Method of synthesizing hybrid metal oxide materials and applications thereof
The present invention relates to metal oxide coating materials that can be used as thin film thin film coatings on various substrate surfaces. The invention also concerns a method of making metal oxide material which are stable in aqueous phase and that can be deposited on a substrate by liquid phase deposition, such as spin-on deposition. The new materials can be patterned lithographically or non-lithographically and are applicable for building up various electronic and opto-electronic device structures, such as anti-reflection layers, high-k interlayer and gate oxide structures for ICs, etch stop layer, CMP stop layer, solar cells, OLEDs packaging, optical thin film filters, optical diffractive grating applications and hybrid thin film diffractive grating structures.
1. A method of forming a film on top of a substrate, comprising the steps of:
applying a composition on a surface of the substrate, wherein the composition consists of a polymerizable intermediate product in a solution, and wherein the intermediate product is obtained from a complex metal oxide precursor composition;
forming a layer of the composition on the surface;
removing a solvent from the layer; and
annealing the intermediate product in the layer to produce a metal oxide film having a thickness in the range of 1 nm to 500 nm with a single deposition run to form a cross-linked metal oxide film,
wherein the complex metal oxide precursor composition consists of either
(1) at least one metal halogenide having the formula I
MeX m I
wherein Me stands for a metal selected from the group consisting of titanium, germanium, tin, antimony, tantalum, and hafnium, X stands for a halogenide and m represents the valence of the metal, and
at least one metal alkoxide having the formula II
MeOR 1 m II
wherein R 1 stands for a linear or branched, aliphatic or alicyclic alkyl group, which optionally is substituted by 1 to 3 substitutents selected from the group consisting of hydroxy, carboxy, anhydride, oxo, nitro and amido groups, and Me and m have the same meaning as above, or
(2) at least one metal compound selected from the group of compounds having the formula III
X n MeOR 1 p III
wherein Me, X and R 1 have the same meaning as above and n is an integer 0 to m, p is an integer 0 to m, and the sum of n+p is equal to m, m having the same meaning as above.
2. A method of forming a film on top of a substrate, comprising the steps of:
applying a composition on a surface of the substrate, wherein the composition consists of a polymerizable intermediate product in a solution in a solvent, and wherein the intermediate product is obtained from a complex metal oxide precursor composition;
forming a layer of the composition on the surface;
removing a solvent from the layer; and
annealing the intermediate product in the layer to produce a metal oxide film having a thickness in the range of 1 nm to 500 nm with a single deposition run to form a cross-linked metal oxide film,
wherein the complex metal oxide precursor composition consists of either
(1) at least one metal halogenide having the formula I
MeX m , I
wherein Me stands for a metal selected from the group consisting of titanium, germanium, tin, antimony, tantalum, and hafnium, X stands for a halogenide and m represents the valence of the metal, and
at least one metal alkoxide having the formula II
MeOR 1 m , II
wherein R 1 stands for a linear or branched, aliphatic or alicyclic alkyl group, which optionally is substituted by 1 to 3 substitutents selected from the group consisting of hydroxy, carboxy, anhydride, oxo, nitro and amido groups, and Me and m have the same meaning as above, or
(2) at least one metal compound selected from the group of compounds having the formula III
X n MeOR 1 p , III
wherein Me, X and R 1 have the same meaning as above and n is an integer 0 to m, p is an integer 0 to m, and the sum of n+p is equal to m, m having the same meaning as above and wherein at least one of the metal oxide precursors of the complex metal oxide precursor composition was reacted with an organic compound, which contains at least one functional group capable of reacting with the metal element of the precursor, to produce the intermediate product.
3. The method according to claim 2 , wherein the intermediate product is processed from aqueous liquid phase.
4. The method according to claim 1 , wherein the intermediate product is processed to give a high refractive index coating.
5. The method according to claim 2 , wherein the layer is annealed at a temperature in the range of 80 to 350° C., to produce a metal oxide film which contains at least some residues of the organic compound.
6. The method according to claim 5 , wherein the intermediate product is processed at a temperature of about 150° C. to give a film having a refractive index of 1.9 or more and at 350° C. to give refractive index of 2.0 or more.
7. The method according to claim 1 , wherein the organic compound contains radiation sensitive carbon double bonds to allow for polymerization of the intermediate product by photo-crosslinking.
8. The method according to claim 2 , comprising forming a film on a substrate selected from the group of glass, plastics, paper, ceramics and laminates.
9. The method according to claim 1 , comprising forming an optical or electrical film coating on a substrate.
10. The method according to claim 1 , wherein the thin film forms a high refractive index film on top of a grating structure or it acts as a protective layer on top of the grating structure.
11. The method according to claim 1 , comprising forming a high dielectric constant film.
12. The method according to claim 1 , comprising forming an anti-reflection coating.
13. The method according to claim 1 , comprising forming a chemical and dry etching stop layer in lithographic processing.
14. The method according to claim 1 , comprising forming a protective coating in an organic light emitting device.
15. The method according to claim 1 , comprising forming an efficiency-enhancing layer in a solar cell.
16. The method according to claim 1 , comprising forming a high index material in an optical thin film filter.
17. The method according to claim 1 , comprising forming an optical diffractive grating and hybrid thin film diffractive grating by embossing, holography lithography and nano-imprinting of the thin film.
18. The method according to claim 1 , comprising forming a high refractive index abrasion resistant coating.
19. The method according to claim 1 , wherein the film is deposited on the substrate by spin-on deposition.
20. The method according to claim 1 , wherein the intermediate product is capable of polymerizing to form a cross-linked polymer having a molecular weight in excess of 5,000 g/mol and up to 250,000 g/mol.
21. The method according to claim 1 , wherein the layer is annealed at a temperature in excess of 500° C.
22. The method according to claim 2 , wherein Me is titanium.
23. The method according to claim 2 , wherein X is chloride.