In situ study of sensor behavior of MoS2 field effect transistor for methyl orange molecule in ultra high vacuum condition.

We investigate the sensor behavior of the MoS2 field effect transistor (FET) device with the deposition of methyl orange (MO) molecule which is widely used as a chemical probe. The channel of the FET is made of the single layer of MoS2 which makes it highly sensitive to the molecule adsorption, but at the same time the behavior depends much on the surface conditions of the MoS2 channel. In order to make the channel-surface conditions more defined, we prepare an in situ experimental system in which the molecule deposition and the surface- and electrical-characterization of the MoS2 FET are executed in a single ultra-high vacuum chamber. This system makes it possible to examine the change of the FET properties with precise control of the molecule coverage in the sub-monolayer region without the effect of the atmosphere. We detected the shift of the I d-V g curve of the MoS2-FET device with the increase of the molecule coverage (θ) of the MO molecule, which is quantitatively analyzed by plotting the threshold voltage (V th) of the I d-V g curve as a function of θ. The V th shifts towards the negative direction and the initial change with θ can be expressed with an exponential function of θ, which can be accounted for with the Langmuir type adsorption of the molecule for the first layer and the charge transfer from the molecule to the substrate. The V th versus θ curve shows a kink at a certain θ, which is conserved as the starting of the second layer growth. We detected the adsorption of MO far less than monolayer and the phase change from the first layer to the second layer growth, which is realized by the benefit of the in situ UHV experimental condition.

Chemistry of the photoisomerization and thermal reset of nitro-spiropyran and merocyanine molecules on the channel of the MoS2 field effect transistor.

We have explored the chemical reaction of the photoisomerization and thermal reaction of the photochromic spiropyran (SP) 1',3'-Dihydro-1',3',3' trimethyl-6-nitrospiro[2H-1 benzopyran-2,2'-(2H)-indole] molecule deposited on the atomic thin channel of a MoS2 field-effect transistor (FET) through the analysis of the FET property. With four monolayers of SP molecules on the channel, we observed a clear shift of the threshold voltage in the drain-current vs gate-voltage plot with UV-light injection on the molecule, which was due to the change of the SP molecule to merocyanine (MC). A complete reset from MC to SP molecule was achieved by thermal annealing, while the injection of green light could revert the FET property to the original condition. In the process of change from MC to SP, two types of decay rates were confirmed. The quick- and slow-decay components corresponded to the molecules attached directly to the substrate and those in the upper layer, respectively. The activation energies for the conversion of MC to SP molecules were estimated as 71 kJ/mol and 90 kJ/mol for the former and latter, respectively. Combined with DFT calculations, we concluded that the Id-Vg shift with photoisomerization from SP to MC is due to the upper layer molecules and the dipole moment in the surface normal direction. Based on the estimated activation energy of 90 kJ/mol for the reset process, we calculated the conversion rate in a controllable temperature range. From these values, we consider that the chemical state of MC can be maintained and switched in a designated time period, which demonstrates the possibility of this system in logical operation applications.

Microfluidic tank assisted nicotine sensing property of field effect transistor composed of an atomically thin MoS2 channel.

We investigated the sensor behavior of a field effect transistor, the channel of which is made of atomically thin MoS2 layers, focusing on the interaction of the MoS2 channel with the solution containing target molecules. For this purpose, we made a newly designed device in which the mask covered the electrodes of the source and the drain in order to make the solution contact only with the channel. In addition, a micro-fluid tank was fabricated above the channel as a solution reservoir. We examined the FET properties of this device for the sensing of the nicotine molecule for the development of a detection system for this molecule in the human body under in vivo conditions. We detected the sensor behavior both for the drop-cast process and for the condition where the channel contacts with the solution. The drain-current vs. gate-voltage variation of the MoS2-FET with the attachment of the nicotine molecule was clearly observed for both cases. For the latter case, the threshold voltage shifted in the negative gate-voltage direction with the increase of the concentration of the nicotine in the solution. This can be explained by the electron transfer from the molecule to the MoS2 channel, which was further confirmed by analyzing the X-ray photoemission spectroscopy and Raman spectroscopy together with the DFT calculation. The sensor can detect the variation of the nicotine concentration in the IPA solution by detecting the Vth change of the MoS2-FET.

Sensor behavior of MoS2 field-effect transistor with light injection toward chemical recognition.

The application of field-effect transistor (FET) devices with atomically thin channels as sensors has attracted significant attention, where the adsorption of atoms/molecules on the channels can be detected by the change in the properties of FET. Thus, to further enhance the chemical sensitivity of FETs, we developed a method to distinguish the chemical properties of adsorbates from the electric behavior of FET devices. Herein, we explored the variation in the FET properties of an MoS2-FET upon visible light injection and the effect of molecule adsorption for chemical recognition. By injecting light, the drain current (I d) increased from the light-off state, which is defined as (ΔI d)ph. We examined this effect using CuPc molecules deposited on the channel. The (ΔI d)ph vs. wavelength continuous spectrum in the visible region showed a peak at the energy for the excitation from the highest occupied orbital (HOMO) to the molecule-induced state (MIS). The energy position and the intensity of this feature showed a sensitive variation with the adsorption of the CuPc molecule and are in good agreement with previously reported photo-absorption spectroscopy data, indicating that this technique can be employed for chemical recognition.

In Situ Study of Molecular Doping of Chlorine on MoS2 Field Effect Transistor Device in Ultrahigh Vacuum Conditions.

We report a precise measurement of the sensor behavior of the field effect transistor (FET) formed with the MoS2 channel when the channel part is exposed to Cl2 gas. The gas exposure and the electrical measurement of the MoS2 FET were executed with in situ ultrahigh-vacuum (UHV) conditions in which the surface analysis techniques were equipped. This makes it possible to detect how much sensitivity the MoS2 FET can provide and understand the surface properties. With the Cl2 gas exposure to the channel, the plot of the drain current versus the gate voltage (I d-V g curve) shifts monotonically toward the positive direction of V g, suggesting that the adsorbate acts as an electron acceptor. The I d-V g shifts are numerically estimated by measuring the onset of I d (threshold voltage, V th) and the mobility as a function of the dosing amounts of the Cl2 gas. The behaviors of both the V th shift and the mobility with the Cl2 dosing amount can be fitted with the Langmuir adsorption kinetics, which is typically seen in the uptake curve of molecule adsorption onto well-defined surfaces. This can be accounted for by a model where an impinging molecule occupies an empty site with a certain probability, and each adsorbate receives a certain amount of negative charge from the MoS2 surface up to the monolayer coverage. The charge transfer makes the V th shifts. In addition, the mobility is reduced by the enhancement of the Coulomb scattering for the electron flow in the MoS2 channel by the accumulated charge. From the thermal desorption spectroscopy (TDS) measurement and density functional theory (DFT) calculations, we concluded that the adsorbate that is responsible for the change of the FET property is the Cl atom that is dissociated from the Cl2 molecule. The monotonic shift of V th with the coverage suggests that the MoS2 device sensor has a good sensitivity to detect 10-3 monolayers (ML) of adsorption corresponding to the ppb level sensor with an activation time of 1 s.