JP2008056790A - Vacuum processing apparatus and vacuum processing process - Google Patents

Abstract

In a vacuum processing apparatus in which two or more kinds of raw material monomers are evaporated and introduced into a vacuum processing chamber to form a synthetic resin film on a substrate, the film forming rate is improved, the use efficiency of the monomer is improved, and the vacuum Reduce exhaust power.
A vacuum processing apparatus for forming a synthetic resin film by evaporating two or more kinds of raw material monomers, introducing them into a vacuum processing chamber, and polymerizing them on a substrate, which causes a polyaddition reaction. (A) A step of evacuating the vacuum chamber using more than one type of raw material monomer; (B) a step of opening the raw material valve and putting in the monomer; (C) a step of stopping the vacuum exhaust and stopping the exhaust valve; By performing the vacuum processing process, it can be solved by performing autonomous film formation without depending on the vacuum exhaust device.
[Selection] Figure 2

Description

  The present invention relates to an apparatus for forming a film in a vacuum and a process thereof. Specifically, after vacuuming the vacuum processing chamber of the vacuum processing apparatus, the vacuum processing apparatus capable of forming a film while autonomously maintaining the vacuum state in the vacuum processing chamber without depending on the vacuum exhaust apparatus, and the vacuum processing apparatus It relates to a vacuum processing process.

  Conventionally, as a vacuum processing apparatus, for example, there has been a vacuum deposition apparatus 40 that forms a film on the surface of a substrate by a deposition polymerization method under vacuum as shown in FIG. 6 (see, for example, Patent Document 1).

  That is, the vacuum vapor deposition apparatus 40 connects the inside of the vacuum processing chamber 41 to an evacuation system 42 constituted by an external vacuum pump and the like, and a base 43 on which a synthetic resin vapor deposition film is to be formed in the vacuum processing chamber 41. The heater 45 provided on the back surface of the substrate holder 44 can be heated to a desired temperature, and is made of glass for evaporating the raw material monomers 58 and 59 of the synthetic resin facing the substrate 43 in the lower part of the vacuum processing chamber 41. It led to the evaporation pipes 46a and 46b so that the entire evaporation pipes 46a and 46b could be heated to a desired temperature by the heaters 47a and 47b wound around them. Further, a heater 49 is provided over the entire inner surface 41 a of the vacuum processing chamber 41.

  In the figure, 50 is a power source of the heater 45, 51 is a power source of the heater 47, 52 is a power source of the heater 49, 53 is a flow rate adjusting valve of each evaporation pipe 46, 54 is a flow rate adjusting of the gas introduction pipe 48. A valve 45 is a shutter interposed between the base 43 and the evaporation tubes 46a and 46b.

  First, pyromellitic dianhydride is filled in the evaporation pipe 46 a as the raw material monomer 58, and 4,4′-diaminodiphenyl ether as the raw material monomer 59 is filled in the 46 b, and the raw materials together with the evaporation pipes 46 a and 46 b and the flow rate adjusting valve 53 are filled. The monomers 58 and 59 are heated to 170 ° C. ± 5 ° C. by the heater 47, respectively. At the same time, the chamber wall inner surface 41 a of the vacuum processing chamber 41 is heated to about 300 ° C. by the heater 49 and the substrate 43 is heated to 150 ° C. by the heater 5.

Next, the total pressure of the atmospheric gas in the vacuum processing chamber 41 is first set to 1 × 10 ⁻⁶ Torr via the vacuum exhaust system 42, and then the flow rate adjustment valve 54 is opened with the shutter 55 closed, and the gas introduction pipe is opened. Then, argon gas is introduced from the inside to set the total pressure to 0.10 Torr, and then the flow rate adjusting valve 53 is opened to introduce the vapors of the raw material monomers 58 and 59 from the evaporation pipes 46a and 46b, and the total pressure to 0.12 Torr. Set.

  Finally, the shutter 55 is opened to deposit a slightly polymerized polyimide polymer of the raw material monomers 58 and 59 on the substrate 43, and the shutter is closed when the predetermined film thickness is reached while completing the polymerization reaction on the substrate. Thus, a polyimide film was obtained.

However, during the polymerization reaction, it was necessary to always move the vacuum exhaust system 42 in order to keep the total pressure at 0.10 Torr. The film formation rate was as slow as 1 cm / sec.
Japanese Examined Patent Publication No. 7-18000 (second page, FIG. 1)

  In the conventional vacuum vapor deposition apparatus, it is necessary to always operate the vacuum exhaust apparatus in order to keep the vacuum chamber in a constant atmosphere. For example, the polyimide film vacuum deposition apparatus uses two types of monomers as raw materials in order to form polyimide. Here, water was generated as a by-product as the polyimide polymerized. Since this water turned into steam and contaminated the atmosphere in the vacuum chamber, it was necessary to evacuate constantly. Therefore, the motor that drives the vacuum pump always consumes power.

  In addition, as described above, for the purpose of discharging the by-product, vacuum evacuation is always performed. In accordance with this, half of the two types of monomers as raw materials are discharged unused. As a result, the film formation rate did not increase. In addition, half of the raw materials were wasted and uneconomical.

  An object of the present invention is to improve the film formation rate, improve the use efficiency of the monomer, and reduce the power for evacuation.

The above-mentioned subject is "a vacuum processing apparatus comprising a vacuum chamber and an evacuation system, wherein the vacuum chamber includes a vacuum processing chamber, two or more raw material chambers, and an evaporation pipe extending from the raw material chamber to the vacuum processing chamber. The flow rate adjusting valve provided in the evaporation pipe, the vacuum exhaust system comprises a vacuum pump, an exhaust pipe, and an exhaust valve,
A vacuum processing apparatus for forming a synthetic resin film comprising evaporating two or more kinds of raw material monomers, introducing them into the vacuum processing chamber and polymerizing them on a substrate, wherein the polymerization is a polyaddition reaction Processing equipment. Is solved by.

Further, the above-mentioned problem is “a vacuum processing apparatus comprising a vacuum chamber and an evacuation system, wherein the vacuum chamber includes a vacuum processing chamber, two or more raw material chambers, and an evaporation chamber that extends from the raw material chamber to the vacuum processing chamber. A flow control valve provided in the pipe and the evaporation pipe, and the evacuation system uses a device comprising a vacuum pump, an exhaust pipe, and an exhaust valve.
In a vacuum processing process of forming a synthetic resin film consisting of evaporating two or more kinds of raw material monomers, introducing them into the vacuum processing chamber, and polymerizing them on a substrate,
Use two or more raw material monomers that cause polyaddition reaction,
(A) exhausting the vacuum chamber;
(B) Opening the raw material valve and adding the raw material monomer;
(C) stopping evacuation and stopping the exhaust valve;
It is solved by a vacuum processing process consisting of.

  By-products can be eliminated or greatly reduced by the polyaddition reaction, so that the film formation reaction proceeds without relying on the vacuum exhaust system, and the atmosphere in the vacuum chamber can be maintained autonomously and continuously. It was. As a result, it was only necessary to stop the vacuum evacuation system or to move it auxiliary.

  During film formation, the exhaust operation is not performed or limited, so that power consumption is small. In the combination of raw material monomers that cause a polyaddition reaction that does not generate any by-products, it is possible to stop the evacuation except that the vacuum chamber is first set to a prescribed vacuum atmosphere.

  Since the exhaust is not performed or limited during the film formation, all the raw material monomers are used for the film formation. As a result, the film formation rate was greatly improved. Naturally, the use efficiency of the raw material monomer has also improved significantly.

  FIG. 1 is an example of a combination of two types of raw material monomers that cause a polyaddition reaction in a vacuum processing apparatus and a vacuum processing process according to an embodiment of the present invention. The diamine monomer 1,12 diaminododecane (1,12-Diaminododecane) and the isocyanate monomer 1,3-bis (isocyanato-methyl) cyclohexane (1,3-Bis (isocyanatomethyl) cyclohexane) overlap. It becomes polyurea by addition reaction. Here, no by-product is produced by the polyaddition reaction.

In the first embodiment and the second embodiment of the present invention, the above combination is used.
Hereinafter, specific embodiments to which the present invention is applied will be described in detail with reference to the drawings.

(Embodiment 1) FIG. 2 is a schematic diagram showing an outline of a vacuum processing apparatus 1 according to an embodiment of the present invention.
FIG. 3 is a principle diagram of a vacuum processing process according to the embodiment of the present invention. The operation of the vacuum processing apparatus 1 of FIG. 2 is equivalently shown.

  In FIG. 2, the vacuum processing apparatus 1 is formed by connecting a vacuum chamber 2 to an evacuation system 3. The vacuum chamber 2 includes a vacuum processing chamber 4, raw material chambers 5, 6, flow rate adjusting valves 10, 11, and evaporation tubes 14a, 14b. The vacuum exhaust system 3 includes a vacuum pump 15, an exhaust valve 10, and an exhaust pipe 18a.

  Two kinds of raw material monomers can be stored in the raw material chambers 5 and 6 by applying a pressure slightly higher than the pressure in the vacuum processing chamber 4 which is a film forming chamber. In particular, a constant temperature can be maintained by a heater (not shown). Further, the wall 4a of the vacuum processing chamber 4 can be heated to about the evaporation temperature of the two kinds of raw material monomers.

  The inside of the vacuum processing chamber 4 is evacuated by the evacuation system 3 and the two kinds of raw material monomers are introduced. Even if the substrate 8 has a complicated shape by heating and introducing the two kinds of raw material monomers to a temperature at which the saturated water vapor pressure becomes equal, a synthetic resin film can be formed on the surface.

Next, the vacuum processing process of the embodiment of the present invention will be described.
First, with the raw material monomer flow rate adjustment valves 10 and 11 and the exhaust valve 20 closed, the base 8 attached to the base holder 9 is held in the vacuum processing chamber 4, and the isocyanate as the raw material monomer 12 is stored in the raw material chamber 5. The monomer 12 and the raw material chamber 6 are filled with the diamine monomer 13 as the raw material monomer 13, respectively.

The isocyanate monomer 12 is kept at 91 ° C. (T ₁ ) and 5.2 Pa (P ₁ ) in the raw material chamber 5. The diamine monomer 13 is maintained at 98 ° C. (T ₂ ) and 0.46 Pa (P ₂ ) in the raw material chamber 6. The inside of the vacuum processing chamber 4 is kept at 30 ° C. (Tc).

Next, the exhaust valve 20 is opened to evacuate the vacuum processing chamber 4. At this time, the vacuum pump of the evacuation system 3 is used. The inside of the vacuum processing chamber 4 becomes a vacuum atmosphere (Pc) of 1 × 10 ⁻³ Pa.

Next, the flow rate adjusting valves 10 and 11 are opened, and two kinds of raw material monomers are introduced into the vacuum processing chamber 4. At the same time or a little later, the exhaust valve 20 is closed and the vacuum exhaust S is stopped. At this time, the conductance C ₁ is applied to the isocyanate monomer 12 and the conductance C ₂ is applied to the diamine monomer 13 by the flow rate adjusting valves 10 and 11. That is, the amount of evaporation is adjusted so that the respective flow rates Q ₁ and Q ₂ have a molar ratio of 1: 1 so that a polyurea film is stoichiometrically formed.

Thereafter, film formation on the substrate 8 proceeds autonomously by the polyaddition reaction.
That is, the gas of the two kinds of raw material monomers of the isocyanate monomer 12 and the diamine monomer 13 becomes a polyurea film, the volume is extremely small, and there are no by-products, so that the vacuum atmosphere in the vacuum processing chamber 4 is maintained. Become. Therefore, as long as two kinds of raw material monomer gases, isocyanate monomer 12 and diamine monomer 13, are supplied, the film formation reaction proceeds autonomously.

The isocyanate monomer 12 is kept at 91 ° C. (T ₁ ) and 5.2 Pa (P ₁ ) in the raw material chamber 5. The diamine monomer 13 is kept at 98 ° C. (T ₂ ) and 0.46 Pa (P ₂ ) in the raw material chamber 6. The inside of the vacuum processing chamber 4 is maintained in a vacuum atmosphere (Pc) of 30 ° C. (Tc) and 6 × 10 ⁻² Pa.

(Embodiment 2) FIG. 4 is a schematic diagram showing an outline of a vacuum processing apparatus 30 according to an embodiment of the present invention.
FIG. 5 is a principle diagram of a vacuum processing process according to the embodiment of the present invention. The operation of the vacuum processing apparatus 30 in FIG. 4 is equivalently shown.

  The vacuum processing apparatus 30 according to the second embodiment is an apparatus devised for forming a polyurea film having a higher quality than that of the first embodiment.

  First, two kinds of raw material monomer gases are mixed in the mixing chamber 7 and rectified by the shower plate 7a so as to be sprayed uniformly on the base 8 to improve the quality of the film formed on the base 8.

  Further, the gas component (released amount) coming out from the wall surface 4a of the vacuum processing chamber 4 is also taken into consideration. That is, the inside of the vacuum processing chamber 4 may be set to the atmosphere for carrying in the substrate and carrying out the finished product. At this time, gas components in the atmosphere are stored in the wall surface 4 a of the vacuum processing chamber 4. This gas component comes out in a high vacuum atmosphere.

  In order to perform exhaust according to the amount of discharge, the vacuum exhaust system 3 ′ has an exhaust adjustment valve 22 capable of conductance adjustment in addition to the exhaust valve 20, and an exhaust valve 21 for switching to the pipe 18b. Is provided. Further, in order to increase the efficiency of restoration of the vacuum atmosphere after the atmosphere is brought in for carrying in the substrate and carrying out the finished product, the pipe 18c for roughing, the exhaust valve 24, and the vacuum pump 16 for roughing are provided.

Next, the vacuum processing process of the embodiment of the present invention will be described.
First, the substrate 8 attached to the substrate holder 9 is held in the vacuum processing chamber 4 with the flow rate adjusting valves 10 and 11, the exhaust valves 20, 21, 23 and 24 and the exhaust adjusting valve 22 closed, and the raw material chamber 5 is filled with an isocyanate monomer 12 as a raw material monomer 12 and a raw material chamber 6 is filled with a diamine monomer 13 as a raw material monomer 13.

The isocyanate monomer 12 is kept at 91 ° C. (T ₁ ) and 5.2 Pa (P ₁ ) in the raw material chamber 5. The diamine monomer 13 is maintained at 98 ° C. (T ₂ ) and 0.46 Pa (P ₂ ) in the raw material chamber 6. The inside of the vacuum processing chamber 4 is kept at 30 ° C. (Tc ′).

Next, the exhaust valve 24 is opened to evacuate the vacuum processing chamber 4. At this time, the vacuum pump 16 for roughing of the evacuation system 3 ′ is used. At this time, the vacuum exhaust S ′ = the vacuum exhaust Seff, and the vacuum processing chamber 4 is exhausted rapidly. A vacuum atmosphere of 1.3 × 10 ^{−1 to} 1.3 × 10 ⁻² is obtained.

Next, the exhaust valve 24 is closed. At the same time or a little later, the exhaust valves 20 and 23 are opened and the vacuum pump 15 is driven. The inside of the vacuum processing chamber 4 is a vacuum atmosphere (Pc ′) of 1 × 10 ⁻³ Pa.

  Next, the flow rate adjusting valves 10 and 11 are opened, and two kinds of raw material monomers are introduced into the vacuum processing chamber 4. At the same time or a little later, the exhaust valve 20 is closed and the exhaust valve 21 and the exhaust adjustment valve 22 are opened.

Thereafter, film formation on the substrate 8 proceeds autonomously by the polyaddition reaction. The exhaust adjustment valve 22 adjusts the conductance C ₀ in accordance with the amount of gas discharged from the wall 4 a in the vacuum processing chamber 4. As a result, the vacuum exhaust Seff is adjusted to a slight flow rate corresponding to the gas discharge amount. At this time, a relationship of 1 / Seff = 1 / S ′ + 1 / C ₀ is established.

The isocyanate monomer 12 is maintained at 91 ° C. (T ₁ ) and 5.2 Pa (P ₁ ) in the raw material chamber 5. The diamine monomer 13 is maintained at 98 ° C. (T ₂ ) and 0.46 Pa (P ₂ ) in the raw material chamber 6. The inside of the vacuum processing chamber 4 is maintained in a vacuum atmosphere (Pc ′) of 30 ° C. (Tc ′) and 6 × 10 ⁻² Pa.

  As mentioned above, although embodiment of invention was described, of course, this invention is not limited to these, A various deformation | transformation is possible based on the technical idea of this invention.

  For example, in Embodiments 1 and 2, the combination of 1,12 diaminododecane and 1,3-bis (isocyanatomethyl) cyclohexane is used, but other combinations may be used. Furthermore, two or more raw material monomers may be used in combination as long as the combination causes a polyaddition reaction. In these cases, the present invention can be similarly applied.

  In the present invention, as the (a) diamine component, any one or both of 1,12-diaminododecane and 1,3-bis (aminomethyl) cyclohexane can be mixed and used.

In the present invention, as the (b) diisocyanate component, 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate or both can be mixed and used.

Moreover, as a preferable polyurea, the polyurea by the combination of the following (a / b) other than embodiment can be mentioned.
1,12 diaminododecane / hexamethylene diisocyanate,
1,3-bis (aminomethyl) cyclohexane / 1,3-bis (isocyanatomethyl) cyclohexane,
1,3-bis (aminomethyl) cyclohexane / hexamethylene diisocyanate,

  In the second embodiment, the shower plate 7a is used as a means for rectifying a mixed gas of two kinds of raw material monomers. For example, a louver structure in which metal thin plates are arranged in parallel, or a metal thin plate is used. A honeycomb structure assembled in a lattice shape, a hexagonal shape, or the like may be used.

Further, the exhaust control valve 22 of the second embodiment is adjusted to conductance C ₀ corresponding to the amount of gas discharged from the wall 4a in the vacuum processing chamber 4, but there are two or more kinds of raw material monomers with slight by-products. You may adjust corresponding to a combination. Any discharge amount that does not hinder autonomous film formation by polyaddition polymerization can be handled.

  Further, there are various types (types) of vacuum pumps used in the vacuum exhaust systems 3 and 3 ′ according to the first and second embodiments, and these can be used by appropriately selecting or combining them. Pumps are, for example, turbo molecular pumps, cryopumps, sorption pumps, sputter pumps, getter pumps, oil diffusion pumps, oil diffusion ejectors, oil rotary pumps, dry pumps, mechanical booster pumps, water seal pumps, reciprocating pumps, steam ejectors Etc.

It is a polyaddition reaction performed with the vacuum processing apparatus of embodiment of this invention. The diamine monomer 1,12-diaminododecane (1,12-Diaminododecane) and the diisocyanate monomer 1,3-bis (isocyanatomethyl) cyclohexane (1,3-Bis (isocyanatomethyl) cyclohexane) It becomes polyurea by addition reaction. It is a schematic diagram of the vacuum processing apparatus 1 of embodiment of this invention. The vacuum chamber 2 includes a vacuum processing chamber 4, raw material chambers 5, 6, flow rate adjusting valves 10, 11, and evaporation tubes 14a, 14b. The vacuum exhaust system 3 includes a vacuum pump 15, an exhaust valve 20, and an exhaust pipe 18a. It is a principle diagram of an embodiment of the present invention. The vacuum processing apparatus 1 of FIG. 2 is equivalently shown. It is a schematic diagram of the other vacuum processing apparatus of embodiment of this invention. The vacuum chamber 2 'includes a vacuum processing chamber 4, raw material chambers 5 and 6, a mixing chamber 7, a shower plate 7a, flow rate adjusting valves 10 and 11, and evaporation tubes 14a and 14b. The vacuum exhaust system 3 'includes vacuum pumps 15, 16, exhaust valves 20, 23, 24, an exhaust adjustment valve 22, exhaust pipes 18a, 18b, 18c, and branches 19a, 19b. It is a principle figure of embodiment of this invention. The vacuum processing apparatus 30 of FIG. 4 is equivalently shown. It is a schematic diagram of the conventional vacuum evaporation system for a comparison.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Vacuum processing apparatus 2, 2 '... Vacuum tank 3, 3' ... Exhaust system, 4 ... Vacuum processing chamber, 4a ... Wall (wall surface) 5, 6, ... -Raw material chamber, 7 ... mixing chamber, 7a ... shower plate, 8 ... base, 9 ... base holder,
10 ... Flow rate adjusting valve, 11 ... Flow rate adjusting valve,
12 ... Raw material monomer (isocyanate monomer), 13 ... Raw material monomer (diamine monomer),
14a, 14b ... evaporation tubes,
15, ... vacuum pump, 16 ... vacuum pump,
18a, 18b, 18c ... exhaust pipe, 19a, 19b ... branch 20 ... exhaust valve, 21 ... exhaust valve, 22 ... exhaust adjustment valve, 23 ... exhaust valve, 24 ...・ Exhaust valve,
30 ... Vacuum processing device,
DESCRIPTION OF SYMBOLS 40 ... Vacuum deposition apparatus, 41 ... Vacuum processing chamber, 41a ... Chamber wall inner surface, 42 ... Vacuum exhaust system, 43 ... Base | substrate, 44 ... Base | substrate holder, 45 ... Heater 46a, 46b ... evaporation tubes, 47a, 47b ... heaters, 48 ... gas introduction pipes, 49 ... heaters,
50, 51, 52 ... Power source, 53a, 53b, 54 ... Flow rate adjusting valve, 58 ... Raw material monomer, 59 ... Raw material monomer,
C ₀ , conductance of exhaust adjustment valve 22, C ₁ , conductance of flow rate adjustment valve 10, C ₂ , conductance of flow rate adjustment valve 11,
P ₁ , P ₂ , pressure in the raw material chamber, Pc, Pc ′, pressure in the vacuum processing chamber,
S ... evacuation, S '... evacuation, Seff ... evacuation (effective exhaust),
T ₁ , T ₂ ... temperature in the raw material chamber, Tc, Tc '... temperature in the vacuum processing chamber,

Claims (7)

A vacuum processing apparatus comprising a vacuum chamber and an evacuation system, wherein the vacuum chamber includes a vacuum processing chamber, two or more raw material chambers, an evaporation pipe extending from the raw material chamber to the vacuum processing chamber, and the evaporation chamber A flow control valve provided in a pipe, and the vacuum exhaust system comprises a vacuum pump, an exhaust pipe, and an exhaust valve. Two or more kinds of raw material monomers are evaporated and introduced into the vacuum processing chamber. A vacuum processing apparatus for forming a synthetic resin film by polymerizing the above, wherein the polymerization is a polyaddition reaction. The vacuum processing apparatus according to claim 1, wherein the vacuum processing apparatus has a mixing chamber for mixing two or more kinds of raw material monomers. 3. The vacuum processing according to claim 1, wherein the vacuum processing apparatus includes a rectification unit for mixing two or more kinds of the raw material monomers between the vacuum processing chamber and the mixing chamber. apparatus. The vacuum processing according to any one of claims 1 to 3, wherein the vacuum processing apparatus has a vacuum exhaust system capable of adjusting conductance for exhaust corresponding to the amount of gas released from the wall in the vacuum chamber. apparatus. The vacuum processing apparatus includes a vacuum exhaust system capable of adjusting a conductance for exhaust corresponding to a byproduct that does not inhibit autonomous film formation by the polyaddition reaction. The vacuum processing apparatus according to any one of 1 to 4. The vacuum processing apparatus comprising the vacuum chamber and the evacuation system, wherein the vacuum chamber includes the vacuum processing chamber, two or more raw material chambers, and an evaporation pipe extending from the raw material chamber to the vacuum processing chamber. And a flow rate adjusting valve provided in the evaporation pipe, the vacuum exhaust system using the vacuum processing apparatus comprising the vacuum pump, the exhaust pipe, and the exhaust valve,
In a vacuum processing process in which two or more kinds of raw material monomers are evaporated and introduced into the vacuum processing chamber, and this is polymerized on the substrate to form the synthetic resin film.
Use two or more raw material monomers that cause polyaddition reaction,
(A) exhausting the vacuum chamber;
(B) opening the raw material valve and adding the raw material monomer;
(C) stopping the vacuum exhaust and closing the exhaust valve;
A vacuum processing process consisting of. Exhausting the gas in accordance with the amount of gas released from the wall in the vacuum chamber after the step (C);
The vacuum processing process according to claim 6, comprising:

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