Mass Production of Carbon Nanotube Transistor Biosensors for Point-of-Care Tests.

Low-dimensional semiconductor-based field-effect transistor (FET) biosensors are promising for label-free detection of biotargets while facing challenges in mass fabrication of devices and reliable reading of small signals. Here, we construct a reliable technology for mass production of semiconducting carbon nanotube (CNT) film and FET biosensors. High-uniformity randomly oriented CNT films were prepared through an improved immersion coating technique, and then, CNT FETs were fabricated with coefficient of performance variations within 6% on 4-in. wafers (within 9% interwafer) based on an industrial standard-level process. The CNT FET-based ion sensors demonstrated threshold voltage standard deviations within 5.1 mV at each ion concentration, enabling direct reading of the concentration information based on the drain current. By integrating bioprobes, we achieved detection of biosignals as low as 100 aM through a plug-and-play portable detection system. The reliable technology will contribute to commercial applications of CNT FET biosensors, especially in point-of-care tests.

Electric-Field-Driven Localization of Molecular Nanowires in Wafer-Scale Nanogap Electrodes.

As integrated circuits continue to scale toward the atomic limit, bottom-up processes, such as epitaxial growth, have come to feature prominently in their fabrication. At the same time, chemistry has developed highly tunable molecular semiconductors that can perform the functions of ultimately scaled circuit components. Hybrid techniques that integrate programmable structures comprising molecular components into devices however are sorely lacking. Here we demonstrate a wafer-scale process that directs the localization of a conductive polymer, Mw = 20 kg mol-1 polyaniline, from dilute solutions into 50 nm vertical nanogap device architectures using electric-field-driven self-assembly. The resulting metal-polymer-metal junctions were characterized by electron microscopy, Raman spectroscopy and transport measurements demonstrating that our technique is highly selective, assembling conductive polymers only in electrically activated nanogaps. Our results represent a step toward scalable hybrid nanoelectronics that seamlessly integrate established lithographic top-down fabrication with bottom-up synthesized molecular functional circuit components.

Wafer-Scale Atomic Assembly for 2D Multinary Transition Metal Dichalcogenides for Visible and NIR Photodetection.

The tunable properties of 2D transition-metal dichalcogenide (TMDs) materials are extensively investigated for high-performance and wavelength-tunable optoelectronic applications. However, the precise modification of large-scale systems for practical optoelectronic applications remains a challenge. In this study, a wafer-scale atomic assembly process to produce 2D multinary (binary, ternary, and quaternary) TMDs for broadband photodetection is demonstrated. The large-area growth of homogeneous MoS2, Ni0.06Mo0.26S0.68, and Ni0.1Mo0.9S1.79Se0.21 is carried out using a succinct coating of the single-source precursor and subsequent thermal decomposition combined with thermal evaporation of the chalcogen powder. The optoelectrical properties of the multinary TMDs are dependent on the combination of heteroatoms. The maximum photoresponsivity of the MoS2-, Ni0.06Mo0.26S0.68-, and Ni0.1Mo0.9S1.79Se0.21-based photodetectors is 3.51 × 10-4, 1.48, and 0.9 A W-1 for 532 nm and 0.063, 0.42, and 1.4 A W-1 for 1064 nm, respectively. The devices exhibited excellent photoelectrical properties, which is highly beneficial for visible and near-infrared (NIR) photodetection.

Synthesis of 2D Gallium Sulfide with Ultraviolet Emission by MOCVD.

Two-dimensional (2D) materials exhibit the potential to transform semiconductor technology. Their rich compositional and stacking varieties allow tailoring materials' properties toward device applications. Monolayer to multilayer gallium sulfide (GaS) with its ultraviolet band gap, which can be tuned by varying the layer number, holds promise for solar-blind photodiodes and light-emitting diodes as applications. However, achieving commercial viability requires wafer-scale integration, contrasting with established, limited methods such as mechanical exfoliation. Here the one-step synthesis of 2D GaS is introduced via metal-organic chemical vapor deposition on sapphire substrates. The pulsed-mode deposition of industry-standard precursors promotes 2D growth by inhibiting the vapor phase and on-surface pre-reactions. The interface chemistry with the growth of a Ga adlayer that results in an epitaxial relationship is revealed. Probing structure and composition validate thin-film quality and 2D nature with the possibility to control the thickness by the number of GaS pulses. The results highlight the adaptability of established growth facilities for producing atomically thin to multilayered 2D semiconductor materials, paving the way for practical applications.

Towards large scale integration of MoS2/graphene heterostructure with ALD-grown MoS2.

In the pursuit of ultrathin and highly sensitive photodetectors, a promising approach involves leveraging the combination of light-sensitive two-dimensional (2D) semiconducting transition-metal dichalcogenides, such as MoS2and the high electrical conductivity of graphene. Over the past decade, exfoliated 2D materials and electron-beam lithography have been used extensively to demonstrate feasibility on single devices. But for these devices to be used in the real-world systems, it is necessary to demonstrate good device performance similar to lab-based devices with repeatability of the results from device to device and a path to large scale manufacturing. To work in this way, a fabrication process of MoS2/graphene vertical heterostructures with a wafer-scale integration in a CMOS compatible foundry environment is evaluated here. Large-scale atomic layer deposition on 8 inch silicon wafers is used for the growth of MoS2layers which are then transferred on a 4 inch graphene-based wafer. The MoS2/graphene phototransistors are fabricated collectively, achieving a minimum channel length of 10µm. The results measured on dozen of devices demonstrate a photoresponsivity of 50 A W-1and a remarkable sensitivity as low as 10 nW at 660 nm. These results not only compete with lab-based photodetectors made of chemical vapor deposition grown MoS2layers transferred on graphene, but also pave the way for the large-scale integration of these emerging 2D heterostructures in optoelectronic devices and sensors.

Enhanced Transport and Optoelectronic Properties of van der Waals Materials on CaF2 Films.

To achieve better properties of van der Waals (vdW) devices, vdW heterointerfaces with substrates such as hexagonal boron nitride (h-BN) were introduced to alleviate adverse substrate effects. However, the premature dielectric breakdown and its scale limitation make wider application of h-BN substrates challenging. Here we report a fluoride-based substrate that substantially improves optoelectronic and transport properties of dichalcogenide devices, with enhancement factors comparable to those of h-BN. A model system of wafer-scale fluoride calcium (CaF2) ultrathin films with the preferable growth direction along [111] is prepared by the magnetron sputtering method. Results show that the constructed SnS2/CaF2 and WS2/CaF2 devices exhibit 1 order of magnitude higher than devices based on the SiO2 substrate in electronic mobility and photoresponsivity. Theoretical calculations reveal that devices based on fluoride substrates are immune from the Coulomb impurity scattering by forming quasi-vdW interfaces, exhibiting great potential for high responsivity and mobility of photogenerated carriers in 2D vdW devices.

Large-Area Flexible Memory Arrays of Oriented Molecular Ferroelectric Single Crystals with Nearly Saturated Polarization.

Molecular ferroelectrics (MFs) have been proven to demonstrate excellent properties even comparable to those of inorganic counterparts usually with heavy metals. However, the validation of their device applications is still at the infant stage. The polycrystalline feature of conventionally obtained MF films, the patterning challenges for microelectronics and the brittleness of crystalline films significantly hinder their development for organic integrated circuits, as well as emerging flexible electronics. Here, a large-area flexible memory array is demonstrated of oriented molecular ferroelectric single crystals (MFSCs) with nearly saturated polarization. Highly-uniform MFSC arrays are  prepared on large-scale substrates including Si wafers and flexible substrates using an asymmetric-wetting and microgroove-assisted coating (AWMAC) strategy. Resultant flexible memory arrays exhibit excellent nonvolatile memory properties with a low-operating voltage of <5 V, i.e., nearly saturated ferroelectric polarization (6.5 µC cm-2 ), and long bending endurance (>103 ) under various bending radii. These results may open an avenue for scalable flexible MF electronics with high performance.

Wafer-Scale Room-Temperature Bonding of Smooth Au/Ti-Based Getter Layer for Vacuum Packaging.

This study demonstrates room-temperature bonding using a getter layer for the vacuum packaging of microsystems. A thick Ti layer covered with an Au layer is utilized as a getter layer because it can absorb gas molecules in the package. Additionally, smooth Au surfaces can form direct bonds for hermetic sealing at room temperature. Direct bonding using a getter layer can simplify the vacuum packaging process; however, typical getter layers are rough in bonding formation. This study demonstrates two fabrication techniques for smooth getter layers. In the first approach, the Au/Ti layer is bonded to an Au layer on a smooth SiO2 template, and the Au/SiO2 interface is mechanically exfoliated. Although the root-mean-square roughness was reduced from 2.00 to 0.98 nm, the surface was still extremely rough for direct bonding. In the second approach, an Au/Ti/Au multilayer on a smooth SiO2 template is bonded with a packaging substrate, and the Au/SiO2 interface is exfoliated. The transferred Au/Ti/Au getter layer has a smooth surface with the root-mean-square roughness of 0.54 nm and could form wafer-scale direct bonding at room temperature. We believe that the second approach would allow a simple packaging process using direct bonding of the getter layer.

Wafer-Scale Production of Transition Metal Dichalcogenides and Alloy Monolayers by Nanocrystal Conversion for Large-Scale Ultrathin Flexible Electronics.

Two-dimensional (2D) transition metal dichalcogenide (TMD) layers are unit-cell thick materials with tunable physical properties according to their size, morphology, and chemical composition. Their transition of lab-scale research to industrial-scale applications requires process development for the wafer-scale growth and scalable device fabrication. Herein, we report on a new type of atmospheric pressure chemical vapor deposition (APCVD) process that utilizes colloidal nanoparticles as process-scalable precursors for the wafer-scale production of TMD monolayers. Facile uniform distribution of nanoparticle precursors on the entire substrate leads to the wafer-scale uniform synthesis of TMD monolayers with the controlled size and morphology. Composition-controlled TMD alloy monolayers with tunable bandgaps can be produced by simply mixing dual nanoparticle precursor solutions in the desired ratio. We also demonstrate the fabrication of ultrathin field-effect transistors and flexible electronics with uniformly controlled performance by using TMD monolayers.

Controllable Synthesis of Wafer-Scale Graphene Films: Challenges, Status, and Perspectives.

The availability of high-quality, large-scale, and single-crystal wafer-scale graphene films is fundamental for key device applications in the field of electronics, optics, and sensors. Synthesis determines the future: unleashing the full potentials of such emerging materials relies heavily upon their tailored synthesis in a scalable fashion, which is by no means an easy task to date. This review covers the state-of-the-art progress in the synthesis of wafer-scale graphene films by virtue of chemical vapor deposition (CVD), with a focus on main challenges and present status. Particularly, prevailing synthetic strategies are highlighted on a basis of the discussion in the reaction kinetics and gas-phase dynamics during CVD process. Perspectives with respect to key opportunities and promising research directions are proposed to guide the future development of wafer-scale graphene films.

Wafer-Scale Highly Oriented Monolayer MoS2 with Large Domain Sizes.

Two-dimensional molybdenum disulfide (MoS2) is an emergent semiconductor with great potential in next-generation scaled-up electronics, but the production of high-quality monolayer MoS2 wafers still remains a challenge. Here, we report an epitaxy route toward 4 in. monolayer MoS2 wafers with highly oriented and large domains on sapphire. Benefiting from a multisource design for our chemical vapor deposition setup and the optimization of the growth process, we successfully realized material uniformity across the entire 4 in. wafer and greater than 100 µm domain size on average. These monolayers exhibit the best electronic quality ever reported, as evidenced from our spectroscopic and transport characterizations. Our work moves a step closer to practical applications of monolayer MoS2.

Wafer-Scale Growth of Single-Crystal 2D Semiconductor on Perovskite Oxides for High-Performance Transistors.

Emerging two-dimensional (2D) semiconducting materials serve as promising alternatives for next-generation digital electronics and optoelectronics. However, large-scale 2D semiconductor films synthesized so far are typically polycrystalline with defective grain boundaries that could degrade their performance. Here, for the first time, wafer-size growth of a single-crystal Bi2O2Se film, which is a novel air-stable 2D semiconductor with high mobility, was achieved on insulating perovskite oxide substrates [SrTiO3, LaAlO3, (La, Sr)(Al, Ta)O3]. The layered Bi2O2Se epilayer exhibits perfect lattice matching and strong interaction with perovskite oxide substrates, which enable unidirectional alignment and seamless mergence of multiple seeds into single-crystal continuous films free of detrimental grain boundaries. The single-crystal Bi2O2Se thin films show excellent spatial homogeneity over the entire wafer and allow for the batch fabrication of high-performance field-effect devices with high mobilities of ∼150 cm2 V-1 s-1 at room temperature, excellent switching behavior with large on/off ratio of >105, and high drive current of ∼45 µA µm-1 at a channel length of ∼5 µm. Our work makes a step toward the practical applications of high-mobility semiconducting 2D layered materials and provides an alternative platform of oxide heterostructure to investigate novel physical phenomena.

Wafer-Scale Synthesis of Graphene on Sapphire: Toward Fab-Compatible Graphene.

The adoption of graphene in electronics, optoelectronics, and photonics is hindered by the difficulty in obtaining high-quality material on technologically relevant substrates, over wafer-scale sizes, and with metal contamination levels compatible with industrial requirements. To date, the direct growth of graphene on insulating substrates has proved to be challenging, usually requiring metal-catalysts or yielding defective graphene. In this work, a metal-free approach implemented in commercially available reactors to obtain high-quality monolayer graphene on c-plane sapphire substrates via chemical vapor deposition is demonstrated. Low energy electron diffraction, low energy electron microscopy, and scanning tunneling microscopy measurements identify the Al-rich reconstruction 31 × 31 R ± 9 ° of sapphire to be crucial for obtaining epitaxial graphene. Raman spectroscopy and electrical transport measurements reveal high-quality graphene with mobilities consistently above 2000 cm2 V-1 s-1 . The process is scaled up to 4 and 6 in. wafers sizes and metal contamination levels are retrieved to be within the limits for back-end-of-line integration. The growth process introduced here establishes a method for the synthesis of wafer-scale graphene films on a technologically viable basis.

Steep Switching of In0.18Al0.82N/AlN/GaN MIS-HEMT (Metal Insulator Semiconductor High Electron Mobility Transistors) on Si for Sensor Applications †.

InAlN/Al/GaN high electron mobility transistors (HEMTs) directly on Si with dynamic threshold voltage for steep subthreshold slope (<60 mV/dec) are demonstrated in this study, and attributed to displacement charge transition effects. The material analysis with High-Resolution X-ray Diffraction (HR-XRD) and the relaxation by reciprocal space mapping (RSM) are performed to confirm indium barrier composition and epitaxy quality. The proposed InAlN barrier HEMTs exhibits high ON/OFF ratio with seven magnitudes and a steep threshold swing (SS) is also obtained with SS = 99 mV/dec for forward sweep and SS = 28 mV/dec for reverse sweep. For GaN-based HEMT directly on Si, this study displays outstanding performance with high ON/OFF ratio and SS < 60 mV/dec behaviors.

Electrochemical Deposition of Conformal and Functional Layers on High Aspect Ratio Silicon Micro/Nanowires.

Development of new synthetic methods for the modification of nanostructures has accelerated materials design advances to furnish complex architectures. Structures based on one-dimensional (1D) silicon (Si) structures synthesized using top-down and bottom-up methods are especially prominent for diverse applications in chemistry, physics, and medicine. Yet further elaboration of these structures with distinct metal-based and polymeric materials, which could open up new opportunities, has been difficult. We present a general electrochemical method for the deposition of conformal layers of various materials onto high aspect ratio Si micro- and nanowire arrays. The electrochemical deposition of a library of coaxial layers comprising metals, metal oxides, and organic/inorganic semiconductors demonstrate the materials generality of the synthesis technique. Depositions may be performed on wire arrays with varying diameter (70 nm to 4 µm), pitch (5 µ to 15 µ), aspect ratio (4:1 to 75:1), shape (cylindrical, conical, hourglass), resistivity (0.001-0.01 to 1-10 ohm/cm2), and substrate orientation. Anisotropic physical etching of wires with one or more coaxial shells yields 1D structures with exposed tips that can be further site-specifically modified by an electrochemical deposition approach. The electrochemical deposition methodology described herein features a wafer-scale synthesis platform for the preparation of multifunctional nanoscale devices based on a 1D Si substrate.

Wafer-Scale Fabrication of Suspended Single-Walled Carbon Nanotube Arrays by Silver Liquid Dynamics.

Suspended single-walled carbon nanotubes (SWNTs) have advantages in mechanical resonators and highly sensitive sensors. Large-scale fabrication of suspended SWNTs array devices and uniformity among SWNTs devices remain a great challenge. This study demonstrates an effective, fast, and wafer-scale technique to fabricate suspended SWNT arrays, which is based on a dynamic motion of silver liquid to suspend and align the SWNTs between the prefabricated palladium electrodes in high temperature annealing treatment. Suspended, strained, and aligned SWNTs are synthesized on a 2 × 2 cm2 substrate with an average density of 10 tubes per micrometer. Under the optimal conditions, almost all SWNTs become suspended. A promising formation model of suspended SWNTs is established. The Kelvin four-terminal resistance measurement shows that these SWNT array devices have extreme low contact resistance. Meanwhile, the suspended SWNT array field effect transistors are fabricated by selective etching of metallic SWNTs using electrical breakdown. This method of large-scale fabrication of suspended architectures pushes the study of nanoscale materials into a new stage related to the electrical physics and industrial applications.

25 nm Single-Crystal Silicon Nanowires Fabricated by Anisotropic Wet Etching.

We report a top-down method for fabricating ultra-high aspect ratio single-crystal silicon nanowires. The fabrication method is based on the standard photolithography technique and anisotropic wet etching of the single-crystal silicon in KOH solution. SiO2 mask nanolines used for patterning single-crystal silicon nanowires are formed by the undercut etching of thin SiO2 layer in buffered hydrofluoric solution. The minimum width of the SiO2 mask nanolines are 50 nm. The length of SiO2 mask nanolines is 2 cm. The single-crystal silicon nanowires have been successfully transferred from the SiO2 mask nanolines by KOH anisotropic wet-chemical etching. The minimum width of the silicon nanowire has obtained to be 25 nm. The fabricated single-crystal silicon nanowires have trapezoidal and triangular cross sections, which are useful for applications in nanoelectronic and nanophotonic elements.

Encoding Active Device Elements at Nanowire Tips.

Semiconductor nanowires and other one-dimensional materials are attractive for highly sensitive and spatially confined electrical and optical signal detection in biological and physical systems, although it has been difficult to localize active electronic or optoelectronic device function at one end of such one-dimensional structures. Here we report a new nanowire structure in which the material and dopant are modulated specifically at only one end of nanowires to encode an active two-terminal device element. We present a general bottom-up synthetic scheme for these tip-modulated nanowires and illustrate this with the synthesis of nanoscale p-n junctions. Electron microscopy imaging verifies the designed p-Si nanowire core with SiO2 insulating inner shell and n-Si outer shell with clean p-Si/n-Si tip junction. Electrical transport measurements with independent contacts to the p-Si core and n-Si shell exhibited a current rectification behavior through the tip and no detectable current through the SiO2 shell. Electrical measurements also exhibited an n-type response in conductance versus water-gate voltage with pulsed gate experiments yielding a temporal resolution of at least 0.1 ms and ∼90% device sensitivity localized to within 0.5 µm from the nanowire p-n tip. In addition, photocurrent experiments showed an open-circuit voltage of 0.75 V at illumination power of ∼28.1 µW, exhibited linear dependence of photocurrent with respect to incident illumination power with an estimated responsivity up to ∼0.22 A/W, and revealed localized photocurrent generation at the nanowire tip. The tip-modulated concept was further extended to a top-down/bottom-up hybrid approach that enabled large-scale production of vertical tip-modulated nanowires with a final synthetic yield of >75% with >4300 nanowires. Vertical tip-modulated nanowires were fabricated into >50 individually addressable nanowire device arrays showing diode-like current-voltage characteristics. These tip-modulated nanowire devices provide substantial opportunity in areas ranging from biological and chemical sensing to optoelectronic signal and nanoscale photodetection.

Nonepitaxial Wafer-Scale Single-Crystal 2D Materials on Insulators.

Next-generation nanodevices require 2D material synthesis on insulating substrates. However, growing high-quality 2D-layered materials, such as hexagonal boron nitride (hBN) and graphene, on insulators is challenging owing to the lack of suitable metal catalysts, imperfect lattice matching with substrates, and other factors. Therefore, developing a generally applicable approach for realizing high-quality 2D layers on insulators remains crucial, despite numerous strategies being explored. Herein, a universal strategy is introduced for the nonepitaxial synthesis of wafer-scale single-crystal 2D materials on arbitrary insulating substrates. The metal foil in a nonadhered metal-insulator substrate system is almost melted by a brief high-temperature treatment, thereby pressing the as-grown 2D layers to well attach onto the insulators. High-quality, large-area, single-crystal, monolayer hBN and graphene films are synthesized on various insulating substrates. This strategy provides new pathways for synthesizing various 2D materials on arbitrary insulators and offers a universal epitaxial platform for future single-crystal film production.

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.