US20040159633A1 - Methods of etching articles via micro contact printing - Google Patents

Abstract

Improved methods of forming a patterned self-assembled monolayer on a surface and derivative articles are provided. According to one method, an elastomeric stamp is deformed during and/or prior to using the stamp to print a self-assembled molecular monolayer on a surface. According to another method, during monolayer printing the surface is contacted with a liquid that is immiscible with the molecular monolayer-forming species to effect controlled reactive spreading of the monolayer on the surface. Methods of printing self-assembled molecular monolayers on nonplanar surfaces and derivative articles are provided, as are methods of etching surfaces patterned with self-assembled monolayers, including methods of etching silicon. Optical elements including flexible diffraction gratings, mirrors, and lenses are provided, as are methods for forming optical devices and other articles using lithographic molding. A method for controlling the shape of a liquid on the surface of an article is provided, involving applying the liquid to a self-assembled monolayer on the surface, and controlling the electrical potential of the surface.

Description

RELATED APPLICATIONS
• This application is a divisional of U.S. application Ser. No. 09/164,733, by Whitesides et al., entitled “Methods of Etching Articles via Microcontact Printing”, filed Oct. 1, 1998, which is a divisional of U.S. application Ser. No. 08/677,309, by Whitesides et al., entitled “Methods of Etching Articles via Microcontact Printing”, filed Jul. 9, 1996, which is a continuation of U.S. application Ser. No. 08/676,951, by Whitesides, et al., entitled “Microcontact Printing On Surfaces and Derivative Articles”, filed Jul. 8, 1996, which is a continuation-in-part of U.S. application Ser. No. 08/397,635, filed Mar. 1, 1995, which is a continuation-in-part of U.S. application Ser. No. 08/131,841, filed Oct. 4, 1993, now U.S. Pat. No. 5,512,131, issued Apr. 30, 1996.[0001]
GOVERNMENT FUNDING
• [0002] This invention was made with government support under Grant Number NIH GM30367 and ONR N00014-86-K-0756. The government has certain rights in the invention.
FIELD OF THE INVENTION
• The present invention relates generally to derivatization and patterning of surfaces and more particularly to the formation of self-assembled molecular monolayers on surfaces using microcontact printing, derivative articles produced thereby, and novel optical elements.[0003]
BACKGROUND OF THE INVENTION
• In fields involving microelectronic devices, sensors, and optical elements, the development of devices that are small relative to the state of the art, controllable, and conveniently and relatively inexpensively reproduced with a relatively low failure rate is important.[0004]
• A well-known method of production of such devices is photolithography. According to this technique, a negative or positive resist (photoresist) is coated onto the exposed surface of a material. The resist then is irradiated in a predetermined pattern, and irradiated (positive resist) or nonirradiated (negative resist) portions of the resist are washed from the surface to produce a predetermined pattern of resist on the surface. This is followed by one or more procedures. For example, the resist may serve as a mask in an etching process in which areas of the material not covered by resist are chemically removed, followed by removal of resist to expose a predetermined pattern of the conducting, insulating, or semiconducting material on the substrate. According to another example, the patterned surface is exposed to a plating medium or to metal deposition under vacuum, followed by removal of resist, resulting in a predetermined plated pattern on the surface of the material. In addition to photolithography, x-ray and electron-beam lithography have found analogous use.[0005]
• While the above-described irradiative lithographic methods may be advantageous in many circumstances, all require relatively sophisticated and expensive apparatus to reproduce a particular pattern on a plurality of substrates, and are relatively time-consuming. Additionally, no method of patterning nonplanar surfaces is commonly available according to these methods. In the field of electronic circuitry, an attempt is often made to save space by stacking planar circuit boards or chips, the boards or chips interconnected with auxiliary contacts. Alternately, a board or chip may be bent or otherwise formed in a nonplanar manner so as to save space, auxiliary contacts connecting components on different sides of the bend. All too often these auxiliary contacts are the cause of circuitry failure, and the attempt to move from the two-dimensional domain to a three-dimensional domain fails. Irradiative lithography provides no remedy to this complication, nor does it provide a method of conveniently and inexpensively reproducing an existing microelectronic circuit pattern, or the surface morphological features of other objects of interest.[0006]
• Additionally, the above-described irradiative techniques are generally not amenable to the patterning of biological species such as proteins, as they typically utilize resists and solvents that are toxic to many biological species.[0007]
• A need exists in the art for a convenient, inexpensive, and reproducible method of plating or etching a surface according to a predetermined pattern. The method would ideally find use on planar or nonplanar surfaces, and would result in patterns having features in the micron and submicron domain. Additionally, the method would ideally provide for convenient reproduction of existing patterns. Additionally, a need exists for the fabrication of surfaces that can pattern portions amenable to attachment of biological species, such as antibodies, antigens, proteins, cells, etc., on the micrometer scale.[0008]
• The study of self-assembled monolayers (SAMs) is an area of significant scientific research. Such monolayers are typically formed of molecules each having a functional group that selectively attaches to a particular surface, the remainder of each molecule interacting with neighboring molecules in the monolayer to form a relatively ordered array. Such SAMs have been formed on a variety of substrates including metals, silicon dioxide, gallium arsenide, and others. SAMs have been applied to surfaces in predetermined patterns in a variety of ways including simple flooding of a surface and more sophisticated methods such as irradiative patterning.[0009]
• Accordingly, a general purpose of the present invention is to solve problems associated with expense, complicated apparatus, and other complications associated with patterning surfaces for electronic, chemical, biological, and optical devices. One object is to provide a method of conveniently and reproducibly producing a variety of SAM patterns on planar and nonplanar surfaces, the patterns having resolution in the submicron domain, and being amenable to plating, etc. Another purpose of the invention is to facilitate the attachment of biomolecules on the submicron scale without loss of biological function. Another purpose of the invention is to provide a method of forming a template from an existing pattern having micron or submicron-domain features, the template conveniently reproducing the preexisting pattern.[0010]
• Another general purpose of the invention is to provide optical elements and devices that are conveniently and inexpensively manufactured, and that are adaptable to a variety of systems.[0011]
SUMMARY OF THE INVENTION
• The present invention provides a method of etching an article that is coated with a thin layer of resist. The method involves contacting a first portion of the resist surface with a stamp to transfer to the first portion a self-assembled monolayer of a molecular species in a first pattern. The self-assembled monolayer is contiguous with an exposed portion of the resist surface in a second pattern. The resist is removed from the surface of the article, according to the second pattern, by contacting the exposed portion of the resist surface with a first etchant that reacts chemically with the resist and that is inert with respect to the self-assembled monolayer. This exposes the surface of the article in the second pattern. A second etchant is applied to the exposed surface of the article that reacts chemically with the article and that is inert with respect to the resist. According to one aspect the resist is an electrical conductor. According to another, the resist is a metal oxide, and can be an oxide of the article. The article can be a semiconductor such as silicon gallium arsenide, or the like, and can have a nonplanar surface.[0012]
• According to one embodiment, the self-assembled monolayer exposes a chemical functionality in the first pattern, and prior to the removing the resist, the molecular species is coated with a protecting species that is compatible with the chemical functionality and incompatible with the first etchant.[0013]
• The present invention provides also a method of etching an article involving contacting a first portion of the surface of the article with a stamp to transfer to the first portion a self-assembled monolayer of a molecular species in a first pattern, the self-assembled monolayer being contiguous with an exposed portion of the surface in a second pattern and exposing a chemical functionality. A protecting species that is compatible with the chemical functionality is applied to the self-assembled monolayer, and the exposed portion of the surface is contacted with an etchant that reacts chemically with the resist and that is incompatible with the protecting species. According to another embodiment, the self-assembled monolayer exposes a chemical functionality, in the first pattern, that is less compatible with the protecting species than is the surface of the article that remains uncovered with the self-assembled monolayer. In this embodiment, the protecting species is positioned on the surface at regions not covered by the self-assembled monolayer and, when the etchant is applied, the etchant etches the article at regions not covered by the protecting species (including those regions originally covered by the self-assembled monolayer).[0014]
• The present invention provides also a method of applying to a surface of an article a self-assembled monolayer of a molecular species. The method involves coating a portion of a stamping surface of a stamp with a self-assembled monolayer-forming molecular species, and transferring from the stamping surface to a first portion of the article surface the molecular species, while applying to a second portion of the article surface contiguous with the first portion a species that is not compatible with the molecular species. According to one aspect the method involves allowing the molecular species to spread evenly from the first portion of the article surface to the second portion of the article surface. According to another aspect the first portion of the article surface includes at least two isolated regions separated by the second portion, and the method involves transferring the molecular species from the stamping surface to the at least two isolated regions of the first portion, while applying to a second portion the species that is not compatible with the molecular species. The molecular species is allowed to spread from each of the at least two isolated regions of the first portion toward each other. The molecular species can be lipophilic and the species that is not compatible with the molecular species hydrophilic, or vice versa, and the article surface can be nonplanar. Prior to or during the transferring step the stamp can be deformed.[0015]
• The present invention also provides a method involving applying to a surface of an article a first region and a second region of a self-assembled monolayer, where the first and the second regions are separated from each other by an intervening region. A species that is incompatible with the molecular species that forms the self-assembled monolayer is applied to the intervening region, and the molecular species is allowed to spread evenly from the first region toward the second region and from the second region toward the first region.[0016]
• The present invention also provides a method of applying to a surface of an article a self-assembled monolayer of a molecular species. The method involves coating a portion of a stamping surface of a flexible stamp with a self-assembled monolayer-forming molecular species, deforming the stamp, and contacting at least a portion of the surface with at least a portion of the stamping surface. The stamp can be deformed by compressing it in a plane approximately parallel to the stamping surface, and/or by applying a force to it in a direction approximately perpendicular to the stamping surface.[0017]
• The present invention also provides a method of making an article, involving etching a pattern into a surface of a template, and molding the article on the surface of the template. This can involve applying to the template a hardenable fluid and-allowing the fluid to harden. For example, a prepolymeric fluid can be applied to the template and polymerized. According to one aspect, the hardenable fluid is a fluid precursor of an elastomer. The etching can be anisotropic etching.[0018]
• The present invention also provides a method of making an article that involves providing a template having a surface anisotropically etched in a pattern, applying a hardenable fluid to the surface, and allowing the fluid to harden.[0019]
• The present invention also provides a method of patterning a self-assembled monolayer on a nonplanar surface of an article. The method involves rolling the nonplanar surface of the article over a stamping surface of a stamp carrying a self-assembled monolayer-forming molecular species, thereby transferring to the nonplanar surface a self-assembled monolayer of the molecular species. According to one aspect, the rolling step involves applying to the nonplanar surface the self-assembled monolayer in a pattern, while leaving portions of the surface contiguous with the self-assembled monolayer exposed. According to one aspect the exposed portions of the surface are etched.[0020]
• The present invention also provides a method of making a lens, involving providing a hardenable fluid precursor of the lens, contacting a surface of the fluid precursor with a liquid that is incompatible with the fluid precursor, and allowing the fluid precursor to harden to form a lens. The precursor can be a prepolymeric fluid, and can be a precursor of an elastomer.[0021]
• The present invention also provides a method of making an article, involving providing a supporting surface having, on a discrete isolated region, a self-assembled monolayer of a molecular species, applying to the self-assembled monolayer a fluid precursor of the article, the precursor having a surface including a first region in contact with the self-assembled monolayer and a second, exposed region contiguous with the first region, contacting the exposed region of the precursor surface with a fluid that is incompatible with the precursor fluid, and allowing the precursor to harden.[0022]
• The present invention also provides a method of making a diffraction grating, involving coating a surface of a template with a hardenable, fluid diffraction grating precursor, allowing the fluid precursor to harden and form a diffraction grating, and removing the diffraction grating from the template.[0023]
• The present invention also provides a method of making an optical element, involving molding an article by coating a mold having an optical surface with a hardenable fluid and allowing the fluid to harden to form an article having an optical surface that correlates to the optical surface of the mold, removing the article from the mold, and contacting the optical surface of the article with a liquid metal.[0024]
• The present invention also provides articles made by the above and other methods, including an article including on its surface an isolated region of a self-assembled monolayer of a molecular species, the isolated region including a lateral dimension of less than 10 microns. Preferably, the dimension is less than 5 microns, more preferably less than 1 micron, more preferably less than 0.5 micron, more preferably less than 0.25 micron, more preferably less than 0.2 micron, more preferably less than[0025]0.15 micron, and most preferably less than 0.1 micron. Also provided is a device including on its surface an pattern of a self-assembled monolayer of a molecular species, the pattern having a lateral dimension of less than 10 microns, or one of the other preferred dimensions above. Also provided is a device including on its surface an pattern of a self-assembled monolayer of a molecular species, the pattern including two closely-spaced regions of a single self-assembled monolayer, or closely-spaced different self-assembled monolayers, the dimension between them being less than 10 microns, or one of the other preferred dimensions above.
• The present invention also provides a diffraction grating including a liquid metal having a surface that is in contact with and correlates to a surface of an article. The article surface correlates to an diffraction grating, and the liquid metal surface is formed thereby into a diffraction grating. The grating can be transparent and flexible, preferably transparent and elastomeric.[0026]
• The present invention also provides an optical element including an elastomer including a void having an optical convex or concave surface, and a liquid metal adjacent the convex or concave surface of the void. Preferably, the liquid metal fills the void and is encapsulated by the elastomer.[0027]
• The present invention also provides a device including an article defining a surface, a first and a second isolated region of a self-assembled monolayer on the surface, the first and second regions separated from each other by less than 10 microns. Preferably, the separation is one of the preferred dimensions above.[0028]
• The present invention also provides a device including an article defining a surface, and a self-assembled monolayer on the surface, forming a pattern having a lateral dimension of less than 10 microns. Preferably, the lateral dimension is one of the preferred dimensions above.[0029]
• The present invention also provides methods utilizing the above and other devices and arrangements, including a method of diffracting electromagnetic radiation. The method involves directing electromagnetic radiation at a liquid metal having a surface that is a diffraction grating to cause diffraction of the electromagnetic radiation, and allowing diffracted electromagnetic radiation to reflect from the surface. The surface of the liquid metal that is a diffraction grating can be deformed (elongated or stretched, bent, compressed, e.g.) to adjust the pattern of diffraction of the electromagnetic radiation.[0030]
• The present invention also provides a method of focusing electromagnetic radiation, involving directing electromagnetic radiation at a liquid metal having a concave surface, and allowing the electromagnetic radiation to reflect from the surface.[0031]
• The present invention also provides a method of controlling the shape of a liquid, involving providing a supporting, electrically-conductive surface having, on a discrete isolated region, a self-assembled monolayer of a molecular species exposing a chemical functionality that is compatible with the liquid, positioning the liquid on the self-assembled monolayer of the molecular species, surrounding the liquid with a fluid electrolyte that is not compatible with the liquid, and adjusting an electrical potential of the electrically-conductive surface to control the shape of the liquid.[0032]
• The present invention also provides a method of printing a self-assembled monolayer on a surface of an article, involving rolling over the surface of the article a nonplanar stamping surface of a stamp carrying a self-assembled monolayer-forming molecular species.[0033]
• Other advantages, novel features and objects of the invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings.[0034]
BRIEF DESCRIPTION OF THE DRAWINGS
• FIGS. 1[0035]a-fillustrate microprinting of a self-assembled molecular monolayer on a surface, utilizing controlled reactive spreading in accordance with the invention;
• FIGS. 2[0036]a-eillustrate silicon surfaces selectively patterned with gold using controlled reactive spreading in conjunction with microprinting in accordance with the invention;
• FIGS. 3[0037]a-cillustrate deformation of a microprinting stamp to achieve patterned self-assembled molecular monolayers with small features in accordance with the invention;
• FIGS. 4[0038]a-dillustrate silicon surfaces selectively patterned with gold via mechanical deformation of a stamp in accordance with the invention;
• FIGS. 5[0039]a-cillustrate a method of applying a patterned self-assembled molecular monolayer to a nonplanar surface in accordance with the invention;
• FIGS. 6[0040]a-cillustrate nonplanar surfaces derivatized using the technique illustrated in FIGS. 5a-c;
• FIG. 7 illustrates an optical fiber having an exterior surface patterned with a self-assembled molecular monolayer according to the invention;[0041]
• FIGS. 8[0042]a-dillustrate a method of etching an article according to the invention;
• FIGS. 9[0043]a-fillustrate a method involving lithographic molding of an article in accordance with the invention;
• FIG. 10 is an atomic force microscope image of an article lithographically molded in accordance with the invention;[0044]
• FIGS. 11[0045]a-fillustrate methods of forming flexible diffraction gratings in accordance with the invention, and a diffraction grating formed thereby;
• FIGS. 12[0046]a-dillustrate a method of forming a flexible lens in accordance with the invention, and a lens formed thereby;
• FIG. 13 illustrates a method for forming an optical element in accordance with the invention;[0047]
• FIG. 14 illustrates apparatus for controlling the shape of a fluid on a surface in lo accordance with the invention;[0048]
• FIGS. 15[0049]aand15billustrate apparatus for controlling the shape of a fluid on two surfaces in accordance with the invention; and
• FIGS. 16[0050]a-eillustrate a method of etching an article in accordance with one embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
• Commonly-owned U.S. patent application Ser. No. 08/131,841, filed Oct. 4, 1993 by Kumar et al. and entitled “Formation of Microstamped Patterns on Surfaces and Derivative Articles”, now U.S. Pat. No. 5,512,131, issued Apr. 30, 1996, the entire content of which is incorporated herein by reference for all purposes, describes stamping, or microprinting, self-assembled monolayers onto surfaces, etching and plating such surfaces, assembling isolated regions of self-assembled monolayers exposing a particular chemical functionality, optionally surrounded by a self-assembled monolayer exposing a different functionality, and derivative articles. U.S. application Ser. No. 08/397,635, filed Mar. 1, 1995, co-pending and commonly-owned, is incorporated herein by reference for all purposes.[0051]
• Referring to FIGS. 1[0052]a-d,a method for applying a self-assembled monolayer of a molecular species to a surface that involves controlled, reactive spreading of the species on the surface is illustrated schematically. The method results in two or more self-assembled molecular monolayers, or two or more regions of a single self-assembled molecular monolayer, that are very closely spaced on the surface. At FIG. 1a,astamp20 is illustrated having asurface22 including a plurality ofindentations24 formed therein that form an indentation pattern. The indentations are contiguous with a stampingsurface26 that defines a stamping pattern. The stamping pattern includes closely-spaced features, that is, the indentations are closely-spaced and this results in the presence of closely-spaced protrusions, the outward-facing surfaces of which define the stampingsurface26.
• Prior to microprinting, stamping[0053]surface26, typically theentire surface22 of the stamp, is coated with amolecular species27.Molecular species27 terminates in a functional group selected to bind to a particular material, and to form an ordered self-assembled monolayer thereupon. In the embodiment illustrated in FIGS. 1a-f,species27 terminates in a functional group selected to bind to asurface28 of anarticle30, and to form a self-assembled monolayer onsurface28. A wide variety of species suitable asspecies27 and surfaces suitable assurface28, that is, species that terminate in a variety of functional groups, and surfaces to which they chemisorb, are described in application Ser. No. 08/131,841.
• [0054]Stamp20 of the present invention may be formed in a variety of ways. In one embodiment,stamp20 is formed by contacting a mold surface with a hardenable material, typically a fluid, which serves as a precursor of the stamp. The fluid is hardened, for example by ionic, nonionic, or free-radical polymerization to form the stamp having a surface contacting the mold surface. A mold surface is advantageously selected to include at least one protrusion, and when the stamp is removed from mold surface, a stamp having a stamping surface including an indentation corresponding to mold surface protrusion results.
• The particular material chosen for formation of[0055]stamp20 should satisfy certain physical characteristics.Stamp20 is advantageously chosen to be elastic, such that stampingsurface26 may very closely conform to minute irregularities insurface28 ofmaterial30 so as to completely transfermolecular species27 thereto, and so as to be amenable to transferring SAMs of molecular materials to nonplanar surfaces. However, stampingsurface26 should not be so elastic that when it is pressed lightly against a surface, stamping surface features deform to the extent that blurring ofmolecular species27 onmaterial surface28 results.
• According to a preferred embodiment,[0056]stamp20 is formed from a polymeric material. Polymeric materials suitable for use in fabrication ofstamp20 may have linear or branched backbones, and may be crosslinked or noncrosslinked, depending upon the particular polymer and the degree of formability desired of the stamp. A variety of elastomeric polymeric materials are suitable for such fabrication, especially polymers of the general classes of silicone polymers, epoxy polymers, and acrylate polymers. Epoxy polymers are characterized by the presence of a three-member cyclic ether group commonly referred to as an epoxy group, 1,2-epoxide, or oxirane. For example, diglycidyl ethers of bisphenol A may be used, in addition to compounds based on aromatic amine, triazine, and cycloaliphatic backbones. Another example includes the well-known Novolac polymers. Materials which may not be suitable for fabrication of stampingsurface26 according to preferred embodiments include polyethylene and polystyrene, which are generally too brittle, (not elastic enough), and polybutadiene, which is generally too elastic.
• Examples of silicone elastomers suitable for use as[0057]stamp20 include those formed from precursors including the chlorosilanes such as methylchlorosilanes, ethylchlorosilanes, and phenylchlorosilanes, and the like. A particularly preferred silicone elastomer is polydimethyl siloxane. Exemplary polydimethyl siloxane polymers include those sold under the trademark Sylgard by the Dow Chemical Company, Midland Mich., and particularly Sylgard 182, Sylgard 184, and Sylgard 186.
• The ability to transfer SAMs to nonplanar surfaces is particularly advantageous in the preparation of microelectronic devices on curved surfaces, for example microconnections between various circuit regions, the connections conforming to a bend to conserve space in an overall circuit-containing region.[0058]Stamp20 should also be formed such that stampingsurface26 comprises an absorbent material selected to absorb SAM-formingmolecular species27 to be transferred to asurface28 to form a SAM thereon. Stampingsurface26 preferably swells to absorbmolecular species27, and/or to absorbmolecular species27 dissolved or suspended in a carrier such as an organic solvent. Such swelling and absorbing characteristics serve the important function of providing good definition of an isolated SAM on a surface. For example, if a dimensional feature of stampingsurface26 includes a substantially square-shaped feature, surface26 should transfermolecular species27 to surface28 ofmaterial30 so as to form SAMs mirroring the substantially square features of stampingsurface26, without blurring. Such blurring results from selection of a stamp which does not absorbmolecular species27. When such a stamp is employed,molecular species27 resides as a fluid on stampingsurface26, rather than partially or fully withinsurface26, and when stampingsurface26contacts material surface28,molecular species27 is dispersed from under stampingsurface26. According to the stamp of the present invention, however,molecular species27 is absorbed into stampingsurface26, and when stampingsurface26contacts material surface28,molecular species27 is not dispersed, but binds to surface28, and removal of stampingsurface26 fromsurface28 results in well-defined SAM features.
• Referring to FIG. 1[0059]b,stamp20 is placed, in a predetermined orientation, adjacent toarticle30 such that stampingsurface26contacts article surface28. Prior to, during, or shortly after stampingsurface26 is brought into contact withsurface28, aspecies32 is applied to portions ofsurface28 ofarticle30 that are not contacted by stampingsurface26. That is,surface28 ofarticle30 includes at least afirst portion34 to which the self-assembled molecular species is transferred from the stamping surface, and at least asecond portion36, contiguous withfirst portion34, to which is appliedspecies32.
• [0060]Species32 is incompatible with self-assembled monolayer-formingmolecular species27. As used herein, “compatible” is used to define species that have at least some mutual attraction, or at least are not mutually repulsive. For example, two polar species are compatible, and two nonpolar species are compatible. Miscible liquids, for example two different aqueous solutions, are compatible species. “Incompatible” is used herein to define species that are mutually repulsive to the extent that they are not miscible. For example, most organic liquids are incompatible with most aqueous solutions. Incompatible liquids will coexist separated by a phase boundary. An etchant that is inert with respect to a species such as a self-assembled monolayer is often inert with respect to the species since it is incompatible with the species. One of ordinary skill in the art can readily select such incompatible species, and a test to determine the compatibility or incompatibility of such species is routine to one of ordinary skill in the art.Species32 is selected as one that does not chemisorb to surface28. Thus,species32 has a lesser affinity forsurface28 than does self-assembled monolayer-formingmolecular species27.
• Typically,[0061]species27 is a hydrophobic liquid or is carried in a hydrophobic liquid, as described in the above-referenced application Ser. No. 08/131,841.Species27 also can be a hydrophilic liquid, or carried in a hydrophilic liquid. When species27 (or a liquid in whichspecies27 is dissolved) is hydrophobic,species32 is selected to be hydrophilic. Whenspecies27 is hydrophilic,species32 is selected to be hydrophobic. It is important only thatspecies27 andspecies32 are incompatible.
• For example,[0062]species27 can include a hydrophobic long-chain alkyl group that terminates in a functional group that spontaneously chemisorbs to surface28, andspecies32 can be water or an aqueous solution. Alternatively,species27 can be a long-chain alkyl group including sufficient heteroatoms to makespecies27 hydrophilic andspecies32 in that case can be a liquid that is sufficiently hydrophobic to be incompatible withspecies27.
• Referring now to FIG,[0063]1c,the method involves allowing stampingsurface26 to remain in contact withsurface28 for a period of time sufficient to allowmolecular species27 to spread fromportion34 ofsurface28 ontoportion36 of the surface. This occurs asspecies27, transferred from stampingsurface26, has a greater affinity forsurface28 ofarticle20 than doesspecies32.
• [0064]Stamp20 is maintained in contact witharticle30 for a period of time sufficient to allowspecies27 to spread oversurface28 to a desired extent. The extent of spreading is, typically, approximately proportional to the time of contact betweenstamp20 andarticle30.Stamp20 is advantageously allowed to contactarticle30 for a period of time sufficient to allowspecies27 to spread from each portion of stampingsurface26 toward an adjacent portion. In this way,species27 is allowed to spread acrosssurface28 to form an increasingly narrow gap38 (FIG. 1d) onsurface28.Gap38 onsurface28 thus is not coated withspecies27.
• The presence of[0065]incompatible species32 applied to portions ofsurface28 that are not coated withspecies27 facilitates the spreading ofspecies27 oversurface28 in a smooth, well-defined manner. That is,species27 does not spontaneously chemisorb at random,isolated portions36 ofsurface28 between adjacent regions of stampingsurface26 via vapor transport or the like. The method of the invention results in very well-defined, very closely-spaced regions ofspecies27 onsurface28.
• In FIG. 1[0066]d,stamp20 has been removed fromarticle30, and a scanning electron micrograph of the surface ofarticle30 that has been patterned according to the embodiment illustrated is shown in FIG. 1e.In the embodiment illustrated,dimension40, the width ofindentations24 between protrusions ofstamp20 that define stampingsurface26, is 3 microns, while the dimension ofgap38 between adjacent regions of self-assembledmonolayer27 that have spread toward each other is 0.1 micron.
• FIG. 1[0067]eis a scanning electron micrograph of asilicon article30, coated with a thin layer of gold, upon the surface of whichspecies27 has been allowed to spread in accordance with the method illustrated in FIGS. 1a-d.After removal ofstamp20, an etchant is applied to the surface. The etchant is not compatible withspecies27, andspecies27 is therefore undisturbed by the etchant. The etchant contacts surface28 of the thin gold layer on silicon article30 (not shown in FIGS. 1a-d) viagap38, and dissolves the gold layer atgap38. The result is illustrated in FIG. 1e,and an atomic force microscope image is shown in FIG. 1f.Following removal of the self-assembled monolayer ofspecies27, a thin gold layer that has been etched atgap38, to form adjacent regions of gold on a silicon surface separated by approximately 0.100 micron, results.
• FIGS. 1[0068]a-dillustrate an end view of astamp20 that includes a plurality of elongated,linear ridges26, separated by recessed portions of the stamp. When such a stamp is brought into contact with a surface of an article in a first orientation, followed by removal of the stamp, rotation of the stamp through 90° relative to the surface of the article, and reapplication of the stamp to the surface, a grid pattern ofspecies27 onsurface28 results. During each application of the stamping surface to the surface of the article, the stamp can be held in contact with the stamping surface for varying periods of time, resulting in a grid of lines ofmolecular species27 of varying width. Scanning electron micrographs of such a procedure are shown in FIGS. 2a-e.The surfaces shown in FIGS. 2a-ewere derivatized by covering a silicon article with thin layer of gold, applyingspecies27 to the gold surface via microprinting with a microstamp, and contacting exposed portions of the gold surface (those portions not covered by the self-assembled monolayer) with an etchant that is not compatible withspecies27 and that dissolves gold. The etchant is thus inert with respect tospecies27. For each of FIGS. 2a-e,stamp20 was applied to the surface in a first orientation for a first period of time (“1st printing”), and applied to the surface in a second orientation rotated 90° from the first orientation for a second period of time (“2nd printing”). The time that stampingsurface26 was allowed to contactsurface28, for each printing step, is listed beside each figure. Control of the length and width of exposed portions of silicon results.Dark portions41 are exposed regions of silicon following etch, andlight regions42 are the self-assembled monolayer on the gold surface. The procedures described with respect to FIGS. 1 and 2 are described in greater detail below in Example 1.
• Referring now to FIGS. 3[0069]a-c,a method for applying a self-assembled monolayer of a molecular species to a surface of an article according to another embodiment of the invention is illustrated, in which a stamp is deformed prior to and/or during transfer of the species to the surface. FIG. 3aillustrates, schematically, an end view of a portion of astamp20 including asurface22 that includes a stampingsurface26 separated byindentations24.Stamp20 is deformed prior to and/or during transfer of a self-assembled monolayer-formingmolecular species27, which coats stamping surface26 (typically coating theentire surface22 of stamp20), to surface28 ofarticle30. Whenstamp20 is deformed prior to transfer, it generally is compressed by applying to the stamp forces parallel to the stamping surface. That is, with reference to FIG. 3b,force is applied to the stamp in the direction ofarrows44. This results in reduction in the dimension of individual portions of stampingsurface26 along the direction of the application of force, as well as reduction of the dimension ofindentations24 in the same direction. That is, features of stampingsurface26 are reduced in size, and in spacing from each other, in the direction parallel to the application of force.
• When stamping surface[0070]26 (generally the entire surface22) ofstamp20 is coated with molecular species27 (not illustrated in FIG. 3b) and allowed to contactsurface28 ofarticle30, a self-assembled monolayer is formed onsurface28 that includes regions having lateral dimensions that correspond approximately to the dimension of features of stampingsurface26. Thus, whenstamp20 is deformed as illustrated in FIG. 3b,self-assembled monolayers, or a self-assembled monolayer having separate regions, is formed on a surface with dimensions smaller than those that would be achieved typically when the stamp is not deformed. Referring to FIG. 3c,stamp20 is illustrated with stampingsurface26 in contact withsurface28 ofarticle30, where the stamp has been deformed by applying a force perpendicular to stampingsurface26, that is, perpendicular to surface28 ofarticle30. This perpendicular force is represented byarrows46, and can be applied independently of, or in combination with, a compressive force on the stamp that is parallel to the stamping surface and that is represented byarrows44. Application of a compressive force represented byarrows44 and/or a perpendicular force represented byarrow46 will result in reduced feature sizes ofspecies27 onsurface28. When a force perpendicular to stampingsurface26 is applied, as represented byarrows46,gap38 between regions ofspecies27 onsurface28 is smaller than the dimension ofindentations24 between regions of stampingsurface26. Thus, the stamp is deformed as illustrated in FIG. 3cwhere the distance between adjacent regions of stampingsurface26 is lessened.
• Although only compressive forces are described with respect to deformation of[0071]stamp20 during microprinting,stamp20 can be deformed by stretching, as well.
• Referring now to FIGS. 4[0072]a-c,scanning electron micrographs showing surfaces derivatized via microstamp deformation are shown. The figures represent printing using a microstamp deformed by compressing the stamp by applying force parallel to the stamping surface (arrows44 of FIG. 3b), independently along perpendicular axes. A silicon article covered with a thin layer of gold was provided, with a self-assembled monolayer applied to the gold surface. Gold was etched from regions to which the monolayer was not applied. In FIGS. 4a-c,light regions48 represent the self-assembled monolayer on the thin gold film on silicon, andregions50 represent exposed silicon surface from which gold has been etched. A stamp used to apply a self-assembled monolayer to the gold surface was fabricated generally as described below in example 1, and included a surface including indentations represented byregions50, defining a stamping surface represented byregions48. FIG. 4aillustrates a surface to which a self-assembled molecular monolayer was applied from the stamp without deformation of the stamp, followed by etching of gold from regions to which the self-assembled monolayer was not applied. In FIG. 4b,the stamp was compressed along an axis parallel to the stamping surface, by applying force as illustrated byarrows52. In FIG. 4c,the stamp was compressed along an axis parallel to the stamping surface, by applying force in the direction ofarrows54, perpendicular to the compressive force applied in FIG. 4b.In FIG. 4d,the stamp was compressed along two perpendicular axes, both axes being parallel to the stamping surface, by applying force as illustrated byarrows52 and54.
• Mechanical deformation of a stamp as described above and illustrated in FIGS. 3[0073]a-cand4a-dcan be employed in conjunction with controlled reactive spreading of molecular species as described above and illustrated in FIGS. 1a-fand2a-e.That is, a stamp can be deformed, and held in contact with a surface to transfer a self-assembled monolayer thereto, while applying, to regions of the surface not contacted by the stamping surface, a species that is not compatible with the molecular species that forms the self-assembled monolayer. This procedure, as described above, advantageously includes allowing the stamp to remain in contact with the surface for a period of time sufficient to allow the molecular species to spread accordingly.
• All of the embodiments of the invention described thus far can be used in conjunction with methods of etching and/or plating a surface as described below, and as described in U.S. application Ser. No. 08/131,841, referenced above.[0074]
• Referring now to FIGS. 5[0075]a-c,a method of transferring a patterned, self-assembled monolayer to a nonplanar surface is illustrated schematically. As used herein, the term “nonplanar” is meant to define a surface, at least a portion of which has a radius of curvature. The method that is illustrated involves rolling a nonplanar surface, that is, the surface of a nonplanar article, over a stamping surface of a stamp carrying a self-assembled monolayer-forming molecular species. The surface that is rolled over the stamp can be that of a cylindrical article, a spherical article, or any other article having a nonplanar surface.Stamp20 in this embodiment is flat, that is, stampingsurface26 defines portions of a plane. In other embodiments (not illustrated), the stamp is nonplanar, that is, formed such that the stamping surface does not define a plane, or is a flexible, planar stamp that is deformed so as to be nonplanar.
• Referring to FIG. 5[0076]a,anarticle30 has anonplanar surface28. According to the embodiment illustrated,article30 is silicon dioxide, coated with a thin layer of titanium (not shown), which is coated with a thin layer of31 of gold. Stampingsurface26 ofstamp20, and generally theentire surface22 ofstamp20 is coated with a self-assembled monolayer formingmolecular species27.Article30 is caused to roll over stampingsurface26, for example, by placingarticle30 between stampingsurface26 and amember56, movingstamp20 andmember56 relative to each other along parallel planes in opposite directions, to cause the article to roll over the stamping surface.Member56 can be made of any material that will not disrupt or contaminatesurface28, and preferably a material that will not disrupt a self-assembled monolayer formed onsurface28.Member56 can be made of the same material from whichstamp20 is made.
• As used herein, the term “roll” refers to action in which a first surface is maintained in constant contact with a second surface (for example,[0077]surface28 ofarticle30 and stampingsurface26, respectively), but only a portion of each surface is in contact with only a portion of the other surface at any given time, and the portion of each surface that is in contact with the portion of the other surface changes continuously.
• Referring now to FIG. 5[0078]b,article30 is illustrated after having been rotated through approximately 260° of rotation on stampingsurface26. As a result, individual, isolated regions of a self-assembled monolayer ofmolecular species27 are formed onsurface28 ofarticle30 around approximately 260° of the surface, corresponding to individual regions of stampingsurface26.
• When this article is subject to a cyanide etch, as described above and described below in Example 2, gold that is not protected by[0079]molecular species27 is removed, as illustrated in FIG. 5c,exposing the thin layer of titanium (titanium dioxide) at regions not covered by the self-assembled monolayer. A nonplanar article, such as that illustrated in FIGS. 5a-c,can be etched in accordance with embodiments of the invention described in application Ser. No. 08/131,841, and described below.
• Referring now to FIGS. 6[0080]a-c,nonplanar articles covered by a thin layer of gold, to which patterned, self-assembled monolayers have been applied, followed by etching of gold from the surface at regions not protected by the self-assembled monolayer, are illustrated. In each case, the nonplanar article was rolled across a substantially planar stamping surface including a stamping pattern (pattern formed by stamping surface26). The stamping pattern includes features similar to those found in typical electronic circuitry. Gold was etched as described above and described below in Example 2.
• FIG. 6[0081]aillustrates a 1 mm diameter glass capillary coated with a thin layer of gold, which was printed according to the pattern illustrated, followed by removal of gold from the areas not covered by a self-assembled monolayer. FIGS. 6band6cshow views, at different magnification, of a lens having a 5 cm radius of curvature, coated with a thin film of gold, microprinted and etched as described herein. In FIGS. 6a-c,light regions are gold covered with a self-assembled monolayer, and dark regions are glass.
• FIG. 7 illustrates an etched optical fiber (glass). The fiber was coated with approximately 200 angstroms of titanium, which is coated with approximately 200-300 angstroms of gold. The exterior surface of the fiber was microstamped with hexadecanethiol, which served as a resist in a subsequent etch. The etch step removed the gold layer not covered by the self-assembled monolayer, and the light regions represent a self-assembled monolayer of hexadecanethiol on gold, while the dark regions represent the exterior surface of the optical fiber covered with titanium.[0082]
• In some instances, when it is desirable to use a self-assembled monolayer as a resist in an etching process, the self-assembled monolayer may not effectively resist the etchant. The present invention provides, for such a situation, a protecting species positioned on a self-assembled monolayer. The protecting species is inert with respect to the etchant by, for example, being incompatible with the etchant. The protecting species is compatible with the exposed functionality of the monolayer. For example, silicon coated with a thin, thermally-formed layer of silicon dioxide, is conveniently etched using hydrofluoric acid/ammonium fluoride. Then, silicon dioxide that has not been etched can serve as a resist for the etching of silicon and, for example, potassium hydroxide/isopropanol. However, many self-assembled molecular monolayers will not withstand (are not inert with respect to) the etchant used to remove silicon dioxide. The present invention provides a protecting species that will resist the etch. Many articles have a native layer of oxide. For example, silicon has a native layer of oxide that is approximately 5 nanometers thick. Generally, such a native layer will not serve as an effected resist. A thermally-formed oxide layer will generally have a thickness of approximately 0.2 microns. Articles having thermally formed layers of oxide thereon are readily available commercially. For example, silicon including a thermally-formed layer of silicon dioxide thereon is available from Silicon Sense Corporation, Nashua, N.H.[0083]
• Referring to FIGS. 8[0084]a-d,a process for etching silicon in accordance with the present invention is illustrated. FIGS. 8a-dare schematic illustrations of the process.
• Referring to FIG. 8[0085]a,asilicon article60 includes, on itssurface62, a thermally-formedlayer64 of silicon dioxide, having asurface66. A self-assembled monolayer68 (for example alkylsiloxane) is patterned onto thesurface66, using any method described herein or other method known to those of skill in the art. Referring to FIG. 8b,molecular species68 is coated with a protectingspecies70 that is compatible with the molecular species. That is,molecular species68 exposes a chemical functionality that is compatible with the protecting species. If the chemical functionality exposed bymolecular species68 is significantly polar, protectingspecies70 should be significantly polar. Protectingspecies70 can be a liquid, and can be a polymerizable species that is polymerized prior to application of the etchant.
• Referring to FIG. 8[0086]b,following application of protectingspecies70 tomolecular species68, a first etchant (for example HF/NH₄F, not shown) is brought into contact with exposed portions ofsurface66, whereupon the portions of silicon dioxide resistlayer64 that are not covered by self-assembledmonolayer68 and protectingspecies70 are dissolved, exposing corresponding portions ofsurface62 of silicon. Subsequently, a silicon etch (for example, KOH/I—PrOH) is added, and the silicon dioxide that had been covered by the self-assembled monolayer and protectingspecies70 acts as a resist for a silicon etch.
• Referring to FIGS. 8[0087]a-d,according to one embodiment an etchant is used that is destructive of a self-assembled monolayer, and in this embodiment a protecting species is advantageously used. According to another embodiment, a resist is used that can be etched with an etchant that does not destroy a self-assembled monolayer, and in this embodiment the protecting species need not be used. An example of the latter embodiment involves etching a silicon article coated with a thin film of gold. The gold in that embodiment defines a resist having a surface, to which can be transferred a self-assembled monolayer in a pattern, the self-assembled monolayer being contiguous with exposed portions of the gold surface in a second pattern. The surface of the article (the surface of silicon) can be exposed by removing gold from the surface (according to the second pattern) by contacting the exposed portions of gold with an species that reacts chemically with gold and that is inert with respect to the self-assembled monolayer. This exposes the surface of the article, according to the second pattern. Then, the exposed surface of the article can be etched, if the etchant is inert with respect to the resist (gold).
• In an alternative method, a self-assembled monolayer can be applied to the surface according to a first pattern, exposing a first functionality. The remaining portions of the surface are filled in with a self-assembled monolayer of a second species exposing a second chemical functionality. A protecting species that is compatible with the second chemical functionality is applied to the surface, and adheres to the self-assembled monolayer of the second species, protecting a pattern on the surface that is complementary to the first pattern, that is, protecting regions of the surface that do not include the first pattern.[0088]
• A variety of materials can be deposited on the surface of the article to serve as a resist. For example, thin layers of metal such as gold, silver, copper, nickel, cadmium zinc, palladium, platinum, iron, chromium, alloys of these and the like can be-deposited by those of skill in the art. Etchants that will dissolve resist such as these should be selected to oxidize atoms from the surface, and to include ligands, such as chelating or coordinating ligands, that will dissolve the oxidized atoms removed from the surface. Etchants or such resists are known to those in the art, and include aqueous etches such as ferricyanide etch, thiosulfate etch, thiourea etch, and the like. Often an adhesive layer is advantageously placed upon the surface of the article prior to application of the resist layer. The adhesive layer generally will be at least ten angstroms thick, and may be much thicker. The thickness of the resist layer, if it is a metal such as gold, is generally approximately 1000 angstroms. However, the resist can be from about 50 angstroms to many thousands of angstroms, depending upon the application.[0089]
• Many etchants will not attack a self-assembled monolayer on a surface, thus the self-assembled monolayer can be printed on such a surface, the resist can be etched from regions where the self-assembled monolayer does not lie, and the article can be etched at regions where the resist has been removed. Some etchants, however, that are particularly reactive, for example, aqua regia, carbon tetrafluoride, potassium iodide-iodine and the like, may harm self-assembled monolayers in some circumstances. Etchants that are particularly destructive of self-assembled monolayers are useful, in some circumstances, to etch certain resists from the surface of articles. For example, etching silicon dioxide from the surface of silicon requires etchants that generally at least partially destroy self-assembled monolayers.[0090]
• According to one embodiment, protecting[0091]species70 is applied to self-assembledmonolayer68 in the following manner. A bath of a fluid that is incompatible with the exposed functionality of self-assembledmonolayer68 is prepared, including a layer of fluid protecting species (or protecting species precursor) over the incompatible fluid. The article illustrated in FIG. 8ais passed through the region of the protecting species, which adheres to self-assembledmonolayer68, and passed into the fluid that is incompatible with the self-assembled monolayer. Where the protecting species is a fluid that is hardened, for example via polymerization, polymerization may take place in the bath, or the article may be removed from the bath prior to polymerization.
• The invention also provides a method for making an article, which utilizes any of the above-described, or known, methods for etching a surface. The etched surface serves as a template for the article according to this method of the invention. The method involves etching a pattern into a surface of a template and molding an article on the surface of the template. An article, formed by molding on the surface of a template, results. An example of such a process is illustrated schematically in FIGS. 9[0092]a-f.FIG. 9aillustrates asilicon article60 including asurface62 coated with a layer of resist64 having asurface66. In the embodiment illustrated, the resist is a thin layer of gold over titanium (100/1000 angstroms). A self-assembled monolayer-formingmolecular species27 is applied to surface22 (in particular, stamping surface26) of astamp20. Referring to FIG. 9b,a self-assembled monolayer ofmolecular species27 is thereby transferred to surface66 of resist64 in a pattern corresponding to the pattern of stampingsurface26 ofstamp20. Self-assembledmonolayer27 can be applied to surface66 according to methods described above and illustrated with reference to FIGS. 1a-5c.An etchant that is chemically reactive with a resist and that is inert with respect to the self-assembled monolayer is brought into contact with exposed portions of the resist surface (portions not covered by self-assembled monolayer27). The resist is etched, exposing portions ofsurface62 of article60 (FIG. 9c). Subsequently,article60 is etched by applying to the exposed portions of surface62 a second etchant that reacts chemically witharticle60 and that is inert with respect to resist64. The result, as illustrated in FIG. 9d,is a pattern etched intoarticle60, which pattern corresponds approximately to a pattern of gaps between closely-spaced regions of self-assembled monolayer27 (FIG. 9a). Removal of resist64 and self-assembled monolayer of molecular species27 (if it has not yet been removed) results in a patternedarticle60 that is useful for many purposes. One useful purpose, in accordance with the invention, involves using the etched surface ofarticle60 as a template for fabrication of an article. In FIG. 9e,an article has been molded ontosurface62 ofarticle60. In particular, ahardenable fluid72, such as a prepolymeric solution, is applied to surface62 ofarticle60 and hardened (polymerized, for example), to formarticle74.Article74 then is removed fromsurface62 ofarticle60, and as illustrated in FIG. 9f includes asurface76 that corresponds to surface62 ofarticle60.Article74 can be a stamp used for microprinting, as described above. Alternatively,article74 can be used as an optical element as described below and as described in U.S. application Ser. No. 08/131,841, referenced above.
• An advantage to forming[0093]article74 from a substrate etched lithographically as illustrated in FIGS. 9a-f,from a self-assembled monolayer applied by a microstamp, is that the surface oftemplate60, if it is an oriented crystal, can be etched to form grooves or pits that form an approximate ridge or point at their deepest portions. The method preferably uses a template that can be etched anisotropically. Generally, any material that forms an oriented crystal can be etched anisotropically using etchants available to those of skill in the art. Such a material can be etched such that a feature etched into its surface has a dimension much smaller than the dimension of the region at the surface of the material to which etchant is applied. For example, silicon is etched anisotropically resulting in grooves that become narrower with depth. An article molded on such a template will include protrusions that decrease in size in a direction away from the center of the article.
• As discussed, according to one embodiment a thin film of a resist, such as gold, coats the surface of the article that is etched. According to another embodiment, the article includes an oxide layer on its surface that can serve as a resist. For example, silicon, titanium, zirconium, germanium, aluminum, copper, and other articles known to those of skill in the art would include a surface layer of oxide that can serve as a resist, or a layer of oxide that can serve as a resist can be grown at the surface by, for example, heating the article in the presence of oxygen. Other articles that can be used in accordance with the invention and that can be coated conveniently with a thin layer of resist are semiconductors including gallium arsenide, indium phosphide, cesium chloride, diamond and the like. These and other materials known to those of skill in the art form oriented crystals that can be etched anisotropically. The articles discussed above including layers of oxide can define articles including resist layers, as described above with reference to FIGS. 8[0094]a-d.
• FIG. 10 is an atomic force microscope image of a polydimethyl siloxane (PDMS)[0095]article74 formed according to the method illustrated with reference to FIGS. 9a-f.According to embodiments in which the article is a microstamp, stampingsurface81 include features having a lateral dimension of approximately 0.100 micron or less. Similar articles can be fabricated including, rather than linear ridges defining stampingsurface81 as illustrated in FIG. 10, small, isolated projections that define stampingsurface81, which projections approximate a point. The projections can be in, for example, an ordered array. In one embodiment the stamping surface comprises at least one resolved feature providing stamping resolution of less than about 100 microns. In another embodiment, the stamping surface comprises at least one resolved feature providing stamping resolution of less than about 10 microns, and preferable less than about 1 micron.
• According to another embodiment of the invention a method is provided for simultaneously writing, on a surface of an article, at least two self-assembled monolayer patterns. The method involves coating a stamping surface of a microstamp with a self-assembled monolayer-forming species, contacting an article surface with the stamping surface, and moving the stamping surface relative to the article surface to write on the surface. For example, a stamp that includes a plurality of protrusions that, at their terminus (stamping surface), approximate points can be used to write, simultaneously, a plurality of lines on an article surface. Such lines can define a pattern that forms the basis of a corresponding electronic circuit, an etched region, or other feature as described in accordance with the invention or apparent to those of ordinary skill in the art. A stamp with such features can be obtained conveniently by patterning a surface of an article that can be anisotropically etched with resist, forming on the surface of the resist a self-assembled monolayer in a grid pattern while leaving isolated regions of the surface of the resist free of self assembled monolayer, etching the resist that is not covered by the self-assembled monolayer, and etching the surface of the article anisotropically to form a plurality of indentations that become narrower with depth until they approximate a plurality of points. This serves as a template for a stamp that includes a plurality of protrusions that terminate in approximate points at their stamping surface (or writing surface).[0096]
• As used herein, the term “writing” is given its ordinary meaning. In the context of a self-assembled monolayer, this means forming a pattern of a self-assembled monolayer on a surface not instantaneously, but progressively, in a manner analogous to the way ink is applied to paper when writing with a pen. In this way, a method is provided that involves writing on a surface of an article simultaneously at least two separate lines of a self-assembled monolayer-forming species.[0097]
• According to embodiments of the present invention in which a self-assembled monolayer is formed on silicon dioxide or glass, advantage can be achieved in aspects of the invention that involve etching, and aspects that involve preparation of surfaces of interest in biological arenas. In aspects that involve etching, when silicon dioxide is used as a resist layer on silicon, advantage in the etching of silicon is achieved as discussed above. Additionally, bulk silicon dioxide or glass can be etched by patterning a self-assembled monolayer of alkylsiloxane, such as octadecylsiloxane, on a surface thereof, optionally coating the self-assembled monolayer with a protecting species, and contacting the surface with an etchant that etches the silicon dioxide or glass.[0098]
• According to aspects of the invention involving the preparation of surfaces of biological interest, a surface such as a silicon dioxide or glass slide or petri dish can be patterned with a self-assembled monolayer of alkylsiloxane that exposes a chemical functionality of biological interest, facilitating studies at that surface. For example, a self-assembled monolayer of alkylsiloxane terminating in a cytophilic functionality can be patterned onto a silicon dioxide or glass surface in accordance with the invention, followed by adherence or immobilization of a cell or cells to the cytophilic functionality. Biological, specifically cytophilic, functionalities in association with self-assembled monolayers are described in copending, commonly-owned application Ser. No. 08/131,841 and in an article entitled “Engineering Cell Shape and Function”, by Singhvi, R., et al.[0099]Science,264, 696 (1994), both incorporated herein by reference. This article describes the formation of islands of self-assembled monolayer terminating in a non-polar functionality (—CH₃) surrounded by regions of polyethylene glycol-terminating self-assembled monolayer. The non-polar terminal functionality of the islands is protein adherent, while the polyethylene glycol functionality is not protein-adherent. Exposure of a surface derivatized as such to a protein matrix such as the purified extracellular matrix protein laminin results in cytophilic, protein-coated islands surrounded by cytophobic regions. Exposure of this surface to cells results in cell attachment preferentially to the adhesive (cytophilic), laminin-coated islands and the cells are prevented from extending onto surrounding non-adhesive (cytophobic) regions. Alternatively, a surface derivatized as described above with a patterned, self-assembled monolayer terminating in non-polar, such as methyl, functionality can be contacted with a cell or cells without first treating the surface with a protein matrix such as laminin. According to some embodiments, the cell or cells will secrete a protein matrix such as laminin that will coat the exposed non-polar functionality, and the cell or cells then will adhere thereto.
• A variety of cell studies can thereby be conducted that involve immobilization of a cell or cells on one or more islands. Procedures involving cell growth, differentiation, culturing, and the like can be tailored by varying the size and/or shape of islands, spacing between islands, and the like. Those of ordinary skill in the art will appreciate that alkylsiloxane-based self-assembled monolayers on glass or silicon dioxide can be prepared that terminate in a variety of chemical or biochemical functionalities amenable to attachment of biological species such as antibodies, antigens, haptens, proteins, sugar and other carbohydrates, etc., prepared in accordance with methods of patterning described herein. Functionalities such as chelates, etc. as described in commonly-owned, copending U.S. patent application Ser. No. 08/312,388 (Bamdad, et al.), incorporated herein by reference, can be provided at the exposed end of molecules making up self-assembled monolayers patterned on glass or silicon dioxide as well.[0100]
• According to some embodiments of the invention the above-described techniques involving patterning glass or silicon dioxide-can be applied to other polar surfaces including polar polymeric surfaces such as oxidized polyethylene or polystyrene. According to these embodiments alkylsiloxane can be patterned onto a polymeric surface oxididized for example via plasma etch to expose polar functionalities such as hydroxyl, carboxylic acid, aldehyde, or the like. These surfaces can form the basis for all embodiments of the invention described herein, including the biological aspects described above.[0101]
• Patterning of alkylsiloxane onto glass, silicon dioxide, or polar polymeric surfaces can be carried out according to chemistry known to those of skill in the art. For example, trichlorosilane or trialkoxysilane such as triethoxysilane, when applied to these surfaces in essentially any solvent in which they can be carried (such as water, hexane, toluene, and the like) will form alkylsiloxane on that surface.[0102]
• The techniques described above involving patterning of alkylsiloxane on glass, silicon dioxide, or polar polymeric surfaces can be carried out on planar or non-planar surfaces, as described herein, and can be combined with techniques described herein involving allowing alkylsiloxane or its precursor to spread onto the surface while contacting the surface simultaneously with a species that is not compatible with the alkylsiloxane or precursor, and involving deforming a stamp from which the alkylsiloxane or precursor is transferred, or both.[0103]
• The present invention also provides a variety of optical elements and devices. One such element is a diffraction grating that can be formed as described above with respect to article[0104]74 (FIG. 9f) or as described in U.S. application Ser. No. 08/131,841, referenced above, in which a variety of optical elements including an optical switch are described. According to a preferred embodiment of the invention, a reflective liquid, such as a liquid metal, is brought into contact with a surface that correlates to a surface of an optical element, and a surface of the liquid metal is thereby formed into an optical surface. A method for making such an article is illustrated schematically in FIGS. 11a-f.In FIG. 11a,atemplate78, for example a commercial diffraction grating, is provided.Template78 can be mounted on asupport80, for example a glass slide. At FIG. 11b,afluid precursor82 is brought into contact withoptical surface79 oftemplate78. In the embodiment illustrated,fluid precursor82 is a prepolymeric solution of polydimethylsiloxane, and is contained in acontainer84, for example a petri dish.Fluid precursor82 is allowed to harden in contact with theoptical surface79. Whereprecursor82 is a prepolymer fluid, it is polymerized. When hardened, anarticle86 that results from hardening of the fluid precursor is removed from template78 (FIG. 11c), and can be removed from container84 (FIG. 11d;alternatively,article86 can remain incontainer84 during application of a liquid metal to surface88, and optional encapsulation, discussed below with reference to FIGS. 11eandf). The resultant article86 (FIG. 11d) has anoptical surface88 that corresponds tooptical surface79 of the template.Article86 is preferably transparent, and is a transparent elastomeric diffraction grating according to a preferred embodiment.
• According to a preferred embodiment,[0105]optical surface88 ofarticle86 is contacted with aliquid metal90, for example gallium, mercury, or other liquid known to those of skill in the art (FIG. 11e).Liquid metal90 includes asurface92 that is in contact with and correlates to surface88 ofarticle86, and surface92 ofliquid metal90 is thereby formed into a diffraction grating. Ifarticle86 is transparent, electromagnetic radiation can be directed througharticle86 atsurface92, and diffracted (FIG. 11e). Afterliquid metal90 is brought into contact witharticle86 so that asurface92 ofliquid90 contacts and correlates withsurface88 ofarticle86,liquid metal90 can be encapsulated by coating exposed surfaces of the liquid metal with a hardenable fluid, preferably the same fluid asfluid precursor82, and the fluid allowed to harden. The result, as illustrated in FIG. 11f,is anoptical element93 that is a liquid metal having asurface92 that is an optical surface, which liquid metal is encapsulated in atransparent article86.
• According to an embodiment in which[0106]article86 is flexible,optical surface92 ofliquid metal90 can be deformed. For example,surface92 can be compressed, elongated or bent. Wherearticle86 is an elastomer,surface92 can be repeatedly elongated and bent. Thus, where the electromagnetic radiation is directed atsurface92 and diffracted, the pattern of diffraction can be adjusted, that is, changed, by manipulatingoptical element93, for example by stretching it.
• The method and article described above with reference to FIGS. 11[0107]a-fcan be used in conjunction with any optical element having a reflective surface, such as diffraction gratings including holographic gratings, blaze gratings (illustrated in FIGS. 11a-f), and the like. For example, a concave mirror can be formed according to one embodiment, and this is described with reference to FIGS. 12a-d.At FIG. 12aatemplate94 having anoptical surface95, for example a glass plano-concave lens, is immersed in afluid precursor82, for example polydimethylsiloxane.Precursor82 is hardened andtemplate94 is removed, and anarticle96 having anoptical surface98 that corresponds to optical95 oftemplate94 remains (FIG. 12b). Referring to FIG. 12c,aliquid metal90 is placed in contact withoptical surface98 ofarticle96, thus anoptical surface100 is formed onliquid metal90, defining anoptical element102. According to oneembodiment article96 is flexible. According to apreferred embodiment article96 is an elastomer.Article102 according to this embodiment includes anelastomer96 including a void104 having a convex or concave surface (convex surface100 as illustrated) and aliquid metal90 adjacent the surface of the void, the liquid metal having an optical surface100 (a concave mirror surface is illustrated that corresponds to the concaveoptical surface95 of template94).
• [0108]Optical element102 can be used to focus electromagnetic radiation directed atoptical surface100 ofliquid metal90 and allowed electromagnetic radiation to reflect from the optical surface. According to an embodiment in whicharticle96 is flexible,article96 can be adjusted, thereby adjustingoptical surface100 ofliquid metal90 and adjusting the focus of the electromagnetic radiation. According to a preferred embodiment in whicharticle96 is an elastomer, this can be done repeatedly.
• Referring to FIG. 12[0109]d,optical element103 is illustrated.Optical element103 results from complete encapsulation ofliquid metal90 byarticle97, which can be formed by taking steps as described above with respect to FIG. 11f.In the embodiment illustrated in FIG. 11f,liquid metal90 completely fills void104 inarticle96.
• Referring now to FIG. 13, a method of making an optical element is illustrated schematically. The method involves providing a substrate[0110]106 that has, on asurface108 thereof, a self-assembledmonolayer110 exposing a first chemical functionality.Monolayer110 is formed in a predetermined shape onsurface108 that corresponds to a shape desired for one portion of the surface of the optical element. A fluid precursor12 of the optical element then is placed uponmonolayer110, and asurface114 offluid precursor112 is contacted with a fluid116 that is incompatible with thefluid precursor112. Alternatively, theincompatible fluid116 can first be applied to surface108 of article106 (and monolayer110), andfluid precursor112 then can be applied tomonolayer110, for example using apipet118. Portions ofsurface108 of article106 that are not covered withmonolayer110 do not attractfluid precursor112. If such portions ofsurface108 are attractive tofluid precursor112, a self-assembledmonolayer120 can be formed around self-assembledmonolayer110, isolatingmonolayer112, that exposes a chemical functionality that does not attractprecursor112.
• When[0111]precursor112 is polydimethylsiloxane that is polymerized to form an optical element that is a plano-convex lens, self-assembledmonolayer110 can be formed from a molecular species terminating in a non-polar functionality, for example hexadecanethiol. In this case, ifsurface108 is not sufficiently repulsive offluid precursor112, then the remaining portions ofsurface108 can be coated with a self-assembled monolayer of a species terminating in a polar functionality, for example a long-chain thiol terminating in a carboxylic acid. This arrangement can be used whensurface108 is a gold surface. Other combinations of surfaces and functional groups that adhere to surfaces are described in application Ser. No. 08/131,841, and/or are known to those with skill in the art.
• The present invention also provides a method for controlling the shape of a liquid, for example a fluid precursor of an optical element. Referring to FIG. 14, the method involves providing a supporting, electrically[0112]conductive surface120.Surface120 can, for example, be an exposed surface of a thin,transparent gold film121 on a transparent (e.g. glass)support122. A self-assembled monolayer is applied to aregion124 ofsurface120 and a fluid126 that is attracted to the chemical functionality exposed by the self-assembled monolayer is applied to the self-assembled monolayer. Ifsurface120 is not repulsive offluid126, then the portion ofsurface120 not covered by the self-assembled monolayer can be covered by a self-assembled monolayer exposing a chemical functionality that is repulsive offluid126. Anelectrolyte fluid128 that is not compatible withfluid126 is placed overfluid126, and an electricalcircuit including surface120 andelectrolyte128 is arranged. For example, areference electrode130 and acounter electrode132 can be immersed inelectrolyte128, andsurface120 can define a working electrode, the working, counter, and reference electrodes being controlled bypotentiostat135. By altering the electrical potential atsurface120, the contact angle formed byliquid126 atsurface120 changes. The change in contact angle is dependent upon the electrical potential. According to one embodiment, the self-assembled monolayer atregion124 is caused to desorb and resorb, during change in electrical potential, at the outermost point of contact betweenfluid126 and the surface selectively, and this causes the contact angle between the fluid and the surface to change.
• In this way, liquid[0113]126 can be used as a lens that can be focused depending on the electrical potential ofsurface120 relative toreference electrode130. A source ofelectromagnetic radiation134 can direct electromagnetic radiation atfluid126, which electromagnetic radiation can be focused and utilized by a sensor or other electromagnetic radiation-receivingapparatus136. Iffluid126 is a hardenable fluid, it can serve as a precursor of a solid lens, and adjusting the electrical potential betweensurface120 andreference electrode130 can adjust the focal length offluid126, followed by hardening offluid126 to produce alens126 having a focal length that has been set by adjusting the potential atsurface120 during lens formation. Hardenable fluids useful asfluid126 include those described above with respect to formation of microstamps and optical elements, and include generally any hardenable fluid that is incompatible with a suitable electrolyte, and that can be placed upon an exposed surface of a self-assembled monolayer.
• When a self-assembled monolayer exposes a redox functionality, the species that forms the spacer portion of the self-assembled monolayer-forming species can advantageously be selected as one that has a reasonably good electron transfer function, for example polyenes, poly-ynes, polyaromatics, and the like can be selected.[0114]
• According to another embodiment,[0115]region124 of surface120 (or the entire surface120) is covered with a self-assembled monolayer exposing a redox functionality. Examples of suitable redox functionalities include ferrocene, quinone, thiophene, pyrrole, and the like. The redox state of the exposed chemical functionality of the self-assembled monolayer can be controlled, which can control the contact angle of a fluid126 at the surface of the self-assembled monolayer.
• While the arrangement in FIG. 14 involves an[0116]electrolyte contacting surface120, surroundingfluid126, and contacting the working and reference electrodes, according to an embodiment in whichfluid126 is an electrolyte, the working and counter electrodes can contact fluid126 directly. In this embodiment,electrolyte128 is not necessary if not needed to aid in the formation of the shape offluid126.
• In the embodiment described with reference to FIG. 14, where[0117]fluid126 is an organic fluid, it may be conveniently applied toregion124 ofsurface120 as follows: anaqueous fluid128 is prepared, and a layer oforganic fluid126 is placed on top ofaqueous solution128.Article122 is passed through the layer oforganic fluid126, whereupon some offluid126 adheres toregion124 ofsurface120, and intoaqueous solution128.
• In FIG. 14, one article only is formed from[0118]fluid126. However, a plurality of articles on a plurality of isolated regions ofsurface120 can be fabricated, and/or used as individual optical elements as illustrated.
• According to another embodiment similar to that illustrated in FIG. 14, a plurality of articles are formed on a[0119]surface120 without the use of electrochemistry. A self-assembled monolayer including an isolated region exposing a particular chemical functionality, or an isolated region of a self-assembled monolayer exposing a chemical functionality surrounded by a surface free of self-assembled monolayer, can be passed through anorganic fluid layer126 on top of anaqueous layer128, whereupon portions offluid126 adhere to compatible portions of the self-assembled monolayer, as illustrated in FIG. 14.Fluid126 can then be hardened, for example via curing, under an aqueous solution, or the article can be removed andfluid regions126 can be cured.
• The present invention also provides a method of forming an article that includes providing a precursor of the article in contact with at least two discreet self-assembled monolayer regions. Referring to FIGS. 15[0120]aand15b,afirst article140 and asecond article142 are illustrated schematically.Article140 includes a thin layer of aconductive species144 on one of its surfaces andarticle142 includes a thin layer of aconductive species146 on one of its surfaces.Articles140 and142, includingconductive layers144 and146 can be identical. On the surface ofconductive layers144 and146, respectively, it is afirst region148 and asecond region150 of a self-assembled monolayer exposing a first chemical functionality. The remaining portions of the surface ofconductive layers144 and146 remain free of self-assembled monolayer, or are covered with a self-assembled monolayer exposing a chemical functionality different from the first chemical functionality. A fluid152 is caused to contact both self-assembledmonolayer148 and150.Fluid152 is compatible with the first chemical functionality exposed by self-assembledmonolayers148 and150.Fluid152 is surrounded byfluid154, which is incompatible withfluid152.Fluid154 can be applied tofluid152 afterfluid152 is applied to self-assembledmonolayers148 and150, orfluid152 can be applied to self-assembledmonolayers148 and150 underfluid154, forexample using pipette156. Iffluid152 is a hardenable fluid, for example, a precursor of a solvent polymer, it can be cured to formarticle158.Article158 can be removed from self-assembled148 and150. According to an alternate embodiment,conductive layers144 and146 are not present.
• According to one embodiment, electrochemical apparatus as illustrated in FIG. 14 (not shown in FIGS. 15[0121]aandb) is provided to adjust the electrical potential of conductinglayers144 and146. Conductinglayers144 and146 can be adjusted independently, and thus, the area of contact betweenfluid152 and self-assembledmonolayers148 and150, respectively, can be adjusted.
• FIGS. 16[0122]a-eillustrate schematically a process for etching an article that is similar to the process described in connection with FIGS. 8a-d,with like numerals referring to corresponding components. Anarticle60, for example silicon, includes, on itssurface62, alayer64 that can be a thermally-formed layer of silicon dioxide having asurface66. A self-assembled monolayer68 (for example alkyl siloxane) is patterned ontosurface66, using any method described herein or other method known to those of skill in the art. Referring to FIG. 16b,a protectingspecies70 is added. While in FIGS. 8a-dprotecting species70 is selected to be compatible with the self-assembled monolayer and relatively incompatible with thesurface66 of the layer ofsilicon dioxide64, in the embodiment illustrated in FIGS. 16a-eprotecting species70 is more compatible withsurface66 than with self-assembledmonolayer68. The protecting species can be a liquid, a polymerizable species, or the like. The compatibility of the protecting species with the self-assembled monolayer or with thesurface66 can be selected and/or adjusted by those of ordinary skill in the art.
• FIG. 16[0123]cillustrates the arrangement after application of an etchant to the surface.Portions63 oflayer64 of silicon dioxide that are protected by protectingspecies70 remain onsurface62 ofarticle60 asmask65. Remaining portions oflayer64 are etched by the etchant. The etchant and protectingspecies70 are selected so as to be incompatible and protectingspecies70 thereby protectsportions63 that definemask65. Subsequently, a silicon etch as described above is added, andsilicon dioxide mask65 acts as a resist for the silicon etch. An exemplary process is described in greater detail below in Example 3, and a photocopy of a scanning electron micrograph (SEM) of a resultant etched surface is shown in FIG. 16e.
• In all of the embodiments described and illustrated herein, methods and devices described in accordance with one embodiment can be utilized with any other embodiment where feasible. For example, the controlled spreading described with reference to FIGS. 1[0124]a-dcan be used in conjunction the stamp deformation as described with reference to FIGS. 3a-c,and these embodiments together or alone can be used for methods and devices discussed with reference to other figures, where feasible. For example, stamp deformation can be used on nonplanar surfaces, controlled spreading can be used in etching as described with reference to FIGS. 8a-d,with lithographic molding as in FIGS. 9a-f,etc. As another example, articles provided in accordance with the inention, especially articles that are diffraction gratings, optical element encapsulants, microstamps, lenses, and the like, all can be fabricated from material or precursors from which others are fabricated, and/or from material described in U.S. application Ser. No. 08/131,841. Many of these articles are tranparent polymers, elastomers, and the like, and these materials are known to those of skill in the art.
• In all of the embodiments described and illustrated herein, self-assembled monolayers that expose a variety of chemical functionalities can be formed. Hydrophobic, hydrophilic, cytophobic, cytophilic, and other functionalities are described in application Ser. No. 08/131,841, and the following references, all incorporated herein:[0125]
• Co-pending, commonly-owned U.S. application Ser. No. 08/312,388, entitled “Molecular Recognition at Surfaces Derivatized with Self-Assembled Monolayers”, by Bamdad, et al.;[0126]
• “Controlled outgrowth of dissociated neurons on patterned substrates”, Kleinfeld, et al,[0127]Journal of Neuroscience,8(11): 4098 (1988);
• “Growth Control in Miniclones of Human Glial Cells”, Westermark, B.[0128]Experimental Cell Research,111, 295-299 (1978);
• “Micropatterned Substratum Adhesiveness: a Model for Morphogenetic Cues Controlling Cell Behavior”, Britland, S., et al[0129]Experimental Cell Research,198, 124-129 (1992);
• “Engineering Cell Shape and Function”, Singhvi, R., et al.[0130]Science,264, 696 (1994);
• “Convenient Methods of Patterning the Adhesion of Mammalian Cells to Surfaces Using Self-Assembled Monolayers of Alkane Thiols on Gold”,[0131]Journal of the American Chemical Society115: 5877-5878 (1993).
• In accordance with the teachings in these and other references, those of skill in the art can utilize the surfaces produced in accordance with the invention in a variety of biological, chemical, physical, and analytical arenas.[0132]
• The function and advantage of these and other embodiments of the present invention will be more fully understood from the examples below. The following examples are intended to illustrate the benefits of the present invention, but do not exemplify the full scope of the invention.[0133]
EXAMPLE 1Fabrication of a Microprinting Stamp
• A polydimethyl siloxane stamp was fabricated. Sylgard™ 184 silicone elastomer, parts “a” and “B” (10, 1 by weight Dow Corning) were mixed in a plastic cup; trapped air was removed under vacuum. The mixture was poured over a master as described by Kumar, et al.,[0134]Langmuir,10, 1498-1511 (1994). The master was held in a polystyrene petri dish and left at room temperature for approximately two hours. It was cured by heating in an oven at 60° C. for approximately two hours.
EXAMPLE 2Controlled Reactive Spreading of a Self-Assembled Monolayer on a Surface
• Hexadecanethiol was selected as[0135]species27 and was purified by chromatography through silica gel in ethanol with concentrations from 0.01 mM to 6.5 mM. Gold films on silicon were prepared by electron beam sputtering. A piece of gold substrate was put into a polystyrene petri dish that was half-filled with deionized water, and thestamp including species27 applied to surface22 was brought into contact with the gold surface. To avoid smearing the gold surface with the stamp, one of two methods were employed. According to the first, the stamp and the gold substrate were taken out of the water together while still in contact, carefully dried in a stream of nitrogen, and then separated. According to the second, the stamp was separated from the gold substrate while under water. The water was replaced with several volumes of clean water to remove any residual species27 (alkanethiol) and the gold substrate then was removed from water and dried in a stream of nitrogen. Each time the stamp was re-used, it was first rinsed with excess ethanol to remove alkanethiol. Gold was removed from the surface of the silicon article using a cyanide solution (KCN) 0.1 M; KOH: 1 M) with vigorous stirring using air (oxygen) as an oxidant.
EXAMPLE 3
• A process for etching silicon is described. The process is described with reference to FIGS. 16[0136]a-e.A silicon wafer (<100>orientation) covered with 0.2 micron-thick thermal silicon dioxide (used as received from MEMC) was cleaned in piranha solution (a mixture 7:3 (v/v) of 98% H₂SO₄and 30% H₂O₂), thoroughly rinsed with deionized water, and used immediately (Caution: piranha solution is an extremely strong oxidant and should be handled with care. Contact with skin can cause serious injury. Contact with eyes can cause blindness). The surface of the wafer was patterned, using a stamp fabricated in accordance with Example 1, with a self-assembled monolayer of —Cl₃SiR, —(EtO)₃SiR (R═—(CH₂)₃NH₂, —(CH₂)₃SH, —(CH₂)₃BR, —(CH₂)NCO, —(CH₂)₂(CF₂)₅CF₃, or —(CH₂)15(CH═CH₂) in hexane for ca. 5 min. Subsequent treatment of the patterned self-assembled monolayers contining vinyl-terminated regions with an aqueous solution of KMnO₄and KiO₄convereted the olefins to carboxylic acids. FIG. 16aillustrates schematically these self-assembled monolayers. A drop of a prepolymer of polymethyl methacrylate (SK-9, Edmund Scientific) or polyurethane (J-91, Edmund Scientifir; NOA81, Norland Products, inc.) was placed on the patterned area. The excess prepolymer was removed by tilting the substrate and allowing the prepolymer to drain off of the surface. The prepolymer was compatible with the chemical functionality exposed by the surface silicon dioxide surface rather than the self-assembled monolayer, thus (FIG. 16b), the prepolymer remaining on the surface selectively wettedregions63 of silicon dioxide uncovered by self-assembledmonolayer68. The prepolymer was cured under a mercury lamp (medium pressure; the distance between the sample and the lamp was about 1 cm) for about 20 minutes to form protectingspecies70 atregions63 interventing regions covered by self-assembledmonolayer68. The surface was exposed to an etchant, specifically NH₄F-buffered aqueous HF solution (250 mL of H₂O, 165.5 g of NH₄F, and 40 Ml of 48% HF). The etchant was incompatible with the protectingspecies70, but removed self-assembledmonolayer68 and the underlying layer of silicon dioxide except at thoseregions63 protected byspecies70, which served asmask65 in a subsequent etch of silicon. Anisotropic etching of silicon was carried out in an aqueous solution of KOH and I—PrOH at 70° C. (400 mL of H₂O, 92 g of KOH, 132 mL of I—PrOH). This etchant removed the protectingspecies70, but not the underlyingsilicon dioxide mask65. That is, portions of silicon not protected bymask65 were anisotropically etched (FIG. 16d). The result is an etched surface of silicon, as represented by the photocopy of the SEM image in FIG. 16e.
• Those skilled in the art would readily appreciate that all parameters listed herein are meant to be exemplary and actual parameters will depend upon the specific application for which the methods and apparatus of the present invention are being used. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, the invention may be practiced otherwise than as specifically described.[0137]

Claims (116)

What is claimed is:

1. A method of plating a pattern of material on a nonplanar surface of an article, comprising:

contacting a first, nonplanar portion of a surface of an article with a stamp to transfer to the first portion a self-assembled monolayer of a molecular species in a first pattern, the self-assembled monolayer being contiguous with an exposed portion of the surface in a second pattern; and

plating the surface of the article with a plating reagent in a pattern dictated by the pattern of the self-assembled monolayer.

2. A method as inclaim 1, wherein the article is a fiber.

3. A device comprising:

an article defining a surface; and

an isolated region of a self-assembled monolayer of a first molecular species on the surface, the isolated region including a lateral dimension of less than about 10 microns, surrounded by a continuous region of a self-assembled monolayer of a second molecular species on the surface, wherein the first molecular species terminates in an end exposed away from the surface having a first functionality and the second molecular species terminates in an end facing away from the surface having a second functionality.

4. A device as inclaim 3, wherein the isolated region of the first molecular species has a lateral dimension of less than about 5 microns.

5. A device as inclaim 3, wherein the isolated region of the first molecular species has a lateral dimension of less than about 1 micron.

6. A device as inclaim 3, wherein the isolated region of the first molecular species has a lateral dimension of less than about 0.25 micron.

7. A device as inclaim 3, wherein the isolated region of the first molecular species has an area of less than about 100 square microns.

8. A device as inclaim 3, wherein the isolated region of the first molecular species has an area of less than about 25 microns.

9. A device as inclaim 3, wherein the isolated region of the first molecular species has an area of less than about 1 square micron.

10. A device as inclaim 3, wherein the isolated region of the first molecular species has an area of less than about 0.06 square micron.

11. A device as inclaim 3, wherein the surface is nonplanar.

12. A device as inclaim 3, wherein the first molecular species terminates in an end facing away from the surface having a hydrophilic functionality and the second molecular species terminates in an end facing away from the surface having a hydrophobic functionality.

13. A device as inclaim 3, wherein the first molecular species terminates in an end facing away from the surface in a hydrophobic functionality and the second molecular species terminates in an end facing away from surface in a hydrophilic functionality.

14. A device as inclaim 13 wherein the surface is nonplanar.

15. A device as inclaim 12 wherein the surface is nonplanar.

16. A kit, comprising:

an article constructed and arranged to transfer a molecular species to a substrate surface, comprising an applicator surface having at least one indentation formed therein and a stamping surface adjacent the at least one indentation, for carrying a self-assembled monolayer-forming molecular species and able to transfer the molecular species to the substrate, the stamping surface formed of a swellable material which absorbs the molecular species; and

a self-assembled monolayer-forming molecular species for application by the stamping surface.

17. The kit as recited inclaim 16, the stamping surface comprising at least one resolved feature providing stamping resolution of less than about 100 microns.

18. The kit as recited inclaim 17, the stamping surface comprising at least one resolved feature providing stamping resolution of less than about 10 microns.

19. The kit as recited inclaim 18, the stamping surface comprising at least one resolved feature providing stamping resolution of less than about 1 micron.

20. The kit as recited inclaim 19, the stamping surface comprising at least one resolved feature providing stamping resolution of less than about 0.25 micron.

21. The kit as recited inclaim 16, the article formed from an elastic material.

22. The kit as recited inclaim 21, the elastic material formed from a hardenable fluid.

23. The kit as recited inclaim 21, the elastic material selected from the group consisting of silicone polymers and copolymers, epoxy polymers and copolymers, and copolymers thereof.

24. A kit, comprising:

an article for transferring a molecular species to a surface, comprising a flexible surface having at least one indentation formed therein and an applicator surface adjacent the at least one indentation for carrying a molecular species and transferring the molecular species to a substrate, the applicator surface including a portion having a lateral dimension of less than about 10 microns, wherein the flexible surface comprises polydimethyl siloxane; and

a self-assembled monolayer-forming molecular species for application by the applicator surface.

25. An optical fiber having a surface, and a self-assembled monolayer on the surface of the optical fiber.

26. A method comprising:

transferring to a surface of a fiber a molecular species from an applicator in a pattern including a portion having a lateral dimension of less than about 10 microns.

27. A method as inclaim 26, wherein the pattern includes a portion having a lateral dimension of less than about 1 micron.

28. A method as inclaim 26, wherein the pattern includes a portion having a lateral dimension of less than about 0.5 micron.

29. A method as inclaim 26, wherein the fiber is an optical fiber.

30. A method as inclaim 26, further comprising etching a portion of the surface of the fiber in a pattern dictated by the pattern of the molecular species.

31. A method as inclaim 26, further comprising plating a portion of the surface of the fiber with a plating agent in a pattern dictated by the pattern of the molecular species.

32. An article comprising:

a flexible member having a flexible surface including at least one indentation formed therein, the at least one indentation formed such that electromagnetic radiation passing through the flexible member when the member is in a first, unstressed conformation forms a first detectable image and formed such that electromagnetic radiation passing through the flexible member when the member is in a second, stressed conformation forms a second detectable image differentiable from the first image; and

a modulator contacting the flexible member and movable between a first position placing the member in the first, unstressed conformation and a second position placing the member in the second, stressed conformation.

33. An article as inclaim 32, further comprising:

a source of electromagnetic radiation positioned to irradiate the flexible member; and

an electromagnetic radiation detector positioned to detect radiation emitted by the electromagnetic radiation source and passing through the flexible member.

34. An article as inclaim 33, the flexible member having a flexible surface including a plurality of indentations formed therein, the indentations formed such that electromagnetic radiation passing through the surface when the member is in the first, unstressed conformation is diffracted according to an ordered diffraction pattern and formed such that electromagnetic radiation passing through the surface when the member is in the second, stressed conformation is blurred.

35. An article as inclaim 34, wherein the source of electromagnetic radiation is positioned to irradiate the flexible member through the flexible surface.

36. An article as inclaim 34, wherein the modulator includes a modulating surface positioned against the flexible surface and movable between the first and second positions.

37. An article as inclaim 36, wherein the modulator includes a peizoelectric member.

38. An article as inclaim 37, further comprising an electrical source in electrical communication with the peizoelectric member, the electrical source switchable between a first signal state in which the peizoelectric member is in the first position and a second signal state in which the peizoelectric member is in the second position.

39. An article as inclaim 32, the article comprising a pressure sensor.

40. An article as inclaim 32, the article comprising an optical switch.

41. A kit, comprising:

an article constructed and arranged to transfer a molecular species to a substrate surface comprising an applicator surface having at least one indentation formed therein and a stamping surface adjacent the at least one indentation, for carrying a self-assembled monolayer-forming molecular species and transferring the molecular species to the substrate, the stamping surface formed of a swellable material which absorbs the molecular species, wherein the stamping surface comprises polydimethyl siloxane; and

a self-assembled monolayer-forming molecular species for application by the stamping surface.

42. The kit as inclaim 24, wherein the applicator surface includes a portion having a lateral dimension of less than about 1 micron.

43. A method comprising:

providing an applicator having a surface including at least one indentation formed therein, the indentation contiguous with an applicating surface defining a first pattern;

coating the applicating surface with a molecular species comprising a functional group selected to bind to palladium;

positioning the applicating surface in a first orientation and contacting a portion of a substrate surface comprising palladium with the applicating surface to hold the molecular species against the substrate surface to allow the functional group to bind thereto; and

removing the applicating surface to provide a self-assembled layer of the molecular species on the substrate surface according to the first pattern.

44. The method ofclaim 43, further comprising providing at least one second portion of the substrate surface free of the self-assembled layer and contiguous with the substrate surface portion onto which the self-assembled layer is provided.

45. The method ofclaim 44, wherein coating the applicator surface further comprises allowing the molecular species to swell into the applicator surface.

46. The method ofclaim 44, further comprising:

positioning the applicator surface in a second orientation different from the first orientation, and contacting a portion of the substrate surface with the applicator surface to hold the molecular species against the substrate surface to allow the functional group to bind thereto; and

removing the applicating surface to provide a self-assembled layer of the molecular species on the substrate surface according to the first pattern in the second orientation.

47. The method ofclaim 46, wherein the self-assembled layer of the molecular species on the substrate surface in the second orientation intersects portions of the self-assembled layer in the first orientation and forms a continuous self-assembled layer therewith.

48. A method for patterning a surface, comprising:

applying instantaneously to a surface comprising palladium a plurality of discrete isolated regions of a first, self-assembled layer forming molecular species while leaving intervening regions free of the species.

49. The method ofclaim 48, wherein the surface comprising palladium is non-planar.

50. The method ofclaim 49, wherein at least one of the discrete isolated regions includes a lateral dimension of less than 200 microns.

51. The method ofclaim 50, wherein at least one of the discrete isolated regions includes a lateral dimension of less than about 100 microns.

52. The method ofclaim 51, wherein at least one of the discrete isolated regions includes a lateral dimension of less than about 5 microns.

53. The method ofclaim 48, wherein the at least one of the discrete isolated regions has an area of less than 1 square micron.

54. The method ofclaim 53, wherein the at least one of the discrete isolated regions has an area of less than 0.06 square microns.

55. An article defining a surface comprising palladium; and

a self-assembled layer of molecular species on the surface defining a pattern, the pattern corresponding to a pattern of an applicating surface able to direct formation of the pattern of the monolayer of the molecular species on the surface.

56. The article ofclaim 55, wherein the pattern includes a lateral dimension of less than 10 microns.

57. The article ofclaim 56, wherein the pattern includes a lateral dimension of less than about 5 microns.

58. The article ofclaim 57, wherein the pattern includes a lateral dimension of less than about 1 micron.

59. The article ofclaim 58, wherein the pattern includes a lateral dimension of less than about 0.25 micron.

60. A method of etching an article having a surface comprising palladium, comprising:

contacting a first portion of the surface with an applicator to transfer to the first portion a self-assembled layer of a molecular species in a first pattern, the self-assembled layer being contiguous with an exposed portion of the surface in a second pattern; and

contacting the article with an etchant that reacts chemically with the article thereby degrading a portion of the article in a pattern dictated by the pattern of the self-assembled layer.

61. The method ofclaim 60, further comprising coating a surface of the applicator with a self-assembled layer forming molecular species prior to contacting a first portion of the surface with the applicator.

62. The method ofclaim 61, wherein the surface of the applicator includes indentations and protrusions, the outward-facing surfaces of which define an applicator surface, the contacting step involving contacting the firs, non-planar portion of the surface with the applicator surface.

63. The method ofclaim 62, the contacting step comprising transferring the self-assembled layer to the non-planar portion of the surface by rolling the firs, non-planar portion of the article over the applicating surface of the applicator.

64. The method ofclaim 60, wherein the etchant is a first etchant.

65. The method ofclaim 64, further comprising contacting the article with a second etchant.

66. The method ofclaim 64, wherein the self-assembled layer resists the first etchant.

67. The method ofclaim 61, comprising applying a protecting species to the self-assembled layer.

68. The method ofclaim 67, wherein the protecting species is inert with respect to the first etchant.

69. A device comprising:

an article defining a surface comprising palladium;

an isolated region of a self-assembled layer of a first molecular species on the surface, the isolated region including a lateral dimension of less than 200 microns.

70. The device ofclaim 69, wherein the isolated region includes a lateral dimension of less than about 110 microns, surrounded by a continuous region of a self-assembled layer of a second molecular species on the surface, wherein the first molecular species comprises a first functionality and the second molecular species comprises a second functionality.

71. The device ofclaim 70, wherein the isolated region of the first molecular species has a lateral dimension of less than about 10 microns.

72. The device ofclaim 71, wherein the isolated region of the first molecular species has a lateral dimension of less than about 5 microns.

73. The device ofclaim 72, wherein the isolated region of the first molecular species has a lateral dimension of less than about 1 micron.

74. The device ofclaim 69, wherein the isolated region of the first molecular species has an area of less than 1 square micron.

75. The device ofclaim 74, wherein the isolated region of the first molecular species has an area of less than 0.06 square micron.

76. A method of plating a pattern of material on a surface of an article comprising palladium, the method comprising:

contacting a first portion of a surface of an article with an applicator to transfer to the first portion a self-assembled layer of a molecular species in a first pattern, the self-assembled layer being contiguous with an exposed portion of the surface in a second pattern; and

plating the surface of the article with a plating reagent in a pattern dictated by the pattern of the self-assembled layer.

77. The method ofclaim 76, wherein the surface of the article is non-planar.

78. A device for adhering at least one biological species in a specific and predetermined pattern comprising:

a surface;

a plurality of immobilization islands in a specific and predetermined pattern over the surface that adhere biological species to the islands, the islands isolated from each other by a background region contiguous with the islands and to which the biological species do not adhere, and wherein the islands or the background region or both comprise a self-assembled monolayer.

79. The device ofclaim 78, wherein the biological species is a cell.

80. The device ofclaim 78, wherein the background region or the immobilization islands comprise more than one self-assembled monolayer.

81. A device for selectively adhering protein in a specific and predetermined pattern comprising:

a surface;

a plurality of immobilization islands in a specific and predetermined pattern over the surface that selectively adhere protein to the islands, the islands isolated from each other by a background region contiguous with the islands and to which the protein does not adhere.

82. A device having a surface, comprising:

islands of a self-assembled monolayer terminating in a non-polar functionality surrounded by regions of a polyethylene glycol-terminating self-assembled monolayer, wherein the nonpolar functionality of the islands is protein adherent, while the polyethylene glycol is not protein adherent.

83. A device for immobilizing at least one biological material in a specific and predetermined pattern comprising:

a surface;

an array of immobilization islands in a specific and predetermined pattern over the surface isolated from each other by at least one background region;

the array of immobilization islands comprising a first self-assembled monolayer having a formula HS(CH₂)_nR in which R comprises at least one first functional group and wherein the at least one first functional group is selected to be biophilic;

the at least one background region comprising a second self-assembled monolayer having a formula HS(CH₂)_nR in which R comprises a second functional group wherein the second functional group is selected to be biophobic; and

wherein the HS(CH₂)_nportion of the first and second self-assembled monolayers are the same.

84. An article defining a surface; the surface comprising a plurality of isolated regions of a molecular species on the surface, the plurality of isolated regions defining a pattern, the pattern corresponding to a pattern of a stamping surface able to direct formation of the pattern of the molecular species on the surface, wherein the molecular species exposes a first chemical functionality.

85. The article ofclaim 84, wherein the plurality of isolated regions comprise a self-assembled monolayer on the surface.

86. The article ofclaim 84, wherein the first chemical functionality selectively binds a species selected from the group consisting of proteins, antibodies, antigens and carbohydrates.

87. A device having a surface, comprising:

a layer of a molecular species, comprising a biological attachment agent, in a first, predetermined pattern, the layer being contiguous with a portion of the surface that is in a second, predetermined pattern, wherein the molecular species terminates in a functional group selected to bind to a particular material.

88. A biological device having a surface, comprising:

a plurality of spaced apart isolated regions of a molecular species over the surface in a predetermined pattern, wherein the molecular species of the isolated regions is a biological attachment agent that facilitates attachment of biomolecules while maintaining the function of the biomolecules.

89. The device ofclaim 88, wherein each isolated region is less than 10 microns.

90. The device ofclaim 89, wherein each isolated region is less than 5 microns.

91. The device ofclaim 90, wherein each isolated region is less than 0.1 microns.

92. The device ofclaim 88, wherein the isolated region of a molecular species in a predetermined pattern is surrounded by an inert background region.

93. A device comprising:

at least one isolated region of a molecular species over the surface in a predetermined pattern, wherein the molecular species of the isolated region is a protein attachment agent that facilitates attachment of at least one protein to the isolated region.

94. An array device comprising:

a surface; and one or more immobilization islands in a pattern over the surface and surrounded by a background region, the background region comprising a species forming a self-assembled monolayer and terminating in a functional group selected to bind to a particular material.

95. A device comprising:

a substrate having a surface material;

at least one isolated region over the surface, each isolated region comprising a molecular species comprising the structure R′-A-R″, where R′ is selected to bind to the surface material, A is a spacer and R″ is a group that is exposed; the molecular species being a biological attachment agent.

96. The device ofclaim 95, wherein the at least one isolated region is surrounded by an inert background region.

97. A device for immobilizing at least one biological material in a specific and predetermined pattern comprising:

a surface;

an array of immobilization islands in a specific and predetermined pattern over the surface isolated from each other by at least one background region;

the pattern corresponding to a pattern of a stamping surface able to direct formation of the pattern of the immobilization islands on the surface;

the array of immobilization islands comprising a first self-assembled monolayer having an at least one first functional group and wherein the at least one first functional group is selected to be biophilic; and

the at least one background region comprising a second self-assembled monolayer having a second functional group wherein the second functional group is selected to be biophobic.

98. A kit comprising:

an article constructed and arranged to transfer a self-assembled monolayer-forming molecular species to a substrate surface, comprising an applicator surface having at least one indentation formed therein and a protrusion pattern adjacent the at least one indentation, the article able to transfer a self-assembled monolayer-forming molecular species from the applicator surface to the substrate surface; and

a self-assembled monolayer-forming molecular species for application to the substrate surface by the article.

99. The kit as recited inclaim 98, the article surface comprising at least one resolved feature providing stamping resolution of less than about 100 microns.

100. The kit as recited inclaim 98, the article surface comprising at least one resolved feature providing stamping resolution of less than about 10 microns.

101. The kit as recited inclaim 98, the article surface comprising at least one resolved feature providing stamping resolution of less than about 1 micron.

102. The kit as recited inclaim 98, the article surface comprising at least one resolved feature providing stamping resolution of less than about 0.25 micron.

103. The kit as recited inclaim 98, the article comprising an elastic material.

104. The kit as recited inclaim 103, the elastic material comprising a hardenable fluid.

105. The kit as recited inclaim 103, the elastic material selected from the group consisting of silicone polymers and copolymers, epoxy polymers and copolymers, and copolymers thereof.

106. The kit as recited inclaim 98, the article comprising polydimethyl siloxane.

107. A kit as inclaim 24, the applicator surface including a portion having a lateral dimension of less than about 1 micron.

108. A kit as inclaim 24, the applicator surface including a portion having a lateral dimension of less than about 0.25 micron.

109. A kit as inclaim 24, the applicator formed of an elastic material.

110. A kit as inclaim 24, the applicator formed of an elastic material formed form a hardenable fluid.

111. The kit as inclaim 110, the elastic material selected from the group consisting of silicone polymers and copolymers, epoxy polymers and copolymers, and copolymers thereof.

112. The kit as inclaim 41, wherein the applicator surface includes a portion having a lateral dimension of less than about 0.25 micron.

113. A kit as inclaim 41, the applicator surface including a portion having a lateral dimension of less than about 1 micron.

114. A kit as inclaim 41, the applicator surface including a portion having a lateral dimension of less than about 0.25 micron.

115. A kit as inclaim 41, the applicator formed of an elastic material.

116. A kit as inclaim 41, the applicator formed of an elastic material formed form a hardenable fluid.

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