First Example of Nonlinear Optical Materials Based on Nanoconjugates of Sandwich Phthalocyanines with Quantum Dots.

We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double- and triple-decker europium(III) complexes 2 and 3 with the A3 B-type phthalocyanine ligand (2,3-bis[2'-(2''-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-n-butoxyphthalocyanine 1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid-capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low-symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open-aperture Z-scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double- and triple-decker EuIII octa-n-butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide-capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π-electron system upon moving from double- to triple-decker complexes significantly improves the OL characteristics, making the low-symmetry triple-decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm-2 input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double- and triple-decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.

GaS:WS2 Heterojunctions for Ultrathin Two-Dimensional Photodetectors with Large Linear Dynamic Range across Broad Wavelengths.

Two-dimensional (2D) photodetectors based on photovoltaic effect or photogating effect can hardly achieve both high photoresponsivity and large linear dynamic range at the same time, which greatly limits many practical applications such as imaging sensors. Here, the conductive-sensitizer strategy, a general design for improving photoresponsivity and linear dynamic range in 2D photodetectors is provided and experimentally demonstrated on vertically stacked bilayer WS2/GaS0.87 under a parallel circuit mode. Owing to successful band alignment engineering, the isotype type-II heterojunction enables efficient charge carrier transfer from WS2, the high-mobility sensitizer, to GaS0.87, the low-mobility channel, under illumination from a broad visible spectrum. The transferred electron charges introduce a reverse electric field which efficiently lowers the band offset between the two materials, facilitating a transition from low-mobility photocarrier transport to high-mobility photocarrier transport with increasing illumination power. We achieved a large linear dynamic range of 73 dB as well as a high and constant photoresponsivity of 13 A/W under green light. X-ray photoelectron spectroscopy, cathodoluminescence, and Kelvin probe force microscopy further identify the key role of defects in monolayer GaS0.87 in engineering the band alignment with monolayer WS2. This work proposes a design route based on band and interface modulation for improving performance of 2D photodetectors and provides deep insights into the important role of strong interlayer coupling in offering heterostructures with desired properties and functions.

Controlling Defects in Continuous 2D GaS Films for High-Performance Wavelength-Tunable UV-Discriminating Photodetectors.

A chemical vapor deposition method is developed for thickness-controlled (one to four layers), uniform, and continuous films of both defective gallium(II) sulfide (GaS): GaS0.87 and stoichiometric GaS. The unique degradation mechanism of GaS0.87 with X-ray photoelectron spectroscopy and annular dark-field scanning transmission electron microscopy is studied, and it is found that the poor stability and weak optical signal from GaS are strongly related to photo-induced oxidation at defects. An enhanced stability of the stoichiometric GaS is demonstrated under laser and strong UV light, and by controlling defects in GaS, the photoresponse range can be changed from vis-to-UV to UV-discriminating. The stoichiometric GaS is suitable for large-scale, UV-sensitive, high-performance photodetector arrays for information encoding under large vis-light noise, with short response time (<66 ms), excellent UV photoresponsivity (4.7 A W-1 for trilayer GaS), and 26-times increase of signal-to-noise ratio compared with small-bandgap 2D semiconductors. By comprehensive characterizations from atomic-scale structures to large-scale device performances in 2D semiconductors, the study provides insights into the role of defects, the importance of neglected material-quality control, and how to enhance device performance, and both layer-controlled defective GaS0.87 and stoichiometric GaS prove to be promising platforms for study of novel phenomena and new applications.

Postgrowth Substitutional Tin Doping of 2D WS2 Crystals Using Chemical Vapor Deposition.

Doping of two-dimensional materials provides them tunable physical properties and widens their applications. Here, we demonstrate the postgrowth doping strategy in monolayer and bilayer tungsten disulfide (WS2) crystals, which utilizes a metal exchange mechanism, whereby Sn atoms become substitutional dopants in the W sites by energetically favorable replacement. We achieve this using chemical vapor deposition techniques, where high-quality grown WS2 single crystals are first grown and then subsequently reacted with a SnS precursor. Thermal control of the exchange doping mechanism is revealed, indicating that a sufficiently high enough temperature is required to create the S vacancies that are the initial binding sites for the SnS precursor and metal exchange occurrence. This results in a better control of dopant distribution compared to the tradition all-in-one approach, where dopants are added during the growth phase. The Sn dopants exhibit an n-type doping behavior in the WS2 layers based on the decreased threshold voltage obtained from transistor device measurements. Annular dark-field scanning transmission electron microscopy shows that in bilayer WS2 the Sn doping occurs only in the top layer, creating vertical heterostructures with atomic layer doping precision. This postgrowth modification opens up ways to selectively dope one layer at a time and construct mixed stoichiometry vertical heterojunctions in bilayer crystals.

Nanoparticle assembly enabled by EHD-printed monolayers.

Augmenting existing devices and structures at the nanoscale with unique functionalities is an exciting prospect. So is the ability to eventually enable at the nanoscale, a version of rapid prototyping via additive nanomanufacturing. Achieving this requires a step-up in manufacturing for industrial use of these devices through fast, inexpensive prototyping with nanoscale precision. In this paper, we combine two very promising techniques-self-assembly and printing-to achieve additively nanomanufactured structures. We start by showing that monolayers can drive the assembly of nanoparticles into pre-defined patterns with single-particle resolution; then crucially we demonstrate for the first time that molecular monolayers can be printed using electrohydrodynamic (EHD)-jet printing. The functionality and resolution of such printed monolayers then drives the self-assembly of nanoparticles, demonstrating the integration of EHD with self-assembly. This shows that such process combinations can lead towards more integrated process flows in nanomanufacturing. Furthermore, in-process metrology is a key requirement for any large-scale nanomanufacturing, and we show that Dual-Harmonic Kelvin Probe Microscopy provides a robust metrology technique to characterising these patterned structures through the convolution of geometrical and environmental constraints. These represent a first step toward combining different additive nanomanufacturing techniques and metrology techniques that could in future provide additively nanomanufactured devices and structures.