Anton Köck

Kinetic parameter estimation and fluctuation analysis of CO at SnO2 single nanowires

In this work, we present calculated numerical values for the kinetic parameters governing adsorption/desorption processes of carbon monoxide at tin dioxide single-nanowire gas sensors. The response of such sensors to pulses of 50 ppm carbon monoxide in nitrogen is investigated at different temperatures to extract the desired information. A rate-equation approach is used to model the reaction kinetics, which results in the problem of determining coefficients in a coupled system of nonlinear ordinary differential equations. The numerical values are computed by inverse-modeling techniques and are then used to simulate the sensor response. With our model, the dynamic response of the sensor due to the gas-surface interaction can be studied in order to find the optimal setup for detection, which is an important step towards selectivity of these devices. We additionally investigate the noise in the current through the nanowire and its changes due to the presence of carbon monoxide in the sensor environment. Here, we propose the use of a wavelet transform to decompose the signal and analyze the noise in the experimental data. This method indicates that some fluctuations are specific for the gas species investigated here.

Single CuO nanowires decorated with size-selected Pd nanoparticles for CO sensing in humid atmosphere

We report on conductometric gas sensors based on single CuO nanowires and compare the carbon monoxide (CO) sensing properties of pristine as well as Pd nanoparticle decorated devices in humid atmosphere. Magnetron sputter inert gas aggregation combined with a quadrupole mass filter for cluster size selection was used for single-step Pd nanoparticle deposition in the soft landing regime. Uniformly dispersed, crystalline Pd nanoparticles with size-selected diameters around 5 nm were deposited on single CuO nanowire devices in a four point configuration. During gas sensing experiments in humid synthetic air, significantly enhanced CO response for CuO nanowires decorated with Pd nanoparticles was observed, which validates that magnetron sputter gas aggregation is very well suited for the realization of nanoparticle-functionalized sensors with improved performance.

Optimized integrated micro-hotplates in CMOS technology

Within this work the development of integrated Micro-HotPlates (μHPs) for gas sensing applications as a System-On Chip (SOC) is presented. As gas sensors exploit resistance variations of sensing materials like SnO₂ at high operating temperatures, integrated μHPs are required for the dynamic and low power operation of these sensors. The optimized μHP structures consist of fully released membranes with polysilicon heaters in the oxide stack and suspension arms to the bulk silicon. Thanks to the optimized μHP design very low power consumption of P_el ~20mW at high temperatures up to T=400°C together with a thermal uniformity of only ΔT~1K across the active area ending up in the highest reported efficiency of =26-20K/mW for standard CMOS hotplates is achieved. Further a rise/fall time t_rise/t_fall =4.5/5.4ms was measured. Long term stability of the μHP has been proven applying ten million measurement cycles. Thermography confirmed the temperature distribution and functionality. The realized hotplates cover a heating area of A_μHP=100×100μm²/70×70μm² at arm lengths of l_arm=70μm/50μm respectively. The chips have been realized in 0.35μm standard CMOS technology and released in a post process MEMS-etching step.

Modeling the Growth of Tin Dioxide Using Spray Pyrolysis Deposition for Gas Sensor Applications

In order for the gas sensor devices to enjoy the miniaturization trend that has consumed much of the electronic device industry, major research in the field is undertaken. The bulky sensor devices of previous generations can not easily be incorporated into a CMOS processing sequence, because of their bulky nature and potential higher cost of production. More recently, materials such as zinc oxide and tin dioxide have shown powerful gas sensing capabilities. Among many potential deposition methods, spray pyrolysis has become a popular approach because of its ease of use and cost effectiveness. A model for spray pyrolysis deposition is developed and implemented within the level set framework. The implementation allows for a smooth integration of multiple processing steps for the manufacture of smart gas sensor devices. From the observations, it was noted that spray pyrolysis deposition, when performed with a gas pressure nozzle, results in good step coverage, analogous to a CVD process. This is mainly due to the atomizing nozzle being placed at a reasonable distance away from the wafer surface and reducing the droplets volume and mass in order to ensure they fully evaporate prior to contact with the substrate surface. A topography simulator for this deposition methodology is presented.

Metal Oxide Nanowires for Gas Sensor Applications

We report on the synthesis of SnO2 and CuO nanowires and their application as gas sensing components. The fabrication of SnO2 and CuO single nanowire devices by optical and electron beam lithography is described, and sensing performance to the toxic gas carbon monoxide is demonstrated. We briefly present the development of CMOS fabricated micro-hotplates as platforms for gas sensors and show our approach for nanowire implementation. Finally, we demonstrate a fully CMOS integrated CuO multi nanowire device and present our roadmap for a fully integrated multi-parameter smart sensor device which could be implemented as safety feature in smart phones.ZusammenfassungWir berichten über die Synthese von SnO2 und CuO Nanodrähten und deren Anwendung als gassensitive Komponenten. Die Herstellung von SnO2 und CuO Einzel-Nanodraht Sensoren mittels optischer Lithographie und Elektronenstrahllithographie wird beschrieben, und die sehr guten Sensoreigenschaften zur Analyse des toxischen Gases Kohlenmonoxid werden gezeigt. Wir fassen die Entwicklung von CMOS hergestellten Mikro-Heizplatten zusammen, die als Bauelement-Plattform für Gassensoren verwendet werden, und zeigen unseren Ansatz zur Implementierung von Nanodrähten. Abschließend wird ein in CMOS Technologie integrierter CuO Multi-Nanodrahtsensor gezeigt. Dieses Bauelement repräsentiert den Entwicklungsprozess hin zu einem vollständig integrierten smarten Multi-Parameter Sensor, der für Sicherheitsanwendungen in einem Smart Phone implementiert werden könnte.

Fully integrated System-On Chip gas sensor in CMOS technology

Within this work the development of an integrated gas sensor as System-On Chip (SOC) in a 0.35μm standard CMOS process plus CMOS compatible SnO₂-deposition and Si-release steps is presented. The SnO₂ layer provides high gas sensitivity to 10ppm for CO in humid air. An optimized Micro-Hotplate (μHP) consisting of a fully released membrane with a poly-Si heater in the oxide stack is designed. Due to the small area of A_μHP=100×100μm² and the switched capacitor temperature controller, low power consumption P_el=24mW at high temperatures T=400°C and short rise time of i_nîe=11.8ms are achieved. The differential setup contains sense and dummy sensors in order to compensate drift and tolerances. The readout stage consists of a gain adjustable amplifier with digital offset compensation and shows a relative error e<;±1%. The complete multichannel chip carries six sensors at a size A_chip=3.4×2.4mm², a power consumption P_chip=180mW and is well suited for various low power gas sensing applications.

Tin oxide nanowire sensors for highly sensitive detection of the toxic gas H2S

We have realized gas sensor devices, which are based on a single SnO2-nanowire or a multiple SnO2-nanowire network as gas sensing components and are very sensitive to the toxic gas H2S. The nanowires are fabricated in a two-step atmospheric pressure synthesis process directly on the Si-chip by spray pyrolysis and subsequent annealing. Exposure of the single SnO2-nanowire sensor H2S with a concentration of only 1.4 ppm decreases the resistance by ~ 30%, while the multiple SnO2-nanowire network sensor exhibits a resistance decrease by ~ 90%. The nanowire sensors have extraordinary sensitivity with resolution limit in the ppb range and are able to measure concentrations well below the threshold limit value of 10 ppm. Due to their high performance the nanowire based sensors are basically suited for the realization of smart gas sensing devices for personal safety issues as well as industrial applications.

Modeling and Analysis of Spray Pyrolysis Deposited SnO2 Films for Gas Sensors

Metal oxide materials such as tin oxide (SnO2) show powerful gas sensing capabilities. Recently, the deposition of a thin tin oxide film at the backend of a CMOS processing sequence has enabled the manufacture of modern gas sensors. Among several potential deposition methods for SnO2, spray pyrolysis deposition has proven itself to be relatively easy to use and cost effective while providing excellent surface coverage on step structures and etched holes. A model for spray pyrolysis deposition using a pressure atomizer is presented and implemented in a Level Set framework. A simulation of tin oxide deposition is performed on a typical gas sensor geometry and the resulting structure is imported into a finite element tool in order to analyze the electrical characteristics and thermo-mechanical stress present in the grown layer after processing. The deposition is performed at 400 °C and the subsequent cooling to room temperatures causes a stress to develop at the material interfaces due to variations in the coefficient of thermal expansion between the different materials.

Modeling the growth of thin SnO2 films using spray pyrolysis deposition

The deposition of a thin tin oxide film allows for the manufacture of modern gas sensors to replace the bulky sensors of previous generations. Spray pyrolysis deposition is used to grow the required sensing thin films, as it can be seamlessly integrated into a standard CMOS processing sequence. A model for spray pyrolysis deposition is developed and implemented within the Level Set framework. The implementation allows for a seamless integration of multiple processing steps for the manufacture of smart gas sensor devices. From observations it was noted that spray pyrolysis deposition, when performed with a gas pressure nozzle, results in good step coverage, analogous to a CVD process. This is due to the liquid droplets evaporating prior to contact with the heated wafer surface and subsequently depositing on top of the exposed silicon in vapor form.

Metal oxide nanowire gas sensors for indoor and outdoor environmental monitoring

We present performance results of SnO2 and CuO nanowire gas sensor devices, where single and multi-nanowire device configurations have been employed in order to optimize sensor design. In particular the response to the target gases CO, H2, and H2S has been measured in dry and humid air; both the SnO2 and CuO nanowire sensors are able to detect CO in the low ppm concentration range, which is important for environmental monitoring. The CuO multi-nanowire devices show an extraordinary high response to H2S with sensitivity in the low ppb concentration. We present our developments of CMOS technology based micro-hotplates, which are employed as platform for gas sensitive thin films and nanowires. Potential heterogeneous integration of nanowires on the micro-hotplate chips as well as an approach towards gas sensor arrays is discussed. We conclude that CMOS integrated multi-nanowire gas sensors are highly promising candidates for the practical realization of multi-parameter sensor devices for indoor and outdoor environmental monitoring.