Greg Gillen

Preliminary evaluation of an SF5+ polyatomic primary ion beam for analysis of organic thin films by secondary ion mass spectrometry

Organic vapor deposited thin films of pure biomolecules, polymer films and biomolecules dispersed in gelatin and biological tissue have been analyzed in a magnetic sector secondary ion mass spectrometer using an SF5+ primary ion beam at keV impact energies. In comparison to Ar+ bombardment under identical conditions, bombardment with SF5+ gives a 10 to 50 fold enhancement in the secondary ion yields for characteristic molecular ions. The SF5+ primary ion beam can be focussed to a small spot allowing molecular ion images to be obtained at micrometer spatial resolution with enhanced sensitivity. More importantly, the decay in molecular ion signal as a function of primary ion dose commonly observed in SIMS using monoatomic primary ions is either eliminated or greatly reduced, allowing molecular depth profiles to be obtained of organic thin films. By continuing to sample intact molecules as sputtering proceeds into the sample, the total number of detected characteristic secondary ions is increased by as much as a factor of approximately 700 for SF5+ bombardment as compared to Ar+ bombardment under identical analytical conditions. This effect is thought to be a result of the high erosion rate and the low penetration depth inherent in the use of a polyatomic primary projectile.

High temperature materials for thin-film thermocouples on silicon wafers

Abstract We have developed an instrumented calibration wafer for radiometric temperature measurements in rapid thermal processing (RTP) tools for semiconductor processing. The instrumented wafers have sputter deposited thin-film thermocouples to minimize the thermal disturbance of the wafer by the sensors. The National Institute of Standards and Technology (NIST) calibration wafer also employs platinum–palladium wire thermocouples to achieve a combined standard uncertainty of 0.4°C in the temperature measurement of the thin-film thermocouple junction at 900°C. The high temperatures of the wafer has required the development of new thin-film material systems. We have reported the results of our testing and characterization of sputtered platinum, palladium, rhodium, and iridium thin films using titanium bond coats on thermally oxidized silicon wafers. Depth profiling with secondary ion mass spectrometry was used to determine the diffusion profiles from the metal film to the silicon after heat treatments as high as 1000°C. Electron microscopy and optical microscopy were used to follow the reactions and the deterioration of the thermoelectric films. In addition, performance tests up to 1000°C in the NIST RTP test bed were used to determine the stability of the material systems. Failure mechanisms and limitations of the thin-film thermocouple materials have been discussed with data on hysteresis and drift in thermometry performance. The results of our evaluations indicated that Rh/Ir thin-film thermocouples have the best properties for wafer temperatures above 900°C.

Negative cesium sputter ion source for generating cluster primary ion beams for secondary ion mass spectrometry analysis

A cesium sputter ion source has been used to generate novel cluster and monoatomic primary ion beams for secondary ion mass spectrometry (SIMS). The source produces a variety of primary ion beam species with sufficient flux to be usable for both organic surface analysis and semiconductor depth profiling. The primary focus of this work is on the generation and use of carbon and carbon-containing cluster primary ion beams for SIMS. Stability of the sputter ion source is a few percent over 20 min, has useful lifetimes of weeks to months, and produces total primary ion beam currents for C2− ions, measured at the sample, of >1 μA at an extraction voltage of 10 kV. Larger cluster ions (Cx−x=4–10 and CsCx−x=2–8) are produced with tens of nA of beam current. Due to the divergence of the source, focused beam operation gives current densities under optimal conditions of 0.4–0.5 mA/cm2. Cluster bombardment studies of organic films using carbon clusters Cx−x=1–10 indicate that large enhancements (up to a factor of 80...

Secondary Ion Mass Spectrometry Using Cluster Primary Ion Beams

Abstract We have a developed a capability for conducting cluster secondary ion mass spectrometry (SIMS) experiments on commercially available SIMS instrumentation. This paper reviews our recent work on cluster ion source development, elemental depth profiling with cluster primary ion beams and the use of cluster ion beams for organic surface characterization. An area of particular interest is the observation that beam-induced damage for some organic materials is substantially reduced under cluster bombardment. This unique feature of cluster SIMS is utilized for molecular depth profiling of selected polymer films and for studying the spatial distribution of high explosive particles by SIMS imaging. We also describe recent studies that may provide additional insight into possible mechanisms for the molecular secondary ion yield enhancement observed for organic thin films under cluster bombardment.

Patterning of self‐assembled alkanethiol monolayers on silver by microfocus ion and electron beam bombardment

Decanethiol [CH3(CH2)9SH] self‐assembled monolayer films on silver substrates have been irradiated in selected areas by focused ion or electron bombardment. Subsequent immersion of the irradiated sample in a solution of a fluoromercaptan [CF3(CF2)2(CH2)2SH] results in attachment of this molecule to the silver surface in the ion or electron‐exposed regions, producing a micrometer spatial‐scale pattern of two chemically distinct alkanethiol monolayers. The coverage of the fluoromercaptan on the bombarded areas was found to reach maximum levels of 70% at ion doses of 6×1013 ions/cm2 and 50% at electron doses of 2×1017 electrons/cm2 as determined by secondary ion mass spectrometry. These methods of maskless patterning may be useful for semiconductor or biosensor device fabrication.

Development of a Triplasmatron Ion Source for the Generation of SF5+ and F- Primary Ion Beams on an Ion Microscope Secondary Ion Mass Spectrometry Instrument

A hot filament duoplasmatron ion source operating with argon has been modified by the addition of an enclosed expansion cup mounted to the extraction side of the duoplasmatron anode. Using sulfur hexafluoride (SF6) as a feed gas, this triplasmatron ion source has been used to generate SF5+ and F− primary ion beams for secondary ion mass spectrometry (SIMS). For positive primary ions, the current extracted from the source is composed of a series of SFx+ cluster ions (x=1–5) with the SF5+ ion being the most intense. SF5+ currents of ∼ 10–20 nA with a maximum of 40 nA are obtained at an extraction voltage of 10 kV. By applying a positive bias to the expansion cup, a localized secondary arc discharge is initiated giving 200 nA–300 nA of SF5+ with a current density of 0.5 mA/cm2. Depending on the operating parameters of the source, lifetimes of greater than 70 h have been achieved. For negative primary ions (with the cup removed), the current extracted from the source is primarily composed of F− ions with a ma...

A method to determine collection efficiency of particles by swipe sampling

A methodology was developed to evaluate particle collection efficiencies from swipe sampling of trace residues. Swipe sampling is used for many applications where trace residues must be collected, including the evaluation of radioactive particle contamination and the analysis of explosives and contraband at screening checkpoints using ion mobility spectrometry (IMS). Collection efficiencies were evaluated for micrometer-sized polystyrene latex (PSL) spheres with respect to the particle size and mode of deposition, collection trap, surface type and swiping force. Test surfaces containing particles were prepared under controlled conditions and swiped with a reproducible technique that allows for the evaluation of frictional forces. Collection efficiencies were determined by optical imaging and particle counting. Of the two IMS collection traps studied, the polytetrafluoroethylene (PTFE) trap has significantly lower collection efficiencies. This is likely to be due to a combination of texture and composition. The larger (42 µm diameter) particles are collected more efficiently than the smaller (9 µm diameter) particles. Particles in a matrix similar to latent fingerprints are collected more efficiently than dry particles. Applying greater force during swiping does not greatly improve collection efficiencies. This fact, coupled with the observation that many particles are detached but not collected, implies that improvements in collection efficiency are dependent on improvements in adhesion of the particles to the collection surface, rather than larger forces to detach the particles.

Use of an SF5+ polyatomic primary ion beam for ultrashallow depth profiling on an ion microscope secondary ion mass spectroscopy instrument

A magnetic sector secondary ion mass spectrometry (SIMS) instrument has been fitted with a modified hot filament duoplasmatron ion source for generation of SF5+ primary ion beams for SIMS depth profiling applications. The SF5+ primary ion beam has been evaluated by depth profiling of several low energy boron ion implants, boron delta-doped structures and a Ni/Cr metal multilayer depth profiling standard reference material. Using 3.0 keV impact SF5+ bombardment at a 52° impact angle with oxygen flooding gives a trailing edge decay length (1/e) for the boron implants and delta-doped layers of 1.3 nm. Under the same conditions, O2+ bombardment gives a trailing edge decay length (1/e) of 2.3 nm. The use of the SF5+ beam without oxygen flooding gives a substantial increase in decay length that is related to the formation of ripples as determined by atomic force microscopy. In the case of the Ni/Cr reference material, a significant reduction in sputter-induced topography is observed with SF5+ bombardment.

Application of Inkjet Printing Technology to Produce Test Materials of 1,3,5-Trinitro-1,3,5 Triazcyclohexane for Trace Explosive Analysis

The feasibility of the use of piezoelectric drop-on-demand inkjet printing to prepare test materials for trace explosive analysis is demonstrated. RDX (1,3,5-trinitro-1,3,5 triazcyclohexane) was formulated into inkjet printable solutions and jetted onto substrates suitable for calibration of the ion mobility spectrometry (IMS) instruments currently deployed worldwide for contraband screening. Gravimetric analysis, gas chromatography/mass spectrometry (GC/MS), and ultraviolet-visible (UV-vis) absorption spectroscopy were used to verify inkjet printer solution concentrations and the quantity of explosive dispensed onto test materials. Reproducibility of the inkjet printing process for mass deposition of the explosive RDX (1,3,5-trinitro-1,3,5 triazcyclohexane) was determined to be better than 2% for a single day of printing and better than 3% day-to-day.

Piezoelectric trace vapor calibrator

The design and performance of a vapor generator for calibration and testing of trace chemical sensors are described. The device utilizes piezoelectric ink-jet nozzles to dispense and vaporize precisely known amounts of analyte solutions as monodisperse droplets onto a hot ceramic surface, where the generated vapors are mixed with air before exiting the device. Injected droplets are monitored by microscope with strobed illumination, and the reproducibility of droplet volumes is optimized by adjustment of piezoelectric wave form parameters. Complete vaporization of the droplets occurs only across a 10°C window within the transition boiling regime of the solvent, and the minimum and maximum rates of trace analyte that may be injected and evaporated are determined by thermodynamic principles and empirical observations of droplet formation and stability. By varying solution concentrations, droplet injection rates, air flow, and the number of active nozzles, the system is designed to deliver—on demand—continuou...