JPS60106964A - Method and apparatus for forming film of hyperfine particles - Google Patents

Abstract

PURPOSE:To form a film of hyperfine particles on a member to be treated by evaporating a metallic material by heating in an atmosphere of a nonoxidizing gas, sending the gas and the evaporated fine particles to a vapor deposition chamber through a pipe by an internal pressure difference, and spouting them from a nozzle. CONSTITUTION:A vessel 1 for generating metallic vapor is filled with a nonoxidizing gas sent from a cylinder 5, and a metal (a) in the vessel 1 is evaporated by heating. The resulting vapor is sent to a vapor deposition vessel 21 through a pipe 19 by the internal pressure difference with a vacuum pump 7, and it is spouted from a nozzle 20 toward the surface of a member (b) to be treated to form a vapor-deposited film. The evaporated fine particles are efficiently deposited on the member (b) in other chamber without causing oxidation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method and apparatus for forming an ultrafine particle film. We proposed a method to form the film by spraying, but when the ultrafine particle film is exposed to the atmosphere, it rapidly oxidizes and the temperature rises.
If it burns, it will burn. Therefore, it is conceivable to use ultrafine particles that have been subjected to slow oxidation treatment in advance and to form a film thereon. However, when a film is formed using the slow oxidation-treated ultrafine particles by the method described above,
Furthermore, even if the film is heat-treated to make the specific resistance as small as possible, for example, the specific resistance of the N1 ultrafine particle film is 1.2 x 10-3Ω-α, and a film with a specific resistance of less than this can be obtained. That is difficult. Therefore, it is desirable to use ultrafine metal particles with fresh active surfaces that are not subject to slow oxidation and to form an ultrafine particle film with extremely low resistivity without being oxidized.

The object of the present invention is to provide a method that allows even ultrafine particles with fresh active surfaces to form a film of ultrafine particles safely without being oxidized by oxygen or water vapor. The metal material is completely heated and evaporated in a metal vapor generation container set in an oxidizing gas atmosphere to form ultrafine particles, which are introduced into the evaporation processing container together with the non-oxidizing gas through a conveying pipe, and then The method is characterized in that the ultrafine particles are applied to the base surface to be treated through a jet of non-oxidizing gas from a nozzle at the tip of the conveying pipe, thereby forming a film of the ultrafine particles on the surface. .

Furthermore, another object of the present invention is to provide a film forming apparatus for carrying out the above-mentioned method, which has a heating device for the metal material therein and is capable of introducing a non-oxidizing gas to produce a friendly metal vapor. a conveyor tube having a nozzle at the tip leading out from the container and the container, and a tip portion having the nozzle of the conveyor tube inside;
A vapor deposition processing container (including an installation part for setting the member to be processed) and into which a non-oxidizing gas is introduced; an exhaust vacuum device connected to the metal vapor generation container and the vapor deposition processing container. .

Next, an example of the method and apparatus of the present invention will be explained with reference to the accompanying drawings. In the drawing, (1) shows a container for producing metal vapor, and the container (
1) is provided with a plasma Th-ch (3) connected to the plasma arc power source (2) as a heating device for the metal material 1, and facing this is a water-cooled copper hearth ( 4). The container (11) is connected to a non-oxidizing gas source (5) in the row section via a supply pipe (6) to supply non-oxidizing gas into the container (1). (11 is connected to an external vacuum pump (7) via an exhaust conduit (8), so that the internal pressure of the container (1) can be maintained at an appropriate gas pressure. (9) is a supply pipe (6) The control valve inserted in the exhaust gas conduit (8) is shown at the end.The non-oxidizing gas source (511't, Ar, He
an inert gas source (5a) such as, a mixed gas source (5b) of an inert gas and an active gas such as N, and a mixed gas source (50) of an inert gas and a reducing gas source such as H8. Tono 3
It consists of seeds, and the supply pipe (6) branches in the middle to form fcs.
It is connected to each gas source (5a) (5b) (, 5c) through two branch pipes (6aJ (6b)C60)k, so that any gas source can be selected and supplied into the container (1). I made it. n(C21 (t3 indicates the on-off valves inserted in the branch pipes, respectively). The branch pipes (6&
) branches off from a conduit I that connects to the t-chi (2). ω indicates the control valve inserted in the conduit I.
) is equipped with a viewing window←Q1 barometer measuring head αη and a pressure gauge αEnoki. Install the pipe by connecting it to Qi@.

The conveyance pipe has a nozzle w'e at its tip, and its tip is hermetically introduced into the vapor deposition processing container Qv, and its nozzle cA
Place it vertically downward. The nozzle (a) is held in place by a suitable holder (not shown) or movably held by remote control. Pace movement device (24t-equipped 1
It is installed on its upper surface so as to face the base b'l nozzle (a) of a workpiece to be processed such as a glass plate. In the conveying pipe (11), mm*c!31 is inserted in the middle part extending into the space between the container (1) and the container CI!υ. Connect to the source Q4) via the supply pipe (c),
A non-oxidizing gas is supplied into the container (21). Further, the container CI) is equipped with the vacuum pump (7) in part 1b.
The inside of the container QXl was maintained at an appropriate gas pressure by connecting it to the container QXl via an exhaust conduit@. @ indicates a control valve inserted in the supply pipe (c). The non-oxidizing gas source (24) is Ar
5) An inert gas source such as Is (24a), a mixed gas source (24a) of an inert gas and an active gas such as N, and a mixed gas source (24a) of an inert gas and a reducing gas such as )
The supply pipe consists of 1 and is connected to each gas fp (24aJ (24bJ (24o)) through three branch pipes (25aJ (25b) (25c)) branched in the middle, and any of the gases #t is selected and O(c)c2■(to) is selected so that it can be supplied into the container round, and each indicates an on-off valve in which a branch pipe decoy is interposed.

A vacuum gauge probe 6υ and a pressure gauge (c) are provided on the top surface of the container (2υ). This shows a heating device such as

Using all of the apparatuses of the present invention described above, a film of ultrafine particles is sprayed onto the base 5 as follows. That is, a one-way nitrogen pump (7) which introduces inert gas from an inert gas source (5) through the supply pipe (6) into the metal vapor generation container (1) is fully operated. , the vacuum pulse 1ao+t- is appropriately adjusted and evacuated to maintain an inert gas pressure in the container (1), for example, normal pressure or a relatively high pressure above normal pressure, e.g. 1.1at.
Maintain an inert gas atmosphere of m. In this state, the plasma power supply (21' (i) is activated to generate a plasma arc discharge between the plasma [-chi (3)) and the water-cooled copper hearth (3). Melt the metal material a.

The metal material a is a general term for metals or alloys thereof.

The heating temperature is appropriately heated to a temperature higher than the melting point of the metal material via the pressure regulator of the plasma atom source (2), etc., and the molten metal is evaporated. On the other hand, operate the vacuum pump (71,
Once the inside of the container (1) is evacuated and vacuumed, control valve ucJ)
f, HmL, the pressure of the inert gas inside the container (1) is maintained at normal pressure or a higher pressure, for example, 1.1 atm.
The inside of the square container C is evacuated and the pressure is reduced to 0.6 atm, for example.
The pressure is maintained at a level lower than the atmospheric pressure inside the container (1). In this state, if you open the conveyor pipe (valve 19), the container (
Due to the pressure difference between the relatively high pressure of the inert gas in the container (1) and the relatively low pressure of the inert gas in the container (2υ),
The inert gas inside flows into the conveying pipe Qt containing all the ultrafine particles of metal vapor, and is vigorously ejected from the nozzle at its tip, carrying the ultrafine particles that have been placed on the lower surface of the pipe in advance. It is sprayed onto the upper surface of the base b to form a linear ultrafine particle film on the surface of the base 5, for example, by the movement of the moving device 4, and then the pressure inside both containers (1) Qυ is adjusted by using the respective gases. This is done with the supply amount and vacuum evacuation. Container (1)
The time from the generation of ultrafine particles in the container (2υ circle) to the formation of a film in the container (2υ circle) was less than 10 seconds. When the valve (21) was opened, the inert gas in the container (1) was generated due to the pressure difference. All the ultrafine particles of metal vapor flow into the transport pipe o9 with force and are ejected from the nozzle (2) at the tip of the transport pipe ←1 in the container 0υ, and the supported ultrafine particles are set on the bottom surface of the base. 1 Moving device (27J) When moving at a constant speed, a predetermined linear ultrafine particle film can be formed. This film is heated under an exhaust vacuum in a container (1). In addition, since the nozzle (7) is surrounded by an atmosphere of inert gas ejected from the nozzle (7), there is no oxidation, and a continuous film of ultrafine particles in the active state is formed, and although the resistivity is significantly reduced, it is easily and smoothly processed. If it is necessary to further reduce the resistivity, the crotch of the heating device can is heated to sinter the ultrafine particles.As a result,
This also has the effect of improving adhesion to the base surface. If a non-oxidizing atmosphere is required in the processing container 12U during heating, for example, an inert gas fi (24aJ) or cine active gas may be appropriately supplied into the container (1) via the supply pipe (25+). I'll do what I do.

Container +1) and Container CI! The difference in gas pressure in container I
The pressure of the non-oxidizing gas within 2υ may also be maintained at normal pressure or higher.1 In this case, a vacuum pump (
7) removes the air inside the container and exhausts it.
If you are a non-oxidizing gas source (foundation), put the gas in a container CI! The non-oxidizing gas is used to maintain the pressure at normal pressure or higher, and the one-way container (1
) Container for pressurizing non-oxidizing gas c! The gas pressure is set higher than the gas pressure within v. This is vacuum pulp tlQl,
- is achieved by adjusting respectively. In the drawing, the vacuum cylinder 7 (71'ii-1) is shared, but it may of course be provided separately for each island.Among the non-oxidizing gases, a mixture of inert gas and N! If nitrogen gas is present in the mixed gas during the generation of ultrafine particles, a nitride film will be formed by reaction with the surface of the high-temperature ultrafine particles.The presence of hydrogen gas will help prevent oxidation of the surface of the high-temperature ultrafine particles.

Although not shown, a gas source containing an active gas such as N or a reducing gas such as N3 may be provided.

In order to take out the base on which the film has been formed in this way, it is preferable to slowly oxidize the surface of the film by gradually opening the on-off valve (not shown) of the container Qυ in advance.

Example 1 A 15.39 ml of N1 ingot was charged into a water-cooled copper hearth in a metal vapor generation container, and the inside of the container was evacuated to a high vacuum (I Pa).
After exhausting to 1.1 atm (0,11 a), argon gas was introduced.
Keep at pressure. Inside the vapor deposition processing container, a pace is set on the base moving device, and the inside of the container is placed under a high vacuum (<I Pa, 7.
After evacuating the 6×10 )-run, argon gas was introduced to maintain the pressure at 0.6 atm (·0.06 MPa, 456 torr). After applying a high frequency to a 19X” torch connected to a DC power source to generate a pilot arc, apply a DC voltage between the torch and the water-cooled steel hearth to transfer the plasma arc discharge WL with a voltage of 52V @ current of 50m, for example. Then, N1 in the water-cooled copper crucible is dissolved.Argon gas is introduced into the one-way container (1) at a rate of 11/1nix, and the vacuum pump osIfi valve t-81itli is turned on to maintain a gas pressure of L1*trrr at all times. Approximately 30 seconds after the start of release, N1 vapor is generated from the Ni molten metal surface, and the formation of smoky N1 ultrafine particles can be visually observed. 1 minute after the start of release, the pulp in the conveying pipe ' T-open, the generated N1 ultrafine particles are transported from the container together with argon gas into the vapor deposition processing container, and sprayed from the nozzle onto the top surface of the paste on the slide glass.◎The paste moves at a speed of 30 layers, and one spray time is 2 minutes long. The width of the film was 041111 and the thickness #'14.1.
When the formed film was taken out into the atmosphere and its electrical resistance was measured, 5.
It showed 8×10 Ω・a. This value was approximately the specific resistance value of a film formed by slowly oxidizing N1 ultrafine particles in an argon atmosphere using the method disclosed in the patent application and then heated to 500°C.

Example 2 T1 was used as a metal member and heated and evaporated with a plasma voltage of 34 V and a current of 50 A to create an ATM (0,
04 MPa, 504) - The test was carried out under the same conditions as in Example 1 except that it was run.
．． Eight films were formed, and the resistivity was 6.5Ωα, resulting in a conductive film.

In addition to the above, illegal activities include Mbs Ta5Zrs Hls M
Various metals such as high melting point metals such as O, W, transition metals such as 1,00, active metals such as A, Or, conductive metals such as Ags O, noble metals such as Au and Pt, or alloys thereof, etc. This makes it possible to form the ultrafine particle film.

Note that 1. In addition to the plasma arc heating described above, as a heating device, arc heating-high frequency induction heating, resistance heating, laser heating, etc. can be used. In this way, according to the present invention,
Consisting of a metal evaporation production container, a vapor deposition processing container, and a conveyance pipe connecting these containers, vapor t% of the metal member generated in the metal evaporation production container together with a non-oxidizing gas introduced into the container Utilizing the difference in pressure between the inside of the container and the inside of the vapor deposition processing container, the gas is introduced into the vapor deposition processing container via the transport pipe, and the gas is applied to the base surface through a nozzle at the tip of the transport pipe. Therefore, a film of ultrafine particles that is not oxidized in one direction can be formed, and a film with relatively low resistivity can be obtained.

[Brief explanation of the drawing]

The drawing is a diagram of an example of a device for carrying out illegal acts. Source of oxidizing gas (7)...Vacuum pump (19-...Transport pipe)...Nozzle seat...Vapor deposition processing container Patent creator Same as above.

Claims (1)

[Claims] A metal material is heated and evaporated to form ultrafine particles in a metal vapor generation container with a non-oxidizing gas atmosphere, and the N is transferred together with the non-oxidizing gas to a vapor deposition processing container via a conveying pipe. 1. Inside the vapor deposition container, the ultrafine particles are sprayed onto the base surface to be treated through the non-oxidizing gas fumes from the nozzle at the tip of the conveying pipe, thereby depositing a film of ultrafine particles on the surface of the base. 2. A method for forming an ultrafine particle film characterized by forming an ultrafine particle film. Scope 1 of special RF requirements, characterized in that the device is pressure-fed or suction-conveyed and emitted from a nozzle.
Formation method described in Section. (5) a metal vapor generation container having a metal material heating device inside (1) and into which a non-oxidizing gas is introduced; A vapor deposition processing container comprising a tip portion having a nozzle and an installation portion for setting a member to be processed, and into which a non-oxidizing gas is introduced, and connected to the metal vapor generation container and the vapor deposition processing container. An ultrafine particle film forming device consisting of an exhaust vacuum device.