High-Performance 2D Ambipolar MoTe2 Lateral Memristors by Mild Oxidation.

2D transition metal dichalcogenides (TMDCs) have been intensively explored in memristors for brain-inspired computing. Oxidation, which is usually unavoidable and harmful in 2D TMDCs, could also be used to enhance their memristive performances. However, it is still unclear how oxidation affects the resistive switching behaviors of 2D ambipolar TMDCs. In this work, a mild oxidation strategy is developed to greatly enhance the resistive switching ratio of ambipolar 2H-MoTe2 lateral memristors by more than 10 times. Such an enhancement results from the amplified doping due to O2 and H2O adsorption and the optimization of effective gate voltage distribution by mild oxidation. Moreover, the ambipolarity of 2H-MoTe2 also enables a change of resistive switching direction, which is uncommon in 2D memristors. Consequently, as an artificial synapse, the MoTe2 device exhibits a large dynamic range (≈200) and a good linearity (1.01) in long-term potentiation and depression, as well as a high-accuracy handwritten digit recognition (>96%). This work not only provides a feasible and effective way to enhance the memristive performance of 2D ambipolar materials, but also deepens the understanding of hidden mechanisms for RS behaviors in oxidized 2D materials.

Full Two-Dimensional Ambipolar Field-Effect Transistors for Transparent and Flexible Electronics.

The unique features of two-dimensional (2D) materials provide significant opportunities for the development of transparent and flexible electronics. Recently, ambipolar 2D semiconductors have advanced innovative applications such as CMOS-like circuits, reconfigurable circuits, and ultrafast neuromorphic image sensors. Here, we report on the fabrication of full 2D ambipolar field-effect transistors (FETs), in which graphene serves as the source/drain/gate electrodes, WSe2 is for the channel, and h-BN is for the dielectric. The produced ambipolar FETs exhibit comparable on-currents in the n-branch and p-branch with on/off ratios up to 108. By using two ambipolar FETs in series, a CMOS-like inverter is demonstrated with a maximum gain of up to 147, which can work in both the first and third quadrants by controlling the supply voltages and input voltages. The full 2D ambipolar FETs yield a transmittance of over 70% for visible light on transparent glass and achieve a curvature radius of less than 0.5 cm for bending on polyethylene terephthalate (PET) substrate. The work is helpful for the application of ambipolar 2D materials-based devices in transparent and flexible electronics.

Controllable Modulation of the Electronic Properties of a Two-Dimensional Ambipolar Semiconductor by Interface Ferroelectric Polarization.

Precise control of charge carrier type and density of two-dimensional (2D) ambipolar semiconductors is the prerequisite for their applications in next-generation integrated circuits and electronic devices. Here, by fabricating a heterointerface between a 2D ambipolar semiconductor (hydrogenated germanene, GeH) and a ferroelectric substrate (PbMg1/3Nb2/3O3-PbTiO3, PMN-PT), fine-tuning of charge carrier type and density of GeH is achieved. Due to ambipolar properties, proper band gap, and high carrier mobility of GeH, by applying the opposite local bias (±8 V), a lateral polarization in GeH is constructed with a change of work function by 0.6 eV. Besides, the built-in polarization in GeH nanoflake could promote the separation of photoexcited electron-hole pairs, which lead to 4 times enhancement of the photoconductivity after poling by 200 V. In addition, a gradient regulation of the work function of GeH from 4.94 to 5.21 eV by adjusting the local substrate polarization is demonstrated, which could be used for data storage at the micrometer size by forming p-n homojunctions. This work of constructing such heterointerfaces provides a pathway for applying 2D ambipolar semiconductors in nonvolatile memory devices, photoelectronic devices, and next-generation integrated circuit.

Strategy for Fabricating Wafer-Scale Platinum Disulfide.

PtS2 is a newly developed group 10 2D layered material with high carrier mobility, wide band gap tunability, strongly bound excitons, symmetrical metallic and magnetic edge states, and ambient stability, making it attractive in nanoelectronic, optoelectronic, and spintronic fields. To the aim of application, a large-scale synthesis is necessary. For transition-metal dichalcogenide (TMD) compounds, a thermally assisted conversion method has been widely used to fabricate wafer-scale thin films. However, PtS2 cannot be easily synthesized using the method, as the tetragonal PtS phase is more stable. Here, we use a specified quartz part to locally increase the vapor pressure of sulfur in a chemical vapor deposition furnace and successfully extend this method for the synthesis of PtS2 thin films in a scalable and controllable manner. Moreover, the PtS and PtS2 phases can be interchangeably converted through a proposed strategy. Field-effect transistor characterization and photocurrent measurements suggest that PtS2 is an ambipolar semiconductor with a narrow band gap. Moreover, PtS2 also shows excellent gas-sensing performance with a detection limit of ∼0.4 ppb for NO2. Our work presents a relatively simple way of synthesizing PtS2 thin films and demonstrates their promise for high-performance ultrasensitive gas sensing, broadband optoelectronics, and nanoelectronics in a scalable manner. Furthermore, the proposed strategy is applicable for making other PtX2 compounds and TMDs which are compatible with modern silicon technologies.

Multisubstituted Azaisoindigo-Based Polymers for High-Mobility Ambipolar Thin-Film Transistors and Inverters.

Ambipolar semiconducting materials have great potential in complementary-like organic logic circuits. Accessing such logic circuits demands balanced hole and electron mobilities. However, the lack of ambipolar high-mobility polymer semiconductors with balanced charge carrier-transporting properties precludes the rapid development of organic logic circuits. In this context, structural modification of semiconductor materials to enhance the electron/hole transport is of great urgency. Herein, a multifunctionalization strategy is used to achieve this goal. Combined electron-withdrawing moieties involving fluorine and pyridinic nitrogen atoms can not only reduce the frontier molecular orbital energies but also planarize the polymer backbone, demonstrating synergetic effects on the control over the carrier injection process at the metal-semiconductor interface and microstructure-sensitive charge transport in the channel. A balanced ambipolar behavior with electron/hole mobilities of 3.88/3.44 cm2 V-1 s-1 was observed, and complementary-like inverters with high gains of greater than 200 were achieved. Microstructure and thin-film morphology were characterized to further reveal the relationship between device performances and macroscopic observables. This multifunctionalization strategy bodes well for developing new ambipolar semiconducting materials.

Orthogonal Ambipolar Semiconductors with Inherently Multi-Dimensional Responses for the Discriminative Sensing of Chemical Vapors.

Numerous examples of field-effect transistor (FET) biosensors and chemical sensors with good sensitivity and selectivity have now been developed. However, effectively discriminating between analytes has required either the use of receptors that selectively bind specific analytes or the fabrication of an array of sensors with varying but nonspecific responses. Both approaches exhibit significant limitations. In the first case, it can be difficult to design sufficiently specific receptors for many compounds, whereas the number of receptors required scales with the number of analytes to be detected, making it impractical to recognize many different compounds. In the second case, existing approaches to FET sensor arrays are generally material-inefficient and provide modest sensitivity. Here, we demonstrate that orthogonal ambipolar semiconductors consisting of semiconducting p-type polymers and n-type small-molecule nanowires with perpendicular in-plane orientations provide a platform with high sensitivity and inherently multi-dimensional response. This allows for discrimination between even closely related derivatives such as aromatic isomers and n-alkyl alcohols varying in length by a single carbon atom resolution using only a single sensor element.

Thiazole-Flanked Diketopyrrolopyrrole Polymeric Semiconductors for Ambipolar Field-Effect Transistors with Balanced Carrier Mobilities.

In this paper we report three thiazole-flanked diketopyrrolopyrrole-based donor-acceptor alternating copolymers as new ambipolar semiconductors and their field-effect transistor devices with balanced hole and electron mobilities. Nitrile groups are introduced into the polymer backbone, and the substituent effect on electronic structures is studied. Different side chains are also involved to tune the interdigitation of the polymers. To probe the structural effects that contribute to the device performances, we provide insight into the thin-film microstructures and morphologies. Top-gate bottom-contact transistors fabricated under ambient conditions exhibit the impressive balanced hole and electron mobilities as high as 1.46 and 1.14 cm2 V-1 s-1, respectively, which are among the highest values reported for ambipolar thiazole-flanked diketopyrrolopyrrole-based polymers. Additionally, this class of ambipolar polymers also shows promise for complementary-like inverters with a high gain value of 163.

Orthogonal Ambipolar Semiconductor Nanostructures for Complementary Logic Gates.

We report orthogonal ambipolar semiconductors that exhibit hole and electron transport in perpendicular directions based on aligned films of nanocrystalline "shish-kebabs" containing poly(3-hexylthiophene) (P3HT) and N,N'-di-n-octyl-3,4,9,10-perylenetetracarboxylic diimide (PDI) as p- and n-type components, respectively. Polarized optical microscopy, scanning electron microscopy, and X-ray diffraction measurements reveal a high degree of in-plane alignment. Relying on the orientation of interdigitated electrodes to enable efficient charge transport from either the respective p- or n-channel materials, we demonstrate semiconductor films with high anisotropy in the sign of charge carriers. Films of these aligned crystalline semiconductors were used to fabricate complementary inverter devices, which exhibited good switching behavior and a high noise margin of 80% of 1/2 Vdd. Moreover, complementary "NAND" and "NOR" logic gates were fabricated and found to exhibit excellent voltage transfer characteristics and low static power consumption. The ability to optimize the performance of these devices, simply by adjusting the solution concentrations of P3HT and PDI, makes this a simple and versatile method for preparing ambipolar organic semiconductor devices and high-performance logic gates. Further, we demonstrate that this method can also be applied to mixtures of PDI with another conjugated polymer, poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene]) (PBTTT), with better hole transport characteristics than P3HT, opening the door to orthogonal ambipolar semiconductors with higher performance.

Toward printed integrated circuits based on unipolar or ambipolar polymer semiconductors.

For at least the past ten years printed electronics has promised to revolutionize our daily life by making cost-effective electronic circuits and sensors available through mass production techniques, for their ubiquitous applications in wearable components, rollable and conformable devices, and point-of-care applications. While passive components, such as conductors, resistors and capacitors, had already been fabricated by printing techniques at industrial scale, printing processes have been struggling to meet the requirements for mass-produced electronics and optoelectronics applications despite their great potential. In the case of logic integrated circuits (ICs), which constitute the focus of this Progress Report, the main limitations have been represented by the need of suitable functional inks, mainly high-mobility printable semiconductors and low sintering temperature conducting inks, and evoluted printing tools capable of higher resolution, registration and uniformity than needed in the conventional graphic arts printing sector. Solution-processable polymeric semiconductors are the best candidates to fulfill the requirements for printed logic ICs on flexible substrates, due to their superior processability, ease of tuning of their rheology parameters, and mechanical properties. One of the strongest limitations has been mainly represented by the low charge carrier mobility (µ) achievable with polymeric, organic field-effect transistors (OFETs). However, recently unprecedented values of µ ∼ 10 cm(2) /Vs have been achieved with solution-processed polymer based OFETs, a value competing with mobilities reported in organic single-crystals and exceeding the performances enabled by amorphous silicon (a-Si). Interestingly these values were achieved thanks to the design and synthesis of donor-acceptor copolymers, showing limited degree of order when processed in thin films and therefore fostering further studies on the reason leading to such improved charge transport properties. Among this class of materials, various polymers can show well balanced electrons and holes mobility, therefore being indicated as ambipolar semiconductors, good environmental stability, and a small band-gap, which simplifies the tuning of charge injection. This opened up the possibility of taking advantage of the superior performances offered by complementary "CMOS-like" logic for the design of digital ICs, easing the scaling down of critical geometrical features, and achieving higher complexity from robust single gates (e.g., inverters) and test circuits (e.g., ring oscillators) to more complete circuits. Here, we review the recent progress in the development of printed ICs based on polymeric semiconductors suitable for large-volume micro- and nano-electronics applications. Particular attention is paid to the strategies proposed in the literature to design and synthesize high mobility polymers and to develop suitable printing tools and techniques to allow for improved patterning capability required for the down-scaling of devices in order to achieve the operation frequencies needed for applications, such as flexible radio-frequency identification (RFID) tags, near-field communication (NFC) devices, ambient electronics, and portable flexible displays.