JPH01159379A - Formation of film - Google Patents

Abstract

PURPOSE:To form a film with high energy efficiency by using a plate electrode provided with a slit having a linear part at the time of forming the film by the gaseous plasma of org. and inorg. compds. CONSTITUTION:The (quasi-)high-temp. gaseous plasma contg. >=1 kind among org. and inorg. compds. is produced by using a discharge electrode, and a substrate is brought into contact with the produced plasma region to form a film on the substrate. In this method, a rectangular flat-plate electrode 1 consisting of an electrically conductive material is used, for example, as the electrode. A slit 3 is cut on one long side from the leading end 2 close to one end of the side in parallel with the short side 4, and extended to one point 5 in the electrode 1 while being turned plural times on its way. Two lead wires 8a and 8b from a coaxial tube 8 are respectively connected to the two positions 6 and 7 on opposite sides of the slit 3 close to the leading end 2, and the electrode 1 is connected to a microwave power source through the lead wires.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for forming a plasma polymer layer on the surface of a substrate using organic compound gas plasma, and a method for forming a film on the surface of the substrate using plasma CVD using inorganic compound gas. In particular, the present invention relates to a method of forming a film that can form the above-mentioned insertion/removal structures on a large-area substrate with high energy efficiency, and is particularly suitable for forming a film made of a diamond-like material.

[Conventional technology]

Conventionally, in forming films using various types of plasma, parallel plate electrodes, hollow cathode cylindrical electrodes (for DC, low frequency and high frequency power supplies), and coils (for high frequency power supplies) are used to generate plasma. , a method using a microwave cavity (for microwave power supply), etc. was used.

[Problem to be solved by the invention]

However, such conventional film forming methods using plasma cannot treat a relatively large substrate surface, and furthermore, these methods have the problem of low energy efficiency.

That is, for example, when a microwave cavity is used, the volume of plasma that can be generated is inherently small, so it is not suitable for treating a large surface area. Although it is possible to generate a large volume of plasma using other plasma generation methods, only the portion of the plasma that comes into contact with the substrate substantially contributes to the formation of a film on the substrate surface.
Most of the large volume of plasma does not directly contribute to film formation, resulting in low energy efficiency. In particular, when a film is formed in a high-temperature plasma region, increasing the plasma volume leads to a significant increase in the power consumption required for excitation due to the high energy density of the plasma, which is a big problem in practice.

In particular, films made of diamond-like substances are used in diamond tools such as indexable tips and saws, and various sliding parts.
It is expected that it will be put to practical use as a heat sink used in devices such as semiconductor lasers, RC packages, and high-print ICs, but for this purpose, it is necessary to be able to manufacture large-area diamond-like materials, and to improve productivity and economy. Improvement is strongly required.

However, since the conventional method using microwave plasma uses a microwave cavity, the volume of plasma that can be generated is inherently small. Therefore, the area of the film obtained in the second treatment is as small as several cm square, making it difficult to apply this method to substrates with large substrate surfaces such as large tools and large mechanical parts. Furthermore, even if the substrate to be processed is small, it is not possible to process many substrates at once, resulting in a problem of low productivity and low economic efficiency. Furthermore, increasing the size of the microwave cavity reduces energy absorption efficiency and is unable to generate the high temperature plasma necessary for film production.

[Means to solve the problem]

Therefore, an object of the present invention is to provide a method that can form various films with high energy efficiency.

As a means for achieving the above object, the present invention provides at least one compound selected from the group consisting of organic compounds and inorganic compounds.
A method for forming a film on a substrate comprising bringing the substrate into contact with a plasma region formed by generating (semi-)high temperature plasma of a gas containing seeds using a discharge electrode, wherein the electrode has a straight portion. The method is a plate-shaped electrode connected to a microwave power source, with a slit having a
(hereinafter referred to as the "first method").

Further, the present invention provides another means for achieving the above-mentioned object by generating (semi-)high temperature plasma of a gas containing at least one selected from the group consisting of organic compounds and inorganic compounds using a discharge electrode. A method of forming a film on a substrate comprising bringing the substrate into contact with a formed plasma region, the plasma region applying a magnetic field to arc-shaped (semi-)high temperature plasma generated between electrodes by DC discharge. The present invention provides a method for forming a film (hereinafter referred to as the "second method") characterized in that the film is formed by moving the film by moving the film.

Among the compounds that can be used as components of the gas provided for discharge in the first and second methods of the present invention, examples of organic compounds include methane, ethane, propane, butane,
Chain or cyclic saturated hydrocarbons such as pentane, octane, and cyclohexane; Unsaturated hydrocarbons containing double or triple bonds such as ethylene, propylene, butadiene, benzene, styrene, acetylene, and allene; Morfluoromethane, difluoromethane , trifluoromethane,
Tetrafluoromethane, monochloromethane, dichloromethane, trichloromethane, tetrachloromethane, monofluorodichloromethane, monofluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, hexafluoroethane, dichloroethane, tetrachloroethane, hexachloroethane, difluorodichloroethane , trifluorotrichloroethane, monofluoropropane, trifluoropropane, pentafluoropropane, perfluoropropane, dichloropropane, tetrachloropropane, hexachloropropane, perchloropropane, difluorodichloropropane, tetrafluorodichloropropane, bromomethane, methylene bromide, bromoform, carbon Tetrabromide, tetrabromoethane, pentabromoethane, methyl iosito, short methane, monofluorobutane, trifluorobutane, tetrafluorobutane, octafluorobutane, difluorobutane1. Monofluoropencune, pentafluoropencune, octachloropencune, perchloropencune, trifluorotrichloropentane, tetrafluorohexane, nonachlorohexane, pentafluorotrichlorohexane, tetrafluorohebutane, hexafluorohebutane, trifluoro Pentachloroheptane, difluorooctane, pentafluorooctane, difluorotetrafluorooctane, monofluorononane,
Halogenated alkanes such as hexafluorononane, decachlorononane, heptafluorohexachlorononane, difluorodecane, pentafluorodecane, tetrachlorodecane, tetrafluorotetrachlorodecane, octadecarylolodecane; allylamine, methylamine, ethylamine, pyridine, pyrimidine, Nitrogen-containing organic compounds such as purine, picoline, and acrylamide; Sulfur-containing organic compounds such as carbon disulfide, methyl mercaptan, and ethyl mercaptan; Alcohols such as methanol, ethanol, and propatool; Nophenolic compounds such as phenol and cresol; Formaldehyde, acetaldehyde, etc. aldehyde compounds; ketone compounds such as acetone and methyl ethyl ketone; and fatty acids such as formic acid, acetic acid and propionic acid; and alkyl esters of these fatty acids such as methyl esters, ethyl esters and butyl esters.

Furthermore, examples of inorganic compounds that can be used in the first and second methods of the present invention include -carbon oxide, carbon dioxide, and diazomethane.

These organic and inorganic compound gases may be mixed with rare gases such as helium, argon, and xenon, and gases such as hydrogen, oxygen, and nitrogen. These gases can be used alone or in combination of two or more.

When producing a film made of diamond-like substances, carbon-containing organic compounds are used among the above, including methane, ethane, propane, butane, ethylene, propylene, butadiene, allylamine, methylamine, ethylamine, carbon disulfide, and methanol. , ethanol, formaldehyde,
Carbon-containing organic compounds of 04 or less, such as methyl ethyl ketone, formic acid, and ethyl acetate, such as acetaldehyde, are preferred.

In addition, when producing a film made of a diamond-like substance, it is necessary to mix hydrogen with a carbon-containing organic compound, but the ratio of hydrogen and carbon-containing organic compound used is 10% hydrogen.
0.1 to 5 mol of carbon-containing organic compound per 0 mol is preferable, and 0.2 to 2 mol is more preferable. If the proportion of the carbon-containing organic compound is too small, the growth rate of the diamond-like substance tends to be slow (on the other hand, if this proportion is too large, the diamond-like substance containing a large amount of amorphous carbon is likely to be generated.

In the first and second methods of the present invention, (semi) high temperature plasma is used. Here, high-temperature plasma is defined as Te /
It is known that a plasma with Tgz 1 is referred to as a quasi-high temperature plasma, and a plasma with l<Te/Tg<10 is referred to as a quasi-high temperature plasma.

In the first method, a plate-shaped electrode (hereinafter simply referred to as "plate-shaped electrode") provided with a slit and having a linear portion connected to a microwave power source is used as a discharge electrode.

The shape of the slit of the plate-shaped electrode may be bent or have an arcuate portion, but if the length is l, then the formula: (where λ is the micrometer to be introduced) wave wavelength, n is 1
or more integer, preferably 1 to 8, more preferably 1
~4. ) is provided with at least one substantially straight portion (hereinafter referred to as "effective straight portion") that satisfies the condition expressed by: If an effective linear portion does not exist in the slit, microwave discharge will not occur normally and plasma cannot be excited to a desired state.

Furthermore, the slit is provided so that the total length of the effective linear portion is 0.1 to 6 C11l/al relative to the area of the substrate surface or plate electrode on which a film is to be formed by plasma. preferable.

Further, the width of the slit is usually one or more and less than λ/2.

FIG. 1 is a perspective view showing an example of a plate-shaped electrode having a slit cut inward from the outer edge. This plate-shaped electrode 1 is made of a conductive material,
It consists of a flat plate that is entirely rectangular. A slit 3 is cut in one long side of the plate-shaped electrode 1 from a starting end (cut point) 2 near one end, parallel to the short side 4, and the slit 3 is bent multiple times at right angles to form the plate-shaped electrode 1. It ends at one point 5 inside.

In FIG. 1, the slit 3 consists of six relatively long effective straight parts AI parallel to the short side 4 of the plate-shaped electrode 1 and six short straight parts AI parallel to the long side that are not effective straight parts (hereinafter referred to as B1 (referred to as an "ineffective straight line part"), and is one continuous slit from the starting end 2 to the ending end 5. Two conductive wires 8a and 8b from the coaxial tube 8 are placed near the starting end of the slit 3 at two locations (6 and 7 in the figure) sandwiching the slit 3.
are connected to each other.

FIG. 2 is a perspective view showing an example of a plate-shaped electrode having a plurality of slits among the plate-shaped electrodes. This plate-shaped electrode 21 also
It is made of a conductive material and consists of a rectangular flat plate. The slits 23 of this plate-shaped electrode 21 are parallel to the short sides 24a and 24b of the plate-shaped electrode 21 and form an effective linear portion A2, and each slit is discontinuous. Moreover, this plate-shaped electrode 21 has its short side 24a
and 24b have coaxial pipe connections 22a, 22b,
They are connected to coaxial tubes 28a and 28b, respectively.

The shape of the slit formed in the plate-shaped electrode is not particularly limited as long as it has a small number of effective linear parts (one in total) as described above, and in addition to the example shown in FIGS. For example, the shape shown in 8 is exemplified.

In the example of FIG. 3, the plate-shaped electrode 31 has a plurality of effective linear portions A″
The slits 32 are arranged so that only the slits are connected continuously through the angle α.
In the example of FIG. 4, the plate electrode 41 is provided with an angle β.
The slit 42 is provided so that a set of two effective linear portions A4 connected via the slits 42 are repeated many times with a short non-effective linear portion B4 in between. In the example of FIG. 5, the slit 53 cut from the center 52 of the long side 51 branches left and right at a point 54, and then bends as in FIG. 1 to form a plurality of effective straight portions A5. respective terminal ends 55 and 5
It stopped at 6. In the example of FIG. 6, a plurality of slits 61, 62, and 63, each forming an effective linear portion, are provided in parallel to a direction forming an angle γ with respect to the long side 65 of the plate electrode 64.

Furthermore, in the first method, in addition to the above, plate electrodes having shapes as shown in FIGS. 7 and 8 can also be used. The plate-shaped electrode 71 in FIG. 7 is made of two support rods made of a conductive material and rods 72, 73, 74, 75, 76 and 77 provided in a ladder shape at equal intervals between the support rods. There is.

A small rectangular space 78° 79 surrounded by a rod corresponds to the above-mentioned slit, and the length A7 of the rectangular space in the longitudinal direction constitutes an effective linear portion. In the example shown in FIG. 8, a plurality of wing-like plates 82 made of a conductive material are installed in one plane on a part where only the inner conduit 81 of the coaxial pipe is exposed, and both ends of the wing-like plates are opposed to each other via the inner conduit. The length 2 is the length of the effective straight section.

Note that the shape of the plate electrode is not limited, and the outline can take various shapes such as a rectangular shape or a circular shape depending on the non-processed surface of the substrate.

Further, it is not particularly necessary to have a flat plate shape, and depending on the three-dimensional shape of the surface to be processed of the substrate, it may be entirely or partially curved, or there may be convex portions or concave portions. FIG. 9 is a cross-sectional view showing a plate-shaped electrode 93 suitable for forming a film on the spherical surface 92 of the base 91, and the lower surface 94 of the electrode 93 is
It is formed into a concave curved surface that conforms to the spherical surface 92 of the base body 91. Further, FIG. 10 shows a base body 102 having a convex portion 101 of a crutch
A plate-shaped electrode 104 suitable for forming a film on the surface 103 of
In this cross-sectional view, the electrode 104 is formed with a concave portion that fits the protrusion 101 of the base 102, and the electrode 104 is formed with a concave portion that fits the protrusion 101 of the base 102. It looks like this.

FIG. 11 shows surfaces 112 and 113 of a plate-shaped base 111.
This is a cross-sectional view showing a plate-shaped electrode 114 suitable for simultaneously forming a film on a substrate, and the electrode 114 is bent in a U-shape.
A film can be formed on the entire surfaces 112 and 113 of the base 111. Furthermore, by arranging a plurality of plate-shaped electrodes in parallel at appropriate intervals and arranging the substrate between them, it is possible to simultaneously form a film on both surfaces of the substrate.

Methods for introducing microwaves into the plate electrode used in the first method include, for example, connecting the other end of a coaxial cable or coaxial pipe connected to a waveguide to the plate electrode; A method in which the other end of a coaxial cable or coaxial tube is connected to one end of a parallel line and then the other end of the parallel line is connected to an electrode, a method using an antenna provided in a waveguide and an antenna provided for the electrode. etc. can be mentioned.

In addition, methods for introducing microwaves into a plate-shaped electrode include a method of introducing microwaves into one end of the plate-shaped electrode and simultaneously introducing another microwave to the other end; These methods can efficiently introduce microwave power into a plate electrode, connect a coaxial tube or coaxial cable to the other end, and connect this to a dummy load. This is effective for obtaining more stable plasma. As a specific example of the method of introducing microwaves into such a plate-shaped electrode, (a
) A method of arranging slits in a plate-shaped electrode so that they are point-symmetric or line-symmetric, and introducing microwaves from different power sources to two points on the electrode that are in a symmetrical relationship, [Yes]) Plate-shaped electrode The slits are arranged point-symmetrically or line-symmetrically, microwaves are introduced into one of the two symmetrical points on the electrode, and a coaxial tube or coaxial cable is connected to the other, and a dummy load is applied to the slits. For example, how to connect to Here, the dummy load is a device that releases microwaves that are not consumed for plasma generation to a liquid such as water or oil via a waveguide or coaxial tube.

Furthermore, in the first method of the present invention, a more stable plasma can be formed by applying a magnetic field to the plate electrode, and in this case, the magnetic flux density near the plate electrode is set to 500 to 2000 Gauss. It is preferable to maintain the magnetic field at a constant temperature, and an electromagnet, for example, can be used as the means for applying the magnetic field.

Further, in the first method of the present invention, a sheet-shaped plasma region is formed so as to cover the surface of the plate-shaped electrode.
If the thickness of this sheet-like plasma region is L (anus)2 and the area is S (mmt), there is a relationship as shown in the formula: % Formula %, and the average energy density in the plasma region is IOW/cd or more. preferable. S
When the value of /L is less than 200, the plasma region formed has a small two-dimensional spread, and the area on which a film can be formed becomes too thick (it is not possible to increase the thickness L of the plasma region).
is usually 1 to 40 mm.

Preferably it is 3 to 20 mm.

In addition, the energy density of the plasma region is on average 10 W/c
+f1 or more, preferably 10 to 1000 W/cd. This energy density is 10W/c++ on average
! If it is less than that, the rate of film formation on the surface of a large substrate will be reduced.

The material of the plate electrode is not particularly limited as long as it is a conductive material.
Specifically, any material can be used as long as it has an electrical conductivity of 10'' Ω -+ cm -+ or higher at room temperature and usually has good heat resistance at 600° C. or higher.

Examples of such materials include iron, cobalt, nickel, manganese, chromium, vanadium, titanium, copper, zinc, yttrium, ruthenium, zirconium, niobium, molybdenum, rhodium, palladium, silver, tantalum,
Transition metals such as tungsten, rhenium, platinum, gold, thallium, lead, and bismuth, aluminum: Alloys of the transition metals and aluminum such as stainless steel, brass, bronze, and super alloys: copper-alumina, copper-silicon oxide, silver-alumina , dispersion-strengthened alloys in which metal oxides are dispersed in metals such as silver-cadmium oxide, nickel-yttrium oxide, etc.; carbon materials such as carbon and graphite; among them, preferred ones have an electrical conductivity of 10 SΩ at room temperature. 'c
1! Examples of the materials listed above include copper, silver, aluminum, copper alloys, and copper-alumina dispersion-strengthened alloys. In addition, the surface of these materials can be coated with glass, ceramics,
It may be coated with an electrical insulator or semiconductive material such as silicon or diamond. The plate electrode is placed inside the reactor used.
Fixed with electrical insulation. Electrical insulators that can be used include, for example, alumina, boron nitride,
Examples include inorganic materials such as quartz glass, silicon nitride, and zirconium oxide; and organic polymers such as nylon and polyethylene. However, if the temperature is high, it is necessary to use inorganic materials.

In the first method, a gas containing at least one selected from organic compounds and inorganic compounds is flowed into the reactor. The flow rates of these gases are generally based on the internal volume of the reactor 100
! per 0.1 to 100,000 cc (STP)/l
It is ll1n. Also, the average pressure inside the reactor is usually 0
．． 5 Torr to 760 Torr-, preferably 1 to
It is 200 Torr. These are within a reasonable range and are selected depending on the type of film to be formed. For example, when forming a film made of a diamond-like substance, a carbon-containing organic compound and hydrogen are used, and the gas flow rate of the carbon-containing organic compound is usually 0.0 per 1001 internal volume of the reactor.
1 to 100.0 OOcc (STP)/min, and the flow rate of hydrogen is 0, 1 to 1 per 1 oz of internal volume of the reactor.
The range is 0000cc(STP)/+l1in.

In forming a film made of a diamond-like material, hydrogen and a carbon-containing organic compound may be separately supplied to the reaction zone and subjected to microwave discharge together with mixing, or they may be supplied to the reaction zone as a pre-mixed gas mixture and subjected to microwave discharge. It may also be subjected to wave discharge. In either case, a rare gas such as helium, argon, or xenon may be mixed with the supplied hydrogen, carbon-containing organic compound, or mixed gas thereof. There is no particular limit to the ratio of rare gas, but it is 80% per 100 moles of hydrogen.
It is preferably less than mol.

Under the above conditions, a sheet-like plasma with a thickness of about 1 to 20 am is usually generated over the entire surface of the plate-like electrode. Therefore, by arranging the substrate in advance or afterward so that the surface to be processed of the substrate comes into contact with the excited plasma,
A film made of a desired diamond-like material can be formed on the surface of the substrate. At this time, for example, the area of the plate electrode is 1
0000mm”, the applied power is approximately 1.5 kW
When , plasma with a thickness of about 5ffII11 is excited on the electrode surface. When the applied power is lowered to 0.8 kll, the plasma thickness becomes as thin as about 2 cylinders, but by bringing the substrate closer to the electrode surface, a film made of the desired diamond-like material can be formed.

In the second method of the present invention, a plasma of a gas containing at least one selected from the group consisting of organic compounds and inorganic compounds is generated between electrodes by DC discharge and moved by applying a magnetic field.

The plasma generated between the electrodes by DC discharge is arc-shaped (semi) high temperature plasma (hereinafter simply referred to as "arc-shaped plasma").

In the second method, electrodes such as those shown in FIGS. 12A-C and 13 are used to generate arc-shaped plasma.

FIG. 12A shows a pair of rod-shaped electrodes 12 connected to a DC power source.
The two electrodes 121 are fixed with an insulator 122 such as alumina at a distance of, for example, 1 to 10 square meters.

Arc-shaped plasma is generated in a part between the discharge electrodes, and is moved in the longitudinal direction of the rod-shaped electrode as indicated by arrow X in the figure by applying a magnetic field generated by an electromagnet (not shown). The arc-shaped plasma generated in a part between the discharge electrodes is
The film protrudes above and below the discharge electrode, and can be formed on a substrate placed close to the discharge electrode.

FIG. 12B shows an example of a discharge electrode having three or more rod-shaped electrodes 121 shown in FIG. 12A, which is suitable for forming a film with a wider area.

FIG. 12C shows an example in which a disc-shaped electrode 123 and electrodes 124, 125, and 126 made of ring-shaped flat plates are arranged concentrically, and a circular slit 127 is formed between each. Electrodes 123-126 are connected to a DC power source as shown. The arc-shaped plasma is generated in a portion of each circular slit 127, slightly protrudes above and below the disc-shaped electrode, and is moved along the circular slit 127 by an electromagnet (not shown). As a result, a film can be formed on the substrate placed close to the electrode. Note that in FIGS. 12A to 12C and the like, it is preferable to cool the electrode by flowing a refrigerant inside the electrode.

The materials for the discharge electrode used in the second method include the first
The same conductive materials as the material of the plate electrode used in the above method can be mentioned.

In the second method, a DC power source is used between the electrodes to generate an arc-shaped plasma, for example, 10 to 900
■Apply the voltage.

In the second method as well, a gas containing at least one selected from organic compounds and inorganic compounds is flowed into the reactor, but the flow rate of these gases is usually 100 to 100,000 cc per 100°C of the internal volume of the reactor. (STP)/wi
It is n.

In particular, in the second method, it is preferable to flow the gas between the electrodes in the form of a jet flow and eject the arc-shaped plasma from the discharge electrode in the form of a plasma jet. The gas flow velocity between the electrodes to generate jet-like arc-shaped plasma in this way is 0.01 to 500 m/
sec, particularly preferably 0.05 to 100 m/sec.

In addition, the average pressure inside the reactor is usually 10 to 760 Torr.
r, the energy density of the plasma is usually 10 to 1000 W/cffl on time average. Second aspect of the present invention
The method for supplying gas to the reaction zone in the method described above can be the same as the first method. Particularly, in order to flow the gas in a jet flow between the discharge electrodes, for example, a pipe 131 as shown in FIG. 13 may be installed on the discharge electrode 132, and gas may be supplied through this pipe 131. This pipe 131 has a discharge electrode 13
A gas ejecting slit 133 is provided opposite to 2 and located between the two discharge electrodes, and gas is supplied from this gas ejecting slit in a jet flow between the two adjacent discharge electrodes. be done.

In the second method, the generated arc-shaped plasma is moved by a magnetic field. The direction of this magnetic field is perpendicular to the direction of current flow due to the DC discharge. The magnitude of the magnetic flux density is usually 80 to 2000 Gauss. To generate this magnetic field, for example, electromagnets that generate a magnetic field in a direction perpendicular to the direction of current flow due to DC discharge are installed above and below or on the left and right sides of the discharge electrode as exemplified above.

By applying this magnetic field, the position of the discharge between the discharge electrodes is moved. For example, when discharge electrodes such as those shown in FIG. 12A or 12B are used, plasma is detected at both ends of the section where the arc-shaped plasma reciprocates. The direction of movement can be reversed by providing a plasma sensor that has the function of issuing a command to reverse the direction of the magnetic field each time. This reversal of the direction of the magnetic field is achieved by measuring the moving speed of the arc-shaped plasma in advance and determining the period based on that.
For example, the direction of the electromagnetic current may be reversed automatically in about 1 second or less.

The first and second methods of the present invention are carried out in a reactor, but the type of reactor used is not particularly limited, and in addition to a bell jar reactor, examples include a rectangular parallelepiped reactor. . The vacuum evacuation device connected to the reactor is not particularly limited either, and various commonly used devices can be used.

In the first and second methods of the present invention, a substrate support means such as a substrate support, a substrate heating means, and a substrate cooling means may be provided as necessary. In particular, when forming a film made of a diamond-like substance, it is preferable to maintain the substrate temperature at 600 to 900°C. When the substrate needs to be heated, an infrared image furnace or resistance heating furnace is used as the substrate support, and when the substrate needs to be cooled, a water-cooled cooling table is used as the substrate support. You can also do that.

The substrate on which a film can be formed by the first and second methods of the present invention is not particularly limited as long as it has heat resistance; for example, alumina, tungsten carbide,
Ceramics such as titanium nitride; Semiconductors such as silicon, germanium, and gallium arsenide; Metals such as molybdenum, tungsten, Kunkle, copper, and iron; Dispersion-strengthened alloys in which metal oxide particles are dispersed in copper or copper alloys; One example is quartz glass.

These substrates may be used as they are, or the surface may be scratched with diamond paste or the like to facilitate the formation of a film.

〔Example〕

Next, the method of the present invention will be explained in detail using examples.

Example 1 A film made of a diamond-like material was produced on a substrate using an apparatus schematically shown in FIG. This device is equipped with a plate electrode 142 fixed horizontally in a bell jar type reactor 141, and the electrode 142 is connected to a microwave power source via a coaxial cable 143 and a microwave introduction terminal 144 of a wavelength 122 cylinder. There is. A base 145 made of alumina provided in the reactor is equipped with an infrared image furnace, and a base 146 placed on the base pedestal can be heated to a desired temperature. An exhaust pipe 147 connected to a vacuum evacuation device and a gas introduction pipe 148 for introducing gas for plasma generation are connected to the bottom of the reactor 141, and valves 147a and 148a are provided respectively. The plate-shaped electrode 142 is made of copper, and as shown in FIG. 15, the two plate-shaped electrodes illustrated in FIG.
43, and the combined dimensions of the two pieces are 16
It is a rectangular plate electrode of 0x180x1mn+. The slit 151 has a slit width of 4 mm, an interval of 15 mm between adjacent effective straight sections indicated by Y in the figure, a length of 61 mm of the effective straight sections indicated by X in the figure, and 22 effective straight sections.

As the base 146, a silicon wafer with a diameter of 2 inches was used. This substrate was placed in a beaker together with diamond particles with an average particle size of 3 μm, and the beaker was held in an ultrasonic cleaning dish filled with water for 10 minutes to perform pretreatment to scratch the substrate surface. placed on top.

The distance between the top surface of the substrate and the plate electrode was maintained at 4 mm.

The gas species for plasma generation, the pressure, the energy density of the plasma, and the substrate temperature were varied as shown in Table 1, and the treatments of experiments k1 to 14 were conducted for 2 hours under the conditions shown in Table 1. The energy density is a value obtained by dividing the input microwave power by the volume of the generated plasma. The temperature of the substrate was controlled by adjusting the power of the infrared imaging furnace, and was measured by a chromel-alumel thermocouple fixed to the substrate. However, during the measurement, the microwave power supply was stopped for a short time.

(1) Table 1 also shows the average thickness, thickness variation, and crystallinity of the film made of the diamond-like material thus obtained on the substrate. Here, the average thickness was determined by observing a cross section of a substrate on which a film made of a diamond-like substance was formed using a scanning electron microscope. The thickness variation is the arithmetic average of the differences between the thickness at 10 randomly selected points on the substrate and the average thickness. In addition, crystallinity is defined as the ratio hd of the peak height near 1330 cm-' (derived from crystalline diamond) in the Raman spectroscopic spectrum to the peak height ha (derived from amorphous carbon) around 1500 cm-'. /ha. The larger this ratio is, the higher the quality of the diamond can be evaluated.

(2) In Experiments 15, 16 and 17, Experiments 5 and 7
A film made of a diamond-like substance was obtained on a molybdenum plate under the same plasma generation conditions as in 11, and gold electrodes 161 were deposited on the surface in the form of spots with a diameter of 11 mm at 18 positions shown in FIG. The electrodes were numbered as shown, and the electrical resistance between each electrode and the molybdenum plate was measured. The results are shown in Table 2. Here, since the magnitude of the electrical resistance value is proportional to the film thickness of the diamond-like material, it can be seen from the results in Table 2 that a film of the diamond-like material was uniformly formed on the molybdenum plate.

Table 2 (unit: Ω) Example 2 A film made of a diamond-like material was produced on a substrate using the apparatus schematically shown in FIG. 17. Elements that are the same as those in the device shown in FIG. 14 are designated by the same numbers. This device is the same as the device shown in FIG. 14 used in Example 1, in order to generate a magnetic field perpendicular to the longitudinal direction of the slit of the plate electrode 172.
Except that a coil 171a is added above the plate-shaped electrode 172, a coil 171b is added below the base 145, and a molybdenum plate-shaped electrode 172 of the same shape and size is used instead of the copper plate-shaped electrode 142. The configuration is similar to that of the device shown in FIG.

The same substrate as in Example 1 was used as the substrate 146, and the distance between the upper surface of the substrate 146 and the plate electrode 172 was maintained at 4 mm. Further, the magnetic field generated by the coils 171a and 171b was set to be 875 Gauss near the base 146.

The gas type, pressure, plasma energy density, and substrate temperature for plasma generation were varied as shown in Table 3, and the treatments of experiments Nα19 to Nα22 were carried out 2 times under the conditions shown in Table 3.
Time went.

The average thickness, variation in thickness, and crystallinity of the film made of the obtained diamond-like substance were measured in the same manner as in Example 1, and the results are shown in Table 3.

Example 3 In the apparatus shown in FIG. 17 used in Example 2, the plate electrode 172 was a rectangular plate electrode of 100 x 80 x 1 (mm) made of molybdenum and had a slit as illustrated in FIG. A film made of a diamond-like material was formed on the substrate using an apparatus similar to that shown in FIG. 17, except that the apparatus used was one having 5 slits with a length of part A2 of 61 mm and a slit width B of 12 mm at intervals of 7+n+++. was manufactured.

The gas type, pressure, plasma energy density, and substrate temperature for plasma generation were varied as shown in Table 3, and the treatments in Experiments Nα23 to Nα26 were carried out 2 times under the conditions shown in Table 3.
Time went.

The average thickness, variation in thickness, and crystallinity of the film made of the obtained diamond-like substance were measured in the same manner as in Example 1, and the results are shown in Table 3.

Example 4 A film of diamond-like material was produced on a substrate by the procedure outlined in FIG. In this device, a discharge electrode 182 equipped with a cooling refrigerant pipe (not shown) is horizontally fixed in a bell jar type reactor 181, and the electrode 182 is connected to a DC power source 186. A base 183 made of alumina provided in the reactor is equipped with an infrared image furnace and a cooling refrigerant pipe (not shown), and maintains the base 184 placed on the base at a desired temperature. be able to. Further, electromagnets 185 are provided above the discharge electrode 182 and below the base pedestal 184, respectively.
a and 185b are arranged horizontally to sandwich them. Electromagnets 185a and 185b are connected to a power source 187 outside the reactor and can form a magnetic field in a direction perpendicular to the current flowing between discharge electrodes 182. At the bottom of the reactor 181, similar to the device shown in FIG.
An exhaust pipe, gas introduction pipe, etc. are provided. These are shown in FIG. 18 with the same numbers as in FIG.

The discharge electrodes 182 are of the type shown in FIG.
It is equipped with five rectangular bar-shaped electrodes 121 with dimensions of 010 x 10 x 200+, and the anodes and cathodes are arranged alternately. Among these, the electrode that serves as the anode is made of copper, and the electrode that serves as the cathode is made of tungsten. The interval between adjacent electrodes is 5 mm, and both ends of the discharge electrode are fixed by an insulator 122 made of alumina.

As the base body 184, a silicon wafer having a size of 70×200×0.3 was placed on the base base 183.

The distance between the top surface of the substrate and the discharge electrode was maintained at 5M.

Further, the voltage of the power supply 187 is adjusted so that the magnetic field generated by the electromagnets 185a and 185b becomes approximately 400 Gauss near the discharge electrode 182, and the arc-shaped plasma is moved. ), arc-shaped plasma is connected to the discharge electrode 1.
Each time the end of 82 was reached, the current of power supply 187 was reversed.

The gas type, pressure, plasma energy density, and substrate temperature for plasma generation were varied as shown in Table 4, and the treatments of experiments Nα27 to 34 were carried out for 1 time under the conditions shown in Table 4.
Time went. Energy density is the input DC power,
This value is calculated by dividing by the total volume of the area where arc-shaped plasma is generated and moved. Further, the substrate temperature was measured in the same manner as in Example 1.

The average thickness, thickness variation, and crystallinity of the obtained diamond-like substance film were measured in the same manner as in Example 1, and the results are shown in Table 4.

Example 5 A film made of a diamond-like material was produced on a substrate using an apparatus schematically shown in FIG. Elements that are the same as those in FIGS. 13 and 18 are designated by the same numbers. This device is similar to the device shown in FIG. 18 used in Example 4, with the discharge electrode 18
2 and an electromagnet 185a located above the electrode 182, a vibrator 131 having a gas ejection slit 133 for ejecting plasma generating gas in a jet flow between the discharge electrodes, as illustrated in FIG. The device is the same as the device shown in FIG. 18 except that four of the devices are installed. This gas ejection slit 133 has a slit width of 1++u++ and a length of 200m.
g+, and is arranged so as to face the center of the slit between the electrodes, as described with reference to FIG.

The distance between the gas ejection slit 133 and the discharge electrode 182 is 5IIIfl+. The pipe 131 is connected to the reactor 191
It is connected to a gas introduction pipe 192 provided at the bottom of the tank for introducing gas for plasma generation.

An exhaust pipe 193 is also connected to the bottom of the reactor 191.

The gas type, pressure, plasma energy density, and substrate temperature for plasma generation were varied as shown in Table 5, and the treatments of experiments Nα35 to Nα42 were carried out for 1 time under the conditions shown in Table 5.
Time went.

The average thickness, variation in thickness, and crystallinity of the film made of the obtained diamond-like substance were measured in the same manner as in Example 1, and the results are shown in Table 5.

〔Effect of the invention〕

According to the method of the present invention, a film can be formed on the surface of a substrate with high energy efficiency. In particular, the first method can form a film on a large substrate surface with high energy efficiency, and the second method can form a thick film (and can form a uniform film) even with relatively low energy. can do.

[Brief explanation of the drawing]

1 and 2 are perspective views showing examples of plate-shaped electrodes used in the first method of the present invention. 3, FIG. 4, FIG. 5, FIG. 6, FIG. 7, and FIG. 8 are plan views showing other examples of plate-shaped electrodes. 9 and 10 are diagrams showing an example of the arrangement relationship between a plate-like electrode and a substrate having three-dimensional irregularities when carrying out the method of the present invention. FIG. 11 is a diagram showing another example of the arrangement relationship between the plate electrode and the base. 12A, B, and C each show examples of discharge electrodes used in the second method of the present invention. FIG. 13 is an explanatory diagram of a pipe provided with a slit for flowing plasma generation gas in a jet flow between a pair of discharge electrodes. FIG. 14 is a schematic diagram showing an example of an apparatus for implementing the method of the present invention, and FIG. 15 is a plan view of a plate-shaped electrode used. FIG. 16 is an explanatory diagram of a substrate on which a diamond-like substance is formed on the surface for measuring electrical resistance in Example 1 (2). Figure 17. 18 and 19 are schematic diagrams showing another example of an apparatus for carrying out the method of the invention. 1.21, 31, 41, 64.93, 104°142.
172...Plate electrode, 3,23,42゜54.151
...Slit, 61,62,63°91.102,1
46.184°...Base, 121°123.124,
125, 132, 182...electrode, 171a, 171
b, 185a, 185b...electromagnet.

Claims (1)

[Claims] 1) A substrate is placed in a plasma region formed by generating (semi-) high temperature plasma of a gas containing at least one selected from the group consisting of organic compounds and inorganic compounds using a discharge electrode. A method of forming a film on a substrate by contacting the substrate, wherein the electrode is a plate-shaped electrode connected to a microwave power source and provided with a slit having a straight section. 2) A substrate made by bringing the substrate into contact with a plasma region formed by generating (semi) high temperature plasma of a gas containing at least one selected from the group consisting of organic compounds and inorganic compounds using a discharge electrode. A method for forming a film on a surface, wherein the plasma region is formed by moving arc-shaped (semi-)high temperature plasma generated between electrodes by DC discharge using a magnetic field.