JPH11283974A - Low-ratio dielectric high-molecular film, formation therefor and interlayer insulating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To give stable characteristics to a low-ratio dielectric high-molecular film through simple processes and to especially apply the high-molecular film to an interlayer insulating film in a semiconductor device. SOLUTION: A low-ration dielectric high-molecular film is formed by a method in which 25 wt.% or more of fluorine is made to be contained in a polyimide film, which is formed on a substrate through deposition polymerization, and as the raw monomer for the deposition polymerization, a monomer having a fluorine-containing substituent is used. For example, as the diamine monomer, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFDB), 5-(perfluorononenyloxy)-1,3-diaminobenzene (17 FMPD) and the like are used, and as the acid component monomer, 2,2'-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 1,4-difluoro-2,3,5,6-benzen tetracarboxylic acid idanhydride (P2FDA) and the like are used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low dielectric constant polymer film used as an interlayer insulating film of a semiconductor device, for example, and a method for forming the same.

[0002]

2. Description of the Related Art Conventionally, as an interlayer insulating film of a semiconductor device, an SOG (Spin on Glass) film or a CV
An SiO ₂ film formed by a D method (Chemical Vapor Deposition) is mainly used. The relative dielectric constant of the interlayer insulating film formed by these methods is about 4,
Recently, with the progress of high integration of LSIs, it has been considered that the reduction of the relative dielectric constant of the interlayer insulating film is a major issue, and an interlayer insulating film having a relative dielectric constant of 4 or less has been required.

In response to such a demand, a SiOF film in which fluorine is added to an SiO ₂ film formed by a plasma CVD method has recently been proposed. According to this film, the relative dielectric constant of an interlayer insulating film is reduced. It can be suppressed to about 3.7 to 3.2.

Also, an amorphous fluorocarbon film has been proposed as a low dielectric constant interlayer insulating film. According to this film, the relative dielectric constant of the interlayer insulating film can be suppressed to about 2.7 to 2.3. it can.

[0005]

However, such a conventional technique has the following problems. That is, while the SiOF film formed by the plasma CVD method can achieve a low dielectric constant, the film characteristics are greatly different depending on the film forming method and film forming conditions, and the film has a large desorption and high hygroscopicity of fluorine in the film. It has been pointed out that the dielectric constant deteriorates due to the instability of the material, and it is difficult to apply the material as a low dielectric constant material in the future.

[0006] Even in the case of an amorphous fluorocarbon film, the film characteristics greatly differ depending on the method of forming the film and the film forming conditions, and it is necessary to sacrifice the heat resistance in order to achieve a low dielectric constant. For this reason, when heated at about 400 ° C. in a process other than the formation of the interlayer insulating film, a gas is easily generated due to the decomposition of the film, and when a film is formed on the interlayer insulating film, a gas is generated between these films and the device is mounted. It has been pointed out that this can be a destructive factor.

On the other hand, it has been proposed to use fluorinated polyimide as a material satisfying the heat resistance and the low relative dielectric constant. However, a film using fluorinated polyimide has a relative dielectric constant of only about 2.7. There is a problem that it is not reduced.

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and has a stable characteristic in a simple process, and is particularly applicable to a low dielectric constant film applicable to an interlayer insulating film of a semiconductor device. It is an object to provide a conductive polymer film and a method for forming the same.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, increased the fluorine content by allowing the polymer film formed by vapor deposition polymerization to contain fluorine. As a result, the relative dielectric constant of the polymer film was found to decrease, and the present invention was completed.

[0010] The invention according to claim 1 based on this finding is characterized in that a polymer film formed on a substrate by vapor deposition polymerization contains a predetermined amount of fluorine. It is a membrane.

According to a second aspect of the present invention, in the first aspect, the polymer film formed on the substrate by vapor deposition polymerization is a polyimide film. It is.

According to the first or second aspect of the invention, the relative dielectric constant of the polymer film is reduced by containing fluorine in the polymer film formed by vapor deposition polymerization. The reason is as follows. Guessed.

That is, fluorine (F) has the highest electronegativity among the elements, and electron bias is small in the CF bond. As a result, the interaction with surrounding atoms (molecules) is reduced as compared with the case where fluorine is not contained, so that the bias (polarizability) of electrons in the film is reduced as a whole, and the relative dielectric constant is reduced. Further, fluorine has a larger electron radius than hydrogen (H) or carbon (C), and the penetration of fluorine increases the distance between molecules and increases the free volume, so that the relative dielectric constant decreases. In particular, the vapor deposition polymerization method,
Since the free volume tends to be larger than the solution method,
The relative dielectric constant can be reduced as compared with the solution method.

As shown in FIG. 1, for example, when the content of fluorine in the polymer film is increased, the relative dielectric constant of the polymer film is reduced in a range where vapor deposition polymerization is possible.
Therefore, the relative dielectric constant of the polymer film can be controlled to a desired value by adjusting the content of fluorine in the polymer film.

In the case of the present invention, the content of fluorine in the polymer membrane is preferably at least 25% by weight, more preferably at least 50% by weight, as in the third aspect of the present invention.

According to the present invention, for example, when the content of fluorine in the polyimide film is 25% by weight or more, the relative dielectric constant can be made 2.7 or less. When the content is 50% by weight or more, the relative dielectric constant can be 2.3 or less.

In the present invention, the content (ratio) of fluorine in the polymer film is obtained by calculation from the molecular formula of the polymer compound to be vapor-deposited and polymerized.

In order to form the low dielectric constant polymer film of the present invention, for example, as described in claim 4, raw material monomers are evaporated in a vacuum, and these are vapor-deposited and polymerized on a substrate. When forming the polymer film, a monomer having a substituent containing fluorine may be used as the raw material monomer. According to the fourth aspect of the present invention, a low dielectric constant polymer film having stable characteristics can be easily formed.

In this case, a monomer having no substituent containing fluorine may be contained as a raw material monomer. However, if only a monomer having a substituent containing fluorine is used, the content of fluorine in the polymer film increases, and the relative dielectric constant of the polymer film can be further reduced.

The method of the present invention comprises the steps of:
The method can be applied to the case of forming various kinds of polymer films such as polyamide, but is particularly suitable for forming a polyimide film using a diamine monomer and an acid component monomer.

As the raw material monomer for the polyimide, various ones can be used, but as described in claim 5, as the diamine monomer, 2,2'-bis (trifluoromethyl) -4,4 ' -Diaminobiphenyl (TFD
B), 4,4'-bis (4-tetrafluoroaminophenoxy)
Octafluorobiphenyl (16FPD), 2,5-diaminotridecanefluoro-n-hexylbenzene (13FP
D), tetrafluoro-m-phenylenediamine (4FMP
D), 5- (perfluorononenyloxy) -1,3-diaminobenzene (17FMPD) and the like can be used.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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Further, the acid component monomer may be a compound according to claim 6
As in the described invention, 1,4-difluoro-2,3,5,6-benzenetetracarboxylic dianhydride (P2FDA), 1,4-bis
(Trifluoromethyl) -2,3,5,6-benzenetetracarboxylic dianhydride (P6FDA), 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FD
A), 4,4'-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride (10FEDA)
And the like.

[0027]

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[0028]

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[0029]

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[0030]

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Among them, TFDB or 17FMPD is used as the diamine monomer, and P2FDA or 6FDA is used as the acid component monomer. The reactivity of the monomer is relatively high, and a defect-free film can be easily prepared. Can be suitably used.

In the present invention, the pressure is 10 ^-3 P
It is preferable to carry out vapor deposition polymerization in a vacuum of about a.

In the present invention, it is preferable to perform a heat treatment after forming a deposition film on the substrate. That is, the heat treatment improves the heat resistance because the polymerization reaction is completed.

In this case, the temperature of the heat treatment is preferably about 400 ° C., and the time is preferably about 60 minutes. The treatment atmosphere may be air, inert gas or vacuum, but in order to prevent the surface of the film from reacting with water or oxygen,
Most effective in a vacuum.

When a semiconductor device is manufactured, if the semiconductor device is heated to a temperature equal to or higher than the maximum temperature of the semiconductor device manufacturing process in the heat treatment step, decomposition of a polymer component in a subsequent process can be prevented.

On the other hand, in the invention according to claim 7, the low dielectric constant polymer film according to any one of claims 1 to 3 is formed between the metal wiring layers formed on the semiconductor substrate. An interlayer insulating film characterized by the following.

According to the seventh aspect of the present invention, since the interlayer insulating film is constituted by the polymer film having a low relative dielectric constant, the capacitance of the capacitor formed between the metal wiring layers is extremely small, and the semiconductor device Operating speed can be greatly improved.

[0038]

Preferred embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 2 shows a schematic configuration of an example of a film forming apparatus for carrying out the present invention. As shown in FIG. 2, the film forming apparatus 1 is a single-wafer apparatus of a multi-chamber system, and takes in and out a substrate 8 such as a Si wafer around a core chamber 2 in which a transfer robot (not shown) is incorporated. An L / UL (load / unload) chamber 3 for performing vapor deposition, a first processing chamber 4 for performing vapor deposition polymerization, a second processing chamber 5 for performing a heat treatment,
A third processing chamber 6 for sputtering aluminum or the like is provided, and these are all connected via a gate valve (not shown).

The core chamber 2, the L / UL chamber 3, and the first to third processing chambers 4 to 6 are connected to a vacuum exhaust system such as a vacuum pump (not shown). Further, the substrate 8 can be freely transferred from the L / UL chamber 3 to the first to third processing chambers 4 to 6 by a robot arranged in the core chamber 2.

FIG. 3 shows a schematic configuration of the first processing chamber 4 of the film forming apparatus 1 shown in FIG. As shown in FIG. 3, above the first processing chamber 4, evaporation sources 40A and 40B for two types of raw material monomers A and B are provided with introduction pipes 41A and 41B.
Connected through. The housings 42A, 42B of the evaporation sources 40A, 40B respectively have an evaporation container 43.
A, 43B are provided. And the evaporation container 43A,
Raw material monomers A and B for forming a polyimide film are injected into 43B, respectively.

In this case, as raw material monomers A and B,
For example, as a diamine monomer, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFDB) or
5- (perfluorononenyloxy) -1,3-diaminobenzene (17FMPD) and the like, and 2,2′-
Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 1,4-difluoro-2,3,5,6-benzenetetracarboxylic dianhydride (P2FDA) and the like are used. Further, heaters 4 for heating the raw material monomers A and B are provided near the evaporation containers 43A and 43B.
4A and 44B are provided.

On the other hand, a heater 49 is wound around each of the introduction pipes 41A and 41B so that the temperatures of the raw material monomers A and B can be controlled. In the middle of each of the introduction pipes 41A and 41B, valves 45A and 45 for adjusting the supply amount of each of the raw material monomers A and B are provided.
B are provided, and by opening and closing them, the film thickness can be controlled at the time of forming the vapor-deposited polymer film.

As shown in FIG. 3, the substrate 8 is supported on a hot plate 46 for heating the lower substrate 8 in the first processing chamber 4. In addition, a mixing tank 47 formed so as to expand downward is provided at an upper portion of the first processing chamber 4. A heater 48 for heating the vapor of the raw material monomers A and B is provided on the inner wall of the mixing tank 47.

FIG. 4A shows a schematic configuration of the second processing chamber 5 of the film forming apparatus 1 of FIG. As shown in FIG. 4A, a hot plate 50 for heating the substrate 8 is provided in the second processing chamber 5. The hot plate 50 is configured so that the temperature of the substrate 8 can be controlled in a wider range (20 to 500 ° C.) than the temperature at the time of manufacturing the semiconductor device, and the heating rate during heating can be adjusted. I have.

FIG. 4 (b) shows a schematic configuration of the third processing chamber 6 of the film forming apparatus 1 of FIG. As shown in FIG. 4B, a DC bipolar sputtering device is provided in the third processing chamber 6. That is, an electrode 61 connected to a DC power supply 60 is provided above the third processing chamber 6, and an aluminum target, for example, is held as the sputtering target 62 on the electrode 61. The substrate 8 to be processed is supported by a hot plate 63 at the lower part of the third processing chamber 6. In addition, an inert gas such as an argon (Ar) gas is introduced into the third processing chamber 6 through an introduction pipe 64.

To form an insulating film in this embodiment, first, in the film forming apparatus 1, the substrate 8 is
Transported from the chamber 3 into the first processing chamber 4, and each of the valves 45A,
45B is opened, the raw material monomers A and B are introduced into the first processing chamber 4, and a polyamic acid film is formed on the substrate 8 by vapor deposition polymerization.

In this case, first, each of the valves 45A, 45B
Is closed, the pressure in the first processing chamber 4 is increased to 3 × 10 ⁻³ P
A high vacuum of about a is set, and the raw material monomers A and B are heated to a predetermined temperature by the heaters 44A and 44B.

After each raw material monomer A, B reaches a predetermined temperature and a required amount of evaporation is obtained, each valve 45
A and 45B are opened, and the raw material monomers A and B are deposited and deposited from above on the substrate 8 at a predetermined evaporation rate, and after forming the polyamic acid film, the valves 45A and 45B are closed. In this case, the evaporation rates of the raw material monomers A and B are controlled so as to have a stoichiometric ratio of 1: 1. Further, the temperature of the substrate 8 is controlled to a predetermined temperature by the hot plate 46.

Thereafter, in the second processing chamber 5, the substrate 8
A predetermined heat treatment is performed on the upper polyamic acid film using a hot plate 50. In this case, the heating condition is to heat to about 400 ° C. at a rate of temperature increase of 5 ° C./min, and to maintain the state for about 60 minutes. This heat treatment is performed, for example, in a vacuum.

If necessary, the substrate 8 can be transferred to the third processing chamber 6 and an aluminum electrode can be formed on the substrate 8 by sputtering.

As described above, according to the present embodiment,
A low dielectric constant polyimide film having stable characteristics can be obtained by a simple process.

FIGS. 5A to 5F show an example of a process for forming an interlayer insulating film of a semiconductor device using the present invention. First, for example, as shown in FIG.
i), a silicon thermal oxide film 22 formed on the surface of the semiconductor substrate 21 and having a window formed at a predetermined position, and a first layer formed on the silicon oxide film and patterned. Substrate 3 having wiring (metal wiring layer) 23
Prepare 1

While heating the substrate 31 to a predetermined temperature,
The polyamic acid film 24a is formed on the entire surface of the substrate 31 to a desired thickness by the above-described vapor deposition polymerization method (FIG. 5B).

Further, heat treatment (imidization treatment) is performed under the above conditions to form an interlayer insulating film 24 made of polyimide having high heat resistance (FIG. 5C).

Next, on the surface of the interlayer insulating film 24, a resist film 25 having a predetermined pattern is formed by a resist process (FIG. 5D), and the resist film 25 is dry-etched. The interlayer insulating film 24 exposed at the window opening is removed (FIG. 5E). After removing the resist film 25, a wiring thin film is formed on the entire surface and patterned to form a second-layer wiring (metal wiring layer).

As a result, the first-layer wiring 23 and the second-layer wiring 26 are electrically connected to each other at the window opening portion 27 from which the interlayer insulating film 24 has been removed. As a result, a semiconductor having a multi-layer wiring The device 35 can be obtained (FIG. 5).
(f)).

According to the present embodiment, since the interlayer insulating film 24 is formed of the polyimide film having a reduced relative dielectric constant, the interlayer insulating film 24 is formed between the first-layer wiring 23 and the second-layer wiring 26. The capacity of the formed capacitor becomes very small, and the operation speed of the semiconductor device 35 can be greatly improved.

Further, according to the present embodiment, a semiconductor device 35 having stable characteristics can be obtained by simple steps using only a vacuum process.

The present invention is not limited to the above-described embodiment, but can be variously modified. For example,
Ultraviolet rays can be applied to the polyimide film formed by vapor deposition polymerization. This makes it possible to further improve the heat resistance of the polyimide film.

Further, the present invention can be applied not only to an interlayer insulating film of a semiconductor device but also to various insulating films. However, the present invention is more effective when applied to an interlayer insulating film of a semiconductor device.

[0061]

EXAMPLES Hereinafter, specific examples of the present invention will be described together with comparative examples. [Embodiment 1] A film forming apparatus 1 shown in FIGS. 2 to 4A and 4B
An element for measuring the relative permittivity was formed on the substrate 8 by using.

First, a 6-inch size having a conductivity of 0.02
The substrate 8 made of (Ω · cm) silicon (Si) is carried into the first processing chamber 4 and placed on the hot plate 46.
A polyamic acid film is formed on the substrate 8 by vapor deposition polymerization.

Here, the starting monomers A and B are T
Using FDB and 6FDA in high vacuum (3 × 10 ^-3 Pa)
In, the TFDB was simultaneously evaporated at a temperature of 111 + 0.1 ° C. and for 6FDA at a temperature of 165.0 + 0.1 ° C. to control the evaporation rate of the raw material monomers A and B. In this case, 6
The composition ratio between FDA and TFDB was controlled so that the stoichiometric ratio in the film was 1: 1.

After the polyamic acid film is formed in this manner, the substrate 8 is carried into the second processing chamber 5 through the core chamber 2, and the polyamic acid film is subjected to a predetermined heat treatment (imidization treatment). Was done.

In this case, the conditions for the heat treatment are as follows:
Heat to 400 ° C at a rate of 400 ° C / min.
Hold for minutes. At this point, the thickness of the polyimide film was 500 nm. Further, the content of fluorine in the polyimide film in this example was 35% by weight.

After performing such a heat treatment, the core chamber 2
Then, the substrate 8 was carried into the third processing chamber 6 via aluminum, and aluminum was sputtered to form an electrode having a thickness of 200 nm, thereby forming an element for measuring a relative dielectric constant. In this case, the temperature of the substrate 8 was kept at 300 ° C., and the pressure in the third processing chamber 6 during sputtering was set to 1 × 10 ⁻¹ Pa.

The relative dielectric constant of this device measured at a frequency of 1 MHz was 2.56. In this case, the value of the relative dielectric constant is determined by a multi-frequency LCR meter (model 4275) manufactured by Yokogawa Hewlett-Packard Company.
The capacitance was measured using A) and calculated.

Example 2 17FMPD and 6FDA were used as raw material monomers A and B for forming a polyimide film.
And 17FMPD is 65.0 + 0.1 ° C., 6FDA
Was prepared by evaporating simultaneously at a temperature of 165.0 + 0.1 ° C. to form a polyamic acid film, and the other conditions were the same as in Example 1 to prepare an element for measuring a relative dielectric constant. In the case of this example, the content of fluorine in the polyimide film was 46% by weight. The relative dielectric constant of this device was measured by the same method as in Example 1, and it was 2.49.

Example 3 As raw material monomers A and B for forming a polyimide film, 17FMPD and P2FD were used.
A, 17FMPD: 65.0 + 0.1 ° C., P2FD
A was simultaneously evaporated at a temperature of 120.0 + 0.1 ° C. to form a polyamic acid film, and an element for measuring a relative dielectric constant was prepared under the same conditions as in Example 1 except for the above. In the case of this example, the content of fluorine in the polyimide film was 43% by weight.
Met. The relative permittivity of this device was measured by the same method as in Example 1, and it was 2.32.

Example 4 TFDB and pyromellitic dianhydride (PMDA) were used as raw material monomers A and B for forming a polyimide film, and TFDB was 111 + 0.1.
With respect to ° C. and PMDA, a polyamic acid film was formed by simultaneously evaporating at a temperature of 123.0 + 0.1 ° C., and an element for measuring dielectric constant was prepared under the same conditions as in Example 1 except for the above.
In the case of this example, the content of fluorine in the polyimide film is
It was 23% by weight. The relative permittivity of this device was measured by the same method as in Example 1, and was 2.9.

Comparative Example After a lower electrode was formed in the same manner as in the above-described example, 4,4′-diaminodiphenyl ether (ODA) was used as raw material monomers A and B,
Using pyromellitic dianhydride (PMDA), a fluorine-free polyimide film is formed under the same conditions as in the other examples, and an electrode is formed on this polyimide film to create an element for relative dielectric constant measurement. did. When the relative dielectric constant of the polyimide film of this device was measured in the same manner as in the example, it was 3.23.

As is clear from Examples 1 to 4 and Comparative Example shown in FIG. 1, according to the present invention, a predetermined amount of fluorine is contained in a polyimide film formed by vapor deposition polymerization, so that the ratio of the polyimide film can be reduced. The dielectric constant could be set to a desired low value.

[0073]

As described above, according to the present invention, a desired low relative dielectric constant polymer film having stable characteristics can be obtained by a simple process. Further, by forming an interlayer insulating film of a multi-layered semiconductor device according to the present invention, a semiconductor device having a high operation speed and stable characteristics can be obtained.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the fluorine content in a polymer film and the relative dielectric constant of the polymer film in the present invention.

FIG. 2 is a schematic configuration diagram of an example of a film forming apparatus for carrying out the present invention.

FIG. 3 is a schematic configuration diagram of a first processing chamber in the film forming apparatus of FIG.

4A is a schematic configuration diagram of a second processing chamber in the film forming apparatus of FIG. 2; and FIG. 4B is a schematic configuration diagram of a third processing chamber in the film forming apparatus of FIG.

5A to 5F are process diagrams showing an example of a process of forming an interlayer insulating film of a semiconductor device by using the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Film-forming apparatus 2 ... Core room 3 ... L / UL room 4 ... 1st
Processing chamber 5 ... second processing chamber 6 ... third processing chamber 8 ...
Substrate (base) 21 Semiconductor substrate 22 Silicon thermal oxide film 23 First-layer wiring 24 Interlayer insulating film 24
a ... polyamic acid film 25 ... resist film 26 ... second-layer wiring 31 ... substrate 35 ... semiconductor device A and B ... raw material monomers 40A and 40B ... evaporation source 41
A, 41B ... Introduction pipe 45A, 45B ... Valve 47 ...
Mixing tank 48, 49 ... heater 50 ... hot plate

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01B 3/24 H01B 3/24 A 3/30 3/30 G H01L 21/768 B32B 7/02 104 // B32B 7/02 104 C23C 14/12 C23C 14/12 H01L 21/90 S (72) Inventor Masayuki Iijima 5-9-7 Tokodai, Tsukuba, Ibaraki Pref. Japan Tsukuba Super Materials Research Laboratory (72) Inventor Masatoshi Sato Ibaraki (72) Inventor Yoshiyuki Ukishima 5-9-7 Tokodai, Tsukuba City, Ibaraki Pref. Tsukuba Super Materials Laboratory, Japan (72) Inventor Yoshikazu Takahashi 5-9-7 Tokodai, Tsukuba City, Ibaraki Pref., Japan Vacuum Technology Co., Ltd.Tsukuba Super Materials Research Laboratory (72) Inventor Shigekuni Sasaki Shinjuku-ku, Tokyo Shinjuku 3-chome 19-2 Nippon Telegraph and Telephone Corporation (72) Inventor Toru Matsuura 3-19-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Japan Telegraph and Telephone Corporation (72) Inventor Fumio Yamamoto Gotenyama, Musashino City, Tokyo 1-3-3 NTT Advanced Technology Co., Ltd.

Claims (7)

[Claims] 1. A low dielectric constant polymer film comprising a predetermined amount of fluorine in a polymer film formed on a substrate by vapor deposition polymerization. 2. The low dielectric constant polymer film according to claim 1, wherein the polymer film formed on the substrate by vapor deposition polymerization is a polyimide film. 3. The method according to claim 1, wherein the content of fluorine in the polymer film is 25% by weight.
The low dielectric constant polymer film according to claim 1, wherein: 4. A method according to claim 1, wherein the raw material monomers are evaporated in a vacuum and vapor-deposited and polymerized on a substrate to form a polymer film, wherein a monomer having a substituent containing fluorine is used as the raw material monomer. Forming a low relative dielectric constant polymer film. 5. A polyimide raw material monomer represented by the following structural formula: Embedded image Embedded image Embedded image Embedded image 5. The method for forming a low dielectric constant polymer film according to claim 4, wherein any one of the diamine monomers represented by the following formulas is used. 6. A raw material monomer for polyimide, having the following structural formula: Embedded image Embedded image Embedded image The method for forming a low dielectric constant polymer film according to claim 4, wherein any one of the acid component monomers represented by the following formulas is used. 7. An interlayer insulating film, wherein the low dielectric constant polymer film according to claim 1 is formed between metal wiring layers formed on a semiconductor substrate. .