JPH0620976A - Plasma vapor phase reactor and plasma vapor phase reaction method - Google Patents

Abstract

PURPOSE:To obtain a plasma vapor phase reactor which can simultaneously process a plurality of substrates and which has a high film growing speed or a high etching speed for the film by a method wherein an opening having a recess for a reaction space or a groove is provided in at least one of a pair of electrodes. CONSTITUTION:A reactive basic body reaches a quart hood 21 and a positive glow pole region 5 through a netlike electrode 2, and high frequency energy is supplied to a pair of electrodes 2, 3. Here, a simple opening or groove is provided in one electrode 3 and an opening having a recess for a reaction space or a groove is provided in the other electrode 2, whereby lines of electric force 5 are focussed at regions 17, 18 to form a high concentration electric flux region. As this result, it is possible to suppress widening of a positive glow pole 25 in the lateral direction and to concentrate a plasma on a region 20 of an electrode center part.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma vapor phase reaction method (that is, a plasma vapor phase film forming method or a plasma etching method, hereinafter simply referred to as a plasma process, that is, a PP method). The present invention relates to a PP method, which uses a parallel plate type electrode method, further arranges a substrate having a surface to be formed in a positive column region, and performs a large amount of film formation or etching.

[0002]

2. Description of the Related Art Conventionally, in the parallel plate type PP method, the surface to be formed is a cathode or an anode.
There is known a method of using a cathode dark portion or an anode dark portion which is generated above or in the vicinity of these electrodes. In such a conventionally known method, the area of the surface to be formed cannot be made larger than the area of the electrode. For this reason, the semiconductor, insulator, or conductor coating can be formed on a large-area substrate, but it cannot have a surface to be formed that is 5 to 30 times as large as the electrode area. That is, it had a drawback that mass production was not possible.

[0003]

Therefore, when a non-single-crystal semiconductor containing amorphous silicon is to be produced by the PCVD method, the production price per 1 cm ^{2 of} the substrate becomes as high as 1 yen or more, and the solar cell, etc. It has a major drawback that it cannot be applied to the production of products whose unit price is low.
In addition, the film formation rate is not sufficient at 1 to 2Å / sec, and from these points, a PCVD method having a large productivity and a large film growth rate of 3 to 10Å / sec has been demanded. The present invention has been made to achieve such an object.

[0004]

That is, the method of the present invention uses a positive column of plasma glow discharge. In the present invention, substrates having a surface to be formed in the positive column region are arranged in parallel and separated from each other. PCVD using such a positive column
Regarding the law, the patent application 57-16372 filed by the present inventor
9, 57-163730 (Plasma vapor phase reactor) (September 1982 2
Application dated 0).

In the present invention, a reaction is caused by such a positive column,
This is a large-scale production. However, since the positive column generally spreads over a large space, the plasma density in the vicinity of the surface to be formed is reduced, and as a result, there is another drawback that only the same film growth rate as in the method using the dark portion can be obtained.

By removing such a defect, the positive column is converged, that is, the spread of the discharge plasma is suppressed, the plasma density in the central portion is further increased, the active reactive gas is increased, and eventually the active reactive gas is increased. The feature is that the film growth rate is increased to 2 to 3 times.

FIG. 1 shows a parallel plate type electrode (2) according to the conventional method,
(3) and its electric lines of force (5) Moreover, the equipotential surface (15) orthogonal to this line of electric power is shown. These electrodes are arranged in the reaction vessel (4) under reduced pressure, and the reactive gas (6) supplied from (7) is discharged from one of the electrodes and the other substrate (1) is discharged. A film is formed on the surface to be formed.

In FIG. 2A, 13.56 MHz is applied between the electrodes (2) and (3) from the high frequency power source (10). Unnecessary reaction products are valve (11) in the exhaust system (8), pressure adjustment valve
(12), Exhausted to the outside by the vacuum pump (13).

In such a conventional method, the lines of electric force (5) are applied perpendicularly to the surface to be formed, so that there is another drawback that the surface to be formed is sputtered (damaged). In FIG. 1B, the needle-shaped electrode (9) is arranged separately from one of the electrodes (2) of FIG. 1A. Here, the electrode (2) (50 cm x 50 cm), the interval between the electrodes (2) and (3) was 4 cm, the needle electrode length was 1 cm, and the interval was 5 cm. Such a needle electrode is shown in FIG.
Even when the device is arranged in the device (A), the lines of electric force are dispersed from the needle-shaped electrode and are supplied in the expanding direction, and are applied vertically to the substrate (1). The equipotential surface (15) is only provided perpendicular to the lines of electric force. Therefore, the needle-shaped electrode does not improve the film quality of the film and the film growth rate, although it has some features such as facilitating the start of discharge even when it is arranged in the device in FIG. 1 (A). It was

FIG. 2 shows an electrode and its outline in the PP method, that is, the PCVD method or the plasma etching method of the present invention. Other parts of this reactor are in accordance with the above-mentioned patent application of the present inventor.

In the drawing, the pair of mesh electrodes (2),
(3) and substrates (1) and (1 ′) having a surface to be formed. The supply of reactive gas is from (23) to the quartz hood (21),
The positive column region (5) is reached through the mesh electrode (2). Substrates (1), (1) are arranged in the positive column region so that their back surfaces are in close contact with each other and parallel to the lines of electric force (5). The substrate is surrounded by a quartz basket. The reaction products are exhausted (24) through the lower hood (22). High-frequency energy is externally supplied to the pair of electrodes (2) and (3) and is discharged to a region (10) where a uniform electric field is formed.

In this drawing, the electrode area is 25 cmφ (electrode spacing
15 cm) or 70 cm × 70 cm (electrode spacing 35 cm), and by forming an opening or groove (14) in this electrode, the first glob in the uniform electric field region of the present invention is formed.
A high-brightness second glow discharge was simultaneously generated in the discharge and the opening or groove (14). As can be seen from this figure, the lower electrode (13) is, for example, simply a hole or groove (0.5
~ 3cm eg only about 1cmφ or about 1cm width). In another example, like the upper electrode, the opening or groove is provided with a curved surface (16) in the direction opposite to the positive column to make it concave. As shown in FIG. 1 (B), in the device of the present invention, the electrodes are not flat or convex on the discharge surface, but conversely, by making the electrodes flat or concave, the lines of electric force (5) become regions (17), It can be seen that convergence occurs at (18) and a high-density electric flux region occurs. By doing so, in addition to the first plasma discharges (27), (28) generated by the conventionally known uniform electric field, the high-intensity second plasma region ( We were able to generate 17) and 18) at the same time.

As a result, in the conventional case, the positive column (25) has a large lateral spread and the plasma is dispersed. However, in the PP device of the present invention, the plasma gathers in the central part (20) of the electrode (3).
5) I was able to show a tendency. Further, by performing the second discharge of this high-intensity plasma, the film growth rate could be increased by 2 to 3 times. For example, using 100% silane, 0.1torr, 30W, (13.56MHz), electrode surface 25cm
When φ is set and the electrode interval is 15 cm, the substrate is 10 cm, and 6 plates are arranged (total area 600 cm ² ).
Without 4), the film growth rate was 1-2 Å / sec, but it was 4-6 Å / sec, which was 2-3 times higher by only providing several holes or grooves (14) in each electrode. It has become possible to increase.

This is compared with the conventional method of FIG.
It can be seen that, in addition to being able to increase the amount of substrates provided by up to 20 times, the film formation rate can be increased by 2 to 3 times, which is excellent in double. In addition, as a result of the convergence of the positive column, this positive column sputters the inner wall of the reactor, activates the water and adhering impurities adsorbed on the inner wall and takes them into the film, and the film quality is improved. Considering that the possibility of deterioration can be further reduced, it was proved to be excellent in triplex.

In the above description, only the production of the semiconductor film is described. However, it is also effective to use the method of the present invention for the plasma etching used for the positive column. That is, for the substrate to be etched, CF
The method of the present invention is particularly effective when an etching gas such as Br or CHF is introduced to perform anisotropic etching on the surface to be processed on the substrate in a direction parallel to the surface of the substrate. That is, plasma etching only requires deep anisotropic etching in the direction perpendicular to the substrate. However, when selective etching is performed to flatten the convex portion of the substrate, the electric field (electric flux) is parallel to the substrate, and decomposition occurs for a bond having a high bond energy of C—F bond. Then, a large amount of F radicals can be obtained by performing a high-intensity plasma discharge in addition to the so-called one-step glow discharge that allows the radicals to have sufficient energy to form radicals, and only the substrate-like convex portions can be obtained. It was possible to perform selective etching, and it was possible to perform it particularly effectively. The present invention is complemented with the following examples.

[0016]

[Example] [Example 1] In the PCVD method using FIG.
The case where silicon is formed is shown. The numbers correspond to those in FIG. In the drawing, the lower mesh electrode (3) is provided with three high-intensity plasma discharge regions and four upper regions. The substrate (1) is arranged in a quartz holder, and this jig is rotated at 3 to 5 times / minute. Non-single-crystal silicon was produced from silane as a reactive gas. That is, the substrate temperature 210
℃, pressure 0.1 torr, silane 30cc / min, discharge output 30W (13.5
6MHz), the film growth rate is 4.1 Å / sec for 20 minutes to achieve a thickness of 5000Å.

It can be seen that no discharge is observed in the outer space of the quartz holder in which the substrate is arranged, and there is little possibility of spattering the stainless wall surface of the reaction vessel and mixing impurities such as water.

As the substrate, 6 pieces of 10 cm × 10 cm are arranged,
In addition to the shape as shown in FIG. 1 (A), the yield of the reactive gas (component forming the coating film / gas to be supplied, etc.) was nearly 8 times. Further, in FIG. 2, it was possible to double the height compared with the case where no opening or groove (14) was provided.

Example 2 In FIG. 3, methane (CH ₄ ) and silane (SiH ₄ ) were mixed at a ratio of 1: 1, and Si _x C _1-x (0
The coating of <x <1) was produced. In the drawing, high-intensity plasma discharge was observed in the groove. As compared with the case where there is no such local discharge, there is a large amount of Si--C bonds that become silicon carbide, and even if chemical etching occurs, the film is hard and dense. Others are the same as in the first embodiment.

[Embodiment 3] In this embodiment, FIG. 2 is used for plasma etching. In FIG.
The case where the silicon nitride film at the apex of the convex portion is removed is shown. Figure 3
As shown in (A), the surface of the silicon single crystal substrate (1) has convex portions (3) having a width of 1 to 2 μm and concave portions (1 to 2 μm). Its depth was 1.5 μm. Further, silicon nitride (31) was formed on the upper surface to a thickness of 1000Å, and then a resist (32) was coated.

Next, using the apparatus shown in FIG. 2, plasma in the direction perpendicular to the drawing (parallel to the surface of the substrate) was added with 5% oxygen to CFBr. The frequency of this plasma was low at 30 KHz. Then, as shown in FIG. 3B, only the resist (32) on the convex portion (33) could be removed. Further, the silicon nitride is removed, and the resist is removed by a known method.
(C) was obtained. After that, various semiconductor devices could be manufactured by providing a process of selectively mixing impurities into the convex portion.

[Embodiment 4] In this embodiment, the silicon single crystal has irregularities, the upper surface is flat, and the depressions are filled with silicon oxide. That is, as shown in FIG. 3 (A), silicon nitride (33) and silicon oxide (32) were laminated and formed on the uneven substrate.

After that, the convex portions are removed by the plasma etching apparatus for applying an electric field in parallel to the substrate surface shown in FIG. 2, and as shown in FIG. 3B, the convex portions (33) and concave portions for the semiconductor are formed. Silicon oxide (23) was left on the upper surfaces of (34) to flatten these upper surfaces.

[Embodiment 5] In this embodiment, the concave portion of the electrode portion of the VLSI is removed. That is, the case is shown in which the recesses of the electrode portion are filled with a conductor to substantially form the electrode lead pattern. In FIG. 4, the semiconductor surface (1)
Buried field insulator (36), source, drain region (37), (38), gate (39), interlayer insulator (41), 1-2μ
It has an opening (42) of mφ (depth ± 0.5 to 2 μm). Even if the lead (43) is not formed on this electrode portion, the groove (4
Due to the concave portion in 2), a fine pattern of 2 μm or less cannot be cut even by using the electron beam exposure technique. For this reason, in this embodiment, an aluminum (43) having silicon added thereto is formed on the entire surface thereof to a thickness of 0.5 to 2 μm. Then, this aluminum has a recess (40). Further, this substrate was subjected to anisotropic plasma etching using a reactive gas of CCl _{4 in} the apparatus shown in FIG.
3) was removed. Thus, the upper surfaces of the concave portions (34) and the convex portions are made substantially flat as shown in FIG. 4 (B). Then, the aluminum selectively remains in the opening (42) and its upper surface (3
3) It became possible to make it a roughly flat surface in (34). For this reason, a second aluminum (44)
Was added to form a film having a thickness of 0.2 to 0.5 μm.

After that, by a known plasma etching apparatus for performing anisotropic etching in the vertical direction, 1 to 2 μm is obtained.
I was able to get the lead of the narrow pattern. 4 and 3 are extremely demanded for manufacturing a three-dimensional device in which semiconductor elements are vertically stacked on a substrate.

[0026]

As described above, according to the present invention, as shown in FIG. 2, in the PP device, the electrodes are provided with holes or grooves, and the lines of electric force are converged in this region to generate high-intensity discharge. Is. In this system, when the substrate is arranged on the parallel plate electrodes as shown in FIG. 1, a part of the substrate may have a high flux reaction region. However, when considering the sputtering effect due to high-intensity discharge, it is effective to improve the film quality by disposing a surface to be formed in this discharge to reduce the sputtering (damage), and as a result, the method of the present invention It was found to be particularly effective for the PP method in which the substrate is arranged in parallel with the lines of electric force by pillars.

Further, the embodiment of the present invention is based on non-single crystal Si and Si.
_x C _1-x . However, using silane and germane, Si _x Ge
_1-x (0 ≦ x <1) Si _x Sn using silane and tin chloride
_{Even 1-x} (0 <x ≦ 1) is effective. Al to AlCl ₃
And Si ₃ N ₄ with SiH ₄ and NH ₃ , SiO ₂ with SiH ₄
And N ₂ O are used to form an insulating film by the PCVD method, or the plasma etching method is used to selectively form the Si film.
The present invention is also effective when removing O ₂ , Si, Si ₃ N ₄ , photoresist and other compound semiconductors.

[Brief description of drawings]

FIG. 1 shows a conventional plasma vapor phase reactor.

FIG. 2 shows an outline of the vicinity of an electrode substrate of a plasma vapor phase reaction apparatus of an example.

FIG. 3 shows another embodiment in which a semiconductor device is manufactured.

FIG. 4 shows another embodiment in which a semiconductor device is manufactured.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 16, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction content]

[Document name] Statement

Title: Plasma vapor phase reaction apparatus and plasma vapor phase reaction method

[Claims]

Detailed Description of the Invention

[Field of Industrial Application ]
Gas phase reactor (ie plasma vapor phase coater or
Plasma etching equipment) and a plasma etching equipment using the equipment.
The present invention relates to a plasma gas phase reaction method.

[Prior Art] Conventionally, plasma gas phase reaction
As a device, a parallel plate type as shown in FIG.
It has been known.

In the structure as shown in FIG . 1 (A),
The surface to be formed on the substrate (1) is a cathode or an anode.
On the (node) or in the immediate vicinity of these electrodes
The film is formed by arranging it in the dark part of the cathode or the dark part of the anode.

FIG . 1 shows a flat plate placed in a vacuum container (4).
A pair of row and plate electrodes (2), (3), placed on the electrode (3)
Substrate (3), high frequency power supply (10), gas supply system (7), exhaust system
(8), valve (11) that constitutes the exhaust system (8), pressure adjustment valve
A vacuum pump (13) is shown.

Further, a voltage is applied from a pair of electrodes (2) and (3).
High-frequency electric field lines of force (5)
The equipotential surface (15) is shown. Plasma shown in FIG.
In the gas phase reactor, the reaction gas supplied from (7)
Is fed from the electrode (2) into the reaction chamber as shown by (6).
And plasma is generated between the electrodes
A film is formed on the formation surface of the other substrate (1). In general
13.56MHz is used as the high frequency supplied from (10).
Be done. In such a conventional method, the lines of electric force (5) are not covered.
Since it is applied perpendicularly to the formation surface, the formation surface is sputtered (damaged).
Will be damaged. FIG. 1B is one of the electrodes of FIG.
(2) with needle electrodes (9) spaced apart from each other
Is.

The example shown in FIG . 1B shows the size of the electrode (2).
Is 50 cm x 50 cm, the distance between the electrodes (2) and (3) is 4 cm, and the needle-shaped electrode is
In this example, the pole length is 1 cm and the needle electrode spacing is 5 cm.
It With this configuration, the lines of electric force are more
It will be dispersed and distributed in the spreading direction, but the substrate
A line of electric force is applied vertically to (1). This
Therefore, by using a needle-shaped electrode (9), discharge start
Although it has some features such as facilitating
Does not particularly improve the film quality or film growth rate of
It was

Further , in the above-mentioned conventionally known method,
Is larger than the area of the electrode (3).
It also had the drawback of not being able to exercise. others
Therefore, a non-single crystal semiconductor containing amorphous silicon is used for PC
When making by VD method (plasma CVD method)
The manufacturing price per 1 cm ² of the board is expensive, and it is expensive.
This has been an obstacle to reducing the manufacturing cost of solar cells and the like.

[Problems to be Solved by the Invention ]
Can process multiple substrates simultaneously and
The film growth rate on the film is high, or
Providing a plasma vapor phase reactor with a high etching rate
The porpose is to do.

[Means for Solving the Problems] A pair of parallel
Plasma gas phase reactor with a substrate placed vertically between plate electrodes
The reaction space on at least one of the pair of electrodes.
The feature is that an opening or groove having a concave shape is provided for
It is a characteristic. In the above configuration, the reaction space
The plaque is the plasma generated between a pair of parallel plate electrodes.
It is a reaction space. The present invention provides a reaction space for electrodes.
By providing an opening or groove having a concave shape,
Electric field lines in the area where the holes or grooves are provided.
It is characterized by concentrating and causing high intensity discharge in this area
To do.

[Operation] Provide a hole or groove in the electrode.
The area where the opening or groove is provided by
To concentrate the lines of electric force and requires plasma
It can be concentrated in various reaction spaces.

[Example 1] The following is a description of the implementation using the present invention.
Here is an example: This embodiment is formed between a pair of parallel plate electrodes.
The reaction is carried out in the sunlight column, and mass production is carried out.
It However, when the positive column method is generally used, the positive column part
Of the plasma near the surface to be formed
The density is reduced, and as a result, it is similar to the method using dark areas.
It has the drawback that only a high film growth rate can be obtained.
Therefore, the positive column is converged by using the present invention.
(Impress) Excuse, that is, the spread of discharge plasma
Hold down and press the plate at the center where the board is placed.
It tried to increase the Zuma density and increase the film growth rate.
An example is the configuration of this embodiment.

In the plasma vapor phase reactor in this embodiment,
The outline is shown in FIG. Plasma vapor phase reactor shown in FIG.
Film is formed using the positive column of plasma glow discharge.
It is a device of the type. In this embodiment, a pair of parallel
By causing discharge between the plate electrodes (2) and (3)
A plurality of substrates having a surface to be formed in the positive column region to be formed
Are arranged in parallel and spaced apart from each other, and
Form a film. The board is backed as shown by (1), (1`)
A set of two combined sheets, separated by multiple spaces
It is provided in the room. A PC using such a positive column
Regarding the VD method, patent application 57-1637 filed by the present inventor
29, 57-163730 (Plasma vapor phase reactor) (September 1982)
Application dated 20th). In addition, the plasma shown in FIG.
Regarding the structure of the other part of the gas phase reactor, the present invention described above
According to a person's patent application.

In the drawing, a parallel plate type
A pair of reticulated electrodes (2) and (3) are placed, and these electrodes (2) and (3 ')
A positive electrode formed by causing an electric discharge between
Substrates (1), (1 ') having the surface to be formed are the back surfaces in the optical column region (25).
Close to each other so that the surface is perpendicular to the electrodes (2) and (3).
It is shown that they are arranged. In this example,
In addition, make sure that this substrate is surrounded by a quartz basket.
There is. In addition, the exhaust of the reaction products goes through the lower hood (22).
Exhaust (24). And in this configuration, the electrodes
When a discharge is generated between (2) and (3), the lines of electric force (5)
Will occur parallel to the surfaces of the substrates (1), (1 ').
The reactive gas reaches the quartz hood (21) from (23) and reticulates.
The pole (2) leads to the positive column region (5). Paired electrodes
High frequency energy is supplied from the outside to (2) and (3),
Discharge occurs between (2) and (3). In this example
As an electrode, 25cmφ (15cm between electrodes) or 70cm ×
The one having a size of 70 cm (electrode spacing of 35 cm) was used. Furthermore this electrode
The opening or groove (14) which is the constitution of the present invention is formed in
There is.

In the area where the holes or grooves are present,
Since the lines of electric force are concentrated, the glow discharge area of high brightness is shaped.
Is made. That is, the high voltage applied from the pair of electrodes (2), (3).
In the part indicated by (27) and (28) due to the frequency electric field
The first glow discharge occurs and the holes or grooves (14)
The lines of electric force are concentrated in the existing area, and the second glow with high brightness
-The discharge is performed. In this embodiment, the lower electrode
(3) is simply a hole or groove (0.5-3 cm, eg about 1 cm)
φ or about 1 cm width) is only formed. Also
By providing the upper electrode (2) with a phase (16),
An open hole or opening with a concave shape to the reaction space
A groove is formed.

In this embodiment, as shown in FIG.
Make a simple hole or groove in one (3) of the pair of electrodes, and
Opening of one electrode (2) with a concave shape to the reaction space
Or, by providing an open groove, the lines of electric force (5) are
7) and (18) converge to form a high-density electric flux region.
I made it As a result, the horizontal spread of the positive column (25)
(Plasma dispersion) can be suppressed as shown in (35).
The plasma in the central area (20) of the electrode.
You can Then, the plasma is collected in the area where the substrate is arranged.
By making it inside, the film growth rate can be improved.
It

For example, the plasma vapor phase reaction apparatus shown in FIG.
, The electrode is 25 cmφ, the electrode interval is 15 cm, and the substrate is
Arrangement of 6 pieces of 10 cm square (total area 600 cm ² ) and film forming conditions
A case of 100% film-forming reactive gaseous silane reaction pressure 0.1torr discharge power 30 W (13.56 MHz), may be a film growth rate and 4～6A / sec
did it. On the other hand, under the above conditions, the opening or groove (1
4) Use a plasma gas phase reactor with electrodes that do not have
When the film is formed by applying the film, the film growth rate is 1-2Å
/ Sec. That is, open holes or grooves (14) on each electrode
The film growth rate can be increased 2-3 times by providing only a few places.
Became possible. Plasma gas phase reactor of this embodiment
As shown in FIG. 1, since a plurality of substrates can be arranged,
5 to 10 times more substrates than the conventional method
You can

Moreover, in addition to the above, the film formation is performed as described above.
Since the long speed can be increased, productivity is improved.
From the point of fulfilling it, it is a double excellent thing. In addition
As a result of the convergence of the positive column, the
The plasma sputters the inner wall of the reactor and adsorbs on this inner wall.
Activated water and impurities in adhering substances and incorporated into the film
To further reduce the possibility of degrading the film quality.
Considering that you can
Is.

Example 2 In Example 1, the semiconductor
Only the preparation of the coating is described. But use the positive column region
When performing the plasma etching that was performed previously,
It is effective to use a plasma vapor phase reactor.

Etching the plasma vapor phase reactor shown in FIG .
Place the substrate to be etched and etch CF ₃ Br, CHF ₃ etc.
Introduce gas to etch the surface to be processed on the substrate
When done, anisotropic etching is performed in the direction parallel to the substrate surface.
I can walk. That is, the electric field (electric flux) is parallel to the substrate
In addition to the one-step glow discharge,
Is due to the high-intensity plasma discharge generated in the area of the aperture
Since a large amount of radicals of
Only the portion can be selectively etched. That is, d
The etching conditions are CF ₃ B with reactive oxygen for etching 5% oxygen added.
r When the reaction pressure is 0.1 torr and the discharge output is 200 W (30 KHz) , the etching rate is 400 Å / min at the convex part,
I was able to get 150Å / min. On the other hand, the above conditions
In, using an electrode with no holes or grooves (14)
Etching was performed using a plasma gas phase reactor
In this case, the etching rate is 140 Å / min for convex and 5 for concave.
It was 0Å / min.

[Embodiment 3] In this embodiment, the plastic shown in FIG.
When a silicon film is formed using a Zuma vapor phase reactor
Is an example of. In the figure, the lower mesh electrode (3) is
Luminance plasma discharge area is provided in 3 places, and 4 places in the upper side.
There is. Substrates (1) and (1 ') are placed in a quartz holder and
The tool is rotating at 3-5 times / minute.

The film forming conditions are shown below. Reactive gas for film formation Silane (30 cc / min) Substrate temperature 210 ℃ Reaction pressure 0.1 torr, Discharge output 30 W (13.56 MHz) In this embodiment, film formation is performed to a thickness of 5000 Å.
It takes 20 minutes and the film growth rate is 4.1 Å / sec.
Be argued. On the other hand, similar film formation can be performed by forming holes or grooves (14).
Using a plasma vapor phase reactor with electrodes without
When the film is formed, the film growth rate is 1.3 Å / sec.
It was.

Further , the quartz holder on which the substrate is arranged is
No discharge was observed in the outer space, and the stainless
Possibility of spattering the wall surface and mixing in impurities such as water
It was also confirmed that there are few. In this embodiment, the substrate
As an example, 6 sheets of 10 cm x 10 cm are arranged to form a film.
It was In addition, the yield of the reactive gas (component that forms the film / supplied
Gas, etc.) is 8% as compared with the film forming apparatus shown in FIG.
I was able to get nearly double. The yield of this reactive gas is
Compared to the case where no holes or grooves (14) are provided in FIG.
It was about twice the total.

[Embodiment 4] This embodiment is based on the plan shown in FIG.
Using Zuma gas phase reactor, Si _x C _1-x (0 <x <1)
It is the example which produced the film of the silicon carbide shown. Example
In this case, methane (CH ₄ ) and silane are used as source gases.
(SiH ₄ ) mixed with reactive gas at a ratio of 1: 1
The reaction pressure is 0.1 torr and the discharge output is 30W (13.56MH
In z), a coating film of Si _x C _1-x (0 <x <1) was prepared. Conclusion
The rate of fruit capsule growth was 4.8 Å / sec. On the other hand, the above conditions
In, using an electrode with no holes or grooves (14)
When a film is formed using a plasma gas phase reactor
In this case, the film growth rate was 1.7 Å / sec. In this example
However, the high-intensity screens shown in (17) and (18) of Fig.
Zuma discharge was observed in the groove. And such stations
Compared to the case without partial discharge, Si-C bond which becomes silicon carbide
Is abundant, and even if chemical etching occurs,
A dense film could be obtained.

[Embodiment 5] This embodiment is based on the plan shown in FIG.
Plasma etching is performed using a Zuma vapor phase reactor.
This is an example of the case. Etching performed in this example
Fig. 3 shows the state of the ring. In this embodiment, the plastic shown in FIG.
The convex portion (33) shown in FIG. 3 (A) using a Zuma gas phase reactor.
The silicon nitride film (31) at the top of is removed. Figure 3
(A) has a convex portion (33) having a width of 1 to 2 μm and a concave portion.
1000 Å of silicon nitride (31) on the surface of silicon single crystal substrate (1)
It is formed to the thickness of, and the resist (32) is coated
The child is shown. The depth of the irregularities is 1.5 μm.

The etching process will be described below. Well
First, the plasma vapor phase reactor shown in FIG. 2 was etched.
Place a substrate with a surface as shown in Fig. 3 (A).
Place. Next, the same conditions as those shown in Example 2
D CF ₃ Br with 5% oxygen added as an etching reaction gas
With a reaction pressure of 0.1 torr and an electric field applied from the electrode.
Plasma etch with 200W output at 30KHz frequency
Perform At this time, the lines of electric force are flat against the substrate surface.
Since it is applied to the rows, the direction perpendicular to the paper surface of FIG.
Anisotropic etching is performed in a direction parallel to. this
The etching rate at this time is 420 Å / min for the convex part and 1 for the concave part.
It was 51Å / min.

For the sake of comparison, the same etching as this is opened.
Plasma gas phase using an electrode without a groove or open groove (14)
When etching is performed using a reactor, etch
The convex speed is 150 Å / min for the convex part and 51 Å / min for the concave part.
It was Then, as shown in FIG. 3 (B),
Only the resist (32) can be removed. The same
Silicon nitride (31) is removed by performing such etching.
Then, the resist (32) is removed by a known method.
By doing so, the shape of FIG. 3 (C) can be obtained.
It After that, if impurities are selectively mixed into this convex portion,
Various semiconductor devices can be manufactured by using different processes.
Can be made.

[Embodiment 6] This embodiment is a system having unevenness.
The upper surface of the recon single crystal was made flat, and the recess was made to have silicon oxide.
Is an example of filling. This embodiment will also be described with reference to FIG.
It In this embodiment, first, as shown in FIG.
Place silicon nitride (31) and silicon oxide (32) on the uneven substrate (1).
Stack. (In this embodiment, (32) is silicon oxide.
Then, using the plasma vapor phase reactor shown in FIG.
The convex portion (33) is removed. The conditions are the same as in Example 2.
I did it in. That is, CF ₃ B containing 5% reactive gas for etching added with oxygen
r When the reaction pressure is 0.1 torr and the discharge output is 200 W (30 KHz) , the etching rate is 410 Å / min on the convex part and concave
I was able to get 148Å / min.

For comparison, here too, apertures or grooves (14)
Using a plasma gas phase reactor using electrodes without
Etching was performed. As a result, the etching rate is convex
The area was 142 Å / min, and the recess was 45 Å / min. Next
Then, as shown in Fig. 3 (B), flatten the upper surfaces of (33) and (34).
To obtain a flat surface.

[Embodiment 7] This embodiment is an electric circuit for VLSI.
Fill the recesses of the poles with a conductor to form an electrode lead pattern.
It is an example made. FIG. 4 shows a part of the VLSI in this embodiment.
Show. In Fig. 4, the embedded film is placed on the semiconductor surface (1).
─ field insulator (36), source, drain region (37), (38),
Gate (39), interlayer insulator (41), 1-2 μmφ aperture (42)
(Depth ± 0.5 to 2 μm) is shown. Structure like this
The source and drain through the hole (42)
Even if the lead is not formed, the recess of the opening (42)
Therefore, a thin pattern of 2 μm or less is used as an electronic beam.
It cannot be formed even by using an exposure technique. Book there
In the example, first, an aluminum alloy with silicon added to these entire surfaces is used.
Form the chamber (43) to a thickness of 0.5-2 μm and
To remove the recess (40) formed with the minumum (43)
And using the plasma vapor phase reactor shown in FIG.
For anisotropic etching in a direction parallel to
It As a result of this etching, only the hole (42)
It becomes a form filled with minium, and there is an opening (42).
The difficulty of patterning due to it is eliminated.

The above anisotropic etching is performed under the following conditions.
It was. Reactive gas for etching CCl ₄ Pressure 0.1 torr Discharge output 200W ( 30KHz ) At this time, the etching rate is 138Å / min in the convex part and in the concave part
It was 47Å / min. For comparison, a groove or hole (1
4) Use a plasma gas phase reactor using electrodes that do not have
When etching is carried out, the protrusions are 138Å /
Min, and the concave portion was 47Å / min. This allows the recess (3
4) can be eliminated and a roughly flat surface can be provided.
It And after the anisotropic etching step, copper is added
The second aluminum (44) which has
Form to thickness.

After this, a known vertical anisotropic etch is performed.
1 ~ 2μm by plasma etching equipment
You can get the lead of narrow pattern. More than
Anisotropic etching in the direction parallel to the substrate
A three-dimensional device that stacks semiconductor elements in the direction perpendicular to the substrate.
Plays an extremely important role in the production of devices.

[0032]

[Effect] As described above, according to the present invention, the electrode has a hole or
By providing an open groove, the film formation speed and etching speed
It has become possible to improve the degree. Therefore, according to the present invention
Therefore, it is possible to cause an efficient plasma gas phase reaction.
It has the effect of being able to. Further, the embodiment of the present invention is not a single unit.
Si, also Si _x C _1-x , but using silane and germane
Si _x Ge _1-x (0 <x <1) with silane and tin chloride
Si _x Sn _1-x (0 <x <1) was used and Al was changed to AlCl ₃ .
In addition, Si ₃ N ₄ is replaced with SiH ₄ and NH _3, and SiO ₂ is replaced with SiH ₄ and N ₂
The present invention can also be applied to the case of forming with O 2. Also
Is SiO ₂ , Si, Si selectively by plasma etching
_When removing ₃ N ₄ , photoresist and other compound semiconductors
In this case, the present invention is effective.

[Brief description of drawings]

FIG. 1 shows a conventional plasma vapor phase reactor.

FIG. 2 shows an outline of a plasma gas phase reactor of an example .
You

FIG. 3 shows another embodiment in which a semiconductor device is manufactured.

FIG. 4 shows another embodiment in which a semiconductor device is manufactured.

Claims (2)

[Claims] 1. A plasma vapor phase reaction apparatus, wherein at least one of a pair of electrodes is provided with an opening or groove having a concave shape with respect to a reaction space. 2. At least one of the pair of electrodes is provided with an opening or groove having a concave shape with respect to the reaction space, and the pair of electrodes is provided in the reaction space in a region where the opening or groove is provided. The method of plasma vapor phase reaction characterized by concentrating electric lines of force of an electric field applied from the electrodes of.