One hundred years after its first successful synthesis in the bulk form in 1914, black phosphorus (black P) was recently rediscovered from the perspective of a 2D layered material, attracting tremendous interest from condensed matter physicists, chemists, semiconductor device engineers, and material scientists. Similar to graphite and transition metal dichalcogenides (TMDs), black P has a layered structure but with a unique puckered single-layer geometry. Because the direct electronic band gap of thin film black P can be varied from 0.3 eV to around 2 eV, depending on its film thickness, and because of its high carrier mobility and anisotropic in-plane properties, black P is promising for novel applications in nanoelectronics and nanophotonics different from graphene and TMDs. Black P as a nanomaterial has already attracted much attention from researchers within the past year. Here, we offer our opinions on this emerging material with the goal of motivating and inspiring fellow researchers in the 2D materials community and the broad readership of PNAS to discuss and contribute to this exciting new field. We also give our perspectives on future 2D and thin film black P research directions, aiming to assist researchers coming from a variety of disciplines who are desirous of working in this exciting research field.

https://www.pnas.org/content/pnas/112/15/4523.full.pdf

The renaissance of black phosphorus

In the quest for higher performance, the dimensions of field-effect transistors (FETs) continue to decrease. However, the reduction in size of FETs comprising 3D semiconductors is limited by the rate at which heat, generated from static power, is dissipated. The increase in static power and the leakage of current between the source and drain electrodes that causes this increase, are referred to as short-channel effects. In FETs with channels made from 2D semiconductors, leakage current is almost eliminated because all electrons are confined in atomically thin channels and, hence, are uniformly influenced by the gate voltage. In this Review, we provide a mathematical framework to evaluate the performance of FETs and describe the challenges for improving the performances of short-channel FETs in relation to the properties of 2D materials, including graphene, transition metal dichalcogenides, phosphorene and silicene. We also describe tunnelling FETs that possess extremely low-power switching behaviour and explain how they can be realized using heterostructures of 2D semiconductors. Field-effect transistors (FETs) with semiconducting channels made from 2D materials are known to have fewer problems with short-channel effects than devices comprising 3D semiconductors. In this Review, a mathematical framework to evaluate the performance of FETs is outlined with a focus on the properties of 2D materials, such as graphene, transition metal dichalcogenides, phosphorene and silicene.

Two-dimensional semiconductors for transistors

Phosphorene, an emerging two-dimensional material, has received considerable attention due to its layer-controlled direct bandgap, high carrier mobility, negative Poisson's ratio and unique in-plane anisotropy. As cousins of phosphorene, 2D group-VA arsenene, antimonene and bismuthene have also garnered tremendous interest due to their intriguing structures and fascinating electronic properties. 2D group-VA family members are opening up brand-new opportunities for their multifunctional applications encompassing electronics, optoelectronics, topological spintronics, thermoelectrics, sensors, Li- or Na-batteries. In this review, we extensively explore the latest theoretical and experimental progress made in the fundamental properties, fabrications and applications of 2D group-VA materials, and offer perspectives and challenges for the future of this emerging field.

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Recent progress in 2D group-VA semiconductors: from theory to experiment

Electrochemistry of Nanostructured Layered Transition-Metal Dichalcogenides

The recent isolation of atomically thin black phosphorus by mechanical exfoliation of bulk layered crystals has triggered an unprecedented interest, even higher than that raised by the first works on graphene and other two-dimensionals, in the nanoscience and nanotechnology community. In this Perspective, we critically analyze the reasons behind the surge of experimental and theoretical works on this novel two-dimensional material. We believe that the fact that black phosphorus band gap value spans over a wide range of the electromagnetic spectrum (interesting for thermal imaging, thermoelectrics, fiber optics communication, photovoltaics, etc.) that was not covered by any other two-dimensional material isolated to date, its high carrier mobility, its ambipolar field-effect, and its rather unusual in-plane anisotropy drew the attention of the scientific community toward this two-dimensional material. Here, we also review the current advances, the future directions and the challenges in this young research...

Black Phosphorus: Narrow Gap, Wide Applications

We investigated the reduction of current fluctuations in few-layer black phosphorus (BP) field-effect transistors resulting from Al2O3 passivation. In order to verify the effect of Al2O3 passivation on device characteristics, measurements and analyses were conducted on thermally annealed devices before and after the passivation. More specifically, static and low-frequency noise analyses were used in monitoring the charge transport characteristics in the devices. The carrier number fluctuation (CNF) model, which is related to the charge trapping/detrapping process near the interface between the channel and gate dielectric, was employed to describe the current fluctuation phenomena. Noise reduction due to the Al2O3 passivation was expressed in terms of the reduced interface trap density values Dit and Nit, extracted from the subthreshold slope (SS) and the CNF model, respectively. The deviations between the interface trap density values extracted using the SS value and CNF model are elucidated in terms of t...

Few-Layer Black Phosphorus Field-Effect Transistors with Reduced Current Fluctuation

We have demonstrated a few-layer black phosphorus (BP) phototransistor of stable operation in ambient air environment and at near-infrared light (λ = 1550 nm). The air-stable electronic and optoelectronic properties of the few-layer BP phototransistor have been achieved by a proper Al2O3 passivation. The optical identification method and qualitative and quantitative electrical characterizations of the few-layer BP phototransistor in dark state confirmed that the device performance was robust in ambient air, to further chemical treatments, and storage of more than six months. In addition, the low-frequency noise characterizations had revealed that the noise spectral density related to the sensitivity of phototransistor was reduced. Owing to the suppression of interaction between few-layer BP and adsorbates arising from the Al2O3 passivation, a fast rise time of the few-layer BP phototransistor, less than 100 μs, had been observed, demonstrating the intrinsic photoresponse properties of few-layer BP. The low dark current of ~4 nA at the operation bias and the reasonable responsivity of ~6 mA W−1 were obtained under the condition lacking adsorbates interactions. Internally, the dark current and responsivity level was tunable by changing the operation bias. Our results are close to the intrinsic properties of the few-layer BP phototransistor, implying that it can be a building block of functioned few-layer BP photodetectors.

http://iopscience.iop.org/article/10.1088/1361-6528/aa55e4/pdf

Air-stable few-layer black phosphorus phototransistor for near-infrared detection

Effects of Silicon Addition on Grain Boundary Segregation Behaviors and Mechanical Properties in α-Iron

The present invention relates to a sensor system having nanomaterials applied as resistors in a bridge circuit. The present invention can provide a credible measurement of microscopic changes in the environment by using nanomaterials, which are highly sensitive to changes in the environment. In addition, the present invention can minimize the deterioration of performance of a sensor that occurs with time by using nanomaterilas as resistors in a bridge circuit, which is frequently used in a sensor, and by protecting the area excluding the nanomaterial area from the external environment, wherein the area excluding the nanomaterial areas is buried in a dielectric. Furthermore, the present invention can change the resistance of the nanomaterials by applying voltage on a gate formed on top of the nanomaterials and thus creating an electric field. Therefore, the resistance of the nanomaterials that make up the resistors in a Wheatstone bridge circuit can be set according to the user's intention, and a more credible measurement can be achieved by accordingly correcting the resistance value depending on the deterioration of performance, eliminating changes in a measurement value due to the deterioration of performance or external noise, and allowing the detection and concentration measurement of a substance that corresponds to the resistance value. Also, the present invention integrates a circuit device, which can automatically control the internal equilibrium condition in the Wheatstone bridge circuit, and a single semiconductor chip, which allows automatic correction of an error without requiring a user to set the condition.

Junhong Na

Papers

Few-Layer Black Phosphorus Field-Effect Transistors with Reduced Current Fluctuation

Air-stable few-layer black phosphorus phototransistor for near-infrared detection

Effects of Silicon Addition on Grain Boundary Segregation Behaviors and Mechanical Properties in α-Iron

Sensor system using nanomaterials and manufacturing method thereof