Anisotropic Superconducting Nb2 CTx MXene Processed by Atomic Exchange at the Wafer Scale.

Superconductivty has recently been induced in MXenes through surface modification. However, the previous reports have mostly been based on powders or cold-pressed pellets, with no known reports on the intrinsic superconsucting properties of MXenes at the nanoale. Here, it is developed a high-temperature atomic exchange process in NH3 atmosphere which induces superconductivity in either singleflakes or thin films of Nb2 CTx MXene. The exchange process between nitrogen atoms and fluorine, carbon, and oxygen atoms in the MXene lattice and related structural adjustments are studied using both experiments and density functional theory. Using either single-flake or thin-film devices, an anisotropic magnetic response of the 2D superconducting transformation has been successfully revealed. The anisotropic superconductivity is further demonstrated using superconducting thin films uniformly deposited over a 4 in. wafers, which opens up the possibility of scalable MXene-based superconducting devices.

Large-Area Metal-Semiconductor Heterojunctions Realized via MXene-Induced Two-Dimensional Surface Polarization.

Direct MXene deposition on large-area 2D semiconductor surfaces can provide design versatility for the fabrication of MXene-based electronic devices (MXetronics). However, it is challenging to deposit highly uniform wafer-scale hydrophilic MXene films (e.g., Ti3C2Tx) on hydrophobic 2D semiconductor channel materials (e.g., MoS2). Here, we demonstrate a modified drop-casting (MDC) process for the deposition of MXene on MoS2 without any pretreatment, which typically degrades the quality of either MXene or MoS2. Different from the traditional drop-casting method, which usually forms rough and thick films at the micrometer scale, our MDC method can form an ultrathin Ti3C2Tx film (ca. 10 nm) based on a MXene-introduced MoS2 surface polarization phenomenon. In addition, our MDC process does not require any pretreatment, unlike MXene spray-coating that usually requires a hydrophilic pretreatment of the substrate surface before deposition. This process offers a significant advantage for Ti3C2Tx film deposition on UV-ozone- or O2-plasma-sensitive surfaces. Using the MDC process, we fabricated wafer-scale n-type Ti3C2Tx-MoS2 van der Waals heterojunction transistors, achieving an average effective electron mobility of ∼40 cm2·V-1·s-1, on/off current ratios exceeding 104, and subthreshold swings of under 200 mV·dec-1. The proposed MDC process can considerably enhance the applications of MXenes, especially the design of MXene/semiconductor nanoelectronics.

Growth of 2D Materials at the Wafer Scale.

Wafer-scale growth has become a critical bottleneck for scaling up applications of van der Waal (vdW) layered 2D materials in high-end electronics and optoelectronics. Most vdW 2D materials are initially obtained through top-down synthesis methods, such as exfoliation, which can only prepare small flakes on a micrometer scale. Bottom-up growth can enable 2D flake growth over a large area. However, seamless merging of these flakes to form large-area continuous films with well-controlled layer thickness and lattice orientation is still a significant challenge. This review briefly introduces several vdW layered 2D materials covering their lattice structures, representative physical properties, and potential roles in large-scale applications. Then, several methods used to grow vdW layered 2D materials at the wafer scale are reviewed in depth. In particular, three strategies are summarized that enable 2D film growth with a single-crystalline structure over the whole wafer: growth of an isolated domain, growth of unidirectional domains, and conversion of oriented precursors. After that, the progress in using wafer-scale 2D materials in integrated devices and advanced epitaxy is reviewed. Finally, future directions in the growth and scaling of vdW layered 2D materials are discussed.

High-Yield Ti3 C2 Tx MXene-MoS2 Integrated Circuits.

It is very challenging to employ solution-processed conducting films in large-area ultrathin nanoelectronics. Here, spray-coated Ti3 C2 Tx MXene films as metal contacts are successfully integrated into sub-10 nm gate oxide 2D MoS2 transistor circuits. Ti3 C2 Tx films are spray coated on glass substrates followed by vacuum annealing. Compared to the as-prepared sample, vacuum annealed films exhibit a higher conductivity (≈11 000 S cm-1 ) and a lower work function (≈4.5 eV). Besides, the annealed Ti3 C2 Tx film can be patterned through a standard cleanroom process without peeling off. The annealed Ti3 C2 Tx film shows a better band alignment for n-type transport in MoS2 channel with small work function mismatch of 0.06 eV. The MoS2 film can be uniformly transferred on the patterned Ti3 C2 Tx surface and then readily processed through the cleanroom process. A large-area array of Ti3 C2 Tx MXene-MoS2 transistors is fabricated using different dielectric thicknesses and semiconducting channel sizes. High yield and stable performance for these transistor arrays even with an 8 nm-thick dielectric layer are demonstrated. Besides, several circuits are demonstrated, including rectifiers, negative-channel metal-oxide-semiconductor (NMOS) inverters, and voltage-shift NMOS inverters. Overall, this work indicates the tremendous potential for solution-processed Ti3 C2 Tx MXene films in large-area 2D nanoelectronics.

All-Solution-Processed Quantum Dot Electrical Double-Layer Transistors Enhanced by Surface Charges of Ti3C2Tx MXene Contacts.

Fully solution-processed, large-area, electrical double-layer transistors (EDLTs) are presented by employing lead sulfide (PbS) colloidal quantum dots (CQDs) as active channels and Ti3C2Tx MXene as electrical contacts (including gate, source, and drain). The MXene contacts are successfully patterned by standard photolithography and plasma-etch techniques and integrated with CQD films. The large surface area of CQD film channels is effectively gated by ionic gel, resulting in high performance EDLT devices. A large electron saturation mobility of 3.32 cm2 V-1 s-1 and current modulation of 1.87 × 104 operating at low driving gate voltage range of 1.25 V with negligible hysteresis are achieved. The relatively low work function of Ti3C2Tx MXene (4.42 eV) compared to vacuum-evaporated noble metals such as Au and Pt makes them a suitable contact material for n-type transport in iodide-capped PbS CQD films with a LUMO level of ∼4.14 eV. Moreover, we demonstrate that the negative surface charges of MXene enhance the accumulation of cations at lower gate bias, achieving a threshold voltage as low as 0.36 V. The current results suggest a promising potential of MXene electrical contacts by exploiting their negative surface charges.

Iontronics Using V2CTx MXene-Derived Metal-Organic Framework Solid Electrolytes.

Electronic applications of porous metal-organic frameworks (MOFs) have recently emerged as an important research area. However, there is still no report on using MOF solid electrolytes in iontronics, which could take advantage of the porous feature of MOFs in the ionic transport. In this article, MXene-derived two-dimensional porphyrinic MOF (MX-MOF) films are demonstrated as an electronic-grade proton-conducting electrolyte. Meanwhile, the MX-MOF film shows high quality, chemical stability, and capability of standard device patterning processes (e.g., dry etching and optical and electron beam lithography). Using the commercialized nanofabrication processes, an electric double-layer (EDL) transistor is demonstrated using the MX-MOF film (derived from V2CTx MXene) as an ionic gate and MoS2 film as a semiconducting channel layer. The EDL transistor, operated by applying an electric field to control the interaction between ions and electrons, is the core device platform in the emerging iontronics field. Therefore, The MX-MOF, confirmed as a solid electrolyte for EDL transistor devices, could have a significant impact on iontronics research and development.

Integration of Electrochemical Microsupercapacitors with Thin Film Electronics for On-Chip Energy Storage.

The development of self-powered electronic systems requires integration of on-chip energy-storage units to interface with various types of energy harvesters, which are intermittent by nature. Most studies have involved on-chip electrochemical microsupercapacitors that have been interfaced with energy harvesters through bulky Si-based rectifiers that are difficult to integrate. This study demonstrates transistor-level integration of electrochemical microsupercapacitors and thin film transistor rectifiers. In this approach, the thin film transistors, thin film rectifiers, and electrochemical microsupercapacitors share the same electrode material for all, which allows for a highly integrated electrochemical on-chip storage solution. The thin film rectifiers are shown to be capable of rectifying AC signal input from either triboelectric nanogenerators or standard function generators. In addition, electrochemical microsupercapacitors exhibit exceptionally slow self-discharge rate (≈18.75 mV h-1 ) and sufficient power to drive various electronic devices. This study opens a new avenue for developing compact on-chip electrochemical micropower units integrated with thin film electronics.

Transparent Electronics Using One Binary Oxide for All Transistor Layers.

A novel process is developed in which thin film transistors (TFTs) comprising one binary oxide for all transistor layers (gate, source/drain, semiconductor channel, and dielectric) are fabricated in a single deposition system at low temperature. By simply changing the flow ratio of two chemical precursors, C8 H24 HfN4 and (C2 H5 )2 Zn, in an atomic layer deposition system, the electronic properties of the binary oxide (Hf x Zn1- x O2- δ or HZO) are tuned from conducting, to semiconducting, to insulating. Furthermore, by carefully optimizing the properties of the various transistor HZO layers, all-HZO thin film transistors are achieved with excellent performance on both glass and plastic substrates. Specifically, the optimized all-HZO TFTs show a saturation mobility of ≈17.9 cm2 V-1 s-1 , low subthreshold swing of ≈480 mV dec-1 , high Ion /Ioff ratio of >109 , and excellent gate bias stability at elevated temperatures. In addition, all-HZO inverters with high DC voltage gain (≈470), and all-HZO ring oscillators with low stage delay (≈408 ns) and high oscillation frequency of 245 kHz are demonstrated. This approach presents a novel, simple, high performance, and cost-effective process for the fabrication of indium-free transparent electronics.

Transparent Flash Memory Using Single Ta2O5 Layer for Both Charge-Trapping and Tunneling Dielectrics.

We report reproducible multibit transparent flash memory in which a single solution-derived Ta2O5 layer is used simultaneously as a charge-trapping layer and a tunneling layer. This is different from conventional flash memory cells where two different dielectric layers are typically used. Under optimized programming/erasing operations, the memory device shows excellent programmable memory characteristics with a maximum memory window of ∼10.7 V. Moreover, the flash memory device shows a stable 2-bit memory performance and good reliability, including data retention for more than 104 s and endurance performance for more than 100 cycles. The use of a common charge-trapping and tunneling layer can simplify the fabrication of advanced flash memories.