Numerical and Experimental Studies of Atomic Layer Deposition for Sustainability Improvement

Atomic layer deposition (ALD) is an approved nano-scale thin films fabrication technique with remarkable uniformity and conformity in surface geometry. This dissertation presents numerical and experimental studies to investigate the transient physical and chemical ALD process in order to improve its sustainability performance in terms of throughput, wastes and emissions. To be specific, in this dissertation, the transient process of ALD is studied extensively through both numerical and experimental approaches to find the influential factors on the two main critical sustainability issues: low throughput and negative environmental impacts. Different numerical schemes are developed and studied for ALD process simulations. In particular, the gas fluid dynamics of the carrier gas flow is studied numerically by introducing and comparing two Lattice Boltzmann Method (LBM) models. To account for the surface deposition process, the strong-coupled physical and chemical process of ALD is recovered numerically by Finite Volume Method (FVM). The 3D transient reactive thermal-fluid dynamic model adopts surface reaction kinetics and mechanisms based on the atomic-level calculations to study the surface deposition process. Experimental investigations are carried out to characterize the growth rate under different deposition conditions. The experimental observations are correlated with the simulations for better understanding the transient physical and chemical ALD process. The experimentally-validated numerical model is further applied for in-depth investigation of two types of batch and spatial ALD process for throughput improvement. A multi-wafer batch ALD with vertical and horizontal wafer arrangements is studied to investigate the influences of wafer layout on the deposition process with both experimental and numerical approaches. An in-line spatial ALD is also studied numerically to investigate three geometric and process factors, gap size, temperature, and pressure on the precursor intermixing and chemical deposition process. Spatial ALD is shown significantly effective in improving the throughput of ALD thin film depositions. To study the adverse environmental impacts of ALD nano-manufacturing technology on Al2O3 nano-scale thin films, numerical simulations with detailed ALD surface reaction mechanisms developed based on Density Functional Theory (DFT) are performed to investigate the effects of four process parameters on ALD film deposition rate, process emissions and wastes. The influential factors on process emissions and wastes are studied and identified

Effects of gap size, temperature and pumping pressure on the fluid dynamics and chemical kinetics of in-line spatial atomic layer deposition of Al2O3

Abstract: Low throughput is a major limitation for industrial level atomic layer deposition (ALD) applications. Spatial ALD is regarded as a promising solution to this issue. With numerical simulations, this paper studies an in-line spatial ALD reactor by investigating the effects of gap size, temperature, and pumping pressure on the flow and surface chemical deposition processes in Al2O3 ALD. The precursor intermixing is a critical issue in spatial ALD system design, and it is highly dependent on the flow and material distributions. By numerical studies, it’s found that bigger gap, e.g., 2 mm, results in less precursor intermixing, but generates slightly lower saturated deposition rate. Wafer temperature is shown as a significant factor in both flow and surface deposition processes. Higher temperature accelerates the diffusive mass transport, which largely contributes to the precursor intermixing. On the other hand, higher temperature increases film deposition rate. Well-maintained pumping pressure is beneficial to decrease the precursor intermixing level, but its effect on the chemical process is shown very weak. It is revealed that the time scale of in-line spatial ALD cycle is only in tens of milliseconds, i.e., ~15 ms. Considering that the in-line spatial ALD is a continuous process without purging step, the ALD cycle time is greatly shortened, and hence the overall throughput is shown as high as ~8 nm/s, compared to several nm/min in traditional ALD

Atomic layer deposition process modeling and experimental investigation for sustainable manufacturing of nano thin films

Abstract: This paper studies the adverse environmental impacts of atomic layer deposition (ALD) nano-manufacturing technology on ALD of Al2O3 nano-scale thin films. Numerical simulations with detailed ALD surface reaction mechanism developed based on Density Functional Theory (DFT), and atomic-level calculations are performed to investigate the effects of four process parameters including process temperature, pulse time, purge time, and carrier gas flow rate on ALD film deposition rate, process emissions and wastes. Full-cycle ALD simulations reveal that the depositions of nano-thin-films in ALD are in essence the chemisorption of the gaseous species and the conversion of surface species. Methane emissions are positively proportional to the film deposition process. The studies show that process temperature fundamentally affects the ALD chemical process by changing the energy states of the surface species. Pulse time is directly related to the precursor dosage. Purge time influences the ALD process by changing the gas-surface interaction time, and higher carrier gas flow rate alters the ALD flow field by accelerating the convective heat and mass transfer in ALD process

Focusing particles by induced charge electrokinetic flow in a microchannel

This is the peer reviewed version of the following article: Song, Y., Wang, C., Li, M., Pan, X. and Li, D. (2016), Focusing particles by induced charge electrokinetic flow in a microchannel. ELECTROPHORESIS, 37: 666–675. doi:10.1002/elps.201500361, which has been published in final form at http://dx.doi.org/10.1002/elps.201500361. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.A novel method of sheathless particle focusing by induced charge electrokinetic flow in a microchannel is presented in this paper. By placing a pair of metal plates on the opposite walls of the channel and applying an electrical field, particle focusing is achieved due to the two pairs of vortex that constrain the flow of the particle solution. As an example, the trajectories of particles under different electrical fields with only one metal plate on one side channel wall were numerically simulated and experimentally validated. Other flow focusing effects, such as the focused width ratio (focused width/channel width) and length ratio (focused length/half-length of metal plate) of the sample solution, were also numerically studied. The results show that the particle firstly passes through the gaps between the upstream vortices and the channel walls. Afterwards, the particle is focused to pass through the gap between the two downstream vortices that determine the focused particle position. Numerical simulations show that the focused particle stream becomes thin with the increases in the applied electrical field and the length of the metal plates. As regards to the focused length ratio of the focused stream, however, it slightly increases with the increase in the applied electrical field and almost keeps constant with the increase in the length of the metal plate. The size of the focused sample solution, therefore, can be easily adjusted by controlling the applied electrical field and the sizes of the metal plates

A two-dimensional hybrid with molybdenum disulfide nanocrystals strongly coupled on nitrogen-enriched graphene via mild temperature pyrolysis for high performance lithium storage

A novel 2D hybrid with MoS₂ nanocrystals strongly coupled on nitrogen-enriched graphene (MoS₂/NGg-C₃N₄) is realized by mild temperature pyrolysis (550 °C) of a self-assembled precursor (MoS₃/g-C₃N₄–H⁺/GO). With rich active sites, the boosted electronic conductivity and the coupled structure, MoS₂/NGg₋C₃N₄ achieves superior lithium storage performance

Crystal structure of CmABCB1 multi-drug exporter in lipidic mesophase revealed by LCP-SFX

がんの多剤排出の原因となっているABCトランスポーターの立体構造をSACLAのX線自由電子レーザーを用いて決定. 京都大学プレスリリース. 2021-12-23.CmABCB1 is a Cyanidioschyzon merolae homolog of human ABCB1, a well known ATP-binding cassette (ABC) transporter responsible for multi-drug resistance in various cancers. Three-dimensional structures of ABCB1 homologs have revealed the snapshots of inward- and outward-facing states of the transporters in action. However, sufficient information to establish the sequential movements of the open–close cycles of the alternating-access model is still lacking. Serial femtosecond crystallography (SFX) using X-ray free-electron lasers has proven its worth in determining novel structures and recording sequential conformational changes of proteins at room temperature, especially for medically important membrane proteins, but it has never been applied to ABC transporters. In this study, 7.7 mono­acyl­glycerol with cholesterol as the host lipid was used and obtained well diffracting microcrystals of the 130 kDa CmABCB1 dimer. Successful SFX experiments were performed by adjusting the viscosity of the crystal suspension of the sponge phase with hy­droxy­propyl methyl­cellulose and using the high-viscosity sample injector for data collection at the SACLA beamline. An outward-facing structure of CmABCB1 at a maximum resolution of 2.22 Å is reported, determined by SFX experiments with crystals formed in the lipidic cubic phase (LCP-SFX), which has never been applied to ABC transporters. In the type I crystal, CmABCB1 dimers interact with adjacent molecules via not only the nucleotide-binding domains but also the transmembrane domains (TMDs); such an interaction was not observed in the previous type II crystal. Although most parts of the structure are similar to those in the previous type II structure, the substrate-exit region of the TMD adopts a different configuration in the type I structure. This difference between the two types of structures reflects the flexibility of the substrate-exit region of CmABCB1, which might be essential for the smooth release of various substrates from the transporter

Investigation of Effects and Mechanisms of Total Flavonoids of Astragalus and Calycosin on Human Erythroleukemia Cells

Flavonoids are found in most parts of plants and have been shown to have multiple biological activities such as anticancer, anti-inflammation, antibacteria, antivirus, and immune-stimulation. Existing data showed that the total flavonoids of Astragalus (TFA) can provide biological system with resistance to injury and can possess antimutagenic, atherosclerotic inhibition, and other biological effects. This study investigated the effects of TFA and calycosin (a compound isolated from TFA), on apoptosis induction, and cell cycle of human erythroleukemia cell line K562 by an array of techniques, including proliferation (MTT), PI staining, Annexin V/PI double staining, and RT-PCR. The experimental data showed that TFA and calycosin could inhibit the proliferation of K562 cells. The 50% inhibiting concentrations of TFA and calycosin were 98.63 µg/mL and 130.32 µg/mL, respectively. However, TFA and calycosin could not induce apoptosis in K562 cells, but could increase the number of the cells in the G 0 /G 1 phase. The level of cyclin D1 mRNA in K562 cells decreased after the treatment with TFA and calycosin. This study provides new insights into the functional mechanism of total flavonoids of Astragalus and calycosin on human erythroleukemia cells

Engineered neutrophil-derived exosome-like vesicles for targeted cancer therapy

Neutrophils are the most abundant innate immune cells in human circulation; however, their derived exosomes have been rarely studied for tumor treatment. Here, we reported that exosomes from neutrophils (N-Ex) induce tumor cell apoptosis by delivering cytotoxic proteins and activating caspase signaling pathway. In addition, we decorated N-Ex with superparamagnetic iron oxide nanoparticles ( SPIONs) to achieve higher tumor-targeting therapeutic effect. We further fabricated exosome-like nanovesicles from neutrophils (NNVs) at high yield. Compared with liposome-loaded doxorubicin (DOX) and natural NNVs, DOX-loaded NNVs show an improved inhibition of tumor cell proliferation. Moreover, DOX-loaded, SPION-decorated NNVs selectively accumulate at the tumor sites under an external magnetic field, effectively restraining tumor growth and extensively prolonging the survival rate in mice. Overall, a simple and effective method to engineer N-Ex and NNVs at clinical applicable scale was developed, which enables the efficient and safe drug delivery for targeted and combined tumor therapy.Peer reviewe

Engineered neutrophil-derived exosome-like vesicles for targeted cancer therapy

Neutrophils are the most abundant innate immune cells in human circulation; however, their derived exosomes have been rarely studied for tumor treatment. Here, we reported that exosomes from neutrophils (N-Ex) induce tumor cell apoptosis by delivering cytotoxic proteins and activating caspase signaling pathway. In addition, we decorated N-Ex with superparamagnetic iron oxide nanoparticles ( SPIONs) to achieve higher tumor-targeting therapeutic effect. We further fabricated exosome-like nanovesicles from neutrophils (NNVs) at high yield. Compared with liposome-loaded doxorubicin (DOX) and natural NNVs, DOX-loaded NNVs show an improved inhibition of tumor cell proliferation. Moreover, DOX-loaded, SPION-decorated NNVs selectively accumulate at the tumor sites under an external magnetic field, effectively restraining tumor growth and extensively prolonging the survival rate in mice. Overall, a simple and effective method to engineer N-Ex and NNVs at clinical applicable scale was developed, which enables the efficient and safe drug delivery for targeted and combined tumor therapy

An isomorphous replacement method for efficient de novo phasing for serial femtosecond crystallography.

SACLAのX線自由電子レーザーを用いた新規タンパク質立体構造決定に世界で初めて成功. 京都大学プレスリリース. 2015-09-14.Serial femtosecond crystallography (SFX) with X-ray free electron lasers (XFELs) holds great potential for structure determination of challenging proteins that are not amenable to producing large well diffracting crystals. Efficient de novo phasing methods are highly demanding and as such most SFX structures have been determined by molecular replacement methods. Here we employed single isomorphous replacement with anomalous scattering (SIRAS) for phasing and demonstrate successful application to SFX de novo phasing. Only about 20,000 patterns in total were needed for SIRAS phasing while single wavelength anomalous dispersion (SAD) phasing was unsuccessful with more than 80,000 patterns of derivative crystals. We employed high energy X-rays from SACLA (12.6 keV) to take advantage of the large anomalous enhancement near the LIII absorption edge of Hg, which is one of the most widely used heavy atoms for phasing in conventional protein crystallography. Hard XFEL is of benefit for de novo phasing in the use of routinely used heavy atoms and high resolution data collection