JPH0611912B2 - Organic thin film forming method, apparatus therefor, and particle beam generator - Google Patents

Description

The present invention relates to a method for forming an organic thin film and an apparatus therefor, and particularly to an organic material suitable for forming a thin film of various organic materials which has come to be widely used in the field of electronics. The present invention relates to a thin film forming method and an apparatus thereof.

[Conventional technology]

As a conventional organic thin film forming method, a wet process (wet method) has been mainly used. The feature of this wet process is that a relatively uniform film can be easily formed as seen in the spin coating method and the cast method. Therefore,
Since the wet process is excellent in productivity, it is widely applied to a film forming process such as a lithography photoresist, an interlayer insulating film of a semiconductor device, or a liquid crystal alignment control film of a liquid crystal display device.

On the other hand, there is a vacuum vapor method as a thin film forming method of the dry process (dry method). For example, Journal of Applied Physics, Vol. 36, No. 4, 194
5 April 1453 to 1460 (JOURNAL OF
APPLIED PHYSICS VOLUME36, NUMBER4 APRIL 1965 pp145
3-1460), the formation of an organic single crystal thin film has been reported. According to this method, it is possible to form a thin film having excellent crystallinity and orientation.

Other methods for forming a thin film by a dry process include:
There is a plasma polymerization method. This is, for example, the Chemical Society of Japan
No. 11 (1987), pages 2019 to 2024, a metal phthalocyanine plasma polymerized film is reported. According to this method, not only a functional thin film having a photoelectric conversion ability can be formed, but also a thin film generally excellent in mechanical strength and heat resistance can be formed.

[Problems to be Solved by the Invention]

The organic thin film forming method by the wet process is excellent in mass productivity and is currently the best thin film forming method. However, considering the technical problems for the organic thin film forming method used for the development of next-generation devices, the conventional wet film forming method is used. The process has presented some challenges that are difficult to address.

For example, a liquid crystal display is required to have high definition, color, and a large screen, and development of a liquid crystal display by an active matrix system in which a display element and a drive circuit are integrated has been vigorously developed. In one display, tens to hundreds of thousands of transistors are formed on a glass plate having a size of several tens cm. Here, the formation of a uniform photoresist film in the transistor manufacturing process has become a problem. In the spin coating method, in order to obtain a uniform film thickness, the substrate is rotated and coated at about 3000 revolutions per minute, but when the size of the substrate is increased, the speed at the edge of the substrate becomes higher as the speed becomes closer to the sonic speed. It is impossible with the current state of the art to stably rotate and hold the substrate and perform uniform coating.

It has been pointed out that the wet process has a problem with the interlayer insulating film of the semiconductor element. Conventionally, the polyimide film used as the insulating film is a polyamic acid varnish obtained by polymerizing a diamino compound and a tetracarboxylic acid (or a derivative thereof) in an organic polar solvent, and casting this on a substrate,
A method of heating and drying and converting to polyimide has been adopted (see, for example, Japanese Patent Publication No. 36-10999). In order to meet the demand for high integration of semiconductor elements, a sufficient insulation performance is required with a film thickness of about 1 μm, but the above method cannot completely remove pinholes, and impurities are likely to be mixed. Due to problems, a film quality that can withstand practical use has not been achieved.

Further, although the organic lubricating layer is also formed by a wet method to prevent the wear of the magnetic disk surface, the magnetic recording layer formed by a wet process is conventionally formed by a dry process in order to meet the needs for improving the recording density. Is becoming more common. Along with this, in order to maintain the quality of the formed film and improve the efficiency of the film formation, a dry process for forming the lubricating layer is required.

In forming an organic thin film by a dry process, which should replace the wet process, the vacuum vapor deposition method and the plasma polymerization method have the advantages described above, but the former is difficult to form a large area and the film formation speed is high. There is a problem that substances that can be vacuum-deposited are limited (for example, substances that cause a polymerization reaction when the temperature is raised for evaporation cannot be used). Regarding the latter, there is a problem that the disorder of the molecular composition or the molecular arrangement is likely to occur, and the control of the molecular chain orientation is difficult.

The present invention has been made in view of the above points, and an object thereof is to form an organic thin film having no pinhole, contamination of impurities, disorder of molecular composition or molecular arrangement, etc., in a large area and at high speed. An object of the present invention is to provide a method for forming an organic thin film, and an apparatus for realizing the method.

Another object is to provide a particle beam generator that utilizes the sputtering phenomenon to obtain a large-area particle beam.

[Means for Solving the Problems]

The above-mentioned purpose is a target composed of an organic compound placed in a vacuum, and a non-molecular force other than the Van der Waals force such as a molecular crystalline bond and a covalent bond due to the Van der Waals force that connects each atom constituting the organic compound. Among crystalline bonds, a particle beam having an energy high enough to break a molecular crystalline bond and not high enough to break a non-molecular crystalline bond, and an energy capable of selectively breaking a molecular crystalline bond Irradiate with a particle beam that has a
A target having molecular crystallinity, which is cut at an energy of about 10 electron volts or less, is irradiated with a particle beam, and particles scattered by sputtering from the target are adhered and deposited on a substrate placed facing this, and a desired particle is deposited. This is achieved by forming a thin film of an organic compound.

Still another object is to provide a vacuum container, an introducing pipe for introducing a gas serving as a raw material of particle beam into the vacuum container, and a cooling temperature of the raw material gas introduced through the introducing pipe. A cooling plate on which a solidified layer of the source gas is formed on the surface, an ion source for irradiating the solidified layer of the source gas formed on the surface of the cooling plate to emit sputtered particles, and particles sputtered by the ion source This is achieved by using a particle beam generator including an opening provided in a part of the vacuum container for taking out.

[Action]

When a target made of the above organic compound is irradiated with a particle beam having the above-mentioned predetermined energy, a molecular crystalline bond and a covalent bond other than the Van der Waals force due to the Van der Waals force connecting the atoms constituting the organic compound Among the non-crystalline bonds (sometimes referred to collectively as heterogeneous molecular crystals) due to, the molecular crystalline bonds are broken, and the molecules linked by the non-molecular crystalline bonds are Scatter. Part of the scattered molecules reach the substrate, and the molecular crystals are bonded again to form a thin film of an organic compound.

In the film formation method by ordinary sputtering, since the target is irradiated with a particle beam of 500 electron volts to several kiloelectron volts, many of the bonds in the organic compound are cut and the target is carbonized. For this reason, it is difficult to form a thin film of an organic compound on the substrate, but in the method of the present invention, the particle beam for irradiating the target is extremely low at about 10 electron volts, so that the raw material is carbonized. There is no. Further, the disorder of the molecular composition etc. in the formed thin film is extremely small.

In addition, since molecules scattered by sputtering have energy of 1 to several electron volts, a dense thin film can be formed, and pinholes and impurities are less likely to be mixed. Furthermore, in the present invention, the molecular crystalline bond is cut by particle beam irradiation to cause sputtering,
The sputtering rate is much higher than that of the conventional method, and high-speed film formation is possible.

Further, in the particle beam generator of the present invention, a gas serving as a raw material of the particle beam is supplied to a cooling plate provided in a vacuum, the gas supplied on the cooling plate is solidified, and a rare gas ion of several kilovolts is supplied. Irradiate with. At that time, the particles emitted by the sputtering are taken out in a beam shape.

〔Example〕

Hereinafter, the present invention will be described in detail based on the illustrated embodiments.

(Example 1) FIG. 1 is an apparatus configuration diagram when the present invention is applied to form a photoresist on a silicon substrate. As shown in the figure, in the vacuum container 1, a target 8 which is a raw material, a silicon substrate 7 mounted by a substrate holder 6,
A heater 5 for heating the silicon substrate 7 and an ion source 2 are arranged. The inside of the vacuum container 1 is evacuated from the exhaust port 9 to 5 × 10 ⁻⁷ Torr by an exhaust device (not shown).

Using the apparatus shown in FIG. 1, a positive resist made of a phenol novolak resin-naphthoxin azide type photosensitizer was formed.

Naphthoquinone diazide sulfonyl ester of 2,3,4-trihydroxybenzophenone (75% by weight: phenol novolak resin (manufactured by Gunei Chemical Industry Co., Ltd., weight average molecular weight: 2000)) as an alkali-soluble polymer and a photosensitive dissolution inhibitor (Toyo Gosei 25% by weight of a photosensitive resin composition is first made into fine particles having a particle size of about 0.5-2 mm, then powdered in an agate bowl, and pressed to form a thin columnar shape (diameter 100 mm). , And a target 8 having a thickness of 1 mm).

When an argon ion beam 20 having an energy of about 6 to 10 electron volts is generated from the ion source 2 and irradiated on the target 8, sputtered particles 21 are scattered and a photoresist film is formed on the 6 inch silicon wafer substrate 7. To be done. The temperature of the substrate 7 was about 60 ° C., and a photoresist film of 1.2 μm was obtained in 20 minutes of film formation (ion irradiation) time. The variation in the film thickness measured using the stylus type film thickness meter was 0.1 μm or less.

Striped pattern mask (stripe width 1 μm,
Pitch 42 μm) and used as a light source PL manufactured by Canon Inc.
After exposing for 4 seconds using A501F (11.0 mW / cm ² , 405 nm), a commercially available developer NMD-3 (manufactured by Tokyo Ohka)
Developed. Next, using a parallel plate dry etching device, CHF ₃ gas pressure 10 mTorr, frequency 13.56 MHz
Etching for 5 minutes under a vacuum, commercial stripper S-502
The resist film was removed by (manufactured by Tokyo Ohka). (Peeling conditions: 140 ° C., 10 minutes).

For comparison, the above-mentioned phenol novolak resin-naphthoquinone azide-based photosensitizer was dissolved in ethyl cellosolve acetate, spin-coated after pre-baking (85 ° C., 25 minutes) and post-baking (145 ° C., 20 minutes) to form a resist film. did. Then, development, etching and peeling were performed in the same process.

As a result of observing the above two samples with a scanning electron microscope, it was confirmed that a good stripe pattern having a pitch of 2 μm, a width of 1 μm, and a depth of 0.5 μm was formed in each sample.

(Example 2) FIG. 2 is an apparatus configuration diagram in the case where the present invention is applied to form a photoresist similar to that of Example 1 on an aluminum plate. As shown in the figure, the vacuum container 1 includes four targets 8 which are raw materials, a substrate 7 attached to the substrate holder 6, an XY stage 17 capable of moving the substrate holder 6 two-dimensionally, and two ions. Source 2 is arranged. The vacuum container 1 is evacuated as in the apparatus shown in FIG.

The size of one target is 150 mm × 150 mm (thickness 1 mm), and the manufacturing method is exactly the same as in Example 1 above. The substrate 7 is a surface-polished 500 mm × 50
An aluminum plate of 0 mm (thickness 3 mm) was used. The target 8 was irradiated with the argon ion beam 20 of about 6 to 10 electron volts generated by the ion source 2 to deposit the sputtered particles 21 on the substrate 7 to form a photoresist film. At that time, the film was formed while moving the substrate 7 two-dimensionally by moving the XY stage 17. It was confirmed that the film formation time was about 40 minutes, and the thickness of the formed resist film was 1.3 μm near the center and 1 to 1.2 μm at the four corners, and the film was formed substantially uniformly.

Using the mask used in Example 1, pattern exposure was carried out at 4 corners and 5 locations at the center, and then etching and peeling were performed. Etching uses the same device as in Example 1,
It was performed under an AlCl ₃ gas of 5 mTorr for 5 minutes. The peeling was the same as in Example 1.

The surface of the five places was observed with a scanning electron microscope, and it was confirmed that the same stripe pattern as in Example 1 was formed.

As shown in Examples 1 and 2, according to the present invention, patterning of a large area, which is difficult in the wet process, is possible, and the sensitivity of the photoresist, which is a drawback of the conventional dry process, or the formation of the photoresist is not satisfactory. Membrane speed is also greatly improved. This is because in the present invention, by utilizing the low energy ion beam (particle beam) sputtering,
This is because the highly sensitive resist material developed so far can be used as it is in the dry process system, and the sputtering rate of the target made of the organic compound is considerably higher than that of the conventional inorganic resist material.

(Example 3) Using the apparatus shown in FIG. 1, a polyimide film (insulating film) was formed on a silicon substrate. Target 8 is 4-
A thin columnar body obtained by pressure-forming aminophthalic anhydride was used, and a 6-inch silicon wafer heated to 300 ° C. was used as the substrate 7. The target 8 was cooled to about room temperature.

The target 8 was irradiated with argon of about 6 to 10 electron volts, and the target 8 was sputtered to form a polyimide film on the substrate 7. Film thickness of 1.5μ in about 25 minutes
A polyimide film of m was obtained. The formed polyimide film was tough and did not show brittleness caused by a decrease in molecular weight.

It was confirmed from the measurement of electric resistance that the formed polyimide film had good insulating properties. Furthermore, it was confirmed that a film without pinholes, which was difficult to avoid by the wet process, was formed.

According to the present invention, until now the polymerization proceeds by heating,
A compound having two carboxylic acids adjacent to each other and an amino group and an ester compound or acid anhydride thereof in one molecule, represented by 4-aminophthalic anhydride, which is difficult to form a film by a vacuum deposition method or the like. , Can be sputtered, deposited on a substrate and polymerized on the substrate with little change. As a result, a polyimide film having excellent insulation performance without pinholes can be obtained.

(Example 4) FIG. 3 is an apparatus configuration diagram in the case where the present invention is applied to form a fluoropolymer film on an aluminum substrate. As shown in the figure, the vacuum container 1 includes a gas supply pipe 11, a cooling head 10, a substrate 7 attached to a substrate holder 6, a heater 5 for heating, an ion source 2, and a laser light generator 15.
Are placed. The vacuum container 1 is evacuated from the exhaust port 9 to about 1 × 10 ⁻⁷ Torr by an exhaust device (not shown). The cooling head 10 can be cooled to a liquid nitrogen temperature level by a refrigerator (not shown). The laser light generator 15 is
It is a pulsed CO ₂ laser with an output of up to 1 J.

The film formation was performed as follows. A mixed gas of HCF ₃ and C ₂ F ₂ is introduced from a gas supply pipe (nozzle) 11 onto the cooling head 10 cooled to the liquid nitrogen temperature to form a solidified layer 23,
This was the target. About 6 generated by ion source 2
When the solidified layer 23 is irradiated with the argon ion beam 20 of 10 electron volts and the infrared laser light 22 having a wavelength of 10.6 μm and 0.5 diule are irradiated, the sputtered particles (molecules) 21 are scattered. Part of the particle 21 is 1
A thin film is formed by depositing on a mirror-polished 5-inch aluminum substrate (thickness 1 mm) 7 held at 00 ° C. For the following evaluation test, a film having a film thickness of 100 Å was formed. The laser light 22 is applied to increase the production of radicals. Without irradiating the laser light 22
Film formation is possible, but in that case the film formation rate is reduced.

The obtained film was estimated to be a cross-linked polymer, and the constituent element ratios were C: 34.8%, H: 12.3%, and F: 52.6%. The deposition rate is 500Å / min. The aluminum substrate coated with this fluorine-containing polymer film was tested for lubrication performance by using a sliding tester. Using a spherical sapphire slider with a diameter of 30 mm, a load of 20 g and a peripheral speed of 20 m / s
The surface after 00 rotation was visually observed and it was confirmed that the lubricating layer was not broken, and it was revealed that this film had excellent lubricating performance. It was also confirmed that this film has good corrosion resistance.

For comparison, film formation was also performed by the plasma polymerization method using the same mixed gas used in this example. It was found that the obtained film was three-dimensionally crosslinked and had good lubricating performance, but was easily corroded. Deposition rate is 35
It is about 0Å / min.

According to the present invention, the solidified layer of HCF ₃ and C ₂ F ₆ mixed gas is
By irradiating with low-energy ions, it is possible to form a chain-like crosslinked polymer thin film on the substrate and not only achieve good sliding performance, but also improve corrosion resistance compared to conventional plasma polymerization methods. However, there is an effect that the film forming rate becomes high.

In the film formation using the apparatus of FIG. 3, the film forming conditions of the pressure and temperature of the raw material for forming the solidified layer are not mentioned. This point will be described in detail.

An embodiment of the present invention will be described with reference to FIG. FIG. 1 is a device configuration diagram of a thin film forming device capable of controlling the pressure / temperature of a raw material. As shown in FIG.
However, in the vacuum container 1, the substrate 7 attached to the substrate holder 6 and the cooling head 1 for forming the solidified layer of the raw material
A raw material introduction pipe 40 for introducing a gas or liquid raw material into a vacuum at 0, normal temperature and normal pressure is arranged. The supply of the raw material to the raw material introduction pipe 40 is
The operation is performed from the pressure / temperature control chamber 42. In the pressure / temperature control chamber 42, the pressure is changed by changing the flow rate of the raw material, and the cooling plate 41 and the heater 43 are operated.
The temperature of the raw material can be controlled.

The device of FIG. 4 operates as follows. A raw material made of an organic compound and having a predetermined pressure and temperature is supplied onto the cooling head 10 from the raw material introduction pipe 40. Since the cooling head 10 is kept at the solidification temperature of the raw material or lower by the refrigerator (not shown), the solidified layer 23 is formed. The solidified layer 23 is generated by the ion source 2 and is about 10
When irradiated with an ion beam of an electron volt or less, the solidified layer 2
Substrate 7 in which particles were sputtered from 3 and kept at a predetermined temperature
A thin film of an organic compound is formed on top.

When the raw material is a gas, the pressure / temperature control chamber 42 controls the supply (blowing) of the gas from the raw material introduction pipe 40 so that the speed is equal to or lower than the speed of sound. If the gas is blown out at a speed equal to or higher than the speed of sound, a shock wave is generated in the vacuum container 1, which adversely affects the film formation. However, if the blowing speed of the gas is lower than the speed of sound, the higher the speed,
It was found that the solidified layer 23 grew quickly. Therefore, at the time of film formation, it is preferable to set an optimum gas blowing rate for supplementing the decrease in the solidified layer 23 due to sputtering without excess or deficiency.

Generally, in order to reduce the influence of the composition change due to the temperature change of the organic compound, the temperature of the raw material and the cooling head 1
The smaller the temperature difference of 0, the better. When using a gaseous source material, in the range of the source material used for film formation so far,
Good film formation was achieved by raising the temperature of the raw material by 5 to 10 ° C. above the boiling point and by lowering the temperature of the cooling head 10 by 5 to 10 ° C. below the melting point of the raw material.

Next, a case where tetrafluoroethylene (CF ₂ = CF ₂ ) is used will be described as a specific example of the raw material. The temperature of the raw material is -70 ° C, and the temperature of the cooling head 10 is -1.
When the temperature is 50 ° C., the raw material having a melting point of −142.5 ° C. is the solidified layer 2
3 is formed. This is sputtered by irradiating it with an argon ion beam 20 of about 6 to 10 electron volts,
A thin film was formed on the aluminum substrate 7 kept at 100 ° C. As a result of examining the constituent element ratio of the formed thin film, the formed thin film was polytetrafluoroethylene. Therefore, it was found that there was almost no compositional disorder observed when the film was formed with the temperature of the raw material being room temperature.

FIG. 5 is a modification of the thin film forming apparatus capable of controlling the pressure / temperature of the raw material. This device is the same as the device of FIG. 4 except that an ion source 45 for irradiating the substrate 7 is arranged. A thin film was formed on the aluminum substrate 7 using the raw material tetrafluoroethylene, using the apparatus shown in FIG. It was confirmed that the formed film was polytetrafluoroethylene with less disorder in composition, similar to the film formed by the apparatus in FIG. Since the substrate 7 is irradiated with the argon ion beam of about 5 electron volts generated by the ion source 45 at the time of film formation, the formed film is denser than the film formed using the apparatus of FIG. Then, it was revealed that the adhesiveness with the substrate 7 was better.

FIG. 6 shows another modification of the thin film forming apparatus capable of controlling the pressure / temperature of the raw material. The apparatus of the same figure is almost the same as that of FIG.
The difference is that it can move above 0. By using this apparatus, the solidified layer 23 can be made uniform in thickness, and the film thickness distribution of the thin film formed on the substrate 7 by sputtering can be made uniform. FIG. 7 shows a modification of the raw material blowing section of the raw material introducing pipe 40. FIG. 7 (a) shows a blowout portion with a large number of holes, FIG. 7 (b) shows a blowout portion which is expanded in a tapered shape so that the raw material is spread over a wide range, and FIG. 7 (c) shows 1 The blowing part having one or a plurality of holes makes a swinging motion. When a film is formed by an apparatus having these blowing parts, there is an effect that the film thickness of the formed thin film becomes more uniform.

As described above, it was confirmed that the apparatus shown in FIG. 3 could form an organic thin film having good lubricating performance. However, in order to apply this thin film forming method to an actual manufacturing process, it is necessary to develop an apparatus for forming a uniform film over a large area. The large area thin film forming apparatus will be described below.

The structure and operation of the large-area thin film forming apparatus will be described with reference to FIGS. 8 and 9. As shown in FIG. 8, in the vacuum container 1, an ion source 2, an introduction pipe 3 for introducing a gas or liquid raw material into a vacuum at room temperature and normal pressure 3, a cooling head 4, a heating filament 5, A substrate holder 6 and a substrate 7 are arranged. The raw material introduction pipe 3 has a pipe shape, and a plurality of holes are formed in the pipe surface in at least one row in the axial direction. The substrate 7 is a rectangular parallelepiped (thickness is thin) that is long in the direction perpendicular to the paper surface in FIG. The cooling head 4 has a columnar shape as shown in FIG. 9, and is cooled to a liquid nitrogen temperature at a minimum by a refrigerator and a drive mechanism 25, and can be rotated around a central axis. . The vacuum container 1 is set to 1 by an exhaust device (not shown).
It is evacuated to about 10 ⁻⁷ Torr.

For example, a mixed gas of HCF ₃ and C ₂ F _{6 is} supplied to the raw material supply pipe 3
Then, it is introduced into a vacuum to form a solidified layer of the mixed gas on the surface of the cooling head 4. When the solidified layer is irradiated with an argon ion beam 20 having an energy of about 6 to 10 electron volts, the sputtered particles 21 are deposited and deposited on the aluminum substrate 7 kept at about 100 ° C. to form an organic thin film. It At this time, although not shown in the figure, the film formation rate can be improved by irradiating the vicinity of the solidified layer with CO ₂ laser light to promote the generation of radicals. With the apparatus shown in FIG. 8, a thin film can be formed on a vertically or horizontally large area substrate.

Another example of the large-area thin film forming apparatus will be described with reference to FIG. In this apparatus, the ion source 2, the raw material introducing pipe 3, the cooling head 4, and the heating filament 5 are arranged in the vacuum container 1 as in the apparatus shown in FIG. Is a substantially square large area, and differs in that it can be moved in the direction of the arrow by the substrate feeding mechanism 19.

Also in the film formation in this apparatus, a solidified layer of the raw material introduced into the vacuum from the raw material supply pipe 3 is formed on the surface of the cooling head 4, and the ion beam from the ion source 2 causes sputtering to form a thin film on the substrate 7. The formation is the same as in the case of the apparatus of FIG. 8, but at this time, the film formation is performed while moving the substrate 7 in the direction of the arrow, so that even if the film formation portion is a large area substrate having a square shape, the film quality is almost the same. An organic thin film with uniform film quality can be formed. Further, since the cooling head 4 is rotated,
The ion beam 20 and the portion forming the solidified layer of the raw material
Since it is possible to separate the portion to be irradiated with, a large amount of ion beam can be irradiated, and the film forming rate becomes higher accordingly.

Another example of the large-area thin film forming apparatus will be described with reference to FIG. In this apparatus, the ion source 2, the raw material introducing tube 3, the cooling head 4, the heating filament 5, the substrate 7, and the substrate feeding mechanism 19 are arranged in the vacuum container 1 as compared with the apparatus shown in FIG. Although the same, the difference is that a slit 30 for shaping sputtered particles and a speed control circuit 32 for changing the feeding (moving) speed of the substrate are provided.

Also in the film formation in this apparatus, it is possible to irradiate the solidified layer of the raw material formed on the surface of the cooling head 4 with the ion beam 20 and form the thin film while moving the sputtered particles 21 on the substrate 7. , Which is similar to the case of FIG. At that time, the thickness of the thin film formed on the substrate 7 can be arbitrarily set by controlling the feed speed of the substrate by the speed control circuit 32 and using the slit 30, and only at a specific portion on the substrate 7. It is also possible to perform selective film formation. This is particularly useful in the thin film transistor formation process for displays.

In the above embodiments, the ion beam is used to irradiate the target or the solidified layer formed on the surface of the cooling head, but other particle beams such as a neutral particle beam and plasma may be used. Similar effects can be obtained by using particles other than argon. The film formation rate depends on the type of particles.

By the way, as a means for generating an extremely low energy particle beam of 50 electron volts or less, after extracting the high energy electron particles from the plasma source, the electron beam is decelerated to generate a low energy particle beam (usually an ion beam). The way to get is often done. However, in this method, in order to suppress the divergence of particle beams during deceleration, an electrostatic lens is used,
If the particle beam is drawn out in a large area, the convergence effect will decrease, so
It was difficult to obtain a large-area particle beam. Therefore, in the present invention, a particle beam generator utilizing the sputtering phenomenon is used. As the particles of the particle beam for irradiating the target or the solidified layer of the raw material, it is desirable that the particles be a gas at room temperature in order to minimize the incorporation of the particles into the target or the film formed on the substrate. In the particle beam generator according to the present invention, a cooling plate provided in a vacuum is supplied with a gas serving as a raw material of the particle beam, the gas supplied on the cooling plate is solidified, and a rare gas ion of several kilovolts is supplied. Irradiate with. At that time, the particles emitted by sputtering,
It is taken out in the shape of a beam.

The structure and operation of the particle generator will be described below with reference to FIG. As shown in the figure, the particle generator comprises a vacuum container 50.
0, a cooling plate 505, a gas supply pipe 512, an ion source 501, which are placed in the same container 500 or adjacent to each other while keeping airtightness.
It consists of an electron beam generator 517 and the like. Ion source 501
Is supplied with gas from the gas supplier 513, and the power source 502
Controlled by. The cooling plate 505 is cooled by the refrigerator 506, is electrically insulated from the vacuum container 500 by the insulator 509, and a DC bias is applied by the bias power supply 510. The raw material gas is supplied to the gas supply pipe 512 from the gas supply pipe 513.

It should be noted that the particle generator is composed of the target 524 and the substrate 52.
The film forming chamber 520 including 5 and the exhaust device 521 are connected in an airtight manner. Then, the vacuum container 500 and the film forming chamber 52
0 is evacuated to about 1 × 10 ⁻⁶ Torr by the exhaust device 521. When the cooling plate 505 is cooled to a liquid nitrogen temperature (−196 ° C.) and argon gas is supplied from the gas supply pipe 512, the argon gas adheres to the cooling plate 505 and is solidified.
An ion source 501 is added to the solidified argon gas 507.
When the argon ions of 3 kiloelectron volts generated in 1 are irradiated, argon sputtered particles 515 are emitted. By irradiating this with the electron beam 518, many sputtered particles 515 are ionized. The sputtered particles spread radially, but among them, the sputtered particles scattered in a direction substantially perpendicular to the surface of the cooling plate 505 are ion beams 51.
9 can be taken out from the particle generator.

FIG. 13 shows the energy distribution of argon particles (ions) in the ion beam 519 measured by an electrostatic energy analyzer. However, the cooling plate 505 is grounded. In this measurement, the energy of argon particles is often about 1 electron volt, and the half width of the energy distribution is several electron volt. FIG. 14 shows the relationship between the bias voltage and the average energy of argon particles obtained by measuring the energy distribution of argon particles while changing the bias potential of the cooling plate 505. With a bias voltage of about 8.5 volts,
It can be seen that an argon ion beam of approximately 10 eV is obtained.

The target 524 is irradiated with the ion beam 519 of about 10 eV, and a film is formed on the substrate 525. In addition to the film formation, the particle beam generator described here can also be used for etching a semiconductor or the like by using chlorine gas instead of argon gas to generate a low energy chlorine ion beam. This particle beam generator does not use a grid to extract the ion beam, so there is less dust in the etching chamber and the energy of the ion beam is low. ) Also has the advantage of being small.

Next, a modified example of the device described in FIG. 12 will be described. The apparatus of FIG. 15 is the same as the apparatus of FIG. 12 except that the cooling plate 505 has a spherical shape. The first point of the apparatus shown in FIG. 15 is that the sputtered particles emitted from the solidified gas 507 can be efficiently converted into an ion beam 519.
It is superior to the device in Figure 2. In the apparatus of FIG. 12, the electron beam 518 is used to ionize the sputtered particles 515, but a laser beam may be used instead.

Another modified example of the apparatus shown in FIG. 16 is that the solidified gas 5
The apparatus is the same as that of FIG. 12 except that two ion sources 501 are used to irradiate 07. The amount of the ion beam 519 that can be generated by the apparatus shown in FIG. 16 is about double that in the apparatus shown in FIG. Further, in order to increase the amount of ion beam, it is possible to further increase the number of ion sources.

〔The invention's effect〕

According to the present invention described above, by irradiating a target made of an organic compound with a particle beam of about 10 electron volts or less, the molecular bonding bond in the target material is broken, but the non-molecular bonding bond is broken. Bond is not broken,
As the sputtered particles are deposited and deposited on the substrate to form an organic thin film, there is an effect that an organic thin film can be formed without pinholes, contamination of impurities, disorder of molecular composition or molecular arrangement, and the like. In addition, it is easy to increase the size of the target, to move the substrate, and to increase the irradiation dose of the particle beam, so that it is possible to form a large-area organic thin film on the substrate at a higher speed than before. .

[Brief description of drawings]

1, FIG. 2, and FIG. 3 are configuration diagrams showing the apparatus used for thin film formation of one embodiment of the present invention, FIG. 4, FIG.
6 and 6 are configuration diagrams showing a thin film organic forming apparatus capable of controlling the pressure / temperature of a raw material, FIG. 7 is a structural diagram of a raw material blowing part of the apparatus of FIGS. 4 to 6, and FIG. FIG. 9 is a block diagram of a large-area organic thin film forming apparatus which is one of the embodiments of the present invention, FIG. 9 is an explanatory diagram for explaining the operation of FIG. 8, FIG. 10 and FIG. FIG. 12 is a constitutional view of a large area organic thin film forming apparatus which is another embodiment of the present invention, FIG. 12 is a constitutional view of a particle beam generator used in the embodiment of the present invention,
3 and 14 are characteristic diagrams showing the characteristic of the device of FIG. 12,
15 and 16 are configuration diagrams of another particle beam generator used in the embodiment of the present invention. 1 ... vacuum container, 2 ... ion source (particle generator),
3, 11, 40 ... Gas introduction tube, 4, 10 ... Cooling head, 6 ... Substrate holder, 7 ... Substrate, 8 ... Target, 15 ... Laser light generator, 17 ... XY stage , 19 ... Substrate feeding mechanism, 20 ... Ion beam, 2
1 ... Sputtered particles, 22 ... Laser light, 23 ... Solidified layer, 30 ... Slit, 32 ... Speed control circuit, 42 ...
... pressure / temperature control room, 45 ... ion source, 500 ... vacuum container, 501 ... ion source, 505 ... cooling plate, 50
7 ... Solidified layer, 509 ... Insulator, 510 ... Bias power supply, 512 ... Gas supply pipe, 513 ... Gas supply device,
515 ... Sputtered particles, 517 ... Electron beam generator, 518 ... Electron beam, 519 ... Ion beam,
520 ... Deposition chamber, 524 ... Target, 525 ...
substrate.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Takayoshi Seki, 4026 Kuji Town, Hitachi City, Hitachi, Ibaraki Prefecture, Hitate Works, Ltd. (72) Inventor, Kiyoshi Miyake, 4026 Kuji Town, Hitachi City, Ibaraki, Hitachi Co., Ltd. Hitachi Research Laboratory (72) Inventor Ko Ohata ▲ Kichi ▼ Kitamachi 4026, Hitachi City, Hitachi, Ibaraki Prefecture Hitachi, Ltd. (72) Inventor Kenichi Natsui Kujicho Hitachi City, Ibaraki Prefecture 4026 Hitachi, Ltd.Hitachi Factory Hitachi In the laboratory (72) Inventor Mitsunori Warabi, 1-280, Higashi Koikekubo, Kokubunji, Tokyo, Hitachi Central Research Laboratory (72) Inventor Keiji Arimatsu 1-1-1, Kokubuncho, Hitachi City, Ibaraki Hitachi Kokubun Co., Ltd. in the factory

Claims (28)

[Claims] 1. A thin film forming method of irradiating a target made of an organic compound with a particle beam to scatter it, and depositing and depositing particles of the target on a substrate, van der Waals force connecting each atom constituting the organic compound. Of non-molecular crystalline crystals due to forces other than the molecular crystalline bond and van der Waals force due to the energy that is high enough to break the molecular crystalline bond and not high enough to break the non-molecular crystalline bond. A method of forming an organic thin film, comprising: irradiating the target with a particle beam having the above-mentioned structure to form a thin film of an organic compound on the substrate. 2. A thin film forming method of irradiating a target made of an organic compound with a particle beam to scatter it, and depositing and depositing particles of the target on a substrate, in a van der Waals force for connecting each atom constituting the organic compound. Among the non-molecular crystalline crystals due to the force other than the molecular crystalline bond and the Van der Waals force due to, the target is irradiated with a particle beam having energy capable of selectively breaking the molecular crystalline bond, A method for forming an organic thin film, comprising forming a thin film of an organic compound on the substrate. 3. In a thin film forming method of irradiating a target made of an organic compound with a particle beam to scatter and depositing and depositing particles of the target on a substrate, the target irradiated with the particle beam constitutes an organic compound. Among the molecular crystalline bonds by the Van der Waals forces that connect the atoms and the non-molecular crystalline crystals by forces other than the Van der Waals forces, the molecular crystalline bonds are broken and the non-molecular crystalline bonds A method for forming an organic thin film, wherein a thin film of an organic compound is formed on the substrate with particles that are sputtered so as not to be cut and scattered. 4. A thin film forming method in which a target made of an organic compound is irradiated with a particle beam and scattered to deposit and deposit particles of the target on a substrate, wherein the target is a particle beam having an energy of about 10 electron volts or less. Irradiate,
A method for forming an organic thin film, comprising forming a thin film of an organic compound on the substrate. 5. A thin film forming method of irradiating a target made of an organic compound with a particle beam to scatter it and depositing and depositing particles of the target, the target having a molecular crystallinity which is cut at an energy of about 10 electron volts or less. A method of forming an organic thin film, comprising: irradiating the particle beam with the particle beam to form a thin film of an organic compound on the substrate. 6. The target is a gas under normal temperature and pressure,
Alternatively, a liquid substance is introduced into a vacuum, and the introduced raw material is adsorbed on the surface of a cooling head cooled below its melting point,
It is what was solidified, The organic thin film forming method in any one of Claims 1-5 characterized by the above-mentioned. 7. A vacuum container, a target placed in the vacuum container, and a particle beam source for generating a particle beam for irradiating the target, wherein the target is sputtered by the particle beam source. In a thin film forming apparatus for depositing particles emitted from the target on a substrate to form a thin film, the target is formed of an organic compound, and
The particle beam source is capable of irradiating a particle beam having an energy of about 10 electron volts or less, and the target is irradiated with the particle beam from the particle beam source to form a thin film of an organic compound on the substrate. An organic thin film forming apparatus characterized by: 8. A vacuum container, a target placed in the vacuum container, and a particle beam source for generating a particle beam for irradiating the target, wherein the target is sputtered by the particle beam source. In a thin film forming apparatus for depositing particles emitted from the target onto a substrate to form a thin film, the target is formed of one having molecular crystallinity that is cut at an energy of about 10 electron volts or less. An organic thin film forming apparatus, comprising: irradiating a particle beam from the particle beam source to form a thin film of an organic compound on the substrate. 9. A vacuum container, a target placed in the vacuum container, and a particle beam source for generating a particle beam for irradiating the target, wherein the target is sputtered by the particle beam source. In a thin film forming apparatus for forming a thin film by adhering and depositing particles emitted from the target on a substrate, an organic compound introducing mechanism for introducing a gas or liquid substance into a vacuum at room temperature and normal pressure And a cooling head that adsorbs the introduced organic compound and solidifies it to form a solidified layer, and a cooling head that cools and holds the introduced substance at a temperature equal to or lower than the melting point of the organic compound, and uses the solidified layer as a target, and particles in the target. An organic thin film forming apparatus, which irradiates a particle beam from a radiation source to form a thin film of an organic compound on the substrate. 10. The organic thin film forming apparatus according to claim 9, further comprising a laser beam generator for irradiating a laser beam in addition to the particle beam source for irradiating the target with a particle beam. 11. The organic compound introducing mechanism comprises a pressure / temperature control chamber capable of controlling the pressure and temperature of the organic compound to a predetermined value, one end of which communicates with the pressure / temperature control chamber, and the other end of which has an outlet. The organic thin film forming apparatus according to claim 9, further comprising: an organic compound introducing tube having the organic compound introducing tube. 12. The organic compound introducing pipe is formed so as to be movable on a cooling head.
The organic thin film forming apparatus described. 13. The outlet of the organic compound introducing pipe,
The organic thin film forming apparatus according to claim 11, comprising a plurality of small holes. 14. The organic thin film forming apparatus according to claim 11, wherein a portion of the organic compound introducing pipe having a blowout port is formed so as to be swingable. 15. A vacuum container, a target placed in the vacuum container, and a particle beam source for generating a particle beam for irradiating the target, wherein the target is sputtered by the particle beam source. In a thin film forming apparatus for forming a thin film by adhering and depositing particles emitted from the target on a substrate, an organic compound introducing mechanism for introducing a gas or liquid substance into a vacuum at room temperature and normal pressure And a cooling head that adsorbs and solidifies the introduced organic compound to form a solidified layer, and cools and holds the introduced substance at a temperature equal to or lower than the melting point of the organic compound, and the cooling head has a cylindrical shape or a cylindrical shape. Along with the formation, the solidified layer is formed on this surface as a target, and the target is irradiated with a particle beam from the particle beam source to form a thin film of an organic compound on the substrate. The organic thin film forming apparatus characterized by. 16. A vacuum container, a target placed in the vacuum container, a particle beam source for generating a particle beam for irradiating the target, and a sputtering process for the target by the particle beam source. A substrate on which particles emitted from a target are deposited to form a thin film and an organic compound at room temperature
An organic compound introduction mechanism for introducing a gas or a liquid substance into a vacuum under normal pressure, and an introduced substance below the melting point of the organic compound in order to adsorb and solidify the introduced organic compound to form a solidified layer. A cooling head for cooling and holding the cooling head, the cooling head is formed in a cylindrical shape or a cylindrical shape, and the substrate is configured to be movable in a direction substantially parallel to the cooling head, and on the surface of the cooling head. An organic thin film characterized by forming the solidified layer as a target, irradiating the target with a particle beam from the particle beam source, and forming a thin film of an organic compound on the substrate while moving the substrate. Forming equipment. 17. The organic thin film according to claim 15, wherein the columnar or cylindrical cooling head is provided with a mechanism for rotating the cooling head around its central axis. Forming equipment. 18. The organic thin film forming apparatus according to claim 16, further comprising a control mechanism for arbitrarily controlling the moving speed of the substrate. 19. A vacuum container, an introduction pipe for introducing a gas as a raw material of particle beam into the vacuum container, and a cooling temperature of the raw material gas introduced through the introduction pipe and a temperature lower than the melting point of the raw material gas. A cooling plate on which a solidified layer of raw material gas is formed, an ion source for irradiating the solidified layer of raw material gas formed on the surface of the cooling plate to release sputtered particles, and for taking out particles sputtered by the ion source And a opening provided in a part of the vacuum container. 20. The particle beam generator according to claim 19, further comprising means for ionizing particles emitted from the solidified layer on the surface of the cooling plate by sputtering. 21. The particle according to claim 19, wherein the cooling plate is electrically insulated from the vacuum container, and further comprises bias voltage applying means for applying a bias voltage to the cooling plate. Line generator. 22. The particle beam generator according to claim 19, wherein the cooling plate is concave toward the opening. 23. The particle beam generator according to claim 19, wherein a plurality of the ion sources are provided. 24. A film forming chamber having a substrate in communication with the opening of the particle beam generator according to claim 19, wherein the substrate is formed by using the particle beam from the particle beam generator in the film forming chamber. A thin film forming apparatus, characterized in that a thin film is formed thereon. 25. A processing chamber having an object to be processed is provided in communication with the opening of the particle beam generator according to claim 19, and the particle beam from the particle beam generator is used in the processing chamber to perform the processing. An etching apparatus for etching a processed object. 26. Irradiating a target made of an organic compound with a particle beam having an energy that is high enough to cut a molecular crystal bond and not high enough to cut a non-molecular crystalline bond among bonds of an organic compound. A method for forming an organic thin film, which comprises forming an organic thin film on a substrate by sputtering and scattering particles by the sputtering. 27. A target made of an organic compound is added to about 1
A method for forming an organic thin film, which comprises irradiating a particle beam having an energy of 0 electron volt or less and performing sputtering to form an organic thin film on a substrate with particles scattered by the irradiation. 28. A vacuum container, a target made of an organic compound placed in the vacuum container, a particle beam for irradiating the target, and a target made of the organic compound by the particle beam. An organic thin film forming apparatus, comprising: a particle beam source that forms an organic thin film by depositing and depositing particles emitted from the target on a substrate by sputtering.