Diffraction and thermal effect of a Bessel-Gaussian laser for Ag nanoparticle deposition.

Nanoparticles are known to sinter at much lower temperatures than the corresponding bulk or micro size particles. A laser-assisted sintering process is considered in this study to sinter Ag nanoparticles by dispensing Ag paste onto an indium tin oxide-coated Si substrate. The Gaussian beam of a CO2 laser source is propagated through axicon and biconvex lenses, and the resulting hollow beam is focused on the Ag paste with a hollow parabolic mirror. A Bessel-Gaussian irradiance distribution is obtained at the focal plane of the parabolic mirror due to the interference of the hollow laser cone. The Fresnel diffraction approximation is considered to determine the phasor of the laser and an analytical approach is implemented to calculate the irradiance distribution of the Bessel-Gaussian beam. This irradiance distribution is utilized as a heat source in a heat conduction model and the temperature distribution is analyzed for thin Ag films formed during the laser sintering of Ag nanoparticles. An analytical expression is obtained for the temperature distribution by solving the heat conduction equation using Fourier transform for finite media. The widths of the deposited Ag lines are predicted from the temperature profiles and the model predictions compare well with the experimental results. The isotherms are found to be geometrically noncongruent with convex and concave tips depending on the locally maximum and minimum irradiances of the Bessel-Gaussian beam, respectively. The convex and concave tips, however, appear in the same isotherm for sufficiently high substrate speed relative to the laser beam.

A Combined Mechanochemical and Calcination Route to Mixed Cobalt Oxides for the Selective Catalytic Reduction of Nitrophenols.

Para-, or 4-nitrophenol, and related nitroaromatics are broadly used compounds in industrial processes and as a result are among the most common anthropogenic pollutants in aqueous industrial effluent; this requires development of practical remediation strategies. Their catalytic reduction to the less toxic and synthetically desirable aminophenols is one strategy. However, to date, the majority of work focuses on catalysts based on precisely tailored, and often noble metal-based nanoparticles. The cost of such systems hampers practical, larger scale application. We report a facile route to bulk cobalt oxide-based materials, via a combined mechanochemical and calcination approach. Vibratory ball milling of CoCl2(H2O)6 with KOH, and subsequent calcination afforded three cobalt oxide-based materials with different combinations of CoO(OH), Co(OH)2, and Co3O4 with different crystallite domains/sizes and surface areas; Co@100, Co@350 and Co@600 (Co@###; # = calcination temp). All three prove active for the catalytic reduction of 4-nitrophenol and related aminonitrophenols. In the case of 4-nitrophenol, Co@350 proved to be the most active catalyst, therein its retention of activity over prolonged exposure to air, moisture, and reducing environments, and applicability in flow processes is demonstrated.

Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy Studies of Hole-Selective Molybdenum Oxide Contacts in Silicon Solar Cells.

In this study, substochiometric hole-selective molybdenum oxide (MoOx) contacts in crystalline silicon (c-Si) solar cells were investigated by a combination of transmission electron microscopy (TEM) and spatially resolved electron energy-loss spectroscopy (SR-EELS). It was observed that a ≈ 4 nm SiOx interlayer grows at the MoOx/c-Si interface during the evaporation of MoOx over a c-Si substrate. SR-EELS analyses revealed the presence of a 1.5 nm diffused MoOx/indium tin oxide (ITO) interface in both as-deposited and annealed samples. Moreover, the presence of a 1 nm thin layer with a lower oxidation state of Mo was detected at the SiOx/MoOx interface in an as-deposited state, which disappears upon annealing. Overall, it was evident that no hole-blocking interlayer is formed at the MoOx/ITO interface during annealing and homogenization of the MoOx layer takes place during the annealing process. Furthermore, device simulations revealed that efficient hole collection is dependent on MoOx work function and that reduction in the work function of MoOx results in loss of band bending and negatively impacts hole selectivity.

Thermal Stability of Hole-Selective Tungsten Oxide: In Situ Transmission Electron Microscopy Study.

In this study, the thermal stability of a contact structure featuring hole-selective tungsten oxide (WOx) and aluminum deposited onto p-type crystalline silicon (c-Si/WOx/Al) was investigated using a combination of transmission line measurements (TLM) and in situ transmission electron microscopy (TEM) studies. The TEM images provide insight into why the charge carrier transport and recombination characteristics change as a function of temperature, particularly as the samples are annealed at temperatures above 500 °C. In the as-deposited state, a ≈ 2 nm silicon oxide (SiOx) interlayer forms at the c-Si/WOx interface and a ≈ 2-3 nm aluminum oxide (AlOx) interlayer at the WOx/Al interface. When annealing above 500 °C, Al diffusion begins, and above 600 °C complete intermixing of the SiOx, WOx, AlOx and Al layers occurs. This results in a large drop in the contact resistivity, but is the likely reason surface recombination increases at these high temperatures, since a c-Si/Al contact is basically being formed. This work provides some fundamental insight that can help in the development of WOx films as hole-selective rear contacts for p-type solar cells. Furthermore, this study demonstrates that in situ TEM can provide valuable information about thermal stability of transition metal oxides functioning as carrier-selective contacts in silicon solar cells.

Transmission Electron Microscopy Studies of Electron-Selective Titanium Oxide Contacts in Silicon Solar Cells.

In this study, the cross-section of electron-selective titanium oxide (TiO2) contacts for n-type crystalline silicon solar cells were investigated by transmission electron microscopy. It was revealed that the excellent cell efficiency of 21.6% obtained on n-type cells, featuring SiO2/TiO2/Al rear contacts and after forming gas annealing (FGA) at 350°C, is due to strong surface passivation of SiO2/TiO2 stack as well as low contact resistivity at the Si/SiO2/TiO2 heterojunction. This can be attributed to the transformation of amorphous TiO2 to a conducting TiO2-x phase. Conversely, the low efficiency (9.8%) obtained on cells featuring an a-Si:H/TiO2/Al rear contact is due to severe degradation of passivation of the a-Si:H upon FGA.