ABSTRACT
Nanoscale metallic titanium (Ti) offers unique energetic and biocompatible characteristics for the aerospace and biomedical industries. A rapid and sustainable method to form purified Ti nanocrystals is still in demand due to their high oxygen affinity. Herein, we report the production of highly purified Ti nanoparticles with a nonequilibrium face center cubic (FCC) structure from titanium tetrachloride (TiCl4) via a capacitively coupled plasma (CCP) route. Furthermore, we demonstrate a secondary H2 treatment plasma as an effective strategy to improve the air stability of a thin layer of nanoparticles by further removal of chlorine from the particle surface. Hexagonal and cubic-shaped Ti nanocrystals of high purity were maintained in the air after the secondary H2 plasma treatment. The FCC phase potentially originates from small-sized grains in the initial stage of nucleation inside the plasma environment, which is revealed by a size evolution study with variations of plasma power input.
ABSTRACT
Transparent conductive oxides (TCOs) are widely used in optoelectronic devices such as flat-panel displays and solar cells. A significant optical property of TCOs is their band gap, which determines the spectral range of the transparency of the material. In this study, a tunable band gap range from 3.35 eV to 3.53 eV is achieved for zinc oxide (ZnO) nanocrystals (NCs) films synthesized by nonthermal plasmas through the removal of surface groups using atomic layer deposition (ALD) coating of Al2O3 and intense pulsed light (IPL) photo-doping. The Al2O3 coating is found to be necessary for band gap tuning, as it protects ZnO NCs from interactions with the ambient and prevents the formation of electron traps. With respect to the solar spectrum, the 0.18 eV band gap shift would allow ~4.1% more photons to pass through the transparent layer, for instance, into a CH3NH3PbX3 solar cell beneath. The mechanism of band gap tuning via photo-doping appears to be related to a combination of the Burstein-Moss (BM) and band gap renormalization (BGN) effects due to the significant number of electrons released from trap states after the removal of hydroxyl groups. The BM effect shifts the conduction band edge and enlarges the band gap, while the BGN effect narrows the band gap.
ABSTRACT
Aluminum oxide, both in amorphous and crystalline forms, is a widely used inorganic ceramic material because of its chemical and structural properties. In this work, we synthesized amorphous aluminum oxide nanoparticles using a capacitively coupled nonthermal plasma utilizing trimethylaluminum and oxygen as precursors and studied their crystallization and phase transformation behavior through postsynthetic annealing. The use of two reactor geometries resulted in amorphous aluminum oxide nanoparticles with similar compositions but different sizes. Size tuning of these nanoparticles was achieved by varying the reactor pressure to produce amorphous aluminum oxide nanoparticles ranging from 6 to 22 nm. During postsynthetic annealing, powder samples of amorphous nanoparticles began to crystallize at 800 °C, forming crystalline θ and γ phase alumina. Their phase transformation behavior was found to be size-dependent in that powders of small 6 nm amorphous particles transformed to form phase-pure α-Al2O3 at 1100 °C, while powders of large 11 nm particles remained in the θ and γ phases. This phenomenon is attributed to the fast rate of densification and neck formation in small amorphous aluminum oxide particles.
