Mithrene and methods of fabrication of mithrene
Described are metal organochalcognides which are bulk nanomaterials, expressing monolayer properties in their as-synthesized states. Also described are certain novel metal organochalcogenide compositions. Further described are several methods of preparation of metal organochaleogenides, both solution- and vapor deposition-based, and methods of use of the resulting metal chalcogenides in assays and devices.
1. A method of preparing a crystalline metal chalcogenide of Formula 1: [M-Z-Ar] ∞ , the method comprising:
providing a first solution comprising a metal ion, M + , in a first solvent, the metal ion obtained by dissolving a metal component, M p X q , in the first solvent;
providing a second solution comprising a diaryl dichalcogenide, Ar-Z-Z-Ar, in a second solvent; and
contacting the first solution with the second so ion to provide the metal chalcogenide a crystalline, bulk nanomaterial; wherein:
M is selected from the group consisting of silver (Ag), lead (Pb), mercury (Hg), gold (Au), copper (Cu) zinc (Zn), tin (Sn), cobalt (Co), thallium (Tl), (Ga), indium (In) and cadmium (Cd);
p is 1 or 2;
X is an oxide or salt selected from the group consisting of O, NO 3 , SO 4 , Cl, Br, CH 3 CO 2 , CF 3 SO 3 , PF 6 , BF 4 , and ClO 4 ;
q is 1, 2, or 3;
Z is sulfur, selenium, tellurium, or combinations thereof; and
Ar is phenyl or naphthyl.
2. The method of claim 1 , wherein M is Ag.
3. The method of claim 1 , wherein the metal component is AgNO 3 .
4. The method of claim 1 , wherein the first solvent and second solvent are immiscible.
5. The method if claim 4 , wherein the first solvent is water and the second solvent is an aromatic hydrocarbon.
6. The method of claim 5 , wherein the second solvent is toluene.
7. The method of claim 4 , wherein the contacting occurs at the interface of the first and second solvents.
8. The method of claim 7 , wherein the contacting occurs over a period from about to about 1 to about 3 days.
9. The method of claim 7 , wherein the contacting occurs at a temperature from about 15° C. to about 100° C.
10. The method of claim 4 , further comprising recovering the crystalline metal chalcogenide by adhering the crystalline material to a substrate.
11. The method of claim 10 , wherein the adhering is performed by passing the substrate through the liquid interface into the first solution, and withdrawing the substrate through the second solution at an angle of about 45 degrees.
12. The method of claim 4 , further comprising recovering the crystalline metal chalcogenide by:
removing the first solution while retaining the crystalline material and the second solution;
removing the second solution while retaining the crystalline material; and
collecting the crystalline material.
13. The method of claim 10 , wherein the substrate is glass or silicon.
14. The method of claim 1 , wherein the concentration of metal ion M + in the first solution is about 0.1 mM to about 100 mM.
15. The method of claim 1 , wherein the concentration of diaryl dichalcogenide in the second solution is about 0.1 mM to about 100 mM.
16. The method of claim 1 , wherein the first solvent and the second solvent are miscible.
17. The method of claim 16 , wherein the contacting further comprises:
a) adding a stabilizing ligand to the first solution with stirring under an inert atmosphere;
b) cooling the resulting solution to a temperature of about −80° C. to about 0° C.;
c) adding the second solution to the cold first solution with stirring;
d) warming the resulting solution from c) to a temperature of about 20° C. to about 30° C. while stirring;
e) diluting the solution of d) with a dilution solvent while rapidly stirring until the mixture is clear and colorless; and
f) collecting the crystalline product by decanting or filtering.
18. The method of claim 16 , wherein the first solvent and second solvent are independently selected from the group consisting of tetrahydrofuran acetonitrile, dimethylsulfoxide, pyridine, chloroform, dichloromethane, benzene, toluene, and methanol.
19. The method of claim 16 , wherein the first solvent and second solvent are the same.
20. The method of claim 19 , wherein the first solvent and second solvent are THF.
21. The method of claim 17 , wherein the stabilizing ligand is a phosphine.
22. The method of claim 17 , wherein the stabilizing ligand is triphenylphosphine.
23. The method of claim 17 , wherein the dilution solvent is diethyl ether or an aliphatic hydrocarbon.
24. A vapor phase deposition method of preparing a substrate coated with a film comprising a metal chalcogenide of Formula I: [M-Z-R] ∞ , the method comprising:
providing a substrate comprising a coating of a metal, M, or an oxide thereof; and
exposing the substrate coated with metal to a vapor phase comprising a first dialkyl or diaryl dichalcogenide, R 2 Z 2 , for a time sufficient to provide a film of a first [M-Z-R] ∞ , on the substrate; wherein:
the metal or oxide thereof is selected from the group consisting of silver, titanium, zinc, lead, copper, indium, gallium and cadmium;
Z is sulfur, selenium, tellurium, or combinations thereof; and
R is phenyl, naphthyl, biphenyl, methyl, ethyl, propyl, butyl or pentyl.
25. The method of claim 24 , wherein M is silver or silver oxide, Z is selenium, and R is phenyl.
26. The method of claim 24 , wherein the time is from about 12 hours to about 14 days.
27. The method of claim 24 , wherein the exposing is conducted at a temperature from about 15° C. to about 100° C.
28. The method of claim 24 , wherein the substrate is glass, quartz, silicon or plastic.
29. The method of claim 24 , wherein the coating of metal on the substrate is about 1 nm to about 100 nm in thickness.
30. The method of claim 24 , wherein the coating of metal on the substrate comprising a first and second layer, the first layer comprising titanium and the second layer comprising silver or silver oxide.
31. The method of claim 24 , wherein the vapor phase further comprises water.
32. The method of claim 31 , wherein the vapor phase is saturated with water.
33. The method of claim 31 , wherein the vapor phase further comprises oxygen.
34. The method of claim 24 , the method further comprising:
exposing the substrate coated with a film of the first [M-Z-R] ∞ to a second dialkyl diaryl dichalcogenide, R 2 Z 2 , in the vapor phase for a time sufficient to provide a film of the second [M-Z-R] ∞ on the substrate; wherein:
the first and second dialkyl or diaryl dichalcogenide are different, and the first and second [M-Z-R] ∞ are different.
35. The method of claim 34 , wherein the film of the first [M-Z-R] ∞ is [Ag-Se-Ph] ∞ and the film of the second [M-Z-R] ∞ is [Ag-Te-Ph] ∞.