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Chemical vapour deposition

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Abstract
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Chemical vapour deposition (CVD) is a powerful technology for producing high-quality solid thin films and coatings. Although widely used in modern industries, it is continuously being developed as it is adapted to new materials. Today, CVD synthesis is being pushed to new heights with the precise manufacturing of both inorganic thin films of 2D materials and high-purity polymeric thin films that can be conformally deposited on various substrates. In this Primer, an overview of the CVD technique, including instrument construction, process control, material characterization and reproducibility issues, is provided. By taking graphene, 2D transition metal dichalcogenides (TMDs) and polymeric thin films as typical examples, the best practices for experimentation involving substrate pretreatment, high-temperature growth and post-growth processes are presented. Recent advances and scaling-up challenges are also highlighted. By analysing current limitations and optimizations, we also provide insight into possible future directions for the method, including reactor design for high-throughput and low-temperature growth of thin films. This Primer on chemical vapour deposition summarizes current and emerging experimental set-ups as well as common characterization approaches used to determine thin film formation and quality as applied to graphene and other novel 2D materials.

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  • Research Article
  • Cite Count Icon 10
  • 10.1360/tb-2019-0696
Recent progress in two-dimensional transition metal<?A3B2 ACK?>dichalcogenides
  • Dec 31, 2019
  • Chinese Science Bulletin
  • Peiling Li + 9 more

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been emerged as a new class of van der Waals materials since the successful isolation of graphene. The strong spin-orbit coupling (SOC) and two-dimensionality give rise to plenty of novel physics including metal-insulator transition, charge density wave (CDW), valleytronics, quantum spin Hall effect, and unconventional superconductivity, which make TMDCs an ideal platform to study the fundamental physics and potential applications. In this review, we firstly introduce the crystal structure of 2D TMDCs materials. Then, we summarize the recent progress in the synthesis, novel physical properties, and applications of 2D TMDCs materials. Finally, a summary and an outlook on the topological superconductivity in this field are presented. 2D TMDCs have a chemical formula of MX2 (M=W, Mo and X=Te, Se, S) with a layered crystal structure. Depending on the coordination environments of M, TMDCs can crystallize in a variety of polytypic structures such as 2 H , 1 T , 1 T ′, and T d phases. In the monolayer 2 H -TMDCs, the breaking of an in-plane mirror symmetry and the presence of the out-of-plane mirror symmetry lead to an Ising spin–orbit coupling (SOC), which serves as an effective out-of-plane field acting on the copper pair and pins the electron spins to out-of-plane directions. This is called Ising superconductivity, which has been observed in gated MoS2, monolayer NbSe2 and TaS2. However, due to the inversion symmetry in monolayer 1 T ′-TMDCs, the introduction of SOC makes them a class of large-gap quantum spin Hall insulators such as monolayer 1 T ′-WTe2. Therefore, if we could consecutively tailor the TMDCs’ structure from 2 H to T d phase, the long-sought topological superconductivity may be realized in one substance by incorporating superconductivity and quantum spin Hall effect together. To explore the extraordinary physics and nanodevice applications, we develop a universal molten-salt-assisted chemical vapor deposition (CVD) method to prepare atomically thin TMDCs, including high-quality 2D superconductors such as monolayer MoTe2 and NbSe2. With the powerful sample growth technique , we demonstrate for the first time that a consecutive structural phase transition from T d to 1 T ′ to 2 H polytype can be realized by increasing the Se concentration in Se-substituted MoTe2. More importantly, the Se-substitution is found to dramatically enhance the superconductivity of the MoTe2 thin film, which is interpreted as the introduction of two-band superconductivity. Furthermore, in bilayer 1 T d-MoTe2, we find that the in-plane upper critical field goes beyond the Pauli paramagnetic limit and shows an emergent two-fold symmetry, which is different from the isotropic in-plane upper critical field in 2 H -TMDCs. We show that this is a result of a new type of asymmetric SOC in 1 T d-TMDCs, which has expanded the well-known Ising SOC. The polytypic structures and strong SOC in 2D TMDCs have led to a variety of novel physics and applications. Recent theoretical works have already shown that 2D TMDCs can be a platform to search for topological superconductivity. With the further development of sample preparation, 2D TMDCs will play an important role in realization of topological quantum computation.

  • Supplementary Content
  • Cite Count Icon 1
  • 10.1016/j.chempr.2021.10.018
Growing twisted bilayer graphene at small angles
  • Nov 1, 2021
  • Chem
  • Kanudha Sharda

Growing twisted bilayer graphene at small angles

  • Research Article
  • 10.1149/ma2017-01/16/991
(Invited) MOCVD of 2D Nanomaterials for Next-Generation Electronic and Optoelectronic Devices
  • Apr 15, 2017
  • Electrochemical Society Meeting Abstracts
  • Michael Heuken + 3 more

The international road map of semiconductors (ITRS) lists 2D materials as possible future materials for electronic devices [ITRS]. Among them, the semiconducting transition metal dichalcogenides (TMDC) like MoS2 or WS2 are the most promising ones. As the miniaturization of electronic devices continues and the sub-5 nm gate limit is reached, direct source-to-drain tunneling will become a problem in Si devices with conventional architecture. 2D TMDC as channel material for FET might overcome this issue in digital CMOS. The larger carrier effective masses of most TMDC result in reduced direct source-to-drain tunneling, while they also yield a large density of states and hence an increased ballistic current in this extreme dimensions [Fiori]. Additionally, the lower in-plane dielectric constants of TMDC enable a better vertical electrostatic control over the channel [Desai]. Still, TMDC will have to compete against other approaches, e.g. multiple-gate transistors [Schwiertz]. Beyond that, other properties of TMDC turn them interesting for future devices, such as their strong absorbance across the visible spectrum for optoelectronic devices [Lotsch]. The first photodetectors, electromluminescent p-n diodes and photovoltaic cells have already been shown [Lopez, Cheng, Tsai]. The excellent mechanical properties additionally enable the realization of different kinds of flexible devices [Schwiertz]. And last but not least, the integration of 2D materials into conventional 3D semiconductor concepts would be another application. For example, the strain originating from the large difference in lattice constants in a 3D heterostructure is often a challenge. Inserting 2D materials might be a solution. Due to the fully terminated surface of a TMDC monolayer, the binding to another material is of van-der-Waals type. Hence, TMDC can be stacked with materials with huge differences in lattice constants without leading to considerable strain or to interface trap densities [Vogel]. First devices with a combination of 2D and 3D materials have already been investigated [Krishna, Lee]. Large-scale fabrication of TMDC is still a challenge to be overcome. Up to now, the most frequently used techniques are either exfoliation of natural layered crystals or the growth via chemical vapor deposition (CVD). Exfoliation is a very time-consuming process with relatively low yield and reproducibility. In CVD, different gaseous precursors decompose on a substrate and react with each other. Thermally evaporated MoO3 and S are commonly used as precursors for the fabrication of MoS2 monolayers via CVD. This technique allows the deposition of monolayered crystallites with a size in the range of micrometers [Dumcenco]. The process is carried out in small experimental reactors, and a uniform deposition on a whole wafer is very challenging. The use of metalorganic precursors is one possibility to enter an industrial scale of fabrication. The development of III/V and II/VI semiconductors has shown that metalorganic chemical vapor deposition (MOCVD) makes controllable and reproducible processes feasible, which are easily scalable and hence suitable for large-area deposition. Additionally, the reactors are well-developed, and a future integration of 2D materials and other semiconductors is within reach. First publications show very good results on the deposition of MoS2 and WSe2 via MOCVD [Kang, Eichfeld]. But despite these works and first simulations of the growth kinetics [Nie], little is known about the growth mechanism. For this reason, we have started to investigate the deposition of 2D MoS2 on an AIXTRON MOCVD reactor.The experiments are carried out in a horizontal hot-wall MOCVD reactor in a 10 × 2 inch configuration. Molybdenum hexacarbonyl (MCO) and Di-tert-butyl sulfide (DTBS) are used as Mo and S sources, respectively. In preliminary experiments, the carrier gas based transport of the precursors into the reactor and possible growth conditions are tested. Their results are used to develop an initial growth process. This process leads to a uniform, wafer-scale deposition of MoS2 on various substrate types such as sapphire (0001), Si (111), and AlN and GaN templates on sapphire substrates. The deposited films mainly consists of MoS2 bilayers and exhibit a very high initial nucleation density. Further investigations of the influence of the growth temperature, the carrier gas composition and the pretreatment of the substrates are carried out. With optimization of these growth parameters, a crystal growth process closer to thermodynamical equilibrium can be achieved. This results in the formation of triangular crystals on sapphire substrates which are also reported from CVD processes and exhibit higher crystal quality [Dumcenco]. Additional experiments are conducted to investigate the nucleation of the films and to further tune nucleation density and lateral growth rate in order to deposit wafer-scale monolayered MoS2 films.

  • Research Article
  • Cite Count Icon 14
  • 10.1016/j.apsusc.2022.154772
Stepwise sulfurization of MoO3 to MoS2 thin films studied by real-time X-ray scattering
  • Sep 11, 2022
  • Applied Surface Science
  • Ashin Shaji + 12 more

Stepwise sulfurization of MoO3 to MoS2 thin films studied by real-time X-ray scattering

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  • Research Article
  • Cite Count Icon 51
  • 10.1007/s11467-023-1286-2
Recent developments in CVD growth and applications of 2D transition metal dichalcogenides
  • May 17, 2023
  • Frontiers of Physics
  • Hui Zeng + 6 more

Two-dimensional (2D) transition metal dichalcogenides (TMDs) with fascinating electronic energy band structures, rich valley physical properties and strong spin–orbit coupling have attracted tremendous interest, and show great potential in electronic, optoelectronic, spintronic and valleytronic fields. Stacking 2D TMDs have provided unprecedented opportunities for constructing artificial functional structures. Due to the low cost, high yield and industrial compatibility, chemical vapor deposition (CVD) is regarded as one of the most promising growth strategies to obtain high-quality and large-area 2D TMDs and heterostructures. Here, state-of-the-art strategies for preparing TMDs details of growth control and related heterostructures construction via CVD method are reviewed and discussed, including wafer-scale synthesis, phase transition, doping, alloy and stacking engineering. Meanwhile, recent progress on the application of multi-functional devices is highlighted based on 2D TMDs. Finally, challenges and prospects are proposed for the practical device applications of 2D TMDs.

  • Research Article
  • Cite Count Icon 12
  • 10.1016/j.apsusc.2023.158541
Role of defects in the photoluminescence and photoresponse of WS2–graphene heterodevices
  • Sep 22, 2023
  • Applied Surface Science
  • Min-Wen Yu + 8 more

Role of defects in the photoluminescence and photoresponse of WS2–graphene heterodevices

  • Research Article
  • Cite Count Icon 15
  • 10.1021/prechem.3c00115
Recent Advances in Spin-coating Precursor Mediated Chemical Vapor Deposition of Two-Dimensional Transition Metal Dichalcogenides.
  • Feb 13, 2024
  • Precision chemistry
  • Dingyi Shen + 11 more

Two-dimensional (2D) transition metal dichalcogenides (TMDs) have garnered widespread interest in the scientific community and industry for their exceptional physical and chemistry properties, and great potential for applications in diverse fields including (opto)electronics, electrocatalysis, and energy storage. Chemical vapor deposition (CVD) is one of the most compelling growth methods for the scalable growth of high-quality 2D TMDs. However, the conventional CVD process for synthesis of 2D TMDs still encounters significant challenges, primarily attributed to the high melting point of precursor powders, and achieving a uniform distribution of precursor atmosphere on the substrate to obtain controllable smaple domains is difficult. The spin-coating precursor mediated chemical vapor deposition (SCVD) strategy provides refinement over traditional methods by eliminating the use of solid precursors and ensuring a more clean and uniform distribution of the growth material on the substrate. Additionally, the SCVD process allows fine-tuning of material thickness and purity by manipulating solution composition, concentration, and the spin coating process. This Review presents a comprehensive summary of recent advances in controllable growth of 2D TMDs with a SCVD strategy. First, a series of various liquid precursors, additives, source supply methods, and substrate engineering strategies for preparing atomically thin TMDs by SCVD are introduced. Then, 2D TMDs heterostructures and novel doped TMDs fabricated through the SCVD method are discussed. Finally, the current challenges and perspectives to synthesize 2D TMDs using SCVD are discussed.

  • Research Article
  • Cite Count Icon 59
  • 10.1021/acs.accounts.1c00519
Functional Grain Boundaries in Two-Dimensional Transition-Metal Dichalcogenides.
  • Oct 31, 2021
  • Accounts of Chemical Research
  • Ping Man + 3 more

ConspectusTwo-dimensional (2D) transition-metal dichalcogenides (TMDs) are a class of promising low-dimensional materials with a variety of emergent properties which are attractive for next-generation electronic and optical devices; such properties include tunable band gaps, high electron mobilities, high exciton binding energies, excellent thermal stability and flexibility. During the synthesis process of these materials, especially chemical vapor deposition, defects such as grain boundaries (GBs) inevitably exist. GBs are the interfaces between differently oriented grains and are line defects in 2D crystals. While GBs can degrade the overall quality of 2D materials and adversely affect some of their electrical and mechanical properties, recent results show that GBs give rise to or enhance a wide range of unique electrical, mechanical, and chemical properties of the GBs in 2D TMDs. The effects of GBs on 2D material properties are complex and diverse, providing exciting opportunities to realize new functionalities by manipulating the local structure and properties. Notably, these effects are strongly related to atom types, dislocation cores, crystal misorientation at GBs, and both in- and out-of-plane deformation. The exploitation of GBs for novel applications requires a deepened understanding of synthesis, postprocessing, defect structures, GB properties, and GB structure-property relationships in 2D materials.In this Account, we first introduce a detailed classification of GBs in 2D TMDs based on atomic structure, symmetry, and the local coordination of both transition metals and chalcogenide atoms. The GB types in typical MoS2 (high-symmetry hexagonal structure) and ReS2 (low-symmetry monoclinic structure) are taken as examples. Next, we describe the properties of GBs in 2D TMDs, including thermodynamic and kinetic, mechanical, thermal, electrical, magnetic, chemical, and electrocatalysis properties as well as several application areas where these may be exploited. Here we provide systematic atomic-level and electronic level explanations of these properties to clarify their dependences on GB structures. Applications that extend from these properties, including functional electronics, chemical sensors, and electrocatalysts, are also described. Finally, we provide several perspectives and suggest promising opportunities for exploiting the novel properties of GBs in 2D TMDs. We expect that this Account will further stimulate the fundamental research of GBs and boost the wide application of multifunctional devices.

  • Research Article
  • Cite Count Icon 23
  • 10.1021/acsami.8b09378
Efficient Defect Healing of Transition Metal Dichalcogenides by Metallophthalocyanine.
  • Jul 25, 2018
  • ACS Applied Materials & Interfaces
  • Hyeyoung Ahn + 6 more

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have attracted great attention as alternatives to graphene with semiconducting band gaps. Mono- or few-layer TMDCs can be prepared by various methods, but regardless of the fabrication methods [such as mechanical exfoliation and chemical vapor deposition (CVD)], TMDCs contain many structural defects, which significantly affect their physical properties and limit their performance in applications. Metallophthalocyanines (MPcs) are organic semiconductors, and as dopants, they are capable of modulating the optical and electrical properties of other semiconducting materials. Here, we report that besides the ability to modulate the optoelectronic properties of 2D TMDCs, MPc molecules can be used to heal defects and improve the physicochemical properties of TMDCs. Doping of planar MPc molecules to TMDCs is achieved by a simple solution dip-coating method and results in a significant improvement in the optical properties and thermal responses of CVD-grown TMDCs, even comparable to those of mechanically exfoliated counterparts. Study of carrier dynamics shows that the adsorption of MPc on the TMDC surface leads to the complete suppression of the mid-gap defect-induced absorption in TMDCs. Furthermore, MPc molecules with a large lateral size are found to effectively reduce the point defects in mechanically exfoliated TMDCs introduced during the preparation process. Our results not only clarify the optoelectronic modulation mechanism of chemical doping but also offer a simple method to control the nanosized defects in 2D TMDCs.

  • Research Article
  • Cite Count Icon 31
  • 10.1021/acs.jpclett.1c02316
Theoretical Study of Chemical Vapor Deposition Synthesis of Graphene and Beyond: Challenges and Perspectives.
  • Aug 13, 2021
  • The Journal of Physical Chemistry Letters
  • Jichen Dong + 4 more

Two-dimensional (2D) materials have attracted great attention in recent years because of their unique dimensionality and related properties. Chemical vapor deposition (CVD), a crucial technique for thin-film epitaxial growth, has become the most promising method of synthesizing 2D materials. Different from traditional thin-film growth, where strong chemical bonds are involved in both thin films and substrates, the interaction in 2D materials and substrates involves the van der Waals force and is highly anisotropic, and therefore, traditional thin-film growth theories cannot be applied to 2D material CVD synthesis. During the last 15 years, extensive theoretical studies were devoted to the CVD synthesis of 2D materials. This Perspective attempts to present a theoretical framework for 2D material CVD synthesis as well as the challenges and opportunities in exploring CVD mechanisms. We hope that this Perspective can provide an in-depth understanding of 2D material CVD synthesis and can further stimulate 2D material synthesis.

  • Research Article
  • Cite Count Icon 29
  • 10.1021/accountsmr.3c00032
Solution-Processed 2D Transition Metal Dichalcogenides: Materials to CMOS Electronics
  • Jun 2, 2023
  • Accounts of Materials Research
  • Taoyu Zou + 1 more

ConspectusTwo-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs) have demonstrated exceptional potential as materials for future complementary metal-oxide-semiconductor (CMOS) technology. This is primarily because of their atomic thickness and excellent electrical and mechanical properties. With advancements in fabrication technology, electronic devices based on 2D TMD materials have rapidly progressed from isolated units for scientific experimentation to integrated circuits with practical applications. Among the different production methods, the solution-processing of 2D TMD nanomaterial dispersions offers the distinct advantages of low-temperature processing and cost-effective manufacturing for large-scale flexible and wearable electronics. A wide range of 2D nanoflake inks with versatile electronic properties can be assembled into atomic-thick thin films with dangling-bond-free van der Waals interfaces between adjacent nanoflakes. Furthermore, direct printing techniques can easily integrate multifunctional devices, such as n-type and p-type transistors, into CMOS devices and more complex integrated circuits. Despite these benefits and previous accomplishments, the field of solution-processed CMOS electronics using 2D TMD semiconducting materials is in its early stages of development and requires further research. One of the current challenges is the production of scalable and high-purity 2D semiconductor mono- and few layers with large lateral sizes and narrow thickness distribution. The field-effect mobility of solution-processed 2D TMD transistors remains lower than that of the transistors manufactured using mechanical exfoliation and chemical vapor deposition methods. In particular, limited research has been conducted on solution-processed p-type 2D TMD transistors. As a result, solution-processed CMOS devices using n-type and p-type 2D TMD transistors are scarce. In this Account, we provide an overview of the recent progress in the field of solution-processed CMOS electronics employing 2D TMD materials. First, we introduce the basic liquid exfoliation methods, such as sonication-assisted exfoliation and molecular intercalation methods, that are commonly utilized to prepare 2D TMD dispersions. In addition, we discuss the production of monolayer 2D materials, which serve as the building blocks for fabricating atomic-thick thin films. Subsequently, we review the typical techniques for depositing 2D inks, including spin coating, drop casting, and inkjet printing. Furthermore, we outline the thin-film patterning process for each technique, which is crucial for integrating multifunctional materials in CMOS devices. Subsequently, we focus on the recent advancements in solution-processed 2D TMD transistors. Furthermore, we explore the various factors that can improve the performance of the devices with regard to charge transport and charge traps. Afterward, we highlight notable applications of solution-processed CMOS technology, such as logic circuits and ring oscillators. Finally, we provide an overview of the challenges and opportunities in the development of solution-processed 2D materials and the integration of multifunctional devices for the advancement of CMOS electronics. This Account aims to provide a comprehensive guide for readers, offering both a broad overview and an in-depth insight into solution-processed 2D material-based electronics, covering a wide range of topics from the preparation of 2D TMD ink to device fabrication and CMOS applications. Therefore, this Account is expected to drive further progress and advancements in this field and promote the realization of practical applications.

  • Single Report
  • 10.2172/2335909
2D-EFICACY: Control of Metastable 2D Carbide[1]Chalcogenide Heterolayers: Strain and Moire Engineering
  • Apr 11, 2024
  • Mauricio Terrones + 1 more

The experimental isolation of graphene led to the discovery of an entirely new world of two-dimensional (2D) materials in which the 2D nature often leads to emergent behaviors not seen in bulk systems. 2D transition metal dichalcogenides (TMDs) exhibit physico-chemical properties that depend on the transition metal, polymorph, thickness, and presence and type of defects. Recently, a group of thin (10-100nm) transition metal carbides (TMCs), such as Mo2C, has been synthesized that exhibit a thickness-dependent superconducting critical temperature (Tc). These thin TMCs are different from MXenes, another class of 2D materials consisting of few layers of nitrides or carbides (<5nm) produced by chemical etching and delamination. The goal of this renewal proposal is to combine experiment and computation to synthesize and elucidate the guiding principles that control the growth, orientation and strain of heterostacks of thin TMCs and TMDs composed with Nb, Ti and W. We expect to stabilize metastable hybrid phases of TMCs sandwiched between TMDs (H-TMD/Cs) with unprecedented physico-chemical properties. As part of previous DOE-funded work by the Terrones/Sinnott groups, thin (10-100 nm thick) Mo2C flakes were successfully synthesized by chemical vapor deposition (CVD). By subsequently exposing Mo2C to H2S, partial chalcogenization was achieved, resulting in heterostacks of MoCx phases and MoS2. The formation of MoS2 led to a deficiency of Mo atoms in the underlying Mo2C, resulting in an inhomogeneous phase change from α-Mo2C to γ’-MoCx and then to γ-MoC. The γ’-MoCx is a strained metastable phase and the heterostack of all three phases demonstrated an increased Tc relative to that of α-Mo2C, from 4 to 6K; its interleaved layered structure consisting of superconducting and semiconducting phases is ideal for future studies of Josephson junction series arrays. Moiré patterns in these heterostacked systems could result in new phenomena, as moiré patterns in bilayer graphene showed unconventional superconductivity and moiré excitons have been observed in twisted TMD heterobilayers. The scientific hypothesis of the proposed synergistic computational and experimental research is that orientation and strain control within confined thin metastable TMCs, sandwiched by stable phases of TMCs and layered TMDs, will depend on kinetic and thermodynamic “knobs” that include fast temperature changes, chalcogen diffusion through preferred crystallographic planes, reaction times, pressure, reactive atmosphere, precursors, and surfactants, which will also tailor properties such as superconductivity, magnetism, ferroelectricity, piezoelectricity, and catalytic performance. We will develop the guiding principles for the synthesis and stabilization of metastable H-TMD/Cs based on Nb, Ti and W. In order to validate the hypothesis, four tasks are proposed: The first task will synthesize ultra-thin TMCs based on Nb, W and Ti, by: 1) adapting the CVD method used for Mo2C, 2) plasma assisted CVD, 3) defect-mediated CVD processes, and 4) cryo-milling of carbide powders. The second task will accomplish the synthesis and basic physico-chemical characterizations of H-TMD/Cs by chalcogenization of the materials synthesized in task one, and by carbonization of TMDs. H-TMD/Cs will also be investigated for their suitability in energy conversion applications such as supercapacitors, Li and multivalent ion batteries, and electrocatalysts, topics of interest to DoE. These tasks will be carried out in close conjunction with density functional theory (DFT) calculations with insights into energetics, lattice parameters, stability, phase diagrams, band structures, and density of states of H-TMD/Cs. The third task will characterize and evaluate strain and moiré patterns at the interfaces of different H-TMD/Cs by high-resolution scanning transmission electron microscopy (HR-STEM), scanning tunneling microscopy (STM), and conductive tip atomic force microscopy. Nudged elastic band calculations with DFT will be performed to understand the chalcogen diffusion process, which will provide insights into the interfaces between different phases of TMCs and TMDs. The fourth task aims at quantifying the stability and dynamics of H-TMD/Cs by in-situ TEM and Raman studies under heating, strain, and electrical biasing. Phonon calculations using DFT will provide a basis for interpreting Raman spectra. This coherent framework involving synthesis, characterization, and computation will result in a broad scientific impact for energy related applications. The ability to develop new H-TMD/Cs will enhance a range of applications that include batteries, catalysts, switches, sensors, quantum computing components and smart coatings.

  • Single Report
  • 10.2172/2335910
2D-EFICACY: Control of Metastable 2D Carbide Chalcogenide Heterolayers: Strain and Moire Engineering
  • Apr 11, 2024
  • Mauricio Terrones + 1 more

The experimental isolation of graphene led to the discovery of an entirely new world of two-dimensional (2D) materials in which the 2D nature often leads to emergent behaviors not seen in bulk systems. 2D transition metal dichalcogenides (TMDs) exhibit physico-chemical properties that depend on the transition metal, polymorph, thickness, and presence and type of defects. Recently, a group of thin (10-100nm) transition metal carbides (TMCs), such as Mo2C, has been synthesized that exhibit a thickness-dependent superconducting critical temperature (Tc). These thin TMCs are different from MXenes, another class of 2D materials consisting of few layers of nitrides or carbides (<5nm) produced by chemical etching and delamination. The goal of this renewal proposal is to combine experiment and computation to synthesize and elucidate the guiding principles that control the growth, orientation and strain of heterostacks of thin TMCs and TMDs composed with Nb, Ti and W. We expect to stabilize metastable hybrid phases of TMCs sandwiched between TMDs (H-TMD/Cs) with unprecedented physico-chemical properties. As part of previous DOE-funded work by the Terrones/Sinnott groups, thin (10-100 nm thick) Mo2C flakes were successfully synthesized by chemical vapor deposition (CVD). By subsequently exposing Mo2C to H2S, partial chalcogenization was achieved, resulting in heterostacks of MoCx phases and MoS2. The formation of MoS2 led to a deficiency of Mo atoms in the underlying Mo2C, resulting in an inhomogeneous phase change from α-Mo2C to γ’-MoCx and then to γ-MoC. The γ’-MoCx is a strained metastable phase and the heterostack of all three phases demonstrated an increased Tc relative to that of α-Mo2C, from 4 to 6K; its interleaved layered structure consisting of superconducting and semiconducting phases is ideal for future studies of Josephson junction series arrays. Moiré patterns in these heterostacked systems could result in new phenomena, as moiré patterns in bilayer graphene showed unconventional superconductivity and moiré excitons have been observed in twisted TMD heterobilayers. The scientific hypothesis of the proposed synergistic computational and experimental research is that orientation and strain control within confined thin metastable TMCs, sandwiched by stable phases of TMCs and layered TMDs, will depend on kinetic and thermodynamic “knobs” that include fast temperature changes, chalcogen diffusion through preferred crystallographic planes, reaction times, pressure, reactive atmosphere, precursors, and surfactants, which will also tailor properties such as superconductivity, magnetism, ferroelectricity, piezoelectricity, and catalytic performance. We will develop the guiding principles for the synthesis and stabilization of metastable H-TMD/Cs based on Nb, Ti and W. In order to validate the hypothesis, four tasks are proposed: The first task will synthesize ultra-thin TMCs based on Nb, W and Ti, by: 1) adapting the CVD method used for Mo2C, 2) plasma assisted CVD, 3) defect-mediated CVD processes, and 4) cryo-milling of carbide powders. The second task will accomplish the synthesis and basic physico-chemical characterizations of H-TMD/Cs by chalcogenization of the materials synthesized in task one, and by carbonization of TMDs. H-TMD/Cs will also be investigated for their suitability in energy conversion applications such as supercapacitors, Li and multivalent ion batteries, and electrocatalysts, topics of interest to DoE. These tasks will be carried out in close conjunction with density functional theory (DFT) calculations with insights into energetics, lattice parameters, stability, phase diagrams, band structures, and density of states of H-TMD/Cs. The third task will characterize and evaluate strain and moiré patterns at the interfaces of different H-TMD/Cs by high-resolution scanning transmission electron microscopy (HR-STEM), scanning tunneling microscopy (STM), and conductive tip atomic force microscopy. Nudged elastic band calculations with DFT will be performed to understand the chalcogen diffusion process, which will provide insights into the interfaces between different phases of TMCs and TMDs. The fourth task aims at quantifying the stability and dynamics of H-TMD/Cs by in-situ TEM and Raman studies under heating, strain, and electrical biasing. Phonon calculations using DFT will provide a basis for interpreting Raman spectra. This coherent framework involving synthesis, characterization, and computation will result in a broad scientific impact for energy related applications. The ability to develop new H-TMD/Cs will enhance a range of applications that include batteries, catalysts, switches, sensors, quantum computing components and smart coatings.

  • Research Article
  • Cite Count Icon 5
  • 10.1360/n972019-00236
Strain regulation of two-dimensional transition metal dichalcogenides
  • May 20, 2019
  • Chinese Science Bulletin
  • Lu Zhou + 1 more

As layered materials beyond graphene discovered after 2004, two-dimensional (2D) transition metal dichalcogenides (TMDs) are vital to fundamental research and practical applications, owing to their unique crystal structures and excellent properties, as well as diversity of the electronic band structures. 2D TMDs have played an important role in electronics, optoelectronics, energy storage and catalysis. To meet with the increasing requirements of programmable and function-integrated devices, property modulation could be concerned as one of the most essential strategies for 2D TMDs. In comparison with conventional external electrical field induction, strain regulation could be much more efficient. In detail, external induction through the electrical field leads to the electron delocalization along the field direction and then induces the transformation of band structures, but electrical field exhibits small modulation for monolayer TMDs. On the contrary, the strain regulation shows excellent tuning efficiency for continuous and reversible modulation. As a result, the strain regulation has become a commonly-used strategy for property tuning of 2D TMDs. On the basis of the lattice transformation, the strain regulation of 2D TMDs can lead to different overlapping of d and p orbits of metal and chalcogen atoms, and then affect the electronic structures of 2D TMDs. Therefore, it can be applied to electronics, optoelectronics, magnetic devices and piezoelectronics. The strategies of introducing strains to 2D TMDs are classified into lattice induction, local deformation, macroscopic regulation and so on. Lattice induction is attributable to the structural distortions and mismatches, including atomic defect induction and lattice mismatch induction. The former one demonstrates that the microenvironment affected by atomic vacancies and doping atoms can introduce strain to 2D TMDs. The latter one means that the lattice mismatches between two materials (between two different TMDs in a heterostructure or between a TMD and the substrate) can result in lattice distortion and then induce the strain. However, strain introduced through lattice induction is fixed and difficult to achieve the reversible modulation. Local deformation refers to the morphological transformation at the scale of several micrometers, which can be induced by the bubbles and wrinkles of 2D TMDs, external forces of tips, as well as patterned substrates. Generally, large but nonuniform strain can be introduced to 2D TMDs through the local deformation, which results in the funnel effects and then induces large property variation. Furthermore, macroscopic regulation introduces the strains to the lattices, including the deformation of flexible substrates (bend, tension and compression), external pressure (applied by the diamond anvil cell) and thermal expansion coefficient mismatch. Macroscopic regulation would be compatible with industrial manufacture to achieve strain regulation on an extremely large scale in the future. There are some other ways to achieve strain regulation such as the design of special stack structures and the induction of the external electrical field. After summarizing the methods of introducing strain to 2D TMDs, we presented the applications based on strain regulation, such as field effect transistors, flexible photodetectors and strain sensors. Finally, we pointed out the further development and challenges of strain regulation of 2D TMDs.

  • Research Article
  • Cite Count Icon 3
  • 10.1016/j.tsf.2020.137943
Growth of 2D-molybdenum disulfide on top of magnetite and iron by chemical methods
  • Mar 13, 2020
  • Thin Solid Films
  • Federico Motti + 6 more

Growth of 2D-molybdenum disulfide on top of magnetite and iron by chemical methods

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