JP2006278512A - Insulating film and its manufacturing method, and electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulating film having a low dielectric constant and high film strength, its efficient manufacturing method, and an electronic device using the insulating film. <P>SOLUTION: The insulating film includes a mesh-like structure wherein carbon-based hollow structural bodies having an air gap in their central parts are linked by at least either of an Si atom and an O atom. The carbon-based hollow structural body is preferably made of at least either of fullerene and carbon nanotube, and they are preferably linked by chemical joint. The electronic device is provided with at least the insulating film, and it is preferably provided with the insulating film as an interlayer dielectric. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an insulating film suitable for multilayer wiring in a semiconductor integrated circuit, which requires high-speed signal propagation, an efficient manufacturing method thereof, and a high-performance electronic device using the insulating film.

In recent years, with the increase in the degree of integration of semiconductor integrated circuits and the improvement in element density, there has been an increasing demand for multilayered semiconductor elements. However, along with the higher integration of semiconductor integrated circuits, the transmission delay in the wiring section has increased. Is a problem.
The transmission delay is caused by the miniaturization of the wiring layer itself due to the miniaturization of the semiconductor device, the high resistance of the wiring layer itself due to the reduction of the wiring cross-sectional area, and the wiring capacitance due to the short distance between the wiring layers. Due to the increase in Therefore, in order to solve the transmission delay problem, it is necessary to lower the resistance of the wiring layer itself and to reduce the capacitance between the wiring layers. As for the reduction in resistance of the wiring layer itself, for example, although wiring using copper has been put into practical use and improved, the distance between wirings is still short, and the problem of wiring capacity remains.

In order to reduce the capacitance between the wiring layers, attempts have been made to lower the dielectric constant of the interlayer insulating film between the wiring layers. For example, nano-sized pores such as adamantane are introduced into the insulating film. A method (see Patent Document 1) is known. In this case, since adamantane has a space inside, the insulating property is improved by the space, but it cannot be said to be sufficient. Since the dielectric constant of the insulating film decreases in proportion to the volume of the space (excluded volume), for example, it is possible to obtain an insulating film having a lower dielectric constant by using fullerene (C ₆₀ ). is there. That is, for example, if the distance between C—C bonds is 1.54 Å (0.154 nm), the excluded volume of adamantane is about 14 ^{３ 3} (0.014 nm ³ ) and has a functional group in the side chain. Even if a large amount is estimated assuming the case, the excluded volume of C ₆₀ is about 268 Å ³ (0.268 nm ³ ) while it is about 51 ^{３ 3} (0.051 nm ³ ). Therefore, as compared to adamantane, a space (displacement volume) it is 5 to 19 times the C _60, it is clear that it is possible to form an insulating film having a lower dielectric constant.

Wherein using the fullerenes C _60, etc. As a method of introducing voids in the insulating film, for example, generally an insulating material that has been conventionally used, the insulating material as a binder, fullerenes such as C ₆₀ Has been proposed in which the periphery of fullerenes is surrounded by an insulating material and the fullerenes are fixed in an insulating film (see Patent Documents 2 to 5). However, these methods are effective when the mixing ratio of fullerenes is low. However, if the mixing ratio of fullerenes is increased for the purpose of further reducing the dielectric constant of the insulating film, the insulating material as the binder is reduced. It becomes insufficient in quantity and cannot combine fullerenes. For this reason, there exists a problem that the intensity | strength of an insulating film falls and it becomes easy to generate | occur | produce a crack only by applying very small stress.
Further, for example, a method has been proposed in which C ₆₀ itself is bonded by photoreaction to be polymerized and used as an insulating layer (see Patent Document 6). In this case, since the polymer formed by direct bonding of fullerene is a metastable phase, there is a problem that the bond between the fullerenes is easily broken due to a temperature rise to form an aggregate of fullerenes and the strength of the insulating film is impaired. .
Therefore, the present situation is that a technique for reducing the wiring capacitance and realizing high-speed signal propagation without reducing the strength of the insulating film has not yet been provided.

Japanese translation of PCT publication No. 2003-530464 JP-A-8-181133 JP 2000-269204 A Japanese Patent Laid-Open No. 11-263916 JP 2003-3119 A Japanese Patent No. 3531520

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide an insulating film having a low dielectric constant and a high film strength, an efficient manufacturing method thereof, and a high-performance electronic device using the insulating film.

As a result of intensive studies in view of the above problems, the present inventors have obtained the following knowledge. That is, the insulating film, a carbon-based hollow structure having voids in the center (e.g., fullerenes such as C ₆₀₎ to include reticulated structure is linked via at least one of Si atoms and O atoms This is the knowledge that even when the fullerene mixing ratio is high, the mechanical strength does not decrease, and an insulating film having a lower volume density and a lower dielectric constant than a conventional insulating film can be obtained.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as described in the following supplementary notes. That is,
The insulating film of the present invention is characterized in that it includes a network structure in which a carbon-based hollow structure having a void in the center is connected through at least one of Si atoms and O atoms. In the insulating film, since the carbon-based hollow structure has a void in the center, a low dielectric constant is realized, and the carbon-based hollow structure is connected via at least one of the Si atom and the O atom. Since the network structure formed in this way is included, a high film strength can be obtained as compared with an insulating film in which the carbon-based hollow structure is simply mixed. For this reason, it is suitably used for an interlayer insulating film in various devices requiring high speed and high reliability, for example, an electronic device such as a highly integrated semiconductor device such as an IC or LSI, and is particularly suitable for the electronic device of the present invention. When the insulating film of the present invention is used as the interlayer insulating film, the capacitance between the wiring layers is reduced, and high-speed signal transmission is possible.
An insulating film manufacturing method of the present invention is a method for manufacturing the insulating film of the present invention, wherein a carbon-based hollow structure having a functional group including a siloxane bond and a silane compound are used as a base material. It includes at least a coating process for applying to the surface and a curing process for curing the applied insulating material. In the method for manufacturing the insulating film, the insulating material containing the carbon-based hollow structure and the silane compound is applied to the surface of the base material in the applying step. In the curing step, the applied insulating material is cured. As a result, a network structure in which the carbon-based hollow structure is connected via at least one of the Si atom and the O atom is formed, and the insulating film of the present invention is efficiently and easily formed. .

  An electronic device according to the present invention includes at least the insulating film according to the present invention. Since the electronic device has the insulating film of the present invention having a low dielectric constant and a high film strength, the signal can be propagated at high speed, and it has high quality and high performance.

  According to the present invention, a conventional problem can be solved, and an insulating film having a low dielectric constant and a high film strength, an efficient manufacturing method thereof, and a high-performance electronic device using the insulating film are provided. Can do.

(Insulating film and manufacturing method thereof)
The insulating film of the present invention comprises a network structure in which carbon-based hollow structures are connected via at least one of Si atoms and O atoms.
The insulating film of the present invention can be manufactured by a known method, but is preferably manufactured by the method of manufacturing an insulating film of the present invention described later.
The method for producing an insulating film of the present invention includes at least a coating process and a curing process, and further includes other processes appropriately selected as necessary.
Hereinafter, the details of the insulating film of the present invention will be clarified through the description of the method of manufacturing the insulating film of the present invention.

<Application process>
The application step is a step of applying an insulating material to the surface of the substrate.

−Insulation material−
The insulating material includes at least a carbon-based hollow structure having a functional group including a siloxane bond and a silane compound, and further includes other components appropriately selected as necessary.

--A carbon-based hollow structure having a functional group containing a siloxane bond--
There is no restriction | limiting in particular as a functional group containing the said siloxane bond, According to the objective, it can select suitably, For example, it represents with the group represented by following General formula (1), and following General formula (2) Preferred examples include groups. The said carbon-type hollow structure may have these functional groups individually by 1 type, and may have both.

ただし、前記一般式（１）中、Ｒ^１及びＲ^２は、互いに同一であってもよいし、異なっていていてもよく、アルキル基及びエーテル基のいずれかを表し、Ｒ^３はアルキル基を表す。
前記アルキル基としては、例えば、メチル基、エチル基、プロピル基などが挙げられる。
前記エーテル基としては、例えば、メトキシ基、エトキシ基，プロポキシ基などが挙げられる。

However, in the general formula (1), R ¹ and R ² may be the same or different from each other, and represent either an alkyl group or an ether group, and R ³ represents an alkyl group. To express.
Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.
Examples of the ether group include a methoxy group, an ethoxy group, and a propoxy group.

ただし、前記一般式（２）中、Ｒ^１及びＲ^２は、互いに同一であってもよいし、異なっていてもよく、アルキル基を表し、Ｒ^３は、架橋基を表し、Ｒ^４及びＲ^５は、互いに同一であってもよいし、異なっていてもよく、アルキル基及びエーテル基のいずれかを表し、Ｒ^６はアルキル基を表す。
前記アルキル基としては、例えば、メチル基、エチル基、プロピル基などが挙げられる。
前記架橋基としては、例えば、アルカノ基、アルケノ基などが挙げられ、具体的には、メタノ基、エタノ基、プロペノ基などが挙げられる。
前記エーテル基としては、例えば、メトキシ基、エトキシ基，プロポキシ基などが挙げられる。

However, in the general formula (2), R ¹ and R ² may be the same as or different from each other, represent an alkyl group, R ³ represents a bridging group, R ⁴ and R 2 ⁵ may be the same as or different from each other, and represents either an alkyl group or an ether group, and R ⁶ represents an alkyl group.
Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.
Examples of the crosslinking group include an alkano group and an alkeno group, and specific examples include a methano group, an ethano group, and a propeno group.
Examples of the ether group include a methoxy group, an ethoxy group, and a propoxy group.

  The carbon-based hollow structure is not particularly limited as long as it has a structure having a void in the center, and can be appropriately selected according to the purpose. For example, a carbon 6-membered ring or a carbon 5-membered ring is mutually Examples of linked structures include fullerenes, carbon nanotubes, carbon nanocones, carbon nanohorns, carbon nanotubes with fullerenes (peapots), and fullerene polymers (dimers, trimers, etc.), but they have thermal stability and uniformity. Fullerene is particularly preferable in terms of excellent properties. These have a structure having a void in a molecule composed only of carbon atoms, and the presence of the void can improve the insulation and lower the dielectric constant of the insulating film.

Here, since the dielectric constant of the insulating film decreases in proportion to the volume (excluded volume) of the gap, for example, the use of fullerene (C ₆₀ ) is lower than the conventionally used adamantane. An insulating film having a dielectric constant can be obtained. That is, for example, if the distance between C—C bonds is 1.54 Å (0.154 nm), the excluded volume of adamantane is about 14 ^{３ 3} (0.014 nm ³ ) and has a functional group in the side chain. Even if a large amount is estimated assuming the case, the excluded volume of C ₆₀ is about 268 Å ³ (0.268 nm ³ ) while it is about 51 ^{３ 3} (0.051 nm ³ ). Therefore, as compared to adamantane, it has it is 5 to 19 times the gap C ₆₀ (excluded volume), it is clear that it is possible to form an insulating film having a lower dielectric constant.

The fullerene is a compound of a hollow spherical molecule having a network structure formed on the surface from carbon atoms. Examples of the fullerene include C ₆₀ and C ₇₀ . Among these, _C60 is preferable in terms of relatively low production cost.
The carbon-based hollow structure may be appropriately synthesized or a commercially available one may be used.

There is no restriction | limiting in particular as a carbon-type hollow structure which has a functional group containing the said siloxane bond, Although it can select suitably according to the objective, For example, what is shown in FIG.1 and FIG.2 is mentioned suitably.
The carbon-based hollow structure shown in FIG. 1 has two functional groups represented by the general formula (1) for one fullerene at the para position of any one carbon 6-membered ring in the fullerene. Examples of the carbon-based hollow structure formed by bonding include a 1,4-dihydro [60] fullerene derivative. In FIG. 1, R ¹ and R ² may be the same as or different from each other, and represent at least one of the above-described alkyl group and ether group, and R ³ represents the above-described alkyl group. Represents.
The 1,4-dihydro [60] fullerene derivative is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,4-ethoxy-dimethylsilyl-dihydro [60] shown in FIG. Preferable examples include fullerene.

The carbon-based hollow structure shown in FIG. 2 has two functional groups represented by the general formula (2) for one fullerene, and the adjacent carbon 6-membered ring and carbon 5-membered ring in the fullerene. Two of the arbitrary combinations are connected to each other, and at this time, the unsaturated bond part in the functional group represented by the general formula (2) is the carbon 6-membered ring and the Each is linked to an arbitrary position of the carbon 5-membered ring and becomes saturated. Examples of the carbon-based hollow structure shown in FIG. 2 include a bissilylmethane [60] fullerene derivative. In FIG. 2, R ¹ and R ² may be the same as or different from each other, and represent the alkyl group described above, and R ³ represents at least any one of the above-described crosslinking group and ether group. R ⁴ and R ⁵ may be the same as or different from each other, and represent at least one of the above-described alkyl group and ether group, and R ⁶ represents an alkyl group.
The bissilylmethane [60] fullerene derivative is not particularly limited and may be appropriately selected depending on the intended purpose. For example, bis (trimethoxysilyl-ethylene-dimethylsilyl-methano) [ 60] Fullerenes are preferred.

In addition to these carbon-based hollow structures, examples of the carbon-based structure having a functional group represented by the general formula (2) include fullerene (for example, C ₆₀ ) and the following structural formula (1). What is obtained by reacting with a monosolyldiazomethane derivative represented by the formula can be suitably used.

The carbon-based hollow structure having a functional group containing a siloxane bond may be appropriately synthesized or a commercially available one may be used.
The carbon-based hollow structure having a functional group containing a siloxane bond may be used alone or in combination of two or more.

--Silane compound--
There is no restriction | limiting in particular as long as it is the silane oxide represented by following General formula (3) as said silane compound, According to the objective, it can select suitably.

ただし、前記一般式（３）中、Ｒは任意の置換基を表す。該置換基としては、例えば、上述したアルキル基などが好適に挙げられる。

However, in said general formula (3), R represents arbitrary substituents. Suitable examples of the substituent include the above-described alkyl groups.

  Specific examples of the silane compound include, for example, tetraethoxysilane represented by the following structural formula (2), triethoxyfluorosilane represented by the following structural formula (3), and the like. These may be used individually by 1 type and may use 2 or more types together.

-Other ingredients-
The other components are not particularly limited and can be appropriately selected from known additives, such as thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), extender pigments, and the like. Furthermore, adhesion promoters to the substrate surface and other auxiliaries (for example, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chains A transfer agent or the like) may be used in combination.

-Base material-
The substrate is not particularly limited, and the material, shape, structure, thickness, and the like can be appropriately selected from known materials, but the insulating film is formed on the substrate and used. For this, an insulating substrate is preferable.

  The insulating substrate is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a resin substrate, such as a glass epoxy substrate, a polyester substrate, a polyimide substrate, a bismaleimide-triazine. Examples include a resin substrate, a thermosetting polyphenylene ether substrate, a fluororesin substrate, a ceramic substrate, a copper-clad laminate, and an RCC (Resin Coated Copper Foil) substrate.

-Application-
The coating method is not particularly limited and can be appropriately selected from known methods. For example, a roll coating method, a bar coating method, a dip coating method, a gravure coating method, a curtain coating method, and a die coating method. , Spray coating method, doctor coating method, spin coating method, and the like. These may be used individually by 1 type and may use 2 or more types together.
In addition, it is preferable to dry after the said application | coating.

Through the above steps, the insulating material is applied to the surface of the base material.
The insulating material may be applied to the entire surface of the base material, or may be applied partially, but is preferably applied to both surfaces and the entire surface of the base material. . The insulating film formed by applying the insulating material to both surfaces and the entire surface of the base material is preferably used as an interlayer insulating film in a highly integrated semiconductor device such as a multilayer wiring board, IC, or LSI. Can do.

<Curing process>
The curing step is a step of curing the insulating material applied to the surface of the substrate.
There is no restriction | limiting in particular as the said hardening method, Although it can select suitably according to the objective, Whole surface heat processing etc. are mentioned suitably.

Examples of the method for the entire surface heat treatment include a method for heating the entire surface of the base material on which the film made of the insulating material is formed after the coating step. The insulating material is cured by heating the entire surface.
As heating temperature in the said whole surface heating, 100-250 degreeC is preferable and 200-230 degreeC is more preferable.
When the heating temperature is less than 100 ° C., improvement in the hardness of the insulating film by heat treatment may not be obtained. When the heating temperature exceeds 250 ° C., the resin in the insulating film is decomposed and the film quality is fragile. May be.
As heating time in the said whole surface heat processing, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.
If the heating time is less than 10 minutes, the hardness of the insulating film may not be sufficient, and even if it exceeds 120 minutes, an effect commensurate with it may not be obtained.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heat processing, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hotplate, IR heater etc. are mentioned.

  Through the above steps, the insulating material applied to the surface of the substrate is cured. As a result, the carbon-based hollow structure is connected via at least one of the Si atom and the O atom to form a network structure, and the insulating film of the present invention is manufactured.

  The insulating film of the present invention includes at least a network structure in which the carbon-based hollow structure is connected via at least one of Si atoms and O atoms, and is appropriately selected as necessary. It contains other atoms.

  The Si atom and the O atom have a function of connecting the carbon-based hollow structures to each other, but the Si atom and the O atom are bonded to form a siloxane bond, and the carbon is bonded through the siloxane bond. It is preferable to connect the system hollow structures.

When the carbon-based hollow structures are connected to each other via the siloxane bond, the carbon-based hollow structure is preferably positioned between at least two of the siloxane bonds. In this case, since the carbon-based hollow structures are not directly bonded to each other, the bond is not broken due to a temperature rise, and the strength of the insulating film can be prevented from being reduced. It is easy to be present in the insulating film at regular intervals, which is advantageous in that the physical properties of the insulating film can be made uniform.
At this time, it is preferable that at least one fluorine atom is bonded to the Si atom forming the siloxane bond. In this case, it is advantageous in that the dielectric constant in the network structure composed of siloxane bonds can be reduced.

  The connection mode is not particularly limited and may be appropriately selected depending on the intended purpose. However, the carbon-based hollow structure can be firmly connected to at least one of the Si atom and the O atom. A chemical bond is preferable in that the film strength of the insulating film can be improved.

As shown in FIG. 5, the network structure is formed of a plurality of chains (polymer chains) 510 formed by connecting the carbon-based hollow structure 500 and at least one of the Si atoms and the O atoms. And a network structure (hereinafter sometimes referred to as “polymer network structure”).
The network structure preferably contains the carbon-based hollow structure as a structural unit of a chain forming the polymer network structure. In this case, the carbon-based hollow structure is continuously present through the Si atom and the O atom in the insulating film without being interrupted in the middle, and the physical properties of the insulating film are uniform. This is advantageous in that it can be realized.
The structural units may be regularly arranged or irregularly arranged, but they are regularly arranged in that the physical properties of the insulating film can be made uniform in the insulating film. In the network structure, it is preferable that the carbon-based hollow structures are located at substantially equal intervals and repeatedly exist.
Moreover, it is preferable that the said carbon-type hollow structure is located in the network intersection of the said polymer network structure. In this case, since the polymer chain spreads three-dimensionally from one carbon-based hollow structure and the carbon-based hollow structures are not directly bonded to each other, the film strength of the insulating film is excellent.
The presence of the network structure can be detected by using, for example, infrared absorption spectroscopy or nuclear magnetic resonance spectroscopy.

  The insulating film of the present invention is not particularly limited as to its physical properties such as shape, structure, size, and thickness, and can be appropriately selected according to the purpose. However, it has a low dielectric constant and high film strength. Preferably there is.

There is no restriction | limiting in particular as said shape, According to the objective, it can select suitably, For example, the film | membrane shape, pattern shape, etc. of the solid formed in the whole surface of a base material are mentioned.
There is no restriction | limiting in particular as said structure, According to the objective, it can select suitably, For example, a single layer structure may be sufficient and a laminated structure may be sufficient.
The size is not particularly limited and can be appropriately selected according to the purpose. For example, when the insulating film is applied to an interlayer insulating film or the like in a semiconductor device, the existing semiconductor device or the like A size corresponding to the size is preferable.
The thickness is not particularly limited and can be appropriately selected according to the purpose. For example, when the insulating film is used as an interlayer insulating film in a semiconductor device, the thickness is made as thin as possible in order to reduce a transmission distance. However, it is usually about 10 to 600 nm and preferably 10 to 300 nm because of insulation reliability and restrictions on manufacturing.

The dielectric constant is preferably as low as the value of the relative dielectric constant. As a method for measuring the relative dielectric constant, for example, a square metal electrode having a side of 1 mm is formed on the insulating film by vacuum deposition, and the dielectric constant is 1 MHz. The relative dielectric constant in alternating current can be easily measured using a commercially available dielectric constant meter.
The film strength is preferably as high as possible, and the film strength can be measured, for example, by a nanoindentation method.

Since the insulating film of the present invention has a low dielectric constant and high film strength, it is stable in various devices that require high speed and high reliability, for example, electronic devices such as highly integrated semiconductor devices such as IC and LSI. It is suitably used for an interlayer insulating film and can be particularly suitably used for the electronic device of the present invention.
According to the method for manufacturing an insulating film of the present invention, the insulating film of the present invention can be manufactured simply and efficiently.

(Electronic device)
The electronic device of the present invention includes at least the insulating film of the present invention, and further includes other members appropriately selected as necessary.
The electronic device preferably includes the insulating film of the present invention as an interlayer insulating film.
As specific examples of the electronic device of the present invention, for example, various semiconductor devices such as flash memory, DRAM, FRAM, and the like can be preferably cited.
Since the electronic device of the present invention has the insulating film of the present invention having a low dielectric constant and high film strength, high-speed signal transmission is possible, and high quality and high performance are achieved.

Hereinafter, as an example of the electronic device of the present invention, an example of a semiconductor device in which the insulating film of the present invention is applied as an interlayer insulating film of a multilayer wiring structure will be described with reference to the drawings.
As shown in FIG. 6, the gate electrode 12 is formed on the silicon wafer 10. Source / drain diffusion layers 14 a and 14 b are formed in the silicon wafer 10 on both sides of the gate electrode 12. A transistor having a gate electrode 12 and source / drain diffusion layers 14a and 14b is formed. Note that an element isolation film 16 for separating transistors is formed on the silicon wafer 10.
An interlayer insulating film 18 and a stopper film 20 are sequentially formed on the entire surface of the silicon wafer 10 on which the transistors are formed. A contact hole 22 reaching the drain diffusion layer 14 b is formed in the interlayer insulating film 18 and the stopper film 20. A titanium nitride film 24 is formed in the contact hole 22 and a conductor plug 26 made of tungsten is embedded. Yes.
On the upper surface of the stopper film 20, an insulating film 28 of the present invention and a cap film 30 made of a silicon oxide film are sequentially formed.
A first wiring groove 32 having a first layer wiring pattern connected to the conductor plug 26 is formed in the insulating film 28 and the cap film 30, and a titanium nitride film 34 is formed in the first wiring groove 32. The first wiring layer 36 made of copper is embedded.
On the upper surface of the cap film 30, a diffusion prevention film 38 made of a silicon nitride film, an insulating film 40 of the present invention, and a diffusion prevention film 42 made of a silicon nitride film are sequentially formed.
A via hole 44 connected to the first wiring layer 36 is formed in the insulating film 40 and the diffusion prevention film 42, a titanium nitride film 46 is formed in the via hole 44, and a via layer 48 made of copper is embedded. It is.
On the upper surface of the diffusion preventing layer 42, an insulating film 50 of the present invention and a cap film 52 made of a silicon oxide film are sequentially formed.
In the insulating film 50 and the cap film 52, a second wiring groove 56 having a second-layer wiring pattern connected to the via layer 48 is formed. In the second wiring trench 56, a titanium nitride film 46 is formed, and a second wiring layer 60 made of copper is embedded.

Next, an example of a method for manufacturing an electronic device according to the present invention will be described with reference to the drawings.
First, an interlayer insulating film 18 and a stopper film 20 are sequentially formed on a silicon wafer 10 on which a transistor having a gate electrode 12 and source / drain diffusion layers 14a and 14b and an element isolation film 16 are formed by a normal semiconductor device process. Form. Next, a contact hole 22 connected to the drain diffusion layer 14 b is formed in the interlayer insulating film 18 and the stopper film 20. Thereafter, a titanium nitride film 24 having a thickness of 50 nm is formed in the contact hole 22 by sputtering. Then, WF ₆ is mixed with hydrogen and reduced to bury the conductor plug 26 made of tungsten in the contact hole 22. Further, the tungsten used to form the titanium nitride film 24 and the conductor plug 26 other than in the contact hole 22 is removed by CMP (see FIG. 7A).

  Subsequently, the insulating material is applied to the entire surface of the stopper film 20 by a spin coat method, dried, and then subjected to a heat treatment at 230 ° C. for 10 minutes in the air, and the silicon wafer is placed in a nitrogen atmosphere having an oxygen concentration of 50 ppm or less Calcination at 210 ° C. for 3 hours. Thus, the insulating film 28 of the present invention having a thickness of 450 nm is formed. Next, a cap film 30 made of a silicon oxide film with a thickness of 50 nm is laminated on the insulating film 28 by a CVD method using TEOS (TetraEthOxySilane) as a raw material.

Next, a resist film 62 that exposes a region where a first layer wiring pattern is to be formed is formed on the cap film 30 by photolithography, and then CF ₄ / CHF ₃ is used using the patterned resist film 62 as a mask. The cap film 30 and the insulating film 28 are etched by RIE (Reactive Ion Etching). Thus, the first wiring groove 32 having the first layer wiring pattern is formed (see FIG. 7B). Then, after forming the first wiring groove 32, the resist film 62 is removed.
Subsequently, a 50 nm thick titanium nitride film 34 and a 50 nm thick seed copper film (not shown) are sequentially formed on the entire surface by sputtering. Next, a copper film 64 having a thickness of 600 nm is formed on the seed copper film by electrolytic plating using the seed copper film as an electrode (see FIG. 7C).
The copper film 64, the seed copper film, and the titanium nitride film 34 formed on the portion other than the first wiring trench 32 are removed by CMP. Here, since the insulating film 28 formed by the insulating film forming method according to the present invention has high mechanical strength, the copper film 64 and the like can be easily removed by CMP. In this manner, the first wiring layer 36 made of the copper film 64 embedded in the first wiring groove 32 is formed (see FIG. 7D).

  Next, the second wiring layer 60 and the via layer 48 that connects the first wiring layer 36 and the second wiring layer 60 are simultaneously formed by the dual damascene method. First, a diffusion prevention film 38 made of a silicon nitride film having a thickness of 50 nm is formed on the entire surface of the silicon wafer 10 on which the first wiring layer 36 is formed by plasma CVD using silane and ammonia gas as raw materials. Next, similarly to the case where the insulating film 28 is formed, the insulating film 40 having a film thickness of 650 nm is formed on the diffusion preventing film 38 by using the insulating material. Then, a diffusion prevention film 42 made of a silicon nitride film is formed on the insulating film 40. An insulating film 50 having a thickness of 450 nm is similarly formed on the diffusion preventing film 42 by the method for manufacturing an insulating film according to the present invention. Further, a cap film 52 made of a silicon oxide film having a thickness of 50 nm is formed on the insulating film 50 by a CVD method using TEOS as a raw material (see FIG. 8A).

Next, a resist film 66 that exposes a region where the via hole 44 is to be formed is formed on the cap film 52 by photolithography, and then the cap film is formed by RIE using CF ₄ / CHF ₃ using the patterned resist film 66 as a mask. 52, the insulating film 50, the diffusion preventing film 42, the insulating film 40, and the diffusion preventing film 38 are sequentially etched. In this way, a via hole 44 connected to the first wiring layer 36 is formed (see FIG. 8B). After the via hole 44 is formed, the resist film 66 is removed.

Next, a resist film 68 that exposes a region where a second-layer wiring pattern is to be formed is formed on the entire surface by photolithography, and then by RIE using CF ₄ / CHF ₃ using the patterned resist film 68 as a mask. The cap film 52 and the insulating film 50 are etched sequentially. Thus, the second wiring groove 56 having the second-layer wiring pattern is formed. (See FIG. 9A). After forming the second wiring groove 56, the resist film 68 is removed. Subsequently, a titanium nitride film 46 having a thickness of 50 nm and a seed copper film (not shown) having a thickness of 50 nm are sequentially formed on the entire surface by sputtering. Then, a 600 nm thick copper film 70 is formed on the seed copper film by electrolytic plating using the seed copper film as an electrode (see FIG. 9B).
The copper film 70, the seed copper film, and the titanium nitride film 46 formed in portions other than the via hole 44 and the wiring groove 56 are removed by CMP. As in the case where the first wiring layer 36 is formed, since the insulating films 50 and 40 have high mechanical strength, the copper film 70 and the like can be easily removed by CMP. Thus, the via layer 48 made of the copper film 70 embedded in the via hole 44 and the second wiring trench 56 and the second wiring layer 60 are simultaneously formed.
A multilayer wiring can be formed by appropriately repeating the above steps. Thus, in the obtained multilayer wiring, the yield of 1 million continuous vias can be 90% or more.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1
-Production of insulating film-
--- Preparation of coating liquid-
A toluene solution of 1,4 ethoxy-dimethylsilyl-dihydro [60] fullerene shown in FIG. 3 and an ethanol solution of tetraethoxysilane (TEOS) represented by the structural formula (2) shown in FIG. Was mixed at a ratio of 1: to prepare a coating solution.

-Application process and curing process-
The obtained coating solution was applied by spin coating on a silicon substrate as a base material doped with boron to impart conductivity, dried, and then heat-treated at 230 ° C. for 10 minutes in the air. It was. Next, heat treatment was performed at 210 ° C. for 3 hours in a nitrogen atmosphere with an oxygen concentration of 50 ppm or less, so that an insulating film (thickness: 200 nm) was formed.

(Example 2)
-Production of insulating film-
--- Preparation of coating liquid-
As the insulating material, a monosilyldiazomethane derivative represented by the structural formula (1), a toluene solution of C60, and an ethanol solution of tetraethoxysilane (TEOS) represented by the structural formula (2) are used: The coating liquid was prepared by mixing at a ratio of 1: 1.5 and reacting at 50 ° C. for 3 hours in an N ₂ atmosphere having an oxygen concentration of 10 ppm or less.

-Application process and curing process-
The obtained coating solution was applied by spin coating on a silicon substrate as a base material doped with boron to impart conductivity, dried, and then heat-treated at 230 ° C. for 10 minutes in the air. It was. Next, heat treatment was performed at 210 ° C. for 3 hours in a nitrogen atmosphere with an oxygen concentration of 50 ppm or less, so that an insulating film (thickness: 200 nm) was formed.

(Example 3)
-Production of insulating film-
--- Preparation of coating liquid-
As the insulating material, a toluene solution of 1,4 ethoxy-dimethylsilyl-dihydro [60] fullerene shown in FIG. 3 and an ethanol solution of triethoxyfluorosilane represented by the structural formula (3) are 2: 1. The coating solution was prepared by reacting at 50 ° C. for 3 hours in an N ₂ atmosphere having an oxygen concentration of 10 ppm or less.

-Application process and curing process-
The obtained coating solution was applied by spin coating on a silicon substrate as a base material doped with boron to impart conductivity, dried, and then heat-treated at 230 ° C. for 10 minutes in the air. It was. Next, heat treatment was performed at 210 ° C. for 3 hours in a nitrogen atmosphere with an oxygen concentration of 50 ppm or less, so that an insulating film (thickness: 200 nm) was formed.

Example 4
-Production of insulating film-
--- Preparation of coating liquid-
As the insulating material, a monosilyldiazomethane derivative represented by the structural formula (1), a toluene solution of C60, and an ethanol solution of tetraethoxysilane (TEOS) represented by the structural formula (2) are used: The mixture was mixed at a ratio of 1: 1.5 and reacted at 50 ° C. for 3 hours in an N ₂ atmosphere having an oxygen concentration of 10 ppm or less. The obtained solution was mixed with a toluene solution of 1,4 ethoxy-dimethylsilyl-dihydro [60] fullerene shown in FIG. 3 at a ratio of 1: 1 to prepare a coating solution.

-Application process and curing process-
The obtained coating solution was applied by spin coating on a silicon substrate as a base material doped with boron to impart conductivity, dried, and then heat-treated at 230 ° C. for 10 minutes in the air. It was. Next, heat treatment was performed at 210 ° C. for 3 hours in a nitrogen atmosphere with an oxygen concentration of 50 ppm or less, so that an insulating film (thickness: 200 nm) was formed.

(Example 5)
-Production of insulating film-
--- Preparation of coating liquid-
As the insulating material, a toluene solution of bis (trimethoxysilyl-ethylene-dimethylsilyl-methano) [60] fullerene shown in FIG. 4 and ethanol of tetraethoxysilane (TEOS) represented by the structural formula (2) The solution was mixed at a ratio of 2: 1 to prepare a coating solution.

-Application process and curing process-
The obtained coating solution was applied by spin coating on a silicon substrate as a base material doped with boron to impart conductivity, dried, and then heat-treated at 230 ° C. for 10 minutes in the air. It was. Next, heat treatment was performed at 210 ° C. for 3 hours in a nitrogen atmosphere with an oxygen concentration of 40 ppm or less, so that an insulating film (thickness: 200 nm) was formed.

(Comparative Example 1)
-Production of insulating film-
In a quartz separable flask, 77.04 g of distilled methyltrimethoxysilane, 24.05 g of distilled tetramethoxysilane, and 0.48 g of distilled tetrakis (acetylacetonate) titanium were dissolved in 290 g of distilled propylene glycol monopropyl ether. Thereafter, the solution was stirred with a three-one motor to stabilize the solution temperature at 60 ° C. Next, 84 g of ion-exchanged water was added to the solution over 1 hour. Subsequently, after making it react at 60 degreeC for 2 hours, 25 g of distilled acetylacetone was added, it was made to react for 30 minutes, and the reaction liquid was cooled to room temperature. Thereafter, a solution containing methanol and water was removed by 149 g evaporation at 50 ° C. to obtain a reaction solution.
To 50 g of the obtained reaction solution, 12 g of fullerene C ₆₀ was added and sufficiently stirred using a homogenizer. This solution was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a coating solution.

  The obtained coating solution was applied by spin coating on the silicon substrate as the base material doped with boron to impart conductivity, thereby forming an insulating film (thickness: 200 nm).

  For the obtained insulating films of Examples 1 to 5 and Comparative Example 1, the relative dielectric constant and film strength were measured. The results are shown in Table 1.

<Measurement of relative dielectric constant and film strength>
The dielectric constant is obtained by forming a square metal electrode (material: Au, thickness: 100 nm) with a side of 1 mm on the insulating films of Examples 1 to 5 by vacuum deposition (film formation rate: 0.1 nm / sec). The relative dielectric constant at 1 MHz alternating current was measured.
The film strength was measured by a nanoindentation method under the condition of an indentation amount of 20 nm.

  From the results in Table 1, it was found that the insulating film of the present invention has a low dielectric constant and a high film strength. On the other hand, since the insulating film of Comparative Example 1 is prepared by simply adding fullerene, a network structure in which fullerene is connected via at least one of Si atoms and O atoms is included in the insulating film. It was not included and was found to be inferior in film strength.

(Example 6)
-Manufacture of electronic devices (semiconductor devices)-
The electronic device (semiconductor device) of the present invention provided with the insulating film of the present invention was manufactured as follows.

First, an interlayer insulating film 18 and a stopper film 20 are sequentially formed on a silicon wafer 10 on which a transistor having a gate electrode 12 and source / drain diffusion layers 14a and 14b and an element isolation film 16 are formed by a normal semiconductor device process. Formed. Next, a contact hole 22 connected to the drain diffusion layer 14 b was formed in the interlayer insulating film 18 and the stopper film 20. Thereafter, a titanium nitride film 24 having a thickness of 50 nm was formed in the contact hole 22 by sputtering. A conductive plug 26 made of tungsten was embedded in the contact hole 22 by reducing WF ₆ mixed with hydrogen. Further, the tungsten used to form the titanium nitride film 24 and the conductor plug 26 other than in the contact hole 22 was removed by CMP (see FIG. 7A).

  Subsequently, the insulating material is applied to the entire surface of the stopper film 20 by a spin coat method, dried, and then subjected to a heat treatment at 230 ° C. for 10 minutes in the air, and the silicon wafer is placed in a nitrogen atmosphere having an oxygen concentration of 50 ppm or less Baked at 210 ° C. for 3 hours. Thus, the insulating film 28 of the present invention having a thickness of 450 nm was formed. Next, a cap film 30 made of a silicon oxide film having a thickness of 50 nm was laminated on the insulating film 28 by a CVD method using TEOS (TetraEthOxySilane) as a raw material.

Next, a resist film 62 that exposes a region where a first layer wiring pattern is to be formed is formed on the cap film 30 by photolithography, and then CF ₄ / CHF ₃ is used using the patterned resist film 62 as a mask. The cap film 30 and the insulating film 28 were etched by RIE (Reactive Ion Etching). Thus, the first wiring groove 32 having the first-layer wiring pattern was formed (see FIG. 7B). Then, after forming the first wiring groove 32, the resist film 62 was removed.
Subsequently, a 50 nm thick titanium nitride film 34 and a 50 nm thick seed copper film (not shown) were sequentially formed on the entire surface by sputtering. Next, a copper film 64 having a thickness of 600 nm was formed on the seed copper film by electrolytic plating using the seed copper film as an electrode (see FIG. 7C).
The copper film 64, the seed copper film, and the titanium nitride film 34 formed in portions other than the first wiring trench 32 were removed by CMP. Here, since the insulating film 28 formed by the insulating film manufacturing method of the present invention has high mechanical strength, the copper film 64 and the like could be easily removed by CMP. Thus, the 1st wiring layer 36 which consists of the copper film 64 embedded in the 1st wiring groove | channel 32 was formed (refer FIG. 7D).

  Next, the second wiring layer 60 and the via layer 48 that connects the first wiring layer 36 and the second wiring layer 60 were simultaneously formed by the dual damascene method. First, a diffusion prevention film 38 made of a silicon nitride film having a thickness of 50 nm was formed on the entire surface of the silicon wafer 10 on which the first wiring layer 36 was formed by plasma CVD using silane and ammonia gas as raw materials. Next, in the same manner as when the insulating film 28 was formed, an insulating film 40 having a thickness of 650 nm was formed on the diffusion preventing film 38 using the insulating material. Then, a diffusion preventing film 42 made of a silicon nitride film was formed on the insulating film 40. An insulating film 50 having a thickness of 450 nm was similarly formed on the diffusion preventing film 42 by the method for forming an insulating film according to the present invention. Further, a cap film 52 made of a silicon oxide film having a thickness of 50 nm was formed on the insulating film 50 by a CVD method using TEOS as a raw material (see FIG. 8A).

Next, a resist film 66 that exposes a region where the via hole 44 is to be formed is formed on the cap film 52 by photolithography, and then the cap film is formed by RIE using CF ₄ / CHF ₃ using the patterned resist film 66 as a mask. 52, the insulating film 50, the diffusion preventing film 42, the insulating film 40, and the diffusion preventing film 38 were sequentially etched. Thus, a via hole 44 connected to the first wiring layer 36 was formed (see FIG. 8B). After the via hole 44 was formed, the resist film 66 was removed.

Next, a resist film 68 that exposes a region where a second-layer wiring pattern is to be formed is formed on the entire surface by photolithography, and then by RIE using CF ₄ / CHF ₃ using the patterned resist film 68 as a mask. The cap film 52 and the insulating film 50 were sequentially etched. Thus, the second wiring groove 56 having the second-layer wiring pattern was formed. (See FIG. 9A). After forming the second wiring groove 56, the resist film 68 was removed. Subsequently, a 50 nm thick titanium nitride film 46 and a 50 nm thick seed copper film (not shown) were sequentially formed on the entire surface by sputtering. Then, a 600 nm thick copper film 70 was formed on the seed copper film by electrolytic plating using the seed copper film as an electrode (see FIG. 9B).
The copper film 70, the seed copper film, and the titanium nitride film 46 formed in portions other than the via hole 44 and the wiring groove 56 were removed by CMP. As in the case where the first wiring layer 36 is formed, the insulating films 50 and 40 have high mechanical strength, so that the copper film 70 and the like can be easily removed by CMP. Thus, the via layer 48 made of the copper film 70 embedded in the via hole 44 and the second wiring trench 56 and the second wiring layer 60 were simultaneously formed.
By repeating the above steps, a semiconductor device having an interlayer insulating film having a multilayer wiring structure as shown in FIG. 6 was manufactured. In the multilayer wiring in the semiconductor device obtained as described above, the yield of 1 million continuous vias could be 90% or more.

ただし、前記一般式（１）中、Ｒ^１及びＲ^２はアルキル基及びエーテル基のいずれかを表し、Ｒ^３はアルキル基を表す。

ただし、前記一般式（２）中、Ｒ^１及びＲ^２はアルキル基を表し、Ｒ^３は架橋基を表し、Ｒ^４及びＲ^５はアルキル基及びエーテル基のいずれかを表し、Ｒ^６はアルキル基を表す。

ただし、前記一般式（３）中、Ｒは任意の置換基を表す。
（付記１４） 一般式（２）で表される官能基を有する炭素系中空構造体が、フラーレンと下記構造式（１）で表されるモノソリルジアゾメタン誘導体とを反応させて得られる付記１３に記載の絶縁膜の製造方法。

（付記１５） 付記１から１２のいずれかに記載の絶縁膜を少なくとも有してなることを特徴とする電子装置。
（付記１６） 絶縁膜を層間絶縁膜として有する付記１５に記載の電子装置。 The preferred embodiments of the present invention are as follows.
(Additional remark 1) The insulating film characterized by the carbon-type hollow structure which has a space | gap in a center part containing the network structure connected through at least any one of Si atom and O atom.
(Supplementary note 2) The insulating film according to supplementary note 1, wherein the carbon-based hollow structure is at least one of fullerene and carbon nanotube.
(Supplementary Note 3) The insulating film according to note 2 fullerene is _{C 60.}
(Supplementary note 4) The insulating film according to any one of supplementary notes 1 to 3, wherein the carbon-based hollow structures are connected via Si atoms and O atoms, and the Si atoms and the O atoms form a siloxane bond.
(Supplementary note 5) The insulating film according to any one of supplementary notes 1 to 4, wherein the connection is performed by a chemical bond.
(Supplementary note 6) The insulating film according to supplementary note 5, wherein the carbon-based hollow structure is disposed between at least two siloxane bonds.
(Supplementary note 7) The insulating film according to any one of supplementary notes 1 to 6, wherein the carbon-based hollow structure is included as a structural unit of a chain forming a network structure.
(Supplementary note 8) The insulating film according to any one of supplementary notes 1 to 7, wherein the carbon-based hollow structure is located at a network intersection of a network structure.
(Supplementary note 9) The insulating film according to any one of supplementary notes 1 to 8, wherein the carbon-based hollow structures are positioned at substantially equal intervals.
(Supplementary note 10) The insulating film according to any one of supplementary notes 1 to 9, wherein at least one fluorine atom is bonded to a Si atom.
(Additional remark 11) The insulating film in any one of Additional remark 1 to 10 used as an interlayer insulation film.
(Additional remark 12) The insulating film in any one of Additional remark 1 to 11 whose thickness of an insulating film is 10-300 nm.
(Additional remark 13) It is a method of manufacturing the insulating film in any one of Additional remark 1 to 12, Comprising: The functional group represented by following General formula (1) and the functional group represented by following General formula (2) An application step of applying an insulating material containing at least one of a carbon-based hollow structure and a silane compound represented by the following general formula (3) to the surface of the substrate, and curing the applied insulating material A method for producing an insulating film, comprising at least a curing step.

However, in said general formula (1), R < ¹ > and R < ² > represents either an alkyl group and an ether group, and R < ³ > represents an alkyl group.

However, in said general formula (2), R < ¹ > and R < ² > represents an alkyl group, R < ³ > represents a crosslinking group, R < ⁴ > and R < ⁵ > represent either an alkyl group and an ether group, and R < ⁶ > is alkyl Represents a group.

However, in said general formula (3), R represents arbitrary substituents.
(Supplementary note 14) Supplementary note 13 obtained by reacting a carbon-based hollow structure having a functional group represented by the general formula (2) with a fullerene and a monosolyldiazomethane derivative represented by the following structural formula (1) The manufacturing method of the insulating film as described in 2.

(Supplementary note 15) An electronic device comprising at least the insulating film according to any one of Supplementary notes 1 to 12.
(Additional remark 16) The electronic device of Additional remark 15 which has an insulating film as an interlayer insulation film.

Since the insulating film of the present invention has a low dielectric constant and a high film strength, it is used in various devices that require high speed and high reliability, for example, an interlayer in an electronic device such as a highly integrated semiconductor device such as an IC or LSI. It is suitably used for an insulating film and can be particularly suitably used for an electronic device of the present invention.
The The insulating film manufacturing method of the present invention is particularly suitable for manufacturing the insulating film of the present invention. Since the electronic device according to the present invention has the insulating film according to the present invention, it is capable of high-speed signal transmission, high performance and high quality, and various semiconductor devices such as flash memory, DRAM, and FRAM. It can be suitably used in the field.

FIG. 1 is a schematic explanatory view showing an example of a carbon-based hollow structure having a functional group represented by the general formula (1). FIG. 2 is a schematic explanatory view showing an example of a carbon-based hollow structure having a functional group represented by the general formula (2). FIG. 3 is a schematic explanatory view showing a specific example of the carbon-based hollow structure of FIG. FIG. 4 is a schematic explanatory view showing a specific example of the carbon-based hollow structure of FIG. FIG. 5 is a schematic cross-sectional explanatory view showing a polymer network structure. FIG. 6 is a schematic cross-sectional explanatory view showing the structure of a semiconductor device in which the insulating film of the present invention is applied as an interlayer insulating film having a multilayer wiring structure. FIG. 7A is a process cross-sectional view (part 1) illustrating the method for manufacturing the semiconductor device in which the insulating film of the present invention is applied as an interlayer insulating film of a multilayer wiring structure. FIG. 7B is a process cross-sectional view (part 2) illustrating the method for manufacturing the semiconductor device in which the insulating film of the present invention is applied as an interlayer insulating film of a multilayer wiring structure. FIG. 7C is a process cross-sectional view (part 3) illustrating the method for manufacturing the semiconductor device in which the insulating film of the present invention is applied as an interlayer insulating film of a multilayer wiring structure. FIG. 7D is a process cross-sectional view (part 4) illustrating the method for manufacturing the semiconductor device to which the insulating film of the present invention is applied as an interlayer insulating film of a multilayer wiring structure; FIG. 8A is a process cross-sectional view (part 5) illustrating the method for manufacturing the semiconductor device to which the insulating film of the present invention is applied as an interlayer insulating film of a multilayer wiring structure. FIG. 8B is a process cross-sectional view (No. 6) showing the method for manufacturing the semiconductor device to which the insulating film of the present invention is applied as an interlayer insulating film of a multilayer wiring structure. FIG. 9A is a process cross-sectional view (No. 7) showing the method for manufacturing the semiconductor device to which the insulating film of the present invention is applied as an interlayer insulating film of a multilayer wiring structure. FIG. 9B is a process cross-sectional view (No. 8) showing the method for manufacturing the semiconductor device to which the insulating film of the present invention is applied as an interlayer insulating film of a multilayer wiring structure.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Silicon wafer 12 Gate electrode 14a, 14b Source / drain diffused layer 16 Element isolation film 18 Interlayer insulating film 20 Stopper film 22 Contact hole 24, 34, 46 Titanium nitride film 26 Conductor plug 28, 40, 50 Insulating film 30, 52 Cap Film 32 First wiring groove 36 First wiring film 38, 42 Diffusion prevention film 44 Via hole 48 Via layer 56 Second wiring groove 60 Second wiring layer 500 Carbon-based hollow structure 510 Polymer chain

Claims (5)

  An insulating film comprising a network structure in which a carbon-based hollow structure having a void in the center is connected through at least one of Si atoms and O atoms.   The insulating film according to claim 1, wherein the carbon-based hollow structure is at least one of fullerene and carbon nanotube.   The insulating film according to claim 1, wherein the connection is performed by a chemical bond. A method for producing the insulating film according to claim 1, wherein at least one of a functional group represented by the following general formula (1) and a functional group represented by the following general formula (2): A coating step of applying an insulating material containing a carbon-based hollow structure having a silane compound represented by the following general formula (3) to the surface of the substrate, and a curing step of curing the applied insulating material; A method for producing an insulating film, comprising:

However, in said general formula (1), R < ¹ > and R < ² > represents either an alkyl group and an ether group, and R < ³ > represents an alkyl group.

However, in said general formula (2), R < ¹ > and R < ² > represents an alkyl group, R < ³ > represents a crosslinking group, R < ⁴ > and R < ⁵ > represent either an alkyl group and an ether group, and R < ⁶ > is alkyl Represents a group.

However, in said general formula (3), R represents arbitrary substituents. An electronic device comprising at least the insulating film according to claim 1.

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