Named after the two‐faced Roman god of transitions, transition metal dichalcogenide (TMD) Janus monolayers have two different chalcogen surfaces, inherently breaking the out‐of‐plane mirror symmetry. The broken mirror symmetry and the resulting potential gradient lead to the emergence of quantum properties such as the Rashba effect and the formation of dipolar excitons. Experimental access to these quantum properties, however, hinges on the ability to produce high‐quality 2D Janus monolayers. Here, these results introduce a holistic 2D Janus synthesis technique that allows real‐time monitoring of the growth process. This prototype chamber integrates in situ spectroscopy, offering fundamental insights into the structural evolution and growth kinetics, that allow the evaluation and optimization of the quality of Janus monolayers. The versatility of this method is demonstrated by synthesizing and monitoring the conversion of SWSe, SNbSe, and SMoSe Janus monolayers. Deterministic conversion and real‐time data collection further aid in conversion of exfoliated TMDs to Janus monolayers and unparalleled exciton linewidth values are reached, compared to the current best standard. The results offer an insight into the process kinetics and aid in the development of new Janus monolayers with high optical quality, which is much needed to access their exotic properties.

The family of layered BiTeX (X = Cl, Br, I) compounds are intrinsic Janus semiconductors with giant Rashba-splitting and many exotic surface and bulk physical properties. To date, studies on these materials required mechanical exfoliation from bulk crystals which yielded thick sheets in nonscalable sizes. Here, we report epitaxial synthesis of Janus BiTeCl and BiTeBr sheets through a nanoconversion technique that can produce few triple layers of Rashba semiconductors (<10 nm) on sapphire substrates. The process starts with van der Waals epitaxy of Bi2Te3 sheets on sapphire and converts these sheets to BiTeCl or BiTeBr layers at high temperatures in the presence of chemically reactive BiCl3/BiBr3 inorganic vapor. Systematic Raman, XRD, SEM, EDX, and other studies show that highly crystalline BiTeCl and BiTeBr sheets can be produced on demand. Atomic level growth mechanism is also proposed and discussed to offer further insights into growth process steps. Overall, this work marks the direct deposition of 2D Janus Rashba materials and offers pathways to synthesize other Janus compounds belonging to MXY family members.

A panoply of unconventional electronic states has been observed in moiré superlattices. Engineering similar bosonic phases remains, however, largely unexplored. We report the observation of a bosonic correlated insulator in WSe 2 /WS 2 moiré superlattices composed of excitons, i.e., tightly bound electron-hole pairs. We develop a pump probe spectroscopy method that we use to observe an exciton incompressible state at exciton filling ν ex = 1 and charge neutrality, indicating a correlated insulator of excitons. With varying charge density, the bosonic correlated insulator continuously transitions into an electron correlated insulator at charge filling ν e = 1, suggesting a mixed correlated insulating state between the two limits. Our studies establish semiconducting moiré superlattices as an intriguing platform for engineering bosonic phases.

Following the rise of interest in the properties of transition metal dichalcogenides, many experimental techniques were employed to research them. However, the temperature dependencies of optical transitions, especially those related to band nesting, were not analyzed in detail for many of them. Here, we present successful studies utilizing the photoreflectance method, which, due to its derivative and absorption-like character, allows investigating direct optical transitions at the high-symmetry point of the Brillouin zone and band nesting. By studying the mentioned optical transitions with temperature from 20 to 300 K, we tracked changes in the electronic band structure for the common transition metal dichalcogenides (TMDs), namely, MoS 2 , MoSe 2 , MoTe 2 , WS 2 , and WSe 2 . Moreover, transmission and photoacoustic spectroscopies were also employed to investigate the indirect gap in these crystals. For all observed optical transitions assigned to specific k -points of the Brillouin zone, their temperature dependencies were analyzed using the Varshni relation and Bose–Einstein expression. It was shown that the temperature energy shift for the transition associated with band nesting is smaller when compared with the one at high-symmetry point, revealing reduced average electron–phonon interaction strength.

Ultrafast charge transfer processes provide a facile way to create interlayer excitons in directly contacted transition metal dichalcogenide (TMD) layers. More sophisticated heterostructures composed of TMD/hBN/TMD enable new ways to control interlayer exciton properties and achieve novel exciton phenomena, such as exciton insulators and condensates, where longer lifetimes are desired. In this work, we experimentally study the charge transfer dynamics in a heterostructure composed of a 1 nm thick hBN spacer between MoSe 2 and WSe 2 monolayers. We observe the hole transfer from MoSe 2 to WSe 2 through the hBN barrier with a time constant of 500 ps, which is over 3 orders of magnitude slower than that between TMD layers without a spacer. Furthermore, we observe strong competition between the interlayer charge transfer and intralayer exciton−exciton annihilation processes at high excitation densities. Our work opens possibilities to understand charge transfer pathways in TMD/hBN/TMD heterostructures for the efficient generation and control of interlayer excitons.