Nanocrystalline graphene and method of forming nanocrystalline graphene

Patent metadata

Field	Value
Publication number	US-2022048773-A1
Application number	US-202117515881-A
Country	US
Kind code	A1
Filing date	Nov 1, 2021
Priority date	Nov 29, 2017
Publication date	Feb 17, 2022
Grant date	—

Abstract

Provided are nanocrystalline graphene and a method of forming the nanocrystalline graphene through a plasma enhanced chemical vapor deposition process. The nanocrystalline graphene may have a ratio of carbon having an sp2 bonding structure to total carbon within the range of about 50% to 99%. In addition, the nanocrystalline graphene may include crystals having a size of about 0.5 nm to about 100 nm.

First claim

1 .- 9 . (canceled)

10 . A method of forming a graphene product including a nanocrystalline graphene through a plasma enhanced chemical vapor deposition process, the nanocrystalline graphene including nano-sized crystals and having a ratio of carbon having an sp 2 bonding structure to total carbon within a range of about 50% to 99%, the method comprising:
growing the nanocrystalline graphene directly on a substrate using a plasma of a reaction gas at a temperature of about 700° C. or less, the reaction gas including a carbon source and an inert gas.

11 . The method of claim 10 , wherein a size of the nano-sized crystals ranges from about 0.5 nm to about 100 nm.

12 . The method of claim 10 , wherein the nanocrystalline graphene includes hydrogen in an amount of about 1 at % to about 20 at %.

13 . The method of claim 10 , wherein the nanocrystalline graphene has a density of about 1.6 g/cc to about 2.1 g/cc.

14 . The method of claim 10 , wherein the reaction gas does not include hydrogen gas.

15 . The method of claim 10 , wherein the reaction gas further includes hydrogen gas.

16 . The method of claim 15 , wherein a volume ratio of the carbon source, the inert gas, and the hydrogen gas is about 1:0.01 to 5000:0 to 300.

17 . The method of claim 10 , wherein the carbon source includes at least one of a hydrocarbon gas or a vapor of a liquid precursor containing carbon.

18 . The method of claim 17 , wherein
the liquid precursor includes at least one of an aromatic hydrocarbon having a chemical formula of C x H y (where 6≤x≤42 and 6≤y≤28), a derivative of the aromatic hydrocarbon, an aliphatic hydrocarbon having a chemical formula of C x H y (where 1≤x≤12 and 2≤y≤26), or a derivative of the aliphatic hydrocarbon.

19 . The method of claim 10 , wherein the inert gas includes at least one of argon gas, neon gas, nitrogen gas, helium gas, krypton gas, or xenon gas.

20 . The method of claim 10 , wherein
the growing the nanocrystalline graphene is performed at a process temperature of about 180° C. to about 700° C.

21 . The method of claim 10 , wherein the growing the nanocrystalline graphene is performed at a process pressure of about 0.001 Torr to about 10 Torr.

22 . The method of claim 10 , wherein the growing the nanocrystalline graphene includes generating the plasma of the reaction gas by at least one of a radio frequency (RF) plasma generating device or a microwave (MW) plasma generating device.

23 . The method of claim 22 , wherein
the plasma of the growing the nanocrystalline graphene is a RF plasma having a frequency range of about 3 MHz to about 100 MHz or a MW plasma having a frequency range of about 0.7 GHz to about 2.5 GHz.

24 . The method of claim 10 , wherein a power for generating the plasma of the reaction gas ranges from about 10 W to about 4000 W.

25 . The method of claim 10 , wherein the substrate includes at least one of a group IV semiconductor material, a semiconductor compound, a metal, or an insulative material.

26 . The method of claim 25 , wherein the group IV semiconductor material includes one of silicon (Si), germanium (Ge), or tin (Sn).

27 . The method of claim 25 , wherein the semiconductor compound includes a material having at least two of silicon (Si), germanium (Ge), carbon (C), zinc (Zn), cadmium (Cd), aluminum (Al), gallium (Ga), indium (In), boron (B), nitrogen (N), phosphorus (P), sulfur (S), selenium (Se), arsenic (As), antimony (Sb), or tellurium (Te) combined with each other.

28 . The method of claim 25 , wherein the metal includes at least one of copper (Cu), molybdenum (Mo), nickel (Ni), aluminum (Al), tungsten (W), ruthenium (Ru), cobalt (Co), manganese (Mn), titanium (Ti), tantalum (Ta), gold (Au), hafnium (Hf), zirconium (Zr), zinc (Zn), yttrium (Y), chromium (Cr), or gadolinium (Gd).

29 . The method of claim 25 , wherein
the insulative material includes at least one of silicon (Si), nickel (Ni), aluminum (Al), tungsten (W), ruthenium (Ru), cobalt (Co), manganese (Mn), titanium (Ti), tantalum (Ta), gold (Au), hafnium (Hf), zirconium (Zr), zinc (Zn), yttrium (Y), chromium (Cr), copper (Cu), molybdenum (Mo), or gadolinium (Gd), or an oxide thereof, or a nitride thereof, or a carbide thereof, or a derivative thereof.

30 . The method of claim 29 , wherein at least one of the oxide, the nitride, the carbide, or the derivative includes hydrogen (H).

31 . The method of claim 25 , wherein the substrate further includes a dopant.

32 . The method of claim 10 , further comprising:
pretreating a surface of the substrate using a reducing gas before the growing of the nanocrystalline graphene.

33 . The method of claim 32 , wherein the reducing gas includes at least one of hydrogen, nitrogen, chlorine, fluorine, ammonia, or a derivative thereof.

34 . The method of claim 33 , wherein the reducing gas further includes an inert gas.

35 . The method of claim 10 , further comprising:
forming a second nanocrystalline graphene after the growing the nanocrystalline graphene directly on the substrate, wherein the growing the nanocrystalline graphene directly on the substrate forms a first nanocrystalline graphene directly on the substrate using a first mixing ratio of the reaction gas to form the plasma, the forming the second nanocrystalline graphene forms the second nanocrystalline graphene on the first nanocrystalline graphene using a second mixing ratio of the reaction gas to form the plasma, and the second mixing ratio is different than the first mixing ratio.

36 . The method of claim 35 , wherein the reaction gas does not include hydrogen gas.

37 . The method of claim 35 , wherein the reaction gas further includes a hydrogen gas.

38 . A device comprising:
a plasma enhanced chemical vapor deposition machine configured to perform the method of claim 10 .

39 . A method of forming a graphene product including a nanocrystalline graphene through a plasma enhanced chemical vapor deposition process, the nanocrystalline graphene including nano-sized crystals and having a ratio of carbon having an sp 2 bonding structure to total carbon within a range of about 50% to 99%, the method comprising:
injecting a reaction gas into a reaction chamber, the reaction gas including a carbon source and an inert gas into a reaction chamber; generating a plasma of the reaction gas in the reaction chamber; and growing the nanocrystalline graphene directly on a surface of a substrate using the plasma of the reaction gas at a temperature of about 700° C. or less.

40 . The method of claim 39 , wherein a size of the nano-sized crystals ranges from about 0.5 nm to about 100 nm.

41 . The method of claim 39 , wherein the nanocrystalline graphene includes hydrogen in an amount of about 1 at % to about 20 at %.

42 . The method of claim 39 , wherein the nanocrystalline graphene has a density of about 1.6 g/cc to about 2.1 g/cc.

43 . The method of claim 39 , further comprising:
pretreating the surface of the substrate using a reducing gas.

44 . The method of claim 39 , further comprising:
forming a second nanocrystalline graphene after the growing the nanocrystalline graphene directly on the surface of the substrate, wherein the grow

Assignees

• Samsung Electronics Co Ltd

Inventors

• Song Hyunjae
• Shin Keunwook
• Shin Hyeonjin
• Lee Changseok
• Kim Changhyun
• Byun Kyungeun
• Lee Seungwon
• Lee Eunkyu

Classifications

• H10D64/0113

  the conductive layers comprising highly doped semiconductor materials, e.g. polysilicon layers or amorphous silicon layers · CPC title

• H10W20/425

  Barrier, adhesion or liner layers · CPC title

• H10W20/4462

  Carbon or carbon-containing materials, e.g. graphene · CPC title

• H10W20/033

  in openings in dielectrics · CPC title

• H10W20/037

  the barrier, adhesion or liner layers being on top of a main fill metal · CPC title