US6413587B1
Expired / Lapsed
US
⏱️ 0.0 years remaining
Method for forming polymer brush pattern on a substrate surface
Assignee: University of California
•
Filing: 1999-03-02
•
Granted: 2002-07-02
•
Expires: 2019-03-02
Abstract
Abstract A method is disclosed for providing a patterned surface wherein predetermined regions of the surface are masked with a self-assembled monolayer ("SAM") covalently bound to a brush polymer overlayer. The remainder of the substrate surface will generally be functionalized with a second self-assembled monolayer. Preferably, the method involves a microcontact printing technique, wherein a molecular moiety capable of spontaneously forming an SAM upon transfer to a surface is "stamped" onto a substrate surface, followed by growth (or covalent attachment) of a polymer on exposed functional groups within the SAM molecules. Coverage of surface regions with both an SAM and a polymer overlayer provides a number of advantages, particularly with regard to surface masking during etching and the like. The method is useful in the manufacture of microelectronic circuitry, biosensors, high-density assay plates, and the like.
Inventors
- 👤 Craig Jon Hawker
- 👤 James Lupton Hedrick
- 👤 Nicholas Abbott
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-07 13:17
CPC Classifications
B; B05; B05D; B05D1/00; B05D1/18; B05D1/185; B05D1/28; B05D1/283; B82; B82Y; B82Y10/00; B82Y30/00; B82Y40/00; G; G03; G03F; G03F7/00; G03F7/0002; G03F7/16; G03F7/165; Y; Y10; Y10T; Y10T428/00; Y10T428/24; Y10T428/24802; Y10T428/24826; Y10T428/24917; Y10T428/26; Y10T428/261; Y10T428/268; Y10T428/269
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
283 words
A method for preparing a substrate having a patterned surface, comprising: (a) providing a substrate having a surface to which molecular moieties can covalently bind; (b) identifying regions on the substrate surface that correspond to a desired surface pattern; (c) derivatizing the identified regions on the substrate surface by contacting the identified regions with a molecular moiety A-B, wherein A is a reactive terminus and B is an inert segment, under conditions effective to bring about covalent binding of the molecular moiety A-B to the surface through the reactive terminus A, thus providing surface-bound B segments in the identified regions with the remainder of the surface comprised of unmodified regions; (d) contacting the derivatized substrate surface provided in (c) with a molecular moiety A′-L-C, wherein A′ is a reactive terminus and may or may not be the same as A, L is a linker, and C is a molecular segment terminating in a functional group, under conditions effective to bring about covalent binding of the molecular moiety A′-L-C to the unmodified regions of the substrate surface through the reactive terminus A′, whereby a modified substrate surface is provided having surface-bound B segments in the derivatized regions and surface-bound C segments on the remainder of the surface; and (e) contacting the modified surface provided in (d) with a polymerizable composition of monomers under conditions effective to result in polymerization of the monomers at an initiation site composed of the functional group of the surface-bound C segment, wherein the polymerization is selected from the group consisting of living free radical polymerization, ring-opening polymerization, metathesis polymerization, and cationic polymerization and results in the binding of a polymer to the functional groups of the surface-bound C segments.
Claim 2
Independent Claim
283 words
A method for preparing a substrate having a patterned surface, comprising: (a) providing a substrate having a surface to which molecular moieties can covalently bind; (b) identifying regions on the substrate surface that correspond to a desired surface pattern; (c) derivatizing the identified regions on the substrate surface by contacting the identified regions with a molecular moiety A-B, wherein A is a reactive terminus and B is an inert segment, under conditions effective to bring about covalent binding of the molecular moiety A-B to the surface through the reactive terminus A, thus providing surface-bound B segments in the identified regions with the remainder of the surface comprised of unmodified regions; (d) contacting the derivatized substrate surface provided in (c) with a molecular moiety A′-L-C, wherein A′ is a reactive terminus and may or may not be the same as A, L is a linker, and C is a molecular segment terminating in a functional group, under conditions effective to bring about covalent binding of the molecular moiety A′-L-C to the unmodified regions of the substrate surface through the reactive terminus A′, whereby a modified substrate surface is provided having surface-bound B segments in the derivatized regions and surface-bound C segments on the remainder of the surface; and (e) contacting the modified surface provided in (d) with a polymerizable composition of monomers under conditions effective to result in polymerization of the monomers at an initiation site composed of the functional group of the surface-bound C segment, wherein the polymerization is selected from the group consisting of living free radical polymerization, ring-opening polymerization, metathesis polymerization, and cationic polymerization and results in the binding of a polymer to the functional groups of the surface-bound C segments.
Claim 3
Dependent Claim
11 words
The method of claim 1 , wherein the substrate is metallic.
Claim 4
Dependent Claim
15 words
The method of claim 1 , wherein the substrate is comprised of a metal oxide.
Claim 5
Dependent Claim
11 words
The method of claim 1 , wherein the substrate is silicon-containing.
Claim 6
Dependent Claim
11 words
The method of claim 1 , wherein the substrate is polymeric.
Claim 7
Dependent Claim
42 words
The method of claim 1 , wherein (b) is conducted by stamping the substrate surface with a stamp coated with the molecular moiety A-B in a pattern that is identical to the pattern defined by the identified regions on the substrate surface.
Claim 8
Dependent Claim
18 words
The method of claim 1 , wherein the surface-bound B segments provided in (c) comprise a self-assembled monolayer.
Claim 9
Dependent Claim
18 words
The method of claim 1 , wherein the surface-bound -L-C segments provided in (d) comprise a self-assembled monolayer.
Claim 10
Dependent Claim
46 words
The method of claim 1 , wherein A is selected from the group consisting of —OH, —SH, —NH 2 , —CONH 2 , —COOH, —SO 3 H, —CN, —PO 3 H, —SiCl 3 , —SiR 2 Cl, —SR and —SSR wherein R is alkyl or aryl.
Claim 11
Dependent Claim
51 words
The method of claim 1 , wherein A′ is selected from the group consisting of —OH, —SH, —NH 2 , —CONH 2 , —COOH, —SO 3 H, —CN —OH, —SH, —NH 2 , —PO 3 H, —SiCl 3 , —SiR 2 Cl, —SR and —SSR wherein R is alkyl or aryl.
Claim 12
Dependent Claim
22 words
The method of claim 1 , wherein B is hydrocarbyl of 1 to 20 carbon atoms containing 0 to 6 ether linkages.
Claim 13
Dependent Claim
23 words
The method of claim 11 , wherein B is saturated alkyl containing 1 to 15 carbon atoms and 0 to 4 ether linkages.
Claim 14
Dependent Claim
22 words
The method of claim 1 , wherein L is hydrocarbylene of 1 to 20 carbon atoms containing 0 to 6 ether linkages.
Claim 15
Dependent Claim
23 words
The method of claim 13 , wherein L is saturated alkylene containing 1 to 15 carbon atoms and 0 to 4 ether linkages.
Claim 16
Dependent Claim
31 words
The method of claim 1 , wherein C is selected from the group consisting of —OH, —NH 2 , —COOH, —SO 3 H, —CN, alkoxyamine, azo, peroxide, halide and sulfonyl halide.
Claim 17
Dependent Claim
34 words
The method of claim 1 , wherein the monomers in (e) are vinyl monomers, the composition of monomers further comprises a living free radical polymerization initiator, and the polymerization is living free radical polymerization.
Claim 18
Dependent Claim
29 words
The method of claim 1 , wherein the monomers in (e) are cyclic esters, the composition of monomers further comprises an organometallic promoter, and the polymerization is ring-opening polymerization.
Claim 19
Dependent Claim
14 words
The method of claim 1 , wherein the polymerization in (e) is metathesis polymerization.
Claim 20
Dependent Claim
14 words
The method of claim 1 , wherein the polymerization in (e) is cationic polymerization.
Claim 21
Independent Claim
200 words
A method for etching a substrate surface, comprising: (a) identifying regions on the surface to be protected from etching; (b) contacting the identified regions with a molecular moiety A′-L-C, wherein A′ is a reactive terminus, L is a linker, and C is a molecular segment terminating in a functional group, under conditions effective to bring about covalent binding of the molecular moiety A′-L-C to the surface through the reactive terminus A′, thus providing surface-bound -L-C segments in the identified regions with the remainder of the surface comprised of unmodified, exposed regions; and (c) contacting the surface derivatized in (b) with a polymerizable composition of monomers under conditions effective to result in polymerization of the monomers at an initiation site composed of the functional group of the surface-bound C segment, wherein the polymerization is selected from the group consisting of living free radical polymerization, ring-opening polymerization, metathesis polymerization, and cationic polymerization and results in the binding of a polymer to the functional groups of the surface-bound C segments; and (d) contacting the surface modified in (c) with a reagent that is selected to degrade the unmodified, exposed regions of the surface but that is inert with respect to the surface-bound polymer.
Claim 22
Independent Claim
200 words
A method for etching a substrate surface, comprising: (a) identifying regions on the surface to be protected from etching; (b) contacting the identified regions with a molecular moiety A′-L-C, wherein A′ is a reactive terminus, L is a linker, and C is a molecular segment terminating in a functional group, under conditions effective to bring about covalent binding of the molecular moiety A′-L-C to the surface through the reactive terminus A′, thus providing surface-bound -L-C segments in the identified regions with the remainder of the surface comprised of unmodified, exposed regions; and (c) contacting the surface derivatized in (b) with a polymerizable composition of monomers under conditions effective to result in polymerization of the monomers at an initiation site composed of the functional group of the surface-bound C segment, wherein the polymerization is selected from the group consisting of living free radical polymerization, ring-opening polymerization, metathesis polymerization, and cationic polymerization and results in the binding of a polymer to the functional groups of the surface-bound C segments; and (d) contacting the surface modified in (c) with a reagent that is selected to degrade the unmodified, exposed regions of the surface but that is inert with respect to the surface-bound polymer.
Claim 23
Dependent Claim
26 words
The method of claim 20 , further including, after (d), removing the surface-bound -L-C groups and the polymer to uncover the identified regions of the surface.
Claim 24
Dependent Claim
18 words
The method of claim 20 , wherein the surface-bound -L-C segments provided in (c) comprise a self-assembled monolayer.
Claim 25
Dependent Claim
12 words
The method of claim 20 , wherein the surface is electrically conductive.
Claim 26
Dependent Claim
34 words
The method of claim 20 , wherein the monomers in (c) are vinyl monomers, the composition of monomers further comprises a living free radical polymerization initiator, and the polymerization is living free radical polymerization.
Claim 27
Dependent Claim
29 words
The method of claim 20 , wherein the monomers in (c) are cyclic esters, the composition of monomers further comprises an organometallic promoter, and the polymerization is ring-opening polymerization.
Claim 28
Dependent Claim
14 words
The method of claim 20 , wherein the polymerization in (c) is metathesis polymerization.
Claim 29
Dependent Claim
14 words
The method of claim 20 , wherein the polymerization in (c) is cationic polymerization.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 2005-07-01 | 2005-12-31 | 2006-07-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2009-07-01 | 2009-12-31 | 2010-07-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2013-07-01 | 2013-12-31 | 2014-07-02 | $7700.00 | Window Closed / Lapsed |