Method of producing a thin metal-organic framework film using vapor phase precursors

Patent metadata

Field	Value
Publication number	US-10094020-B2
Application number	US-201515304850-A
Country	US
Kind code	B2
Filing date	Apr 29, 2015
Priority date	Apr 30, 2014
Publication date	Oct 9, 2018
Grant date	Oct 9, 2018

Abstract

A method of producing a metal-organic framework (MOF) film on a substrate is disclosed, the method comprising providing a substrate having a main surface and forming on said main surface a MOF film using an organometallic compound precursor and at least one organic ligand, wherein each of said organometallic compound precursor and said at least one organic ligand is provided only in vapour phase.

First claim

The invention claimed is:

1. A method of producing a metal organic framework (MOF) film on a substrate, the method comprising:
providing a substrate having a main surface; and
forming on said main surface a MOF film using an organometallic compound precursor, selected to form an organometallic compound, and at least one organic ligand,
wherein each of said organometallic compound precursor and said at least one organic ligand is provided in vapor phase.

2. The method according to claim 1 , wherein said main surface further comprises a conformal layer of a dielectric material.

3. The method according to claim 1 , wherein said forming of said MOF film comprises initiating at least a cyclic reaction sequence repeatedly by exposing said main surface to said organometallic compound precursor, thereby depositing said organometallic compound on the exposed surface, and wherein said cyclic reaction sequence is repeated for a first pre-determined number of cycle times ranging between 1 to 100.

4. The method according to claim 3 , wherein said first predetermined number of cycle times ranges between 1 to 20.

5. The method according to claim 3 , wherein said cyclic reaction sequence uses a Molecular Layer Deposition (MLD) process, and wherein said cyclic reaction sequence comprises:
performing a first purge step to remove unreacted organometallic compound precursor;
subjecting said exposed main surface to said at least one organic ligand; and
performing a second purge step to remove unreacted organic ligand.

6. The method according to claim 3 , wherein said cyclic reaction sequence uses an Atomic Layer Deposition (ALD) process, and wherein said cyclic reaction sequence comprises:
performing a first purge step to remove unreacted organometallic compound precursor;
subjecting said exposed main surface to an oxidizing agent, thereby forming a metal oxide on said substrate;
performing a second purge step to remove unreacted oxidizing agent; and
subjecting said metal oxide to said at least one organic ligand for a predetermined duration involving a one-step solid vapour deposition process thereby at least partially converting said metal oxide into said MOF film.

7. The method according to claim 6 , wherein said predetermined duration is determined to provide full conversion of said metal oxide into said MOF film.

8. The method according to claim 6 , wherein said predetermined duration is determined to provide only partial conversion of said metal oxide into said MOF film.

9. The method according to claim 6 , wherein said metal oxide is ZnO.

10. The method according to claim 6 , wherein the cyclic reaction sequence of forming said metal oxide and the subsequent subjection of said metal oxide to said at least one organic ligand is repeated for a second predetermined number of cycle times to produce said MOF film with a pre-determined thickness.

11. The method according to claim 1 , wherein said organometallic compound precursor comprises a metal ion or a cluster of metal ions selected from a group consisting of Zn, Fe, In, Co, Cu, Mn, Li, B, Cd, Hg and Pr.

12. The method according to claim 1 , wherein said organometallic compound precursor comprises a metal ion or a cluster of metal ions selected from a group consisting of Mg, Al, Zr, Hf, Ti and Ta.

13. The method according to claim 1 , wherein said at least one organic ligand is an azole-based organic ligand selected from the group consisting of 2-methylimidazole, 3-(2-pyridyl)-5-(4-pyridyl-1,2,4-triazole or 4,5-dichloroimidazole.

14. The method according to claim 1 , wherein each of said organometallic compound precursor and said at least one organic ligand is provided in a vapor phase.

15. The method according to claim 1 , wherein prior to said forming, further comprising pre-conditioning said main surface of said substrate.

16. The method according to claim 15 , wherein said pre-conditioning step comprises oxidizing said main surface of said substrate.

17. The method according to claim 16 , wherein said oxidizing comprises exposing said main surface of said substrate to ozone or oxygen plasma.

18. The method according to claim 3 , wherein said first predetermined number of cycle times ranges between 1 to 15.

19. The method according to claim 3 , wherein said first predetermined number of cycle times ranges between 1 to 5.

Assignees

• Imec Vzw
• Univ Leuven Kath

Inventors

• Stassen Ivo
• Ameloot Rob
• De Vos Dirk
• Vereecken Philippe M

Classifications

• H10P14/6938

  the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides · CPC title

• H10P14/6339

  deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD · CPC title

• H10P14/6334

  using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition (deposition by physical ablation of a target H10P14/6329) · CPC title

• H10P14/665

  Porous materials · CPC title

• C23C16/45527

  characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations · CPC title