JPH07102364A - Omnidirectional simultaneous vapor-deposition polymerizer - Google Patents

Abstract

PURPOSE:To provide the polymerizer without its vaporization source container being easily broken, easy to attach and detach, without condensing the raw material monomer when deposited and polymerized and further convenient to handle. CONSTITUTION:A vaporization source container 35 consisting of a bottomed metallic straight tube 34 is inserted and fitted into one end of an inlet tube 61 with the other end opened to a treating chamber 1 through an O ring 37 and airtightly connected, and a freely detachable heating cylinder 70 traveling on a guide rail 86 is provided to control the temp. of the container 35.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an omnidirectional simultaneous vapor deposition polymerization apparatus used for simultaneously forming a polymer film on the entire surface of a material to be vapor deposited.

[0002]

2. Description of the Related Art Conventionally, as a method of forming various polymer films used for an insulating film of semiconductor elements, a passivation film, a soft error prevention film, a capacitor dielectric film, etc., a wet method and a polymer deposition method are used. Methods and plasma polymerization methods are known.

The wet method is a method in which a polymer obtained by polymerizing raw material monomers in an appropriate solvent is applied on a substrate, the polymer vapor deposition method is a method in which the polymer itself is vapor-deposited on the substrate, and the plasma polymerization method is It is a method of polymerizing monomer vapor into a plasma and depositing it on a substrate. However, each of these methods has inconveniences, an ultra-thin film cannot be obtained by the wet method, adhesion is insufficient, and impurities are easily mixed in. However, even in the plasma polymerization method, decomposition occurred at the time of polymerization, and it was difficult to obtain a polymer having a high molecular weight.

As a method of forming a polymer film which eliminates the disadvantages of these conventional methods, the present applicant has filed Japanese Patent Application Laid-Open No. 61-78463.
JP-A-63-166691 and JP-A-63-166961 disclose vapor deposition polymerization methods in which various monomers are evaporated in a vacuum and polymerized on a substrate. JP-A-4-173963, JP-A-5-132763, Japanese Patent Laid-Open No. 5-132764 discloses an omnidirectional simultaneous vapor deposition polymerization apparatus as an apparatus for carrying out the above vapor deposition polymerization method.

An omnidirectional simultaneous vapor deposition polymerization apparatus as a first conventional example will be described below with reference to FIGS. 5 and 6.

In FIGS. 5 and 6, the vacuum processing chamber 1 of the omnidirectional simultaneous vapor deposition polymerization apparatus 80 is connected to the vacuum exhaust system 2 via a valve 17. Further, evaporation source containers 5a and 5b are connected to the introduction pipes 6a and 6b open to the vacuum processing chamber 1 via valves 18a and 18b. Raw material monomers 3 or 4 for the polymer film are stored in the evaporation source containers 5a and 5b, respectively, and heaters 12a and 12b for heating are wound and attached around the evaporation source containers 5a and 5b.

Inside the vacuum processing chamber 1, the tips 9 of four supporting members 8 extending radially around the rotary shaft 7 are provided.
The barrels 10 each having a hexagonal cross section are fixed to each other and arranged in an annular shape.

The conventional omnidirectional simultaneous vapor deposition polymerization apparatus 80 is configured as described above. For example, a polymer film is simultaneously formed on the entire surface of a substantially U-shaped vapor-deposited material 20 as shown in FIG. In case of making it, a plurality of materials 2 to be vapor-deposited in the barrel
After accommodating 0, the motor 11 is driven to rotate each barrel 10 around the rotary shaft 7, and while maintaining the vacuum processing chamber 1 at a predetermined pressure by the vacuum exhaust system 2, each introduction pipe 6a, 6b. The raw material monomers 3 and 4 vapor of the polymer film are introduced into the vacuum processing chamber 1 from the above, and the raw material monomers 3 and 4 are simultaneously vapor-deposited and polymerized on the entire surface of the deposition target material 20 to form a polymer film. There is. As described above, the evaporation source containers 5a and 5b and the introduction pipes 6a and 6b actually exist in two series, but for the sake of simplification, the evaporation source will be hereafter simplified unless it is necessary to distinguish them. The container 5 and the introduction pipe 6 will be described.

Specifically, a heater for heating is wound around the evaporation source container 5, and an evaporation source container 15 made of Pyrex glass as shown in FIG. 8 is used (a heating heater is not shown). . That is, raw material monomer 3 (or 4)
Of the introduction pipe 6 by means of a flange 13 joined with a Kovar glass 19 and having a rubbing portion 14 which can be easily attached and detached for filling, unloading or replacement of
And hexagon socket bolts (not shown).

However, in addition to the glass evaporation source container 15 being easily damaged during handling, the rubbing portion 14
When the vacuum processing chamber 1 is evacuated, adiabatic expansion in the rubbing section 14 causes local cooling, and the raw material monomer 3 (or 4) being sent as vapor is It may be condensed and solidified at that place to block the path from the glass evaporation source container 15 to the introduction pipe 6. When one of the two series is blocked, the quantitative balance between the raw material monomers 3 and 4 is lost, and the formation of the polymer film on the substrate does not proceed as expected.

To solve these problems, FIG.
There is a second conventional example omnidirectional simultaneous vapor deposition polymerization apparatus having a metal evaporation source container 25 shown in FIG. FIG. 9 shows a tubular metal evaporation source container 25 around which a heating heater is wound (not shown), and a flange 26 welded and fixed to the container 25 is welded and fixed to the introduction pipe 6 via an O-ring 27 made of a binder rubber. The flange 16 and the hexagon socket bolt 28 are joined together.

However, since the metal evaporation source container 25 used in the second conventional example has a large heat capacity (= specific heat × weight) of the flanges 16 and 26, it is difficult for the temperature to rise, and the raw material to be heated and sent as steam is fed. The monomer 3 (or 4) may condense and solidify inside the flanges 16 and 26 and also block the path. Further, if the flanges 16 'and 26' having a small heat capacity, that is, small flanges, are used, there is a new problem that it takes time to fill the raw material monomer 3 (or 4) into the metal evaporation source container 25. Furthermore, since the hexagon socket bolt 28 is used to connect to the introduction pipe 6, the metal evaporation source container 25 cannot be easily attached and detached.

In both the first conventional example and the second conventional example, winding the heating heater around the evaporation source container 15 or 25 is a troublesome work itself, and the heating heater is wound. The evaporation source container 15 or 25 may be troublesome to handle.

[0014]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, has an evaporation source container that is not easily damaged, is easily attached and detached, and does not condense or solidify raw material monomers. It is an object of the present invention to provide an omnidirectional simultaneous vapor deposition polymerization apparatus in which an evaporation source container can be easily handled.

[0015]

[Means for Solving the Problems] The above object is to form a polymer film on the surface of the vacuum processing chamber and an inlet pipe for introducing the vapor of the raw material monomer of the polymer film from the external evaporation source container. In an omnidirectional simultaneous vapor deposition polymerization apparatus in which a barrel for containing a material to be vapor-deposited is arranged, the evaporation source container is made of metal, and its opening is removably inserted into the introduction pipe and fitted by a seal ring. An omnidirectional simultaneous vapor deposition polymerization apparatus, wherein the temperature control unit is airtightly connected, and further, a temperature control unit having a shape that covers the whole with a gap from the evaporation source container is detachably provided, Achieved by

Further, the above object is to accommodate, in the vacuum processing chamber, an introduction pipe for introducing the vapor of the raw material monomer of the polymer film from the external evaporation source container, and the material to be vapor-deposited on which the polymer film is to be formed. In an omnidirectional simultaneous vapor deposition polymerization apparatus in which a barrel is arranged, the evaporation source container is made of metal, has a side wall portion which is hermetically and detachably attached via a seal ring, and is filled with the raw material monomer. The container to be inserted is inserted and taken out via the side wall part that has been removed, and further, a temperature control part having a shape that covers the entire evaporation source container in a sheath-like shape is detachably provided. And an omnidirectional simultaneous vapor deposition polymerization apparatus.

[0017]

In the omnidirectional simultaneous vapor deposition polymerization apparatus of claim 1, since the evaporation source container is made of metal, it is not easily damaged and can be easily attached and detached because it is inserted and fitted into the introduction pipe. ,
There is no portion with a large heat capacity in the path leading to the introduction pipe, and therefore there is no risk of condensation of the raw material monomer vapor. Further, since the temperature control unit of the evaporation source container is detachable, handling of the evaporation source container is not troublesome.

Further, in the omnidirectional simultaneous vapor deposition polymerization apparatus according to the second aspect, since the evaporation source container is made of metal, it is not easily damaged and the raw material monomer is charged through the removable side wall portion. Since another container should be taken in and out, the operation is simple, and there is no portion with a large heat capacity in the path leading to the introduction pipe, so there is no risk of condensation of the raw material monomer vapor.
Further, since the temperature control unit of the evaporation source container is detachable, handling of the evaporation source container is not troublesome.

[0019]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An omnidirectional simultaneous vapor deposition polymerization apparatus according to an embodiment of the present invention will be described below with reference to its evaporation source container, with reference to the drawings. The same parts as those in the conventional example described above are designated by the same reference numerals, and detailed description thereof will be omitted.

FIG. 1 shows the vicinity of the evaporation source container of the omnidirectional simultaneous vapor deposition polymerization apparatus according to the first embodiment of the present invention. The entire structure is similar to that shown in the first conventional example, and the vacuum processing chamber 1 One end of the introduction pipe 61 is connected to the above with a flange. In addition, as shown in the first conventional example, in reality, two introduction pipes are connected up and down like 6a and 6b. However, for simplification, only the upper introduction pipe 61 will be shown below. explain. Referring also to FIG. 2 in which a main portion is enlarged, the other end of the introduction pipe 61 is expanded to form an insertion female portion 62, and a holding portion 63 of the sealing O-ring 37 is formed at the tip thereof. There is.

On the other hand, the evaporation source container 35 made of metal is composed of a straight pipe portion 34 with a bottom and an insertion male portion 32 on the opening side, and a projection 33 for pressing and holding the O-ring 37 is provided at the boundary thereof. ing. The evaporation source container 35a (35b) is provided with an introduction pipe 61.
At this time, the O-ring 37 is sandwiched between the holding portion 63 and the protrusion 33, and both are airtightly connected in vacuum. A heat insulating material 64 is wound around the introduction pipe 61 if necessary, and this is shown by a chain double-dashed line.

Further, the heating cylinder 70 as a heating source for the evaporation source containers 35a and (35b) is provided with an evaporation source container 35a (35b).
And are provided so as to cover the whole with a gap. That is, in the heating cylinder 70, the resistance heating electric wire 71 is wound around the inner cylinder 74 between the inner cylinder 74 and the outer cylinder 75, and this is wrapped with glass wool 73 as a heat insulating material. In addition, a space is provided around the outer cylinder 75 that becomes hot to form the outer wall 7
6 is provided. Incidentally. The resistance heating electric wire 71 is led out to the outside by the connecting portions 72a and 72b, and is connected to a power source (not shown) via the conduit 84 on the support base 83.

The heating cylinder 70 is connected to the supporting bases 81 and 83 by bolts 77 fixed at two points on the lower surface of the outer cylinder 75 and nuts 78 screwed to the bolts 77. The support bases 81 and 83 can travel on the guide rails 86 by the riders 81R and 83R coupled to the support bases 81 and 83, respectively.
6 is fixed on a rail fixing base 87 supported by a supporting column 88.

Further, the support base 81 has a positioning member 82.
Is attached to the heating cylinder 70 by contacting the stopper 85 provided at the end of the rail fixing base 87.
Is positioned.

The first embodiment is constructed as described above,
Next, this operation will be described.

From the opening of the evaporation source container 35 from which the heating cylinder 70 has been removed and the insertion fitting has been removed, the raw material monomer 3 is introduced.
(Or 4) is supplied, and the O-ring 37 is fitted into the insertion male part 32 up to the position of the protrusion 33, and then the insertion male part 3 is inserted.
2 is inserted and fitted into the insertion female portion 62 of the introduction pipe 61. Since the insertion fitting length is sufficiently long, the inserted evaporation source container 35 does not come off and fall even under atmospheric pressure.

Next, the vacuum processing chamber 1 is evacuated with the vacuum valve 18 open, and the evaporation source container 35 is also evacuated. At this time, the evaporation source container 35 is pressed against the introduction pipe 61 via the O-ring 37 by the atmospheric pressure, and the airtightness of the connection is obtained. After that, after closing the vacuum valve 18, the heating cylinder 70 that has been heated in advance is guided to the guide rail 86.
The evaporation source container 35 is moved along the above until it covers the whole. The positioning is performed by abutting the positioning member 82 integrated with the heating cylinder 70 and the stopper 85 on the rail fixing base 87.

As a result, the evaporation source container 35 is heated to a predetermined temperature, the raw material monomers 3 (or 4) are vaporized, and the respective vapor pressures are exhibited. When the vacuum valve 18 is opened at this stage, the raw material monomer 3 (or 4) is introduced into the vacuum processing chamber 1 through the introduction pipe 61,
At the same time, vapor deposition polymerization is performed on the entire surface of the vapor deposition target material 20 in the barrel 10 provided therein.

When the vapor deposition polymerization is completed, the heating cylinder 70 is moved along the guide rail 86 to move away from the evaporation source container 35, the evaporation source container 35 is cooled, and then the atmosphere is introduced into the vacuum processing chamber 1 and the vacuum valve is used. Inlet pipe 61 after closing 18
And the evaporation source container 35 are removed from each other.

The omnidirectional simultaneous vapor deposition polymerization apparatus of the first embodiment using this evaporation source container 35 and the evaporation source container 25 (FIG. 9).
Vapor-deposition polymerization was carried out by the omnidirectional simultaneous vapor-deposition polymerization device of the second conventional example using the above, and the situation was compared. That is, one of the evaporation source containers 35a or 25a is filled with 4,4′-diaminodiphenyl ether (ODA) as a raw material monomer, and the other evaporation source container 35b or 25b is filled with pyromellitic dianhydride (PMDA). Then, vapor deposition polymerization was performed under the conditions shown below, and a polyamic acid film was formed on the vapor deposition target material 20 (FIG. 7) to compare the conditions. (ODA) (PMDA) Heating temperature 200 ± 1 ° C. 210 ± 1 ° C. Pressure in vacuum processing chamber 0.01 Torr or less Evaporation polymerization time 1 hour In addition, heating ODA to 200 ° C. and PMDA to 210 ° C. is both moles. This is to evaporate at a ratio of 1: 1.

When the evaporation source 35 of the first embodiment was used, the polyamic acid film was formed on the entire surface of the material 20 to be vapor-deposited without causing any problems, but the evaporation source of the second conventional example was used. When the container 25 is used, pyromellitic dianhydride (PMDA) is condensed and crystallized in the passages after the flanges 16 and 26 connecting the evaporation source container 25 and the introduction pipe 6, and the passage is clogged. Was there.

That is, according to the evaporation source container 35 used in the first embodiment, since it is made of metal, it does not break like glass, and the connection with the introduction pipe 61 is insertion fitting. It is easy to put on and take off. Moreover, since there is no part with a large heat capacity such as a flange, the raw material monomer 3
(Or 4) does not condense or solidify. Furthermore, since the heating is performed by attaching and detaching the heating cylinder 70, there is no trouble in handling as in the second conventional example in which the resistance heating electric wire is wound.

Next, a second embodiment of the present invention will be described. The second embodiment is different from the first embodiment only in the evaporation source container, and is otherwise constructed and operates in exactly the same manner.

FIG. 3 shows the metallic evaporation source container 45. The projection 4 which should press the insertion male part 42 and the O-ring 47.
3 is also the insertion male part 3 of the evaporation source container 35 in the first embodiment.
2, similar to the protrusion 33, but having a monomer reservoir 44 as a portion for holding the raw material monomer 3 (or 4), which is suitable for holding the raw material monomer 3 (or 4) when it is liquid I am trying. Although not shown, the heating cylinder corresponding to the heating cylinder 70 used in the first embodiment is adapted to the shape of the evaporation source container 45.

The third embodiment of the present invention will be described below. Also in this embodiment, only the evaporation source container is different from the first embodiment, and the other parts are constructed and operate in exactly the same manner, so only different parts will be described.

FIG. 4 shows an evaporation source container 5 used in this embodiment.
5 is shown. The evaporation source containers 35 and 45 used in the first and second embodiments both hold and heat the raw material monomer 3 (or 4) in the same container.
In the evaporation source container 55 of this embodiment, each function is performed by an independent container. That is, the metal evaporation source container 55 is directly connected to the vacuum valve 18 ′, and the side wall 56 is attached to the main body 54 thereof in an airtight and removable manner via the O-ring 57 by an attachment mechanism (not shown). ing. The raw material monomer 3 (or 4) is held in another metal container 58 inserted in the main body 54. The evaporation source container 55 is of course heated by a heating cylinder corresponding to the heating cylinder 70 (not shown) that covers the main body 54.

To explain this action, the vacuum valve 18 '
Is closed, the side wall 56 is removed, and the container 58 holding the raw material monomer 3 (or 4) is inserted into the main body 54. Then, the side wall 56 fitted with the O-ring 57 is attached to the main body 5
4, the vacuum valve 18 is opened to open the vacuum processing chamber 1.
Is evacuated, and at the same time, the evaporation source container 55 is also evacuated.
Next, the vacuum valve 18 is closed, and a heating cylinder for heating the evaporation source container 55 is attached. When the raw material monomer 3 (or 4) reaches a predetermined vapor pressure by heating, the vacuum valve 18 is opened, and the vapor of the raw material monomer 3 (or 4) is sent to the vacuum processing chamber 1 via the introduction pipe 61. Be done. When the vapor deposition polymerization is completed, the heating cylinder is removed to cool the evaporation source container 55, then the atmosphere is introduced into the vacuum processing chamber 1 to break the vacuum, the vacuum valve 18 'is closed, and then the side wall 56 is removed. The raw material monomer container 58 is taken out.

In the case of the apparatus of this embodiment, the evaporation source container 5
5 is made of metal and does not break like glass, and the raw material monomer 3 (or 4) is supplied and taken out from the side wall 56.
Since it can be carried out by attaching and detaching the raw material monomer 3 (or 4), there is no portion having a large heat capacity between the evaporation source container 55 and the vacuum valve 18.
Does not condense and solidify to block the path. Further, since the heating cylinder is separately provided, there is no trouble in attaching and detaching the side wall 56.

Although the respective embodiments of the present invention have been described above, needless to say, the present invention is not limited to these, and various modifications can be made based on the technical idea of the present invention.

For example, in each of the above embodiments, the evaporation source container 3
Although 5, 45 and 55 are connected horizontally, they may be connected vertically.

In each of the embodiments, the vacuum valve 1 is provided at the connecting portion between the introduction pipe 61 and the evaporation source vessels 35, 45, 55.
Although 8 and 18 'are provided, the vacuum valves 18 and 18' may be omitted. The heating cylinder 70 that has been preheated, or a corresponding heating cylinder (not shown) is attached to the evaporation source containers 35, 45,
Since it is mounted on 55, heating can be performed in a short time depending on the kind of the raw material monomer, and there is little need to wait for a long time with the vacuum valves 18 and 18 ′ closed.

In each embodiment, the resistance heating wire 7
Although the heating cylinder 70 around which 1 is wound or the heating cylinder corresponding thereto is used, other heating means such as a mantle heater or dielectric heating means can be used if the attachment / detachment is simple.

In each of the examples, the heating cylinder 70 or a heating cylinder corresponding thereto is exemplified by vapor deposition polymerization of a polyamic acid film using 4,4'-diaminodiphenyl ether and pyromellitic dianhydride as raw material monomers. However, since there are some that evaporate below room temperature depending on the type of raw material monomer, optimal temperature control is possible for these before vapor deposition polymerization, during vapor deposition polymerization, and according to each stage after vapor deposition polymerization. Cooling means are required. Therefore, the temperature control unit of the present invention also includes cooling means.

[0044]

EFFECTS OF THE INVENTION In the omnidirectional simultaneous vapor deposition polymerization apparatus according to the present invention, since the evaporation source container is made of metal, it does not easily break like glass and does not have a portion with a large heat capacity. There is no risk of solidification and blockage of the passage, and the supply and removal of the raw material monomer are carried out by inserting or withdrawing the evaporation source container or by attaching or detaching the side wall, so that it can be carried out easily. Further, since the temperature control unit is of a detachable type, handling of the evaporation source container is not troublesome.

[Brief description of drawings]

FIG. 1 is a cutaway side view in the vicinity of an evaporation source container of an omnidirectional simultaneous vapor deposition polymerization apparatus according to a first embodiment of the present invention.

FIG. 2 is a cutaway enlarged side view of a main part of the evaporation source container.

FIG. 3 is a cutaway side view of an evaporation source container used in an omnidirectional simultaneous vapor deposition polymerization apparatus according to a second embodiment of the present invention.

FIG. 4 is a cutaway side view of an evaporation source container used in an omnidirectional simultaneous vapor deposition polymerization apparatus according to a third embodiment of the present invention.

FIG. 5 is a schematic side view of an omnidirectional simultaneous vapor deposition polymerization apparatus according to a first conventional example.

FIG. 6 shows a device of a first conventional example [6]-
[6] It is sectional drawing of a line direction.

FIG. 7 is a perspective view of a vapor deposition target material on which a polymer film is to be formed by vapor deposition polymerization.

FIG. 8 is a side view of a specific evaporation source container used in the omnidirectional simultaneous vapor deposition polymerization apparatus of the first conventional example.

FIG. 9 is a cutaway side view of an evaporation source container used in an omnidirectional simultaneous vapor deposition polymerization apparatus of a second conventional example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Vacuum processing chamber 35 Evaporation source container 37 O-ring 45 Evaporation source container 47 O-ring 55 Evaporation source container 57 O-ring 61 Introducing pipe 70 Heating cylinder 80 Omnidirectional simultaneous vapor deposition polymerization device

Claims (2)

[Claims] 1. An introduction pipe for introducing a vapor of a raw material monomer of a polymer film from an external evaporation source container into a vacuum processing chamber,
In an omnidirectional simultaneous vapor deposition polymerization apparatus in which a barrel containing a material to be vapor-deposited for forming a polymer film is arranged, the evaporation source container is made of metal, and its opening is removably inserted into the introduction pipe. Fitted and airtightly connected by a seal ring, and further, a temperature control unit having a shape that covers the outer periphery with a gap from the evaporation source container is detachably provided in all directions. Simultaneous vapor deposition polymerization equipment. 2. An introduction pipe for introducing a vapor of a raw material monomer for a polymer film from an external evaporation source container into the vacuum processing chamber,
In an omnidirectional simultaneous vapor deposition polymerization apparatus in which a barrel for accommodating a material to be vapor-deposited to form a polymer film on the surface is arranged, the evaporation source container is made of metal, and is hermetically and removable via a seal ring. It has a side wall attached, is inserted and taken out through the side wall part from which the container to be filled with the raw material monomer is removed, and has a shape covering the outer periphery with a gap from the evaporation source container. An omnidirectional simultaneous vapor deposition polymerization apparatus, wherein a temperature control unit is detachably provided.