MXPA98003530A - Method of contact printing on metal alloy-coated polymer films - Google Patents

Abstract

The present invention comprises methods of contact printing of patterned, self-assembling monolayers of alkanethiolates, carboxylic acids, hydroxamic acids, and phosphonic acids on thermoplastic films metallized with an alloy such as nickel/gold, the compositions produced thereby, and the use of these compositions. Patterned self-assembling monolayers allow for the controlled placement of fluids thereon which contain a chemically reactive, indicator functionality. The optical sensing devices produced thereby when the film is exposed to an analyte and light, can produce optical diffraction patterns which differ depending on the reaction of the self-assembling monolayer with the analyte of interest. The light can be in the visible spectrum, and be either reflected from the film, or transmitted through it, and the analyte can be any compound reacting with the fluid on the self-assembling monolayer. The present invention also provides a flexible support for a self-assembling monolayer on a metal alloy.

Description

METHOD PE PRINTING BY CONTACT ON POLYMER FILMS COATED METAL ALLOY Technical Field The present invention is in the field of contact printing and, more specifically, the present invention pertains to the field of microcontact printing on polymer films.

Background of the Invention Microcontact printing is a technique for forming organic monolayer patterns with μm and submicron side dimensions. It offers experimental simplicity and flexibility to form certain types of patterns. This rests on a remarkable ability of the self-assembled monolayers of long-chain alkammoniums to form on gold and other metals. These patterns can act as nanometer protective layers by protecting the supporting metal from corrosion through suitably formulated etchants, or, it can allow selective placement of the fluid over hydrophilic regions of the standard. The self-assembled monolayer patterns having dimensions that can be less than 1 μm are formed by using alknetiol as an "ink", and by printing them on the metal support using an elastomeric "stamp". The stamp is manufactured by molding a silicone elastomer using a reproducer prepared by X-ray or optical microlithography or by other techniques.

Microcontact printing of self-assembled monolayers with pattern gives microfabrication a number of new capabilities. First, the microcontact print makes it possible to form patterns that are distinguished only by their constituent functional groups; this capability allows the control of surface properties such as free interfacial energies with great precision. Second, because the microcontact print is based on the molecular self-assembly, it generates a system that is (at least locally) close to a thermodynamic minimum and is intrinsically defect rejector and autocurator. Simple procedures, with minimal protection against surface contamination by adsorbed materials or by particles, can lead to surprisingly low levels of defects in the final structures. This procedure can be carried out at atmospheric pressure, in an unprotected laboratory atmosphere. Therefore, microcontact printing is especially useful in laboratories that do not have routine access to the equipment normally used in microfabrication, or for which the cost of equipment capital is a serious concern. Third, self-assembled patterned monolayers can be designed to act as protective coatings with a number of chemical-wet pickling agents.

Working with liquid strippers suffers from the disadvantages of handling solvents and waste disposal, but also enjoys the substantial advantages: a high degree of control over surface contamination; reduced damage to the substrate of energetic interactions with atoms or ions; the ability to manipulate sensitive and complex organic functionality. Because the self-assembled monolayers are only 1-3 nm thick, there is little loss in edge definition due to the thickness of the protective layer; The main determinants of edge resolution seem to be the fidelity of the contact impression and the anisotropy of the pickling of the underlying metal. In the best current cases, size characteristics of 0.2 μm can be manufactured; The resolution of edge in the systems showing this resolution in characteristic size is less than 50 nm.

In the prior art, a gold film of 5 to 2000 nanometers thick is typically supported on a glass sheet or si / Si02 plate primed titanium. Titanium serves as an adhesion promoter between gold and support. However, the silicon insert is rigid, brittle and can not transmit light. These silicon plates do not either. suitable for a large-scale continuous printing process, such as letter printing, gravure printing, direct printing, and screen printing (see the book Fundamentos de Impresión by A. Glassman Editores, (Tappi Press Atlanta, GA 1981 ); Encyclopedia Britannica, volume 26, pages 76-92, 110-111 (Encyclopedia Britannica, Inc. 1991)). In addition, the silicon must be treated in a separate step with an adhesion promoter such as Cr or Ti, or Au will not adhere properly, preventing the formation of a well-ordered and stable self-assembling monolayer. Finally, the silicon is opaque, so that a diffraction pattern obtained must be created with non-transmitted reflected light. What is necessary is an easy, efficient and simple method of printing by contact on a flexible, optically transparent substrate that is docile to continuous processing.

Synthesis of the Invention The present invention comprises contact printing methods of self-assembled monolayers with alkanolamides, carboxylic acids, hydroxamic acids and phosphonic acids on thermoplastic films metallized with an alloy such as nickel / gold, the compositions produced by them and the use of these compositions.

The self-assembling monolayers with pattern allow the controlled placement of the fluids on them which may contain an indicator of chemically reactive functionality. The optical sensing devices produced therewith when the film is exposed to an analyte and light can produce optical diffraction patterns which differ depending on the reaction of the self-assembling monolayer with the analyte of interest. The light may be in the visible spectrum, and may be either reflected from the film, or transmitted through it, and the analyte may be any compound that reacts with the self-assembling monolayer. The present invention also provides a flexible support for a self-assembling monolayer on a metal alloy.

The present invention includes a support for a self-assembling monolayer on a metal alloy that does not require an adhesion promoter for the formation of a highly ordered self-assembling monolayer. The present invention also provides a support for a self-assembling monolayer on a metal alloy which is suitable for continuous rather than letter manufacturing. Finally, the present invention provides a low cost disposable sensor which can be mass produced.

These and other objects, features and advantages of the present invention will become apparent upon review of the following detailed description of the described embodiments.

Brief Description of the Figures Figure 1 is a self-assembling monolayer per-contact printing scheme, using a nickel / gold coated polymer substrate as an example. A polydimethylsiloxane (silicone elastomer PDMS 184; Dow Corning Corporation, Midland, MI) is polymerized with a silicone player containing a predetermined pattern. The PDMS is peeled from the replicate, and then exposed to a solution containing HS (CH2) 15CH3. The alkali-thiol coated stamp is then stamped onto the gold / nickel coated substrate. Thereafter, the surface of the substrate is exposed to a solution containing a different alkane thiol such as HSÍCH ^^ OH.

Figure 2 is a secondary electron microscope image of field emission of 10 microdiameter circles of self-assembling hydrophilic monolayers formed by printing 16-mercaptohexadecanoic acid onto the metallized MYLAR® with a Ni / Au alloy, as described in FIG. Example 1.

Figure 3a is an optical photomicrograph at a 300x magnification of 10 micron diameter circles of self-assembling hydrophilic monolayers by printing 16-mercaptohexadecanoic acid, as described in Example 1, below, and after exposure to an adhesive Optical, curable, high-energy surface. The adhesive was cured by exposure to ultraviolet (UV) light.

Figure 3b is a photograph of the diffraction pattern formed by visible light shown through the self-assembling monolayer pattern described by Figure 3a.

Figures 4a and 4b are a secondary electron micrograph image of field emission of circles of 10 microns in diameter formed of self-assembled photocurable polymers on the hydrophilic self-assembling monolayers, printed as described in Example 1.

Detailed description The present invention provides contact printing methods of self-assembled monolayers with alkanolamides, carboxylic acids, hydroxamic acids, and phosphonic acids on polymer films metallized with an alloy such as nickel / gold., thermoplastic polymer films desirably, the compositions produced by means of them, and the use of these compositions. Self-assembling patterned monolayers allow controlled placement of fluids on them which may contain a chemically reactive indicator functionality. The term "self-assembling monolayers with pattern thereon" as used herein means self-assembling monolayers in any part on the metallized polymer films including a solid pattern.

In one embodiment, optical sensor devices can be produced according to the present invention. When the film with the self-assembling monolayers thereon is exposed to an analyte that is capable of reacting with the self-assembling monolayer, the film will produce optical diffraction patterns which differ depending on the reaction of the self-assembling monolayer with the analyte of interest. The liquid may be a high surface tension fluid such as water. The light may be in the visible spectrum, and either be reflected from the film, or be transmitted through it, and the analyte may be any compound that reacts with the self-assembling monolayer.

Self-assembling monolayers of organic compounds on metal or inorganic surfaces have become incrngly important in many arof material science. Although there are many different systems of self-assembling monolayers based on different organic compounds and supports, the desired systems are those of alcanetiolates, HS (CH2) nR. Typically, a gold film, 5 to 2000 nm thick, is supported on a Si / Si02 glass sheet or titanium primed plate. Titanium serves as an adhesion promoter between gold and support. The alknetiols are quimoadsorben on the gold surface of a solution in which the gold film was immersed, and formed. alcanetiolatos adsorbed with loss of hydrogen. Adsorption can also occur from steam. The self-assembling monolayers formed on gold of the long chain alknetiolates of the structure X (CH2) nY (CH2) mS are highly ordered and can be considered as crystalline or crystalline molecular arrays. A wide variety of organizational functional groups (X, Y) can be incorporated within the surface or interior of the monolayer.

The self-assembling monolayers can therefore be tailored to provide a wide variety of material properties: wettability and protection against corrosion by chemical strippers are especially relevant for the μCP. In one embodiment of the invention, there are two or more self-assembling monolayers with different chemical properties. In another embodiment of the invention, a first self-assembling monolayer is hydrophobic, and a second self-assembling monolayer is hydrophilic.

Figure 1 delineates the procedure used for microcontact printing. An elastomeric stamp is used to transfer the alkali metal "ink" contact to a surface coated with a metal alloy. In a preferred embodiment, the alloy surface is predominantly gold. Preferred alloys are those such as nickel / gold, which are known to show an enrichment in the gold surface concentration in relation to their volume concentration. The prediction of the surface segregation of a metal of an alloy is described in M.P. Seah, "Quantitative Prediction of Surface Segregation", Journal of Catalysis, volume 57, pages 450-457 (1979), and JJ Burton et al., "Prediction of Surface Segregation of Alloys of Volume Phase Diagrams", Letters of Physical Review, volume 37, No. 21, pages 1433-1436 (November 22, 1976), both incorporated herein by reference. In one embodiment of the invention, the metal alloy has a surface enrichment of a metal by reacting with the self-assembling monolayer. If the seal is patterned, a self-assembling monolayer with pattern is formed. The seal or stamp is manufactured by setting polydi ethylsiloxane (PDMS) on a reproducer having the desired pattern. The reproducers are prepared using standard photolithographic techniques, or constructed from existing materials having microscale surface characteristics.

In a typical experimental procedure, a photolithographically produced reproducer is placed in a glass plastic Petri dish, and a 10: 1 (w: w or v: v) ratio mixture of silicone elastomer 184 SYLGARD and silicone elastomer 184 SYLGARD setting agent (Dow Corning Corporation) is poured onto it. The elastomer is allowed to sit for approximately 30 minutes at room temperature, pressed to degas, and then cured for 1-2 hours at 60 ° C, and gently peeled off the player. The "inking" of seal or elastomeric die is achieved by exposing the die to a solution of 0.1 to 1.0 mM of an alknetiol in anhydrous ethanol, either by pouring the solution on the surface of the die or by rubbing the die gently. with a stick with cotton known as Q-tip that has been saturated with the inking solution. The die is allowed to dry until no visible liquids are visible on the surface of the die (typically around 60 seconds), either under ambient conditions, or by exposure to a stream of nitrogen gas. After inking, the die is applied (typically by hand) to a metal alloy, for example, a nickel / gold surface. A very light manual pressure is used to assist the full contact between the die and the surface. The die is then gently peeled from the surface. After removal of the die, the surface is washed of excess thiol and the patterned metal alloy surface can be subjected to chemical etchants (see below) that selectively remove non-derivatized areas from the metal alloy surface, and if desired, the underlying support or supports. Alternatively, additional derivatization of the unsealed areas can be achieved, either by using a second die, or by washing the entire surface with a different alknetiol.

The elastomeric character of the die is essential for the success of this process. The polydimethylsiloxane (PDMS), when set, is elastomeric enough to allow good die and surface conformation contact, even when for surfaces with a significant relief, this contact is essential for an efficient contact transfer of the alknetol ink to the film coated with alloy. The elastomeric properties of the polydimethylsiloxane are also important when the die is removed from the player: if the die was rigid (as is the player) it would be difficult to separate the die and the player after setting without damaging one of the two substrates. The polydimethylsiloxane is also rigid enough to retain its shape, even for submicron dimensions: we have successfully generated patterns with lines as small as 200 nm wide. The surface of the polydimethylsiloxane has an interfacial free energy (y = 22.1 dynes / cm), and the die does not adhere to the film coated with metal alloy. The die is durable: we have used the same die up to 100 times over a period of several months without significant degradation in performance. The polymeric nature of the polydimethylsiloxane also plays a critical role in the inking process, by allowing the die to absorb the alknetiol ink by swelling.

The microcontact printing on the metal alloy surfaces can be carried out with a variety of alknetiol inks. Alcanetols that do not undergo reactive spreading (after application to the metal alloy film) are required for the formation of small characteristics with high resolution. For stamping in the air, one can use autophobic alcanetiols such as hexadecanetiol. The microcontact printing of other non-autophobic alknetiols, for example, HS (CH 2) lsCOOH, can be carried out by printing under a liquid such as water. Self-assembling monolayers with alcanetolles pattern on metal alloy provide an excellent protective layer character with a number of chemical-wet pickling agents.

In one embodiment of the present invention, the self-assembling monolayer is formed of a carboxy-terminated alkyleneol stamped with a patterned elastomeric die on a nickel / gold surface thermoplastic film such as MYLAR®. The alknetiol is inked with a solution of alknetol in ethanol, dried and brought into contact with a nickel / gold surface. The alknetium is transferred to the surface only in those regions where the die contacts the surface, producing a self-assembling monolayer pattern which is defined by the die pattern. Optionally, the unmodified nickel / gold surface areas near the stamping areas can be made hydrophobic by reacting with a thiol of methyl-terminated alkane.

A more detailed description of the methods and compositions of the present invention goes on. All publications cited here are incorporated by reference in their entirety.

Any thermoplastic film on which a metal substrate can be deposited is suitable for the present invention. These include, but are not limited to polymers such as polyethylene terephthalate (MYLAR®) acrylonitrile-butadiene-styrene, acrylonitrile-methyl acrylate copolymer, cellophane, cellulosic polymers such as ethyl cellulose, cellulose acetate, acetate butyrate of cellulose, cellulose propionate, cellulose triacetate, cellulose triacetate, polyethylene, polyethylene-vinyl acetate copolymers, ionomers (polymers of ethylene) polyethylene-nylon copolymers, polypropylene, polymers of methyl pentene, polyvinyl fluoride, and aromatic polysulfones . Preferably, the plastic film has an optical transparency of more than 80%. Other suitable thermoplastics and suppliers can be found, for example, in reference works such as the Modern Plastics Encyclopedia (McGraw-Hill Publishing Co., New York 1923-1996).

In one embodiment of the invention, the thermoplastic film with the metal coating thereon has an optical transparency of between about 5% and 95%. A more desired optical transparency for the thermoplastic film used in the present invention is about 20% and 80%. In a desired embodiment of the present invention, the thermoplastic film has at least an optical transparency of approximately 80%, and the thickness of the metal coating is such as to maintain an optical transparency greater than about 20%, so that that diffraction patterns can be produced by either reflected or transmitted light. This corresponds to a metal coating thickness of around 20 nm. However, in other embodiments of the invention, the gold thickness may be between about 1 nm and 1000 nm.

The preferred metal alloy for deposition on the film is gold and other metal. However, alloys of silver, aluminum, copper, iron, zirconium, platine, nickel can also be used. Preferred metals are those that do not form non-oxides, and therefore help in the formation of more predictable self-assembling monolayers. The tai alloys such as Ni / Au, Pt / Au, and Cu / Au, which show Au surface enrichment, are adequate.

In principle, any surface with corrugations of appropriate size can be used with players. The microcontact printing process begins with an appropriate relief structure, from which an elastomeric die is forged. This tempered "reproducer" can be generated photolithographically, or by other methods such as commercially available diffraction gratings. In an embodiment, the die can be made polydimethylsiloxane.

In an embodiment of the present invention, the self-assembling monolayer has the following general formula: X-R-Y X is reactive with metal or metal oxide. For example X can be asymmetric or symmetrical disulfide (-R'SSR, - RSSR), sulfide (-R'SR, -RSR), diselenide (-R'Se-SeR), selenide (-R'SeR,, -RSeR), thiol (-SH), nitrile (-CN), isonitrile, nitro (-N02), selenol (-SeH), trivalent phosphorus compounds, isothiocyanate, xanthate, thiocarbamate, phosphine, thioacid or diothioacid, carboxylic acids, hydroxylic acids, and hydroxamic acids.

The R and R 'are hydrocarbon chains which may be optionally interrupted by hetero atoms which are preferably unbranched for the safety of an optimum dense packing. At room temperature, R is greater than or equal to seven carbon atoms in length, in order to overcome the natural random placement of the self-assembling monolayer. At colder temperatures, R may be shorter. In a preferred embodiment, R is - (CK2) n- where n is between 10 and 12, inclusive. The carbon chain can optionally be perfluorinated.

And it can also have any surface property of interest. For example, Y may be any among the large number of groups used for immobilization in liquid chromatography techniques, such as hydroxy, carboxyl, amino, aldehyde, hydrazide, carbonyl, epoxy or vinyl groups. Examples of sensor layer materials are set out in the book "Self-assembling Monolayers with Pattern Using Microcontact Printing: A New Technology for Biosensors?" of Milan Mrksich and George M. Whitesides, published in TIBTECH, June 1995 (volume 13), pages 228-235, incorporated herein by reference.

Self-agglomerating monolayers of alkyl phosphonic, hydroxamic and carboxylic acids can also be used for the methods and compositions of the present invention. Since the alknetols are not absorbed to the surface and to uchc metal oxides, carboxylic acids, phosphonic acids. and hydroxamic acids may be preferred for X to: those metal oxides. See J.P. Folkers, G.M. Whitesides others, Langmuir, 1995, volume 11, pages 813-824.

R can also be of the form (CH2) a-Z- (CH2) b,. where a20, b27, and Z is any chemical compound of interest such as sulfones, urea, lactam, etc.

The die can be applied in air or under a fluid such as in water to prevent the diffusion of excess alknetiol. For continuous or large-scale printing processes, it is more desirable to print the air, since shorter contact times are desirable for those processes.

In one embodiment of the present invention, the pattern is formed on the metallized thermoplastic polymer with the self-assembling monolayer. In another embodiment of the present invention, the pattern relief is formed with the self-assembling monolayer. After the stamping process, the metallized areas on the plastic can optionally be passivated, for example, with a self-assembling monolayer finished with methyl such as hexadecyl mercaptan.

This invention is further illustrated by the following example which should not be considered in any way as imposing limitations on the scope thereof. On the contrary, it should be clearly understood that it can be resorted to several other modalities, modifications and equivalents thereof, which, after reading the description given here, may suggest itself to those experts in art without departing from the spirit and scope of the present invention.

Example 1 Print of MYLAR® (polyethylene terephthalate) coated with nickel / gold with patterns of 16-mercaptohexadecanoic and hexadecanetiol A nickel / gold alloy was coated with jet on 7 mil of MYLAR® with a thickness of 15.9 nM. The composition had 65% visible light transmittance and 65 ohms / cm2 of resistance. The following results of the XPS surface analysis were obtained.

ND means "undetected," for example, less than 0.2 atom-percent.

These results show that the outermost surface of the Ni / Au alloy is predominantly Au, for example, Ni was not detected until after approximately 5.0 nM was removed. Therefore, the alloy has a surface that looks like pure gold and can be used as a "pure gold" surface for contact printing.

The modified MYLAR® film with a nickel / alloy top deposited with jet was obtained from Courtaulds Performance Films (from 21034 Osborne Street, of Canoga Park, Ca 91304). The hydroxyl-terminated carboxy alkanol standards were stamped onto the metallized Ni / Au MYLAR® using CH3 (CH2) 15SH and HOC (O) (CH2) 14SH acid by the following method. (See Figure 1). A pattern of photocurable substance exposed and developed from circles of 10 microns in diameter on a silicon wafer was used as the reproducer. Polydimethylsiloxane (PDMS); silicone elastomer 184; Dow Corning Company, Midland, MI), was polymerized on a reproducer to produce a die with circles of 10 microns in diameter spaced by a separation of 5 microns. The die was inked by exposure to a solution (1 to 10 mM in ethanol) of 16-mercaptohexadecanoic acid) and allowed to air dry. The substrate was contacted with the die for 50 seconds and washed for 2 to 4 seconds with a solution of hexadecanetiol (1 to 10 mM in ethanol). The substrate was finally washed for 10 seconds in ethanol and dried in a stream of nitrogen. The results of this printing are shown in Figure 2.

These self-assembling hydrophilic monolayer circles allow selective placement of high surface tension fluids such as water, triethylene glycol or ultraviolet lighttable urethane acrylic adhesives. These liquids may contain dissolved and suspended reagents which react chemically or physically with the target analytes, thereby making the coated plastic film a collection of 10 micron reactors suitable for low cost disposable chemical sensors. An example of such a device is shown in Figure 3a.

The diffraction of visible light was shown with these compositions. Both reflected and transmitted diffraction patterns were observed when laser illumination of 5 mW, 670 nM was used. Figure 3b is a photograph of the diffraction pattern formed by visible light shown through the self-assembling monolayer pattern of Figure 3a. The rainbow diffraction colors were observed with the transmitted white light.

Measurement of Contact Angles The contact angles were measured on a Rame-Hart Model 100 goniometer at room temperature and ambient humidity. The water for the contact angles was deionized and distilled in a Teflon and glass apparatus. The advance and retreat of the contact angles was measured on both sides of at least three drops of each liquid per stage, the data in the figures represent the average of these measurements. The following method was used to measure the contact angles: a drop of approximately 1-2 microliters in volume was cultured on the tip end of a pipette (Micro-Electrapette syringe, from Matrix Technologies, from Lowell, MA). The tip was then lowered to the surface until the drop contacted the surface). The drop was advanced by slowly increasing the volume of the drop. { rate of approximately 1 microliter / second). The advancing contact angles of the water were measured immediately after the front of the drop had moved smoothly for a short distance across the surface. The angles that are retracted were taken after the drop had been gently retracted through the surface by decreasing the volume of the drop.

Photoelectronic Spectroscopy of Ra os X (XPS) X-ray photoelectron spectra were collected on an SSX-100 Surface Science spectrometer using a monochromatized Al K-alpha source (hv 1486.6 volts electron). The spectra were recorded using a spot size of 600 micrometers and a step power over the detector of 50 electron volts (acquisition time for an analysis was approximately 1.5 minutes). For the monolayers, the spectra were collected for carbon and oxygen using the ls peaks at 285 and 530 eV, respectively; the binding energies for the elements in the monolayer were referred to the peak due to the hydrocarbon in the C ls region, for which we set the binder energy to 284.6 eV. The spectra for the solid hydroxamic acid were collected using a 4.5 eV electronic flood gun to dissipate the charge in the sample. The binding energies for the substrates were not standardized to a reference sample. All spectra were adjusted using a peak form of 80% Gaussian / 20% Lorentzian and a Shirley background subtraction. See J.P. Folkers, G.M. Whitesides et al., Langmuir, volume 11, No. 3, pages 813-824 (1995).

Condensation Figures Condensation figures (CFs) are arrays of liquid droplets that form with the condensation of steam on a solid surface. The examination of the condensation figures has historically been used as a method to characterize the degree of contamination on an otherwise homogeneous surface. One is able to impose a pattern on arrays of condensed droplets by patterning the surface underlying them in regions of a different free vapor-solid interfacial energy and to characterize the condensation patterns by photomicroscopy and optical diffraction. It has been shown that patterns with pattern condensation can appropriately be used as optical diffraction gratings and that the examination of the diffraction patterns provides both a rapid and non-destructive method for characterizing self-assembled monolayers with pattern and an approach to perceive the environment. Because «that the shape of the condensation figures, that is, the size, density, and distribution of the droplets is sensitive to environmental factors, condensation figures of appropriate size and pattern diffraction light can be used as sensors. The principle is demonstrated by correlating the temperature of a standard substrate in hydrophobic and hydrophilic regions, in an atmosphere of constant relative humidity, with the intensity of the light diffracted from the condensation figures on these regions.

Suitable standards are formed from self-assembled monolayers (self-assembling monolayers) over gold / nickel by using combinations of hexadecanetiol [CH3 (CH2) 15SH], 16-mercaptohexadecanoic acid [HS (CH2) 14COOH], and 11-mercaptoundecanol [HS (CH ) ^ OH]. Several techniques are now available to prepare patterns of two or more self-assembling monolayers having dimensions of 0.1 to 10 μm.

At 20oC an incident ray of light from a laser (neon-helium laser, wavelength = 632.8 nm) produced a single transmitted point because no water had condensed on the surface, and the transmission of regions covered with different Self-assembling monolayers were effectively indistinguishable. When the surface was exposed to moist, warm air, the water droplets were preferably condensed on the hydrophilic regions. The diffraction patterns appeared in the light transmitted from the surface.

Under these conditions, the light was coherently transmitted from the regions where water had not condensed and spread through the regions where the water had condensed. The condensation figures disappeared in several seconds as the water droplets that had condensed on the self-assembling monolayers evaporated.

The ability to form condensation shapes can be established by the relative contact angles of the water on the hydrophobic and hydrophilic self-assembling monolayers. Unprimed monolayers of the appropriate thiol were repaired by immersing the substrate in a diluted solution for one hour, followed by ethanol rinsing and air drying.

The contact angles of water on Au (Ni) / MyLAR reacted with CH3 (CH2) 15SH and H0C (0) (CH2) 14SH were 100o and 62o, respectively. The contact angle of Au (Ni) / MyLAR not treated for water was 73-77D. This water contact angle is similar to that obtained for Si-coated plates of Au, which is 73-74 (data not shown).

The condensation figures [Science, Volume 263, 60, (1994), incorporated herein by reference] with equivalent optical diffraction can be formed on Au / Ni: MYLAR®, relative to the known art with Au: Si0x. This chemistry of alcanetiols reacted with Au / Ni: MYLAR is similar to that reported in the literature for Au: SiOx.

A secondary electron microscope image of field emission of 10 micron diameter circles of self-assembling hydrophilic monolayers formed by printing 16-mercaptohexadecanoic acid onto MYLAR® metallized with Ni / Au alloy is shown in Figure 2. Figure 3 is an optical photomicrograph to an amplification of 300x of circles of 10 microns in diameter of self-assembling monolayers formed by the printing of 16-mercaptohexadecanoic acid, and then with exposure to an optical adhesive, settable of high surface energy. The adhesive was cured by exposure to ultraviolet (UV) light.

Figure 3b is a photograph of the diffraction pattern formed by visible light shown through the self-assembling monolayer pattern described in Figure 3a.

Figures 4a and 4b are secondary electron micrograph images of field emission of circles of 10 microns in diameter formed of self-assembling photofractile polymers on self-assembling hydrophilic monolayers.

Those skilled in the art will now see that certain modifications can be made to the invention described herein with respect to the illustrated embodiments, without departing from the spirit of the present invention. And even though the invention has been described above with respect to the preferred embodiments, it will be understood that the invention is adapted to numerous rearrangements, modifications, and alterations, all of which arrangements, modifications and alterations are intended to be within the scope of the appended claims. .

Claims (39)

R E I V I ND I C A C I O N S

1. A film with self-assembling monolayers with a pattern on it that includes: a polymer film coated with a metal alloy; Y a self-assembling monolayer printed on the polymer film.

2. The film as claimed in clause 1, characterized in that the metals to be alloyed are selected from the group consisting essentially of gold, silver, nickel, platinum, aluminum, iron, copper, and zirconium.

3. The film as claimed in clause 1, characterized in that the alloy coating is between about 1 nanometer and 1000 nanometers thick.

4. The film as claimed in clause 1, characterized in that the polymer film is polyethylene terephthalate, acrylonitrile-butadiene-styrene, acrylonitrile-methylacrylate copolymer, cellophane, cellulosic polymers such as ethyl cellulose, cellulose acetate, butyrate cellulose acetate, cellulose propionate, cellulose triacetate, cellulose triacetate, polyethylene, vinyl acetate-polyethylene copolymers, vinyl acetate-polyethylene copolymers, ionomers (ethylene polymers), nylon-polyethylene copolymers, polypropylene, methyl polymers Pentene, polyvinyl fluoride, and aromatic polysulfones.

5. The film as claimed in clause 4, characterized in that the polymer film is polyethylene terephthalate.

6. The film as claimed in clause 1, characterized in that the polymer film is optically transparent.

7. The film as claimed in clause 1, characterized in that the polymer film has an optical transparency of between 5% and 95%.

8. The film as claimed in clause 1, characterized in that the polymer film has an optical transparency of between about 20% and 80%.

9. The film as claimed in clause 1, characterized in that the self-assembling monolayer is formed of compounds with the following general formula: X-R-Y where : X is reactive with the metal or metal oxide on the polymer film; R is a hydrocarbon chain; Y And it is a compound with which "any property of interest.

10. The movie as claimed in clause 9, characterized in that: X is an asymmetric or symmetrical disulfide (-R'SSR, -RSSR), sulfur (-R'SR, -RSR), diselenide (-R'Se-SeR), selenide (R'SeR, -RSeR), thiol (-SH), nitrile (-CN), isonitrile, nitro (-N02), selenol (-SeH), trivalent phosphorus compounds isothiocyanate, xanthate, thiocarbamate, phosphine, thioacid, or dithioacid , carboxylic acids, hydroxylic acids, and hydroxamic acids; R and R 'are hydrocarbon chains which may be optionally interrupted by heteroatoms, and which may optionally be perfluorinated, and which are preferably branched; Y And it is optionally hydroxy, carboxyl amino, aldehyde, hydrazide, carbonyl, epoxy or vinyl groups.

11. The film as claimed in clause 9, characterized in that R is greater than 7 carbon atoms in length.

12. The film as claimed in clause 9, characterized in that R is a compound of the form (CH2) a-Z- (CH2) b, wherein a20, b27, and Z is any chemical functionality of interest.

13. The film as claimed in clause 12, characterized in that Z is selected from the group consisting of sulfones, lactams, and urea.

14. The film as claimed in clause 1, characterized in that there are two or more self-assembling monolayers with different chemical properties.

15. The film as claimed in clause 1, characterized in that a first self-assembling monolayer is hydrophobic and a second self-assembling monolayer is hydrophilic.

16. A method for making a film with a self-assembling monolayer pattern comprising embossing a pattern of self-assembling monolayers on a polymer film coated with a metal alloy.

17. The method as claimed in clause 16, characterized in that the metals to be alloyed are selected from the group consisting essentially of gold, silver, nickel, platinum, aluminum, iron, copper and zirconium.

18. The method as claimed in clause 17, characterized in that the metal alloy coating is between about 1 nanometer and 1000 nanometers in thickness.

19. The method as claimed in clause 16, characterized in that the alloy is a nickel / gold alloy.

20. The method as claimed in clause 16, characterized in that the polymer film is polyethylene terephthalate, acrylonitrile-butadiene-styrene, acrylonitrile-methyl acrylate copolymer, cellophane, cellulosic polymers such as ethyl cellulose, cellulose acetate, butyrate of cellulose acetate, cellulose propionate, triacetate and cellulose, cellulose triacetate, polyethylene, polyethylene-vinyl acetate copolymers, ionomers, (ethylene polymers) nylon-polyethylene copolymers, polypropylene, methyl pentene polymers, polyvinyl fluoride and aromatic polysulfones.

21. The method as claimed in clause 20, characterized in that the polymer film is polyethylene terephthalate.

22. The method as claimed in clause 16, characterized in that the polymer film is optically transparent.

23. The method as claimed in clause 16, characterized in that the polymer film has an optical transparency of between 5% and 95%.

24. The method as claimed in clause 16, characterized in that the polymer film has an optical transparency of between about 20% and 80%.

25. The method as claimed in clause 16, characterized in that the self-assembling monolayer is formed of compounds with the following general formula: X-R-Y where : X is reactive with the metal or metal oxide on the polymer film; R is a hydrocarbon chain; Y And it is a compound with any property of interest.

26. The method as claimed in clause 25, characterized by "that: X is an asymmetric or symmetrical disulfide (-R'SSR, -RSSR), sulfide (-R'SR, -RSR), diselenide (-R'Se-SeR), selenide (R'SeR, -RSeR), thiol ( -SH), nitrile (-CN), isonitrile, nitro (-N02), selenol (-SeH), trivalent phosphorus compounds isothiocyanate, xanthate, thiocarbamate, phosphine, thioacid, or dithioacid, carboxylic acids, hydroxylic acids, and hydroxamic acids; R and R 'are hydrocarbon chains which may be optionally interrupted by heteroatoms, and which may optionally be perfluorinated, and which are not preferably branched; Y And it is optionally hydroxy, carboxyl amino, aldehyde, hydrazide, carbonyl, epoxy or vinyl groups.

27. The method as claimed in clause 25, characterized in that R is greater than 7 carbon atoms in length.

28. The method as claimed in clause 25, characterized in that R is a compound of the form (CH2) a-Z- (CH2) b, wherein a20, b27, and Z is any chemical functionality of interest.

29. The method as claimed in clause 28, characterized in that Z is selected from the group consisting of sulfones, lactams, and urea.

30. The method as claimed in clause 16, characterized in that there are two or more self-assembling monolayers with different chemical properties.

31. The method as claimed in clause 16, characterized in that a first self-assembling monolayer is hydrophobic, and a second self-assembling monolayer is hydrophilic.

32. The film as claimed in clause 1, characterized in that the polymer is a thermoplastic polymer.

33. The method as claimed in clause 16, characterized by "that the polymer film is a thermoplastic polymer film.

34. The film as claimed in clause 1, characterized in that the metal alloy is selected from the group consisting of Ni / Au, Pt / Au and Cu / Au.

35. The method as claimed in clause 16, characterized in that the metal alloy is selected from the group consisting of Ni / Au, Pt / Au and Cu / Au.

36. A film with self-assembling monolayers with a pattern on it that includes: a polymer film coated with metal alloy; and a self-assembling monolayer printed on the polymer film; wherein the metal alloy has a surface enrichment of a metal by reacting with the self-assembling monolayer.

37. The film as claimed in clause 36, characterized in that the metal alloy is selected from the group consisting of Ni / Au, Pt / Au and Cu / Au.

38. A method for making a film with a self-assembling monolayer pattern comprising embossing a pattern of self-assembling monolayers on a polymer film coated with a metal alloy, wherein the metal alloy has a surface enrichment of a metal by reacting with the monolayer Self-assembly

39. The method as claimed in clause 38, characterized in that the metal alloy is selected from the group consisting of Ni / Au, Pt / Au and Cu / Au. R E S M E N The present invention comprises contact printing methods of self-assembling monolayers with alkanolamides, carboxylic acids, hydroxamic acids, and phosphonic acids on thermoplastic films metallized with an alloy such as nickel / gold, the compositions produced therewith, and the use of these compositions. Self-assembling patterned monolayers allow controlled placement of fluid over them that contain a chemically reactive indicator functionality. The optical sensing devices produced therewith when the film is exposed to an analyte and the light can produce optical diffraction patterns which differ depending on the reaction of the self-assembling monolayer with the analyte of interest. The light may be in the visible spectrum, and may be either reflected from the film, or transmitted through it, and the analyte may be any compound that reacts with the fluid on the self-assembling monolayer. The present invention also provides a flexible support for a self-assembling monolayer on a metal alloy.