Spin Crossover (SCO) is a promising switching phenomenon when implemented in electronic devices as molecules, thin films or nanoparticles. Among the properties modulated along this phenomenon, optically induced mechanical changes are of tremendous importance as they can work as fast light-induced mechanical switches or allow to investigate and control microstructural strains and fatigability. The development of characterization techniques probing 2 nanoscopic behaviour with high spatio-temporal resolution allows to trigger and visualize such mechanical changes of individual nanoscopic objects. Here we use Ultrafast Transmission Electron Microscopy (UTEM) to precisely probe the length changes of individual switchable nanoparticles induced thermally by nanosecond laser pulses. This allows us to reveal the mechanisms of spin switching, leading to the macroscopic expansion of SCO materials. This study was conducted on individual pure SCO nanoparticles and SCO nanoparticles encapsulating gold nanorods that serve for plasmonic heating under laser pulses. Length changes are compared with time-resolved optical measurements performed on an assembly of these particles.

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Photo-Thermal Switching of Individual Plasmonically Activated Spin Crossover Nanoparticle Imaged by Ultrafast Transmission Electron Microscopy.

An ultrathin surface layer with extraordinary molecular mobility has been discovered and intensively investigated on thin-film polymer materials for decades. However, because of the lack of suitable characterization techniques, it remains largely unexplored whether such a surface mobile layer also exists on individual polymeric nanospheres. Here, we propose a thermal-optical imaging technique to determine the glass transition (Tg) and rubber-fluid transition (Tf) temperatures of single isolated polystyrene nanospheres (PSNS) in a high-throughput and nonintrusive manner for the first time. Two distinct steps, corresponding to the glass transition and rubber-fluid transition, respectively, were clearly observed in the optical trace of single PSNS during temperature ramping. Because the transition temperature and size of the same individuals were both determined, single nanoparticle measurements revealed the reduced apparent Tf and increased Tg of single PSNS on the gold substrate with a decreasing radius from 130 to 70 nm. Further experiments revealed that the substrate effect played an important role in the increased Tg. More importantly, a gradual decrease in the optical signal was detected prior to the glass transition, which was consistent with a surface layer with enhanced molecular mobility. Quantitative analysis further revealed the thickness of this layer to be ∼8 nm. This work not only uncovered the existence and thickness of a surface mobile layer in single isolated nanospheres but also demonstrated a general bottom-up strategy to investigate the structure-property relationship of polymeric nanomaterials by correlating the thermal property (Tg and Tf) and structural features (size) at single nanoparticle level.

Optical Imaging of the Molecular Mobility of Single Polystyrene Nanospheres.

Molecular Memory Near Room Temperature in an Iron Polyanionic Complex

Thermogravimetric analysis (TGA) is a key material characterization method for studying the thermal stability and thermochemical process. However, the common TGA for bulk samples lacks sufficient spatial information, which blurs the intrinsic thermal decomposition characteristic and limits the understanding of the structure-performance relationship. Here, we report a dark-field microscope (DFM) method for studying thermal desorption process of I2 from I2-loaded zeolitic imidazolate framework-8 (I2@ZIF-8). Because of the high spatial resolution, DFM enables the imaging and tracking of the local mass loss of I2 in single I2@ZIF-8 particles at different reaction temperatures. We obtain from the DFM images the single-particle thermogravimetric and differential thermogravimetric curves to evaluate the inherent thermal stability of single I2@ZIF-8 particles. We also find the heterogeneous thermal decomposition property among different I2@ZIF-8 particles. Furthermore, we demonstrate the capacity of DFM to quantitatively determine thermal kinetics parameters such as the diffusion coefficient and activation energy of I2 in individual and multiple ZIF-8 particles. These useful results are essential for developing high-efficient porous adsorbents for the capture of I2.

Thermal Stability and Kinetics of Single I2@ZIF-8 Particles.

Imaging adsorption of iodide on single Cu2O microparticles reveals the acid activation mechanism.

The magnetic hysteresis property during the spin transition of spin-crossover (SCO) materials holds great promise for their applications in spin electronics, information storage, thermochromic, and nanophotonic devices. Existing studies often measured the averaged property of a bulk sample consisting of lots of individuals. When considering the significant heterogeneity among different individuals and the inevitable interparticle interactions, ensemble measurement not only blurred the structure-property relationship but also compromised the intrinsic hysteresis property and cyclability. Herein, we employed a recently developed surface plasmon resonance microscopy (SPRM) method to measure the thermal hysteresis curve of single isolated SCO nanoparticles. The thermal-induced spin transition was found to alter the optical contrast of single SCO nanoparticles, which was optically readout using SPRM in a quantitative, nonintrusive, and high-throughput manner. Single nanoparticle measurements revealed an intrinsic transition temperature that was independent of the temperature scan rate and superior stability after over 11 000 cycles of single SCO nanoparticles. Correlations between the hysteresis and the size and morphology of the same individuals further uncovered the significant nanoparticle-to-nanoparticle heterogeneity with implications for the size-property relationship and rational design of SCO materials with improved performance.

Wenrui Lei

Papers

Imaging the Thermal Hysteresis of Single Spin-Crossover Nanoparticles.