The ultimate aim of any detection method is to achieve such a level of sensitivity that individual quanta of a measured entity can be resolved. In the case of chemical sensors, the quantum is one atom or molecule. Such resolution has so far been beyond the reach of any detection technique, including solid-state gas sensors hailed for their exceptional sensitivity1, 2, 3, 4. The fundamental reason limiting the resolution of such sensors is fluctuations due to thermal motion of charges and defects5, which lead to intrinsic noise exceeding the sought-after signal from individual molecules, usually by many orders of magnitude. Here, we show that micrometre-size sensors made from graphene are capable of detecting individual events when a gas molecule attaches to or detaches from graphene's surface. The adsorbed molecules change the local carrier concentration in graphene one by one electron, which leads to step-like changes in resistance. The achieved sensitivity is due to the fact that graphene is an exceptionally low-noise material electronically, which makes it a promising candidate not only for chemical detectors but also for other applications where local probes sensitive to external charge, magnetic field or mechanical strain are required.

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Detection of individual gas molecules adsorbed on graphene

The integration of novel materials such as single-walled carbon nanotubes and nanowires into devices has been challenging, but developments in transfer printing and solution-based methods now allow these materials to be incorporated into large-area electronics1,2,3,4,5,6. Similar efforts are now being devoted to making the integration of graphene into devices technologically feasible7,8,9,10. Here, we report a solution-based method that allows uniform and controllable deposition of reduced graphene oxide thin films with thicknesses ranging from a single monolayer to several layers over large areas. The opto-electronic properties can thus be tuned over several orders of magnitude, making them potentially useful for flexible and transparent semiconductors or semi-metals. The thinnest films exhibit graphene-like ambipolar transistor characteristics, whereas thicker films behave as graphite-like semi-metals. Collectively, our deposition method could represent a route for translating the interesting fundamental properties of graphene into technologically viable devices.

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Large-area ultrathin films of reduced graphene oxide as a transparent and flexible electronic material

The interactions between four different graphenes (including pristine, B- or N-doped and defective graphenes) and small gas molecules (CO, NO, NO2 and NH3) were investigated by using density functional computations to exploit their potential applications as gas sensors. The structural and electronic properties of the graphene-molecule adsorption adducts are strongly dependent on the graphene structure and the molecular adsorption configuration. All four gas molecules show much stronger adsorption on the doped or defective graphenes than that on the pristine graphene. The defective graphene shows the highest adsorption energy with CO, NO and NO2 molecules, while the B- doped graphene gives the tightest binding with NH3. Meanwhile, the strong interactions between the adsorbed molecules and the modified graphenes induce dramatic changes to graphene's electronic properties. The transport behavior of a gas sensor using B- doped graphene shows a sensitivity two orders of magnitude higher than that of pristine graphene. This work reveals that the sensitivity of graphene-based chemical gas sensors could be drastically improved by introducing the appropriate dopant or defect.

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Improving gas sensing properties of graphene by introducing dopants and defects: a first-principles study.

Alternating graphene (G) and titania (Ti0.91O2) multilayered nanosheets are fabricated using layer-by-layer electrostatic deposition followed by UV irradiation. Successful assemblies of graphene oxide (GO) and titania nanosheets in sequence with polyethylenimine as a linker is confirmed by UV–vis absorption and X-ray diffraction. Photocatalytic reduction of GO into G can be achieved upon UV irradiation. Ultrafast photocatalytic electron transfer between the titania and graphene is demonstrated using femtosecond transient absorption spectroscopy. Efficient exciton dissociation at the interfaces coupled with cross-surface charge percolation allows efficient photocurrent conversion in the multilayered Ti0.91O2/G films.

Multilayer Hybrid Films Consisting of Alternating Graphene and Titania Nanosheets with Ultrafast Electron Transfer and Photoconversion Properties

Field emission from graphene is challenging because the existing deposition methods lead to sheets that lay flat on the substrate surface, which limits the field enhancement. Here we describe a simple and general solution based method for the deposition of field emitting graphene/polymer composite thin films. The graphene sheets are oriented at some angles with respect to the substrate surface leading to field emission at low threshold fields (∼4Vμm−1). Our method provides a route for the deposition of graphene based thin film field emitter on different substrates, opening up avenues for a variety of applications.

Field emission from graphene based composite thin films

We describe probes of a local electric field, which are capable of detecting an electric charge as small as the charge of one electron e, operational under ambient conditions and having a spatial resolution down to 100nm. The submicron-sized probes were made from a high-density high-mobility two-dimensional electron gas, which is sensitive to the presence of electric charges near its surface. We demonstrate the possibility of using such microprobes for life-science applications by measuring an electric response of individual yeast cells to abrupt changes in their environment.

Submicron sensors of local electric field with single-electron resolution at room temperature

We report on mesoscopic Hall sensors made from various materials and their suitability for accurate magnetization studies of submicron samples over a wide temperature range and, especially, at room temperature. Among the studied devices, the best stability and sensitivity have been found for Hall probes made from a high-concentration two-dimensional electron gas (HC-2DEG). Even at 300 K, such submicron probes can reliably resolve local changes in dc magnetic field of ≈1 G, which corresponds to a flux sensitivity of less than 0.1 φ0 (φ0=h/e is the flux quantum). The resolution increases 100 times at temperatures below 80 K. It is also much higher for the detection of ac magnetic fields because resistance fluctuations limiting the low-frequency stability of the studied devices can be eliminated. Our second choice for room-temperature Hall micromagnetometry is gold Hall probes, which can show a sensitivity of the order of 10 G. The capabilities of HC-2DEG and gold micromagnetometers are demonstrated by measuring nm-scale movements of individual domain walls in a ferromagnet.

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A. O. Volkov

Papers

Submicron sensors of local electric field with single-electron resolution at room temperature

Submicron probes for Hall magnetometry over the extended temperature range from helium to room temperature