JP2003273112A - Method for selectively growing columnar carbon structure, and electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for selectively growing a columnar carbon structure in which columnar carbon structures such as carbon nano-tubes or the like are selectively grown only at essential portions, and to provide an electronic device. <P>SOLUTION: Catalyst metal 5 is deposited on the whole surface of a substrate 1 where a diffusion-proof film pattern 4 is provided followed by heat treatment so that only the catalyst metal 5 that exists at an area other than the diffusion- proof film pattern 4 is diffused in the depth direction. Subsequently, the columnar carbon structures 6 are selectively grown starting from the catalyst metal 5 which have remained without being diffused on the diffusion-proof film pattern 4. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for selectively growing a columnar carbon structure and an electronic device,
For example, a columnar carbon structure for improving wiring electromigration resistance in a via hole portion that connects wirings of a multilayer wiring used in a semiconductor integrated circuit device typified by SiULSI, particularly a multilayer wiring structure using carbon nanotubes The present invention relates to a selective growth method for a columnar carbon structure and an electronic device.

[0002]

2. Description of the Related Art In wiring used in a semiconductor integrated circuit device typified by SiULSI, it is important to reduce the resistance of a wiring material as the wiring rule is reduced.
Cu, which has a lower resistance, is being adopted as an alternative to the l-wiring as a wiring material. In this case, a multilayer Cu wiring is formed on a silicon substrate via an interlayer insulating film.

In this semiconductor integrated circuit device having a multilayer Cu wiring structure, the interlayer insulating film has a low dielectric constant (l) such as BCB (benzocyclobutene) resin in order to reduce the capacitance between wirings.
ow-k) film is used, and the wirings are connected by Cu embedded in the via hole.

In the case of such a multi-layer wiring structure structure, although Cu having a low resistance is used as the metal material,
In the miniaturized via hole part, electromigration due to current concentration occurs, so that Cu
In some cases, voids may be generated to increase the resistance, or in an extreme case, the wire may be broken.

In order to solve such a problem caused by electromigration, the problem is solved by applying a wiring material having a large allowable current density for electromigration, and carbon nanotubes are one of the candidates.

Due to their structure, carbon nanotubes are electrically charged.
Material whose child structure is metallic or semiconductor
And metallic carbon nanotube electroma
Allowable current density for migration is 10⁸A / cm
²Table and Cu 10⁶A / cm ²2 digits larger than the table
It is known to have excellent physical properties. Also,
Structurally, carbon nanotubes have a diamond structure.
It is close and has excellent heat resistance.

Here, the structure of a semiconductor integrated circuit device in which carbon nanotubes are applied to the wiring portion in the vertical direction will be described with reference to FIG. See FIG. 6. FIG. 6 is a cross-sectional view showing the structure of a conventionally proposed carbon nanotube.
S is formed on the silicon substrate 31 on which devices such as FET are formed.
Cu wiring 33 is formed via the iO ₂ film 32, and Fe, Co, and Ni are formed by vapor deposition / lift-off using a resist pattern formed by photolithography at a predetermined wiring portion in the vertical direction.
A catalytic metal pattern 34 made of, for example, is formed.

Then, a thermal CVD method or a plasma CV method is used.
By using the D method to form a film while applying an electric field in the vertical direction, the carbon nanotubes 35 are grown in the electric field direction, that is, in the vertical direction using the catalyst metal pattern formed in the vertical wiring planned portion as a catalyst.

Next, an interlayer insulating film 36 is formed by applying a BCB (benzocyclobutene) resin having a relative dielectric constant of 2.8, and then a Cu film is deposited again, and then the carbon nanotubes 35 at a plurality of locations are deposited. The upper layer Cu wiring 37 is formed by patterning by ion etching so as to connect with each other. By repeating such steps for the required number of layers, it is possible to realize a semiconductor integrated circuit device excellent in electromigration resistance.

[0010]

However, in this method, the particulate catalytic metal residue generated in the lift-off process for forming the catalytic metal pattern contaminates the surface, and carbon nanotubes grow from the catalytic metal residue. It is problematic and can cause unwanted short circuits.

When the degree of integration of the semiconductor integrated circuit device is further increased, the wiring rule is further reduced, and it becomes difficult to form a catalyst metal pattern for growing fine vias made of carbon nanotubes by resist patterning by photolithography. There is a possibility that problems such as

Therefore, an object of the present invention is to selectively form a columnar carbon structure such as a carbon nanotube only in a required portion.

[0013]

FIG. 1 is a block diagram showing the principle of the present invention. Means for solving the problems in the present invention will be described with reference to FIG. In order to achieve the above object, according to the present invention, in the selective growth method of the columnar carbon structure 6, the catalyst metal 5 is deposited on the entire surface of the substrate 1 provided with the diffusion resistant film pattern 4, and then heat treatment is performed. Only the catalyst metal 5 existing in the region other than the diffusion resistant film pattern 4 is diffused in the depth direction, and then,
It is characterized in that the columnar carbon structures 6 are selectively grown starting from the catalyst metal 5 remaining on the anti-diffusion film pattern 4 without being diffused.

After depositing the catalytic metal 5 in this manner,
By performing the heat treatment, only the catalyst metal 5 existing in the region other than the diffusion resistant film pattern 4 can be diffused in the depth direction, and thus the diffused catalyst metal 9 becomes a growth nucleus of the columnar carbon structure 6. However, the columnar carbon structures 6 can be grown only on the diffusion resistant film pattern 4.

As described above, by not using the lift-off method, the surface is not contaminated by the particulate catalytic metal residue, and the columnar carbon structure 6 can be grown only in a necessary portion. Since the particle-shaped catalyst metal residue has the same diameter or the same thickness as the catalyst metal pattern, only the particle-shaped catalyst metal residue is not lost by diffusion due to the heat treatment.

In this case, the diffusion resistant film pattern 4 may be either an oxide film or a nitride film, but the metal thin film pattern 3
It is preferable to use a metal oxide formed by oxidizing at least the surface thereof from the viewpoint of the ease of manufacturing a thin diffusion resistant film, and the metal thin film pattern 3 may be entirely oxidized.

The anti-diffusion film pattern 4 is the diameter of the metal thin film pattern 3 provided on the substrate 1 at the tip of the cantilever of a scanning probe microscope typified by, for example, an AFM (atomic force microscope). May be formed by selectively anodizing by applying a voltage through a conductive member having a needle-shaped tip of 20 nm or less, whereby a very small number of columnar carbon structures such as one are formed. Only the object 6 can be selectively grown, and a via can be formed for the ultrafine wiring pattern 2.

The present invention also relates to an electronic device,
Anti-diffusion film pattern 4, catalytic metal 5 formed on anti-diffusion film pattern 4, catalytic metal 9 diffused in the depth direction in a region other than anti-diffusion film pattern 4, and anti-diffusion film pattern 4 It has a columnar carbon structure 6 formed starting from the catalyst metal 5 above.

In this case, the diffusion-resistant film pattern 4 is formed on the substrate 1
It may be formed on the metal wiring pattern 2 formed on the substrate 1, or may be formed on the metal wiring pattern 2 formed on the substrate 1. The diffusion resistance to the metal 5 is maintained, and electrical conduction due to the tunnel current becomes possible.

Further, as the diffusion resistant film, T which is easy to oxidize is used.
Oxides of metal elements selected from the group consisting of i, Ta, Pr, Hf, Zr, and Pd are suitable.

Further, the metal wiring pattern 2 is preferably made of a metal selected from the group consisting of Cu, Al, and Au, which are excellent in low resistance, and the catalytic metal 5 is Ni, Fe, or
Alternatively, Co is preferable.

The columnar carbon structure 6 in the present invention is not limited to pure carbon nanotubes, and the electronic device is not limited to the semiconductor integrated circuit device, and an optical integrated circuit using a ferroelectric substance is used. The present invention is also applied to other electronic devices such as devices, in which the columnar carbon structure 6 is used as a via connecting the upper and lower metal wiring patterns 2 and 8 provided via the interlayer insulating film 7, It is possible to configure a multilayer wiring structure having excellent migration resistance.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Here, with reference to FIG. 2 and FIG. 3, a manufacturing process of a carbon nanotube via according to a first embodiment of the present invention will be described. Each drawing is a cross-sectional view of a main part of the semiconductor integrated device at a process key point. 2 (a). First, the silicon substrate 11 on which active elements such as FETs are formed.
After depositing a Cu film having a thickness of, for example, 100 nm on the SiO ₂ film 12 by a sputtering method, ion etching is performed using a resist pattern (not shown) having a predetermined wiring pattern shape as a mask. Cu by etching the exposed Cu film
The wiring 13 is formed.

Then, for example, 2 is formed in the region where the via is formed.
After forming the resist pattern 14 having an opening of μm × 2 μm, the Ti films 15 and 16 having a thickness of, for example, 2 nm are deposited by using the sputtering method.

2B, the resist pattern 14 and the unnecessary Ti film 16 are removed by the lift-off method, and the Ti film 15 is selectively left only in the via formation region, and then exposed to oxygen plasma. As a result, the surface of the Ti film 15 is oxidized to form a Ti oxide film 17 having a thickness of 1 to 2 nm.

Next, referring to FIG. 2C, Fe fine particles 18 serving as a catalyst for growth of carbon nanotubes are deposited on the entire surface by vapor deposition. The particle size of the Fe fine particles in this case is, for example, 20 nm.

Next, as shown in FIG. 2D, a Ti oxide film 17 is formed by performing a heat treatment at 900 ° C. for 1 hour in a nitrogen gas atmosphere.
The Fe fine particles 18 deposited in other regions are diffused in the depth direction to drive the Fe diffusion particles 19 into the Cu wiring 13, the SiO ₂ film 12, or the silicon substrate 11. At this time, since the thickness of the Ti oxide film 17 is 1 to 2 nm, F
It serves as a diffusion barrier against diffusion of e, and the Fe fine particles 18 remain on the Ti oxide film 17.

Next, referring to FIG. 3 (e), the substrate heating temperature is set to 800 to 900 ° C. by using the thermal CVD method with CH ₄ + H ₂ as the source gas,
The carbon nanotubes 20 are vertically grown to a length of, for example, about 1 μm by using the Fe particles 18 as a catalyst in a state where a voltage of 200 V is applied to the substrate to form an electric field in the vertical direction. The length of the carbon nanotube 20 can be controlled by the growth time.

Next, as shown in FIG. 3F, BCB, which is a low dielectric constant (low-k) film, is formed on the entire surface.
A resin is spin-coated to form a film having a thickness of 1 μm to form an interlayer insulating film 21. At this time, the tip portion of the carbon nanotube 20 needs to have a thickness that exposes the interlayer insulating film 21.

Next, referring to FIG. 3 (g), the thickness is, for example, 1
After depositing a Cu film having a thickness of 00 nm, the exposed Cu film is etched by ion etching using a resist pattern (not shown) having a shape of a wiring pattern connecting the carbon nanotubes 20 grown at a plurality of positions as a mask. Thus, the upper Cu wiring 22 is formed. By repeating this process for the required number of layers, a semiconductor integrated circuit device using the carbon nanotubes 20 as vias is completed.

As described above, in the first embodiment of the present invention, after the catalyst metal is deposited, the catalyst metal in the unnecessary region is driven in the depth direction by thermal diffusion, so that the via formation region is formed. Only the carbon nanotubes 20 can be selectively grown.

The thickness of the Ti oxide film 17 is 1-2 nm.
Therefore, a tunnel current flows through the Ti oxide film 17, and the Cu wiring 13 on the lower layer side and the Cu wiring 22 on the upper layer side can be electrically connected via the carbon nanotube 20.

Next, with reference to FIGS. 4 and 5, a process of manufacturing the carbon nanotube via according to the second embodiment of the present invention will be described. Each drawing is a cross-sectional view of a main part of the semiconductor integrated device at a process key point. 4A, first, similarly to the first embodiment, the SiO ₂ film 12 is formed on the silicon substrate 11 on which active elements such as FETs are formed.
Through the thickness by the sputtering method, for example,
After depositing a Cu film of 100 nm, the exposed Cu film is etched by ion etching using a resist pattern (not shown) having a predetermined wiring pattern shape as a mask to form the Cu wiring 13.

Then, for example, 2 is formed in the region where the via is formed.
After forming the resist pattern 14 having an opening of μm × 2 μm, the Ti films 15 and 16 having a thickness of, for example, 2 nm are deposited by using the sputtering method.

4B, the resist pattern 14 and the unnecessary Ti film 16 are removed by the lift-off method to selectively leave the Ti film 15 only in the via formation region, and then the cantilever 23 of the AFM. Is used as a cathode and a current is caused to flow through the moisture in the atmosphere by the power source 24 to locally anodize a part of the surface of the Ti film 15 to form a T film having a thickness of 1 to 2 nm.
The i oxide film 25 is formed. In this case, the size of the Ti oxide film 25 can be miniaturized on the nano scale, and for example, the diameter or the size of one side is 20 nm.

After FIG. 4C, Fe fine particles 18 serving as a catalyst for growing carbon nanotubes are deposited on the entire surface by vapor deposition, as in the first embodiment described above.

Next, as shown in FIG. 4D, a Ti oxide film 25 is formed by performing a heat treatment at 900 ° C. for 1 hour in a nitrogen gas atmosphere.
The Fe fine particles 18 deposited in the other regions are diffused in the depth direction to drive the Fe diffused particles 19 into the Cu wiring 13, the SiO ₂ film 12, or the silicon substrate 11, and only on the Ti oxide film 25. The Fe fine particles 18 are left. At this time, the Fe fine particles 18 deposited on the Ti film 15 diffuse into the Cu wiring 13 or the Ti film 15.

Next, referring to FIG. 5 (e), the substrate heating temperature is set to 800 to 900 ° C. by using the thermal CVD method with CH ₄ + H ₂ as the source gas,
The carbon nanotubes 20 are vertically grown to a length of, for example, about 1 μm by using the Fe particles 18 as a catalyst in a state where a voltage of 200 V is applied to the substrate to form an electric field in the vertical direction. At this time, since the size of the Ti oxide film 25 is set to the diameter or the size of each side is 20 nm, only one carbon nanotube 26 grows.

Next, referring to FIG. 5 (f), a BCB having a low dielectric constant (low-k) film is formed on the entire surface.
A resin is spin-coated to form a film having a thickness of 1 μm to form an interlayer insulating film 21. At this time, the tip portion of the carbon nanotube 20 needs to have a thickness that exposes the interlayer insulating film 21.

Next, referring to FIG. 5 (g), the thickness is, for example, 1
After depositing a Cu film having a thickness of 00 nm, the exposed Cu film is etched by ion etching using a resist pattern (not shown) having a shape of a wiring pattern connecting the carbon nanotubes 20 grown at a plurality of positions as a mask. Thus, the upper Cu wiring 22 is formed. By repeating this process for the required number of layers, a semiconductor integrated circuit device using the carbon nanotubes 20 as vias is completed.

As described above, in the second embodiment of the present invention, since the Ti oxide film 25 is formed by anodic oxidation using a cantilever, the size of the Ti oxide film 25 should be nanoscale. As a result, since the number of carbon nanotubes 20 to be grown can be set to only one, it becomes possible to form a multilayer wiring structure having an ultrafine wiring pattern which is difficult in a normal lithography process.

Also in this case, since the film thickness of the Ti oxide film 25 is 1 to 2 nm, a tunnel current flows through this Ti oxide film 25 and the Cu wiring 13 on the lower layer side through this carbon nanotube 20. The upper layer Cu wiring 22 can be electrically connected.

Although the respective embodiments of the present invention have been described above, the present invention is not limited to the configurations and conditions described in the respective embodiments, and various modifications can be made. For example, although the fine particles of the catalytic metal are used in each of the above-described embodiments, the fine particles are not limited, and a film deposited by a sputtering method to have a thickness of, for example, about two atomic layers may be used. Also in this case, the catalyst metal layer deposited in the region other than the Ti oxide film also diffuses in the depth direction by thermal diffusion and disappears from the surface.

Although Fe is used as the catalyst metal in each of the above-mentioned embodiments, it is not limited to Fe and Co or Ni may be used.
In this case as well, it may be used as fine particles or as an atomic layer level film.

In each of the above embodiments, the diffusion barrier is formed of the Ti oxide film, but the diffusion barrier is not limited to the Ti oxide film, and Ta, Pr, Hf, Z may be used.
A metal oxide film obtained by oxidizing a metal film of r, Pd, or the like may be used.

Further, in each of the above-mentioned embodiments, it is difficult to form a thin oxide film with high precision, so the metal film is formed and then oxidized. However, when the film formation precision increases. Needless to say, the metal oxide film may be directly formed.

In each of the above embodiments, only the surface of the metal thin film is oxidized, but the metal thin film is 1 nm thick.
If the film can be formed with high accuracy below, the metal thin film may be wholly oxidized in the film thickness direction, and in that case, a tunnel current can be passed.

The diffusion barrier is not limited to the metal oxide film, but a nitride film may be used.
The diffusion barrier may be formed by directly nitriding the surface of the thin film or the metal thin film in a nitrogen atmosphere to form SiN, TiN, or TaN.

Further, in each of the above embodiments, the wiring is formed of Cu, but the wiring is not limited to pure Cu, and Cu alloy or the like may be used. Alternatively, a low resistivity material such as Au may be used.

In the second embodiment, only one carbon nanotube is grown, but the number of carbon nanotubes is not limited to one when such selective oxidation is used, and a plurality of carbon nanotubes are grown. You can let me do it.

In the second embodiment, the conductive cantilever of AFM (Atomic Force Microscope) is used as the cathode for anodic oxidation.
The probe of (scanning tunnel microscope) may be used as the cathode.

Further, although carbon nanotubes have been described in the above embodiments, the carbon nanotubes need not be strictly defined, and columnar carbon structures in which carbon nanotubes and fullerenes are mixed may be used. Is.

Although carbon nanotubes are grown by the thermal CVD method in each of the above-mentioned embodiments, the carbon nanotubes are not limited to the thermal CVD method, and plasma C
Other growth methods such as the VD method may be used.

Further, in each of the above-mentioned embodiments, the multi-layer wiring process of the semiconductor integrated circuit device has been described, but the invention is not limited to the semiconductor integrated circuit device, and an optical deflection element or an optical modulation element is integrated. The present invention also covers a manufacturing process of a multi-layer wiring structure of another electronic device such as an optical integrated circuit device using the reduced ferroelectric.

Here, the detailed features of the present invention will be described again with reference to FIG. Referring again to FIG. 1 (Appendix 1), after depositing the catalyst metal 5 on the entire surface of the substrate 1 provided with the diffusion resistant film pattern 4, the catalyst metal 5 existing in the region other than the diffusion resistant film pattern 4 is subjected to heat treatment.
Columnar carbon structure 6 in which only the columnar carbon structure 6 is diffused in the depth direction, and then the columnar carbon structure 6 is selectively grown from the catalyst metal 5 remaining on the anti-diffusion film pattern 4 as a starting point. Selective growth method for objects. (Supplementary Note 2) The selective growth method for a columnar carbon structure according to Supplementary Note 1, wherein the diffusion resistant film pattern 4 is made of a metal oxide formed by oxidizing at least the surface of the metal thin film pattern 3. (Supplementary Note 3) After forming the diffusion resistant film pattern 4 made of a metal oxide by selectively anodizing the metal thin film pattern 3 provided on the substrate 1, a catalyst metal 5 is deposited on the entire surface, and then heat treatment is performed. By diffusing only the catalyst metal 5 existing in the area other than the diffusion resistant film pattern 4 in the depth direction, the catalyst metal 5 remaining without being diffused on the diffusion resistant film pattern 4 is used as a starting point. A method for selectively growing a columnar carbon structure, which comprises selectively growing the columnar carbon structure 6. (Supplementary Note 4) In the anodizing step, the selective growth of the columnar carbon structure according to Supplementary Note 3, wherein a voltage is applied through a conductive member having a needle-shaped tip having a diameter of 20 nm or less at the most distal end. Method. (Supplementary Note 5) The anti-diffusion film pattern 4, the catalyst metal 5 formed on the anti-diffusion film pattern 4, the catalyst metal 9 diffused in the depth direction in a region other than the anti-diffusion film pattern 4, An electronic device having a columnar carbon structure 6 formed on the diffusion film pattern 4 starting from the catalyst metal 5. (Appendix 6) Metal wiring pattern 2 formed on substrate 1
A diffusion resistant film pattern 4 formed on the metal wiring pattern, a catalyst metal 5 formed on the diffusion resistant film pattern 4, and a region other than the diffusion resistant film pattern 4 in the depth direction. An electronic device comprising a diffused catalyst metal 9 and a columnar carbon structure 6 formed on the oxidation resistant film pattern starting from the catalyst metal 5. (Supplementary Note 7) The electronic device according to Supplementary Note 5 or 6, wherein the diffusion resistant film has a thickness of 1 to 2 nm. (Supplementary Note 8) The diffusion resistant film is made of Ti, Ta, Pr, H.
8. The electronic device according to any one of appendices 5 to 7, which is an oxide of a metal element selected from the group consisting of f, Zr, and Pd. (Supplementary Note 9) The metal wiring pattern 2 includes Cu, Al,
Alternatively, it consists of a metal element from the group consisting of Au, and
9. The electronic device according to any one of appendices 5 to 8, wherein the catalyst metal 5 is Ni, Fe, or Co. (Supplementary Note 10) The columnar carbon structure 6 is a carbon nanotube via that connects the upper and lower metal wiring patterns 2 and 8 forming the semiconductor integrated circuit device, according to any one of Supplementary Notes 5 to 9. Electronic device.

[0056]

According to the present invention, when a columnar carbon structure such as a carbon nanotube is selectively grown, the catalytic metal deposited in an unnecessary area is chased in the depth direction of the substrate by thermal diffusion to remove it from the surface. Since the columnar carbon structure does not grow in an undesired position,
This makes it possible to accurately form a multilayer wiring structure having excellent electromigration resistance, which in turn contributes greatly to the realization of a semiconductor integrated circuit device of ultra-high integration.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a principle configuration of the present invention.

FIG. 2 is an explanatory diagram of a manufacturing process up to the middle of the first embodiment of the present invention.

FIG. 3 is an explanatory diagram of the manufacturing process after FIG. 2 of the first embodiment of the present invention.

FIG. 4 is an explanatory diagram of a manufacturing process up to the middle of the second embodiment of the present invention.

FIG. 5 is an explanatory diagram of the manufacturing process after FIG. 4 of the second embodiment of the present invention.

FIG. 6 is an explanatory diagram of a conventional carbon nanotube via.

[Explanation of symbols]

1 Substrate 2 Metal Wiring Pattern 3 Metal Thin Film Pattern 4 Diffusion Resistant Film Pattern 5 Catalyst Metal 6 Columnar Carbon Structure 7 Interlayer Insulating Film 8 Metal Wiring Pattern 9 Diffused Catalyst Metal 11 Silicon Substrate 12 SiO ₂ Film 13 Cu Wiring 14 Resist Pattern 15 Ti film 16 Ti film 17 Ti oxide film 18 Fe fine particles 19 Fe diffusion particles 20 Carbon nanotube 21 Interlayer insulating film 22 Upper layer Cu wiring 23 Cantilever 24 Power supply 25 Ti oxide film 26 Carbon nanotube 31 Silicon substrate 32 SiO ₂ film 33 Cu wiring 34 Catalyst Metal pattern 35 Carbon nanotube 36 Interlayer insulating film 37 Upper layer Cu wiring

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Claims (5)

[Claims] 1. A catalyst metal is deposited on the entire surface of a substrate provided with a diffusion resistant film pattern, and then a heat treatment is performed to diffuse only the catalyst metal existing in regions other than the diffusion resistant film pattern in the depth direction, and then, A method for selectively growing a columnar carbon structure, which comprises selectively growing a columnar carbon structure starting from a catalyst metal remaining on the anti-diffusion film pattern without being diffused. 2. A diffusion resistant film pattern made of a metal oxide is formed by selectively anodizing a metal thin film provided on a substrate, a catalytic metal is deposited on the entire surface, and then a heat treatment is performed. After diffusing only the catalyst metal existing in the region other than the diffusion-resistant film pattern in the depth direction, the columnar carbon structure is selectively originated from the catalyst metal remaining without diffusing on the diffusion-resistant film pattern. A method for selectively growing a columnar carbon structure, which comprises growing the columnar carbon structure. 3. A diffusion resistant film pattern, a catalyst metal formed on the diffusion resistant film pattern, a catalyst metal diffused in a depth direction in a region other than the diffusion resistant film pattern, and on the diffusion resistant film pattern. 2. A columnar carbon structure formed from the catalyst metal as a starting point. 4. The electronic device according to claim 3, wherein the diffusion resistant film has a thickness of 1 to 2 nm. 5. The diffusion resistant film is made of Ti, Ta, Pr, H.
The electronic device according to claim 3, which is an oxide of a metal element selected from the group consisting of f, Zr, and Pd.