A Tale of Two Transitions: Unraveling Two Distinct Polymorph Transition Mechanisms in One n-Type Single Crystal for Dynamic Electronics

Cooperativity is used by living systems to circumvent energetic and entropic barriers to yield highly efficient molecular processes. Cooperative structural transitions involve the simultaneous, concerted displacement of molecules in a crystalline material, in stark contrast to the more typical molecule-by-molecule nucleation and growth mechanism often breaking the single crystallinity. Cooperative transitions have acquired much attention in the research community for their low transition barriers, ultrafast kinetics, and structural reversibility. On the other hand, cooperative transitions are rarely observed in molecular crystals and the molecular origin is not well understood. Single crystals of 2-dimensional quinoidal terthiophene (2DQTT-o-B), a high-performance n-type organic semiconductor, demonstrate two thermally-activated, reversible phase transitions with one exhibiting a cooperative mechanism and the second exhibiting a nucleation and growth mechanism. In situ microscopy, single crystal and grazing incidence X-ray diffraction (GIXD), along with Raman spectroscopy suggest a reorientation of the alkyl side chains results in a cooperative transition behavior. On the other hand, the nucleation and growth transition is coincident with both side chain melting and the emergence of new spin-spin interactions between conjugated cores, confirmed through in situ electron paramagnetic resonance spectroscopy (EPR). This is the first observation of biradical interactions directly initiating a structural transition. Through studying these fundamental mechanisms, we establish alkyl chain conformation and disorder as integral to rationally controlling these polymorphic behaviors for novel electronic applications.

Nucleation/Growth and Optical Proprieties of Co-doped ZnO Electrodeposited on ITO Substrate

A Co-doped ZnO layer was prepared by electrodeposition method on indium doped tin oxide (ITO) substrate using a cathodic reduction from nitrate medium with different doping percentages of cobalt. The bath temperature was controlled at 70 °C. The films were cathodically electrodeposited in a bath containing 5 mM Zn(NO3)2. 6H2O, while the source of Co is Co(NO3)2.6H2O where 0.1M KNO3 was used as supporting electrolyte. The nucleation and growth mechanism of Co-doped ZnO nuclei have been studied by cyclic voltammetry and chronoamperometry. The cyclic voltammetry shows that the electrodeposition of ZnO and Co-doped ZnO at a negative potential around -1.0 V versus saturated calomel electrode (SCE) is a quasi-reversible reaction controlled by the diffusion process. Comparing current transients curves obtained by the chronoamperometric method with the theoretical curves of current density j versus t ½ allows us to say that the nucleation is 3D instantaneous, as shown in SEM analysis. The presence of Co does not modify the nucleation and growth mechanism. The XRD patterns show that the substitution of zinc by cobalt does not change the würtzite crystal structure, but the crystallite size decreases with the cobalt percentage. The transmittance spectra indicate that the Co-doped ZnO films are transparent in the visible range. The optical gap increases with the doping percentage of cobalt.

Gamma Irradiation-Assisted Synthesis of Silver Nanoparticle and Their Antimicrobial Applications: A Review

This review presents an introduction to the synthesis of silver nanoparticles (Ag-NPs) by gamma irradiation method. This method offers some benefits over the conventional methods because it provides fully reduced and highly pure nanoparticles free from by-products or chemical reducing agents, and is capable of controlling the particle size and structure. The nucleation and growth mechanism of metallic nanoparticles are also discussed. The competition between nucleation and growth process in the formation of nanoparticles can determine the size of nanoparticles which is influenced by certain parameters such as the choice of solvents and stabilizer, the precursor to stabilizer ratio, pH during synthesis, and absorbed dose. The present review, summarizes the gamma irradiation synthesis of Ag-NPs procedure, advantages, applications and their antibacterial properties.

Effect of Electrosynthesis Potential on Nucleation, Growth, Adhesion, and Electronic Properties of Polypyrrole Thin Films on Fluorine-Doped Tin Oxide (FTO)

Polypyrrole (PPy) is one of the most attractive conducting polymers for thin film applications due to its good electrical conductivity, stability, optical properties, and biocompatibility. Among the technologies in which PPy has gained prominence are optoelectronics and solar energy conversion, where transparent electrodes such as fluorine-doped tin oxide (FTO) or indium tin oxide (ITO) are frequently used. However, FTO substrates have the notable advantage that their components are widely available in nature, unlike those of ITO. Recognizing the importance that the FTO/polypyrrole system has gained in various applications, here, we studied for the first time the nucleation and growth mechanism of electro-synthesized PPy on FTO. Additionally, the effect of the synthesis potential (0.9, 1.0, 1.1, and 1.2 V vs. Ag/AgCl) on the homogeneity, adhesion, conductivity, and HOMO energy levels of PPy films was determined. From current–time transients and scanning electron microscopy, it was found that films synthesized at 0.9 and 1.0 V exhibit 3D growth with progressive nucleation (as well as lower homogeneity and higher adhesion to FTO). In contrast, films synthesized at 1.1 and 1.2 V follow 2D growth with instantaneous nucleation. It was also evident that increasing the polymerization potential leads to polymers with lower conductivity and more negative HOMO levels (versus vacuum). These findings are relevant to encourage the use of electro-synthesized PPy in thin film applications that require a high control of material properties.