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.

Graphene has emerged as a promising material for optoelectronics due to its potential for ultrafast and broad-band photodetection. The photoresponse of graphene junctions is characterized by two competing photocurrent generation mechanisms: a conventional photovoltaic effect and a more dominant hot-carrier-assisted photothermoelectric (PTE) effect. The PTE effect is understood to rely on variations in the Seebeck coefficient through the graphene doping profile. A second PTE effect can occur across a homogeneous graphene channel in the presence of an electronic temperature gradient. Here, we study the latter effect facilitated by strongly localised plasmonic heating of graphene carriers in the presence of nanostructured electrical contacts resulting in electronic temperatures of the order of 2000 K. At certain conditions, the plasmon-induced PTE photocurrent contribution can be isolated. In this regime, the device effectively operates as a sensitive electronic thermometer and as such represents an enabling technology for development of hot carrier based plasmonic devices.

Heterophase homojunction formation in atomically thin 2D layers is of great importance for next-generation nanoelectronics and optoelectronics applications. Technologically challenging, controllable transformation between the semiconducting and metallic phases of transition metal chalcogenides is of particular importance. Here, we demonstrate that controlled laser irradiation can be used to directly ablate PdSe2 thin films using high power, or trigger the local transformation of PdSe2 into a metallic phase PdSe2-x using lower laser power. Such transformations are possible due to the low decomposition temperature of PdSe2 compared to other 2D transition metal dichalcogenides. Scanning transmission electron microscopy is used to reveal the laser-induced Se-deficient phases of PdSe2 material. The process sensitivity to the laser power allows patterning flexibility for resist free device fabrication. The laser patterned devices demonstrate that a laser-induced metallic phase PdSe2-x is stable with increased conductivity by a factor of about 20 compared to PdSe2. These findings contribute to 2 the development of nanoscale devices with homojunctions and scalable methods to achieve structural transformations in 2D materials.

Hybrid plasmonic metal-graphene systems are emerging as a class of optical metamaterials that facilitate strong light-matter interactions and are of potential importance for hot carrier graphene-based light harvesting and active plasmonic applications. Here we use femtosecond pump-probe measurements to study the near-field interaction between graphene and plasmonic gold nanodisk resonators. By selectively probing the plasmon-induced hot carrier dynamics in samples with tailored graphene-gold interfaces, we show that plasmon-induced hot carrier generation in the graphene is dominated by direct photoexcitation with minimal contribution from charge transfer from the gold. The strong near-field interaction manifests as an unexpected and long-lived extrinsic optical anisotropy. The observations are explained by the action of highly localized plasmon-induced hot carriers in the graphene on the subresonant polarizability of the disk resonator. Because localized hot carrier generation in graphene can be exploited to drive electrical currents, plasmonic metal-graphene nanostructures present opportunities for novel hot carrier device concepts.