Controlling surface adsorption to enhance the selectivity of porphyrin based gas sensors

Abstract

This study reports an enhancement in the selectivity of the vapor sensing properties of free base porphyrin 5,10,15,20-tetrakis[3,4-bis(2-ethylhexyloxy)phenyl]-21H,23H-porphine (EHO) Langmuir–Schaefer (LS) films. These sensors respond by changing color upon adsorption of the analyte gas to the sensor surface. The enhanced selectivity is achieved by adding selective barrier layers of 4-tert-Butylcalix[4]arene, 4-tert-Butylcalix[6]arene and 4-tert-Butylcalix[8]arene embedded in PMMA (Poly(methyl methacrylate)) on top of the porphyrin sensor films to control the gaseous adsorption onto the sensor surface. The Langmuir properties of EHO, PMMA and calix[n]arene monolayers were investigated by surface pressure–area (Π–A) isotherms in order to determine the most efficient transfer pressure. Six layer EHO films were transferred onto glass and silicon substrates to investigate their optical and structural characteristics. The three different calix[n]arenes were embedded within PMMA layers to act as the selective barrier layers which were deposited on top of the six layer EHO films. The different calix[n]arene molecules vary in size and each was mixed with PMMA in specific ratios in order to control the selectivity of the resulting barrier layers. Spectroscopic Ellipsometry (SE) and Atomic Force Microscopy (AFM) measurements were carried out to analyze the structure of the porous barrier layers. It was found that the orientation of the calix[8]arene molecules was well controlled within the Langmuir layers such that molecular ring lies flat on the EHO layers when deposited. However, the calix[6]arene and calix[4]arene molecules were quite not so reliably oriented. The sensor films (with and without the addition of the different selective barrier layers) were exposed to various carboxylic acid vapors. More specifically, acetic acid, butyric acid and hexanoic acid were chosen due to their different molecular sizes. The uncovered EHO films were highly sensitive to all the carboxylic acids. The porosity of the barrier layers which influences their selectivity was investigated by changing the size of the acid molecules. Upon deposition of a barrier layer on top of EHO film the sensing response rate and magnitude were changed depending on both the barrier layer structure and molecular size of the analyte vapor. The optical sensing results show that by controlling the size of the pores in the barrier layer it can be used as a size selective layer which limits the diffusion of analyte molecules into the sensor and in extreme cases stopping the diffusion completely. Therefore the selectivity of this sensor system has been enhanced by adding a controllable barrier layer. The enhanced sensors have been used to differentiate between acetic, butyric and hexanoic acids.