JP2022100723A - Graphene nanoribbon precursor, graphene nanoribbon, electronic device, method for manufacturing graphene nanoribbon, and method for manufacturing electronic device - Google Patents

Abstract

To provide a graphene nanoribbon precursor, a graphene nanoribbon, an electronic device, a method for manufacturing the graphene nanoribbon, and a method for manufacturing the electronic device, capable of modulating the band gap of GNR in various ways.SOLUTION: A graphene nanoribbon precursor has a predetermined structural formula. In this structural formula, n1 is 1, 2 or 4, n2 is n1-1, X and Y are F, Cl, Br, or I. When the desorption temperatures of X and Y from carbon atoms constituting a six-membered ring are TX and TY, respectively, the relationship TX<TY holds.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a graphene nanoribbon precursor, a graphene nanoribbon, an electronic device, a method for manufacturing a graphene nanoribbon, and a method for manufacturing an electronic device.

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

On the other hand, nano-sized graphene has a small difference between the number of carbon atoms on the edge and the number of carbon atoms inside the edge, and the shape of graphene itself and the shape of the edge have a large effect, and bulk graphene. It shows a physical property that is significantly different from that of. As a nano-sized graphene, a ribbon-shaped pseudo-one-dimensional graphene having a width of several nm, a so-called graphene nanoribbon (GNR), is known. The physical characteristics of GNR vary greatly depending on the edge structure and ribbon width.

There are two types of GNR edge structures: armchair edges in which carbon atoms are arranged in a two-atom cycle and zigzag edges in which carbon atoms are arranged in a zigzag pattern. In the armchair edge type GNR (AGNR), the AGNR exhibits semiconducting properties because a finite bandgap is widened by the quantum confinement effect and the edge effect. On the other hand, the zigzag edge type GNR (ZGNR) exhibits metallic properties.

AGNR is called N-AGNR due to the number N of carbon atoms in the ribbon width direction. For example, an AGNR having an anthracene in which three six-membered rings are arranged in the ribbon width direction of the AGNR as a basic unit is called a 7-AGNR. Further, AGNR may be classified into three subfamilies of N = 3p, 3p + 1, 3p + 2 (where p is a positive integer) depending on the value of N. Theoretical calculations show that the bandgap size (Eg) of N- _AGNR within the same subfamily decreases with increasing N value (ie, ribbon width). Further, among each subfamily, E _g has a magnitude relationship of E _g ^{3p + 1} > E _g ^3p > E _g ^{3p + 2} .

In recent years, an example has been reported in which the bandgap is controlled by heterojunction of AGNRs having different ribbon widths and periodically changing the topology phase in the ribbon length direction.

Japanese Unexamined Patent Publication No. 2019-48791 Special Table 2015-504046

L. Yang et al., Phys. Rev. Lett. 99, 186801 (2007) M. Y. Han et al., Phys. Rev. Lett. 98, 206805 (2007) D. V. Kosynkin et al., Nature 458, 872 (2009) X. Li et al., Science 319, 1229 (2008) J. Cai et al., Nature 466, 470 (2010) D. J. Rizzo et al., Nature 560, 204 (2018) T. Cao et al., Rhys. Rev. Lett. 119, 076401 (2017)

So far, there are limited reports of GNR precursors capable of producing GNRs in which N-AGNRs having a topological invariant Z ₂ of 0 and 1 are heterojunctioned next to each other, and the bandgap cannot be modulated in various ways.

An object of the present disclosure is to provide a graphene nanoribbon precursor, a graphene nanoribbon, an electronic device, a method for manufacturing a graphene nanoribbon, and a method for manufacturing an electronic device capable of variously modulating the band gap of GNR.

According to one embodiment of the present disclosure, it has a structural formula represented by the following chemical formula (1), and in the following chemical formula (1), n ₁ is 1, 2 or 4, and n ₂ is n. _1-1 , X and Y are F, Cl, Br or I, and T is when the desorption temperatures of _X and _Y from the carbon atoms constituting the six-membered ring are TX and TY, respectively. A graphene nanoribbon precursor with an _X < _TY relationship is provided.

According to the present disclosure, the bandgap of GNR can be modulated in various ways.

It is a figure which shows the structural formula of the GNR precursor which concerns on 1st Embodiment. It is a figure (the 1) which shows the manufacturing method of GNR using the GNR precursor which concerns on 1st Embodiment. It is a figure (the 2) which shows the manufacturing method of GNR using the GNR precursor which concerns on 1st Embodiment. It is a figure which shows the structural formula of GNR which concerns on 1st Embodiment. It is a figure which shows the structural formula of the GNR precursor which concerns on 2nd Embodiment. It is a figure which shows the manufacturing method of the GNR precursor which concerns on 2nd Embodiment. It is a figure (the 1) which shows the manufacturing method of GNR using the GNR precursor which concerns on 2nd Embodiment. It is a figure (the 2) which shows the manufacturing method of GNR using the GNR precursor which concerns on 2nd Embodiment. It is a figure which shows the repeating unit of the structural formula of GNR which concerns on 2nd Embodiment. It is a figure which shows the band dispersion of GNR which concerns on 2nd Embodiment. It is a figure which shows the structural formula of the GNR precursor which concerns on 3rd Embodiment. It is a figure which shows the manufacturing method of the GNR precursor which concerns on 3rd Embodiment. It is a figure (the 1) which shows the manufacturing method of GNR using the GNR precursor which concerns on 3rd Embodiment. It is a figure (the 2) which shows the manufacturing method of GNR using the GNR precursor which concerns on 3rd Embodiment. It is a figure which shows the repeating unit of the structural formula of GNR which concerns on 3rd Embodiment. It is a figure which shows the band dispersion of GNR which concerns on 3rd Embodiment. It is a figure which shows the structural formula of the GNR precursor which concerns on 4th Embodiment. It is a figure which shows the manufacturing method of the GNR precursor which concerns on 4th Embodiment. It is a figure (the 1) which shows the manufacturing method of GNR using the GNR precursor which concerns on 4th Embodiment. It is a figure (the 2) which shows the manufacturing method of GNR using the GNR precursor which concerns on 4th Embodiment. It is a figure which shows the repeating unit of the structural formula of GNR which concerns on 4th Embodiment. It is a figure which shows the band dispersion of GNR which concerns on 4th Embodiment. It is a top view which shows the electronic apparatus which concerns on 5th Embodiment. It is sectional drawing which shows the electronic apparatus which concerns on 5th Embodiment. It is a top view (the 1) which shows the manufacturing method of the electronic apparatus which concerns on 5th Embodiment. It is a top view (No. 2) which shows the manufacturing method of the electronic apparatus which concerns on 5th Embodiment. It is a top view (No. 3) which shows the manufacturing method of the electronic apparatus which concerns on 5th Embodiment. It is a top view (the 4) which shows the manufacturing method of the electronic apparatus which concerns on 5th Embodiment. It is a top view (No. 5) which shows the manufacturing method of the electronic apparatus which concerns on 5th Embodiment. It is sectional drawing (the 1) which shows the manufacturing method of the electronic apparatus which concerns on 5th Embodiment. It is sectional drawing (the 2) which shows the manufacturing method of the electronic apparatus which concerns on 5th Embodiment. It is sectional drawing which shows the electronic apparatus which concerns on 6th Embodiment. It is sectional drawing (the 1) which shows the manufacturing method of the electronic apparatus which concerns on 6th Embodiment. It is sectional drawing (the 2) which shows the manufacturing method of the electronic apparatus which concerns on 6th Embodiment. It is sectional drawing (the 3) which shows the manufacturing method of the electronic apparatus which concerns on 6th Embodiment. It is sectional drawing (the 4) which shows the manufacturing method of the electronic apparatus which concerns on 6th Embodiment. It is sectional drawing (the 5) which shows the manufacturing method of the electronic apparatus which concerns on 6th Embodiment. It is sectional drawing (the 6) which shows the manufacturing method of the electronic apparatus which concerns on 6th Embodiment. It is sectional drawing (the 7) which shows the manufacturing method of the electronic apparatus which concerns on 6th Embodiment. It is sectional drawing which shows the electronic apparatus which concerns on 7th Embodiment. It is sectional drawing (the 1) which shows the manufacturing method of the electronic apparatus which concerns on 7th Embodiment. It is sectional drawing (the 2) which shows the manufacturing method of the electronic apparatus which concerns on 7th Embodiment. It is sectional drawing (the 3) which shows the manufacturing method of the electronic apparatus which concerns on 7th Embodiment. It is sectional drawing (the 4) which shows the manufacturing method of the electronic apparatus which concerns on 7th Embodiment. It is sectional drawing (the 5) which shows the manufacturing method of the electronic apparatus which concerns on 7th Embodiment.

Hereinafter, embodiments of the present disclosure will be specifically described with reference to the accompanying drawings. In the present specification and the drawings, components having substantially the same functional configuration may be designated by the same reference numerals to omit duplicate explanations.

(First Embodiment)
First, the first embodiment will be described. The first embodiment relates to a graphene nanoribbon (GNR) and a GNR precursor suitable for producing the same. FIG. 1 is a diagram showing a structural formula of the GNR precursor according to the first embodiment.

The GNR precursor 100 according to the first embodiment has the structural formula shown in FIG. In FIG. 1, n ₁ is ₁ , 2 or 4, and n ₂ is n 1-1. That is, n ₂ is 0, 1 or 3. X and Y are F, Cl, Br or I. When the desorption temperatures of _X and _Y from the carbon atoms constituting the six-membered ring are TX and TY, respectively, the relationship of _TX < _TY is established. That is, the GNR precursor 100 according to the first embodiment comprises a basic skeleton of ditriphenylene and has a different number of six-membered rings of n ₁ and n ₂ .

Here, a method for producing GNR using the GNR precursor 100 according to the first embodiment will be described. 2 to 3 are diagrams showing a method for producing GNR using the GNR precursor according to the first embodiment. In this method, GNR is produced in situ by a bottom-up method.

First, the surface of the substrate on which GNR is grown is cleaned. The surface cleaning treatment can remove organic contaminants on the surface of the substrate and improve the flatness of the surface.

Next, the temperature of the substrate is maintained at an initial temperature lower than the desorption temperature _TX under high vacuum without exposing the surface-cleaned substrate to the atmosphere, and the GNR precursor 100 is heated and sublimated. The sublimated GNR precursor 100 is deposited on the substrate.

After that, the substrate is heated to a first temperature equal to or higher than the desorption temperature of Br and lower than the desorption temperature of F. On the substrate at the first temperature, a deX reaction of the GNR precursor 100 and a CC bond reaction between the GNR precursors 100 at the desorption point of X are induced. As a result, as shown in FIG. 2, the polymer 140 arranged in one direction is stably formed.

Subsequently, the substrate is heated to a second temperature equal to or higher than the desorption temperature _TY . On the substrate at the second temperature, the de-Y reaction of the GNR precursor 100 and the CC bond reaction between the GNR precursors 100 at the desorption point of Y are induced, and the de-H reaction and the cyclization are induced. A reaction is induced. As a result, AGNR150 is formed from the polymer 140 as shown in FIG. The AGNR150 is a repeating unit of the structural formula 130 shown in FIG.

The AGNR 150 alternately includes the first segment 151 and the second segment 152 having different topological invariants Z ₂ in the ribbon length direction, and the adjacent first segment 151 and the second segment 152 are heterozygous. For example, if the topological invariant Z _{2 of the first segment 151 is 0, the topological invariant Z 2 of the second segment 152 is 1, and if the topological invariant Z 2 of} the first segment 151 is 1, the first The topological invariant Z ₂ of the two segments 152 is zero. The AGNR150 can be called a topological AGNR.

As described above, the GNR precursor 100 according to the first embodiment comprises a basic skeleton of ditriphenylene and has a different number of six-membered rings of n ₁ and n ₂ . By producing the AGNR 150 using the GNR precursor 100, the AGNR 150 can contain the first segment 151 and the second segment 152 having different topological invariants Z ₂ alternately in the ribbon length direction. By heterojunction of the first segment 151 and the second segment 152 having different topological invariants Z ₂ so as to be adjacent to each other, a new toporological band appears in the band gap of AGNR150. Therefore, according to the first embodiment, the periodic change of the topology phase can be given in the ribbon length direction of the AGNR150, and the band gap of the AGNR150 can be modulated according to the values of n ₁ and n ₂ .

Further, by using the GNR precursor 100 according to the first embodiment, a long AGNR150 can be stably produced by a bottom-up method.

As will be described in detail in the second to fourth embodiments, in the synthesis of the GNR precursor 100, a reaction is carried out according to the desired structure and electronic properties (band gap, work function, electron affinity) of AGNR150. The skeleton and modifying group of the compound can be appropriately selected.

(Second Embodiment)
Next, the second embodiment will be described. The second embodiment relates to GNR and a GNR precursor suitable for producing the same. FIG. 5 is a diagram showing a structural formula of the GNR precursor according to the second embodiment.

The GNR precursor 200 according to the second embodiment has the structural formula shown in FIG. That is, the GNR precursor 200 according to the second embodiment has a structural formula in which n ₁ is 1, n ₂ is 0, X is Br, and Y is F in FIG. 1. The desorption temperature _TX of Br from the carbon atom constituting the 6-membered ring is lower than the desorption temperature _TY of F from the carbon atom constituting the 6-membered ring. That is, the GNR precursor 200 according to the second embodiment comprises a basic skeleton of ditriphenylene and has a different number of six-membered rings of n ₁ and n ₂ .

Here, a method for producing the GNR precursor 200 according to the second embodiment will be described. FIG. 6 is a diagram showing a method for producing a GNR precursor according to the second embodiment.

First, a coupling reaction using Lewis acid is carried out on a mixture of 2-amino-4-fluoronaphthalene 211 and aniline 212 to prepare a diaminophenylnaphthalene derivative 213. Next, a Sandmeyer reaction is carried out with the amino group of the diaminophenylnaphthalene derivative 213 to prepare the diiodophenylnaphthalene derivative 214. Next, the iodine of the diiodophenylnaphthalene derivative 214 is subjected to a stannylization reaction to prepare a ditrimethyltin phenylnaphthalene derivative 215. Then, the monomer 217 is prepared by a coupling reaction between the ditrimethyltin phenylnaphthalene derivative 215 and 2-bromo-3,4-diiodo-1-methylbenzene216.

Separately, a coupling reaction using Lewis acid is carried out on a mixture of 2-amino-4-bromonaphthalene 221 and aniline 222 to prepare a diaminophenylnaphthalene derivative 223. Next, a Sandmeyer reaction is carried out with the amino group of the diaminophenylnaphthalene derivative 223 to prepare the diiodophenylnaphthalene derivative 224. Next, the iodine of the diiodophenylnaphthalene derivative 224 is subjected to a stannylization reaction to prepare a ditrimethyltin phenylnaphthalene derivative 225. Then, the monomer 227 is prepared by a coupling reaction between the ditrimethyltin phenylnaphthalene derivative 225 and 2-fluoro-3,4-diiodo-1-methylbenzene226.

Then, the monomer 217 and the monomer 227 are coupled to form a dimer. In this way, the GNR precursor 200 is synthesized as a dimer.

The above reaction conditions and solvent are examples, and the GNR precursor 200 may be produced using other reaction conditions and solvents.

Next, a method for producing GNR using the GNR precursor 200 according to the second embodiment will be described. 7 to 8 are diagrams showing a method for producing GNR using the GNR precursor according to the second embodiment. In this method, AGNR250 containing 10-AGNR as the first segment 251 and 6-AGNR as the second segment 252 is produced in situ by a bottom-up method.

First, the surface of the substrate on which GNR is grown is cleaned. In this surface cleaning treatment, for example, Ar ion sputtering on the surface and annealing under ultra-high vacuum are set as one cycle, and this is carried out in a plurality of cycles. For example, in each cycle, in Ar ion sputtering, the ion acceleration voltage is 1.0 kV, the ion current is 10 μA, the time is 1 minute, and in annealing, the vacuum degree is maintained at 5 × 10 ^-7 Pa or less. The temperature is 400 ° C. to 500 ° C., and the time is 10 minutes. For example, the number of cycles is 3 cycles. The surface cleaning treatment can remove organic contaminants on the surface of the substrate and improve the flatness of the surface.

As the substrate, a substrate having a catalytic action can be used, for example, a metal single crystal substrate having a surface Miller index of (111) can be used. Examples of the material of the substrate include Au, Cu, Ni, Rh, Pd, Ag, Ir and Pt. In order to control the directivity of the AGNR250, a single crystal substrate having a high exponential plane having a step and terrace periodic structure having a width of several nm may be used. The Miller index on the surface of such a substrate is, for example, (788). For example, an Au substrate having a surface Miller index of (788) can be used. As the substrate, a metal thin film substrate in which the above-mentioned metal thin film such as Au is deposited on an insulating substrate such as mica, sapphire, and MgO may be used. In order to control the position and directivity of the AGNR250, a metal thin film patterned into a fine line having a width of several nm by electron beam lithography and etching may be used. Semiconductor substrates such as group IV semiconductors, group III-V compound semiconductors, group II-VI compound semiconductors, and transition metal oxide semiconductors may be used.

Next, the temperature of the substrate is maintained at an initial temperature lower than the desorption temperature of Br under ultra-high vacuum without exposing the surface-cleaned substrate to the atmosphere, and the GNR precursor 200 is heated to sublimate. Let me. For example, the temperature of the substrate is room temperature of about 25 ° C. Further, for example, a K-cell type evaporator is used for heating and sublimation of the GNR precursor 200, the basic vacuum degree in the vacuum chamber is 5 × ^10-8 Pa or less, and the heating temperature is 180 ° C. to 220 ° C. The sublimated GNR precursor 200 is deposited on the substrate. For example, the vapor deposition rate is 0.05 nm / min to 0.10 nm / min, and the vapor deposition film thickness is 0.5 ML to 1 ML. 1ML (monolayer) is about 0.25 nm.

After that, the substrate is heated to a first temperature equal to or higher than the desorption temperature of Br and lower than the desorption temperature of F. For example, the first temperature is 150 ° C. to 250 ° C., and the heating rate from the initial temperature to the first temperature is 1 ° C./min to 5 ° C./min. Since the C—Br binding energy is lower than the CF binding energy, the deBr reaction of the GNR precursor 200 and the C of the GNR precursors 200 at the desorption point of Br on the substrate at 150 ° C to 250 ° C. -C bond reaction is induced. As a result, as shown in FIG. 7, the polymer 240 arranged in one direction is stably formed.

Subsequently, the temperature of the substrate is heated to a second temperature equal to or higher than the desorption temperature of F. For example, the second temperature is 300 ° C. to 400 ° C., and the heating rate from the first temperature to the second temperature is 1 ° C./min to 5 ° C./min. On a substrate at 300 ° C. to 400 ° C., a de-F reaction and a CC bond reaction between GNR precursors 200 at the desorption point of F are induced, and a de-H reaction and a cyclization reaction occur. Induced. As a result, AGNR250 is formed from the polymer 240 as shown in FIG. The AGNR 250 is a repeating unit of the structural formula 230 shown in FIG.

The AGNR 250 contains the first segment 251 of 10-AGNR and the second segment 252 of 6-AGNR alternately in the ribbon length direction, and the adjacent 10-AGNR and 6-AGNR are heterozygous. Further, the topological invariant Z ₂ of 10-AGNR is 1, and the topological invariant Z ₂ of 6-AGNR is 0. That is, the AGNR 250 alternately includes the first segment 251 and the second segment 252 having different topological invariants Z ₂ in the ribbon length direction, and the adjacent first segment 251 and the second segment 252 are heterojunctioned. There is. Thus, the AGNR 250 has a periodic structure of topological phases of 10-AGNR and 6-AGNR. Therefore, according to AGNR250, a bandgap Eg different from any of 10-AGNR and 6- _AGNR can be obtained. The AGNR 250 can be called a topological AGNR.

FIG. 10 shows the band variance calculated by the first-principles simulation (density functional theory / generalized gradient approximation: DFT-GGA) of AGNR250 according to the second embodiment. As shown in FIG. 10, the bandgap Eg of _AGNR250 was 0.57 eV.

(Third Embodiment)
Next, the third embodiment will be described. The third embodiment relates to GNR and a GNR precursor suitable for producing the same. FIG. 11 is a diagram showing a structural formula of the GNR precursor according to the third embodiment.

The GNR precursor 300 according to the third embodiment has the structural formula shown in FIG. That is, the GNR precursor 300 according to the third embodiment has a structural formula in which n ₁ is 2, n ₂ is 1, X is Br, and Y is F in FIG. 1. The desorption temperature _TX of Br from the carbon atom constituting the 6-membered ring is lower than the desorption temperature _TY of F from the carbon atom constituting the 6-membered ring. That is, the GNR precursor 300 according to the third embodiment comprises a basic skeleton of ditriphenylene and has a different number of six-membered rings of n ₁ and n ₂ .

Here, a method for producing the GNR precursor 300 according to the third embodiment will be described. FIG. 12 is a diagram showing a method for producing a GNR precursor according to a third embodiment.

First, a coupling reaction using Lewis acid is carried out on a mixture of 2-amino-4-fluoroanthracene 311 and 2-amino-naphthalene 312 to prepare a diaminonaphthylanthracene derivative 313. Next, a Sandmeyer reaction is carried out with respect to the amino group of the diaminonaphthylanthracene derivative 313 to prepare the diiodonaftyl anthracene derivative 314. Next, the iodine of the diiodonaftyl anthracene derivative 314 is subjected to a stannylization reaction to prepare the ditrimethyltinnaphthylanthracene derivative 315. Then, the monomer 317 is prepared by a coupling reaction between the ditrimethyltinnaphthylanthracene derivative 315 and 1-bromo-2,3-diiodo-7-methylnaphthalene 316.

Separately, a coupling reaction using Lewis acid is carried out on a mixture of 2-amino-4-bromoanthracene 321 and 2-amino-naphthalene 322 to prepare a diaminonaphthylanthracene derivative 323. Next, a Sandmeyer reaction is carried out with respect to the amino group of the diaminonaphthylanthracene derivative 323 to prepare the diiodonaftyl anthracene derivative 324. Next, the iodine of the diiodonaftyl anthracene derivative 324 is subjected to a stanylation reaction to prepare a ditrimethyltinnaphthylanthracene derivative 325. Then, the monomer 327 is prepared by a coupling reaction between the ditrimethyltinnaphthylanthracene derivative 325 and 1-fluoro-2,3-diiodo-7-methylnaphthalene 326.

Then, the monomer 317 and the monomer 327 are coupled to form a dimer. In this way, the GNR precursor 300 is synthesized as a dimer.

The above reaction conditions and solvent are examples, and the GNR precursor 300 may be produced using other reaction conditions and solvents.

Next, a method for producing GNR using the GNR precursor 300 according to the third embodiment will be described. 13 to 14 are diagrams showing a method for producing GNR using the GNR precursor according to the third embodiment. In this method, AGNR350 containing 14-AGNR as the first segment 351 and 10-AGNR as the second segment 352 is produced in situ by a bottom-up method.

First, the surface of the substrate on which GNR is grown is cleaned in the same manner as in the second embodiment. As the substrate, the same substrate as in the second embodiment can be used. Next, the temperature of the substrate is maintained at an initial temperature lower than the desorption temperature of Br under ultra-high vacuum without exposing the surface-cleaned substrate to the atmosphere, and the GNR precursor 300 is heated and sublimated. Let me. For example, the temperature of the substrate is room temperature of about 25 ° C. Further, for example, a K-cell type evaporator is used for heating and sublimation of the GNR precursor 300, the basic vacuum degree in the vacuum chamber is 5 × ^10-8 Pa or less, and the heating temperature is 230 ° C. to 270 ° C. The sublimated GNR precursor 300 is deposited on the substrate.

After that, the temperature of the substrate is heated to a first temperature equal to or higher than the desorption temperature of Br and lower than the desorption temperature of F. For example, the first temperature is 150 ° C. to 250 ° C., and the heating rate from the initial temperature to the first temperature is 1 ° C./min to 5 ° C./min. On a substrate at 150 ° C. to 250 ° C., a deBr reaction and a CC bond reaction between GNR precursors 300 at the desorption point of Br are induced. As a result, as shown in FIG. 13, the polymer 340 arranged in one direction is stably formed.

Subsequently, the temperature of the substrate is heated to a second temperature equal to or higher than the desorption temperature of F. For example, the second temperature is 300 ° C. to 400 ° C., and the heating rate from the first temperature to the second temperature is 1 ° C./min to 5 ° C./min. On a substrate at 300 ° C. to 400 ° C., a de-F reaction and a CC bond reaction between GNR precursors 300 at the desorption point of F are induced, and a de-H reaction and a cyclization reaction occur. Induced. As a result, AGNR350 is formed from the polymer 340 as shown in FIG. The AGNR350 is a repeating unit of the structural formula 330 shown in FIG.

The AGNR350 contains the first segment 351 of 14-AGNR and the second segment 352 of 10-AGNR alternately in the ribbon length direction, and the adjacent 14-AGNR and 10-AGNR are heterozygous. Further, the topological invariant Z ₂ of 14-AGNR is 0, and the topological invariant Z ₂ of 10-AGNR is 1. That is, the AGNR350 alternately includes the first segment 351 and the second segment 352 having different topological invariants Z ₂ in the ribbon length direction, and the adjacent first segment 351 and the second segment 352 are heterozygous. There is. Thus, the AGNR350 has a periodic structure of topological phases of 14-AGNR and 10-AGNR. Therefore, according to AGNR350, a bandgap Eg different from any of 14-AGNR and 10- _AGNR can be obtained. The AGNR350 can be called a topological AGNR.

The band dispersion calculated by DFT-GGA of AGNR350 according to the third embodiment is shown in FIG. As shown in FIG. 16, the bandgap Eg of _AGNR350 was 0.45 eV.

(Fourth Embodiment)
Next, the fourth embodiment will be described. The fourth embodiment relates to GNR and a GNR precursor suitable for producing the same. FIG. 17 is a diagram showing a structural formula of the GNR precursor according to the fourth embodiment.

The GNR precursor 400 according to the fourth embodiment has the structural formula shown in FIG. That is, the GNR precursor 400 according to the third embodiment has a structural formula in which n ₁ is 4, n ₂ is 3, X is Br, and Y is F in FIG. 1. The desorption temperature _TX of Br from the carbon atom constituting the 6-membered ring is lower than the desorption temperature _TY of F from the carbon atom constituting the 6-membered ring. That is, the GNR precursor 400 according to the fourth embodiment comprises a basic skeleton of ditriphenylene and has a different number of six-membered rings of n ₁ and n ₂ .

Here, a method for producing the GNR precursor 400 according to the fourth embodiment will be described. FIG. 18 is a diagram showing a method for producing a GNR precursor according to a fourth embodiment.

First, a coupling reaction using Lewis acid is carried out on a mixture of 2-amino-4-fluoropentacene 411 and 2-amino-tetracene 412 to prepare a diaminotetrasenylpentacene derivative 413. Next, a Sandmeyer reaction is carried out with the amino group of the diaminotetrasenyl pentacene derivative 413 to prepare the diiodotetrasenyl pentacene derivative 414. Next, the iodine of the diiodotetrasenylpentacene derivative 414 is subjected to a stannylization reaction to prepare the ditrimethyltin tetrasenylpentacene derivative 415. Then, the monomer 417 is prepared by a coupling reaction between the ditrimethyltin tetrasenylpentacene derivative 415 and 1-bromo-2,3-diiodo-9-methyltetracene 416.

Separately, a coupling reaction using Lewis acid is carried out on a mixture of 2-amino-4-bromopentacene 421 and 2-amino-tetracene 422 to prepare a diaminotetrasenylpentacene derivative 423. Next, a Sandmeyer reaction is carried out with respect to the amino group of the diaminotetrasenyl pentacene derivative 423 to prepare the diiodotetrasenyl pentacene derivative 424. Next, the iodine of the diiodotetrasenylpentacene derivative 424 is subjected to a stannylization reaction to prepare a ditrimethyltin tetrasenylpentacene derivative 425. Then, the monomer 427 is prepared by a coupling reaction between the ditrimethyltin tetrasenylpentacene derivative 425 and 1-fluoro-2,3-diiodo-9-methyltetracene 426.

Then, the monomer 417 and the monomer 427 are coupled to form a dimer. In this way, the GNR precursor 400 is synthesized as a dimer.

The above reaction conditions and solvent are examples, and the GNR precursor 400 may be produced using other reaction conditions and solvents.

Next, a method for producing GNR using the GNR precursor 400 according to the fourth embodiment will be described. 19 to 20 are diagrams showing a method for producing GNR using the GNR precursor according to the fourth embodiment. In this method, AGNR450 containing 22-AGNR as the first segment 451 and 18-AGNR as the second segment 452 is produced in situ by a bottom-up method.

First, the surface of the substrate on which GNR is grown is cleaned in the same manner as in the second embodiment. As the substrate, the same substrate as in the second embodiment can be used. Next, the temperature of the substrate is maintained at an initial temperature lower than the desorption temperature of Br under ultra-high vacuum without exposing the surface-cleaned substrate to the atmosphere, and the GNR precursor 400 is heated and sublimated. Let me. For example, the temperature of the substrate is room temperature of about 25 ° C. Further, for example, a K-cell type evaporator is used for heating and sublimation of the GNR precursor 400, the basic vacuum degree in the vacuum chamber is 5 × ^10-8 Pa or less, and the heating temperature is 330 ° C. to 370 ° C. The sublimated GNR precursor 300 is deposited on the substrate.

After that, the temperature of the substrate is heated to a first temperature equal to or higher than the desorption temperature of Br and lower than the desorption temperature of F. For example, the first temperature is 150 ° C. to 250 ° C., and the heating rate from the initial temperature to the first temperature is 1 ° C./min to 5 ° C./min. On a substrate at 150 ° C. to 250 ° C., a deBr reaction and a CC bond reaction between GNR precursors 400 at the desorption point of Br are induced. As a result, as shown in FIG. 19, the polymer 440 arranged in one direction is stably formed.

Subsequently, the temperature of the substrate is heated to a second temperature equal to or higher than the desorption temperature of F. For example, the second temperature is 300 ° C. to 400 ° C., and the heating rate from the first temperature to the second temperature is 1 ° C./min to 5 ° C./min. On a substrate at 300 ° C. to 400 ° C., a de-F reaction and a CC bond reaction between GNR precursors 400 at the desorption point of F are induced, and a de-H reaction and a cyclization reaction occur. Induced. As a result, AGNR450 is formed from the polymer 440 as shown in FIG. The AGNR450 is a repeating unit of the structural formula 430 shown in FIG.

The AGNR450 contains the first segment 451 of 22-AGNR and the second segment 452 of 18-AGNR alternately in the ribbon length direction, and the adjacent 22-AGNR and 18-AGNR are heterozygous. Further, the topological invariant Z ₂ of 22-AGNR is 1, and the topological invariant Z ₂ of 18-AGNR is 0. That is, the AGNR450 alternately includes the first segment 451 and the second segment 452 having different topological invariants Z ₂ in the ribbon length direction, and the adjacent first segment 451 and the second segment 452 are heterojunctioned. There is. As described above, AGNR450 has a periodic structure of topological phases of 22-AGNR and 18-AGNR. Therefore, according to AGNR450, a bandgap Eg different from that of 22-AGNR and 18- _AGNR can be obtained. The AGNR450 can be called a topological AGNR.

FIG. 22 shows the band dispersion calculated by DFT-GGA of AGNR450 according to the fourth embodiment. As shown in FIG. 22, the bandgap Eg of _AGNR450 was 0.10 eV.

(Fifth Embodiment)
Next, the fifth embodiment will be described. A fifth embodiment relates to an electronic device including a field effect transistor (FET) using AGNR as a channel. FIG. 23 is a top view showing the electronic device according to the fifth embodiment. FIG. 24 is a cross-sectional view showing the electronic device according to the fifth embodiment. FIG. 24 corresponds to a cross-sectional view taken along the line XXIV-XXIV in FIG.

As shown in FIGS. 23 and 24, the electronic device 500 according to the fifth embodiment has an insulating substrate 501 and an AGNR 503 provided above the insulating substrate 501. AGNR503 is, for example, AGNR150 according to the first embodiment. A metal layer 502S is formed between one end of the AGNR503 in the ribbon length direction and the insulating substrate 501, and a metal layer 502D is formed between the other end and the insulating substrate 501. A source electrode 504 in contact with one end of the AGNR 503 and the metal layer 502S and a drain electrode 505 in contact with the other end of the AGNR 503 and the metal layer 502D are formed on the insulating substrate 501. A gate insulating layer 507 and a gate electrode 506 are formed on the AGNR 503 between the source electrode 504 and the drain electrode 505.

For example, the insulating substrate 501 is a mica substrate that is cleaved to have a clean surface, and the metal layers 502S and 502D are Au layers having a thickness of 10 nm to 50 nm. The source electrode 504, the drain electrode 505, and the gate electrode 506 have, for example, a Ti film having a thickness of 0.5 nm to 1 nm and a Cr film having a thickness of 30 nm to 50 nm on the Ti film, and the gate insulating layer 507 has a gate insulating layer 507. It is a _Y2O3 layer having a thickness of ₅ nm to 10 nm.

Next, a method of manufacturing the electronic device 500 according to the fifth embodiment will be described. 25 to 29 are top views showing a method of manufacturing an electronic device according to a fifth embodiment. 30 to 31 are sectional views showing a method of manufacturing an electronic device according to a fifth embodiment. FIG. 30 corresponds to a cross-sectional view taken along the line XXX-XXXI in FIG. 28, and FIG. 31 corresponds to a cross-sectional view taken along the line XXXI-XXXI in FIG. 29.

First, as shown in FIG. 25, a metal layer is deposited on the insulating substrate 501, and the metal layer is patterned by electron beam lithography and dry etching to form a metal pattern 502. For example, the insulating substrate 501 is a mica substrate that is cleaved to expose a clean surface, and the metal layer is an Au layer having a thickness of 10 nm to 50 nm. The Au layer can be deposited on the cleavage plane of the mica substrate by the vapor deposition method. By depositing the Au layer while heating the mica substrate to a temperature of 400 ° C. to 550 ° C., the surface of the Au layer can be oriented toward the (111) plane. Cu, Ni, Rh, Pd, Ag, Ir or Pt may be used as the material of the metal layer. The epitaxial crystal plane of the metal layer can be controlled according to the type of the substrate.

The polymerization and cyclization reactions of the GNR precursor are not induced on the surface of the insulating substrate 501. Therefore, the position and size of the AGNR can be controlled from the position and size of the metal pattern 502. For example, the longitudinal dimension (length) of the metal pattern 502 is adjusted in consideration of the channel length of the FET to be manufactured, and the lateral dimension (width) is adjusted in consideration of the ribbon width of the AGNR used for the FET. adjust. For example, the length of the metal pattern 502 is 50 nm to 500 nm, and the width is 1 nm to 5 nm.

In the patterning of the metal layer, an electron beam resist is spin-coated on the metal layer, and a mask pattern for etching the metal layer is formed on the electron beam resist. As the electron beam resist, a resist obtained by diluting ZEP 520A (manufactured by Zeon Corporation) 1: 1 with ZEP-A (manufactured by Zeon Corporation) can be used. Then, using the mask pattern, the metal layer is etched by Ar ion milling. In this way, the metal pattern 502 can be formed.

Then, as shown in FIG. 26, AGNR503 is formed on the metal pattern 502. AGNR503 can be formed using the GNR precursor 100 according to the first embodiment. As a pretreatment for the formation of AGNR503, a surface cleaning treatment of the metal pattern 502 is performed. By this surface cleaning treatment, organic contaminants such as resist residue adhering to the surface of the metal pattern 502 can be removed, and the flatness of the (111) surface of the Au layer can be further improved. The AGNR503 is formed in situ in an ultra-high vacuum vacuum chamber without exposing the surface-cleaned metal pattern 502 to the atmosphere.

For example, the GNR precursor 100 is deposited on the surface of the metal pattern 502 while keeping the temperature of the insulating substrate 501 and the metal pattern 502 at room temperature, and then the temperature of the insulating substrate 501 and the metal pattern 502 is set to 380 ° C to 420 ° C. The temperature rises. As a result, a polymerization reaction, a cyclization reaction, and the like of the GNR precursor 100 are induced, and AGNR503 whose position and size are controlled by the metal pattern 502 is formed. That is, AGNR503 is self-organized so as to extend along the longitudinal direction of the metal pattern 502.

Subsequently, as shown in FIG. 27, the source electrode 504 is formed on one end of the AGNR503 and the drain electrode 505 is formed on the other end by electron beam lithography, vapor deposition, and lift-off. The source electrode 504 and the drain electrode 505 are two-layer electrodes including, for example, a Ti film and a Cr film on the Ti film. In the formation of the source electrode 504 and the drain electrode 505, a two-layer resist is spin-coated on the AGNR503, the metal pattern 502 and the insulating substrate 501, and an electrode pattern is formed on the two-layer resist by electron beam lithography. For example, a diluted resist of ZEP 520A is used for the upper layer of the two-layer resist, and PMGI SFG2S (manufactured by KAYAKU Advanced Materials, Inc.) is used for the lower layer which is the sacrificial layer. After forming the electrode pattern, a Ti film having a thickness of 0.5 nm to 1 nm and a Cr film having a thickness of 30 nm to 50 nm are deposited by a vapor deposition method. Subsequently, it is lifted off by removing the two-layer resist. In this way, the source electrode 504 and the drain electrode 505 are formed.

Then, as shown in FIGS. 28 and 30, a gate stack structure of the gate electrode 506 and the gate insulating layer 507 is formed on the AGNR503 by electron beam lithography, a vapor deposition method, and a lift-off. This gate stack structure is formed so that an opening 508 is formed between the source electrode 504 and the drain electrode 505. For example, the gate length is 8 nm to 12 nm, the gate insulating layer 507 is a _Y2O3 layer, and the gate electrode 506 is a _two -layer electrode including a Ti film and a Cr film on the Ti film. In the formation of the gate electrode 506 and the gate insulating layer 507, the two-layer resist is spin-coated and a gate pattern is formed on the two-layer resist by electron beam lithography in the same manner as in the formation of the source electrode 504 and the drain electrode 505. For example, a diluted resist of ZEP 520A is used as the upper layer of the two-layer resist, and PMGI SFG2S is used as the lower layer which is the sacrificial layer. After forming the gate pattern _, a Y2O3 layer having a thickness of ₅ nm to 10 nm, a Ti film having a thickness of 0.5 nm to 1 nm, and a Cr film having a thickness of 30 nm to 50 nm are deposited by a vapor deposition method. Subsequently, it is lifted off by removing the two-layer resist. In this way, the gate stack structure of the gate electrode 506 and the gate insulating layer 507 is formed. _{The Y2O3} layer can be formed by depositing Y metal while introducing _O2 gas into the vacuum chamber. SiO ₂ , HfO ₂ , ZrO ₂ , La ₂ O ₃ or TiO ₂ may be used as the material of the gate insulating layer 507. Even when these materials are used, the gate insulating layer 507 can be formed by depositing a metal while introducing O ₂ gas into the vacuum chamber.

Then, as shown in FIGS. 29 and 31, the portion of the metal pattern 502 that is not covered by the source electrode 504 or the drain electrode 505 is removed by wet etching to form a void 509. As a result, the metal layers 502S and 502D are formed from the metal pattern 502. When Au is used in the metal pattern, an aqueous KI solution can be used as the etchant. Since the source electrode 504, the drain electrode 505, and the gate electrode 506 are two-layer electrodes including a Ti film and a Cr film, they have excellent etching resistance to an aqueous KI solution. After the wet etching of the metal pattern 502, washing with pure water and rinsing with isopropyl alcohol are sequentially performed. Subsequently, as a drying treatment, for example, a supercritical drying treatment using CO ₂ gas is performed. The supercritical drying treatment using CO ₂ gas is suitable for preventing the AGNR503 from being cut by the surface tension or capillary force of the solution.

In this way, the electronic device 500 including the FET having the AGNR503 as a channel can be manufactured. The electronic device 500 can be operated by the graphene-specific high mobility carrier.

(Sixth Embodiment)
Next, the sixth embodiment will be described. A sixth embodiment relates to an electronic device including a back gate type thin film transistor (TFT) using an AGNR network film as a channel. FIG. 32 is a cross-sectional view showing the electronic device according to the sixth embodiment.

As shown in FIG. 32, the electronic device 600 according to the sixth embodiment is formed on an insulating substrate 601, a gate electrode 606 formed on the insulating substrate 601 and an insulating substrate 601 and a gate electrode 606, and is a gate electrode. It has an insulating layer 607 that covers the 606. The electronic device 600 has an AGNR network film 603 provided on the insulating layer 607 above the gate electrode 606. The network film 603 is a film formed by contacting a plurality of AGNR150s according to the first embodiment with each other. The source electrode 604 and the drain electrode 605 are formed on the insulating layer 607 so as to be in contact with both ends of the network film 603. A protective layer 621 is formed on the network film 603 between the source electrode 604 and the drain electrode 605. The insulating layer 607 functions as a gate insulating layer.

As the insulating substrate 601, for example, a Si substrate on which a thermal oxide film is formed can be used. As the network film 603, for example, a network film containing a plurality of AGNR150 is formed. As the protective layer 621, for example, a film that does not easily chemically bond with C constituting the network film 603 can be used. Specifically, Cr _{2O 3} , SiO ₂ , Al ₂ O ₃ , Sc ₂ O ₃ , MnO ₂ , and so on. Layers of ZnO, _Y2O3 , _{ZrO2 , MoO3} and _RuO2 can be used for the protective layer 621. _In this example, the _Cr2O3 layer is formed as the protective layer 621.

The source electrode 604, the drain electrode 605 and the gate electrode 606 have, for example, a Ti film having a thickness of 0.5 nm to 2 nm and a Cr film having a thickness of 20 nm to 50 nm on the Ti film, and the source electrode 604 and the drain. The distance from the electrode 605 is, for example, 10 nm to 50 nm. As the material of the insulating layer 607, HfO ₂ , Al ₂ O ₃ , Si ₃ N ₄ , HfSiO, HfAlON, Y ₂ O ₃ , SrTiO ₃ , PbZrTIO ₃ , Bathio ₃ , and the like can be used. In this example, an HfO ₂ film having a thickness of 5 nm to 10 nm is formed as the insulating layer 607.

Next, a method of manufacturing the electronic device 600 according to the sixth embodiment will be described. 33 to 40 are sectional views showing a method of manufacturing an electronic device according to a sixth embodiment.

First, as shown in FIG. 33, a metal layer 652 is formed on the insulating substrate 651. The insulating substrate 651 and the metal layer 652 are included in the growth substrate 650. Next, the AGNR network film 603 is formed on the metal layer 652. As the insulating substrate 651, 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 Miller index of (111) on the surface, or the like can be used. As the metal layer 652, 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 651, and an Au layer is used as the metal layer 652.

The network film 603 can be formed by using the GNR precursor 100 according to the first embodiment. As a pretreatment for forming the network film 603, the surface cleaning treatment of the metal layer 652 is performed in the same manner as the surface cleaning treatment of the metal pattern 502. The network film 603 is formed in situ in an ultra-high vacuum vacuum chamber without exposing the surface-cleaned metal layer 652 to the atmosphere. In the formation of the network film 603, the vapor deposition film thickness of the GNR precursor 100 is 2ML to 4ML. By setting the vapor deposition film thickness of the GNR precursor 100 to 2 ML to 4 ML, it is possible to form a network film 603 in which the individual AGNRs are in contact with each other.

After that, the protective layer 621 is formed on the network film 603. The protective layer 621 protects the channel from the residue of the organic support layer used in the subsequent transfer of the channel. As the protective layer 621, a layer that does not easily chemically bond with C constituting the network film 603 can be used, and the Cr _{2O 3} layer 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 layer 621. When the Cr ₂ O ₃ layer is used, for example, after the network film 603 is formed, a Cr metal layer is formed on the network film 603 in situ by a vapor deposition method without exposure from a vacuum chamber, and the film is exposed to the atmosphere. The Cr metal layer can be transformed into a Cr ₂ O ₃ layer by natural oxidation. For example, the vapor deposition rate of the Cr metal layer is 0.01 nm / sec to 0.05 nm / sec, and the thickness is 1 nm to 3 nm. Layers 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 also be formed in the same manner. It should be noted that Ti and Ni are likely to chemically bond with C constituting the network film 603 to form TiC _x and NiC _x .

Subsequently, as shown in FIG. 34, an organic support layer 622 is formed on the protective layer 621. As the support layer 622, for example, a layer of polymethylcrylic (PMMA) of acrylic resin is used. The layer of PMMA can be formed to a thickness of 100 nm to 500 nm by, for example, a spin coating method. As the support layer 622, an epoxy resin, a heat release tape, an adhesive tape, various photoresists, and an electron beam resist may be used. These laminated films may be used.

Next, as shown in FIG. 35, by removing the metal layer 652, the laminate of the support layer 622, the protective layer 621, and the network film 603 is separated from the insulating substrate 651. When the Au layer is used as the metal layer 652, the metal layer 652 can be removed by wet etching using an KI aqueous solution. After that, the laminated body of the protective layer 621 and the network film 603 is washed with pure water and dried.

On the other hand, as shown in FIG. 36, the gate electrode 606 is separately formed on the insulating substrate 601 and the insulating layer 607 is formed on the insulating substrate 601 and the gate electrode 606. As the insulating substrate 601, for example, a Si substrate on which a thermal oxide film is formed can be used. As the gate electrode 606, a two-layer electrode of a Ti film and a Cr film can be formed by the same method as the gate electrode 506 in the fifth embodiment. As the insulating layer 607, _two HfO layers can be formed by an atomic layer deposition (ALD) method. For example, the thickness of the insulating layer 607 is 5 nm to 10 nm.

Then, the laminated body of the protective layer 621 and the network film 603 is superposed on the laminated body of the insulating substrate 601 and the gate electrode 606 and the insulating layer 607 so that the network film 603 is in contact with the insulating layer 607. In this way, the network film 603 is transferred onto the insulating layer 607.

Then, as shown in FIG. 37, the support layer 622 is removed. When a PMMA layer is used as the support layer 622, the support layer 622 can be removed by immersing it in acetone at about 70 ° C. After removing the support layer 622, a rinsing treatment with, for example, isopropyl alcohol is performed. In general, it is difficult to completely remove PMMA on graphene, and its residue can degrade the properties of graphene. In the present embodiment, since the protective layer 621 is formed between the network film 603 and the support layer 622 of the PMMA, deterioration of the characteristics of the network film 603 due to the residue of PMMA can be suppressed.

Then, as shown in FIG. 38, the protective layer 621 is provided with an opening 624 for a source that exposes a part of the network film 603 and an opening 625 for a drain that exposes another part of the network film 603. Form. In the formation of the openings 624 and 625, 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 secondary cerium ammonium nitrate.

Subsequently, as shown in FIG. 39, a source electrode 604 in contact with the network film 603 through the opening 624 and a drain electrode 605 in contact with the network film 603 through the opening 625 are formed on the insulating layer 607. As the source electrode 604 and the drain electrode 605, a two-layer electrode of a Ti film and a Cr film can be formed by the same method as the source electrode 504 and the drain electrode 505 in the fifth embodiment.

In this way, the electronic device 600 including the TFT having the network film 603 as a channel can be manufactured. The electronic device 600 can be operated by the graphene-specific high mobility carrier.

(7th Embodiment)
Next, the seventh embodiment will be described. A seventh embodiment relates to an electronic device including a top gate type TFT using an AGNR network film as a channel. FIG. 40 is a cross-sectional view showing the electronic device according to the seventh embodiment.

As shown in FIG. 40, the electronic device 700 according to the seventh embodiment has an insulating substrate 601 and a network film 603 provided on the insulating substrate 601. The network film 603 is a film formed by contacting a plurality of AGNR150s according to the first embodiment with each other. The source electrode 704 and the drain electrode 705 are formed on the insulating substrate 601 so as to be in contact with both ends of the network film 603. A protective layer 621 is formed on the network film 603 between the source electrode 704 and the drain electrode 705. The insulating layer 707 is formed so as to spread on the source electrode 704, the protective layer 621, and the drain electrode 705, and the gate electrode 706 is formed on the insulating layer 707. The insulating layer 707 functions as a gate insulating film.

The source electrode 704, the drain electrode 705, and the gate electrode 706 have, for example, a Ti film having a thickness of 0.5 nm to 2 nm and a Cr film having a thickness of 20 nm to 50 nm on the Ti film, and the source electrode 704 and the drain. The distance from the electrode 705 is, for example, 10 nm to 50 nm. As the material of the insulating layer 707, HfO ₂ film, Al ₂ O ₃ , Si ₃ N ₄ , HfSiO, HfAlON, Y ₂ O ₃ , SrTiO ₃ , PbZrTIO ₃ , Bathio ₃ and the like can be used. In this example, an HfO ₂ film having a thickness of 5 nm to 10 nm is formed as the insulating layer 707.

Next, a method of manufacturing the electronic device 700 according to the seventh embodiment will be described. 41 to 45 are sectional views showing a method of manufacturing an electronic device according to a seventh embodiment.

First, as shown in FIG. 41, a laminate of the support layer 622, the protective layer 621, and the network film 603 is formed in the same manner as in the sixth embodiment. Next, the laminated body of the protective layer 621 and the network film 603 is superposed on the insulating substrate 601 so that the network film 603 is in contact with the insulating substrate 601. In this way, the network film 603 is transferred onto the insulating substrate 601.

Then, as shown in FIG. 42, the support layer 622 is removed.

Subsequently, as shown in FIG. 43, the protective layer 621 has an opening 624 for a source that exposes a part of the network film 603 and an opening 625 for a drain that exposes another part of the network film 603. To form.

Next, as shown in FIG. 44, a source electrode 704 in contact with the network film 603 through the opening 624 and a drain electrode 705 in contact with the network film 603 through the opening 625 are formed on the insulating substrate 601. As the source electrode 704 and the drain electrode 705, a two-layer electrode of a Ti film and a Cr film can be formed by the same method as the source electrode 604 and the drain electrode 605 in the sixth embodiment.

After that, as shown in FIG. 45, an insulating layer 707 and a gate electrode 706 extending on the source electrode 704, the protective layer 621 and the drain electrode 705 are formed. The insulating layer 707 and the gate electrode 706 can be formed as follows.

First, a resist pattern having an opening is formed in a region forming the insulating layer 707 and the gate electrode 706. As the resist pattern, for example, a resist pattern having a two-layer structure is used. Next, an opening is formed in the region forming the insulating layer 707 and the gate electrode 706 by electron beam lithography. Then, for example, under a high vacuum of 1 × 10 ^-5 Pa or less, Hf metal is vapor-deposited while introducing O ₂ gas to form an HfO ₂ layer inside the opening and on the resist pattern, and HfO ₂ is formed. A Ti film and a Cr film are formed on the layer. Then, the resist pattern is removed together with the HfO ₂ layer, the Ti film and the Cr film on the resist pattern. That is, lift off is performed. In this way, the insulating layer 707 and the gate electrode 706 can be formed.

In this way, the electronic device 700 provided with the TFT having the network film 603 as a channel can be manufactured.

In this way, the electronic device 700 provided with the TFT having the network film 603 as a channel can be manufactured. The electronic device 700 can be operated by the graphene-specific high mobility carrier.

The material of the insulating substrate 601 is not limited. As the insulating substrate 601, a transparent glass substrate, a flexible polyethylene terephthalate (PET) substrate, or the like may be used. Such a glass substrate and a PET substrate are suitable for application to a display.

Further, the materials of 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 on the Ti film may be used as a source electrode, a drain electrode and a gate electrode. Further, the transparent electrode material may be used for the source electrode, the drain electrode and the gate electrode. Examples of the transparent electrode material include indium tin oxide ₍ ITO), In2O3, SnO2, _AlZNO and _GaZnO .

Although the preferred embodiments and the like have been described in detail above, they are not limited to the above-described embodiments and the like, and various embodiments and the like described above can be applied without departing from the scope of the claims. Modifications and substitutions can be added.

Hereinafter, various aspects of the present disclosure will be described together as an appendix.

（付記３）
第１リボン幅を備えた第１セグメントと、
前記第１リボン幅よりも小さい第２リボン幅を備えた第２セグメントと、
を含み、
前記第１セグメントと前記第２セグメントとがリボン長さ方向に周期的にヘテロ接合していることを特徴とする付記２に記載のグラフェンナノリボン。
（付記４）
前記第１セグメントと前記第２セグメントとの間でトポロジカル不変量Ｚ_２が相違することを特徴とする付記３に記載のグラフェンナノリボン。
（付記５）
付記２乃至４のいずれか１項に記載のグラフェンナノリボンを電界効果トランジスタのチャネルに有することを特徴とする電子装置。
（付記６）
金属基材上で、付記１に記載のグラフェンナノリボン前駆体を第１温度に加熱して、Ｘの脱離及びＣ－Ｃ結合反応を誘起し、前記金属基材上にポリマーを得る工程と、
前記ポリマーを前記第１温度よりも高い第２温度に加熱して、Ｙの脱離及びＣ－Ｃ結合反応を誘起する工程と、
を有することを特徴とするグラフェンナノリボンの製造方法。
（付記７）
前記第１温度は、Ｔ_Ｘ以上Ｔ_Ｙ未満の温度であり、
前記第２温度は、Ｔ_Ｙ以上の温度であることを特徴とする付記６に記載のグラフェンナノリボンの製造方法。
（付記８）
付記６又は７に記載の方法により、前記金属基材上にグラフェンナノリボンを製造する工程と、
前記グラフェンナノリボンをチャネルに有するトランジスタを形成する工程と、
を有することを特徴とする電子装置の製造方法。
（付記９）
前記トランジスタを形成する工程は、
前記グラフェンナノリボンに接するソース電極及びドレイン電極を形成する工程と、
前記金属基材のうち前記ソース電極と前記ドレイン電極との間の部分を除去する工程と、
前記ソース電極と前記ドレイン電極との間の部分で、前記グラフェンナノリボン上にゲート絶縁層及びゲート電極を形成する工程と、
を有することを特徴とする付記８に記載の電子装置の製造方法。
（付記１０）
前記トランジスタを形成する工程は、
絶縁基板の上方にゲート電極及びゲート絶縁層を形成する工程と、
前記ゲート絶縁層上に前記グラフェンナノリボンを転写する工程と、
前記絶縁基板の上方に、前記グラフェンナノリボンに接するソース電極及びドレイン電極を形成する工程と、
を有することを特徴とする付記８に記載の電子装置の製造方法。
（付記１１）
前記トランジスタを形成する工程は、
絶縁基板上に前記グラフェンナノリボンを転写する工程と、
前記絶縁基板の上方に、前記グラフェンナノリボンに接するソース電極及びドレイン電極を形成する工程と、
前記ソース電極と前記ドレイン電極との間の部分で、前記グラフェンナノリボンの上方にゲート絶縁層及びゲート電極を形成する工程と、
を有することを特徴とする付記８に記載の電子装置の製造方法。 (Appendix 1)
It has a structural formula represented by the above chemical formula (1) and has a structural formula.
In the above chemical formula (1),
n ₁ is 1, 2 or 4
n ₂ is n _1-1 ,
X and Y are F, Cl, Br or I,
A graphene nanoribbon precursor characterized in that the relationship of _TX < _TY is established when the desorption temperatures of _X and _Y from the carbon atoms constituting the six-membered ring are TX and TY, respectively.
(Appendix 2)
It consists of repeating units of the structural formula represented by the following chemical formula (2).
In the following chemical formula (2)
n ₁ is an integer of 1 or more and 6 or less.
n ₂ is a graphene nanoribbon characterized by being n _1-1 .

(Appendix 3)
The first segment with the first ribbon width and
A second segment having a second ribbon width smaller than the first ribbon width,
Including
The graphene nanoribbon according to Appendix 2, wherein the first segment and the second segment are periodically heterozygous in the ribbon length direction.
(Appendix 4)
The graphene nanoribbon according to Appendix 3, wherein the topological invariant Z ₂ is different between the first segment and the second segment.
(Appendix 5)
An electronic device comprising the graphene nanoribbon according to any one of Supplementary Provisions 2 to 4 in the channel of a field effect transistor.
(Appendix 6)
A step of heating the graphene nanoribbon precursor according to Appendix 1 to a first temperature on a metal substrate to induce elimination of X and a CC binding reaction to obtain a polymer on the metal substrate.
The step of heating the polymer to a second temperature higher than the first temperature to induce the elimination of Y and the CC bond reaction.
A method for producing graphene nanoribbons, which comprises.
(Appendix 7)
The first temperature is a temperature of _TX or more and less than _TY .
The method for producing graphene nanoribbons according to Appendix 6, wherein the second temperature is _TY or higher.
(Appendix 8)
A step of manufacturing graphene nanoribbons on the metal substrate by the method described in Appendix 6 or 7.
The step of forming a transistor having the graphene nanoribbon in the channel and
A method for manufacturing an electronic device, which comprises.
(Appendix 9)
The step of forming the transistor is
A step of forming a source electrode and a drain electrode in contact with the graphene nanoribbon, and
A step of removing a portion of the metal substrate between the source electrode and the drain electrode, and
A step of forming a gate insulating layer and a gate electrode on the graphene nanoribbon in a portion between the source electrode and the drain electrode.
The method for manufacturing an electronic device according to Appendix 8, wherein the device is characterized by the above.
(Appendix 10)
The step of forming the transistor is
The process of forming the gate electrode and the gate insulating layer above the insulating substrate,
The step of transferring the graphene nanoribbon onto the gate insulating layer and
A step of forming a source electrode and a drain electrode in contact with the graphene nanoribbon above the insulating substrate, and
The method for manufacturing an electronic device according to Appendix 8, wherein the device is characterized by the above.
(Appendix 11)
The step of forming the transistor is
The process of transferring the graphene nanoribbon onto the insulating substrate,
A step of forming a source electrode and a drain electrode in contact with the graphene nanoribbon above the insulating substrate, and
A step of forming a gate insulating layer and a gate electrode above the graphene nanoribbon in a portion between the source electrode and the drain electrode.
The method for manufacturing an electronic device according to Appendix 8, wherein the device is characterized by the above.

100, 200, 300, 400: GNR precursor 140, 240, 340, 440: Polymer 150, 250, 350, 450, 503: AGNR
151, 251, 351 and 451: 1st segment 152, 252, 352, 452: 2nd segment 500, 600, 700: Electronic device 504, 604, 704: Source electrode 505, 605, 705: Drain electrode 506, 606, 706: Gate electrode 603: Network film

Claims (8)

It has a structural formula represented by the following chemical formula (1) and has a structural formula.
In the following chemical formula (1)
n ₁ is 1, 2 or 4
n ₂ is n _1-1 ,
X and Y are F, Cl, Br or I,
A graphene nanoribbon precursor characterized in that the relationship of _TX < _TY is established when the desorption temperatures of _X and _Y from the carbon atoms constituting the six-membered ring are TX and TY, respectively.

It consists of repeating units of the structural formula represented by the following chemical formula (2).
In the following chemical formula (2)
n ₁ is an integer of 1 or more and 6 or less.
n ₂ is a graphene nanoribbon characterized by being n _1-1 .

The first segment with the first ribbon width and
A second segment having a second ribbon width smaller than the first ribbon width,
Including
The graphene nanoribbon according to claim 2, wherein the first segment and the second segment are periodically heterozygous in the ribbon length direction. The graphene nanoribbon according to claim 3, wherein the topological invariant Z ₂ is different between the first segment and the second segment. An electronic device comprising the graphene nanoribbon according to any one of claims 2 to 4 in the channel of a field effect transistor. A step of heating the graphene nanoribbon precursor according to claim 1 to a first temperature on a metal substrate to induce elimination of X and a CC binding reaction to obtain a polymer on the metal substrate. ,
The step of heating the polymer to a second temperature higher than the first temperature to induce the elimination of Y and the CC bond reaction.
A method for producing graphene nanoribbons, which comprises. The first temperature is a temperature of _TX or more and less than _TY .
The method for producing graphene nanoribbons according to claim 6, wherein the second temperature is _TY or higher. A step of manufacturing graphene nanoribbons on the metal substrate by the method according to claim 6 or 7.
The step of forming a transistor having the graphene nanoribbon in the channel and
A method for manufacturing an electronic device, which comprises.

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