JPS6062113A - Plasma cvd equipment - Google Patents

Abstract

PURPOSE:To contrive uniformity of thickness and homogeneity of quality of a film to be formed by supplying electric energy to mutually orthogonal directions for each of two pairs of electrodes. CONSTITUTION:In a reaction chamber, a plasma vapor phase reaction is carried out by supplying energy with a pair of electrodes 23, 25 for the first electric field 90 which is approximately in parallel with the surface of a substrate where a film is formed. Simultaneously, the other orthogonal electric field 91 is supplied energy with the second pair of electrodes 72, 82 and each pair of electrodes is connected to the first or the second high-frequency oscillator 85 respectively. This prevents unequality of thickness of the film to be formed and can reduce dispersion of a required thickness in all the square area of the film including the circumference and the center.

Description

[Detailed description of the invention] The present invention relates to a plasma CVD apparatus.

The present invention selectively provides a cylindrical space (referred to as a space or reaction space) electrically floating above an anode and a cathode in a reaction vessel, and a substrate having a surface to be formed (floating substrate) disposed in this space. By supplying a reactive gas and causing plasma discharge of this reactive gas mainly in this cylindrical space, preferably only in this space, a reaction chamber located outside this cylindrical space at a distance of 5 to 20 cm. The purpose is to increase the film growth rate and improve productivity by preventing reaction products from adhering to the inner wall in the form of flakes (snowflakes). Furthermore, the present invention relates to a plasma CVD apparatus that improves the production yield of a reaction product formed on a surface to be formed (reaction product formed into a film/reactive gas supplied).

Conventionally, in a method in which a pair of parallel flat plates are used and the surface to be formed is oriented on one of the electrodes, the production yield is only 1 to 3%. The present invention is characterized in that this yield can be increased approximately 20 times to 20 to 50% by confining the plasma in space.

The present invention generates a first electric field approximately parallel to the formation surface of the substrate to cause a plasma reaction, further supplies a second electric field perpendicular to this electric field, and further sets the frequencies of these two electric fields to be the same. It is characterized by having a Lissajous coating with a phase shift, and promoting uniformity in the thickness and quality of the formed coating.

In the present invention, a supply means and an exhaust means provided in a reaction container are opposed to each other, a cylindrical space is created between them using a substrate holder, the inner wall of this space is substantially used as a surface to be formed, and a first
By applying a second electric field and a second electric field, reaction products caused by the plasma reaction are prevented from dissipating from this space to the outside space inside the reaction vessel, and as a result, reaction products that cause pinholes in the formed film are prevented. The purpose is to prevent the occurrence of 7 lakes and to facilitate maintenance of the equipment.

The present invention has the following objectives: 5. A reactive gas is passed from a supply means through a net-like or porous negative electrode (cathode), flows along the surface of the substrate to be formed in a cylindrical space, and generates a plasma discharge to form a coating. Perform formation. Furthermore, the system is characterized by a gas curtain structure in which unnecessary reaction products and carrier gas pass through another mesh-like or porous positive electrode (anode'), reach an exhaust means, and are evacuated.

Furthermore, the present invention provides a cathode dark area and an anode dark area (
In order to prevent the spread of dark areas (hereinafter simply referred to as dark areas) and sputtering (damage) to the substrate surface, which may lead to non-uniformity of the coating and deterioration of characteristics, a mesh or porous conductor electrically suspended from the electrode is installed as a grid. It is characterized by being arranged as follows.

In addition, the present invention allows the holder (also referred to as a substrate holding jig) and the substrate constituting the cylindrical space to be supplied from a first preliminary chamber connected to one side of the reaction chamber, and furthermore, after plasma CVD. , the holder and the substrate are controlled in the second preliminary chamber, and a continuous production process is provided.

Conventionally, in the plasma vapor phase reaction method, only a pair of electrodes are arranged in parallel to form a parallel plate type electrode, a substrate is placed on one of the electrodes, and a plasma discharge is generated between the electrodes by the glow discharge method. Formation of semiconductor coatings, etc. was performed. In such a method using only a pair of electrodes, the uniformity of the coating can be maintained within a variation range of ±5%.

However, in this method, the surface on which the electrode is formed cannot be made larger than the area of the electrode. Therefore, it has the disadvantage of being completely unsuitable for mass production.

On the other hand, as in the present invention, a large number of substrates are arranged vertically in a forest at a certain distance (2 to 6 cm) from each other so that the electric field is approximately parallel to the surface on which the substrates are formed between parallel plate type electrodes. There is a known method for arranging the An example of this is a patent application filed by the present inventor (Plasma gas phase reactor, patent application No. 167280, filed September 25, 1980).

That is, since the so-called floating plasma gas phase reaction method (referred to as the TFPCCVD method) is used, in which the substrate is electrically isolated from any electrode and a gas phase reaction is performed in a positive column, it is possible to form a large amount of film. It has the characteristic of being able to Therefore, compared to the conventional method of disposing a substrate on one electrode of a parallel plate type electrode, productivity could be increased by 5 to 20 times. However, in such FPCVD method, the uniformity of the film thickness obtained is one of the first problems.
It was as shown in the figure.

Figure 1 (A> shows the substrate (5) and electrodes (23>, <25)
It shows the relative positional relationship with. Approximately 500 on the board (5)
Silicon is formed to have a thickness of 0.0 mm, but as shown in (C) between the pair of electrodes (23>, (25), the area near the electrodes becomes thicker, and (B >, < D), ( As shown in E), the center of the electrode is thick and the edge of the substrate is thin.For this reason, the thickness of the film formed on the upper and lower edges (corners) of the substrate (5) 2 is the same as that of the upper and lower edges of the center. The thickness was 20 to 30% thinner than the thickness of the other parts.

That is, in the floating PCVD method invented by the present inventors, since the surface to be formed is floating in terms of potential, the charges that have been charged up on this substrate and the ions in the plasma repel each other, resulting in a flight. Sputtering of the coating surface due to the active particles inside can be reduced. Furthermore, in order to promote this, the high-frequency electric field used for the plasma reaction is supplied in a laminar flow along the surface to be formed, that is, the electric field is arranged so as to be approximately parallel to the surface to be formed. ing. However, if only the electric field is generated by a pair of electrodes, the electric field at the end will be dissipated outward, and the electric flux density will become small. As a result, it is determined that the thickness of the film on the surface under which the electrode is formed is thinner.

Therefore, in the present invention, in order to prevent such non-uniformity in film thickness and to keep the variation in thickness within ±5% with respect to a predetermined thickness at all peripheral parts and central parts of the rectangular formation surface, the electrodes are 2
It is characterized in that the electrodes are arranged in pairs and electrical energy is supplied to each pair of electrodes in directions perpendicular to each other.

That is, by supplying a second electric field orthogonal or approximately orthogonal (hereinafter simply referred to as orthogonal) to the first electric field, the electric flux density at the end portions was prevented from becoming small. Furthermore, the present invention reduces the extent to which plasma energy sputters the surface to be formed by setting the surface of the substrate to be electrically floating from these two electrodes.

That is, in the present invention, a main electric field is generated by a pair of first electrodes disposed in the vertical direction, and a second electric field is generated perpendicularly thereto.
It generates an electric field. These two electric fields are orthogonal or approximately orthogonal to each other, and have a positional relationship such that they are both disposed approximately parallel to the surface to be formed. The present invention is characterized in that these two pairs of electrodes are disposed in one reaction chamber, and a film such as a non-single crystal semiconductor is formed in this reaction space.

The present invention prevents the reactive gas from dispersing throughout the reaction chamber, provides a cylindrical space using the formation surface of the substrate, and places the back surfaces of the substrates in close contact with each other in this cylindrical space. The surfaces on which the formation is to be formed are arranged in parallel at a certain distance, for example, 2 to 10 cm, typically 4 to 6 cm, and the substrates stand in a row to selectively guide the reactive gas into the cylindrical space. As a result, the reactive gas collection efficiency has been improved from the conventional 1 to 3% to 10%.
It is characterized by being increased by 20 to 50%, which is ~30 times.

Furthermore, in order to prevent the flakes deposited on the upper part of the reaction chamber from falling onto the surface of the substrate to be formed if the film formation is repeated many times, the formation of pinholes may occur on the substrate. It is characterized in that the surface on which it is formed is vertically aligned along with gravity.

The present invention promotes uniformity of film thickness and homogeneity of film quality at the upper, lower, center, and peripheral parts of a substrate whose surfaces to be formed are arranged approximately parallel to each other with a certain gap as described above.
Rod-shaped infrared lamps were arranged perpendicularly to each other from above and below to uniformly heat the entire cylindrical space. i.e. 10cn+0 or 10-60cm in the electrode direction,
Medium 15-100c111 board e.g. 20cm x 6
The temperature distribution of a 0 cm substrate is 100 to 650
The temperature is, for example, within 200 ±5°C.

In this way, the continuous production method is the basic condition, and in addition to improving the properties of the coating inside the reaction chamber, it also prevents unnecessary reaction products from adhering to the inner wall of the chamber, and conversely, the appearance of the upper reaction vessel is improved. By making the inner wall the side surface of the cylindrical space, it is as if a new inner wall is created each time a film is produced, that is, each time a new holder is inserted into the reaction vessel, so even with repeated film formation, layers can be stacked. You can prevent it from happening.

That is, it has the great feature of being able to prevent the generation of flakes.

Furthermore, in the present invention, the supply hood and the exhaust hood are covered outside the electrode and with an insulating hood (quartz, etc.) at the reactive gas inlet and exhaust port to prevent parasitic discharge with the reaction chamber wall surface, and to prevent parasitic discharge between the electrode and the space. By providing a floating grid between them, it was possible to prevent the anode dark region and cathode dark region from extending into this space, that is, to create a positive column region in which the electric field intensity in this space was extremely low. As a result, it was possible to prevent spatter on the surface to be formed due to spatter (reactive substance) having strong kinetic energy accelerated in the dark part of a strong electric field in this space, and to improve the film quality.

Such a gas phase reaction device eliminates the mixing of impurities in the lower (formed surface) semiconductor layer that has already been formed into other semiconductor layers to be formed thereon, and furthermore, it is possible to prevent the stacking of multiple semiconductor layers. The thickness of the mixture at the interface is reduced to about 1/10 to 115 of the conventional thickness for 200 to 300 people, and the variation in film thickness within a substrate or between substrates of the same batch is within ±5% (for example, for 5000 people When it comes to thickness, the variation is 1
(within 250 people).

The plasma CVD apparatus of the present invention will be shown below according to the drawings.

Example 1 A plasma CVD apparatus of the present invention is shown according to FIG.

In FIG. 2, the reaction chamber (2) has a first preparatory chamber (1) on one side for loading the substrate, and a first preparatory chamber (1) on the other side for taking out the substrate and the holder constituting the cylindrical space. It has two spare rooms (3).

First preliminary room (single reaction room (2), second preliminary room (3)
The continuous throw part has gate valves (43), <44), and this gate valve (44) is connected to the substrate (4), <5>, and the boulder (6).
>, (7) are open for movement in the reaction chamber, and the insertion and insertion of substrates (4) and 2 holders (6) from the door (11) in the preliminary chamber (1) of the plasma reaction box 1, and the second spare room (3)
Close the door (12) when removing the substrate or holder from the door (12). When loading and unloading boards, use the preliminary room (1>
, <3> is supplied with nitrogen from (20>, (32)) to bring it to atmospheric pressure.

In the first preliminary chamber (1), insert the board (4) and holder (6) into the guide (9) from the outside at atmospheric pressure, and then
1), and is equipped with an infrared lamp (15), <15') and a vacuum evacuation means (29) in order to heat and vacuum degas the adsorbed material on the substrate. This preliminary chamber was evacuated.

Thereafter, the gate valve (43) is opened and the substrate (5) and holder (7) are moved into the reaction chamber (2) which has been evacuated in advance. This movement was performed using the step motor (8) located in the first preliminary chamber. First, the holder containing the guide (9) was lifted approximately 1.5 cm upwards, and then moved to the reaction chamber (2).
I extended the guide and moved the holder inside. After reaching the center, stop the guide and lower the holder about 1.5 cm downward by lowering the guide. Then, a fin shut (39) is provided at a position in the middle of the height to receive the disc-shaped disk on the upper part of the holder (7), and the holder (7) is held here and the cylindrical space (100"
) is provided. Thereafter, the guide passes under the disk and is shrunk and stored in the first preliminary chamber (1).

Furthermore, the gate valve (43) is closed.

After this, the first preliminary chamber was brought to atmospheric pressure with nitrogen (20),
The next board (4) and holder (6) are inserted into the guide (9), and this process is repeated.

The mechanism inside the reaction chamber (2) will be described.

The reaction chamber (2) is equipped with a reactive gas supply system (97) and a vacuum evacuation system (98).

The reactive gas supply system (97) includes a valve (51), a flow meter (52) and a carrier gas (33) as a doping system.
), reactive gas (34), (,35l (36), < 3
7) It consists of more than one. Silicide gas as reactive gas,
Things that are gaseous at room temperature, such as germanium compound gases, are (
34), and a doping gas for P or N type (for example, diborane, phosphine) can be supplied from (35).

Further, substances that are liquid at room temperature, such as tin chloride, aluminum chloride, and antimony chloride, are supplied by a bubbler (36). These gases become gases under reduced pressure, so
Sufficient control is possible with a flow meter. Further, during vapor deposition, the temperature of this bubbler (36) was controlled using an electronic constant temperature bath.

These reactive gases are supplied to the supply means (4) from the supply port (27).
6) is sprayed downward by the nozzle (also called hood) <24). The air outlet of this hood is 1-2111
A large number of 111 holes (42) are drilled to allow the air to blow out evenly over the whole area. The back of this hood is made of an insulating material to prevent parasitic discharge from occurring on the walls of the reaction chamber.

Furthermore, a negative electrode (23) for plasma discharge is provided between the holes (42), and this is connected to an oscillator (21810KHz to 50MHZ) for supplying electrical energy via the lead (49).
z e.g. 13.56MH2 or 30KFlz 10
W ~ IKW). Other positive terminal (22)
is provided on the hood of the exhaust means (47) and connected to the mesh-like or porous positive electrode (25).

In addition, a second oscillator (85810KHz ~ 50Mt (z
For example, 13.56MHz or 30KHz 10'W~
An electrode (72) <82) was provided so that a second electric field was generated in the front-rear direction in the drawing by a power of 1KW).

By using these two pairs of electrodes, when the same frequency is used, a Lissajous pattern can be created, and a uniform coating can be formed up to the periphery.

Furthermore, a pair of electrodes (23), <25) and a reaction space (10
0) (cylindrical space) is provided with a stainless steel conductor in the form of a mesh (holes 1 to 3 cm) or porous (holes are 1 to 3 clIlφ), and these grids (40) and <41> allow discharge to occur. A space where the generated dark area is placed within the sunlight pillar (100
) to avoid sputtering the substrate surface. With this floating grid (40), <41), even if the pressure in the reaction chamber changes in the range of 0.01 to 5 torr, the pressure will be low (e.g. 0.05 torr) and the dark area will extend into the space (100). , the surface of the substrate to be formed is no longer sputtered. It has now become possible to create a film with good quality.

The exhaust means (47) has approximately the same shape as the supply means (24), and both are made of transparent quartz (insulating film).
The reaction products, carrier gas, and unnecessary gases from the cylindrical space (100-) are uniformly made into a flow M through the holes throughout the body and are exhausted to the vacuum pump (30) through the exhaust port (28).

During film formation, the fin shaft (39) rotates while being vacuum isolated from the external stamp motor (19). Therefore, the board held by this fin shaft (
5) The holder (7) is rotated 3 to 10 times per revolution to uniformly form a film on the substrate.

Furthermore, in a device such as
After forming the film in step D, the substrate and holder were transferred to a second preliminary chamber (3) that was evacuated. That is, after evacuating the gas in the reaction chamber (2) 2 and the second preliminary chamber (3), the holder and substrate were transferred by opening the gate valve (44).

To move, extend the guide (10) from the right direction and move it to the reaction chamber (2).
After reaching the holder (7) and lifting it approximately 1 cm above, the guide is retracted and taken out to the second preliminary chamber. Gate valve (
44) was closed and supplied with nitrogen (32) to atmospheric pressure.

In this way, the plasma gas phase reaction between the reaction chamber and the first and second preliminary chambers as shown in FIG. 2 could be operated continuously.

Of course, it is also possible to draw out the substrate and holder on which the film has been formed into the first preliminary chamber and omit the second preliminary chamber.

FIG. 3 shows a longitudinal sectional view of the reaction chamber (2) in FIG. 2, viewed from the preliminary chamber (3) side. First and second electric fields (90), <91
) is clearly shown.

In the drawings, the heater (18) <18') uses a halogen lamp heating element. The reaction space (100) was heated to 100 to 650°C, for example 250°C, by a heater. The reactive gas decomposed silane, for example.

Further, a first electric field (90) is applied to the substrate (20) approximately parallel to the surface to be formed on the pair of main electrodes (23) and (25).
) to perform a plasma gas phase reaction.

At the same time, another orthogonal electric field (91) is applied to the second pair of electrodes (
72>, <82. ), each connected by a high frequency oscillator (21) and another high frequency oscillator (85).

Reactive gas is supplied from (33), (34), <38) to means (46).

The substrate (5>5) in the space (100) was evacuated by the evacuation means (47) to the vacuum pump (37) of the evacuation system (98).

When amorphous silicon was prepared using silane as a film, the thickness of 5000 cm was set at 300 cc/min, the formation rate was 20 cm/sec, and the substrate (20 cm x 60 cm)
20 sheets, total area 24000, pressure Q, Q
It was set to 13 torr. As a result, the center area varied by 5,000 people, and the vertical peripheral area was 3,000 people (with a variation of ±20%) using the conventional method without the second electric field, but with the method of the present invention, it was 4,500 people (±5%). We were able to significantly improve the uniformity.

FIG. 4 shows the distribution when non-single crystal silicon is formed to a thickness of 0.5 μm in FIG. 3.

As is clear from the drawing, the substrate (5-input first electrode (23>
, <25>, the second electrodes (72>, <82) are arranged, and the thickness distribution in each cross section is (B), <C), <
D>, <E). It has been found that all of these cross-sectional views have extremely uniformity compared to FIG. 1, and the variation is within ±10%, which is sufficient for practical use.

Furthermore, this dangling bond of silicon or carbon is changed to 5 by hydrogen.
Rather than neutralizing with t-H, C-H, 5i-F, C
It goes without saying that it may be carried out using -F and a halide gas, especially a fluoride gas (this concentration is preferably 40 atomic % or less, for example 2 to 5 atomic %). Regarding the types, as mentioned above,
Not a single layer but a ■ group SinGe, 5ixC1-x (
0<x<l), 5ixGe +-x (0<x<1),
5ixSn l-X (0<x<1> or multiple layers with junctions formed by changing their conductivity types, or other semiconductors such as GaAs, GaAlAs+ BP+, etc.) Needless to say.

Example 3 In this example, a silicon semiconductor film was manufactured by using the plasma CVD apparatus of Example 1 and supplying silane from (34) as a reactive gas.

The substrate temperature was 250°C. The growth rate of the film was 8 persons/second when a high frequency (using 13.56 MHz) electric field was set at 50 mA, 300 cc of silane was added for 7 minutes, and the pressure during plasma CVD was Q and 1 torr. As a result, compared to 1 to 3 people per second in the conventional parallel plate electrode system, for example, the former can be used at 60 people per second in the same reaction vessel.
cm x 60 cm 1 piece, whereas in the plasma CVD apparatus of the present invention, T is 20 cm x 60 cm
The total area was 8 times larger, with 20 sheets, and the film growth rate was 10 to 25 people/second, which was 6 times as large. As a result, a total of 48 times more mass production has become possible.

More importantly, in conventional equipment, C
When performing the VD operation, silicon flakes of 3 to 10 microns were deposited on the inner walls of the chamber. However, in the plasma CVD apparatus of the present invention, even if a film with a thickness of 0.5μ is repeatedly formed 100 times, only flakes are observed on the inner wall of the reaction vessel. there were.

Since the semiconductor layer thus formed has a long distance in the plasma state, its photoconductivity also ranges from 2X10''4 to 'yxio-El.
(Q Ctn )', dark conductivity 3 x to-9~I
X 10''(QCII+)'.

This is because the conventional method in which the electric field direction of the plasma is perpendicular to the surface to be formed has a photoconductivity of 3 x 10'S to 3 x 101 (o
cm)-', dark conductivity 5 x 10'8~1 x io
-'l +ocm)-', the optical photosensitivity (photoconductivity/dark conductivity) of the semiconductor film was improved by a factor of 106 or more.

Although this embodiment is a case in which impurities are not actively added, a P- or N-type semiconductor film having a similar high electrical conductivity can be produced even if a P- or N-type impurity is added.

In addition, P, I, and N type semiconductors are stacked to form PI, NI, and PIl.
j, it is also possible to create a PN junction.

Example 4 In this example, a conductive metal was produced using the plasma CVD apparatus of Example 1.

In the following, a case will be described in which metal aluminum is formed by plasma CVD.

In Figure 2, the bubbler (36) was filled with aluminum chloride. Aluminum chloride was heated to 40 to 60° C. in an electronic thermostat. Furthermore, from (39), 100 cc of helium, an inert gas, was added as a carrier gas.
A flow rate of 7 minutes was introduced, and aluminum chloride mixed in the helium was introduced.

Further, hydrogen was introduced from (33) at a flow rate of 60 to 100 cc for 7 minutes. The substrate temperature is 200-550℃, for example 300℃
I chose ℃. The high frequency electric field is 100-300W, e.g.
0W was supplied.

In this way, we were able to form a film with a thickness of 0.5 to 1 μm at a growth rate of 5 people/sec on a substrate with 20 sheets of 20 cm x 60 cm, and with a uniformity of less than ±5%. .

Additionally, triethylaluminum (TE) is used as a starting material.
A) was filled into the bubbler (36) in Figure 2.

Furthermore, there was no need to introduce carrier gas into (39). By setting the temperature of the bubbler to 60°C, the flow rate was set to 60 cc/min in the flowmeter. Furthermore, 500 cc of hydrogen was introduced from (33) over 7 minutes, and plasma CVD was performed.

The reaction pressure was 0.1-Q, 3 torr, and the high frequency was IQ.
By setting OKHz and IK-, a total of 100 5-inch silicon wafers, 5 of each substrate, were inserted.

Metallic aluminum could then be produced on these substrates at a growth rate of 7 people/min.

At this time, even if a conductor was formed in the upper space, the discharge did not become unstable, and metal aluminum with a thickness of 1 to 2 microns could be deposited.

At this time, 7 ml of hydrogen was added to the reaction chamber (2) from the external pipe 38).
00cc was introduced for 7 minutes. By doing so, it was possible to further reduce the amount of flakes adhering to the inner wall of the container. Therefore, even when the film was formed 30 times to a thickness of 1 to 2 μm, no fogging was observed on the inner wall of the container or the viewing window.

In particular, in the plasma CVD of the present invention, it is possible that two electrodes for plasma discharge are connected to each other due to leakage current.
ie, the supply hood and holder are electrically separated, and the holder and the lower hood are likewise separated. Furthermore, since there was little adhesion to the inner wall of the reaction vessel around it, the discharge did not become unstable due to leakage current in any of these electrical circuits.

In this example, aluminum was used, but it is also possible to make a film of metallic iron nickel or cobalt using carbonyl compounds of iron, nickel, and cobalt, for example.

Example 5 In this example, a silicon nitride film was produced using the plasma CVD apparatus of Example 1.

That is, in the case of Figure 1, silane is reduced by 2 from (34).
00cc 7 minutes, 800cc of ammonia from (35)
/min was introduced. The substrate temperature is 300℃ and 0.1torr.
r, 20 boards of 10cm x 60cm or 5
It was possible to form a thickness of 1,000 to 5,000 layers on 100 inch wafers.

The uniformity of the film was within ±5% within and between lots.

Example In this embodiment, silicon oxide is formed.

That is, 200 cc of silane (SiH2,) was added for 7 minutes from (34), and nitrogen peroxide (N20) was added to (35).
At the same time, 200 cc/min of nitrogen was introduced from (33) for 7 minutes.

The high frequency power was 30KHz and 500W. The frequencies of the first and second electric fields were the same, and the phases were shifted by 90° to form two litharge waveforms. Although it is possible to set the substrate temperature at 100 to 400°C, if it was formed at 250°C, the uniformity of the film could be kept within ±3% and ±5% when 0.5μ was formed.Example 7 In this example, a compound conductor such as tungsten silicide, molybdenum silicide, or metallic tungsten or molybdenum was made. That is, in Example 1, the bubbler (3
Molybdenum chloride or tungsten fluoride was introduced into 6), silane was further supplied from (35), and plasma CVD was performed with tandem or molybdenum and silicon at a predetermined ratio, for example, 1:2. As a result, 250℃, 3
At 00W and 13.56MHz, a growth rate of 4 to 6 people/second could be obtained for a thickness of 0.4μ.

By adjusting the amount of reactive gas, this compound metal and the heat-resistant metal can be formed into a multilayer structure.

As is clear from the above explanation, the plasma CV of the present invention
O devices can be formed on any semiconductor, conductor, or insulator. In particular, by doping impurities into a semiconductor or conductor that is structurally sensitive, it was possible to stack a plurality of semiconductor layers doped with P- or N-type impurities.

Although the floating grid in the present invention is provided on the first electrode side, the film quality can be improved by providing it on the second electrode side or both.

Further, in the present invention, only plasma CVD is shown.

However, in addition to this electrical energy, optical energy such as ultraviolet light or infrared light may be simultaneously applied to perform a photoplasma CVD method.

[Brief explanation of the drawing]

FIG. 1 shows the non-uniformity of film thickness on a substrate obtained by a conventional method. FIGS. 2 and 3 schematically show a manufacturing apparatus for forming a semiconductor film for carrying out the present invention. FIG. 4 shows the uniformity of the film thickness of the substrate obtained by the method of the present invention. patent applicant

Claims (1)

[Claims] A reaction vessel maintained at a reduced pressure of 1.1 atmospheres or less, a system for supplying a reactive gas to the reaction vessel, and an exhaust system for evacuating unnecessary reaction products or carrier gas. The plasma vapor phase reaction apparatus includes a cylindrical space for guiding the reactive gas provided in the reaction container from the supply means to the exhaust means, and the substrate is disposed within the space, and A film is formed on the substrate by having means for supplying a first electric field approximately parallel to the surface of the substrate and a second electric field perpendicular or approximately perpendicular to the first electric field. Plasma CVD equipment. 2. In claim 1, a pair of first electrodes that surround a substrate disposed in a cylindrical space and generate a first electric field, and a second electrode that is orthogonal or approximately orthogonal to the electric field. a pair of second electrodes that generate an electric field;
A plasma CVD apparatus characterized in that the back surfaces of the first and second electrodes are covered with an insulating hood. 3. In claim 1, the first electric field and the second electric field
A plasma CVD apparatus characterized in that the electric fields of are of the same frequency and have two resurge waveforms. 4. An anti-responder maintained at a reduced pressure of 1 atmosphere or less;
In a plasma gas phase reactor equipped with a system for supplying a reactive gas to the reaction vessel and an exhaust system for evacuating unnecessary reaction products or carrier gas, the reactive gas provided in the reaction vessel is having a cylindrical space leading from the supplying means to the exhausting means, disposing the substrate in the space, and applying a first electric field approximately parallel to the surface of the substrate;
It has means for supplying a second electric field orthogonal to or approximately orthogonal to the first electric field, and a mesh or a grid of a porous conductor is disposed between the space and the first or second electrode. A plasma CVD apparatus characterized by: