Deposition and Microfabrication

Physical structures ranging in size from miniature objects (nanomaterials) to electrical devices (thin films) with planned properties can be made using the deposition and microfabrication capability. Materials with specific surface, bulk and interfacial properties for energy and environmental applications can be designed and made using these integrated capabilities.

Resources and Techniques

  • Functionalized surfaces – Design and manufacture surfaces optimized for specific functions related to catalysis and other areas.
  • Model systems for geochemistry/biogeochemistry – Grow model oxide and mineral films with varying structure and complexity.
  • Materials with designed properties – Film growth and ion implantation for materials with specific properties.
  • Chemical and biological sensing – Film and surface layer deposition and modification, micro and nano-lithography, and solution synthesis capabilities.
  • Microfabrication – Engineering, software development and fabrication are used to design and fabricate next-generation components.

Additonal Information:

Description

Capability Details
• Unique oxygen-plasma-assisted molecular beam epitaxy system for designing and constructing high-quality oxide thin films
• Spin coating and wet chemical synthesis to prepare thin films and nanostructures
• Focused ion beam for nanolithography and deposition and manipulation of structures at the nano scale
• Microfabrication suite for designing and etching complex patterns into varied substrates
• Hybrid physical vapor deposition system for depositing thin films of metals, oxides, nitrides and alloys with high purity and thickness control
• Pulsed laser deposition for growing complex oxides films
• Low-energy ion deposition for preparing ultra-pure films of complex molecules, including biomolecules, through a mass-selected soft-landing process
• Diverse and unrivaled expertise in advanced signal acquisition and processing instrumentation, signal analysis algorithms, laboratory automation systems and scientific data management solutions

Instruments

This instrument is newly available to EMSL users. For more information about this instrument and the science it will help enable, see the ...
Custodian(s): Ryan Kelly, Hardeep S Mehta
The FEI Helios Nanolab dual-beam focused ion beam/scanning electron microscopy (FIB/SEM) microscope combines two important high-resolution...
Custodian(s): Bruce Arey
Only available at EMSL, the Discovery Deposition System has been customized to be a fully automated multi-functional "hybrid" instrument with...
This instrument is newly available to EMSL users. For more information about this instrument and the science it will help enable, see the ...
Custodian(s): Ryan Kelly, Hardeep S Mehta
The mass-selected ion deposition system is a new instrument constructed at EMSL. The apparatus, shown in Figure 1, includes a high-transmission...
Custodian(s): Julia Laskin

Publications

Electrochemical performance of the existing state-of-the art capacitors is not very high, key scientific barrier is that its charge storage mechanism...
The metallic compound MnBi is a promising rare-earth-free permanent magnet material. Compare to other rare-earth-free candidates, MnBi stands out for...
We report on ab initio molecular dynamics simulations of Ca-rich montmorillonite systems, in different hydration states in the presence of...
In H2 fuel cells, performance depends on factors controlling turnover frequency and energy efficiency in the electrocatalytic oxidation of H2. Nature...
Understanding hydrogen formation on TiO2 surfaces is of great importance as it could provide fundamental insight into water splitting for hydrogen...

Science Highlights

Posted: September 10, 2014
Scientists at EMSL and Pacific Northwest National Laboratory have generated a material that allows oxygen to efficiently move through it at...
Posted: August 07, 2013
Predictive models of biogeochemical interactions in soils are more accurate and scalable if they consider the reaction chemistry that occurs in...
Posted: July 29, 2013
Scientists have gained the first quantitative insights into electron transfer from minerals to microbes by studying that transfer in a nature-...
Posted: May 20, 2013
Pacific Northwest National Laboratory scientists working at EMSL wrote a review of how microfluidic devices are being used in scientific instruments...
Posted: March 19, 2013
One of the most noteworthy concerns for the U.S. Department of Energy is controlling atmospheric carbon dioxide to mitigate its effects on global...

Physical structures ranging in size from miniature objects (nanomaterials) to electrical devices (thin films) with planned properties can be made using the deposition and microfabrication capability. Materials with specific surface, bulk and interfacial properties for energy and environmental applications can be designed and made using these integrated capabilities.

Resources and Techniques

  • Functionalized surfaces – Design and manufacture surfaces optimized for specific functions related to catalysis and other areas.
  • Model systems for geochemistry/biogeochemistry – Grow model oxide and mineral films with varying structure and complexity.
  • Materials with designed properties – Film growth and ion implantation for materials with specific properties.
  • Chemical and biological sensing – Film and surface layer deposition and modification, micro and nano-lithography, and solution synthesis capabilities.
  • Microfabrication – Engineering, software development and fabrication are used to design and fabricate next-generation components.

Additonal Information:

Effect of Composition and Heat Treatment on MnBi Magnetic Materials.

Abstract: 

The metallic compound MnBi is a promising rare-earth-free permanent magnet material. Compare to other rare-earth-free candidates, MnBi stands out for its high intrinsic coercivity (Hci) and its large positive temperature coefficient. Several groups have demonstrated that the Hci of MnBi compound in thin film or in powder form can exceed 12 kOe and 26 kOe at 300 K and 523 K, respectively. Such steep increase in Hci with increasing temperature is unique to MnBi. Consequently, MnBi is a highly sought-after hard phase for exchange coupling nanocomposite magnets. The reaction between Mn and Bi is peritectic, so Mn tends to precipitate out of the MnBi liquid during the solidification process. As result, the composition of the Mn-Bi alloy with the largest amount of the desired LTP (low temperature phase) MnBi and highest saturation magnetization will be over-stoichiometric and rich in Mn. The amount of additional Mn required to compensate the Mn precipitation depends on solidification rate: the faster the quench speed, the less Mn precipitates. Here we report a systematic study of the effect of composition and heat treatments on the phase contents and magnetic properties of Mn-Bi alloys. In this study, Mn-Bi alloys with 14 compositions were prepared using conventional metallurgical methods such as arc melting and vacuum heat treatment, and the obtained alloys were analyzed for compositions, crystal structures, phase content, and magnetic properties. The results show that the composition with 55 at.% Mn exhibits the highest LTP MnBi content and the highest magnetization. The sample with this composition shows >90 wt.% LTP MnBi content. Its measured saturation magnetization is 68 emu/g with 2.3 T applied field at 300 K; its coercivity is 13 kOe and its energy product is 12 MGOe at 300 K. A bulk magnet fabricated using this powder exhibits an energy product of 8.2 MGOe.

Citation: 
Cui J, JP Choi, E Polikarpov, ME Bowden, W Xie, G Li, Z Nie, N Zarkevich, MJ Kramer, and DD Johnson.2014."Effect of Composition and Heat Treatment on MnBi Magnetic Materials."Acta Materialia 79:374-381. doi:10.1016/j.actamat.2014.07.034
Authors: 
J Cui
JP Choi
E Polikarpov
ME Bowden
W Xie
G Li
Z Nie
N Zarkevich
MJ Kramer
DD Johnson
Volume: 
Issue: 
Pages: 
Publication year: 
2014

In Situ One-Step Synthesis of Hierarchical Nitrogen-Doped Porous Carbon for High Performance Supercapacitors.

Abstract: 

Electrochemical performance of the existing state-of-the art capacitors is not very high, key scientific barrier is that its charge storage mechanism wholly depends on adsorption of electrolyte on electrode. We present a novel method for the synthesis of nitrogen -doped porous carbons and address the drawback by precisely controlling composition and surface area. Nitrogen-doped porous carbon was synthesized using a self-sacrificial template technique without any additional nitrogen and carbon sources. They exhibited exceptionally high capacitance (239 Fg-1) due to additional pseudocapacitance originating from doped nitrogen. Cycling tests showed no obvious capacitance decay even after 10,000 cycles, which meets the requirement of commercial supercapacitors. Our method is simple and highly efficient for the production of large quantities of nitrogen-doped porous carbons.

Citation: 
Jeon JW, R Sharma, P Meduri, BW Arey, HT Schaef, J Lutkenhaus, JP Lemmon, PK Thallapally, MI Nandasiri, BP McGrail, and SK Nune.2014."In Situ One-Step Synthesis of Hierarchical Nitrogen-Doped Porous Carbon for High Performance Supercapacitors."ACS Applied Materials & Interfaces 6(10):7214-7222. doi:10.1021/am500339x
Authors: 
JW Jeon
R Sharma
P Meduri
BW Arey
HT Schaef
J Lutkenhaus
JP Lemmon
PK Thallapally
MI Nasiri
BP McGrail
SK Nune
Instruments: 
Volume: 
6
Issue: 
10
Pages: 
7214-7222
Publication year: 
2014

Microstructural Response of Variably Hydrated Ca-Rich Montmorillonite to Supercritical CO2.

Abstract: 

We report on ab initio molecular dynamics simulations of Ca-rich montmorillonite systems, in different hydration states in the presence of supercritical CO2. Analysis of the molecular trajectories provides estimates of the relative H2O:CO2 ratio per interspatial cation. The vibrational density of states in direct comparison with dipole moment derived IR spectra for these systems provide unique signatures that can used to follow molecular transformation. In a co-sequestration scenario, these signatures could be used to identify the chemical state and fate of Sulfur compounds. Interpretation of CO2 asymmetric stretch shift is given based on a detailed analysis of scCO2 structure and intermolecular interactions of the intercalated species. Based on our simulations, smectites with higher charge interlayer cations at sub-single to single hydration states should be more efficient in capturing CO2, while maintaining caprock integrity. This research would not have been possible without the support of the office of Fossil Energy, Department of Energy. The computational resources were made available through a user proposal of the EMSL User facility, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

Citation: 
Lee MS, BP McGrail, and VA Glezakou.2014."Microstructural Response of Variably Hydrated Ca-Rich Montmorillonite to Supercritical CO2."Environmental Science & Technology 48(15):8612-8619. doi:10.1021/es5005889
Authors: 
MS Lee
BP McGrail
VA Glezakou
Instruments: 
Volume: 
48
Issue: 
15
Pages: 
8612-8619
Publication year: 
2014

Structures and Stabilities of (MgO)n Nanoclusters.

Abstract: 

Global minima for (MgO)n structures were optimized using a tree growth−hybrid genetic algorithm in conjunction with MNDO/MNDO/d semiempirical molecular orbital calculations followed by density functional theory geometry optimizations with the B3LYP functional. New lowest energy isomers were found for a number of (MgO)n clusters. The most stable isomers for (MgO)n (n > 3) are 3-dimensional. For n < 20, hexagonal tubular (MgO)n structures are more favored in energy than the cubic structures. The cubic structures and their variations dominate after n = 20. For the cubic isomers, increasing the size of the cluster in any dimension improves the stability. The effectiveness of increasing the size of the cluster in a specific dimension to improve stability diminishes as the size in that dimension increases. For cubic structures of the same size, the most compact cubic structure is expected to be the more stable cubic structure. The average Mg−O bond distance and coordination number both increase as n increases. The calculated average Mg−O bond distance is 2.055 Å at n = 40, slightly smaller than the bulk value of 2.104 Å. The average coordination number is predicted to be 4.6 for the lowest energy (MgO)40 as compared to the bulk value of 6. As n increases, the normalized clustering energy ΔE(n) for the (MgO)n increases and the slope of the ΔE(n)vs n curve decreases. The value of ΔE(40) is predicted to be 150 kcal/mol, as compared to the bulk value ΔE(∞) = 176 kcal/mol. The electronic properties of the clusters are presented and the reactive sites are predicted to be at the corners.

Citation: 
Chen M, AR Felmy, and DA Dixon.2014."Structures and Stabilities of (MgO)n Nanoclusters."Journal of Physical Chemistry A 118(17):3136-3146. doi:10.1021/jp412820z
Authors: 
M Chen
AR Felmy
DA Dixon
Instruments: 
Volume: 
118
Issue: 
17
Pages: 
3136-3146
Publication year: 
2014

Physical Properties of Ambient and Laboratory-Generated Secondary Organic Aerosol.

Abstract: 

The size and thickness of organic aerosol particles collected by impaction in five field campaigns were compared to those of laboratory generated secondary organic aerosols (SOA). Scanning transmission x-ray microscopy (STXM) was used to measure the total carbon absorbance (TCA) by individual particles as a function of their projection areas on the substrate. Because they flatten less upon impaction, particles with higher viscosity and surface tension can be identified by a steeper slope on a plot of TCA vs. size. The slopes of the ambient data are statistically similar indicating a small range of average viscosities and surface tensions across five field campaigns. Steeper slopes were observed for the plots corresponding to ambient particles, while smaller slopes were indicative of the laboratory generated SOA. This comparison indicates that ambient organic particles have higher viscosities and surface tensions than those typically generated in laboratory SOA studies.

Citation: 
O'Brien RE, A Neu, SA Epstein, A MacMillan, B Wang, ST Kelly, S Nizkorodov, A Laskin, RC Moffet, and MK Gilles.2014."Physical Properties of Ambient and Laboratory-Generated Secondary Organic Aerosol."Geophysical Research Letters 41(2):4347-4353. doi:10.1002/2014GL060219
Authors: 
RE O'Brien
A Neu
SA Epstein
A MacMillan
B Wang
ST Kelly
S Nizkorodov
A Laskin
RC Moffet
MK Gilles
Facility: 
Volume: 
41
Issue: 
2
Pages: 
4347-4353
Publication year: 
2014

Secondary Ion Mass Spectrometry Imaging of Dictyostelium discoideum Aggregation Streams.

Abstract: 

High resolution imaging mass spectrometry could become a valuable tool for cell and developmental biology, but both, high spatial and mass spectral resolution are needed to enable this. In this report, we employed Bi3 bombardment time-of-flight (Bi3 ToF-SIMS) and C60 bombardment Fourier transform ion cyclotron resonance secondary ion mass spectrometry (C60 FTICR-SIMS) to image Dictyostelium discoideum aggregation streams. Nearly 300 lipid species were identified from the aggregation streams. High resolution mass spectrometry imaging (FTICR-SIMS) enabled the generation of multiple molecular ion maps at the nominal mass level and provided good coverage for fatty acyls, prenol lipids, and sterol lipids. The comparison of Bi3 ToF-SIMS and C60 FTICR-SIMS suggested that while the first provides fast, high spatial resolution molecular ion images, the chemical complexity of biological samples warrants the use of high resolution analyzers for accurate ion identification.

Citation: 
Debord JD, DF Smith, CR Anderton, RM Heeren, L Pasa-Tolic, RH Gomer, and FA Fernandez-Lima.2014."Secondary Ion Mass Spectrometry Imaging of Dictyostelium discoideum Aggregation Streams."PLoS One 9(6):e99319. doi:10.1371/journal.pone.0099319
Authors: 
JD Debord
DF Smith
CR Anderton
RM Heeren
L Pasa-Tolic
RH Gomer
FA Fernez-Lima
Instruments: 
Volume: 
Issue: 
Pages: 
Publication year: 
2014

Automated High-Pressure Titration System with In Situ Infrared Spectroscopic Detection.

Abstract: 

A fully automated titration system with infrared detection was developed for investigating interfacial chemistry at high pressures. The apparatus consists of a high-pressure fluid generation and delivery system coupled to a high-pressure cell with infrared optics. A manifold of electronically actuated valves is used to direct pressurized fluids into the cell. Precise reagent additions to the pressurized cell are made with calibrated tubing loops that are filled with reagent and placed in-line with the cell and a syringe pump. The cell’s infrared optics facilitate both transmission and attenuated total reflection (ATR) measurements to monitor bulk-fluid composition and solid-surface phenomena such as adsorption, desorption, complexation, dissolution, and precipitation. Switching between the two measurement modes is accomplished with moveable mirrors that direct radiation from a Fourier transform infrared spectrometer into the cell along transmission or ATR light paths. The versatility of the high-pressure IR titration system is demonstrated with three case studies. First, we titrated water into supercritical CO2 (scCO2) to generate an infrared calibration curve and determine the solubility of water in CO2 at 50 °C and 90 bar. Next, we characterized the partitioning of water between a montmorillonite clay and scCO2 at 50 °C and 90 bar. Transmission-mode spectra were used to quantify changes in the clay’s sorbed water concentration as a function of scCO2 hydration, and ATR measurements provided insights into competitive residency of water and CO2 on the clay surface and in the interlayer. Finally, we demonstrated how time-dependent studies can be conducted with the system by monitoring the carbonation reaction of forsterite (Mg2SiO4) in water-bearing scCO2 at 50 °C and 90 bar. Immediately after water dissolved in the scCO2, a thin film of adsorbed water formed on the mineral surface, and the film thickness increased with time as the forsterite began to dissolve. However, after approximately 2.5 hours, the trend reversed, and a carbonate precipitate began to form on the forsterite surface, exposing dramatic chemical changes in the thin-water film. Collectively, these applications illustrate how the high-pressure IR titration system can provide molecular-level information about the interactions between variably wet scCO2 and minerals relevant to underground storage of CO2 (geologic carbon sequestration). The apparatus could also be utilized to study high-pressure interfacial chemistry in other areas such as catalysis, polymerization, food processing, and oil and gas recovery.

Citation: 
Thompson CJ, PF Martin, J Chen, P Benezeth, HT Schaef, KM Rosso, AR Felmy, and JS Loring.2014."Automated High-Pressure Titration System with In Situ Infrared Spectroscopic Detection."Review of Scientific Instruments 85(4):Article No. 044102. doi:10.1063/1.4870411
Authors: 
CJ Thompson
PF Martin
J Chen
P Benezeth
HT Schaef
KM Rosso
AR Felmy
JS Loring
Instruments: 
Volume: 
Issue: 
Pages: 
Publication year: 
2014

Molecular Hydrogen Formation from Proximal Glycol Pairs on TiO2(110).

Abstract: 

Understanding hydrogen formation on TiO2 surfaces is of great importance as it could provide fundamental insight into water splitting for hydrogen production using solar energy. In this work, hydrogen formation from glycols having different numbers of methyl end-groups have been studied using temperature pro-grammed desorption on reduced, hydroxylated, and oxidized TiO2(110) surfaces. The results from OD-labeled glycols demon-strate that gas-phase molecular hydrogen originates exclusively from glycol hydroxyl groups. The yield is controlled by a combi-nation of glycol coverage, steric hindrance, TiO2(110) order and the amount of subsurface charge. Combined, these results show that proximal pairs of hydroxyl aligned glycol molecules and subsurface charge are required to maximize the yield of this redox reaction. These findings highlight the importance of geometric and electronic effects in hydrogen formation from adsorbates on TiO2(110).

Citation: 
Chen L, Z Li, RS Smith, BD Kay, and Z Dohnalek.2014."Molecular Hydrogen Formation from Proximal Glycol Pairs on TiO2(110)."Journal of the American Chemical Society 136(15):5559-5562. doi:10.1021/ja500992b
Authors: 
L Chen
Z Li
RS Smith
BD Kay
Z Dohnalek
Facility: 
Volume: 
136
Issue: 
15
Pages: 
5559-5562
Publication year: 
2014

Arginine-Containing Ligands Enhance H-2 Oxidation Catalyst Performance.

Abstract: 

In H2 fuel cells, performance depends on factors controlling turnover frequency and energy efficiency in the electrocatalytic oxidation of H2. Nature uses the hydrogenase enzymes to oxidize H2 at high turnover frequencies (up to 20,000 s-1) and low overpotentials (<100 mV), while the fastest synthetic catalyst reported to date only oxidizes H2 at 50 s-1 under 1 atm H2. Here we report a water-soluble complex incorporating the amino acid arginine, [NiII(PCy2NArg2)2]6+, that operates at 210 s-1 (180 mV overpotential) under 1 atm H2 and 144,000 s-1 (460 mV overpotential) under 133 atm H2. The complex functions from pH 0-14 with rates increasing at lower pH values. The arginine groups impart water solubility and play a critical role in enhancing turnover frequency, most consistent with an intramolecular Arg-Arg interaction that controls the structure of the catalyst active site. This work was funded by the Office of Science Early Career Research Program through the US DOE, BES (AD, WJS), and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US DOE, BES (JASR). PNNL is operated by Battelle for the US DOE.

Citation: 
Dutta A, JA Roberts, and WJ Shaw.2014."Arginine-Containing Ligands Enhance H-2 Oxidation Catalyst Performance."Angewandte Chemie International Edition 53(25):6487-6491. doi:10.1002/anie.201402304
Authors: 
A Dutta
JA Roberts
WJ Shaw
Facility: 
Volume: 
53
Issue: 
25
Pages: 
6487-6491
Publication year: 
2014

Controlling SEI Formation on SnSb-Porous Carbon Nanofibers for Improved Na Ion Storage.

Abstract: 

Porous carbon nanofiber (CNF)-supported tin-antimony (SnSb) alloys is synthesized and applied as sodium ion battery anode. The chemistry and morphology of the solid electrolyte interphase (SEI) film and its correlation with the electrode performance are studied. The addition of fluoroethylene carbonate (FEC) in electrolyte significantly reduces electrolyte decomposition and creates a very thin and uniform SEI layer on the cycled electrode surface which could promote the kinetics of Na-ion migration/transportation, leading to excellent electrochemical performance.

Citation: 
Ji L, M Gu, Y Shao, X Li, MH Engelhard, BW Arey, W Wang, Z Nie, J Xiao, CM Wang, J Zhang, and J Liu.2014."Controlling SEI Formation on SnSb-Porous Carbon Nanofibers for Improved Na Ion Storage."Advanced Materials 26(18):2901-2908. doi:10.1002/adma.201304962
Authors: 
Ji L
M Gu
Y Shao
X Li
MH Engelhard
BW Arey
W Wang
Z Nie
J Xiao
CM Wang
J Zhang
J Liu
Facility: 
Instruments: 
Volume: 
26
Issue: 
18
Pages: 
2901-2908
Publication year: 
2014

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