Large-area Synthesis Research Articles

A Universal Strategy for Synthesis of Large-Area and Ultrathin Metal Oxide/rGO Film Towards Scalable Fabrication of High-Performance Wearable Microsupercapacitors.

High-performance wearable microsupercapacitor (MSC) as energy storage components is highly desirable for developing self-powering wearable electronics. However, synthesis of MSC electrode film concurrently possessing large area, ultrathin thickness, and high areal energy storage capability is still challenging. Herein, a universal strategy is reported to synthesize large-area and ultrathin metal oxide nanoparticles (MONPs)/reduced graphene oxide (rGO) hybrid-structured films by attaching self-assembled film of a wide range of MONPs onto self-assembled rGO film and subsequent carbonization. Combining a template-assisted patterning strategy and a floating film salvaging process, flexible symmetric and asymmetric MSCs based on MONPs@C/rGO films can be easily prepared in large areas. MONP agglomeration is avoided and its pseudocapacitive behavior is well utilized, thereby realizing a high areal specific capacitance of 9.32 mF cm-2 in Fe3O4@C/rGO-based symmetric MSC at a film thickness of only 275 nm, corresponding to a high volumetric specific capacitance of 338.9 F cm-3. Moreover, the MnO@C/rGO‖Fe3O4@C/rGO-based asymmetric MSC delivers a high volumetric energy density of 69.8 mWh cm-3. The MSCs also demonstrate their efficient power supply in wearable self-powering systems. This work provides a new route for scalable preparation of high-performance wearable MSCs, and also enables customizable fabrication and performance tuning of MSCs.

Ambient Synthesis of Vanadium-Based Prussian Blue Analogues Nanocubes for High-Performance and Durable Aqueous Zinc-Ion Batteries with Eutectic Electrolytes.

Prussian blue analogues (PBAs) have been widely studied in aqueous zinc-ion batteries (AZIBs) due to the characteristics of large specific surface area, open aperture, and straightforward synthesis. In this work, vanadium-based PBA nanocubes were firstly prepared using a mild in situ conversion strategy at room temperature without the protection of noble gas. Benefiting from the multiple-redox active sites of V3+/V4+, V4+/V5+, and Fe2+/Fe3+, the cathode exhibited an excellent discharge specific capacity of 200 mAh g-1 in AZIBs, which is much higher than those of other metal-based PBAs nanocubes. To further improve the long-term cycling stability of the V-PBA cathode, a high concentration water-in-salt electrolyte (4.5 M ZnSO4+3 M Zn(OTf)2), and a water-based eutectic electrolyte (5.55 M glucose+3 M Zn(OTf)2) were designed to successfully inhibit the dissolution of vanadium and improve the deposition of Zn2+ onto the zinc anode. More importantly, the assembled AZIBs maintained 55 % of their highest discharge specific capacity even after 10000 cycles at 10 A g-1 with superior rate capability. This study provides a new strategy for the preparation of pure PBA nanostructures and a new direction for enhancing the long-term cycling stability of PBA-based AZIBs at high current densities for industrialization prospects.

Atomic Nb-doping of WS2 for high-performance synaptic transistors in neuromorphic computing

Owing to the controllable growth and large-area synthesis for high-density integration, interest in employing atomically thin two-dimensional (2D) transition-metal dichalcogenides (TMDCs) for synaptic transistors is increasing. In particular, substitutional doping of 2D materials allows flexible modulation of material physical properties, facilitating precise control in defect engineering for eventual synaptic plasticity. In this study, to increase the switch ratio of synaptic transistors, we selectively performed experiments on WS2 and introduced niobium (Nb) atoms to serve as the channel material. The Nb atoms were substitutionally doped at the W sites, forming a uniform distribution across the entire flakes. The synaptic transistor devices exhibited an improved switch ratio of 103, 100 times larger than that of devices prepared with undoped WS2. The Nb atoms in WS2 play crucial roles in trapping and detrapping electrons. The modulation of channel conductivity achieved through the gate effectively simulates synaptic potentiation, inhibition, and repetitive learning processes. The Nb-WS2 synaptic transistor achieves 92.30% recognition accuracy on the Modified National Institute of Standards and Technology (MNIST) handwritten digit dataset after 125 training iterations. This study’s contribution extends to a pragmatic and accessible atomic doping methodology, elucidating the strategies underlying doping techniques for channel materials in synaptic transistors.

Opto-electronic responses of large area WSe2 layers synthesized by chemical conversion of WO3 thin films

Atomically thin tungsten diselenide (WSe2) has drawn much interest due to its remarkable optical properties and potential applications in next-generation optoelectronics and energy harvesting devices. High-quality, wafer-scale synthesis of such two-dimensional (2D) semiconductors is necessary for their practical applications. Chemical vapor deposition (CVD) is a promising method for synthesizing large-area thin films of 2D materials where the constituent elements are of widely different vapor pressure. Herein, we demonstrate large-area synthesis of the 2H phase of WSe2 with a precise control over the 2D film thickness. The first step of this process is the deposition of tungsten trioxide (WO3) films of a well-defined thickness by thermal evaporation over large areas. The subsequent selenization of these films in an atmospheric pressure CVD reactor, yields high-quality uniform films of WSe2. The quality of these films is ascertained by measuring their characteristic Raman active vibrational modes and layer thickness dependent optical absorption and photoluminescence. The photoconductivity (PC) of these films has been measured with 405, 532 and 915 nm laser excitation. We note an increase in the PC of the films with their thickness. The best photoresponsivity and detectivity obtained are 11.3 mA/W and 1.42 × 108 Jones respectively. These results are promising to create photo-transistor arrays over large areas using such WO3 processed films.

(Invited) Low Temperature Atomic Layer Deposition Processes for Large-Area Synthesis of 2D Transition Metal Dichalcogenides

2D materials have been the focus of intense research in the last decade due to their unique physical properties. This presentation will highlight our recent progress on the large-area synthesis of two-dimensional transition metal chalcogenides for nanoelectronics using advanced atomic layer deposition cycle schemes. First, how we can use advanced cycle schemes to deposit wafer-scale polycrystalline MoS2 thin films at very low temperatures down to 100 °C. We have identified the critical role of hydrogen during the plasma step in controlling the composition and properties of molybdenum sulfide films. By increasing the H2/H2S ratio or adding an extra hydrogen plasma step to our ALD process, we are able to deposit pure polycrystalline MoS2 films at temperatures as low as 100 °C. To the best of our knowledge, this represents the lowest temperature for crystalline MoS2 films prepared by any chemical gas-phase method.[1]The most dominant methods for preparing MoS2 via ALD is to alternately expose a substrate to a metalorganic precursor and a hydrogen sulfide (H2S) or a plasma containing H2S. H2S is a corrosive, toxic, and flammable gas that is heavier than air, which makes it hazardous and expensive to store, install, and transport. Alternative sulfur precursors in the solid or liquid phase would be beneficial in terms of cost and safety and would require the installation of no additional hardware for most ALD reactors. In the second half of this contribution, the widely researched ALD process using bis(tert-butylimido)bis(dimethylamino)molybdenum(IV) ((tBuN)2(NMe2)2Mo) and H2S plasma is compared to a novel ALD process using (tBuN)2(NMe2)2Mo, hydrogen plasma, and di-tert-butyl disulfide (TBDS), which is an inexpensive, liquid-phase sulfur precursor.[1] M. Mattinen et al., Chem. Mater. (2022), 34, 5104

Development of Self-Doped Monolayered 2D MoS2 for Enhanced Photoresponsivity.

Transition metal dichalcogenides (TMDs) exist in two distinct phases: the thermodynamically stable trigonal prismatic (2H) and the metastable octahedral (1T) phase. Phase engineering has emerged as a potent technique for enhancing the performance of TMDs in optoelectronics applications. Nevertheless, understanding the mechanism of phase transition in TMDs and achieving large-area synthesis of phase-controlled TMDs continue to pose significant challenges. This study presents the synthesis of large-area monolayered 2H-MoS2 and mixed-phase 1T/2H-MoS2 by controlling the growth temperature in the chemical vapor deposition (CVD) method without use of a catalyst. The field-effect transistors (FETs) devices fabricated with 1T/2H-MoS2 mixed-phase show an on/off ratio of 107. Photo response devices fabricated with 1T/2H-MoS2 mixed-phase show ≈55 times enhancement in responsivity (from 0.32 to 17.4AW-1) and 102 times increase in the detectivity (from 4.1×1010 to 2.48×1012cmHzW-1) compare to 2H-MoS2. Introducing the metallic 1T phase within the 2H phase contributes additional carriers to the material, which prevents the electron-hole recombination and thereby increases the carrier density in the 1T/2H-MoS2 mixed-phase in comparison to 2H-MoS2. This work provides insights into the self-doping effects of 1T phase in 2H MoS2, enabling the tuning of 2D TMDs properties for optoelectronic applications.

Large-scale synthesis of defect-free phosphorene on nickel substrates: enabling atomistic thickness devices

Addressing the main challenges of defect-free, large-scale synthesis of low-dimensional materials composed of phosphorus atoms is essential for advancing promising phosphorene-based technologies. Using molecular dynamics simulation, we demonstrate the large-scale and defect-free synthesis of phosphorene on Nickel (Ni) substrates. We showed that substrate orientation is crucial in the controllable synthesis of different phosphorene allotropes. Specifically, blue phosphorene was successfully grown on Ni (111) and Ni (100) surfaces, while γ-phosphorene, referred to here as Navy phosphorene, was grown on Ni (110). In addition, temperature control (high temperature) and cooling rate (slow cooling) are also crucial in the formation of P6 hexagons. Finally, we report that the phosphorus pentamers (P5) are the essential precursor for phosphorene synthesis. This work provides a robust framework for understanding and controlling the synthesis of large-area, single-crystalline monolayer phosphorene.

Controlled epitaxial growth of strain-induced large-area bilayer MoS2 by chemical vapor deposition based on two-stage strategy

Two-dimensional (2D) bilayer transition metal dichalcogenides (TMDCs) have attracted considerable attention due to their promising applications in the fields of electronics, optoelectronics, valleytronics and nonlinear optics. However, the precise synthesis of large-area, high-yield and uniform bilayer MoS2 semiconductors remains a significant challenge. Herein, we have developed one two-stage chemical vapor deposition strategy based on strain engineering, enabling the controlled preparation of large-area (4 × 6 cm2) bilayer MoS2 nanostructures. Systematic characterizations indicate that compressive strain was introduced during the growth of first layer MoS2, which effectively induces the synthesis of the second layer MoS2. First-principles calculations based on density functional theory further reveal the mechanism of strain induced controllable growth of bilayer MoS2. Field-effect transistors based on AA and AB stacking bilayer MoS2 have been fabricated exhibiting excellent electronic properties. Our work provides a new pathway for the precise preparation of bilayer TMDCs nanostructures, offering experimental support for their application in the field of electronic and optoelectronic devices.

Epitaxial Growth of Large-Area Monolayers and van der Waals Heterostructures of Transition-Metal Chalcogenides via Assisted Nucleation.

The transition-metal chalcogenides include some of the most important and ubiquitous families of 2D materials. They host an exceptional variety of electronic and collective states, which can in principle be readily tuned by combining different compounds in van der Waals heterostructures. Achieving this, however, presents a significant materials challenge. The highest quality heterostructures are usually fabricated by stacking layers exfoliated from bulk crystals, which - while producing excellent prototype devices - is time consuming, cannot be easily scaled, and can lead to significant complications for materials stability and contamination. Growth via the ultra-high vacuum deposition technique of molecular-beam epitaxy (MBE) should be a premier route for 2D heterostructure fabrication, but efforts to achieve this are complicated by non-uniform layer coverage, unfavorable growth morphologies, and the presence of significant rotational disorder of the grown epilayer. This work demonstrates a dramatic enhancement in the quality of MBE grown 2D materials by exploiting simultaneous deposition of a sacrificial species from an electron-beam evaporator during the growth. This approach dramatically enhances the nucleation of the desired epi-layer, in turn enabling the synthesis of large-area, uniform monolayers with enhanced quasiparticle lifetimes, and facilitating the growth of epitaxial van der Waals heterostructures.

Ultrathin, large area β-Ni(OH)2 crystalline nanosheet as bifunctional electrode material for charge storage and oxygen evolution reaction

Bifunctional electrode materials are highly desirable for meeting increasing global energy demands and mitigating environmental impact. However, improving the atom-efficiency, scalability, and cost-effectiveness of storage systems, as well as optimizing conversion processes to enhance overall energy utilization and sustainability, remains a significant challenge for their application. Herein, we devised an optimized, facile, economic, and scalable synthesis of large area (cm2), ultrathin (∼2.9 ± 0.3 nm) electroactive nanosheet of β-Ni(OH)2, which acted as bifunctional electrode material for charge storage and oxygen evolution reaction (OER). The β-Ni(OH)2 nanosheet electrode shows the volumetric capacity of 2.82 Ah.cm−3(0.82 µAh.cm−2) at the current density of 0.2 mA.cm−2. The device shows a high capacity of 820 mAh.cm−3 with an ultrahigh volumetric energy density of 0.33 Wh.cm−3 at 275.86 W.cm−3 along with promising stability (30,000 cycles). Furthermore, the OER activity of ultrathin β-Ni(OH)2 exhibits an overpotential (η10) of 308 mV and a Tafel value of 42 mV dec-1 suggesting fast reaction kinetics. The mechanistic studies are enlightened through density functional theory (DFT), which reveals that additional electronic states near the Fermi level enhance activity for both capacitance and OER.

Large-Area Synthesis and Fabrication of Few-Layer hBN/Monolayer RGO Heterostructures for Enhanced Contact Surface Potential.

Hexagonal boron nitride (hBN) has a property similar to that of graphene, and it has become one of the most popular materials due to its flexible physical and chemical properties for a variety of applications, especially in nanoelectronics. Enhanced properties of hBN-based heterostructures are crucial for future electronic devices. In this work, a sheet-like hBN crystal was synthesized and transferred onto SiO2/Si substrate and reduced graphene oxide (RGO)/SiO2/Si substrate. Accordingly, the hBN and hBN/RGO films are investigated by optical microscopy, X-ray diffraction, high-resolution transmission electron microscopy, Raman spectroscopy, and atomic force microscopy. The thickness of a single hBN layer is approximately 0.4 nm. A few layers of hBN stacked in large areas are mostly observed in both hBN and the hBN/RGO films. By using Kelvin probe force microscopy, it was found that the hBN/RGO heterostructure has a contact surface potential higher than that of the hBN layer. The large-scale synthesis and fabrication of hBN/RGO films could be extended to fabricate other van der Waals heterostructures.

Fabrication of Large-Area Multi-Stimulus Responsive Thin Films via Interfacially Confined Irreversible Katritzky Reaction.

Fabrication of large-area thin films through irreversible reactions remains a formidable task. This study reports a breakthrough strategy for in situ synthesis of large-area, free-standing, robust and multi-stimulus responsive thin films through a catalyst-free and irreversible Katritzky reaction at a liquid-liquid interface. The as resulted films are featured with adjustable thickness of 1-3 μm and an area up to 50 cm2. The thin films exhibit fast photo-mechanical motions (a response time of ca 0.1 s), vapor-mechanical motions, as well as photo-chromic and solvato-chromic behaviors. It was revealed that the reason behind the observable motions is proton transfer from the imine groups to the carbonyl structures within the film induced by photo- and/or dimethyl sulfoxide-stimulus. In addition, the films can harvest anionic radicals and the radicals as captured can be efficiently degraded under UV light illumination. This study provides a new strategy for fabricating smart thin films via interfacially confined irreversible Katritzky reaction.

Unveiling the potential of vanadium-doped CVD-grown p-type MoS2 in vertical homojunction UV–Vis photodiodes

2D materials are a popular choice for the fabrication of p-n diodes for applications in integrated optoelectronics owing to their outstanding properties such as strong light-matter interactions, high mobility, and tunable band gap. The synthesis of monolayer and few-layer 2D materials with both p-type and n-type behavior is thus essential for the design and fabrication of such devices. However, the large-scale direct synthesis of p-type 2D materials is still a challenge as most of these materials are either n-type or ambipolar. Here, we report the successful synthesis of large-area, p-type MoS2 layers doped with vanadium on SiO2/Si substrates, achieving flake sizes >100 μm. By varying the concentration of the vanadium precursor, we precisely controlled the doping level, achieving vanadium atomic percentages ranging from 0.70 % to 1.57 %. Back gate field-effect transistors (FETs) were fabricated, enabling the tuning of device characteristics to exhibit ambipolar or p-type behavior. Moreover, a vertical p-n MoS2 homojunction was fabricated for rectification and optoelectronic applications, demonstrating a high responsivity of up to 978.1 A/W and a specific detectivity (D*) of 1.06 × 1012 Jones at λ = 365 nm with varied powers of the incident light source. This work demonstrates the role of vanadium as a dopant for tunable electrical transport behavior as well as for the fabrication of a photodiode, which can be used for high-performance optoelectronic devices in the future.

Uniform Synthesis of Bilayer Hydrogen Substituted Graphdiyne for Flexible Piezoresistive Applications.

Graphdiyne (GDY) has garnered significant attention as a cutting-edge 2D material owing to its distinctive electronic, optoelectronic, and mechanical properties, including high mobility, direct bandgap, and remarkable flexibility. One of the key challenges hindering the implementation of this material in flexible applications is its large area and uniform synthesis. The facile growth of centimeter-scale bilayer hydrogen substituted graphdiyne (Bi-HsGDY) on germanium (Ge) substrate is achieved using a low-temperature chemical vapor deposition (CVD) method. This material's field effect transistors (FET) showcase a high carrier mobility of 52.6cm2V-1s-1 and an exceptionally low contact resistance of 10Ωµm. By transferring the as-grown Bi-HsGDY onto a flexible substrate, a long-distance piezoresistive strain sensor is demonstrated, which exhibits a remarkable gauge factor of 43.34 with a fast response time of ≈275ms. As a proof of concept, communication by means of Morse code is implemented using a Bi-HsGDY strain sensor. It is believed that these results are anticipated to open new horizons in realizing Bi-HsGDY for innovative flexible device applications.

Understanding the growth mechanisms of γ-GeSe for polymorph-selective large-area deposition

This work unveils the pivotal roles of Au catalysts and substrates in the polymorph-selective, large-area synthesis of γ-GeSe. The demonstrated synthesis of γ-GeSe will advance energy storage and optoelectronics applications with the new polymorph.

Advancements in the Preparation and Application Research of TMDCs

Two-dimensional transition metal dichalcogenides(TMDCs)have been widely applied in the fields of light, electricity, magnetism, and heat due to their excellent physicochemical properties, including high photoluminescence quantum yield, outstanding thermal conductivity, good mechanical flexibility, and high charge carrier mobility. Tungsten disulfide (WS2) is a typical TMDCs, and optimizing its crystal structure and achieving high-quality large-area synthesis are of great significance for realizing its large-scale applications. This paper introduces the structure and electronic properties of tungsten disulfide, provides a comprehensive review of its main preparation methods, and summarizes its research progress in various application fields. Finally, the future development directions in the field of two-dimensional materials, including tungsten disulfide, are discussed, emphasizing the importance of further research and development to promote their widespread applications in various fields.

Heteroepitaxial Growth of Black Phosphorus on Tin Monosulfide.

Black phosphorus (Black P), a layered semiconductor with a layer-dependent bandgap and high carrier mobility, is a promising candidate for next-generation electronics and optoelectronics. However, the synthesis of large-area, layer-precise, single crystalline Black P films remains a challenge due to their high nucleation energy. Here, we report the molecular beam heteroepitaxy of single crystalline Black P films on a tin monosulfide (SnS) buffer layer grown on Au(100). The layer-by-layer growth mode enables the preparation of monolayer to trilayer films, with band gaps that reflect layer-dependent quantum confinement.

(Invited) Advanced Atomic Layer Deposition Cycle Schemes for Large-Area Synthesis of 2D Transition Metal Dichalcogenides

2D materials have been the focus of intense research in the last decade due to their unique physical properties. This presentation will highlight our recent progress on the large-area synthesis of two-dimensional transition metal chalcogenides for nanoelectronics using advanced atomic layer deposition cycle schemes. First, how we can use advanced cycle schemes to deposit wafer-scale polycrystalline MoS2 thin films at very low temperatures down to 100 °C. We have identified the critical role of hydrogen during the plasma step in controlling the composition and properties of molybdenum sulfide films. By increasing the H2/H2S ratio or adding an extra hydrogen plasma step to our ALD process, we are able to deposit pure polycrystalline MoS2 films at temperatures as low as 100 °C. To the best of our knowledge, this represents the lowest temperature for crystalline MoS2 films prepared by any chemical gas-phase method.[1]ALD-grown 2D films tend to exhibit a high density of out-of-plane 3D structures in addition to 2D horizontal layers. While the out-of-plane 3D structures are ideal for catalysis applications, the presence of such 3D structures can hinder charge transport, which hampers device applications. In this presentation I will show how we used mechanistic insight obtained by HRTEM to tune the shape and density of the 3D structures during plasma-enhanced ALD using advanced atomic layer deposition schems. The obtained morphology control was further confirmed by electrical measurements.[2]Earlier [3] we have shown that ALD is an excellent technique to make MoxW1-xS2 alloys with precise control over the alloy composition. Here, I will focus on how (plasma-enhanced) atomic layer deposition can aid in synthesizing doped 2DTMCs with precise control over the doping concentration by using elaborate ALD dosing schemes.[1] M. Mattinen et al., Chem. Mater. (2022), 34, 5104[2] S. Balasubramanyam, et al. ACS Appl. Mater. Interfaces (2020), 12, 3873[3] J. J. P. M. Schulpen et al. 2D Mater. (2022), 9, 025016

Effects of inorganic seed promoters on MoS2 few-layers grown via chemical vapor deposition

In the last years, transition metal dichalcogenides (TMDs), especially at the two-dimensional (2D) limit, gained a large interest due to their unique optical and electronic properties. Among them, MoS2 received great attention from the scientific community due to its versatility, workability, and applicability in a large number of fields such as electronics, optoelectronics and electrocatalysis. To open the possibility of 2D-MoS2 exploitation, its synthesis over large macroscopic areas using cost-effective methods is fundamental. In this study, we report a method for the synthesis of large-area (∼cm2) few-layers MoS2 via liquid precursor CVD (L-CVD), where the Mo precursor (i.e. ammonium heptamolybdate AHM) is provided via a solution that is spin-coated over the substrate. Given the capability of organic and inorganic molecules, such as alkaline salts, to enhance MoS2 growth, we investigated the action of different inorganic salts as seed promoters. In particular, by using visible Raman spectroscopy, we focused on the effect of Na(OH), KCl, KI, and Li(OH) on the thickness, morphology, uniformity and degree of coverage of the grown MoS2. We optimized the process tuning parameters such as the volume of spin-coated solution, the growth temperature, and the seed promoter concentration, to synthesise the lowest possible thickness which resulted to be 2 layers (2L) of the highest quality. We witnessed that the addition of an inorganic seed promoter in the solution improves the extension of the grown MoS2 promoting lateral growth front, and therefore the degree of coverage. From this study, we conclude that, amongst the investigated seed promoters, K-based salts proved to grant the growth of high-quality two-layer MoS2 with optimal and uniform coverage of the SiO2/Si substrate surface.

Low-Temperature Centimeter-Scale Growth of Layered 2D SnS for Piezoelectric Kirigami Devices.

Tin monosulfide (SnS) is a promising piezoelectric material with an intrinsically layered structure, making it attractive for self-powered wearable and stretchable devices. However, for practical application purposes, it is essential to improve the output and manufacturing compatibility of SnS-based piezoelectric devices by exploring their large-area synthesis principle. In this study, we report the chemical vapor deposition (CVD) growth of centimeter-scale two-dimensional (2D) SnS layers at temperatures as low as 200 °C, allowing compatibility with processing a range of polymeric substrates. The intrinsic piezoelectricity of 2D SnS layers directly grown on polyamides (PIs) was confirmed by piezoelectric force microscopy (PFM) phase maps and force-current corroborative measurements. Furthermore, the structural robustness of the centimeter-scale 2D SnS layers/PIs allowed for engraving complicated kirigami patterns on them. The kirigami-patterned 2D SnS layer devices exhibited intriguing strain-tolerant piezoelectricity, which was employed in detecting human body motions and generating photocurrents irrespective of strain rate variations. These results establish the great promise of 2D SnS layers for practically relevant large-scale device technologies with coupled electrical and mechanical properties.