JP5703439B2 - Method for forming metal plate and osmium film - Google Patents

Description

  The present invention relates to a film formation processing jig for forming a thin film on a plate having a through-hole having a very small diameter by a single plasma film formation process, and a plasma CVD (Chemical Vapor) using the film formation processing jig. The present invention relates to a deposition apparatus, a metal plate, and a method for forming an osmium film.

  FIG. 8 is a cross-sectional view schematically showing a conventional plasma CVD apparatus. FIG. 9 is a front view showing the aperture plate. The aperture plate 107 is a part for focusing an electron beam in an electron microscope, and the plasma CVD apparatus shown in FIG. 8 is an apparatus for forming a metal film on the surface of the aperture plate 107.

  As shown in FIG. 8, the conventional plasma CVD apparatus has a chamber 101, and a gas shower electrode 102 and a lower electrode 103 as parallel plate type upper electrodes are arranged in the chamber 101. The gas shower electrode 102 is connected to a source gas supply source 104. The gas shower electrode 102 and the chamber 101 are connected to the ground potential.

  A substrate 106 is placed on the lower electrode 103, and an aperture plate 107 is attached on the substrate 106. A radio frequency power source (RF power source) 109 is connected to the lower electrode 103 via a matching box 108.

  The aperture plate 107 shown in FIG. 9 is a plate having a thickness of 10 to 500 μm, and has a first through hole (attachment through hole) 107a having a diameter of about 2 mm. The aperture plate 107 is provided with a plurality of second through holes (not shown) having a diameter of about 2 to 100 μm, and the second through holes are holes for focusing an electron beam in an electron microscope. The portions where a metal film needs to be formed on the aperture plate 107 are a portion located in the vicinity of the second through hole on the front and back surfaces of the aperture plate, and an inner surface of the second through hole.

  A method of forming a metal film on the aperture plate 107 using the conventional plasma CVD apparatus is as follows.

  An aperture plate 107 is attached on a substrate 106 such as a wafer, and this substrate 106 is placed on the lower electrode 103 in the chamber 101. Next, a source gas is supplied to the gas shower electrode 102 by the source gas supply source 104, and this source gas is ejected from the gas shower electrode 102 toward the lower electrode 103 in a shower shape. Then, by outputting a high frequency from the RF power source 109 to the lower electrode 103 via the matching box 108, a metal film is formed on the surface of the aperture plate 107 and the inner side surface of the second through hole by plasma CVD.

  Thereafter, the substrate 106 is taken out from the chamber 101, the aperture plate 107 is peeled off from the substrate 106, and the substrate 106 is attached to the chamber 106 so that the opposite surface (back surface) of the aperture plate 107 is exposed. It is placed on the inner lower electrode 103. Thereafter, a metal film is formed on the back surface of the aperture plate 107 and the inner surface of the second through hole in the same manner as the metal film is formed on the surface of the aperture plate 107 described above.

  In the conventional plasma CVD apparatus, the inner surface of the second through hole in the plate having the second through hole having a very small diameter such as an aperture plate, and the vicinity of the second through hole on the front and back surfaces of the plate In order to form a thin film on the portion located at, two film forming processes must be performed as described above. For this reason, the subject that the cost of the film-forming process to a plate became high occurred. In addition, when the film formation process is performed twice, the first metal film formed by the first film formation process and the second metal film formed by the second film formation process are always performed. An interface may be formed, and as a result, there may be a problem of peeling from the interface between the first metal film and the second metal film.

  On the other hand, it has been proposed to form an osmium film, which is a metal film, on the front and back surfaces of the aperture plate and the inner surface of the second through hole. Since this osmium film has high resistance to an electron beam, it is expected to exhibit higher performance than other metal films.

However, in the above-described parallel plate type conventional plasma CVD apparatus, since plasma is likely to diffuse, heavy OsO ₄ gas, which is a raw material gas for forming an osmium film, is unlikely to enter the second through hole having a minimum diameter, As a result, an osmium film could not be formed on the inner surface of the second through hole with good uniformity. In other words, even if an osmium film is formed on the inner surface of the second through-hole by the conventional plasma CVD apparatus, since the uniformity of the osmium film is low, high performance cannot be obtained as a result. .

The present invention has been made in consideration of the above-described circumstances, and its purpose is for a film forming process for forming a thin film on a plate having a through hole having a very small diameter by a single plasma film forming process. An object is to provide a jig and a plasma CVD apparatus using the film forming jig.
Another object of the present invention is to provide a metal plate in which an osmium film is formed with good uniformity on the inner surface of a through hole having a very small diameter.
Another object of the present invention is to provide an osmium film forming method for forming an osmium film on the surface of a metal object.

In order to solve the above-described problems, a film-forming treatment jig according to the present invention holds the plate in a state where the through hole, the front surface and the back surface of the plate are exposed by sandwiching the plate having the through hole. Members,
An electrode member to which the holding member is attached;
A film formation processing jig comprising:
The electrode member is electrically connected to an electrode to which plasma power of a plasma CVD apparatus is applied.

  According to the film forming jig, the plate having the through hole, the holding member for holding the plate in a state where the front surface and the back surface of the plate are exposed by sandwiching the plate having the through hole. A thin film can be formed by a single plasma film formation process. At the same time, the electrode member to which the holding member is attached is electrically connected to the electrode to which the plasma power of the plasma CVD apparatus is applied, so that the electrode member can function as a part of the electrode. it can.

  Moreover, in the film-forming treatment jig according to the present invention, it is preferable that the electrode member has a hook for placing on the transfer arm.

A plasma CVD apparatus according to the present invention includes a chamber,
A first electrode disposed in the chamber;
A second electrode disposed in the chamber and disposed to face the first electrode;
A power source electrically connected to at least one of the first electrode and the second electrode, to which plasma power is applied;
A source gas introduction mechanism for introducing a source gas into the chamber;
A film forming device comprising: a holding member that holds the plate in a state where the plate having the through hole is sandwiched and the front and back surfaces of the plate are exposed; and an electrode member to which the holding member is attached. A processing jig;
A plasma CVD apparatus comprising:
When forming a thin film by plasma CVD on the front and back surfaces of the plate held by the holding member and the inner side surface of the through hole, the electrode member is electrically connected on the second electrode, The plate held by the holding member is positioned between the first electrode and the second electrode, so that the electrode member functions as a part of the second electrode.

Moreover, in the plasma CVD apparatus according to the present invention, the electrode member has a ridge,
It is also possible to have a transport mechanism for transporting the film-forming treatment jig into the chamber by placing the bag on the transport arm.

  The plasma CVD apparatus according to the present invention may further include a plasma wall disposed in the chamber and disposed around the plate positioned between the first electrode and the second electrode, The plasma wall is preferably connected to a float potential. Thus, the flow of the source gas introduced into the chamber can be concentrated around the plate by the plasma wall, and the plasma can be confined by the plasma wall to increase the plasma density.

  In the plasma CVD apparatus according to the present invention, the source gas is introduced by the source gas introduction mechanism in a direction substantially parallel to the surface of the plate located between the first electrode and the second electrode. Is preferred.

A plasma CVD apparatus according to the present invention includes a chamber,
An upper electrode disposed in the chamber;
A lower electrode disposed in the chamber and disposed below to face the upper electrode;
A power source electrically connected to at least one of the upper electrode and the lower electrode, to which plasma power is applied;
A source gas introduction mechanism for introducing a source gas into the chamber, the source gas introduction mechanism for flowing the source gas from the upper electrode side toward the lower electrode side;
A holding member for holding the plate in a state where the plate having a through hole is sandwiched to expose the through hole, the front surface and the back surface of the plate, an electrode member to which the holding member is attached, and an electrode member A film-forming processing jig provided with
A transport mechanism that transports the film-forming treatment jig into the chamber by placing the bag on a transport arm;
A plasma CVD apparatus comprising:
When forming a thin film by plasma CVD on the front and back surfaces of the plate held by the holding member and the inner side surface of the through-hole, the electrode member is electrically connected on the lower electrode, The plate held by the holding member is positioned between the upper electrode and the lower electrode, and the plate is positioned so as to be substantially parallel to the surface and the direction perpendicular to the upper surface of the lower electrode. The electrode member functions as a part of the second electrode.

In the plasma CVD apparatus according to the present invention, it is preferable that the plate is an aperture plate, the diameter of the through hole is 100 μm or less, and the thin film is an osmium film.
In the plasma CVD apparatus according to the present invention, the plasma power is preferably high frequency power.

The metal plate according to the present invention comprises a plate having a through hole with a diameter of 100 μm or less, and an inner surface of the through hole and a front surface and a back surface of the plate located near the through hole by a plasma CVD apparatus. A metal plate having an osmium film formed by film treatment,
The plasma CVD apparatus comprises:
A chamber;
An upper electrode disposed in the chamber;
A lower electrode disposed in the chamber and disposed below to face the upper electrode;
A power source electrically connected to at least one of the upper electrode and the lower electrode, to which plasma power is applied;
The plate is electrically connected to the lower electrode, and the plate is positioned between the upper electrode and the lower electrode by sandwiching the plate, and the through hole, the front surface and the back surface of the plate are exposed. A holding member for holding the plate;
A plasma wall disposed in the chamber, located around the plate and connected to a float potential;
A source gas introduction mechanism that introduces a source gas into the chamber, the source gas flowing from the upper electrode side toward the lower electrode side, and the source gas flowing in a direction along the front and back surfaces of the plate A raw material gas introduction mechanism,
It is characterized by comprising.

  According to the metal plate, an osmium film can be formed on the inner surface of a through hole having a very small diameter with higher uniformity than in the prior art, and the osmium film is formed by a single film formation process. Therefore, an interface like a film formed multiple times on this osmium film does not occur.

Moreover, the metal plate which concerns on this invention WHEREIN: It is preferable that the thickness of the said osmium film | membrane is 10 nm or more and 50 nm or less.
In the metal plate according to the present invention, the plasma power is preferably high-frequency power.
In the metal plate according to the present invention, the metal plate may be an aperture plate.

In the method for forming an osmium film according to the present invention, a metal object is disposed in a chamber,
While introducing OsO ₄ gas at a flow rate of 0.1 to 3 cc / min (preferably 0.1 to 1 cc / min) and an inert gas for sustaining discharge into the chamber, the pressure in the chamber is adjusted to 13 to 40 Pa,
An osmium film is formed on the surface of the metal object by converting the gas in the chamber into plasma using a high-frequency output having a density of 0.25 to 2.0 W / cm ² .
Incidentally, H ₂ gas at a flow rate of 5 to 15 cc / min may be introduced into the chamber, or the metal material may be heated to a temperature of 200 to 300 ° C. to form a film. The metal object may be a metal plate. The inert gas may be He or Ar.

According to the film formation method of the osmium film, the raw material gas is applied to the osmium film formed on the metal by using the RF discharge by the high frequency output and defining the ranges of the high frequency output density, the OsO ₄ gas and the pressure. It is possible to suppress the oxygen contained in. Such an osmium film has the property of being resistant to electron beams.
On the other hand, when an osmium film is formed on the surface of a metal object using DC discharge, oxygen of the raw material gas tends to remain in the osmium film, and it is difficult to suppress the remaining oxygen. Thus, the osmium film in which oxygen remains is disadvantageous in that it is weak to electron beams.
The reason why the above-described difference occurs between the RF discharge and the DC discharge is that a stable discharge is obtained in the case of the RF discharge, so that it is possible to suppress the remaining oxygen of the raw material gas, but not in the case of the DC discharge. Since stable discharge is obtained, it is considered that oxygen remaining in the source gas cannot be suppressed.

As described above, according to the present invention, a film formation processing jig for forming a thin film on a plate having an extremely small diameter through-hole by a single plasma film formation process, and the film formation processing jig A plasma CVD apparatus using can be provided.
According to another aspect of the present invention, it is possible to provide an aperture plate in which an osmium film is formed with good uniformity on the inner surface of a through hole having a very small diameter.
According to another aspect of the present invention, it is possible to provide a method for forming an osmium film, which forms an osmium film on the surface of a metal object.

Embodiments of the present invention will be described below with reference to the drawings.
FIG. 1 is a plan view showing an overall configuration of a plasma CVD apparatus according to an embodiment of the present invention. FIG. 2 is a cross-sectional view taken along line 2a-2a shown in FIG. FIG. 3 is a cross-sectional view schematically showing the film forming chamber, the plasma power source, and the source gas supply mechanism shown in FIG.

  As shown in FIGS. 1 and 2, the plasma CVD apparatus has a cleaning chamber 1 and a film formation chamber 2. The cleaning chamber 1 is connected to the transfer chamber 5 via the first gate 6, and the transfer chamber 5 is connected to the first transfer mechanism 3. In the first transfer mechanism 3, a film formation processing jig 8 holding the aperture plate 107 is inserted into the transfer chamber 5, and the film formation process jig 8 in the transfer chamber 5 is opened to the first gate 6. Through the cleaning chamber 1. The film forming chamber 2 is connected to the transfer chamber 5 via the second gate 7, and the transfer chamber 5 is connected to the second transfer mechanism 4. The second transport mechanism 4 transports the film forming processing jig 8 in the transport chamber 5 to the lower side of the film forming chamber 2 through the opened second gate 7.

The transfer chamber 5 and the film forming chamber 2 and their surroundings will be described in detail with reference to FIGS.
As shown in FIG. 2, the transfer chamber 5 has a lid 9 that can be freely opened and closed. In the transfer chamber 5, a mounting table 10 on which the film-forming processing jig 8 is mounted, and a vertical movement mechanism 11 that moves the film-forming processing jig 8 mounted on the mounting table 10 up and down. Has been placed. The vertical movement mechanism 11 has a placement part 11a for placing the film forming processing jig 8 and a movement mechanism 11b for moving the placement part 11a up and down. In addition, an evacuation mechanism such as a vacuum pump is connected to the transfer chamber 5, and the inside of the transfer chamber 5 can be evacuated by the evacuation mechanism. The film formation processing jig 8 holding the aperture plate 107 is inserted into the transfer chamber 5 by opening the lid 9 with the second gate 7 closed, and placing the aperture plate 107 on the mounting table 10. Is carried out by placing the film-forming treatment jig 8 holding the film and then closing the lid 9.

  As shown in FIG. 2, the film forming chamber 2 has an outer chamber 12, and the outer chamber 12 is connected to the transfer chamber 5 through a second gate 7 that can be opened and closed. Further, an evacuation mechanism such as a vacuum pump is connected to the outer chamber 12, and the inside of the outer chamber 12 can be evacuated by this evacuation mechanism.

As shown in FIGS. 2 and 3, an inner chamber 13 is disposed inside the outer chamber 12. A gas shower electrode 14 as an upper electrode is disposed on the inner chamber 13. A first gas supply mechanism that supplies hydrogen gas and a second gas supply mechanism that supplies OsO ₄ gas are connected to the gas shower electrode 14.

  The first gas supply mechanism has a hydrogen gas supply source 29, and one end of a pipe 18 is connected to the hydrogen gas supply source 29. One end of a valve 24 is connected to the other end of the pipe 18, and one end of the pipe 17 is connected to the other end of the valve 24. One end of a mass flow controller (MFC) 27 is connected to the other end of the pipe 17, and one end of the pipe 16 is connected to the other end of the mass flow controller 27. One end of the valve 23 is connected to the other end of the pipe 16, and one end of the pipe 15 is connected to the other end of the valve 23. A gas shower electrode 14 is connected to the other end of the pipe 15.

The second gas supply mechanism has an OsO ₄ gas supply source 30, and one end of a pipe 22 is connected to the OsO ₄ gas supply source 30. One end of a valve 26 is connected to the other end of the pipe 22, and one end of the pipe 21 is connected to the other end of the valve 26. One end of a mass flow controller (MFC) 28 is connected to the other end of the pipe 21, and one end of the pipe 20 is connected to the other end of the mass flow controller 28. One end of the valve 25 is connected to the other end of the pipe 20, and one end of the pipe 19 is connected to the other end of the valve 25. A gas shower electrode 14 is connected to the other end of the pipe 19. The OsO ₄ gas supply source 30 includes a heater 31, and solid OsO ₄ is heated and sublimated by the heater 31 to generate OsO ₄ gas. The pipes 19 to 21, the valves 25 and 26, and the mass flow controller 28 are each heated to about 80 ° C. by a heater (not shown). This makes it possible to OsO ₄ gas generated in the OsO ₄ gas supply source 30 is introduced into the gas shower electrode 14 without being solidified.

The gas shower electrode 14, the inner chamber 13 and the outer chamber 12 are connected to the ground potential.
A lower electrode 32 is disposed below the inner chamber 13, and a high frequency power source (RF power source) 34 is connected to the lower electrode 32 via a matching box 33. The high frequency power source can use a frequency in the range of 100 kHz to 27 MHz.

  In addition, as shown in FIG. 2, this apparatus has a vertical movement mechanism 35 that moves the lower electrode 32 up and down between the lower part of the outer chamber 12 and the lower part of the inner chamber 13. In the state where the lower electrode 32 is moved below the outer chamber 12 by the vertical movement mechanism 35, the film formation processing jig 8 in the transfer chamber 5 is held and opened by the transfer arm 4 a of the second transfer mechanism 4. The film forming jig 8 is moved below the outer chamber 12 by the transfer arm 4a through the second gate 7, and the film forming jig 8 is placed on the lower electrode 32 and attached, fitted, or electrically connected. Connect to. Then, the transfer arm 4a is returned to the transfer chamber 5 and the second gate 7 is closed. Thus, the lower electrode 32 to which the film formation processing jig 8 is attached is moved up and down by the vertical movement mechanism 35, thereby moving the lower electrode 32 from below the outer chamber 12 to the lower portion of the inner chamber 13. A film forming jig 8 electrically connected to the lower electrode 32 is disposed in the inner chamber 13. In this way, the aperture plate 107 is disposed between the gas shower electrode 14 and the lower electrode 32, and is substantially parallel to the direction (indicated by the arrow 36) in which the source gas is ejected from the gas shower electrode 14 in a shower shape. Located in. This position is a film forming position 38 when the aperture plate 107 is formed.

  The film formation processing jig 8 is formed of, for example, SUS, and also functions as a part of the lower electrode. For this reason, when high-frequency power is applied from the RF power source 34 to the lower electrode 32 through the matching box 33, this high-frequency power is applied to the aperture plate 107 through the film-forming processing jig 8. The specific structure of the film forming jig 8 and a holding method for holding the aperture plate 107 on the structure will be described later.

  As shown in FIG. 3, a plasma wall 37 made of ceramics, quartz glass or glass is disposed around the aperture plate 107 in the inner chamber 13. The plasma wall 37 has a role of rectifying the flow of the source gas introduced from the gas shower electrode 14 so as to concentrate around the aperture plate 107 and a role of confining the plasma around the aperture plate 107 to increase the plasma density. It will be done. If these roles can be fulfilled, the shape and material of the plasma wall 37 can be variously changed, but in this embodiment, the shape as shown in FIG. 3 is adopted.

  In other words, the plasma wall 37 is disposed outside the cylindrical rectifying member 37a and the cylindrical rectifying member 37b that controls the flow of the source gas, and suppresses discharge between the inner chamber wall and the outer chamber wall. And a cylindrical rectifying member 37c. The upper portions of the cylindrical rectifying members 37a and 37c are connected by a ring-shaped rectifying member 37b. The plasma wall 37 is connected to the float potential 60. The source gas from the gas shower electrode 14 can be concentrated around the aperture plate 107 by the ring-shaped rectifying member 37b and the cylindrical rectifying member 37a, and as a result, the use efficiency of the source gas can be improved. Further, the cylindrical rectifying member 37c can suppress the diffusion of the plasma to increase the plasma density, and can stabilize the discharge around the aperture plate 107.

  Next, a specific structure of the film forming jig 8 and a holding method for holding the aperture plate 107 on the jig will be described with reference to FIGS.

  4A is a front view showing a film formation processing jig holding the aperture plate, and FIG. 4B is a plan view of the film formation processing jig shown in FIG. . FIG. 5A is a plan view showing a state where the film formation processing jig is transported, and shows a state where the film formation processing jig is placed on the transport arm. FIG. 6B is a front view showing the film-forming treatment jig and the transfer arm shown in FIG.

  As shown in FIGS. 4A and 4B, the holding member 39 has a cylindrical shape. The holding member 39 holds the four aperture plates 107 with the edges thereof being sandwiched. This holding state is a state in which the second through hole (the very small diameter through hole described in FIG. 9) and the front and back surfaces of the aperture plate 107 are exposed.

  The holding member 39 is attached to the flange member 49. As a result, each of the four aperture plates 107 held by the holding member 39 can be held in a state in which the aperture plate 107 stands in a direction perpendicular to the upper surface of the flange member 49. As shown in FIG. 4A, the flange member 49 includes a cylindrical member 49a and a convex flange 49b provided around the upper portion of the cylindrical member 49a. As shown in FIGS. 5A and 5B, the flange 49b is for placing on the transfer arm 4a. That is, by positioning the transfer arm 4a around the cylindrical member 49a and positioning the flange 49b by the positioning portions 52 to 55, the transfer arm 4a is placed on the transfer arm 4a, so that the film forming processing jig 8 is moved to the transfer arm 4a. It can be in a state where it can be conveyed. When the film formation processing jig 8 is connected to the lower electrode 32 shown in FIG. 3, the eaves member 49 becomes an electrode member and functions as a part of the lower electrode.

  Next, a method for forming an osmium film on the aperture plate using the plasma CVD apparatus will be described.

  First, as shown in FIG. 4, the four aperture plates 107 are held on the holding member 39 of the film-forming treatment jig 8, and as shown in FIGS. 2 and 5, the moving mechanism 11 b is raised to place the mounting table. The film-forming treatment jig 8 placed on 10 is placed on the placement portion 11a. Then, the moving mechanism 11b is further raised, and the transfer arm 4a is moved below the film-forming treatment jig 8 placed on the placement portion 11a. Next, the moving mechanism 11b is lowered to lower the film formation processing jig 8 together with the mounting portion 11a, thereby placing the flange 49b of the film formation processing jig 8 on the transfer arm 4a. In this way, the film formation processing jig 8 is placed on the transfer arm 4a, and the film formation processing jig 8 can be transferred by the transfer arm 4a. Thereafter, the film forming jig 8 is transferred from the transfer chamber 5 to the cleaning chamber 1 by the first transfer mechanism 3, and the aperture plate 107 is cleaned. Next, the film forming process jig 8 is transferred from the cleaning chamber 1 to the transfer chamber 5 by the first transfer mechanism 3.

  Next, as shown in FIG. 2, the film-forming processing jig 8 is brought into a state where it can be transferred by the transfer arm 4 a, and the film-forming processing jig 8 is transferred from the transfer chamber 5 to the film-forming chamber 2 by the second transfer mechanism 4. And the film formation processing jig 8 is positioned at the film formation position 38.

Next, as shown in FIG. 3, hydrogen gas and OsO ₄ gas are supplied to the gas shower electrode 14 by the first gas supply mechanism and the second gas supply mechanism, and hydrogen is supplied from the gas shower electrode 14 toward the aperture plate 107. Gas and OsO ₄ gas are supplied. At this time, the reason why the source gas is caused to flow from top to bottom (in the direction of gravity) as indicated by an arrow 36 is that the molecular weight of the OsO ₄ gas is large. Conversely, in the case of a raw material gas having a low molecular weight, it is not necessary to flow from the top to the bottom as long as it can be supplied to the front and back surfaces of the aperture plate with good uniformity, and the flow direction of the raw material gas can be changed as appropriate. is there.

Next, high frequency power is supplied to the lower electrode 32 by the RF power source 34 and high frequency power is applied to the aperture plate 107, whereby the front and back surfaces of the aperture plate 107, the second through-hole (the extremely small diameter described in FIG. 9). An osmium film having a thickness of 10 nm or more is formed on the inner surface of the through hole) with high uniformity by a single film formation process by plasma CVD. The chemical reaction at this time is as follows. As shown in the following formulas (1) and (2), the gas is ionized in the plasma, and the film formation reaction of the following formula (3) occurs on the aperture plate.
H ₂ + 2e ⁻ → 2H ⁺ + 4e ⁻ (1)
OsO ₄ + e ⁻ → OsO ₄ ⁺ + 2e ⁻ (2)
OsO ₄ ⁺ + 8H ⁺ + 9e ⁻ → Os ↓ + 4H ₂ O ↑ (3)

  The reason why the osmium film is formed on the aperture plate 107 is that the osmium film has higher resistance to the electron beam than other metal films, so that the lifetime can be increased and the light beam condensing property is also improved. Because it can.

  According to the above embodiment, since the film formation processing jig 8 has the structure as described above, the film formation processing jig 8 can be transferred by the transfer arm 4a as shown in FIG. The transported film forming processing jig 8 can be attached or fitted to the lower electrode 32. And since the film-forming processing jig 8 attached to the lower electrode 32 also functions as the lower electrode, as shown in FIG. 3, by supplying high-frequency power to the lower electrode 32, the film-forming processing jig The high frequency power can be applied to the aperture plate 107 through 8. Further, the aperture plate 107 can be held by the holding member 39 of the film forming processing jig 8 with its front and back surfaces exposed. For this reason, by performing the film forming process once by the plasma CVD apparatus, the through hole in the plate having the extremely small diameter through hole (described as the second through hole in FIG. 9) such as the aperture plate 107. An osmium film can be formed on the inner surface of the plate and portions located in the vicinity of the through holes on the front and back surfaces of the plate. Accordingly, it is possible to reduce the processing time of the film forming process on the plate, and as a result, it is possible to reduce the cost of the film forming process.

In the present embodiment, since the plasma wall 37 connected to the float potential 60 is arranged around the aperture plate 107, the source gas from the gas shower electrode 14 can be concentrated around the aperture plate 107. In addition, the plasma density can be increased by suppressing the diffusion of the plasma and concentrating the plasma on the aperture plate 107. As a result, even when a film forming material gas having a large molecular weight and a heavy molecular weight, such as OsO ₄ gas, is used, an osmium film can be formed with good uniformity on the inner surface of the extremely small diameter through hole.

  Note that the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention. For example, as shown in FIG. 6, six aperture plates 107 may be held by the holding member 39 of the film forming processing jig.

  In the above embodiment, the high-frequency power source 34 is connected to the lower electrode 32 and the ground potential is connected to the upper electrode 14. However, the high-frequency power source is connected to the upper electrode 14 and the ground potential is connected to the lower electrode 32. Alternatively, a first high-frequency power source may be connected to the upper electrode 14 and a second high-frequency power source may be connected to the lower electrode 32. It is also possible to change the high-frequency power source to another plasma power source. Examples of other plasma power sources include a microwave power source, a DC discharge power source, a pulse-modulated high-frequency power source, and a microwave power source. And a DC discharge power source.

  Moreover, in the said embodiment, although the electrode is arrange | positioned up and down like the upper electrode 14 and the lower electrode 32, it is not limited to this, It is also possible to arrange | position an electrode on right and left.

  Next, experimental conditions in which an osmium film is formed on an aperture plate having an extremely small through-hole using the plasma CVD apparatus according to the above-described embodiment and the results of the experiment will be described.

(Experimental conditions)
High frequency power density: 0.25 to 2.0 W / cm ²
High frequency frequency: 13.56 MHz
OsO ₄ gas flow rate: 0.1-3 cc / min H ₂ gas flow rate: 5-15 cc / min Ar gas flow rate: 5-15 cc / min Pressure: 13-40 Pa
Deposition time: 10-50 seconds Heating temperature: 200-300 ° C
Os film thickness: 10-50 nm

(Experimental result)
FIG. 7 schematically shows an aperture plate 107 on which an osmium film 110 is formed by experiment, and the vicinity of a through-hole (second through-hole) 107b having a minimum diameter (specifically, 2 to 100 μm) of the aperture plate. It is sectional drawing which cut | disconnected. As shown in FIG. 7, since the osmium film 110 is formed by one film formation process, an interface is formed like a thin film formed by two film formation processes as in the conventional technique. In addition, it was confirmed that the osmium film 110 can be formed with good uniformity on the inner surface of the through hole 107b having a very small diameter. As a result, the osmium film 110 can be prevented from being peeled off, and the osmium film 110 having a long lifetime because of its extremely high light-condensing property and high resistance to the electron beam is formed in the through-hole 107b having a very small diameter. We were able to.

It is a top view which shows the whole structure of the plasma CVD apparatus by embodiment which concerns on this invention. FIG. 2 is a cross-sectional view taken along line 2a-2a shown in FIG. It is sectional drawing which shows typically the film-forming chamber, plasma power supply, and raw material gas supply mechanism which are shown in FIG. (A) is a side view which shows the film-forming processing jig holding the aperture plate, and (B) is a top view of the film-forming processing jig shown in (A). (A) is a plan view showing a state in which the film formation processing jig is transported, and shows a state in which the film formation processing jig is placed on the transport arm. It is a side view which shows the jig | tool for a film-forming process shown in A), and a conveyance arm. It is a top view which shows the modification of the film-forming process jig | tool holding the aperture plate. It is sectional drawing which cut | disconnected the through-hole vicinity of the very small diameter of the aperture plate by which the osmium film | membrane was formed by experiment. It is sectional drawing which shows the conventional plasma CVD apparatus roughly. It is a top view which shows an aperture plate.

DESCRIPTION OF SYMBOLS 1 ... Cleaning chamber, 2 ... Deposition chamber, 3 ... 1st conveyance mechanism, 4 ... 2nd conveyance mechanism, 5 ... Conveyance chamber, 6 ... 1st gate, 7 ... 2nd gate, 8 ... Deposition processing jig , 9 ... Lid, 10 ... Mounting table, 11 ... Vertical movement mechanism, 11a ... Mounting part, 11b ... Moving mechanism, 12 ... Outer chamber, 13 ... Inner chamber, 14 ... Gas shower electrode, 15-22 ... Piping, 23 to 26 ... valve, 27.28 ... mass flow controller (MFC), 29 ... hydrogen gas supply source, 30 ... OsO ₄ gas supply source, 31 ... heater, 32 ... lower electrode, 33 ... matching box, 34 ... high frequency power source (RF 35) Vertical movement mechanism, 36 ... Arrow, 37 ... Plasma wall, 37a ... Cylindrical rectifying member, 37b ... Ring-shaped rectifying member, 37c ... Cylindrical rectifying member, 38 ... Deposition position, 39 ... Holding Holding member, 49 ... 鍔 member, 49a ... cylindrical member, 49b ... 鍔, 52-55 ... positioning portion, 60 ... float potential, 101 ... chamber, 102 ... gas shower electrode, 103 ... lower electrode, 104 ... source gas supply source 106 ... Substrate 107 ... Aperture plate 107a ... First through hole 107b ... Minimum diameter through hole (second through hole) 108 ... Matching box 109 ... High frequency power supply (RF power supply) 110 ... Osmium film

Claims (3)

Place metal objects in the chamber,
While introducing OsO ₄ gas at a flow rate of 0.1 to 3 cc / min and an inert gas for maintaining discharge into the chamber, the pressure in the chamber is maintained at 13 to 40 Pa,
An osmium film is formed on a surface of the metal object by converting the gas in the chamber into plasma using a high frequency output having a density of 0.25 to 2.0 W / cm ² . Film forming method. In claim 1,
The method for forming an osmium film, wherein the metal object is a metal plate. In claim 1 or 2,
In the chamber, the OsO ₄ H and a flow rate of 5 to 15 cc / min in addition to the gas and the inert gas for maintaining the discharge ₂ A method for forming an osmium film, wherein a gas is introduced.

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