Graphene coated metallic surfaces, devices and method of manufacture thereof

1 . A method for coating a metal surface with graphene comprising the steps of

obtaining a metal having a surface;

obtaining a first graphene molecular precursor comprising at least one compound selected from the group consisting of:

compound A having molecular formula I

G

-

X

i

1

⁢

Y

m

1

⁢

Y

n

2

,

and

formula

⁢

I

compound B having molecular formula II

G

-

X

i

1

⁢

X

j

2

⁢

Y

m

1

⁢

Y

n

2

formula

⁢

II

wherein,

G is a C 6 -C 100 hydrocarbon component,

X 1 is a tethering group to the surface of the metal material,

X 2 is selected from at least one of:

a tethering group to a graphene surface X 2G ,

a tethering group to a metal layer X 2M , and

a tethering group to a non-metal layer X 2N ,

Y 1 , Y 2 are independently selected from the group consisting of hydrogen, halogen radical, hydroxyl and —COOH and i, j, m and n are independent integer numbers having a value selected between 1 and 20, and wherein

(I)

(i) the first graphene molecular precursor further comprises compound C having formula III and optionally compound D having molecular formula IV

G

-

Y

m

1

⁢

Y

n

2

;

formula

⁢

III

G

-

X

j

2

⁢

Y

m

1

⁢

Y

n

2

formula

⁢

IV

and the mol ratio between compound C and the combined amount of compounds A, B and D is between 1:10 to 1000:1, or

(ii) X 1 is selected from the group consisting of —R 1 COOR 2 , —R 1 SO 3 R 2 , —R 1 PO 3 H 2 , —R 1 COH, and R 1 SH wherein R 1 is selected from a bond, C 1-8 saturated or unsaturated, substituted or unsubstituted alkyl; R 2 is H or C 1-8 saturated or unsaturated, substituted or unsubstituted alkyl;

depositing said first graphene molecular precursor on top of the metal surface to obtain a surface at least partially coated with the at least one graphene molecular precursor and bound to the at least one graphene molecular precursor; and

transforming the deposited first graphene molecular precursor into a surface bound graphene interfacial layer,

to obtain a graphene coated metal surface comprising a graphene interfacial layer bound to the surface of the metal; or

(II)

depositing said first graphene molecular precursor on top of the metal surface to obtain a surface at least partially coated with the at least one graphene molecular precursor and bound to the at least one graphene molecular precursor; and

transforming the deposited first graphene molecular precursor into a surface bound graphene interfacial layer to obtain a graphene coated metal surface comprising a graphene interfacial layer bound to the surface of the metal,

obtaining a second graphene precursor comprising at least one compound selected from the group consisting of compound A, compound B, compound C having formula III, compound D having molecular formula IV,

compound E having molecular formula V

G

-

X

i

3

⁢

Y

m

1

⁢

Y

n

2

,

and

formula

⁢

V

compound F having molecular formula VI

G

-

X

i

2

⁢

X

j

3

⁢

Y

m

1

⁢

Y

n

2

formula

⁢

VI

wherein, G is a C 6 -C 100 hydrocarbon component, X 3 is a tethering group to the surface of the graphene coating being different than the tethering group X 2 , Y 1 , Y 2 are independently selected from the group consisting of hydrogen, halogen radical and —COOH and i, j, m and n are independent integer numbers having a value selected between 1 and 20;

and wherein at least one compound of the first graphene molecular precursor, the second graphene molecular precursor or both first and second molecular precursors, is functionalized by group X 2G

depositing the second graphene molecular precursor on top of a graphene coating of the graphene coated metal surface to obtain a graphene coated material wherein the graphene coated metal surface being at least partially coated with the second graphene molecular precursor; and

transforming the deposited second graphene precursor into a top graphene coating;

to obtain a graphene coating comprising at least a graphene interfacial layer and a top graphene coating, the graphene interfacial layer being bound to the surface of the metal.

2 . The method of claim 1 wherein depositing comprises depositing by vacuum deposition.

3 . The method according to claim 2 wherein the vacuum deposition is atomic layer deposition.

4 . The method of claim 1 wherein G is a C 10 -C 100 polycyclic aromatic hydrocarbon (PAH), optionally comprising heteroatoms selected from silicon, sulfur, nitrogen and oxygen.

5 . The method of claim 1 wherein X 2G is selected from the group consisting of C 6 -C 20 aryl unsubstituted or substituted by an electron withdrawing group, C 6 -C 20 substituted or unsubstituted heteroaryl, —R 1 X, —NR 3 R 4 , —R 1 COOH, —R 1 SO 3 R 2 , and —R 1 PO 3 H 2 , wherein R 1 is selected from a bond, C 1-8 saturated or unsaturated, substituted or unsubstituted alkyl, X is selected from —OH, —Cl, —Br, —F, or —I, R 3 and R 4 are independently selected from H, C 1-8 saturated or unsaturated optionally derivatized alkyl.

6 . The method of claim 5 wherein the electron withdrawing group is selected from the group consisting of a halide, —CN, —NO 2 , —CHO, —COOR 2 , and —C(═O) R 5 , wherein R 2 is H or C 1-8 saturated or unsaturated, substituted or unsubstituted alkyl and R 5 is C 1-8 saturated or unsaturated, substituted or unsubstituted alkyl.

7 . The method of claim 1 wherein X 2N is selected from the group consisting of C 1-8 siloxyl, —R 1 SO 3 R 2 , —R 1 PO 3 H 2 , —SiR 1 R 2 R 3 , —NR 4 R 5 , —R 5 COOR 6 and R 7 SH wherein R 1 , R 2 , and R 3 are independently selected from H, —OH, —Cl, —Br, —F, —I, C 1-8 saturated or unsaturated optionally derivatized alkyl, and at least one of R 1 , R 2 , and R 3 is —Cl, —Br, —F or —I; R 4 and R 5 are independently selected from H, C 1-8 saturated or unsaturated optionally derivatized alkyl; R 6 is H or C 1-8 saturated or unsaturated optionally derivatized alkyl; R 7 is a bond or C 1-8 saturated or unsaturated optionally derivatized alkyl.

8 . The method of claim 1 wherein Y 1 and Y 2 are independently selected from the group consisting of H, —OH, —Cl, —Br, —F, —I.

9 . The method of claim 1 further comprising maintaining the temperature of the metallic surface at below 400° C.

10 . The method of claim 1 further comprising at least one of: (i) detecting the Raman scattering while radiating with a second radiation source, IR light, characterizing presence of graphene, the Raman scattering is indicative of a presence of a full layer of graphene; (ii) measuring contact angle of the surface; (iii) detecting fluorescence of the surface; and (iv) measuring surface contact angle of the substrate and identifying typical surface contact angle measurement as evidence for formation of a desired surface after each step of the manufacturing process.

11 . The method of claim 1 , wherein at least one of the following holds true: (i) the graphene coating being bound to the metal surface by covalent bonds; (ii) the graphene coating defect ratio is lower than 1E-10 defects/cm 2 ; and (iii) the graphene coated metal material is for use in a device selected from the group consisting of interconnection, a device selected from back end of lines (BEOL), nano-electro mechanical device; Organic LED, transparent conductive electrodes, electro-optical sensor, graphene transistor, or a high conduction interconnect.

12 . The method of claim 1 wherein for condition (II), the steps of obtaining a second graphene molecular precursor, depositing of said second graphene molecular precursor on top of the graphene coating and transforming the deposited graphene molecular precursor to a top graphene coating are repeated to obtain a graphene coating comprising at least three graphene coatings, the graphene interfacial layer being bound to the first surface.

13 . The method of claim 1 wherein for condition (II), at least one of the compounds of the second graphene molecular precursor comprises a compound having a tethering group X 2n , and further comprising: depositing a non-metal material on top of the top graphene coating to obtain a layered structure comprising a graphene coating bound to the metal surface and bound to a non-metal material layer on top of the graphene coating.

14 . The method of claim 1 wherein for condition (II), the metal material is a first metal material, at least one of the compounds of the second graphene molecular precursor comprises a compound having a tethering group X 2m and further comprising the step of depositing a second metal having a surface being same as, or different from the first metal surface on top of the top graphene coating, to obtain a layered structure comprising a graphene coating bound to the metal surface and bound to the second metal material layer on top of the graphene coating.

15 . The method of claim 1 wherein for condition (II), at least two separate first graphene molecular precursor mixtures are obtained, at least one mixture comprising compound C and at least one other mixture comprising compound A and compound B, wherein depositing comprises separately depositing separate mixtures to obtain an interspersed coating with at least two graphene molecular precursors.

16 . The method of claim 1 wherein the metal material is a first metal material and at least one compound of the first graphene molecular precursor having tethering groups X 2m to a second metal having a surface being same as, or different from the first metal material, and further comprising depositing a second metal having a surface being same as, or different from the first metal surface on top of the graphene interfacial layer, to obtain a layered structure comprising a graphene interfacial layer bound to the metal surface and bound to the second metal material layer on top of the graphene interfacial layer.

17 . The method of claim 1 wherein for condition (II), (i) the first graphene molecular precursor comprises a compound comprising X 2G being a basic group—and the second graphene molecular precursor comprises a compound comprising X 2G being an acidic group —R 1 COOH, or (ii) the first graphene molecular precursor comprises a compound comprising X 2G being an acidic group —R 1 COOH, and the second graphene molecular precursor comprises a compound comprising X 2G being a basic group X 2 is —NR 3 R 4 .

18 . A graphene coated metal surface comprising a covalent bond between the graphene coating and the metal surface, using the method of claim 1 .

19 . The graphene coated metal surface according to claim 18 further characterized by at least one of:

(i) a graphene defect density equal to or lower than 10 12 defects per cm 2 ;

(ii) essentially free of catalytic metal residue;

(iii) graphene coverage higher than 90%;

(iv) comprises at least two layers of graphene coatings;

(v) comprising at least a graphene interfacial layer bound to the surface of the metal material and a top graphene coating positioned above the bottom graphene coating;

(vi) comprises between 2-6 layers of graphene;

(vii) comprises a bond between two adjacent graphene coatings;

(viii) comprises a bond selected from a covalent bond and a π-π interaction between two adjacent graphene coatings;

(ix) a top graphene layer of the graphene coating is bound to a surface of a material deposited on top of said top graphene layer.

20 . A device comprising a graphene coated metal surface of claim 19 .