Design of a new instrument for cold neutron prompt gamma-ray activation analysis at NIST

A new instrument for cold neutron prompt gamma-ray activation analysis (CNPGAA) is being designed and constructed at the NIST Center for Neutron Research (NCNR). The new instrument is expected to have lower gamma-ray and neutron background and better detection limits for most elements than the current cold neutron PGAA instrument. Other advantages over the current facility will include the ability to analyze larger samples and greater overall measurement capability due to the addition of scanning stages, cryostats, and sample changers.     

Studies in neutron depth profiling

This paper describes first the application of neutron depth profiling (NDP) for measuring the distribution of⁶Li in LiAlO₂ ceramics. Using a surface barrier detector for detecting³H produced in⁶Li(n, )³H,⁶Li was profiled to a depth of 14 m in the ceramics. Secondly, a new methodology is presented for NDP with enhanced capabilities based on measuring the energy of recoiling nuclei from (n, p) and (n, ) reactions by time-of-flight mass spectrometry. The scope of recoil nucleus time-of-flight mass spectrometry (RN-TOF-MS) includes profiling of¹⁰B,¹⁴N,¹⁷O,³³S,³⁵Cl,⁴⁰K. Probe depths may be of a few tens nanometers. RN-TOF-MS complements and refines NDP based on charged particle (p or ) spectrometry.     

Development of time-of-flight neutron depth profiling at Penn State University

Neutron depth profiling (NDP) is a nondestructive, near-surface technique, which utilizes a thermal/cold neutron beam to determine the concentration of specific light elements versus the depth in materials. The depth distribution is obtained by measuring the energy loss spectrum of protons, alphas, or recoil atoms in the substrate materials. For conventional NDP, the depth resolution is highly dependent on the limited ability of the detectors and associated electronics. A novel technique, the time-of-flight (TOF) method that is based on a completely different energy-measurement mechanism, can greatly improve the depth resolution for the accurate measurement of the dopant depth profile in especially shallow junction devices. Such a set of TOF NDP facility is being constructed at the 1 MW Breazeale Nuclear Reactor at Penn State University, Radiation Science and Engineering Center. In the TOF-NDP, a timing start signal is obtained from electrons emitted simultaneously with a neutron-induced recoil particle leaving the surface of the sample. The same particle generates the subsequent stop signal, whereby the residual energy of the particle is much more precisely determined from the particle flight time than currently obtained by the use of surface barrier detectors. In this paper, the Penn State conventional NDP measurement results will be presented and TOF-NDP facility will be described.     

Analytical applications of neutron depth profiling

Using a low-energy neutron beam as an isotopic probe, neutron depth profiling (NDP) provides quantitative depth profiles in nearly all solid matrix materials. Several of the light elements, such as He, Li, B, and N can be nondestructively analyzed by NDP. The information obtained using NDP is difficult if not impossible to determine by non-nuclear techniques. As a result, NDP is used collaboratively with techniques such as SIMS, RBS, FTIR, PGAA, and AES. Profiles measured by NDP are given for semiconductor and optical processing materials, and light weight alloys. Improvements in the technique are discussed with emphasis on the use of intense cold neutron beams.     

New approaches for neutron depth profiling

The scope of NDP can be expanded by measuring (via time-of-flight) the kinetic energies of the recoils emitted from (n,p) or (n,) reactions. When they occur inside a solid, the energies of the emerging recoils reveal depth from which they originated. The Recoil Nucleus Time-of-Flight NDP (RN-TOF-NDP) technique can reveal the depth distribution of some isotopes (e.g.,¹⁰B,²¹⁰Bi) with a resolution of a few Å. Furthermore, it is possible to detect atomic and molecular species ejected at the surface site where the recoil emerges from the solid. This paper discusses the methodology for RN-TOF-NDP and its applications including surface analysis based on atomic and molecular ions codesorbed with the recoils.     

Advancement of light-element neutron depth profiling at the University of Texas

The University of Texas (UT) at Austin has collaborated with the National Institute of Standards and Technology for comparisons of concentration versus depth profiles of samples containing ¹⁰B. Technology sharing from NIST has allowed UT to avoid many initial set backs such that significant advancements in the UT-NDP facility’s experimental and analytical methodology have been achieved. UT has analyzed two samples loaned to them from NIST. The collaborative effort between the two institutions has given the UT-NDP facility the proper tools to begin profiling more advanced samples in hopes of meeting the capabilities set by NIST in the NDP field. The UT-NDP facility was able to profile a borosilicate surface deposit onto silicon such that the concentrations of ¹⁰B at various depths of the deposit were determined and fit well to a Pearson distribution.     

Inverse iteration algorithm for neutron depth profiling

The objective of this work was to determine the sorption properties of soil underneath the National Radioactive Waste Disposal facility (NRWD) in Ró?an (NE Poland) for strontium (Sr) and caesium (Cs). The soil underneath the disposal was mainly sands consisted with quartz. The NRWD is a Low and Intermediate Level Wastes type facility. The procedure was new for our laboratory and turned out to be simple and effective. Sorption process analyses were carried out according to pH, ionic strength, time changes and tracer concentration in the solution. We also determined the Langmuir adsorption isotherms.     

NIST transmission density instrument

The Optical Technology Division of NIST has developed a new instrument for measuring ISO standard visual diffuse transmission densities using the diffuse influx mode. This instrument is used to calibrate both X-ray and photographic film step tablet Standard Reference Materials. The design, characterization, and operation of the instrument are detailed. The instrument was fully characterized both to verify compliance with the applicable international standards and to determine the combined uncertainty in transmission density associated with the calibrations. Results from comparisons with other laboratories are also presented.     

Development and applications of time-of-flight neutron depth profiling (TOF-NDP)

Neutron depth profiling (NDP) is a surface analysis technique based on the irradiation of samples with thermal or sub-thermal neutrons, and subsequent release of charged particles. Emitted particles rapidly lose kinetic energy primarily through interactions with the electrons of the substrate material. The depth of the reaction site can be found by using stopping power correlations. In conventional NDP, particle residual energy is measured by using a silicon semiconductor detector. In time-of-flight NDP (TOF-NDP), the energy can be determined by particle flight time. Time measurement can be made more sensitively than the energy measurement. Silicon semiconductor detectors can be replaced by microchannel plates (MCP). In this study, TOF-NDP concept will be briefly explained; Penn State TOF-NDP facility will be introduced; preliminary measurements performed with an alpha-source will be presented.     

Mapping of neutron flux gradient at NIST reactor to optimize neutron activation analysis of53Mn

Determination of⁵³Mn in meteorites by neutron activation analysis requires a thermal neutron flux high enough to ensure adequate production of⁵⁴Mn from⁵³Mn with a sufficiently low fast neutron component to minimize its production through fast neutron reactions. Thermal and fast neutron fluxes were mapped as a function of sample position within the NIST research reactor in order to determine the optimum position for irradiation of⁵³Mn.     

Cold neutron prompt gamma activation analysis at NIST: A progress report

An instrument for prompt gamma-ray activation analysis is now in operation at the NIST Cold Neutron Research Facility (CNRF). The cold neutron beam is relatively free of contamination by fast neutrons and reactor gamma rays, and the neutron fluence rate is 1.5·10⁸ cm^–2·s^–1 (thermal equivalent). As a result of a compact target-detector geometry the sensitivity is better by a factor of as much as seven than that obtained with an existing thermal instrument, and hydrogen background is a factor of 50 lower. We have applied this instrument to multielement analysis of the Allende meteorite and other materials.     

Neutron depth profiling applications at The University of Texas research reactor

The neutron depth profiling (NDP) technique has become an increasingly important method to nondestructively measure the absolute concentration versus depth of various elements in substrates. A permanent NDP facility is operational at a tangential beam port of the 1-MW TRIGA Mark II research reactor at The University of Texas at Austin (UT). This facility was developed to perform materials research, specifically measurements of interest to the microelectronics industry. Applications of the UT-NDP facility include measurements of boron-10 profiles in borophosphosilicate glass samples and helium-3 depth profiles of implanted helium-3 in metals, alloys and amorphous materials. A study is underway to determine radiation damage and microstructural changes in stainless steel samples by helium irradiation using NDP and Transmission Electron Microscopy. Another study, currently planned, is to measure surface wear by measuring the depth profiles of implanted beryllium-7 and sodium-22 in various materials.     

Status monitoring of ion sputter relevant parameters of an XPS depth profiling instrument

An X-ray photoelectron spectroscopy (XPS) instrument is utilized for sputter depth profiling of thin films. Relevant instrumental parameters are the ion gun sputter rate, the contamination level of the sputter ion gun, and the purity of the sputter ion gun gas supply as well as the vacuum quality of the instrument at the sample position. A long-term recording of these instrumental parameters ensures the reliability of the measured depth profile data. The ion gun sputter rate was estimated using the standard ISO conform depth profiling of a SiO₂ reference layer of known thickness. Two new procedures are developed to determine the other relevant parameters. Gases that are emitted by the ion sputter gun get implanted into a Si target. An analysis of the implanted gases allows judging on the contamination level of the sputter gun and the purity of the sputter gun gas supply. The vacuum condition of an XPS microprobe at the sample position is monitored by the recontamination of a sputtered Ti surface by adsorbed residual gas particles.     

Measurement of lithium diffusion coefficient in thin metallic multilayer by neutron depth profiling

Diffusion of Li ions in thin sandwich films with copper or lead encompassing layers (obtained by ion beam sputtering deposition technique) has been studied. These metals are promising candidates for electrodes in lithium-ion batteries. It is because they exhibit an ability to store and release Li ions during charging and discharging processes. Lithium diffusion was induced in samples by thermal annealing cycles. The lithium depth profile was measured using a nondestructive neutron depth profiling technique after each thermal annealing step. The analysis of experimental data allowed to evaluate the lithium depth profiles and directly calculate the diffusion coefficients.     

A new approach to express ToF SIMS depth profiling

We propose a new approach to express SIMS depth profiling on a TOF.SIMS‐5 time‐of‐flight mass spectrometer. The approach is based on the instrument capability to independently perform raster scans of sputter and probe ion beams. The probed area can be much smaller than the diameter of a sputter ion beam, like in the AES depth profiling method. This circumstance alleviates limitations on the sputter beam–raster size relation, which are critical in other types of SIMS, and enables analysis on a curved‐bottomed sputter crater. By considerably reducing the raster size, it is possible to increase the depth profiling speed by an order of magnitude without radically degrading the depth resolution. A technique is proposed for successive improvement of depth resolution through profile recovery with account for the developing curvature of the sputtered crater bottom in the probed area. Experimental study of the crater bottom form resulted in implementing a method to include contribution of the instrumental artifacts in a nonstationary depth resolution function within the Hofmann's mixing–roughness–information depth model. The real‐structure experiment has shown that the analysis technique combining reduction of a raster size with a successive nonstationary recovery ensures high speed of profiling at ~100 µm/h while maintaining the depth resolution of about 30 nm at a 5 µm depth. Copyright © 2015 John Wiley & Sons, Ltd.     

The application of instrumental neutron activation analysis for the certification of the new NIST Fly Ash SRM

The National Institute of Standards and Technology (NIST) recently released the second renewal of its Trace Elements in Coal Fly Ash Standard Reference Material (SRM 1633b). This new material is currently certified for 23 major, minor and trace elements, and concentrations of an additional 24 elements are provided for information only purposes. Current plans are to certify the concentrations of a number of rare earths upon completion of additional analytical work now in progress. Instrumental neutron activation analysis (INAA) has played a major role in the certification of this new material in view of its potential for accuracy, multielemental capability, ability to assess homogeneity, high sensitivity for many elements, and essentially blank-free nature. For an element to be certified in a NIST SRM its concentration is usually determined by at least two independent analytical techniques. INAA has provided analytical information for 15 of the 23 elements certified, as well as for 22 of the 24 elements listed for information only. In addition, INAA has provided much of the homogeneity information for this SRM. This paper will describe these analytical procedures, and highlight those designed to optimize and assess the accuracy of the INAA measurements.     

Benchmarking and analysis of 6Li neutron depth profiling of lithium ion cell electrodes

The University of Texas at Austin Neutron Depth Profiling (UT-NDP) facility was utilized to analyze varying cathode compositions in lithium battery materials. Battery materials included LiCoO₂, LiMn_1/3Ni_1/3Co_1/3O₂, and LiFePO₄. The cells were made at The University of Texas at Austin as coin cells with lithium anodes. The NDP analysis method for Li in battery materials was benchmarked between two facilities and with computational models.