JPH0324262A - Formation of organic thin film and device thereof and corpuscular ray generator - Google Patents

Abstract

PURPOSE:To form the org. thin film which is free from pinholes and intrusion of impurities by irradiating an org. compd. target with corpuscular rays which cut the molecular crystalline bonds of the org. compd. but do not cut the non- molecular crystalline bonds at the time of forming the thin film by the above- mentioned target. CONSTITUTION:An argon ion beam 20 is generated from an ion source 2 in a vacuum vessel 1 evacuated to a vacuum and the target 8 consisting of the org. compd. is irradiated with this beam by which sputtering particles 21 are splashed and the org. thin film is formed on a heated substrate 7. The target is then irradiated with the particle rays having the energy of about <=10 electron volts so as to cut the molecular crystalline bonds by Van der Waals force connecting the respective atoms constituting the org. compd. but not to cut the non-molecular crystalline bonds by the force exclusive of the Van der Waals force. The org. thin film which is free from disturbance in molecular compsn., molecular arrangement, etc., is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for forming an organic thin film and an apparatus therefor. Concerning thin film forming methods and equipment. [Prior Art] As a conventional method for forming an organic thin film, a wet process (wet method) has been mainly used. The feature of this wet process is that it can easily form a relatively uniform film, as seen in the spin coating method and the casting method. Therefore,
Since the wet process has excellent productivity, it is widely applied to film forming processes such as photoresists for lithography, interlayer insulating films for semiconductor devices, and liquid crystal alignment control films for liquid crystal display devices.

On the other hand, as a dry process (dry method) thin film forming method, there is a vacuum vapor method. For example, Journal of Applied Physics, Volume 36, Nα4, 194
5 April pages 1453 to 1460 (JOUR
NAL OF APPLIED PI{YSICSVO
LUME36. NUMBER4 APRIL 196
5 pp1453-1460), there is a report on the formation of organic single crystal thin films. According to this method, it is possible to form a thin film with excellent crystallinity and orientation.

Other dry process methods for forming thin films include:
There is a plasma polymerization method. This is, for example, Journal of the Chemical Society of Japan 81111 (1987) pages 2019 to 202
On page 4, a cyanine plasma polymerized film with a metal lid is reported. According to this method, it is not only possible to form a functional thin film with photoelectric conversion ability, but also to form a thin film that generally has excellent mechanical strength and heat resistance.

[Problem to be solved by the invention]

The organic thin film formation method using the wet process has excellent mass productivity and is currently the best thin film formation method.However, when considering the technical issues with the organic thin film formation method used for the development of next-generation devices, the conventional wet process It has been cursed with some challenges that are difficult to deal with.

For example, liquid crystal displays are required to have higher definition, color, and larger screens, and active matrix liquid crystal displays that integrate display elements and drive circuits are being actively developed.

A single display has tens to hundreds of thousands of transistors formed on a glass plate several tens of square meters in size. Here, uniform formation of a photoresist film in the transistor manufacturing process has become a problem. In the spin coating method, coating is performed by rotating the substrate at about 3000 revolutions per minute in order to obtain a uniform film thickness, but as the substrate becomes larger, the speed at the edge of the substrate becomes faster, approaching the speed of sound. It is impossible with current technology to stably rotate and hold the substrate and apply uniform coating.

Problems with the wet process have also been pointed out for the glabella insulating film of semiconductor devices. Conventionally, polyimide films used as insulating films are made by polymerizing diamino compounds and tetracarboxylic acids (or their derivatives) in an organic polar solvent to form a polyamic acid varnish, which is then cast onto a substrate.
A method of heat drying and polyimidation has been adopted (for example, see Japanese Patent Publication No. 10999/1983). In response to the demand for higher integration of semiconductor devices, sufficient insulation performance is required with a film thickness of about 1 μm, but pinholes cannot be completely removed using the above methods, and impurities are likely to be mixed in. Due to these problems, film quality that can withstand practical use has not been achieved. Additionally, an organic lubricant layer is still formed wet to prevent wear on the magnetic disk surface, but in order to meet the need for increased recording density, the magnetic recording layer, which was conventionally formed by a wet process, is now formed by a dry process. It's starting to look like this. Along with this, in order to maintain the quality of the formed film and improve the efficiency of film formation, it has become necessary to use a dry process for forming the lubricant layer.

In forming organic thin films by dry processes, which should replace wet processes, vacuum evaporation and plasma polymerization have the above-mentioned advantages, but with the former, it is difficult to form large-area films, or the film speed is slow. , 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).

) There is a problem. Regarding the latter, there are problems in that the molecular composition and molecular arrangement are easily disturbed, and it is difficult to control the molecular chain orientation. The present invention was made in view of the above points, and its purpose is to form an organic thin film over a large area and at high speed without pinholes, impurity contamination, and disturbances in molecular composition and molecular arrangement. The purpose of the present invention is to provide a method for forming an organic thin film that can be performed, and an apparatus for realizing the method.

Another object of the present invention is to provide a particle beam generator that utilizes the sputtering phenomenon to obtain a large area particle beam. [Means for solving the problem] The above purpose is to connect a target made of an organic compound placed in a vacuum with molecular crystalline bonds due to the Van der Waals force that connect the atoms constituting the organic compound. A particle beam with energy high enough to break molecular crystalline bonds but not high enough to break non-molecular crystalline bonds among non-molecular crystalline bonds caused by other than Van der Waals forces such as bonds, selective irradiation with particle beams that have energy that can break molecular crystalline bonds, or particle beams that have energy of about 10 electron volts or less, or targets with molecular crystallinity that can be broken by energy of about 10 electron volts or less. This is accomplished by irradiating a particle beam and depositing particles scattered from a target by sputtering on a substrate placed opposite to the target to form a thin film of the desired organic compound.

Furthermore, another purpose is to provide a vacuum vessel, an introduction tube for introducing gas that becomes a raw material for particle beams into the vacuum vessel, and a system for cooling and maintaining the raw material gas introduced through the introduction tube at a temperature below the melting point. A cooling plate on which a solidified layer of raw material gas is formed; an ion source that irradiates the solidified layer of raw material gas formed on the surface of the cooling plate to release sputtered particles; This is achieved by using a particle beam generator consisting of an opening provided in a part of the vacuum container for extraction.

[Effect]

A target made of the above organic compound. When irradiated with the particle beam with the predetermined energy mentioned above, molecular crystalline bonds due to the Van der Waals force that connect the atoms constituting the organic compound, and amorphous bonds due to non-Van der Waals forces such as covalent bonds (both (collectively referred to as heterogeneous molecular crystals), molecular crystalline bonds are broken and molecules connected by non-molecular crystalline bonds are scattered by sputtering. Some of the scattered molecules reach the substrate, where molecular crystals bond again to form a thin film of an organic compound.

In conventional sputtering, the target is irradiated with a particle beam of 500 electron volts to several kiloelectron volts, which breaks many of the molecular bonds in organic compounds.
The target is carbonized. For this reason, it is difficult to form a thin film of an organic compound on a substrate, but in the method of the present invention, the particle beam that irradiates the target 11 is extremely low at about 10 electron volts, so the raw material is carbonized. There are no such problems. Furthermore, the disturbance in the molecular composition etc. within the formed thin film is extremely small6.Moreover, the molecules scattered by sputtering have an energy of 1 to several electron volts, so it is possible to form a dense thin film, and pinholes can be formed. There is little generation of impurities or contamination of impurities. Furthermore, in the present invention, molecular crystalline bonds are broken by particle beam irradiation to cause sputtering.
The sputtering rate is considerably higher than that of conventional methods, and high-speed film formation is possible. Furthermore, in the particle beam generator of the present invention, the gas that is the raw material for the particle beam is supplied to a cooling plate installed in a vacuum, the supplied gas is solidified on the cooling plate, and it is converted into rare gas ions of several kilovolts. Irradiate with. At that time, the particles emitted by sputtering are taken out in the form of a beam. [Example] Hereinafter, the present invention will be described in detail based on the illustrated example.

(Example 1) Figure 1 is a diagram of an apparatus configuration when the present invention is applied to form photoresist on a silicon substrate. As shown in the figure, the vacuum vessel 1 contains a target 8 which is a raw material.
, a silicon substrate 7 attached by a substrate holder 6, a heater 5 for heating this silicon substrate 7, and an ion source 2 are arranged. The inside of the vacuum container 1 is 5 x 1 0-7 by an exhaust device (not shown) from an exhaust port 9.
It is evacuated to Torr.

Using the apparatus shown in FIG. 1, a positive resist consisting of a phenol novolac resin and a naphthoxine azide based photosensitizer was formed.

Phenol novolac resin (manufactured by Gunei Chemical Industry Co., Ltd., weight average molecular weight 2000) is 75% by weight as an alkali-soluble polymer, and naphthoquinonediazide sulfonyl ester of 2,3,4-trihydroxybenzophenone (manufactured by Toyo Gosei Co., Ltd.) is used as a photosensitive dissolution inhibitor. A photosensitive resin composition consisting of 25 wt% , thickness 1IIn). An argon ion beam 20 having an energy of about 6 to 10 electron volts is generated from the ion source 2, and when the target 8 is irradiated with the argon ion beam 20, sputtered particles 21 are scattered and a photoresist film is formed on the 6-inch silicon wafer substrate 7. be done. The temperature of the substrate 7 was about 60° C., and a 1.2 μm photoresist film was obtained in a film formation (ion irradiation) time of 20 minutes. The variation in film thickness measured using a stylus-type film thickness meter was 0.1 μm or less. Striped pattern mask (stripe width 1 μm,
Pitch of 42 μm) was used as the light source, and P manufactured by Canon Inc. was used as the light source.
LA5(IIF (1 1.0mW/a#, 405n
After exposure for 4 seconds using a commercially available developer NMD-
3 (manufactured by Tokyo Ohka). Next, using a parallel plate dry etching device, CIF3 gas pressure↓Qm
Torr. Etching was performed for 5 minutes at a frequency of 13.56 MHz, and the resist film was removed using a commercially available stripping solution S-502 (manufactured by Tokyo Ohka Co., Ltd.) (peeling conditions: 140°C, 10
minutes). For comparison, the above phenol novolak resin and naphthoquinone diazide photosensitizer were dissolved in ethyl cellosolve acetate, and after spin coating, prebaking (85°C, 25 minutes),
A resist film was formed through post-baking (145° C., 20 minutes). Next, development, etching, and peeling were performed using 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 with a pitch of 2 μm, a width of 1 μm, and a depth of 0.5 μm was formed in both samples.

(Example 2) FIG. 2 is a diagram showing the configuration of an apparatus in which the present invention is applied to form a photoresist similar to that in Example 1 on an aluminum plate. As shown in the figure, the vacuum chamber {includes four targets 8 that are raw materials, a substrate 7 attached to a substrate holder 6, an x-Y stage 17 that can move the substrate holder 6 two-dimensionally, and two ion Source 2 is arranged. The vacuum container 1 is evacuated similarly to the apparatus shown in FIG.

The dimensions of one target are 150 m x 1
50 pieces (thickness 1mm), and how to make them is as follows.
This is exactly the same as Example 1. As the substrate 7, a surface-polished aluminum plate of 500 an x 500 nn (thickness: 3 nn) was used. The target 8 was irradiated with an argon ion beam 20 of about 6 to 10 electron volts generated by the ion source 2, and 2 l of sputtered particles were deposited on the substrate 7 to form a photoresist film. At this time, the film was formed while moving the substrate 7 two-dimensionally by moving the X-Y stage 17. The coating time was approximately 40 minutes, and the thickness of the formed resist film was 1.3 μm near the center.
It was confirmed that the corners were coated almost uniformly with a thickness of ~1.2 μm.

Using the mask used in Example 1, pattern exposure was performed at five locations at the four corners and the center, followed by etching and peeling. For etching, the same equipment as in the example was used.
The test was carried out for 5 minutes under AQCQs gas of 5 mTorr. Peeling was carried out in the same manner as in Example t.

The surfaces at five locations were observed using a scanning electron microscope, and it was confirmed that a stripe pattern similar to that in Example 1 was formed. As shown in Example 1.2, according to the present invention, it is possible to pattern a large area, which is difficult with a wet process, and it also reduces the sensitivity of the photoresist, which was a drawback of the conventional dry process. Film speed is also significantly improved. In the present invention, by using sputtering with a low-energy ion beam (particle beam), the highly sensitive resist materials developed so far can be used as they are in a dry process system, and the target made of the organic compound can be used as is. This is because the sputtering rate of this material is considerably higher than that of conventional inorganic resist materials. (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 6-inch silicon wafer heated to 300° C. was used as the substrate 7, which was a thin cylinder made of aminophthalic anhydride formed under pressure. Note that the target 8 was cooled to about room temperature.

The target 8 was irradiated with argon at about 6 to 10 electron volts, and the target 8 was sputtered to form a polyimide film on the substrate 7. Film thickness of 1.5 in approximately 25 minutes of film formation time
A μm polyimide film was obtained. The polyimide film formed was strong and showed no brittleness caused by a decrease in molecular weight. It was confirmed from electrical resistance measurements that the formed polyimide film had good insulation properties. Furthermore, it was confirmed that a film was formed without pinholes, which are difficult to avoid in a wet process.

According to the present invention, polymerization progresses by heating,
Two carboxylic acids adjacent to an amino group in one molecule, such as 4-aminophthalic anhydride, or their ester compounds, which are difficult to form using vacuum evaporation methods, etc.
It becomes possible to sputter a compound containing anhydride and anhydride with almost no change, deposit it on a substrate, and polymerize it on the substrate. As a result, a polyimide film with excellent insulation performance and no pinholes can be obtained.

(Example 4) FIG. 3 is a diagram of an apparatus configuration when the present invention is applied to form a fluorine-containing polymer 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 the substrate holder 6, a heater 5, ions g2, and a laser beam generator 15.
is placed.

The vacuum container 1 is evacuated to about IX10-7 Torr through an exhaust port 9 by an exhaust device (not shown).

The cooling head 10 can be cooled to about the temperature of liquid nitrogen using a refrigerator (not shown). The laser light generator 15 is a pulsed CO2 laser with a maximum output of 1 joule.

Film formation was performed as follows. H C F s and C2F2
The mixed gas was introduced from the gas supply pipe (nozzle) 11 onto the cooling head 10 cooled to liquid nitrogen temperature to form a solidified layer 23, which was used as a target.

The solidified layer 23 is irradiated with an argon ion beam 20 of approximately 6 to 0 electron volts generated by the ion source 2, and
When the infrared laser beam 22 with a wavelength of 10.6 μm is irradiated with 0.5 Joule, the sputtered particles (molecules) 21 are scattered. The part ■ of the particle 21 is a mirror-polished 5-inch aluminum substrate (thickness 1) held at 100°C.
A thin film is formed on top. For the following evaluation test, 100 people formed a film with a thickness of 100. Note that the laser beam 22 is irradiated to increase the generation of radicals.
Although it is possible to form a film without irradiating the laser beam 22,
In that case, the film formation rate decreases.

The obtained film is estimated to be a crosslinked polymer, and the constituent element ratio is C.
: 34.8%, H: 12.3%, F: 52.6%. The film formation rate was 500 A/min. The lubrication performance of the aluminum substrate coated with this fluoropolymer film was tested using a sliding tester.

Using a spherical sapphire slider with a diameter of 30ai, a load of 20
We visually measured the surface after 20,000 rotations at a circumferential speed of 20 m/s and confirmed that the lubricating layer was not destroyed, which revealed that this film had excellent lubrication performance6. It was also confirmed that this film had good corrosion resistance.

For comparison, film formation was also performed using the plasma polymerization method using the same gas mixture as used in this example. Although the obtained film was three-dimensionally crosslinked and had good lubrication performance, it was found that it was easily corroded. The film speed is 35
The rate is about 0 inputs/minute.

According to the present invention, by irradiating a solidified layer of HCF3 and C 2 Fa mixed gas with low-energy ions, a chain-shaped crosslinked polymer thin film can be formed on a substrate, and good sliding performance can be achieved. Not only can this be realized, but it also has the effect of improving corrosion resistance and increasing the film speed compared to conventional plasma polymerization methods.

In film formation using the apparatus shown in FIG. 3, no mention is made of the film conditions such as the pressure and temperature of the raw materials for forming the solidified layer. This point will be explained in detail.

An embodiment of the present invention will be described with reference to FIG. This figure is an apparatus configuration diagram of an a-film forming apparatus capable of controlling the pressure and temperature of the raw material. As shown in the figure, an ion source 2 is placed in a vacuum chamber 1.
However, inside the vacuum container 1 are a substrate 7 attached to a substrate holder 6 and a cooling head for forming a solidified layer of the raw material↓
0, and a raw material introduction pipe 40 for introducing a gaseous or liquid raw material into the vacuum at room temperature and pressure. The raw material is supplied to the raw material introduction pipe 40 by
This is carried out from the pressure/temperature control chamber 42. In the pressure/temperature control chamber 42, the pressure can be controlled by changing the flow rate of the raw material, and the temperature of the raw material can be controlled by operating the cooling plate 4l and the heater 43.

The apparatus of FIG. 4 operates as follows. A raw material made of an organic compound and brought to a predetermined pressure and temperature is supplied onto the cooling head 10 from a raw material inlet pipe 40 . Since the cooling head 10 is maintained at a temperature below the solidification temperature of the raw material by a refrigerator (not shown), a solidified layer 23 is formed. This solidified layer 23 was generated by the ion source 2.
When irradiated with an ion beam of ff1 covolt or less, particles are sputtered from the solidified layer 23 and a thin film of an organic compound is formed on the substrate 7 kept at a predetermined temperature.

When the raw material is a gas, the supply (blowout) of the gas from the raw material introduction pipe 40 is controlled by the pressure/temperature control chamber 42 so that the speed is less than the speed of sound. When gas is blown out at a speed higher than the speed of sound, m-impact waves are generated within the vacuum container 1, which has an undesirable effect on film formation. However, if the gas blowing velocity is less than the speed of sound, the higher the velocity, the more
It was found that the length of the solidified layer 23 was faster. Therefore, when forming a film, it is preferable to set an optimum gas blowing speed to replenish the loss of the solidified layer 23 due to sputtering.

In general, in order to reduce the effects of composition changes due to temperature changes in organic compounds, the temperature of the raw material and the temperature of the cooling head 1 are
The smaller the temperature difference at 0, the better.

When using a gaseous raw material, the temperature of the raw material is 5°C to 10°C higher than the boiling point, and the temperature of the cooling head 10 is . [Good film formation was achieved when the temperature was 5°C to 10°C lower than the melting point of the raw material.

Next, a case where tetrafluoroethylene (CFz=CFz) is used as a specific example of the raw material will be described. The temperature of the raw material is -70℃, 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. forms a solidified layer 23 . This was sputtered by irradiating it with an argon ion beam 20 of about 6 to 10 electron volts to form a thin film on the aluminum substrate 7 maintained at 100°C.

As a result of examining the compositional element ratio of the formed thin film, it was found that the formed i-film was polytetrafluoroethylene←CFt-CFx+
i5, and it was found that there was almost no disturbance in the composition that was observed when the film was formed with the temperature of the raw material at room temperature.

FIG. 5 shows a modification of the thin film forming apparatus capable of controlling the pressure and temperature of the raw material. This apparatus is the same as that of FIG. 4, except that an ion source 45 for irradiating the substrate 7 is provided. Using the apparatus shown in FIG. 5, a thin film was formed on the aluminum substrate 7 using tetrafluoroethylene as a raw material. It was confirmed that the formed film was polytetrafluoroethylene with less disordered composition, similar to the film formed with the apparatus shown in FIG. During one film, the substrate 7 is irradiated with an argon ion beam of about 5 electron volts generated by the ion source 45, so the formed film is
It was found that the film was denser and had better adhesion to the substrate 7 than the film formed using the apparatus shown in the figure.

FIG. 6 shows another modification of the thin film forming apparatus capable of controlling the pressure and temperature of the raw material. The device shown in this figure is almost the same as that shown in FIG. 4, except that the raw material introduction pipe 40 is
The difference is that it is possible to move above 0. By using this apparatus, the thickness of the solidified layer 23 can be made approximately equal, and the 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 part of the raw material introduction pipe 40. Figure 7 (
Figure a) has many holes drilled in the balloon, and figure (b)
Figure (c) shows one in which the blowing part is widened in a taber shape so that the raw material spreads over a wide range, and Figure (c) shows one in which the blowing part has one or more holes and swings. be. When a certain film is formed using a device having these blow-off parts, the thickness of the formed thin film becomes more uniform. As mentioned above, it was confirmed that an organic thin film having good lubrication performance could be formed using the apparatus shown in FIG.

However, in order to apply this thin film forming method to an actual manufacturing process, it is necessary to develop an apparatus that can uniformly form a film over a large area. Below, we will explain the large-area thin film forming apparatus. The structure and operation of the large-area thin film forming apparatus will be explained using FIGS. 8 and 9. As shown in FIG. 8, the vacuum chamber 1 contains ions g2, an introduction pipe 3 for introducing gas or liquid raw materials into the vacuum at room temperature and normal pressure, a cooling head 4, a heating filament 5, and a substrate. A holder 6 and a substrate 7 are arranged. The raw material introduction tube 3 has a pipe shape, and a plurality of holes are formed in at least one row in the axial direction on the surface of the tube. The substrate 7 has a rectangular parallelepiped shape (thickness is thin) that is long in the direction perpendicular to the plane of the paper in FIG.

The cooling head 4 has a cylindrical shape as shown in FIG. 9, and is cooled to a minimum temperature of liquid nitrogen using a refrigerator and an active mechanism 25, and is rotatable around a central axis. ．． The vacuum container 1 is evacuated to about 0-7 Torr by an exhaust device (not shown). For example, a combined gas of H C Fa and CzFefi is introduced into a vacuum through the raw material supply pipe 3. A solidified layer of mixed gas is formed on the surface of the cooling head 4. The solidified layer is approximately 6
When irradiated with an argon ion beam 20 having an energy of ~10 electron volts, the sputtered particles 21
It adheres and deposits on the aluminum substrate 7 maintained at about 00° C. to form a 1a thin film. At that time, although not shown in the figure, the coating speed can be improved by irradiating the vicinity of the solidified layer with C 0 2 laser light to promote the generation of radicals.

The apparatus shown in FIG. 8 can form a thin film on a large-area substrate that is vertically or horizontally long.

Another example of a large-area thin film forming apparatus will be explained using FIG. 10. In this apparatus, the ion source 2, raw material introduction tube 3, cooling head 4, and heating filament 5 are arranged in the vacuum container 1, which is the same as in the apparatus shown in FIG. Reference numeral 7 has a large area that is approximately square, and differs in that it can be moved in the direction of the arrow in the figure by a substrate feeding mechanism 19.

In film formation using this apparatus, a solidified layer of the raw material introduced into vacuum from the raw material supply pipe 3 is formed on the surface of the cooling head 4, and sputtering is caused by the ion beam from the ion source 2 to form a thin film on the substrate 7. The film is formed in the same manner as in the case of the apparatus shown in FIG. Organic thin films with uniform quality and film quality can be formed. In addition, since the cooling head 4 is rotated,
The part forming the solidified layer of the raw material and the ion beam 20
Since the irradiated portion of the ion beam can be separated, a large amount of ion beam can be irradiated, and the coating speed increases accordingly.

Still another example of a large-area thin film forming apparatus will be explained using FIG. 11. In this device, an ion source 2 is placed in a vacuum container l.
, raw material introduction pipe 3, cooling head 4, heating filament 5
, the substrate 7 and the substrate feeding mechanism 19 are arranged the same as in the apparatus shown in FIG. The difference is that it is equipped with 32.

In film formation in this apparatus, the solidified layer of the raw material formed on the surface of the cooling head 4 is irradiated with the ion beam 20, and the sputtered particles 21 are formed into a thin film while moving the substrate 7. , is the same as the case in Fig. 10. At this time, by controlling the feeding speed of the substrate with the speed control circuit 32 and using the slit 30, the thickness of the thin film formed on the substrate 7 can be arbitrarily set, and only a specific part of the substrate 7 can be formed. , it is also possible to carry out selective coating. This is particularly useful in thin film transistor formation processes for displays.

In the examples so far, an ion beam is used to irradiate the target 1- or the solidified layer formed on the surface of the cooling head, but other particle beams such as a neutral particle beam or plasma may also be used. good.

Similar effects can be obtained by using particles other than argon. Filming speed varies depending on the type of particle.

by the way. As a means of generating a particle beam with extremely low energy of 50 electron volts or less, a method is to extract the high-energy electric particles from a plasma source and then decelerate them to obtain low-energy particles 1 (usually an ion beam). is often done. However, this method uses an electrostatic lens to suppress the divergence of the particle beam during deceleration.
When the particle beam is drawn out over a large area, the convergence effect becomes smaller, so
It was difficult to obtain a particle beam with a large area. Therefore, the present invention uses a particle beam generator that utilizes the sputtering phenomenon. The particles of the particle beam for irradiating the target or the solidified layer of the raw material are preferably those that are gaseous at room temperature in order to minimize the incorporation of particles into the target or the film formed on the substrate. In the particle beam generator of the present invention, a gas that is a raw material for particle beams is supplied to a cooling plate installed in a vacuum, the supplied gas is solidified on the cooling plate, and the gas is converted into rare gas ions of several kilovolts. Irradiate with. At that time, the particles released by sputtering are
It is taken out in a beam shape.

The structure and operation of the particle generator will be explained below using FIG. 12. As shown in the figure, the particle generator includes a vacuum container 50.
0, a cooling plate 505, a gas supply pipe 512, an ion source 501.
1! There is some from the child beam generator 517 and the like. Ion source 50
1 is supplied with gas from a gas supply device 513, and a power supply 50
Controlled by 2. The cooling plate 505 is cooled by a refrigerator 506 and is electrically insulated from the vacuum container 500 by an insulator 509, and a DC bias is applied by a bias power supply 510. The gas compensation supply pipe 512 is supplied with raw material gas from a gas supply device 513.

The above particle generator includes a target 524 and a substrate 52.
5 and an exhaust device 521 in an airtight manner. And vacuum! 18500, the film forming chamber 520 is evacuated to about 1×10-BTorr using an exhaust device 52l. The cooling plate 505 is heated to liquid nitrogen temperature (= 1
When the cooling plate 505 is cooled to about 96° C. and argon gas is supplied from the gas supply pipe 512, the argon gas adheres to the cooling plate 505 and solidifies. When this solidified argon gas 507 is irradiated with 3 kiloelectron volt argon ions generated by the ion source 501, argon sputter particles 515
is released. By irradiating this with an electron beam 518, many sputtered particles 515 are ionized.

The sputtered particles spread radially, and the sputtered particles scattered in a direction approximately perpendicular to the surface of the cooling plate 505 can be extracted from the particle generator as an ion beam 519.

FIG. 3 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 the argon particles is often about 1 electron volt, and the half-width of the energy distribution is several electron volts.

In FIG. 14, the energy distribution of argon particles was measured while changing the bias potential of the cooling plate 505, and the relationship between the bias voltage and the average energy of the argon particles was determined. With a bias voltage of about 8.5 volts, approximately 10
It can be seen that an argon ion beam of electron volts can be obtained.

The target 524 is irradiated with the ion beam 519 of approximately 11a subvolt, and a film is formed on the substrate 525. In addition to film formation, the particle beam generator described here can also be used for etching semiconductors and the like by generating a low-energy chlorine ion beam using chlorine gas instead of argon gas. This particle beam generator does not use a grid to extract the ion beam, so there is less dust in the processing chamber where etching is performed, and the energy of the ion beam is low. ) is also advantageous.

Next, a modification of the apparatus explained in FIG. 12 will be explained. The device shown in FIG. 15 is the same as the device shown in FIG. 12 except that the cooling plate 505 has a spherical shape. The first feature of the apparatus shown in FIG.
It is better than the device shown in Figure 2. Note that in the apparatus shown in FIG. 12, the electron beam 528 is used to ionize the sputtered particles 515, but a laser beam may be used instead.

Another variation of the device of FIG. 16 is that the solidified gas 5
The apparatus is the same as the apparatus shown in FIG. 12, except that two ion sources 501 are used to irradiate 07. The amount of ion beam 519 that can be generated with the apparatus shown in FIG. 16 is approximately twice that of the apparatus shown in FIG. In addition, AEON beer
In order to increase the amount of , it is also possible to further increase the number of ion sources.

〔Effect of the invention〕

According to the present invention described above, by irradiating a target made of an organic compound with a particle beam of approximately 10 electron volts or less, molecular bonds in the target material are severed, but non-molecular bonds are The bond is not broken,
Since the sputtered particles adhere and deposit on the substrate to form an organic thin film, it is possible to form an organic thin film free from bottle holes, impurity contamination, and disturbances in molecular composition and molecular arrangement.

In addition, it is easy to make the target larger, make the substrate movable, and increase the amount of particle beam irradiation, which has the effect of allowing large-area organic thin films to be deposited on the substrate faster than before. .

[Brief explanation of the drawing]

Figures 1, 2, and 3 are block diagrams showing an apparatus used for forming a thin film according to an embodiment of the present invention, and Figures 4 and 5 respectively.
, and 6 are configuration diagrams showing a thin film organic forming apparatus capable of controlling the pressure and temperature of the raw material, FIG. 7 is a structural diagram of the raw material blowing part of the apparatus shown in FIGS. The figure shows the structure 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. 12 is a block diagram of a large-area organic thin film forming apparatus which is another embodiment of the present invention, FIG.
Figures 3 and 14 are characteristic diagrams showing the characteristics of the device in Figure 12;
Figures 5 and 6 are diagrams of other particle beam generators used in the embodiments of the present invention. 1... Vacuum container, 2... Ion source (particle generator)
, 3, 11. 40... Gas introduction pipe, 4, ↓ O... Cooling head, 6... Substrate holder, 7... Substrate, 8.
...Target, 15...Laser beam generator, 17.
...X-Y stage, 19... Board feeding mechanism, 20.
...Ion beam, 2l...Sputtered particles, 22...
・Laser light, 23... Solidified layer, 30... Slit, 3
2... Speed control circuit, 42... Pressure/temperature control chamber,
45... Ion source, 500... Vacuum container, 501.
... Ion source, 505 ... Cooling plate, 507 ... Solidified layer, 509 ... Clamping object, 510 ... Bias power supply,
512... Gas supply pipe, 513... Gas supply device, 5
15... Sputtered particles, 517... Electron beam generator, 518... Electron beam, 5↓9... Ion beam, 52o... Film forming chamber, 524 Fig. 4 Fig. 5 Fig. 6 Figure 7 Figure 10 Figure 1. 1 Figure l2 Figure 513 Figure 13 Figure l4 Figure +2345 Particle energy feVl +0 0 10 20 30 Pias voltage (V)

Claims (28)

[Claims] 1. In a thin film forming method in which a target made of an organic compound is irradiated with a particle beam and scattered, and the particles of the target are deposited on a substrate, molecular crystallinity is generated by the Van der Waals force that connects the atoms constituting the organic compound. Among non-molecular crystals caused by forces other than bonds and Van der Waals forces, particle beams with energy high enough to break molecular crystal bonds but not high enough to break non-molecular crystal bonds. A method for forming an organic thin film, comprising irradiating the target to form a thin film of an organic compound on the substrate. 2. In a thin film forming method in which a target made of an organic compound is irradiated with a particle beam and scattered, and the particles of the target are deposited on a substrate, molecular crystallinity is generated by the Van der Waals force that connects the atoms constituting the organic compound. The target is irradiated with a particle beam having energy that can selectively break molecular crystalline bonds among non-molecular crystalline crystals due to forces other than bonds and Van der Waals force, and a thin film of an organic compound is formed on the substrate. An organic thin film forming method characterized by forming. 3. In a thin film forming method in which a target made of an organic compound is irradiated with a particle beam and scattered, and the particles of the target are deposited on a substrate, the target irradiated with the particle beam connects each atom constituting the organic compound. Sputtering is performed to ensure that the molecular crystalline bonds are broken and the non-molecular crystalline bonds are not broken between the molecular crystalline bonds due to the Van der Waals force and the non-molecular crystalline bonds due to forces other than the Van der Waals force. and forming a thin film of an organic compound on the substrate using the scattered particles. 4. In a thin film forming method in which a target made of an organic compound is irradiated with a particle beam to be scattered, and the particles of the target are deposited on a substrate, the target is irradiated with a particle beam having an energy of about 10 electron volts or less, and the particles of the target are scattered. An organic thin film forming method characterized by forming a thin film of an organic compound thereon. 5. In a thin film forming method in which a target made of an organic compound is irradiated with a particle beam to scatter and particles of the target are attached and deposited, the particle beam is applied to a target having molecular crystallinity that can be cut with an energy of about 10 electron volts or less. A method for forming an organic thin film, comprising: irradiating the substrate to form a thin film of an organic compound on the substrate. 6. The target is characterized in that a gas or liquid substance is introduced into a vacuum at room temperature and pressure, and the introduced raw material is adsorbed and solidified on the surface of a cooling head that has been cooled to below its melting point. The organic thin film forming method according to any one of claims 1 to 5. 7. comprising a vacuum container, a target placed in the vacuum container, and a particle beam source that generates a particle beam for irradiating the target, and sputtering the target with the particle beam source to emit the particle beam from the target. In a thin film forming apparatus that forms a thin film by depositing particles on a substrate,
The target is formed of an organic compound, and the particle beam source is capable of irradiating a particle beam with 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 the substrate. An organic thin film forming apparatus characterized by forming a thin film of an organic compound thereon. 8. comprising a vacuum container, a target placed in the vacuum container, and a particle beam source that generates a particle beam for irradiating the target, and sputtering the target with the particle beam source to emit the particle beam from the target. In a thin film forming apparatus that forms a thin film by depositing particles on a substrate,
The target is formed of a material having molecular crystallinity that can be cut by an energy of about 10 electron volts or less, 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. An organic thin film forming apparatus characterized by the following. 9. comprising a vacuum container, a target placed in the vacuum container, and a particle beam source that generates a particle beam for irradiating the target, and sputtering the target with the particle beam source to emit the particle beam from the target. In a thin film forming apparatus that forms a thin film by depositing particles on a substrate,
There is an organic compound introduction mechanism for introducing a gas or liquid substance into a vacuum at room temperature and pressure, and a system for adsorbing and solidifying the introduced organic compound to form a solidified layer. a cooling head that cools and maintains the organic compound below the melting point, targeting the solidified layer;
An organic thin film forming apparatus characterized in that a thin film of an organic compound is formed on the substrate by irradiating the target with a particle beam from a particle beam source. 10. 10. The organic thin film forming apparatus according to claim 9, further comprising a laser beam generator for irradiating a laser beam separately from a particle beam source for irradiating the target with a particle beam. 11. The organic compound introduction mechanism includes a pressure/temperature control chamber that can control the pressure and temperature of the organic compound to a predetermined value, and an organic compound introduction pipe that communicates with the pressure/temperature control chamber at one end and has an outlet at the other end. The organic thin film forming apparatus according to claim 9, further comprising: 12. 12. The organic thin film forming apparatus according to claim 11, wherein the organic compound introduction pipe is formed so as to be movable on a cooling head. 13. 12. The organic thin film forming apparatus according to claim 11, wherein the outlet of the organic compound introduction tube is comprised of a plurality of small holes. 14. 12. The organic thin film forming apparatus according to claim 11, wherein a portion of the organic compound inlet pipe having an outlet is formed so as to be swingable. 15. comprising a vacuum container, a target placed in the vacuum container, and a particle beam source that generates a particle beam for irradiating the target, and sputtering the target with the particle beam source to emit the particle beam from the target. A thin film forming device that forms a thin film by depositing particles on a substrate has an organic compound introduction mechanism for introducing a gas or a liquid substance into a vacuum at room temperature and pressure, and In order to adsorb and solidify the organic compound to form a solidified layer, the cooling head is provided to cool and maintain the introduced substance below the melting point of the organic compound, and the cooling head is formed in a cylindrical or cylindrical shape. An organic thin film forming apparatus characterized in that the solidified layer is formed on a surface of 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. 16. a vacuum container, a target placed in the vacuum container, a particle beam source that generates a particle beam for irradiating the target, and a particle beam emitted from the target by sputtering the target with the particle beam source. A substrate on which particles are attached and deposited to form a thin film, an organic compound introduction mechanism for introducing gas or liquid substances into vacuum at room temperature and pressure, and an organic compound introduction mechanism that adsorbs and absorbs the introduced organic compounds.
In order to solidify and form a solidified layer, the introduced substance is provided with a cooling head that cools and maintains the introduced substance below the melting point of the organic compound, and the cooling head is formed in a cylindrical or cylindrical shape, and the substrate is connected to the cooling head. The cooling head is configured to be movable in a substantially parallel direction, and the solidified layer is formed on the surface of the cooling head to serve as a target, and the target is irradiated with a particle beam from the particle beam source while the substrate is moved. An organic thin film forming apparatus characterized in that a thin film of an organic compound is formed on the substrate. 17. The cylindrical or cylindrical cooling head is
17. The organic thin film forming apparatus according to claim 15, further comprising a mechanism for rotating the cooling head around its central axis. 18. 17. 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 tube for introducing gas that becomes the raw material of the particle beam into the vacuum container, and a solidified layer of the raw material gas on the surface of the vacuum container, which is cooled and maintained at a temperature below the melting point of the raw material gas introduced by the introduction tube. an ion source for emitting sputtered particles by irradiating a solidified layer of raw material gas formed on the surface of the cooling plate; and a vacuum vessel for taking out the particles sputtered by the ion source. An opening provided in a part of the particle beam generator. 20. 20. The particle beam generator according to claim 19, further comprising means for ionizing particles emitted by sputtering from the solidified layer on the surface of the cooling plate. 21. 19. The cooling plate is electrically insulated from the vacuum vessel and includes bias voltage applying means for applying a bias voltage to the cooling plate.
The particle beam generator described. 22. 20. The particle beam generator according to claim 19, wherein the cooling plate has a concave surface toward the opening. 23. The particle beam generator according to claim 19, wherein a plurality of said ion sources are provided. 24. A film forming chamber having a substrate is provided in communication with the opening of the particle beam generator according to claim 19, and a thin film is formed on the substrate using the particle beam from the particle beam generator in the film forming chamber. A thin film forming apparatus characterized by: 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 object to be processed is etched in the processing chamber using the particle beam from the particle beam generator. An etching device characterized by: 26. Sputtering is performed by irradiating a target made of an organic compound with a particle beam whose energy is high enough to break molecular crystal bonds among the organic compound bonds, but not high enough to break non-molecular crystal bonds. An organic thin film forming method characterized by forming an organic thin film on a substrate using flying particles. 27. A method for forming an organic thin film, which comprises sputtering a target made of an organic compound by irradiating it with a particle beam having an energy of about 10 electron volts or less, thereby forming an organic thin film on a substrate using the scattered particles. 28. A vacuum container, a target made of an organic compound placed in the vacuum container, and a particle beam for irradiating the target are generated, and the target made of the organic compound is sputtered with the particle beam. An organic thin film forming apparatus comprising: a particle beam source that forms an organic thin film by depositing particles emitted from a target onto a substrate.