JP2002275619A - Apparatus for producing organic polymer thin film and method for producing organic polymer thin film - Google Patents

Abstract

(57) [Problem] To produce an organic polymer thin film even when using a plurality of raw material monomers having significantly different surface residence times or reaction energies on a substrate surface, and to obtain a film composition and a film structure. SOLUTION: A plurality of vapor deposition sources of a vapor deposition polymerization apparatus containing a plurality of vapor deposition sources and a substrate to be vapor-deposited at least an organic polymer thin film in a vacuum vessel are independently provided. Alternatively, a pulse valve which can be opened and closed at an arbitrary time interval in conjunction therewith, a raw material tank for charging a raw material monomer, and a heater for controlling the temperature in the evaporation source are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for producing an organic polymer thin film which can be used as an electronic material, an optical material, a sensor, a separation film, a substrate protective film, and the like, and a method for producing an organic polymer thin film. More specifically, the present invention relates to a vapor deposition polymerization apparatus for producing the organic polymer thin film and a method for producing an organic polymer thin film by vapor deposition polymerization.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an organic polymer thin film, a raw material monomer is evaporated in a vacuum vessel and adhered onto a substrate to be vapor-deposited (hereinafter, referred to as a "substrate"). There is a vapor deposition polymerization method in which a polymer thin film is formed by a polymerization reaction of raw material monomers (deposited). For example, in the preparation of a thin film by vapor deposition polymerization of polyimide, which is a heat-resistant polymer, a polyamic acid that is a precursor of polyimide is deposited on a substrate using monomers appropriately selected from a dibasic acid compound and a diamine compound as raw materials. Is synthesized from a monomer on a substrate and polymerized (for example, Y. Takahashi, M. Iijima, K. Inagawa,
and A.Itoh, J.Vac.Sci.Technol., A5 (4), p2253 (198
7)) Compared to the method of thinning a polyamic acid that has already been polymerized, not only is the film thickness controllable, but also the controllability of the thin film structure such as molecular orientation (for example, J .Sakata, and M.Mochizuki, Thin Solid Fi
lms, vol.277 (1-2), p180 (1996)).

[0003] As described above, the vapor deposition polymerization method by vacuum vapor deposition of an organic polymer is excellent in controllability of the film thickness and the like at the time of producing a thin film. However, when a plurality of raw material monomers are used in this vapor deposition polymerization method, the plurality of generally used raw material monomers cause a polymerization reaction efficiently on the surface of the substrate, so that the surface residence times on the substrate are the same. And the reaction energy of the polymerization is low.

[0004] When the surface residence time of a plurality of raw material monomers is not the same as each other, before the raw material monomers deposited on the substrate surface move on the substrate surface and come into contact with each other to cause polymerization, the surface residence time is short. This is to avoid such a situation since the raw material monomer component is detached from the substrate surface. The term “surface residence time” means the time that the raw material monomer released from the evaporation source stays on the substrate surface from the time it adheres to the substrate surface until it leaves the substrate surface.

That is, in the above-mentioned polyimide thin film preparation, since the surface residence time of the raw material monomer is almost the same and the reaction energy is appropriate for vapor deposition polymerization, the controllability of film thickness and the like is obtained by vapor deposition polymerization. It can be said that a thin film excellent in quality can be manufactured. On the other hand, even when the surface residence time of a plurality of raw material monomers is not about the same, it is possible to sufficiently polymerize by introducing more raw material monomers having a short surface residence time. This leads to a decrease in film efficiency.

For controlling the film composition in the vapor deposition polymerization, it is important to control the amount of the raw material monomer introduced into the vapor deposition apparatus. However, since the raw material monomer having a short surface residence time has a high vapor pressure, this raw material monomer is difficult to control. Introducing a larger amount of this causes a problem that the degree of vacuum in the vacuum vessel is reduced and the controllability of the amount of each raw material monomer introduced is reduced. In this regard, as a method for precisely controlling the introduction amount of the raw material monomer, for example, Japanese Patent Application Laid-Open No. Hei 7-26023 proposes an apparatus and a film forming method for introducing a carrier gas containing a predetermined concentration of the raw material monomer. I have. According to this method, when two types of raw material monomers are used for vapor deposition polymerization, the difference in the surface residence time between the respective raw material monomers on the substrate surface affects the film formation rate, but is controlled by controlling the amount of the raw material monomers introduced. It is possible to produce a polymer thin film having the following composition.

However, when three or more kinds of starting monomers are used, the influence of the difference in the surface residence time between these starting monomers cannot be ignored, and the polymerization between the starting monomers having a long surface residence time has priority. As the polymerization proceeds, the polymerization reaction tends to be biased on the surface of the substrate, and the controllability of the composition and structure of the polymer film is reduced. Also, from the viewpoint of reaction energy, only the polymerization reaction between the raw material monomers having low reaction energy is prioritized, and the polymerization of other raw material monomers is suppressed.

For this reason, in vapor deposition polymerization using three or more kinds of raw material monomers, it is still difficult to precisely control a film composition, a film structure, and the like. One example of a thin film using three or more types of raw material monomers is polyamideimide. Polyamideimide is expected to be used as a separation membrane that can be used in a membrane separation process that is an energy-saving process because it can produce a membrane having selective permeability of molecules in addition to excellent chemical resistance and heat resistance (for example, , M. Langsam, DVLaciak, J. Polymer.Sc
i.:Part A: Polymer Chemistry, Vol.38, p1951 (200
0)).

However, as described above, in the conventional vapor deposition polymerization method, for example, three kinds of raw material monomers such as a dibasic acid compound, a diamine compound, and tetracarboxylic acid chloride are formed on the surface of the substrate by each raw material monomer. Because the surface residence time and the reaction energy between each raw material monomer are greatly different, it is difficult to precisely control the synthesis of a polyamideimide thin film using these three types of monomers (tetracarboxylic acid chloride is more difficult than diamine compounds and dibasic acid compounds). The surface residence time is short, and the reaction energy between the tetracarboxylic acid chloride and the diamine compound is higher than the reaction energy between the dibasic acid compound and the diamine compound).

Therefore, in general, a polyamideimide film has been produced by a solution polymerization method in which a raw material monomer having an imide bond in a skeleton is synthesized and the raw material monomer is polymerized (for example, Chin-Ping Yang, Ruei). -Shin
Chen, Chi-Chi Huang, J. Polymer.Sci .: Part A: Polyme
r Chemistry, vol. 37, 2421 (1999)). However, in the case of the solution polymerization method, the raw material monomer of the polymer material is dissolved in an appropriate solvent, and the solution is dropped on the substrate and polymerized.
Precise control of the film thickness is difficult.

Therefore, considering a sensor utilizing selective permeability or an electronic material utilizing its physical properties, a thin film is manufactured by a dry process without using a solvent capable of precisely controlling the film thickness. Is desired. In other words, if a vapor deposition polymerization method capable of synthesizing a thin film under precise control can be established even between monomers whose surface residence time or reaction energy differs greatly, a method of producing a functional organic polymer thin film having a wide applicable range can be provided. become.

Accordingly, the present invention has been made in view of the above-mentioned circumstances, and even when a plurality of raw material monomers having greatly different surface residence times or reaction energies on a substrate surface are used, the organic polymer thin film can be used. It is an object of the present invention to provide a deposition source, a deposition polymerization apparatus, and a method for producing an organic polymer thin film by vapor deposition polymerization, which can be produced and can precisely control a film composition and a film structure.

[0013]

SUMMARY OF THE INVENTION As a result of intensive study, the present inventors have focused on the problems found in the conventional vapor deposition polymerization apparatus and the method for producing an organic polymer thin film by vapor deposition polymerization as described above, and the demands for them. Such a vapor deposition source is a vapor deposition source used in a vapor deposition polymerization apparatus, and includes a pulse valve that can be opened and closed at arbitrary time intervals.

Further, the apparatus for producing an organic polymer thin film according to the present invention is a vapor deposition polymerization apparatus containing at least a substrate to be vapor-deposited in a vacuum vessel and a plurality of vapor deposition sources. Each of the deposition sources has a pulse valve that can be opened and closed at an arbitrary time interval independently or in conjunction with each other, a raw material tank filled with a raw material monomer, and a heater that controls the temperature in the vapor deposition source. I do.

In the vapor deposition polymerization apparatus, it is preferable that three or more vapor deposition sources are contained in the vacuum vessel.
Further, the method for producing an organic polymer thin film according to the present invention is a method for producing an organic polymer thin film using a plurality of raw material monomers by a vapor deposition polymerization apparatus having a substrate to be deposited on which an organic polymer thin film is deposited, The introduction time of the plurality of raw material monomers is determined based on the surface residence time remaining on the substrate surface from the time when each raw material monomer adheres to the surface of the substrate to be vapor-deposited and then leaves the substrate surface. Is introduced into the vacuum vessel while controlling the pressure.

Further, the method for producing an organic polymer thin film according to the present invention is a method for producing an organic polymer thin film using a plurality of raw material monomers by a vapor deposition polymerization apparatus, wherein the plurality of raw material monomers are replaced with each raw material monomer. It is characterized in that it is introduced into the vacuum vessel while controlling the introduction time based on the reaction energy between the two.

The method for producing an organic polymer thin film is characterized in that the plurality of starting monomers are two kinds of starting monomers forming an imide bond, and the starting monomers forming an amide bond with a diamine compound in this combination. It is preferable that Further, the method for producing an organic polymer thin film having a laminated structure is such that, by using the method for producing an organic polymer thin film, an organic polymer thin film having a different structure or composition is formed alternately or arbitrarily using a plurality of raw material monomers. Then, it is preferable to stack the formed organic polymer thin films.

As described above, by using a pulse valve which can be opened and closed at an arbitrary time interval, the polymerization reaction can be suppressed even when a plurality of raw material monomers having greatly different surface residence times or reaction energies on a substrate are used. It is possible to prevent the unbalanced polymerization reaction from proceeding, and it is possible to deposit an amount of the raw material monomer equal to or less than a monolayer on the surface of the substrate, so that an organic polymer thin film can be formed, and the film composition and film Precise control of the structure is possible.

[0019]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of a vapor deposition source, a vapor deposition polymerization apparatus, and a method for producing an organic polymer thin film by vapor deposition polymerization according to the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic view of one embodiment of a vapor deposition polymerization apparatus according to the present invention. As shown in FIG. 1, the vapor deposition polymerization apparatus 1 includes a substrate 14 on which an organic polymer thin film is deposited, and a deposition source 20 for filling the substrate 14 with a raw material monomer.
And a vacuum pump 12, a vacuum pump 12 for evacuating the vacuum vessel 10, a support 16 for mounting the base 14, and a temperature-adjustable cover 18.

The vacuum container 10 is operated by a vacuum pump 12.
It is evacuated to 10 before the introduction of the raw material monomer.^-FourP
a or less, preferably 10^-6It is exhausted to Pa or less. What
In addition, by introducing the raw material monomer, the vacuum vessel 10
The vacuum pump 12 was operated because the internal pressure changed.
The pressure inside the vacuum vessel 10 during deposition is 10
^-3-10^-FivePa, preferably 10^-Four-10^-FivePa
It is desirable.

A substrate 1 on which an organic polymer thin film is deposited.
4 is appropriately selected from conventionally known ones according to the type of the thin film to be obtained. For the substrate 14 to be deposited, for example, an inorganic substance such as a metal, a metal oxide, or glass, or an organic substance such as a polymer can be used. The support base 16 is provided with a heater (not shown) capable of controlling the base 14 at a desired temperature while attaching the base 14 to enable the base 14 to be vapor-deposited while cooling or heating the base 14. Are preferably used.

In the case of a monomer having a short surface residence time, the temperature of the substrate 14 is preferably low, and in the case of a monomer having a high reaction energy, the temperature of the substrate 14 is preferably high. Is preferably in the range of −90 ° C. to + 800 ° C. The cover 18 is not particularly limited as long as it can control the temperature. However, in order to reduce the influence on the substrate 14 due to the heat generated by the vapor deposition source 20 described later, the cover 18
It is preferable that the temperature can be set so that the portion accommodating the deposition source 20 can be cooled within zero. For example, a stainless steel cover may be provided from the viewpoint of corrosion resistance, and a circulating water pipe 19 may be provided so that the temperature can be adjusted (cooled) by the circulating water (FIG. 1).

As shown in FIG. 2, the evaporation source 20 includes a cover 22, which covers the entire evaporation source 20, a handle 23, a raw material tank 24, a joint 25, a heater 26, a pulse valve 28, and a nozzle 30. And It is preferable that two or more vapor deposition sources 20 are installed in the vapor deposition polymerization apparatus 1. That is, the present invention is not limited to the three units shown in FIG. 1. For example, by providing a utility port (not shown) in the vacuum vessel 10, more vapor deposition sources 20 are attached as necessary. It is possible.
This makes it possible to form a thin film by copolymerization using a plurality of raw material monomers.

The cover 22 is not particularly limited as long as it covers the entire vapor deposition source 20, but for example, a stainless steel cover can be used from the viewpoint of corrosion resistance. The raw material tank 24 is for filling a raw material monomer to be vapor-deposited on the base body 14, and is detachable from the vapor deposition source 20 via a joint 25 by a handle 23, and the heater 26 is heated to a temperature at which the raw material monomer is vaporized. There is no particular limitation as long as it can be set, but it is preferable that the temperature in the evaporation source 20 can be heated to a temperature of 200 ° C. or higher.

The pulse valve 28 serves to control the introduction of the raw material monomer into the vacuum vessel 10, for example, to serve as a lid. By opening the pulse valve 28, the raw material monomer filled in the raw material tank 24 and evaporated by the heater 26 can be introduced into the vacuum vessel 10 through the nozzle 30. Conversely, the vacuum vessel 10 for the raw material monomer evaporated by closing the pulse valve 28
Can be stopped.

Such a pulse valve 28 can be controlled to open and close at an arbitrary time interval, for example, 1/1.
Open / close control is possible in a time unit of about 000 seconds, preferably in a time unit of about 1/10000 second,
Alternatively, a material capable of controlling the amount of the raw material monomer released at one time to a very small amount of about a monolayer relative to the surface of the substrate 14 is desirably used.

When a plurality of vapor deposition sources 20 are attached to the vapor deposition polymerization apparatus 1, it is preferable that the respective pulse valves 28 can be controlled to open and close independently or in conjunction with each other. The vacuum vessel 1 is provided by such an evaporation source 20.
If directivity is given to the raw material monomer introduced into 0, the diffusion of the raw material monomer to other than the surface of the base 14 can be reduced.

Further, using such a deposition source 20
The pressure inside the vapor deposition polymerization apparatus 1 when introducing each raw material monomer
The rise in force can be suppressed, and the vacuum
10 ^-FourPa can be kept below Pa. In addition, raw material
Quick recovery of vacuum after stopping the introduction of nomer, high purity organic high
It becomes possible to produce a molecular thin film. Pulse valve 2
Raw material introduced into vacuum vessel 10 by one opening operation of 8
The amount of monomer is controlled by adjusting the amount of the evaporation source 20 for each raw material monomer.
By controlling the heat temperature and the opening / closing time of the pulse valve 28,
Can be done. Open / close control of the pulse valve 28 of each deposition source 20
Are programmed in advance by computer control.
Can be performed according to the order of introduction of each raw material monomer
preferable.

For example, in a method for producing an organic polymer thin film by vapor deposition polymerization using three kinds of raw material monomers, raw material monomers A and B having the same surface residence time and causing a polymerization reaction, and raw material monomers A and B When a thin film of polymer D synthesized from raw material monomer C which causes a polymerization reaction with raw material monomer A is shorter than the surface residence time, a polymerization reaction between raw material monomer A and raw material monomer B is usually performed. Only progresses preferentially, starting monomer A
And C are less likely to undergo a polymerization reaction.

Therefore, in order to avoid such a problem, the introduction time, the time interval, and the introduction amount of each raw material monomer are appropriately adjusted by using the pulse valve 28 by the method for producing an organic polymer thin film according to the present invention. To produce an organic polymer thin film having a desired structure and composition. That is, the raw material monomer A to cause a polymerization reaction with both monomers of the raw material monomer B and C, while introducing the T _A Time vacuum vessel 10 with a pulse valve, a raw material monomer C T _C Time,
The raw material monomer B is introduced T _B Time. Here, the raw material monomer B is introduced after the introduction of the raw material monomer C is stopped, or when the raw material monomers B and C are introduced together, by introducing the raw material monomer B for a T _B time shorter than the T _C time, Not only the polymerization reaction of the raw material monomer A and the raw material monomer B, but also the polymerization reaction of the raw material monomer A and the raw material monomer C can efficiently proceed to produce an organic polymer thin film having a desired raw material monomer component ratio.

In the above case, even if the starting monomer B and the starting monomer C are introduced at the same time,
Does not react with the starting monomer C, or the reaction between the starting monomer B and the starting monomer A proceeds preferentially over the reaction between the starting monomer B and the starting monomer C,
The reaction between the starting monomer B and the starting monomer C can be neglected.

The control of the reaction time between each raw material monomer by the amount and time of the raw material monomer introduced as described above can suppress not only the difference in surface residence time but also the bias of the polymerization reaction due to the difference in reaction energy. That is, the polymerization time of the reaction monomer having a low reaction energy is increased by increasing the time of introduction of the material monomer of the combination having a high reaction energy from the time of introduction of the material monomer of the combination having a low reaction energy between the material monomers in which the reaction proceeds in the vapor deposition polymerization. Only the reaction can be prevented from dominantly occurring.

An organic polymer thin film having a desired structure and composition can be produced by repeating the order of introducing each raw material monomer. In the case of forming an organic polymer thin film having a laminated structure of different polymers, for example, polymerizable raw material monomers G and H for producing polymer E and heavy synthetic raw material monomers I and J for producing polymer F are used. Of 4
First, the raw material monomers G and H are introduced into the vacuum vessel 10 using the four evaporation sources 20 filled with the raw material monomers G, H, I, and J, and the introduction of the raw material monomers G and H is stopped. Thereafter, the starting monomers I and J are introduced, and a laminated film of the polymers E and F is formed on the substrate 14 in order.

By repeating the order of introduction of each raw material monomer, a laminated film of polymers E and F can be formed. In addition, when forming the laminated film, when the raw material monomers of the films to be laminated are common, for example, the common raw material monomer is M, and the raw material monomer M and the raw material monomer K are polymerized to form the polymer O. On the other hand, when polymerizing the raw material monomer M and the raw material monomer L to form the polymer P, the raw material monomer M is introduced while using the evaporation source 20 filled with the three raw material monomers K, L, and M, respectively. By alternately introducing the raw material monomers K and L, a laminated film of the polymers O and P can be formed.

As described above, by adjusting the temperature of each evaporation source 20 and opening and closing the pulse valve 28 of each evaporation source 20 in an appropriate order, the surface residence time on the surface of the substrate 14 greatly differs. In addition to efficiently producing a polymer thin film between a plurality of raw material monomers, the composition of the polymer thin film, the laminated structure, and the like can be controlled. Examples of the polymerizable raw material monomer that can be used in a vapor deposition polymerization apparatus having such a structure include a raw material compound that generates polyimide, polyamide, polyamideimide, polyurethane, polyurea, and the like, for example, a diamine compound, a dibasic acid compound, Diol compounds, bisphenol compounds, glycol compounds,
And diisocyanate compounds.

As the diamine compound, for example, phenylenediamine, phenylenetetramine, 4,4-diaminodiphenyl ether, 4,4-diaminodiphenylmethane and the like can be preferably used. As the dibasic acid compound, for example, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, terephthalic acid, isophthalic acid, and acid anhydrides and acid chlorides thereof can be preferably used.

Diol compounds, bisphenol compounds,
Alternatively, as the glycol compound, for example, bisphenol, bisphenol diacetate, xylylene glycol, cyclohexanedimethanol and the like can be preferably used. As the diisocyanate compound, for example, phenylene diisocyanate, biphenylene diisocyanate, 4,4-diphenylmethane diisocyanate and the like can be preferably used.

[0038]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0039]

Example 1 By ternary system of ODA-TPA-PMDA
Preparation of Polyamideimide Thin Film Using the vapor deposition polymerization apparatus shown in FIGS. 1 and 2, 4,4-diaminodiphenyl ether (O
DA), terephthalic acid chloride (TPC), and pyromellitic anhydride (PMDA) to prepare a polyamideimide thin film. The substrate was a mirror-polished Si surface and the substrate temperature was room temperature.

The vacuum vessel 10 is evacuated to 10 ^-6 Pa,
The deposition source 20a containing ODA was heated to about 168 ° C., the deposition source 20b containing TPC was heated to about 54 ° C., the deposition source 20c containing PMDA was heated to about 170 ° C., and the introduction procedure of each raw material monomer shown in FIG. A vapor-deposited polymer film was prepared. That is, first, the pulse valve 28a of the evaporation source 20a is opened to introduce ODA into the vacuum vessel 10 for 1.5 seconds, and the pulse valve 28a is closed 1.5 seconds after introduction.

At this time, the pulse valve 28a is opened and O
With the start of introduction of DA, the evaporation source 20b also opens the pulse valve 28b to introduce TPC into the vacuum chamber 10 for 1.2 seconds, and closes the pulse valve 28b 1.2 seconds after introduction. Further, one second after the start of introduction of ODA, the evaporation source 2
0c, the pulse valve 28c is opened, and PMDA is introduced into the vacuum chamber 10 for 0.5 second.
After a second, the pulse valve 28c is closed.

After closing each pulse valve 28a-c,
Pulse valve 28 until 5 seconds have passed since the start of ODA introduction
a to c are closed. In other words, 5 seconds as one cycle, only ODA and TPC are introduced from 0 to 1 second,
Introduce all of ODA, TPC and PMDA until ~ 1.2 sec, introduce only ODA and PMDA until 1.2 ~ 1.5 sec, and introduce all raw material monomers until 1.5 ~ 5 sec To stop.

The pulse valve opening / closing time of each raw material monomer deposition source and the order of introduction of each raw material monomer were adjusted, and while ODA necessary for forming both imide bonds and amide bonds was introduced on the surface of the substrate, TPC was first used. Was introduced, and before the ODA introduction was stopped, a polyamideimide thin film was produced in an introduction order in which PMDA was introduced in a time shorter than the TPC introduction time. The thickness of the polyamide-imide film to be formed can be adjusted by the number of repetitions of the introduction procedure.

The procedure for introducing each raw material monomer shown in FIG.
The thin film obtained after the repetition of 00 times has a thickness of about 150 n.
m and a good adhesion to the Si surface of the substrate 14. After the obtained film was subjected to a heat treatment at about 150 ° C., FT-IR measurement was performed. FIG. 4 shows the results. As shown in FIG. 4, at peaks observed in the FT-IR spectrum, 1238, 1378, 1723,
1776 cm ⁻¹ is derived from an imide bond,
Since 21, 1530, 1650, and 3320 cm ^-1 are derived from amide bonds, it was confirmed that a polyamideimide thin film was obtained.

[0045]

Comparative Example 1 Based on ternary system of ODA-TPA-PMDA
Of polyamide-imide film prepared in Example 1, the installation procedure of the raw material monomer and that shown in FIG. 5, to prepare a polyamideimide film. That is, with 5 seconds as one cycle, all raw material monomers are simultaneously introduced, all raw material monomers are introduced from 0 to 1.5 seconds after the start of introduction, and all raw material monomers are introduced from 1.5 to 5 seconds. Stop the deployment.

The thin film obtained after repeating the procedure of introducing each raw material monomer shown in FIG. 5 100 times has a thickness of about 150
It was a film with a uniform thickness of nm, and had good adhesion to the Si surface of the substrate. FIG. 6 shows the result of FT-IR measurement after the obtained film was subjected to a heat treatment at 150 ° C. As shown in FIG. 6, at peaks observed in the FT-IR spectrum, 1238, 1378, 1723, and 1776 cm ⁻¹
Is derived from an imide bond. On the other hand, since no peak around 3320 cm ⁻¹ derived from the amide bond is observed,
It was confirmed that the formation of the amide bond was suppressed and the imide bond was preferentially formed.

That is, the ODA of the raw material monomer is PM
A monomer that forms a polyamic acid that is a precursor of a polyimide by reacting with DA and forms an amide bond by reacting with TPC. Among these three types of starting monomers, TPC is higher than PMDA and ODA. Has a short surface residence time. Therefore, even if these three types of raw material monomers are simultaneously deposited, TPC having a short surface residence time due to the influence of the surface residence time causes a slow polymerization reaction with ODA,
It was suggested that the polyamic acid composed of PMDA-ODA was formed predominantly.

[0048]

Example 2 By ternary system of DAD-TPC-PMDA
Polyamideimide thin film In Example 1, the raw material monomer ODA was changed to diaminodecane (DAD), and the deposition source containing DAD was heated to about 65 ° C.
The procedure for introducing the raw material monomers was as shown in FIG. 7 to prepare a polyamide-imide thin film.

That is, 5 seconds is one cycle,
Introduce all starting monomers at the same time
All the raw material monomers are introduced until second, only DAD and TPC are introduced until 0.6 to 1 second, and all the raw material monomers are stopped from 1 to 5 seconds. DAD as a raw material monomer is a monomer that forms a polyamic acid, which is a precursor of polyimide, by reacting with PMDA and forms an amide bond by reacting with TPC.

The thin film obtained after repeating the introduction procedure of FIG. 7 80 times was a uniform film having a thickness of 100 nm, and had good adhesion to the Si surface of the substrate. FIG. 8 shows the result of FT-IR measurement after the obtained film was subjected to a heat treatment at about 150 ° C. As shown in FIG.
At the peak seen in the R spectrum, 1723 cm
^-1 is derived from an imide bond, 1650, 332
Since 0 cm ^-1 is derived from an amide bond, it was confirmed that a polyamideimide thin film was obtained.

[0051]

Example 3 Laminated film of polyamide / polyimide Under the same conditions as in Example 1, a laminated thin film composed of polyamide and polyimide was produced. First, a layer of a polyamic acid, which is a precursor of polyimide, is formed for 5 minutes by introducing only ODA and PMDA.
0c is closed to stop the introduction of PMDA, and then the pulse valve 28 of the TPC deposition source 20b is closed.
b, open TPC and continue to introduce OD
By forming polyamide for 5 minutes between A and A, a laminated polymer thin film having a thickness of about 30 nm consisting of a polyimide layer and a polyamide layer was obtained on the substrate surface.

FIG. 9 shows the result of FT-IR measurement of the obtained laminated thin film. As shown in FIG. 9, at peaks observed in the FT-IR spectrum, 1238, 137
8, 1723 and 1776 cm ^-1 are derived from imide bonds, and 1221, 1650 and 3320 cm ^-1 are derived from amide bonds. Thus, it was confirmed that a polyamideimide thin film was obtained.

The FT after immersing this laminated thin film in dimethylformamide (DMF) in which polyamide is dissolved
FIG. 10 shows the results of the IR measurement. As shown in FIG. 10, at the peaks seen in the FT-IR spectrum,
Since 1240, 1380, and 1720 cm ⁻¹ are derived from imide bonds and no peaks derived from amide bonds are observed, the existence of an organic thin film consisting of polyimide alone on the Si surface was confirmed.

In the case of a laminated thin film of a polyimide layer / polyamide layer / Si in which a polyimide layer is formed after a polyamide layer is formed on a Si substrate by the same method, D
Since the organic thin film was completely removed from the Si surface by immersion in MF, the polyamide layer / polyimide layer / Si
It was confirmed that an organic polymer thin film having a laminated structure of was obtained.

[0055]

According to the present invention, the composition and structure of a thin film can be improved even in the case where a plurality of raw material monomers having greatly different surface residence times or reaction energies on the surface of a substrate, which have conventionally been difficult to produce a vapor-deposited polymer film, are used. A polymer thin film can be produced with good controllability such as a laminated structure.

Therefore, the selection range of the raw material monomers to which the method of preparing the organic polymer thin film which can be used for electronic materials, optical materials, separation membranes and the like can be applied by the dry process is widened, and the amount of the raw material monomer is extremely small. By controlling the introduction, an ultrathin organic polymer film or a laminated organic polymer thin film can be produced.

[Brief description of the drawings]

FIG. 1 is a schematic structural diagram of one embodiment of a vapor deposition polymerization apparatus according to the present invention.

FIG. 2 is a schematic structural view of a raw material monomer deposition source installed in the vapor deposition polymerization apparatus.

FIG. 3 is a diagram showing a process for producing a polyamideimide film.
It is a figure which shows the introduction procedure of three types of raw material monomers, ODA, TPC, and PMDA.

FIG. 4 is a diagram showing the procedure for introducing the starting monomer shown in FIG.
It is a figure which shows the FT-IR spectrum of the polyamideimide thin film produced from three types of raw material monomers of DA, TPC, and PMDA.

FIG. 5 is a diagram showing a process for producing a polyamideimide film;
It is a figure which shows the introduction procedure of three types of raw material monomers, ODA, TPC, and PMDA.

FIG. 6 is a diagram illustrating the procedure for introducing the starting monomer shown in FIG.
It is a figure which shows the FT-IR spectrum of the polyamideimide thin film produced from three types of raw material monomers of DA, TPC, and PMDA.

FIG. 7 is a diagram showing a process for producing a polyamideimide film.
It is a figure which shows the introduction | transduction procedure of three types of raw material monomers of DAD, TPC, and PMDA.

FIG. 8 is a diagram showing D in the introduction procedure of the raw material monomer shown in FIG. 7;
It is a figure which shows the FT-IR spectrum of the polyamideimide thin film produced from three types of monomers of AD, TPC, and PMDA.

FIG. 9 is a diagram showing an FT-IR spectrum of a polyamide / polyimide laminated film produced on a Si substrate from the three kinds of monomers of ODA, TPC, and PMDA by the vapor deposition polymerization apparatus.

FIG. 10 is a diagram showing a process for producing Si from three kinds of monomers of ODA, TPC and PMDA by the vapor deposition polymerization apparatus according to the present invention.
The polyamide / polyimide laminated film prepared on the substrate
It is a figure which shows the FT-IR spectrum after immersion in MF.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Deposition polymerization apparatus 10 Vacuum container 14 Substrate 20 Deposition source 24 Raw material tank 26 Heater 28 Pulse valve

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Sadaaki Yamamoto 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc. (72) Inventor Shoko Ono 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc. (72) Inventor: Takayuki Miyamae 1-1, Higashi 1-1, Tsukuba, Ibaraki Pref. National Institute of Advanced Industrial Science and Technology Inside of Materials Engineering Laboratory (72) Inventor: Shoichi Nozoe 1-1, Higashi, Tsukuba, AIST (72) Inventor Kiyomi Tsukagoshi 1-6-1-2-905-402 Takezono, Tsukuba, Ibaraki F-term (reference) 4J031 CA06 CA12 CA13 CA14 CA16 CA49 CE06 CF07 CG02 CG26 CG39 4J043 PA04 QB31 QB33 RA06 RA35 SA06 SB01 TA12 TA14 TA22 TA26 TB03 UA121 UA122 UA131 UA132 UA771 UB011 UB121 UB152 VA021 VA022 VA041 VA062 XA02 XA06 XB27 XB39 YA06 ZB11 4K029 BA62 CA11 DA08 DB14 EA0 0

Claims (7)

[Claims] 1. A vapor deposition source for use in a vapor deposition polymerization apparatus,
An evaporation source comprising a pulse valve that can be opened and closed at an arbitrary time interval. 2. A vapor deposition polymerization apparatus containing at least a substrate to be vapor-deposited and a plurality of vapor deposition sources in a vacuum vessel for depositing an organic polymer thin film, wherein each of the plurality of vapor deposition sources is at least individually or interlocked with each other. A vapor deposition polymerization apparatus comprising: a pulse valve that can be opened and closed at arbitrary time intervals; a raw material tank for charging raw material monomers; and a heater for controlling the temperature in the vapor deposition source. 3. The vapor deposition polymerization apparatus according to claim 2, wherein three or more vapor deposition sources are contained in the vacuum vessel. 4. A method for producing an organic polymer thin film using a plurality of raw material monomers by a vapor deposition polymerization apparatus provided with a substrate to be deposited on which an organic polymer thin film is deposited, wherein the plurality of raw material monomers are each The monomer is introduced into the vacuum vessel while controlling the introduction time based on the surface residence time remaining on the substrate surface from the time when the monomer adheres to the surface of the substrate to be deposited until the monomer leaves the substrate surface. A method for producing an organic polymer thin film, comprising: 5. A method for producing an organic polymer thin film using a plurality of raw material monomers by a vapor deposition polymerization apparatus, wherein the introduction time of the plurality of raw material monomers is controlled based on a reaction energy between the raw material monomers. A method for producing an organic polymer thin film, wherein the organic polymer thin film is introduced into a vacuum vessel while being introduced. 6. The method according to claim 1, wherein the plurality of raw material monomers are two types of raw material monomers in a combination forming an imide bond, and a raw material monomer forming an amide bond with a diamine compound in the combination. A method for producing an organic polymer thin film according to claim 4. 7. A method for producing an organic polymer thin film according to claim 4 or 5, wherein an organic polymer thin film having a different structure or composition is formed alternately or arbitrarily using a plurality of raw material monomers. A method for producing an organic polymer thin film having a laminated structure, wherein the formed organic polymer thin films are laminated.