Metal-semiconductor Heterostructures Research Articles

Electrical contact property and control effects for stable T(H)-TaS2/C3B metal-semiconductor heterojunctions.

Metal-semiconductor heterojunctions are the basis for developing new electronic devices. Here, T(H)-TaS2/C3B metal-semiconductor heterostructures are constructed by different phase T- and H-TaS2 monolayers combined with the C3B monolayer. The calculated corrected binding energies, phonon band structures, elastic constants, and molecular dynamics simulations indicated that both heterojunctions are highly stable, meaning that T(H)-TaS2/C3B heterojunctions possibly exist in experiments. The electronic property calculations showed that the intrinsic T(H)-TaS2/C3B heterojunction is an n(p)-type Schottky contact with a low Schottky barrier height (SBH), which is very important for the design of high-performance field-effect transistors. The electronic properties of the T(H)-TaS2/C3B heterojunctions can be controlled by varying the vertical strain and external electric field; however, the strain only resulted in a small change in the heterojunction SBH. Nevertheless, under external electrical field control, the T-TaS2/C3B heterojunction could manage a transition from an n-type Schottky contact to an n-type Ohmic contact and the H-TaS2/C3B heterojunction could be altered from a p-type Schottky contact to a p-type Ohmic contact. These findings provide theoretical insights into the electronic and electrical contact properties of the T(H)-TaS2/C3B heterojunction, which could be beneficial for developing n-type MOS and p-type MOS transistors.

Achieving ultra-low contact barriers in MX2/SiH (M = Nb, Ta; X = S, Se) metal-semiconductor heterostructures: first-principles prediction.

Minimizing the contact barriers at the interface, forming between two different two-dimensional metals and semiconductors, is essential for designing high-performance optoelectronic devices. In this work, we design different types of metal-semiconductor heterostructures by combining 2D metallic MX2 (M = Nb, Hf; X = S, Se) and 2D semiconductor SiH and investigate systematically their electronic properties and contact characteristics using first principles calculations. We find that all the MX2/SiH (M = Nb, Ta; X = S, Se) heterostructures are energetically stable, suggesting that they could potentially be synthesized in the future. Furthermore, the generation of the MX2/SiH metal-semiconductor heterostructures leads to the formation of the Schottky contact with ultra-low Schottky barriers of a few tens of meV. This finding suggests that all the 2D MX2 (M = Nb, Ta; X = S, Se) metals act as effective electrical contact 2D materials to contact with the SiH semiconductor, enabling electronic devices with high charge injection efficiency. Furthermore, the tunneling resistivity of all the MX2/SiH (M = Nb, Ta; X = S, Se) MSHs is low, confirming that they exhibit high electron injection efficiency. Our findings underscore fundamental insights for the design of high-performance multifunctional Schottky devices based on the metal-semiconductor MX2/SiH heterostructures with ultra-low contact barriers and high electron injection efficiency.

How the secrets behind photocurrents are revealed in Ag-TiO2 heterostructures-based plasmonic photoelectrochemical systems: A collaborative approach of EC-SERS and photoelectrochemical methods

Plasmon-mediated chemical reactions (PMCR) have garnered growing interest as a promising concept for photocatalysis. However, in electrochemical systems at solid–liquid interfaces, the photo-induced charge transfer on the surface of metal–semiconductor heterostructures involves complex processes and mechanisms, which are still poorly understood. We explore the plasmon-mediated carrier transfer mechanism and the synergistic effect of light and electric fields on Ag-TiO2 heterostructures, through a combination of electrochemical surface-enhanced Raman spectroscopy and photoelectrochemical methods, with para-aminothiophenol (PATP) serving as a probe molecule. The results show that photocurrent responses are dependent on not only excitation wavelengths and applied potentials, but also the irreversibility of redox. The relationship between photocurrent responses and the chemical transformation between PATP and 4,4′-dimercaptoazobenzene is established, reflecting the photo-induced charge transfer of the heterostructures. The collaboration of spectroscopic and photoelectrochemical methods provide valuable insights into the chemical transformation and kinetic information of adsorbed molecules on the heterostructure during PMCR, offering opportunities for modulating of photocatalytic activities of hot carriers.

Low-Voltage IGZO Field-Effect Ultraviolet Photodiode

Abstract In the era of Internet of Things (IoTs), an energy-efficient ultraviolet (UV) photodetector (PD) is highly desirable considering the massive usage scenarios such as environmental sterilization, fire alarm and corona discharge monitoring. So far, common self-powered UV PDs are mainly based on metal-semiconductor hetero-structures or p–n heterojunctions, where the limited intrinsic built-in electric field restricts further enhancement of the photoresponsivity. In this work, an extremely low-voltage field-effect UV PD is proposed using a gate-drain shorted amorphous IGZO (a-IGZO) thin film transistor (TFT) architecture. A combined investigation of the experimental measurements and technology computer-aided design (TCAD) simulations suggests that the reverse current (I R) of field-effect diode (FED) is highly related with the threshold voltage (V th) of the parental TFT, implying an enhancement-mode TFT is preferable to fabricate the field-effect UV PD with low dark current. Driven by a low bias of −0.1 V, decent UV response has been realized including large UV/visible (R 300/R 550) rejection ratio (1.9 × 103), low dark current (1.15 × 10−12 A) as well as high photo-to-dark current ratio (PDCR, ∼ 103) and responsivity (1.89 A/W). This field-effect photodiode provides a new platform to construct UV PDs with well-balanced photoresponse performance at a low bias, which is attractive for designs of large-scale smart sensor networks with high energy efficiency.

EM and CT synergistic SERS enhancement in Si/TiO2/Ag heterostructures via local interfacial effect

The Si/TiO2/Ag heterostructures with high SERS sensitivity were prepared by sol–gel and electrochemical self-assembly. The electromagnetic (EM) and charge transferring (CT) synergistic mechanism for SERS enhancement was explored by FDTD. The “localized interfacial effect (LIE)” of metal–semiconductor heterostructures can result in the CT between them and the charge carriers’ redistribution, which can facilitate the probe molecules’ adsorption and generate the 3D volume-enhancement of electromagnetic fields, therefore improve the SERS performance effectively. Furthermore, the morphology of Ag was flexibly regulated by changing the applied voltage, and the optimal SERS performance was achieved. With the R6G as a probe molecule, the ultra-low concentration of 10-13 M can be detected. The EF is estimated to be about 1.75 × 1011, and the RSD is about 4.3 %. The photocatalytic effect of Si/TiO2/Ag heterostructure can realize the SERS substrates’ UV self-cleaning and recyclable use with high stability.

ScN/GaN(11̅00): A New Platform for the Epitaxy of Twin-Free Metal-Semiconductor Heterostructures.

We study the molecular beam epitaxy of rock-salt ScN on the wurtzite GaN(11̅00) surface. To this end, ScN is grown on freestanding GaN(11̅00) substrates and self-assembled GaN nanowires exhibiting (11̅00) sidewalls. On both substrates, ScN crystallizes twin-free thanks to a specific epitaxial relationship, namely ScN(110)[001]∥GaN(11̅00)[0001], providing a congruent, low-symmetry interface. The 13.1% uniaxial lattice mismatch occurring in this orientation mostly relaxes within the first few monolayers of growth by forming a near-coincidence site lattice, where 7 GaN planes coincide with 8 ScN planes, leaving the ScN surface nearly free of extended defects. Overgrowth of the ScN with GaN leads to a kinetic stabilization of the zinc blende phase, that rapidly develops wurtzite inclusions nucleating on {111} nanofacets, commonly observed during zinc blende GaN growth. Our ScN/GaN(11̅00) platform opens a new route for the epitaxy of twin-free metal-semiconductor heterostructures including closely lattice-matched GaN, ScN, HfN, and ZrN compounds.

Metal-semiconductor heterojunction accelerates the plasmonically powered photoregeneration of biological cofactors.

Photocatalysis with plasmonic nanoparticles (NPs) is emerging as an attractive strategy to make and break chemical bonds. However, the fast relaxation dynamics of the photoexcited charge carriers in plasmonic NPs often result in poor yields. The separation and extraction of photoexcited hot-charge carriers should be faster than the thermalization process to overcome the limitation of poor yield. This demands the integration of rationally chosen materials to construct hybrid plasmonic photocatalysts. In this work, the enhanced photocatalytic activity of gold nanoparticle-titanium dioxide metal-semiconductor heterostructure (Au-TiO2) is used for the efficient regeneration of nicotinamide (NADH) cofactors. The modification of plasmonic AuNPs with n-type TiO2 semiconductor enhanced the charge separation process, because of the Schottky barrier formed at the Au-TiO2 heterojunction. This led to a 12-fold increment in the photocatalytic activity of plasmonic AuNP in regenerating NADH cofactor. Detailed mechanistic studies revealed that Au-TiO2 hybrid photocatalyst followed a less-explored light-independent pathway, in comparison to the conventional light-dependent path followed by sole AuNP photocatalyst. NADH regeneration yield reached ~70% in the light-independent pathway, under optimized conditions. Thus, our study emphasizes the rational choice of components in hybrid nanostructures in dictating the photocatalytic activity and the underlying reaction mechanism in plasmon-powered chemical transformations.

Probing impact on magnetic behavior of cobalt layer grown on thick MoS2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document} layer

Understanding the metal-semiconductor heterostructure interface is crucial for the development of spintronic devices. One of the prospective candidates and extensively studied semiconductors is molybdenum disulfide (MoS2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document}). Herein, utilizing Kerr microscopy, we investigated the impact of thick MoS2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document} on the magnetic properties of the 10 nm Co layer. A comparative study on Co/MoS2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\hbox {Co}/\\hbox {MoS}_{2}$$\\end{document} and Co/Si shows that coercivity increased by 77% and the Kerr signal decreased by 26% compared to Co grown on Si substrate. In addition, the Co domain structure significantly changed when grown on MoS2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document}. The plausible reason for the observed magnetic behavior can be that the Co interacts differently at the interface of MoS2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document} as compared to Si. Therefore, our studies investigate the interfacial effect on the magnetic properties of Co grown on thick MoS2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document} layer. Furthermore, our results will help in developing next-generation spintronic devices.

Synthesis of NbSe2/Bilayer Nb‐Doped WSe2 Heterostructure from Exfoliated WSe2 Flakes

Forming heterostructures of 2D metals and semiconductors using chemical vapor deposition (CVD) has significant potential to effectively reduce contact resistance in electronic devices. However, semiconducting transition metal dichalcogenide (TMD) layers in metal–semiconductor heterostructures are currently restricted to monolayers despite the superior mobility and density of states in bilayer TMDs. Herein, NbSe2/bilayer Nb‐doped WSe2 metal/semiconductor heterostructure from exfoliated WSe2 flakes are synthesized first. The exfoliated WSe2 bulk crystals on an Nb‐coated substrate are heated to 950 °C under a flow of selenium vapor, and then the NbSe2/bilayer Nb‐doped WSe2 heterostructures are formed. Statistics on the number of Nb‐doped WSe2 layers grown on a 1 cm × 1 cm CVD substrate shows that 65% of the Nb‐doped WSe2 layers are grown as bilayers. X‐ray photoelectron spectroscopy, optical microscopy, and transmission electron microscopy clearly clarify the number of Nb‐doped WSe2 layers and heterostructure of NbSe2/bilayer Nb‐doped WSe2. Electrical measurements using Cr contacts show that bilayer Nb‐doped WSe2 displays 7‐ and 10‐times higher mobility and on/off ratio than monolayer Nb‐doped WSe2. The mobility and on/off ratio are further doubled in NbSe2/bilayer Nb‐doped WSe2 contact compared to Cr/bilayer Nb‐doped WSe2 contact, attributed to a clean interface in vertical stack heterostructure, enhancing electrical performance.

Controllable electronic properties, contact barriers and contact types in a TaSe2/WSe2 metal-semiconductor heterostructure.

Two-dimensional (2D) metallic TaSe2 and semiconducting WSe2 materials have been successfully fabricated in experiments and are considered as promising contact and channel materials, respectively, for the design of next-generation electronic devices. Herein, we design a metal-semiconductor (M-S) heterostructure combining metallic TaSe2 and semiconducting WSe2 materials and investigate the atomic structure, electronic properties and controllable contact types of the combined TaSe2/WSe2 M-S heterostructure using first-principles calculations. Our results reveal that the TaSe2/WSe2 M-S heterostructure can adopt four different stable stacking configurations, all of which exhibit enhanced elastic constants compared to the constituent monolayers. Furthermore, the TaSe2/WSe2 M-S heterostructure exhibits p-type Schottky contact (SC) with Schottky barriers ranging from 0.36 to 0.49 eV, depending on the stacking configurations. The TaSe2/WSe2 M-S heterostructure can be considered as a promising M-S contact for next-generation electronic Schottky devices owing to its small tunneling resistivity of about 2.14 × 10-9 Ω cm2. More interestingly, the TaSe2/WSe2 M-S heterostructure exhibits tunable contact types and contact barriers under the application of an electric field. A negative electric field induces a transition from Schottky contact type to ohmic contact (OC) type. On the other hand, a positive electric field leads to a transformation from p-type SC to n-type SC. Our findings provide valuable insights into the practical applications of the TaSe2/WSe2 M-S heterostructure towards next-generation electronic devices.

Effective concentration ratio driven phase engineering of MBE-grown few-layer MoTe2.

The polymorphic nature of ultrathin transition metal dichalcogenide (TMDC) materials makes the phase engineering of these materials an interesting field of investigation. Understanding the phase-controlling behavior of different growth parameters is crucial for obtaining large-area growth of a desirable phase. Here, we report a detailed study on the effect of growth parameters for engineering different phases of few-layer MoTe2 on sapphire using molecular beam epitaxy (MBE). Our study shows that the 2H phase of MoTe2 is stabilized in a certain regime of the flux ratio and growth temperature, while on both the lower, as well as, the higher sides of this regime, the 1T' phase is favored. The combined effect of growth parameters is explained using the effective concentration ratio of Te and Mo at the growth surface, which is found to be the primary factor governing the phase selectivity in few-layer MoTe2. XPS and KPFM investigations show the contribution of excess carrier doping in driving the phase change. The effect of the sapphire substrate on the crystallinity and phase-dependent morphological features has also been studied. This knowledge of versatile and controlled phase engineering of few-layer MoTe2 paves the way for fabricating large-scale hetero-phase-based metal-semiconductor heterostructures for future electronic and optoelectronic device applications.

Fabrication of Heterostructural FeNi3-Loaded Perovskite Catalysts by Rapid Plasma for Highly Efficient Photothermal Reverse Water Gas Shift Reaction.

Metal-semiconductor heterostructured catalysts have attracted great attention because of their unique interfacial characteristics and superior catalytic performance. Exsolution of nanoparticles is one of the effective and simple ways for in-situ growth of metal nanoparticles embedded in oxide surfaces and their favorable dispersion and stability. However, both high-temperature and a reducing atmosphere are required simultaneously in conventional exsolution, which is time-consuming and costly, and particles often agglomerate during the process. In this work, Ca0.9Ti0.8Ni0.1Fe0.1O3-δ (CTNF) is exposed to dielectric blocking discharge (DBD) plasma at room temperature to fabricate alloying FeNi3 nanoparticles from CTNF perovskite. FeNi3-CTNF has outstanding catalytic activity for photothermal reverse water gas shift reaction (RWGS). At 350°C under full-spectrum irradiation, the carbon monoxide (CO) yield of FeNi3-CTNF (10.78mmol g-1 h-1) is 11 times that of pure CaTiO3(CTO), and the CO selectivity is 98.9%. This superior catalytic activity is attributed to the narrow band gap, photogenerated electron migration to alloy particles, and abundant surface oxygen vacancies. The carbene pathway reaction is also investigated through in-situ Raman spectroscopy. The present work presents a straightforward method for the exsolution of nanoalloys in metal-semiconductor heterostructures for photothermal CO2 reduction.

Ferroelectric Schottky diodes of CuInP2S6 nanosheet

Ferroelectricity in van der Waals (vdW) layered material has attracted a great deal of interest recently. CuInP2S6 (CIPS), the only vdW layered material whose ferroelectricity in the bulk was demonstrated by direct polarization measurements, was shown to remain ferroelectric down to a thickness of a few nanometers. However, its ferroelectric properties have just started to be explored in the context of potential device applications. We report here the preparation and measurements of metal-ferroelectric semiconductor-metal heterostructures using nanosheets of CIPS obtained by mechanical exfoliation. Four bias voltage and polarization dependent resistive states were observed in the current–voltage characteristics, which we attribute to the formation of ferroelectric Schottky diode, along with switching behavior.

Two-step electrodeposition synthesis of lamellar Ni@NiCo phosphate heterostructures as cathodes for high-performance hybrid supercapacitors

Porous structures grown in situ increase the electrode contact area with the electrolyte, reduce ion diffusion distance, and enhance electrode material electrochemical properties. In this paper, we have adopted a dual-channel electrodeposition strategy with simultaneous electrodeposition and phosphorylation to construct metal-semiconductor contact heterostructures by depositing Ni@NiCo phosphate microspherical nanostructures directly on a copper foam (CF) (Ni@NiCoP/CF) framework at room temperature. The results show that Ni@NiCoP/CF has excellent electrochemical performance with a high specific capacity of 200 mAh g–1 at 1 A g–1, 147.2 mAh g–1 at 20 A g–1 and 93.6 % after 5000 cycles, showing excellent ration performances and cycling stability. In addition, the hybrid supercapacitor composed of Ni@NiCoP/CF as the positive electrode and activated carbon as the negative electrode achieves a high energy density of 48.7 Wh kg−1 at 874 W kg−1 and has excellent cycling stability with 113.23 % capacity retention after 30,000 charge/discharge cycles at a high current density of 10 A g–1. This study serves as a guide for the development of high-performance capacitor cathode materials with high electrochemical activity and capacity.

Nanorod length-dependent photodriven H2 production in 1D CdS-Pt heterostructures.

Colloidal quantum confined semiconductor-metal heterostructures are promising candidates for solar energy conversion because their light absorbing semiconductor and catalytic components can be independently tuned and optimized. Although the light-to-hydrogen efficiencies of such systems have shown interesting dependences on the morphologies of the semiconductor and metal domains, the mechanisms of such dependences are poorly understood. Here, we use Pt tipped 0D CdS quantum dots (with ∼4.6nm diameter) and 1D CdS nanorods (of ∼13.8, 27.8, 66.6, and 88.9nm average rod lengths) as a model system to study the distance-dependence of charge separation and charge recombination times and their impacts on photo-driven H2 production. The H2 generation quantum efficiency increases from 0.2% ± 0.0% in quantum dots to 28.9% ± 0.4% at a rod length of 28nm and shows negligible changes at longer rod lengths. The half-life time of electron transfer from CdS to Pt increases monotonically with rod length, from 0.7 ± 0.1 in quantum dots to 170.2 ± 29.5ps in the longest rods, corresponding to a slight decrease in electron transfer quantum efficiency from 92% to 81%. The amplitude-weighted average lifetime of charge recombination of the electron in Pt with the hole in CdS increases from 4.7 ± 0.4 µs in quantum dots to 149 ± 34 µs in 28nm nanorods, and the lifetime does not increase further in longer rods, resembling the trend in the observed H2 generation quantum efficiency. Our result suggests that the competition of the charge recombination process with the hole removal by the sacrificial electron donor plays a dominant role in the observed nanorod length dependent overall light driven H2 generation quantum efficiency.

On-Chip Monolithically Integrated UltravioletLow-Threshold Plasmonic Metal-Semiconductor Heterojunction Nanolasers.

The metal-semiconductor heterojunction is imperative for the realization of electrically driven nanolasers for chip-level platforms. Progress in developing such nanolasers has hitherto rarely been realized, however, because of their complexity in heterojunction fabrication and the need to use noble metals that are incompatible with microelectronic manufacturing. Most plasmonic nanolasers lase either above a high threshold (101 -103 MW cm-2 ) or at a cryogenic temperature, and lasing is possible only after they are removed from the substrate to avoid the large ohmic loss and the low modal reflectivity, making monolithic fabrication impossible. Here, for the first time, record-low-threshold, room-temperature ultraviolet (UV) lasing of plasmon-coupled core-shell nanowires that are directly grown on silicon is demonstrated. The naturally formed core-shell metal-semiconductor heterostructure of the nanowires leads to a 100-fold improvement in growth density over previous results. This unprecedentedly high nanowire density creates intense plasmonic resonance, which is outcoupled to the resonant Fabry-Pérot microcavity. By boosting the emission strength by a factor of 100, the hybrid photonic-plasmonic system successfully facilitates a record-low laser threshold of 12kW cm-2 with a spontaneous emission coupling factor as high as ≈0.32 in the 340-360nm range. Such architecture is simple and cost-competitive for future UV sources in silicon integration.

Engineering Dumbbell-Shaped Au Nanobipyramid/Ag-CeO2 Plasmonic Bimetal-Semiconductor Heterostructures for Nitroaromatic Reduction

Precisely engineering the morphology of plasmonic metal–semiconductor heterostructures (PMSHs) is essential for fully utilizing the localized surface plasmon resonance (LSPR) function. However, most of the PMSHs mainly depend on the LSPR contribution of a single plasmonic metal, while the bimetal semiconductor heterostructures have been rarely reported. Herein, a series of dumbbell-shaped bimetal semiconductor heterostructures, based on Au nanobipyramids (AuNBPs, average length of 96 ± 3 nm, waist diameter of 29 ± 3 nm), lateral surfaces covered with rice-shaped Ag layers (thickness less than 5 nm), and a tip loaded with cap-shaped CeO2 (average size of 44 nm), were engineered. By simply tuning the dose of Ag+ and CTAC, we can precisely engineer the morphology of PMSHs from dumbbell-shaped monometal semiconductors (AuNBP–CeO2) to a core/shell/shell structure (AuNBP@Ag@CeO2) and to the dumbbell-shaped bimetal semiconductor AuNBP/Ag–CeO2. Notably, the AuNBP/Ag–CeO2 nanostructure exhibits higher activity in photocatalytic nitroreduction of 4-NP than AuNBP–CeO2. Mechanism analysis demonstrated that the bimetal semiconductor dumbbell-shaped AuNBP/Ag–CeO2 shows stronger electromagnetic field enhancement than the monometal semiconductor dumbbell-shaped AuNBP–CeO2, which promotes the generation of hot electrons more efficiently. This work offers an insight into precisely engineering plasmonic bimetallic semiconductor heterostructures for photocatalytic applications.

Sustainable fabrication of cellulose aerogel embedded with ZnO@noble metal (Ag, Au, Ag-Au) NPs for sensitive and reusable SERS application

Nanostructured materials with designable microstructure fabricated through a facile and green method are highly desired for practical applications in nanotechnology. Herein, without using any toxic reagents, flexible cellulose aerogel nanocomposites embedded with ZnO@noble metal nanoparticles (NPs) were successfully prepared from a cellulose dope. Morphology, structure, and mechanical properties of the nanocomposite were characterized. Flower-liker ZnO particles were synthesized through cellulose mineralization and it acted as a platform for efficient photocatalytic synthesis of noble metal (Ag, Au, Ag-Au) NPs. The noble metal NPs were well dispersed in the three-dimensional (3D) cellulose skeleton, resulting in abundant “hot spots” for high Surface Enhanced Raman Scattering (SERS) signal enhancement. Using rhodamine 6 G (R6G) molecules as probe molecules, the detection limits and calculated enhancement factors approached to 10−10 M and 4.8 × 107, respectively. Particularly, the photocatalytic capabilities of noble metal-semiconductor heterostructure embedded in porous aerogel made it a self-cleaned SERS substrate. There was little sensitivity loss after recycling use for 3 times. This work presented a sustainable and cost-reduction strategy to construct sensitive SERS substrate.

Tunable Schottky barrier in graphene/XAg4Y (X, Y = S, Se, Te) heterostructures

Two-dimensional (2D) metal-semiconductor heterostructures have attracted extensive interest in future integrated electronics and energy-related applications. Here, the modulated electronic properties and interface contact of G/XAg4Y (X, Y = S, Se, and Te) heterostructures are investigated via first-principles methods. G/XAg4Y with G/SAg4Y and G/SeAg4Y are n-type Schottky contacts whose Φn range from 1.07 to 1.22 eV, while those with G/TeAg4Y are p-type Schottky contacts whose Φp range from 1.17 to 1.20 eV. Because of interfacial charge transfer, the n-type Schottky contacts of G/XAg4Y with G/SAg4Y and G/SeAg4Y evolve to p-type Schottky contacts by applying positive external electric fields or reducing the interlayer distances. Oppositely, the p-type Schottky contacts of the G/XAg4Y with the G/TeAg4Y change to n-type Schottky contacts by applying a negative external electric field or increasing the interlayer distances. These predicted results show that G/XAg4Y heterostructures possess interlayer-distance and electric-field dependent Schottky barrier height, which possesses potential in future integrated electronics and energy-related applications.

Epitaxial growth of highly symmetrical branched noble metal-semiconductor heterostructures with efficient plasmon-induced hot-electron transfer

Epitaxial growth is one of the most commonly used strategies to precisely tailor heterostructures with well-defined compositions, morphologies, crystal phases, and interfaces for various applications. However, as epitaxial growth requires a small interfacial lattice mismatch between the components, it remains a challenge for the epitaxial synthesis of heterostructures constructed by materials with large lattice mismatch and/or different chemical bonding, especially the noble metal-semiconductor heterostructures. Here, we develop a noble metal-seeded epitaxial growth strategy to prepare highly symmetrical noble metal-semiconductor branched heterostructures with desired spatial configurations, i.e., twenty CdS (or CdSe) nanorods epitaxially grown on twenty exposed (111) facets of Ag icosahedral nanocrystal, albeit a large lattice mismatch (more than 40%). Importantly, a high quantum yield (QY) of plasmon-induced hot-electron transferred from Ag to CdS was observed in epitaxial Ag-CdS icosapods (18.1%). This work demonstrates that epitaxial growth can be achieved in heterostructures composed of materials with large lattice mismatches. The constructed epitaxial noble metal-semiconductor interfaces could be an ideal platform for investigating the role of interfaces in various physicochemical processes.