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Shining light on growth-dependent surface chemistry of organic crystals: a polarised Raman spectroscopic and computational study of aspirin
摘要： Understanding and controlling crystal surfaces is a critical problem in contemporary materials science. Organic crystal surfaces present the additional complexity of multiple terminations with different functional groups. These alternate terminations influence the surface chemistry and exert control on many material properties. While established tools for surface characterization exist, few provide the chemical information required to unambiguously identify functional groups. Polarized Raman spectroscopy is a versatile tool that can provide detailed chemical information on molecular materials, and, when used in a microscope configuration, can be used to map substrates on a micron scale. In this work, we demonstrate the use of polarized Raman to study the surface chemistry of aspirin. By analyzing crystals grown under a variety of conditions, we relate the growth solvent to the surface termination and reconcile the conflicting results in the literature on the nature of the <100> surface. Our results are supported by detailed first-principles modelling of the surfaces and their vibrational spectra. This study establishes the potential of polarized Raman microscopy as a tool for organic surface science that, when combined with predictive modelling, provides a powerful means to understand and ultimately control surface chemistry.
关键词： aspirin,first-principles modelling,crystal growth,polarized Raman spectroscopy,surface termination,lattice dynamics
更新于2025-09-23 15:23:52
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Towards a comprehensive understanding of the Si(100)-2×1 surface termination through hydrogen passivation using methylamine and methanol: a theoretical approach
摘要： Using density functional theory, we explored the termination process of Si (100)-2 × 1 reconstructed surface mechanistically through the dehydrogenation of small molecules, considering methyl amine and methanol as terminating reagents. At first, both the terminating reagents form two types of adduct through adsorption on the Si (100)-2 × 1 surface, one in chemisorption mode and the other via physisorption, from which the dehydrogenation process is initiated. By analyzing the activation barriers, it was observed that termination of the Si-surface through the dehydrogenation is kinetically almost equally feasible using either reagent. We further examined in detail the mechanism for each termination process by analyzing geometrical parameters and natural population analysis charges. From bonding evaluation, it is evident that hydrogen abstraction from adsorbates on the Si-surface is asymmetric in nature, where one hydrogen is abstracted as hydride by the electrophilic surface Si and the other hydrogen is abstracted as proton by the neucleophilic surface Si. Moreover, it was also observed that hydride transfer from adsorbate to the Si-surface occurs first followed by proton transfer. Overall, our theoretical interpretation provides a mechanistic understanding of the Si (100)-2 × 1 reconstructed surface termination by amine and alcohol that will further motivate researchers to design different types of decorated semiconductor devices.
关键词： Bonding evaluation,Si(100)-2 × 1 reconstructed surface,Dehydrogenation,Potential energy surface,Surface termination
更新于2025-09-23 15:21:01
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Controlling the fluorescence properties of nitrogen vacancy centers in nanodiamonds
摘要： Controlling the fluorescence properties of nitrogen vacancy centers in nanodiamonds is an important factor for their use in medical and sensor applications. However, reports providing a deep understanding of the potential factors influencing these properties are rare and focus only on a few influencing factors. The current contribution targets this issue and we report a comprehensive study of the fluorescence properties of NVs in nanodiamonds as a function of electron irradiation fluence and surface termination. Here we show that process parameters such as defect center interactions, in particular, different nitrogen defects and radiation induced lattice defects, as well as surface functionalities have a strong influence on the fluorescence intensity, fluorescence lifetime and the charge state ratio of the NV centers. By employing a time-correlated single photon counting approach we also established a method for fast macroscopic monitoring of the fluorescence properties of ND samples. We found that the fluorescence properties of NV centers may be controlled or even tuned depending upon the radiation treatment, annealing, and surface termination.
关键词： fluorescence lifetime,charge state ratio,nanodiamonds,surface termination,nitrogen vacancy centers,fluorescence properties,electron irradiation
更新于2025-09-19 17:15:36
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Comparison of geometry models in the study of perovskite heterostructures
摘要： Based on the first-principles calculations, the influence of different geometry models on the theoretical results about the electronic properties of LaAlO3/SrTiO3 perovskite heterostructures has been studied. The results show that the superlattice model can indicate n-type conductivity of interfaces, but it is limited to describe the insulator-metal transition of heterostructures. The sandwich and thin film models with the vacuum layer can take into account the surface termination effect on the electronic properties of the interface. The AlO2 or LaO atomic layer as the outmost surface termination is selected during constructing the model, leading to the distinct electronic properties of the heterostructures. The build-in electric filed appears in the AlO2-terminated structure, whereas it does not exist in LaO-terminated structure. Therefore, the AlO2-terminated structure can give a clear description about the insulator-metal transition of heterostructure and the charge transfer mechanism. The build-in electric filed, the atomic rumpling and surface termination effect of perovskite materials codetermine the conductivity of interfaces. The results would be helpful to construct theoretical model and understand the novel electronic properties during investigating other perovskite heterostructures.
关键词： perovskite heterostructure,surface termination,theoretical models,first-principles method
更新于2025-09-10 09:29:36
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Effects of Surface Termination and Layer Thickness on Electronic Structures of LaNiO <sub/>3</sub> Thin Films
摘要： We investigate the e?ects of surface termination and layer thickness on the electronic structures of LaNiO3 thin ?lms on SrTiO3 substrate using ?rst-principles density-functional theory calculations. The NiO2-terminated ?lm with one unit cell thickness shows a pseudogap at the Fermi level owing to the negative charge transfer energy, whereas the 1.5-unit-cell-thick LaO-terminated ?lm exhibits an insulating gap of 1.0 eV as a result of the large exchange splitting. The metallic state is quickly restored for thicker ?lms with either NiO2 or LaO termination, resembling that in bulk nickelate. Our results indicate the strong dependence of the electronic properties on layer thickness and provide insightful information into the metal–insulator transition in LaNiO3 thin ?lms.
关键词： surface termination,electronic structures,layer thickness,LaNiO3 thin films,metal–insulator transition
更新于2025-09-04 15:30:14