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We present a comparison of common electron microscopy sample preparation methods for studying crystallisation processes from solution using both scanning and transmission electron microscopy (SEM and TEM). We focus on two widely studied inorganic systems: calcium sulphate, gypsum (CaSO4·2H2O) and calcium carbonate (CaCO3). We find significant differences in crystallisation kinetics and polymorph selection between the different sample preparation methods, which indicate that drying and chemical quenching can induce severe artefacts that are capable of masking the true native state of the crystallising solution. Overall, these results highlight the importance of cryogenic (cryo)‐quenching crystallising solutions and the use of full cryo‐TEM as the most reliable method for studying the early stages of crystallisation. [ABSTRACT FROM AUTHOR]

Calcium carbonate biomineralization is remarkable for the ability of organisms to produce calcite or aragonite with perfect fidelity, where this is commonly attributed to specific anionic biomacromolecules. However, it is proven difficult to mimic this behavior using synthetic or biogenic anionic organic molecules. Here, it is shown that cationic polyamines ranging from small molecules to large polyelectrolytes can exert exceptional control over calcium carbonate polymorph, promoting aragonite nucleation at extremely low concentrations but suppressing its growth at high concentrations, such that calcite or vaterite form. The aragonite crystals form via particle assembly, giving nanoparticulate structures analogous to biogenic aragonite, and subsequent growth yields stacked aragonite platelets comparable to structures seen in developing nacre. This mechanism of polymorph selectivity is captured in a theoretical model based on these competing nucleation and growth effects and is completely distinct from the activity of magnesium ions, which generate aragonite by inhibiting calcite. Profiting from these contrasting mechanisms, it is then demonstrated that polyamines and magnesium ions can be combined to give unprecedented control over aragonite formation. These results give insight into calcite/aragonite polymorphism and raise the possibility that organisms may exploit both amine‐rich organic molecules and magnesium ions in controlling calcium carbonate polymorph. [ABSTRACT FROM AUTHOR]

The large area deposition and synthesis of 10 mm × 10 mm atomically thin Yb3+‐doped MoS2 films by femtosecond pulsed laser deposition on a silica glass optical platform for device applications are demonstrated for the first time. The presence of Yb3+‐ion doping is confirmed using photoluminescence (PL), X‐ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The Yb3+‐doped MoS2 films, when excited with a 976 nm laser, exhibit room temperature PL with a peak at 1002 nm. The XPS and Raman spectroscopic analyses of the Yb3+‐doped and undoped films show that the deposited films are a mixture of 2H‐ and 1T‐MoS2 after postdeposition annealing at 500 °C. The density functional theory analysis shows that the 1T phase is metastable by +77 kJ (≈0.8 eV) mol‐1, when compared with the 2H state at 0 K. Ultrafast transient nonlinear optical spectroscopic measurements prove that the saturable absorption of undoped MoS2 is significantly modified after Yb3+‐ion doping, by displaying dopant‐host structure charge transfer. The complex transient absorption line shape shows a combination of bleach (negative) signals at the A (670 nm) and B (630 nm) exciton energies, and a strong induced absorption below the A exciton level. The results presented herein provide critical insight in designing novel rare‐earth‐ion doped 2D materials and devices. [ABSTRACT FROM AUTHOR]

We review the use of transmission electron microscopy (TEM) and associated techniques for the analysis of beam-sensitive materials and complex, multiphase systems in-situ or close to their native state. We focus on materials prone to damage by radiolysis and explain that this process cannot be eliminated or switched off, requiring TEM analysis to be done within a dose budget to achieve an optimum dose-limited resolution. We highlight the importance of determining the damage sensitivity of a particular system in terms of characteristic changes that occur on irradiation under both an electron fluence and flux by presenting results from a series of molecular crystals. We discuss the choice of electron beam accelerating voltage and detectors for optimizing resolution and outline the different strategies employed for low-dose microscopy in relation to the damage processes in operation. In particular, we discuss the use of scanning TEM (STEM) techniques for maximizing information content from high-resolution imaging and spectroscopy of minerals and molecular crystals. We suggest how this understanding can then be carried forward for in-situ analysis of samples interacting with liquids and gases, provided any electron beam-induced alteration of a specimen is controlled or used to drive a chosen reaction. Finally, we demonstrate that cryo-TEM of nanoparticle samples snap-frozen in vitreous ice can play a significant role in benchmarking dynamic processes at higher resolution. This article is part of a discussion meeting issue 'Dynamic in situ microscopy relating structure and function'.