Black Phosphorus Field-effect Transistors Research Articles

Near-field detection of gate-tunable anisotropic plasmon polaritons in black phosphorus at terahertz frequencies

Polaritons in two-dimensional layered crystals offer an effective solution to confine, enhance and manipulate terahertz (THz) frequency electromagnetic waves at the nanoscale. Recently, strong THz field confinement has been achieved in a graphene-insulator-metal structure, exploiting THz plasmon polaritons (PPs) with strongly reduced wavelength (λp ≈ λ0/66) compared to the photon wavelength λ0. However, graphene PPs propagate isotropically, complicating the directional control of the THz field, which, on the contrary, can be achieved exploiting anisotropic layered crystals, such as orthorhombic black-phosphorus. Here, we detect PPs, at THz frequencies, in hBN-encapsulated black phosphorus field effect transistors through THz near-field photocurrent nanoscopy. The real-space mapping of the thermoelectrical near-field photocurrents reveals deeply sub-wavelength THz PPs (λp ≈ λ0/76), with dispersion tunable by electrostatic control of the carrier density. The in-plane anisotropy of the dielectric response results into anisotropic polariton propagation along the armchair and zigzag crystallographic axes of black-phosphorus. The achieved directional subwavelength light confinement makes this material system a versatile platform for sensing and quantum technology based on nonlinear optics.

Memory effect and coexistence of negative and positive photoconductivity in black phosphorus field effect transistor for neuromorphic vision sensors.

Black phosphorus (BP) field-effect transistors with ultrathin channels exhibit unipolar p-type electrical conduction over a wide range of temperatures and pressures. Herein, we study a device that exhibits mobility up to 100 cm2 V-1 s-1 and a memory window up to 1.3 μA. Exposure to a supercontinuum white light source reveals that negative photoconductivity (NPC) and positive photoconductivity (PPC) coexist in the same device. Such behavior is attributed to the chemisorbed O2 molecules, with a minor role of physisorbed H2O molecules. The coexistence of NPC and PPC can be exploited in neuromorphic vision sensors, requiring the human eye retina to process the optical signals through alerting and protection (NPC), adaptation (PPC), followed by imaging and processing. Our results open new avenues for the use of BP and other two-dimentional (2D) semiconducting materials in transistors, memories, and neuromorphic vision sensors for advanced applications in robotics, self-driving cars, etc.

Quantum Transport Properties of Monolayer MoS2, WS2, and Black Phosphorus: A Comparative Study

A comparative study of the performance analysis of dual-gate ballistic monolayer Molybdenum disulfide (MoS2), tungsten disulfide (WS2), and black phosphorus (BP) field-effect transistors (FETs) is presented. A thorough investigation of output and transfer characteristics infers that WS2 FET exhibits better performance as compared to MoS2 and BP. Furthermore, among all three FETs (MoS2, WS2, and BP), the WS2 based FET has a higher carrier velocity. However, variation of gate capacitance (CG) with gate voltage (VG) reflects a very good electrostatic gate control of MoS2 FET due to higher surface charge accumulation. Except for CG, the overall performance of WS2 based FET is better than MoS2 and BP.

Black Phosphorus Field-Effect Transistors with Improved Contact via Localized Joule Heating.

Two-dimensional (2D) black phosphorus (BP) is considered an ideal building block for field-effect transistors (FETs) owing to its unique structure and intriguing properties. To achieve high-performance BP-FETs, it is essential to establish a reliable and low-resistance contact between the BP and the electrodes. In this study, we employed a localized Joule heating method to improve the contact between the 2D BP and gold electrodes, resulting in enhanced BP-FET performance. Upon applying a sufficiently large source-drain voltage, the zero-bias conductance of the device increased by approximately five orders of magnitude, and the linearity of the current-voltage curves was also enhanced. This contact improvement can be attributed to the formation of gold phosphide at the interface of the BP and the gold electrodes owing to current-generated localized Joule heat. The fabricated BP-FET demonstrated a high on/off ratio of 4850 and an on-state conductance per unit channel width of 1.25 μS μm-1, significantly surpassing those of the BP-FETs without electrical annealing. These findings offer a method to achieve a low-resistance BP/metal contact for developing high-performance BP-based electronic devices.

Percolation-Based Metal-Insulator Transition in Black Phosphorus Field Effect Transistors.

The existence of a novel phenomenon, such as the metal-insulator transition (MIT) in two-dimensional (2D) systems, affords emerging functional properties that provide new aspects for future electronics and optoelectronics. Here, we report the observation of the MIT in black phosphorus field effect transistors by tuning the carrier density (n) controlled by back-gate bias. We find that the conductivity follows an n dependence as σ(n) ∝ nα with α ∼ 1, which indicates the presence of screened Coulomb impurity scattering at high carrier densities in the temperature range of 10-300 K. As n decreases, the screened Coulomb impurity scattering breaks down, developing strong charge density inhomogeneity leading to a percolation-based transition at the critical carrier density (nC). At low carrier densities (n < nC), the system is in the insulating regime, which is expressed by Mott variable range hopping that demonstrates the role of disorder in the system. In addition, the extracted average values of critical exponent δ are ∼1.29 ± 0.01 and ∼1.14 ± 0.01 for devices A and B, respectively, consistent with the 2D percolation exponent of 4/3, confirming the 2D percolation-based MIT in BP devices. Our findings strongly suggest that the 2D MIT observed in BP is a classical percolation-based transition caused by charge inhomogeneity induced by screened Coulomb charge impurity scattering around a transition point controlled by n through back-gate bias.

Temperature dependent black phosphorus transistor and memory

We studied the temperature dependent transport properties and memory behaviour of ultrathin black phosphorus field-effect transistors. The devices show electrical conductance and field-effect mobility that decreases with the rising temperature. The field effect mobility, which depends also on the gate voltage sweep range, is 283 cm2V−1s−1 at 150 K and reduces to 33 cm2V−1s−1 at 340 K, when the voltage gate sweep range is 50 V. The transfer characteristics show a hysteresis width that increases with the temperature and is exploited to enable non-volatile memories with a wider programming window at higher temperatures.

Highly Specific Antibiotic Detection on Water-Stable Black Phosphorus Field-Effect Transistors.

Two-dimensional (2D) black phosphorus (BP) has been reported to have appealing semiconducting properties as the sensing channel in field-effect transistor (FET) sensors. However, the intrinsic instability of BP in water greatly hinders its application, and little is known about its sensing performance and mechanism in aqueous medium. Herein, a water-stable BP FET sensor for antibiotic detection is reported. A novel surface engineering strategy with Ag+ coordination and melamine cyanurate (MC) supramolecular passivation is utilized to enhance the stability and transistor performance of BP. With molecularly imprinted polymers (MIPs) as the detection probe for tetracycline, the BPAg(+)/MC/MIPs sensor shows high sensitivity to tetracycline with a detection limit of 7.94 nM and a quick response within 6 s as well as high selectivity against other antibiotics with similar molecular structures. A new sensing mechanism relying on the conjugation effect of the probe structure is proposed, and new knowledge about alkalinity-enhanced and ionic strength-related response from the electrostatic gating effect is given based on the solution chemistry impact study. This work offers an efficient surface engineering strategy to enable the application of 2D BP for antibiotic detection in aqueous medium and presents a new sensing mechanism in chemical analysis by FET sensors.

Alkene-Catalyzed Rapid Layer-by-Layer Thinning of Black Phosphorus for Precise Nanomanufacturing.

Black phosphorus (BP) is a promising material for electronic and optoelectronic applications. However, it is still challenging to obtain geometrically well-defined BP with desirable thickness. The method involving rapid BP surface reaction via alkene-catalyzed oxidation and easy removal of reactants by a mechanical effect was proposed to achieve the precise layer-by-layer thinning and real-time thickness monitoring of BP for nanopatterning with high spatial resolution based on mechanical scanning probe nanolithography. The enhanced electron affinity of oxygen with the assistance of a carbon-carbon double bond (C═C) in the alkene was demonstrated by density functional theory calculations, shortening the BP surface oxidation period by 99%, which provides access for the rapid thinning. The few-layer BP nanoflake with nested structure and arbitrary thickness on various substrates and the nanopatterned heterojunctions (BP/graphene and BP/hexagonal boron nitride) can be precisely fabricated by the adjustment of scanning number under a small load. This thinning technology was efficient and universal, which could be used to fabricate a BP field-effect transistor with a thinned channel to enhance the capability for current modulation, showing great potential applications for designing high-performance nanodevices.

Wavelength‐Controlled Photocurrent Polarity Switching in BP‐MoS2 Heterostructure

AbstractLayered 2D van der Waals semiconductors and their heterostructures have been shown to exhibit positive photoconductance (PPC) in many studies. A few recent reports have demonstrated negative photoconductance (NPC) as well that can enable broadband photodetection besides multi‐level optoelectronic logic and memory. Controllable and reversible switching between PPC and NPC is a key requirement for these applications. This report demonstrates visible‐to‐near infrared wavelength‐driven NPC and PPC, along with reversible switching between the two, in an air stable, high mobility, broadband black phosphorus field effect transistor covered with a few layer MoS2 flake. The crossover switching wavelength can be tuned by varying the MoS2 bandgap through its flake thickness and the NPC and PPC photoresponsivities can be modulated using electrostatic gating as well as laser power. Recombination‐driven NPC and PPC, as supported by density functional theory calculations, allows for reversible switching. Further, gate voltage‐dependent negative persistent photoconductance is well‐suited for optosynaptic applications.

Detecting the Knowledge Domains of Compound Semiconductors.

The development of compound semiconductors (CS) has received extensive attention worldwide. This study aimed to detect and visualize CS knowledge domains for quantifying CS research patterns and emerging trends through a scientometric review based on the literature between 2011 and 2020 by using CiteSpace. The combined dataset of 24,622 bibliographic records were collected through topic searches and citation expansion to ensure adequate coverage of the field. While research in “solar cell” and “perovskite tandem” appears to be the two most distinctive knowledge domains in the CS field, research related to thermoelectric materials has grown at a respectable pace. Most notably, the deep connections between “thermoelectric material” and “III-Sb nanowire (NW)” research have been demonstrated. A rapid adaptation of black phosphorus (BP) field-effect transistors (FETs) and gallium nitride (GaN) transistors in the CS field is also apparent. Innovative strategies have focused on the opto-electronics with engineered functionalities, the design, synthesis and fabrication of perovskite tandem solar cells, the growing techniques of Sb-based III–V NWs, and the thermal conductivity of boron arsenide (BAs). This study revealed how the development trends and research areas in the CS field advance over time, which greatly help us to realize its knowledge domains.

Memory effects in black phosphorus field effect transistors

We report the fabrication and the electrical characterization of back-gated field effect transistors with a black phosphorus (BP) channel. We show that the hysteresis of the transfer characteristic, due to intrinsic defects, can be exploited to realize non-volatile memories. We demonstrate that gate voltage pulses allow to trap and store charge inside the defect states, which enable memory devices with endurance over 200 cycles and retention longer than 30 min. We show that the use of a protective poly(methyl methacrylate) layer, positioned on top of the BP channel, does not affect the electrical properties of the device but avoids the degradation caused by the exposure to air.

Ultrahigh Anisotropic Transport Properties of Black Phosphorus Field Effect Transistors Realized by Edge Contact

AbstractHighly anisotropic black phosphorus (BP) has recently attracted significant interest for electronic and optoelectronic devices. To date, in‐plane anisotropic properties of BP field effect transistors (FETs) have been reported only with top contact. However, the 2D top contact geometry is unable to measure the in‐plane electrical conductance precisely, due to the presence of the out‐of‐plane conductance, resulting in underestimation of anisotropy. Here, 1D edge contact method is employed to measure the in‐plane conductance precisely along the armchair and zigzag directions of BP without the contribution of out‐of‐plane conductance. The conductance and mobility anisotropies for BP FETs are measured with edge contact at 300 K to be ≈5.5 and ≈7.5, respectively. The results further show that the mobility of BP FETs with edge contact weakly depends on temperature, indicating that the edge roughness scattering limits the mobility. In contrast, the mobility of BP FETs with top contact strongly depends on temperature, showing that the impurity scattering and phonon scattering limit the mobility at below and above 150 K, respectively. Finally, a scattering phase diagram is demonstrated to understand the role of different scattering mechanisms on the modulation of mobility anisotropy in BP FETs with edge and top contacts.

Two-dimensional transistors with reconfigurable polarities for secure circuits

Security is a critical aspect in modern circuit design, but research into hardware security at the device level is rare as it requires modification of existing technology nodes. With the increasing challenges facing the semiconductor industry, interest in out-of-the-box security solutions has grown, even if this implies introducing novel materials such as two-dimensional layered semiconductors. Here, we show that high-performance, low-voltage, two-dimensional black phosphorus field-effect transistors (FETs) that have reconfigurable polarities are suitable for hardware security applications. The transistors can be dynamically switched between p-FET and n-FET operation through electrostatic gating and can achieve on–off ratios of 105 and subthreshold swings of 72 mV dec−1 at room temperature. Using the transistors, we create inverters that exhibit gains of 33.3 and are fully functional at a supply voltage of 0.2 V. We also create a security primitive circuit with polymorphic NAND/NOR obfuscation functionality with sub-1-V operation voltages, and the robustness of the polymorphic gate against power supply variations is tested using Monte Carlo simulations. Transistors that use two-dimensional black phosphorus as the active material can dynamically switch between p-type and n-type operation, and can be used to create security primitive circuits with polymorphic NAND/NOR obfuscation functionality.

Organic Field Effect Transistors: Noncovalent Functionalization and Passivation of Black Phosphorus with Optimized Perylene Diimides for Hybrid Field Effect Transistors (Adv. Mater. Interfaces 23/2020)

The noncovalent functionalization of two-dimensional black phosphorus (BP) with tailor made perylene diimides (PDI) leads to the efficient passivation of BP field effect transistors (FET). This straightforward wet chemical approach allows to preserve the electronic properties under environmental conditions. More details can be found in article number 2001290 by Gonzalo Abellán, Andreas Hirsch, and co-workers.

Photogating-Induced Controlled Electrical Response in 2D Black Phosphorus

Photo-induced tunability in charge carriers can be proven as a promising alternative approach to traditional electrostatic gating because of its flexibility to operate in noncontact mode. We have established a reversibly tunable optical gating technique on a few-layer black phosphorus (BP) flake by shining a laser beam, with variation in incident power and energy. The laser power-dependent evolution of Raman spectra of the BP flake is compared with the effect of conventional electrostatic gating. The comparison shows identical linear redshift in characteristic vibrational modes; thereby, a correlation between the laser power and induced charge carrier density is established. The transfer characteristics of BP field effect transistor (FET) under varying laser power validate the optical tunability of the gating effect and demonstrate identical variation in charge carrier density, found in conventional back-gated BP FET.

Contact resistance assessment and high-frequency performance projection of black phosphorus field-effect transistor technologies

In this work, an evaluation of the contact quality of black phosphorus field-effect transistors from different technologies previously reported is performed by means of an efficient and reliable contact resistance extraction methodology based on individual device practical characteristics. A good agreement is achieved between the extracted values with the Y-function method used here and reference values obtained with other methods considering internal values as well as with more expensive methods involving fabricated test structures. The method enables a direct evaluation of different steps in the same technology and it embraces the temperature dependence of the contact characteristics. Channel phenomena have no impact on the extracted contact resistance values. High-frequency performance projections are obtained for fabricated devices based on the extracted contact resistance.

Black phosphorus field effect transistors stable in harsh conditions via surface engineering

Black phosphorus (BP) has potential for fabricating p-type transistors in ultra-thin 2D-material complementary circuits. However, as the synergetic effect of water and oxygen leads to performance degradation under an ambient atmosphere, it is urgent to develop a passivation strategy for robust stability. Herein, a scalable superhydrophobic passivation layer is designed to improve the stability of BP transistors, which consists of fluoroalkylsilane-coated titanium dioxide (TiO2) nanoparticles. Due to the superhydrophobic property of the passivation layer, the BP transistors preserve intrinsic performance in extremely wet conditions, including humid air, water, HCl, and KOH. After 28 days in atmospheric conditions, the performance presents only 20% channel current degradation and the device can work even after 60 days. This work not only experimentally demonstrates robust stable BP transistors in harsh conditions but also provides a highly efficient and damage-free strategy to suppress the influence of water adsorption in atmospheric conditions for highly stable 2D materials devices.

In Situ Cleaning and Fluorination of Black Phosphorus for Enhanced Performance of Transistors with High Stability.

Most two-dimensional (2D) semiconductors suffer from intrinsic instability under ambient conditions, especially 2D black phosphorus (BP). Although much effort has been made to study the passivation of 2D materials against corrosion by oxygen and water molecules, facile and effective passivation with long-term stability is still challenging; in particular, selective passivation, which is critical for integration into nanoelectronics, is still lacking. Here, we develop a novel passivation route for BP using a fluorinated self-assembled thin film of PFSA (perfluorosulfonic acid, PFSA), where the surface modifier with high hydrophobicity on BP presents extremely stable characteristics over five months under ambient conditions. Moreover, we report for the first time in situ cleaning and selective fluorination of only BP flakes on a SiO2/Si substrate by a spin-coating process followed by ultrasonication, which was attributed to the formation of P-F covalent bonds on the BP surface. Selectively fluorinated BP shows not only enhanced stability in air but also electrical properties of the BP field-effect transistor (FET), with the on-current of the BP FET increasing and presenting enhanced carrier mobility (125 cm2 V-1 s-1) and on/off ratio (104). This significant finding sheds light on fabricating vertical 2D heterostructures to realize high performance and reliability with versatile 2D materials. This work demonstrates an emerging passivation approach for long-term stability together with superior electrical properties, which paves the way for integrating 2D semiconductors into critical channel materials in FETs that are favorable for next-generation digital logic circuits.

Native Oxide Seeded Spontaneous Integration of Dielectrics on Exfoliated Black Phosphorus.

Two-dimensional (2D) semiconductors have been a central focus for next-generation electronics and optoelectronics owing to their great potential to extend the scaling limits in a silicon transistor. However, due to the lack of surface dangling bonds in most 2D semiconductors, such as graphene and transition metal dichalcogenides (TMDs), the direct growth of the high-κ film on these 2D materials via an atomic layer deposition (ALD) technique often produces dielectrics with poor quality, which hinders their integration in the modern semiconductor industry. Here, we comprehensively investigate the ALD growth of the Al2O3 layer on 2D exfoliated black phosphorus (BP). Intriguingly, we found that the 2D BP with "silicon-like" characteristics possesses a native surface oxide layer PxOy after air exposure. The PxOy-induced surface dangling bonds enable the spontaneous integration of the high-quality Al2O3 layer on the BP flake without any pretreatments to functionalize the surface. Additionally, the Al2O3 layer could effectively passivate BP to prevent its degradation in ambient conditions, which addresses the most serious problem of the BP material. Moreover, the Al2O3-encapsulated BP field-effect transistor (FET) exhibits good electrical transport performance, with a high hole mobility of ∼420 cm2 V-1 s-1 and electron mobility of ∼80 cm2 V-1 s-1. Moreover, the high-quality Al2O3 layer can also be integrated into the top-gated BP transistor and inverter. Our findings reveal the silicon-like characteristics of BP for the high-κ ALD dielectric growth technology, which promises the seamless integration of 2D BP in the modern semiconductor industry.

Phase-Engineered Molybdenum Telluride/Black Phosphorus Van der Waals Heterojunctions for Tunable Multivalued Logic.

Recently, multivalued logic (MVL) circuits have attracted tremendous interest due to their ability to process more data by increasing the number of logic states rather than the integration density. Here, we fabricate logic circuits based on molybdenum telluride (MoTe2)/black phosphorus (BP) van der Waals heterojunctions with different structural phases of MoTe2. Owing to the different electrical properties of the 2H and mixed 2H +1T' phases of MoTe2, tunable logic devices have been realized. A logic circuit based on a BP field-effect transistor (FET) and a BP/MoTe2 (2H + 1T') heterojunction FET displays the characteristics of binary logic. However, a drain voltage-controlled transition from binary to ternary logic has been observed in BP FET- and BP/ MoTe2 (2H) heterojunction FET-based logic circuits. Also, a change from binary to ternary characteristics has been observed in BP/MoTe2 (2H)-based inverters at low temperature below 240 K. We believe that this work will stimulate the assessment of the structural phase transition in metal dichalcogenides toward advanced logic circuits and offer a pathway to substantialize the circuit standards for future MVL systems.