Corneliu N. Colesniuc

Selective Detection of Vapor Phase Hydrogen Peroxide with Phthalocyanine Chemiresistors

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.

Ultrathin organic transistors for chemical sensing

Ultrathin cobalt phthalocyanine transistors of 4 ML have been fabricated for chemical sensing. Compared to 50 ML devices, the ultrathin transistors show faster response times, higher base line stabilities, and sensitivity enhancements of 1.5–20 for the five analytes tested. The enhanced response for the ultrathin transistors provides insight into the device physics. The absorption of analytes changes the surface doping level and trap energies. The changes in surface trap energies perturb the charge transport properties of the ultrathin devices, thereby, making these devices more sensitive.

Analyte chemisorption and sensing on n- and p-channel copper phthalocyanine thin-film transistors

Chemical sensing properties of phthalocyanine thin-film transistors have been investigated using nearly identical n- and p-channel devices. P-type copper phthalocyanine (CuPc) has been modified with fluorine groups to convert the charge carriers from holes to electrons. The sensor responses to the tight binding analyte dimethyl methylphosphonate (DMMP) and weak binding analyte methanol (MeOH) were compared in air and N(2). The results suggest that the sensor response involves counterdoping of pre-adsorbed oxygen (O(2)). A linear dependence of chemical response to DMMP concentration was observed in both n- and p- type devices. For DMMP, there is a factor of 2.5 difference in the chemical sensitivity between n- and p-channel CuPc thin-film transistors, even though it has similar binding strength to n- and p-type CuPc molecules as indicated by the desorption times. The effect is attributed to the difference in the analyte perturbation of electron and hole trap energies in n- and p-type materials.

Ultralow drift in organic thin-film transistor chemical sensors by pulsed gating

A pulsed gating method has been developed to enhance the baseline stability of organic thin-film transistor (OTFT) chemical sensors. Trap states in the organic films are the major source of the OTFTs baseline drift under static gate bias, which is identified as the bias stress effect (BSE). BSE typically reduces the baseline current by 60% over 20h in phthalocyanine based OTFT sensors. The baseline drift has been reduced below 1% over 20h in the absence of the analyte using the pulsed gating method. With pulsed gating, the baseline drift on exposure to 15 methanol pulses is less than 0.09%∕h, and the response to this analyte is fully recoverable. Similar ultralow drift results were obtained for methanol sensing on three different phthalocyanine OTFTs. Combining the pulsed gating with low duty cycle analyte pulses, this method is also applicable to obtain ultralow drift (0.04%∕h) even for low vapor pressure analytes such as organophosphonate nerve agent simulants.

Ambient induced degradation and chemically activated recovery in copper phthalocyanine thin film transistors

The electrical degradation (aging) of copper phthalocyanine (CuPc) organic thin film transistors (OTFTs) was investigated. Thick (1000 ML) and ultrathin (4 ML) 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 (ML) CuPc OTFTs were characterized in ambient air, clean dry air, clean humidified air, and NOx 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 f...

Bilayer processing for an enhanced organic-electrode contact in ultrathin bottom contact organic transistors

A bilayer lift-off process has been employed to fabricate optimal electrode contact geometry for statistical characterization of ultrathin organic thin-film transistors (OTFTs). For over 100 p-channel ultrathin (12 ML) copper phthalocyanine (CuPc) OTFTs, the bilayer photoresist lift-off process increased the field effect mobility by two orders of magnitude, decreased the contact resistance by three orders of magnitude, increased the on/off ratio by one order of magnitude, and the threshold voltage was decreased by a factor of three compared to conventionally processed devices. The generality of the method was validated by fabricating OTFTs in four different phthalocynaines and CuPc OTFTs with eight different channel thicknesses.

Mobility saturation in tapered edge bottom contact copper phthalocyanine thin film transistors

Copper phthalocyanine (CuPc) thin film transistors were fabricated using a tapered edge bottom contact device geometry, and mobility saturation was observed for devices with CuPc thicknesses of 12 monolayers (MLs) and greater. The mobility saturation is attributed to a significantly decreased contact resistance resulting from a bilayer resist lift-off method, as compared with a single layer resist lift-off method. Threshold voltages are also found to saturate above 12 ML CuPc thicknesses.