is a block diagram showing the first embodiment, and FIG. 2 is a block diagram showing the second embodiment. It is.

First, the container designated by the reference numeral 1 in FIG. An evaporation boat 3 on which a solid first raw material 2 made of Si or the like is placed is provided on the bottom 1a, and the solid evaporation boat 3 has a heating means 3a for heating the first raw material 2. .

A first variable power source 4a is provided above the heating means 3a and the evaporation boat 3, and steam 2a from the first raw material 2 is provided.
An ionization means 4 consisting of a thermionic emission ionization electrode constituting an excitation means for exciting the vapor 2a is provided, and the excitation state of the vapor 2a is controlled according to the excitation state of the ionization means 4.

A substrate 6 held by a holding means 5 is provided on the top plate 1c of the container 1, and a second substrate 6 is provided on the top plate 1c of the container 1.
A variable power supply 7 is connected.

An ion gun 8 connected to a third variable power source 8a is arranged at a position on the side wall 1d of the container 1 that substantially corresponds to the ionization means 4 at an angular position such that the ion beam 8b flies toward the substrate 6. A gas 8d such as hydrogen, which is a second raw material, is provided at the gas supply port 8c of the ion gun 8.
is configured to be supplied.

The first embodiment of the present invention is configured as described above, and its operation will be described below.

First, the first raw material 2 is evaporated by a heating means 3a such as resistance heating, discharge heating, or electron beam heating, and the ionization means 4, which is an excitation device arranged above the evaporation board 3, excites the vapor 2a. Excitation methods include discharge and thermionic emission.

The excitation causes at least some of the evaporated particles to become ionized. The ions thus formed are accelerated by the electric field between them and the substrate 6 and collide with the substrate 6. The evaporated particles that have not been ionized are deposited on the substrate 6 without being accelerated. The degree of acceleration (kinetic energy of particles) can be adjusted arbitrarily by controlling the strength of the electric field. The strength of the electric field can be changed depending on the purpose, and can also be changed in the process of compound production.
It is possible to increase the electric field strength by increasing the potential difference so that the ions strongly collide with the substrate 6 to increase the adhesion force, and then to lower the electric field strength to reduce the internal stress of the compound. This ion collision effect makes it possible to produce dense compounds without voids or cavities.

Separately from this, the second raw material 8d is excited by the ion gun 8 by discharge or thermionic irradiation, and the at least partially ionized second raw material 8d is accelerated using an electric field, and the substrate 6 is
to collide with. As a result, most of the second raw material 8d collides with the substrate 6 and reacts without colliding with the first raw material 2, but
Some of the colliding raw materials excite each other and the same≦substrate 6
collide with The collision energy of this second JjX material 8d can be arbitrarily controlled by adjusting the electric field strength.

In this way, by imparting independently controlled kinetic energy to at least a portion of both raw materials 2.8d and causing them to collide with the substrate 6 to form a compound, high adhesive force and high density that cannot be obtained with conventional methods are obtained. , high coverage is obtained, and compounds with accurately controlled compositions can be produced at low temperatures and at high speed.

Specifically, the operation of the present invention will be described below when Si is used as the first raw material 2 and hydrogen is used as the second raw material 8d. Since Si atoms are heavy and hydrogen atoms are light, the adhesion force of hydrogenated amorphous silicon formed by the reaction of both raw materials to the substrate is mainly determined by the bonding energy of Si with the substrate 6.

Bonding energy usually depends on temperature, but when synthesizing a compound at a low temperature, the higher the Si collision energy, the greater the bonding force.When depositing a compound on the substrate 6, if the energy of the colliding particles is too large, Sputtering occurs and the production rate actually decreases.

However, by colliding particles with appropriate energy, a dense and dense compound can be produced on the substrate 6.

Hydrogen can also be supplied from the atmosphere, but hydrogen molecules have poor reactivity, and it is virtually impossible to react with hydrogen at the concentration required for hydrogenated amorphous silicon.To increase the reaction efficiency, hydrogen atoms must be decomposed to increase the reaction efficiency. It is necessary to excite it by a method such as ionization or ionization. Furthermore, the excited hydrogen collides with the substrate with a kinetic energy above a certain level, thereby further increasing the reaction efficiency. When this hydrogen is made to collide as ions, the amount of collided ions can be grasped as the value of the current flowing through the substrate 6, and by controlling this, an appropriate amount of hydrogen can be made to collide with the substrate 6. Therefore, the composition of the compound can be easily controlled.

Since the Si is evaporated by heating, it can be evaporated at a higher speed than by methods such as sputtering.

By reacting this with excited hydrogen, compounds can be produced at rates not possible with other methods. Moreover, doping can also be performed by using two or more types of gases, such as using a mixed gas of hydrogen boride and hydrogen instead of hydrogen.

For example, when producing an oxide, it is not possible to form an oxide having the same composition as the raw material on the substrate 6 for various reasons using conventional vapor deposition methods or ion blasting methods, resulting in a composition lacking in oxygen. In such a case, oxygen is used in the atmosphere inside the container 1 to cause a reaction to compensate for the lack of oxygen. At this time, if the oxygen is oxygen molecules, the reactivity is poor and the reaction efficiency is poor, so it is necessary to increase the oxygen pressure or increase the flow rate. However, when the pressure inside the container 1 increases, problems occur such as the evaporation rate decreases and the heating means 3a cannot be operated normally. By using oxygen as the second raw material and exciting it so that it collides with the substrate 6, the reaction efficiency is significantly increased, so there is no need to increase the pressure inside the container 1, and an oxide with an appropriate composition can be produced at high speed.

(Experimental Example) In order to accelerate the first raw material 2, it is common to set the substrate 6 to a negative potential, and it is desirable to set the electric field strength to 10V-30KV. In addition, an electric field of IKV or higher is desirable in order to increase the adhesion force, and 50KV or higher in order to lower the internal stress.
In order to accelerate the second raw material 8d, which is preferably 0V or less, an ion gun, an ion accelerator, etc. can be used, and the same method as for the first raw material 2 can be used. The kinetic energy of the second raw material 8d is 10 eV-1
0 KeV is desirable.

Specific examples of the combination of the first raw material 2 and the second raw material 8d include the first raw material 2, the second raw material 8d, metals and alloys, gases metals and alloys, vaporized particle oxides of metals, gas nitrides, gases, and the like.

Furthermore, the configuration shown in FIG. 2 is another example of the configuration shown in FIG. shall be explained.

An ionization means 4A consisting of an ionization arc discharge electrode constituting an excitation means for exciting the steam 2a generated from the first raw material 2 is provided, and the excitation of the steam 2a is performed according to the excited state of the ionization means 4A. The state is controlled.

An ion accelerator 8A is disposed at a position on the side wall 1d of the container 1 that substantially corresponds to the ionization means 4A at an angular position such that the ion beam 8bB flies toward the substrate 6. The second raw material 8
An evaporation boat 10 on which metal of dA is placed and has a heating means 10a is installed therein.

Therefore, in the configuration shown in FIG. 2, the vapor 2a is excited by the ionization means 4A, and at least some of the evaporated particles thereof are ionized, similarly to the operation described above.

Further, the evaporated particles of 8 dA of the second raw material evaporated by the heating means 10a of the evaporation boat 10 are excited by the ion accelerator 8A, and at least a part of the ion beam of 8 dB is accelerated through the electric field and collides with the substrate 6. do.

Note that the arrangement in the container 1 described above is an example, and other arrangements not shown may also be used.
Similar effects can be obtained.

Further, if necessary, the third raw material may be supplied as an atmospheric gas directly to the vicinity of the substrate 6 in the container 1 without using an excitation means.

[Effects of the Invention] Since the method and apparatus for producing a compound according to the present invention are configured as described above, the following effects can be obtained.

(1) Since the vapor of the first raw material evaporated from the evaporation boat is excited by the ionization heating means,
The material collides with the substrate in an ionized and accelerated state, and the second raw material is also ionized and collides with the substrate, so by controlling the strength of the electric field, the degree of acceleration can be freely controlled. By controlling the adhesion force and internal stress of the reaction product (compound) generated on the substrate, and by the impact of ions on the substrate, it is possible to produce a dense compound without voids or cavities.

(2) In addition, because at least a portion of each raw material is given independently controlled kinetic energy and collides with the substrate to form a compound, it has high adhesion, density, and coverage that cannot be obtained with conventional methods. properties, and compounds with precisely controlled compositions can be produced rapidly at low temperatures.

[Brief explanation of the drawing]

The drawings are for showing the method and apparatus for producing a compound according to the present invention, and FIG. 1 is a schematic diagram showing the first embodiment, and FIG. 2 is a schematic diagram showing the second embodiment. 1 is a container, 2 is a first raw material, 3a is a heating means, 4°4a is an ionization means, 6 is a substrate, 8 is an ion gun, 8A is an ion accelerator, 8d and 8dA are second raw materials, 10a is for the second raw material It is a heating means.

Claims (4)

[Claims] (1). After the first raw material (2) is evaporated as a vapor in a reduced pressure container (1), at least a part of the vapor is excited and collides with the substrate (6), independent of the first raw material (2). The excited second raw material (8d) is caused to collide with the substrate (6), and reaction products of each of the raw materials (2, 8d) are deposited on the substrate (6). Method of manufacturing the compound. (2). 2. The method for producing a compound according to claim 1, wherein the first raw material (2) is made of a metal or a compound, and the second raw material (8d) is made of a gas. (3). Substrate (6) provided in a depressurized container (1)
On the other hand, the first raw material (2) evaporated by the heating means (3a)
In an apparatus for producing a compound, the heating means (
ionization means (4) located above 3a); and ions provided in the container (1) for exciting and accelerating at least a part of the second raw material (8d) and causing it to collide with the substrate (6). a gun (8), the ionization means (4) and the ion gun (8) are each independently controlled, and each of the raw materials (
2, 8d) is ionized and collides with the substrate (6) to form a compound. (4). Substrate (6) provided in a depressurized container (1)
On the other hand, the first raw material (2) evaporated by the heating means (3a)
In an apparatus for producing a compound, the heating means (
3a); and an ionization means (4A) located above the container (1) for exciting and accelerating at least a part of the vapor of the second raw material (8 dA) and causing it to collide with the substrate (6). An ion accelerator (8A) and the ion accelerator (
8A) for heating the second raw material (8 dA), at least a part of each of the raw materials (2,8 dA) is ionized and heated to the substrate ( 6) Collision with each other to form a compound.