Accelerated Reaction Kinetics in Microdroplets: Overview and Recent Developments

2020 ◽  
Vol 71 (1) ◽  
pp. 31-51 ◽  
Author(s):  
Zhenwei Wei ◽  
Yangjie Li ◽  
R. Graham Cooks ◽  
Xin Yan

Various organic reactions, including important synthetic reactions involving C–C, C–N, and C–O bond formation as well as reactions of biomolecules, are accelerated when the reagents are present in sprayed or levitated microdroplets or in thin films. The reaction rates increase by orders of magnitude with decreasing droplet size or film thickness. The effect is associated with reactions at the solution–air interface. A key factor is partial solvation of the reagents at the interface, which reduces the critical energy for reaction. This phenomenon is of intrinsic interest and potentially of practical value as a simple, rapid method of performing small-scale synthesis.

2000 ◽  
Vol 649 ◽  
Author(s):  
Xi Chen ◽  
Joost J. Vlassak

ABSTRACTNanoindentation is a technique commonly used for measuring thin film mechanical properties such as hardness and stiffness. Typically, shallow indentations with contact depths less than 10-20% of the film thickness are used to ensure that measurements are not affected by the presence of the substrate. In this study, we have used the finite element method to investigate the effect of substrate and pile-up on hardness and stiffness measurements of thin film systems. We find that: i) for soft films on hard substrates, the hardness is independent of the substrate as long as the indentation depth is less than 50% of the film thickness; ii) as soon as the hardness exceeds that of the substrate, the substrate effect becomes significant, even for indentations as shallow as 5% of the film thickness; iii) if the film is at least 40 times harder than the substrate, the plastic zone is mostly confined to the substrate while the film conforms to the deformed substrate by bending. We define a substrate effect factor and construct a map that may be useful in the interpretation of indentation measurements on thin films. It is found that the yield stress mismatch is a key factor characterizing the hardness of thin film system, and the elastic mismatch is important when making stiffness measurements. The results obtained in this study are very useful when it is difficult to avoid the influence of the substrate on the measurements.


Soft Matter ◽  
2021 ◽  
Author(s):  
Marcel Gawek ◽  
Sherif Madkour ◽  
Paulina Szymoniak ◽  
Jörg Radnik ◽  
Andreas Schoenhals

The composition of the surface layer in dependence from the distance of the polymer/air interface in thin films with thicknesses below 100 nm of miscible polymer blends on a spatial...


1998 ◽  
Vol 536 ◽  
Author(s):  
A. B. Pevtsov ◽  
N. A. Feoktistov ◽  
V. G. Golubev

AbstractThin (<1000 Å) hydrogenated nanocrystalline silicon films are widely used in solar cells, light emitting diodes, and spatial light modulators. In this work the conductivity of doped and undoped amorphous-nanocrystalline silicon thin films is studied as a function of film thickness: a giant anisotropy of conductivity is established. The longitudinal conductivity decreases dramatically (by a factor of 109 − 1010) as the layer thickness is reduced from 1500 Å to 200 Å, while the transverse conductivity remains close to that of a doped a- Si:H. The data obtained are interpreted in terms of the percolation theory.


Coatings ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 510
Author(s):  
Yongqiang Pan ◽  
Huan Liu ◽  
Zhuoman Wang ◽  
Jinmei Jia ◽  
Jijie Zhao

SiO2 thin films are deposited by radio frequency (RF) plasma-enhanced chemical vapor deposition (PECVD) technique using SiH4 and N2O as precursor gases. The stoichiometry of SiO2 thin films is determined by the X-ray photoelectron spectroscopy (XPS), and the optical constant n and k are obtained by using variable angle spectroscopic ellipsometer (VASE) in the spectral range 380–1600 nm. The refractive index and extinction coefficient of the deposited SiO2 thin films at 500 nm are 1.464 and 0.0069, respectively. The deposition rate of SiO2 thin films is controlled by changing the reaction pressure. The effects of deposition rate, film thickness, and microstructure size on the conformality of SiO2 thin films are studied. The conformality of SiO2 thin films increases from 0.68 to 0.91, with the increase of deposition rate of the SiO2 thin film from 20.84 to 41.92 nm/min. The conformality of SiO2 thin films decreases with the increase of film thickness, and the higher the step height, the smaller the conformality of SiO2 thin films.


Nanomaterials ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 1409
Author(s):  
Ofelia Durante ◽  
Cinzia Di Giorgio ◽  
Veronica Granata ◽  
Joshua Neilson ◽  
Rosalba Fittipaldi ◽  
...  

Among all transition metal oxides, titanium dioxide (TiO2) is one of the most intensively investigated materials due to its large range of applications, both in the amorphous and crystalline forms. We have produced amorphous TiO2 thin films by means of room temperature ion-plasma assisted e-beam deposition, and we have heat-treated the samples to study the onset of crystallization. Herein, we have detailed the earliest stage and the evolution of crystallization, as a function of both the annealing temperature, in the range 250–1000 °C, and the TiO2 thickness, varying between 5 and 200 nm. We have explored the structural and morphological properties of the as grown and heat-treated samples with Atomic Force Microscopy, Scanning Electron Microscopy, X-ray Diffractometry, and Raman spectroscopy. We have observed an increasing crystallization onset temperature as the film thickness is reduced, as well as remarkable differences in the crystallization evolution, depending on the film thickness. Moreover, we have shown a strong cross-talking among the complementary techniques used displaying that also surface imaging can provide distinctive information on material crystallization. Finally, we have also explored the phonon lifetime as a function of the TiO2 thickness and annealing temperature, both ultimately affecting the degree of crystallinity.


Coatings ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 23
Author(s):  
Weiguang Zhang ◽  
Jijun Li ◽  
Yongming Xing ◽  
Xiaomeng Nie ◽  
Fengchao Lang ◽  
...  

SiO2 thin films are widely used in micro-electro-mechanical systems, integrated circuits and optical thin film devices. Tremendous efforts have been devoted to studying the preparation technology and optical properties of SiO2 thin films, but little attention has been paid to their mechanical properties. Herein, the surface morphology of the 500-nm-thick, 1000-nm-thick and 2000-nm-thick SiO2 thin films on the Si substrates was observed by atomic force microscopy. The hardnesses of the three SiO2 thin films with different thicknesses were investigated by nanoindentation technique, and the dependence of the hardness of the SiO2 thin film with its thickness was analyzed. The results showed that the average grain size of SiO2 thin film increased with increasing film thickness. For the three SiO2 thin films with different thicknesses, the same relative penetration depth range of ~0.4–0.5 existed, above which the intrinsic hardness without substrate influence can be determined. The average intrinsic hardness of the SiO2 thin film decreased with the increasing film thickness and average grain size, which showed the similar trend with the Hall-Petch type relationship.


2020 ◽  
Vol 102 (21) ◽  
Author(s):  
Stephan Geprägs ◽  
Björn Erik Skovdal ◽  
Monika Scheufele ◽  
Matthias Opel ◽  
Didier Wermeille ◽  
...  

1990 ◽  
Vol 43 (5) ◽  
pp. 583
Author(s):  
GL Price

Recent developments in the growth of semiconductor thin films are reviewed. The emphasis is on growth by molecular beam epitaxy (MBE). Results obtained by reflection high energy electron diffraction (RHEED) are employed to describe the different kinds of growth processes and the types of materials which can be constructed. MBE is routinely capable of heterostructure growth to atomic precision with a wide range of materials including III-V, IV, II-VI semiconductors, metals, ceramics such as high Tc materials and organics. As the growth proceeds in ultra high vacuum, MBE can take advantage of surface science techniques such as Auger, RHEED and SIMS. RHEED is the essential in-situ probe since the final crystal quality is strongly dependent on the surface reconstruction during growth. RHEED can also be used to calibrate the growth rate, monitor growth kinetics, and distinguish between various growth modes. A major new area is lattice mismatched growth where attempts are being made to construct heterostructures between materials of different lattice constants such as GaAs on Si. Also described are the new techniques of migration enhanced epitaxy and tilted superlattice growth. Finally some comments are given On the means of preparing large area, thin samples for analysis by other techniques from MBE grown films using capping, etching and liftoff.


Molecules ◽  
2021 ◽  
Vol 26 (6) ◽  
pp. 1615
Author(s):  
Amy Boylan ◽  
Thien S. Nguyen ◽  
Brian J. Lundy ◽  
Jian-Yuan Li ◽  
Ravikrishna Vallakati ◽  
...  

Two key factors bear on reaction rates for the conjugate addition of alkenyl boronic acids to heteroaryl-appended enones: the proximity of inductively electron-withdrawing heteroatoms to the site of bond formation and the resonance contribution of available heteroatom lone pairs to stabilize the developing positive charge at the enone β-position. For the former, the closer the heteroatom is to the enone β-carbon, the faster the reaction. For the latter, greater resonance stabilization of the benzylic cationic charge accelerates the reaction. Thus, reaction rates are increased by the closer proximity of inductive electron-withdrawing elements, but if resonance effects are involved, then increased rates are observed with electron-donating ability. Evidence for these trends in isomeric substrates is presented, and the application of these insights has allowed for reaction conditions that provide improved reactivity with previously problematic substrates.


2021 ◽  
Vol 2 (1) ◽  
pp. 168-186
Author(s):  
Bahareh Vafakish ◽  
Lee D. Wilson

The nanoreactor concept and its application as a modality to carry out chemical reactions in confined and compartmentalized structures continues to receive increasing attention. Micelle-based nanoreactors derived from various classes of surfactant demonstrate outstanding potential for chemical synthesis. Polysaccharide (glycan-based) surfactants are an emerging class of biodegradable, non-toxic, and sustainable alternatives over conventional surfactant systems. The unique structure of glycan-based surfactants and their micellar structures provide a nanoenvironment that differs from that of the bulk solution, and supported by chemical reactions with uniquely different reaction rates and mechanisms. In this review, the aggregation of glycan-based surfactants to afford micelles and their utility for the synthesis of selected classes of reactions by the nanoreactor technique is discussed. Glycan-based surfactants are ecofriendly and promising surfactants over conventional synthetic analogues. This contribution aims to highlight recent developments in the field of glycan-based surfactants that are relevant to nanoreactors, along with future opportunities for research. In turn, coverage of research for glycan-based surfactants in nanoreactor assemblies with tailored volume and functionality is anticipated to motivate advanced research for the synthesis of diverse chemical species.


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