JP7315166B2 - Method for producing graphene nanoribbon network film and method for producing electronic device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for manufacturing a graphene nanoribbon network film and a method for manufacturing an electronic device.

Graphene is a material with a two-dimensional sheet structure in which C atoms are arranged in a honeycomb. The charge mobility of graphene is extremely high even at room temperature, and graphene exhibits unique electronic properties such as ballistic conduction and half-integer quantum Hall effect. Since the π-electron conjugation extends two-dimensionally, graphene has a substantially zero bandgap and exhibits metallic properties (gapless semiconductor). In recent years, research and development of electronic devices that take advantage of these characteristic electronic functions have been actively carried out.

On the other hand, nano-sized graphene has a small difference between the number of C atoms at the edge and the number of C atoms inside the edge, and the shape of the graphene itself and the shape of the edge have a large effect, and bulk graphene exhibits physical properties that are significantly different. As nano-sized graphene, ribbon-shaped quasi-one-dimensional graphene with a width of several nanometers, so-called graphene nanoribbon (GNR), is known. The physical properties of GNRs vary greatly with edge structure and ribbon width.

There are two types of edge structures of GNRs: an armchair edge in which C atoms are arranged in a two-atom cycle, and a zigzag edge in which C atoms are arranged in a zigzag pattern. Armchair-edge GNRs (AGNRs) exhibit semiconducting properties because the finite bandgap is widened by quantum confinement effects and edge effects. On the other hand, the zigzag edge type GNR (ZGNR) exhibits metallic properties.

In general, an AGNR having N CC dimer lines in the width direction of the ribbon is called "N-AGNR". For example, AGNR whose basic unit is anthracene, in which three six-membered rings are arranged in the ribbon width direction, is called 7-AGNR.

With regard to GNR applications, attempts have been made to use GNR network films containing multiple GNRs in the channels of field effect transistors.

However, using conventional GNR network membranes as channels does not provide good charge mobility.

JP-A-10-139411 JP 2015-525186 A JP 2008-266112 A JP 2011-166070 A

A. Bachtold et al. , Science 294, 1317 (2001) J. Cai et al. , Nature 466, 470 (2010) T. Dienel et al. , Nano Lett. 15, 5185 (2015)

An object of the present disclosure is to provide a method for manufacturing a graphene nanoribbon network film and a method for manufacturing an electronic device that can obtain excellent charge mobility.

This disclosureone ofAccording to the form, the crystal structure is a (111) surface of the metal membrane of a cubic grid, and the process of stuffing the graphenna nano -ribbon precursor with a structural formula represented by the following chemical formula (1) at the first temperature, and on the (111) surface (111), the graphene nano ribbon precursor is higher than the second temperature above the first temperature. The process of heating the degree of X and the C -C combination reaction of X and obtaining a polymer on the (111) surface, and the process of heating the polymer to the third temperature higher than the second temperature above, and inducing the withdrawal and C -C bond reaction, and the above -mentioned polymer above. By heating to the temperature of 4 to the exit of Z and the C -C combination reaction, the process of obtaining multiple graphenna nano ribbons arranged at an angle of 60 degrees at (111) on the (111) surface, and the above -mentioned temperature of multiple graphene nano -ribbons is higher than the temperature of 4. To the temperature of 5Hold for 1 to 3 hoursand sp²and a step of orbitally hybridized six-membered ring conjugation,the fifth temperature is 450° C. to 500° C.;In the following chemical formula (1), n₁is an integer of 1 or more and 6 or less, and X, Y and Z are F, Cl, Br, I, H, OH, SH, SO₂H, SO₃H, SO₂NH₂, PO₃H.₂, NO, NO₂, NH₂, CH₃, CHO, COCH₃, COOH, CONH₂, COCl, CN, CF₃, CCl₃, CBr₃or CI₃and the desorption temperatures of X, Y, and Z from the carbon atoms constituting the six-membered ring are respectively T_X, T_Y., T_Z.and T_X<T_Y.≦T_Z.Provided is a method for producing a graphene nanoribbon network film in which the relationship holds.

According to another aspect of the present disclosure, an electronic device is provided having the above graphene nanoribbon network film in the channel of a field effect transistor.

According to another aspect of the present disclosure, there is provided a method for manufacturing an electronic device, comprising the steps of: manufacturing a graphene nanoribbon network film on the (111) plane of the metal film; and forming a field effect transistor having the graphene nanoribbon network film in a channel.

According to the technique of the present disclosure, excellent charge mobility can be obtained.

1 is a schematic diagram showing a GNR network film according to a first embodiment; FIG. FIG. 2 is a diagram (part 1) showing GNRs included in the first embodiment; FIG. 2 is a diagram (part 2) showing GNRs included in the first embodiment; FIG. 1 is a perspective view (part 1) showing a method for manufacturing a GNR network film according to the first embodiment; FIG. 2 is a perspective view (part 2) showing the method for manufacturing the GNR network film according to the first embodiment; FIG. 2 is a schematic diagram showing a method for manufacturing a GNR network film according to the first embodiment; FIG. 1 is a diagram (part 1) showing GNR before heating; FIG. 2 is a diagram (part 2) showing GNR before heating; FIG. 1 is a diagram (part 1) showing a method for synthesizing GNR; FIG. 2 is a diagram (part 2) showing a GNR synthesizing method; FIG. 3 is a diagram (part 3) showing a GNR synthesizing method; FIG. 4 is a diagram (part 4) showing a GNR synthesizing method; FIG. 1 is a diagram (part 1) showing a method for synthesizing a GNR precursor; FIG. 2 is a diagram (part 2) showing a method for synthesizing a GNR precursor; FIG. 1 is a diagram (Part 1) showing the structural formulas of raw materials of GNR precursors; FIG. 2 is a diagram (part 2) showing structural formulas of raw materials of GNR precursors; 1 is a diagram (1) showing a specific example of a GNR synthesizing method; FIG. FIG. 2 is a diagram (part 2) showing a specific example of a GNR synthesizing method; FIG. 1 is a diagram (part 1) showing a microscopic photograph of a GNR network film according to the first embodiment; FIG. 2 is a diagram (part 2) showing a microscopic photograph of the GNR network film according to the first embodiment; FIG. 3 is a diagram (No. 3) showing a micrograph of the GNR network film according to the first embodiment; It is a sectional view showing an electronic device concerning a 2nd embodiment. FIG. 11 is a plan view (Part 1) showing the method of manufacturing the electronic device according to the second embodiment; FIG. 12 is a plan view (part 2) showing the method for manufacturing the electronic device according to the second embodiment; FIG. 13 is a plan view (No. 3) showing the method for manufacturing the electronic device according to the second embodiment; FIG. 10 is a plan view (part 4) showing the method for manufacturing the electronic device according to the second embodiment; FIG. 11 is a plan view (No. 5) showing the method for manufacturing the electronic device according to the second embodiment; FIG. 11 is a plan view (No. 6) showing the method of manufacturing the electronic device according to the second embodiment; FIG. 10 is a cross-sectional view (part 1) showing the method of manufacturing the electronic device according to the second embodiment; FIG. 11 is a cross-sectional view (part 2) showing the method for manufacturing the electronic device according to the second embodiment; FIG. 13 is a cross-sectional view (part 3) showing the method of manufacturing the electronic device according to the second embodiment; FIG. 10 is a cross-sectional view (part 4) showing the method for manufacturing the electronic device according to the second embodiment; FIG. 10 is a cross-sectional view (No. 5) showing the method for manufacturing the electronic device according to the second embodiment; FIG. 11 is a cross-sectional view (No. 6) showing the method for manufacturing the electronic device according to the second embodiment; It is a sectional view showing an electronic device concerning a 3rd embodiment. FIG. 11 is a cross-sectional view (Part 1) showing the method of manufacturing the electronic device according to the third embodiment; FIG. 12 is a cross-sectional view (part 2) showing the method for manufacturing the electronic device according to the third embodiment; FIG. 13 is a cross-sectional view (Part 3) showing the method for manufacturing the electronic device according to the third embodiment; FIG. 14 is a cross-sectional view (part 4) showing the method for manufacturing the electronic device according to the third embodiment; FIG. 15 is a cross-sectional view (No. 5) showing the method for manufacturing the electronic device according to the third embodiment; FIG. 16 is a cross-sectional view (No. 6) showing the method for manufacturing the electronic device according to the third embodiment; FIG. 16 is a cross-sectional view (No. 7) showing the method for manufacturing the electronic device according to the third embodiment; FIG. 14 is a cross-sectional view (No. 8) showing the method for manufacturing the electronic device according to the third embodiment; It is a sectional view showing an electronic device concerning a 4th embodiment. FIG. 11 is a cross-sectional view (part 1) showing the method for manufacturing an electronic device according to the fourth embodiment; FIG. 12 is a cross-sectional view (part 2) showing the method for manufacturing the electronic device according to the fourth embodiment; FIG. 14 is a cross-sectional view (part 3) showing the method for manufacturing the electronic device according to the fourth embodiment; FIG. 14 is a cross-sectional view (part 4) showing the method for manufacturing the electronic device according to the fourth embodiment; FIG. 15 is a cross-sectional view (No. 5) showing the method for manufacturing the electronic device according to the fourth embodiment; 4 is a diagram showing the relationship between the CC dimer line and the ribbon width W. FIG.

Embodiments of the present disclosure will be specifically described below with reference to the accompanying drawings. In the present specification and drawings, constituent elements having substantially the same functional configuration may be denoted by the same reference numerals, thereby omitting redundant description.

(First embodiment)
A first embodiment relates to graphene nanoribbon (GNR) network films. FIG. 1 is a schematic diagram showing a GNR network film according to the first embodiment. 2A and 2B are diagrams showing GNRs included in the GNR network film according to the first embodiment.

A GNR network membrane 1 according to the first embodiment includes a plurality of GNRs 2 . As shown in FIGS. 2A and 2B, a plurality of GNRs 2 are arranged at angles of integral multiples of 60 degrees. In addition, multiple GNR2s are sp ^2- orbital hybrid six-membered ring junctions. That is, multiple GNR2s are bonded to each other via at least one six-membered ring 3 . This sp ^2- orbital hybrid six-membered ring junction occurs, for example, between the ends of GNR2.

According to the first embodiment, a plurality of GNR2s are arranged at an angle of an integral multiple of 60 degrees with respect to each other, and are sp ^2- orbital hybrid six-membered ring junctions with each other, so that excellent charge mobility can be obtained not only inside the GNR2s but also between the GNR2s. Therefore, excellent charge mobility can be obtained in the entire GNR network film 1 .

Next, a method for manufacturing the GNR network film according to the first embodiment will be described. 3A-3B are perspective views showing a method for manufacturing a GNR network film according to the first embodiment.

In this method, first, a metal film 12 is formed on an insulating substrate 11 as shown in FIG. 3A. As the insulating substrate 11, for example, a mica substrate, a sapphire (α-Al ₂ O ₃ ) crystal substrate having a c-plane surface, an MgO crystal substrate having a surface Miller index of (111), or the like can be used. As the metal film 12, a film of Au, Ag, Cu, Ni, Rh, Pd, Ir, or Pt having a face-centered cubic (fcc) crystal structure and a surface Miller index of (111) can be used. The growth substrate 10 includes an insulating substrate 11 and a metal film 12 .

For example, a mica substrate is cleaved in the atmosphere to produce a mica substrate with a clean surface, and this mica substrate is introduced into a vacuum chamber having a basic degree of vacuum of 1×10 ⁻⁷ Pa or less, and subjected to annealing treatment at a temperature of 300° C. to 500° C. for 12 to 24 hours. Next, while maintaining a temperature of 300° C. to 500° C., an Au film is formed on the clean surface of the mica substrate by vapor deposition. For example, the deposition rate is 0.05 nm/sec to 1.0 nm/sec, and the thickness of the Au film is 100 nm to 200 nm. The Au film thus formed has a surface Miller index of (111).

In order to increase the adhesion between the Au film and the mica substrate, a Ti film having a thickness of 0.5 nm to 1 nm, for example, may be formed on the mica substrate before forming the Au film. Moreover, the method of forming the metal film 12 is not limited to the vapor deposition method, and the metal film 12 may be formed by a sputtering method, a pulse laser deposition method, a molecular beam epitaxy method, or the like.

After forming the metal film 12, the surface of the metal film 12 is cleaned. In this surface cleaning treatment, for example, Ar ion sputtering on the surface of the metal film 12 and annealing under ultra-high vacuum are defined as one cycle, and this is performed in a plurality of cycles. For example, in each cycle, in Ar ion sputtering, the ion acceleration voltage is set to 1.0 kV, the ion current is set to 10 μA, and the time is set to 1 minute. In the annealing, the temperature is set to 400° C. to 500° C. and the time is set to 10 minutes while maintaining the degree of vacuum of 5×10 ⁻⁷ Pa or less. For example, the number of cycles is assumed to be 3 cycles. When an Au film is formed as the metal film 12, a 23×√3 reconstructed surface of Au (111) is obtained by surface cleaning treatment, further improving flatness at the atomic level.

Next, as shown in FIG. 3A, a GNR film 13 having an armchair-shaped edge structure is formed on the surface of the metal film 12 which has undergone surface cleaning treatment, without exposing the surface of the metal film 12 to the atmosphere. In this method, the GNR film 13 is formed in situ. FIG. 4 is a schematic diagram showing the GNR film 13. As shown in FIG. 5A and 5B are diagrams showing GNRs 2 included in the GNR film 13. FIG. As shown in FIG. 4, the GNR film 13 includes multiple GNRs 2 . In addition, since the (111) plane of fcc has 6-fold rotational symmetry, there are three directions in which GNR2 extends on the surface of the metal film 12, and as shown in FIGS. 5A and 5B, these three directions form an angle of 60 degrees or 120 degrees. In other words, a plurality of GNR2s are oriented on the (111) plane with an angle that is an integer multiple of 60 degrees.

A method for synthesizing GNR2 will now be described. 6A to 6D are diagrams illustrating a method of synthesizing GNRs.

First, as shown in FIG. 6A, a GNR precursor 100 is prepared. In FIG. 6A, _n1 is an integer of 1 or more and 6 or less. X, Y and Z are F, Cl, Br, I, H, OH, SH, _SO2H , _SO3H , _SO2NH2 , _PO3H2 , NO, _NO2 , _{NH2 , CH3 ,} CHO, _COCH3 , COOH, _CONH2 , COCl, CN, _CF3 , _CCl3 , _CBr3 or _CI3 . When the desorption temperatures of X, Y, and Z from the carbon atoms constituting the six-membered ring are _TX , _TY , and _TZ , respectively, the relationship _TX < _TY ≤ _TZ is established.

Then, under vacuum, the temperature of the growth substrate 10 is maintained at a first temperature below the desorption temperature _TX , and the GNR precursor 100 is heated and sublimated. At this time, on the metal film 12 at the first temperature, due to the interaction between the metal film 12 and the molecules of the GNR precursor 100, a plurality of molecules of the GNR precursor 100 are deposited on the (111) plane while arranging in any of the above three directions within the (111) plane of fcc while reversing the convex direction.

After that, the temperature of the growth substrate 10 is heated to a second temperature equal to or higher than the desorption temperature _TX and lower than the desorption temperature _TY under vacuum, and held at the second temperature. A de-X conversion and a C—C bond reaction of the GNR precursor 100 are induced on the metal film 12 at the second temperature, and as shown in FIG. 6B, a polymer 110 is stably formed in which a plurality of molecules of the GNR precursor 100 are arranged in one of the above three directions while reversing the convex direction. The polymers 110 are oriented on the surface of the metal film 12 at angles that are integral multiples of 60 degrees.

Subsequently, the growth substrate 10 is heated to a third temperature higher than or equal to the desorption temperature _TY and lower than the desorption temperature _TZ , and held at the third temperature. As a result, de-Y and cyclization reactions are induced, and polymer 120 is stably formed from polymer 110 as shown in FIG. 6C.

Subsequently, the temperature of the growth substrate 10 is heated to a fourth temperature equal to or higher than the desorption temperature _TZ , and held at the fourth temperature. As a result, de-Zation and cyclization reactions are induced, and GNR2 with an armchair-shaped edge structure is synthesized from the polymer 120, as shown in FIG. 6D.

When the desorption temperature _TY and the desorption temperature _TZ are equal, the third temperature should be equal to or higher than the desorption temperature _TY and the desorption temperature _TZ . By making the third temperature equal to or higher than the desorption temperature _TY and the desorption temperature _TZ , the formation of polymer 120 is omitted and GNR2 is synthesized from polymer 110 .

In this way, when the GNR precursor 100 is heated, X is detached, C bonded to X is bonded between the GNR precursors 100, Y is detached, C bonded to Y is bonded between the GNR precursors 100, Z is detached, and C bonded to Z is bonded between the GNR precursors 100. The sequence of the GNR precursor 100 is determined by the bond between the Cs bonded to X, and the subsequent bond between the Cs bonded to Y and Z fixes the structure of GNR2. Therefore, long GNR2 can be stably synthesized. For example, it is possible to stably synthesize GNR2 of several tens of nm level.

Next, a method for synthesizing the GNR precursor 100 will be described. 7A-7B are diagrams illustrating a method of synthesizing the GNR precursor 100. FIG.

First, a substance 160 whose structural formula is shown in FIG. 8A and a substance 130 whose structural formula is shown in FIG. 8B are prepared. The material shown in FIG. 8A is, for example, 1,4-dibromo-2,3-diiodobenzene, and the material 130 shown in FIG. 8B is, for example, the boronic acid of benzene, naphthalene, anthracene, naphthacene, pentacene, or hexacene.

These are then dissolved in a solvent, a catalyst is added, and the mixture is stirred in the presence of a base to cause the Suzuki coupling reaction. By continuing stirring and evaporating the solvent, a substance 140 in which one iodine (I) contained in the substance 160 is mono-coupled is obtained as shown in FIG. 7A.

Substance 140 and substance 130 shown in FIG. 7A are then dissolved in a solvent, a catalyst is added, and the mixture is stirred in the presence of a base to cause a Suzuki coupling reaction. By continuing stirring and evaporating the solvent, the GNR precursor 100 in which iodine (I) contained in the substance 140 is mono-coupled is obtained as shown in FIG. 7B.

Then, the GNR precursor 100 is purified by, for example, column chromatography.

GNR precursor 100 can be synthesized in this manner.

After the GNR film 13 is formed, the temperature of the growth substrate 10 is heated to a fifth temperature higher than the fourth temperature and held at the fifth temperature. As a result, as shown in FIGS. 1, 2A, and 2B, two GNRs 2 located close to each other among the plurality of GNRs 2 included in the GNR film 13 are sp ^2- orbital hybrid six-membered ring junctions while maintaining their stretching directions. This sp ^2- orbital hybrid six-membered ring junction occurs, for example, between two GNR2 ends. Thus, as shown in FIG. 3B, the GNR film 13 is changed into the GNR network film 1, and the GNR network film 1 can be obtained.

GNRs 2 overlapping each other may exist in the GNR film 13 before heating at the fifth temperature. However, at this stage, the GNR2s are only in physical contact and there is no sp ^2- orbital hybridization six-membered ring junction between them. For this reason, when the GNR film 13 is used as a channel, carrier scattering is likely to occur at the contact portion between the GNRs 2, and mobility as excellent as that of the GNR network film 1 cannot be obtained.

Various GNR precursors have been proposed for use in growing GNRs by the bottom-up method, but GNRs produced using conventional GNR precursors contain defects such as five-membered ring junctions and seven-membered ring junctions. Therefore, carrier scattering is likely to occur, and mobility as excellent as that of the GNR network film 1 cannot be obtained.

The six-membered ring junction of sp ^2- orbital hybrids between adjacent GNRs 2 depends on the vapor deposition rate of the GNR precursor 100, the vapor deposition film thickness, and the distance from the vapor deposition source to the metal film 12. FIG. Therefore, it is preferable to adjust these conditions appropriately for each vapor deposition apparatus.

A specific example of a method for synthesizing GNR2 will now be described. 9A and 9B are diagrams showing a specific example of a GNR synthesizing method. In this specific example, a cleaved mica substrate is used as the insulating substrate 11 and an Au film having a surface Miller index of (111) is used as the metal film 12 . A mica substrate can be heated to 450° C. and an Au film having a thickness of 100 nm can be formed by vapor deposition. For example, the deposition rate is 1.0 nm/sec until the thickness reaches 50 nm, and then 0.05 nm/sec.

In this example, first, a GNR precursor 101 is provided as shown in FIG. 9A. GNR precursor 101 has a structural formula where _n1 is 3, X is Br, and Y and Z are H in FIG. 6A. The desorption temperature of Br from the carbon atoms forming the six-membered ring is lower than the desorption temperature of H from the carbon atoms forming the six-membered ring. The GNR precursor 101 is, so to speak, 1,2-bis-(2-anthracenyl)-3,6-dibromobenzen.

Next, under an ultra-high vacuum of 5×10 ⁻⁸ Pa or less, the temperature of the growth substrate 10 is maintained at a first temperature lower than the desorption temperature of Br, and the GNR precursor 101 is heated and sublimated. For example, a K-cell type evaporator is used for heating and sublimating the GNR precursor 101, the deposition rate is 0.1 nm/min to 0.5 nm/min, and the deposition film thickness is 1 ML (monolayer) to 3 ML. 1 ML is approximately 0.25 nm. On the Au film at the first temperature, due to the interaction between the Au film and the molecules of the GNR precursor 101, multiple molecules of the GNR precursor 101 align in any of the above three directions within the fcc (111) plane while reversing the convex orientation. The first temperature is, for example, a room temperature of 20.degree. C. to 30.degree.

Thereafter, the growth substrate 10 is heated to a second temperature equal to or higher than the Br desorption temperature and lower than the H desorption temperature, and held at the second temperature. DeBr of the GNR precursor 101 and C—C bond reaction are induced on the Au film at the second temperature, and a polymer is stably formed in which a plurality of molecules of the GNR precursor 101 are arranged in one of the above three directions. The polymers are oriented on the surface of the Au film at angles that are integral multiples of 60 degrees. For example, the second temperature is 150° C. to 250° C., and the holding time at the second temperature is 10 minutes to 1 hour.

Subsequently, the growth substrate 10 is heated to a third temperature higher than the desorption temperature of H, for example 400° C., and held at the third temperature. As a result, dehydrogenation and cyclization reactions are induced, and 17-AGNR151 with an armchair edge structure is synthesized from the polymer as shown in FIG. 9B. For example, the third temperature is 350° C. to 450° C., and the retention time at the third temperature is 10 minutes to 1 hour.

In this way, when the GNR precursor 101 is heated, Br is eliminated, and the Cs bonded to Br are bonded between the GNR precursors 101, and then H is eliminated, and the Cs bonded to H are bonded between the GNR precursors 101. The sequence of the GNR precursor 101 is determined by the C-to-C binding with Br, and the subsequent binding of the C-to-H binding fixes the structure of 17-AGNR151. Therefore, long 17-AGNR151 can be stably synthesized. For example, it is possible to stably synthesize 17-AGNR151 of several tens of nm level.

In this manner, 17-AGNR151 is synthesized as GNR2 and the GNR film 13 can be formed.

After forming the GNR film 13, the GNR network film 1 can be formed as follows. That is, the growth substrate 10 is heated to a fifth temperature higher than the third temperature, eg, 450° C. to 500° C., and held at the fifth temperature for 1 hour to 3 hours. As a result, of the plurality of 17-AGNRs 151 contained in the GNR film 13, two 17-AGNRs 151 located close to each other are sp ^2- orbital hybrid six-membered ring junctions while maintaining their stretching directions. This sp ^2- orbital hybrid six-membered ring junction occurs, for example, between two 17-AGNR151 ends. In this manner, the GNR film 13 is transformed into the GNR network film 1, and the GNR network film 1 can be obtained.

10A-10C show scanning tunneling microscope (STM) images of GNR network membranes fabricated according to the above embodiment. FIG. 10A shows an STM image taken with a sample bias V _s of −1.0 V and a tunnel current I _t of 50 pA. 10B and 10C show STM images taken with a sample bias V _s of −1.2 V and a tunnel current I _t of 50 pA. FIG. 10A shows a larger area than FIGS. 10B and 10C. FIG. 10B shows a region where two 17-AGNRs are joined at an angle of 60 degrees to a six-membered sp ^2- orbital hybrid. FIG. 10C shows a region where two 17-AGNRs are joined at an angle of 120 degrees to a six-membered sp ^2- orbital hybrid. As shown in FIGS. 10A-10C, GNR network membranes can be synthesized containing 17-AGNR with six-membered ring junctions of sp ^2- orbital hybrids at angles of integer multiples of 60 degrees.

(Second embodiment)
A second embodiment relates to an electronic device including a top-gate field effect transistor (FET) using a GNR network film as a channel. FIG. 11 is a cross-sectional view showing an electronic device according to the second embodiment.

As shown in FIG. 11, an electronic device 200 according to the second embodiment has an insulating substrate 211, a metal film 212 formed on the insulating substrate 211, and a GNR network film 201 formed on the metal film 212. As the GNR network film 201, the GNR network film 1 according to the first embodiment is used. A source electrode 213 s and a drain electrode 213 d are formed on the metal film 212 so as to be in contact with both ends of the GNR network film 201 . A portion of the metal film 212 between the source electrode 213s and the drain electrode 213d, that is, a portion not covered by the source electrode 213s and the drain electrode 213d is removed. An insulating film 214 is formed below the GNR network film 201 to cover the upper surface of the insulating substrate 211 , the side surfaces of the metal film 212 and the lower surface of the GNR network film 201 . An insulating film 215 functioning as a gate insulating film is formed above the GNR network film 201 to cover the side and top surfaces of the source electrode 213s, the drain electrode 213d, and the GNR network film 201 . A gate electrode 213g is formed on the insulating film 215 between the source electrode 213s and the drain electrode 213d.

As the insulating substrate 211, for example, a mica substrate, a sapphire (α-Al ₂ O ₃ ) crystal substrate having a c-plane surface, an MgO crystal substrate having a surface Miller index of (111), or the like can be used. As the metal film 212, a film of Au, Ag, Cu, Ni, Rh, Pd, Ir, or Pt having a crystal structure of fcc and a surface Miller index of (111) can be used. The growth substrate 10 includes an insulating substrate 211 and a metal film 212 . In this example, a mica substrate is used as the insulating substrate 211 and an Au film is used as the metal film 212 . A GNR network film including, for example, a plurality of 17-AGNRs is formed as the GNR network film 201 .

The source electrode 213s, the drain electrode 213d, and the gate electrode 213g have, for example, a Ti film with a thickness of 0.5 nm to 2 nm and a Cr film thereon with a thickness of 20 nm to 50 nm, and the distance between the source electrode 213s and the drain electrode 213d is, for example, 10 nm to 50 nm.

As materials for the insulating films 214 and 215, _HfO2 film _{, Al2O3 , Si3N4} , HfSiO, HfAlON, _{Y2O3 , SrTiO3} , _PbZrTiO3 , _BaTiO3 , and the like can be used. In this example, HfO ₂ films with a thickness of 5 nm to 10 nm are formed as the insulating films 214 and 215 .

Since the electronic device 200 according to the second embodiment uses the GNR network film 1 according to the first embodiment as the GNR network film 201, excellent charge mobility can be obtained. Therefore, for example, a current on/off ratio of about 10 ⁵ can be realized, and a field effect mobility of several tens to several hundred cm ² /(V·s) can be expected.

Next, a method for manufacturing an electronic device according to the second embodiment will be described. 12A to 12F are plan views showing the method for manufacturing the electronic device according to the second embodiment, and FIGS. 13A to 13F are cross-sectional views showing the method for manufacturing the electronic device according to the second embodiment. 13A to 13F correspond to cross-sectional views taken along line II in FIGS. 12A to 12F.

First, as shown in FIGS. 12A and 13A, a metal film 212 is formed on an insulating substrate 211 . The growth substrate 210 includes an insulating substrate 211 and a metal film 212 . Next, a GNR network film 201 is formed on the metal film 212 .

After that, as shown in FIGS. 12B and 13B, the GNR network film 201 is processed into a channel shape.

Subsequently, as shown in FIGS. 12C and 13C, a source electrode 213s and a drain electrode 213d are formed on the metal film 212 so as to be in contact with both ends of the GNR network film 201. As shown in FIGS. The source electrode 213s and the drain electrode 213d can be formed as follows.

First, a resist pattern having openings in a region for forming the source electrode 213s and a region for forming the drain electrode 213d is formed. As the resist pattern, for example, a resist pattern having a two-layer structure is used. In this case, polymethylglutarimide (PMGI) (manufactured by MicroChem, Inc., USA), for example, can be used for the sacrificial layer resist of the lower layer, and a resist obtained by diluting ZEP520A manufactured by Nippon Zeon Co., Ltd. at 1:1 with ZEP-A manufactured by Nippon Zeon Co., Ltd. can be used for the electron beam resist of the upper layer. Next, by electron beam lithography, openings are formed in a region for forming the source electrode 213s and a region for forming the drain electrode 213d. After that, a Ti film and a Cr film are formed inside the opening and on the resist pattern by vapor deposition under a high vacuum of, for example, 1×10 ⁻⁵ Pa or less. For example, the vapor deposition rate of the Ti film is 0.05 nm/sec to 0.1 nm/sec, and the vapor deposition rate of the Cr film is 0.1 nm/sec to 1 nm/sec. After that, the resist pattern is removed together with the Ti film and Cr film thereon. That is, liftoff is performed. Thus, the source electrode 213s and the drain electrode 213d can be formed. The Ti film and Cr film can also be formed by a sputtering method, a pulse laser deposition method, or the like.

Next, as shown in FIGS. 12D and 13D, the portions of the metal film 212 that are not covered with the source electrode 213s and the drain electrode 213d are removed by wet etching. That is, a portion of the metal film 212 between the source electrode 213s and the drain electrode 213d is removed. If the metal film 212 is an Au film, a potassium iodide (KI) aqueous solution can be used as an etchant. Since the source electrode 213s and the drain electrode 213d are two-layer electrodes including a Ti film and a Cr film, they have excellent etching resistance to a KI aqueous solution. After that, washing with pure water and rinsing with isopropyl alcohol are sequentially performed. Subsequently, a supercritical drying process using CO ₂ gas is performed as a drying process. A supercritical drying process using CO ₂ gas is suitable for preventing the GNR network film 201 from breaking due to surface tension or capillary force of the solution.

12E and 13E, an insulating film 214 is formed below the GNR network film 201, and an insulating film 215 is formed above the GNR network film 201. Next, as shown in FIGS. The insulating film 214 covers the upper surface of the insulating substrate 211 , the side surfaces of the metal film 212 and the lower surface of the GNR network film 201 below the GNR network film 201 . The insulating film 215 covers the side and top surfaces of the source electrode 213s, the drain electrode 213d, and the GNR network film 201 above the GNR network film 201, and functions as a gate insulating film. The insulating films 214 and 215 can be formed, for example, by an atomic layer deposition (ALD) method. When the HfO ₂ film is formed by the ALD method, for example, tetrakis(dimethylamino)hafnium and H ₂ O are used as precursors, and the deposition temperature is set to 230°C to 270°C. Since the ALD method has no directivity in the deposition direction, the entire exposed surface of the GNR network film 201 is covered with insulating films 214 and 215 . A method for forming the insulating films 214 and 215 is not limited and can be selected as appropriate according to the material.

After that, as shown in FIGS. 12F and 13F, a gate electrode 213g is formed on the insulating film 215 between the source electrode 213s and the drain electrode 213d. The gate electrode 213g can be formed by a method similar to the method for forming the source electrode 213s and the drain electrode 213d.

Subsequently, the insulating film 215 is formed with an opening 215s exposing at least part of the upper surface of the source electrode 213s and an opening 215d exposing at least part of the upper surface of the drain electrode 213d. In forming the openings 215s and 215d, for example, an electron beam resist is formed, an opening pattern is formed in the electron beam resist by electron beam lithography, and reactive ion etching is performed using a chlorine-based mixed gas. The chlorine-based mixed gas includes, for example, BCl ₃ , Cl ₂ and O ₂ .

In this manner, an electronic device 200 having an FET with the GNR network film 201 as a channel can be manufactured.

(Third Embodiment)
The third embodiment relates to an electronic device including a bottom-gate FET using a GNR network film as a channel. FIG. 14 is a cross-sectional view showing an electronic device according to the third embodiment.

As shown in FIG. 14, the electronic device 300 according to the third embodiment has an insulating substrate 351, a gate electrode 313g formed on the insulating substrate 351, and an insulating film 315 formed on the insulating substrate 351 and the gate electrode 313g and covering the gate electrode 313g. The electronic device 300 has a GNR network film 301 provided on the insulating film 315 above the gate electrode 313g. As the GNR network film 301, the GNR network film 1 according to the first embodiment is used. A source electrode 313 s and a drain electrode 313 d are formed on the insulating film 315 so as to be in contact with both ends of the GNR network film 301 . A protective film 302 is formed on the GNR network film 301 between the source electrode 313s and the drain electrode 313d. The insulating film 315 functions as a gate insulating film.

As the insulating substrate 351, for example, a Si substrate on which a thermal oxide film is formed can be used. A GNR network film including, for example, a plurality of 17-AGNRs is formed as the GNR network film 301 . As _the protective film ₃₀₂ , for example, _{a film that is difficult} to chemically bond with C constituting _{the GNR network film 301} can be used _. In this example, a Cr ₂ O ₃ film is formed as the protective film 302 .

The source electrode 313s, the drain electrode 313d, and the gate electrode 313g have, for example, a Ti film with a thickness of 0.5 nm to 2 nm and a Cr film thereon with a thickness of 20 nm to 50 nm, and the distance between the source electrode 313s and the drain electrode 313d is, for example, 10 nm to 50 nm. As a material _of the insulating film 315, _HfO2 film, _{Al2O3 , Si3N4} , HfSiO, HfAlON, _Y2O3 , _{SrTiO3 ,} PbZrTiO3 _{, BaTiO3} , or the like can be used. In this example, an HfO ₂ film with a thickness of 5 nm to 10 nm is formed as the insulating film 315 .

Since the electronic device 300 according to the third embodiment uses the GNR network film 1 according to the first embodiment as the GNR network film 301, excellent charge mobility can be obtained. Therefore, for example, a current on/off ratio of about 10 ⁵ can be realized, and a field effect mobility of several tens to several hundred cm ² /(V·s) can be expected.

Next, a method for manufacturing an electronic device according to the third embodiment will be described. 15A to 15H are cross-sectional views showing the method of manufacturing the electronic device according to the third embodiment.

First, as shown in FIG. 15A, a metal film 312 is formed on an insulating substrate 311 . The growth substrate 310 includes an insulating substrate 311 and a metal film 312 . Next, a GNR network film 301 is formed on the metal film 312 . As the insulating substrate 311, for example, a mica substrate, a sapphire (α-Al ₂ O ₃ ) crystal substrate having a c-plane surface, an MgO crystal substrate having a surface Miller index of (111), or the like can be used. As the metal film 312, a film of Au, Ag, Cu, Ni, Rh, Pd, Ir, or Pt having a crystal structure of fcc and a surface Miller index of (111) can be used. In this example, a mica substrate is used as the insulating substrate 311 and an Au film is used as the metal film 312 .

After that, as shown in FIG. 15B, a protective film 302 is formed on the GNR network film 301 . The protective film 302 protects the channel from residues of the organic-based support film used during subsequent transfer of the channel. As the protective film 302, a film that is difficult to chemically bond with C constituting the GNR network film 301 can be used, and _{a Cr2O3} film is particularly preferable. SiO ₂ , Al ₂ O ₃ , Sc ₂ O ₃ , MnO ₂ , ZnO, Y ₂ O ₃ , ZrO ₂ , MoO ₃ and RuO ₂ can also be used for the protective film 302 . When a Cr ₂ O ₃ film is used, for example, after the GNR network film 301 is formed, a Cr metal film is formed on the GNR network film 301 in situ without being exposed from a vacuum chamber by a vapor deposition method, and exposed to the atmosphere, thereby allowing the Cr metal film to be changed into a Cr ₂ O ₃ film by natural oxidation. For example, the Cr metal film has a deposition rate of 0.01 nm/sec to 0.05 nm/sec and a thickness of 1 nm to 3 nm. Films of SiO ₂ , Al ₂ O ₃ , Sc ₂ O ₃ , MnO ₂ , ZnO, Y ₂ O ₃ , ZrO ₂ , MoO ₃ and RuO ₂ can be formed in a similar manner. Note that Ti and Ni are likely to chemically bond with C constituting the GNR network film 301 to form TiC _x and NiC _x .

Subsequently, as shown in FIG. 15C, an organic support film 322 is formed on the protective film 302 . As the support film 322, for example, a polymethyl methacrylate (PMMA) film of acrylic resin is used. The PMMA film can be formed with a thickness of 100 nm to 500 nm by spin coating, for example. As the support film 322, an epoxy resin, a heat peeling tape, an adhesive tape, various photoresists, and an electron beam resist may be used. A laminated film of these may be used.

Next, as shown in FIG. 15D, the metal film 312 is removed to separate the laminate of the support film 322, the protective film 302 and the GNR network film 301 from the insulating substrate 211. Next, as shown in FIG. When an Au film is used as the metal film 312, the metal film 312 can be removed by wet etching using a KI aqueous solution. After that, the layered body of the protective film 302 and the GNR network film 301 is washed with pure water and dried.

On the other hand, as shown in FIG. 15E, the gate electrode 313g is separately formed on the insulating substrate 351, and the insulating film 315 is formed on the insulating substrate 351 and the gate electrode 313g. As the insulating substrate 351, for example, a Si substrate on which a thermal oxide film is formed can be used. As the gate electrode 313g, a two-layer electrode of a Ti film and a Cr film can be formed by the same method as the gate electrode 213g in the second embodiment. As the insulating film 315, a HfO ₂ film can be formed by the same method as the insulating film 215 in the second embodiment.

Then, as shown in FIG. 15E, the laminated body of the protective film 302 and the GNR network film 301 is overlaid on the laminated body of the insulating substrate 351, the gate electrode 313g and the insulating film 315 so that the GNR network film 301 is in contact with the insulating film 315.

The support film 322 is then removed, as shown in FIG. 15F. When a PMMA film is used as the support film 322, the support film 322 can be removed by immersion in acetone at about 70.degree. After removing the support film 322, a rinse process using, for example, isopropyl alcohol is performed. In general, it is difficult to completely remove PMMA on graphene, and the residue may deteriorate the properties of graphene. In this embodiment, since the protective film 302 is formed between the GNR network film 301 and the PMMA support film 322, deterioration of the characteristics of the GNR network film 301 due to PMMA residue can be suppressed.

15G, the protective film 302 is formed with a source opening 302s exposing a part of the GNR network film 301 and a drain opening 302d exposing another part of the GNR network film 301. Then, as shown in FIG. In forming the openings 302s and 302d, for example, an electron beam resist is formed, an opening pattern is formed in the electron beam resist by electron beam lithography, and wet etching is performed using ceric ammonium nitrate.

15H, a source electrode 313s contacting the GNR network film 301 through the opening 302s and a drain electrode 313d contacting the GNR network film 301 through the opening 302d are formed on the insulating film 315. As shown in FIG. As the source electrode 313s and the drain electrode 313d, two-layer electrodes of a Ti film and a Cr film can be formed by the same method as the source electrode 213s and the drain electrode 213d in the second embodiment.

In this manner, an electronic device 300 having an FET with the GNR network film 301 as a channel can be manufactured.

The material of the insulating substrate 351 is not limited. As the insulating substrate 351, a transparent glass substrate, a flexible polyethylene terephthalate (PET) substrate, or the like may be used. Such glass substrates and PET substrates are suitable for application to displays.

(Fourth embodiment)
The fourth embodiment relates to an electronic device including a top-gate FET using a GNR network film as a channel. FIG. 16 is a cross-sectional view showing an electronic device according to a fourth embodiment.

As shown in FIG. 16 , an electronic device 400 according to the fourth embodiment has an insulating substrate 351 and a GNR network film 301 provided on the insulating substrate 351 . As the GNR network film 301, the GNR network film 1 according to the first embodiment is used. A source electrode 413 s and a drain electrode 413 d are formed on the insulating substrate 351 so as to be in contact with both ends of the GNR network film 301 . A protective film 302 is formed on the GNR network film 301 between the source electrode 413s and the drain electrode 413d. An insulating film 415 is formed over the source electrode 413 s , the protective film 302 and the drain electrode 413 d , and a gate electrode 413 g is formed over the insulating film 415 . The insulating film 415 functions as a gate insulating film.

The source electrode 413s, the drain electrode 413d, and the gate electrode 413g have, for example, a Ti film with a thickness of 0.5 nm to 2 nm and a Cr film thereon with a thickness of 20 nm to 50 nm, and the distance between the source electrode 413s and the drain electrode 413d is, for example, 10 nm to 50 nm. As a material _of the insulating film 415, _HfO2 film, _{Al2O3 , Si3N4} , HfSiO, HfAlON, _Y2O3 , _{SrTiO3 , PbZrTiO3} , _BaTiO3 , or the like can be used. In this example, an HfO ₂ film with a thickness of 5 nm to 10 nm is formed as the insulating film 415 .

Since the electronic device 400 according to the fourth embodiment uses the GNR network film 1 according to the first embodiment as the GNR network film 301, excellent charge mobility can be obtained. Therefore, for example, a current on/off ratio of about 10 ⁵ can be realized, and a field effect mobility of several tens to several hundred cm ² /(V·s) can be expected.

Next, a method for manufacturing an electronic device according to the fourth embodiment will be described. 17A to 17E are cross-sectional views showing the method for manufacturing an electronic device according to the fourth embodiment.

First, as shown in FIG. 17A, a laminate of a support film 322, a protective film 302 and a GNR network film 301 is formed in the same manner as in the third embodiment. Next, the laminate of the protective film 302 and the GNR network film 301 is overlaid on the insulating substrate 351 such that the GNR network film 301 is in contact with the insulating substrate 351 .

After that, as shown in FIG. 17B, the support film 322 is removed.

Subsequently, as shown in FIG. 17C, the protective film 302 is formed with a source opening 302s exposing a portion of the GNR network film 301 and a drain opening 302d exposing the other portion of the GNR network film 301. As shown in FIG.

Next, as shown in FIG. 17D, a source electrode 413s contacting the GNR network film 301 through the opening 302s and a drain electrode 413d contacting the GNR network film 301 through the opening 302d are formed on the insulating substrate 351. Next, as shown in FIG. As the source electrode 413s and the drain electrode 413d, two-layer electrodes of a Ti film and a Cr film can be formed by the same method as the source electrode 213s and the drain electrode 213d in the second embodiment.

After that, as shown in FIG. 17E, an insulating film 415 and a gate electrode 413g extending over the source electrode 413s, protective film 302 and drain electrode 413d are formed. The insulating film 415 and the gate electrode 413g can be formed as follows.

First, a resist pattern having openings in regions where the insulating film 415 and the gate electrode 413g are to be formed is formed. As the resist pattern, for example, a resist pattern having a two-layer structure is used. Next, by electron beam lithography, openings are formed in regions where the insulating film 415 and the gate electrode 413g are to be formed. After that, under a high vacuum of, for example, 1×10 ⁻⁵ Pa or less, Hf metal is vapor-deposited while introducing O ₂ gas to form an HfO ₂ film inside the opening and on the resist pattern, and a Ti film and a Cr film are formed on the HfO ₂ film. After that, the resist pattern is removed together with the HfO ₂ film, Ti film and Cr film thereon. That is, liftoff is performed. Thus, the insulating film 415 and the gate electrode 413g can be formed.

In this manner, an electronic device 400 having an FET with the GNR network film 301 as a channel can be manufactured.

Materials for the source electrode, the drain electrode, and the gate electrode are not limited. For example, a laminate of a Ti film and an Au film, Pt film or Pd film thereon may be used for the source electrode, drain electrode and gate electrode. Also, a transparent electrode material may be used for the source electrode, the drain electrode and the gate electrode. Transparent electrode materials include indium tin oxide (ITO), _In2O3 , _SnO2 , AlZnO and _GaZnO .

The GNRs contained in the GNR network membrane are not limited to 17-AGNR. For example, 9-AGNR, 13-AGNR, 21-AGNR, 25-AGNR, 29-AGNR, etc. may be included in the GNR network membrane. Table 1 shows the relationship between the _n1 value of AGNR, the number N of CC dimer lines in the ribbon width direction, the ribbon width W and the bandgap _Eg . The bandgap E _g is a value calculated from first-principles simulations considering many-body effects, in which the edge-modifying groups of AGNR are all H. FIG. 18 shows the relationship between the CC dimer line and the ribbon width W. As shown in FIG.

As shown in Table 1, the number (n ₁ ) of six-membered rings modified at C configurations 1 and 2 of the six-membered ring containing the modifying group X systematically controls the ribbon width of N-AGNR to achieve bandgap engineering. In this specification, graphene nanoribbons mean those having six or less six-membered rings (n ₁ ). This is because when the number of six-membered rings (n ₁ ) is 7 or more, the bandgap becomes small, making it difficult to use as a semiconductor.

Hereinafter, various aspects of the present invention will be collectively described as appendices.

(Appendix 1)
having a plurality of graphene nanoribbons arranged at angles of integral multiples of 60 degrees with respect to each other;
The graphene nanoribbon network film, wherein the plurality of graphene nanoribbons are sp ^2- orbital hybrid six-membered ring junctions.
(Appendix 2)
The graphene nanoribbon network film according to appendix 1, wherein the plurality of graphene nanoribbons are joined end-to-end.
(Appendix 3)
depositing a graphene nanoribbon precursor having a structural formula represented by the above chemical formula (1) on the (111) plane of a metal film having a face-centered cubic crystal structure at a first temperature;
heating the graphene nanoribbon precursor on the (111) face to a second temperature higher than the first temperature to induce X elimination and C—C bonding reactions to obtain a polymer on the (111) face;
heating the polymer to a third temperature higher than the second temperature to induce elimination of Y and a C—C bonding reaction;
heating the polymer to a fourth temperature equal to or higher than the third temperature to induce desorption of Z and a C—C bond reaction to obtain a plurality of graphene nanoribbons arranged on the (111) plane at an angle of an integer multiple of 60 degrees to each other;
heating the plurality of graphene nanoribbons to a fifth temperature that is higher than the fourth temperature to cause the plurality of graphene nanoribbons to sp ^2- orbital hybrid six-membered ring junctions with each other;
has
In the above chemical formula (1),
n ₁ is an integer of 1 or more and 6 or less,
X, Y and Z are F, Cl, Br, I, H, OH, SH, _SO2H , _SO3H , _SO2NH2 , _PO3H2 , NO, _NO2 , _{NH2 , CH3 ,} CHO, _COCH3 , COOH, _CONH2 , COCl, CN, _CF3 , _CCl3 , _CBr3 or _CI3 ;
A method for producing a graphene nanoribbon network film, characterized in that a relationship of TX < TY ≤ _TZ holds, where _TX , TY, and _TZ are desorption temperatures of _X , _Y , and _Z from carbon atoms constituting a six-membered ring.
(Appendix 4)
the first temperature is less than the desorption temperature _Tx of X;
the second temperature is greater than or equal to the desorption temperature _TX and less than the desorption temperature _TY of Y;
the third temperature is greater than or equal to the desorption temperature T _Y and less than the desorption temperature T _Z of Z;
The method for producing a graphene nanoribbon network film according to appendix 3, wherein the fourth temperature is equal to or higher than the desorption temperature _TZ .
(Appendix 5)
5. The method for producing a graphene nanoribbon network film according to appendix 3 or 4, wherein Y and Z are the same, and the third temperature and the fourth temperature are equal to each other.
(Appendix 6)
An electronic device comprising the graphene nanoribbon network film according to appendix 1 or 2 in a channel of a field effect transistor.
(Appendix 7)
A step of producing a graphene nanoribbon network film on the (111) plane of the metal film by the method according to any one of Appendices 3 to 5;
forming a field effect transistor having the graphene nanoribbon network film as a channel;
A method of manufacturing an electronic device, comprising:
(Appendix 8)
The step of forming the field effect transistor includes:
forming a source electrode and a drain electrode in contact with the graphene nanoribbon network film on the metal film;
removing a portion of the metal film between the source electrode and the drain electrode;
forming a gate insulating film and a gate electrode on the graphene nanoribbon network film in a portion between the source electrode and the drain electrode;
The method for manufacturing an electronic device according to Supplementary Note 7, characterized by comprising:
(Appendix 9)
The step of forming the field effect transistor includes:
forming a gate electrode and a gate insulating film over an insulating substrate;
transferring the graphene nanoribbon network film onto the gate insulating film;
forming source and drain electrodes over the insulating substrate in contact with the graphene nanoribbon network film;
The method for manufacturing an electronic device according to Supplementary Note 7, characterized by comprising:
(Appendix 10)
The step of forming the field effect transistor includes:
transferring the graphene nanoribbon network film onto an insulating substrate;
forming source and drain electrodes over the insulating substrate in contact with the graphene nanoribbon network film;
forming a gate insulating film and a gate electrode over the graphene nanoribbon network film in a portion between the source electrode and the drain electrode;
The method for manufacturing an electronic device according to Supplementary Note 7, characterized by comprising:

1, 201, 301: GNR network membrane 2: GNR
3: Six-membered ring 10: Growth substrate 11: Insulating substrate 12: Metal film 13: GNR film 200, 300, 400: Electronic device 213s, 313s, 413s: Source electrode 213d, 313d, 413d: Drain electrode 213g, 313g, 413g: Gate electrode

Claims (5)

depositing a graphene nanoribbon precursor having a structural formula represented by the following chemical formula (1) on the (111) plane of a metal film having a face-centered cubic crystal structure at a first temperature;
heating the graphene nanoribbon precursor on the (111) face to a second temperature higher than the first temperature to induce X elimination and C—C bonding reactions to obtain a polymer on the (111) face;
heating the polymer to a third temperature higher than the second temperature to induce elimination of Y and a C—C bonding reaction;
heating the polymer to a fourth temperature equal to or higher than the third temperature to induce desorption of Z and a C—C bond reaction to obtain a plurality of graphene nanoribbons arranged on the (111) plane at an angle of an integer multiple of 60 degrees to each other;
holding the plurality of graphene nanoribbons at a fifth temperature higher than the fourth temperature for 1 hour to 3 hours to bond the plurality of graphene nanoribbons to each other with sp ² orbital hybrid six-membered rings;
has
the fifth temperature is 450° C. to 500° C.;
In the chemical formula (1) below,
n ₁ is an integer of 1 or more and 6 or less,
X, Y and Z are F, Cl, Br, I, H, OH, SH, _SO2H , _SO3H , _SO2NH2 , _PO3H2 , NO, _NO2 , _{NH2 , CH3 ,} CHO, _COCH3 , COOH, _CONH2 , COCl, CN, _CF3 , _CCl3 , _CBr3 or _CI3 ;
A method for producing a graphene nanoribbon network film, characterized in that a relationship of TX < TY ≤ _TZ holds, where _TX , TY, and _TZ are desorption temperatures of _X , _Y , and _Z from carbon atoms constituting a six-membered ring.

the first temperature is less than the desorption temperature _Tx of X;
the second temperature is greater than or equal to the desorption temperature _TX and less than the desorption temperature _TY of Y;
the third temperature is greater than or equal to the desorption temperature T _Y and less than the desorption temperature T _Z of Z;
The method for producing a graphene nanoribbon network film according to claim 1 , wherein the fourth temperature is equal to or higher than the desorption temperature _TZ . The method for producing a graphene nanoribbon network film according to claim 1 or 2 , wherein Y and Z are the same, and the third temperature and the fourth temperature are equal to each other. The method for producing a graphene nanoribbon network film according to any one of claims 1 to 3, wherein the thickness of the graphene nanoribbon precursor to be vapor-deposited is 1 ML to 3 ML. producing a graphene nanoribbon network film on the (111) plane of the metal film by the method of any one of claims 1 to 4 ;
forming a field effect transistor having the graphene nanoribbon network film as a channel;
A method of manufacturing an electronic device, comprising:

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