WO2003087590A2 - Method of self-assembly and self-assembled structures - Google Patents

Method of self-assembly and self-assembled structures Download PDF

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Publication number
WO2003087590A2
WO2003087590A2 PCT/US2003/011078 US0311078W WO03087590A2 WO 2003087590 A2 WO2003087590 A2 WO 2003087590A2 US 0311078 W US0311078 W US 0311078W WO 03087590 A2 WO03087590 A2 WO 03087590A2
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WIPO (PCT)
Prior art keywords
substrate
structures
self
liquid
display
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PCT/US2003/011078
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French (fr)
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WO2003087590A3 (en
Inventor
Heiko O. Jacobs
Andrea R. Tao
Alexander Schwartz
David H. Gracias
George M. Whitesides
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President And Fellows Of Harvard College
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Application filed by President And Fellows Of Harvard College filed Critical President And Fellows Of Harvard College
Priority to AU2003230860A priority Critical patent/AU2003230860A1/en
Publication of WO2003087590A2 publication Critical patent/WO2003087590A2/en
Publication of WO2003087590A3 publication Critical patent/WO2003087590A3/en

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    • H01L24/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
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    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
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    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
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    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/50—Multistep manufacturing processes of assemblies consisting of devices, each device being of a type provided for in group H01L27/00 or H01L29/00
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    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
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    • H01L2224/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
    • H01L2224/95053—Bonding environment
    • H01L2224/95085—Bonding environment being a liquid, e.g. for fluidic self-assembly
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/18—Printed circuits structurally associated with non-printed electric components
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/341—Surface mounted components

Definitions

  • the present invention is directed to self-assembly of structures, and, in particular, to self- assembly by action of a liquid patterned onto a substrate.
  • the invention is directed to methods of self-assembly and self-assembled structures.
  • the present invention is directed to method of self-assembling a plurality of structures.
  • the method includes patterning a first liquid onto a first substrate, and, while at least a portion of the first liquid remains in liquid form, self-assembling at least a portion of the plurality of structures onto the substrate by action of the first liquid and according to the pattern of the first liquid.
  • the present invention is directed to a method of self- assembly.
  • the method of self-assembly includes self-assembling at least 100 independent structures according to a predetermined pattern and on a substrate in less than 5 minutes with at least 95% accuracy.
  • the present invention is directed to an apparatus including a first non-planar substrate a second non-planar substrate, and a plurality of structures arranged in a pattern and connected to the first substrate and the second substrate.
  • each of the plurality of structures has an average diameter of less than one millimeter and some of the plurality of structures are selected from the group consisting of electronic components, optical components, and mixtures thereof.
  • the present invention is directed to a display.
  • the display includes a first substrate and a first plurality of electrical connectors in contact with the first substrate, at least some of the first plurality of electrical connectors being in electrical connection with one another.
  • the display further includes a second substrate and a second plurality of electrical connectors in contact with the second substrate, at least some of the second plurality of electrical connectors being in electrical connection with one another.
  • the display further includes a plurality of display elements each electrically connected to at least one of the first plurality of electrical connectors and the second plurality of connectors. In this embodiment, each of the plurality of display elements has an average diameter of less than 1 millimeter.
  • the present invention is directed to an electronic device.
  • the electronic device includes a first non-planar substrate and a first plurality of electrical connectors in contact with the first non-planar substrate, at least some of first plurality of electrical connectors being in electrical connection with one another.
  • the electronic device further includes a second non-planar substrate, a second plurality of electrical connectors in contact with the second non-planar substrate, at least some of the second plurality of electrical connectors being in electrical connection with one another.
  • the electronic device further includes a plurality of electronic elements each electrically connected to at least one of the first plurality of electrical connectors and the second plurality of electrical connectors.
  • the present invention is directed to a method including allowing a plurality of structures to self-assemble on a first substrate and allowing a second substrate to self-align on the plurality of structures.
  • the present invention is directed to an apparatus including a non-planar substrate, and a plurality of independent structures arranged in a pattern and connected to the non-planar substrate.
  • Each of the structures have an average diameter of less than one millimeter.
  • the pattern includes greater than 200 independent structures per square centimeter surface area of the substrate.
  • the present invention is directed to a display including a substrate, and a plurality of self-assembled, independent light-emitting devices arranged in a pattern on the substrate. It should be understood that other embodiments of the invention may include any combination of features disclosed herein including features in the above-identified embodiments.
  • FIG. 1 is an elevated perspective view of one embodiment of the present invention
  • FIG.2 is an elevated perspective view of another embodiment of the present invention.
  • FIG. 3 is an elevated perspective view of another embodiment of the present invention.
  • FIG. 4 is an elevated perspective view of another embodiment of the present invention.
  • FIG. 5 is an elevated perspective view of another embodiment of the present invention.
  • FIG. 6 is an elevated perspective view of one embodiment of the present invention.
  • FIG. 7 is a photocopy of a photomicrograph of one embodiment of the present invention.
  • FIG. 7 is a photocopy of a photomicrograph of another embodiment of the present invention.
  • FIG. 8 is a photocopy of a photomicrograph of another embodiment of the present invention
  • FIG. 9 is a photocopy of a photomicrograph of another embodiment of the present invention.
  • FIG. 10 is a photocopy of a photomicrograph of another embodiment of the present invention.
  • FIG. 11 is a photocopy a photomicrograph of another embodiment of the present invention at three magnification levels
  • FIG. 12 is a photocopy of a photomicrograph of another embodiment of the present invention at two magnification levels.
  • FIG. 13 is a photocopy of a photomicrograph of another embodiment of the present invention at two magnification levels.
  • the present invention is directed to self-assembly of structures, and, in particular, to self-assembly by action of a liquid patterned onto a substrate.
  • Self-assembly is intrinsically parallel, and has the potential for sub-micron accuracy in positioning.
  • Self-assembly is also relatively insensitive to certain types of error in registration. Accordingly, the present invention includes methods of self-assembling a plurality of structures.
  • one embodiment of the present invention is directed to a method of self-assembling a plurality of structures 10.
  • the method of this embodiment includes patterning a first liquid 20 onto a first substrate 30 and, while at least a portion of first liquid 20 remains in liquid form, self-assembling at least a portion of the plurality of structures 10 onto substrate 30 by action of first liquid 20 and according to the pattern of first liquid 20.
  • structures 10 may be light-emitting diodes (LEDs)
  • substrate 30 may be a flexible material
  • liquid 20 may be solder.
  • the solder may be patterned onto the substrate and the action of the solder used to self-assemble the LEDs to construct a device suitable for use as a display. This method will be better understood with the following description of the structures that may be used to conduct the method.
  • Substrate 30 may be constructed of any material and in any manner that allows liquid 20 to be patterned thereon.
  • substrate 30 may have a wide variety of surface textures, contours and shapes.
  • substrate 30 may be round, square, rectangular, or irregular; flat, curved, or corrugated; and smooth, textured, or rough.
  • substrate 30 may be of any thickness, from a thin sheet to a block, sphere or other shape.
  • Substrate 30 may also be of any hardness or stiffiiess upon which it is possible to pattern liquid 20.
  • substrate 30 may be relatively hard and inflexible, flexible, elastomeric, or even floppy.
  • substrate 20 may be supported by another surface so that liquid 20 may be patterned thereon.
  • the method of the invention may be considered in selecting substrate 30.
  • the shape and hardness or stiffness of substrate 30 may be selected based upon the application for the device.
  • substrate 30 may be, for example, regularly shaped and inflexible.
  • substrate 30 may be, for example, cylindrical and inflexible, or flat, but flexible.
  • substrate 30 may be highly flexible or elastomeric.
  • substrate 30 may have particular optical properties.
  • substrate 30 may be translucent and transparent.
  • substrate 30 may be constructed from a wide variety of materials.
  • substrate 30 may be constructed of stiffer materials such as some metals, some polymeric materials, and silicon wafers.
  • substrate 30 is to be flexible, other polymeric materials or metals may be used. It should be recognized that some materials, such as some metals, may be relatively stiff if thick and flexible if thinner; accordingly the thickness of substrate 30 may be considered in selecting a material.
  • substrate 30 may be constructed from multiple materials, such as in a laminate arrangement. The manner in which fluid 20 is to be patterned onto substrate 30 may also be considered when selecting substrate 30. For example, it may be desired to be able to use photolithographic techniques on substrate 30, as will be described in greater detail below.
  • substrate 30 may be bent or flexed as part of the construction of a device constructed by an embodiment of the method of the present invention, or in use of the device.
  • substrate 30 may be flexed into a desired shape, which may be non-planar.
  • substrate 30 may be flexed into a curved shape, such as a cylinder. It should be understood that the term "non-planar" refers to any non-planar shape including curved shapes, such as cylinders.
  • substrate 30 may be fixed in that shape if desired. For example, it may be treated to reduce its flexibility or may be held on the desired shape with suitable structure. In some embodiments, such as where substrate 30 is formed into a cylinder, substrate 30 may be attached to itself in some manner to fix it in a desired shape. Where substrate 30 is flexed as part of the construction of a device, it may be flexed at any time in the construction process. For example, substrate 30 may be flexed prior to self-assembly of substrates 10, during self-assembly, or after self-assembly.
  • Liquid 20 may be patterned on to substrate 30 in any manner and using any materials that allow liquid 30 to be applied to substrate 30 in the desired pattern.
  • liquid 20 may be painted, stamped, printed or otherwise patterned onto substrate 30.
  • liquid 20 may be applied to substrate 30 photolithographically in solid form and later liquefied, for example by melting.
  • a precursor 32 may be patterned onto the surface of substrate 30 and used to facilitate formation of a desired pattern of liquid 20.
  • precursor 32 may be a material that either has an affinity or repulsion for liquid 20. hi the former case, it may be easier to apply liquid 20 where precursor 32 is present, and in the later case, precursor 32 may inhibit application of liquid 20 where precursor 32 is present.
  • both a precursor with an affinity for liquid 20 and a precursor which repulses liquid 20 may be used in conjunction to facilitate patterning of liquid 20. Any of the techniques described above for the patterning of liquid 20 on substrate 30 may also be used to pattern precursor 32 on substrate 30.
  • liquid 20 may be applied to substrate 30 and precursor 32 allowed to control its pattern.
  • liquid 20 may be painted, pipetted, or the like, onto substrate 30 or substrate 30 may be dipped into liquid 20.
  • Precursor 32 may then either maintain liquid 20 on substrate 30 where precursor 32 is located, or repulse liquid 20 from such locations, depending on the action of precursor 32.
  • liquid 20 is dip coated onto substrate 20 and maintained on substrate 20 by an affinity for precursor 32.
  • the action of liquid 20 may be any action that results in the desired patterning of structures 10.
  • the action may be a physical phenomena, such as capillary action or surface tension.
  • liquid 20 may be selected such that it has a relatively high surface affinity for the material of structure 10 compared to its affinity for the surrounding environment.
  • structure 10 may be held by liquid 20 because this results in a lower energy state for the system.
  • Liquid 20 may by any liquid that allows self-assembly of structures 10 by its action.
  • liquid 20 may be a liquid having a relatively high affinity for the material of structures 10 compared to their environment.
  • Particular embodiments may require additional features of liquid 20.
  • liquid 20 is desired to be part of a electrical connection between structures 10, it may be desired that liquid 20 is electrically conductive.
  • Liquid suitable for use as liquid 20 in some embodiments is solder. Solder has good capillary action with many materials which structures 10 may be constructed from. Solder is also electrically conductive, a liquid at relatively low temperatures, and may be dip coated onto certain metal precursors, such as copper.
  • Liquid 20 may be selected such that structures 10 can be fixed to substrate 30 once self- assembly is complete.
  • liquid 20 is a solid at temperatures at which a device assembled according to an embodiment of the present invention is intended to be used.
  • a metal that is a solid at room temperature, but melts at a relatively low temperature, such as solder may be useable in such and embodiment.
  • liquid 20 cures, hardens, or sets after a period of time sufficient for self- assembly.
  • a glue, epoxy, or prepolymer may be used in such an embodiment.
  • Self-assembly of structures 10 onto substrate 30 may be aided by the environment provided for self-assembly.
  • an environment may be provided that reduces possible hurdles to self-assembly, such as gravity, and/or improves the action of the liquid.
  • self-assembly may occur at least partially within a carrier 40.
  • Carrier 40 may be any liquid that does not inhibit self-assembly, and preferably promotes self-assembly.
  • Carrier 40 may be denser than air, and is preferably of similar density to structures 10, reducing the effect of gravity on the self-assembly process.
  • Carrier 40 may also be a material that is compatible with, i.e.
  • Carrier 40 may also be a material that has a relatively high free energy at the interface between it and liquid 20 carrier interface.
  • carrier 40 may be capable reducing and/or inhibiting the formation of, a layer on liquid 20 or structure 10 that inhibits self-assembly.
  • carrier 40 may be sufficiently acidic to reduce and/or inhibit formation of an oxide layer on certain materials.
  • carrier 40 may have a pH of less than about 7, less than about 5, about 3, or even lower.
  • carrier 40 comprises water. Carrier 40 may be heated to melt liquid 20 for self- assembly, if required.
  • Self-assembly conditions is meant to define those conditions under which, when intended mating surfaces (those surfaces shaped or otherwise configured to provide mating such as the surfaces of substrate 30 and structure 10) are in contact in good register, the components (e.g., substrate 30 and structure 10) are not separated under the assembly conditions, but when the same surfaces are in contact but not in good register they either break free of contact or slide relative to each other until in good register, and where unintended mating surfaces are in contact, they do not remain in contact.
  • Self-assembly conditions may be those of agitation, as described further below.
  • the self-assembly process may be physically promoted.
  • self-assembly may be promoted through agitation of structures 10.
  • Agitation may be provided in any manner that is sufficient to promote self-assembly, but not so great that it risks damage to the device being constructed or removes assembled structures from the substrate. Agitation may be in multiple directions, for example as illustrated by direction indicators 80 in FIG. 3. Agitation may also be used to correct defects.
  • a substrate with structures attached may be subjected to additional agitation in the absence of other structures. This agitation may be vigorous, for example, it may comprise vigorous tapping of a container with a carrier 40 and the substrate and structures therein.
  • structures may sometimes straddle two independent assembly sites. This defect may was reduced or eliminated by increasing the space between such assembly sites. Reducing the width of electrical connectors may also reduce or eliminate connection of structures onto them.
  • Other potential defects may consist of missing or misaligned structures. These defects may arise from defects in the assembly sites for the structures. These types of defects may be avoided by careful patterning of the liquid. Pieces of structures assembling onto assembly sites may also result in defects. This problem may be reduced or eliminated by screening the structures and eliminating broken structures.
  • structures 10 may be electrically connected in any manner that provides the desired connections, avoids undesired connections, and does not interfere with use of any device that structures 10 are part of.
  • desired electrical connections are provided as the structures are self-assembled.
  • the structures themselves may include structure that connects them as they are assembled.
  • liquid 20 may be used to electrically connect the structures as desired by providing a suitable pattern.
  • liquid 20 may be electrically conductive.
  • precursor 32 may used to electrically connect structures 10 as desired.
  • precursor 32 may be constructed as an electrical network with larger areas pr precursor material available as assembly sites for connection to structures 10. Such a precursor arrangement may be particularly suited to construction by photolithography or common other semiconductor fabrication techniques.
  • liquid 20 may still be desired to be conductive if structures 10 are not in direct contact with the precursor.
  • Structures 10 for use according to embodiments of the method of the present invention may include any structure able to be self-assembled. Structures 10 may have any shape of geometry. Typically, structures 10 will have at least one relatively flat surface as this may promote self-assembly onto a relatively flat substrate. However, as has been noted, substrate 30 need not be flat and, furthermore, structures 10 need no match the shape of the substrate in all embodiments. Because self-assembly has is particularly advantageous compared to conventional assembly techniques where structures 10 are relatively small, structures 10 may each have an average diameter of no more than one millimeter, no more than 500 micrometers, no more than 300 micrometers, no more than 150 micrometers, or even smaller. As used herein, "average diameter” refers to the average of all of the distances that may be measured from one side to the other side of a three dimensional object through its center.
  • Structures 10 may be constructed from any material that is capable of being self- assembled. In embodiments of the present invention where the method of the invention is being used to construct electronic devices, structures 10 may be constructed from materials commonly used in the manufacture of semiconductors, such as metal and silicon. Structures 10 may include microelectronics. As used herein, "microelectronics,” refers to any circuitry less than 1 millimeter in average diameter capable of effecting the a flow of electricity and may range from a resistor to a complex microchip. In one embodiment, structures 10 include one or more light-emitting diodes (LEDs). Including LEDs in the device may allow it to be used as a display, or to provide signals, such as results or errors, to a user.
  • LEDs light-emitting diodes
  • Structures 10 may be treated or comprise structure intended to improve self-assembly.
  • structures may include a coating or layer that has a relatively low interfacial free energy with liquid 20, promoting self-assembly.
  • a layer of gold is placed on one side of structures 10 to promote self-assembly.
  • the method of the present invention may include connecting a second substrate 34 to at least some of structures 10 connected to substrate 30. Adding a second substrate allows connection of the structures at two locations, typically on opposite sides of the structures. This may allow completion of an electrical circuit with structures 10 in the middle. Second substrate 34 may be constructed of any of the materials that first substrate 30 may be constructed from.
  • second substrate 34 self-aligns with at least some of the plurality of structures during connection of second substrate 34.
  • Self-alignment may be facilitated by applying a second liquid 22 to at least some of the plurality of structures 10.
  • Second liquid 22 may be the same as liquid 20 and may be any of the liquids described above for use as liquid 20.
  • Second substrate may include components, such as wires 38, arranged to line up with structures 10, facilitating alignment and providing electrical connection.
  • Second substrate 34 may be generally positioned by hand, or the like, and then may self-align to provided a desired alignment.
  • the spacing between the structures and the second substrate is as uniform as possible, as are the positioning of the structures relative desired connection sites on the second substrate. In one embodiment, variations in structure height of as much as 70 micrometers and variations in lateral placement of up to 60 micrometers were tolerated by the self-alignment process.
  • Second substrate 34 may be connected to structures 10 such that, after connection, it is substantially parallel to the first substrate.
  • parallel means that two surfaces are substantially equidistant from one another over the length and width of the surface and includes two curved, equidistant surfaces, such as substrates 30 and 34 as illustrated in FIG. 6.
  • first and second substrates 30, 34 may be arranged as inner and outer cylinders.
  • Embodiments of the method of the present invention have been demonstrated to be capable of self-assembling at least 100, 500, 1000 or even 1500 independent structures according to a predetermined pattern and on a substrate in less than 5 minutes with at least 95% accuracy.
  • % accuracy refers to the number of properly assembled structures over the total number of structures that were desired to be assembled. More structures than are desire to be assembled (for example more structures than sites for self- assembly) may be used to facilitate self-assembly, but these structures are not counted toward the number of structures desired to be assembled in determining accuracy.
  • 100 or more independent structures may be assembled with at least 95% accuracy in less than three minutes and/or within a 5 square centimeter area. In other embodiments, 100 or more independent structures may be assembled with at least 98%, or even 100% accuracy in less than 5 minutes.
  • Some embodiments of the present invention include a high density of self-assembled structures on the surface area of the substrate. For example, some embodiments include greater than 200 independent structures per square centimeter surface area of the substrate. Other embodiments may include greater than 300, or greater than 500 independent structures per square centimeter surface area of the substrate. The number of independent structures per surface area of the substrate may be selected based on the requirements of a particular application.
  • inventions may also include large numbers of self-assembled independent structures on a substrate.
  • embodiments may include greater than 500 structures, greater than 1000 structures, greater than 1500 structures, or even more.
  • the number of independent structures may be selected based on the requirements of a particular application.
  • Example 1 Patterning a liquid on a substrate
  • the photoresist was developed, and the exposed copper was removed by etching with an aqueous ferric chloride solution (1.4 g of FeCl 3 per milliliter of H 2 O, pH 1.3). Finally, the protective photoresist was dissolved in acetone and the underlying copper squares (precursors) were coated with the low-melting solder (mp ⁇ 50 °C, Small Parts, Y-LMA-117) by dipping the substrates into a solder bath.
  • a dicing saw was used to cut a wafer of photodiode material (GaAs, #P3031, Optodiode Corp., Newbury Park, CA 91320) into 280 ⁇ m wide squares that were 200 ⁇ m thick.
  • the semi automated dicing saw (General Signal Tempress model 602) that we used provided an accuracy of 40 ⁇ m.
  • 113 LEDs were constructed into a cylindrical display, as illustrated in FIGS. 7-11. It was noted that assembly was not linear and that structures self-assembled faster after some initial structures had self-assembled. Without wishing to be bound by any particular theory, it is hypothesized that once structures had settled that they slowed other structures tumbling past the substrate in their vicinity, allowing them to assemble more rapidly.
  • Silicon wafers were coated with 10 nm of Cr and 400 nm of Au by thermal evaporation onto the backside.
  • a dicing saw was used to cut the wafers into equally sized blocks, 280 ⁇ m x 280 ⁇ m wide and 400 ⁇ m tall.
  • the silicon blocks were used to mimic integrated device segments and to avoid the expense of LEDs.
  • the backside metallization serves as binding site during the self-assembly. 1500 silicon cubes were self-assembled on an area of 5 square centimeters in less than three minutes with an accuracy of about 98%, as illustrated in FIGS 12 and 13.

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Abstract

The present invention is directed to self-assembly of structures, and, in particular, to self-assembly by action of a liquid patterned onto a substrate. In one embodiment, the present invention is directed to method of self-assembling a plurality of structures. The method includes patterning a first liquid onto a first substrate, and, while at least a portion of the first liquid remains in liquid form, self-assembling at least a portion of the plurality of structures onto the substrate by action of the first liquid and according to the pattern of the first liquid. In another embodiment, the present invention is directed to a display. The display includes a first substrate and a first plurality of electrical connectors being in electrical connection with one another. The display further includes a second substrate, at least some of the second plurality of electrical connectors being in electrical connection with one another. The display further includes a plurality of display elements each electrically connected to at least one of the first plurality of electrical connectors and the second plurality of connectors. In this embodiment, each of the plurality of display elements has an average diameter of less than 1 millimeter.

Description

METHOD OF SELF-ASSEMBLY AND SELF-ASSEMBLED STRUCTURES
Background Field
The present invention is directed to self-assembly of structures, and, in particular, to self- assembly by action of a liquid patterned onto a substrate.
Related Art
How to assemble individual structures into more complex forms is an increasing important problem. This is particularly true where such structures are relatively small, such as in some microelectronic and optical applications. The last three decades have produced a range of new manufacturing technologies focused on assembly: serial pick-and-place, serial wire-bonding, serial packaging, and parallel wafer-to-wafer transfer. Each has limitations: pick-and place is inefficient with large numbers of components, and with components having small dimensions (e.g. < 100 micrometers) whose interactions may be dominated by adhesive forces, rather than gravity; both micro-manipulator-based assembly and wafer-to-wafer transfer methods work poorly on non-planar surfaces, in cavities, and in fabrication of three- dimensional systems; serial processes are generally slow.
Summary
The invention is directed to methods of self-assembly and self-assembled structures.
In one embodiment, the present invention is directed to method of self-assembling a plurality of structures. The method includes patterning a first liquid onto a first substrate, and, while at least a portion of the first liquid remains in liquid form, self-assembling at least a portion of the plurality of structures onto the substrate by action of the first liquid and according to the pattern of the first liquid.
In another embodiment, the present invention is directed to a method of self- assembly. The method of self-assembly includes self-assembling at least 100 independent structures according to a predetermined pattern and on a substrate in less than 5 minutes with at least 95% accuracy.
In another embodiment, the present invention is directed to an apparatus including a first non-planar substrate a second non-planar substrate, and a plurality of structures arranged in a pattern and connected to the first substrate and the second substrate. In this embodiment, each of the plurality of structures has an average diameter of less than one millimeter and some of the plurality of structures are selected from the group consisting of electronic components, optical components, and mixtures thereof.
In another embodiment, the present invention is directed to a display. The display includes a first substrate and a first plurality of electrical connectors in contact with the first substrate, at least some of the first plurality of electrical connectors being in electrical connection with one another. The display further includes a second substrate and a second plurality of electrical connectors in contact with the second substrate, at least some of the second plurality of electrical connectors being in electrical connection with one another. The display further includes a plurality of display elements each electrically connected to at least one of the first plurality of electrical connectors and the second plurality of connectors. In this embodiment, each of the plurality of display elements has an average diameter of less than 1 millimeter.
In another embodiment, the present invention is directed to an electronic device. The electronic device includes a first non-planar substrate and a first plurality of electrical connectors in contact with the first non-planar substrate, at least some of first plurality of electrical connectors being in electrical connection with one another. The electronic device further includes a second non-planar substrate, a second plurality of electrical connectors in contact with the second non-planar substrate, at least some of the second plurality of electrical connectors being in electrical connection with one another. The electronic device further includes a plurality of electronic elements each electrically connected to at least one of the first plurality of electrical connectors and the second plurality of electrical connectors.
In another embodiment, the present invention is directed to a method including allowing a plurality of structures to self-assemble on a first substrate and allowing a second substrate to self-align on the plurality of structures.
In another embodiment, the present invention is directed to an apparatus including a non-planar substrate, and a plurality of independent structures arranged in a pattern and connected to the non-planar substrate. Each of the structures have an average diameter of less than one millimeter. The pattern includes greater than 200 independent structures per square centimeter surface area of the substrate.
In another embodiment, the present invention is directed to a display including a substrate, and a plurality of self-assembled, independent light-emitting devices arranged in a pattern on the substrate. It should be understood that other embodiments of the invention may include any combination of features disclosed herein including features in the above-identified embodiments.
Other advantages, novel features, and embodiments of the invention will become apparent from the following detailed description of non-limiting embodiments of the invention when considered in conjunction with the accompanying drawings, which are schematic and which are not intended to be drawn to scale. In the figures, each identical or nearly identical component that is illustrated in various figures typically is represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment of the invention shown where illustration is not necessary to allow those of ordinary skill in the art to understand the invention. In cases where the present specification and a document incorporated by reference include conflicting disclosure, the present specification shall control.
Brief Description of the Drawings
FIG. 1 is an elevated perspective view of one embodiment of the present invention;
FIG.2 is an elevated perspective view of another embodiment of the present invention;
FIG. 3 is an elevated perspective view of another embodiment of the present invention;
FIG. 4 is an elevated perspective view of another embodiment of the present invention;
FIG. 5 is an elevated perspective view of another embodiment of the present invention;
FIG. 6 is an elevated perspective view of one embodiment of the present invention;
FIG. 7 is a photocopy of a photomicrograph of one embodiment of the present invention;
FIG. 7 is a photocopy of a photomicrograph of another embodiment of the present invention;
FIG. 8 is a photocopy of a photomicrograph of another embodiment of the present invention; FIG. 9 is a photocopy of a photomicrograph of another embodiment of the present invention;
FIG. 10 is a photocopy of a photomicrograph of another embodiment of the present invention;
FIG. 11 is a photocopy a photomicrograph of another embodiment of the present invention at three magnification levels;
FIG. 12 is a photocopy of a photomicrograph of another embodiment of the present invention at two magnification levels; and
FIG. 13 is a photocopy of a photomicrograph of another embodiment of the present invention at two magnification levels.
Detailed Description
The present invention is directed to self-assembly of structures, and, in particular, to self-assembly by action of a liquid patterned onto a substrate. Self-assembly is intrinsically parallel, and has the potential for sub-micron accuracy in positioning. Self-assembly is also relatively insensitive to certain types of error in registration. Accordingly, the present invention includes methods of self-assembling a plurality of structures.
Referring now to the Figures, and, in particular FIGS. 1-6, one embodiment of the present invention is directed to a method of self-assembling a plurality of structures 10. The method of this embodiment includes patterning a first liquid 20 onto a first substrate 30 and, while at least a portion of first liquid 20 remains in liquid form, self-assembling at least a portion of the plurality of structures 10 onto substrate 30 by action of first liquid 20 and according to the pattern of first liquid 20. By way of illustration, but not limitation, structures 10 may be light-emitting diodes (LEDs), substrate 30 may be a flexible material, and liquid 20 may be solder. The solder may be patterned onto the substrate and the action of the solder used to self-assemble the LEDs to construct a device suitable for use as a display. This method will be better understood with the following description of the structures that may be used to conduct the method.
Substrate 30 may be constructed of any material and in any manner that allows liquid 20 to be patterned thereon. For example, substrate 30 may have a wide variety of surface textures, contours and shapes. By way of illustration and not limitation, substrate 30 may be round, square, rectangular, or irregular; flat, curved, or corrugated; and smooth, textured, or rough. Similarly, substrate 30 may be of any thickness, from a thin sheet to a block, sphere or other shape. Substrate 30 may also be of any hardness or stiffiiess upon which it is possible to pattern liquid 20. For example, substrate 30 may be relatively hard and inflexible, flexible, elastomeric, or even floppy. In some embodiments, substrate 20 may be supported by another surface so that liquid 20 may be patterned thereon.
The nature and purpose of the device to be constructed according to this embodiment the method of the invention may be considered in selecting substrate 30. For example, the shape and hardness or stiffness of substrate 30 may be selected based upon the application for the device. In one embodiment, where the device is for use in a solid state circuit, substrate 30 may be, for example, regularly shaped and inflexible. In another embodiment, where the device is for use as a cylindrical display, as illustrated inn FIGS. 7-10, substrate 30 may be, for example, cylindrical and inflexible, or flat, but flexible. In a third embodiment, where the device is intended to be able to be folded up and stored, substrate 30 may be highly flexible or elastomeric.
In some embodiments, substrate 30 may have particular optical properties. For example, where device 50 is for use as a display, or it is otherwise desired to be able to pass light through substrate 30, substrate 30 may be translucent and transparent.
It will be clear to one of skill in the art from the foregoing that substrate 30 may be constructed from a wide variety of materials. For example, where substrate 30 is to be relatively stiff, it may be constructed of stiffer materials such as some metals, some polymeric materials, and silicon wafers. Where substrate 30 is to be flexible, other polymeric materials or metals may be used. It should be recognized that some materials, such as some metals, may be relatively stiff if thick and flexible if thinner; accordingly the thickness of substrate 30 may be considered in selecting a material. In some embodiments, substrate 30 may be constructed from multiple materials, such as in a laminate arrangement. The manner in which fluid 20 is to be patterned onto substrate 30 may also be considered when selecting substrate 30. For example, it may be desired to be able to use photolithographic techniques on substrate 30, as will be described in greater detail below.
Where substrate 30 is flexible, substrate 30 may be bent or flexed as part of the construction of a device constructed by an embodiment of the method of the present invention, or in use of the device. For example, substrate 30 may be flexed into a desired shape, which may be non-planar. For example, substrate 30 may be flexed into a curved shape, such as a cylinder. It should be understood that the term "non-planar" refers to any non-planar shape including curved shapes, such as cylinders.
Where substrate 30 is flexed into a desired shape, it may be fixed in that shape if desired. For example, it may be treated to reduce its flexibility or may be held on the desired shape with suitable structure. In some embodiments, such as where substrate 30 is formed into a cylinder, substrate 30 may be attached to itself in some manner to fix it in a desired shape. Where substrate 30 is flexed as part of the construction of a device, it may be flexed at any time in the construction process. For example, substrate 30 may be flexed prior to self-assembly of substrates 10, during self-assembly, or after self-assembly.
Liquid 20 may be patterned on to substrate 30 in any manner and using any materials that allow liquid 30 to be applied to substrate 30 in the desired pattern. For example, liquid 20 may be painted, stamped, printed or otherwise patterned onto substrate 30. In embodiments where substrate is suitable for photolithography, liquid 20 may be applied to substrate 30 photolithographically in solid form and later liquefied, for example by melting.
In another embodiment, a precursor 32 may be patterned onto the surface of substrate 30 and used to facilitate formation of a desired pattern of liquid 20. For example, precursor 32 may be a material that either has an affinity or repulsion for liquid 20. hi the former case, it may be easier to apply liquid 20 where precursor 32 is present, and in the later case, precursor 32 may inhibit application of liquid 20 where precursor 32 is present. In some embodiments, both a precursor with an affinity for liquid 20 and a precursor which repulses liquid 20 may be used in conjunction to facilitate patterning of liquid 20. Any of the techniques described above for the patterning of liquid 20 on substrate 30 may also be used to pattern precursor 32 on substrate 30.
It should be understood that not all methods of the invention involve using a precursor and that the liquid may be patterned on the substrate in the absence of a precursor.
Where substrate 30 includes a precursor 32, liquid 20 may be applied to substrate 30 and precursor 32 allowed to control its pattern. For example, liquid 20 may be painted, pipetted, or the like, onto substrate 30 or substrate 30 may be dipped into liquid 20. Precursor 32 may then either maintain liquid 20 on substrate 30 where precursor 32 is located, or repulse liquid 20 from such locations, depending on the action of precursor 32. h one preferred embodiment, liquid 20 is dip coated onto substrate 20 and maintained on substrate 20 by an affinity for precursor 32. Those of skill in the art will be able to identify suitable precursors based on the liquid to be used and the desired action (affinity or repulsion) of precursor 32 on the liquid.
The action of liquid 20 may be any action that results in the desired patterning of structures 10. For example, the action may be a physical phenomena, such as capillary action or surface tension. Where the action is capillary action, liquid 20 may be selected such that it has a relatively high surface affinity for the material of structure 10 compared to its affinity for the surrounding environment. In such an embodiment, structure 10 may be held by liquid 20 because this results in a lower energy state for the system.
Liquid 20 may by any liquid that allows self-assembly of structures 10 by its action. For example, where the action of liquid 20 is capillary action, liquid 20 may be a liquid having a relatively high affinity for the material of structures 10 compared to their environment. Particular embodiments may require additional features of liquid 20. For example, where liquid 20 is desired to be part of a electrical connection between structures 10, it may be desired that liquid 20 is electrically conductive. Liquid suitable for use as liquid 20 in some embodiments is solder. Solder has good capillary action with many materials which structures 10 may be constructed from. Solder is also electrically conductive, a liquid at relatively low temperatures, and may be dip coated onto certain metal precursors, such as copper.
Liquid 20 may be selected such that structures 10 can be fixed to substrate 30 once self- assembly is complete. In one embodiment, liquid 20 is a solid at temperatures at which a device assembled according to an embodiment of the present invention is intended to be used. For example, a metal that is a solid at room temperature, but melts at a relatively low temperature, such as solder, may be useable in such and embodiment. In another embodiment, liquid 20 cures, hardens, or sets after a period of time sufficient for self- assembly. For example, a glue, epoxy, or prepolymer may be used in such an embodiment.
Self-assembly of structures 10 onto substrate 30 may be aided by the environment provided for self-assembly. For example, an environment may be provided that reduces possible hurdles to self-assembly, such as gravity, and/or improves the action of the liquid. Accordingly, self-assembly may occur at least partially within a carrier 40. Carrier 40 may be any liquid that does not inhibit self-assembly, and preferably promotes self-assembly. Carrier 40 may be denser than air, and is preferably of similar density to structures 10, reducing the effect of gravity on the self-assembly process. Carrier 40 may also be a material that is compatible with, i.e. doesn't corrode or otherwise damage, structures 10, substrate 30 and any associated components. Carrier 40 may also be a material that has a relatively high free energy at the interface between it and liquid 20 carrier interface. In another embodiment, carrier 40 may be capable reducing and/or inhibiting the formation of, a layer on liquid 20 or structure 10 that inhibits self-assembly. For example, carrier 40 may be sufficiently acidic to reduce and/or inhibit formation of an oxide layer on certain materials. For example, carrier 40 may have a pH of less than about 7, less than about 5, about 3, or even lower. In one embodiment, carrier 40 comprises water. Carrier 40 may be heated to melt liquid 20 for self- assembly, if required.
"Self-assembly conditions" is meant to define those conditions under which, when intended mating surfaces (those surfaces shaped or otherwise configured to provide mating such as the surfaces of substrate 30 and structure 10) are in contact in good register, the components (e.g., substrate 30 and structure 10) are not separated under the assembly conditions, but when the same surfaces are in contact but not in good register they either break free of contact or slide relative to each other until in good register, and where unintended mating surfaces are in contact, they do not remain in contact. Self-assembly conditions may be those of agitation, as described further below.
In some embodiments, the self-assembly process may be physically promoted. For example, self-assembly may be promoted through agitation of structures 10. Agitation may be provided in any manner that is sufficient to promote self-assembly, but not so great that it risks damage to the device being constructed or removes assembled structures from the substrate. Agitation may be in multiple directions, for example as illustrated by direction indicators 80 in FIG. 3. Agitation may also be used to correct defects. A substrate with structures attached may be subjected to additional agitation in the absence of other structures. This agitation may be vigorous, for example, it may comprise vigorous tapping of a container with a carrier 40 and the substrate and structures therein. This may correct defects such as structures assembled on electrical connectors between liquid coated assembly sites intended for the structures and multiple structures positioned on a single assembly site intended for one structure. After correcting any defects, additional structures may be self-assembled onto substrate. The cycle of self-assembly and removal of incorrectly positioned structures may be repeated to achieve a desired accuracy. In addition to the defects of structures assembled on electrical connectors between liquid coated assembly sites intended for the structures and multiple structures positioned on an assembly site intended for one structure, structures may sometimes straddle two independent assembly sites. This defect may was reduced or eliminated by increasing the space between such assembly sites. Reducing the width of electrical connectors may also reduce or eliminate connection of structures onto them. Other potential defects may consist of missing or misaligned structures. These defects may arise from defects in the assembly sites for the structures. These types of defects may be avoided by careful patterning of the liquid. Pieces of structures assembling onto assembly sites may also result in defects. This problem may be reduced or eliminated by screening the structures and eliminating broken structures.
In some embodiments, it may be desired to electrically connect structures 10. Structures 10 may be electrically connected in any manner that provides the desired connections, avoids undesired connections, and does not interfere with use of any device that structures 10 are part of. In a preferred embodiment, desired electrical connections are provided as the structures are self-assembled. For example, the structures themselves may include structure that connects them as they are assembled. As another example, liquid 20 may be used to electrically connect the structures as desired by providing a suitable pattern. In such an embodiment, liquid 20 may be electrically conductive. In another embodiment, precursor 32 may used to electrically connect structures 10 as desired. For example, precursor 32 may be constructed as an electrical network with larger areas pr precursor material available as assembly sites for connection to structures 10. Such a precursor arrangement may be particularly suited to construction by photolithography or common other semiconductor fabrication techniques. In an embodiment where the precursor is used to form electrical connections between structures, liquid 20 may still be desired to be conductive if structures 10 are not in direct contact with the precursor.
Structures 10 for use according to embodiments of the method of the present invention may include any structure able to be self-assembled. Structures 10 may have any shape of geometry. Typically, structures 10 will have at least one relatively flat surface as this may promote self-assembly onto a relatively flat substrate. However, as has been noted, substrate 30 need not be flat and, furthermore, structures 10 need no match the shape of the substrate in all embodiments. Because self-assembly has is particularly advantageous compared to conventional assembly techniques where structures 10 are relatively small, structures 10 may each have an average diameter of no more than one millimeter, no more than 500 micrometers, no more than 300 micrometers, no more than 150 micrometers, or even smaller. As used herein, "average diameter" refers to the average of all of the distances that may be measured from one side to the other side of a three dimensional object through its center.
Structures 10 may be constructed from any material that is capable of being self- assembled. In embodiments of the present invention where the method of the invention is being used to construct electronic devices, structures 10 may be constructed from materials commonly used in the manufacture of semiconductors, such as metal and silicon. Structures 10 may include microelectronics. As used herein, "microelectronics," refers to any circuitry less than 1 millimeter in average diameter capable of effecting the a flow of electricity and may range from a resistor to a complex microchip. In one embodiment, structures 10 include one or more light-emitting diodes (LEDs). Including LEDs in the device may allow it to be used as a display, or to provide signals, such as results or errors, to a user.
Structures 10 may be treated or comprise structure intended to improve self-assembly. For example, structures may include a coating or layer that has a relatively low interfacial free energy with liquid 20, promoting self-assembly. In one embodiment, a layer of gold is placed on one side of structures 10 to promote self-assembly.
In some embodiments, the method of the present invention may include connecting a second substrate 34 to at least some of structures 10 connected to substrate 30. Adding a second substrate allows connection of the structures at two locations, typically on opposite sides of the structures. This may allow completion of an electrical circuit with structures 10 in the middle. Second substrate 34 may be constructed of any of the materials that first substrate 30 may be constructed from.
In a preferred embodiment, second substrate 34 self-aligns with at least some of the plurality of structures during connection of second substrate 34. Self-alignment may be facilitated by applying a second liquid 22 to at least some of the plurality of structures 10. Second liquid 22 may be the same as liquid 20 and may be any of the liquids described above for use as liquid 20. Second substrate may include components, such as wires 38, arranged to line up with structures 10, facilitating alignment and providing electrical connection. Second substrate 34 may be generally positioned by hand, or the like, and then may self-align to provided a desired alignment. Preferably, the spacing between the structures and the second substrate is as uniform as possible, as are the positioning of the structures relative desired connection sites on the second substrate. In one embodiment, variations in structure height of as much as 70 micrometers and variations in lateral placement of up to 60 micrometers were tolerated by the self-alignment process.
Second substrate 34 may be connected to structures 10 such that, after connection, it is substantially parallel to the first substrate. As used herein, "parallel" means that two surfaces are substantially equidistant from one another over the length and width of the surface and includes two curved, equidistant surfaces, such as substrates 30 and 34 as illustrated in FIG. 6. In one embodiment, first and second substrates 30, 34 may be arranged as inner and outer cylinders.
Embodiments of the method of the present invention have been demonstrated to be capable of self-assembling at least 100, 500, 1000 or even 1500 independent structures according to a predetermined pattern and on a substrate in less than 5 minutes with at least 95% accuracy. As used herein, "% accuracy," refers to the number of properly assembled structures over the total number of structures that were desired to be assembled. More structures than are desire to be assembled (for example more structures than sites for self- assembly) may be used to facilitate self-assembly, but these structures are not counted toward the number of structures desired to be assembled in determining accuracy. In some embodiments, 100 or more independent structures may be assembled with at least 95% accuracy in less than three minutes and/or within a 5 square centimeter area. In other embodiments, 100 or more independent structures may be assembled with at least 98%, or even 100% accuracy in less than 5 minutes.
Some embodiments of the present invention include a high density of self-assembled structures on the surface area of the substrate. For example, some embodiments include greater than 200 independent structures per square centimeter surface area of the substrate. Other embodiments may include greater than 300, or greater than 500 independent structures per square centimeter surface area of the substrate. The number of independent structures per surface area of the substrate may be selected based on the requirements of a particular application.
Certain embodiments may also include large numbers of self-assembled independent structures on a substrate. For example, embodiments may include greater than 500 structures, greater than 1000 structures, greater than 1500 structures, or even more. The number of independent structures may be selected based on the requirements of a particular application.
EXAMPLES
Example 1 - Patterning a liquid on a substrate
In order to demonstrate pattering a liquid on a substrate, fabrication starting with sheets of a flexible copper-polyimide composite (Pyralux LF 9110, DuPont, Wilmington, Deleware). The substrate was primed with hexamethyldisilazane, and spin-coated with photoresist (Microposit 1813, Shipley, Marlborough, MA). After a soft-bake at 115 °C for 5 min, the substrate was exposed to UN light through a positive mask with pattern corresponding to the pattern required for the liquid (here solder). The photoresist was developed, and the exposed copper was removed by etching with an aqueous ferric chloride solution (1.4 g of FeCl3 per milliliter of H2O, pH 1.3). Finally, the protective photoresist was dissolved in acetone and the underlying copper squares (precursors) were coated with the low-melting solder (mp ~ 50 °C, Small Parts, Y-LMA-117) by dipping the substrates into a solder bath.
Example 2 - Control of surface chemistries
All surfaces are desired to be free from contamination for self-assembly. In order to demonstrate a suitable cleaning technique, structures (LEDs and silicon circuit elements) were cleaned in acetone, methanol, and concentrated sulfuric acid before transferring them into ME LIPORE® water. A small amount of soap (Triton 100, one drop (10 μL) per one liter of H2O) was added to prevent the formation of bubbles during the assembly, and as was a small amount of acetic acid (pH 3.0) to dissolve oxides that continuously form in the aqueous solution. The pH was adjusted carefully to avoid dissolution of the solder itself. To reduce the formation of oxides the water was deoxygenated by bubbling Ν2 through it.
Fabrication of LEDs for use as structures
To make a large number of diodes a dicing saw was used to cut a wafer of photodiode material (GaAs, #P3031, Optodiode Corp., Newbury Park, CA 91320) into 280 μm wide squares that were 200 μm thick. The semi automated dicing saw (General Signal Tempress model 602) that we used provided an accuracy of 40 μm. 113 LEDs were constructed into a cylindrical display, as illustrated in FIGS. 7-11. It was noted that assembly was not linear and that structures self-assembled faster after some initial structures had self-assembled. Without wishing to be bound by any particular theory, it is hypothesized that once structures had settled that they slowed other structures tumbling past the substrate in their vicinity, allowing them to assemble more rapidly.
Fabrication of silicon blocks for use as structures
Silicon wafers were coated with 10 nm of Cr and 400 nm of Au by thermal evaporation onto the backside. A dicing saw was used to cut the wafers into equally sized blocks, 280 μm x 280 μm wide and 400 μm tall. The silicon blocks were used to mimic integrated device segments and to avoid the expense of LEDs. For both the LEDs and the silicon blocks, the backside metallization serves as binding site during the self-assembly. 1500 silicon cubes were self-assembled on an area of 5 square centimeters in less than three minutes with an accuracy of about 98%, as illustrated in FIGS 12 and 13.
It will be understood that each of the elements described herein, or two or more together, may be modified or may also find utility in other applications differing from those described above. While particular embodiments of the invention have been illustrated and described, the present invention is not intended to be limited to the details shown, since various modifications and substitutions may be made without departing in any way from the spirit of the present invention as defined by the following claims.
What is claimed is:

Claims

Claims
1. A method of self-assembling a plurality of structures, comprising: patterning a first liquid onto a first substrate; and while at least a portion of the first liquid remains in liquid form, self-assembling at least a portion of the plurality of structures onto the substrate by action of the first liquid and according to the pattern of the first liquid.
2. The method of claim 1, wherein the first substrate is flexible.
3. The method of claim 2, further comprising flexing the first substrate.
4 The method of claim 3, further comprising flexing the first substrate such that it is non-planar.
5. The method of claim 4, further comprising flexing the first substrate such that it is curved.
6. The method of claim 5, further comprising forming a cylinder from the first substrate.
7. The method of claim 3, wherein the first substrate is flexed prior to self-assembling of the plurality of structures.
8. The method of claim 3, wherein the first substrate is flexed subsequent to self- assembling of the plurality of structures.
9. The method of claim 1, wherein the first substrate is non-planar.
10. The method of claim 9, wherein the first substrate is curved.
11. The method claim 10, wherein the first substrate is cylindrical.
12. The method of claim 1, wherein the action of the first liquid includes capillary action.
13 The method of claim 1, further comprising electrically connecting at least some of the plurality of structures.
14. The method of claim 13, wherein the at least some of the plurality of structure are electrically connected during self-assembly.
15. The method of claim 14, wherein the first liquid is electrically conductive.
16. The method of claim 15, where the first liquid includes solder.
17. The method of claim 1, wherein self-assembly occurs at least partially within a carrier.
18. The method of claim 17, wherein the carrier comprises water.
19. The method of claim 17, wherein the carrier has a pH of less than 7.
20. The method of claim 19, wherein the carrier has a pH of less than 5.
21. The method of claim 17, wherein the action of the first liquid includes minimization of the free energy of the first liquid-carrier interface.
22. The method of claim 17, further comprising agitating the carrier during self- assembling of the plurality of elements.
23. The method of claim 1 , wherein the plurality of structures each have an average diameter of no more than one millimeter.
24. The method of claim 23, wherein the plurality of structures each have an average diameter of no more than 500 micrometers.
25. The method of claim 24, wherein the plurality of structures each have an average diameter of no more than 300 micrometers.
26. The method of claim 25, wherein the plurality of structures each have an average diameter of no more than 150 micrometers.
27. The method of claim 1, wherein at least a portion of the structures comprise silicon.
28. The method of claim 1, wherein at least a portion of the plurality of structures comprise microelectronics.
29. The method of claim 1, wherein at least a portion a portion of the plurality of the structures comprise light-emitting diodes.
30. The method of claim 1, further comprising patterning a material having an affinity for the first liquid onto the first substrate.
31. The method of claim 30, wherein the material is patterned with photolithography.
32. The method of claim 30, wherein the material is copper.
33. The method of claim 1, further comprising connecting a second substrate to at least some of the plurality of structures.
34. The method of claim 33, wherein the second substrate, after connection, is substantially parallel to the first substrate.
35. The method of claim 33, wherein the second substrate self-aligns with at least some of the plurality of structures during connection.
36. The method of claim 33, further comprising applying a second liquid to at least some of the plurality of structures.
37. The method of claim 33, wherein at least one of the first and second substrates is one of translucent and transparent.
38. The method of claim 1, wherein the first substrate is one of translucent and transparent.
39. A method of self-assembly, comprising: self-assembling at least 100 independent structures according to a predetermined pattern and on a substrate in less than 5 minutes with at least 95% accuracy.
40. The method of claim 39, wherein at least 500 independent structures are self- assembled according to a desired pattern and on a substrate in less than 5 minutes with at least 95% accuracy.
41. The method of claim 40, wherein at least 1000 independent structures are self- assembled according to a desired pattern and on a substrate in less than 5 minutes with at least 95% accuracy.
42. The method of claim 41, wherein at least 1500 independent structures are self- assembled according to a desired pattern and on a substrate in less than 5 minutes with at least 95% accuracy.
43. The method of claim 39, wherein the self-assembly occurs in less than 3 minutes.
44. The method of claim 39, wherein all of the structures are assembled within a 5 square centimeter area.
45. The method of claim 39, wherein the accuracy is at least 98%.
46. The method of claim 45, wherein the accuracy is 100%.
47. The method of claim 39, wherein the independent structures have an average diameter of less than 500 micrometers.
48. The method of claim 40, wherein the independent structures have an average diameter of less than 300 micrometers.
49. The method of claim 49, wherein the independent structures have an average diameter of less than 150 micrometers.
50. An apparatus, comprising: a first non-planar substrate; a second non-planar substrate; and a plurality of structures arranged in a pattern and connected to the first substrate and the second substrate; wherein each of the plurality of structures has an average diameter of less than one millimeter; and wherein some of the plurality of structures are selected from the group consisting of electronic components, optical components, and mixtures thereof.
51. The apparatus of claim 50, wherein one of the first substrate and the second substrate is flexible.
52. The apparatus of claim 50, wherein the first and second substrates are arranged as inner and outer cylinders with the plurality of structures between them.
53. A display, comprising: a first substrate; a first plurality of electrical connectors in contact with the first substrate, at least some of the first plurality of electrical connectors being in electrical connection with one another; a second substrate; a second plurality of electrical connectors in contact with the second substrate, at least some of the second plurality of electrical connectors being in electrical connection with one another; and a plurality of display elements each electrically connected to at least one of the first plurality of electrical connectors and the second plurality of connectors; wherein each of the plurality of display elements has an average diameter of less than 1 millimeter.
54. The display of claim 53, wherein at least some of the display elements comprise a light-emitting diode.
55. An electronic device, comprising: a first non-planar substrate; a first plurality of electrical connectors in contact with the first non-planar substrate, at least some of first plurality of electrical connectors being in electrical connection with one another; a second non-planar substrate; a second plurality of electrical connectors in contact with the second non-planar substrate, at least some of the second plurality of electrical connectors being in electrical connection with one another; and a plurality of electronic elements each electrically connected to at least one of the first plurality of electrical connectors and the second plurality of electrical connectors.
56. The electronic device of claim 55, wherein each of the plurality of electronic elements has an average diameter of less than 1 millimeter.
57. A method, comprising: allowing a plurality of structures to self-assemble on a first substrate; and allowing a second substrate to self-align on the plurality of structures.
58. The method of claim 57, wherein self-assembly is provided by action of a liquid patterned onto the first substrate.
59. The method of clam 57, wherein the plurality of structures comprise electrically conductive elements.
60. The method of claim 57, wherein the plurality of structures are less than 1 millimeter in average diameter.
61. The method of claim 57, wherein the substrates are flexible.
62. The method of claim 57, wherein the substrates are non-planar.
63. An apparatus comprising: a non-planar substrate; and a plurality of independent structures arranged in a pattern and connected to the non- planar substrate, each of the structures having an average diameter of less than one millimeter, wherein the pattern includes greater than 200 independent structures per square centimeter surface area of the substrate.
64. The apparatus of claim 63, wherein the pattern includes greater than 300 independent structures per square centimeter surface area of the substrate.
65. The apparatus of claim 63, wherein the pattern includes greater than 400 independent structures per square centimeter surface area of the substrate.
66. The apparatus of claim 63, wherein the structures comprise electronic or optical components.
67. The apparatus of claim 63, wherein the independent structures comprise LED's.
68. The apparatus of claim 63, wherein the pattern includes greater than 1,000 independent structures.
69. The apparatus of claim 63, wherein the pattern includes greater than 1,500 independent structures.
70. The method of claim 1, wherein greater than 200 structures are self assembled per square centimeter surface area of the substrate.
71. The method of claim 1, wherein greater than 300 structures are self assembled per square centimeter surface area of the substrate.
72. The method of claim 1, wherein the substrate is curved.
73. The method of claim 1, wherein greater than 1000 structures are self assembled.
74. The method of claim 1, wherein greater than 1500 structures are self assembled.
75. A display comprising: a substrate; and a plurality of self-assembled, independent light-emitting devices arranged in a pattern on the substrate.
76. The display of claim 75, wherein the pattern includes greater than 200 structures per square centimeter surface area of the substrate.
77. The display of claim 75, wherein the pattern includes greater than 300 structures per square centimeter surface area of the substrate.
78. The display of claim 75, wherein the pattern includes greater than 500 structures per square centimeter surface area of the substrate
79. The display of claim 75, wherein the pattern includes greater than 500 structures.
80. The display of claim 75, wherein the pattern includes greater than 1000 structures.
81. The display of claim 75, wherein the pattern includes greater than 1500 structures.
82. The display of claim 75, wherein the substrate is non-planar.
83. The display of claim 82, wherein the substrate is curved.
PCT/US2003/011078 2002-04-10 2003-04-10 Method of self-assembly and self-assembled structures WO2003087590A2 (en)

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US7504331B2 (en) 2005-07-27 2009-03-17 Palo Alto Research Center Incorporated Method of fabricating self-assembled electrical interconnections
US7525194B2 (en) 2005-07-27 2009-04-28 Palo Alto Research Center Incorporated System including self-assembled interconnections
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US7592269B2 (en) 2003-11-04 2009-09-22 Regents Of The University Of Minnesota Method and apparatus for depositing charge and/or nanoparticles
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7232771B2 (en) 2003-11-04 2007-06-19 Regents Of The University Of Minnesota Method and apparatus for depositing charge and/or nanoparticles
US7592269B2 (en) 2003-11-04 2009-09-22 Regents Of The University Of Minnesota Method and apparatus for depositing charge and/or nanoparticles
US7504331B2 (en) 2005-07-27 2009-03-17 Palo Alto Research Center Incorporated Method of fabricating self-assembled electrical interconnections
US7525194B2 (en) 2005-07-27 2009-04-28 Palo Alto Research Center Incorporated System including self-assembled interconnections
EP2066495A1 (en) * 2006-09-27 2009-06-10 Samsid Technologies LLC Security device using reversibily self-assembling systems
EP2066495A4 (en) * 2006-09-27 2009-11-04 Samsid Technologies Llc Security device using reversibily self-assembling systems
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WO2011054611A2 (en) 2009-10-26 2011-05-12 Evonik Goldschmidt Gmbh Method for the self-assembly of electrical, electronic or micromechanical components on a substrate
WO2011054611A3 (en) * 2009-10-26 2011-10-13 Evonik Goldschmidt Gmbh Method for the self-assembly of electrical, electronic or micromechanical components on a substrate
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