Improving the performance of micro-machined metal oxide gas sensors: Optimization of the temperatura modulation mode via pseudorandom sequences.

Identificador:  TDX:1907

Handle: https://hdl.handle.net/20.500.11797/TDX1907

Autors:  Vergara Tinoco, Alexander

Resum:
One of the major problems in gas sensing systems that use metal oxide devices is the lack of reproducibility, stability and selectivity. In order to tackle these troubles experienced with metal oxide gas sensors, different strategies have been developed in parallel. Some of these are related to the improvement of materials, or the use of sample conditioning and pre-treating methods. Other widely used techniques include taking benefit of the unavoidable partially overlapping sensitivities by using sensor arrays and pattern recognition techniques or the use of dynamic features from the gas sensor response.In the last years, modulating the working temperature of metal oxide gas sensors has been one of the most used methods to enhance sensor selectivity. This occurs because, since, the sensor response is different at different working temperatures, and therefore, measuring the sensor response at n different temperatures is, in some cases, similar to the use of an array comprising n different sensors. This allows for measuring multivariate information from every single sensor and helps in keeping low the dimensionality of the measurement system needed to solve a specific application. Although the good results reported, until now, the selection of the frequencies used to modulate the working temperature remained an empirical process and that is not an accurate method to ensure that the best results are reached for a given application.In view of this context, the principal objective of this doctoral thesis was to develop a systematic method to determine which are the optimal temperature modulation frequencies to solve a given gas analysis problem. This method, which is borrowed from the field of system identification, has been developed and introduced for the first time in the area of gas sensors. It consists of studying the sensor response to gases when the operating temperature is modulated via maximum-length pseudo-random sequences. Such signals share some properties with white noise and, therefore, can be of help to estimate the linear response of a system with non-linearity (e.g., the impulse response of a sensor-gas system).The optimization process is conducted by selecting among the spectral components of the impulse response estimates, the few that better help either discriminating or quantifying the target gases of a given gas analysis application. Since spectral components are directly related to modulating frequencies, the selection of spectral components results in the determination of the optimal temperature modulating frequencies.In the first experiments, pseudo-random binary signals (PRBS) were employed to modulate the working temperature of micro-machined metal oxide gas sensors in a frequency range from 0 up to 112.5 Hz. The upper frequency is slightly higher than the cutoff frequency of the sensor membranes. The outcome of this initial study was that the important modulating frequencies were in the range between 0 and 1 Hz. This is understandable, since the kinetics of reaction and adsorption processes taking place at the sensor surface (i.e., physisorption/chemisorption/ionosorption) are slow and if these are to be altered by the thermal modulation, low frequency modulating signals need to be devised. This explains why low-frequency temperature-modulating signals (i.e. in the mHz range) have been used with micro-hotplate gas sensors, even though the thermal response of their membranes is much faster (typically, near 100 Hz).In the experiments that followed the first ones, an evolved method to determine the optimal temperature modulating frequencies for micro-hotplate gas sensors was introduced, which was based on the use of maximum length multilevel pseudo-random sequences (MLPRS). Multilevel signals were considered instead of the binary ones because the former can provide a better estimate than the latter of the linear dynamics of a process with non-linearity. And it is well known that temperature-modulated metal oxide gas sensors present non-linearity in their response.These systematic studies were fully validated by synthesizing multi-sinusoidal signals at the optimal frequencies previously identified using pseudo-random sequences. When the sensors had their operating temperatures modulated by a signal with a frequency content that corresponded to the optimal, the gases and gas mixtures considered could be perfectly discriminated and the building of accurate calibration models to predict gas concentration was found to be possible. In some cases, the validation process was conducted on sensors that had not been used for optimization purposes (e.g. a different sensor array from the same fabrication batch).Summarizing, the new method developed in this thesis for selecting the optimal modulating frequencies is shown to be consistent and effective. The method applies generally and could be used in any gas analysis problem or extended to other type of sensors (e.g. conducting polymer sensors).The scientific contributions of this thesis are collected in four journal papers and thirteen conference proceedings.