JP3118121B2 - Microwave plasma CVD apparatus and deposited film forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a plasma CVD apparatus using microwave energy and a method for forming a deposited film using microwave energy.

[0002]

2. Description of the Related Art Film formation using a microwave plasma CVD apparatus is performed, for example, as follows. That is, a gas is introduced into the film forming chamber of the microwave plasma CVD apparatus, and simultaneously, microwave energy is supplied to generate plasma in the film forming chamber to excite and decompose the gas to be disposed in the film forming chamber. A deposited film is formed on the substrate.

In a microwave plasma CVD apparatus, microwave energy is used as a gas excitation source because electrons can be accelerated by an electric field having a higher frequency than RF energy, and gas molecules are ionized in a chain. This is because it can be excited. Therefore, there are advantages in that gas excitation efficiency and decomposition efficiency are high, high-density plasma can be formed relatively easily, and film formation can be performed at high speed.

The present inventor has proposed a microwave plasma CVD apparatus using an annular waveguide having a plurality of slots formed on an inner surface thereof as a uniform and efficient microwave introduction apparatus (Patent Application No. H3-). 293010). FIG. 9 shows this microwave plasma CVD apparatus. In FIG.
Reference numeral 1101 denotes a plasma generation chamber; 1102, a quartz tube forming the plasma generation chamber 1101; 1103, an annular waveguide with a slot for introducing microwaves into the plasma generation chamber 1101;
A microwave introduction unit for introducing 103. Reference numeral 1106 denotes a two-distribution block for dividing microwaves into two, 1107 denotes a plurality of slots formed inside the annular waveguide 1104,
Reference numeral 1108 denotes a plasma generating gas introducing means, 1111 denotes a film forming chamber connected to the plasma generating chamber 1101, 1112 denotes a coated substrate, 1113 denotes a support for the substrate 1112, 1114 denotes a heater for heating the substrate 1112, and 1115 denotes a film forming gas. Introducing means 1116 is exhaust gas. Plasma generation and film formation are performed as follows. The inside of the plasma generation chamber 1101 and the inside of the film formation chamber 1111 are evacuated via an exhaust system (not shown). Subsequently, the gas for plasma generation is supplied to the gas inlet 1
It is introduced into the plasma generation chamber 1101 at a predetermined flow rate via 108. Next, the conductance valve (not shown) provided in the exhaust system (not shown) is adjusted, and the plasma generation chamber 1 is adjusted.
The inside of 101 is maintained at a predetermined pressure. A desired power is supplied from a microwave power supply (not shown) into the plasma generation chamber 1101 via the annular waveguide 1103. In this way, electrons are accelerated by the microwave electric field, and the plasma generation chamber 1
A high-density plasma is generated in 101. At this time, the film forming gas is supplied through the film forming gas introduction pipe 1115 to the film forming chamber 111.
When introduced into the substrate 1, the film-forming gas is excited by the generated high-density plasma, and a film is formed on the surface of the coating substrate 1112 placed on the support 1113. At this time, a film-forming gas may be introduced into the plasma-generating gas inlet 1108 depending on the application.

[0005]

However, in the apparatus shown in FIG. 9, the plasma generation chamber 110 of the vacuum chamber is not used.
A wall must be provided to maintain the pressure differential between the microwave introduction tube 1 and the atmospheric pressure, and to provide a microwave passage, ie, a quartz tube 1102. At this time, depending on the substance to be grown on the substrate, the thin film adheres to the inner wall of the quartz tube during use. In such a case, a problem may occur that the microwave cannot be efficiently introduced into the plasma generation chamber because the microwave is absorbed by the thin film. Such a phenomenon is particularly significant when a conductive film is formed because the conductive film does not transmit microwaves.

[0006]

SUMMARY OF THE INVENTION The present invention has been accomplished as a result of solving the above-mentioned problems in the conventional microwave plasma CVD apparatus and making intensive efforts to solve the above-mentioned problems. In the present invention, the inside of the microwave conduit, which has been conventionally placed under the atmospheric pressure, can be depressurized by the decompression means of the plasma generation chamber through the slot provided in the microwave waveguide. By doing so, the quartz tube 1102 of the apparatus shown in FIG. 9 is not always necessary, and even if a deposited film is grown on the coating substrate 1112, a thin film does not adhere to the inner wall of the quartz tube, and the adhered substance causes microscopic formation. It has been found that the waves are absorbed and the introduction of microwaves into the plasma generation chamber is not hindered.

Further, the inventor of the present invention connected a means for introducing a gas for plasma generation to the microwave waveguide, and also connected the inside of the microwave waveguide to the plasma generation chamber through a slot provided in the microwave waveguide. By reducing the pressure by the pressure reducing means connected to the chamber and making the pressure in the microwave waveguide higher than the pressure in the plasma generation chamber, plasma is less likely to be generated in the microwave waveguide and plasma is effectively generated in the plasma generation chamber. I got the knowledge that it can be done.

[0008] The present invention has been made based on these findings. The first embodiment of the microwave plasma CVD apparatus according to the present invention is as follows. That is, the plasma generating chamber is depressurized by the exhaust means, and microwave energy is supplied into the plasma generating chamber via a microwave waveguide connected to the plasma generating chamber, and the plasma energy is communicated with the plasma generating chamber or the plasma generating chamber. In a microwave plasma CVD apparatus for forming a deposited film on a substrate disposed in a formed film forming chamber, a plurality of slots are formed in the waveguide on the side of the plasma generating chamber to generate the plasma. A gas to be introduced is introduced into the plasma generation chamber through the slot.

A second aspect of the microwave plasma CVD apparatus according to the present invention is as follows. That is, the plasma generating chamber is depressurized by the exhaust means, microwave energy is supplied to the plasma generating chamber through a microwave waveguide connected to the plasma generating chamber, and plasma is generated in the plasma generating chamber. A microwave plasma CV for forming a deposited film on a substrate disposed in the plasma generation chamber or in a film formation chamber communicating with the plasma generation chamber.
The apparatus D is characterized in that the microwave waveguide can also be depressurized by the exhaust means so that a pressure difference is provided between the plasma generation chamber and the microwave waveguide.

The present invention also includes a method for forming a deposited film.
That is, in the method of forming a deposited film according to the present invention, the plasma generating chamber is depressurized by an exhaust unit, and microwave energy is supplied to the plasma generating chamber through a microwave waveguide connected to the plasma generating chamber. In a deposition film forming method of generating plasma in a generation chamber and forming a deposition film on a substrate disposed in the plasma generation chamber or a deposition chamber connected to the plasma generation chamber, the microwave waveguide is exhausted. The pressure is reduced by means, and a deposition film is formed while supplying a gas for generating the plasma to the plasma generation chamber through the microwave waveguide.

According to the present invention, the above-mentioned problems are solved,
An efficient deposition film can be formed.

That is, according to the present invention, microwave CVD
This eliminates the need for a quartz tube constituting the inner wall of the plasma generation chamber of the apparatus, and eliminates the problem that the introduction of a microwave to the plasma generation chamber is prevented by the thin film adhering to the inner wall of the quartz tube. Therefore, the maintenance cycle of the device is lengthened, and the reliability and operation rate of the device are improved. Furthermore,
According to the present invention, efficient plasma can be generated,
A high-quality deposited film can be efficiently formed.

In the present invention, the pressure in the plasma generating chamber is desirably kept at 0.5 Torr or less, and the pressure in the microwave waveguide is desirably kept at 1.0 Torr or more.

Since plasma is hardly produced at a pressure of 1 Torr or more, it has an effective function for generating plasma only in the plasma generation chamber. Therefore, the use of this device makes it possible to uniformly introduce microwaves into the plasma generation chamber efficiently and to generate uniform and high-density plasma.

FIG. 1 shows an example of this apparatus. The formation of the deposited film using the apparatus shown in FIG.
03 is depressurized by the exhaust means 116, and a deposition film is formed while supplying a gas for generating plasma to the plasma generation chamber 101 through the microwave waveguide 103. Further, this apparatus is a microwave plasma CVD apparatus in which the microwave waveguide 103 can also be depressurized by the exhaust means 116, and a pressure difference is provided between the plasma generation chamber 101 and the microwave waveguide 103. Further, the apparatus has a structure in which a plurality of slots are formed in the waveguide on the side of the plasma generation chamber, and the gas for generating the plasma is introduced into the plasma generation chamber through the slots. This is a microwave plasma CVD apparatus.

Generation of plasma and film formation using this apparatus are performed as follows. The inside of the plasma generation chamber 101 and the inside of the film formation chamber 111 are evacuated via an exhaust system (not shown). Subsequently, the gas for plasma generation is supplied to the gas inlet 1
08 and the waveguide 103 and the slot 1 at a predetermined flow rate.
07, and is introduced into the plasma generation chamber 101. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted so that the inside of the plasma generation chamber 101 and the film formation chamber 1 are adjusted.
11 is kept at a predetermined pressure. By supplying desired power from a microwave power supply (not shown) to the plasma generation chamber 101 through the waveguide 103, the plasma generation chamber 10
A plasma is generated in 1. At this time, if the film-forming gas is introduced into the film-forming chamber 111 through the film-forming gas introduction pipe 115, the film-forming gas is excited by the generated high-density plasma and is placed on the support 113. A deposited film is formed on the surface of the coated substrate 112 thus formed. At this time, a film-forming gas may be introduced into the plasma-generating gas inlet 108 depending on the application.

In using the microwave introduction device of the present invention, the frequency of the microwave used is 2.45 GHz.
Other than z, it can be appropriately selected from the range of 0.8 GHz to 20 GHz.

The shape of the waveguide used in the present invention may be cylindrical or other shapes such as a disk or a polygon depending on the shape of the plasma generating chamber. Regarding the cross-sectional shape of the waveguide, microwaves can be propagated in a rectangular shape with the same dimensions as the WRT-2 standard waveguide, and in any size, circular, semi-circular or other shape. All you have to do is. Regarding the constituent material of the annular waveguide, even if stainless steel is copper-coated and silver-coated two-layer plating is applied, metals, alloys such as Cu, A1, Fe, and Ni,
A1, W, Mo, Ti, Ta, Cu, Ag on insulators such as glass, quartz, silicon nitride, alumina, acrylic, polycarbonate, polyvinyl chloride, polyimide, etc.
Any material can be used as long as it has sufficient mechanical strength and its surface is covered with a conductive layer having a thickness equal to or greater than the penetration depth of microwaves, such as those coated with a metal thin film.

The slot provided in the microwave plasma CVD apparatus of the present invention may have a rectangular shape whose long side is perpendicular to the direction in which the microwave travels, or may be inclined even if the long side is parallel to the direction in which the microwave travels. However, not only rectangular, but also circular, polygonal, iron array type, or star type, the microwave can be introduced from the slot, and the conductance is such that the pressure in the waveguide is high enough to prevent discharge in the waveguide. You only need to have it. However, in consideration of efficient introduction and easy adjustment of the leak rate, the long side is 40 mm to 60 mm × 0.5 mm perpendicular to the direction in which the microwave travels.
A rectangular shape of 3 mm to 3 mm is optimal. The length of the slots is adjusted so that the amount of microwave leakage from each slot is substantially equal. The length of the slot may be adjusted by attaching a conductive tape or using a shutter. The interval between the slots provided is one of the guide wavelengths.
/ 4 may be an integral multiple thereof, and may not be provided in a portion where plasma generation is not necessary.

The microwave CVD apparatus of the present invention mainly discharges only when microwaves are introduced into the plasma generation chamber without discharging inside the waveguide, but depending on the application, it may resonate inside the waveguide. It is possible to discharge and supply a high density of nonionic active species from a portion where the discharge is strong. In this case, the shape of the slot can be adopted as long as it has a conductance such that the pressure in the waveguide is in a range where a discharge occurs in the waveguide, and the long side is 40 mm perpendicular to the traveling direction of the microwave. A rectangular shape of about 60 mm × 2 mm to 5 mm is optimal.

Further, a magnetic field generating means may be provided for increasing the density of the plasma. As the magnetic field generating means, a permanent magnet other than a coil can be used as long as it can generate a magnetic field perpendicular to the electric field near the slot of the waveguide. Also, the magnetic circuit can be used with a magnetic field other than a mirror magnetic field, a divergent magnetic field, a multi-cusp magnetic field, or a cylindrical magnetron magnetic field. When using a coil, other cooling means such as a water cooling mechanism or air cooling may be used to prevent overheating.

By using the above-mentioned microwave plasma CVD apparatus, a high-quality deposited film is uniformly and efficiently formed on a coating substrate disposed in a plasma generation chamber or a film formation chamber connected to the plasma generation chamber. can do.

Further, by using this microwave plasma CVD apparatus, the microwave can be introduced into the plasma generation chamber without passing through the quartz tube, so that a film for absorbing the microwave is formed on the quartz tube, and the microwave is generated. The introduction into the plasma generation chamber does not become difficult, the maintenance cycle is lengthened, and the reliability and operation rate of the apparatus are improved.

[0024]

[Examples of Plasma CVD Apparatus] The microwave plasma CVD apparatus of the present invention will be described more specifically with reference to examples of the apparatus, but the present invention is not limited to these examples.

Apparatus Example 1 FIG. 1A shows a microwave plasma CVD apparatus using an annular waveguide which is an example of the present invention, and FIG. 1B shows a microwave introduction apparatus. 101 is a plasma generation chamber, 103
Is an annular waveguide with a slot for introducing microwaves into the plasma generation chamber 101, 104 is a microwave introduction unit for introducing microwaves into the annular waveguide 103, and 105 is a microwave introduction unit provided in the introduction unit 104. It is a window. 106 is a distribution block for distributing microwave into two, 107 is a plurality of slots formed inside the annular waveguide 103, 108
Is a plasma generating gas introducing means, and 111 is a film forming chamber connected to the plasma generating chamber. 112 is a coated substrate, 113
Denotes a support for the base 112, 114 denotes a heater for heating the base 112, 115 denotes a film forming gas introducing unit, and 116 denotes an exhaust system.

The annular waveguide 103 has an inner wall cross-sectional dimension of W
It is 27 mm x 96 mm, the same as the RT-2 standard waveguide, and has a center diameter of 354 mm. The material of the annular waveguide 103 is made of stainless steel to maintain mechanical strength, and its inner wall surface is coated with copper in order to suppress microwave propagation loss and further coated with silver to form a two-layer plating. Is given.

The shape of the slot 107 is a rectangle having a length of 42 mm and a width of 2 mm, and is formed at intervals of 1/4 of the guide wavelength. The guide wavelength depends on the frequency of the microwave used and the cross-sectional dimension of the waveguide, but the frequency is 2.45 GHz.
Is about 159 mm when using the microwave and the waveguide having the above dimensions. In the used annular waveguide 103, 28 slots are formed at intervals of about 40 mm.

The microwave introduction unit 104 includes a 4-stub tuner, a directional coupler, an isolator, and 2.45 GHz.
Are connected in order.

The generation of the plasma and the film formation are performed as follows. The inside of the plasma generation chamber 101 and the inside of the film formation chamber 111 are evacuated via an exhaust system (not shown). Subsequently, a gas for plasma generation is introduced into the plasma generation chamber 101 through the annular waveguide 103 and the slot 107 at a predetermined flow rate through the gas inlet 108. Next, the exhaust system (not shown)
The inside of the plasma generation chamber 101 and the inside of the film formation chamber 111 are maintained at a predetermined pressure by adjusting a conductance valve (not shown) provided in the apparatus. A desired power is supplied from a microwave power supply (not shown) through the annular waveguide 103 to the plasma generation chamber 10.
1, plasma is generated in the plasma generation chamber 101. At this time, when the film-forming gas is introduced into the film-forming chamber 111 through the film-forming gas introduction pipe 115, the film-forming gas is excited by the generated high-density plasma and is placed on the support 113. A film is formed on the surface of the coated substrate 112. At this time, a film-forming gas may be introduced into the plasma-generating gas inlet 108 depending on the application.

The microwave plasma C shown in FIG.
Using a VD apparatus, N ₂ flow rate 500 sccm, pressure 5
Plasma was generated under the conditions of mTorr and microwave power of 1 kW, and the uniformity of the electron density of the obtained plasma was evaluated. Evaluation of the uniformity of the electron density was performed by the probe method as follows. The voltage applied to the probe is
The current flowing through the probe was measured with an IV measuring instrument while changing the range from 50 to +50 V, and the electron density was calculated from the obtained IV curve by the method of Langmuir. The electron density was measured at 19 points in the center section of the plasma generation chamber, and the uniformity was evaluated based on the dispersion of the maximum value / minimum value. As a result, the electron density was 9.6 × 10 in the φ200 plane.
¹¹ / cm ³ ± 4.8%, confirming that high-density and uniform plasma was formed.

Apparatus Example 2 FIG. 2 shows an example of a microwave plasma CVD apparatus using a disc-shaped waveguide. 201 is a plasma generation chamber, 203
Is a disc-shaped waveguide with slots for introducing microwaves into the plasma generation chamber 201; 204 is an introduction section for introducing microwaves into the disc-shaped waveguide 203; and 205 is a microwave introduction provided on the introduction section. It is a window. 206 is a distribution block for distributing microwaves into two, and 207 is a disc-shaped waveguide 20
A plurality of slots formed inside 3, a gas introduction means 208 for plasma generation, and a film formation chamber 211 connected to the plasma generation chamber. 212 is a coated substrate, 213 is a substrate 2
12, a support 214, a heater for heating the substrate, 214
Denotes a film forming gas introducing means, and 215 denotes an exhaust system. To the microwave introduction unit 204, a 4-stub tuner, a directional coupler, an isolator, and a microwave power supply (not shown) having a frequency of 2.45 GHz are sequentially connected.

The generation of the plasma and the film formation are performed as follows. The interior of the plasma generation chamber 201 and the interior of the film formation chamber 211 are evacuated via an exhaust system (not shown). Subsequently, a gas for plasma generation is introduced into the plasma generation chamber 201 through the disk-shaped waveguide 203 and the slot 207 at a predetermined flow rate through the gas inlet 208. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber 201 and the inside of the film formation chamber 211 at a predetermined pressure. Then microwave power supply (not shown)
By supplying more desired power into the plasma generation chamber 201 through the disk-shaped waveguide 203, the plasma generation chamber 2
Plasma is generated in 01. At this time, if the film-forming gas is introduced into the film-forming chamber 211 via the film-forming gas introduction pipe 215, the film-forming gas is excited by the generated plasma, and the coating placed on the support 213 is formed. A film is formed on the surface of the base 212. At this time, a film formation gas may be introduced into the plasma generation gas inlet 208 depending on the use.

The microwave plasma C shown in FIG.
Using a VD apparatus, N ₂ flow rate 500 sccm, pressure 3
Plasma was generated under the conditions of mTorr and microwave power of 800 W, and the uniformity of the electron density of the obtained plasma was evaluated. As a result, the electron density was 8.4 in the φ200 plane.
× 10 ¹¹ / cm ³ ± 3.6%, confirming that a high-density and uniform plasma was formed.

Apparatus Example 3 FIG. 3 shows an example of a magnetic field microwave plasma CVD apparatus.
FIG. 3A shows a microwave introduction device. 3
01 is a plasma generation chamber, 303 is a slotted annular waveguide for introducing microwaves into the plasma generation chamber 301,
Reference numeral 304 denotes an introduction unit for introducing microwaves into the annular waveguide 303, and reference numeral 305 denotes a microwave introduction window provided in the introduction unit 304. Reference numeral 306 denotes a distribution block for distributing the microwave into two, 307 denotes a plurality of slots formed inside the annular waveguide 304, and 308 denotes a gas introduction means for generating plasma. Reference numeral 309 denotes a coil for generating a magnetic field parallel to the electric field in the plasma generation chamber 301, reference numeral 311 denotes a plasma generation chamber connected to the plasma generation chamber, reference numeral 312 denotes a coated substrate, and reference numeral 313 denotes a substrate 3.
A support 12 for heating the substrate 312;
315 is a film forming gas introducing means, and 316 is an exhaust system.

The generation of the plasma and the film formation are performed as follows. The inside of the plasma generation chamber 301 and the inside of the film formation chamber 311 are evacuated via an exhaust system (not shown). Subsequently, a gas for plasma generation is introduced into the plasma generation chamber 301 through the annular waveguide 303 and the slot 307 at a predetermined flow rate through the gas inlet 308. Next, the exhaust system (not shown)
The inside of the plasma generation chamber 301 is maintained at a predetermined pressure by adjusting a conductance valve (not shown) provided in the chamber.
Next, desired electric power is supplied from a DC power supply (not shown) to the coil 30.
9 and a central magnetic flux density of 8 in the plasma generation chamber 301.
After generating a uniform magnetic field of 7.5 mT, a desired power is supplied from the microwave power supply (not shown) into the plasma generation chamber 301 through the annular waveguide 303. Electrons helically moving around the lines of magnetic force generated in the plasma generation chamber 301 by the coil 309 are accelerated by resonantly absorbing microwaves, and high-density plasma is generated in the plasma generation chamber 301. At this time, if the film forming gas is introduced into the film forming chamber 311 through the film forming gas introducing pipe 315, the film forming gas reacts with the plasma generating gas excited by the generated high density plasma. The coated substrate 3 placed on the support 313
12 are formed. At this time, a film formation gas may be introduced into the plasma generation gas introduction port 308 depending on the use.

Apparatus Example 4 FIG. 4A shows an example of a microwave isolation plasma CVD apparatus.
FIG. 4B shows a microwave introduction device. Reference numeral 401 denotes a plasma generation chamber; 403, an annular waveguide with slots for introducing microwaves into the plasma generation chamber 401;
Is an introduction part for introducing microwaves into the annular waveguide 403,
Reference numeral 405 denotes a microwave introduction window provided in the introduction unit 404. 406 is a distribution block that distributes microwaves in two,
407, a plurality of slots formed inside the annular waveguide 404; 408, gas introduction means for plasma generation;
Is a film formation chamber connected to the plasma generation chamber. 412, a coated substrate; 413, a support for the substrate 412;
12, a heater for heating 12, a film formation gas introducing means,
Reference numeral 416 denotes an exhaust system, and 417 denotes a porous separation plate for separating the plasma generation chamber 401 and the film formation chamber 411.

The generation of the plasma and the film formation are performed as follows. The inside of the plasma generation chamber 401 is evacuated via an exhaust system (not shown). Subsequently, a gas for plasma generation is supplied at a predetermined flow rate through the gas inlet 408 to the annular waveguide 4.
03 and the slot 407 are introduced into the plasma generation chamber 401. Next, the conductance valve (not shown) provided in the exhaust system (not shown) is adjusted, and the plasma generation chamber 4 is adjusted.
01 is maintained at a predetermined pressure. By supplying desired power from a microwave power supply (not shown) to the plasma generation chamber 401 through the annular waveguide 403, plasma is generated in the plasma generation chamber 401. At this time, if the film-forming gas is introduced into the film-forming chamber 411 via the film-forming gas introduction pipe 415, the film-forming gas reacts with the plasma-generating gas excited by the generated plasma and is supported. A film is formed on the surface of the coated substrate 412 placed on the body 413. At this time, a film forming gas may be introduced into the plasma generating gas inlet 408 depending on the use.

Apparatus Example 5 An example of an optically assisted microwave plasma CVD apparatus is shown in FIG.
FIG. 5A shows a microwave introduction device. 5
01 is a plasma generation chamber, 503 is a slotted annular waveguide for introducing microwaves into the plasma generation chamber 501,
Reference numeral 504 denotes a microwave introduction unit for introducing microwaves into the annular waveguide 503, and reference numeral 505 denotes a microwave introduction window provided in the introduction unit 504. Reference numeral 506 denotes a distribution block for distributing microwaves in two parts, 507 denotes a plurality of slots formed inside the annular waveguide 503, 508 denotes a gas generating means for generating plasma, and 511 denotes a plasma generating chamber connected to the plasma generating chamber. . 512, a coated substrate; 513, a support for the substrate 512; 514, a heater for heating the substrate 512;
Denotes a film formation gas introducing means, and 516 denotes an exhaust system. 521
Reference numeral 525 denotes an illumination system for irradiating visible or ultraviolet light to the surface of the substrate 512, and reference numeral 525 denotes a light introduction window for introducing visible or ultraviolet light from the illumination system 521 into the film formation chamber 511 through the plasma generation chamber 501. Here, the illumination system 521 includes a light source 522, a reflect mirror 523 for condensing light from the light source 522, and an integrator 524 including a number of convex lenses for uniformizing the light.

The generation of the plasma and the film formation are performed as follows. Plasma generation chamber 50 via an exhaust system (not shown)
1 and the inside of the film forming chamber 511 are evacuated. Subsequently, the surface of the base 512 is irradiated with visible or ultraviolet light from the illumination system 521 through the light introduction window 525, and the base 512 is maintained at a desired temperature. Further, a gas for plasma generation is introduced into the plasma generation chamber 501 through the annular waveguide 503 and the slot 507 at a predetermined flow rate through the gas inlet 508. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber 501 at a predetermined pressure. By supplying desired power from a microwave power supply (not shown) to the plasma generation chamber 501 via the annular waveguide 503, the plasma generation chamber 501 is provided.
Plasma is generated inside. At this time, the film introduction gas introduction pipe 5
When the film-forming gas is introduced into the generation chamber 511 through the line 15, the film-forming gas is excited by the generated high-density plasma, and forms on the surface of the coating substrate 512 placed on the support 513. Film. At this time, since the surface is activated by visible or ultraviolet light, a higher quality film can be formed. At this time, a film formation gas may be introduced into the plasma generation gas inlet 508 depending on the use.

The light source 522 of the illumination system 521 includes a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon-mercury lamp, a xenon lamp, a deuterium lamp,
r resonance line lamp, Kr resonance line lamp, Xe resonance line lamp, excimer laser, Ar ⁺ laser second harmonic, N ₂ laser, a wavelength that is absorbed by the precursor adhering to the substrate surface such as YAG laser third harmonic Any light source can be used.

Apparatus Example 6 FIG. 6A shows a bias microwave plasma CVD apparatus.
FIG. 6B shows a microwave introduction device. 6, reference numeral 601 denotes a plasma generation chamber; 603, an annular waveguide with slots for introducing microwaves into the plasma generation chamber 601; and 604, an introduction unit for introducing microwaves into the annular waveguide 603. 605 is a microwave introduction window provided in the introduction section 604, 606 is a distribution block for dividing microwaves into two, 607 is a plurality of slots formed inside the annular waveguide 603, and 608 is a gas introduction means for plasma generation. , 611 are plasma generation chambers connected to the plasma generation chamber. 612, a coated substrate; 613, a support for the substrate 612; 614, a heater for heating the substrate 612; 615, a film-forming gas introduction unit; and 616, an exhaust system. 618 is a high-frequency rod for applying a high-frequency bias to the support 613, and 619 is an insulating rod for insulating the support 613 from the ground potential.

The generation of the plasma and the film formation are performed as follows. Plasma generation chamber 60 via an exhaust system (not shown)
1 and the inside of the film forming chamber 611 are evacuated. Subsequently, a gas for plasma generation is introduced into the plasma generation chamber 601 via the annular waveguide 603 and the slot 607 at a predetermined flow rate through the gas inlet 608. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber 601 and the inside of the film formation chamber 611 at a predetermined pressure. Further, a high-frequency rod 618 is provided on the support 613.
, A desired power is supplied from a microwave power supply (not shown) to the plasma generation chamber 601 via the annular waveguide 603, thereby generating plasma in the plasma generation chamber 601. At this time, if the film-forming gas is introduced into the film-forming chamber 611 through the film-forming gas introduction pipe 615, the film-forming gas is excited by the generated plasma, and the ionic components are generated on the surface of the support. The coated substrate 6 accelerated by the sheath electric field and placed on the support 613
12 is formed on the surface. At this time, a film forming gas may be introduced into the plasma generating gas inlet 608 depending on the use.

Apparatus Example 7 FIG. 7A shows a microwave plasma CVD apparatus provided with an annular microwave introduction apparatus and a disk-shaped microwave introduction apparatus. Fig. 8 shows a disk-shaped microwave introduction device.
FIG. 8B shows an annular microwave introduction device in FIG. 701 is a plasma generation chamber, 703a and 703b are slotted waveguides for introducing microwaves into the plasma generation chamber 701 (703a is a disk-shaped waveguide, 703b is an annular waveguide, and thereafter, the end of the index) A attached to
b represents a disk-shaped waveguide and an annular waveguide, respectively. ) And 704 are microwave introduction sections for introducing microwaves into the annular waveguide 703, and 705 is a microwave introduction window provided in the introduction section 704. Reference numeral 706 denotes a distribution block for distributing microwaves into two parts, 707 denotes a plurality of slots formed inside the annular waveguide 703, 708 denotes a gas generating means for plasma generation, and 711 denotes a film formation chamber connected to the plasma generation chamber. . 712 is a coated substrate, 713 is a substrate 712
714, a heater for heating the substrate 712, 71
Reference numeral 5 denotes a film forming gas introducing unit, and 716 denotes an exhaust system.

The pressure in the plasma generating chamber or the film forming chamber in the microwave plasma CVD apparatus of the present invention can be preferably selected from the range of 0.5 mTorr to 0.5 Torr.

The substrate temperature at the time of forming a film by the microwave plasma CVD apparatus of the present invention slightly varies depending on the kind of film forming gas to be used, the kind of deposited film, and the purpose of use. In the range of 100 to 400 ° C, optimally in the range of 100 to 400 ° C.

In the formation of a deposited film by the microwave plasma CVD apparatus of the present invention, Si ₃ N ₄ , SiO ₂ , Ta ₂ O ₅ , TiO ₂ ,
Insulating film such as TiN, Al ₂ O ₃ , AlN, MgF ₂ ,
semiconductor films such as a-Si, poly-Si, SiC, and GaAs, metal films such as Al, W, Mo, Ti, and Ta;
Various deposited films can be formed efficiently.

The microwave plasma CVD apparatus of the present invention can be applied to surface modification. For example, by appropriately selecting a gas to be used, Si, Al, Ti, Zn, Ta
Oxidation treatment or nitridation treatment, as well as doping treatment of B, As, P, etc., can be applied to the substrate or the surface layer. Further, the film forming technique employed in the present invention can be applied to a cleaning method. In that case, it can be used for cleaning oxides, organic substances, heavy metals, and the like.

The substrate to be formed by the plasma CVD apparatus of the present invention may be a semiconductor, a conductive one, or an electrically insulating one. Also,
To these substrates, a DC bias of -500 V to +200 V or an AC bias of a frequency of 40 Hz to 300 MHz may be applied in order to improve performance such as denseness, adhesion, and step coverage.

As the conductive substrate, Fe, Ni, Cr,
Al, Mo, Au, Nb, Ta, V, Ti, Pt, Pb
And alloys thereof, such as brass and stainless steel.

Examples of the insulating substrate include SiO ₂ -based quartz and various glasses, Si ₃ N ₄ , NaCl, KCl, LiF,
In addition to inorganic substances such as CaF ₂ , BaF ₂ , Al ₂ O ₃ , AlN, and MgO, films of organic substances such as polyethylene, polyester, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, and polyimide; A sheet and the like.

As a gas for forming a deposited film, a generally known gas can be used.

The gas which is easily decomposed by the action of the plasma and can be deposited alone can be supplied via a film-forming gas introducing means in the film-forming chamber to achieve a stoichiometric composition and prevent film adhesion in the plasma-generating chamber. It is desirable to introduce it into the film formation chamber. Further, it is desirable that a gas that is not easily decomposed by the action of the plasma and that is difficult to be deposited alone is introduced into the plasma generation chamber through the plasma generation gas inlet in the plasma generation chamber.

When a Si-based semiconductor thin film such as a-Si, poly-Si, or SiC is formed, a material containing Si atoms introduced through a film-forming gas introducing means includes S
inorganic silanes such as iH ₄ and Si ₂ H ₆ , organic silanes such as tetraethylsilane (TES), tetramethylsilane (TMS) and dimethylsilane (DMS), SiF
₄ , Si ₂ F ₆ , SiHF ₃ , SiH ₂ F ₂ , SiCl
₄ , Si ₂ Cl ₆ , SiHCl ₃ , SiH ₂ Cl ₂ , S
Halosilanes such as iH ₃ Cl and SiCl ₂ F ₂ , etc., which are in a gaseous state at normal temperature and pressure or can be easily gasified. In this case, examples of the plasma generating gas introduced through the plasma generating gas inlet include H ₂ , He, Ne, Ar, Kr, Xe, and Rn.

In the case of forming a thin film of a Si compound such as Si ₃ N ₄ or SiO ₂ , the raw material containing Si atoms to be introduced through a film introducing gas introducing means includes SiH ₄ , Si
Inorganic silanes such as ₂ H ₆ , tetraethoxysilane (T
EOS), organic silanes such as tetramethoxysilane (TMOS), octamethylcyclotetrasilane (OMCTS), SiF ₄ , Si ₂ F ₆ , SiHF ₃ , SiH ₂
F ₂ , SiCl ₄ , Si ₂ Cl ₆ , SiHCl ₃ , Si
Examples include halosilanes such as H ₂ Cl ₂ , SiH ₃ Cl, and SiCl ₂ F ₂ , which can be in a gaseous state at normal temperature and normal pressure or can be easily gasified. In this case, the raw materials introduced through the gas inlet for plasma generation include N ₂ , NH ₃ , N ₂ H ₄ , hexamethyldisilazane (HMDS), O ₂ , O ₃ , H ₂ O, NO , N ₂ O, N
O _{2 and the} like.

When a metal thin film of Al, W, Mo, Ti, Ta, etc. is formed, the raw material containing a metal atom to be introduced through a film-forming gas introducing means includes trimethyl aluminum (TMAl), triethyl aluminum ( TEA
l), triisobutylaluminum (TIBAl), dimethylaluminum hydride (DMAIH), tungsten carbonyl (W (CO) ₆ ), molybdenum carbonyl (Mo (CO) ₆ ), trimethylgallium (TM)
Ga), organic metals such as triethylgallium (TEGa), and halogenated metals such as AlCl ₃ , WF ₆ , TiCl ₃ , and TaCl ₅ . In this case, the gas for plasma generation introduced through the gas introduction port for plasma generation includes H ₂ , He, Ne, Ar, Kr, and X.
e and Rn.

Al ₂ O ₃ , AlN, Ta ₂ O ₅ , TiO
_When a metal compound thin film such as TiN or WO ₃ is formed, trimethylaluminum (TMA) is used as a raw material containing a metal atom to be introduced through a film-forming gas introducing means.
l), triethylaluminum (TEAl), triisobutylaluminum (TIBAl), dimethylaluminum hydride (DMAlH), tungsten carbonyl (W (CO) ₆ ), molybdenum carbonyl (Mo)
(CO) ₆ ), organic metals such as trimethylgallium (TMGa) and triethylgallium (TEGa), AlCl
₃ , metal halides such as WF ₆ , TiCl ₃ , and TaCl ₅ . In this case, the raw material gas introduced through the plasma generating gas inlet is O ₂ ,
O ₃ , H ₂ O, NO, N ₂ O, NO ₂ , N ₂ , NH ₃ ,
N ₂ H ₄ and hexamethyldisilazane (HMDS) are exemplified.

The oxidizing gas introduced through the gas inlet for plasma generation when the substrate is formed on an oxidized surface is as follows:
O ₂ , O ₃ , H ₂ O, NO, N ₂ O, NO _{2 and the} like can be mentioned. In addition, as the nitriding gas introduced through the gas inlet for plasma generation when the substrate is subjected to the nitriding surface treatment, N ₂ , NH ₃ , N ₂ H ₄ , hexamethyldisilazane (HMDS) and the like can be mentioned. In this case, since no film is formed, no source gas is introduced through the film-forming gas introduction means, or a gas similar to the gas introduced through the plasma generation gas introduction port is introduced.

The cleaning gas introduced through the gas inlet for plasma generation for cleaning organic substances on the surface of the substrate includes O ₂ , O ₃ , H ₂ O, NO, N ₂ O,
NO _{2 and the} like. The cleaning gas introduced from the gas inlet for plasma generation for cleaning inorganic substances on the substrate surface includes F ₂ , CF ₄ , C
H ₂ F ₂ , C ₂ F ₆ , CF ₂ Cl ₂ , SF ₆ , NF _{3 and the} like can be mentioned. In this case, since no film is formed, no source gas is introduced through the film-forming gas introduction means, or a gas similar to the gas introduced through the plasma generation gas introduction port is introduced.

[0059]

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 Using a microwave plasma CVD apparatus shown in FIG. 1A, a silicon nitride film for a magneto-optical disk was formed.

As the base 112, a polycarbonate (PC) substrate (3.5 inches in diameter) was used. First, P
After placing the C substrate 112 on the substrate support 113, the inside of the plasma generation chamber 101 and the film formation chamber 111 was evacuated via an exhaust system (not shown), and the pressure was reduced to a value of 10 ⁻⁶ Torr. Nitrogen gas was introduced into the plasma generation chamber 101 through the plasma generation gas inlet 108 at a flow rate of 200 sccm. At the same time, a monosilane gas is supplied at a flow rate of 200 sccm through the film-forming gas introduction means 115 at a flow rate of 200 sccm.
1 was introduced. Next, the conductance valve (not shown) provided in the exhaust system (not shown) is adjusted, and the film forming chamber 1 is adjusted.
11 was maintained at 20 mTorr. A power of 1 kW was supplied from a microwave power supply of 2.45 GHz into the plasma generation chamber 101 via the annular waveguide 103. Thus,
Plasma was generated in the plasma generation chamber 101. At this time, the nitrogen gas introduced through the plasma generating gas inlet 108 is excited and decomposed into an active species in the plasma generating chamber 101, transported in the direction of the silicon substrate 112, and formed into the film forming gas introducing means 115. Reacts with the monosilane gas introduced through the silicon substrate to form a silicon nitride film.
12 was formed with a thickness of 100 nm. After the film formation, the film quality such as the film formation speed and the refractive index was evaluated.

The deposition rate of the obtained silicon nitride film is 8
It is extremely large at 50 nm / min, and the film quality has a refractive index of 2.
2. It was confirmed that the film was a very good film having a stress of 1.8 × 10 ⁹ dyn / cm ² . Also, the formed film is Si
Despite the silicon-rich film having a / N ratio of 3.1 and high conductivity, a film having a stable film thickness and film quality was obtained up to 10,000 times, which is a maintenance cycle determined by the generation of particles.

COMPARATIVE EXAMPLE 1 A silicon nitride film similar to that of Example 1 was formed by using the apparatus shown in FIG. 9 instead of the apparatus shown in FIG.

In the apparatus shown in FIG. 1 used in Example 1, the microwave waveguide 103 and the plasma generation chamber 101 are not separated by a quartz tube, whereas the apparatus shown in FIG. The device is separated from the other by a quartz tube 1102.

In this comparative example, a nitrogen gas was introduced from the gas introduction port 1108 for plasma generation,
A film was formed in the same manner as in Example 1 except that monosilane gas was introduced from Step 15.

Thus, in this example, approximately 10
Maintenance had to be performed in order to remove deposits on the quartz tube in the formation of the deposited film 100 times.

Example 2 Using the microwave plasma CVD apparatus shown in FIG.
A silicon nitride film for protecting a semiconductor element was formed.

As the base 212, a P-type single crystal silicon substrate (plane orientation [100], resistivity 10 Ω · cm) was used. First, after the silicon substrate 212 is set on the base support 213, the inside of the plasma generation chamber 201 and the film formation material 211 is evacuated via an exhaust system (not shown), and 10 ^-6 To
The pressure was reduced to the value of rr. Subsequently, a heater (not shown) was energized to heat the silicon substrate 212 to 300 ° C., and the substrate was kept at this temperature. Gas inlet 20 for plasma generation
The nitrogen gas was introduced into the plasma generation chamber 201 at a flow rate of 500 sccm through the nozzle 8. At the same time, monosilane gas was introduced into the film formation chamber 211 at a flow rate of 100 sccm via the film formation gas introduction means 215. Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted to maintain the inside of the film forming chamber 211 at 30 mTorr.
A power of 500 W was supplied from a microwave power source of 2.45 GHz into the plasma generation chamber 201 through the disk-shaped waveguide 203. Thus, plasma was generated in the plasma generation chamber 201. At this time, the plasma generation gas inlet 2
08 introduced through the plasma generation chamber 20
Excited and decomposed into active species in the silicon substrate 2
The silicon nitride film was transported in the direction of No. 12 and reacted with the monosilane gas introduced via the film-forming gas introduction means 215, and a silicon nitride film was formed on the silicon substrate 212 to a thickness of 1.0 μm. After the film formation, film quality such as film formation speed and stress was evaluated. The stress was determined by measuring the change in the amount of warpage of the substrate before and after film formation using a laser interferometer Zygo (trade name).

The film formation rate of the obtained silicon nitride film is 4
Extremely large at 60 nm / min, and film quality is 1.1 × stress.
10 ⁹ dyn / cm ² , leak current 1.2 × 10 ^-10 A
/ Cm ² , and a very high quality film with a dielectric strength of 9 MV / cm. Further, a film having a stable film thickness and film quality was obtained up to 1000 times, which is a maintenance cycle determined by the generation of particles.

Example 3 Using the microwave plasma CVD apparatus shown in FIG. 3A, an i-layer of a pin junction type photovoltaic layer for a solar cell was formed. As the substrate 312, a SUS430BA band-shaped substrate coated with an Al film as a lower electrode was used.

First, after the base is set on the base support 313, the plasma generation chamber 301 is set via an exhaust system (not shown).
Then, the inside of the film forming chamber 311 was evacuated to a pressure of 10 ⁻⁶ Torr. Subsequently, a heater (not shown) was energized to heat the substrate 312 to 300 ° C., and the substrate was kept at this temperature. Hydrogen gas was introduced into the plasma generation chamber 311 at a flow rate of 100 sccm through the plasma generation gas inlet 308. At the same time, a monosilane gas of 300 sccm and a silicon tetrafluoride gas of 1
It was introduced into the film forming chamber 311 at a flow rate of 0 sccm. Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted to maintain the inside of the plasma generation chamber 301 and the inside of the film formation chamber 311 at 10 mTorr. 2.45G
Power of 1200 W was supplied from the microwave power supply of 1 Hz into the plasma generation chamber 301 through the annular waveguide 303.
Thus, plasma was generated in the plasma generation chamber 301. The hydrogen gas introduced through the plasma generating gas inlet 308 is excited and decomposed into active species in the plasma generating chamber 301, transported in the direction of the substrate 312, and introduced through the film forming gas introducing means 315. Reacts with the monosilane gas and the silicon tetrafluoride gas, and forms i-type a-Si:
An H: F film was formed on the substrate 312. After the formation of the three pin layers, film quality such as uniformity and photoelectric conversion efficiency was evaluated. The photoelectric conversion efficiency was evaluated under irradiation with light having an intensity of 0.1 W / cm ² .

The obtained pin-type a-Si: H: F film has a good uniformity of ± 2.8% and a photoelectric conversion efficiency of 9.8%.
, And the characteristics were stable. In addition, despite the high conductivity of the formed film, a film having a stable film thickness and quality was obtained up to 1000 times, which is a maintenance cycle determined by the generation of particles.

Example 4 Using the microwave-isolated plasma CVD apparatus shown in FIG. 4A, a selective Al film for semiconductor element wiring was formed.

As the substrate 412, a substrate in which a patterned BPSG film was formed on a P-type single crystal silicon substrate (plane orientation [100], resistivity 10 Ω · cm) was used. First, after the silicon substrate 412 is set on the base support 413, the inside of the plasma generation chamber 401 and the film formation material 411 are evacuated via an exhaust system (not shown), and 10 ^-6 Torr
The pressure was reduced to the value of r. Subsequently, a heater (not shown) was energized to heat the silicon substrate 412 to 260 ° C., and the substrate was kept at this temperature. Gas inlet 408 for plasma generation
, A hydrogen gas was introduced into the plasma generation chamber 411 at a flow rate of 200 sccm. At the same time, dimethyl aluminum hydride (DMA
1H) Gas was introduced into the film formation chamber 411 at a flow rate of 50 sccm. Next, the conductance valve (not shown) provided in the exhaust system (not shown) is adjusted to
01 in 0.1 Torr and the inside of the film forming chamber 411 in 0.03 T
orr. A power of 500 W was supplied from a 2.45 GHz microwave power supply into the plasma generation chamber 401 through the annular waveguide 403. Thus, plasma was generated in the plasma generation chamber 401. The hydrogen gas introduced via the plasma generation gas inlet 408 is excited and decomposed into an active species in the plasma generation chamber 401 and is transported in the direction of the silicon substrate 412.
By reacting with the dimethyl aluminum hydride gas introduced through No. 15, an Al film was selectively formed only on the silicon substrate 412 with a thickness of 0.8 μm. After the film formation, the film formation rate, uniformity, and resistivity were evaluated.

The deposition rate and uniformity of the obtained Al film are 80
nm / min ± 2.7%, good film quality, resistivity 4 × 1
It was confirmed to be relatively good quality of 0 ^-6 Ω · cm. Further, although the formed film was a conductive film, a film having a stable film thickness and film quality was obtained up to 2000 times, which is a maintenance cycle determined by the generation of particles.

Example 5 A silicon oxide film for semiconductor device interlayer insulation was formed using the microwave-isolated plasma CVD apparatus shown in FIG.

As the base 412, a P-type single crystal silicon substrate (plane orientation [100], resistivity 10 Ωcm) was used. First, after the silicon substrate 412 is set on the base support 413, the inside of the plasma generation chamber 401 and the film formation material 411 are evacuated via an exhaust system (not shown), and 10 ^-6 Torr
The pressure was reduced to the value of r. Subsequently, a heater (not shown) was energized to heat the silicon substrate 412 to 300 ° C., and the substrate was kept at this temperature. Gas inlet 408 for plasma generation
, Oxygen gas was introduced into the plasma generation chamber 411 at a flow rate of 500 sccm. At the same time, tetraethoxysilane (TEOS) gas is
It was introduced into the film formation chamber 411 at a flow rate of 00 sccm. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted so that the inside of the plasma generation chamber 401 becomes 0.1 mm.
The inside of the film forming chamber 411 was maintained at 0.05 Torr for 1 Torr. 1500 W from microwave power supply of 2.45 GHz
Is supplied to the plasma generation chamber 40 through the annular waveguide 403.
1. Thus, plasma was generated in the plasma generation chamber 401. Gas inlet 40 for plasma generation
The oxygen gas introduced through the plasma generation chamber
Is excited and decomposed into active species in the silicon substrate 41.
The silicon oxide film was transported in the direction 2 and reacted with the tetraethoxysilane gas introduced through the film-forming gas introduction means 415, and a silicon oxide film was formed on the silicon substrate 412 to a thickness of 0.8 μm. After film formation, film formation speed, uniformity, dielectric strength,
And the step coverage was evaluated. The step coverage was measured by observing the cross section of a silicon oxide film formed on an Al step formed in a line pattern of 0.35 μm line and space with a scanning electron microscope (SEM). The ratio of the upper film thickness (cover factor) was determined and evaluated.

The film formation rate and uniformity of the obtained silicon oxide film were as good as 180 nm / min ± 2.7%, and the film quality was 9.3 MV / cm in the withstand voltage, and the cover factor was 0.9. Was confirmed. Further, a film having a stable film thickness and film quality was obtained up to 1000 times, which is a maintenance cycle determined by the generation of particles.

Embodiment 6 An optically assisted microwave plasma CV shown in FIG.
A silicon oxide film for semiconductor device gate insulation was formed using a D apparatus.

As the substrate 512, a P-type single crystal silicon substrate (plane orientation [100], resistivity 10 Ω · cm) was used. After the silicon substrate 512 is set on the base support 513, the plasma generation chamber 5 is connected via an exhaust system (not shown).
And the inside of the film forming chamber 511 is evacuated to 10 ^-6 Torr.
The pressure was reduced to the value of. Subsequently, the ultra-high pressure mercury lamp of the illumination system 521 is turned on to emit light so that the light illuminance on the surface of the silicon substrate 512 becomes 0.6 W / cm ^2.
Twelve surfaces were irradiated. Subsequently, a heater (not shown) was energized to heat the silicon substrate 512 to 300 ° C., and the silicon substrate was kept at this temperature. Oxygen gas was introduced into the plasma generation chamber 501 through the plasma generation gas inlet 508 at a flow rate of 500 sccm. At the same time, the monosilane gas is supplied at a flow rate of 50 sccm through the film forming gas introducing means 515.
At a flow rate of? Next, the conductance valve (not shown) provided in the exhaust system (not shown) was adjusted to make the inside of the plasma generation chamber 501 0.05 torr.
The inside of the film forming chamber 511 was maintained at 0.02 Torr at rr. Next, 50 from the microwave power supply of 2.45 GHz
0 W power was supplied into the plasma generation chamber 501 via the annular waveguide 503. Thus, the plasma generation chamber 501
A plasma was generated inside. At this time, the oxygen gas introduced through the plasma generation gas inlet 508 is excited and decomposed in the plasma generation chamber 501 to become active species such as oxygen atoms, and is transported in the direction of the silicon substrate 512 to form a film. The silicon oxide film reacted with the monosilane gas introduced through the use gas introduction means 515 to form a 0.1 μm thick silicon oxide film on the silicon substrate 512. After film formation, film formation speed,
The uniformity, leakage current, dielectric strength, and interface state density were evaluated. The interface state density was determined from a CV curve obtained when a 1 MHz rf was applied, which was obtained by a capacitance meter.

The film formation rate and uniformity of the obtained silicon oxide film were as good as 110 nm / min ± 2.3%.
Leakage current 4 × 10 ^-11 A / cm ² , withstand voltage ¹¹ MV
/ Cm and an interface state density of 6 × 10 ¹⁰ cm ⁻² , and it was confirmed that the film was an extremely good film. Further, a film having a stable film thickness and film quality was obtained up to 1000 times, which is a maintenance cycle determined by the generation of particles.

Embodiment 7 Bias microwave plasma CVD shown in FIG.
Using an apparatus, a silicon oxide film and a silicon nitride film for preventing optical element reflection were formed.

As the substrate 612, a BK7 glass substrate was used. After placing the glass substrate 612 on the base support 613, the inside of the plasma generation chamber 601 and the film formation chamber 611 are evacuated via an exhaust system (not shown), and 10 ^-6 Torr
The pressure was reduced to the value of r. Subsequently, a heater (not shown) was energized to heat the glass substrate 612 to 300 ° C., and the silicon substrate was kept at this temperature. Nitrogen gas was introduced into the plasma generation chamber 601 at a flow rate of 200 sccm through the plasma generation gas inlet 608. At the same time, a monosilane gas was introduced into the film formation chamber 611 at a flow rate of 30 sccm via the film formation gas introduction means 615. Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted, and the inside of the film forming chamber 611 was maintained at 10 mTorr.
Then, 500 W from a microwave power supply of 2.45 GHz
Is supplied to the plasma generation chamber 60 through the annular waveguide 603.
1. Thus, plasma was generated in the plasma generation chamber 601. At this time, the nitrogen gas introduced through the plasma generation gas inlet 608 is excited and decomposed in the plasma generation chamber 601 to become active species such as nitrogen atoms, and is transported in the direction of the glass substrate 612 to form a film. Reacts with the monosilane gas introduced through the introduction gas introduction means 615 to form a silicon nitride film on the glass substrate 612 by 61 n.
m.

Next, oxygen gas was introduced into the plasma generation chamber 601 at a flow rate of 200 sccm through the plasma generation gas inlet 608. At the same time, gas introduction means 6 for film formation
A monosilane gas was introduced into the film formation chamber 611 at a flow rate of 30 sccm. Next, the conductance valve (not shown) provided in the exhaust system (not shown) is adjusted,
The inside of the film forming chamber 611 was kept at 10 mTorr. Then
A power of 500 W was supplied from a microwave power supply of 2.45 GHz into the plasma generation chamber 601 via the annular waveguide 603. Thus, plasma was generated in the plasma generation chamber 601. At this time, the plasma generating gas inlet 60
Oxygen gas introduced through the plasma generation chamber 60
Excited and decomposed into active species such as oxygen atoms in 1,
It is transported in the direction of the glass substrate 612 and reacts with the monosilane gas introduced through the film-forming gas introduction means 615,
A silicon oxide film was formed on the glass substrate 612 with a thickness of 86 nm. After the film formation, the film formation speed and the reflection characteristics were evaluated.

The film formation rates of the obtained silicon nitride film and silicon oxide film were 110 nm / min and 130 n / min, respectively.
m / min, and the film quality was confirmed to be very good optical characteristics, with a reflectivity at around 500 nm of 0.3%. Further, a film having a stable film thickness and film quality was obtained up to 8000 times, which is a maintenance cycle determined by the generation of particles.

[0086]

According to the present invention, the quartz tube constituting the inner wall of the plasma generation chamber of the microwave CVD apparatus is not required, and the introduction of the microwave into the plasma generation chamber is achieved by attaching a thin film to the inner wall of the quartz tube. The problem of being disturbed is eliminated. Therefore, the maintenance cycle of the device is lengthened, and the reliability and operation rate of the device are improved.

Further, the plasma generation chamber 101, the slot 1
07, the microwave waveguide 103 is evacuated. Therefore, the pressure of the microwave waveguide is higher than that of the plasma generation chamber. Therefore, no plasma is generated in the microwave waveguide, and the microwave is efficiently generated. Plasma can be created in the plasma generation chamber.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a microwave plasma CVD apparatus using an annular waveguide according to the present invention.

FIG. 2 is a schematic view showing an example of a microwave plasma CVD apparatus using a disk-shaped waveguide according to the present invention.

FIG. 3 is a schematic view showing one example of a magnetic field microwave plasma CVD apparatus of the present invention.

FIG. 4 is a schematic diagram showing one example of a microwave isolation plasma CVD apparatus of the present invention.

FIG. 5 is an optically assisted microwave plasma CVD of the present invention.
It is a schematic diagram which shows an example of an apparatus.

FIG. 6 is a schematic view showing one example of a bias microwave plasma CVD apparatus of the present invention.

FIG. 7 is a schematic diagram showing an example of a microwave plasma CVD apparatus provided with the annular microwave introduction apparatus of the present invention and a microwave introduction apparatus on a disk.

FIG. 8 is a schematic diagram showing an example of a microwave plasma CVD apparatus in which an annular microwave introduction apparatus of the present invention and a microwave introduction apparatus on a disk are provided, and FIG. The device is shown, and (C) shows an annular microwave introduction device.

FIG. 9 shows a conventional microwave plasma CVD using a quartz tube.
It is a schematic diagram which shows an example of an apparatus.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-36640 (JP, A) JP-A-63-103088 (JP, A) JP-A-4-80372 (JP, A) JP-A 63-030 121665 (JP, A) JP 55-21988 (JP, B2) JP 5 9513 (JP, B2) JP 5-21983 (JP, B2) (58) Fields surveyed (Int. Cl. ⁷ , DB name) C23C 16/00-16/56 C23F 1/00-4/04 H01L 21/205 H01L 21/3065 H01L 21/31 H05H 1/46

Claims (19)

(57) [Claims] 1. A plasma generating chamber is depressurized by an exhaust means, and microwave energy is supplied to the plasma generating chamber through a microwave waveguide connected to the plasma generating chamber, whereby the plasma generating chamber or the plasma generating chamber is supplied with microwave energy. In a microwave plasma CVD apparatus for forming a deposited film on a substrate disposed in a film forming chamber communicating with a chamber, a plurality of slots are formed in the waveguide such that long sides thereof intersect with the traveling direction of the microwave. A plasma CVD apparatus formed on a surface on the side of the plasma generation chamber, wherein a gas for generating the plasma is introduced into the plasma generation chamber through the slot. 2. The shape of the slot has a short side of 0.5 m.
The plasma CVD according to claim 1, wherein the rectangular shape has a length in a range of m to 3 mm and a long side in a range of 40 mm to 60 mm.
apparatus. 3. The plasma CVD apparatus according to claim 2, wherein an interval between said slots is controlled to １ ／ of a wavelength of said microwave energy in said waveguide or an integral multiple thereof. 4. The plasma CVD apparatus according to claim 1, wherein said plasma generation chamber has a substantially columnar shape, said waveguide surrounds an outer peripheral portion of said plasma generation chamber, and an outer shape thereof is substantially a cylindrical shape. . 5. The plasma according to claim 1, wherein the plasma generation chamber has a substantially columnar shape, the waveguide faces a circular flat portion of the plasma generation chamber, and the outer shape is a substantially disk shape. CVD equipment. 6. A means for generating a magnetic field perpendicular to the electric field of the microwave and having a magnetic flux density approximately 3.57 × 10 −11 (T / Hz) times the frequency of the microwave in the plasma generation chamber. The plasma CVD apparatus according to claim 1. 7. The plasma CVD apparatus according to claim 1, wherein a substrate support is provided at a position separated from said plasma. 8. The plasma C according to claim 1, further comprising means for irradiating visible or ultraviolet light to the surface of the coated substrate.
VD device. 9. The plasma CVD apparatus according to claim 1, further comprising means for applying an rf bias to said substrate support. 10. A microwave plasma apparatus for reducing the pressure of a plasma generation chamber by an exhaust means and supplying microwave energy to the plasma generation chamber via a microwave waveguide connected to the plasma generation chamber to generate plasma. A plurality of slots in the waveguide are formed on the surface on the side of the plasma generation chamber such that long sides thereof intersect with the traveling direction of the microwave, and the gas for generating the plasma is supplied to the slots. A microwave plasma device, wherein the microwave plasma device is introduced into the plasma generation chamber through a plasma generator. 11. The shape of the slot is such that the short side is 0.5
mm-3mm, long side 40mm-60mm
The microwave plasma device according to claim 10, wherein the microwave plasma device has a rectangular shape in the range. 12. The microwave plasma apparatus according to claim 11, wherein an interval between the slots is controlled to １ ／ of a wavelength of the microwave energy in the waveguide or an integer multiple thereof. 13. The microwave plasma apparatus according to claim 10, wherein the plasma generation chamber has a substantially columnar shape, the waveguide surrounds an outer peripheral portion of the plasma generation chamber, and the outer shape is substantially a cylindrical shape. 14. The microwave plasma according to claim 10, wherein the plasma generation chamber has a substantially columnar shape, the waveguide faces a circular flat portion of the plasma generation chamber, and the outer shape is a substantially disk shape. apparatus. 15. The microwave plasma apparatus according to claim 10, wherein a substrate support is disposed at a position separated from said plasma. 16. The microwave plasma apparatus according to claim 15, further comprising means for applying an rf bias to said substrate support. 17. A microwave plasma apparatus for generating a plasma by reducing the pressure of a plasma generation chamber by an exhaust means and supplying microwave energy to the plasma generation chamber through a microwave waveguide connected to the plasma generation chamber. A method for performing plasma processing on a substrate by using the apparatus, wherein the apparatus according to claim 1 or 10 is used as the microwave plasma apparatus. 18. The plasma generation chamber according to claim 17, wherein the pressure in the plasma generation chamber is lower than the pressure in the microwave waveguide.
The method described in. 19. The pressure in the plasma generation chamber is set at 0.5
19. The method according to claim 18, wherein the control is performed in a range of mTorr to 0.5 Torr.