Flexographic printed nanogranular LBZA derived ZnO gas sensors: Synthesis, printing and processing

Abstract

Within this document, investigations of the processes towards the production of a flexographic printed ZnO gas sensor for breath H2 analysis are presented. Initially, a hexamethylenetetramine (HMTA) based, microwave assisted, synthesis method of layered basic zinc acetate (LBZA) nanomaterials was investigated. Using the synthesised LBZA, a dropcast nanogranular ZnO gas sensor was produced. The testing of the sensor showed high sensitivity towards hydrogen with response (Resistanceair/ Resistancegas) to 200 ppm H2 at 328 °C of 7.27. The sensor is highly competitive with non-catalyst surface decorated sensors and sensitive enough to measure current H2 guideline thresholds for carbohydrate malabsorption (Positive test threshold: 20 ppm H2, Predicted response: 1.34). Secondly, a novel LBZA synthesis method was developed, replacing the HMTA by NaOH. This resulted in a large yield improvement, from a [OH-] conversion of 4.08 at% to 71.2 at%. The effects of [OH-]/[Zn2+] ratio, microwave exposure and transport to nucleation rate ratio on purity, length, aspect ratio and polydispersity were investigated in detail. Using classical nucleation theory, analysis of the basal layer charge symmetries, and oriented attachment theory, a dipole-oriented attachment reaction mechanism is presented. The mechanism is the first theory in literature capable of describing all observed morphological features along length scales. The importance of transport to nucleation rate ratio as the defining property that controls purity and polydispersity is then shown. Using the NaOH derived LBZA, a flexographic printing ink was developed, and proof-of-concept sensors printed. Gas sensing results showed a high response to 200 ppm H2 at 300 °C of 60.2. Through IV measurements and SEM analysis this was shown to be a result of transfer of silver between the electrode and the sensing layer during the printing process. Finally, Investigations into the intense pulsed light treatment of LBZA were conducted. The results show that dehydration at 150 °C prior to exposure is a requirement for successful calcination, producing ZnO quantum dots (QDs) in the process. SEM measurements show mean radii of 1.77-2.02 nm. The QDs show size confinement effects with the exciton blue shifting by 0.105 eV, and exceptionally low defect emission in photoluminescence spectra, indicative of high crystalline quality, and high conductivity. Due to the high crystalline quality and amenity to printing, the IPL ZnO QDs have numerous potential uses ranging from sensing to opto-electronic devices.