Crouzier Loïc, Feltin Nicolas, Delvallée Alexandra, Pellegrino Francesco, Maurino Valter, Cios Grzegorz, Tokarski Tomasz, Salzmann Christoph, Deumer Jérôme, Gollwitzer Christian, Hodoroaba Vasile-Dan
Laboratoire National de Métrologie et d'Essais (LNE), 29 Avenue Roger Hennequin, CEDEX, 78197 Trappes, France.
Dipartimento di Chimica and NIS Inter-Department Centre, University of Torino, Via P. Giuria 7, 10125 Torino, Italy.
Nanomaterials (Basel). 2021 Dec 10;11(12):3359. doi: 10.3390/nano11123359.
In this paper, the accurate determination of the size and size distribution of bipyramidal anatase nanoparticles (NPs) after deposition as single particles on a silicon substrate by correlative Scanning Electron Microscopy (SEM) with Atomic Force Microscopy (AFM) analysis is described as a new measurement procedure for metrological purposes. The knowledge of the exact orientation of the NPs is a crucial step in extracting the real 3D dimensions of the particles. Two approaches are proposed to determine the geometrical orientation of individual nano-bipyramides: (i) AFM profiling along the long bipyramid axis and (ii) stage tilting followed by SEM imaging. Furthermore, a recently developed method, Transmission Kikuchi Diffraction (TKD), which needs preparation of the crystalline NPs on electron-transparent substrates such as TEM grids, has been tested with respect to its capability of identifying the geometrical orientation of the individual NPs. With the NPs prepared homogeneously on a TEM grid, the transmission mode in a SEM, i.e., STEM-in-SEM (or T-SEM), can be also applied to extract accurate projection dimensions of the nanoparticles from the same sample area as that analysed by SEM, TKD and possibly AFM. Finally, Small Angle X-ray Scattering (SAXS) can be used as an ensemble technique able to measure the NPs in liquid suspension and, with ab-initio knowledge of the NP shape from the descriptive imaging techniques, to provide traceable NP size distribution and particle concentration.
本文描述了一种新的计量学测量方法,通过相关扫描电子显微镜(SEM)与原子力显微镜(AFM)分析,精确测定双锥锐钛矿纳米颗粒(NPs)沉积在硅衬底上作为单个颗粒后的尺寸和尺寸分布。了解NPs的确切取向是提取颗粒真实三维尺寸的关键步骤。提出了两种确定单个纳米双锥体几何取向的方法:(i)沿双锥体长轴进行AFM轮廓分析,(ii)样品台倾斜后进行SEM成像。此外,还测试了一种最近开发的方法——透射菊池衍射(TKD),该方法需要在电子透明衬底(如TEM网格)上制备结晶NPs,以确定其识别单个NPs几何取向的能力。当NPs均匀制备在TEM网格上时,SEM中的透射模式,即扫描透射电子显微镜(STEM-in-SEM,或T-SEM),也可用于从与SEM、TKD以及可能的AFM分析相同的样品区域中提取纳米颗粒的精确投影尺寸。最后,小角X射线散射(SAXS)可作为一种整体技术,用于测量液体悬浮液中的NPs,并根据描述性成像技术对NP形状的初步了解,提供可溯源的NP尺寸分布和颗粒浓度。