JP3489191B2 - Forming method of deposited film - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a polymer vapor deposition film used as, for example, an insulating film, a moisture-proof film, a lubricating film or the like of electronic parts such as semiconductor devices.

[0002]

2. Description of the Related Art Conventionally, as a method for forming a vapor deposition film of this type, there are methods shown in FIGS.

This product forms a polyimide thin film by heating and evaporating tetracarboxylic dianhydride and diamine as the two kinds of raw material monomers A and B, and depositing them on an object C such as an electronic component and polymerizing them. Is the way to do it.

First, the object C is put into the rotary barrel D. On the other hand, the raw material monomers A and B are in powder form and
As shown in Fig. 4, for example, the raw material monomer A is weighed in Fig. 2 (a), and after being charged into the evaporation pipe E from the opening E _{1 in} Fig. 2 (b),
In the same figure (c), the evaporating pipe E is horizontal, and it is attached to the introducing pipe G in the same figure (d). Similarly, the raw material monomer B is also attached to another introduction pipe H while being accommodated in another evaporation pipe F. Next, the vacuum chamber I is evacuated to a predetermined pressure by the vacuum pump I, and then the raw material monomers A and B are heated by the heaters K and L provided outside the outer and bottom surfaces of the evaporation tubes E and F, respectively. Then, the raw material vapor is introduced into the vacuum chamber J from the inlets G ₁ and H ₁ provided in the inlet pipes G and H, and the polyamic acid film is formed on the surface of the object C in the rotary barrel D rotated by the motor M. It is formed. Then, after the heating and the exhaust are stopped, the polyamide acid film is heat-treated to form a polyimide thin film on the surface of the object C 1.

[0005]

Generally, in a polymer compound formed by a condensation reaction of two or more kinds of raw material monomers, the molar ratio of the raw materials greatly affects the degree of polymerization. A polymer film with a high degree of polymerization has heat resistance, mechanical properties (strength, elastic modulus, adhesion with an object, etc.), electrical properties (dielectric strength, etc.), etc. Excellent physical properties.

However, in the above-described conventional method for forming a vapor-deposited film, for example, when the powdery raw material monomer A is accommodated in the evaporation pipe E, the raw material monomer A is opened as shown in FIG. After charging the evaporation pipe E from ₁ and installing it in the introduction pipe G with the evaporation pipe E horizontal,
In the inside of the evaporation pipe E, it is difficult for A to be distributed in a uniform layer from the back of the pipe to the opening E ₁ as shown in FIG. 6 (a).

As shown in the figure, the heater K is arranged so as to heat the outer side surface and the bottom surface of the evaporation tube E, and therefore the temperature of the raw material monomer A contained in the evaporation tube E is reduced. As shown in (b) of the same figure, the distribution becomes higher at the inner part of the tube near the bottom surface due to the heat of both the outer surface and the bottom surface, while it becomes lower easily at the part near the opening E ₁ for heat dissipation.

Therefore, the raw material monomer A is, for example, as shown in FIG.
As shown in (a), when there is a relatively large amount of distribution in the inner part of the tube, as shown in (b) of the figure, the evaporation starts quickly, and the evaporation rate is generally fast. As shown in (a), when there is a relatively large distribution near the opening E ₁ of the pipe, as shown in (b) of the figure, the start of evaporation is slow, and the evaporation rate as a whole is also high. slow.

That is, it is difficult to control the molar ratio of the two kinds of raw material monomers A and B, and the degree of polymerization, that is, the physical properties of the polymer vapor deposition film is not stable.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for forming a vapor deposition film which can further stabilize the physical properties of the vapor deposition film.

[0011]

In order to solve the above-mentioned problems, the method for forming a vapor-deposited film according to claim 1 stores two or more kinds of monomers in a plurality of evaporation tubes each having an opening in one. In the method for forming a vapor deposition film, which is formed by simultaneously heating and evaporating in a vacuum to form a vapor deposition film made of a polymer of the monomer on an object, after filling the monomer into a box-shaped filling container having an upper opening, The filling container is placed horizontally and inserted into the evaporation tube through the opening.

Further, a compartment is provided in the filling container, and the monomer is filled in a predetermined place in the compartment.

Further, in the method for forming a deposited film according to claim 2, in the method for forming a deposited film according to claim 1, vibration is applied to the filling container filled with the monomer.

[0014]

According to the method for forming a vapor-deposited film of claim 1, when the monomer is filled in a box-shaped filling container having an upper opening, the monomer can be visually distributed over substantially the entire opening, and then the filling is performed. Since the container is placed in a horizontal state and inserted into the evaporation tube through the opening, the monomer can be accommodated in the evaporation tube while maintaining the distribution state as it is.

Further, since the filling container is partitioned,
When heated by a heater or the like in a state of being housed in the evaporation tube, the monomer can be filled in the place of the section which is heated more uniformly in consideration of the temperature distribution.

According to the method for forming a vapor-deposited film of the second aspect , it is possible to make the filling distribution state of the monomer more uniform by vibrating the filling container.

[0017]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to FIGS. This product has two kinds of raw material monomers 1,2
Powdered pyromellitic dianhydride, which is tetracarboxylic acid dianhydride, and powdered 4,4′-diaminodiphenyl ether, which is diamine, are heated and vaporized respectively to be vapor-deposited and polymerized on an object 3 such as an electronic component. This is a method of forming a polyimide thin film.

Numerals 4 and 5 are evaporation pipes, which are formed in a cylindrical shape with a bottom and have openings 4a and 5a on one side, and heaters 41 and 51 are arranged on the outside thereof so as to heat the outer surface and the bottom surface, respectively. Set up.

Numerals 6 and 7 are filling containers, which are formed in a box shape with an upward opening, and whose internal volume is divided into three parts at both ends and the central part, and the central parts are filled with the raw material monomers 1 and 2, As will be described later, they are inserted into the evaporation tubes 4 and 5, respectively.

Introducing pipes 8 and 9 are formed in a tubular shape with one end 8a, 9a opening in a trumpet shape, and a plurality of introducing ports 8b, 9b are arranged in rows in the longitudinal direction.

Reference numeral 10 denotes a vacuum chamber, which is formed in a box shape with a bottom and one end of which is open. Introducing pipes 8 and 9 are provided on both sides of the bottom of the vacuum chamber.
A is affixed to the outside and inlets 8b and 9b are positioned parallel to each other so that they are located inside, and they are fixed through each other, and a vacuum pump 10a is connected to the side surface.

Reference numeral 11 denotes a rotary barrel, which is formed of a net-like material into a tubular shape, and in which a large number of objects 3 are put, the net-like portion faces the inlets 8b and 9b of the inlet pipes 8 and 9. It is installed in the vacuum chamber 10 so that the opening of the vacuum chamber 10 is covered.
10b is closely fitted via the gasket 10c, and the motor 11
The axis rotates by d.

A method of forming a polyimide thin film on the object 3 using the above apparatus will be described below.

First, as shown in FIG. 2, raw material monomer 1
Is weighed in Fig. (A), put into the central part of the filling container 6 in Fig. (B), and then filled in the filling container 6 in Fig. (C).
Vibration is applied to the sample to homogenize the filling distribution state of the raw material monomer 1, and the filling container 6 is made horizontal as shown in FIG.
It is inserted into the inside through the opening 4a, and the opening 4a of the evaporation tube 4 is attached in close contact with the one end 8a of the introduction tube 8 through the gasket 4b in the same figure (e). Similarly, the raw material monomer 2 is also inserted into the evaporation pipe 5 using the filling container 7, and the opening 5a of the evaporation pipe 5 is attached to the one end 9a of the introduction pipe 9 in close contact with the gasket 5b. Attach it to another introduction tube H while it is housed in the evaporation tube F.

Next, the vacuum chamber 10 is evacuated to a pressure of 10 ^-1 Torr or less by the vacuum pump 10a, and the evaporation pipes 4,5 are heated to the heaters 41,5.
Heat each by 1 and feed monomer 1 to 230 degrees Celsius
Degree, the raw material monomer 2 is evaporated to about 220 degrees Celsius, and the raw material vapor is introduced into the vacuum chamber 10 through the inlets 8b and 9b of the inlet pipes 8 and 9, and the inside of the rotary barrel 11 rotated by the motor 11d. A polyamic acid film is formed on the surface of the object 3. Then, after stopping heating and exhausting, the polyamide acid film is heat-treated to form a polyimide thin film on the surface of the object 3.

In such a method for forming a vapor-deposited film, when the raw material monomers 1 and 2 are filled in the box-shaped filling containers 4 and 5, which are opened upward, almost all the opening in the central portion divided by visual observation is spread. It can be distributed in an appropriate amount, and the filling distribution can be made more uniform by vibrating the filling containers 4,5, and then the filling containers 4,5 can be horizontally placed in the evaporation pipes 4,5. Since it is inserted through the openings 4a and 5a, the raw material monomers 1 and 2 can be accommodated in the evaporation pipes 4,5 while maintaining a uniform distribution state.

As for the heaters 41 and 51, as shown in FIG. 3, for example, in the case of the heater 41, the temperature distribution inside the evaporation pipe 4 in which the outer and bottom surfaces of the evaporation pipe 4 are heated is shown in FIG. As shown in Fig. 4, the inner part of the tube near the bottom surface gets higher due to the heat from both the outer surface and the bottom surface, while the part near the opening 4a has a low temperature that easily dissipates heat, but a container for the raw material monomer 1 is filled.
Since the both ends divided into 4 are not filled but only the central part is filled, the temperature distribution of the raw material monomer 1 is relatively uniform and heated as indicated by the two-dot chain line.

Therefore, the two kinds of raw material monomers 1 and 2 are polymerized at a predetermined molar ratio by evaporating at a constant rate, and have heat resistance and mechanical properties (strength, elastic modulus, adhesion to an object, etc.). A polyimide thin film having stable physical properties such as electrical properties (dielectric strength, etc.) can be formed on the surface of the object 3.

In this example, pyromellitic dianhydride is used as the raw material monomer 1, but 3,3 ',
4,4'-biphenyltetracarboxylic dianhydride, 3,4 '
It may be a tetracarboxylic acid dianhydride such as 3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride or 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride. Although 4,4'-diaminodiphenyl ether is used as the monomer 2, a diamine such as 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylsulfone may be used.

Further, in this embodiment, an example of forming a polyimide thin film has been shown, but other polymer vapor deposition film may be formed, and in that case, the raw material monomers are not limited to two kinds, and may be more than two kinds. Of course.

Further, in this embodiment, the filling containers 4,5 are divided into three sections, but the heaters 41, which heat the evaporation pipes 4,5,
When the temperature distribution differs depending on the position and type of 51, the number, position, and area of the partition, and the partition portion filled with the raw material monomer may be appropriately set accordingly.

Further, in this embodiment, the filling distribution states of the raw material monomers 1 and 2 are made uniform by vibrating the filling containers 4 and 5, but when it is difficult to attach them by a vibrating device or the like. , People use tools such as spatula for raw material monomer
The method of stroking the surface of 1 or 2 may be used.

[0033]

According to the method of forming a vapor deposition film of claim 1,
When the monomer is filled in a box-shaped filling container having an upper opening, it can be visually distributed over almost the entire opening, and then the filling container is horizontally placed and inserted into the evaporation tube through the opening. The monomer can be stored in the evaporation tube while maintaining the distribution state as it is.Therefore, the monomer is polymerized at a predetermined molar ratio by evaporating at a constant rate, and a polymer vapor deposition film with stable physical properties is deposited on the surface of the object. Can be formed.

Since the filling container is divided,
When heated by a heater, etc., when it is housed in the evaporation tube, the monomer can be filled into the locations of the compartments that are heated more uniformly considering the temperature distribution, and therefore the polymer vapor deposition film with more stable physical properties is targeted. It can be formed on the surface of objects.

Further, according to the method for forming a vapor-deposited film of claim 2 , by vibrating the filling container, the filling distribution state of the monomer can be made more uniform, and therefore, it is further more than in the case of claim 1. A polymer vapor deposition film having stable physical properties can be formed on the surface of an object.

[Brief description of drawings]

FIG. 1 is a sectional front view showing the entire apparatus according to an embodiment of the present invention.

FIG. 2 is a process drawing showing a method for accommodating the above monomer in an evaporation tube.

FIG. 3 is a diagram illustrating a temperature distribution of a monomer contained in the evaporation tube of the above.

FIG. 4 is a sectional front view showing the entire conventional apparatus.

FIG. 5 is a process diagram showing a method for accommodating the above monomer in an evaporation tube.

FIG. 6 is a diagram illustrating a temperature distribution of a monomer contained in the evaporation tube of the above.

FIG. 7 is a diagram illustrating an evaporation rate in the case where a relatively large amount of the above-mentioned monomer is distributed deep inside the evaporation tube.

FIG. 8 is a diagram illustrating an evaporation rate when the above monomer is distributed in a relatively large amount near the opening of the evaporation tube.

[Explanation of symbols]

1 monomer 2 Monomer 3 Target 4 Evaporation tube 4a opening 5 Evaporation tube 5a opening

─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Katsunobu Yamada 1048 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works, Ltd. (56) References JP-A-5-132763 (JP, A) JP-A-4-214011 ( JP, A) JP-A-7-102364 (JP, A) Actual development Sho 50-39441 (JP, U) Japanese Patent Sho 53-43904 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23C 14/12

Claims (2)

(57) [Claims] 1. A vapor deposition film comprising a polymer of the above-mentioned monomers is formed on an object by accommodating two or more kinds of monomers in a plurality of evaporation tubes each having an opening in one side and simultaneously heating and evaporating in a vacuum. In the method for forming a vapor-deposited film, a compartment is provided in a box-shaped filling container with an upper opening, and the compartment is
A method for forming a vapor-deposited film, which comprises filling the monomer in a certain position and then placing the filling container in a horizontal state and inserting it into the evaporation tube through an opening. 2. The container filled with the monomer is vibrated.
The addition method of forming a deposited film according to claim 1, wherein Rukoto.