Two-Step Conversion of Metal and Metal Oxide Precursor Films to 2D Transition Metal Dichalcogenides and Heterostructures.

The widely studied class of two-dimensional (2D) materials known as transition metal dichalcogenides (TMDs) are now well-poised to be employed in real-world applications ranging from electronic logic and memory devices to gas and biological sensors. Several scalable thin film synthesis techniques have demonstrated nanoscale control of TMD material thickness, morphology, structure, and chemistry and correlated these properties with high-performing, application-specific device metrics. In this review, the particularly versatile two-step conversion (2SC) method of TMD film synthesis is highlighted. The 2SC technique relies on deposition of a solid metal or metal oxide precursor material, followed by a reaction with a chalcogen vapor at an elevated temperature, converting the precursor film to a crystalline TMD. Herein, the variables at each step of the 2SC process including the impact of the precursor film material and deposition technique, the influence of gas composition and temperature during conversion, as well as other factors controlling high-quality 2D TMD synthesis are considered. The specific advantages of the 2SC approach including deposition on diverse substrates, low-temperature processing, orientation control, and heterostructure synthesis, among others, are featured. Finally, emergent opportunities that take advantage of the 2SC approach are discussed to include next-generation electronics, sensing, and optoelectronic devices, as well as catalysis for energy-related applications.

Spalling-Induced Liftoff and Transfer of Electronic Films Using a van der Waals Release Layer.

Heterogeneous integration strategies are increasingly being employed to achieve more compact and capable electronics systems for multiple applications including space, electric vehicles, and wearable and medical devices. To enable new integration strategies, the growth and transfer of thin electronic films and devices, including III-nitrides, metal oxides, and 2D materials, using 2D boron nitride (BN)-on-sapphire templates are demonstrated. The van der Waals (vdW) BN layer, in this case, acts as a preferred mechanical release layer for precise separation at the substrate-film interface and leaves a smooth surface suitable for vdW bonding. A tensilely stressed Ni layer sputtered on top of the film induces controlled spalling fracture that propagates at the BN/sapphire interface. By incorporating controlled spalling, the process yield and sensitivity are greatly improved, owed to the greater fracture energy provided by the stressed metal layer relative to a soft tape or rubber stamp. With stress playing a critical role in this process, the influence of residual stress on detrimental cracking and bowing is investigated. Additionally, a back-end selected area lift-off technique is developed which allows for isolation and transfer of individual devices or arbitrary shapes.

In situ transmission electron microscopy of transistor operation and failure.

Microscopy is typically used as a post-mortem analytical tool in performance and reliability studies on nanoscale materials and devices. In this study, we demonstrate real time microscopy of the operation and failure of AlGaN/GaN high electron mobility transistors inside the transmission electron microscope. Loading until failure was performed on the electron transparent transistors to visualize the failure mechanisms caused by self-heating. At lower drain voltages, thermo-mechanical stresses induce irreversible microstructural deformation, mostly along the AlGaN/GaN interface, to initiate the damage process. At higher biasing, the self-heating deteriorates the gate and catastrophic failure takes place through metal/semiconductor inter-diffusion and/or buffer layer breakdown. This study indicates that the current trend of recreating the events, from damage nucleation to catastrophic failure, can be replaced by in situ microscopy for a quick and accurate account of the failure mechanisms.

Heterogeneous Pyrolysis: A Route for Epitaxial Growth of hBN Atomic Layers on Copper Using Separate Boron and Nitrogen Precursors.

Growth of hBN on metal substrates is often performed via chemical vapor deposition from a single precursor (e.g., borazine) and results in hBN monolayers limited by the substrates catalyzing effect. Departing from this paradigm, we demonstrate close control over the growth of mono-, bi-, and trilayers of hBN on copper using triethylborane and ammonia as independent sources of boron and nitrogen. Using density functional theory (DFT) calculations and reactive force field molecular dynamics, we show that the key factor enabling the growth beyond the first layer is the activation of ammonia through heterogeneous pyrolysis with boron-based radicals at the surface. The hBN layers grown are in registry with each other and assume a perfect or near perfect epitaxial relation with the substrate. From atomic force microscopy (AFM) characterization, we observe a moiré superstructure in the first hBN layer with an apparent height modulation and lateral periodicity of ∼10 nm. While this is unexpected given that the moiré pattern of hBN/Cu(111) does not have a significant morphological corrugation, our DFT calculations reveal a spatially modulated interface dipole layer which determines the unusual AFM response. These findings have improved our understanding of the mechanisms involved in growth of hBN and may help generate new growth methods for applications in which control over the number of layers and their alignment is crucial (such as tunneling barriers, ultrathin capacitors, and graphene-based devices).

Light-matter coupling in large-area van der Waals superlattices.

Two-dimensional (2D) crystals have renewed opportunities in design and assembly of artificial lattices without the constraints of epitaxy. However, the lack of thickness control in exfoliated van der Waals (vdW) layers prevents realization of repeat units with high fidelity. Recent availability of uniform, wafer-scale samples permits engineering of both electronic and optical dispersions in stacks of disparate 2D layers with multiple repeating units. Here we present optical dispersion engineering in a superlattice structure comprising alternating layers of 2D excitonic chalcogenides and dielectric insulators. By carefully designing the unit cell parameters, we demonstrate greater than 90% narrow band absorption in less than 4 nm of active layer excitonic absorber medium at room temperature, concurrently with enhanced photoluminescence in square-centimetre samples. These superlattices show evidence of strong light-matter coupling and exciton-polariton formation with geometry-tuneable coupling constants. Our results demonstrate proof of concept structures with engineered optical properties and pave the way for a broad class of scalable, designer optical metamaterials from atomically thin layers.

Turn of the decade: versatility of 2D hexagonal boron nitride.

The era of two-dimensional (2D) materials, in its current form, truly began at the time that graphene was first isolated just over 15 years ago. Shortly thereafter, the use of 2D hexagonal boron nitride (h-BN) had expanded in popularity, with use of the thin isolator permeating a significant number of fields in condensed matter and beyond. Due to the impractical nature of cataloguing every use or research pursuit, this review will cover ground in the following three subtopics relevant to this versatile material: growth, electrical measurements, and applications in optics and photonics. Through understanding how the material has been utilized, one may anticipate some of the exciting directions made possible by the research conducted up through the turn of this decade.

Two-dimensional BN buffer for plasma enhanced atomic layer deposition of Al2O3 gate dielectrics on graphene field effect transistors.

Here, we investigate the use of few-layer metal organic chemical vapor deposition (MOCVD) grown BN as a two-dimensional buffer layer for plasma enhanced atomic layer deposition (PE-ALD) of Al2O3 on graphene for top gated field effect transistors (FETs). The reactive nature of PE-ALD enables deposition of thin (2 nm) dielectrics directly on graphene and other two-dimensional materials without the need for a seed or functionalization layer; however, this also leads to significant oxidation of the graphene layer as observed by Raman. In FETs, we find this oxidation destroys conductivity in the graphene channel. By transferring thin (1.6 nm) MOCVD BN layers on top of graphene channels prior to PE-ALD, the graphene is protected from oxidation enabling BN/Al2O3 layers as thin as 4 nm. Raman and X-ray photoelectron spectroscopy on BN films show no significant oxidation caused by PE-ALD of Al2O3. Inserting the BN layer creates an atomically abrupt interface significantly reducing interface charges between the graphene and Al2O3 as compared to use of a 2 nm Al buffer layer. This results in a much smaller Dirac voltage (- 1 V) and hysteresis (0.9 V) when compared to FETs with the Al layer (VDirac = - 6.1 V and hysteresis = 2.9 V).

Large-area ultrathin Te films with substrate-tunable orientation.

Anisotropy in a crystal structure can lead to large orientation-dependent variations of mechanical, optical, and electronic properties. Material orientation control can thus provide a handle to manipulate properties. Here, a novel sputtering approach for 2D materials enables growth of ultrathin (2.5-10 nm) tellurium films with rational control of the crystalline orientation templated by the substrate. The anisotropic Te 〈0001〉 helical chains align in the plane of the substrate on highly oriented pyrolytic graphite (HOPG) and orthogonally to MgO(100) substrates, as shown by polarized Raman spectroscopy and high-resolution electron microscopy. Furthermore, the films are shown to grow in a textured fashion on HOPG, in contrast with previous reports. These ultrathin Te films cover exceptionally large areas (>1 cm2) and are grown at low temperature (25 °C) affording the ability to accommodate a variety of substrates including flexible electronics. They are robust toward oxidation over a period of days and exhibit the non-centrosymmetric P3121 Te structure. Raman signals are acutely dependent on film thickness, suggesting that optical anisotropy persists and is even enhanced at the ultrathin limit. Hall effect measurements indicate orientation-dependent carrier mobility up to 19 cm2 V-1 s-1. These large-area, ultrathin Te films grown by a truly scalable, physical vapor deposition technique with rational control of orientation/thickness open avenues for controlled orientation-dependent properties in semiconducting thin films for applications in electronic and optoelectronic devices.

Transferrable AlGaN/GaN High-Electron Mobility Transistors to Arbitrary Substrates via a Two-Dimensional Boron Nitride Release Layer.

Mechanical transfer of high-performing thin-film devices onto arbitrary substrates represents an exciting opportunity to improve device performance, explore nontraditional manufacturing approaches, and paves the way for soft, conformal, and flexible electronics. Using a two-dimensional boron nitride release layer, we demonstrate the transfer of AlGaN/GaN high-electron mobility transistors (HEMTs) to arbitrary substrates through both direct van der Waals bonding and with a polymer adhesive interlayer. No device degradation was observed because of the transfer process, and a significant reduction in device temperature (327-132 °C at 600 mW) was observed when directly bonded to a silicon carbide (SiC) wafer relative to the starting wafer. With the use of a benzocyclobutene (BCB) adhesion interlayer, devices were easily transferred and characterized on Kapton and ceramic films, representing an exciting opportunity for integration onto arbitrary substrates. Upon reduction of this polymer adhesive layer thickness, the AlGaN/GaN HEMTs transferred onto a BCB/SiC substrate resulted in comparable peak temperatures during operation at powers as high as 600 mW to the as-grown wafer, revealing that by optimizing interlayer characteristics such as thickness and thermal conductivity, transferrable devices on polymer layers can still improve performance outputs.

A Computational and Experimental Investigation of the Phonon and Optical Properties of Au2P3.

In a combined experimental and theoretical study of gold phosphide (Au2P3), we investigate its vibrational properties, band structure, and dielectric properties, providing new insight into the properties of this underexplored material. Using a simple synthesis route, Au2P3 thin films were produced, enabling the first reported Raman analysis of this material. Coupled with first-principles calculations of these Raman modes, this analysis reveals that low-frequency vibrations are due to Au or mixed Au to P, and at higher frequencies, they are due to P vibrations. Further band structure and dielectric calculations reveal Au2P3 to be a narrow band (0.16 eV) indirect semiconductor. This work helps to fill major gaps in our understanding of key properties in this material that will benefit future research in this field.

Synthesis and characterization of ZnO nano-plant-like electrodes.

Dye-sensitized solar cells (DSSCs) have received considerable attention as a cost-effective alternative to conventional inorganic solar cells. These cells operate on a process similar to photosynthesis, the process by which green plants generate chemical energy from sunlight. A thick semiconductor nanoparticle film provides a large surface area for the adsorption of energy by light harvesting organic dye molecules which then "inject" electrons into the nanostructured semiconductor electrode. This process is accompanied by a charge transfer to the dye from an electron donor mediator supplied by an electrolyte, resetting the cycle. A significant increase in the long-term stability and the efficiency of DSSCs has been realized during the last few years. However, still the current nanoparticle-based DSSCs suffer from the trap-limited diffusion transport mechanism of electrons, a slow mechanism that limits the device efficiency, especially at longer wavelengths. Recently we have developed a new version of the dye-sensitized cells in which the traditional electrode (sintered nanoparticle film) is replaced by a specially designed ZnO electrode possessing an exotic 'nanoplant-like' morphology. This advance fixes a major efficiency limiting factor in current nanoparticle-based DSSCs. The direct electrical pathway, provided by the interconnected nanoplants, provides rapid collection of carriers generated throughout the device, and significantly enhances the conversion efficiency of the system over that of sintered nanoparticle based solar cells.

Wafer scale BN on sapphire substrates for improved graphene transport.

Wafer scale (2") BN grown by metal organic chemical vapor deposition (MOCVD) on sapphire was examined as a weakly interacting dielectric substrate for graphene, demonstrating improved transport properties over conventional sapphire and SiO2/Si substrates. Chemical vapor deposition grown graphene was transferred to BN/sapphire substrates for evaluation of more than 30 samples using Raman and Hall effects measurements. A more than 2x increase in Hall mobility and 10x reduction in sheet carrier density was measured for graphene on BN/sapphire compared to sapphire substrates. Through control of the MOCVD process, BN films with roughness ranging from <0.1 nm to >1 nm were grown and used to study the effects of substrate roughness on graphene transport. Arrays of graphene field effect transistors were fabricated on 2" BN/sapphire substrates demonstrating scalability and device performance enhancement.

Recent Progress on Stability and Passivation of Black Phosphorus.

From a fundamental science perspective, black phosphorus (BP) is a canonical example of a material that possesses fascinating surface and electronic properties. It has extraordinary in-plane anisotropic electrical, optical, and vibrational states, as well as a tunable band gap. However, instability of the surface due to chemical degradation in ambient conditions remains a major impediment to its prospective applications. Early studies were limited by the degradation of black phosphorous surfaces in air. Recently, several robust strategies have been developed to mitigate these issues, and these novel developments can potentially allow researchers to exploit the extraordinary properties of this material and devices made out of it. Here, the fundamental chemistry of BP degradation and the tremendous progress made to address this issue are extensively reviewed. Device performances of encapsulated BP are also compared with nonencapsulated BP. In addition, BP possesses sensitive anisotropic photophysical surface properties such as excitons, surface plasmons/phonons, and topologically protected and Dirac semi-metallic surface states. Ambient degradation as well as any passivation method used to protect the surface could affect the intrinsic surface properties of BP. These properties and the extent of their modifications by both the degradation and passivation are reviewed.

Synthesis of Crystalline Black Phosphorus Thin Film on Sapphire.

Black phosphorus (BP) has recently attracted significant attention due to its exceptional physical properties. Currently, high-quality few-layer and thin-film BP are produced primarily by mechanical exfoliation, limiting their potential in future applications. Here, the synthesis of highly crystalline thin-film BP on 5 mm sapphire substrates by conversion from red to black phosphorus at 700 °C and 1.5 GPa is demonstrated. The synthesized ≈50 nm thick BP thin films are polycrystalline with a crystal domain size ranging from 40 to 70 µm long, as indicated by Raman mapping and infrared extinction spectroscopy. At room temperature, field-effect mobility of the synthesized BP thin film is found to be around 160 cm2 V-1 s-1 along armchair direction and reaches up to about 200 cm2 V-1 s-1 at around 90 K. Moreover, red phosphorus (RP) covered by exfoliated hexagonal boron nitride (hBN) before conversion shows atomically sharp hBN/BP interface and perfectly layered BP after the conversion. This demonstration represents a critical step toward the future realization of large scale, high-quality BP devices and circuits.

Synthesis, characterization, and green luminescence in ZnO nanocages.

In this paper, we report the synthesis, characterization and observation of green luminescence in ZnO nanocages. A novel low temperature solution-based technique has been developed for growing highly porous ZnO nano-cages from coarse ZnO precursor powders. Various samples, prepared in this study, were characterized using several different characterization tools such as X-ray diffraction, Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy, Raman, Photoluminescence and Optical Transmission Spectroscopy. It has been shown that ZnO nanocages exhibit green luminescence, with PL data showing a broad green peak at 510 nm. The shift and broadening in the luminescence peaks are understood to arise because of the onset of deep level defects in the system.

How Important Is the Metal-Semiconductor Contact for Schottky Barrier Transistors: A Case Study on Few-Layer Black Phosphorus?

Black phosphorus (BP) is a recently rediscovered layered two-dimensional (2D) semiconductor with a direct band gap (0.35-2 eV), high hole mobility (300-5000 cm2/Vs), and transport anisotropy. In this paper, we systematically investigated the effects of metal-semiconductor interface/contacts on the performance of BP Schottky barrier transistors. First, a "clean" metal-BP contact is formed with boron nitride (BN) passivation. It is found that the contact resistance of the clean metal-BP contact is seven times less than the previously reported values. As a result, high-performance top-gate BP transistors show a record high ON-state drain current (I on) of 940 µA/µm. Second, BN tunneling barriers are formed at the source/drain contacts to help understand the abnormally high OFF-state drain current (I off) in devices with clean metal-BP contacts. This high I off is attributed to the electron tunneling current from the drain to the channel. Finally, the I on/I off of BP field-effect transistors can be significantly improved by using an asymmetric contact structure. By inserting a thin BN tunneling barrier at the drain side, I off is reduced by a factor of ∼120 with a cost of 20% reduction in I on. This case study of contacts on BP reveals the importance of understanding the metal-semiconductor contacts for 2D Schottky barrier transistors in general.

Flexible Gallium Nitride for High-Performance, Strainable Radio-Frequency Devices.

Flexible gallium nitride (GaN) thin films can enable future strainable and conformal devices for transmission of radio-frequency (RF) signals over large distances for more efficient wireless communication. For the first time, strainable high-frequency RF GaN devices are demonstrated, whose exceptional performance is enabled by epitaxial growth on 2D boron nitride for chemical-free transfer to a soft, flexible substrate. The AlGaN/GaN heterostructures transferred to flexible substrates are uniaxially strained up to 0.85% and reveal near state-of-the-art values for electrical performance, with electron mobility exceeding 2000 cm2 V-1 s-1 and sheet carrier density above 1.07 × 1013 cm-2 . The influence of strain on the RF performance of flexible GaN high-electron-mobility transistor (HEMT) devices is evaluated, demonstrating cutoff frequencies and maximum oscillation frequencies greater than 42 and 74 GHz, respectively, at up to 0.43% strain, representing a significant advancement toward conformal, highly integrated electronic materials for RF applications.