Interface Doping for Ohmic Organic Semiconductor Contacts Using Self‐Aligned Polyelectrolyte Counterion Monolayer

Contact resistance limits the performance of organic field‐effect transistors, especially those based on high‐mobility semiconductors. Despite intensive research, the nature of this phenomenon is not well understood and mitigation strategies are largely limited to complex schemes often involving co‐evaporated doped interlayers. Here, this study shows that solution self‐assembly of a polyelectrolyte monolayer on a metal electrode can induce carrier doping at the contact of an organic semiconductor overlayer, which can be augmented by dopant ion‐exchange in the monolayer, to provide ohmic contacts for both p‐ and n‐type organic field‐effect transistors. The resultant 2D‐doped profile at the semiconductor interface is furthermore self‐aligned to the contact and stabilized against counterion migration. This study shows that Coulomb potential disordering by the polyelectrolyte shifts the semiconductor density‐of‐states into the gap to promote extrinsic doping and cascade carrier injection. Contact resistivities of the order of 0.1–1 Ω cm² or less have been attained. This will likely also provide a platform for ohmic injection into other advanced semiconductors, including 2D and other nanomaterials.     

Atomic Insight into Thermolysis‐Driven Growth of 2D MoS2

Understanding and controlling the transformations of transition metal dichalcogenides (TMDs) from amorphous precursors into two‐dimensional (2D) materials is important for guiding synthesis, directing fabrication, and tailoring functional properties. Here, the combined effects of thermal energy and electron beam irradiation are explored on the structural evolution of 2D MoS₂ flakes through the thermal decomposition of a (NH₄)₂MoS₄ precursor inside an ultrahigh vacuum (10^?9 Torr) scanning transmission electron microscope (STEM). The influence of reaction temperature, growth substrate, and the initial precursor morphology on the resulting 2D MoS₂ flake morphology, edge structures, and point defects are explored. Although thermal decomposition occurs extremely fast at elevated temperatures and is difficult to capture using current STEM techniques, electron beam irradiation can induce local transformations at lower temperatures, enabling direct observation and interpretation of critical growth steps including oriented attachment and transition from single‐ to multilayer structures at atomic resolution. An increase in the number of layers of the MoS₂ flakes from island growth is investigated using electron beam irradiation. These findings provide insight into the growth mechanisms and factors that control the synthesis of few‐layer MoS₂ flakes through thermolysis and toward the prospect of atomically precise control and growth of 2D TMDs.     

Dual Functionalization of Liquid‐Exfoliated Semiconducting 2H‐MoS2 with Lanthanide Complexes Bearing Magnetic and Luminescence Properties

Liquid exfoliated, atomically thin semiconducting transition metal dichalcogenides (TMDs), as inorganic equivalents of graphene, have attracted great interest due to their distinctive physical, optoelectronic, and chemical properties. Functionalization of 2D TMDs brings new prospects for applications in optoelectronics, quantum technologies, catalysis, and medicine. In this report, dual functionalization of 2D semiconducting 2H‐MoS₂ nanosheets through simultaneous incorporation of magnetic and luminescent properties is demonstrated. A facile method is proposed for tuning the properties of the TDM semiconductors and accessing multimodal platforms, consisting in covalent grafting of lanthanide complexes onto the surface of 2D TMDs. Dual functionalization of liquid‐exfoliated MoS₂ nanosheets is demonstrated simultaneously with both europium (III) and gadolinium (III) complexes to form a colloidally stable luminescent (with millisecond lifetimes) and paramagnetic MoS₂‐based nanohybrid material. This work is the first example of transition metal dichalcogenide nanosheets functionalized with preformed lanthanide complexes. These findings open new prospects for covalent functionalization of TMDs with molecular species bearing specific functionalities as a means to tune the optoelectronic properties of the semiconductors, in order to create advanced materials and devices with a wide range of functionalities.     

Mass Production of High‐Quality Transition Metal Dichalcogenides Nanosheets via a Molten Salt Method

2D transition metal dichalcogenides (TMDs) are well suited for energy storage and field–effect transistors because of their thickness‐dependent chemical and physical properties. However, as current synthetic methods for 2D TMDs cannot integrate both advantages of liquid‐phase syntheses (i.e., massive production and homogeneity) and chemical vapor deposition (i.e., high quality and large lateral size), it still remains a great challenge for mass production of high‐quality 2D TMDs. Here, a molten salt method to massively synthesize various high‐crystalline TMDs nanosheets (MoS₂, WS₂, MoSe₂, and WSe₂) with the thicknesses less than 5 nm is reported, with the production yield over 68% with the reaction time of only several minutes. Additionally, the thickness and size of the as‐synthesized nanosheets can be readily controlled through adjusting reaction time and temperature. The as‐synthesized MoSe₂ nanosheets exhibit good electrochemical performance as pseudocapacitive materials. It is further anticipates that this work will provide a promising strategy for rapid mass production of high‐quality nonoxides nanosheets for energy‐related applications and beyond.     

Piezo‐Phototronic Effect for Enhanced Flexible MoS2/WSe2 van der Waals Photodiodes

The recent discoveries of transition‐metal dichalcogenides (TMDs) as novel 2D electronic materials hold great promise to a rich variety of artificial van der Waals (vdWs) heterojunctions and superlattices. Moreover, most of the monolayer TMDs become intrinsically piezoelectric due to the lack of structural centrosymmetry, which offers them a new degree of freedom to interact with external mechanical stimuli. Here, fabrication of flexible vdWs p–n diode by vertically stacking monolayer n‐MoS₂ and a few‐layer p‐WSe₂ is achieved. Electrical measurement of the junction reveals excellent current rectification behavior with an ideality factor of 1.68 and photovoltaic response is realized. Performance modulation of the photodiode via piezo‐phototronic effect is also demonstrated. The optimized photoresponsivity increases by 86% when introducing a −0.62% compressive strain along MoS₂ armchair direction, which originates from realigned energy‐band profile at MoS₂/WSe₂ interface under strain‐induced piezoelectric polarization charges. This new coupling mode among piezoelectricity, semiconducting, and optical properties in 2D materials provides a new route to strain‐tunable vdWs heterojunctions and may enable the development of novel ultrathin optoelectronics.     

High‐Performance Transition Metal Dichalcogenide Photodetectors Enhanced by Self‐Assembled Monolayer Doping

Most doping research into transition metal dichalcogenides (TMDs) has been mainly focused on the improvement of electronic device performance. Here, the effect of self‐assembled monolayer (SAM)‐based doping on the performance of WSe₂‐ and MoS₂‐based transistors and photodetectors is investigated. The achieved doping concentrations are ≈1.4 × 10¹¹ for octadecyltrichlorosilane (OTS) p‐doping and ≈10¹¹ for aminopropyltriethoxysilane (APTES) n‐doping (nondegenerate). Using this SAM doping technique, the field‐effect mobility is increased from 32.58 to 168.9 cm² V^?1 s in OTS/WSe₂ transistors and from 28.75 to 142.2 cm² V^?1 s in APTES/MoS₂ transistors. For the photodetectors, the responsivity is improved by a factor of ≈28.2 (from 517.2 to 1.45 × 10⁴ A W^?1) in the OTS/WSe₂ devices and by a factor of ≈26.4 (from 219 to 5.75 × 10³ A W^?1) in the APTES/MoS₂ devices. The enhanced photoresponsivity values are much higher than that of the previously reported TMD photodetectors. The detectivity enhancement is ≈26.6‐fold in the OTS/WSe₂ devices and ≈24.5‐fold in the APTES/MoS₂ devices and is caused by the increased photocurrent and maintained dark current after doping. The optoelectronic performance is also investigated with different optical powers and the air‐exposure times. This doping study performed on TMD devices will play a significant role for optimizing the performance of future TMD‐based electronic/optoelectronic applications.     

Large‐Scale Fabrication of MoS2 Ribbons and Their Light‐Induced Electronic/Thermal Properties: Dichotomies in the Structural and Defect Engineering

Controlled design and patterning of layered transition metal dichalcogenides (TMDs) into specific dimensions and geometries hold great potential for next‐generation micro/nanoscale electronic applications. Herein, the large‐scale fabrication of MoS₂ ribbons with widths ranging from micro‐ to nanoscale is reported. Their unique electric and thermal properties introduced by the shape change and defect creation are also demonstrated, with particular focus on the performance associated with light–matter interactions. The theoretical calculation indicates significantly increased absorption and scattering efficiency of the MoS₂ ribbons with decreasing width. As a result, enhanced photocarrier generation ability is detected on their phototransistors with defect‐modulated light‐response behavior. The light‐induced thermal transport properties of the MoS₂ ribbons are further studied. A decreased thermal conductivity is observed on narrower ribbons, attributed to the defects created during fabrication. It is also found that the effect of phonon scattering at ribbon edges on their thermal conductivity is insignificant, and the thermal transport has no obvious dependence on the ribbon direction at such width scale. This study evaluates the prospects for designing and fabricating TMD semiconductors with specific geometries for future optoelectronic applications.     

High‐Performance Flexible Multilayer MoS2 Transistors on Solution‐Based Polyimide Substrates

Transition metal dichalcogenides (TMDs) layers of molecular thickness, in particular molybdenum disulfide (MoS₂), become increasingly important as active elements for mechanically flexible/stretchable electronics owing to their relatively high carrier mobility, wide bandgap, and mechanical flexibility. Although the superior electronic properties of TMD transistors are usually integrated into rigid silicon wafers or glass substrates, the achievement of similar device performance on flexible substrates remains quite a challenge. The present work successfully addresses this challenge by a novel process architecture consisting of a solution‐based polyimide (PI) flexible substrate in which laser‐welded silver nanowires are embedded, a hybrid organic/inorganic gate insulator, and multilayers of MoS₂. Transistors fabricated according to this process scheme have decent properties: a field‐effect‐mobility as high as 141 cm² V^?1 s^?1 and an I_on/I_off ratio as high as 5 × 10⁵. Furthermore, no apparent degradation in the device properties is observed under systematic cyclic bending tests with bending radii of 10 and 5 mm. Overall electrical and mechanical results provide potentially important applications in the fabrication of versatile areas of flexible integrated circuitry.     

Surface‐Shielding Nanostructures Derived from Self‐Assembled Block Copolymers Enable Reliable Plasma Doping for Few‐Layer Transition Metal Dichalcogenides

Precise modulation of electrical and optical properties of 2D transition metal dichalcogenides (TMDs) is required for their application to high‐performance devices. Although conventional plasma‐based doping methods have provided excellent controllability and reproducibility for bulk or relatively thick TMDs, the application of plasma doping for ultrathin few‐layer TMDs has been hindered by serious degradation of their properties. Herein, a reliable and universal doping route is reported for few‐layer TMDs by employing surface‐shielding nanostructures during a plasma‐doping process. It is shown that the surface‐protection oxidized polydimethylsiloxane nanostructures obtained from the sub‐20 nm self‐assembly of Si‐containing block copolymers can preserve the integrity of 2D TMDs and maintain high mobility while affording extensive control over the doping level. For example, the self‐assembled nanostructures form periodically arranged plasma‐blocking and plasma‐accepting nanoscale regions for realizing modulated plasma doping on few‐layer MoS₂, controlling the n‐doping level of few‐layer MoS₂ from 1.9 × 10¹¹ cm^?2 to 8.1 × 10¹¹ cm^?2 via the local generation of extra sulfur vacancies without compromising the carrier mobility.     

Morphology Engineering in Monolayer MoS2‐WS2 Lateral Heterostructures

In recent years, heterostructures formed in transition metal dichalcogenides (TMDs) have attracted significant attention due to their unique physical properties beyond the individual components. Atomically thin TMD heterostructures, such as MoS₂‐WS₂, MoS₂‐MoSe₂, MoS₂‐WSe₂, and WSe₂‐WS₂, are synthesized so far via chemical vapor deposition (CVD) method. Engineering the morphology of domains including size and shape, however, still remains challenging. Here, a one‐step CVD strategy on the morphology engineering of MoS₂ and WS₂ domains within the monolayer MoS₂‐WS₂ lateral heterostructures through controlling the weight ratio of precursors, MoO₃ and WO₃, as well as tuning the reaction temperature is reported. Not only can the size ratio in terms of area between WS₂ and MoS₂ domains be easily controlled from less than 1 to more than 20, but also the overall heterostructure size can be tuned from several to hundreds of micrometers. Intriguingly, the quantum well structure, a WS₂ stripe embedded in the MoS₂ matrix, is also observed in the as‐synthesized heterostructures, offering opportunities to study quantum confinement effects and quantum well applications. This approach paves the way for the large‐scale fabrication of MoS₂‐WS₂ lateral heterostructures with controllable domain morphology, and shall be readily extended to morphology engineering of other TMD heterostructures.     

Low Voltage and Ferroelectric 2D Electron Devices Using Lead‐Free BaxSr1‐xTiO3 and MoS2 Channel

Coupling between non‐toxic lead‐free high‐k materials and 2D semiconductors is achieved to develop low voltage field effect transistors (FETs) and ferroelectric non‐volatile memory transistors as well. In fact, low voltage switching ferroelectric memory devices are extremely rare in 2D electronics. Now, both low voltage operation and ferroelectric memory function have been successfully demonstrated in 2D‐like thin MoS₂ channel FET with lead‐free high‐k dielectric Ba_xSr_1‐xTiO₃ (BST) oxides. When the BST surface is coated with a 5.5‐nm‐ultrathin poly(methyl methacrylate) (PMMA)‐brush for improved roughness, the MoS₂ FET with BST (x = 0.5) dielectric results in an extremely low voltage operation at 0.5 V. Moreover, the BST with an increased Ba composition (x = 0.8) induces quite good ferroelectric memory properties despite the existence of the ultrathin PMMA layer, well switching the MoS₂ FET channel states in a non‐volatile manner with a ±3 V low voltage pulse. Since the employed high‐k dielectric and ferroelectric oxides are lead‐free in particular, the approaches for applying high‐k BST gate oxide for 2D MoS₂ FET are not only novel but also practical towards future low voltage nanoelectronics and green technology.     

Low‐Temperature‐Processed Printed Metal Oxide Transistors Based on Pure Aqueous Inks

Additive patterning of transparent conducting metal oxides at low temperatures is a critical step in realizing low‐cost transparent electronics for display technology and photovoltaics. In this work, inkjet‐printed metal oxide transistors based on pure aqueous chemistries are presented. These inks readily convert to functional thin films at lower processing temperatures (T ≤ 250 °C) relative to organic solvent‐based oxide inks, facilitating the fabrication of high‐performance transistors with both inkjet‐printed transparent electrodes of aluminum‐doped cadmium oxide (ACO) and semiconductor (InO_x ). The intrinsic fluid properties of these water‐based solutions enable the printing of fine features with coffee‐ring free line profiles and smoother line edges than those formed from organic solvent‐based inks. The influence of low‐temperature annealing on the optical, electrical, and crystallographic properties of the ACO electrodes is investigated, as well as the role of aluminum doping in improving these properties. Finally, the all‐aqueous‐printed thin film transistors (TFTs) with inkjet‐patterned semiconductor (InO_x ) and source/drain (ACO) layers are characterized, which show ideal low contact resistance (R _c < 160 Ω cm) and competitive transistor performance (µ _lin up to 19 cm² V^?1 s^?1, Subthreshold Slope (SS) ≤150 mV dec^?1) with only low‐temperature processing (T ≤ 250 °C).     

2D TMD Channel Transistors with ZnO Nanowire Gate for Extended Nonvolatile Memory Applications

2D transition metal dichalcogenides (TMDs) have been extensively studied due to their excellent physical properties. Mixed dimensional devices including 2D materials have also been studied, motivated by the possibility of any synergy effect from unique structures. However, only few such studies have been conducted. Here, semiconducting 1D ZnO nanowires are used as thin gate material to support 2D TMD field effect transistors (FETs) and 2D stack‐based interface trap nonvolatile memory. For the trap memory, deep level electron traps formed at the first MoS₂/second MoS₂ stack interface are exploited, since the first MoS₂ is treated in an atomic layer deposition chamber for a short while. On the one hand, a complementary inverter type memory device can also be achieved using a long single ZnO wire as a common gate to simultaneously support both n‐ and p‐channel TMD FETs. In addition, it is found that the semiconducting ZnO nanowire itself operates as an n‐type channel when the TMD materials can become a top‐gate to charge the ZnO channel. It means that 2D (bottom gated) and 1D channel (top gated) FETs are respectively operational in a single device structure. The 1D–2D mixed devices seem deserving broad attention in both aspects of novelty and functionality.     

Precise Single‐Step Electrophoretic Multi‐Sized Fractionation of Liquid‐Exfoliated Nanosheets

Transition metal dichalcogenides (TMDs) 2D nanomaterials' integration into the industry has been hampered by the ability to mass produce nanosheets of designed sizes. Large‐scale exfoliation is possible with liquid‐phase exfoliation, but precise subsequent isolation of a specified size dimension has yet to be realized. Herein, a precise and efficient method for both size fractionation and nanosheet retrieval is demonstrated using electrophoretic isolation of MoS₂ nanosheets in low melting agarose. This can be applied to find out the relative size distribution and sizes within a sample of MoS₂. Fractionation can be estimated visually by the relative spread of sizes based on their banding within the agarose. The additional degrees of freedom conferred by the agarose allow for more precise design and control over the size selection process. This serves as a quick and easy method of discerning and isolating the desired size range of MoS₂ for further downstream applications in a single step. Nanosheets separated by the procedure retain their structural properties and display size dependency shown empirically and theoretically. This technique is versatile and can be varied according to the needs. It may truly bring large‐scale isolation that much needed step closer to industrial scale production.     

Quantitative Analysis of Current–Voltage Characteristics of Semiconducting Nanowires: Decoupling of Contact Effects

A metal‐semiconductor‐metal (M‐S‐M) model for quantitative analysis of current–voltage (I–V) characteristics of semiconducting nanowires is described and applied to fit experimental I–V curves of Bi₂S₃ nanowire transistors. The I–V characteristics of semiconducting nanowires are found to depend sensitively on the contacts, in particular on the Schottky barrier height and contact area, and the M‐S‐M model is shown to be able to reproduce all experimentally observed I–V characteristics using only few fitting variables. A procedure for decoupling contact effects from that of the intrinsic parameters of the semiconducting nanowires, such as conductivity, carrier mobility and doping concentration is proposed, demonstrated using experimental I–V curves obtained from Bi₂S₃ nanowires and compared with the field‐effect based method.     

Graphene-Enhanced Metal Transfer Printing for Strong van der Waals Contacts between 3D Metals and 2D Semiconductors

2D semiconductors have shown great potentials for ultra-short channel field-effect transistors (FETs) in next-generation electronics. However, because of intractable surface states and interface barriers, it is challenging to realize high-quality contacts with low contact resistances for both p- and n- 2D FETs. Here, a graphene-enhanced van der Waals (vdWs) integration approach is demonstrated, which is a multi-scale (nanometer to centimeter scale) and reliable (≈100% yield) metal transfer strategy applicable to various metals and 2D semiconductors. Scanning transmission electron microscopy imaging shows that 2D/2D/3D semiconductor/graphene/metal interfaces are atomically flat, ultraclean, and defect-free. First principles calculations indicate that the sandwiched graphene monolayer can eliminate gap states induced by 3D metals in 2D semiconductors. Through this approach, Schottky barrier-free contacts are realized on both p- and n-type 2D FETs, achieving p-type MoTe₂, p-type black phosphorus and n-type MoS₂ FETs with on-state current densities of 404, 1520, and 761 µA µm⁻¹, respectively, which are among the highest values reported in literature.     

Tunable Room‐Temperature Synthesis of ReS2 Bicatalyst on 3D‐ and 2D‐Printed Electrodes for Photo‐ and Electrochemical Energy Applications

The advancement in 3D‐printing technologies conveniently offers boundless opportunities for the customization of a practical substrate or electrode for diverse functionalities. ReS₂ is an attractive transition metal dichalcogenide (TMD), showing strong photoelectrochemical activities. Two advanced systems are merged for the next step in electrochemistry—the limits of the prevailing synthesis techniques of TMDs operating at high temperature or low pressure, which are not compatible with 3D‐printed polymer electrodes that can withstand only comparatively low temperatures, are overcome. A unique NH₄ReS₄ precursor is separately prepared to conduct subsequent ReS₂ electrodeposition at room temperature on 3D‐printed carbon and 2D‐printed carbon electrodes. The deposited ReS₂ is investigated as a dual‐functional electro‐ and photocatalyst in hydrogen evolution reaction and photoelectrochemical oxidation of water. Moreover, the electrodeposition conditions can be adjusted to optimize the catalytic activities. These encouraging outcomes demonstrate the simplicity yet versatility of TMDs based on electrodeposition technique on a rationally designed conductive platform, which creates numerous possibilities for other TMDs and on other low‐temperature substrates for electrochemical energy devices.     

Transition Metal Dichalcogenide‐Based Transistor Circuits for Gray Scale Organic Light‐Emitting Displays

Two types of transition metal dichalcogenide (TMD) transistors are applied to demonstrate their possibility as switching/driving elements for the pixel of organic light‐emitting diode (OLED) display. Such TMD materials are 6 nm thin WSe₂ and MoS₂ as a p‐type and n‐type channel, respectively, and the pixel is thus composed of external green OLED and nanoscale thin channel field effect transistors (FETs) for switching and driving. The maximum mobility of WSe₂‐FETs either as switch or as driver is ≈30 cm² V^?1 s^?1, in linear regime of the gate voltage sweep range. Digital (ON/OFF‐switching) and gray‐scale analogue operations of OLED pixel are nicely demonstrated. MoS₂ nanosheet FET‐based pixel is also demonstrated, although limited to alternating gray scale operation of OLED. Device stability issue is still remaining for future study but TMD channel FETs are very promising and novel for their applications to OLED pixel because of their high mobility and I _D ON/OFF ratio.     

Performance enhancement of III–V compound multijunction solar cell incorporating transparent electrode and surface treatment

To enhance the performance of tandem‐type III–V compound multijunction solar cells, the transparent indium‐tin‐oxide (ITO) film was used to replace conventional metal electrode for increasing the incident light area. For performing ohmic contact between the n‐AlInP window layer and the ITO film, a transition layer of Au/AuGeNi thin metals was used and investigated. Besides, to improve ohmic performance and to passivate the surface states, (NH₄)₂S_x surface treatment was used. The conversion efficiency of the (NH₄)₂S_x‐treated triple‐junction solar cells was increased more than 3.09%. Furthermore, an improved oblique SiO₂/SiO₂/ITO triple antireflection structure was designed to reduce the reflectivity of illuminating sunlight. The conversion efficiency of the (NH₄)₂S_x‐treated triple‐junction solar cell with improved antireflection structure could be improved more than 4.23%. Simple and effective approaches were designed to improve the performances of tandem‐type III–V triple‐junction solar cells. Copyright © 2010 John Wiley & Sons, Ltd.     

An improved and simple parameter extraction method and scaling model for RF MOSFETs up to 40 GHz

In this article, a simple and efficient extraction procedure for the extrinsic gate, drain and source resistances is presented. The substrate network parameter, C _sub, dependent on the drain–source (V _ds) voltage is extracted in transistor cut-off region. The scaling rules of the extrinsic and intrinsic parameters are given in detail. Good agreement is obtained between the simulated and measured results for the 0.13?µm radio frequency metal oxide semiconductor field effect transistors in the frequency range of 0.1–40?GHz.