This subject matter relates to the synthesis of elastic, bio-compatible functional microstructures wherein the designed electrical functionalities are achieved by mixing conducting nano to micro-particles with PDMS gels, in which the critical volume fraction of solid particles is chosen to ensure good conductivity, reliable mechanical properties, as well as desirable thermal characteristics. By using such composites, a methodology for constructing planar and three-dimensional microstructures by soft-lithographic technique has been developed. Applications such as electrodes, conducting strips, two and three-dimensional microstructures for electrical wiring connections, micro heaters, micro heater arrays, flexible thermochromic displays, and applications for microfluidic devices are demonstrated, all with demonstrated elastic flexibility and fall-proof characteristics while maintaining their functionalities. Results obtained are very promising for the utilization of such composites in micro-fabrications, especially for bio-chips.
In recent years, there has been considerable progress on fabricating microfluidic devices with multiple functionalities, with the goal of attaining lab-on-a-chip [1-3] integration. These efforts have benefited from the development of micro-fabrication technologies such as soft lithography [4]. Polydimethylsiloxane (PDMS) has played an important role for building micro-structures owing to its properties such as transparency, bio-compatibility, and good flexibility [5]. Some complicated micro-devices can be realized by using simple manufacturing techniques such as micro molding with PDMS materials (U.S. Pat. Nos. 7,125,510; 6,692,680; and 6,679,471). However, PDMS is a nonconducting polymer, and patterning metallic structures is very difficult due to the weak adhesion between metal and PDMS. Hence the integration of conducting structures into PDMS has been a critical issue, especially for those applications such as electrokinetic micro-pumps, micro sensors, micro heaters, ER actuators etc. [6-7] that require electrodes for control and signal detection.
Gawron et al. [8] first reported the embedding of thin carbon fibers into PDMS-based microchips for capillary electrophoresis detection. Lee et al. [9] reported the transfer and subsequent embedding of thin films of gold patterns into PDMS via adhesion chemistries mediated by a silane coupling agent. Lim et al. [10] developed a method of transferring and stacking metal layers onto a PDMS substrate by using serial and selective etching techniques. As shown in the U.S. Pat. No. 6,323,659, the electrodes comprising a base material and filler material was disclosed to be used to determine the presence of water in a material. Where a conductive electrode may be formed by depositing carbon black on the elastomer surface, that is accomplished either by wiping on the dry powder or by exposing the elastomer to a suspension of carbon black in a solvent. Alternatively, the electrode may be formed by constructing the entire layer out of an elastomer doped with conductive material (i.e. carbon black or finely divided metal particles). However, incompatibility between PDMS and metal usually causes failures in the fabrication process, especially in the bonding of two materials. Therefore, selection of a right composite with good conductivity, reliable mechanical property, as well as desired thermal characteristics for constructing micro-devices is of great urgency. In particular, the construction of the micro-devices with three-dimensional conducting structures, such as three-dimensional wiring and packaging, represents challenges for the micro-fabrication processing. PDMS-based conducting composites may be promising materials for micro-device fabrication.
The present invention relates generally to micro fabrication techniques and PDMS composite materials. More particularly, the present invention relates to the synthesis of elastic, bio-compatible functional microstructures wherein the designed electrical functionalities are achieved by mixing conducting nano-to-micro particles with PDMS gels, in which the critical volume fraction of solid particles is chosen to ensure good conductivity, reliable mechanical properties, and desirable thermal characteristics. By using such composites, improved methodologies have been developed for constructing planar and three-dimensional microstructures by soft-lithographic techniques. The composites of the inventive subject matter may be used to fabricate a variety of useful microstructures. For example specific embodiments of the present subject matter may include electrodes, conducting strips, two and three-dimensional microstructures for electrical wiring connections, micro heaters, micro heater arrays, flexible thermochromic displays, and applications for microfluidic devices. Furthermore, structures made with the inventive composites and/or methods further demonstrate elastic flexibility and fall-proof characteristics while maintaining their functionalities.
One embodiment of the present subject matter relates to a fabricated planar structure, three-dimensional structure, or combinations thereof, comprising at least one PDMS-based conducting composite, wherein the structure provides predesigned electrical conductivity and mechanical characteristics. A further embodiment of the present subject matter relates to a fabricated planar structure, three-dimensional structure, or combination thereof, wherein the at least one PDMS-based conducting composite comprises (a) Ag+PDMS; (b) Carbon black (C)+PDMS; or (c) combinations thereof. In one embodiment of the present subject matter, the at least one PDMS-based conducting composite comprises Ag+PDMS at a Ag wt/PDMS wt concentration ranging from about 83% to about 90% by weight. In a more preferred embodiment, the Ag wt/PDMS wt concentration ranges from about 84% to about 87% by weight. Another embodiment of the present subject matter relates to the fabricated planar structure, three-dimensional structure, or combination thereof, wherein the at least one PDMS-based conducting composite comprises C+PDMS at a carbon black wt/PDMS wt concentration ranging from about 10% to about 30% by weight. In a more preferred embodiment, the carbon black wt/PDMS wt concentration ranges from about 15% to 27%. In yet another embodiment of the present subject matter, the Ag+PDMS composite comprises Ag particles ranging in average size from about 1.0 μm to about 2.2 μm. In another embodiment, the C+PDMS composite comprises carbon black particles ranging in average size from about 30 nm to 100 nm.
Another embodiment of the present subject matter relates to the fabricated planar structure, three-dimensional structure, or combination thereof, wherein the fabricated structure is a rod array, a multilayer wiring co-junction, or a cross bridge, comprising the predesigned electrical conductivity and mechanical characteristics. In one embodiment of the present subject matter, the fabricated structure or predesigned pattern is fabricated using soft-lithographic techniques. In another embodiment of the present subject matter, the fabricated structure is embedded in PDMS bulk material by molding into designed shapes and patterns. In yet another embodiment of the present subject matter, the fabricated structure comprises at least one conducting wiring structure having a minimum size of 10 microns. In a preferred embodiment of the present subject matter, the fabricated structure is mechanically elastic and flexible while maintaining the designed electrical conductivity. In another preferred embodiment of the present subject matter, the fabricated structure is fall-proof.
One embodiment of the present subject matter relates to using the inventive fabricated composites for use as a micro-heater, or device comprising a micro-heater. In a particular embodiment of the present subject matter, the micro-heater, or device comprising a micro-heater, comprises a heater strip that is at least 25 microns wide or long. In another embodiment of the present subject matter, the maximum local temperature generated by the heater strip can range from ambient temperature to 250° C. In a further embodiment of the present subject matter, the micro-heater, or device comprising a micro-heater, having (a) an overall structure that is mechanically elastic and flexible while maintaining local heating functionalities; (b) an overall structure that is fall-proof; or (c) combinations thereof.
Another embodiment of the present subject matter relates to using the inventive fabricated composites for use as a thermal array. In a particular embodiment of the present subject matter, the thermal array comprises a temperature sensing mechanism that may optionally control conductivity in the heater strip. In a further embodiment of the present subject matter, the thermal array further comprises a temperature sensing mechanism comprising at least one thermochromic microcolor bar whose color can be sensed optically. In a still further embodiment of the present subject matter, the thermal array comprises a temperature sensing mechanism comprising at least one thermochromic microcolor bar whose color can be sensed optically, and wherein detection of color from the at least one thermochromic microcolor bar is monitored optically and subsequent conductivity through the heating strip is controlled through an electro-optic feedback system that stops heating when the desired thermochromic microcolor bar is activated by the desired threshold temperature.
An additional embodiment of the present subject matter relates to using the inventive fabricated composites for use as a thermally activated display. In one embodiment of the present subject matter, the thermally activated display comprises (a) a thermochromic composite and (b) a Ag+PDMS composite; and wherein the fabricated structure is thermochromic, electrical conducting, and flexible. In another embodiment of the present subject matter, the thermally activated display comprises (a) a thermochromic composite layer contacting (b) a Ag+PDMS composite layer. In a further embodiment of the present subject matter, the thermally activated display comprises the fabricated Ag+PDMS structure embedded with a conductive wire pattern corresponding to a predesigned pattern for display.
A further embodiment of the present subject matter relates to using the inventive fabricated composites for use as a thermally activated display embedded with a multiplicity of independent conductive wire patterns localized in a matrix-like array of independent pixels; wherein each pixel may independently display a color the same or different from a neighboring pixel based upon the degree of heating supplied by the conductive wiring to each individual pixel. In one embodiment of the present subject matter, the thermally activated display comprises (a) a thermochromic composite layer contacting (b) a Ag+PDMS composite layer; wherein the conductive wire patterns are embedded in the Ag+PDMS layer. In another embodiment of the present subject matter, the thermally activated display comprises Ag+PDMS at a Ag wt/PDMS wt concentration ranging from about 84% to about 88% by weight. In yet another embodiment of the present subject matter, the thermally activated display comprises microencapsulated thermochromic powder as the thermochromic composite.
Another embodiment of the present subject matter relates to using the inventive fabricated composites in a process for making a thermally activated display comprising: (a) mixing microencapsulated thermochromic powder with PDMS at a particle concentration of 20% (w/w); (b) mixing silver powder with PDMS at a Ag wt/PDMS wt concentration ranging from about 84% to about 88% by weight to form a gel-like mixture; (c) embedding at least one conductive wire pattern in the Ag+PDMS mixture; (d) applying a layer of (a) to the gel-like mixture of Ag+PDMS; and (e) curing the layered composites.
The inventive subject matter relates to the synthesis of elastic, bio-compatible functional microstructures wherein the designed electrical functionalities are achieved by mixing conducting nano-to-micro-sized particles with PDMS gels, in which the critical volume fraction of solid particles is chosen to ensure good conductivity, reliable mechanical properties, as well as desirable thermal characteristics. By using such composites, a methodology for constructing planar and three-dimensional microstructures by soft-lithographic technique has been developed. Applications such as electrodes, conducting strips, two and three-dimensional microstructures for electrical wiring connections, micro heaters, micro heater arrays, flexible thermochromic displays, and applications for microfluidic devices are demonstrated, all with demonstrated elastic flexibility and fall-proof characteristics while maintaining their functionalities. Results obtained are very promising for the utilization of such composites in micro-fabrications, especially for bio-chips.
As used herein, the phrase “PDMS-based conducting composite” means a composite chemical structure comprising at least one conducting particle component that imparts electrical conductivity to all or a portion of the entire structure. The phrase “conducting particle component” refers to a nano-sized or micro-sized particle component that is electrically conductive. In some embodiments, this particle component is selected from silver powder or carbon black. Other electrically conductive particle components known to one of ordinary skill in the art may also be used to prepare PDMS-based conducting composites.
As used herein, the phrase “mechanically elastic and flexible” refers to the ability of PDMS-based conducting composites to bend under light to moderate mechanical stress without causing substantial permanent deformation of the structure or without disrupting electrical conductivity of the structure. Light to moderate mechanical stress includes wrapping or applying a thin layered structure over a curved or irregular surface, or bending a structure with the fingers to conform to a frame or holder.
As used herein, the term “fall-proof” refers to the ability of PDMS-based conducting composites, and structures substantially made from PDMS-based conducting composites, to resist breakage or fracture of the structure and its conducting properties as a result of mechanical stress caused by a sudden collision, such as, for example, being knocked off a support or falling on a hard surface.
As used herein, the phrase “thermochromic color bar” refers to a device or composition comprising a thermochromic chemical composition in at least one localized area that changes color in response to temperature. Generally, the temperature-changing color can be sensed optically. For example, the color may be sensed by a photodetector, such as the human eye, photographic film, a CCD camera, etc. A thermochromic color bar may include a single localized thermochromic chemical composition that changes colors across a broad color spectrum in response to temperature. Alternatively, a thermochromic color bar may include two or more localized thermochromic chemical compositions, wherein each localized thermochromic chemical composition changes colors in response to a narrow range of temperatures, and wherein a series of such localized compositions may be arranged to sense changes across a broader range of temperatures.
Synthesis of PDMS-based conducting composites: The inventive subject matter relates to composites formed from the mixing of conducting nano-to-micro-sized particles with PDMS gels, wherein a critical volume fraction of solid particles is chosen to ensure good conductivity, reliable mechanical properties, as well as desirable thermal characteristics. In one embodiment, the conducting composites comprise conducting nano-to-micro-sized particles selected from particles of silver (Ag) or carbon black (C), wherein these particles are mixed with PDMS to form the conductive composites Ag+PDMS and C+PDMS that are appropriate for the micro-fabrications. The synthesis process comprises mixing either silver or carbon black with PDMS gels at designed concentrations. In one embodiment of the present subject matter, the Ag wt/PDMS wt concentration ranges from about 83% Ag to about 90% Ag by weight. In a further embodiment, the Ag wt/PDMS wt concentration ranges from about 84% Ag to 87% Ag by weight. In another embodiment, the carbon black (C) wt/PDMS wt concentration ranges from about 10% C to about 30% C by weight. In a further embodiment, the C wt/PDMS wt concentration ranges from about 15% C to 27% C by weight. In yet another embodiment, the silver or carbon black particle sizes range from about 1-2 μm for silver and range from about 30 to 100 nanometers for carbon black, respectively, as can be seen in the insets of
Characterizing PDMS-based conducting composites: The conductivities of two examples of composites are shown in
The resistivities of well-cured composites exhibit variations with temperature T, as shown in
The mechanical reliability of PDMS-based conducting composites under deformation processing was examined. In one example, to measure the mechanical reliability of the two composites under deformation processing, two 25×2×1 mm3 strips of C+PDMS (26 wt % carbon) and Ag+PDMS (86 wt % Ag) were prepared for the experiment in a pulling system (MTS, Alliance RT/5). By stretching and restoring the sample with a constant speed of 1.5 mm/min, the variation of conductivity under strain was monitored. The results are shown in
Fabrication of Planar micro-structures: One example of a procedure to embed one layer of conductive composite into PDMS elastomer is schematically illustrated in
SEM images of examples of different patterns fabricated with Ag+PDMS composites are shown in
Three-dimensional wiring: Three dimensional connections of electrical signals is an important issue in integrated micro chips, e.g., transfer of electrical signals among different layers, communication between inner and outer layered components in multilayered chips. Structures comprising the PDMS-based conducting composites of the inventive subject matter may also be fabricated with integrated electrical circuitry and/or structures that allow connections of electrical signals. For example, for the microstructure depicted in
Fabrication and characterization of the micro-heaters: PDMS-based conducting composites may also be used to fabricate a micro-heater. An example of using a PDMS-based conducting composite is shown in
To verify the heating capability of the micro-heaters in the examples, an infrared (IR) camera (FLIR Systems trademark, model Prism DS) was employed to detect both the heat images and the local temperatures. The IR camera was placed right over the micro-heater to record the thermal characteristics when the micro-heater was subject to different applied voltages. By using this infrared sensing technique, accurate temperature readings as well as comprehensive thermal distribution patterns were obtained. The relationship between temperature and applied voltage was determined by focusing the IR camera on the central helical range of the micro-heater. The measured results for a heater with ˜75 μm wide strips are shown in
Fabrication and Characterization of Flexible Thermochromic Displays
Another example of using PDMS-based conducting composites of the inventive subject matter is for a flexible display device. Flexible display devices fabricated using PDMS-based conducting composites of the inventive subject matter may offer the further advantages of contributing to lighter weight, increased portability, and/or increased durability. [11, 12] Many flexible display devices are based on liquid crystals combined with polymeric structures. For example, displays with high flexibility can be fabricated using liquid crystal encapsulated as single pixels in elastomer substrate, [13] or in field-induced polymer structures. [14] To drive the displays, conducting wires/patterns are indispensable for transmitting the controlling signals. Recently, an ultralow-power organic circuit has been realized. [15] It was reported that the electric circuits can be fabricated with electric and photolithography, [16, 17] direct ink-jet printing with conductive compositions, [18, 19].
Some embodiments of the present subject matter provide for the design and fabrication of a thermally activated display using films made of thermochromic composite and embedded conductive wiring patterns. Thermo-chromic powder is a material whose optical properties (e.g., color) are tunable by varying the temperature, in a reversible and repeatable manner. Preparations of such material have been mainly studied with respect to the reversible thermochromic effect. [20-22] Owing to the accurate, rapid, and stable characteristics, [23] this material promises broad applications ranging from smart windows, color filters, and temperature sensors. [24, 25] Polydimethylsiloxane (PDMS) plays an important role for our thermal displays, mainly due to its desirable wetting characters with thermochromic nanoparticles and silver powders. Thus the thermochromic or conducting polymer gel can be easily made. [26]
The display of the inventive subject matter is based on the use of two materials: (a) thermochromic polymers and (b) a conductive particle+PDMS conductive composite as described throughout the specification. A variety of thermochromic polymers known to one of ordinary skill in the art may be used to fabricate the display. In one embodiment, microencapsulated thermochromic powder (for example, 3 7 μm in diameter, Lijinkeji Co. Ltd) may be employed whose color, for example, is dark green at room temperature and turns white, for example, above 60° C. When the powder is mixed with PDMS, for example, PDMS 2025 (Dow Coning 184), at a particle concentration of 20% (w/w), for example, and thoroughly ground, a liquid-like composite is formed that has a dark-green color. To prepare the conducting composite, micron-sized silver powder (1.2 2.2 μm), for example, is used and mixed with PDMS at the silver concentration of 86.3% (w/w), for example. After vigorously stirring, the composite formed a gel-like soft mixture. With soft-lithographic technique, the conducting composite offers advantages of ease in patterning microconducting wires and in integrating electrical circuits, for example. When the thermochromic composite is spun at a speed of 400 rpm for 18 seconds onto the designed patterns and cured after a short bake, a thermochromic display is formed, with the thickness of 150 μm, for example. Owing to the PDMS matrix, the thermochromic and conducting composite exhibits polymeric properties with excellent flexibility. The ease in shaping the conducting patterns offers a great advantage in the design of the display devices of the inventive subject matter.
An important feature in the performance of a display is the response time to the applied voltage. An example was carried out at ambient temperature, for example, 20.4° C., on a testing sample with 80Ω resistance. A charge coupled device camera was employed to record image evolution when the thin thermochromic film is subjected to a step-function DC voltage. Images were arranged in a time sequence, and the image which resulted in the most complete and accurate logo for the example display was recorded and is shown as inset (b) in
To overcome the problem of overheating, for example, periodic square pulse trains with a fixed duty cycle were used. This can avoid excessive heating, maintain the desired clear image, as well as decrease power consumption. To optimize the square pulse duration t and voltage V, a series of experiments were carried out with the pulse period T fixed at 20 ms. The table in
The mechanical property of the PDMS-based thermochromic material and conducting composite endows the thermochromic display with high flexibility. The thickness of the film, for example, ˜150 μm, enables the film to bend, fold, and distorted at discretion while preserving the normal displaying functions.
Based on the ease of fabrication and simple architecture, the thermochromic display can have advantages in lowering the display unit cost. The heating pulse control scheme can also provide lower power consumption, and the light weight and mechanical flexibility can provide additional portability, convenience, and durability. With matrix-like thermal pixels, for example, programmable images can be generated with digital control.
Fabrication and Characterization of Microfluidic Reaction Systems
Another example of using PDMS-based conducting composites of the inventive subject matter is for a microfluidic reaction system. Flexible display devices fabricated using PDMS-based conducting composites of the inventive subject matter may offer the further advantages of contributing to lighter weight, increased portability, and/or increased durability.
The terms “microfluidic chip” and “microfluidic reaction system” as used in the inventive subject matter are interchangeable and refer to a device that conveniently supports the separation and/or analysis of chemical and/or biological sample sizes that are as small as a few nanoliters or less. In general, these chips are formed with a number of microchannels that may be connected to a variety of reservoirs containing fluid materials. The fluid materials may be driven or displaced within these microchannels throughout the chip using electrokinetic forces, pumps and/or other driving mechanisms. These microfluidic devices may utilize Micro-Electromechanical-Systems (MEMS) elements: for example, chemical sensors; biosensors; micro-valves; micro-pumps; micro-heaters; micro-pressure transducers; micro-flow sensors; micro-electrophoresis columns for DNA, RNA, and/or protein analysis; micro-heat exchangers; micro-chem-lab-on-a-chip; etc. These microfluidic devices can conveniently provide mixing, separation, and/or analysis of fluid samples within an integrated system that is formed on a single chip. The term “bio-chip” as used in the inventive subject matter refers to a “microfluidic chip” that is primarily used for the separation and/or analysis of biological samples.
Temperature is a basic environmental parameter which can affect many material properties. Various types of temperature sensors are available, such as fiber-optic sensors for high-temperature measurements, [29] sensors of organic thin film transistors, [30] etc. Recent interest on microfluidic chips for chemical and biological functions [31] has focused attention on temperature control in these systems, as thermal detection and control are important in microreactions and bioprocesses, e.g., experiments regarding DNA sequencing and cell biology applications. [32] Platinum thin film has been commonly used as a temperature sensor in microchips. [33] It has been reported that thermal microscopic scan, using fluorescent particles as sensor, has also been employed. [34] In another approach, infrared cameras are frequently utilized to not only obtain surface temperature distributions via images [35] but also constitute a feedback system for temperature control. [36] Low cost infrared sensors have been developed for these purposes. [37]
For its ease of fabrication, biocompatibility, and other merits, polydimethylsiloxane (PDMS) is considered as a primary base material for microchip fabrications. [38] However, owing to its weak bonding characteristic with metallic materials, it is difficult to implement microtemperature sensors inside PDMS chips during the soft lithographic fabrication process. In addition, since the material would shield signals from IR cameras, contactless sensing of local temperature inside the microchips is difficult. To solve the problems mentioned above, a design and fabrication of thermochromic microcolor bars is presented in the inventive subject matter, which provides a local temperature indicator inside the microfluidic chip which can be sensed optically. Together with the embedded PDMS/silver particle-based microheater and optical sensor of the inventive subject matter [39], a further embodiment provides that the local thermal characteristics of microfluidic chips can be easily monitored and controlled through a feedback electronic system.
To show the functionality of our approach, a microfluidic chip for a well-known chemical reaction experiment, for example, as shown in
In another embodiment, in order to precisely control the local temperature inside the microfluidic chip, a temperature detection and feedback control system for the microheater is designed and constructed, an example shown as a flowchart in
In case the desired set temperature should be maintained for a long period of time, the analog control signal can be converted to digital form and stored in random access memory. The signal selector is then disconnected from the feedback loop and instead receive the control signal from the CPU after a reverse digital to analog conversion. In this way, the optical-electronic feedback control loop would serve only for the initial calibration purpose, with the subsequent temperature control independent from the microscope and the CCD camera.
A chemical reaction experiment was carried out to test the functionality of the thermochromic color bar and the associated temperature control aspects the system. Liquid solutions of sodium thiosulfate and hydrochloric acid in concentrations of 3 and 6 mol/L, respectively, were injected into the microchannels at the velocity of 0.02 ml/m with a syringe pump. When the two chemical solutions were mixed, reaction occurred and sulfur (yellow in color) became visible. Hence, on the right panels of
In order to quantitatively validate the temperature control, an oscilloscope was used to record synchronous signals to the microheater and the voltage output from the CdS sensor.
Having described the invention in detail and by reference to the embodiments thereof, it will be apparent that modifications and variations are possible, including the addition of elements or the rearrangement or combination or one or more elements, without departing from the scope of the invention which is defined in the appended claims. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
This application claims the benefit of U.S. Provisional Application No. 60/860,713 filed Nov. 24, 2006. The aforementioned provisional application's disclosure is incorporated herein by reference in its entirety.
Number | Name | Date | Kind |
---|---|---|---|
6017587 | Kleyer et al. | Jan 2000 | A |
6323659 | Krahn | Nov 2001 | B1 |
6679471 | Domeier et al. | Jan 2004 | B2 |
6692680 | Lee et al. | Feb 2004 | B2 |
7001191 | Nishizawa | Feb 2006 | B2 |
7125510 | Huang | Oct 2006 | B2 |
20040192834 | Nakayoshi et al. | Sep 2004 | A1 |
20080198098 | Gelbman et al. | Aug 2008 | A1 |
20080277631 | Smela et al. | Nov 2008 | A1 |
Number | Date | Country |
---|---|---|
2373279 | Sep 2002 | GB |
0128292 | Apr 2001 | WO |
2004003937 | Jan 2004 | WO |
WO 2004003937 | Jan 2004 | WO |
2006004282 | Jan 2006 | WO |
WO 2006004282 | Jan 2006 | WO |
WO 2006004282 | Jan 2006 | WO |
Number | Date | Country | |
---|---|---|---|
20080123174 A1 | May 2008 | US |
Number | Date | Country | |
---|---|---|---|
60860713 | Nov 2006 | US |