Wafer-Scale Transferrable GaN Enabled by Hexagonal Boron Nitride for Flexible Light-Emitting Diode.

Epitaxy growth and mechanical transfer of high-quality III-nitrides using 2D materials, weakly bonded by van der Waals force, becomes an important technology for semiconductor industry. In this work, wafer-scale transferrable GaN epilayer with low dislocation density is successfully achieved through AlN/h-BN composite buffer layer and its application in flexible InGaN-based light-emitting diodes (LEDs) is demonstrated. Guided by first-principles calculations, the nucleation and bonding mechanism of GaN and AlN on h-BN is presented, and it is confirmed that the adsorption energy of Al atoms on O2 -plasma-treated h-BN is over 1 eV larger than that of Ga atoms. It is found that the introduced high-temperature AlN buffer layer induces sufficient tensile strain during rapid coalescence to compensate the compressive strain generated by the heteromismatch, and a strain-relaxation model for III-nitrides on h-BN is proposed. Eventually, the mechanical exfoliation of single-crystalline GaN film and LED through weak interaction between multilayer h-BN is realized. The flexible free-standing thin-film LED exhibits ≈66% luminescence enhancement with good reliability compared to that before transfer. This work proposes a new approach for the development of flexible semiconductor devices.

Atomic Mechanism of Strain Alleviation and Dislocation Reduction in Highly Mismatched Remote Heteroepitaxy Using a Graphene Interlayer.

Remote heteroepitaxy is known to yield semiconductor films with better quality. However, the atomic mechanisms in systems with large mismatches are still unclear. Herein, low-strain single-crystalline nitride films are achieved on highly mismatched (∼16.3%) sapphire via graphene-assisted remote heteroepitaxy. Because of a weaker interface potential, the in-plane compressive strain at the interface releases by 30%, and dislocations are prevented. Meanwhile, the lattice distortions in the epilayer disappear when the structure climbs over the atomic steps on substrates because graphene renders the steps smooth. In this way, the density of edge dislocations in as-grown nitride films reduces to the same level as that of the screw dislocations, which is rarely observed in heteroepitaxy. Further, the indium composition in InxGa1-xN/GaN multiquantum wells increases to ∼32%, enabling the fabrication of a yellow light-emitting diode. This study demonstrates the advantages of remote heteroepitaxy for bandgap tuning and opens opportunities for photoelectronic and electronic applications.

Atomic-Scale Mechanism of Spontaneous Polarity Inversion in AlN on Nonpolar Sapphire Substrate Grown by MOCVD.

The performance of nitride devices is strongly affected by their polarity. Understanding the polarity determination and evolution mechanism of polar wurtzite nitrides on nonpolar substrates is therefore critically important. This work confirms that the polarity of AlN on sapphire prepared by metal-organic chemical vapor deposition is not inherited from the nitrides/sapphire interface as widely accepted, instead, experiences a spontaneous polarity inversion during the growth. It is found that at the initial growth stage, the interface favors the nitrogen-polarity, rather than the widely accepted metal-polarity or randomly coexisting. However, the polarity subsequently converts into the metal-polar situation, at first locally then expanding into the whole area, driven by the anisotropy of surface energies, which results in universally existing inherent inverse grain boundaries. Furthermore, vertical two-dimensional electron accumulation originating from the lattice symmetry breaking at the inverse grain boundary is first revealed. This work identifies another cause of high-density defects in nitride epilayers, besides lattice mismatch induced dislocations. These findings also offer new insights into atomic structure and determination mechanism of polarity in nitrides, providing clues for its manipulation toward the novel hetero-polarity devices.

Influence of the interface structure and strain on the rectification performance of lateral MoS2/graphene heterostructure devices.

We systematically study the influence of interface configuration and strain on the electronic and transport properties of lateral MoS2/graphene heterostructures by first-principles calculations and quantum transport simulations. We first identify the favorable heterostructure configurations with C-S and/or C-Mo bonds at the interfaces. Strain can be applied to graphene or MoS2 and would not change the relative stabilities of different heterostructures. Band alignment calculations show that all the lateral heterostructures have n-type Schottky contacts. The current-voltage characteristics of the lateral MoS2/graphene heterostructure diodes exhibit good rectification performance. Too strong and too weak interface interactions do not benefit electronic transport. The MoS2/graphene heterostructures with moderate C-S bonds at the interface have larger currents through the junctions than those with C-Mo bonds at the interface. The maximal rectification ratio of the lateral diode with strain applied to MoS2 can reach up to 105. With strain applied to graphene, the currents through the heterostructures can increase by 1-2 orders of magnitude due to the reduced Schottky barrier heights at the interface, but the rectification ratio is reduced with a maximal value of 104. Our calculations can serve as a theoretical guide to design rectifier and diode devices based on two-dimensional lateral heterostructures.

Large Band Edge Tunability in Colloidal Nanoplatelets.

We study the impact of organic surface ligands on the electronic structure and electronic band edge energies of quasi-two-dimensional (2D) colloidal cadmium selenide nanoplatelets (NPLs) using density functional theory. We show how control of the ligand and ligand-NPL interface dipoles results in large band edge energy shifts, over a range of 5 eV for common organic ligands with a minor effect on the NPL band gaps. Using a model self-energy to account for the dielectric contrast and an effective mass model of the excitons, we show that the band edge tunability of NPLs together with the strong dependence of the optical band gap on NPL thickness can lead to favorable photochemical and optoelectronic properties.

Enhancement of tunneling current in phosphorene tunnel field effect transistors by surface defects.

The effects of the staggered double vacancies, hydrogen (H), 3d transition metals, for example cobalt, and semiconductor covalent atoms, for example, germanium, nitrogen, phosphorus (P) and silicon adsorption on the transport properties of monolayer phosphorene were studied using density functional theory and non-equilibrium Green's function formalism. It was observed that the performance of the phosphorene tunnel field effect transistors (TFETs) with an 8.8 nm scaling channel length could be improved most effectively, if the adatoms or vacancies were introduced at the source channel interface. For H and P doped devices, the upper limit of on-state currents of phosphorene TFETs were able to be quickly increased to 2465 µA µm-1 and 1652 µA µm-1, respectively, which not only outperformed the pristine sample, but also met the requirements for high performance logic applications for the next decade in the International Technology Roadmap for Semiconductors (ITRS). It was proved that the defect-induced band gap states make the effective tunneling path between the conduction band (CB) and valence band (VB) much shorter, so that the carriers can be injected easily from the left electrode, then transfer to the channel. In this regard, the tunneling properties of phosphorene TFETs can be manipulated using surface defects. In addition, the effects of spin polarization on the transport properties of doped phosphorene TFETs were also rigorously considered, H and P doped TFETs could achieve a high ON current of 1795 µA µm-1 and 1368 µA µm-1, respectively, which is closer to realistic nanodevices.

Quasi van der Waals Epitaxy of Single Crystalline GaN on Amorphous SiO2/Si(100) for Monolithic Optoelectronic Integration.

The realization of high quality (0001) GaN on Si(100) is paramount importance for the monolithic integration of Si-based integrated circuits and GaN-enabled optoelectronic devices. Nevertheless, thorny issues including large thermal mismatch and distinct crystal symmetries typically bring about uncontrollable polycrystalline GaN formation with considerable surface roughness on standard Si(100). Here a breakthrough of high-quality single-crystalline GaN film on polycrystalline SiO2/Si(100) is presented by quasi van der Waals epitaxy and fabricate the monolithically integrated photonic chips. The in-plane orientation of epilayer is aligned throughout a slip and rotation of high density AlN nuclei due to weak interfacial forces, while the out-of-plane orientation of GaN can be guided by multi-step growth on transfer-free graphene. For the first time, the monolithic integration of light-emitting diode (LED) and photodetector (PD) devices are accomplished on CMOS-compatible SiO2/Si(100). Remarkably, the self-powered PD affords a rapid response below 250 µs under adjacent LED radiation, demonstrating the responsivity and detectivity of 2.01 × 105 A/W and 4.64 × 1013 Jones, respectively. This work breaks a bottleneck of synthesizing large area single-crystal GaN on Si(100), which is anticipated to motivate the disruptive developments in Si-integrated optoelectronic devices.

Tuning semiconductor band edge energies for solar photocatalysis via surface ligand passivation.

Semiconductor photocatalysts capable of broadband solar photon absorption may be nonetheless precluded from use in driving water splitting and other solar-to-fuel related reactions due to unfavorable band edge energy alignment. Using first-principles density functional theory and beyond, we calculate the electronic structure of passivated CdSe surfaces and explore the opportunity to tune band edge energies of this and related semiconductors via electrostatic dipoles associated with chemisorbed ligands. We predict substantial shifts in band edge energies originating from both the induced dipole at the ligand/CdSe interface and the intrinsic dipole of the ligand. Building on important induced dipole contributions, we further show that, by changing the size and orientation of the ligand's intrinsic dipole moment via functionalization, we can control the direction and magnitude of the shifts of CdSe electronic levels. Our calculations suggest a general strategy for enabling new active semiconductor photocatalysts with both optimal opto-electronic, and photo- and electrochemical properties.

Quasi-van der Waals Epitaxy of a Stress-Released AlN Film on Thermally Annealed Hexagonal BN for Deep Ultraviolet Light-Emitting Diodes.

The heteroepitaxy of high-quality aluminum nitride (AlN) with low stress is essential for the development of energy-efficient deep ultraviolet light-emitting diodes (DUV-LEDs). In this work, we realize that quasi-van der Waals epitaxy growth of a stress-released AlN film with low dislocation density on hexagonal boron nitride (h-BN)/sapphire suffered from high-temperature annealing (HTA) treatment and demonstrate its application in a DUV-LED. It is revealed that HTA effectively improves the crystalline quality and surface morphology of monolayer h-BN. Guided by first-principles calculations, we demonstrate that h-BN can enhance lateral migration of Al atoms due to the ability to lower the surface migration barrier (less than 0.14 eV), resulting in the rapid coalescence of the AlN film. The HTA h-BN is also proved to be efficient in reducing the dislocation density and releasing the large strain in the AlN epilayer. Based on the low-stress and high-quality AlN film on HTA h-BN, the as-fabricated 290 nm DUV-LED exhibits 80% luminescence enhancement compared to that without h-BN, as well as good reliability with a negligible wavelength shift under high current. These findings broaden the applications of h-BN in favor of III-nitride and provide an opportunity for further developing DUV optoelectronic devices on large mismatched heterogeneous substrates.

Improving performance of monolayer arsenene tunnel field-effect transistors by defects.

We systematically investigate the transport properties of monolayer arsenene tunneling field-effect transistors (TFETs) along the armchair and zigzag directions using first-principles calculations based on density functional theory (DFT) combined with the non-equilibrium Green's function (NEGF) approach. We introduce five types of defects at the source-channel interface and study their influences on the device performance. The pristine arsenene TFETs along the armchair direction have large ON-state currents due to the small effective masses, but still cannot meet the International Technology Roadmaps of Semiconductor 2022 (ITRS 2022) requirements for high performance (HP) devices. The adsorption of one and two H atoms can significantly enhance the ON-state currents to above 1412 µA µm-1 and reduce subthreshold swing (SS) to below 60 mV decade-1 for both n- and p-type devices, satisfying the ITRS 2022 requirements for HP devices. Besides, the p-type As and the n-type Li adatoms can improve the performance of p-type and n-type devices, respectively. The pristine arsenene TFETs along the zigzag direction with low ON-state currents already meet the ITRS 2022 requirements for low-power (LP) devices. The performance of the p-type TFETs as LP devices can be improved by p-type SV and the As adatom by increasing the ON-state currents and/or reducing the SS. On the other hand, the adsorption of one H adatom can remarkably increase the ON-state current of the p-type TFET to 1563 µA µm-1 and reduce SS to 34 mV decade-1, allowing the device to work as an HP device. We further confirm that the enhancement of the ON-state currents is due to the shortening of the band-to-band tunneling path through the defect induced gap states. Our calculations provide a theoretical guide to improve the performance of TFETs based on arsenene or other monolayer materials by suitable defects.

Graphene-driving strain engineering to enable strain-free epitaxy of AlN film for deep ultraviolet light-emitting diode.

The energy-efficient deep ultraviolet (DUV) optoelectronic devices suffer from critical issues associated with the poor quality and large strain of nitride material system caused by the inherent mismatch of heteroepitaxy. In this work, we have prepared the strain-free AlN film with low dislocation density (DD) by graphene (Gr)-driving strain-pre-store engineering and a unique mechanism of strain-relaxation in quasi-van der Waals (QvdW) epitaxy is presented. The DD in AlN epilayer with Gr exhibits an anomalous sawtooth-like evolution during the whole epitaxy process. Gr can help to enable the annihilation of the dislocations originated from the interface between AlN and Gr/sapphire by impelling a lateral two-dimensional growth mode. Remarkably, it can induce AlN epilayer to pre-store sufficient tensile strain during the early growth stage and thus compensate the compressive strain caused by hetero-mismatch. Therefore, the low-strain state of the DUV light-emitting diode (DUV-LED) epitaxial structure is realized on the strain-free AlN template with Gr. Furthermore, the DUV-LED with Gr demonstrate 2.1 times enhancement of light output power and a better stability of luminous wavelength compared to that on bare sapphire. An in-depth understanding of this work reveals diverse beneficial impacts of Gr on nitride growth and provides a novel strategy of relaxing the vital requirements of hetero-mismatch in conventional heteroepitaxy.

Strain-induced band gap modification in coherent core/shell nanostructures.

Using first-principles calculations within density functional theory, we study the relative impacts of quantum confinement and strain on the electronic structure of two II-VI semiconductor compounds with a large lattice-mismatch, CdSe and CdTe, in core/shell nanowire geometries with different core radii and shell thicknesses. For fixed CdSe core radius, we find that the electronic band gap in the core is significantly reduced with increasing CdTe shell thickness, by an amount comparable to that expected from quantum confinement, due to the development of a large and highly anisotropic strain throughout the heterostructure. A straightforward analysis allows us to separate quantitatively changes in band gap due to quantum confinement and strain. Our studies elucidate and quantify the importance of strain in determining the electronic and optical properties of core/shell nanostructures.

Direct growth of wafer-scale highly oriented graphene on sapphire.

Direct chemical vapor deposition (CVD) growth of wafer-scale high-quality graphene on dielectrics is of paramount importance for versatile applications. Nevertheless, the synthesized graphene is typically a polycrystalline film with high density of uncontrolled defects, resulting in a low carrier mobility and high sheet resistance. Here, we report the direct growth of highly oriented monolayer graphene films on sapphire wafers. Our growth strategy is achieved by designing an electromagnetic induction heating CVD operated at elevated temperature, where the high pyrolysis and migration barriers of carbon species are easily overcome. Meanwhile, the embryonic graphene domains are guided into good alignment by minimizing its configuration energy. The thus obtained graphene film accordingly manifests a markedly improved carrier mobility (~14,700 square centimeters per volt per second at 4 kelvin) and reduced sheet resistance (~587 ohms per square), which compare favorably with those from catalytic growth on polycrystalline metal foils and epitaxial growth on silicon carbide.

A Linear Relationship between the Charge Transfer Amount and Level Alignment in Molecule/Two-Dimensional Adsorption Systems.

We systematically study the adsorption of tetrathiafulvalene (TTF), tetracyanoquinodimethane (TCNQ), and tetracyanoethylene (TCNE) on a variety of two-dimensional (2D) monolayers with weak van der Waals (vdW) interactions based on density functional theory. We confirm that TTF can act as an effective donor when its highest occupied molecular orbital (HOMO) level is higher than the conduction band minimum (CBM) state of 2D materials, while TCNQ and TCNE can act as effective acceptors when their lowest unoccupied molecular orbital (LUMO) levels are lower than the valence band maximum (VBM) state of 2D materials. Moreover, our calculations reveal a linear relationship between the charge transfer amount and level alignment between the molecule and 2D monolayer. In other words, the charge transfer is linearly dependent on the energy difference between the HOMO level and 2D CBM state for the donor molecule or the energy difference between the LUMO level and 2D VBM state for the acceptor molecule. The linear relationship indicates that the charge transfer is insensitive to the local binding environments due to the weak vdW interaction. However, the linear relationship cannot be applied to atoms or molecules that are chemisorbed on 2D materials.

High-performance 5.1 nm in-plane Janus WSeTe Schottky barrier field effect transistors.

Using ab initio quantum-transport simulations, we studied the intrinsic transfer characteristics and benchmarks of the ballistic performance of 5.1 nm double-gated Schottky-barrier field effect transistors (SBFETs) consisting of in-plane (IP) heterojunctions of metallic-phase (1T or 1T') MTe2 (M = Ti, Zr, Hf, Cr, Mo, W) and semiconducting-phase (2H) WSe2, WTe2 and Janus WSeTe. The 2H-phase Janus WSeTe is a semiconductor with an indirect bandgap (1.26 eV), which is less than the bandgap of 2H-phase WSe2 (1.64 eV) and is greater than the bandgap of 2H-phase WTe2 (1.02 eV). The band alignments show that all IP 1T/2H contacts are Schottky-barrier contacts with the Fermi levels of 1T or 1T' MTe2 (M = Ti, Zr, Hf, Cr, Mo, W) located within the bandgaps of 2H WSe2, WTe2 and Janus WSeTe. Although double-gated IP WSe2-SBFETs can satisfy the OFF current requirement, their ON currents all fall below the requirements of the high performance transistor outlined by the ITRS (International Technology Roadmap for Semiconductors, 2013 version) for the production year 2028. Double-gated IP WTe2-SBFETs cannot overcome the short channel effect leading to minimum drain currents all beyond the OFF current requirement of ITRS (2013 version) for the production year 2028. Fortunately, double-gated IP WSeTe-SBFETs with 1T MoTe2 or 1T' WTe2 electrodes can overcome the short channel effect and satisfy the requirements of the high-performance transistor outlined by the ITRS (2013 version) for the production year 2028.

Graphene-Assisted Quasi-van der Waals Epitaxy of AlN Film on Nano-Patterned Sapphire Substrate for Ultraviolet Light Emitting Diodes.

This protocol demonstrates a method for graphene-assisted quick growth and coalescence of AlN on nano-pattened sapphire substrate (NPSS). Graphene layers are directly grown on NPSS using catalyst-free atmospheric-pressure chemical vapor deposition (APCVD). By applying nitrogen reactive ion etching (RIE) plasma treatment, defects are introduced into the graphene film to enhance chemical reactivity. During metal-organic chemical vapor deposition (MOCVD) growth of AlN, this N-plasma treated graphene buffer enables AlN quick growth, and coalescence on NPSS is confirmed by cross-sectional scanning electron microscopy (SEM). The high quality of AlN on graphene-NPSS is then evaluated by X-ray rocking curves (XRCs) with narrow (0002) and (10-12) full width at half-maximum (FWHM) as 267.2 arcsec and 503.4 arcsec, respectively. Compared to bare NPSS, AlN growth on graphene-NPSS shows significant reduction of residual stress from 0.87 GPa to 0.25 Gpa, based on Raman measurements. Followed by AlGaN multiple quantum wells (MQWS) growth on graphene-NPSS, AlGaN-based deep ultraviolet light-emitting-diodes (DUV LEDs) are fabricated. The fabricated DUV-LEDs also demonstrate obvious, enhanced luminescence performance. This work provides a new solution for the growth of high quality AlN and fabrication of high performance DUV-LEDs using a shorter process and less costs.

Quasi-2D Growth of Aluminum Nitride Film on Graphene for Boosting Deep Ultraviolet Light-Emitting Diodes.

Efficient and low-cost production of high-quality aluminum nitride (AlN) films during heteroepitaxy is the key for the development of deep ultraviolet light-emitting diodes (DUV-LEDs). Here, the quasi-2D growth of high-quality AlN film with low strain and low dislocation density on graphene (Gr) is presented and a high-performance 272 nm DUV-LED is demonstrated. Guided by first-principles calculations, it is found that AlN grown on Gr prefers lateral growth both energetically and kinetically, thereby resulting in a Gr-driven quasi-2D growth mode. The strong lateral growth mode enables most of dislocations to annihilate each other at the AlN/Gr interface, and therefore the AlN epilayer can quickly coalesce and flatten the nanopatterned sapphire substrate. Based on the high quality and low strain of AlN film grown on Gr, the as-fabricated 272 nm DUV-LED shows a 22% enhancement of output power than that with low-temperature AlN buffer, following a negligible wavelength shift under high current. This facile strategy opens a pathway to drastically improve the performance of DUV-LEDs.

Interaction between hydrogen molecules and metallofullerenes.

Within first-principles density functional theory, we explore the feasibility of using metallofullerenes as efficient hydrogen storage media. In particular, we systematically investigate the interaction between hydrogen molecules and La encapsulated all-carbon fullerenes, C(n) (20 < or = n < or = 82), focusing on the role of transferred charges between the metal atoms and fullerenes on the affinity of hydrogen molecules to the metallofullerenes. Our calculations show that three electrons are transferred from La atom to fullerene cages, while the induced charges are mostly screened by the fullerene cages. We find the local enhancement of molecular hydrogen affinity to the fullerenes to be sensitively dependent on the local bonding properties, rather than on the global charging effects.

Improved Epitaxy of AlN Film for Deep-Ultraviolet Light-Emitting Diodes Enabled by Graphene.

The growth of single-crystal III-nitride films with a low stress and dislocation density is crucial for the semiconductor industry. In particular, AlN-derived deep-ultraviolet light-emitting diodes (DUV-LEDs) have important applications in microelectronic technologies and environmental sciences but are still limited by large lattice and thermal mismatches between the epilayer and substrate. Here, the quasi-van der Waals epitaxial (QvdWE) growth of high-quality AlN films on graphene/sapphire substrates is reported and their application in high-performance DUV-LEDs is demonstrated. Guided by density functional theory calculations, it is found that pyrrolic nitrogen in graphene introduced by a plasma treatment greatly facilitates the AlN nucleation and enables fast growth of a mirror-smooth single-crystal film in a very short time of ≈0.5 h (≈50% decrease compared with the conventional process), thus leading to a largely reduced cost. Additionally, graphene effectively releases the biaxial stress (0.11 GPa) and reduces the dislocation density in the epilayer. The as-fabricated DUV-LED shows a low turn-on voltage, good reliability, and high output power. This study may provide a revolutionary technology for the epitaxial growth of AlN films and provide opportunities for scalable applications of graphene films.

Atomic mechanism of strong interactions at the graphene/sapphire interface.

For atomically thin two-dimensional materials, interfacial effects may dominate the entire response of devices, because most of the atoms are in the interface/surface. Graphene/sapphire has great application in electronic devices and semiconductor thin-film growth, but the nature of this interface is largely unknown. Here we find that the sapphire surface has a strong interaction with some of the carbon atoms in graphene to form a C-O-Al configuration, indicating that the interface interaction is no longer a simple van der Waals interaction. In addition, the structural relaxation of sapphire near the interface is significantly suppressed and very different from that of a bare sapphire surface. Such an interfacial C-O-Al bond is formed during graphene growth at high temperature. Our study provides valuable insights into understanding the electronic structures of graphene on sapphire and remote control of epitaxy growth of thin films by using a graphene-sapphire substrate.