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. See a complete list of Deposition and Microfabrication instruments.

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.

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

EMSL's molecular beam epitaxy (MBE) deposition system is used for the synthesis and characterization of novel oxide, ceramic, and mineral materials...
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...
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

In0.20Ga0.80N/GaN multi-quantum wells grown on [0001]-oriented GaN substrates with and without an InGaN buffer layer were characterized using three-...
The N-glycan diversity of human serum glycoproteins, i.e. the human blood serum N-glycome, is complex due to the range of glycan structures...
Sources, optical properties, and chemical composition of atmospheric brown carbon (BrC) aerosol are uncertain, making it challenging to estimate its...
Catalysis by single isolated atoms of precious metals has attracted much recent interest since it promises the ultimate economy in atom efficiency....
Ferrocene (Fc) and N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethyl-sulfonimide (Fc1N112-TFSI) were dissolved in carbonate...

Science Highlights

Posted: December 19, 2014
Strontium titanate and other titanium oxides hold the promise of turning sunlight into fuel. They are excellent candidates for solar hydrolysis –...
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...

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. See a complete list of Deposition and Microfabrication instruments.

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.

Influence of Adsorption Site and Wavelength on the Photodesorption of NO from the (Fe,Cr)3O4(111) Mixed Oxide Surface.

Abstract: 

The photochemical properties of nitric oxide on a mixed oxide single crystal surface was examined in ultrahigh vacuum (UHV) using temperature programmed desorption (TPD), photon stimulated desorption (PSD) and low energy electron diffraction (LEED). The mixed oxide was a 75% Fe and 25% Cr corundum (0001) oxide film prepared on an -Al2O3(0001) crystal, however its surface became terminated with a magnetite-like (111) structure after sputter/anneal cleaning, leading to a surface designated of (Fe,Cr)3O4(111). TPD of NO from the (Fe,Cr)3O4(111) surface revealed three chemisorbed states at 220, ~315 and 370 K assigned to NO binding at Fe3+, Cr3+ and Fe2+ sites, respectively. No significant thermal chemistry of NO was detected. NO photodesorption, the primary photochemical pathway in UHV, was sensitive to the adsorption site, with rates at the three adsorption sites following the trend: Fe3+ > Fe2+ > Cr3+. Multiexponential rate behavior seen in the overall NO PSD spectra was linked directly to site heterogeneity being manifested as a convolution of the individual NO photodesorption rates at the three types of surface sites. The photodesorption rate with UV light (365 nm) was ~10 times greater than that in the visible, but the per-photon rates across the visible spectrum (from 460 to 630 nm) were independent of the wavelength, which is suggestive of localized photon absorption at the adsorption site. Results in this study demonstrate that the adsorption site plays a critical role in determining photochemical rates on complex oxide surfaces. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multi-program national laboratory operated for DOE by Battelle. The research was performed using EMSL, 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: 
Henderson MA.2014."Influence of Adsorption Site and Wavelength on the Photodesorption of NO from the (Fe,Cr)3O4(111) Mixed Oxide Surface."Journal of Physical Chemistry C 118(36):21021-21030. doi:10.1021/jp506602x
Authors: 
MA Henderson
Facility: 
Volume: 
118
Issue: 
36
Pages: 
21021-21030
Publication year: 
2014

Diffusional Motion of Redox Centers in Carbonate Electrolytes .

Abstract: 

Ferrocene (Fc) and N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethyl-sulfonimide (Fc1N112-TFSI) were dissolved in carbonate solvents and self diffusion coefficents (D) of solutes and solvents were measured by 1H and 19F pulsed field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy. The organic solvents were propylene carbonate (PC), ethyl methyl carbonate (EMC) and a ternary mixture that also includes ethylene carbonate (EC). Results from NMR studies over the temperature range of 0-50 °C and for various concentrations (0.25 - 1.7 M) of Fc1N112-TFSI are compared to values of D simulated with classical molecular dynamics (MD). The measured self-diffusion coefficients gradually decreased as the Fc1N112-TFSI concentration increased in all solvents. Since the peaks for the two ions (Fc1N212 and TFSI) are separated in one-dimensional NMR spectra, separate diffusion coefficients could be measured and DTFSI is larger than DFc1N112 in all samples measured. The EC, PC and EMC have the same D in the neat solvent mixture and when Fc is dissolved in EC/PC/EMC at a concentration of 0.2 M, probably due to the interactions between common carbonyl structures within EC, PC and EMC. A difference in D (DPC < DEC < DEMC), and both a higher Ea for translational motion and higher effective viscosity for PC in the mixture containing Fc1N112-TFSI reflect the interaction between PC and Fc1N112+, which is a relatively stronger interaction than that between Fc1N112+ and other solvent species. In the EC/PC/EMC solution that is saturated with Fc1N112-TFSI, we find that DPC = DEC = DEMC and Fc1N112+ and all components of the EC/PC/EMC solution have the same Ea for translational motion, while the ratio DEC/PC/EMC/DFc1N112+ is approximately 3. These results reflect the lack of available free volume for independent diffusion in the saturated solution. The Fc1N112+ transference numbers lie around 0.4 and increases slightly as the temperature is increased in the PC and EMC solvents. The trends observed for D from simulations are in good agreement with experimental results and provide molecular level understanding of the solvation structure of Fc1N112-TFSI dissolved in EC/PC/EMC.

Citation: 
Han KS, NN Rajput, X Wei, W Wang, JZ Hu, KA Persson, and KT Mueller.2014."Diffusional Motion of Redox Centers in Carbonate Electrolytes ."Journal of Chemical Physics 141(10):104509. doi:10.1063/1.4894481
Authors: 
KS Han
NN Rajput
X Wei
W Wang
JZ Hu
KA Persson
KT Mueller
Instruments: 
Volume: 
0
Issue: 
0
Pages: 
0
Publication year: 
2014

Low-Temperature Carbon Monoxide Oxidation Catalysed by Regenerable Atomically Dispersed Palladium on Alumina.

Abstract: 

Catalysis by single isolated atoms of precious metals has attracted much recent interest since it promises the ultimate economy in atom efficiency. Previous reports have been confined to reducible oxide supports such as FeOx, TiO2 or CeO2. Here we show that isolated Pd atoms can be stabilized on industrially relevant gamma-alumina supports. At low Pd loadings (≤0.5 wt%) these catalysts contain exclusively atomically dispersed Pd species. The addition of lanthanum-oxide to the alumina, long known for its ability to improve alumina stability, is found to also help in the stabilization of isolated Pd atoms. Aberration-corrected scanning transmission electron microscopy (AC-STEM) confirms the presence of intermingled Pd and La on the gamma-alumina surface. Operando X-ray absorption spectroscopy, performed on Pd/La-alumina and Pd/gamma-alumina (0.5 wt% Pd) demonstrates the presence of catalytically active atomically dispersed ionic Pd in the Pd/La-doped gamma-alumina system. CO oxidation reactivity measurements show onset of catalytic activity at 40 ˚C, indicating that the ionic Pd species are not poisoned by CO. The reaction order in CO and O2 is positive, suggesting a reaction mechanism that is different from that on metallic Pd. The catalyst activity is lost if the Pd species are reduced to their metallic form, but the activity can be regenerated by oxidation at 700 ˚C in air. The high-temperature stability of these ionic Pd species on commercial alumina supports makes this catalyst system of potential interest for low-temperature exhaust treatment catalysts.

Citation: 
Peterson E, A DelaRiva, S Lin, RS Johnson, H Guo, J Miller, JH Kwak, CHF Peden, B Kiefer, LF Allard, F Ribeiro, and AK Datye.2014."Low-Temperature Carbon Monoxide Oxidation Catalysed by Regenerable Atomically Dispersed Palladium on Alumina."Nature Communications 5:Article No. 4885. doi:10.1038/ncomms5885
Authors: 
E Peterson
A DelaRiva
S Lin
RS Johnson
H Guo
J Miller
JH Kwak
CHF Peden
B Kiefer
LF Allard
F Ribeiro
AK Datye
Volume: 
0
Issue: 
0
Pages: 
0
Publication year: 
2014

Effect of Solar Radiation on the Optical Properties and Molecular Composition of Laboratory Proxies of Atmospheric Brown Carbon

Abstract: 

Sources, optical properties, and chemical composition of atmospheric brown carbon (BrC) aerosol are uncertain, making it challenging to estimate its contribution to radiative forcing. Furthermore, optical properties of BrC may change significantly during its atmospheric aging. We examined the effect of solar photolysis on the molecular composition, mass absorption coefficient, and fluorescence of secondary organic aerosol prepared by high-NOx photooxidation of naphthalene (NAP SOA). The aqueous solutions of NAP SOA was observed to photobleach with an effective half-time of 15 hours (with sun in its zenith) for the loss of the near-UV (300 -400 nm) absorbance. The molecular composition of NAP SOA was significantly modified by photolysis, with the average SOA formula changing from C14.1H14.5O5.1N0.08 to C11.8H14.9O4.5N0.02 after 4 hours of irradiation. The average O/C ratio did not change significantly, however, suggesting that it is not a good metric for assessing the extent of photolysis-driven aging in NAP SOA (and in BrC in general). In contrast to NAP SOA, the photolysis of BrC material produced by aqueous reaction of limonene+O3 SOA (LIM/O3 SOA) with ammonium sulfate was much faster, but it did not result in a significant change in the molecular level composition. The characteristic absorbance of the aged LIM/O3 SOA in the 450-600 nm range decayed with an effective half-time of <0.5 hour. This result emphasizes the highly variable and dynamic nature of different types of atmospheric BrC.

Citation: 
Lee HJ, PK Aiona, A Laskin, J Laskin, and S Nizkorodov.2014."Effect of Solar Radiation on the Optical Properties and Molecular Composition of Laboratory Proxies of Atmospheric Brown Carbon ."Environmental Science & Technology 48(17):10217-10226. doi:10.1021/es502515r
Authors: 
HJ Lee
PK Aiona
A Laskin
J Laskin
S Nizkorodov
Volume: 
48
Issue: 
17
Pages: 
10217-10226
Publication year: 
2014

Polysialylated N-Glycans Identified in Human Serum Through Combined Developments in Sample Preparation, Separations and

Abstract: 

The N-glycan diversity of human serum glycoproteins, i.e. the human blood serum N-glycome, is complex due to the range of glycan structures potentially synthesizable by human glycosylation enzymes. The reported glycome, however, is limited by methods of sample preparation, available analytical platforms, e.g., based upon electrospray ionization-mass spectrometry (ESI-MS), and software tools for data analysis. In this report, several improvements have been implemented in sample preparation and analysis to extend ESI-MS glycan characterization and to provide an improved view of glycan diversity. Sample preparation improvements include acidified, microwave-accelerated, PNGase F N-glycan release, and sodium borohydride reduction were optimized to improve quantitative yields and conserve the number of glycoforms detected. Two-stage desalting (during solid phase extraction and on the analytical column) increased the sensitivity by reducing analyte signal division between multiple reducing-end-forms or cation adducts. On-line separations were improved by using extended length graphitized carbon columns and adding TFA as an acid modifier to a formic acid/reversed phase gradient which provides additional resolving power and significantly improved desorption of both large and heavily sialylated glycans. To improve MS sensitivity and provide gentler ionization conditions at the source-MS interface, subambient pressure ionization with nanoelectrospray (SPIN) has been utilized. When method improvements are combined together with the Glycomics Quintavariate Informed Quantification (GlyQ-IQ) recently described1 these technologies demonstrate the ability to significantly extend glycan detection sensitivity and provide expanded glycan coverage. We demonstrate application of these advances in the context of the human serum glycome, and for which our initial observations include detection of a new class of heavily sialylated N-glycans, including polysialylated N-glycans.

Citation: 
Kronewitter SR, I Marginean, JT Cox, R Zhao, CD Hagler, AK Shukla, TS Carlson, JN Adkins, DG Camp, II, RJ Moore, KD Rodland, and RD Smith.2014."Polysialylated N-Glycans Identified in Human Serum Through Combined Developments in Sample Preparation, Separations and Electrospray ionization-mass spectrometry."Analytical Chemistry 86(17):8700-10. doi:10.1021/ac501839b
Authors: 
SR Kronewitter
I Marginean
JT Cox
R Zhao
CD Hagler
AK Shukla
TS Carlson
JN Adkins
DG Camp
II
RJ Moore
KD Rodl
RD Smith
Facility: 
Instruments: 
Volume: 
86
Issue: 
17
Pages: 
8700-10
Publication year: 
2014

Composition and Interface Analysis of InGaN/GaN Multiquantum-Wells on GaN Substrates Using Atom Probe Tomography.

Abstract: 

In0.20Ga0.80N/GaN multi-quantum wells grown on [0001]-oriented GaN substrates with and without an InGaN buffer layer were characterized using three-dimensional atom probe tomography. In all samples, the upper interfaces of the QWs were slightly more diffuse than the lower interfaces. The buffer layers did not affect the roughness of the interfaces within the quantum well structure, a result attributed to planarization of the surface of the 1st GaN barrier layer which had an average root-mean-square roughness of 0.177 nm. The In and Ga distributions within the MQWs followed the expected distributions for a random alloy with no indications of In clustering.

Citation: 
Liu F, L Huang, RF Davis, LM Porter, DK Schreiber, SVNT Kuchibhatla, V Shutthanandan, S Thevuthasan, E Preble, T Paskova, and KR Evans.2014."Composition and Interface Analysis of InGaN/GaN Multiquantum-Wells on GaN Substrates Using Atom Probe Tomography."Journal of Vacuum Science and Technology B--Microelectronics and Nanometer Structures 32(5):Article No. 051209. doi:10.1116/1.4893976
Authors: 
F Liu
L Huang
RF Davis
LM Porter
DK Schreiber
SVNT Kuchibhatla
V Shutthanan
S Thevuthasan
E Preble
T Paskova
KR Evans
Volume: 
0
Issue: 
0
Pages: 
0
Publication year: 
2014

Symmetries of migration related segments of all [001] coincidence site lattice tilt boundaries in (001) projections for all

Abstract: 

Utilizing bicrystallography in two dimensions (2D), the symmetries of migration related segments of Coincidence Site Lattice (CSL) boundaries are derived for projections along their [001] tilt axis in grain boundaries of crystalline materials that possess the holohedral point symmetry of the cubic system (i.e. m3m). These kinds of “edge-on” projections are typical for atomic resolution imaging of such tilt boundaries with Transmission Electron Microscopes (TEM). This fact facilitates the visual confirmation of our predictions by recently published Zcontrast scanning TEM investigations [H. Yang et al., Phil. Mag. 93 (2013) 1219] and many other TEM studies.

Citation: 
Moeck P, BW York, and ND Browning.2014."Symmetries of migration related segments of all [001] coincidence site lattice tilt boundaries in (001) projections for all holohedral cubic materials."Crystal Research & Technology 49(9):708-720. doi:10.1002/crat.201400071
Authors: 
P Moeck
BW York
ND Browning
Instruments: 
Volume: 
49
Issue: 
9
Pages: 
708-720
Publication year: 
2014

Micro-Spectroscopic Imaging and Characterization of Individually Identified Ice Nucleating Particles from a Case Field Study.

Abstract: 

The effect of anthropogenic and biogenic organic particles on atmospheric glaciation processes is poorly understood. We use an optical microscopy (OM) setup to identify the location of ice nuclei (IN) active in immersion freezing and deposition ice nucleation for temperatures of 200-273 K within a large population of particles sampled from an ambient environment. Applying multi-modal micro-spectroscopy methods we characterize the physicochemical properties of individual IN in particle populations collected in central California. Chemical composition and mixing state analysis of particle populations are performed to identify characteristic particle-type classes. All particle-types contained organic material. Particles in these samples take up water at subsaturated conditions, induce immersion freezing at subsaturated and saturated conditions above 226 K, and act as deposition IN below 226 K. The identified IN belong to the most common particle-type classes observed in the field samples: organic coated sea salt, Na-rich, and secondary and refractory carbonaceous particles. Based on these observations, we suggest that the IN are not always particles with unique chemical composition and exceptional ice nucleation propensity; rather, they are common particles in the ambient particle population. Thus, particle composition and morphology alone are insufficient to assess their potential to act as IN. The results suggest that particle-type abundance is also a crucial factor in determining the ice nucleation efficiency of specific IN types. These findings emphasize that ubiquitous organic particles can induce ice nucleation under atmospherically relevant conditions and that they may play an important role in atmospheric glaciation processes.

Citation: 
Knopf DA, PA Alpert, B Wang, RE O'Brien, ST Kelly, A Laskin, MK Gilles, and RC Moffet.2014."Micro-Spectroscopic Imaging and Characterization of Individually Identified Ice Nucleating Particles from a Case Field Study."Journal of Geophysical Research. D. (Atmospheres) 119(17):10,365-10,381. doi:10.1002/2014JD021866
Authors: 
DA Knopf
PA Alpert
B Wang
RE O'Brien
ST Kelly
A Laskin
MK Gilles
RC Moffet
Facility: 
Instruments: 
Volume: 
0
Issue: 
0
Pages: 
0
Publication year: 
2014

Experimental and Theoretical Studies on the Fragmentation of Gas-Phase Uranyl-, Neptunyl- and Plutonyl-Diglycolamide Complexes.

Abstract: 

Fragmentation of actinyl(VI) complexes UVIO2(L)22+, NpVIO2(L)22+ and PuVIO2(L)22+ (L = tetramethyl-3-oxa-glutaramide, TMOGA) produced by electrospray ionization was examined in the gas phase by collision induced dissociation (CID) in a quadrupole ion trap mass spectrometer. Cleavage of the C-Oether bond was observed for all three complexes, with dominant products being UVIO2(L)(L-86)+ with charge reduction, and NpVIO2(L)(L-101)2+ and PuVIO2(L)(L-101)2+ with charge conservation. The neptunyl and plutonyl complexes also exhibited substantial L+ loss to give pentavalent complexes NpVO2(L)+ and PuVO2(L)+, whereas the uranyl complex did not, consistent with the comparative An 5f-orbital energies and the AnVIO22+/AnVO2+ (An = U, Np, Pu) reduction potentials. CID of NpVO2(L)2+ and PuVO2(L)2+ was dominated by neutral ligand loss to form NpVO2(L)+ and PuVO2(L)+, which hydrated by addition of residual water in the ion trap; UVO2(L)2+ was not observed. Theoretical calculations of the structures and bonding of the AnVIO2(L)22+ complexes using density functional theory reveal that the metal centers are coordinated by six oxygen atoms from the two TMOGA ligands. The results are compared with radiolytic decomposition of TMOGA in solution.

Citation: 
Gong Y, HS Hu, L Rao, J Li, and JK Gibson.2013."Experimental and Theoretical Studies on the Fragmentation of Gas-Phase Uranyl-, Neptunyl- and Plutonyl-Diglycolamide Complexes."Journal of Physical Chemistry A 117(40):10544-10550. doi:10.1021/jp4076977
Authors: 
Y Gong
HS Hu
L Rao
J Li
JK Gibson
Instruments: 
Volume: 
117
Issue: 
40
Pages: 
10544-10550
Publication year: 
2013

A general mechanism for stabilizing the small sizes of precious metal nanoparticles on oxide supports.

Abstract: 

We recently discovered that MgAl2O4 spinel {111} nano-facets optimally stabilize the small sizes of platinum nanoparticles even after severe high temperature aging treatments. Here we report the thermal stabilities of other precious metals with various physical and chemical properties on the MgAl2O4 spinel {111} facets, providing important new insights into the stabilization mechanisms. Besides Pt, Rh and Ir can also be successfully stabilized as small (1-3 nm) nanoparticles and even as single atomic species after extremely severe (800 °C, 1 week) oxidative aging. However, other metals either aggregate (Ru, Pd, Ag, and Au) or sublimate (Os) even during initial catalyst synthesis. On the basis of ab initio theoretical calculations and experimental observations, we rationalize that the exceptional stabilization originates from lattice matching, and the correspondingly strong attractive interactions at interfaces between the spinel {111} surface oxygens and epitaxial metals\metal oxides. On this basis, design principles for catalyst support oxide materials that are capable in stabilizing precious metals are proposed.

Citation: 
Li WZ, L Kovarik, D Mei, MH Engelhard, F Gao, J Liu, Y Wang, and CHF Peden.2014."A general mechanism for stabilizing the small sizes of precious metal nanoparticles on oxide supports."Chemistry of Materials 26(19):5475-5481. doi:10.1021/cm5013203
Authors: 
Li WZ
L Kovarik
D Mei
MH Engelhard
F Gao
J Liu
Y Wang
CHF Peden
Volume: 
26
Issue: 
19
Pages: 
5475-5481
Publication year: 
2014

Pages