JPH07116596B2 - Thin film forming method and apparatus thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thin film forming method and an apparatus thereof, and in particular,
The present invention relates to a thin film forming method suitable for forming a thin film of a semiconductor, a dielectric, a metal, an insulator, an organic substance, and the like, and an apparatus thereof.

[Conventional technology]

Conventionally, it has been known to use a sputtering method to form a thin film of a metal or a dielectric material. The method is
"Thin film handbook, Japan Society for the Promotion of Science, 131st Committee,
(Ohm Co., December 1983) ”, pages 171 to 195, magnetron sputtering for further high-speed film formation such as DC bipolar sputtering, bias sputtering, and high frequency sputtering. It spans a wide variety of areas such as rings. Also, an ion beam sputtering deposition method as described on pages 190 to 191 of the above document is known.

All of these methods utilize a phenomenon in which a substance in a solid state at room temperature is sputtered by an ion beam or ions in plasma. Therefore, the film formation rate is limited by the sputtering rate of the substance in the solid state.

On the other hand, cooling gases such as carbon monoxide and methane, combining these molecules with the van der Waals force, and sputtering the substance in the solidified state by ion irradiation are, for example, "day soap ingestion". Bi-Electronic Transition DIET
II (Desorption Induced by Electronic Transition DI
ET II) "(edited by W. Brenig, D. Menzel, published by Schewringer, 1985) at pages 170-176.

In this case, the number of atoms or molecules decomposed by spattering by a substance in which a gas such as carbon monoxide or methane is solidified per irradiated ion, the so-called spatter rate is
It is known to be about 100-1000.

Further, a method of irradiating a gas or a solidified substance with a focused laser beam to rapidly give energy to these substances to bring them into a plasma state and forming a thin film by using particles generated in the plasma is disclosed in Japanese Patent Laid-Open Publication No. No. 63-177414.

[Problems to be Solved by the Invention]

Among the above-mentioned conventional techniques, the sputtering method using ions or plasma is all used as a target material for spattering at a solid state at room temperature, and by the spattering mechanism shown on pages 171 to 179 of the “thin film band book”. In this method, the target material is decomposed and scattered, and the scattered spatter particles form a film. in this case,
The spatula rate of the target per ion incident on the spatula target has a value of 1-10, and as a result,
There was a problem that the film formation rate was as slow as 0.1-1 nm / sec.
In principle, the purity of the deposited film does not become higher than that of the target for sputtering, and if a high-purity target for sputtering is not available, a thin film containing impurities and having poor quality. There was a problem that I could only get it.

In the thin film forming method using laser-generated plasma, the mechanism of generating plasma particles is that the target absorbs the energy of photons. Therefore, the kinetic energy of the plasma particles created in this way is smaller than the kinetic energy of the sputter particles created by the irradiation of the target with ions having a large momentum, and therefore the formed curtain is There is a problem in that the properties such as adhesion strength are inferior to those formed by the conventional sputtering method in which large ions are irradiated.

The present invention has been made in view of the above points, and an object of the present invention is to provide a thin film forming method and an apparatus for forming a thin film of high purity and high quality at high speed.

Further, another object of the present invention is to provide a processing method and apparatus capable of efficiently processing any object to be processed such as metal, dielectric, organic substance, semiconductor and the like.

[Means for Solving the Problems]

The first purpose mentioned above is the Van der Waals force in a vacuum,
Alternatively, a target for spattering made of a substance formed by bonding atoms or molecules by hydrogen bonding force is irradiated with a particle beam such as an ion beam, an electron beam, or plasma to cause spattering of the target, and the generated spatter particles are This is accomplished by forming a desired thin film on the substrate by flying in space and irradiating the substrate.

Further, the other purpose described above is to irradiate a substrate with sputter particles generated by spattering a target made of the above-mentioned substances, thereby making it possible to obtain a desired substrate such as a metal, a dielectric, an organic substance, or a semiconductor. It is achieved by processing.

[Action]

In the present invention, the spattering target is usually used as a target for sputtering by solidifying a substance that is in a gas state or a liquid state at room temperature and normal pressure by a method such as cooling to below the melting point. .
That is, in the conventional sputtering deposition method, at room temperature and atmospheric pressure, a substance in which atoms and molecules are strongly bonded to each other by metal bond, ionic bond, or covalent bond is used as a target for sputtering, so the sputtering rate is increased. However, in the present invention, by using a substance in a weakly bonded state by the Van der Waals force, or a hydrogen bonding force as a target for sputtering, the target is subjected to ion irradiation. The mechanism is different, and the number of sputter particles per ion is as large as about 100 to 1000, which enables high-speed film formation.

In addition, by utilizing the above-mentioned action, metal, dielectric, organic matter,
If a substrate material such as a semiconductor is processed, the processing becomes effective.

〔Example〕

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

(Example 1) FIG. 1 shows an apparatus configuration diagram when the present invention is applied to form a metal titanium thin film on a glass substrate.

As shown in the figure, the vacuum vessel 7 has a gas introduction pipe 8 for introducing titanium tetrachloride, which is a raw material of metallic titanium, a refrigerator head 9 for solidifying titanium tetrachloride, and a substrate on which a glass substrate 10 is attached. A holder 11 and an ion source 12 are arranged. First, the inside of the vacuum container 7 is a vacuum pump (not shown).
To 1 × 10 ^-7 Torr by vacuum evacuation, and then the temperature of the frozen base head 9 is changed from room temperature to the melting point of titanium tetrachloride, −25.
Keep cooling to -50 ℃ below ℃. Next, the gas introduction hole 8
Titanium tetrachloride vapor is sprayed onto the freezer head 9 at a rate of 2 cc / min to form a solidified layer 13 of titanium tetrachloride in 5 minutes. Its size is about 100 mm in diameter and 4 mm in thickness.

On the other hand, with the heater 14 for heating the substrate, the diameter is 150 mm and the thickness is 1 m.
The glass substrate 10 of m is heated to 200 ° C. and held, and thereafter, argon gas is introduced from the gas introduction hole 15 for the ion source at a flow rate of 0.5 cc / min, the ion source 12 is operated, and the acceleration energy is 3 keV.
Then, the solidified layer 13 of titanium tetrachloride is irradiated with the argon ion beam 16. At this time, the amount of argon ion current is 1 mA.

As a result of performing the above-mentioned irradiation with argon ions for 10 minutes, the solidified layer 13 of titanium tetrachloride was subjected to a spatula effect by the argon ions and its thickness was reduced to 1 mm. At the same time, 2
A thin film 17 having a metallic luster was formed on the glass substrate 10 heated to 00 ° C.

Metallic thin film 17 formed on this glass substrate 10
Was subjected to an Auger analysis, and a spectrum showing the presence of titanium was obtained. Impurities in this metal film were below the detection limit of Auger analysis, and only a slight amount of carbon was present on the surface and at the interface between the titanium film and the glass substrate, and chlorine, which is thought to be due to titanium tetrachloride, was detected. Nakatsuta.
Further, it was found that the titanium film thickness was 0.6 μm in the step measurement by the Tarisstep method.

In the present embodiment, the titanium thin film was formed using titanium tetrachloride, but other metals and semiconductors also contain these elements, and liquid or gaseous substances at room temperature and pressure are reduced to the melting point or lower. It is possible to cool and form a solidified layer that is bonded by the Van der Waals force, and to form a thin film of any metal or semiconductor by the same method as in this embodiment.

(Example 2) FIG. 2 is a device configuration diagram when the present invention is applied to form a titanium silicide alloy film.

As shown in the figure, the vacuum vessel 20 was evacuated to 1 × 10 ⁻⁷ Torr by a vacuum pump (not shown), and then the freezer head 21 was kept at −90 ° C. 3cc each of titanium tetrachloride (melting point: -25 ° C) and silicon tetrachloride (melting point: -70 ° C) were introduced through two gas introduction holes 22 and 23, and titanium tetrachloride and silicon tetrachloride A mixed solidified layer 24 was formed. At this time, the size of the solidified layer is 40 mm in diameter and about 3 mm in thickness.

Next, neon gas is introduced into the ion source 25 through the gas introduction hole 26, and the neon ion beam 27 is extracted at an acceleration voltage of 1 keV,
The solidified layer 24 was irradiated. At the same time, a silicon wafer substrate 28 having a diameter of 3 inches was placed in the vacuum container 20 and heated and held at 300 ° C. by the heater 29.

As a result of 10 minutes of irradiation of neon ion beam, the solidified layer 24
The thickness of the silicon wafer substrate 2
A thin film 19 was deposited on the 8. The thickness of the thin film 19 was 700 nm when measured by the Tarisstep method. In addition, when the elemental composition analysis of the thin film 19 was performed by a separate laser backscattering ion spectrometer, titanium to silicon was 2: 1.
It turned out to be the ratio of. The electric resistance value of this thin film 19 was almost the same as the electric resistance value of the titanium silicide film formed by the co-evaporation method.

In this example, a binary alloy called titanium silicide was prepared by ion-sputtering the mixed solidified layer of two kinds of gases of titanium tetrachloride and silicon tetrachloride, but this example is not necessarily limited to two kinds of gases. However, the present invention can also be applied to forming various thin films composed of multi-component elements by ion-sputtering a mixed solidified layer of a plurality of gas species provided with a plurality of gas introduction holes.

(Example 3) FIG. 3 shows an apparatus configuration diagram when the present invention is applied to produce a multi-source substance or a multilayer thin film using a plurality of substances having significantly different melting points as raw materials.

In this embodiment, CF ₄ (melting point: −184 ° C.) and WF ₆ (melting point: 2.3 ° C.) are used to form a multilayer film of carbon and tungsten.

In a vacuum container 30 evacuated to 1 × 10 ⁻⁷ Torr, two cooling heads 31,32, two gas introduction holes 33,34 and two ion sources similar to those used in Example 1 were used. 35, 36 and a silicon wafer substrate 37 having a diameter of 3 inches were arranged. This silicon wafer substrate 37 is heated to 400 ° C by the heater 38.
Retained.

The temperatures of the cooling heads 31 and 32 are limited to −200 ° C. and −10 ° C., respectively, and 4 cc of CF ₄ and WF ₆ gases are introduced from the gas introduction holes 33 and 34, respectively, and the CF ₄ solidified layer 39 and WF ₆ are introduced. A solidified layer 40 and a solidified layer 40 were formed.

A neon ion beam 41, 42 from the ion source 53, 36 to the above two solidified layers 39, 40, respectively, at intervals of 10 seconds 50 times, and a CF ₄ solidified layer
39 and WF ₆ solidified layer 40 were irradiated. As a result, on the silicon wafer substrate 37, as shown in FIG. 4, a multi-layer film 43 composed of carbon 44 and tungsten 45 could be formed.
The carbon film 44 and the tungsten film 45 each have a thickness of 1 nm,
It was 3 nm. The carbon / tungsten multilayer film 43 thus formed can be used as a mirror for axial X-rays.

In this embodiment, a binary multi-layer film was formed by forming two solidified layers and a spatula mechanism, but this embodiment is not limited to the binary multi-layer film, and two or more may be formed. It can also be applied to the formation of a plurality of solidified layer forming / sputtering mechanisms to form a multi-layered film / alloy film having a multidimensional complex structure.

(Embodiment 4) FIG. 5 shows an excitation beam such as an ion beam, an electron beam or a radical beam on the surface of the substrate in order to form a higher quality thin film in the thin film forming method shown in the first embodiment. It is the figure which shows the device block diagram which simultaneously irradiates at the time of thin film formation.

The structure of this embodiment is the same as that shown in FIG. 1 except that an ion source 50 for irradiating the substrate is added.

Next, the operation will be described. 1 x 10 for the vacuum container 51
After exhausting to ^-7 Torr, the cooling head 52 is cooled to -50 ° C, 5 cc of SiCl ₄ gas is introduced from the gas introduction hole 53, and the size of 40 mm in diameter x 4 mm thick SiCl ₄ is placed on the cooling head 52. A gas solidified layer 54 was formed, and then a glass substrate 55 having a diameter of 100 mm and a thickness of 1 mm was heated to 200 ° C. by a heater 56. Argon gas is introduced into the first ion source 57 and the acceleration energy is 1 keV.
The argon ion beam 58 is applied to the SiCl ₄ solidified layer 54 for 10 minutes at the same time, and at the same time, the argon gas is also introduced into the second ion source 50, and the glass substrate 55 is accelerated with an acceleration energy of 1500 eV.
The surface was illuminated. As a result, reaction intermediate product particles 59 of SiCl ₃ , SiCl ₂ , SiCl, etc., which have been sputtered from the solidified layer 54 and reached the surface of the glass substrate 55 by the first argon ion beam irradiation.
Is the heating effect of the substrate and the ion bombardment effect on the substrate surface,
Furthermore, the surface decomposition reaction was accelerated and the deposition of 60 of the silicon film was accelerated.

Impurities in the silicon film 60 deposited on the glass substrate 55 are
When measured by secondary ion mass spectrometry, the amount of chlorine was below the detection limit and only the isotope peak of silicon was observed. Also. The thickness of the obtained polycrystalline silicon film is 1 μm
Therefore, a larger film formation rate was obtained as compared with the case where the second ion beam was not irradiated.

In this example, argon ion irradiation was performed in order to accelerate the film formation reaction on the substrate surface, but in addition to this, depending on the properties of the desired thin film, the electron beam is irradiated on the substrate surface. The film formation reaction can be accelerated by irradiating radical particles such as hydrogen or irradiating light such as excimer laser light.

Further, instead of the argon ion beam used in this example, it is also possible to irradiate the surface of the substrate with a nitrogen ion beam and cause a chemical reaction on the surface of the substrate to form a silicon nitride film. It is also possible to irradiate the surface of the substrate with a surface reaction to form a silicon oxide film.

(Example 5) FIG. 6 shows an apparatus configuration in the case where the present invention is carried out to produce an iron nitride by using a molecular beam vapor deposition apparatus.

As shown in the figure, 10 cc of nitrogen gas having a melting point of 77K is introduced from a gas introduction hole 63 into a cooling head 62 cooled to 70K in a vacuum chamber 61 of a molecular beam deposition apparatus that has been evacuated to 2 × 10 ^-10 Torr. did. Then, on the cooling head 62, the diameter 30
mm, a solidified layer 64 of nitrogen having a thickness of 5 mm is formed, and at the same time, helium gas 66 is introduced into the ion source 65, and the nitrided solidified layer 64 is sputtered at an acceleration energy of 1 keV to form spatter nitrogen particles 67. Raised. Further, an electron beam evaporation source 68 containing pure iron pellets having a purity of 5N was operated to generate iron vapor 69.

The nitrogen spatter particles 67 and the iron vapor 69 generated in this way are heated by the heater 70 and kept at 300 ° C.
The shutters 72 and 73 were alternately opened and closed for 1 second so that the (001) crystal substrate 71 was irradiated. After irradiation for 10 minutes, the GaAs crystal substrate 71 is taken out from the vacuum container 61,
Foil 74 deposited by X-ray diffraction and Auger elemental analysis
Analysis of the composition and structure revealed that it was an iron nitride film epitaxially grown on the GaAs crystal surface. The film thickness was 20 nm and its structure was Fe ₁₆ N ₂ .

As described above, by using the molecular beam vapor deposition apparatus and incorporating the sputter particle generation portion of the present embodiment therein, it is possible to realize a vapor deposition method that cannot be performed only by the conventional molecular beam vapor deposition method.

(Example 6) FIG. 7 is a device configuration diagram when the present invention is used for forming an organic thin film in which a metal is dispersed by using a cluster ion beam vapor deposition device.

As shown in the figure, in the vacuum container 80 of the cluster ion beam vapor deposition apparatus that was evacuated to 2 × 10 ⁻⁷ Torr,
A cooling head 81 cooled to 120 ° C. is arranged, and a solidified layer 82 of methylamine (CH ₃ —NH ₂ ) having a melting point of −93.46 ° C. is placed thereon.
Was formed. The size was 5 cm in diameter and 5 mm in thickness.

Then, acceleration energy from the ion source 83 is applied to the solidified layer 82.
A helium ion beam 84 of 3 keV and a current amount of 100 μA was irradiated to generate spatter particles 85, which were then irradiated onto a substrate 86.
At the same time, gold cluster ions 88 were generated from the gold cluster ion generator 87 arranged in the vacuum container 80, accelerated with an accelerating voltage of 8 keV, and irradiated onto the substrate 86. As the substrate 86, a flexible polyimide film having a size of 100 mm × 100 mm and a thickness of 10 μm, on which a copper thin film was vapor-deposited with a thickness of 100 nm, was used.

Irradiation of the above-mentioned spatter particles 85 and gold cluster ions
After irradiation with 88 at the same time for 10 minutes, the flexible polyimide film substrate 86 was taken out from the vacuum container 80. As a result, C-N containing uniformly dispersed gold and containing amino groups was obtained.
An -H-based organic thin film 89 is formed with a thickness of 400 nm, and its resistance value changes very sensitively to the amount of water in the air,
It changed from 10 ^-10 ohm.cm to ^{10 -1} ohm.cm.

In this way, a thin film of a new substance can be formed by using a cluster ion beam vapor deposition apparatus or the like and incorporating the sputter particle generation portion of this embodiment therein.

(Embodiment 7) FIG. 8 is a device configuration diagram in the case where the present invention is applied to a high frequency bipolar electrode sputtering device to form a cubic boron nitride thin film.

As shown in the figure, in the parallel plate type high frequency sputtering electrode placed in a vacuum container 90 which is evacuated to 2 × 10 ⁻⁷ Torr, a refrigerator is attached to an upper electrode 91 to which a high frequency voltage of 13.56 MHz is applied. 92 is connected and the temperature of the electrode surface is -150 ° C.
Cooled to. Ammonia gas (melting point: −77.7 ° C.) and boron trifluoride (melting point: −127) are introduced through the gas introduction hole 93.
) And argon gas (melting point: -189.2 ° C) are introduced at 5 cc / min, 10 cc / min, and 10 cc / min, respectively, and the upper electrode 91
A solidified layer 94 of these mixed gases having a thickness of about 5 mm was formed on the surface of the.

A silicon wafer substrate 96 having a diameter of 3 inches was arranged on the lower ground electrode 95.

Under the above conditions, the gas pressure inside the vacuum container 90 is set to 3 × 10 ^-4 Torr.
While maintaining at, a high frequency voltage of 200 W was applied and an argon discharge was performed for 10 minutes. After that, when the thin film 97 having a thickness of 400 nm deposited on the silicon substrate was measured by the X-ray diffraction method,
It was found to be boron nitride having a cubic structure. Its hardness was 2000 in Vickers hardness.

In the present embodiment, the method of forming the condensed gas solidified layer on the electrode part of the bipolar high frequency sputtering device is adopted, but the present embodiment is applied to other sputtering devices such as a triode sputtering device and a magnetron sputtering device. It is also possible.

Example 8 This example shows an apparatus for uniformly forming a solidified layer of condensed gas. As shown in FIG. 9 (a), when the copper cooling holder 101 having a diameter of 10 cm is connected to the cooler head 102 in the vacuum container 100, the temperature on the surface of the cooling holder 101 is −60 ° C. at the center, and the surrounding area. The spacer 103 was sandwiched so that the temperature became −40 ° C. at a portion, and a gas introduction hole 104 having 400 small holes with a diameter of 0.1 mm was formed on the circumference in the vicinity of the cooling holder 101. As a result, the temperature distribution in the radial direction on the surface of the cooling holder during cooling is low in the central portion and high in the peripheral portion near the gas introduction hole 104, as shown in FIG. 9B. A titanium tetrachloride gas was introduced at a flow rate of 2 cc / min, and a solidified layer 105 of titanium tetrachloride having a thickness of 4 mm was formed on the surface of the copper cooling holder 101 having a diameter of 10 cm, as shown in FIG. 9 (c). Were uniformly formed, and the film thickness distribution was within 5%.

In this way, the temperature distribution on the surface of the cooling holder is controlled so that the portion farther from the gas introduction hole is lower than the temperature of the closer portion, so that the temperature distribution is uniform for any gas. A solidified layer of thickness can be created.

(Example 9) FIG. 10 shows the structure of a cooling target for forming a uniform thin film used in the present invention.

As shown in the figure, in the vacuum vessel 110, a cooling target 112 having a diameter of 8 cm for depositing the solidified layer 118 is structured to be rotatable by a bearing, and heat is conducted between the rotary cooling target 112 and the refrigerator head 113. A structure in which thin copper wires 114 having a large ratio are bundled and brought into contact with each other. Keep the refrigerator head 112 at -80 ° C and use the rotary cooling target 1
When 12 was rotated at a rate of 1 revolution per minute, the temperature of the surface of the cooling target 112 reached -50 ° C.

Under the above conditions, the titanium tetrachloride gas is supplied to the rotary cooling target 112 at a flow rate of 0.5 cc / minute from the gas introduction hole 115 arranged near the outer periphery of the cooling target 112, or the vacuum container 110 is used.
The helium ion beam 117 extracted from the ion source 116 attached to the was sputtered on the titanium tetrachloride solidified layer 118 formed on the rotating target 112 at an accelerating voltage of 1 kV, and the size placed in the vacuum vessel 110 was 100 mm in diameter. Glass substrate 11
When the titanium metal film 120 was formed on the film 9, the variation in the film thickness was within 3%.

In this embodiment, since the cooling target 112 is rotating at a constant speed, even if the cooling target 112 is sputtered by the helium ion beam 117, the solidified layer 118 is always constantly formed. Generation conditions are constant over time, and a uniform thin film can be formed.

In this embodiment, the cooling target 112 is connected to the gas introduction hole 1
Although the method of rotating the ion beam 117 is adopted, the same effect can be obtained by changing the cooling target 112 to the gas introduction hole 115.
It can also be obtained by moving the ion beam 117 relative to the ion beam 117 by means such as a linear reciprocating motion.

(Example 10) FIG. 11 shows a method for forming a thin film uniformly on a large-area substrate.
It is a block diagram which shows the principle of the method of operating the irradiation position of the ion beam which spreads the condensed gas solidification layer surface of a large area in time.

A solidified layer 121 of titanium tetrachloride having a thickness of 5 mm was formed on a surface of a cooling target 126 having a side of 40 cm and kept at −50 ° C., and a helium ion beam 122 extracted from an ion source 127 was formed on the surface of the scanning electrode 123. Then, the solidified layer 121 was electrically operated two-dimensionally to irradiate a 30 cm square area of the solidified layer 121. As a result, 30c
It was possible to uniformly form the titanium metal film 125 having a thin film of 500 mm on the glass substrate 124 having an area of m × 30 cm × 1 mm.

In the present embodiment, the ion beam is scanned by an electrical method, but it is also possible to scan the ion beam by a mechanical method or the like. Also, the substrate on which the thin film is to be formed is moved relative to the cooling target,
It is also possible to form a uniform thin film in a large area.

(Embodiment 11) FIG. 12 shows an apparatus configuration diagram when the present invention is applied to the processing of a silicon semiconductor by sputtering a solidified layer of sulfur hexafluoride with an ion beam.

As shown in the figure, the vacuum container 130 is set to 1 × 1 by a vacuum pump.
After evacuation to 0 ^-7 Torr, freezer head 131 is
The temperature was maintained at 100 ° C., 3 cc of sulfur hexafluoride (melting point: −50.8 ° C.) was introduced into the refrigerator head 131 through the gas introduction hole 132, and a solidified layer of sulfur hexafluoride 133 was formed on the refrigerator head 131. . The size of the solidified layer at this time was 40 mm in diameter and about 5 mm in thickness.

Next, an argon gas is introduced into the ion source 134 through the gas introduction hole 135, an argon ion beam 136 is extracted at an accelerating voltage of 1 keV, and the solidified layer 133 is irradiated with the sputter particles F, SF, SF ₂ and SF _3. It was generated radicals 137 of SF _4, SF ₅ or the like.

A silicon wafer substrate 139 having a diameter of 3 inches which was patterned by a photoresist mask 138 was placed in a vacuum container 130, and the surface thereof was irradiated with the above-mentioned spatula radical 137 for 10 minutes. As a result, the thickness of the solidified layer 133 was reduced to 1 mm, and the portion of the surface of the silicon wafer substrate 135 not covered with the photoresist mask 138 was etched to a depth of 2 μm.

In the present embodiment, the solidified layer of sulfur hexafluoride gas was ion-sputtered to process a silicon semiconductor.However, in the present invention, a radical species such as a halogen atom that chemically reacts with a workpiece is generated. Any compound to be processed can be processed by using a solidified layer that can be formed.

(Example 12) FIG. 13 shows that a solidified substance of titanium tetrachloride is formed in a place different from the vacuum container 150 for forming the thin film, and the titanium tetrachloride substance in the solidified state is formed into a thin film. 1 shows an apparatus for forming a titanium thin film by the method of the present invention by introducing it into a vacuum container 150 for performing the above.

As shown in the figure, the vacuum container 150 is connected to another vacuum container 152 via a gate valve 151. In the vacuum container 150, a target holder 154 for storing a solidified substance 153 of titanium tetrachloride, an ion source 155, and a glass substrate 157 on which a titanium thin film 156 is to be formed are arranged.

In the vacuum container 152, a cylinder 158 containing titanium tetrachloride,
A gas leak valve 159, a gas introduction pipe 160, a refrigerator 161, and a solidified substance conveying head 162 are attached.

After evacuating the vacuum vessel 152 to 1 × 10 ^-6 Torr, the refrigerator 161 is operated to reduce the temperature of the refrigerator head to −50.
℃ was made. Next, the gas leak valve 159 was opened, titanium tetrachloride gas was introduced into the vacuum container 152, and the pressure inside the vacuum container 152 was set to 1 × 10 ^-2 Torr. After 30 minutes, when the gas leak valve 159 is closed, a solidified product 163 of titanium tetrachloride having a thickness of about 5 mm is formed on the refrigerator head 161.
Moreover, the degree of vacuum returned to 1 × 10 ^-6 Torr.

At this time, the gate valve 151 is closed and the vacuum container 150 is
It was evacuated to 1 × 10 ^-9 Torr by another vacuum pump.

Next, using the solidified substance conveying head 162, a small piece of the solidified substance 163 of titanium tetrachloride was scraped off by about 3 mm, the gate valve 151 was opened, and the small piece was conveyed onto the target holder 154.

The solidified material conveying head 162 is returned into the vacuum container 152, the gate valve 151 is closed, and the freezing head 161 is again closed in the same manner.
A solidified material of titanium tetrachloride was formed on top. Then, the above operation was repeated 10 times to deposit 10 small pieces of the solidified substance of titanium tetrachloride on the target holder 154.

By a method similar to that described in Example 1, argon gas was introduced into the vacuum container 150, and an argon ion beam with an acceleration energy of 3 keV generated from the ion source 155 was used.
The glass substrate 15 is sputtered with the solidified substance of titanium tetrachloride.
It was possible to obtain a titanium thin film 156 having a thickness of 0.6 μm on 7.

According to this method, only titanium tetrachloride in a solidified state is introduced into the vacuum container 150, and titanium tetrachloride gas is less likely to be adsorbed on the wall surface of the vacuum container 150. The degree of vacuum can always be kept low.
Therefore, the vacuum container 150 can be always kept clean, and the quality of the formed film is improved. Further, the life of the vacuum container 150 is long.

(Example 13) FIG. 14 shows that when a raw material is cooled by a freezer to form a material in a state where it is bound by a Van der Waals force, the temperature of the freezer is lowered step by step, A device for forming a solidified layer of the raw material gas by first solidifying, in the first cooling process, components of the gas remaining in the film which are not desired to be taken into the film, and then introducing the raw material into the refrigerator head. FIG. 15 shows the constitution, and the temperature change of the refrigerator head at that time.

As the raw material of the example shown in the figure, titanium tetrachloride having a melting point of -25 ° C was selected as in Example 1.

As shown in FIG. 14, in a vacuum container 170, a 0.2 mmφ enamel wire heater 173 was connected to a refrigerator head 172 of a gas helium refrigerator 17 having a refrigerating capacity of 5 W utilizing the adiabatic expansion phenomenon of gas helium. The heater 173 is energized by a heater control power supply 174 to heat the refrigerator head 172. A thermocouple 175 is attached to the refrigerator head 172 using a chromel-alumel wire, and the output power of the heater control electrode 174 is controlled based on the electromotive force of the thermocouple 175, and the difference with a constant refrigerator output is set. , Control the temperature of the refrigerator head 172.

Next, the specific method will be described.

First, in the vacuum container 170, the refrigerator 171 is operated, a current of 0.2 A is applied to the heater 173, and the temperature of the refrigerator head 172 is kept at room temperature (25 ° C) for 10 minutes as shown in Fig. 15. The temperature was changed to −10 ° C. and kept at −10 ° C. for 1 hour.

In the meantime, residual gas components such as water remaining in the vacuum container 170 are adsorbed and frozen on the surface of the refrigerator head 172.
As shown, a first solidified layer 176 was created.

Next, with the refrigerator output in the same state, set the heater energization current to 0.
The temperature of the refrigerator head 172 was lowered to -50 ° C from -10 ° C after 10 minutes, as shown in Fig. 15. Thereafter, while maintaining the temperature at −50 ° C., titanium tetrachloride gas was introduced through the gas introduction hole 177 at a rate of 2 cc / min for 30 minutes, and titanium tetrachloride having an average thickness of 8 mm was formed around the first solidified layer 176. A solidified layer 178 was formed.

The substrate 180 was irradiated with an argon ion beam 179 with an acceleration energy of 3 keV for 10 minutes so that only the solidified layer 178 of titanium tetrachloride formed in this way was sputtered. A metallic titanium film 181 was formed.

As a result, the light reflectance of the formed titanium metal film was as high as 10% as compared with the case of Example 1. In addition, as in this example, before introducing the raw material, the refrigerator head 173
Temperature, or by placing a cooling panel in the vacuum container 170 and adsorbing and trapping residual gas components such as water in the vacuum container 170 at those temperatures, a thin film containing less of these impurity gases is formed. can do.

(Embodiment 14) FIG. 17 is a schematic view of a thin film forming apparatus for facilitating the formation of a high quality thin film by providing a cooling panel in the vacuum container for adsorbing and trapping the gas evaporated from the solidified substance. Show.

In the figure, in the vacuum container 190, a refrigerator head 191,
An ion source 192, a substrate 193 with a heating mechanism, and a gas introduction hole 194 are provided.

A cooling trap 196 containing liquid nitrogen 195 was placed around these, and the temperature was set to 80K.

As a result, as shown in detail in FIG. 18, the solidified condensation layer 197 of the source gas (titanium tetrachloride, etc.) is irradiated with the ion beam 198, and the spatter particles 199 and the evaporated particles 2 are spread in all directions.
Generate 00. Of these, particles that do not reach the substrate 193 are re-condensed and solidified on the surface of the cooling trap 196, and are captured, and do not reach the substrate 193 again.

Thanks to the trap action of this cooling trap 196, the substrate 1
It is possible to extremely suppress the particles once reflected on the inner wall of the vacuum container 190 from reaching the surface of 93 again.
The quality of the film formed on the substrate 193 was easily controlled.

(Example 15) FIG. 19 shows an example of an apparatus for forming a multilayer thin film on a substrate 217, in which two refrigerator heads 211 and 212, two gas introduction holes 213 and 214, and two ion sources 215 and 216 are provided in a vacuum container 210. Show.

In the figure, the temperatures of the refrigerator heads 211 and 212 are cooled to −100 ° C. below the melting points of silicon tetrachloride (SiCl ₄ ) and germanium tetrachloride (GeCl ₄ ), respectively, through the gas introduction holes 213 and 214.
Introducing the above gases independently, silicon tetrachloride,
Solidified layers 218 and 219 of germanium tetrachloride were prepared.

Then, as shown in FIGS. 20 (a) and 20 (b), the ion source
The operating time of 215, 216 is changed, and alternately for 10 seconds each, Ar
The solidified layers 218 and 219 were respectively irradiated with (argon) ion beams, and the solidified layers 218 and 219 were intermittently sputtered.

As a result, on the substrate 217, the spatter particles 220 containing silicon and the spatter particles 221 containing germanium are alternately swung, and the film thickness is on the glass substrate 217 heated to 200 ° C. An ultrathin laminated thin film of 5 nm of Si and Ge was formed.

In this case, the two ion sources 215 and 216 are alternately ignited, but the ion sources 215 and 216 may be operated continuously and only the ion beam extraction voltage may be controlled in a pulsed manner.

Further, as shown in FIG. 21, it is effective to change the time for irradiating the solidified layers 218 and 219 with the ion beam 226 extracted from one ion source 225 by switching the electromagnetic scanning unit 227. is there.

Further, as shown in FIGS. 22 (a) and 22 (b), the ion source 215
By partially overlapping the timing of 216 and 216,
As a _{-Si x Ge 1_x -Ge-Ge x} Si 1_x -Si (0 ≦ x ≦ 1), it is easy to continuously control the composition.

〔The invention's effect〕

According to the present invention described above, a particle beam such as an ion beam, an electron beam, or a plasma is applied to a sputtering target that is made of an atom or a substance formed by combining atoms by a Van der Waals force or a hydrogen bonding force in a vacuum. Is irradiated to cause the target to be sputtered, the generated spatter particles are allowed to fly in space, and a desired thin film is formed on the substrate by irradiating the substrate, so that the Van der Waals force or hydrogen is applied. Condensed gas substances bound with weak binding energy called binding force can be decomposed and scattered at high speed by ions or plasma, which is effective for high-speed, high-purity, high-quality film formation. .

Further, by irradiating the substrate with the sputtering particles generated by sputtering the target made of the substances as described above, it is possible to efficiently process a desired substrate such as a metal, a dielectric, an organic substance or a semiconductor. There is also an effect that can be done.

[Brief description of drawings]

FIG. 1 is a diagram showing an apparatus configuration when the present invention is applied to form a metal titanium thin film, and FIG. 2 is a diagram showing an apparatus configuration when the present invention is applied to create titanium silicide. FIG. 3 is a diagram showing an apparatus configuration when the present invention is applied to produce an ultrathin multilayer thin film of tungsten and carbon, and FIG. 4 is a sectional view of the formed ultrathin multilayer thin film of tungsten and carbon. FIG. 5 is a diagram showing an apparatus configuration in which an ion irradiation apparatus is attached to a substrate for accelerating a film formation reaction, and FIG. 6 is a diagram showing an apparatus configuration when the present invention is combined with a molecular beam vapor deposition method. Is a diagram showing an apparatus configuration when the present invention is combined with a cluster ion beam vapor deposition method, FIG. 8 is a diagram showing an apparatus configuration when the present invention is combined with a high frequency bipolar electrode sputtering vapor deposition method, and FIG. 9 (a). Is a cooling device for uniform film formation. Shows a device configuration of bracts portion, 9
FIG. 9 (b) is a characteristic diagram showing the radial temperature distribution of the cooling target, FIG. 9 (c) is a sectional view showing details of the vicinity of the cooling target, and FIG. 10 is a cooling target portion for performing uniform film formation. FIG. 11 is a diagram showing the apparatus configuration, FIG. 11 is a principle diagram of a cooling target sputtering method for forming a uniform film on a large-area substrate, and FIG. 12 is the present invention applied for etching a silicon semiconductor. Showing the device configuration when
The figure shows the apparatus configuration when the solidified substance is formed in a place different from the container for forming the thin film, and this is introduced into the container to form the thin film, and Fig. 14 is the Van der Waals. When making a substance in a state of being bound by force, of the gas remaining in the container, the components that do not want to be taken into the film are first solidified, and then a diagram showing the device configuration when forming a solidified layer of the raw material gas, FIG. 15 is a characteristic diagram showing the temperature change of the refrigerator head at that time, FIG. 16 is a diagram showing details of the solidified layer on the refrigerator head of FIG. 14, and FIG. 17 is a diagram showing gas evaporated from the solidified substance. FIG. 18 is a diagram showing a device configuration in which a cooling panel for adsorbing and trapping is provided in a vacuum container, FIG. 18 is a diagram showing details of a refrigerator head portion in FIG. 17, and FIG. 19 is a device configuration for forming a multilayer thin film. Figures 20 (a) and 20 (b) show the operating time of different ion sources. FIG. 21 is a diagram showing the structure of an apparatus in which the time for irradiating the solidified layer with the ion beam is changed by switching the electromagnetic scanning section, and FIGS. 22 (a) and 22 (b) show different ions. It is a figure which shows the other example of the operation timing of a source. 7,20,30,51,61,80,90,100,110,130 …… Vacuum container, 8,10,
119,124 …… Glass substrate, 9,21,102,113,131 …… Refrigerator head, 11 …… Substrate holder, 12,25,35,36,50,57,65,8
3,116,127,134 …… Ion source, 13 …… Solidified layer of titanium tetrachloride, 14,29,38,56,70 …… Substrate heating heater, 15 …… Ion source gas introduction hole, 16,58,136 …… Argon ion beam, 17,19,74,97 …… Thin film, 22,23,26,33,34,53,63,93,1
04,115,132,135 …… Gas inlet, 24,54,82,94,111,121,
133 …… Solidified layer, 27, 41, 42 …… Neon ion beam, 28,
37 …… Silicon wafer, 31,32,52,62,81 …… Cooling head, 39 …… CF ₄ solidified layer, 40 …… WF ₆ solidified layer, 43 …… Multilayer film, 44 …… Carbon film, 45… … Tungsten film, 55,86
…… Substrate, 59 …… Reaction intermediate product, 60 …… Silicon film,
64 …… Nitrogen solidified layer, 66 …… Helium gas, 67 …… Spatter nitrogen particles, 68 …… Electron beam evaporation source, 69 …… Iron vapor, 71 …… GaAs crystal substrate, 72, 73 …… Shatter, 84, 117 ,
122 …… Helium ion beam, 85 …… Spatter particles, 8
7 …… Cluster ion generator, 88 …… Gold cluster ions, 89 …… Organic thin film, 91 …… Upper electrode, 92 …… Refrigerator, 95 …… Ground electrode, 96,139 …… Silicon wafer substrate, 101 …… Cooling holder, 103 …… Spacer, 112,12
6 ... Cooling target, 114 ... Copper wire, 118 ... Titanium tetrachloride solidified layer, 120, 125 ... Titanium metal film, 123 ... Scan electrode, 137 ... Radical, 138 ... Photoresist mask.

Claims (34)

[Claims] 1. A raw material consisting of atoms or molecules bonded by the Van der Waals force or hydrogen bonding force is irradiated with a particle beam such as an ion beam, an electron beam, or plasma, and the raw material is subjected to a spatula action. A method for forming a thin film, which comprises irradiating a substrate with generated particles to form a thin film having at least a part of the raw material as a constituent element on the substrate. 2. A raw material is adsorbed or occluded on a target which is kept at a temperature below the melting point of a liquid or gaseous thin film raw material under normal temperature and pressure,
The state is created by the Van der Waals force or the hydrogen bonding force, and the target is subjected to the van der Waals force bonding or the hydrogen bonding force state substance by irradiating an ion beam, an electron beam, or a particle beam such as plasma to a spatula. Then, a thin film forming method is characterized in that the substrate is irradiated with spatter particles generated by this sputtering to form a thin film on the substrate. 3. At least a part of the particles generated by the sputtering effect is ionized in space by electron bombardment or laser light irradiation means, and at least a part of the ions is included, or both the particles and the sputtering particles are included in the substrate. The thin film forming method according to claim 1 or 2, wherein the thin film is formed by irradiating the film. 4. A thin film raw material gas or liquid material is brought into contact with a target kept at a temperature below the melting point to form a van der Waals force coupling layer of the raw material on the target. A raw material consisting of a wars force coupling layer is sputtered with an ion beam, and a sputtering target particle generated by this spattering is applied to a substrate whose surface state is controllable to form a thin film having at least a part of the raw material as a constituent element. A method for forming a thin film, which comprises forming on a substrate. 5. A thin film raw material, which is a gas at room temperature and atmospheric pressure,
Alternatively, a liquid substance is introduced into a vacuum, and the target substance is solidified by contacting and adsorbing it on the surface of the target that is cooled to a temperature below the melting point of the source substance in the vacuum, and the solidified source substance is ion beam-sputtered. Then, the substrate is irradiated with the sputtering particles generated by the sputtering to form a thin film having at least a part of the raw material as a constituent element on the substrate. 6. A thin film raw material, which is a gas at room temperature and atmospheric pressure,
Alternatively, the liquid substance is solidified by previously cooling it to a temperature not higher than the melting point of the substance in a place different from the vacuum container for forming the thin film, introducing the solidified substance into a vacuum, and introducing into the vacuum. Thin film formation, characterized in that a solidified substance is sputtered with an ion beam, and the substrate is irradiated with spatter particles generated by the spattering to form a thin film having at least a part of the raw material as a constituent element on the substrate. Method. 7. A thin film raw material, which is a gas under normal temperature and pressure,
Or at least two kinds of liquid substances are introduced into a vacuum,
The solidified layer in which at least two kinds of raw materials are mixed is formed by bringing the raw materials into contact with the surface of the cooling target, which is kept at a temperature lower than any melting point of the raw materials introduced into the vacuum, and the fixing is performed. Ion beam or electron beam,
Or irradiate a particle beam such as plasma to spatter,
A method of forming a thin film, which comprises irradiating a substrate with the sputtering particles to form a thin film. 8. An atomic substance composed of atoms or molecules bound by the Van der Waals force or hydrogen bonding force is irradiated with a particle beam such as an ion beam, an electron beam, or plasma, and the starting substance is subjected to a sputtering action. Own at least two spatter particles that generate,
A thin film forming method characterized in that a thin film made of multiple substances or a multi-layer thin film is formed on a substrate by simultaneously or intermittently controlling the time for performing the spattering for generating the spatter particles at at least two places. . 9. A thin film raw material gas or liquid material is brought into contact with a target kept at a temperature below the melting point to form a van der Waals force coupling layer of the raw material on the target. The raw material consisting of the Wars force coupling layer is sputtered with an ion beam, and at least two spatter particle generation portions generated by this spatter are owned, and the time for performing the spattering for generating the spatter particles at these at least two places is performed at the same time. Alternatively, by intermittently controlling, a thin film made of multiple substances on the substrate,
Alternatively, a thin film forming method characterized by forming a multilayer thin film. 10. A thin-film raw material, which is a gas or liquid substance introduced into a vacuum at room temperature and atmospheric pressure, and is brought into contact with and adsorbed on a target surface cooled to a temperature not higher than the melting point of the raw material in the vacuum. Time to carry out spattering in which the raw material is solidified, the solidified raw material is sputtered with an ion beam, and there are at least two parts for generating spatter particles generated by the spattering, and the spatter particles are generated at these at least two places. A thin film forming method comprising simultaneously or intermittently controlling the above to form a thin film or a multi-layered thin film made of a multiplicity of substances on a substrate. 11. The target surface is subjected to temperature control so that the temperature of a portion of the target surface, which is distant from the introduction hole introduced into the vacuum, is lower than the temperature of a portion of which the distance is short. 6. The thin film forming method according to claim 2, 4, or 5, wherein the van der Waals force coupling layer or the solidified layer of the raw material is formed with a uniform thickness. 12. A method of heating the substrate, or irradiating the substrate surface with another excitation beam such as an ion beam, an electron beam, a radical or light, thereby accelerating the thin film forming process on the substrate surface. Claims 1, 2, 4, 5, 6 characterized
Or the thin film forming method described in 7. 13. A van der Waals force coupling layer or a solidified layer of a raw material is irradiated with laser light, and the binding layer or the solidified layer in a portion irradiated with the laser light is partially evaporated to have an outer shape. 11. The thin film forming method according to claim 1, 2, 4, 5, 6, 7, 8, 9, or 10, wherein the shaping is controlled. 14. An atom bonded by a Van der Waals force,
Alternatively, a substance composed of molecules is irradiated with a particle beam such as an ion beam, an electron beam, or plasma, and the sputtering material generated by the sputtering effect from the substance is irradiated onto a substrate material such as a metal, a dielectric, an organic substance, or a semiconductor. A processing method comprising processing the substrate. 15. A gas or liquid substance is brought into contact with a target that is maintained at a temperature below its melting point, and a Juan der Waals force coupling layer of the gas or liquid substance is formed on the target. By irradiating a substance composed of a force coupling layer with a particle beam such as an ion beam, an electron beam, or plasma, the spatula particles generated by the spattering action from the Van der Waals force coupling layer are separated into metal, dielectric, organic, semiconductor, etc. A processing method comprising irradiating a substrate material to process the substrate. 16. A gas or liquid substance is introduced into a vacuum at room temperature and a normal pressure, and the substance is solidified by contacting and adsorbing on a target surface cooled to a temperature below the melting point of the substance in the vacuum, This solidified substance is irradiated with a particle beam such as an ion beam, an electron beam, or plasma, and the spatter particles generated by the spattering action from the solidified layer are irradiated onto a substrate material such as a metal, a dielectric, an organic substance, or a semiconductor. A processing method comprising: processing the substrate. 17. A vacuum container, a raw material substance introducing means for introducing a gas or a liquid substance as a thin film raw material into the vacuum container, and a gas or a liquid substance introduced by the raw material substance introducing means. The temperature is kept below the melting point,
A target for forming a van der Waals force coupling layer of the introduced substance on the surface, and a particle beam source for irradiating the van der Waals force coupling layer of the target with a particle beam such as an ion beam, an electron beam or plasma. And a substrate on which a thin film having at least a part of the raw material as a constituent element is formed on the surface thereof, by irradiating the particle beam from the particle beam source and irradiating with spatter particles generated by sputtering. A thin film forming apparatus characterized by being provided. 18. A vacuum container, and a raw material introducing means for introducing a gas or liquid substance into the vacuum container, which is a thin film raw material at room temperature and under normal pressure, and cooled to a temperature lower than room temperature to introduce the raw material. A target that adsorbs or occludes the gas or liquid substance introduced by the means on the surface, a charged particle source that irradiates the target portion with charged particles to cause a sputtering, and a charged particle from the charged particle source is irradiated. A thin film forming apparatus comprising: a substrate on which a thin film is formed by irradiating vapor deposition particles generated by being sputtered. 19. A vacuum container, a raw material substance introducing means for introducing a gas or a liquid substance as a thin film raw material into the vacuum container, and a gas or a liquid substance introduced by the raw material substance introducing means. The temperature is kept below the melting point,
A target for contacting the introduced substance on the surface to form a Van der Waals force coupling layer, an ion source for irradiating the van der Waals force coupling layer of the target with an ion beam, and an ion from the ion source. A thin film, characterized in that it is provided with a substrate on which a thin film having at least a part of the raw material as a constituent element is formed on the surface, which is irradiated with spatter particles generated by being irradiated with a beam and sputtered. Forming equipment. 20. A vacuum container, a raw material introducing means for introducing a gas or a liquid substance into the vacuum container, which is a thin film raw material at room temperature and normal pressure, and a raw material introduced by the raw material introducing means. Cooled to a temperature below the melting point of the target, a target for contacting and adsorbing the introduced substance on the surface to form a solidified layer of the introduced substance, and an ion source for irradiating the solidified layer of the target with an ion beam for sputtering. And a substrate on which a thin film having at least a part of the raw material as a constituent element is formed on the surface of the raw material is irradiated with the sputter particles generated by the irradiation of the ion beam from the ion source and the sputtering. A thin film forming apparatus. 21. A vacuum vessel, at least two raw material substance introducing means for introducing at least two kinds of gas or liquid substances into the vacuum vessel, which are thin film raw materials at room temperature and normal pressure, and the raw material substance introduction. A gas introduced by the means, or a target whose temperature is kept below the melting point of the liquid substance and which forms a solidified layer in which at least two kinds of raw material are mixed by contacting the introduced substance on the surface, and the target. A particle beam source that irradiates a solidified layer in which at least two kinds of raw materials are mixed with a particle beam such as an ion beam, an electron beam, or plasma, and a particle beam from the particle beam source is irradiated to be sputtered. And a substrate on which a thin film is formed by irradiating the generated spatter particles. 22. A vacuum container, at least two raw material introducing means for introducing a thin film raw material into the vacuum container, and a melting point of the raw material introduced by each of the at least two raw material introducing means. The temperature of the target substance is maintained and at least two targets on which a Juan de Waals force coupling layer of the introduced substance is formed, and the respective van der Waals force coupling layers of the at least two targets, At least two particle beam sources that simultaneously or intermittently irradiate a particle beam such as a beam, an electron beam, or plasma, and the particle beams from the at least two particle beam sources simultaneously or intermittently The spatter particles from at least two locations, which are generated by being irradiated to the surface and sputtered, are irradiated to form a thin film made of a multi-dimensional substance or a multi-layered thin film. Thin film forming apparatus characterized by comprising a substrate made. 23. A heating device for heating the substrate in order to accelerate a thin film forming process on the substrate surface, wherein the heating device is provided. Thin film forming equipment. 24. In order to accelerate a thin film forming process on the substrate surface, an excitation beam irradiation means for irradiating the substrate surface with an excitation beam such as an ion beam, an electron beam, a radical, or light is provided. Claims 17, 18, 19, 20, characterized by
21. The thin film forming apparatus as described in 21 or 22. 25. A van der Waals force coupling layer or a solidified layer of the target is irradiated with laser light, and the binding layer or the solidified layer of the portion irradiated with the laser light is partially evaporated to obtain an outer shape. A laser light irradiating means for controlling the shaping of the laser beam is provided.
The thin film forming apparatus as described in 0, 21, or 22. 26. The van der Waals force coupling layer of the target, or a temperature lower than the temperature of the cooling body for forming the solidified layer, and adsorbing / trapping a gas unnecessarily evaporated from the binding layer or the solidified layer. A cooling panel plate to be provided in the vacuum container, claim 17, 18,
The thin film forming apparatus according to 19, 20, 21, or 22. 27. In order to uniformly form the target van der Waals force coupling layer or the solidified layer of the target and to perform the sputtering, the cooler head for forming the binding layer or the solidified layer is rotated or linearly. Claims 17, 18, 19, 20, 21, characterized by comprising means for reciprocating motion,
23. The thin film forming apparatus as described in 22. 28. The van der Waals substance is obtained by adsorbing or occluding the raw substance on a target, which is kept at a temperature below the melting point of the thin film raw substance in the liquid or gaseous state at room temperature and normal pressure. Produces a state bound by force, irradiates the van der Waals force-bonded state substance with ions in the plasma to cause spattering, and irradiates the spatter particles generated by this spattering onto the substrate whose surface state is controlled, A method for forming a thin film, comprising forming a thin film having at least a part of the raw material as a constituent element on the substrate. 29. A thin film raw material containing elements forming a desired thin film as constituent elements is bound by a Van der Waals force, and the thin film raw material bound by the Van der Waals force is ion beam or electron beam, or It is desired to irradiate a particle beam of plasma or the like to sputter, and to irradiate a substrate whose surface state is controlled with the spatter particles generated by this spatter, and which has at least a part of the raw material as a constituent element. A method for forming a thin film, which comprises forming a thin film. 30. Among the sputtering particles irradiated onto the substrate, particles that react with an element unnecessary to form a desired thin film and remove the unnecessary element are applied to the substrate during thin film formation. 30. The method for forming a thin film according to claim 29, wherein irradiation is performed. 31. An atom bonded by a Van der Waals force,
Alternatively, a raw material consisting of molecules is irradiated with a particle beam such as an ion beam, an electron beam, or plasma to generate spatter particles from the raw material by a spatter action, and at the same time, the raw material is continuously supplied from the outside. Then, while always maintaining a constant amount of the raw material consisting of atoms or molecules bonded by the Van der Waals force, the substrate is irradiated with the spatula particles, and at least a part of the raw material is formed on the substrate as a constituent element. A thin film forming method, comprising forming a thin film. 32. A molecular beam deposition apparatus, a vacuum deposition apparatus for depositing a desired substance on the substrate in the vacuum container,
23. The thin film forming apparatus according to claim 17, 18, 19, 20, 21, or 22, further comprising a cluster ion beam vapor deposition apparatus. 33. A vacuum container, an introducing means for introducing a gas or a liquid substance into the vacuum container, a temperature introduced below the melting point of the gas or the liquid substance introduced by the introducing means, and a surface thereof. A target on which a van der Waals force coupling layer of the introduced substance is formed, and a particle beam source for irradiating the van der Waals force coupling layer of the target with a particle beam such as an ion beam, an electron beam, or plasma And a substrate material such as a metal, a dielectric, an organic substance, or a semiconductor, which is processed by being irradiated with spatter particles generated by being irradiated with a particle beam from the particle beam source and being sputtered. And processing equipment. 34. A vacuum container, and an introducing means for introducing a gas or a liquid substance into the vacuum container at room temperature and normal pressure.
A gas, which is introduced by the introducing means, or a target whose temperature is maintained below the melting point of the liquid substance to form a solidified layer of the introduced substance by contacting and adsorbing the introduced substance on the surface, and the target solidification A particle beam source that irradiates a layer with a particle beam such as an ion beam, an electron beam, or plasma, and spatters it, and a particle beam from the particle beam source irradiates the particle that is sputtered to generate spatter particles. A processing apparatus comprising a substrate material such as a metal, a dielectric, an organic substance, and a semiconductor to be processed.