ULTRA-THIN MICROPOROUS/HYBRID MATERIALS

• US 20100178468A1
• Filed: 11/14/2008
• Published: 07/15/2010
• Est. Priority Date: 02/13/2006
• Status: Active Grant

• Current Assignee: National Technology & Engineering Solutions Of Sandia LLC (Honeywell International Inc.)
• Original Assignee: UNM Rainforest Innovations (f/k/a STC.UNM) (The University of New Mexico)
• Inventors: JIANG, Ying-Bing, Brinker, C. Jeffrey, Cecchi, Joseph L.
• Granted Patent: US 8,187,678 B2
• Time in Patent Office: Days
• US Class Current: 428/164
• CPC Class Codes: B01D 67/0002 Organic membrane manufacture
• CPC Class Codes: B01D 67/0079 Manufacture of membranes comprising organic and inorganic components
• CPC Class Codes: B01D 67/0083 Thermal after-treatment
• CPC Class Codes: B01D 67/009 with wave-energy, particle-radiation or plasma
• CPC Class Codes: B01D 69/122 Separate manufacturing of ultra-thin membranes
• CPC Class Codes: B01D 69/148 Organic/inorganic mixed matrix membranes
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/45536 Use of plasma, radiation or electromagnetic fields
• CPC Class Codes: C23C 16/45555 applied in non-semiconductor technology
• CPC Class Codes: Y10T 428/24521 with component conforming to contour of nonplanar surface
• CPC Class Codes: Y10T 428/24545 Containing metal or metal compound
• CPC Class Codes: Y10T 428/249953 Composite having voids in a component [e.g., porous, cellular, etc.]

Abstract

Ultra-thin hybrid and/or microporous materials and methods for their fabrication are provided. In one embodiment, the exemplary hybrid membranes can be formed including successive surface activation and reaction steps on a porous support that is patterned or non-patterned. The surface activation can be performed using remote plasma exposure to locally activate the exterior surfaces of porous support. Organic/inorganic hybrid precursors such as organometallic silane precursors can be condensed on the locally activated exterior surfaces, whereby ALD reactions can then take place between the condensed hybrid precursors and a reactant. Various embodiments can also include an intermittent replacement of ALD precursors during the membrane formation so as to enhance the hybrid molecular network of the membranes.

Claims

1. A method for forming an ultra-thin material comprising:

locally activating an exterior surface of a porous support using a remote plasma irradiation such that a plurality of internal pore surfaces are left non-activated; and

depositing a hybrid precursor on the locally activated exterior surface using an atomic layer deposition (ALD) process, wherein the deposited hybrid precursor reacts with a reactant and to form a thin layer material on the exterior surface of the porous support.

2. The method of claim 1, further comprising forming a hierarchical porous support by forming a mesoporous film using evaporation-induced self-assembly on a porous substrate, wherein the mesoporous film comprises alumina or silica and the porous substrate comprises alumina or silica.

3. The method of claim 1, further comprising forming a topographic feature on the porous support to increase an area of local activation, wherein the topographic feature comprises a trench structure with each surface of a plurality of side walls and a trench bottom being activated for forming the thin layer material.

4. The method of claim 1, wherein the step of locally activating the exterior surface comprises:

hydroxylating the exterior surface and the plurality of internal pore surfaces of the porous support;

passivating the hydroxylated surface; and

applying the remote plasma irradiation locally on the passivated exterior surface leaving the internal pore surfaces passivated.

5. The method of claim 4, wherein the step of hydroxylating comprises exposure to UV or ozone.

6. The method of claim 1, wherein the local activation of the exterior surface comprises:

preparing a hydroxylated porous support comprising one or more hydroxyl-groups (—

OH) on each surface of the exterior surface and the plurality of internal pore surfaces;

passivating each surface with one or more non-active groups comprising an alkyl-group; and

locally activating the exterior surface using the remote plasma radiation to convert non-active groups on the exterior surface into active groups for the deposition of the hybrid precursor.

7. The method of claim 1, wherein the hybrid precursor comprises a general formula comprising (X)₃Si—

R′

—

Si(X), (RO)₃Si—

R′

—

Si(OR), R′

—

SiX₃, R′

—

Si(OR)₃, (R′

—

SiX₂)₂O, R′

_nSiX_4-n, M(X)_n, or M(OR)_n, wherein R′

is an inert organic ligand comprising an alkyl, an aromatic group or derivatives thereof;

X is a halide ligand or an active ligand being capable of reacting with the activated exterior surface;

OR is an alkoxide ligand;

M is a metal comprising Si, Ti, Zr, or Al, and n is an integer of 4 or less.

8. The method of claim 1, wherein the hybrid precursor comprises one or more inert organic ligands R′

comprising an alkyl group and two or more active ligands comprising a halide ligand, or an alkoxide ligand;

wherein the hybrid precursor is terminated or bridged with the one or more inert organic ligands R′

comprising —

CH₃, —

C₂H₅, —

C₆H₅, —

CH₂—

, —

C₂H₄—

, or —

C₆H₄—

.

9. The method of claim 1, wherein the hybrid precursor comprises one or more of TiCl₄, ZrCl₄, BTEE (bis(triethoxysilyl)ethane, (C₂H₅O)₃—

Si—

C₂H₄—

Si—

(OC₂H₅)₃), Bis(triethoxysilyl)ethane ((—

CH₂Si(OC₂H₅)₃)₂), Bis(triethoxysilyl)benzene (C₆H₄(Si(OC₂H₅)₃)₂), or 4,4′

-Bis(triethoxysilyl)-1,1′

-biphenyl ((—

C₆H₄Si(OC₂H₅)₃)₂) or CH₃Si(OC₂H₅)₃).

10. The method of claim 1, wherein the reactant comprises one or more of O₂, H₂O, H₂O₂, H₂, or a silane with one or more hydroxyl groups.

11. The method of claim 1, further comprising sulfonating a benzene ring of the thin layer material formed on the locally activated exterior surface to obtain sulfonic acid for providing proton conductivity.

12. An ultra-thin material formed by the method of claim 10, wherein the ultra-thin material is non-porous and comprises a membrane, a barrier layer, a dielectric layer, a low k dielectric layer, or a sensor.

13. The method of claim 1, further comprising treating the thin layer material with an energy source comprising a UV source and a heat source to form a porous thin layer material.

14. An ultra-thin porous material formed by the method of claim 13, wherein the ultra-thin material is a porous membrane, a porous barrier layer, a porous dielectric layer, a porous low k dielectric layer, or a porous sensor material.

15. An ultra-thin material comprising:

a hierarchical porous support comprising a topographical feature; and

an ultra-thin hybrid layer conformally disposed on an exterior surface of the hierarchical porous support by an atomic layer deposition (ALD) process;

wherein the exterior surface comprises an exposed surface of the topographical feature and an exposed surface of the hierarchical porous support.

16. The ultra-thin material of claim 15, wherein the hierarchical porous support comprises a mesoporous film of an evaporation-induced self-assembly on a porous substrate, wherein each of the mesoporous film and the porous substrate comprises an alumina or a silica.

17. The ultra-thin material of claim 15, wherein the hierarchical porous support further comprises a plurality of internal pore surfaces that is passivated to the ALD process.

18. The ultra-thin material of claim 15, wherein the topographical feature comprises a trench structure having an aspect ratio of about 1 or greater.

19. The ultra-thin material of claim 15, wherein the ultra-thin hybrid layer is porous or non-porous and comprises a membrane, a barrier layer, a dielectric layer, a low k dielectric layer, or a sensor material.

20. The ultra-thin material of claim 15, wherein the ultra-thin hybrid layer is formed from an ALD hybrid precursor comprising a general formula of (X)₃Si—

R′

—

Si(X), (RO)₃Si—

R′

—

Si(OR), R′

—

SiX₃, R′

—

Si(OR)₃, (R′

—

SiX₂)₂O, R′

_nSiX_4-n, M(X)_n or M(OR)_n, wherein R′

is an inert organic ligand comprising an alkyl group, an aromatic group or derivatives thereof;

X is a halide ligand or any active ligand being capable reating with the activated exterior surface;

OR is an alkoxide ligand;

M is a metal comprising Si, Ti, Zr, or Al; and

n is an integer of 4 or less.

21. A method for forming an ultra-thin material comprising:

(a) locally activating an exterior surface of a porous support using a remote plasma irradiation, leaving a plurality of internal pore surfaces non-activated;

(b) depositing a first hybrid precursor on the locally activated exterior surface;

(c) reacting the deposited first hybrid precursor with a reactant forming a thin layer on the exterior surface of the porous support;

(d) repeating steps (a)-(c) as desired to form a first plurality of thin layers on the exterior surface of the porous support;

(e) locally activating a surface of the first plurality of thin layers;

(f) depositing a second hybrid precursor on the activated local surface of the first plurality of thin layers;

(g) reacting the deposited second hybrid precursor with a reactant to form a thin layer on the first plurality of thin layers; and

(h) repeating steps of (e)-(g) as desired to form a second plurality of thin layers on the first plurality of thin layers.

22. The method of claim 21, wherein the first hybrid precursor comprises a general formula of (X)₃Si—

R′

—

Si(X), (RO)₃Si—

R′

—

Si(OR), R′

—

SiX₃, R′

—

Si(OR)₃, (R′

—

SiX₂)₂O, or R′

_nSiX_4-n, wherein R′

is an inert organic ligand comprising an alkyl group, an aromatic group or derivatives thereof;

X is a halide ligand or any active ligand being capable reating with the activated exterior surface;

OR is an alkoxide ligand; and

n is an integer of 4 or less.

23. The method of claim 21, wherein the second hybrid precursor comprises a general formula of M(X)_n or M(OR)_n, wherein M is a metal comprising Si, Ti, Zr, or Al;

X is a halide ligand;

OR is an alkoxide ligand; and

n is an integer of 4 or less.

24. A membrane formed by the method of claim 21, wherein the ultra-thin material comprises the first plurality of thin layers and the second plurality of thin layers.

25. The method of claim 21, further comprising forming a porous material by treating the first plurality of thin layers and the second plurality of thin layers with an energy source comprising a UV source and a heat source.

26. A method of making a hybrid material comprising:

providing a hybrid precursor for an atomic layer deposition (ALD) process, wherein the hybrid precursor comprises a general formula of (X)₃Si—

R′

—

Si(X), R′

—

SiX₃, R′

—

Si(OR)₃, (R′

—

SiX₂)₂O, R′

_nSiX_4-n, M(X)_n, or M(OR)_n, wherein R′

is an inert organic ligand comprising an alkyl group, an aromatic group or derivatives thereof;

X is a halide ligand or any active ligand for the ALD process;

OR is an alkoxide ligand;

M is a metal comprising Si, Ti, Zr, or Al; and

n is an integer of 4 or less; and

forming the hybrid material on a support by the ALD process using the provided hybrid precursor.

27. The method of claim 26, further comprising sulfonating a benzene ring of the ALD-deposited hybrid material formed on the support to obtain sulfonic acid for providing proton conductivity.

28. The method of claim 26, further comprising treating the ALD-deposited hybrid material with an energy source, wherein the energy source comprises a UV source or heat source.

29. The method of claim 26, further comprising using an additional precursor selected from the group consisting of TiCl₄ and TMOS to intermittently replace the hybrid precursor comprising BTEE during the ALD process.

30. A device comprising the hybrid material of claim 26, wherein the device is selected from the group consisting of a barrier layer, a dielectric layer, a membrane, and a sensor.