Graphene nanoribbons as semiconductors for organic thin film transistors

Patent metadata

Field	Value
Publication number	US-10014475-B2
Application number	US-201314785323-A
Country	US
Kind code	B2
Filing date	Apr 17, 2013
Priority date	Apr 17, 2013
Publication date	Jul 3, 2018
Grant date	Jul 3, 2018

Abstract

Disclosed herein are graphene nanoribbons, controllable and reproducible methods of synthesizing graphene nanoribbons, and uses thereof. Transistors containing graphene nanoribbons are also disclosed.

First claim

What is claimed is:

1. A method for synthesizing a graphene nanoribbon, the method comprising:
coupling a first aryl monomer and a second aryl monomer to provide a linearly conjugated aryl compound intermediate;
endcapping the linearly conjugated aryl compound intermediate;
coupling the linearly conjugated aryl compound intermediate with a mono-substituted acetylene compound to provide a linearly conjugated aryl compound having a formula (I):

wherein n is an integer of 1 to 100,000;
R 1 to R 4 are independently selected from H

R 5 to R 7 are independently selected from H, alkyl, aryl, and trimethylsilyl;
performing polycyclization of the linearly conjugated aryl compound to provide a graphene nanoribbon precursor, wherein performing polycyclization of the linearly conjugated aryl compound to provide a graphene nanoribbon precursor comprises heating to a temperature of about 20° C. to about 150° C. for about 1 to about 36 hours; and
performing cyclodehydrogenation of the graphene nanoribbon precursor to provide the graphene nanoribbon.

2. A method for synthesizing a graphene nanoribbon, the method comprising:
coupling a first aryl monomer and a second aryl monomer to provide a linearly conjugated aryl compound intermediate;
coupling the linearly conjugated aryl compound intermediate with a mono-substituted acetylene compound to provide a linearly conjugated aryl compound having a formula (I):

wherein n is an integer of 1 to 100,000;
R 1 to R 4 are independently selected from H and

R 5 to R 7 are independently selected from H, alkyl, aryl, and trimethylsilyl;
performing polycyclization of the linearly conjugated aryl compound to provide a graphene nanoribbon precursor; and
performing cyclodehydrogenation of the graphene nanoribbon precursor to provide the graphene nanoribbon.

3. The method of claim 2 , wherein the first aryl monomer has a formula (II):

wherein R 1 to R 6 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, lithium, trifluoromethanesulfonate, mesylate, tosylate, bismuth, a boronic acid, a boronic ester, a boronate ester, an organoborane, an organotrifluoroborate, a magnesium halide, a stannane, a silicon trihalide, an organosilane, an acetyloxy, and a zinc halide; and
wherein the second aryl monomer has a formula (III):

wherein R 7 to R 12 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, lithium, trifluoromethanesulfonate, mesylate, tosylate, bismuth, a boronic acid, a boronic ester, a boronate ester, an organoborane, an organotrifluoroborate, a magnesium halide, a stannane, a silicon trihalide, an organosilane, an acetyloxy, and a zinc halide.

4. The method of claim 2 , wherein the first aryl monomer has a formula (V):

wherein R 1 to R 5 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, lithium, trifluoromethanesulfonate, mesylate, tosylate, bismuth, a boronic acid, a boronic ester, a boronate ester, an organoborane, an organotrifluoroborate, a magnesium halide, a stannane, a silicon trihalide, an organosilane, an acetyloxy, and a zinc halide; and
wherein the second aryl monomer has a formula (VI):

wherein R 7 to R 11 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, lithium, trifluoromethanesulfonate, mesylate, tosylate, bismuth, a boronic acid, a boronic ester, a boronate ester, an organoborane, an organotrifluoroborate, a magnesium halide, a stannane, a silicon trihalide, an organosilane, an acetyloxy, and a zinc halide.

5. The method of claim 2 , wherein the first aryl monomer is a dihalophenyl diboronate compound and the second aryl monomer is a dihalodiodobenzene compound.

6. The method of claim 2 , wherein coupling a first aryl monomer and a second aryl monomer to provide a linearly conjugated aryl compound intermediate comprises contacting the first aryl monomer with the second aryl monomer in a molar ratio of about 2:1 to about 1:2.

7. The method of claim 6 , wherein coupling a first aryl monomer and a second aryl monomer to provide a linearly conjugated aryl compound intermediate further comprises adding a catalyst.

8. The method of claim 2 , wherein coupling a first aryl monomer and a second aryl monomer to provide a linearly conjugated aryl compound intermediate further comprises adding a solvent, an aqueous base, or a combination thereof.

9. The method of claim 2 , wherein coupling a first aryl monomer and a second aryl monomer to provide a linearly conjugated aryl compound intermediate further comprises heating to a temperature of about 20° C. to about 120° C. for a period of about 1 hour to about 36 hours.

10. The method of claim 2 , further comprising coupling the linearly conjugated aryl compound intermediate with a mono-substituted acetylene compound to form the linearly conjugated aryl compound, wherein the mono-substituted acetylene compound has a formula (IV):

wherein R 12 is selected from hydrogen, aryl, polycyclic aryl, alkyl, copper, zinc, magnesium, tin, boron, silicon, indium, aluminum, lithium, sodium, zinc chloride, mercury chloride, manganese (II) chloride, magnesium bromide, tributyl boron lithium, tributyl aluminum lithium, dibutyl aluminum, trimethyl silicon, tributyl tin, or bis(cyclopentadienyl)dimethyl zirconium; and
R 13 is selected from hydrogen, trimethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, triethylsilyl, triisopropylsilyl, alkyl, phenyl, furanyl, thiophenyl, pyridyl, or poly (m-phenylene) comprising about 2 to about 20 m-phenylene units.

11. The method of claim 10 , wherein R 13 is hydrogen and R 14 is trimethylsilyl.

12. The method of claim 10 , wherein coupling the linearly conjugated aryl compound intermediate with a mono-substituted acetylene compound to form the linearly conjugated aryl compound further comprises contacting the linearly conjugated aryl compound with a fluoride source.

13. The method of claim 12 , further comprising adding a solvent.

14. The method of claim 1 , wherein endcapping the linearly conjugated aryl compound intermediate occurs prior to the polycyclization of the linearly conjugated aryl compound to provide a graphene nanoribbon precursor.

15. The method of claim 1 , wherein endcapping the linearly conjugated aryl compound intermediate comprises coupling the linearly conjugated aryl compound intermediate with an aryl monomer of formula (VI):

wherein R 14 is hydrogen, fluorine, chlorine, bromine, iodine,

Assignees

• Empire Technology Dev Llc

Inventors

• Klein Josef Peter

Classifications

• H10P14/3406 Primary

  Carbon, e.g. diamond-like carbon · CPC title

• H10P14/24

  using chemical vapour deposition [CVD] · CPC title

• C07C2/76

  by condensation of hydrocarbons with partial elimination of hydrogen · CPC title

• C01B32/184

  Preparation · CPC title

• H01L21/0262

  Electricity · mapped topic