The sensitivities of metallophthalocyanine (MPcs: M = Co, Ni, Cu, Zn, and H(2)) chemiresistors to vapor phase electron donors were examined using 50 nm MPc films deposited on interdigitated electrodes. Sensor responses were measured as changes in current at constant voltage. Analytes were chosen to span a broad range of Lewis base and hydrogen bond base strengths. The MPc sensor responses were correlated exponentially with binding enthalpy. These exponential fits were consistent with the van't Hoff equation and standard free energy relationships. Sensor recovery times were found to depend exponentially on binding enthalpy, in agreement with the Arrhenius equation. Relative sensitivities of all MPcs were compared via two-way ANOVA analysis. Array response patterns were differentiated via linear discriminant analysis, and analyte identification was achieved over a range of concentrations with 95.1% classification accuracy for the strong binding analytes. The ability to distinguish among different analytes, regardless of their concentration, through normalization of the responses to a reference sensor is particularly noteworthy.

The gas sensing behaviors of cobalt phthalocyanine (CoPc) and metal-free phthalocyanine (H2Pc) thin films were investigated with respect to analyte basicity. Chemiresistive sensors were fabricated by deposition of 50 nm thick films on interdigitated gold electrodes via organic molecular beam epitaxy (OMBE). Time-dependent current responses of the films were measured at constant voltage during exposure to analyte vapor doses. The analytes spanned a range of electron donor and hydrogen-bonding strengths. It was found that, when the analyte exceeded a critical base strength, the device responses for CoPc correlated with Lewis basicity, and device responses for H2Pc correlated with hydrogen-bond basicity. This suggests that the analyte-phthalocyanine interaction is dominated by binding to the central cavity of the phthalocyanine with analyte coordination strength governing CoPc sensor responses and analyte hydrogen-bonding ability governing H2Pc sensor responses. The interactions between the phthalocyanine films and analytes were found to follow first-order kinetics. The influence of O2 on the film response was found to significantly affect sensor response and recovery. The increase of resistance generally observed for analyte binding can be attributed to hole destruction in the semiconductor film by oxygen displacement, as well as hole trapping by electron donor ligands.

The use of hydrogen peroxide as a precursor to improvised explosives has made its detection a topic of critical importance. Chemiresistor arrays comprised of 50 nm thick films of metallophthalocyanines (MPcs) are redox selective vapor sensors of hydrogen peroxide. Hydrogen peroxide is shown to decrease currents in cobalt phthalocyanine sensors while it increases currents in nickel, copper, and metal-free phthalocyanine sensors; oxidation and reduction of hydrogen peroxide via catalysis at the phthalocyanine surface are consistent with the pattern of sensor responses. This represents the first example of MPc vapor sensors being oxidized and reduced by the same analyte by varying the metal center. Consequently, differential analysis by redox contrast with catalytic amplification using a small array of sensors may be used to uniquely identify peroxide vapors. Metallophthalocyanine chemiresistors represent an improvement over existing peroxide vapor detection technologies in durability and selectivity in a greatly decreased package size.

Use of electron-beam induced crosslinking (EBIX) to pattern films of thiolate-monolayer-protected gold-nanoparticles (MPNs) on chemiresistor (CR) vapor sensors is described. MPNs with alkyl, cyanoalkyl, phenoxyalkyl, and hydroxyfluoroalkyl thiolate tail groups were patterned on integrated arrays of interdigital electrodes using electron doses of 500-750 C=cm 2 . The dc resis- tances of solvent cast films of these MPNs decrease and the baseline-normalized changes in resistance to each of five organic vapors increase to different degrees with increasing electron-beam dose. Relative responses patterns from an array of MPN-coated CR sensors for the test vapors change after EBIX patterning and the diversity of responses is diminished, on average, but it is still projected to be sufficient for the discrimination of most of the individual test vapors and binary mixtures. Results are rationalized in terms of expected changes in ligand structures and film properties following EBIX patterning using known models of electronic conduction, and vapor-induced changes of conduction, through MPN films. The implications of the results for creating arrays of densely packed MPN-coated CRs as detectors for microanalytical systems are considered.Index Terms-Chemiresistor, electron beam, nanoparticle, sensor array, vapor sensor.

Use of electron-beam induced crosslinking to pattern films of monolayer-protected gold nanoparticles (MPNs) onto a chemiresistor (CR) sensor array is described. Each of the four CRs comprises a 100 µm(2) set of interdigital electrodes (IDEs) with 100 nm widths and spaces, separated from adjacent devices by 4 µm. Films of four MPNs, each with a different thiolate monolayer, were successively patterned on the IDEs. Vapor exposures yield rapid, reversible changes in CR resistances and differential vapor sensitivities comparable to those reported for larger CRs with unpatterned MPN films. The array response patterns facilitate vapor discrimination. This is the smallest MPN-coated CR array yet reported. The advantages of using such an array as the detector in microfabricated gas chromatographic analyzers are considered.

The electrical degradation ͑aging͒ of copper phthalocyanine ͑CuPc͒ organic thin film transistors ͑OTFTs͒ was investigated. Thick ͑1000 ML͒ and ultrathin ͑4 ML͒ channel thicknesses were used in bottom contact OTFTs to correlate the electrical effects of aging with film microstructure. Proper TFT saturation behavior was unattainable in thick devices subject to ambient aging; however ultrathin devices were significantly less susceptible and maintained good saturation and subthreshold behavior. Therefore 1000 monolayer ͑ML͒ CuPc OTFTs were characterized in ambient air, clean dry air, clean humidified air, and NO x environments to isolate the ambient components that induce aging. Thick channel devices which had been aged in ambient air to the point of losing all saturation behavior could be restored to proper saturation behavior by exposure to clean humidified air. The data are consistent with aging resulting primarily from adsorption of strong oxidants from ambient air within the grain boundaries of the CuPc films.

The performance of arrays of small, densely integrated chemiresistor (CR) vapor sensors with electron-beam patterned interface layers of thiolate-monolayer-protected gold nanoparticles (MPNs) is explored. Each CR in the array consists of a 100-μm(2) interdigital electrode separated from adjacent devices by 4 μm. Initial studies involved four separate arrays, each containing four CRs coated with one of four different MPNs, which were calibrated with five vapors before and after MPN-film patterning. MPNs derived from n-octanethiol (C8), 4-(phenylethynyl)-benzenethiol (DPA), 6-phenoxyhexane-1-thiol (OPH), and methyl-6-mercaptohexanoate (HME) were tested. Parallel calibrations of MPN-coated thickness-shear-mode resonators (TSMR) were used to derive partition coefficients of unpatterned films and to assess transducer-dependent factors affecting responses. A 600-μm(2) 4-CR array with four different patterned MPN interface layers, in which the MPN derived from 7-hydroxy-7,7-bis(trifluoro-methyl)heptane-1-thiol (HFA) was substituted for HME, was then characterized. This is the smallest multi-MPN array yet reported. Reductions in the diversity of the collective response patterns are observed with the patterned films, but projected vapor discrimination rates remain high. The use of such arrays as ultralow-dead-volume detectors in microscale gas chromatographic analyzers is discussed.

Density functional theory (DFT) simulations were used to determine the binding strength of 12 electron-donating analytes to the zinc metal center of a zinc phthalocyanine molecule (ZnPc monomer). The analyte binding strengths were compared to the analytes' enthalpies of complex formation with boron trifluoride (BF(3)), which is a direct measure of their electron donating ability or Lewis basicity. With the exception of the most basic analyte investigated, the ZnPc binding energies were found to correlate linearly with analyte basicities. Based on natural population analysis calculations, analyte complexation to the Zn metal of the ZnPc monomer resulted in limited charge transfer from the analyte to the ZnPc molecule, which increased with analyte-ZnPc binding energy. The experimental analyte sensitivities from chemiresistor ZnPc sensor data were proportional to an exponential of the binding energies from DFT calculations consistent with sensitivity being proportional to analyte coverage and binding strength. The good correlation observed suggests DFT is a reliable method for the prediction of chemiresistor metallophthalocyanine binding strengths and response sensitivities.