Helium release rates from erbium and zirconium ditritide films were measured with 3-s time resolution. All films exhibited some variability in 3He release rates on this time scale, but the nonuniformity of the release rate was greatest for samples undergoing the transition into accelerated release, which occurs when the occluders approach the maximum quantities of helium that they can retain. The 3He release rate variability appeared to be associated with the spontaneous release of helium in bursts of about 109 atoms. The release of bursts of helium was also stimulated by vibrating or flexing the film substrates. Although these effects are not expected based on the diffusion of isolated helium atoms of the lattice, the effects of temperature on helium release rates were consistent with the diffusion model. These observations lead to the conclusion that two distinct mechanisms are responsible for the release of helium from the metal ditritide films.

A simple, inexpensive film-thickness monitor has been developed which accurately and independently determines the thickness of a film at any time during a deposition process. The principle of operation is the change in resistance of a vacuum-deposited film on a polished sapphire substrate maintained at a constant deposition temperature. The device, which is easily calibrated and automated, was found to have routine application to many types of metal film depositions in production and the development laboratory. The relationship between film deposition thickness and measured conductance was found to be linear for metal films over a wide range of thickness at constant substrate temperatures, from room temperature to 600 °C. Data is presented which compares film thickness, as measured by interferometric and differential weighing techniques, with that predicted from resistance measurements. The monitor has been used for following changes in resistance during in situ, reactive, and air-exposed hydriding and for resistivity determinations of occluder film hydrides of erbium, scandium, and titanium.

A recent short history of reactive evaporation by D. M. Mattox [History Corner—A Short History of Reactive Evaporation, SVC Bulletin (Society of Vacuum Coaters, Spring 2014), p. 50–51] describes various methods for producing oxides, nitrides, carbides, and some compounds, but hydrides were not mentioned. A study was performed in the mid-1970s at the General Electric Company Neutron Devices Department in Largo, FL, by the author to study preparation of thin film hydrides using reactive evaporation and to determine their unique characteristics and properties. Films were produced of scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), and the rare earth praseodymium (Pr), neodymium (Nd), gadolinium (Gd), dysprosium (Dy), and erbium (Er) hydrides by hot crucible filament and electron beam evaporation in atmospheres of deuterium and tritium gases. All-metal vacuum systems were used and those used with tritium were dedicated for this processing. Thin film test samples 1000 nm thick were prepared on 1.27 cm diameter molybdenum disk substrates for each occluder (i.e., an element that can react with hydrogen to form a hydride) material. Loading characteristics as determined by gas-to-metal atomic ratios, oxidation characteristics as determined by argon–sputter Auger analysis, film structure as determined by scanning electron microscope analysis, and film stress properties as determined by a double resonator technique were used to define properties of interest. Results showed hydrogen-to-metal atomic ratios varied from 1.5 to 2.0 with near maximum loading for all but Pr and Nd occluders which correlated with the oxidation levels observed, with all occluder oxidation levels being variable due to vacuum system internal processing conditions and the materials used. Surface oxide levels varied from ∼80 Å to over 1000 Å. For most films studied, results showed that a maximum loading ratio of near 2.0 and a minimum surface oxide level of ∼80 Å could be obtained with a bulk film oxygen level of ∼0.54 oxygen as determined by microprobe analysis when an evaporation rate of ∼0.313 mg/cm2 min was used in an atmosphere of D2 or T2 gas at a system deposition pressure of 1 × 10−3 Torr (1.33 × 10−1 Pa) in an evaporation time of ∼2 min. Platelet type (i.e., a film microstructure showing an overlay of flat plates with large grain sizes) film structures were observed for most films with some film mechanical properties determined (i.e., grain size and Vickers μ-hardness), and reduced stress levels were seen with initial normalized differential (tensile) stress levels being (1.0–4.0) × 108 dyne/cm2 for tritium loaded samples and (1.5 ± 0.5) × 109 dyne/cm2 for deuterium loaded samples. Also, stress aging characteristics were determined for some hydride films prepared in a radioactive tritium gas atmosphere. Tritium loading, however, had the undesirable characteristic of having to dispose of the internal processing system fixtures, which can be minimized, but the reactive evaporation technique produced desirable thin films.

An important aspect of understanding industrial processing is to know the characteristics of the materials used in such processes. A study was performed to determine the effects of hydriding chamber material on the degree of hydriding for the commercial production of thin film hydride targets for various research universities, commercial companies, and government national laboratories. The goal was to increase the degree of hydriding of various thin film hydrides and to study the vacuum environment during air-exposure hydriding. For this purpose, dynamic residual gas analysis during deuterium gas hydride processing was utilized with erbium thin films, employing a special set-up for direct dynamic hydride gas sampling during processing at elevated temperature and full loading gas pressure. Complete process data for (1) a copper–(1.83 wt. %)beryllium wet hydrogen fired passivated (600 °C–1 h) externally heated pipe hydriding chamber are reported. Dynamic residual gas analysis comparisons during hydriding are presented for hydriding chambers made from (2) alumina (99.8 wt. %), (3) copper (with an interior aluminum coating ∼10 k Å thick, and (4) for a stainless-steel air-fired passivated (900 °C–1 h) chamber. Dynamic data with deuterium gas in the chamber at the hydriding temperature (450 °C) showed the presence and growth of water vapor (D2O) and related mixed ion species(H2O+, HDO+, D2O+, and OD+) from hydrogen isotope exchange reactions during the 1 h process time. Peaks at mass-to-charge ratios (i.e., m/e) of 12(C+), 16(CD2+), 17(CHD2+), and 18(CD3+, OD+) increased for approximately the first half hour of a 1 h hydriding process and then approach steady state. Mass-to-charge peaks at 19(HDO+) and 20(D2O+) continue to increase throughout the process cycle. Using the m/e = 20 (D2O+) peak intensity from chamber (1)–Cu(1.83 wt. %)Be as a standard, the peak intensity from chamber (4)—stainless-steel (air-fired) was 7.1× higher, indicating that the surface of stainless-steel had a larger concentration of reactive oxygen and/or water than hydrogen. The (D2O+) peak intensity from chamber (3)—Cu (interior Al coating) was 1.55× larger and chamber (2)—alumina(99.8%) was 1.33× higher than Cu(1.83 wt. %)Be. Thus copper–(1.83 wt. %)beryllium was the best hydriding chamber material studied followed closely by the alumina (99.8 wt. %) chamber. Gas take-up by Er occluder targets processed in Cu(1.83 wt. %)Be hydriding chambers (i.e., gas/metal atomic ratios) correlate with the dynamic RGA data.

Aluminum has desirable characteristics of good thermal properties, good electrical characteristics, good optical properties, and the characteristic of being nonmagnetic and having a low atomic weight (26.98 g atoms), but because of its low melting point (660 °C) and ability as a reactive metal to alloy with most common metals in use, it has been ignored as a substrate material for use in processing thin films. The author developed a simple solution to this problem, by putting a permeation barrier of alumina (Al2O3) onto the surface of pure Al substrates by using a standard chemical oxidation process of the surface (i.e., anodization), before additional film deposition of reactive metals at temperatures up to 500 °C for 1-h, without the formation of alloys or intermetallic compounds to affect the good properties of Al substrates. The chromic acid anodization process used (MIL-A-8625) produced a film barrier of ∼(500–1000) nm of alumina. The fact that refractory Al2O3 can inhibit the reaction of metals with Al at temperatures below 500 °C suggests that Al is a satisfactory substrate if properly oxidized prior to film deposition. To prove this concept, thin film samples of Cr, Mo, Er, Sc, Ti, and Zr were prepared on anodized Al substrates and studied by x-ray diffraction, Rutherford ion back scattering, and Auger/argon sputter surface profile analysis to determine any film substrate interactions. In addition, a major purpose of our study was to determine if ErD2 thin films could be produced on Al substrates with fully hydrided Er films. Thus, a thin film of ErD2 on an anodized Al substrate was prepared and studied, with and without the alumina permeation barrier. Films for study were prepared on 1.27 cm diameter Al substrates with ∼500 nm of the metals studied after anodization. Substrates were weighed, cleaned, and vacuum fired at 500 °C prior to use. The Al substrates were deposited using standard electron beam cold crucible evaporation techniques, and after deposition the Er film was hydrided with D2 gas using a standard nonair exposure hydriding technique. All processing was conducted in an all metal ion pumped ultrahigh vacuum system. Results showed that e-beam deposition of films studied onto Al substrates could be successfully performed, if a permeation barrier of Al2O3 from 500 to 1000 nm was made prior to thin film deposition up to temperatures of 500 °C for 1-h. Hydrides also, could be produced with full gas/metal atomic ratios of ∼2.0 as evidenced by the ErD2 films produced. Thus, the use of a simple permeation barrier of Al2O3 on Al substrates prior to additional metal film deposition was proven to be a successful method of producing both thin metal films and hydride films of various types for many applications.