Space-Confined Growth of Ultrathin P-Type GeTe Nanosheets for Broadband Photodetectors.

As p-type phase-change degenerate semiconductors, crystalline and amorphous germanium telluride (GeTe) exhibit metallic and semiconducting properties, respectively. However, the massive structural defects and strong interface scattering in amorphous GeTe films significantly reduce their performance. In this work, two-dimensional (2D) p-type GeTe nanosheets are synthesized via a specially designed space-confined chemical vapor deposition (CVD) method, with the thickness of the GeTe nanosheets reduced to 1.9 nm. The space-confined CVD method improves the crystallinity of ultrathin GeTe by lowering the partial pressure of the reactant gas, resulting in GeTe nanosheets with excellent p-type semiconductor properties, such as a satisfactory on/off ratio of 105. Temperature-dependent electrical measurements demonstrate that variable-range hopping and optical-phonon-assisted hopping mechanisms dominate transport behavior at low and high temperatures, respectively. GeTe devices exhibit significantly high responsivity (6589 and 2.2 A W-1 at 633 and 980 nm, respectively) and detectivity (1.67 × 1011 and 1.3 × 108 Jones at 633 and 980 nm, respectively), making them feasible for broadband photodetectors in the visible to near-infrared range. Furthermore, the fabricated GeTe/WS2 diode exhibits a rectification ratio of 103 at zero gate voltage. These satisfactory p-type semiconductor properties demonstrate that ultrathin GeTe exhibits enormous potential for applications in optoelectronic interconnection circuits.

Enhancing photoluminescence of WSe2 in vapor grown WSe2/VOCl bilayer heterojunctions via surface passivation.

Monolayer tungsten selenide (WSe2) has attracted attention due to its direct bandgap-generated strong light emission and light-matter interaction. Herein, vertical WSe2/VOCl bilayer heterojunctions with enhanced PL of WSe2 were synthesized by the vapor growth method. The morphology, crystal structure, and chemical composition of the WSe2/VOCl heterojunctions were systematically investigated, which confirmed the successful formation of the heterojunctions. The PL emission intensity of WSe2 obtained from the WSe2/VOCl heterojunction was about 2.4 times higher than that of the WSe2 monolayer, demonstrating the high optical quality of the WSe2/VOCl heterojunction, which was further confirmed by time-resolved PL measurements. The insulator top VOCl, which was deposited on the surface of the semiconductor bottom WSe2 as a surface passivation material, reducing the impurities and resulting in an atomically clean surface, successfully enhanced the PL emission of the bottom WSe2. This vertical WSe2/VOCl bilayer heterojunction with PL enhancement could provide a promising platform for optical devices.

Photoluminescence Lightening: Extraordinary Oxygen Modulated Dynamics in WS2 Monolayers.

Transition metal dichalcogenide monolayers exhibit ultrahigh surface sensitivity since they expose all atoms to the surface and thereby influence their optoelectronic properties. Here, we report an intriguing lightening of the photoluminescence (PL) from the edge to the interior over time in the WS2 monolayers grown by physical vapor deposition method, with the whole monolayer brightened eventually. Comprehensive optical studies reveal that the PL enhancement arises from the p doping induced by oxygen adsorption. First-principles calculations unveil that the dissociation of chemisorbed oxygen molecule plays a significant role; i.e., the dissociation at one site can largely promote the dissociation at a nearby site, facilitating the photoluminescence lightening. In addition, we further manipulate such PL brightening rate by controlling the oxygen concentration and the temperature. The presented results uncover the extraordinary surface chemistry and related mechanism in WS2 monolayers, which deepens our insight into their unique PL evolution behavior.

A Sulfur-Bridging Sulfonate-Modified Zinc(II) Phthalocyanine Nanoliposome Possessing Hybrid Type I and Type II Photoreactions with Efficient Photodynamic Anticancer Effects.

Phthalocyanines are potentially promising photosensitizers (PSs) for photodynamic therapy (PDT), but the inherent defects such as aggregation-caused quenching effects and non-specific toxicity severely hinder their further application in PDT. Herein, we synthesized two zinc(II) phthalocyanines (PcSA and PcOA) monosubstituted with a sulphonate group in the alpha position with "O bridge" and "S bridge" as bonds and prepared a liposomal nanophotosensitizer (PcSA@Lip) by thin-film hydration method to regulate the aggregation of PcSA in the aqueous solution and enhance its tumor targeting ability. PcSA@Lip exhibited highly efficient production of superoxide radical (O2∙-) and singlet oxygen (1O2) in water under light irradiation, which were 2.6-fold and 15.4-fold higher than those of free PcSA, respectively. Furthermore, PcSA@Lip was able to accumulate selectively in tumors after intravenous injection with the fluorescence intensity ratio of tumors to livers was 4.1:1. The significant tumor inhibition effects resulted in a 98% tumor inhibition rate after PcSA@Lip was injected intravenously at an ultra-low PcSA@Lip dose (0.8 nmol g-1 PcSA) and light dose (30 J cm-2). Therefore, the liposomal PcSA@Lip is a prospective nanophotosensitizer possessing hybrid type I and type II photoreactions with efficient photodynamic anticancer effects.

Unidirectional Rashba spin splitting in single layer WS2(1-x)Se2xalloy.

Atomically thin two-dimensional (2D) layered semiconductors such as transition metal dichalcogenides have attracted considerable attention due to their tunable band gap, intriguing spin-valley physics, piezoelectric effects and potential device applications. Here we study the electronic properties of a single layer WS1.4Se0.6alloys. The electronic structure of this alloy, explored using angle resolved photoemission spectroscopy, shows a clear valence band structure anisotropy characterized by two paraboloids shifted in one direction of thek-space by a constant in-plane vector. This band splitting is a signature of a unidirectional Rashba spin splitting with a related giant Rashba parameter of 2.8 ± 0.7 eV Å. The combination of angle resolved photoemission spectroscopy with piezo force microscopy highlights the link between this giant unidirectional Rashba spin splitting and an in-plane polarization present in the alloy. These peculiar anisotropic properties of the WS1.4Se0.6alloy can be related to local atomic orders induced during the growth process due the different size and electronegativity between S and Se atoms. This distorted crystal structure combined to the observed macroscopic tensile strain, as evidenced by photoluminescence, displays electric dipoles with a strong in-plane component, as shown by piezoelectric microscopy. The interplay between semiconducting properties, in-plane spontaneous polarization and giant out-of-plane Rashba spin-splitting in this 2D material has potential for a wide range of applications in next-generation electronics, piezotronics and spintronics devices.

Aggregation-Enhanced Sonodynamic Activity of Phthalocyanine-Artesunate Conjugates.

The clinical prospect of sonodynamic therapy (SDT) has not been fully realized due to the scarcity of efficient sonosensitizers. Herein, we designed phthalocyanine-artesunate conjugates (e.g. ZnPcT4 A), which could generate up to ca. 10-fold more reactive oxygen species (ROS) than the known sonosensitizer protoporphyrin IX. Meanwhile, an interesting and significant finding of aggregation-enhanced sonodynamic activity (AESA) was observed for the first time. ZnPcT4 A showed about 60-fold higher sonodynamic ROS generation in the aggregated form than in the disaggregated form in aqueous solutions. That could be attributed to the boosted ultrasonic cavitation of nanostructures. The level of the AESA effect depended on the aggregation ability of sonosensitizer molecules and the particle size of their aggregates. Moreover, biological studies demonstrated that ZnPcT4 A had high anticancer activities and biosafety. This study thus opens up a new avenue the development of efficient organic sonosensitizers.

Nanostructured Phthalocyanine Assemblies with Efficient Synergistic Effect of Type I Photoreaction and Photothermal Action to Overcome Tumor Hypoxia in Photodynamic Therapy.

Most photodynamic therapy (PDT) paradigms work through the highly O2-dependent type II photoreaction to generate singlet oxygen (1O2). The hypoxic microenvironment of solid tumors severely hampers therapeutic outcomes. Here, we present a novel design that could transfer the photophysical and photochemical properties of traditional phthalocyanine-based photosensitizers from type II photoreaction to efficient type I photoreaction and vibrational relaxation-induced photothermal conversion. These features enable the obtained nanostructured phthalocyanine assemblies (e.g., NanoPcAF) to display excellent phototherapies under both normoxic and hypoxic conditions. Moreover, NanoPcAF has a high level of accumulation in tumor tissues after intravenous injection, and 94% of tumor growth is inhibited in a preclinical model at a NanoPcAF dose of 0.8 nmol g-1 and light dose of 300 J cm-2.

Twist-angle-dependent interlayer exciton diffusion in WS2-WSe2 heterobilayers.

The nanoscale periodic potentials introduced by moiré patterns in semiconducting van der Waals heterostructures have emerged as a platform for designing exciton superlattices. However, our understanding of the motion of excitons in moiré potentials is still limited. Here we investigated interlayer exciton dynamics and transport in WS2-WSe2 heterobilayers in time, space and momentum domains using transient absorption microscopy combined with first-principles calculations. We found that the exciton motion is modulated by twist-angle-dependent moiré potentials around 100 meV and deviates from normal diffusion due to the interplay between the moiré potentials and strong exciton-exciton interactions. Our experimental results verified the theoretical prediction of energetically favourable K-Q interlayer excitons and showed exciton-population dynamics that are controlled by the twist-angle-dependent energy difference between the K-Q and K-K excitons. These results form a basis to investigate exciton and spin transport in van der Waals heterostructures, with implications for the design of quantum communication devices.

Observation and Active Control of a Collective Polariton Mode and Polaritonic Band Gap in Few-Layer WS2 Strongly Coupled with Plasmonic Lattices.

Two-dimensional semiconductors host excitons with very large oscillator strengths and binding energies due to significantly reduced carrier screening. Two-dimensional semiconductors integrated with optical cavities are emerging as a promising platform for studying strong light-matter interactions as a route to explore a variety of exotic many-body effects. Here, in few-layered WS2 coupled with plasmonic nanoparticle lattices, we observe the formation of a collective polaritonic mode near the exciton energy and the formation of a complete polariton band gap with energy scale comparable to the exciton-plasmon coupling strength. A coupled oscillator model reveals that the collective mode arises from the cooperative coupling of the excitons to the plasmonic lattice diffraction orders via exciton-exciton interactions, leading to ultrastrong coupling. The emergence of the collective mode is accompanied by a superlinear increase of the polariton mode splitting as a function of the square root of the exciton oscillator strength. The presence of these many body effects, which are enhanced in systems which lack bulk polarization, not only allows the formation of a collective mode with periodically varying field profiles, but also further enhances the exciton-plasmon coupling. By integrating the hybrid WS2-plasmonic lattice device with a field-effect transistor, we demonstrate active tuning of the collective mode and the polariton band gap. We also report electrically tunable waveguiding in the polariton band gap region through a line defect, which can be turned off with gate bias that can extinguish the collective mode and the polariton band gap. These systems provide new opportunities for obtaining a deeper and systematic understanding of many body cooperative phenomena in two-dimensional materials coupled with periodic photonic systems and for designing more complex and actively controllable polaritonic devices including switchable polariton lasers, waveguides, and optical logical elements.

Wavelength-Tunable Interlayer Exciton Emission at the Near-Infrared Region in van der Waals Semiconductor Heterostructures.

The wavelength-tunable interlayer exciton (IE) from layered semiconductor materials has not been achieved. van der Waals heterobilayers constructed using single-layer transition metal dichalcogenides can produce continuously changed interlayer band gaps, which is a feasible approach to achieve tunable IEs. In this work, we design a series of van der Waals heterostructures composed of a WSe2 layer with a fixed band gap and another WS2(1-x)Se2x alloy layer with continuously changed band gaps. The existence of IEs and tunable interlayer band gaps in these heterobilayers is verified by steady-state photoluminescence experiments. By tuning the composition of the WS2(1-x)Se2x alloy layers, we realized a very wide tunable band gap range of 1.97-1.40 eV with a wavelength-tunable IE emission range of 1.52-1.40 eV from the heterobilayers. The time-resolved photoluminescence experiments show the IE emission lifetimes over nanoseconds.

Noncovalent Indocyanine Green Conjugate of C-Phycocyanin: Preparation and Tumor-Associated Macrophages-Targeted Photothermal Therapeutics.

Fabrication of a multifunctional near-infrared (NIR) theranostic nanoplatform has attracted increasing attention. Indocyanine green (ICG), a clinic-approved NIR fluorescence-imaging agent, is an excellent photothermal agent candidate. However, the stability and tumor targeting are still great obstacles for its wide application. In this work, C-phycocyanin (CPC) as a tumor-associated macrophages (TAMs) targeted vehicle was used to fabricate noncovalent ICG conjugate of CPC (ICG@CPC) via self-assembly in aqueous media. Compared to free ICG, ICG@CPC displays improved stabilities in aqueous solutions and under light irradiation and threefold increase in photothermal conversion efficiency. The in vitro results indicated that ICG@CPC could be selectively internalized into J774A.1 cells via SR-A-mediated endocytosis and lead to enhanced photocytotoxicity against J774A.1 cells. In vivo results showed that ICG@CPC had significantly improved drug accumulation in the tumor and photothermal therapeutic efficacy relative to ICG alone. This study for the first time utilizes CPC as a TAMs-targeted nanocarrier for ICG and may promote further rational design of ICG-based photothermal nanodrugs for precise and efficient cancer theranosis.

A non-aggregated silicon(IV) phthalocyanine-lactose conjugate for photodynamic therapy.

To develop a highly efficient photosensitizer for photodynamic therapy (PDT), we have designed and synthesized a phthalocyanine-lactose conjugate (Pc-Lac) through axial modification of silicon(IV) phthalocyanine with lactose moieties. With the lactose substituents, Pc-Lac is highly hydrophilic and non-aggregated with efficient reactive oxygen species (ROS) generation in aqueous media. With these desirable properties, Pc-Lac shows high photocytotoxicity and cellular uptake toward HepG2 cells. In addition, in vivo fluorescence imaging shows that Pc-Lac could selectively remain at tumor site, leading to its enhanced photodynamic efficacy against H22 tumor-bearing mice. Therefore, Pc-Lac shows a great potential as a highly efficient molecular photosensitizer for PDT.

Probing and Manipulating Carrier Interlayer Diffusion in van der Waals Multilayer by Constructing Type-I Heterostructure.

van der Waals multilayer heterostructures have drawn increasing attention due to the potential for achieving high-performance photonic and optoelectronic devices. However, the carrier interlayer transportation behavior in multilayer structures, which is essential for determining the device performance, remains unrevealed. Here, we report a general strategy for studying and manipulating the carrier interlayer transportation in van der Waals multilayers by constructing type-I heterostructures, with a desired narrower bandgap monolayer acting as a carrier extraction layer. For heterostructures comprised of multilayer PbI2 and monolayer WS2, we find similar interlayer diffusion coefficients of ∼0.039 and ∼0.032 cm2 s-1 for electrons and holes in the PbI2 multilayer by fitting the time-resolved carrier dynamics based on the diffusion model. Because of the balanced carrier interlayer diffusion and the injection process at the heterointerface, the photoluminescence emission of the bottom WS2 monolayer is greatly enhanced by up to 106-fold at an optimized PbI2 thickness of the heterostructure. Our results provide valuable information on carrier interlayer transportation in van der Waals multilayer structures and pave the way for utilizing carrier behaviors to improve device performances.

WO3-WS2 Vertical Bilayer Heterostructures with High Photoluminescence Quantum Yield.

Atomically thin two-dimensional (2D) transition metal dichalcogenides (TMDCs) are attractive for applications in a wide range of optoelectronic devices, due to their tremendous interesting physical properties. However, the photoluminescence quantum yield (PLQY) of TMDCs has been found to be too low, due to abundant defects and strong many-body effect. Here, we present a direct physical vapor growth of WO3-WS2 bilayer heterostructures, with WO3 monolayer domains attached on the surface of large-size WS2 monolayers. Optical characterizations revealed that the PLQY of the as-grown WO3-WS2 heterostructures can reach up to 11.6%, which is 2 orders of magnitude higher than that of WS2 monolayers by the physical vapor deposition growth method (PVD-WS2) and about 13-times higher than that of mechanical exfoliated WS2 (ME-WS2) monolayers, representing the highest PLQY reported for direct growth TMDCs materials so far. The PL enhancement mechanism has been well investigated by time-resolved optical measurements. The fabrication of WO3-WS2 heterostructures with ultrahigh PLQY provides an efficient approach for the development of highly efficient 2D integrated photonic applications.

Vapor growth of CdS nanowires/WS2 nanosheet heterostructures with sensitive photodetections.

Heterostructures based on two-dimensional (2D) transition metal dichalcogenides semiconductors are reported to be promising building-blocks for next-generation integrated optoelectronic systems, owing to their atomic thin interface and interface-induced properties. Previously reported works have mostly been directed to focus on the 2D/2D heterostructures, and their optoelectronic performance is still inferior to the expectations for practical applications, mainly attributed to their non-ideal optical absorption when the thickness is confined at atomic scale. In this work, we have reported on high sensitivity photodetectors based on one-dimensional (1D)/2D heterostructures consisting of CdS nanowire and WS2 nanosheets grown by direct chemical vapor deposition. The components of the heterostructures were confirmed by x-ray diffraction, x-ray photoelectron spectroscopy, transmission electron microscope, photoluminescence and Raman spectra measurements, confirming the high quality heterostructures. Photodetectors were then fabricated based on the as-synthesized CdS/WS2 heterostructures, showing superior photodetection performances with a photoresponsivity of ∼50 A W-1 and an ultrahigh photodetectivity of ∼1012 Jones. Much higher responsivity of 5472 A W-1 and detectivity of 5 × 1013 Jones can be achieved through applying back gate voltage. The direct growth of such 1D/2D heterostructures may pave the way toward high performance integrated optoelectronics and systems.

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.

Highly positive-charged zinc(II) phthalocyanine as non-aggregated and efficient antifungal photosensitizer.

A new tetra-α-substituted zinc(II) phthalocyanine containing dodeca-amino groups (compound 4) and its quaternized analogue (compound 5) have been prepared and evaluated for their photoactivities against Candida albicans. Compared with the dodeca-amino phthalocyanine 4, the dodeca-cationic phthalocyanine 5 exhibits a higher photodynamic inactivation against C. albicans with an IC90 value down to 1.46 µM, which can be attributed to its non-aggregated nature in aqueous environments and more efficient cellular uptake. More interestingly, 5 shows a higher photodynamic inactivation on C. albicans due to its stronger affinity to C. albicans cells than mammalian cells. These results suggest that the highly positive-charged phthalocyanine 5 is a potential non-aggregated antifungal photosensitizer, which shows some selectivity toward the fungus.

[Non-covalent albumin conjugates of silicon (IV) phthalocyanines axially substituted with nucleoside: preparation and in vitro photodynamic activities].

The interactions of bovine serum albumin (BSA) with five novel silicon (N) phthalocyanines(SiPcl-5) axially modified by nucleosides (cytidine, 5-N-cytidine, methyl cytidine, uridine and methyl uridine) derivatives were studied by fluorescence spectroscopy. The results show that there are strong interactions between these silicon phthalocyanines and BSA with a binding constant of (4.90-83.18) x 10(5) mol(-1) x L. Therefore, the non-covalent BSA conjugate of bis(2', 3'-O-isopropyl-cytidine-oxy) phthalocyaninatosilicon(IV) (SiPc1) was further been prepared. The molar ratio of phthalocyanine to albumin was found to be 1:1 for the obtained SiPcl-BSA conjugate. The absorption spectra of SiPc1 and SiPc1-BSA in the visible region have no significant difference, both showing an Q-band maximum at about 686 nm. It indicates that the spectroscopic characteristics of SiPc1 are not affected by binding to albumin. The SiPcl-BSA conjugate exhibits high photodynamic activity against human hepatoma cell line HepG2 with an IC50 value of 3.0 x 10(-7) mol x L(-1). By comparsion, SiPc1-BSA has a higher photodynamic activity than SiPc1 (in PBS formation, IC50 = 7.0 x 10(-7) mol x L(-1)), which can be attributed to its higher cellular uptake.

Hierarchical processing enabled by 2D ferroelectric semiconductor transistor for low-power and high-efficiency AI vision system.

The growth of data and Internet of Things challenges traditional hardware, which encounters efficiency and power issues owing to separate functional units for sensors, memory, and computation. In this study, we designed an α-phase indium selenide (α-In2Se3) transistor, which is a two-dimensional ferroelectric semiconductor as the channel material, to create artificial optic-neural and electro-neural synapses, enabling cutting-edge processing-in-sensor (PIS) and computing-in-memory (CIM) functionalities. As an optic-neural synapse for low-level sensory processing, the α-In2Se3 transistor exhibits a high photoresponsivity (2855 A/W) and detectivity (2.91 × 1014 Jones), facilitating efficient feature extraction. For high-level processing tasks as an electro-neural synapse, it offers a fast program/erase speed of 40 ns/50 µs and ultralow energy consumption of 0.37 aJ/spike. An AI vision system using α-In2Se3 transistors has been demonstrated. It achieved an impressive recognition accuracy of 92.63% within 12 epochs owing to the synergistic combination of the PIS and CIM functionalities. This study demonstrates the potential of the α-In2Se3 transistor in future vision hardware, enhancing processing, power efficiency, and AI applications.

[Synthesis and photodynamic anticancer activity of silicon phthalocyanine axially modified by nucleoside derivatives].

A new axially modified silicon phthalocyanine, di [5'-(2', 3'-O-isopropyl)-5-methyl cytidineoxy] silicon phthalocyanine (SiPcG), was prepared and characterized by 1H NMR and HRMS. This compound is essentially nonaggregated in N,N-dimethyformamide and 1% cremophor EL aqueous solution. It shows a Qband at 676 nm and fluorescence emission at 685 nm in DMF, and exhibits a Q-band at 679 nm and fluorescence emission at 689 nm in 1% cremophor EL aqueous solution. The SiPcG shows a high photodynamic activity against human hepatoma cells HepG2 with an IC50 value down to 7.8 x 10(-8) mol x L(-1). Fluorescence confocal microscopy study indicated that the SiPcG locates preferentially in the mitochondria of cells. The research results show that the SiPcG is highly potential as a new anti-cancer photosensitizer.