Atomic imaging of the irreversible sensing mechanism of NO2 adsorption on copper phthalocyanine.

Ambient NO2 adsorption onto copper(II) phthalocyanine (CuPc) monolayers is observed using ultrahigh vacuum (UHV) scanning tunneling microscopy (STM) to elucidate the molecular sensing mechanism in CuPc chemical vapor sensors. For low doses (1 ppm for 5 min) of NO2 at ambient temperatures, isolated chemisorption sites on the CuPc metal centers are observed in STM images. These chemisorbates almost completely desorb from the CuPc monolayer after annealing at 100 °C for 30 min. Conversely, for high NO2 doses (10 ppm for 5 min), the NO2 induces a fracture of the CuPc domains. This domain fracture can only be reversed by annealing above 150 °C, which is consistent with dissociative chemisorption into NO and atomic O accompanied by surface restructuring. This high stability implies that the domain fracture results from tightly bound adsorbates, such as atomic O. Existence of atomic O on or under the CuPc layer, which results in domain fracture, is revealed by XPS analysis and ozone-dosing experiments. The observed CuPc domain fracturing is consistent with a mechanism for the dosimetric sensing of NO2 and other reactive gases by CuPc organic thin film transistors (OTFTs).

Air-stable spin-coated naphthalocyanine transistors for enhanced chemical vapor detection.

Air-stable organic thin-film transistor (OTFT) sensors fabricated using spin-cast films of 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine (OBNc) demonstrated improved chemical vapor sensitivity and selectivity relative to vacuum-deposited phthalocyanine (H(2)Pc) OTFTs. UV-vis spectroscopy data show that annealed spin-cast OBNc films exhibit a red-shift in the OBNc Q-band λ(max) which is generally diagnostic of improved π-orbital overlap in phthalocyanine ring systems. Annealed OBNc OTFTs have mobilities of 0.06 cm(2) V(-1) s(-1), low threshold voltages (|V(th)| < 1 V), and on/off ratios greater than 10(6). These air-stable device parameters are utilized for sensing modalities which enhance the sensitivity and selectivity of OBNc OTFTs relative to H(2)Pc OTFTs. While both sensors exhibit mobility decreases for all analytes, only OBNc OTFTs exhibit V(th) changes for highly polar/nonpolar analytes. The observed mobility decreases for both sensors are consistent with electron donation trends via hydrogen bonding by basic analytes. In contrast, V(th) changes for OBNc sensors appear to correlate with the analyte's octanol-water partition coefficient, consistent with polar molecules stabilizing charge in the organic semiconductor film. The analyte induced V(th) changes for OBNc OTFTs can be employed to develop selective multiparameter sensors which can sense analyte stabilized fixed charge in the film.

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.