TW578291B - Method of self-latching for adhesion during self-assembly of electronic or optical components - Google Patents

Abstract

A method for assembling components on a substrate including the steps of: (a) selectively coating at least a first receptor site of the substrate with a liquid precursor that forms a solid adhesive upon contact with an initiator; (b) providing each of the components with an adhesion surface that has the initiator; and (c) depositing the components on the substrate in a manner that causes a first of the components to contact the at least first receptor site whereupon contact between the initiator and the liquid precursor causes formation of the adhesive which affixes the first compound to the first receptor site. In a preferred embodiment of the invention, the precursor is a liquid monomer and the initiator initiates a polymerization reaction upon contact with the monomer to form a solid polymer.

Description

578291

V. Description of the Invention (1) 1 Field of the Invention The present invention relates to a method for self-assembling microstructures. In particular, the present invention relates to self-assembling and adhering components to microstructures. More specifically, the invention relates to the permanent attachment of components to microstructures during the self-assembling step. 1 Bright background In a self-assembling program, components can be combined without placing the components in a special structure. Because the required structure is the lowest energy state available to the system, the components are assembled in a special structure. Terfort et al. (Three-dimensional self-assembly of millimeter-scale components, Nature Vol. 386, March 13, 1997, pages 162-164) describe a self-assembling micro-assembly by generating hydrophilic and water-repellent surfaces. In the structural procedure, the water-repellent surfaces are adhered to each other, and a liquid is used as a lubricant to allow the components to adjust each other's position by lateral movement, and a photopolymerizable adhesive can be used to wet the components. As the system approaches equilibrium, the system is exposed to ultraviolet radiation and the components attach to a permanent form. U.S. Patent No. 5,824,186 and related patents describe the use of a eutectic layer (gold, silver, solder) for bonding in a heating step after the transfer step. Conventional techniques also describe methods for achieving locking in self-positioning objects, such as including the use of a UV-polymerizable adhesive, the use of a metal solder at a temperature sufficient to melt the solder, or the use of heat or freezing The components in place to harden the polymerizable coating used in combination. In each of the above methods, after the self-positioning combination step is completed, another processing step is performed to permanently lock the object in place. For UV photopolymerization

578291 V. Description of the invention (2) Adhesive, the system must be exposed to ultraviolet light for a period of time, and the combined object and coating must be transparent to the wavelength of ultraviolet light. For systems using solder, the system must be cooled below the melting temperature of the solder. In the case of thermally polymerized systems, the adhesive is hardened only after the composition is completed. The inventor is not aware of any self-assembling system that permanently adheres during the assembly process, nor is the inventor aware of any other that can selectively harden when individual components or components are positioned in or on an appropriate position on a substrate. Adhesive technology. SUMMARY OF THE INVENTION The present invention relates, in particular, to a method for combining objects on a substrate, specifically, this method relates to self-assembly by which an object is attached to a substrate. More specifically, this method is about self-assembly and attaching an object to or in a socket on a substrate. One advantage of the present invention is that once an object is self-positioned on or in a socket on or on a substrate ', no additional steps are required to permanently attach the object to the substrate or socket. In this application, the terms "self-localization," "self-assembly," and "self-assembly" are used interchangeably. According to the present invention, a method for assembling a component on a substrate is provided. The method includes the following steps: ya) selectively coating at least a first acceptor address of the substrate with a precursor to initiate a A solid adhesive is formed when the agent is contacted; each component is provided with a bonding surface containing an initiator; and the manner in which the component / child accumulates on the substrate can cause a first component to contact at least the first receptor address. The contact between the initiator and the liquid precursor causes an adhesive to form to attach the first compound to the first acceptor site.

578291

V. Description of the invention (3)

In an embodiment of the present invention, step (c) includes depositing a slurry containing a carrier fluid and a plurality of components on a substrate, the precursor and the initiator are not mixed with the carrier fluid, and the components are adhered. The surface has a lower surface energy in the precursor than in the carrier fluid. The first acceptor site may have a hydrophilic surface and have a water-repellent region around the first acceptor site, or the first acceptor site may have a water-repellent surface and have a surround around the first acceptor site A hydrophilic region. If the surface of the first acceptor site is hydrophilic, the bonding surface of each component includes a hydrophilic material attracted to the surface of the first acceptor site; if the surface of the first acceptor site is water repellent, each The adhesive surface of the component comprises a water-repellent material that is one of the surfaces attracted to the first acceptor site. In a preferred embodiment of the present invention, the surface of the first acceptor site is hydrophilic and the area around the first acceptor site is water-repellent, and the bonding surface of each component includes a hydrophilic material.

In another preferred embodiment of the present invention, the precursor is a liquid monomer, and the initiator initiates a polymerization reaction to form a solid polymer when it contacts the monomer. The precursor may be, for example, an epoxide monomer, and the initiator may be a base by which a polymerization reaction is initiated upon contact with the monomer to form a solid polymer. Alternatively, the precursor may be, for example, a liquid cyanoarylate monomer, and the initiator includes a weak base to initiate a polymerization reaction when the monomer is contacted to form a solid polymer. The weak base may be selected from the group consisting of ammonium , Amine, alcohol or ether selected monofunctional molecule. In a preferred embodiment, the present invention includes applying an alkyl compound having a chemical formula HS (CH2) nX (where X = NH2 or OHin = 5_2〇) to gold by depositing a gold film on the device. Membrane formation is performed by monofunctionalization of an amine or alcohol moiety. 6 578291 V. As defined in the description of the invention (5), it can be formed by local area lithography and / or chemical techniques used to generate hydrophilicity or water repellency and separate Surrounded by a region of the substrate that is water-repellent or hydrophilic, and may be a recess, may be substantially flat relative to the substrate, or may even protrude from the substrate. The socket on the substrate is formed by a method known in the art such as an etch mask or selective coating. Once the socket is formed, the substrate is treated so that the socket is hydrophilic and the area surrounding the socket is water repellent; or vice versa. "Combined fluid" or "carrier fluid" can be used interchangeably to refer to the fluid used around the socket, and other names can be used to refer to these fluids. In a preferred embodiment of the present invention, the adhesion of the socket and the object A hydrophilic coating is used on the surface. Therefore, an object may have a surface or side that is preliminarily contacted or adhered to the surface of the receptor site. The "adhesive surface" used in this article refers to this surface. In order to ensure that only the adhesive surface adheres to the surface Receptor, in a preferred embodiment of the present invention, the adhesive surface should have a hydrophilic coating, but the non-adhesive surface should have a water-repellent coating (if the adhesive uses two polar materials, it is located in a non-polar combined fluid Middle), this will ensure that the correct surface is glued to the socket. (In another embodiment of the present invention using a non-polar precursor and initiator in a precursor composition fluid, the bonding surface should be water-repellent, and the other surfaces on the object should be hydrophilic). In a preferred embodiment, the adhesive surface of an object attached to a socket or a substrate is coated with a hydrophilic material, and a different hydrophilic material is applied to the socket by positioning the object in the correct position (such as in the socket). The process of attaching the object in place is initiated, and the effect of self-assembling the object to the substrate occurs because the interface between the hydrophilic coating and the hydrophilic material on the substrate or socket can be reduced.

V. Explanation of the invention (6) When the hydrophilic coating is used on the socket and the adhesive surface of the object, all non-adhesive surfaces should be water-repellent, so that the two-part adhesive can use polar materials. In another alternative embodiment, a water-repellent coating is used for the adhesive surface of the socket and the object, and a hydrophilic coating is used on the surrounding surface. This requires the use of a non-polar adhesive. The socket can be formed by several techniques. In a preferred embodiment of the present invention, a socket has the important property of hydrophilicity and the surrounding substrate is water repellent. This property allows the socket to be selectively wetted by a polar adhesive when the substrate is immersed in a non-polar combination fluid. Those skilled in the art understand many ways to make a surface hydrophilic or water-repellent. The present invention adopts methods to make a region hydrophilic, and these methods are compatible with the steps that need to make adjacent regions water-repellent. One example is: patterning Au on 8 丨 using standard techniques, oxidizing exposed Si with a hydrogen peroxide treatment (making the si surface hydrophilic), and immersing the Au surface in a thiol / alcohol The mixture was made to make the Au surface water-repellent, and the oxidized region was kept hydrophilic throughout the thiol / alcohol treatment. Another possible way to make the socket on the original water-repellent substrate hydrophilic is to use Imidex film, which is polyimide thermoplastic (Iniidex is a registered trademark of General Electric Company Corporation). At that time, it was water-repellent and became hydrophilic after being exposed to oxygen plasma. The inventors have used lithography technology to pattern the photoresist to protect the substrate from the plasma, so only the socket is exposed to light. The inventors have confirmed that plasma exposure makes the socket hydrophilic while the rest of the substrate is still water repellent. Has several trichlorosilane compounds containing 9 578291

V. Description of the invention (7) Polar or non-polar makes the surface of Si or glass hydrophilic or water-repellent organic terminal group. Those skilled in the art can pattern such coatings in accordance with conventional practices to form a substrate. On the build socket. In the joint examination of the same application as this application, the application named "Method for Combining Socket Addresses and Component Microstructures with Complementary Shapes,"

------ (the content of this case is incorporated herein by reference), the inventor PD

Brewer, Hunter, LM, Deckard describe a socket that can be self-assembled and in which objects and sockets have a matching 幵 > / shape The invention uses a three-dimensional shape The method of driving the object onto the socket by matching includes: (a) providing a plurality of microstructure components, each component having a bottom having the same three-dimensional shape; (b) a mold having at least one protrusion formed from a surface, Therefore, the at least one protrusion has the same shape; (a mold is used to mold a moldable substrate to form a molded substrate, and one surface of the molded substrate includes at least one recess having the same shape; and (D) positioning a first one of the plurality of microstructured components in the at least one recess. The positioning step may include: mixing the microstructured component with a fluid to form a slurry; and depositing the slurry on the molding substrate On the surface, the first of the plurality of microstructured components is self-aligned in the recess. Although the present invention does not need to use a three-dimensional shaped socket and uses the technology of this application and joint examination of applications to improve the combination operation In a preferred embodiment of the present invention, a two-part adhesive system is used in which the initiator or hardener is delivered to a small object or component in a combination or carrier fluid. In the embodiment, these two-part systems have the following main requirements:

10 578291 V. Description of the invention (8) a) The hydrophilic material applied to the socket and the hydrophilic material used for coating the object should be insoluble in the combination or carrier fluid; b) The hydrophilic material applied to the socket is in the combination or The socket should be preferentially wetted in the carrier fluid, and the hydrophilic material coated on the object must selectively wet the small combination in the combined fluid; c) It is better to make the objects easily adhere to each other due to capillary forces when using a liquid film to make The object is coated. In a preferred embodiment of the present invention, the socket on the substrate is treated by a solid polymer monomer or a material that has not been polymerized before lying. The humidification technique known in this technology is used to achieve selective wetting. Place this unpolymerized precursor or monomer in or on the socket address. The monomer or unpolymerized precursor of the solid polymer is preferably a liquid. The system attached to the socket is coated with a hydrophilic material that is a polymerization initiator or a hardener. The "initiator" herein is used interchangeably with the "hardener", and these materials initiate the polymerization reaction. When the coated object self-locates to the socket, it comes into contact with the liquid precursor or monomer. The object itself will be aligned and adhered by capillary force. The contact system initiates the polymerization reaction, and the combination of the unpolymerized monomer and the precursor and the initiator or hardener forms a kind of adhesive to lock or attach the object in place. The unpolymerized precursor or unit on the socket The initiator and the initiator coated on the object should not be mixed with the carrier fluid, and the surface energy of the polymerization initiator should be lower in the unpolymerized precursor than in the carrier fluid. The unpolymerized precursor Or the monomer is preferably a polar fluid, a preferred precursor

11 V. Description of the invention (9) It is cyanopropane, and the material is cyanopropionate. Cyanopropionic acid esters undergo anionic polymerization in the presence of weak bases such as water. The "0H" (also known as 〇ΓΓ) used in this article represents a weak base. Other examples of weak bases are ammonium (ΝΗ3) , Amine (R-NH2), pentyl alcohol_11), and ether (R-0-R), where R represents an organic root (such as methyl, ethyl (C2H5-), etc.). Si-OH is usually used to treat glass or

The surface of SiO2, which is weakly alkaline and initiates a polymerization reaction in one embodiment of the present invention. In addition to cyanoacrylate, there are other compounds that can be used as monomers, so long as these compounds can initiate polymerization during the self-assembly procedure. Based on the above factors, other means such as UV exposure, pulsed heating, or the addition of a chemical initiator or other steps are not ideal. One of the advantages of cyanoacrylates is that water or other weak systems on the surface of the assembled component initiate polymerization. In an embodiment that is a variation of the cyanoacrylate and trace water embodiment, the surface of the combined component is specifically pre-loaded with a weakly basic functional group. This embodiment is performed by ensuring that a Initiator to improve the reliability of the bonding process. The use of cyanoacrylates polymerized with very weak bases as adhesives requires that, unless special measures are taken, OH may appear on almost any hydrophilic surface. Water can be absorbed from the air onto these surfaces, or reacted with the surface and left in OH · to terminate, which will then initiate a polymerization reaction. This property can be used without the need to coat the component with a weak test. The component can contain cyanoacrylate which is absorbed from the air and is sufficient to trigger the poly when exposed to the cyanoacrylate in the socket. ΟΙΓ. However, the disadvantages of using this technology are: care must be taken to ensure that the initiator does not appear on the surface of the socket; or, if it does, the amount that appears on the surface of the socket before the initiator is added is not sufficient to harden the cyanoacrylic acid

In order to avoid the possibility of water from the air causing hardening of the cyanoacrylate in the socket before the components are assembled, a preferred embodiment of the present invention includes a method for treating the bonding surface and the socket (rather than relying on the surface and Reaction of trace amounts of water in the air) to provide a surface separation step with the desired properties. This preferred embodiment uses cyanoacrylate as the adhesive, but the bonding surface of the combined object is deliberately treated to attach a polar initiator, and these sockets do become polar, but before the initiator is added to the combined object No polymerization was initiated. It is possible to use an All layer when preparing the bonded surface of a composite object. This Au layer is loaded with alkylthiol molecules terminated with a weak base. The formation of the socket may use a similar procedure with an ester-terminated alkyl mercaptan molecule. Examples of weakly basic initiators used in this preferred embodiment include molecules ending with amine (R_NH2) or alcohol groups. One implementation of this embodiment is to deposit a gold (Au) film on the bottom side of the module (about 100 OA), and then make an alkyl mercaptan compound (HS (CH2) nX, where X-NH2 or OH and n = 5 -20) Reacts with gold surface. Alkyl mercaptans may be applied to the gold surface in a diluted form (< 1%) by mixing with alcohols such as ethanol or methanol. The reaction of alkyl mercaptan with gold can take place at room temperature and can take about 24 hours to Finishing the single-layer covering of the surface, this procedure generates a gold surface that is functionalized with an amine or alcohol initiator, which constitutes a terminal group of thiol molecules attached to the surface. By coating the components, it can be combined 13 578291 V. Description of the invention (11) The cyanoacrylate polymerization is indeed carried out. In the preparation of hydrophilic sockets, the surfaces of these sockets may be coated with a substance that does not initiate or inhibit polymerization. One example is the use of an Au surface to define the socket, followed by the use of an ester-terminated alkylthiol molecule. Cover the socket. This surface should be hydrophilic (due to the polar nature of the terminal groups), but not sufficiently basic to initiate polymerization. Epoxides are another example of a monomeric compound that can be used in the present invention. These molecules also undergo anionicity induced by the addition of a base compound of moderate strength such as amine (R-NH2) or sodium methoxide (NaOCH3). Polymerization. In this embodiment, the epoxy compound may be selectively coated on the surface of the socket site, and the component may be coated with an amine initiator compound. The epoxy resin compound used in this case can be a low molecular weight polymer, so the epoxy resin compound can be made to have a low viscosity. This embodiment is very similar to the cyanoacrylate embodiment, but requires a stronger base to Initiate the polymerization reaction (an advantage of this embodiment is that the surface of the socket is less prone to initiating the polymerization reaction due to the accidental contamination caused by the surface having a 0Η reaction with trace amounts of water in the air). The low molecular weight epoxide allows a thin coating to be applied to the socket surface, which can be further polymerized with a hardener consisting of a mildly strong base, which is chemically adsorbed to the bonding surface of the combined object. The embodiment with OH · using an cyanoacrylate as an initiator can be performed at room temperature (ie, about 15 to 25 °), but in certain cases it may be advantageous for this and other embodiments to use a temperature other than room temperature Operation. The reaction rate is usually a function of temperature. One may want to control the reaction rate by controlling the temperature. For example, one may want to use the temperature to slow down or speed up the reaction rate.

14 578291 V. Description of the invention (l2) There are certain requirements for the temperature to be maintained: the fluid should be liquid; the temperature should not be high enough to decompose the coating; and if the combination uses a specific alkane (with a limited flash Flash point), the temperature should be kept low to prevent the combined fluid from burning. It has non-polar alkanes and perfluorocarbons that are solid at room temperature and can be used as a combined fluid, but it is generally easier to use a similar compound that has fewer carbon atoms and has similar behavior but is liquid at room temperature. In a preferred embodiment, the initiator or hardener of the polymerization reaction does not dissolve or react in the carrier fluid, should provide a high interface energy relative to the carrier fluid, and should provide a surface that is preferentially wetted by the liquid on the socket. Examples of such initiators are water or OH groups. The combination or carrier flow system is a fluid capable of forming a slurry containing the parts to be combined. The combination or carrier should be at least miscible with the adhesive. The combination or carrier fluid may be a non-polar fluid such as liquid alkane, perfluoro Alkanes or perfluorocarbons. Pentadecane or perfluoromethyldecaline can be used as a combination or carrier fluid. If the surface, combined fluid, and initiator also have a reversed non-polar / polar nature, a non-polar precursor can also be used to perform the combined procedure. Because the properly positioned object is held tightly in place, a strong force can be used to remove an object that is not selectively adhered to the substrate. Alternatively, after the initial assembly step, objects that are not properly stuck in the socket address can be removed by withdrawing the assembly fluid. Figure 1 is a schematic diagram of the combined procedure. The hydrophilic sockets 2 and 4 in the Si substrate 6 are surrounded by an Au film 10 with a water-repellent coating. The sockets 2 and 4 are in a perfluorodecaline. Cyanopropane

15 578291 V. Description of the invention (l3) The ester adhesive 8 is selectively wetted. The capillary force caused by the high interface energy of perfluorodecalin / cyanoacrylate is to capture the hydrophilic glass beads 12, 14. After a glass film of water absorbed on the bead surface captures the glass beads, the adhesive hardens. The method of the present invention is illustrated by the following examples which do not limit the scope of the present invention. Example 1 Glass beads captured by a socket filled with cyanoacrylate A substrate has hydrophilic sockets and the sockets are separated by a water-repellent area. KOH and plasma-etched silicon nitride are used to form a mask for the KOH etching step, and a socket about 20 microns deep is etched into the Si wafer. After removing the nitride with hydrogen fluoride, a chromium / gold layer is deposited over the wafer, and the metal is etched from near the socket. The substrate was subsequently treated with H202 to oxidize the exposed Si to make it hydrophilic, and then the substrate was immersed in a solution of hexadecane thiol in ethanol overnight on a surface still covered by gold. A water-repellent layer is formed. Subsequently, a socket was selectively wetted with a cyanoacrylate adhesive, and a few drops of ethyl cyanoacrylate adhesive (S 5cP viscosity Loctite 420) were placed on the substrate (other experiments used a similar Loctite 493, a low viscosity cyanoacrylate. Then cover the substrate with non-polar fluid perfluorofluorenyl decalin. Other experiments use non-polar liquid pentadecane. Perfluoromethyl decalin is denser than cyanoacrylate, but pentadecane is not as good as cyanoacrylate. dense. And then swirled through the fluoromethyl decalin to cyanoacrylate

16 578291 V. Description of the invention (l4) Push the edge of the wafer to displace the cyanoacrylic acid from the surface of the substrate. Use a pipette to remove most of the excess cyanoacrylate, polar cyanoacrylate The ester system preferentially wets the hydrophilic socket while leaving a pool of cyanoacrylate in the socket. In the water-repellent region, the perfluoromethyl decalin type shifts the cyanoacrylate. Figure 2 shows a large drop of receding ethyl cyanoacrylate (left side of the photo) displaced by perfluoromethyl decalin. The square pad (55 micron side length) in the center is oxidized Si and is composed of hexadecane The thiol-treated Au is surrounded. The cyanoacrylate preferentially wets the oxidized Si pad, as shown by the meniscus of the fluid on the pad and the fluid in the receding large drop. For flat mats, occasionally f leaves small droplets of cyanoacrylate. But for most pads, the cyanoacrylate is either completely displaced or it is too thin to be observed with an optical microscope. An observable socket with a small low cyanoacrylate catches the beads as they roll over the pad. After the substrate is withdrawn from the combined fluid, the beads are firmly glued to the pad. For mats without observable droplets of cyanoacrylate, no capture and adhesion of beads was observed. A substrate with a flat socket was also used for the combination experiment, and uncoated glass beads having a diameter of 50 micrometers were dropped into perfluoromethyl decalin. In order to keep more cyanoacrylate on the socket, using the slightly concave socket described above, the procedure described when applying cyanoacrylate and being subjected to transgassing methyl zeolite is repeated, which is greatly increased in this case. The proportion of the socket captures the glass beads, the substrate is withdrawn from the combined fluid, and a pipette filled with perfluoromethyl naphthalene is used to rinse the substrate with excess beads. The beads captured in the socket remain firmly attached during this procedure, indicating good

578291 V. Description of the invention (l5) Good bonding. Figures 3 and 4 show the optical microscope images of the combined glass beads. In Figure 3, 50 micron glass beads fill four of the six sockets, of which the socket is about 50 micrometers wide. The glass beads at the bottom left are obvious. Off-center, off-center beads (especially for larger sockets) are generally glued to one corner of the socket. Figure 4 shows that 50 micron diameter beads are captured on a smaller socket (about 30 microns wide). As shown in the linear configuration of the three beads to the right of the photo, these beads have a greatly improved centering effect, with smaller objects and the socket Better shape matching should result in improved centering effect during the self-positioning procedure. Glass beads are suitable for sockets, have a hydrophilic surface and are easily accessible. For these experiments, glass beads are used, and the described technique is not limited to having this. Shaped objects. Although specific embodiments of the invention have been shown and described, those skilled in the art can make other modifications and improvements, so it should be understood that the invention is not limited to the special form shown in the figure, and the scope of patent application is intended to cover without departing from the scope of patent application All modifications that define the spirit and scope of the invention. Comparison of component numbers 2, 4 ... hydrophilic socket 6 ... silicon substrate 8 ... cyanoacrylate adhesive 10 ... gold film 12, 14 .... hydrophilic glass beads

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Claims (1)

夂 'Application patent scope 1 · A method for assembling a component on a substrate, the method includes the following steps ... (a) selectively coating at least one first substrate of the substrate with a liquid precursor (B) each component is provided with a bonding surface containing the initiator; and (c) the manner in which the components are deposited on the substrate can cause a first adhesive A component is in contact with the at least -receptor address' at this time the contact between the initiator and the liquid precursor causes the adhesive to form to attach the first component to the first acceptor address. 2. The method of claim 1, wherein the step (i) comprises depositing a slurry having a carrier fluid and a plurality of these components on the substrate, and the precursor and the initiator are related to the The carrier fluids are not mixed, and the bonding surfaces of the components have a lower surface energy in the front lying body than in the carrier fluid. 3. The method according to item 2 of the patent application, wherein the first receptor site has a hydrophilic surface and a region around the first receptor site is water-repellent 'or the first receptor site has -The water-repellent surface and the area around the first acceptor site is hydrophilic, if the surface of the -receptor site is hydrophilic, the bonding surface of each of these components is For the hydrophilic material on the surface of the body site, if the surface of the first receptor site is water-repellent, the bonding surface of each of these components includes a water-repellent material attracted to the surface of the first receptor site. 4. The method of claim 3 in the scope of patent application, wherein the surface of the -receptor site is hydrophilic and the area around the first acceptor site is water repellent 6. The scope of the patent application, each of these components The surface system contains the hydrophilic material. 5. The method of claim 3, wherein the precursor is a liquid monomer, and the initiator initiates a polymerization reaction to form a solid polymer when it contacts the monomer. 6. The method of claim 5 in which the precursor is a cyanoacrylate monomer or an epoxide monomer. 7. The method according to item 5 of the patent application, wherein the surface of the first receptor site is water-repellent and the area around the first receptor site is hydrophilic I4, each bonding surface of the first component The system contains the water-repellent material. 8. The method according to item 4 of the scope of patent application, which comprises, before this step, providing the substrate with a plurality of sockets separated from each other by regions, processing the plurality of sockets to become hydrophilic and treating the regions. The treatment becomes water-repellent. 9. The method according to item 8 of the application, wherein the precursor is a polar fluid and step (a) includes depositing the polar fluid and a combined fluid on a surface of the substrate, so that the polar fluid has priority Wet the hydrophilic sockets and remove excess polar fluid from the surface of the substrate. 10. The method according to item 9 of the application, wherein the polar fluid comprises a liquid cyanoacrylate monomer, and the initiator comprises a weak base to initiate a polymerization reaction to form a solid polymerization when contacting the monomer. Thing. 11. The method of claim 10, wherein the initiator comprises a weak test selected from the group of the following: ammonium, amine, alcohol, and ether. 12. The method of claim 11 in which the weak base is an alcohol of the chemical formula R-OH or an amine of the chemical formula r_Nh2. 20 d / ozy 丄 ', the method of claiming patent scope such as the patent claim No. 9 method, wherein the initiator is formed by contacting the surface of 1 σ of each of these components with water appearing in the air On the bonding surface of each of these components. The method of claim 9 wherein the bonding surface of each of these components includes Si-O. 15. The method of claim 9, which includes coating the initiator on the adhesive surface of each of these components. A method as claimed in claim 15 of the patent scope, which comprises depositing a gold film on each of these components and then applying an alkyl compound having a chemical formula HS (CH2) nX and 2 or 0H and η-5 to 20 To the gold film to form a gold surface that is functionalized with an -amine or alcohol moiety. The method of claim 9 of the patent scope, wherein the polar flow system includes a liquid epoxide monomer, and the initiator includes-check to initiate a polymerization reaction to form a solid polymer when in contact with the early body . 18. The method of claim 17 in the scope of patent application, wherein the test is a amine or sodium methylate. The method as broadly described in claim 9 wherein the substrate comprises Shi Xi. For example, the method of applying for the scope of patent No. 19, wherein the plural number is treated with nitrogen peroxide. twenty one