Emergence of threefold symmetric helical photocurrents in epitaxial low twinned Bi2Se3.

We present evidence of a strong circular photon drag effect (PDE) in topological insulators (TIs) through the observation of helicity-dependent topological photocurrents with threefold rotational symmetry using THz spectroscopy in epitaxially-grown Bi2Se3 with reduced crystallographic twinning. We establish how twinned domains introduce competing nonlinear optical (NLO) responses inherent to the crystal structure that obscure geometry-sensitive optical processes through the introduction of a spurious mirror symmetry. Minimizing the twinning defect reveals strong NLO response currents whose magnitude and direction depend on the alignment of the excitation to the crystal axes and follow the threefold rotational symmetry of the crystal. Notably, photocurrents arising from helical light reverse direction for left/right circular polarizations and maintain a strong azimuthal dependence-a result uniquely attributable to the circular PDE, where the photon momentum acts as an applied in-plane field stationary in the laboratory frame. Our results demonstrate new levels of control over the magnitude and direction of photocurrents in TIs and that the study of single-domain films is crucial to reveal hidden phenomena that couple topological order and crystal symmetries.

Preservation of Topological Surface States in Millimeter-Scale Transferred Membranes.

Ultrathin topological insulator membranes are building blocks of exotic quantum matter. However, traditional epitaxy of these materials does not facilitate stacking in arbitrary orders, while mechanical exfoliation from bulk crystals is also challenging due to the non-negligible interlayer coupling therein. Here we liberate millimeter-scale films of the topological insulator Bi2Se3, grown by molecular beam epitaxy, down to 3 quintuple layers. We characterize the preservation of the topological surface states and quantum well states in transferred Bi2Se3 films using angle-resolved photoemission spectroscopy. Leveraging the photon-energy-dependent surface sensitivity, the photoemission spectra taken with 6 and 21.2 eV photons reveal a transfer-induced migration of the topological surface states from the top to the inner layers. By establishing clear electronic structures of the transferred films and unveiling the wave function relocation of the topological surface states, our work lays the physics foundation crucial for the future fabrication of artificially stacked topological materials with single-layer precision.

Topological Surface State Evolution in Bi2Se3 via Surface Etching.

Topological insulators are materials that have an insulating bulk interior while maintaining gapless boundary states against back scattering. Bi2Se3 is a prototypical topological insulator with a Dirac-cone surface state around Γ. Here, we present a controlled methodology to gradually remove Se atoms from the surface Se-Bi-Se-Bi-Se quintuple layers, eventually forming bilayer-Bi on top of the quintuple bulk. Our method allows us to track the topological surface state and confirm its robustness throughout the surface modification. Importantly, we report a relocation of the topological Dirac cone in both real space and momentum space as the top surface layer transitions from quintuple Se-Bi-Se-Bi-Se to bilayer-Bi. Additionally, charge transfer among the different surface layers is identified. Our study provides a precise method to manipulate surface configurations, allowing for the fine-tuning of the topological surface states in Bi2Se3, which represents a significant advancement toward nanoengineering of topological states.

Growth optimization and crossover of transport mechanisms in Bi2Se3thin films.

We report the growth, structural characterization, and transport studies of Bi2Se3thin film on single crystalline silicon (Si), Si/SiO2, quartz, and glass substrates by thermal evaporation method. Our results show that 300 °C is the optimum substrate temperature to obtain thec-axis (001) oriented Bi2Se3films on all the substrates. The film grown on the Si substrate has the minimum crystalline disorder. The energy-dispersive x-ray spectroscopy results show that film on Si substrate is bismuth deficient, the film on Si/SiO2substrate is selenium deficient, and the film on quartz substrate is near perfect stoichiometric providing a way to tune the electronic properties of Bi2Se3films through substrate selection. The film grown on quartz shows the highest mobility (2.7 × 104cm2V-1s-1) which drops to 150 cm2V-1s-1for Si, 60 cm2V-1s-1for Si/SiO2, and 0.9 cm2V-1s-1for glass substrate. Carrier concentration is n-type for Bi2Se3films on Si (∼1018cm-3), quartz (∼1018cm-3) and Si/SiO2(∼1019cm-3) substrate with a clear indication of frozen out effect around 50 K for Si/SiO2and Si substrate. Longitudinal resistivity of Bi2Se3film on Si/SiO2substrate shows different behavior in three different temperature regions: temperature dependent resistivity region due to electron-phonon scattering, a nearly temperature independent resistivity region due to electron-phonon and electron-ion scattering, and a quantum coherent transport region.

Mesoporous Semiconductive Bi2Se3 Films.

Bi2Se3 is a semiconductive material possessing a bandgap of 0.3 eV, and its unique band structure has paved the way for diverse applications. Herein, we demonstrate a robust platform for synthesizing mesoporous Bi2Se3 films with uniform pore sizes via electrodeposition. Block copolymer micelles act as soft templates in the electrolyte to create a 3D porous nanoarchitecture. By controlling the length of the block copolymer, the pore size is adjusted to 9 and 17 nm precisely. The nonporous Bi2Se3 film exhibits a tunneling current in a vertical direction of 52.0 nA, but upon introducing porosity (9 nm pores), the tunneling current increases significantly to 684.6 nA, suggesting that the conductivity of Bi2Se3 films is dependent on the pore structure and surface area. The abundant porous architecture exposes a larger surface area of Bi2Se3 to the surrounding air within the same volume, thereby augmenting its metallic properties.

Engineering Heat Transport Across Epitaxial Lattice-Mismatched van der Waals Heterointerfaces.

Artificially engineered 2D materials offer unique physical properties for thermal management, surpassing naturally occurring materials. Here, using van der Waals epitaxy, we demonstrate the ability to engineer extremely insulating thermal metamaterials based on atomically thin lattice-mismatched Bi2Se3/MoSe2 superlattices and graphene/PdSe2 heterostructures with exceptional thermal resistances (70-202 m2 K/GW) and ultralow cross-plane thermal conductivities (0.012-0.07 W/mK) at room temperature, comparable to those of amorphous materials. Experimental data obtained using frequency-domain thermoreflectance and low-frequency Raman spectroscopy, supported by tight-binding phonon calculations, reveal the impact of lattice mismatch, phonon-interface scattering, size effects, temperature, and interface thermal resistance on cross-plane heat dissipation, uncovering different thermal transport regimes and the dominant role of long-wavelength phonons. Our findings provide essential insights into emerging synthesis and thermal characterization methods and valuable guidance for the development of large-area heteroepitaxial van der Waals films of dissimilar materials with tailored thermal transport characteristics.

Electrochemical biosensor based on topological insulator Bi2Se3 tape electrode for HIV-1 DNA detection.

A large-size Bi2Se3 tape electrode (BTE) was prepared by peeling off a 2 × 1 × 0.5 cm high-quality single crystal. The feasibility of using the flexible BTE as an efficient bioplatform to load Au nanoparticles and probe DNA for HIV-1 DNA electrochemical sensing was explored. Differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) show that the resultant biosensor has a wide linear range from 0.1 fM to 1 pM, a low detection limit of 50 aM, excellent selectivity, reproducibility and stability, and is superior to the pM DNA detection level of Pt-Au, graphene-AuNPs hybrid biosensors. This outstanding performance is attributed to the intrinsic surface state of Bi2Se3 topological insulator in facilitating electron transfer. Therefore, BTE electrochemical biosensor platform has great potential in the application for sensitive detection of DNA biomarkers.

Towards More Accurate Determination of the Thermoelectric Properties of Bi2Se3 Epifilms by Suspension via Nanomachining Techniques.

We report on the characterization of the thermoelectric properties of Bi2Se3 epifilms. MBE-grown Bi2Se3 films on GaAs (111) A are nanomachined with integrated Pt elements serving as local joule heaters, thermometers, and voltage probes. We suspended a 4 µm × 120 µm Bi2Se3 by nanomachining techniques. Specifically, we selectively etched GaAs buffer/substrate layers by citric acid solution followed by a critical point drying method. We found that the self-heating 3ω method is an appropriate technique for the accurate measurement of the thermal conductivity of suspended Bi2Se3. The measured thermoelectric properties of 200 nm thick Bi2Se3 at room temperature were κ=1.95 W/m K, S=−102.8 µV/K, σ = 75,581 S/m and the figure of merit was ZT=0.12. The study introduces a method to measure thermal conductivity accurately by suspending thin films.

NIR-Triggered Multi-Mode Antitumor Therapy Based on Bi2 Se3 /Au Heterostructure with Enhanced Efficacy.

Of all the reaction oxygen species (ROS) therapeutic strategies, NIR light-induced photocatalytic therapy (PCT) based on semiconductor nanomaterials has attracted increasing attention. However, the photocatalysts suffer from rapid recombination of electron-hole pairs due to the narrow band gaps, which are greatly restricted in PCT application. Herein, Bi2 Se3 /Au heterostructured photocatalysts are fabricated to solve the problems by introducing Au nanoparticles (NPs) in situ on the surface of the hollow mesoporous structured Bi2 Se3 . Owing to the lower work function of Au NPs, the photo-induced electrons are easier to transfer and assemble on their surfaces, resulting in the increased separation of the electron-hole pairs with efficient ROS generation. Besides, Bi2 Se3 /Au heterostructures also enhance the photothermal efficiency due to the effective orbital overlaps with accelerated electron migrations according to density functional theory calculations. Moreover, the PLGA-PEG and the doxorubicin (DOX) are introduced for photothermal-triggered drug release in the system. The Bi2 Se3 /Au heterostructures also displays excellent infrared thermal (IRT) and computed tomography (CT) dual-modal imaging property for promising cancer diagnosis. Collectively, Bi2 Se3 /Au@PLGA-PEG-DOX exhibits prominent tumor inhibition effect based on synchronous PTT, PCT and chemotherapy triggered by NIR light for efficient antitumor treatment.

Designer Topological Insulator with Enhanced Gap and Suppressed Bulk Conduction in Bi2Se3/Sb2Te3 Ultrashort-Period Superlattices.

A novel approach to suppress bulk conductance in three-dimensional (3D) topological insulators (TIs) using short-period superlattices (SLs) of two TIs is presented. Evidence for superlattice gap enhancement (SGE) was obtained from the reduction of bulk background doping from 1.2 × 1020 cm-3 to 8.5 × 1018 cm-3 as the period of Bi2Se3/Sb2Te3 SLs is decreased from 12 nm to 5 nm. Tight binding calculations show that, in the ultrashort-period regime, a significant SGE can be achieved for the resulting SL. Ultrathin short-period SLs behave as new designer TIs with bulk bandgaps up to 60% larger than the bandgap of the constituent layer of largest bandgap, while retaining topological surface features. Evidence for gap formation was obtained from ellipsometric measurements. Analysis of the weak antilocalization cusp in low-temperature magneto-conductance confirms that the top and bottom surfaces of the SL structure behave as Dirac surfaces. This approach represents a promising platform for building truly insulating TIs.

Suppression of Persistent Photoconductivity of Rubrene Crystals using Gate-Tunable Rubrene/Bi2 Se3 Diodes with Photoinduced Negative Differential Resistance.

Organic single-crystalline semiconductors show great potential in high-performance photodetectors. However, they suffer from persistent photoconductivity (PPC) due to the charge trapping, which has severely hindered high-speed imaging applications. Here, a universal strategy of solving the PPC by integrating with topological insulator Bi2 Se3 is provided. The rubrene/Bi2 Se3 heterojunctions are selected as an example for general demonstration due to the reproducibly high mobility and broad optoelectronic applications of rubrene crystals. By virtue of high carrier concentration on Bi2 Se3 surface and the strong built-in electrical field, the photoresponse of the heterotransistor is significantly reduced for more than two orders (from over 10 s to 54 ms), meanwhile the photoresponsivity can reach 124 A W-1 . To the best of knowledge, this operating speed is among the fastest responses in organic-inorganic heterojunctions. The heterotransistor also shows unique negative differential resistance under positive gate bias, which can be explained by photoinduced de-trapping of electron trap states in the bulk rubrene crystals. Besides, the rubrene/Bi2 Se3 heterojunction behaves as a gate-tunable backward-like diode due to the inhomogenous carrier distribution in the thick rubrene crystal and inversion of relative Fermi level positions. The findings demonstrate versatile functionalities of the rubrene/Bi2 Se3 heterojunctions for various emerging optoelectronic applications.

Solution to the Hole-Doping Problem and Tunable Quantum Hall Effect in Bi2Se3 Thin Films.

Bi2Se3, one of the most widely studied topological insulators (TIs), is naturally electron-doped due to n-type native defects. However, many years of efforts to achieve p-type Bi2Se3 thin films have failed so far. Here, we provide a solution to this long-standing problem, showing that the main culprit has been the high density of interfacial defects. By suppressing these defects through an interfacial engineering scheme, we have successfully implemented p-type Bi2Se3 thin films down to the thinnest topological regime. On this platform, we present the first tunable quantum Hall effect (QHE) study in Bi2Se3 thin films and reveal not only significantly asymmetric QHE signatures across the Dirac point but also the presence of competing anomalous states near the zeroth Landau level. The availability of doping tunable Bi2Se3 thin films will now make it possible to implement various topological quantum devices, previously inaccessible.

Revealing Optical Transitions and Carrier Recombination Dynamics within the Bulk Band Structure of Bi2Se3.

Bismuth selenide (Bi2Se3) is a prototypical 3D topological insulator whose Dirac surface states have been extensively studied theoretically and experimentally. Surprisingly little, however, is known about the energetics and dynamics of electrons and holes within the bulk band structure of the semiconductor. We use mid-infrared femtosecond transient reflectance measurements on a single nanoflake to study the ultrafast thermalization and recombination dynamics of photoexcited electrons and holes within the extended bulk band structure over a wide energy range (0.3 to 1.2 eV). Theoretical modeling of the reflectivity spectral line shapes at 10 K demonstrates that the electrons and holes are photoexcited within a dense and cold electron gas with a Fermi level positioned well above the bottom of the lowest conduction band. Direct optical transitions from the first and the second spin-orbit split valence bands to the Fermi level above the lowest conduction band minimum are identified. The photoexcited carriers thermalize rapidly to the lattice temperature within a couple of picoseconds due to optical phonon emission and scattering with the cold electron gas. The minority carrier holes recombine with the dense electron gas within 150 ps at 10 K and 50 ps at 300 K. Such knowledge of interaction of electrons and holes within the bulk band structure provides a foundation for understanding how such states interact dynamically with the topologically protected Dirac surface states.

Three-dimensional Architecture Enabled by Strained Two-dimensional Material Heterojunction.

Engineering the structure of materials endows them with novel physical properties across a wide range of length scales. With high in-plane stiffness and strength, but low flexural rigidity, two-dimensional (2D) materials are excellent building blocks for nanostructure engineering. They can be easily bent and folded to build three-dimensional (3D) architectures. Taking advantage of the large lattice mismatch between the constituents, we demonstrate a 3D heterogeneous architecture combining a basal Bi2Se3 nanoplate and wavelike Bi2Te3 edges buckling up and down forming periodic ripples. Unlike 2D heterostructures directly grown on substrates, the solution-based synthesis allows the heterostructures to be free from substrate influence during the formation process. The balance between bending and in-plane strain energies gives rise to controllable rippling of the material. Our experimental results show clear evidence that the wavelengths and amplitudes of the ripples are dependent on both the widths and thicknesses of the rippled material, matching well with continuum mechanics analysis. The rippled Bi2Se3/Bi2Te3 heterojunction broadens the horizon for the application of 2D materials heterojunction and the design and fabrication of 3D architectures based on them, which could provide a platform to enable nanoscale structure generation and associated photonic/electronic properties manipulation for optoelectronic and electromechanic applications.

Bifunctional Au@Bi2 Se3 Core-Shell Nanoparticle for Synergetic Therapy by SERS-Traceable AntagomiR Delivery and Photothermal Treatment.

For the first time, topological insulator bismuth selenide nanoparticles (Bi2 Se3 NP) are core-shelled with gold (Au@Bi2 Se3 ) i) to represent considerably small-sized (11 nm) plasmonic nanoparticles, enabling accurate bioimaging in the near-infrared region; ii) to substantially improve Bi2 Se3 biocompatibility, iii) water dispersibility, and iv) surface functionalization capability through straightforward gold-thiol interaction. The Au@Bi2 Se3 is subsequently functionalized for v) effective targeting of SH-SY5Y cancer cells, vi) disrupting the endosome/lysosome membrane, vii) traceable delivery of antagomiR-152 and further synergetic oncomiR knockdown and photothermal therapy (PTT). Unprecedentedly, it is observed that the Au shell thickness has a significant impact on evoking the exotic plasmonic features of Bi2 Se3 . The Au@Bi2 Se3 possesses a high photothermal conversion efficiency (35.5%) and a remarkable surface plasmonic effect (both properties are approximately twofold higher than those of 50 nm Au nanoparticles). In contrast to the siRNA/miRNA delivery methods, the antagomiR delivery is based on strand displacement, in which the antagomiR-152 is displaced by oncomiR-152 followed by a surface-enhanced Raman spectroscopy signal drop. This enables both cancer cell diagnosis and in vitro real-time monitoring of the antagomiR release. This selective PTT nanoparticle can also efficiently target solid tumors and undergo in vivo PTT, indicating its potential clinical applications.

Photoinduced Inverse Spin Hall Effect of Surface States in the Topological Insulator Bi2Se3.

The three-dimensional (3D) topological insulator (TI) Bi2Se3 exhibits topologically protected, linearly dispersing Dirac surface states (SSs). To access the intriguing properties of these SSs, it is important to distinguish them from the coexisting two-dimensional electron gas (2DEG) on the surface. Here, we use circularly polarized light to induce the inverse spin Hall effect in a Bi2Se3 thin film at different temperatures (i.e., from 77 to 300 K). It is demonstrated that the photoinduced inverse spin Hall effect (PISHE) of the top SSs and the 2DEG can be separated based on their opposite signs. The temperature and power dependence of the PISHE also confirms our method. Furthermore, it is found that the PISHE in the 2DEG is dominated by the extrinsic mechanism, as revealed by the temperature dependence of the PISHE.

Catalytic topological insulator Bi2Se3 nanoparticles for invivo protection against ionizing radiation.

Bi2Se3 nanoparticles (NPs) have attracted wide interests in biological and medical applications. Layer-like Bi2Se3 with high active surface area is promising for free radical scavenging. Here, we extended the medical applications of Bi2Se3 NPs further to in vivo protection against ionizing radiation based on their superior antioxidant activities and electrocatalytic properties. It was found that Bi2Se3 NPs can significantly increase the surviving fraction of mice after exposure of high-energy radiation of gamma ray. Additionally, the Bi2Se3 NPs can help to recover radiation-lowered red blood cell counts, white blood cell counts and platelet levels. Further investigations revealed that Bi2Se3 NPs behaved as functional free radical scavengers and significantly decreased the level of methylenedioxyamphetamine. In vivo toxicity studies showed that Bi2Se3 NPs did not cause significant side effects in panels of blood chemistry, clinical biochemistry and pathology.

Thermal Stability and Anisotropic Sublimation of Two-Dimensional Colloidal Bi2Te3 and Bi2Se3 Nanocrystals.

The structural and compositional stabilities of two-dimensional (2D) Bi2Te3 and Bi2Se3 nanocrystals, produced by both colloidal synthesis and by liquid phase exfoliation, were studied by in situ transmission electron microscopy (TEM) during annealing at temperatures between 350 and 500 °C. The sublimation process induced by annealing is structurally and chemically anisotropic and takes place through the preferential dismantling of the prismatic {011̅0} type planes, and through the preferential sublimation of Te (or Se). The observed anisotropic sublimation is independent of the method of nanocrystal's synthesis, their morphology, or the presence of surfactant molecules on the nanocrystals surface. A thickness-dependent depression in the sublimation point has been observed with nanocrystals thinner than about 15 nm. The Bi2Se3 nanocrystals were found to sublimate below 280 °C, while the Bi2Te3 ones sublimated at temperatures between 350 and 450 °C, depending on their thickness, under the vacuum conditions in the TEM column. Density functional theory calculations confirm that the sublimation of the prismatic {011̅0} facets is more energetically favorable. Within the level of modeling employed, the sublimation occurs at a rate about 700 times faster than the sublimation of the {0001} planes at the annealing temperatures used in this work. This supports the distinctly anisotropic mechanisms of both sublimation and growth of Bi2Te3 and Bi2Se3 nanocrystals, known to preferentially adopt a 2D morphology. The anisotropic sublimation behavior is in agreement with the intrinsic anisotropy in the surface free energy brought about by the crystal structure of Bi2Te3 or Bi2Se3.

FeSe2-Decorated Bi2Se3 Nanosheets Fabricated via Cation Exchange for Chelator-Free 64Cu-labeling and Multimodal Image-Guided Photothermal-Radiation Therapy.

Multifunctional theranostic agents have become rather attractive to realize image-guided combination cancer therapy. Herein, we develop a novel method to synthesize Bi2Se3 nanosheets decorated with mono-dispersed FeSe2 nanoparticles (FeSe2/Bi2Se3) for tetra-modal image-guided combined photothermal & radiation tumor therapy. Interestingly, upon addition of Bi(NO3)3, pre-made FeSe2 nanoparticles via cation exchange would be gradually converted into Bi2Se3 nanosheets, on which remaining FeSe2 nanoparticles are decorated. The yielded FeSe2/Bi2Se3 composite-nanostructures were then modified with polyethylene glycol (PEG). Taking advantages of the high r2 relaxivity of FeSe2, the X-ray attenuation ability of Bi2Se3, the strong near-infrared (NIR) optical absorbance of the whole nanostructure, as well as the chelate-free radiolabeling of 64Cu on FeSe2/Bi2Se3-PEG, in vivo magnetic resonance (MR)/computer tomography (CT)/photoacoustic (PA)/position emission tomography (PET) multimodal imaging was carried out, revealing efficient tumor homing of FeSe2/Bi2Se3-PEG after intravenous injection. Utilizing the intrinsic physical properties of FeSe2/Bi2Se3-PEG, in vivo photothermal & radiation therapy to achieve synergistic tumor destruction was then realized, without causing obvious toxicity to the treated animals. Our work presents a unique method to synthesize composite-nanostructures with highly integrated functionalities, promising not only for nano-biomedicine, but also potentially for other different nanotechnology fields.

Metabolizable Ultrathin Bi2 Se3 Nanosheets in Imaging-Guided Photothermal Therapy.

Poly(vinylpyrrolidone)-encapsulated Bi2 Se3 nanosheets with a thickness of 1.7 nm and diameter of 31.4 nm are prepared by a solution method. Possessing an extinction coefficient of 11.5 L g(-1) cm(-1) at 808 nm, the ultrathin Bi2 Se3 nanosheets boast a high photothermal conversion efficiency of 34.6% and excellent photoacoustic performance. After systemic administration, the Bi2 Se3 nanosheets with the proper size and surface properties accumulate passively in tumors enabling efficient photoacoustic imaging of the entire tumors to facilitate photothermal cancer therapy. In vivo biodistribution studies reveal that they are expelled from the body efficiently after 30 d. The ultrathin Bi2 Se3 nanosheets have large clinical potential as metabolizable near-infrared-triggered theranostic agents.