JPS626638B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vapor deposition coating apparatus for metal thin films.

In recent years, various products have been coated with metals or metal oxides by vapor deposition to improve the characteristics of these products.

For example, as shown in FIG. 1, a metal oxide 200 is deposited on the surface of a deposition object 100 made of various products to improve the characteristics of the various products depending on their purpose. In other words, when the deposition target 100 is a visible light-transmitting glass body, optical properties, especially low light absorption, high refractive index, and high reflectance, can be improved, and it can be used as a glass that resists heat rays, etc. things, vehicles,
It is used in the glass of refrigerators and other appliances to save energy by reducing the cooling load, and when deposited on incandescent light bulbs, it improves the light emitting efficiency of these light bulbs.

Further, by coating the insulator with a metal oxide by vapor deposition, it is possible to improve the dielectric constant and insulation properties.

Further, by coating the surface of a product made of various materials including metal or plastic with a metal oxide by vapor deposition, it is possible to improve properties such as corrosion resistance, heat resistance, and abrasion resistance.

Further, as shown in FIG. 2, a metal oxide thin film 200a, a metal vapor deposited thin film 2
00b and metal oxide vapor-deposited thin films 200c are successively formed to cover the surface of the object to be vapor-deposited with a multilayer coating. In this way, metal oxide thin film 2
By forming the metal thin film 200b between 00a and 200c in a sandwich pattern, this metal thin film 2
00b can be used as an electrical conductor, and is used, for example, as a transparent conductor for display elements or as a heater for defogging vehicle window glasses.

These metal oxide vapor-deposited thin films or metal vapor-deposited thin films will have significantly superior or inferior properties depending on the vapor deposition coating method.

That is, it is important that the metal oxide vapor-deposited thin film 200 has fewer oxygen vacancies, and the smaller the oxygen vacancies, the better the optical properties, dielectric constant, durability, and other properties can be achieved. Further, the metal vapor deposited thin film 200b needs to have good acid resistance in order to obtain improved characteristics such as low absorption of transmitted light, high reflectance of light, and low electrical resistance.

However, conventional methods for depositing metals or metal oxides onto objects have been mainly performed by sputtering or evaporation.

This sputter deposition is performed in an oxygen atmosphere such as a sputtering gas such as a mixed gas of argon and oxygen, and although it is possible to reduce oxygen vacancies in the metal oxide deposited thin film, the deposition rate is slow. In addition, in order to maintain this film formation rate at an optimum value, delicate gas mixture adjustment had to be made, which was a hassle. Another disadvantage is that active oxygen plasma is generated during sputtering, and this oxygen plasma causes deterioration of various parts of the vapor deposition coating apparatus, such as the ion gauge, rubber packing, or ring.

Furthermore, when forming a multi-layered thin film of metal oxide and metal as shown in FIG. 2 by sputter deposition, not only does the formation of a metal oxide thin film suffer from the above-mentioned disadvantages, but also the metal In some cases, this sputter deposition is carried out in an oxygen-containing atmosphere, which has the disadvantage that oxidation occurs during metal deposition, increasing the light absorption rate and electrical resistance of the metal deposited thin film.

On the other hand, when forming a deposited thin film by evaporating a metal or metal oxide, the material to be evaporated is held in a vapor deposition tank, and the material to be evaporated is heated with a heater or a high-energy electron beam. The vapor-deposited thin film is formed by vapor-depositing vapor onto an object to be vapor-deposited.

However, in this type of method, for example, when metal oxides are evaporated, the vapor pressures of the metal and oxygen are different, so the proportion of oxygen in the metal oxide is extremely small compared to the metal; Since the process is carried out in an almost vacuum state, oxidation of the deposited area is difficult, making it extremely difficult to form a metal oxide vapor-deposited thin film with a small amount of oxygen vacancies. The disadvantage was that it was difficult to form.

The present invention has been made in view of the above-mentioned conventional problems, and its purpose is to provide a metal that can improve the characteristics of a thin film, regardless of whether the thin film is formed of a metal oxide or a metal on an object to be deposited. An object of the present invention is to provide a thin film vapor deposition coating device.

In order to achieve the above object, a first apparatus of the present invention includes: a deposition tank that holds an object to be evaporated therein using a holding part; an ion beam irradiation device that irradiates an ion beam toward the object to be evaporated; , the vapor deposition tank has a sputtering device for sputtering a metal or metal oxide onto the surface of the object to be vapor deposited, with a sputtering surface facing the object to be vapor deposited, and the ion beam irradiation device includes: an ion source; , an ion passage tube which guides the ion beam from the ion source to the vapor deposition tank and is provided with a predetermined exhaust system; and an orifice for maintaining a predetermined pressure difference between the evaporation tank and the passage pipe; and a deflector provided near the exit of the ion passage pipe for controlling the irradiation position of the ion beam onto the object to be deposited to a desired position. , the sputtering device and the ion beam irradiation device are controlled separately and independently, and the ion beam is implanted into the vapor deposition portion of the metal or metal oxide film deposited on the object to be vapor-deposited. Coating equipment. Further, a second apparatus of the present invention includes: a vapor deposition tank that holds an object to be deposited therein using a holding part; and an ion beam irradiation device that irradiates an ion beam toward the object to be vapor deposited, the vapor deposition tank The sputtering device sputters a metal or metal oxide onto the surface of the object to be vapor-deposited, with the sputtering surface facing the object to be vapor-deposited; a vapor deposition device that evaporates and deposits on a surface; and the ion beam irradiation device is configured to alternately perform sputter deposition of a metal or metal oxide and vapor deposition of the metal or metal oxide on the object to be vaporized, and the ion beam irradiation device includes an ion source, an ion passage tube that guides the ion beam from the ion source to the vapor deposition tank and is provided with a predetermined exhaust system, and an ion passage tube that is provided at a predetermined position of the ion passage tube and that directs the ion beam to a desired direction. an orifice that narrows the ion beam to a diameter of 1, and maintains a predetermined pressure difference between the evaporation tank and the passage tube, and an orifice that is installed near the exit of the ion passage tube and deflects the irradiation position of the ion beam onto the object to be deposited to a desired position. a deflector for controlling, separately and independently controlling vapor deposition by the sputtering device and evaporator and ion beam irradiation using the ion beam irradiation device, and controlling the vapor deposition by the sputter device and the evaporator and the ion beam irradiation using the ion beam irradiation device, and It is characterized by implanting an ion beam into the vapor deposition area.

Preferred embodiments of the present invention will be described below based on the drawings.

FIG. 3 shows a metal thin film vapor deposition coating apparatus according to the present invention.

A feature of the present invention is that the thin film of metal or metal oxide is formed not only by sputter deposition, but by implanting a desired ion beam into the sputter deposition area.

In the apparatus shown in FIG. 3 of this embodiment, a holding section 14 for holding a deposition object 12 is provided in the vapor deposition tank 10.

Further, a sputtering device 18 is provided for sputtering a metal or metal oxide onto the object 12 with a sputtering surface 16 facing the object 12 . An ion beam irradiation device 20 that irradiates an ion beam toward a predetermined portion of the vapor deposited body 12 is provided,
By the sputtering action of the sputtering device and the ion beam irradiation action of the ion beam irradiation device 20, a desired evaporated thin film of metal or metal oxide is formed on the surface of the object to be evaporated 12.

That is, the sputtering device 18 is composed of a magnetron sputter source 22 and a sputter target 24.
By supplying RF or DC power to the sputter target 24, sputter deposition of a metal or metal oxide is performed, and a desired thin film of the metal or metal oxide is formed on the object 12 to be deposited.

On the other hand, the ion beam irradiation device 20 has an ion source 26
It has an ion passage tube 28 that guides ions from the ion source to the deposition tank 10 and an ion beam extraction electrode 30 that extracts the ion beam near the entrance of the ion passage tube 28. An ion beam acceleration electrode 32 for accelerating the ion beam is provided. Further, an orifice 34 is provided near the ion beam accelerating electrode 32.
The orifice 34 makes it possible to focus the ion beam to a desired diameter and to maintain a pressure difference between the vapor deposition tank 10 and the passage pipe 28.

Furthermore, an ion beam deflector 36 for controlling the course of the ion beam is provided in the vapor deposition tank 10 on the exit side of the ion passage tube 28, and the ion beam is deflected and scanned along a desired location.

The apparatus of this embodiment is provided with a control device (not shown) that controls the ion supply amount of the ion beam, the ion acceleration energy, and the pointing direction of the ion beam. This control device is controlled separately from the sputtering device, and the ion implantation concentration can be changed continuously or stepwise by driving this control device.

Therefore, according to the apparatus of this embodiment, the ions extracted from the ion source 26 by the ion beam extraction electrode 30 are accelerated and scanned by the ion beam accelerating electrode 32 and the ion beam deflector 36, and are applied to the deposition target 12. Irradiation is applied to a predetermined area.

The vapor deposition tank 10, the ion passage tube 28, and the ion source 26 are provided with exhaust systems 38a, 38b, and 38c, and the ion source 26 and the ion passage tube 2 are
8. The interior of the vapor deposition tank 10 is maintained at a low pressure state.

The metal thin film vapor deposition coating apparatus according to the present invention has the above-mentioned configuration, and the metal thin film vapor deposition coating method according to the present invention will be described below using this apparatus.

In this first embodiment, a visible glass substrate for vehicles is used as the deposition target 12, and when a single layer of metal oxide, in this embodiment titanium dioxide, is deposited on the deposition target 12, exhaust gas is first used. System 38a,3
8b and 38c to lower the pressure of the vapor deposition tank 10, passage pipe 28, and ion source 26 to desired pressures, respectively. In this first embodiment, the pressure of the passage pipe 28 and the ion source 26 is lower than that of the vapor deposition tank 10. become
Then, an inert gas such as argon or xenon is introduced into the vapor deposition tank 10, and a metal oxide is sputter-deposited using a magnetron sputter in this inert gas atmosphere.

That is, RF or DC power is applied to the magnetron sputter source 22 and the two sputter targets are
The titanium oxide is evaporated in sputters, and a deposited thin film is formed on the object 12 to be deposited. At this time, a desired voltage is applied to the ion beam extraction electrode 30 and the ion beam accelerating electrode 32, so that the density of the ion beam from the ion source 26 is 10 ¹³ to 10 ¹⁸ particles/cm ² ·sec, and the oxygen pressure is An oxygen ion beam set at a high height is extracted and accelerated, and the direction of this oxygen beam is controlled by an ion beam deflector 36. Oxygen ions are then irradiated onto a predetermined portion of the metal oxide evaporation portion formed on the evaporation object 12 with a beam having a desired diameter that is variably set in the range of 10 ^-4 cm to 1 cm in diameter.
As a result of this, oxygen ions are injected into the vapor deposition area, and as a result, it is possible to form a metal oxide vapor deposited thin film with few oxygen vacancies, that is, a titanium dioxide vapor deposited thin film, and in this example, the glass substrate is transparent to visible light. It becomes possible to form a film that resists heat rays.

As mentioned above, in the formation of a single-layer vapor-deposited thin film of a metal oxide in this example, since the oxygen ion beam is concentratedly irradiated, the density of oxygen ions is high in the irradiated area, and therefore the metal oxide vapor-deposition film formation rate is high. It is possible to maintain

In addition, since oxygen ions are injected into the metal oxide evaporation area by concentrated irradiation with an oxygen ion beam, large amounts of oxygen ions are prevented from diffusing into the evaporation tank, resulting in parts such as rubber gaskets used in the equipment. deterioration can be avoided.

Furthermore, in the first embodiment, although the pressure of the ion source 26 is lower than that of the vapor deposition tank 10 in which the sputter source 22 is disposed, the pressure of oxygen is set higher, so that the accelerated oxygen ions As a result of being quickly passed through the space within the deposition tank 10 and immediately injected into the sputter deposition section, the vapor deposition tank 1 is released as gas molecules.
There is almost no increase in the average oxygen concentration (oxygen partial pressure) within 0.

Furthermore, in the first embodiment, since the pressure inside the ion passage tube 28 is lower than that inside the vapor deposition tank 10, oxygen molecules enter the vapor deposition tank 10 through the orifice 34.
Natural intrusion into the interior of the substrate is extremely rare, and therefore good sputter deposition can be performed without adversely affecting sputtering.

Next, a second process is performed to form a multi-tank thin film on the deposition target 12.
In the case of the embodiment, this is done as follows. In forming this multilayer film, the vapor deposition tank 10, the ion passage tube 2
8, and that the inside of the ion source 26 is maintained at a low pressure and that the density of the ion beam and the diameter of the ion beam can be set within a predetermined range are similar to the first embodiment, but this embodiment is different from the first embodiment. The point is that metal ions, silver ions in this example, are implanted into the ion source 26 in order to form a metal thin film by the ion beam, and in order to perform ion beam film formation, the vapor deposition tank 10 The inside is filled with a mixed gas of inert gas and oxygen.

The formation of this multilayered thin film consists of a first film forming step in which a metal oxide thin film is formed by sputter deposition in an oxygen-containing atmosphere, and a metal oxide thin film is irradiated with metal ions to oxidize the metal oxide. and a second film forming step of forming a metal thin film in a material metal thin film, in the first film forming step of which,
A metal oxide, in this embodiment, titanium dioxide, is sputter-deposited by the sputtering action of the magnetron sputter source 22, and this evaporated thin film is formed on the object 12 to be evaporated.

Then, in the second film forming step, simultaneously with the sputter deposition of the titanium dioxide, metal ions are irradiated and implanted into the titanium dioxide deposited portion.
That is, the ion beam extraction electrode 30, the ion beam acceleration electrode 32, and the ion beam deflector 36
By this action, silver ions are irradiated from the ion source 26 onto a predetermined portion of the metal oxide thin film, and the silver ions are implanted into the titanium dioxide vapor deposited portion. As a result, a two-layer thin film consisting of a titanium dioxide vapor-deposited film and a silver thin film is formed on the vapor-deposited body 12.

Next, the silver ion irradiation operation is stopped and only sputter deposition of titanium dioxide is performed for a predetermined period of time, thereby forming a three-layer deposited thin film consisting of a titanium dioxide thin film, a silver thin film, and a titanium dioxide thin film on the deposition target 12. This makes it possible to form a multilayer visible light-transmitting heat ray shielding film on a glass substrate.

According to this second embodiment, since sputter deposition is performed in an atmosphere containing oxygen, it is possible to reduce oxygen vacancies in the metal oxide deposited thin film, and since the metal thin film is formed by ion beam irradiation implantation, silver Oxidation of the ion thin film is prevented and it is possible to form a thin film with various excellent properties.

In this embodiment, the reason why the silver thin film is prevented from oxidizing even though the inside of the vapor deposition tank 10 is exposed to an atmosphere containing oxygen is that the silver thin film is formed by ion implantation.

In other words, the ions are implanted by irradiating and penetrating the sputter-deposited titanium dioxide vapor deposited film to a predetermined depth. At this implantation site, the ions are protected by the titanium dioxide vapor deposition film and are protected from oxygen in the atmosphere and oxygen plasma. As a result, oxidation of the silver thin film is prevented. Furthermore, it was confirmed by computer simulation of the spectral characteristics that this silver thin film was not oxidized by the oxygen atoms of the titanium dioxide deposited film.

Generally, it is known that strain is generated in a film when ions are implanted into the film, but in this example, the film thickness of silver and titanium dioxide is thin, and the film thickness of titanium dioxide is thin. Since the ion implantation was carried out simultaneously, the occurrence of distortion due to film stress was alleviated, and in this example, the occurrence of the above-mentioned distortion was not observed, and a good three-layer thin film could be formed.

A characteristic feature of the first and second embodiments is that the metal oxide is sputter-deposited using a magnetron sputter type sputter source. Therefore, it is possible to increase the density of the plasma by focusing the plasma generated during sputtering near the target using a magnetic field, thereby preventing the plasma from flowing into the ion source 26 from the evaporation tank 10. Furthermore, by increasing the density of the plasma, passage of the irradiated ions into the plasma is avoided, and the problem that the sputtering effect is obstructed by ion implantation can be prevented.

Furthermore, since the plasma density is increased as described above, oxygen ion plasma is prevented from diffusing into the vapor deposition tank 10, and deterioration of the rubber packing used in the vapor deposition tank 10 can be prevented.

In addition, in the first and second embodiments, the ion source 26
Since the operating pressure of the ion source 26 is lower than that of the sputtering device, the pressure of the ion source 26 is lower than the sputtering pressure of the vapor deposition tank 10, and the gas in the vapor deposition tank 10 is ionized in response to the differential pressure between the two. It is possible to naturally discharge the air from the exhaust system 38b through the passage pipe 28. Therefore, for example, in the first and second embodiments, the pressure inside the vapor deposition tank 10 is 2×10 ^-3 to 6×10 ^-3 Torr. Even if the pressure in the passage pipe 28 is 2×10 ^-5 to 6×
It is possible to maintain the pressure difference between the vapor deposition tank 10 and the passage pipe 28 so that it can be maintained at 10 ^-8 Torr,
Furthermore, it is possible to suppress the increase in pressure within the vapor deposition tank 10 that occurs when the ion beam collides with the object 12 to be vapor deposited.

Furthermore, as described above, this embodiment device is provided with devices for controlling the ion supply amount of the ion beam, ion acceleration energy, and ion beam pointing direction. In the first and second embodiments, the ion beam density is increased to 10 ¹³ by controlling the energy, that is, controlling the ion concentration in the ion source 26 and controlling the ion beam extraction electrode 30 and the ion beam acceleration electrode 32.
It is possible to set the ion energy in the range of ~10 ¹⁸ ions/cm ² ·sec and the ion energy in the range of several 100 eV to several MeV, and by controlling these as desired, the amount of ions implanted into the deposited film can be controlled continuously or intermittently. As shown in FIG. 4, the optical refractive index of the metal oxide thin film can be changed appropriately depending on the distance from the surface. It also becomes possible to form an optical path for guiding light and the like.

Similarly, in the case of a multi-bath vapor deposition film, it is possible to change the implantation concentration of metal ions, thereby eliminating the need to separate the boundary between the metal oxide vapor deposited thin film and the metal thin film, as shown in Figure 5. It is possible to continuously change the concentration of metal depending on the distance from the substrate surface, and by forming it in this way, the boundary between the metal oxide thin film and the metal thin film becomes unclear, and this makes it possible to It becomes possible to increase the strength of vapor deposition.

In the first and second embodiments, the ion supply energy, that is, mainly the ion implantation acceleration voltage, is determined by the ion implantation depth from the surface of the metal oxide deposited thin film,
It is determined by considering the ion implantation amount and its distribution.

Usually, the sputter deposition of metal oxide and the ion implantation are performed at the same time, so the thickness of the sputter-deposited film increases over time. The distance traveled becomes longer. For this reason, the ion supply energy is controlled so that the ion implantation energy is gradually increased over time, that is, the ion acceleration voltage is gradually increased so that the ions can reach a predetermined implantation site.

On the other hand, when ions are implanted into the surface of a metal oxide deposited film or into a very shallow part, a low-energy ion beam is used to implant the ions, for example, an oxygen ion beam is implanted into the surface of a metal oxide deposited film. In this case, it is possible to supply oxygen to the surface of the metal oxide thin film having an oxygen-deficient structure to be deposited on the substrate of the deposition object 100, thereby increasing the oxygen concentration on the substrate and keeping the sputtering yield of the deposited thin film low. is possible. The oxygen ion implantation conditions for forming this single-layer thin film are particularly taken into consideration, including the sputtering deposition rate and the amount of oxygen vacancies in the deposited film.

In addition, by controlling the direction of the ion beam, that is, by controlling the ion beam deflector 36, it is possible to irradiate the ion beam uniformly onto the vapor deposition area or to concentrate on a specific area. It is possible to form channels with a concentrated ion concentration or vice versa.

For example, as shown in FIG. 6, it is possible to form an optical circuit 300 by forming a mesh-like high refractive index region with a small amount of oxygen vacancies in a metal oxide vapor deposition part, and vice versa. It becomes possible to form an electric circuit by forming a mesh-like electrically conductive region with a large number of electrically conductive regions. Furthermore, in the case of forming a multi-layer vapor deposited thin film of a metal oxide vapor deposited thin film and a metal thin film, it is possible to form passages with a high concentration of silver in the titanium dioxide vapor deposited thin film as shown in FIG. Therefore, it is possible to form an electric circuit 302 by providing this high silver concentration portion vertically and horizontally, and it is suitable to use this circuit 302 in anti-fog glass with a hot wire heater or the like.

The structure of the method and apparatus for depositing a metal thin film according to the present invention is as described above, and a specific embodiment of the present invention using sputter deposition will be described below.

Example Distance between target and substrate: 15 cm Evaporation object: Silica glass of 5 cm length x 5 cm width x 0.8 mm thickness Target material: Titanium dioxide (TiO ₂ ) sintered target with a diameter of 6.7 cm Vapor deposition tank and ion source atmosphere :Argon gas 3x
10 ^-3 Torr Sputtering power: 500W・RF Amount of implanted ions: Oxygen ions (O ₂ ⁺ ) 1×10 ¹⁵
/sec Acceleration energy: 500 to 1000V Thin film formation rate: 1 Å/sec Ion beam diameter: 1 cm diameter on the surface of the evaporator Beam operation method: Scan the entire evaporation area at a cycle of 1 second, while heating the evaporator Alternatively, cooling is not performed, and the object to be evaporated is
It was rotated at a cycle of 10 seconds.

Results: A titanium dioxide thin film with a thickness of approximately 1000 Å was obtained after 17 minutes of film formation.

Visible light absorption rate: Absorption rate of 0.1% or less at a wavelength of 5000 Å Refractive index: 2.5 Amount of oxygen defects: 1% or less (Rutherford backscattering method) The titanium dioxide vapor-deposited thin film of this example was heat treated (in air at 1000°C for 24 hours) Even after this, no change in absorption rate was observed. This vapor-deposited thin film has low absorption and high refractive index, and is extremely effective in forming multilayer reflectors for lasers.

Next, a case in which the main constituent elements of this embodiment are missing will be shown as a comparative example, and the effect will be clarified by comparison with the embodiment.

All of these comparative examples lack the unique structure of this embodiment, in which oxygen ions are implanted in the sputter deposition portion by irradiation with an oxygen ion beam.

Comparative Example Film-forming conditions: The same equipment as in the example was used. Oxygen ion beam irradiation from the ion source was stopped, and a titanium dioxide thin film was sputter-formed in an argon gas atmosphere.

Other film-forming conditions were the same as in Examples Film-forming speed: 1 Å/sec Visible light absorption rate: Absorption rate 2% or less at a wavelength of 5000 Å Refractive index: 2.2 Amount of oxygen vacancies: 1-2% (Rutherford backscattering method) It is understood that in this comparative example, since no oxygen ions were implanted, the amount of oxygen vacancies was large and the optical characteristics were inferior to the results of this example.

Comparative example Film-forming conditions: Sputter deposition of titanium dioxide thin film in an argon-oxygen mixed gas atmosphere (argon:oxygen mixture ratio 90:10) Other conditions were the same as the comparative example Film-forming speed: 0.3 to 0.4 Å/sec Visible light absorption rate: absorption rate of 0.1% or less at a film thickness of 1000 Å Refractive index: 2.5 The comparative example has a small amount of oxygen vacancies because the mixed gas contains oxygen, and therefore has good optical characteristics.

However, since oxygen ion beam irradiation is not performed, the film formation rate is extremely slow, resulting in a lack of productivity.

Examples First step: Step of forming titanium dioxide by vapor deposition on the object to be vapor-deposited.

Distance between target and object to be evaporated: 15cm Object to be evaporated: Silica glass of 5cm length x 5cm width x 0.8mm thickness Target material: Titanium dioxide (TiO ₂ ) Sputtering atmosphere: Argon-oxygen mixed gas (mixture ratio of 90 to argon) Sputtering pressure: 3 x 10 ^-3 Torr Sputtering power: Output 500W/RF Film deposition rate: 1 Å/min Film deposition time: 7 minutes.

2nd process Step of implanting silver ions into the titanium dioxide deposited area.

Silver ion implantation was performed simultaneously without interrupting the sputter deposition of titanium dioxide.

Amount of implanted ions: 1×10 ¹⁵ silver ions/sec Ion acceleration energy: 500 to 1000 V Ion beam diameter: 1 cm diameter at the evaporation area Ion beam scanning method: Scans the entire evaporation area at a cycle of 1 second Heating the object to be evaporated or Cooling: To ensure uniform film quality without cooling, the entire object to be evaporated was
It rotated with a period of seconds.

Ion implantation time: 3 minutes 30 seconds.

In the third step, the ion implantation is stopped and only the TiO ₂ film is formed.

Spatuta time: 30 seconds Other conditions are the same as in the first step.

Results Results of the first step TiO ₂ film thickness: 420 Å Refractive index: 2.4 or more Absorption rate: 1% or less at wavelength 500 Å Oxygen vacancy 1%
Below (backscattering method) It should be noted that no change in absorption rate was observed due to thermal oxidation (in air, 1000°C, 24 hours) after film formation.

Results of the second step: Thickness of the deposited silver film: 150 Å Distance of the deposited silver film from the substrate surface: 360 Å to 510 Å Results after the third step: A three-layer film of titanium dioxide, silver, and titanium dioxide is formed on the glass substrate. Obtained.

Thickness of first layer titanium dioxide vapor deposited thin film: 360Å Second layer silver thin film thickness: 150Å Thickness of third layer titanium dioxide vapor deposited thin film: 360Å Conductivity: Approximately 2Ω/square Optical properties: As shown in FIG.

According to FIG. 8, a titanium dioxide layer with a small amount of oxygen vacancies is obtained, so good visible light transmittance is obtained, and since the silver thin film is prevented from oxidizing, it has high heat ray reflection. (Hei) is made possible.

Next, a case in which the main constituent elements of this embodiment are missing will be shown as a comparative example, and the effect will be clarified by comparison with the embodiment.

All of these comparisons lack the unique structure of this embodiment in which silver ion implantation in the sputter deposition area is performed by irradiation with a silver ion beam.

Comparative Example Film-forming conditions and method: The Ag layer was created using DC sputtering with an Ag target without using the ion source of the example, and other conditions were almost the same as in the example. TiO ₂ 1st layer: 360 Å (RF sputtering) Ag layer: 150 Å (DC sputter) TiO ₂ second layer: 360 Å (RF sputter) Results Optical properties: As shown in Figure 9.

Electrical conductivity: 200Ω/square In Comparative Example 1, the sputter-deposited silver thin film was oxidized during the sputter-evaporation of titanium dioxide during the formation of the third layer, and as a result, the optical properties and conductivity were lower than in this example. It is understood that this is extremely inferior.

Comparative Example 2 Film forming conditions and method: Same as Comparative Example except that sputtering of titanium dioxide was performed in an argas atmosphere (3×10 ⁻³ Torr).

Results Optical properties: As shown in Figure 10 In Comparative Example 2, each layer was formed in an oxygen-free atmosphere, so oxidation of the silver thin film was prevented, but oxygen vacancies in the titanium dioxide vapor-deposited thin film The refractive index of the TiO ₂ layer is low (2.0-2.3) due to the large amount
The TiO ₂ layer had a large amount of visible absorption (absorption rate of 1-20% at a film thickness of 1000 Å), which resulted in insufficient antireflection in the visible region, resulting in a large amount of visible absorption and a decrease in visible transmittance. .

In addition, in order to prevent such deterioration of optical properties, preliminary treatment is troublesome, such as requiring a conditioning treatment of the titanium dioxide target in advance, such as preliminary sputtering treatment in an argon-oxygen mixed gas. There is a drawback.

If such preliminary treatment is omitted, there is a problem that the quality of the titanium dioxide deposited film gradually deteriorates as the number of times the film is formed increases.

As mentioned above, in this example, a three-layer deposited thin film of titanium dioxide, silver, and titanium dioxide is formed, but in this example, sputtering of titanium dioxide is performed in an oxygen atmosphere, so The amount of oxygen vacancies in the titanium oxide deposited thin film is small, and since the silver deposited thin film is formed by the implantation action of a silver ion beam, the oxidation effect of the silver deposited thin film is prevented, making it possible to form a deposited thin film with extremely high characteristics.

As explained above, according to the present invention, it is possible to form a metal oxide vapor-deposited thin film with few oxygen vacancies and a metal vapor-deposited thin film that is hardly oxidized on the surface of the object to be vapor-deposited, thereby improving optical properties, dielectric constant, durability, etc. It is possible to form a vapor-deposited thin film with excellent seedability properties.

In addition, in each of the above-mentioned Examples, an example was shown in which silver was used as the metal and titanium dioxide was used as the metal oxide, but it is also possible to use other metals and metal oxides in this example.

In addition, in forming a multilayer vapor-deposited thin film, it is possible to form the vapor-deposited thin film by alternately performing sputter deposition and vapor deposition, and then implant desired ions into each of these vapor-deposited parts to form a multi-layer vapor-deposited thin film. .

FIG. 11 shows a third embodiment of the invention in which a multilayer deposited film is formed by alternately performing sputter deposition and evaporation deposition.
The apparatus of the embodiment is shown, and the same members as those of the apparatus of FIG. 3 in the first and second embodiments of the present invention are given the same reference numerals, and the explanation thereof will be omitted.

A feature of the apparatus shown in FIG. 11 is that an evaporator 42 for evaporating the material to be evaporated 40 is provided near the sputtering apparatus 18.

This evaporator 40 is provided with a crucible 44 or a boat that accommodates a material to be evaporated 42 made of metal or metal oxide facing the object to be evaporated 12,
Further, a heating device (not shown) is provided to evaporate the material to be evaporated 42 housed in the crucible 44 .

The heating device is composed of an electric heater such as a heater, or a high-energy electron beam generator installed near the material 40 to be evaporated and heats and evaporates the material 40 to be evaporated. This makes it possible to alternately form evaporation-deposited thin films and sputter-deposited thin films on the surface of the object 12 to be deposited. Therefore, for example, the sputter target 24 and the material to be evaporated 40 are made of different materials,
Sputtering easy material to sputtering gate 24
In addition, it is possible to select materials that are easily evaporated as the material to be evaporated 40, and to form a multilayered thin film with a wide variety of variations through evaporation of these materials.

In the third embodiment, the material to be evaporated 40 is evaporated while maintaining the degree of vacuum in the evaporation tank 10 at a pressure of 10 ^-4 to ^{10 -10} Torr.

Generally, it is difficult to achieve an ultra-vacuum pressure of 10 ^-10 Torr, but in this third embodiment, a heater 46 is provided on the outer periphery of the vapor deposition tank 10. The inside of the vapor deposition tank 10 is evacuated while being heated, thereby easily realizing the ultra-vacuum pressure.

As described above, in the third embodiment, a multilayer thin film is formed by ion implantation by alternately performing the sputter deposition thin film and the evaporation deposition film in the first or second embodiment. Second
Since the formation of the sputter-deposited thin film and the ion irradiation control in the embodiment have been described in detail, their explanation will be omitted, and a specific example of the formation of the ion-implanted layer of the evaporation-deposited thin film in the third embodiment will be shown below.

(1) Pretreatment Step In this third example, in order to increase the adhesion strength of the deposited thin film to the object to be deposited, a pretreatment, that is, ion irradiation of argon gas to the object to be deposited, was performed prior to the formation of the deposited thin film.

Pre-treatment conditions: The vacuum pressure inside the vapor deposition layer is set to 10 ⁹ Torr, and an argon ion beam with a beam diameter of 1 mmφ is applied.
A 1 cm x 1 cm area of the object to be deposited was irradiated with an acceleration energy of 1000 eV for 10 minutes.

The irradiation amount of argon ions at this time is 10 ¹⁴
pieces/ ^cm2・sec.

As a result of pretreatment, the contamination layer on the substrate surface was removed and the substrate surface was activated.

(2) Evaporation deposition and ion implantation process Distance between material to be evaporated and substrate: 30 cm Object to be evaporated: Iron alloy 5 cm long x 5 cm wide x 0.8 mm thick Material to be evaporated: Titanium metal (housed in a water-cooled crucible) ) Deposited layer vacuum degree: approximately 1×10 ⁸ Torr to 2×10 ⁸ Torr Evaporation heating method: Titanium metal was irradiated with an electron beam to evaporate it by heating.

Titanium film formation rate: 1 Å/sec Ion implantation method: Evaporation of titanium and implantation of nitrogen ions are carried out simultaneously Nitrogen ion implantation conditions: Amount of implanted ions: 1×10 ¹⁵ pieces/cm ²・sec Implantation energy: 500eV ion beam Diameter: 1 mmφ Ion beam scanning area: 1 cm x 1 cm To ensure uniform film quality, the object to be deposited was rotated at a cycle of 50 times/minute.

Results: After about 2 hours of film formation, a titanium nitride thin film with a thickness of about 8000 Å was formed.

The characteristics of the X-ray photoelectron spectroscopy spectrum of this deposited thin film are shown in Figure 2, and the Auger electron analysis results of the titanium nitride deposited thin film obtained by gradually removing spatter from the titanium nitride deposited thin film are shown in Figure 13. has been done.

According to the characteristic results shown in FIG. 12, it is clear that the titanium nitride deposited thin film of this example deviates from the stoichiometric composition, and an extremely good deposited thin film is formed by this third example.

Furthermore, as is clear from FIG. 13, the ratio of titanium and nitrogen in the deposited thin film is constant, so the third
By the method of the embodiment, it is possible to form a homogeneous titanium nitride vapor-deposited thin film, and it is possible to improve the desired characteristics of the object to be vapor-deposited.

In the third embodiment, a sputter deposition layer is further formed with ion implantation on the titanium nitride deposited film, and a multilayer deposited thin film is formed on the object to be deposited.

Although the third embodiment shows an example of evaporation of a titanium nitride thin film, it is also possible to form a film of other compounds by evaporation.

As described above, according to the present invention, a deposited thin film is formed by directly injecting ions into the deposition area of a target object using an ion beam irradiation device, and in this case, the deposition and ion beam irradiation are performed separately. Since it is controlled independently, it is possible to form thin films with high properties according to the purpose of various products.

Further, according to the present invention, an ion passage tube, an orifice, and an exhaust system are provided between the vapor deposition tank that performs vapor deposition and the ion source of the ion beam irradiation device, and the pressure difference between the two is maintained at an appropriate value. This makes it possible to implant ions into the deposition target under optimal conditions.

Furthermore, according to the present invention, the ion beam irradiation device is provided with an orifice that narrows the ion beam to a desired diameter, and an ion beam deflector is provided near the exit of the ion passage tube, so that the diameter can be sufficiently narrowed down. The ion beam is deflected and scanned arbitrarily toward a desired position on the surface of the object to be evaporated, and the ion beam is irradiated uniformly or concentrated on a specific part of the evaporation area. It becomes possible to obtain an optically excellent thin film.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view showing an example in which a single-layer vapor deposited thin film is formed on a vapor-deposited object, FIG. 2 is a cross-sectional view showing an example in which a multi-layer vapor-deposited thin film is formed on a vapor-deposited object, and FIG. 3 is a cross-sectional view showing an example in which a multilayer vapor-deposited thin film is formed on a vapor-deposited object. A configuration diagram showing a metal thin film vapor deposition coating apparatus according to
FIG. 4 is a characteristic diagram showing the relationship between film thickness and refractive index when the oxygen content concentration is changed appropriately according to the film thickness.
Figure 5 is a characteristic diagram showing the relationship between the distance from the surface and the silver atom concentration when the silver concentration is changed appropriately according to the distance from the surface of the metal oxide vapor deposited film, and Figure 6 is the characteristic diagram of the metal oxide vapor deposited film. A perspective view showing an example of controlling the irradiation direction of an oxygen ion beam within the vapor deposition area and forming an optical circuit within this metal oxide vapor-deposited thin film. Figure 7 shows the irradiation direction control of the silver ion beam into the metal oxide vapor deposition area. FIG. 8 is a perspective view showing an example in which an electric circuit is constructed in a metal oxide vapor-deposited thin film by performing the above steps, and FIG. Figure 9 is a characteristic diagram of transmittance and reflectance versus wavelength for a three-layer thin film formed by sputter deposition in an argon atmosphere, and Figure 10 is a three-layer thin film formed in an oxygen-free atmosphere. A characteristic diagram of transmittance and reflectance of a thin film with respect to wavelength. FIG. 11 is a configuration diagram showing a device according to a third embodiment of the present invention. FIG. 12 is a diagram showing a configuration of a device according to a third embodiment of the invention.
FIG. 13 is a characteristic diagram of the X-ray photoelectron spectroscopy spectrum of the titanium nitride vapor-deposited thin film formed by the example, and FIG. 13 is a singular diagram showing the results of Auger electron analysis of the titanium nitride vapor-deposited thin film formed by the second method of the present invention. 10... Vapor deposition tank, 12... Evaporation target, 200,
200a, 200c...Metal oxide vapor deposited thin film, 2
00b...Metal vapor deposited thin film, 14...Holding part, 16
...Sputtering surface, 18... Sputtering device, 20...
... Ion beam irradiation device, 24 ... Sputter target, 40 ... Evaporation target material, 42 ... Evaporation device.

Claims (1)

[Claims] 1. A vapor deposition tank that holds an object to be deposited inside using a holding part, and an ion beam irradiation device that irradiates an ion beam toward the object to be vapor deposited, The ion beam irradiation device includes a sputtering device that sputters a metal or metal oxide onto the surface of the object to be deposited, with a sputtering surface facing the object to be vaporized, and the ion beam irradiation device includes an ion source and ions directed from the ion source to a vapor deposition tank. An ion passage tube that guides the beam and is provided with a predetermined exhaust system, and an ion passage tube that is provided at a predetermined position of this ion passage tube, focuses the ion beam to a desired diameter, and is between the vapor deposition tank and the passage tube. an orifice that maintains a predetermined pressure difference; and a deflector that is provided near the exit of the ion passage tube and that deflects and controls the irradiation position of the ion beam onto the object to be deposited to a desired position, and the sputtering device and the ion beam 1. A metal thin film vapor deposition coating apparatus, characterized in that an irradiation device is controlled separately and an ion beam is implanted into a vapor deposited portion of a metal or metal oxide film deposited on an object to be vapor deposited. 2. The vapor deposition coating apparatus for metal thin films according to claim 1, wherein the sputtering apparatus is a magnetron type sputtering apparatus that focuses and controls plasma generated during sputtering using a magnetic field. 3. In the apparatus according to claim 1 or 2, the sputtering apparatus is configured to perform sputter deposition of a metal oxide on the surface of an object to be deposited in an inert gas atmosphere to form a metal oxide thin film. , the ion beam irradiation device is configured to irradiate an oxygen ion beam to the metal vapor deposition area, and is characterized in that it simultaneously supplies the sputtered metal and the ion beam to form a metal oxide thin film with few oxygen vacancies. Vapor deposition coating equipment for metal thin films. 4. In the apparatus according to claim 1 or 2, the sputtering apparatus is formed to perform sputter deposition of a metal oxide in an atmosphere containing oxygen to deposit a metal oxide thin film on the surface of the object to be deposited. The ion beam irradiation device is produced to form a metal thin film in the metal oxide thin film by irradiating and implanting metal ions into the metal oxide thin film, and a multilayer film of the metal oxide thin film and the metal thin film is formed on the deposited object. 1. A metal thin film vapor deposition coating device, characterized in that it forms a metal thin film. 5. In the apparatus according to any one of claims 1 to 4, the object to be deposited is a glass substrate, and the metal oxide thin film is formed on the glass substrate as a visible light-transmitting, heat ray-resistant film. Features: Vapor deposition coating equipment for metal thin films. 6. A vapor deposition tank that holds an object to be deposited inside using a holding part, and an ion beam irradiation device that irradiates an ion beam toward the object to be vapor deposited, and the vapor deposition tank is configured to apply a sputtered surface to the object to be vapor deposited. A sputtering device sputter-deposit a metal or metal oxide onto the surface of the object to be vapor deposited, and a vapor deposition device which evaporates and deposits a metal or metal oxide onto the surface of the object to be vapor deposited, with the evaporation surface facing the object to be vapor deposited. an ion beam irradiation device, the ion beam irradiation device includes: an ion source; an ion passage tube that guides an ion beam from a source to a deposition tank and is provided with a predetermined exhaust system; an orifice that maintains a predetermined pressure difference between the ion passage tube and the ion passage tube; and a deflector that is provided near the exit of the ion passage tube and that deflects and controls the irradiation position of the ion beam onto the object to be deposited to a desired position. , separately and independently controlling the vapor deposition by the sputtering device and the evaporator and the ion beam irradiation using the ion beam irradiation device, and implanting the ion beam into the vapor deposited portion of the metal or metal oxide film deposited on the object to be vapor deposited. A metal thin film vapor deposition coating apparatus characterized by: 7. The vapor deposition coating apparatus of claim 6, wherein the sputtering apparatus is a magnetron-type sputtering apparatus that focuses and controls plasma generated during sputtering using a magnetic field.