Point defects in semiconductors can trap free charge carriers and localize excitons. The interaction between these defects and charge carriers becomes stronger at reduced dimensionalities, and is expected to greatly influence physical properties of the hosting material. We investigated effects of anion vacancies in monolayer transition metal dichalcogenides as two-dimensional (2D) semiconductors where the vacancies density is controlled by α-particle irradiation or thermal-annealing. We found a new, sub-bandgap emission peak as well as increase in overall photoluminescence intensity as a result of the vacancy generation. Interestingly, these effects are absent when measured in vacuum. We conclude that in opposite to conventional wisdom, optical quality at room temperature cannot be used as criteria to assess crystal quality of the 2D semiconductors. Our results not only shed light on defect and exciton physics of 2D semiconductors, but also offer a new route toward tailoring optical properties of 2D semiconductors by defect engineering.

Significance A new class of heterostructures consisting of layered transition metal dichalcogenide components can be designed and built by van der Waals (vdW) stacking of individual monolayers into functional multilayer structures. Nonetheless, the optoelectronic properties of this new type of vdW heterostructure are unknown. Here, we investigate artificial semiconductor heterostructures built from single-layer WSe 2 and MoS 2 . We observe spatially direct absorption but spatially indirect emission in this heterostructure, with strong interlayer coupling of charge carriers. The coupling at the hetero-interface can be readily tuned by inserting hexagonal BN dielectric layers into the vdW gap. The generic nature of this interlayer coupling is expected to yield a new family of semiconductor heterostructures having tunable optoelectronic properties through customized composite layers.

In the monolayer limit, transition metal dichalcogenides become direct-bandgap, light-emitting semiconductors. The quantum yield of light emission is low and extremely sensitive to the substrate used, while the underlying physics remains elusive. In this work, we report over 100 times modulation of light emission efficiency of these two-dimensional semiconductors by physical adsorption of O2 and/or H2O molecules, while inert gases do not cause such effect. The O2 and/or H2O pressure acts quantitatively as an instantaneously reversible "molecular gating" force, providing orders of magnitude broader control of carrier density and light emission than conventional electric field gating. Physi-sorbed O2 and/or H2O molecules electronically deplete n-type materials such as MoS2 and MoSe2, which weakens electrostatic screening that would otherwise destabilize excitons, leading to the drastic enhancement in photoluminescence. In p-type materials such as WSe2, the molecular physisorption results in the opposite effect. Unique and universal in two-dimensional semiconductors, the effect offers a new mechanism for modulating electronic interactions and implementing optical devices.

Air-stable doping of transition metal dichalcogenides is of fundamental importance to enable a wide range of optoelectronic and electronic devices while exploring their basic material properties. Here we demonstrate the use of benzyl viologen (BV), which has one of the highest reduction potentials of all electron-donor organic compounds, as a surface charge transfer donor for MoS2 flakes. The n-doped samples exhibit excellent stability in both ambient air and vacuum. Notably, we obtained a high electron sheet density of ~1.2 × 10(13) cm(-2), which corresponds to the degenerate doping limit for MoS2. The BV dopant molecules can be reversibly removed by immersion in toluene, providing the ability to control the carrier sheet density as well as selective removal of surface dopants on demand. By BV doping of MoS2 at the metal junctions, the contact resistances are shown to be reduced by a factor of >3. As a proof of concept, top-gated field-effect transistors were fabricated with BV-doped n(+) source/drain contacts self-aligned with respect to the top gate. The device architecture, resembling that of the conventional Si transistors, exhibited excellent switching characteristics with a subthreshold swing of ~77 mV/decade.