JP2002110671A - Method for manufacturing semiconductor element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a semiconductor element through stable glow discharge plasma treatment, by continuously generating a uniform glow discharge plasma under a pressure close to the atmospheric pressure, when manufacturing an interlayer insulating film and/or a passivation film in the step of manufacturing the element. SOLUTION: The method for manufacturing the semiconductor element comprises the steps of introducing a material gas between facing electrodes under a pressure near atmospheric pressure, in the case of forming the interlayer insulating film and/or the passivation film of the element, applying a pulse-like electric field between the opposed electrodes, thereby generating the glow discharge plasma in the material gas, and forming the interlayer insulating film and/or the passivation film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a semiconductor device in which an interlayer insulating film and / or a passivation film in a semiconductor device is formed by a normal pressure plasma CVD method.

[0002]

2. Description of the Related Art Generally, as shown in FIG. 1, a general structure of a semiconductor device is a substrate 1, a silicon film 2, a source electrode 3, a drain electrode 4, an interlayer insulator 5, a gate electrode 6, a passivation film ( Protection film) 7 and the like.
Here, the substrate is made of a glass substrate or a wafer substrate, the electrodes are made of a metal or a metal compound such as Al or Cu, and the passivation film and the interlayer insulator are made of silicon oxide, silicon nitride, It is made of silicon or the like, and as the silicon layer, P, B, a-Si layer and a-Si
It is made of a material doped with As, Ge, or the like.

[0003] In a semiconductor device, these materials are combined according to required functions, and after cleaning a base material and the like, a thin film such as an electrode, an insulating film and a silicon layer is formed thereon, and further, doping, annealing, and resist treatment are performed. (For example, coating, developing, baking, resist stripping, etc.), and subsequently, a complicated process of repeating exposure, development, etching and the like. In these manufacturing steps, it is important to form a thin film such as an insulating film, a protective film, an electrode, and a silicon layer, and a plasma processing method is mainly used as the forming method.

[0004] As a method for forming a thin film, there are generally low pressure plasma CVD, normal pressure thermal CVD, vapor deposition, sputtering and the like. In the conventional atmospheric pressure plasma CVD, the gas species is limited, such as in a helium atmosphere. For example,
A method of performing treatment in a helium atmosphere is disclosed in JP-A-2-486.
Japanese Patent Application Laid-Open No. 4-745 discloses a method for performing a treatment in an atmosphere comprising argon, acetone and / or helium.
No. 25 discloses this.

However, in each of the above methods, plasma is generated in a gas atmosphere containing an organic compound such as helium or acetone, and the gas atmosphere is limited. Furthermore, helium is industrially disadvantageous because it is expensive, and when an organic compound is contained, the organic compound itself often reacts with the object to be treated, and the desired surface modification treatment cannot be performed. There is.

Furthermore, the conventional method has a low processing speed and is disadvantageous for industrial processes. In addition, when a plasma-polymerized film is formed, the film decomposition speed is higher than the film formation speed, and a good quality thin film is obtained. There was a problem that can not be obtained.

[0007]

SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to provide a method for manufacturing an interlayer insulating film and / or a passivation film in a process of manufacturing a semiconductor device, in which a uniform glow discharge plasma is formed under a pressure near atmospheric pressure. And a method for easily producing a thin film on a semiconductor element by using a method for performing a stable glow discharge plasma treatment.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a thin film can be easily formed by a discharge plasma method capable of realizing a stable discharge state under atmospheric pressure conditions. Heading, the present invention has been completed.

That is, a first aspect of the present invention (the first aspect of the present invention) relates to the formation of an interlayer insulating film and / or a passivation film in a semiconductor device by a plasma CVD method.
A source gas is introduced between the counter electrodes under a pressure near the atmospheric pressure,
By applying a pulsed electric field between the opposed electrodes,
A method for manufacturing a semiconductor device, comprising forming a source gas into a glow discharge plasma to form an interlayer insulating film and / or a passivation film.

The second aspect of the present invention (the invention of claim 2)
Means that the pulsed electric field has a voltage rise time of 100μ
s or less, the method for manufacturing a semiconductor device according to the first invention, wherein the electric field intensity is 10 to 1000 kV / cm.

The third aspect of the present invention (the third aspect of the present invention)
A solid dielectric is provided on at least one of the opposing surfaces of the opposing electrode, a base material is disposed between one electrode and the solid dielectric or between the solid dielectrics, and a thin film is formed on the surface of the base material. The method of manufacturing a semiconductor device according to the first or second invention, characterized by forming

A fourth aspect of the present invention (the fourth aspect of the present invention).
Arranges a solid dielectric container having a gas outlet on one electrode, provides another electrode facing the gas outlet, and arranges a base material between the gas outlet and the other electrode. The method of manufacturing a semiconductor device according to the first or second aspect of the present invention, wherein the raw material gas converted into plasma is continuously discharged from the gas outlet to form a thin film on the surface of the base material.

A fifth aspect of the present invention (the invention of claim 5).
A solid dielectric is installed on at least one of the opposing surfaces of the opposing electrodes, and a raw material gas that has been turned into plasma between one electrode and the solid dielectric or between the solid dielectrics is sprayed on the base material, The method according to the first or second aspect, wherein a thin film is formed on the surface of the base material.

A sixth aspect of the present invention (the invention of claim 6).
When a solid dielectric is provided on at least one of the opposing surfaces of the opposing electrode, and when a raw material gas that has been turned into plasma between one electrode and the solid dielectric or between the solid dielectrics is blown onto the substrate. A semiconductor element according to the first or second invention, wherein a plasma-like gas is selectively induced on the surface of the substrate by applying an electric field to the substrate, and a thin film is formed on the surface of the substrate. It is a manufacturing method.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the production of a thin film of a semiconductor device according to the present invention, a source gas is excited by utilizing a plasma generated by applying a pulsed electric field under a pressure near atmospheric pressure.
A method based on normal-pressure plasma that decomposes, and more specifically, a solid dielectric is installed on at least one opposing surface of an opposing electrode, a substrate is placed between the opposing electrodes, and an electric field is applied between the electrodes. A method for performing glow discharge plasma treatment by disposing a solid dielectric container provided with a gas outlet on one electrode, applying an electric field between the electrodes, and continuously feeding the source gas excited from the gas outlet. A method of discharging and treating the substrate, and a method of blowing the excitation raw material gas generated between the electrodes onto the substrate. The applied electric field is pulsed, and the voltage rise time is 1
An atmospheric pressure discharge plasma processing method for manufacturing a semiconductor device, wherein the electric field intensity is set to 10 to 1000 kV / cm for not more than 00 μs.

It is known that under a pressure near the atmospheric pressure, except for a specific gas such as helium or ketone, a stable plasma discharge state is not maintained and an instantaneous transition to an arc discharge state occurs. It is considered that by applying the applied electric field, a cycle of stopping the discharge before starting the arc discharge and restarting the discharge is realized.

At pressures near atmospheric pressure, the method of applying a pulsed electric field of the present invention
It is possible to stably generate discharge plasma in an atmosphere that does not contain a component that takes a long time from a plasma discharge state such as helium to an arc discharge state.

According to the method of the present invention, glow discharge plasma can be generated regardless of the type of gas existing in the plasma generation space. In the atmospheric pressure plasma treatment under a specific gas atmosphere as well as the plasma treatment under the known low pressure condition, it is essential to perform the treatment in a closed vessel shielded from the outside air. According to the processing method, the processing can be performed in an open system or a low airtight system that prevents free flow of gas.

Further, since a high-density plasma state can be realized by the process at the atmospheric pressure, it has a great significance in performing a semiconductor device manufacturing process such as a continuous process. The realization of the high-density plasma state involves two functions of the present invention.

First, when the electric field strength is 10 to 1000 kV /
By applying a pulsed electric field having a steep rise of 100 cm or less and a rise time of 100 cm or less, gas molecules existing in the plasma generation space are efficiently excited. Applying a pulsed electric field with a slow rise corresponds to the stepwise application of energies with different magnitudes.First, the excitation of molecules that ionize with low energy, that is, molecules with a small first ionization potential, takes precedence. When the next higher energy is applied, already ionized molecules are excited to a higher level, and it is difficult to efficiently ionize molecules existing in the plasma generation space. On the other hand, according to a pulse electric field having a rise time of 100 μs or less, energy is simultaneously applied to molecules existing in the space, and the absolute number of ionized molecules in the space is large,
That is, the plasma density is high.

Second, since a plasma in a gas atmosphere other than helium can be stably obtained, a molecule having more electrons than helium, that is, a molecule having a larger molecular weight than helium is selected as an atmosphere gas, and as a result, the electron density is reduced. This is the effect of realizing a high space. In general, molecules having many electrons are easier to ionize. As described above, helium is a component that is difficult to ionize, but once it is ionized, it does not lead to an arc, and since it exists in a glow plasma state for a long time, it has been used as an atmospheric gas in atmospheric pressure plasma. However, if it is possible to prevent the discharge state from shifting to an arc, using molecules that are easily ionized and have a large mass number can increase the absolute number of molecules in the ionized state in space and increase the plasma. Density can be increased. In the prior art, it is impossible to generate glow discharge plasma in an atmosphere other than in an atmosphere in which helium is present at 90% or more. 4
Although it is disclosed in JP-A-74525, it is not possible to perform stable and high-speed processing at a practical level according to additional tests by the present inventors. Also, since acetone is contained in the atmosphere, treatments other than for the purpose of hydrophilicity are disadvantageous.

As described above, the present invention is stable only in an atmosphere in which molecules having more electrons than helium are present in excess, specifically, in an atmosphere containing a compound having a molecular weight of 10 or more at 10% by volume or more. It enables glow discharge, thereby realizing a high-density plasma state advantageous for surface treatment.

The above-mentioned pressure near the atmospheric pressure is defined as 1.333.
× 10 ^{4 to} 10.664 × 10 ⁴ Pa. Above all, 9.331 in which pressure adjustment is easy and the apparatus is simple.
The range is preferably from × 10 ^{4 to} 10.297 × 10 ⁴ Pa.

The first (the third aspect of the present invention) of the plasma processing method of the present invention is performed in an apparatus having a pair of opposed electrodes, and a solid dielectric placed on at least one of the opposed surfaces of the electrodes. . The portion where plasma is generated is between the solid dielectric and the electrode when a solid dielectric is installed on one of the electrodes, and between the solid dielectrics when the solid dielectric is installed on both of the electrodes. Space. Processing is performed by disposing a base material between the solid dielectric and the electrode or between the solid dielectrics.

For example, FIG. 2 shows an example of an apparatus for performing a surface treatment. In this device, the electrode facing surfaces of the upper electrode 12 and the lower electrode 13 are covered with a solid dielectric, and a discharge plasma is generated in a space between the upper electrode 12 and the lower electrode 13. The container 10 has a raw material gas inlet 16,
A gas exhaust port 19 is provided, and the source gas is supplied to the discharge plasma generation space through the source gas supply unit 161 and the source gas inlet 16, and is exhausted from the gas outlet 19 to the outside of the container 10. In the present process, since the portion that is in contact with the generated discharge plasma is processed, the upper surface of the base material 15 to be processed is processed in the example of FIG. When it is desired to treat both surfaces of the substrate to be treated, the substrate to be treated may be set up in a space where discharge plasma is generated.

The source gas is preferably supplied uniformly to the plasma generating space. In the apparatus shown in FIG. 2, the source gas inlet 16 has a gas flow rectifying mechanism and is exhausted from the gas exhaust port 19. This makes the gas flow in the plasma generation space uniform.

The material of the container 10 includes, for example, resin and glass, but is not particularly limited. Metals such as stainless steel and aluminum can also be used as long as they have a structure insulated from the electrodes.

Examples of the above-mentioned electrodes include those made of simple metals such as copper and aluminum, alloys such as stainless steel and brass, and intermetallic compounds. The counter electrode is
In order to avoid occurrence of arc discharge due to electric field concentration, it is preferable that the distance between the opposed electrodes is substantially constant. Examples of an electrode structure that satisfies this condition include a parallel plate type, a cylindrical opposed plate type, a spherical opposed plate type, a hyperboloid opposed plate type, and a coaxial cylindrical type structure.

The solid dielectric is provided on one or both of the opposing surfaces of the electrodes. At this time, it is preferable that the solid dielectric and the electrode on the side to be installed are in close contact with each other and completely cover the opposing surface of the contacting electrode. This is because if there is a portion where the electrodes directly face each other without being covered by the solid dielectric, an arc discharge is likely to occur therefrom.

The shape of the solid dielectric may be a sheet or a film, but preferably has a thickness of 0.01 to 4 mm. If the thickness is too large, a high voltage is required to generate discharge plasma. If the thickness is too small, dielectric breakdown may occur when a voltage is applied, and arc discharge may occur.

As the material of the solid dielectric, for example,
Plastics such as polytetrafluoroethylene and polyethylene terephthalate, glass, silicon dioxide, metal oxides such as aluminum oxide, zirconium dioxide, and titanium dioxide; double oxides such as barium titanate; Can be

It is preferable that the solid dielectric has a relative dielectric constant of 2 or more (the same applies in a 25 ° C. environment).
Specific examples of the dielectric having a relative dielectric constant of 2 or more include polytetrafluoroethylene, glass, and a metal oxide film. In order to stably generate a high-density discharge plasma, it is preferable to use a fixed dielectric having a relative dielectric constant of 10 or more. Although the upper limit of the relative permittivity is not particularly limited, about 18,500 of actual materials are known. As a solid dielectric having a relative dielectric constant of 10 or more, for example, a metal oxide film mixed with 5 to 50% by weight of titanium oxide and 50 to 95% by weight of aluminum oxide, or a metal oxide film containing zirconium oxide Is preferred.

The distance between the electrodes is determined by the thickness of the solid dielectric,
It is appropriately determined in consideration of the magnitude of the applied voltage, the purpose of utilizing the plasma, and the like, but is preferably 0.1 to 50 mm, and more preferably 5 mm or less. If it exceeds 50 mm, it is difficult to generate uniform discharge plasma.

The second aspect of the plasma processing method of the present invention is as follows.
According to a fourth aspect of the present invention, a solid dielectric container having a gas outlet on one electrode (ground electrode) is provided, and another electrode is provided so as to face the gas outlet, and the gas outlet is provided. And disposing a substrate to be treated between the other electrode and continuously discharging the source gas from the gas outlet, and simultaneously applying an electric field between the one electrode and the other electrode. This is a processing method for generating discharge plasma.

For example, FIG. 3 is a diagram showing a cross section of an example of a discharge plasma processing apparatus using an excitation gas blown out between the generating electrodes. In FIG. 3, reference numeral 11 denotes a power supply. Reference numeral 12 denotes an application-side electrode. 13 represents another electrode. Reference numeral 14 denotes a solid dielectric container. Reference numeral 15 denotes a substrate to be treated. Reference numeral 16 denotes a gas inlet for introducing a raw material gas into the solid dielectric container. 1
7 denotes a gas outlet. Reference numeral 18 denotes a jig for changing a distance between one electrode and another electrode.

In the method using the solid dielectric container according to the present invention, an electric field is applied between the electrode 12 and the electrode 13 in a state where the raw material gas is introduced into the solid dielectric container 14 so that the solid dielectric container is formed. 14, a discharge plasma is generated. The gas inside the solid dielectric container 14 is blown out from the gas outlet 17 toward the substrate 15 to be processed, and the components of the raw material gas excited into the plasma state come into contact with the surface of the substrate 15 to be processed. Is performed. Therefore, by changing the relative position between the solid dielectric container 14 and the base material 15, the processing position of the base material can be changed, and a simple apparatus and a small amount of source gas can be used to process a large-area base material. , A partial designation process becomes possible.

The power supply 11 is adapted to apply a pulsed electric field. By applying a pulse electric field having a rise time and a fall time within the above ranges and an electric field intensity, a stable discharge state can be realized under conditions near atmospheric pressure. Such a pulsed electric field will be described later.

The shape of the one electrode 12 and the other electrode 13 is not particularly limited, and may be a curved shape such as a cylindrical shape or a spherical shape in addition to the flat shape shown in the figure.

The distance from the center of the discharge space to the inside of the solid dielectric container 14, the center of the gas outlet 17, and to the other electrode 13 depends on the thickness and material of the solid dielectric container 14.
The thickness is appropriately determined depending on the thickness and material of the base material 15, the magnitude of the applied voltage, and the like, but is preferably 0.5 to 30 mm.
If it exceeds 30 mm, a high voltage is required, the discharge state is likely to shift to arc discharge, and uniform surface treatment becomes difficult.

The shape of the solid dielectric container 14 used in the present invention is not particularly limited.
Spherical and the like.

The solid dielectric container 14 has one electrode 1
2 are provided. FIGS. 4 and 5 are diagrams illustrating an example of the arrangement of one electrode 12 and the solid dielectric container 14. When the solid dielectric container 14 is rectangular, one electrode 12 may be provided on a surface other than the surface on which the gas outlet 17 is provided. The thickness of the surface of the solid dielectric container 14 on which one electrode 12 is provided is preferably 0.03 to 30 mm. 0.03m
If it is less than m, dielectric breakdown may occur when a high voltage is applied, and arc discharge may occur.

The solid dielectric container 14 is provided with the gas inlet 1
6 and a gas outlet 17. The shape of the gas discharge port 17 is not particularly limited, and examples thereof include a slit-like shape, a shape having a large number of holes, and a tip-like shape formed by a solid dielectric container. Figures 6, 7, and 8
FIG. 4 is a diagram illustrating an example of a gas outlet 17.

The solid dielectric container of the present invention may have a gas storage capability in addition to the form having the gas inlet shown in FIG.

The jig 18 in FIG. 3 can change the distance between the other electrode 13 and the gas outlet 17 freely. With the jig 18, for example, when the substrate 15 to be treated is a large-area object, the surface treatment can be performed by continuously moving the other electrode 13 and the gas outlet 17 while keeping the distance constant. When only a part of the base material 15 is treated, a continuous surface treatment, a partial surface treatment, or the like can be performed by freely changing the interval between the other electrode 13 and the gas outlet 17. However, if the distance between the gas outlet 17 and the substrate 15 to be processed is too long, the probability of contact with air increases and the processing efficiency decreases, so care must be taken.

Further, the third method of the plasma processing method of the present invention
(Invention of claim 5) In the present invention, a solid dielectric is provided on at least one opposing surface of a counter electrode, and a raw material gas excited between one electrode and the solid dielectric or between the solid dielectrics is provided. Is sprayed onto a substrate to form a thin film on the surface of the substrate.

FIG. 9 shows an example of the apparatus. In a container 10 having a gas inlet 16 and a gas outlet 17,
A solid dielectric is provided on at least one of the opposing surfaces of the opposing electrodes 12 and 12 ', and the source gas excited between one of the electrodes and the solid dielectric or between the solid dielectrics is continuously discharged in the direction of the arrow. Then, a thin film 22 is formed on the surface of the film-shaped or plate-shaped substrate 21 which is being moved by a roll from the gas outlet 17 and is sprayed on the surface of the substrate.

In the thin film formation by this method, the semiconductor element or the like to be formed is not directly exposed to the high electric field plasma space, but carries the gas in the plasma state only to the surface to form the thin film. This is a preferred method in which the thermal burden is reduced.

In the third method of the present invention, a thin film can be formed by applying an electric field to the substrate to selectively induce a plasma-like gas on the surface of the substrate. invention). Examples of the electric field include a pulsed or high-frequency electric field, a continuous wave, and a constant electric field load (for example, a constant voltage). For example, as shown in FIG.
The power supply 11 can be connected to the substrate 21 to apply a pulsed electric field or the like.

Hereinafter, the pulse electric field of the present invention will be described. FIG. 11 shows an example of the pulse voltage waveform. Waveform (a),
(B) is an impulse waveform, waveform (c) is a pulse waveform, and waveform (d) is a modulation waveform. Although FIG. 11 shows the case where the voltage application is repeated positive and negative, a pulse of a type that applies a voltage to either the positive or negative polarity side may be used. Further, a pulse electric field on which a direct current is superimposed may be applied. The waveform of the pulse electric field in the present invention is not limited to the above-mentioned waveforms, and may be modulated using pulses having different pulse shapes, rise times, and frequencies. Such modulation is suitable for performing high-speed continuous surface treatment.

The rise time and fall time of the pulse electric field are 100 μs or less, preferably 10 μs or less.
μs or less. If it exceeds 100 μs, the discharge state easily transitions to an arc and becomes unstable, making it difficult to maintain a high-density plasma state due to a pulsed electric field. Further, the shorter the rise time and the fall time, the more efficiently the gas is ionized during the generation of plasma, but it is actually difficult to realize a pulse electric field with a rise time of less than 40 ns. More preferably, it is 50 ns to 5 μs. Here, the rise time refers to the time during which the voltage (absolute value) continuously increases, and the fall time refers to the time during which the voltage (absolute value) continuously decreases.

It is preferable that the fall time of the pulse electric field is also steep.
It is preferable that the time scale is less than μs. Although it differs depending on the pulse electric field generation technology, for example, in the power supply device used in the embodiment of the present invention, the rise time and the fall time can be set to the same time.

The electric field strength of the pulse electric field is 10 to 10
00 kV / cm, preferably 20 to 300 kV / cm.
cm. If the electric field intensity is less than 10 kV / cm, it takes too much time for the treatment, and if the electric field intensity exceeds 1000 kV / cm, arc discharge is likely to occur.

The frequency of the pulse electric field is 0.5 kHz
It is preferable that it is above. When the frequency is less than 0.5 kHz, the processing takes too much time because the plasma density is low. The upper limit is not particularly limited, but is 13.56M which is commonly used.
Hz or a high-frequency band such as 500 MHz used experimentally. Considering the ease of matching with the load and the handleability, the frequency is preferably 500 kHz or less. By applying such a pulsed electric field, the processing speed can be greatly improved.

The duration of one pulse in the pulse electric field is preferably 200 μs or less, more preferably 3 to 200 μs. here,
One pulse duration, which is shown in FIG. 11 as an example, refers to a continuous ON time of one pulse in a pulse electric field formed by repetition of ON and OFF.

From the above characteristics, the apparatus of the present invention can be used to manufacture an interlayer insulating film and a passivation film on a substrate by changing a gas type, an electrolytic condition, and a film forming environment in the manufacture of a semiconductor device. (Protective film) can be formed as a thin film.

As the raw material gas for forming the thin film of the interlayer insulating film and the passivation film (protective film) of the present invention, for example, a silane-based gas and an oxygen gas, an alkoxysilane-based gas such as tetraethoxysilane and an oxygen gas are used. A thin film of a metal oxide such as SiO ₂ can be formed. Note that the formation of a thin film can be promoted by mixing an oxygen gas, an ozone gas, or the like into the silane-based source gas. A silane compound gas such as SiH ₄ or Si ₂ H ₆ ;
Si ₃ N ₄ , a-S using halogen-based silane compound gas such as SiH ₂ Cl ₂ and anhydrous ammonia or nitrogen gas
A nitride thin film such as iN can be formed. further,
Using hydrocarbon gas silane such compound gas and C ₂ H ₄ as described above, the fluorine compound-based thin film by using the formation of a-SiC film, and a silane-based compound gas and fluorine gas as described above Etc. can be formed.

From the viewpoints of economy and safety, it is preferable to carry out the treatment in an atmosphere in which the raw material gas is diluted with an inert gas. Examples of the inert gas include rare gases such as neon, argon, and xenon, and nitrogen gas. These may be used alone or in combination of two or more. Conventionally, at a pressure near the atmospheric pressure, processing in the presence of helium has been performed, but according to the method of applying a pulsed electric field of the present invention, as described above, compared to helium Stable processing in inexpensive argon or nitrogen gas is possible.

Conventionally, at a pressure near the atmospheric pressure, the treatment has been performed in an atmosphere in which helium is present in a large excess, but according to the method of the present invention, argon and nitrogen are less expensive than helium. And high-density plasma state by increasing the processing speed by performing the processing in the presence of a gas having a large molecular weight and a large number of electrons. Has great industrial advantages.

The mixing ratio of the raw material gas to the inert gas is appropriately determined depending on the type of the gas. If the concentration of the source gas is too high, an extra reaction that does not contribute to film formation tends to occur. Therefore, the concentration of the source gas is preferably 0.001 to 10% by volume, more preferably 0.001 to 0.5% by volume. % By volume.

The glow discharge plasma treatment of the present invention may be carried out by heating or cooling the substrate, but it is sufficiently possible at room temperature, and is characterized in that the treatment can be carried out at a lower temperature than the film forming temperature of the conventional method. is there. The time required for the glow discharge plasma treatment is appropriately determined in consideration of the applied voltage, the type of the source gas, the ratio in the mixed gas, and the like.

In the atmospheric pressure discharge using a pulsed electric field according to the present invention, the discharge can be generated at the atmospheric pressure directly between the electrodes without depending on the kind of gas at all. The high-speed processing can be realized by the atmospheric pressure plasma apparatus according to the procedure and the processing method. In addition, semiconductor element processing parameters for each thin film can be adjusted by parameters such as pulse frequency, voltage, and electrode spacing. Furthermore, selective excitation can be performed by frequency control including the shape and modulation of the applied pulse electric field, and the film formation rate of a specific compound can be selectively improved, and the purity of impurities and the like can be controlled.

The interlayer insulator according to the manufacturing method of the present invention has I
The present invention can be applied to the manufacture of other semiconductor elements such as a C circuit, a solar cell, and a switch of a liquid crystal display.

[0063]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 A parallel plate type electrode as shown in FIG. 9 was used. Electrode 12 (stainless steel (SUS304), width 300 mm x length 100
mm x thickness 20mm) and electrode 12 '(stainless steel (SU
S304) Made, width 300 mm x length 100 mm x thickness 2
0 mm) as a solid dielectric and sprayed with alumina to a thickness of 1 mm, placed in parallel at a spacing of 2 mm, and placed at a position 5 mm away from the blow-out port at a polyimide film (size: 100 × 100 mm, thickness: 50 μm) ) Was installed as a substrate for film formation.

The inside of the apparatus is 1.333 × 10 with an oil rotary pump.
^TwoEvacuation was performed until Pa was reached. Next, it is equipped with argon gas.
10.13 × 10^FourPa and then as raw material gas
0.16% of tetraethoxysilane and 16% of oxygen
The gas diluted with Lugon gas is introduced into the apparatus through the introduction pipe 16.
Was introduced. The pallet shown in FIG. 11A is placed between the electrodes 12 and 12 '.
Pulse rise speed 5μs, frequency 1
0 kHz, voltage V_PP20kV, under 95kPa (atmospheric pressure
When film formation was carried out in (bottom), SiO 2 was formed on the film. _TwoThin film
Generation was confirmed. The deposition rate at this time is 100 nm
/ Min.

Comparative Example 1 In Example 1, the applied electric field was 150 MHz s.
A SiO ₂ thin film was formed on a polyimide film in the same manner as in Example 1 except that in-wave was used and helium was used as a carrier gas. Although the formation of the SiO ₂ thin film was confirmed, the deposition rate was 50 nm / min.
Met.

Comparative Example 2 The same apparatus as in Example 1 was used.
Using a 56 MHz, 200 W sin wave electric field condition,
A SiO ₂ thin film was formed on a polyimide film in the same manner as in Example 1 except that the reaction was performed in an environment of 13 Pa. Although the formation of the SiO ₂ thin film was confirmed, the film formation rate was 30 nm / min.

Example 2 Using the apparatus shown in FIG. 4, a film was formed as a stainless sheet using the electrode 13 as a substrate and an electrode. The distance between the gas outlet 17 and the substrate / electrode was 2 mm. Under the same raw material gas and the same conditions as in Example 1, a pulsed electric field was applied under atmospheric pressure, and the raw material gas that was turned into plasma on the stainless steel base material was sprayed from the gas outlet 17 to form a SiO ₂ thin film on the stainless steel base material. Generation was confirmed. The deposition rate at this time is 100 nm
/ Min.

Example 3 Using the apparatus shown in FIG. 9, silane gas 0.3 was used as a source gas.
%. Using a gas obtained by diluting ammonia gas 10% with argon gas, using the same pulse waveform as in Example 1, pulse rising speed 5 μs, frequency 10 kHz, voltage V _PP 2
When a film was formed at 0 kV and 95 kPa (atmospheric pressure), a plasma-like gas was induced from the plasma generation space to the wafer substrate, and an a-SiN thin film was formed.

[0070]

According to the method of manufacturing a semiconductor device to which a pulsed electric field is applied according to the present invention, under a pressure near atmospheric pressure,
Irrespective of the gas atmosphere, stable and uniform discharge plasma can be generated, and a thin film of an interlayer insulator and a passivation film required for a semiconductor element can be easily formed. Further, the method of the present invention can reduce equipment cost as compared with the conventional low pressure method. Further, instead of a high-cost gas such as helium, a low-cost gas such as argon or nitrogen gas can be used. Furthermore, since high-speed film formation by high-density plasma is possible, high-speed productivity can be achieved, and high-level processing can be performed in a short time. In particular, since low-temperature processing is possible, high-speed continuous processing and the like can be performed. It has great significance in performing industrial processes.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a configuration of a semiconductor element.

FIG. 2 is a schematic sectional view showing one example of a discharge plasma processing apparatus of the present invention.

FIG. 3 is a schematic sectional view showing another example of the discharge plasma processing apparatus of the present invention.

FIG. 4 is a diagram showing an example of an arrangement of a solid dielectric container and one electrode of a discharge plasma processing apparatus.

FIG. 5 is a diagram showing an example of an arrangement of a solid dielectric container and one electrode of a discharge plasma processing apparatus.

FIG. 6 is a diagram illustrating an example of a gas outlet of a discharge plasma processing apparatus.

FIG. 7 is a diagram illustrating an example of a gas outlet of the discharge plasma processing apparatus.

FIG. 8 is a diagram illustrating an example of a gas outlet of a discharge plasma processing apparatus.

FIG. 9 is a diagram of an example of a gas discharge discharge plasma processing apparatus.

FIG. 10 is a diagram of an example of a gas discharge discharge plasma processing apparatus.

FIG. 11 is a voltage waveform diagram showing an example of a pulse electric field according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Silicon film 3 Source electrode 4 Drain electrode 5 Interlayer insulator 6 Gate electrode 7 Passivation film 10 Container 11 Power supply 12 Upper electrode 13 Lower electrode 14 Solid dielectric container 15 Object to be processed 16 Source gas inlet 161 Source gas supply unit 17 Gas outlet 18 Jig 19 Gas exhaust 21 Substrate 22 Thin film

Claims (6)

[Claims] In a method of forming an interlayer insulating film and / or a passivation film in a semiconductor device by a plasma CVD method, a source gas is introduced between opposed electrodes under a pressure near atmospheric pressure, and a pulsed electric field is applied between the opposed electrodes. A method for producing a glow discharge plasma by applying a source gas to form an interlayer insulating film and / or a passivation film. 2. A pulse-like electric field having a voltage rise time of 100 μs or less and an electric field intensity of 10 to 1000 kV / c.
2. The method according to claim 1, wherein m is m. 3. A solid dielectric is provided on at least one opposing surface of the opposing electrode, and a base material is arranged between one electrode and the solid dielectric or between the solid dielectrics. 3. The method according to claim 1, wherein a thin film is formed on the surface. 4. A solid dielectric container provided with a gas outlet on one electrode, another electrode provided opposite the gas outlet, and a base between the gas outlet and the other electrode. 3. The method according to claim 1, wherein a material is arranged, the raw material gas converted into plasma is continuously discharged from the gas outlet, and a thin film is formed on the surface of the base material. 4. 5. A solid dielectric is provided on at least one of the opposing surfaces of the opposing electrode, and a raw material gas that has been turned into plasma between one electrode and the solid dielectric or between the solid dielectrics is used as a base material. 3. The method according to claim 1, wherein a thin film is formed on the surface of the substrate by spraying. 6. A solid dielectric is provided on at least one of the opposing surfaces of the opposing electrode, and a raw material gas that has been turned into plasma between one electrode and the solid dielectric or between the solid dielectrics is used as a base material. The semiconductor according to claim 1, wherein, when spraying, a plasma-like gas is selectively induced on the surface of the substrate by applying an electric field to the substrate to form a thin film on the surface of the substrate. Device manufacturing method.