QCM Sensors Combining Highly Nanostructured Metal-Blacks Sublayers and Active Self-Assembled Monolayers
Authors: Hruška Martin , Tomeček David , Havlová Šárka , Fitl Přemysl , Guerkboukha Mohamed Amine , Gadenne Virginie , Patrone Lionel , Vrňata Martin 
Published: May 2020

Introduction

Quartz Crystal Microbalance (QCM) sensors are characterized by many potential applications. They are being widely used as biosensors, in pharmacological applications, for combustion control, environmental pollution monitoring, etc. [1]. Regardless the specific application, the recognition resolution of quartz chips is usually determined and restrained according to the Sauerbray equation (For example for 10 MHz QCM, the change of resonance frequency in 1 Hz corresponds to 4.4 ng/cm2 of adsorbed mass per surface). This fact is crucial mainly for gas sensor application where we need to detect concentration down to ppm or even ppb levels. However, there are some possibilities on how to enhance the QCM sensor properties and amplify their sensitivity, for instance by increasing the specific surface area of QCM electrodes, and thus providing more bonding sites for the analyte [2]. In this contribution, we propose a novel method that uses nanostructured materials called metal-blacks as a sublayer for the increase of active sensor surface, in combination with self-assembled monolayers (SAMs) that serves as a receptor layer.

Metal-Blacks

Metal-blacks – MBs are highly nanoporous and nanostructured materials with a large surface area. Their name originates in black colour, caused by the absorption of incident light on their surface. The incident light penetrates into the pores and channels where it undergoes multiple reflections in cavities and where it is almost completely absorbed. Due to the very large surface area, MBs are ideal materials for enhancement of QCM gas sensors properties [3].

Experimental

The nanostructured layers of black gold (BAu) and black palladium (BPd) were prepared by evaporation from a tungsten boat at an elevated pressure of 200 Pa. Prepared layers of MBs were then characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The SAMs of zinc octacarboxylphthalocyanine ZnPc(COOH)8 were prepared by two-step grafting method, where ZnPc(COOH)8 is covalently bonded to the molecule of aminothiophenol, which serves as an surface anchor via its gold/palladium-sulfur bond. The preparation procedure was as follows. At first, the QCM electrodes with MB layers were degreased in a sonicated ethanol bath during a few minutes and then dried under a nitrogen flow. Second, the QCM samples were cleaned by UV-ozone treatment and immediately immersed into 10-4 M solution of aminothiophenol in ethanol/DMF solvent for 24h. Third, after the 24h incubation time, the samples were moved into 10-4 M solution of the macrocycles and left there for another 24h. In the end, the samples were carefully rinsed with the solvent to eliminate adsorbed molecular overlayers and subsequently washed with ethanol in order to remove solvent residues and dried under nitrogen flux.
Once prepared, QCM sensor impedance spectra were obtained by impedance analyzer Agilent 4294A. Responses towards different analytes (EtOH, CH4, H2O, NO2, toluene, acetaldehyde) were measured in a glass chamber that enables the measurement of up to 6 sensors at the same time. Sensors were measured at a constant gas flow and room temperature. The sensor resonant frequencies were measured by oscillattor circuits in connection with an NI PCI-6602 card used as a precise counter

Results and Conclusions

In this contribution, we have proved that highly nanoporous and nanostructured materials (such as metal-blacks), which have a large specific surface area, provide more binding sites for analytes and, hence, increase the response of the QCM sensors. As an example measurement, we present the response of QCMs with BAu towards ethanol vapours (Fig. 1). The curves illustrate that the response of the sensor with the BAu electrode is 10-times bigger than the one of the standard QCM (152Hz/15Hz). For the combined layer (BAu + ZnPc(COOH)8), the response amplification is not so large but it is still significant. In this case, the response is 3-times bigger than the one from the QCM with ZnPc(COOH)8 only (without BAu). However, in contrast with QCM with just bare BAu, the surface modification with SAMs layers influences the sensor selectivity. The combined layers of MBs and SAMs then result in a selective sensor with increased sensitivity. According to the presented results metal-blacks are promising materials that can significantly boost the sensitivity of QCM sensors and still preserve the selectivity of its active layers.

References

[1] Johannsmann, D. The Quartz Crystal Microbalance in Soft Matter Research: Fundamentals and Modeling; Springer International Publishing, 2014.
[2] Chappanda, K. N.; Shekhah, O.; Yassine, O.; Patole, S. P.; Eddaoudi, M.; Salama, K. N. The Quest for Highly Sensitive QCM Humidity Sensors: The Coating of CNT/MOF Composite Sensing Films as Case Study. Sensors Actuators B Chem.
2018, 257, 609–619. https://doi.org/10.1016/J.SNB.2017.10.189.
[3] Novotný, M.; Fitl, P.; Sytchkova, A.; Bulíř, J.; Lanačok, J.; Pokorný, P.; Najdek, D.; Boan, J. Pulsed Laser Treatment of Gold and Black Gold Thin Films Fabricated by Thermal Evaporation. Open Phys.
2009, 7 (2), 327–331. https://doi.org/10.2478/s11534-009-0027-7.

Figure 1