The invention relates generally to chemical vapor sensing
Environmental pollution due to hazardous chemical vapors is an issue of critical importance due to its adverse effects on health and global warming. Chemical detectors to sense the presence of such organic compounds as aromatic and halogenated hydrocarbons are available1-9 based on a variety of sensing layers and the development of multi-pixel arrays.10-13 A majority of these sensors are based on polymer coatings as sensing layers.1-3,5-9,11,12 Recently, supramolecular materials have also been demonstrated as suitable coatings for sensors.14-21 The interaction of chemical vapors with these sensing layers is transduced using, for example, mass transduction techniques such as Quartz Crystal Microbalance (QCM),6,18 Surface Acoustic Wave (SAW)7,19 or optical methods such as Surface Plasmon Resonance (SPR).16,20,21 Electrical transduction schemes using capacitance measurements on interdigitated electrodes have also been reported.22
Liquid crystals (LC) have amplifying properties.23-30 This amplification is a result of the cooperative realignment of liquid crystal molecules by external perturbations, in this case the presence of a chemical vapor.31-34 Cholesteric and nematic liquid crystal mixtures have been used as sensitive layers on mass sensitive transducers.27 The variation in partition coefficient for different chemical vapors gives rise to sensor response which differs for each type of chemical, suggesting that LC sensing layers may be used to produce a sensor with some selectivity.23-28 These studies have been conducted with liquid crystals that are not uniformly aligned, therefore selectivity and sensitivity have been comparable to that achieved using isotropic polymer sensing layers. Recently, it has been shown that multi-component mixtures of homogenously aligned nematic liquid crystals can be used as sensing layers for volatile organic compounds using optical transducers and inter-digitated capacitor structures.29,30
The device for detecting an analyte comprises a substrate, an alignment layer on the substrate, a film comprising 4-pentyl-4′-cyanobiphenyl on the alignment layer, a flow cell capable of delivering air suspected of containing the analyte to the film, and an apparatus capable of measuring a physical property of the film.
The method of detecting an analyte comprises: providing a device comprising a substrate, an alignment layer on the substrate, and a film comprising 4-pentyl-4′-cyanobiphenyl on the alignment layer; exposing the film to air suspected of containing the analyte; and measuring a change in a physical property of the film in response to exposing the film.
A more complete appreciation of the invention will be readily obtained by reference to the following Description of the Example Embodiments and the accompanying drawings.
In the following description, for purposes of explanation and not limitation, specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known methods and devices are omitted so as to not obscure the description of the present invention with unnecessary detail.
Described is a method to use thin films of 4-pentyl-4′-cyanobiphenyl (5CB) liquid crystal that can be spin coated onto surfaces. The purpose of this is to enhance the selectivity of detection for chemical vapors. The 5CB may cooperatively amplify the perturbation caused by exposure to chemical vapors so as to allow for a highly sensitive chemical vapor detector.
A problem with current chemical vapor detectors is that they are still prone to false alarms and are relatively bulky. The problem of false alarms is caused by the limited selectivity and sensitivity of sensing layers for chemical threats and therefore there is a need for new materials with enhanced selectivity and sensitivity. The widely available nematic liquid crystal 5CB may be used as a sensing layer for chemical vapors such as toluene, benzene, m-xylene, p-xylene, acetonitrile, and ethyl acetate. 5CB has a convenient room temperature nematic range and high chemical stability even in the presence of water vapor and oxygen.35 This nematic liquid crystal also has a large positive refractive index anisotropy (on the order of 0.2) rendering it suitable for significant sensitivity amplification due to a phase transition into the isotropic phase. Once the LC layer is deposited on a gold-coated optical substrate, the white-light SPR transduction method allows for efficient measurement of the refractive index (RI) change induced in the LC layer by exposure to chemical vapors.
The surface plasmon resonance technique is an effective transduction scheme for probing the change in single component liquid crystal order due to chemical vapor exposure. The liquid crystal order may be perturbed to different extents by different vapors, which can lead to selectivity. At high concentrations of the vapor, a complete phase transition from the nematic to the isotropic phase may not be induced, as confirmed by polarized optical micrography, although the SPR response may show signal saturation. Depending on the structure and shape of the vapor molecule, the transition from ordered nematic to disordered nematic may take place at different relative concentrations of vapor. Close to the nematic-isotropic phase transition temperature the sensitivity can be enhanced and therefore used to detect concentrations of analyte at low ppm levels. The kinetics of response to different vapors may be different. This could be considered an additional parameter for determining selectivity. Further, due to the weak intermolecular forces between chemical vapor and LC, recycling of the sensor may be feasible.
The device may enable highly sensitive and selective chemical vapor detectors that rely on coating materials. Applicability may be broad in that the liquid crystal material can be coated onto many different transduction platforms: optical platforms such as surface plasmon resonance, optical waveguides, interferometers; electrical platforms such as capacitive transducers; mechanical platforms such as AFM cantilevers, SAW devices and QCM microbalances that translate the mass change from analyte deposition onto liquid crystal into a frequency change that can be measured.
The high selectivity is seen from the ability to discriminate between chemical isomers such m-xylene and p-xylene. It is also seen that holding the temperature of the 5CB closer to a phase transition (about 5° C. below the nematic-isotropic phase transition) temperature may increase the sensitivity of the 5CB by two orders of magnitude. This sensitivity may be increased even further by holding the liquid crystal closer to the phase transition temperature (for example, 0.1° C. below the phase transition). However, if a large dynamic range is desired instead of sensitivity, the liquid crystal may be held further away from the phase transition.
Uniformly aligned nematic liquid crystal films may be obtained by spin coating the liquid crystal layer onto a rubbed polyimide surface. This eliminates the need for a second alignment layer to be used (which is typically the case for most liquid crystal applications i.e. the liquid crystal is sandwiched between two plates whose inner surfaces have an alignment layer).
The liquid crystal film may also comprise a cavitand molecule, such as, but not limited to, those disclosed in the US Patent Application to Shenoy et al. entitled “CAVITANDS FOR CHEMICAL VAPOR SENSING,” designated as 97183US2, and filed on the same day as the present application
The kinetics of the SPR response may be used as an additional selectivity parameter in addition to the strength of the SPR signal. This may allow for further discrimination between chemical vapors.
The substrate can by made from any material that is compatible with the alignment layer and with the method of measuring the physical property. When the physical property is optical or is measured by optical techniques, the substrate may be a transparent material, such as but not limited to glass. Additional layers may be coated on the glass such as a chromium adhesion layer and a gold layer. The alignment layer can assist in making the 5CB layer isotropic. Suitable alignment layers include, but are not limited to, rubbed polyimide.
A variety of physical properties of the film may be measured, such as, but not limited to, optical, refractive index, electrical, and mass. Suitable apparatus and/or methods for measuring the physical property include, but are not limited to, surface plasmon resonance, interferometry, capacitive transductance, atomic force microscope, surface acoustic wave, and quartz crystal microbalance.
The device may include a system, such as but not limited to a computer, for correlating a change in the physical property of the film and/or the kinetics of such a change to information regarding the analyte, such as but not limited to, concentration and identification. The device may also include a temperature controller. This may be used to maintain the temperature of the 5CB at a temperature that may enhance sensitivity. Such temperature control may occur during the exposing, the measuring, or both.
Having described the invention, the following examples are given to illustrate specific applications of the invention. These specific examples are not intended to limit the scope of the invention described in this application.
Fabrication of substrate with 5CB—To prepare substrates for surface plasmon resonance measurements, an approximately 2 nm thick chromium adhesion layer was first deposited onto a cleaned glass substrate (1 mm×20 mm×20 mm, nD=1.92286 SNPH2, Optimax System Inc., USA) using a vacuum evaporator (Edwards Auto 306). This was followed by vapor deposition of a nearly 50 nm thick gold layer using a gold coin (Canadian coin, 99.99%). Evaporation was performed at a vacuum of 10−6 bar. The evaporation rate, as indicated by the read out on the instrument, was in the range of 0.02-0.04 nm/s. The thickness of the deposited metal film was determined by a quartz crystal thickness monitor.
Next a rubbed polyimide alignment layer was fabricated on top of the gold layer. For this, a solution of 1:100 (w/w) polyimide (PI2556):solvent (T9039) was spin coated onto the gold-coated substrate at 6000 rpm for 40 sec. The substrate was heated on a hot plate at 80° C. for 3 min to let the solvent evaporate and then heated further for 2 hr at 250° C. in an oven. The thickness of the alignment layer was determined to be between 10 to 15 nm by multi-wavelength spectroscopic ellipsometry (EC110) at an incident angle of 70 degrees. The unidirectional rubbing of the polyimide alignment layer was performed using a commercial automated rubbing machine (SPB8OPN, SUPER PILLOW BLOCK, THOMSON INDUSTRIES INC.).
Homogenously aligned 5CB films with a free air interface were then deposited as follows.36 A flat Mylar O-ring, ˜100 μm thick and ˜5 mm inner diameter was placed on the substrate. A small drop of 5CB (˜1 microliter) in the isotropic phase (the liquid crystal was heated until it was clear indicating that it is above 35° C., the nematic to isotropic phase transition temperature of 5CB) was dispensed from a hypodermic needle into the well formed by the Mylar O-ring. The droplet completely wet and spread uniformly over the polyimide alignment layer, but was contained by the O-ring, as 5CB does not wet a mylar surface. The substrate was then slowly cooled to room temperature. The optical textures were observed using polarized optical microscopy to be characteristic of uniformly aligned nematic films. The thickness of the liquid crystal material deposited was controlled by the amount of 5CB dispensed into the well and the size of the well.
SPR apparatus—Real-time measurement of the refractive index (RI) of the sensing layers was performed using a custom-built white-light SPR instrument. White-light SPR is a well-established technique for measuring changes in the refractive index of thin layers.30,37 In the Kretschmann configuration38 used in this white-light SPR sensor, TM-polarized, collimated white light (wavelength range ˜500-1100 nm) directed through the side of a high-RI prism strikes the gold-coated sensing surface at an angle above the critical angle. The light reflected from this surface is collected and analyzed by a spectrophotometer. Certain wavelengths of incident light will excite surface plasma waves at the interface between the gold layer and the sensing layer, and the loss of this energy will be observed as a decrease in reflectivity at those wavelengths. The wavelengths at which this occurs vary with the refractive index of the sensing layer near the gold surface, therefore a measurement of RI may be obtained by analysis of reflection spectra.
The instrument is similar to that described by Homola et al.37 but modified for ease of adjustment and operation at high RI. A schematic of the instrument is shown in
To allow control of the exposure of the substrate to organic vapors, a Teflon flow cell 65 comprising an inlet 70 and outlet 75 for the chemical vapors and a rectangular aperture 80 for the prism and substrate was constructed. An O-ring ensured a good seal between the prism/substrate and Teflon chamber. A temperature controlled water circulating unit (control to within 0.1° C.) was coupled to the Teflon chamber through a metal coil to control the liquid crystal temperature.
To generate ppm levels of organic vapors, a diffusion vial (D-5.0 mm capillary, VICI Metronics), filled with the organic compound using 5 mL syringe needles (VICI Metronics), was placed in a U-tube containing glass beads on one side of the tube and diffusion vial on the other. The U-tube was placed in a temperature controlled water bath (controlled to within 0.1° C.) from PolySciences, Inc. The chemical vapors were diluted with a stream of dinitrogen (carrier gas). The flow of both the carrier gas and the chemical vapor were controlled to within an accuracy of 1-2% using computer-interfaced mass flow controllers (DFC26, AALBORG INC.) and mixed in the appropriate proportion before being introduced into the flow cell. Care was taken to ensure that the experiment was performed after the vapor had attained equilibrium with respect to its concentration.
Alignment of the 5CB liquid crystal film on the rubbed polyimide coated substrate was examined using transmission polarized light microscopy. As expected for an optically uniaxial film, rotation of the substrate caused the intensity of transmitted light to go from a maximum (when the liquid crystal optic axis is oriented at an angle of 45 degrees with respect to the axis of either polarizer or analyzer) to a minimum (when the optic axis is aligned parallel to the axis of either polarizer or analyzer). This implies that the alignment layer forces the LC molecules to preferentially align along the rubbing direction. Though the orientation at the air interface may be homeotropic, the uniformly dark and bright images confirm that the projection of the optic axis is oriented along the rubbing direction.36
Sensitivity to benzene—
The shifts in response may be caused by the perturbation of liquid crystal due to incorporation of vapors and resulting decrease in the liquid crystal order. The height of the initial peak depended on the change of liquid crystal from ordered to less ordered due to vapor interaction with the LC. The subsequent decay of response at low concentrations may be explained as a result of a gradual change in order from disordered to somewhat more ordered as benzene molecules self-orient themselves within the liquid crystal molecules. As seen in
Upper limit of concentration measurement for benzene—
Optical texture—The optical texture of 5CB after exposure to vapors was examined under a polarizing microscope and it was confirmed that the initial uniform alignment of the liquid crystal film could be recovered. The optical extinction was not observed at any orientation of liquid crystal substrate with respect to the polarizer. However, 5CB does not appear to undergo a clear phase transition into the isotropic phase (which would give a dark image at all orientation of the liquid crystal substrate). In contrast, when the regenerated liquid crystal substrate was rotated into different orientations with respect to polarizer, optical extinction was observed. These optical characteristics indicated that 5CB was oriented non-uniformly because of the presence of the vapors and oriented uniformly in the absence of the vapors.
Other vapors—To demonstrate how the LC response is different for different types of chemical vapors, curves showing variation of resonance wavelength shift with respect to the relative saturation pressure of six different vapors are shown in
The resonance wavelength shift observed appears to be dependent upon both the refractive index of the vapor introduced and the extent of disorder induced (which can be different for different vapors). For example, both ethyl acetate and acetonitrile have lower refractive indices than the aromatic vapors, and so the resonance wavelength shift may be expected to be smaller when these vapors are partitioned into the liquid crystal film.
The bar graphs of
Kinetics—Layer response time was observed to vary with the type of vapor. Two typical experimental adsorption response curves are shown in
High sensitivity—To illustrate the high sensitivity that can be achieved using liquid crystals, SPR response data are shown for m-xylene vapors at 0.27 ppm to 0.85 ppm. (
The response time may also be affected by holding the liquid crystal closer to the phase transition temperature. The adsorption kinetic (
Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that the claimed invention may be practiced otherwise than as specifically described. Any reference to claim elements in the singular, e.g., using the articles “a,” “an,” “the,” or “said” is not construed as limiting the element to the singular.
All references are incorporated herein.
This application claims priority to U.S. Provisional Patent Application Nos. 60/662,340 and 60/662,341, both filed on Mar. 15, 2005, and both incorporated herein by reference. US Patent Application to Shenoy et al. entitled “CAVITANDS FOR CHEMICAL VAPOR SENSING,” designated as 97183US2, and filed on the same day as the present application, is incorporated herein by reference.
Number | Date | Country | |
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60662341 | Mar 2005 | US | |
60662340 | Mar 2005 | US |