• Korean Journal of Mineralogy and Petrology
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• v.35 no.4
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• pp.409-421
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• 2022

Achieving a highly resolved spatial distribution of Mn-bearing minerals and elements in the natural ferromanganese nodules can provide detailed knowledge of the temporal variations of geochemical conditions affecting the formation processes of nodules. While a recent study utilizing Raman spectroscopy has reported the changes in the manganate mineral phases with growth for spherical nodules from the Arctic Sea, the distributions of minerals and elements in the nodules from the shallow Arctic Sea with non-spherical forms have not yet fully elucidated. Here, we reported the micro-laser Raman spectra with varying data acquisition points along three different profiles from the center to the outermost rim of the non-spherical ferromanganese nodules collected from the East Siberian Sea (~73 m). The elemental distributions in the nodule (such as Mn, Fe, etc.) were also investigated by energy dispersive X-ray spectroscopy (EDS) analysis to observe the internal structure and mineralogical details. Based on the microscopic observation, the internal structures of a non-spherical nodule can be divided into three different regions, which are sediment-rich core, iron-rich substrate, and Mn-Fe layers. The Raman results show that the Mn-bearing mineral phases vary with the data acquisition points in the Mn-Fe layer, suggesting the changes in the geochemical conditions during nodule formation. In addition, we also observe that the mineral composition and structural characteristics depend on the profile direction from the core to the rim. Particularly, the Raman spectra obtained along one profile show the lack of Fe-(oxy)hydroxides and the noticeably high crystallinity of Mn-bearing minerals such as birnessite and todorokite. On the other hand, the spectra obtained along the other two profiles present the presence of significant amount of amorphous or poorly-ordered Fe-bearing minerals and the low crystallinity of Mn-bearing minerals. These results suggest that the diagenetic conditions varied with the different growth directions. We also observed the presence of halite in several layers in the nodule, which can be evidence of the alteration of seawater after nodule formation. The current results can provide the opportunity to obtain detailed knowledge of the formation process and geochemical environments recorded in the natural non-spherical ferromanganese nodule.

• Korean Journal of Materials Research
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• v.23 no.11
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• pp.613-619
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• 2013

$Cu_2ZnSn(S_x,Se_{1-x})_4$ (CZTSSe) thin films were prepared by sulfurization of evaporated precursor thin films. Precursor was prepared using evaporation method at room temperature. The sulfurization was carried out in a graphite box with S powder at different temperatures. The temperatures were varied in a four step process from $520^{\circ}C$ to $580^{\circ}C$. The effects of the sulfurization temperature on the micro-structural, morphological, and compositional properties of the CZTSSe thin films were investigated using X-ray diffraction (XRD), Raman spectra, field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The XRD and Raman results showed that the sulfurized thin films had a single kesterite crystal CZTSSe. From the FE-SEM and TEM results, the $Mo(S_x,Se_{1-x})_2$ (MoSSe) interfacial layers of the sulfurized CZTS thin films were observed and their thickness was seen to increase with increasing sulfurization temperature. The microstructures of the CZTSSe thin films were strongly related to the sulfurization temperatures. The voids in the CZTSSe thin films increased with the increasing sulfurization temperature.

• Proceedings of the Korean Vacuum Society Conference
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• 2015.08a
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• pp.120.2-120.2
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• 2015

We propose a novel direct writing technique with a femtosecond laser enabling selective modification of not only the morphology of conducting polymer thin films but also the orientation and alignment of the polymer crystal. Surface relief gratings resulting from photoexpansion on P3HT:PCBM and PEDOT:PSS thin films were fabricated by femtosecond laser direct writing. The photoexpansion was induced at laser fluence below the ablation threshold of the thin film. The morphology (size and shape) of photoexpansion could be quantitatively controlled by laser writing parameters such as focused beam size, writing speed, and laser fluence. GIWAX results showed that face-on P3HT crystals were largely increased in the photoexpansion in comparison with pristine region of the thin film. In addition, the face-on P3HTs in the photoexpansion were aligned with their orientation along the polarization of the laser. The micro-RAMAN spectra confirmed that neither chemical composition change nor the polymer chain breaking was observable after femtosecond laser irradiation. We believe that this laser direct writing technique opens a new door to the fabrication of more efficient OPVs via non-contact, toxic-free approach.

• Korean Journal of Materials Research
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• v.8 no.10
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• pp.884-889
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• 1998

Amorphous silicon films of large area have been crystallized by a line shape excimer laser beam of one dimensional scanning with a gaussian profile in the scanning direction. In order to characterize the crystalline phase transition of thickness variables in excimer laser annealing(ELA), angle wrapping method was used. And also to characterize the residual stresses of crystalline phase transition in the case of angle wrapped-crystalline silicon on corning 7059 glass, polarized raman spectroscopies were measured at various laser energy density and substrate temperature. The residual stress varies from $9.0{\times}10^9$ to $9.9{\times}10^9$, and from $9.9{\times}10^9$ to $1.2{\times}10^10$dyne/${cm}^2$ of the substrate temperature at room temperature and varies from $8.1{\times}10^9$ to $9.0{\times}10^9$, and from $9.0{\times}10^9$ to $9.9{\times}10^9$dyne/${cm}^2$ of the substrate temperature at $400^{\circ}C$ as a function of direction from surface to substrate. According to the direction from the surface in liquid phase to the interface and from the interface to near the substrate in solid phase of recrystallized Si thin film, respectively. Thus, the stress is increased from(Liquid phase to solid phase) with phase transition.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.154-155
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• 2012

The promise of nano-crystalites (nc) as a technological material, for applications including display backplane, and solar cells, may ultimately depend on tailoring their behavior through doping and crystallinity. Impurities can strongly modify electronic and optical properties of bulk and nc semiconductors. Highly doped dopant also effect structural properties (both grain size, crystal fraction) of nc-Si thin film. As discussed in several literatures, P atoms or radicals have the tendency to reside on the surface of nc. The P-radical segregation on the nano-grain surfaces that called self-purification may reduce the possibility of new nucleation because of the five-coordination of P. In addition, the P doping levels of ${\sim}2{\times}10^{21}\;at/cm^3$ is the solubility limitation of P in Si; the solubility of nc thin film should be smaller. Therefore, the non-activated P tends to segregate on the grain boundaries and the surface of nc. These mechanisms could prevent new nucleation on the existing grain surface. Therefore, most researches shown that highly doped nc-thin film by using conventional PECVD deposition system tended to have low crystallinity, where the formation energy of nucleation should be higher than the nc surface in the intrinsic materials. If the deposition technology that can make highly doped and simultaneously highly crystallized nc at low temperature, it can lead processes of next generation flexible devices. Recently, we are developing a novel CVD technology with a neutral particle beam (NPB) source, named as neutral beam assisted CVD (NBaCVD), which controls the energy of incident neutral particles in the range of 1~300eV in order to enhance the atomic activation and crystalline of thin films at low temperatures. During the formation of the nc-/pm-Si thin films by the NBaCVD with various process conditions, NPB energy directly controlled by the reflector bias and effectively increased crystal fraction (~80%) by uniformly distributed nc grains with 3~10 nm size. In the case of phosphorous doped Si thin films, the doping efficiency also increased as increasing the reflector bias (i.e. increasing NPB energy). At 330V of reflector bias, activation energy of the doped nc-Si thin film reduced as low as 0.001 eV. This means dopants are fully occupied as substitutional site, even though the Si thin film has nano-sized grain structure. And activated dopant concentration is recorded as high as up to 1020 #/$cm^3$ at very low process temperature (＜ $80^{\circ}C$) process without any post annealing. Theoretical solubility for the higher dopant concentration in Si thin film for order of 1020 #/$cm^3$ can be done only high temperature process or post annealing over $650^{\circ}C$. In general, as decreasing the grain size, the dopant binding energy increases as ratio of 1 of diameter of grain and the dopant hardly be activated. The highly doped nc-Si thin film by low-temperature NBaCVD process had smaller average grain size under 10 nm (measured by GIWAXS, GISAXS and TEM analysis), but achieved very higher activation of phosphorous dopant; NB energy sufficiently transports its energy to doping and crystallization even though without supplying additional thermal energy. TEM image shows that incubation layer does not formed between nc-Si film and SiO2 under later and highly crystallized nc-Si film is constructed with uniformly distributed nano-grains in polymorphous tissues. The nucleation should be start at the first layer on the SiO2 later, but it hardly growth to be cone-shaped micro-size grains. The nc-grain evenly embedded pm-Si thin film can be formatted by competition of the nucleation and the crystal growing, which depend on the NPB energies. In the evaluation of the light soaking degradation of photoconductivity, while conventional intrinsic and n-type doped a-Si thin films appeared typical degradation of photoconductivity, all of the nc-Si thin films processed by the NBaCVD show only a few % of degradation of it. From FTIR and RAMAN spectra, the energetic hydrogen NB atoms passivate nano-grain boundaries during the NBaCVD process because of the high diffusivity and chemical potential of hydrogen atoms.