Karen Lee Krafcik

Color Detection Using Chromophore-Nanotube Hybrid Devices

We present a nanoscale color detector based on a single-walled carbon nanotube functionalized with azobenzene chromophores, where the chromophores serve as photoabsorbers and the nanotube as the electronic read-out. By synthesizing chromophores with specific absorption windows in the visible spectrum and anchoring them to the nanotube surface, we demonstrate the controlled detection of visible light of low intensity in narrow ranges of wavelengths. Our measurements suggest that upon photoabsorption, the chromophores isomerize from the ground state trans configuration to the excited state cis configuration, accompanied by a large change in dipole moment, changing the electrostatic environment of the nanotube. All-electron ab initio calculations are used to study the chromophore-nanotube hybrids and show that the chromophores bind strongly to the nanotubes without disturbing the electronic structure of either species. Calculated values of the dipole moments support the notion of dipole changes as the optical detection mechanism.

High aspect ratio patterning with a proximity ultraviolet source

A considerably less expensive option to synchrotron exposures of thick film photoresists is to use a proximity UV exposure tool. The use of UV radiation, however, is potentially limited by aerial image degradation as the image propagates through the thick photoresist layer. In addition to diffraction, run-out from uncollimated light or absorption in the resist easily dominate the aerial image problems for thick films. Alternatively, thick film lithography may be limited by the ability of present photoresists to print the aerial image. With some formulations, calculated line-and-space theoretical limits can be printed for 150-μm thick films. Typical aspect ratios for films greater than 200-μm thick exceed 20:1 with good process linearity and sidewall profiles and extension to 700-μm thick films is shown. We show that present commercial formulations of photoresists and not aerial image are likely the limiting factor in the practical resolution of final features from proximity UV printing. In particular, the redeposition of partially dissolved resist during drying after development leads to feature degradation. Released electrodeposited metal parts are also produced and demonstrated.

Low-distortion, high-strength bonding of thermoplastic microfluidic devices employing case-II diffusion-mediated permeant activation

We demonstrate a new method for joining thermoplastic surfaces to produce microfluidic devices. The method takes advantage of the sharply defined permeation boundary of case-II diffusion to generate dimensionally controlled, activated bonding layers at the surfaces being joined. The technique is capable of producing bonds that exhibit cohesive failure, while preserving the fidelity of fine features in the bonding interface. This approach is uniquely suited to production of layered microfluidic structures, as it allows the bond-forming interface between plastic parts to be precisely manipulated at micrometre length scales. Distortions in microfluidic device channels are limited to the size scale of the permeant-swollen layer; 6 microm deep channels are routinely produced with no detectable cross-sectional distortions. Conventional thermal diffusion bonding of identical parts yields less strongly bonded microfluidic structures with increasingly severe dimensional compressions as bonding temperatures approach the thermoplastic glass-transition temperature: a preliminary rheological analysis is consistent with the observed compressions. The bond-enhancing procedure is easily integrated in standard process flows, uses inexpensive reagents, and requires no specialized equipment.

Etching of Surfactant from Solution-Processed, Type-Separated Carbon Nanotubes and Impact on Device Behavior

Semiconducting single-walled carbon nanotubes (SWCNTs) have great potential for use in electronic and optoelectronic devices. However, methods for synthesizing SWCNTs produce a mixture of metallic and semiconducting materials, which require additional processing to separate by electronic type. Purification and enrichment of the semiconducting fraction is readily achieved by using the centrifugation of aqueous suspensions of SWCNTs with the help of surfactants, but this leaves residual surfactant on the SWCNT surface that can impact their electronic and optical properties. Here, we present a detailed study of the sodium taurodeoxycholate (STDC) surfactant removal process during vacuum annealing, showing that it occurs through fragmentation of the surfactant, and that complete removal requires exceedingly high temperatures, which indicates strong binding to the SWCNTs. We then present an approach based on air oxidation and mild annealing to completely remove the surfactant while maintaining the SWCNT properties. Using this approach, we compare single SWCNT electronic devices with and without STDC and show that, despite the very strong surfactant binding, it does not affect device performance substantially.

Physical removal of metallic carbon nanotubes from nanotube network devices using a thermal and fluidic process

Electronic and optoelectronic devices based on thin films of carbon nanotubes are currently limited by the presence of metallic nanotubes. Here we present a novel approach based on nanotube alkyl functionalization to physically remove the metallic nanotubes from such network devices. The process relies on preferential thermal desorption of the alkyls from the semiconducting nanotubes and the subsequent dissolution and selective removal of the metallic nanotubes in chloroform. The approach is versatile and is applied to devices post-fabrication.

Injection molded microfluidic devices for biological sample separation and detection

We are developing a variety of microsystems for the separation and detection of biological samples. At the heart of these systems, inexpensive polymer microfluidic chips carry out sample preparation and analysis. Fabrication of polymer microfluidic chips involves the creation of a master in etched silicon or glass; plating of the master to produce a nickel stamp; large lot chip replication by injection molding; precision chip sealing; and chemical modification of channel surfaces. Separation chips rely on insulator-based dielectrophoresis for the separation of biological particles. Detection chips carry out capillary electrophoresis to detect fluorescent tags that identify specific biological samples. Since the performance and reliability of these microfluidic chips are very sensitive to fluidic impedance, electromagnetic flux, and zeta potential, the microchannel dimensions, shape, and surface chemistry have to be tightly controlled during chip fabrication and use. This paper will present an overview of chip design, fabrication, and testing. Dimensional metrology data, surface chemistry characterization, and chip performance data will be discussed in detail.

Design and fabrication of a meso-scale stirling engine and combustor.

Power sources capable of supplying tens of watts are needed for a wide variety of applications including portable electronics, sensors, micro aerial vehicles, and mini-robotics systems. The utility of these devices is often limited by the energy and power density capabilities of batteries. A small combustion engine using liquid hydrocarbon fuel could potentially increase both power and energy density by an order of magnitude or more. This report describes initial development work on a meso-scale external combustion engine based on the Stirling cycle. Although other engine designs perform better at macro-scales, we believe the Stirling engine cycle is better suited to small-scale applications. The ideal Stirling cycle requires efficient heat transfer. Consequently, unlike other thermodynamic cycles, the high heat transfer rates that are inherent with miniature devices are an advantage for the Stirling cycle. Furthermore, since the Stirling engine uses external combustion, the combustor and engine can be scaled and optimized semi-independently. Continuous combustion minimizes issues with flame initiation and propagation. It also allows consideration of a variety of techniques to promote combustion that would be difficult in a miniature internal combustion engine. The project included design and fabrication of both the engine and the combustor. Two engine designs were developed. The first used a cylindrical piston design fabricated with conventional machining processes. The second design, based on the Wankel rotor geometry, was fabricated by through-mold electroforming of nickel in SU8 and LIGA micromolds. These technologies provided the requisite precision and tight tolerances needed for efficient micro-engine operation. Electroformed nickel is ideal for micro-engine applications because of its high strength and ductility. A rotary geometry was chosen because its planar geometry was more compatible with the fabrication process. SU8 lithography provided rapid prototypes to verify the design. A final high precision engine was created via LIGA. The micro-combustor was based on an excess enthalpy concept. Development of a micro-combustor included both modeling and experiments. We developed a suite of simulation tools both in support of the design of the prototype combustors, and to investigate more fundamental aspects of combustion at small scales. Issues of heat management and integration with the micro-scale Stirling engine were pursued using CFD simulations. We found that by choice of the operating conditions and channel dimensions energy conversion occurs by catalysis-dominated or catalysis-then-homogeneous phase combustion. The purpose of the experimental effort in micro-combustion was to study the feasibility and explore the design parameters of excess enthalpy combustors. The efforts were guided by the necessity for a practical device that could be implemented in a miniature power generator, or as a stand-alone device used for heat generation. Several devices were fabricated and successfully tested using methane as the fuel.

Imaging latex-carbon nanotube composites by subsurface electrostatic force microscopy

Electrostatic modes of atomic force microscopy have shown to be non-destructive and relatively simple methods for imaging conductors embedded in insulating polymers. Here we use electrostatic force microscopy to image the dispersion of carbon nanotubes in a latex-based conductive composite, which brings forth features not observed in previously studied systems employing linear polymer films. A fixed-potential model of the probe-nanotube electrostatics is presented which in principle gives access to the conductive nanoparticles depth and radius, and the polymer film dielectric constant. Comparing this model to the data results in nanotube depths that appear to be slightly above the film-air interface. This result suggests that water-mediated charge build-up at the film-air interface may be the source of electrostatic phase contrast in ambient conditions.

Sacrificial layer for the fabrication of electroformed cantilevered LIGA microparts

The use of silver filled PMMA as a sacrificial layer for the fabrication of multilevel LIGA microparts is presented. In this technique, a bottom level of standard electroformed LIGA parts is first produced on a metallized substrate such as a silicon wafer. A methyl methacrylate formulation mixed with silver particles is then cast and polymerized around the bottom level of metal parts to produce a conducting sacrificial layer. A second level of PMMA x-ray resist is adhered to the bottom level of metal parts and conducting PMMA and patterned to form another level of electroformed features. This presentation will discuss some the requirements for the successful fabrication of multilevel, cantilevered LIGA microparts. It will be shown that by using a silver filled PMMA, a sacrificial layer can be quickly applied around LIGA components; cantilevered microparts can be electroformed; and the final parts can be quickly released by dissolving the sacrificial layer in acetone.

Ideal system morphology and reflectivity measurements for model development and validation

This paper describes measurements being made on a series of material systems for the purpose of developing a radiative-transfer model that describes the reflectance of light by granular solids. It is well recognized that the reflectance spectra of granular materials depend on their intrinsic (n(λ) and k(λ)) and extrinsic (morphological) properties. There is, however, a lack of robust and proven models to relate spectra to these parameters. The described work is being conducted in parallel with a modeling effort1 to address this need. Each follows a common developmental spiral in which material properties are varied and the ability of the model to calculate the effects of the changes are tested. The parameters being varied include particle size/shape, packing density, material birefringence, optical thickness, and spectral contribution of a substrate. It is expected that the outcome of this work will be useful in interpreting reflectance data for hyperspectral imaging (HSI), and for a variety of other areas that rely on it.