Tunable Band Alignment Research Articles

Vapor growth of WSe2/WS2 heterostructures with stacking dependent optical properties

Two-dimensional (2D) vertically stacked heterostructures based on layered transition-metal dichalcogenides (TMDCs) have remarkable potential in future applications due to their rich interlayer related properties, such as interlayer excitons, tunable interlayer band alignments. However, the controlled growth of TMDC bilayer heterostructures with preferred stacking structure remains challenging. Here, we report a two-step van der Waals epitaxial vapor growth of WSe2/WS2 vertically stacked bilayer heterostructures with controllable commensurate crystallographic alignments (so called AA and AB stacking), by controlling the deposition temperature. Moire patterns were obtained in both AA and AB stacked WSe2/WS2 heterostructures. The stacking configuration of the vertical heterostructures was verified by the second harmonic generation signals. Photoluminescence and Raman spectroscopy studies further confirm that the heterostructures with different stacking configuration have obviously different optical properties, which is ascribed to the distinct interlayer coupling and resonance excitation between the distinguishing AA and AB stacked heterostructures. The controlled growth of AA and AB stacked heterostructures could provide an importance platform not only for fundamental researches but also for functional electronic and optoelectronic device applications.

Ferroelectric and dipole control of band alignment in the two dimensional InTe/In2Se3 heterostructure

Two dimensional (2D) ferroelectric materials are gaining growing attention due to their nontrival ferroelectricity, and the 2D ferroelectric heterostructures with tunable electronic, optoelectronic, or even magnetic properties, show many novel properties that do not exist in their constituents. In this work, by using the first-principles calculations, we investigate the ferroelectric and dipole control of electronic structures of the 2D ferroelectric heterostructure InTe/In2Se3. It is found that band alignment is closely dependent on the ferroelectric polarization of In2Se3. By switching the polarization of In2Se3, the band alignment of InTe/In2Se3 switches from a staggered (type II) to a straddling type (type I), and the band gap changes from indirect gap 0.76 eV to direct gap 0.15 eV. When the ferroelectric field of In2Se3 is reversed, the band alignment of InTe/In2Se3 switches from type-I to type-II, and the band gap changes from indirect gap 0.76 eV to direct gap 0.15 eV. In addition, we find that the interlayer dipole can also effectively modulate the band structure and induce the type-I to type-II band alignment transition. Our present results indicate that the 2D ferroelectric heterostructure with the tunable band alignment and band gap can be of great significance in the optoelectronic devices.

Tailoring the electronic properties of graphyne/blue phosphorene heterostructure via external electric field and vertical strain

We design novel graphyne/blue phosphorene van der Waals (vdW) heterostructures (G/BP) under the external electric fields (Efield) and strains. It is demonstrated that the G/BP is a type-I semiconductor with a direct band gap of approximately 0.378 eV. The external Efield and strains not only have important effects on the band structure which undergoes a fascinating direct-indirect and semiconductor-metal transitions, but also influence the band alignment which experiences transition from type-I to type-II. In brief, the features of tunable bandgap and controllable band alignment endow G/BP with potential for application in future optoelectronic devices.

Direct Vapor Growth of 2D Vertical Heterostructures with Tunable Band Alignments and Interfacial Charge Transfer Behaviors.

2D vertical van der Waals (vdW) heterostructures with atomically sharp interfaces have attracted tremendous interest in 2D photonic and optoelectronic applications. Band alignment engineering in 2D heterostructures provides a perfect platform for tailoring interfacial charge transfer behaviors, from which desired optical and optoelectronic features can be realized. Here, by developing a two‐step chemical vapor deposition strategy, direct vapor growth of monolayer PbI2 on monolayer transition metal dichalcogenides (TMDCs) (WS2, WSe2, or alloying WS2(1− x )Se2 x), forming bilayer vertical heterostructures, is demonstrated. Based on the calculated electron band structures, the interfacial band alignments of the obtained heterostructures can be gradually tuned from type‐I (PbI2/WS2) to type‐II (PbI2/WSe2). Steady‐state photoluminescence (PL) and time‐resolved PL measurements reveal that the PL emissions from the bottom TMDC layers can be modulated from apparently enhanced (for WS2) to greatly quenched (for WSe2) compared to their monolayer counterparts, which can be attributed to the band alignment–induced distinct interfacial charge transfer behaviors. The band alignment nature of the heterostructures is further demonstrated by the PL excitation spectroscopy and interlayer exciton investigation. The realization of 2D vertical heterostructures with tunable band alignments will provide a new material platform for designing and constructing multifunctional optoelectronic devices.

Facet-Dependent Photocatalytic Behaviors of ZnS-Decorated Cu2O Polyhedra Arising from Tunable Interfacial Band Alignment.

ZnS particles were grown over Cu2O cubes, octahedra, and rhombic dodecahedra for examination of their facet-dependent photocatalytic behaviors. After ZnS growth, Cu2O cubes stay photocatalytically inactive. ZnS-decorated Cu2O octahedra show enhanced photocatalytic activity, resulting from better charge carrier separation upon photoexcitation. Surprisingly, Cu2O rhombic dodecahedra give greatly suppressed photocatalytic activity after ZnS deposition. Electron paramagnetic resonance spectra agree with these experimental observations. Time-resolved photoluminescence profiles provide charge-transfer insights. The decrease in the photocatalytic activity is attributed to an unfavorable band alignment caused by significant band bending within the Cu2O(110)/ZnS(200) plane interface. A modified Cu2O-ZnS band diagram is presented. Density functional theory calculations generating plane-specific band energy diagrams of Cu2O and ZnS match well with the experimental results, showing that charge transfer across the Cu2O(110)/ZnS(200) plane interface would not happen. This example further illustrates that the actual photocatalysis outcome for semiconductor heterojunctions cannot be assumed because interfacial charge transfer is strongly facet-dependent.

Vertical WS2/SnS2 van der Waals Heterostructure for Tunneling Transistors

Van der Waals heterostructures composed of two-dimensional (2D) transition metal dichalcogenides (TMD) materials have stimulated tremendous research interest in various device applications, especially in energy-efficient future-generation electronics. Such ultra-thin stacks as tunnel junction theoretically present unprecedented possibilities of tunable relative band alignment and pristine interfaces, which enable significant performance enhancement for steep-slope tunneling transistors. In this work, the optimal 2D-2D heterostructure for tunneling transistors is presented and elaborately engineered, taking into consideration both electric properties and material stability. The key challenges, including band alignment and metal-to-2D semiconductor contact resistances, are optimized separately for integration. By using a new dry transfer technique for the vertical stack, the selected WS2/SnS2 heterostructure-based tunneling transistor is fabricated for the first time, and exhibits superior performance with comparable on-state current and steeper subthreshold slope than conventional FET, as well as on-off current ratio over 106 which is among the highest value of 2D-2D tunneling transistors. A visible negative differential resistance feature is also observed. This work shows the great potential of 2D layered semiconductors for new heterostructure devices and can guide possible development of energy-efficient future-generation electronics.

Band Alignment Engineering in Two-Dimensional Lateral Heterostructures.

Two-dimensional (2D) heterostructures have aroused widespread attentions due to the fascinating properties originating from the interfaces and the derived potential applications in modern electronics and optoelectronics. The interfacial band alignment engineering of 2D heterostructures would open up promising routes toward the flexible design and optimization of the electronic and optoelectronic properties. Herein, we report a one-step chemical vapor deposition method for the growth of band alignment continuously modulated WS2-WS2(1- x)Se2 x (0 < x ≤ 1) monolayer lateral heterostructures, with atomically sharp interfaces at the junction area. Local photoluminescence (PL) and Raman measurements demonstrate the position-dependent composition and band gap information on the as-grown nanosheets. Kelvin probe force microscopy (KPFM) investigations further confirm the tunable band alignments in the heterostructures, where a continuously decreased Fermi level difference between the core and the shell regions is observed with the x value varied from 1 to 0. The direct growth of high-quality atomic-level junctions with controllable band alignment marks an important step toward the potential applications of 2D semiconductors in integrated electronic and optoelectronic devices.

Tunable band alignment in two-phase-coexistence Nb3O7F nanocrystals with enhanced light harvesting and photocatalytic performance

A two-phase-coexistence technique offers intriguing variables to maneuver novel and enhanced functionality in a single-component material. Most importantly, new band alignment and perfect interfaces between two phases can strongly affect local photoelectronic properties. However, previous efforts to achieve two-phase coexistence were mainly restricted to specific systems and methods. Here we demonstrate a phase-transition route to acquire two-phase-coexistence niobium oxyfluoride (Nb3O7F) nanocrystals for the first time. Based on key distinguishing features of the experimental results and theoretical analysis, the phase transition of Nb3O7F involves an organic/inorganic hybrid, heat treating, Al-doping, lattice deformation and structural rearrangement. The band gap can be effectively tuned from 3.03 eV to 2.84 eV, and the VBM can be tuned from 1.49 eV to 1.69 eV according to the phase proportion. Benefiting from uniform nanocrystal size, tunable band alignment and an optimized interfacial structure, the two-phase coexistence markedly enhances visible-light harvesting and the photocatalytic performance of Nb3O7F nanocrystals. The results not only demonstrate an opportunity to explore two-phase coexistence of novel nanocrystals, but also illustrate the role of two-phase coexistence in achieving enhanced photoelectronic properties.

Highly sensitive MoS2 photodetectors with graphene contacts

Two-dimensional materials such as graphene and transition metal dichalcogenides (TMDs) are ideal candidates to create ultra-thin electronics suitable for flexible substrates. Although optoelectronic devices based on TMDs have demonstrated remarkable performance, scalability is still a significant issue. Most devices are created using techniques that are not suitable for mass production, such as mechanical exfoliation of monolayer flakes and patterning by electron-beam lithography. Here we show that large-area MoS2 grown by chemical vapor deposition and patterned by photolithography yields highly sensitive photodetectors, with record shot-noise-limited detectivities of 8.7 × 1014 Jones in ambient condition and even higher when sealed with a protective layer. These detectivity values are higher than the highest values reported for photodetectors based on exfoliated MoS2. We study MoS2 devices with gold electrodes and graphene electrodes. The devices with graphene electrodes have a tunable band alignment and are especially attractive for scalable ultra-thin flexible optoelectronics.

Band offsets in new BN/BX (X = P, As, Sb) lateral heterostructures based on bond-orbital theory

Identifying heterostructures with tunable band alignments remains a difficult challenge. Here, based on bond-orbital theory, we propose a series of new BN/BX (X = P, As, Sb) lateral heterostructures (LHS). Our first principles calculations reveal that the LHS interlines have a substantial impact on the electronic properties. Importantly, we start with the chemical concepts, such as bond length and strength as well as orbital overlap interaction, in an attempt to thoroughly investigate the electronic properties, namely the band offset, the band gap (Eg) and the state of the energy level. We demonstrate that the newly designed BN/BX LHS have profound implications for developing advanced optoelectronics, such as high-performance light-emitting diodes and lasers. Furthermore, the new BN/BX LHS designed from the chemical viewpoint can shed new light on overcoming the enormous hurdle of ineffective and laborious material design.

Tunable band alignment and dielectric constant of solution route fabricated Al/HfO2/Si gate stack for CMOS applications

The solution route deposition method will reduce the fabrication cost, and it is compatible with existing Si technology. Here, we systematically investigate the impact of annealing temperature on the electrical and dielectric properties along with the band alignment of HfO2 thin films with silicon. The films were fabricated using the hafnium isopropoxide adduct precursor, which is environment friendly and non-toxic in ambient conditions. We have analyzed the band alignment of HfO2/Si stack by using ultra-violet photoelectron spectroscopic and current-voltage (J-V) plot to understand its impact on electrical transport. The bandgap of HfO2 films estimated from Plasmon energy loss spectra is 5.9 eV. The composition analysis is done with X-ray photoelectron spectroscopy that suggests a good stoichiometric ratio of 1:1.96. The atomic force microscopy studies display a smooth surface with the roughness of 1.4 Å without any cracks in the films. It is found that the current conduction mechanisms and barrier heights at both the interfaces are influenced by the annealing temperature; a temperature of 450 °C results in an optimum performance. Interestingly, the high value of dielectric constant (23) in the amorphous phase is attributed to the existence of cubic like short range order in HfO2 films. Moreover, a low leakage current density of 1.4 × 10−9 A/cm2 at −1 V and 1.48 × 10−8 A/cm2 at +1 V in gate and substrate injection modes is achieved. The obtained defect activation energies of 0.91 eV, 0.87 eV, and 0.93 eV for the films annealed at 350 °C, 450 °C, and 550 °C lay below the conduction band edge of HfO2. These energy levels are ascribed to three and four fold oxygen vacancy related traps. The formation of dipoles at the interface, change in the microstructure, and oxygen migration at the interfacial layer are the possible causes for the observed parametric variations in the metal–insulator–semiconductor structure. The electrical properties can be tuned by utilizing suitable annealing temperatures.

2D lateral heterostructures of monolayer and bilayer phosphorene

Bilayer/monolayer phosphorene lateral heterostructures with tunable band alignment.

Size and strain tunable band alignment of black-blue phosphorene lateral heterostructures.

Single-element lateral heterostructures composed of black and blue phosphorene are not only free from lattice mismatch but also exhibit rich physical properties related to the seamlessly stitched interfaces, providing the building blocks for designing atomically thin devices. Using first-principles calculations, we investigate the influence of interface structure, size effect and strain engineering on the electronic structure, effective masses and band alignment of black-blue phosphorene lateral heterostructures. The lateral heterostructure with an octatomic-ring interface presents a strong metallic feature due to the interface states, while a metal-semiconductor transition takes place in the system with a hexatomic-ring interface upon hydrogen passivation. Following a reciprocal scaling law, the band gap is tuned in a wide energy range by synchronously increasing the widths of black and blue phosphorene or by only widening that of black phosphorene. Moreover, type-II band alignment is observed in the width ranges of 2.0-3.1 nm and 3.7-4.2 nm, out of which it is type-I. However, the band gap and effective masses show small changes if only the width of blue phosphorene is altered. When the lateral heterostructure is tensile loaded, the effective mass ratio of hole to electron is enlarged by an order of magnitude at a strain of 4% along the zigzag direction. Meanwhile, the band alignment undergoes a crossover from type-I to type-II at a strain of 2%, facilitating efficient electron-hole separation for light detection and harvesting.

(Invited) Photocatalytic CO2 Conversion to Selective Hydrocarbons Using Graphene Oxides and Related 2D Hybrids

Photocatalytic conversion of carbon dioxide (CO2) to hydrocarbons makes possible simultaneously harvesting solar energy for production of fuels or useful chemicals, as well as reducing CO2 for a greener society, two birds with one stone for the pressing global energy and environmental problems of our time. Here, we describe a highly efficient photocatalytic conversion of CO2 to selective hydrocarbons using graphene oxides (GOs) and their related 2D hybrids as photo-catalysts. Several approaches have been employed to synthesize GOs and reduced GOs (rGOs) with tunable bandgap and band alignment with respect to the CO2 reduction level. The functionalities of the GOs/rGOs were investigated by UV-Vis, cyclic voltammetry, and x-ray photoemission spectroscopy. Under visible light, the photocatalytic conversion of CO2 to methanol of GOs/rGOs is several-fold higher than that of TiO2 (e.g., commercial P-25). Further, metal and metal sulfides, especially the 2D materials such as MoS2, as well as optically active polymers, were deposited onto GO as co-catalysts or sensitizers, to enhance the photocatalysis reaction. Besides methanol, other selective hydrocarbons including acetaldehyde were also detected. Total solar to fuel yield of ~200 times enhancement over that of P-25 has been achieved. In all these GOs-2D hybrids, the photo-catalytic performance is always much better than that of constituent component when used alone. Detailed preparation and characterization of the catalysts will be presented. The role and interplay of the constituent components will also be discussed.

Tunable Band Alignment with Unperturbed Carrier Mobility of On-Surface Synthesized Organic Semiconducting Wires.

The tunable properties of molecular materials place them among the favorites for a variety of future generation devices. In addition, to maintain the current trend of miniaturization of those devices, a departure from the present top-down production methods may soon be required and self-assembly appears among the most promising alternatives. On-surface synthesis unites the promises of molecular materials and of self-assembly, with the sturdiness of covalently bonded structures: an ideal scenario for future applications. Following this idea, we report the synthesis of functional extended nanowires by self-assembly. In particular, the products correspond to one-dimensional organic semiconductors. The uniaxial alignment provided by our substrate templates allows us to access with exquisite detail their electronic properties, including the full valence band dispersion, by combining local probes with spatial averaging techniques. We show how, by selectively doping the molecular precursors, the product’s energy level alignment can be tuned without compromising the charge carrier’s mobility.

Microscopic basis for the band engineering of Mo1-xWxS2-based heterojunction.

Transition-metal dichalcogenide layered materials, consisting of a transition-metal atomic layer sandwiched by two chalcogen atomic layers, have been attracting considerable attention because of their desirable physical properties for semiconductor devices, and a wide variety of pn junctions, which are essential building blocks for electronic and optoelectronic devices, have been realized using these atomically thin structures. Engineering the electronic/optical properties of semiconductors by using such heterojunctions has been a central concept in semiconductor science and technology. Here, we report the first scanning tunneling microscopy/spectroscopy (STM/STS) study on the electronic structures of a monolayer WS2/Mo1−xWxS2 heterojunction that provides a tunable band alignment. The atomically modulated spatial variation in such electronic structures, i.e., a microscopic basis for the band structure of a WS2/Mo1−xWxS2 heterojunction, was directly observed. The macroscopic band structure of Mo1−xWxS2 alloy was well reproduced by the STS spectra averaged over the surface. An electric field of as high as 80 × 106 Vm−1 was observed at the interface for the alloy with x = 0.3, verifying the efficient separation of photoexcited carriers at the interface.

HfSe2 thin films: 2D transition metal dichalcogenides grown by molecular beam epitaxy.

In this work, we demonstrate the growth of HfSe2 thin films using molecular beam epitaxy. The relaxed growth criteria have allowed us to demonstrate layered, crystalline growth without misfit dislocations on other 2D substrates such as highly ordered pyrolytic graphite and MoS2. The HfSe2 thin films exhibit an atomically sharp interface with the substrates used, followed by flat, 2D layers with octahedral (1T) coordination. The resulting HfSe2 is slightly n-type with an indirect band gap of ∼ 1.1 eV and a measured energy band alignment significantly different from recent DFT calculations. These results demonstrate the feasibility and significant potential of fabricating 2D material based heterostructures with tunable band alignments for a variety of nanoelectronic and optoelectronic applications.

Band alignment of ZnO/CdSe quantum dots heterojunction determined by ultraviolet photoelectron spectroscopy using synchrotron radiation

Band alignments of ZnO/CdSe nanocrystal quantum-dots (NQDs) heterojunctions are determined by ultraviolet photoelectron spectroscopy using synchrotron radiation source. To obtain ideal heterojunction interface, 1,2-ethanedithiol was used for CdSe NQDs as a ligand substitute. A type II band alignment of the ZnO/CdSe NQDs heterojunctions with changeable band offsets by varying the sizes of CdSe NQDs is concluded. The tunable band alignment of ZnO/CdSe NQDs heterojunctions is beneficial to the improvement of the design and fabrication of quantum-dot-sensitized solar cells.

Band alignment determination of ZnO/PbSe heterostructure interfaces by synchrotron radiation photoelectron spectroscopy

Band offsets at ZnO/PbSe heterostructure interfaces are determined by synchrotron radiation photoelectron spectroscopy. A type-I band alignment with the valence band offset (VBO) ΔEV = 0.73 eV and conduction band offset (CBO) ΔEC = 2.36 eV is concluded for ZnO/PbSe film heterojunctions. The approach is extended to ZnO/PbSe nanocrystal (NC) heterojunctions, which reveals that band alignment can be adjusted via varying the dot size and a type-II alignment is formed when the dot size is ⩽5 nm. The small conduction band offset of the ZnO/PbSe film heterojunction and the tunable band alignment of the ZnO/PbSe NCs heterojunction with different crystal sizes shall benefit the design and fabrication of improved optoelectronic devices.