An Electrochemical Biochip for Measuring Low Concentrations of Analytes With Adjustable Temporal Resolutions.

Electrochemical micro-sensors made of nano-graphitic (NG) carbon materials could offer high sensitivity and support voltammetry measurements at vastly different temporal resolutions. Here, we implement a configurable CMOS biochip for measuring low concentrations of bio-analytes by leveraging these advantageous features of NG micro-sensors. In particular, the core of the biochip is a discrete-time ∆Σ modulator, which can be configured for optimal power consumption according to the temporal resolution requirements of the sensing experiments while providing a required precision of ≈ 13 effective number of bits. We achieve this new functionality by developing a design methodology using the physical models of transistors, which allows the operating region of the modulator to be switched on-demand between weak and strong inversion. We show the application of this configurable biochip through in-vitro measurements of dopamine with concentrations as low as 50 nM and 200 nM at temporal resolutions of 100 ms and 10 s, respectively.

Nano-engineering the material structure of preferentially oriented nano-graphitic carbon for making high-performance electrochemical micro-sensors.

Direct synthesis of thin-film carbon nanomaterials on oxide-coated silicon substrates provides a viable pathway for building a dense array of miniaturized (micron-scale) electrochemical sensors with high performance. However, material synthesis generally involves many parameters, making material engineering based on trial and error highly inefficient. Here, we report a two-pronged strategy for producing engineered thin-film carbon nanomaterials that have a nano-graphitic structure. First, we introduce a variant of the metal-induced graphitization technique that generates micron-scale islands of nano-graphitic carbon materials directly on oxide-coated silicon substrates. A novel feature of our material synthesis is that, through substrate engineering, the orientation of graphitic planes within the film aligns preferentially with the silicon substrate. This feature allows us to use the Raman spectroscopy for quantifying structural properties of the sensor surface, where the electrochemical processes occur. Second, we find phenomenological models for predicting the amplitudes of the redox current and the sensor capacitance from the material structure, quantified by Raman. Our results indicate that the key to achieving high-performance micro-sensors from nano-graphitic carbon is to increase both the density of point defects and the size of the graphitic crystallites. Our study offers a viable strategy for building planar electrochemical micro-sensors with high-performance.

Hybrid CMOS-Graphene Sensor Array for Subsecond Dopamine Detection.

We introduce a hybrid CMOS-graphene sensor array for subsecond measurement of dopamine via fast-scan cyclic voltammetry (FSCV). The prototype chip has four independent CMOS readout channels, fabricated in a 65-nm process. Using planar multilayer graphene as biologically compatible sensing material enables integration of miniaturized sensing electrodes directly above the readout channels. Taking advantage of the chemical specificity of FSCV, we introduce a region of interest technique, which subtracts a large portion of the background current using a programmable low-noise constant current at about the redox potentials. We demonstrate the utility of this feature for enhancing the sensitivity by measuring the sensor response to a known dopamine concentration in vitro at three different scan rates. This strategy further allows us to significantly reduce the dynamic range requirements of the analog-to-digital converter (ADC) without compromising the measurement accuracy. We show that an integrating dual-slope ADC is adequate for digitizing the background-subtracted current. The ADC operates at a sampling frequency of 5-10 kHz and has an effective resolution of about 60 pA, which corresponds to a theoretical dopamine detection limit of about 6 nM. Our hybrid sensing platform offers an effective solution for implementing next-generation FSCV devices that can enable precise recording of dopamine signaling in vivo on a large scale.