Growth and Dispersion Control of SnO2 Nanocrystals Employing an Amino Acid Ester Hydrochloride in Solution Synthesis: Microstructures and Photovoltaic Applications.

Tin oxide (SnO2) is a technologically important semiconductor with versatile applications. In particular, attention is being paid to nanostructured SnO2 materials for use as a part of the constituents in perovskite solar cells (PSCs), an emerging renewable energy technology. This is mainly because SnO2 has high electron mobility, making it favorable for use in the electron transport layer (ETL) in these devices, in which SnO2 thin films play a role in extracting electrons from the adjacent light-absorber, i.e., lead halide perovskite compounds. Investigation of SnO2 solution synthesis under diverse reaction conditions is crucial in order to lay the foundation for the cost-effective production of PSCs. This research focuses on the facile catalyst-free synthesis of single-nanometer-scale SnO2 nanocrystals employing an aromatic organic ligand (as the structure-directing agent) and Sn(IV) salt in an aqueous solution. Most notably, the use of an aromatic amino acid ester hydrochloride salt-i.e., phenylalanine methyl ester hydrochloride (denoted as L hereafter)-allowed us to obtain an aqueous precursor solution containing a higher concentration of ligand L, in addition to facilitating the growth of SnO2 nanoparticles as small as 3 nm with a narrow size distribution, which were analyzed by means of high-resolution transmission electron microscopy (HR-TEM). Moreover, the nanoparticles were proved to be crystallized and uniformly dispersed in the reaction mixture. The environmentally benign, ethanol-based SnO2 nanofluids stabilized with the capping agent L for the Sn(IV) ions were also successfully obtained and spin-coated to produce a SnO2 nanoparticle film to serve as an ETL for PSCs. Several SnO2 ETLs that were created by varying the temperature of nanoparticle synthesis were examined to gain insight into the performance of PSCs. It is thought that reaction conditions that utilize high concentrations of ligand L to control the growth and dispersion of SnO2 nanoparticles could serve as useful criteria for designing SnO2 ETLs, since hydrochloride salt L can offer significant potential as a functional compound by controlling the microstructures of individual SnO2 nanoparticles and the self-assembly process to form nanostructured SnO2 thin films.

Manufacturing a TiO2-Based Semiconductor Film with Nanofluid Pool Boiling and Sintering Processes toward Solar-Cell Applications.

For the first time, nanofluid boiling was applied as a process for the creation of a semiconductor TiO2 nanoparticle film that can be deposited onto a conductive substrate (F-doped SnO2 glass: FTO). A steel-base device designed for pool boiling was used to deposit a TiO2-based nanofluid consisting of nanoparticles with an average size of about 20 nm. The boiling of the nanofluid directly on the FTO glass substrate allowed for the deposition of the nanoparticles onto the FTO surface. In principle, the surface responsible for transferring heat to the fluid can be covered with these nanoparticles when the nanofluid boils. Using the as-deposited films, crystal growth of the TiO2 nanoparticle was controlled by varying the strategies of the post-sintering profile. The maximum temperatures, periods, and ramping rates for the obtained samples were systematically changed. Scanning electron microscopy (SEM) revealed that a densely packed TiO2-nanoparticle layer was obtained for the as-deposited substrate via pool boiling. For the maximum temperature at 550 °C, the TiO2 grain sizes became larger (~50 nm) and more round-shaped TiO2 nanostructures were identified. Notably, we have demonstrated for the first time how the sintering of TiO2 nanoparticles proceeds for the nanoporous TiO2 films using high-resolution transmission electron microscopy (TEM) measurements. We found that the TiO2 nanoparticles fused with each other and crystal growth occurred through neighboring 2-4 nanoparticles for the 550 °C sample, which was proved by the TEM analysis that continuous lattice fringes corresponding to the (101) anatase phase were clearly observed through the entire area of some nanoparticles aligned horizontally. In addition, the loss of the TiO2 nanofluid (precursor solution) was completely avoided in our TiO2 deposition. Unlike the commonly used spin-coating method, nanofluid pool boiling would provide an alternative cost-effective approach to manufacture semiconductor layers for various applications, such as solar cells.