Programmable Interfacial Band Configuration in WS2/Bi2O2Se Heterojunctions.

van der Waals heterojunctions based on transition-metal dichalcogenides (TMDs) offer advanced strategies for manipulating light-emitting and light-harvesting behaviors. A crucial factor determining the light-material interaction is in the band alignment at the heterojunction interface, particularly the distinctions between type-I and type-II alignments. However, altering the band alignment from one type to another without changing the constituent materials is exceptionally difficult. Here, utilizing Bi2O2Se with a thickness-dependent band gap as a bottom layer, we present an innovative strategy for engineering interfacial band configurations in WS2/Bi2O2Se heterojunctions. In particular, we achieve tuning of the band alignment from type-I (Bi2O2Se straddling WS2) to type-II and finally to type-I (WS2 straddling Bi2O2Se) by increasing the thickness of the Bi2O2Se bottom layer from monolayer to multilayer. We verified this band architecture conversion using steady-state and transient spectroscopy as well as density functional theory calculations. Using this material combination, we further design a sophisticated band architecture incorporating both type-I (WS2 straddles Bi2O2Se, fluorescence-quenched) and type-I (Bi2SeO5 straddles WS2, fluorescence-recovered) alignments in one sample through focused laser beam (FLB). By programming the FLB trajectory, we achieve a predesigned localized fluorescence micropattern on WS2 without changing its intrinsic atomic structure. This effective band architecture design strategy represents a significant leap forward in harnessing the potential of TMD heterojunctions for multifunctional photonic applications.

Identifying Luminescent Boron Vacancies in h-BN Generated Using Controlled He+ Ion Irradiation.

The defect emission from h-BN at 1.55 eV is interesting as it enables optical readout of spins. It is necessary to identify the nature of the relevant point defects for its controlled introduction. However, it is challenging to engineer point defects in h-BN without changing the local atomic structure. Here, we controllably introduce boron vacancies in h-BN using an ultrahigh spatial resolution and low-energy He+ ion beam. By optimizing the He+ ion irradiation conditions, we control the quantity and location of defects spatially and along the depth of h-BN to achieve a robust photoluminescence emission at 1.55 eV from 10 K to room temperature. We show that as-generated defects activate an additional Raman mode at 1295 cm-1. Electron energy loss spectroscopy confirms introduction of boron vacancies without modification of the local h-BN crystal structure. Our results provide a deterministic strategy to create scalable boron vacancy emitters in h-BN for quantum photonics.

Atomic Origins of Enhanced Ferroelectricity in Nanocolumnar PbTiO3 /PbO Composite Thin Films.

Nanocomposite films hold great promise for multifunctional devices by integrating different functionalities within a single film. The microstructure of the precipitate/secondary phase is an essential element in designing composites' properties. The interphase strain between the matrix and secondary phase is responsible for strain-mediated functionalities, such as magnetoelectric coupling and ferroelectricity. However, a quantitative microstructure-dependent interphase strain characterization has been scarcely studied. Here, it is demonstrated that the PbTiO3 (PTO)/PbO composite system can be prepared in nano-spherical and nanocolumnar configurations by tuning the misfit strain, confirmed by a three-dimensional reconstructive microscopy technique. With the atomic resolution quantitative microscopy with a depth resolution of a few nanometers, it is discovered that the strained region in PTO is much larger and more uniform in nanocolumnar compared to nano-spherical composites, resulting in much enhanced ferroelectric properties. The interphase strain between PbO and PTO in the nanocolumnar structure leads to a giant c/a ratio of 1.20 (bulk value of 1.06), accompanied by a Ti polarization displacement of 0.48 Å and an effective ferroelectric polarization of 241.7 µC cm-2 , three times compared to the bulk value. The quantitative atomic-scale strain and polarization analysis on the interphase strain provides an important guideline for designing ferroelectric nanocomposites.

Tunable Optical Properties of Thin Films Controlled by the Interface Twist Angle.

Control of materials properties has been the driving force of modern technologies. So far, materials properties have been modulated by their composition, structure, and size. Here, by using cathodoluminescence in a scanning transmission electron microscope, we show that the optical properties of stacked, >100 nm thick hexagonal boron nitride (hBN) films can be continuously tuned by their relative twist angles. Due to the formation of a moiré superlattice between the two interface layers of the twisted films, a new moiré sub-band gap is formed with continuously decreasing magnitude as a function of the twist angle, resulting in tunable luminescence wavelength and intensity increase of >40×. Our results demonstrate that moiré phenomena extend beyond monolayer-based systems and can be preserved in a technologically relevant, bulklike material at room temperature, dominating optical properties of hBN films for applications in medicine, environmental, or information technologies.

Review of Adaptive Programmable Materials and Their Bioapplications.

Adaptive programmable materials have attracted increasing attention due to their high functionality, autonomous behavior, encapsulation, and site-specific confinement capabilities in various applications. Compared to conventional materials, adaptive programmable materials possess unique single-material architecture that can maintain, respond, and change their shapes and dimensions when they are subjected to surrounding environment changes, such as alternation in temperature, pH, and ionic strength. In this review, the most-recent advances in the design strategies of adaptive programmable materials are presented with respect to different types of architectural polymers, including stimuli-responsive polymers and shape-memory polymers. The diverse functions of these sophisticated materials and their significance in therapeutic agent delivery systems are also summarized in this review. Finally, the challenges for facile fabrication of these materials and future prospective are also discussed.