With the rise of two-dimensional (2D) transition-metal dichalcogenide (TMD) semiconductors and their prospective use in commercial (opto)electronic applications, it has become key to develop scalable and reliable TMD synthesis methods with well-monitored and controlled levels of impurities. While metal–organic chemical vapor deposition (MOCVD) has emerged as the method of choice for large-scale TMD fabrication, carbon (C) incorporation arising during MOCVD growth of TMDs has been a persistent concernespecially in instances where organic chalcogen precursors are desired as a less hazardous alternative to more toxic chalcogen hydrides. However, the underlying mechanisms of such unintentional C incorporation and the effects on film growth and properties are still elusive. Here, we report on the role of C-containing side products of organosulfur precursor pyrolysis in MoS2 thin films grown from molybdenum hexacarbonyl Mo(CO)6 and diethyl sulfide (CH3CH2)2S (DES). By combining in situ gas-phase monitoring with ex situ microscopy and spectroscopy analyses, we systematically investigate the effect of temperature and Mo(CO)6/DES/H2 gas mixture ratios on film morphology, chemical composition, and stoichiometry. Aiming at high-quality TMD growth that typically requires elevated growth temperatures and high DES/Mo(CO)6 precursor ratios, we observed that temperatures above DES pyrolysis onset (≳600 °C) and excessive DES flow result in the formation of nanographitic carbon, competing with MoS2 growth. We found that by introducing H2 gas to the process, DES pyrolysis is significantly hindered, which reduces carbon incorporation. The C content in the MoS2 films is shown to quench the MoS2 photoluminescence and influence the trion-to-exciton ratio via charge transfer. This finding is fundamental for understanding process-induced C impurity doping in MOCVD-grown 2D semiconductors and might have important implications for the functionality and performance of (opto)electronic devices.
The possibility to fabricate freestanding single crystal complex oxide films has raised enormous interest to be integrated in next‐generation electronic devices envisaging distinct and novel properties that can deliver unprecedented performance improvement compared to traditional semiconductors. The use of the water‐soluble Sr3Al2O6 (SAO) sacrificial layer to detach the complex oxide film from the growth substrate has significantly expanded the complex oxide perovskite membranes library. Nonetheless, the extreme water sensitivity of SAO hinders its manipulation in ambient conditions and restricts the deposition approaches to those using high vacuum. This study presents a pioneering study on the role of Ca‐substitution in solution processed SAO (Sr3−xCaxAl2O6 with x ⩽ 3) identifying a noticeable improvement on surface film crystallinity preserving a smooth surface morphology while favoring the manipulation in a less‐restricted ambient conditions. Then, the study focuses on the effect of the sacrificial composition on the subsequent ex situ deposition of La0.7Sr0.3MnO3 (LSMO) by pulsed laser deposition, to obtain epitaxial films with a variable degree of strain. Finally, epitaxial and strain‐free LSMO membranes with metal‐insulator transition at 290 K are delivered. This study offers a hybrid and versatile approach to prepare and easily manipulate crystalline perovskite oxide membranes by facilitating ex situ growth on SAO‐based sacrificial layer.
Layered Bi-misfit cobaltates, such as Bi2Sr2Co2Oy, are the natural superlattice of an electrically insulating rocksalt (RS) type Bi2Sr2O4 layer and electrically conducting CoO2 layer, stacked along the crystallographic c-axis. RS and CoO2 layers are related through charge compensation reactions (or charge transfer). Therefore, thermoelectric transport properties are affected when doping or substitution is carried out in the RS layer. In this work, we have shown improved thermoelectric properties of spark plasma sintered Bi2Sr2-xCaxCo2Oy alloys (x = 0, 0.3 and 0.5). The substitution of Ca atoms affects the thermal properties by introducing point-defect phonon scattering, while the electronic conductivity and thermopower remain unaltered.
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