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2D Materials and Van der Waals Heterostructures: Physics and Applications

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A special issue of Nanomaterials (ISSN 2079-4991).

Deadline for manuscript submissions: closed (31 May 2019) | Viewed by 73663

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Prof. Dr. Antonio Di Bartolomeo

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Department of Physics “E.R. Caianiello”, University of Salerno, 84084 Fisciano, Italy
Interests: optical and electrical properties of nanostructured materials such as carbon nanotubes, graphene, and 2D materials; van der Waals heterostructures and Schottky junctions; field-effect transistors; non-volatile memories; solar cells; photodetectors; field emission devices
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Dear Colleagues,

The advent of graphene, and more recently of layered 2D materials, has opened new perspectives in electronics, optoelectronics, energy harvesting and sensing applications. Layered 2D materials can be fabricated with relatively inexpensive production methods, integrated into existing semiconductor technologies, and offer new physical, chemical and mechanical properties. Electrically they can behave as metals, semiconductors, insulators or even superconductors. Consisting of covalently bonded and dangling-bond free lattices, they can form heterojunctions with each other or with bulk materials, without the need of a close lattice matching. In these heterojunctions, the participant materials are held together by weak van der Waals forces, which do not introduce significant changes at the atomic scale and essentially maintain the original electronic structure of the materials. Hence, van der Waals heterojunctions offer the opportunity to combine layers with different properties as the building blocks to engineer new functional materials for high-performance device or sensor applications. A great advantage is that the easy stacking of a variety of 2D materials allows a far greater number of combinations than any traditional growth method.

A great deal of work has been done thus far on the synthesis and characterization of layered 2D materials, such as graphene, transition metal dichalcogenides, hexagonal boron nitride, black phosphorus, silicene, organic perovskites, etc. Many of them have been used to fabricate stacked 2D-2D heterostructures, 2D/3D heterojunctions with common bulk semiconductors, such as Si, GaA, SiC or even 0D-2D and 1D-2D hybrids. The underlying physics and the possible applications in photodetection, biochemical sensing, strain gauges, photovoltaic energy generation or energy harvesting has been attracting the attention of both theorists and experimentalists.

The purpose of the present Special Issue is to collect state-of-the-art work on layered 2D materials and, in particular, on their van der Waals heterojunctions, both from a fundamental and application perspective. Review articles or research papers dealing with the fabrication and the properties of 2D materials and of their van der Waals heterojunctions, or with their use in electronic devices and sensors, are solicited and welcomed.

Prof. Antonio Di Bartolomeo
Guest Editor

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Keywords

2D Materials: graphene, transition metal dichalcogenide, black phosphorus, silicene, germanene, hexagonal boron nitride
Van der Waals heterojunctions
Schottky and PN junctions
Van der Waals photodiodes and phototransistors
Field effect transistors
Van der Waals tunneling devices and vertical transistors
Memory devices
Bio-chemical sensors
Photovoltaic solar cells
Energy harvesting devices and supercapacitors
Ohmic and Schottky contacts

Published Papers (13 papers)

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Editorial

Jump to: Research

10 pages, 247 KiB

Open AccessEditorial

Emerging 2D Materials and Their Van Der Waals Heterostructures

by Antonio Di Bartolomeo

Nanomaterials 2020, 10(3), 579; https://doi.org/10.3390/nano10030579 - 22 Mar 2020

Cited by 90 | Viewed by 5957

Abstract

Two-dimensional (2D) materials and their van der Waals heterojunctions offer the opportunity to combine layers with different properties as the building blocks to engineer new functional materials for high-performance devices, sensors, and water-splitting photocatalysts. A tremendous amount of work has been done thus far to isolate or synthesize new 2D materials as well as to form new heterostructures and investigate their chemical and physical properties. This article collection covers state-of-the-art experimental, numerical, and theoretical research on 2D materials and on their van der Waals heterojunctions for applications in electronics, optoelectronics, and energy generation. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

Research

Jump to: Editorial

10 pages, 2884 KiB

Open AccessArticle

Graphene Schottky Junction on Pillar Patterned Silicon Substrate

by Giuseppe Luongo, Alessandro Grillo, Filippo Giubileo, Laura Iemmo, Mindaugas Lukosius, Carlos Alvarado Chavarin, Christian Wenger and Antonio Di Bartolomeo

Nanomaterials 2019, 9(5), 659; https://doi.org/10.3390/nano9050659 - 26 Apr 2019

Cited by 24 | Viewed by 3784

Abstract

A graphene/silicon junction with rectifying behaviour and remarkable photo-response was fabricated by transferring a graphene monolayer on a pillar-patterned Si substrate. The device forms a 0.11 eV Schottky barrier with 2.6 ideality factor at room temperature and exhibits strongly bias- and temperature-dependent reverse current. Below room temperature, the reverse current grows exponentially with the applied voltage because the pillar-enhanced electric field lowers the Schottky barrier. Conversely, at higher temperatures, the charge carrier thermal generation is dominant and the reverse current becomes weakly bias-dependent. A quasi-saturated reverse current is similarly observed at room temperature when the charge carriers are photogenerated under light exposure. The device shows photovoltaic effect with 0.7% power conversion efficiency and achieves 88 A/W photoresponsivity when used as photodetector. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

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17 pages, 4252 KiB

Open AccessArticle

Designing a Novel Monolayer β-CSe for High Performance Photovoltaic Device: An Isoelectronic Counterpart of Blue Phosphorene

by Qiang Zhang, Yajuan Feng, Xuanyu Chen, Weiwei Zhang, Lu Wu and Yuexia Wang

Nanomaterials 2019, 9(4), 598; https://doi.org/10.3390/nano9040598 - 11 Apr 2019

Cited by 7 | Viewed by 3460

Abstract

Using the first-principles method, an unmanufactured structure of blue-phosphorus-like monolayer CSe (β-CSe) was predicted to be stable. Slightly anisotropic mechanical characteristics in β-CSe sheet were discovered: it can endure an ultimate stress of 5.6 N/m at 0.1 along an armchair direction, and 5.9 N/m at 0.14 along a zigzag direction. A strain-sensitive transport direction was found in β-CSe, since β-CSe, as an isoelectronic counterpart of blue phosphorene (β-P), also possesses a wide indirect bandgap that is sensitive to the in-plane strain, and its carrier effective mass is strain-dependent. Its indirect bandgap character is robust, except that armchair-dominant strain can drive the indirect-direct transition. We designed a heterojunction by the β-CSe sheet covering α-CSe sheet. The band alignment of the α-CSe/β-CSe interface is a type-II van der Waals p-n heterojunction. An appreciable built-in electric field across the interface, which is caused by the charges transfering from β-CSe slab to α-CSe, renders energy bands bending, and it makes photo-generated carriers spatially well-separated. Accordingly, as a metal-free photocatalyst, α-CSe/β-CSe heterojunction was endued an enhanced solar-driven redox ability for photocatalytic water splitting via lessening the electron-hole-pair recombination. This study provides a fundamental insight regarding the designing of the novel structural phase for high-performance light-emitting devices, and it bodes well for application in photocatalysis. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

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12 pages, 3434 KiB

Open AccessArticle

Facile and Controllable Synthesis of Large-Area Monolayer WS₂ Flakes Based on WO₃ Precursor Drop-Casted Substrates by Chemical Vapor Deposition

by Biao Shi, Daming Zhou, Shaoxi Fang, Khouloud Djebbi, Shuanglong Feng, Hongquan Zhao, Chaker Tlili and Deqiang Wang

Nanomaterials 2019, 9(4), 578; https://doi.org/10.3390/nano9040578 - 09 Apr 2019

Cited by 25 | Viewed by 4831

Abstract

Monolayer WS₂ (Tungsten Disulfide) with a direct-energy gap and excellent photoluminescence quantum yield at room temperature shows potential applications in optoelectronics. However, controllable synthesis of large-area monolayer WS₂ is still challenging because of the difficulty in controlling the interrelated growth parameters. Herein, we report a facile and controllable method for synthesis of large-area monolayer WS₂ flakes by direct sulfurization of powdered WO₃ (Tungsten Trioxide) drop-casted on SiO₂/Si substrates in a one-end sealed quartz tube. The samples were thoroughly characterized by an optical microscope, atomic force microscope, transmission electron microscope, fluorescence microscope, photoluminescence spectrometer, and Raman spectrometer. The obtained results indicate that large triangular monolayer WS₂ flakes with an edge length up to 250 to 370 μm and homogeneous crystallinity were readily synthesized within 5 min of growth. We demonstrate that the as-grown monolayer WS₂ flakes show distinctly size-dependent fluorescence emission, which is mainly attributed to the heterogeneous release of intrinsic tensile strain after growth. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

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10 pages, 4801 KiB

Open AccessArticle

Strain-Tunable Visible-Light-Responsive Photocatalytic Properties of Two-Dimensional CdS/g-C₃N₄: A Hybrid Density Functional Study

by Guangzhao Wang, Feng Zhou, Binfang Yuan, Shuyuan Xiao, Anlong Kuang, Mingmin Zhong, Suihu Dang, Xiaojiang Long and Wanli Zhang

Nanomaterials 2019, 9(2), 244; https://doi.org/10.3390/nano9020244 - 12 Feb 2019

Cited by 46 | Viewed by 3761

Abstract

By means of a hybrid density functional, we comprehensively investigate the energetic, electronic, optical properties, and band edge alignments of two-dimensional (2D) CdS/g-C

_{3}

_{4}

heterostructures by considering the effect of biaxial strain and pH value, so as to improve the photocatalytic [...] Read more.

By means of a hybrid density functional, we comprehensively investigate the energetic, electronic, optical properties, and band edge alignments of two-dimensional (2D) CdS/g-C

_{3}

_{4}

heterostructures by considering the effect of biaxial strain and pH value, so as to improve the photocatalytic activity. The results reveal that a CdS monolayer weakly contacts with g-C

_{3}

_{4}

, forming a type II van der Waals (vdW) heterostructure. The narrow bandgap makes CdS/g-C

_{3}

_{4}

suitable for absorbing visible light and the induced built-in electric field between the interface promotes the effective separation of photogenerated carriers. Through applying the biaxial strain, the interface adhesion energy, bandgap, and band edge positions, in contrast with water, redox levels of CdS/g-C

_{3}

_{4}

can be obviously adjusted. Especially, the pH of electrolyte also significantly influences the photocatalytic performance of CdS/g-C

_{3}

_{4}

. When pH is smaller than 6.5, the band edge alignments of CdS/g-C

_{3}

_{4}

are thermodynamically beneficial for oxygen and hydrogen generation. Our findings offer a theoretical basis to develop g-C

_{3}

_{4}

-based water-splitting photocatalysts. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

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11 pages, 1079 KiB

Open AccessArticle

High Sensitivity Surface Plasmon Resonance Sensor Based on Two-Dimensional MXene and Transition Metal Dichalcogenide: A Theoretical Study

by Yi Xu, Yee Sin Ang, Lin Wu and Lay Kee Ang

Nanomaterials 2019, 9(2), 165; https://doi.org/10.3390/nano9020165 - 29 Jan 2019

Cited by 131 | Viewed by 7653

Abstract

MXene, a new class of two-dimensional nanomaterials, have drawn increasing attention as emerging materials for sensing applications. However, MXene-based surface plasmon resonance sensors remain largely unexplored. In this work, we theoretically show that the sensitivity of the surface plasmon resonance sensor can be [...] Read more.

{Ti}_{3} C_{2} T_{x}

MXene and transition metal dichalcogenides. A high sensitivity of

198^{\circ}

/RIU (refractive index unit) with a sensitivity enhancement of 41.43% was achieved in aqueous solutions (refractive index ∼1.33) with the employment of monolayer

{Ti}_{3} C_{2} T_{x}

MXene and five layers of

{WS}_{2}

at a 633 nm excitation wavelength. The integration of

{Ti}_{3} C_{2} T_{x}

MXene with a conventional surface plasmon resonance sensor provides a promising approach for bio- and chemical sensing, thus opening up new opportunities for highly sensitive surface plasmon resonance sensors using two-dimensional nanomaterials. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

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13 pages, 3820 KiB

Open AccessArticle

Two Dimensional β-InSe with Layer-Dependent Properties: Band Alignment, Work Function and Optical Properties

by David K. Sang, Huide Wang, Meng Qiu, Rui Cao, Zhinan Guo, Jinlai Zhao, Yu Li, Quanlan Xiao, Dianyuan Fan and Han Zhang

Nanomaterials 2019, 9(1), 82; https://doi.org/10.3390/nano9010082 - 09 Jan 2019

Cited by 44 | Viewed by 10341

Abstract

Density functional theory calculations of the layer (L)-dependent electronic band structure, work function and optical properties of β-InSe have been reported. Owing to the quantum size effects (QSEs) in β-InSe, the band structures exhibit direct-to-indirect transitions from bulk β-InSe to few-layer β-InSe. The work functions decrease monotonically from 5.22 eV (1 L) to 5.0 eV (6 L) and then remain constant at 4.99 eV for 7 L and 8 L and drop down to 4.77 eV (bulk β-InSe). For optical properties, the imaginary part of the dielectric function has a strong dependence on the thickness variation. Layer control in two-dimensional layered materials provides an effective strategy to modulate the layer-dependent properties which have potential applications in the next-generation high performance electronic and optoelectronic devices. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

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10 pages, 1431 KiB

Open AccessArticle

Optical Properties of Graphene/MoS₂ Heterostructure: First Principles Calculations

by Bin Qiu, Xiuwen Zhao, Guichao Hu, Weiwei Yue, Junfeng Ren and Xiaobo Yuan

Nanomaterials 2018, 8(11), 962; https://doi.org/10.3390/nano8110962 - 21 Nov 2018

Cited by 62 | Viewed by 7808

Abstract

The electronic structure and the optical properties of Graphene/MoS₂ heterostructure (GM) are studied based on density functional theory. Compared with single-layer graphene, the bandgap will be opened; however, the bandgap will be reduced significantly when compared with single-layer MoS₂. Redshifts of the absorption coefficient, refractive index, and the reflectance appear in the GM system; however, blueshift is found for the energy loss spectrum. Electronic structure and optical properties of single-layer graphene and MoS₂ are changed after they are combined to form the heterostructure, which broadens the extensive developments of two-dimensional materials. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

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13 pages, 4838 KiB

Open AccessFeature PaperArticle

Environmental Effects on the Electrical Characteristics of Back-Gated WSe₂ Field-Effect Transistors

by Francesca Urban, Nadia Martucciello, Lisanne Peters, Niall McEvoy and Antonio Di Bartolomeo

Nanomaterials 2018, 8(11), 901; https://doi.org/10.3390/nano8110901 - 03 Nov 2018

Cited by 58 | Viewed by 5827

Abstract

We study the effect of polymer coating, pressure, temperature, and light on the electrical characteristics of monolayer

{WSe}_{2}

back-gated transistors with

Ni / Au

contacts. Our investigation shows that the removal of a layer of poly(methyl methacrylate) (PMMA) or a decrease of [...] Read more.

We study the effect of polymer coating, pressure, temperature, and light on the electrical characteristics of monolayer

{WSe}_{2}

back-gated transistors with

Ni / Au

contacts. Our investigation shows that the removal of a layer of poly(methyl methacrylate) (PMMA) or a decrease of the pressure change the device conductivity from p- to n-type. From the temperature behavior of the transistor transfer characteristics, a gate-tunable Schottky barrier at the contacts is demonstrated and a barrier height of

~

70 meV in the flat-band condition is measured. We also report and discuss a temperature-driven change in the mobility and the subthreshold swing that is used to estimate the trap density at the

{WSe}_{2} {/ SiO}_{2}

interface. Finally, from studying the spectral photoresponse of the

{WSe}_{2}

, it is proven that the device can be used as a photodetector with a responsivity of

~ 0.5 {AW}^{- 1}

700 nm

and

0.37 mW / {cm}^{2}

optical power. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

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12 pages, 2936 KiB

Open AccessArticle

Physical Properties and Photovoltaic Application of Semiconducting Pd₂Se₃ Monolayer

by Xiaoyin Li, Shunhong Zhang, Yaguang Guo, Fancy Qian Wang and Qian Wang

Nanomaterials 2018, 8(10), 832; https://doi.org/10.3390/nano8100832 - 14 Oct 2018

Cited by 16 | Viewed by 4993

Abstract

Palladium selenides have attracted considerable attention because of their intriguing properties and wide applications. Motivated by the successful synthesis of Pd₂Se₃ monolayer (Lin et al., Phys. Rev. Lett., 2017, 119, 016101), here we systematically study its physical properties and device applications using state-of-the-art first principles calculations. We demonstrate that the Pd₂Se₃ monolayer has a desirable quasi-direct band gap (1.39 eV) for light absorption, a high electron mobility (140.4 cm²V⁻¹s⁻¹) and strong optical absorption (~10⁵ cm⁻¹) in the visible solar spectrum, showing a great potential for absorber material in ultrathin photovoltaic devices. Furthermore, its bandgap can be tuned by applying biaxial strain, changing from indirect to direct. Equally important, replacing Se with S results in a stable Pd₂S₃ monolayer that can form a type-II heterostructure with the Pd₂Se₃ monolayer by vertically stacking them together. The power conversion efficiency (PCE) of the heterostructure-based solar cell reaches 20%, higher than that of MoS₂/MoSe₂ solar cell. Our study would motivate experimental efforts in achieving Pd₂Se₃ monolayer-based heterostructures for new efficient photovoltaic devices. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

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8 pages, 2749 KiB

Open AccessArticle

Electronic and Magnetic Properties of Stone–Wales Defected Graphene Decorated with the Half-Metallocene of M (M = Fe, Co, Ni): A First Principle Study

by Kefeng Xie, Qiangqiang Jia, Xiangtai Zhang, Li Fu and Guohu Zhao

Nanomaterials 2018, 8(7), 552; https://doi.org/10.3390/nano8070552 - 20 Jul 2018

Cited by 19 | Viewed by 4253

Abstract

The geometrical, electronic structure, and magnetic properties of the half-metallocene of M (M = Fe, Co, Ni) adsorbed on Stone–Wales defected graphene (SWG) were studied using the density functional theory (DFT), aiming to tune the band structure of SWG. The introduction of cyclopentadienyl (Cp) and half-metallocene strongly affected the band structure of SWG. The magnetic properties of the complex systems originated from the 3D orbitals of M (M = Fe, Co, Ni), the molecular orbital of Cp, and SWG. This phenomenon was different from that found in a previous study, which was due to metal ion-induced sandwich complexes. The results have potential applications in the design of electronic devices based on SWG. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

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17 pages, 6599 KiB

Open AccessArticle

Visible Light Driven Photoanodes for Water Oxidation Based on Novel r-GO/β-Cu₂V₂O₇/TiO₂ Nanorods Composites

by Shuang Shuang, Leonardo Girardi, Gian Andrea Rizzi, Andrea Sartorel, Carla Marega, Zhengjun Zhang and Gaetano Granozzi

Nanomaterials 2018, 8(7), 544; https://doi.org/10.3390/nano8070544 - 18 Jul 2018

Cited by 25 | Viewed by 5122

Abstract

This paper describes the preparation and the photoelectrochemical performances of visible light driven photoanodes based on novel r-GO/β-Cu₂V₂O₇/TiO₂ nanorods/composites. β-Cu₂V₂O₇ was deposited on both fluorine doped tin oxide (FTO) and TiO₂ nanorods (NRs)/FTO by a fast and convenient Aerosol Assisted Spray Pyrolysis (AASP) procedure. Ethylenediamine (EN), ammonia and citric acid (CA) were tested as ligands for Cu²⁺ ions in the aerosol precursors solution. The best-performing deposits, in terms of photocurrent density, were obtained when NH₃ was used as ligand. When β-Cu₂V₂O₇ was deposited on the TiO₂ NRs a good improvement in the durability of the photoanode was obtained, compared with pure β-Cu₂V₂O₇ on FTO. A further remarkable improvement in durability and photocurrent density was obtained upon addition, by electrophoretic deposition, of reduced graphene oxide (r-GO) flakes on the β-Cu₂V₂O₇/TiO₂ composite material. The samples were characterized by X-ray Photoelectron Spectroscopy (XPS), Raman, High Resolution Transmission Electron Microscopy (HR-TEM), Scanning Electron Microscopy (SEM), Wide Angle X-ray Diffraction (WAXD) and UV-Vis spectroscopies. The photoelectrochemical (PEC) performances of β-Cu₂V₂O₇ on FTO, β-Cu₂V₂O₇/TiO₂ and r-GO/β-Cu₂V₂O₇/TiO₂ were tested in visible light by linear voltammetry and Electrochemical Impedance Spectroscopy (EIS) measurements. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

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9 pages, 6611 KiB

Open AccessArticle

Hybrid Density Functional Study on the Photocatalytic Properties of Two-dimensional g-ZnO Based Heterostructures

by Guangzhao Wang, Dengfeng Li, Qilong Sun, Suihu Dang, Mingmin Zhong, Shuyuan Xiao and Guoshuai Liu

Nanomaterials 2018, 8(6), 374; https://doi.org/10.3390/nano8060374 - 28 May 2018

Cited by 15 | Viewed by 3644

Abstract

In this work, graphene-like ZnO (g-ZnO)-based two-dimensional (2D) heterostructures (ZnO/WS₂ and ZnO/WSe₂) were designed as water-splitting photocatalysts based on the hybrid density functional. The dependence of photocatalytic properties on the rotation angles and biaxial strains were investigated. The bandgaps of ZnO/WS₂ and ZnO/WSe₂ are not obviously affected by rotation angles but by strains. The ZnO/WS₂ heterostructures with appropriate rotation angles and strains are promising visible water-splitting photocatalysts due to their appropriate bandgap for visible absorption, proper band edge alignment, and effective separation of carriers, while the water oxygen process of the ZnO/WSe₂ heterostructures is limited by their band edge positions. The findings pave the way to efficient g-ZnO-based 2D visible water-splitting materials. Full article

(This article belongs to the Special Issue 2D Materials and Van der Waals Heterostructures: Physics and Applications)

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