Quantifying the uncertainty of picosecond pulsed laser ablation in sapphire
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In this study, a novel, to the best of our knowledge, method of wet chemical etching of sapphire workpieces (such as optics, wafers, windows, and cones), called the sapphire advanced mitigation process (or sapphire AMP), has been developed that exposes sub-surface mechanical damage created during the optical fabrication process and significantly enhances the surface laser damage resistance (> 2×) and mechanical strength (up to ~ 2.6×). Sapphire AMP involves first treating the workpiece with a mixture of sulfuric and phosphoric acid ([H 2 SO 4 ]:[H 3 PO 4 ]= 1 : 3) at 220°C, followed with phosphoric acid at 160°C, then with sodium hydroxide base (NaOH) and surfactant at 40°C, and finally with a high-pressure deionized water spray rinse. Sapphire AMP has been demonstrated on both A- and C-plane sapphire workpieces. The mechanism of this etch process involves the reaction of the sapphire (Al 2 O 3 ) surface with sulfuric acid (H 2 SO 4 ) forming aluminum sulfate [Al2(SO4)3], which has low solubility. The high phosphoric acid content in the first and second steps of sapphire AMP results in the efficient conversion of Al 2 (SO 4 ) 3 to aluminum phosphate (AlPO 4 ), which is very soluble, greatly reducing reaction product redeposition on the workpiece surface. Sapphire AMP is shown to expose sub-surface mechanical damage on the sapphire surface created during the grinding and polishing processes, whose etched morphology has either isotropic or anisotropic evolution depending on the nature of the initial surface damage. Sapphire AMP was also designed to remove the key known surface, laser absorbing precursors (namely, foreign chemical impurities, the fracture surface layer of preexisting sub-surface damage, and reaction product or foreign species redeposition or precipitation). Static and sliding indention induced surface microfractures on sapphire are shown after sapphire AMP to have a significant decrease in the fast photoluminescence intensity (a known metric for measuring the degree of laser damaging absorbing precursors). In addition, the onset of laser damage (at 351 nm 3 ns) on sapphire AMP treated workpieces was shown to increase in fluence from ~ 4 to >9.5J/cm 2 . Finally, biaxial ball-on-ring mechanical tests on sapphire disks showed an increase in the failure stress from 340 MPa (with pre-existing 28 µm flaws) to ~ 900MPa after sapphire AMP, which is attributed to the blunting of the surface microfractures.
A room temperature sapphire acoustics resonator incorporated into an oscillator represents a possible opportunity to improve on quartz ultrastable oscillator (USO) performance, which has been a staple for NASA missions since the inception of spaceflight. Where quartz technology is very mature and shows a performance improvement of perhaps 1 dB/decade, these sapphire acoustic resonators when integrated with matured quartz electronics could achieve a frequency stability improvement of 10 dB or more. As quartz oscillators are an essential element of nearly all types of frequency standards and reference systems, the success of MSAR would advance the development of frequency standards and systems for both groundbased and flight-based projects. Current quartz oscillator technology is limited by quartz mechanical Q. With a possible improvement of more than x 10 Q with sapphire acoustic modes, the stability limit of current quartz oscillators may be improved tenfold, to 10(exp -14) at 1 second. The electromagnetic modes of sapphire that were previously developed at JPL require cryogenic temperatures to achieve the high Q levels needed to achieve this stability level. However sapphire fs acoustic modes, which have not been used before in a high-stability oscillator, indicate the required Q values (as high as Q = 10(exp 8)) may be achieved at room temperature in the kHz range. Even though sapphire is not piezoelectric, such a high Q should allow electrostatic excitation of the acoustic modes with a combination of DC and AC voltages across a small sapphire disk (approximately equal to l mm thick). The first evaluations under this task will test predictions of an estimated input impedance of 10 kilohms at Q = 10(exp 8), and explore the Q values that can be realized in a smaller resonator, which has not been previously tested for acoustic modes. This initial Q measurement and excitation demonstration can be viewed similar to a transducer converting electrical energy to mechanical energy and back. Such an electrostatic tweeter type excitation of a mechanical resonator will be tested at 5 MHz. Finite element calculation will be applied to resonator design for the desired resonator frequency and optimum configuration. The experiment consists of the sapphire resonator sandwiched between parallel electrodes. A DC+AC voltage can be applied to generate a force to act on a sapphire resonator. With the frequency of the AC voltage tuned to the sapphire resonator frequency, a resonant condition occurs and the sapphire Q can be measured with a high-frequency impedance analyzer. To achieve high Q values, many experimental factors such as vacuum seal, gas damping effects, charge buildup on the sapphire surface, heat dissipation, sapphire anchoring, and the sapphire mounting configuration will need attention. The effects of these parameters will be calculated and folded into the resonator design. It is envisioned that the initial test configuration would allow for movable electrodes to check gap spacing dependency and verify the input impedance prediction. Quartz oscillators are key components in nearly all ground- and space-based communication, tracking, and radio science applications. They play a key role as local oscillators for atomic frequency standards and serve as flywheel oscillators or to improve phase noise in high performance frequency and timing distribution systems. With ultra-stable performance from one to three seconds, an Earth-orbit or moon-based MSAR can enhance available performance options for spacecraft due to elimination of atmospheric path degradation.
The goal of this work was to investigate the in-core performance of sapphire optical fiber temperature sensors and to develop clad sapphire optical fibers for in-core instrumentation. We fabricated clad sapphire optical fibers and evaluated the distributed sensing performance of these sensors via optical backscatter reflectometry under high fluence and combined radiation and temperature effects. A series of irradiations was completed to evaluate the effect of irradiation on sapphire optical fiber temperature sensors and to determine the operational limits of these sensors. (1) Objective 1: Fabricate sapphire optical fiber sensors. (2) Objective 2: Evaluate the clad sapphire fiber to verify single-mode behavior and determine and characterize the light modes supported by optical fibers. (3) Objective 3: Characterize the in-core temperature sensing of sapphire optical fiber, as well as the combined temperature and irradiation effects. (4) Objective 4: Evaluate the lifetime and performance of the sensor under irradiation to high neutron fluence. Objectives 1, 2, and 3 were completed during the first 2 years of the project. Due to the Covid pandemic, Objective 4, a high-fluence irradiation performed at the Massachusetts Institute of Technology Research Reactor (MITR), was delayed, as partner facilities were subject to mandatory shutdowns and required a 1 year, no-cost extension. This irradiation was eventually completed on December 12, 2022. This work indicates that sapphire optical fiber sensors may be a solution for ultra-high-temperature applications in which traditional silica optical fibers are prone to fail. Sapphire sensors are potentially suitable for experiments featuring temperatures above 700°C for long periods of time, or for any length of time above 1000°C. Experiments featuring a low total fluence, such as irradiations conducted in the Transient Reactor Test (TREAT) facility, also represent good applications for sapphire optical sensors. Additional work is required to characterize the sapphire fiber cladding performance, which falls outside the scope of this project, as well as the effects of high temperatures on the response of the fiber. A comprehensive material study is recommended as future work to evaluate the attenuation in sapphire under irradiation, and how that attenuation changes with irradiation temperature. The drift and attenuation in the fiber at temperatures of up to 1600°C and a total fluence of up to 2.9 x 10 17 n/cm 2 was minimal, and the fibers returned to baseline after being heated to 1600°C under irradiation. This is promising for the future use of sapphire optical fibers in advanced reactors.
The electrooptic effect in ZnTe has recently attracted research attention, and various device structures using ZnTe have been explored. For application to practical terahertz wave detector devices based on ZnTe thin films, sapphire substrates are preferred because they enable the optical path alignment to be simplified. ZnTe/sapphire heterostructures were focused upon, and ZnTe epilayers were prepared on highly mismatched sapphire substrates by molecular beam epitaxy. Epitaxial relationships between the ZnTe thin films and the sapphire substrates with their various orientations were investigated using an X-ray diffraction pole figure method. (0001) c-plane, (1-102) r-plane, (1-100) m-plane, and (11-20) a-plane oriented sapphire substrates were used in this study. The epitaxial relationship between ZnTe and c-plane sapphire was found to be (111) ZnTe//(0001) sapphire with an in-plane orientation relationship of [−211] ZnTe//[1-100] sapphire. It was found that the (211)-plane ZnTe layer was grown on the m-plane of the sapphire substrates, and the (100)-plane ZnTe layer was grown on the r-plane sapphire. When the sapphire substrates were inclined from the c-plane towards the m-axis direction, the orientation of the ZnTe thin films was then tilted from the (111)-plane to the (211)-plane. The c-plane of the sapphire substrates governs the formation of the (111) ZnTe domain and the ZnTe epilayer orientation. These crystallographic features were also related to the atom arrangements of ZnTe and sapphire.
A spatial heterodyne Raman spectrometer (SHRS), constructed using a modular optical cage and lens tube system, is described for use with a commercial silica and a custom single-crystal (SC) sapphire fiber Raman probe. The utility of these fiber-coupled SHRS chemical sensors is demonstrated using 532 nm laser excitation for acquiring Raman measurements of solid (sulfur) and liquid (cyclohexane) Raman standards as well as real-world, plastic-bonded explosives (PBX) comprising 1,3,5- triamino- 2,4,6- trinitrobenzene (TATB) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) energetic materials. The SHRS is a fixed grating-based dispersive interferometer equipped with an array detector. Each Raman spectrum was extracted from its corresponding fringe image (i.e., interferogram) using a Fourier transform method. Raman measurements were acquired with the SHRS Littrow wavelength set at the laser excitation wavelength over a spectral range of ∼1750 cm −1 with a spectral resolution of ∼8 cm −1 for sapphire and ∼10 cm −1 for silica fiber probes. The large aperture of the SHRS allows much larger fiber diameters to be used without degrading spectral resolution as demonstrated with the larger sapphire collection fiber diameter (330 μm) compared to the silica fiber (100 μm). Unlike the dual silica fiber Raman probe, the dual sapphire fiber Raman probe did not include filtering at the fiber probe tip nearest the sample. Even so, SC sapphire fiber probe measurements produced less background than silica fibers allowing Raman measurements as close as ∼85 cm −1 to the excitation laser. Despite the short lengths of sapphire fiber used to construct the sapphire probe, well-defined, sharp sapphire Raman bands at 420, 580, and 750 cm −1 were observed in the SHRS spectra of cyclohexane and the highly fluorescent HMX-based PBX. SHRS measurements of the latter produced low background interference in the extracted Raman spectrum because the broad band fluorescence (i.e., a direct current, or DC, component) does not contribute to the interferogram intensity (i.e., the alternating current, or AC, component). SHRS spectral resolution, throughput, and signal-to-noise ratio are also discussed along with the merits of using sapphire Raman bands as internal performance references and as internal wavelength calibration standards in Raman measurements.
This report summarizes technical progress on the program “Single-Crystal Sapphire Optical Fiber Sensor Instrumentation,” funded by the National Energy Technology Laboratory of the U.S. Department of Energy, and performed by the Center for Photonics Technology of the Bradley Department of Electrical and Computer Engineering at Virginia Tech. This project was completed in three phases, each with a separate focus. Phase I of the program, from October 1999 to April 2002, was devoted to development of sensing schema for use in high temperature, harsh environments. Different sensing designs were proposed and tested in the laboratory. Phase II of the program, from April 2002 to April 2009, focused on bringing the sensor technologies, which had already been successfully demonstrated in the laboratory, to a level where the sensors could be deployed in harsh industrial environments and eventually become commercially viable through a series of field tests. Also, a new sensing scheme was developed and tested with numerous advantages over all previous ones in Phase II. Phase III of the program, September 2009 to December 2013, focused on development of the new sensing scheme for field testing in conjunction with materials engineering of the improved sensor packaging lifetimes. In Phase I, three different sensing principles were studied: sapphire air-gap extrinsic Fabry-Perot sensors; intensity-based polarimetric sensors; and broadband polarimetric sensors. Black body radiation tests and corrosion tests were also performed in this phase. The outcome of the first phase of this program was the selection of broadband polarimetric differential interferometry (BPDI) for further prototype instrumentation development. This approach is based on the measurement of the optical path difference (OPD) between two orthogonally polarized light beams in a single-crystal sapphire disk. At the beginning of Phase II, in June 2004, the BPDI sensor was tested at the Wabash River coal gasifier facility in Terre Haute, Indiana. Due to business conditions at industrial partner and several logistical problems, this field test was not successful. An alternative high-temperature sensing system using sapphire wafer-based extrinsic Fabry-Perot interferometry was then developed as a significant improvement over the BPDI solution. From June 2006 to June 2008, three consecutive field tests were performed with the new sapphire wafer sensors at the TECO coal gasifier in Tampa, Florida. One of the sensors survived in the industrial coal gasifier for 7 months, over which time the existing thermocouples were replaced twice. The outcome of these TECO field tests suggests that the sapphire wafer sensor has very good potential to be commercialized. However packaging and sensor protection issues need additional development. During Phase III, several major improvements in the design and fabrication process of the sensor have been achieved through experiments and theoretical analysis. Studies on the property of the key components in the sensor head, including the sapphire fiber and sapphire wafer, were also conducted, for a better understanding of the sensor behavior. A final design based on all knowledge and experience has been developed, free of any issues encountered during the entire research. Sensors with this design performed well as expected in lab long-term tests, and were deployed in the sensing probe of the final coal-gasifier field test. Sensor packaging and protection was improved through materials engineering through testing of packaging designs in two blank probe packaging tests at Eastman Chemical in Kingsport, TN. Performance analysis of the blank probe packaging resulted in improve package designs culminating in a 3rd generation probe packaging utilized for the full field test of the sapphire optical sensor and materials designed sensor packaging.
Much research has been done to reduce dislocation densities for the growth of GaN on sapphire, but has paid little attention to the elastic behavior at the GaN/sapphire interface. In this study, we have examined effects of the addition of Si to a sapphire substrate on its elastic property and on the growth of GaN deposit. Si atoms are added to a c-plane sapphire substrate by ion implantation. The ion implantation results in scratches on the surface, and concomitantly, inhomogeneous distribution of Si. The scratch regions contain a higher concentration of Si than other regions of the sapphire substrate surface, high-temperature GaN being poorly grown there. However, high-temperature GaN is normally grown in the other regions. The GaN overlayer in the normally-grown regions is observed to have a lower TD density than the deposit on the bare sapphire substrate (with no Si accommodated). As compared with the film on an untreated, bare sapphire, the cathodoluminescence defect density decreases by 60 % for the GaN layer normally deposited on the Si-ion implanted sapphire. As confirmed by a strain mapping technique by transmission electron microscopy (geometric phase analysis), the addition of Si in the normally deposited regions forms a surface layer in the sapphire elastically more compliant than the GaN overlayer. The results suggest that the layer can largely absorb the misfit strain at the interface, which produces the overlayer with a lower defect density. Our results highlight a direct correlation between threading-dislocation density in GaN deposits and the elastic behavior at the GaN/sapphire interface, opening up a new pathway to reduce threading-dislocation density in GaN deposits.
Sapphire-reinforced NiAl matrix composites with chromium or tungsten as alloying additions were synthesized using casting and zone directional solidification (DS) techniques and characterized by a fiber pushout test as well as by microhardness measurements. The sapphire-NiAl(Cr) specimens exhibited an interlayer of Cr rich eutectic at the fiber-matrix interface and a higher interfacial shear strength compared to unalloyed sapphire-NiAl specimens processed under identical conditions. In contrast, the sapphire-NiAl(W) specimens did not show interfacial excess of tungsten rich phases, although the interfacial shear strength was high and comparable to that of sapphire-NiAl(Cr). The postdebond sliding stress was higher in sapphire-NiAl(Cr) than in sapphire-NiAl(W) due to interface enrichment with chromium particles. The matrix microhardness progressively decreased with increasing distance from the interface in both DS NiAl and NiAl(Cr) specimens. The study highlights the potential of casting and DS techniques to improve the toughness and strength of NiAl by designing dual-phase microstructures in NiAl alloys reinforced with sapphire fibers.
Dielectric loss is known to limit state-of-the-art superconducting qubit lifetimes. Recent experiments imply upper bounds on bulk dielectric loss tangents on the order of 100 parts per billion but because these inferences are drawn from fully fabricated devices with many loss channels, these experiments do not definitely implicate or exonerate the dielectric. To resolve this ambiguity, we devise a measurement method capable of separating and resolving bulk dielectric loss with a sensitivity at the level of 5 ×10 –9 . The method, which we call the dielectric dipper, involves the in situ insertion of a dielectric sample into a high-quality microwave cavity mode. Smoothly varying the participation of the sample in the cavity mode enables a differential measurement of the dielectric loss tangent of the sample. The dielectric dipper can probe the low-power behavior of dielectrics at cryogenic temperatures and does so without the need for any lithographic process, enabling controlled comparisons of substrate materials and processing techniques. We demonstrate the method with measurements of sapphire grown by edge-defined film-fed growth (EFG) in comparison to high-grade sapphire grown by the heat-exchanger method (HEMEX). For EFG sapphire, we infer a bulk loss tangent of 63(8) ×10 –9 and a substrate-air interface loss tangent of 15(3) ×10 –4 (assuming a sample surface thickness of 3 nm). For a typical transmon, this bulk loss tangent would limit device quality factors to Q ≲20 ×10 6 , suggesting that bulk loss is likely the dominant loss mechanism in the longest-lived transmons on sapphire. We also demonstrate this method on HEMEX sapphire and bound its bulk loss tangent to be less than 19(6) ×10 –9 . As this bound is about 3 times smaller than the bulk loss tangent of EFG sapphire, the use of HEMEX sapphire as a substrate would lift the bulk dielectric coherence limit of a typical transmon qubit to several milliseconds.
High-quality, wide-aperture optical access is usually required for the advanced laser diagnostics that can now make a wide variety of non-intrusive measurements of combustion processes. Specially processed and mounted sapphire windows are proposed to provide this optical access to extreme environment. Through surface treatments and proper thermal stress design, single crystal sapphire can be a mechanically equivalent replacement for high strength steel. A prototype sapphire window and mounting system have been developed in a successful NASA SBIR Phase 1 project. A large and reliable increase in sapphire design strength (as much as 10x) has been achieved, and the initial specifications necessary for these gains have been defined. Failure testing of small windows has conclusively demonstrated the increased sapphire strength, indicating that a nearly flawless surface polish is the primary cause of strengthening, while an unusual mounting arrangement also significantly contributes to a larger effective strength. Phase 2 work will complete specification and demonstration of these windows, and will fabricate a set for use at NASA. The enhanced capabilities of these high performance sapphire windows will lead to many diagnostic capabilities not previously possible, as well as new applications for sapphire.
We describe the development and testing of two sapphire fiber sensor designs intended for use in high temperature environments. The first is a birefringence-balanced polarimetric sapphire fiber sensor. In this sensor, two single crystal sapphire rods, acting as the birefringence sensing element, are connected to each other in such a way that the slow axis of the first rod is aligned along with the fast axis of the second rod, and the fast axis of the first rod is along the slow axis of the second rod. This sensor has been demonstrated for measurement of temperature up to 1500 C. The second is a sapphire-fiber-based intrinsic interferometric sensor. In this sensor, a length of uncoated, unclad, structural-graded multimode sapphire fiber is fusion spliced to a singlemode silica fiber to form a Fabry-Perot cavity. The reflections from the silica-to-sapphire fiber splice and the free endface of the sapphire fiber give rise to the interfering fringe output. This sensor has been demonstrated for the measurement of temperature above 1510 C, and a resolution of 0.1 C has been obtained.
A new use for electron beam brazing was recently developed by NASA Lewis Research Center's Manufacturing Engineering Division. This work was done to fabricate a fiberoptic probe (developed by Sentec Corporation) that could measure high temperatures less than 600 deg C of vibrating machinery, such as in jet engine combustion research. Under normal circumstances, a sapphire fiber would be attached to platinum by a ceramic epoxy. However, no epoxies can adhere ceramic fibers to platinum under such high temperatures and vibration. Also, since sapphire and platinum have different thermal properties, the epoxy bond is subjected to creep over time. Therefore, a new method had to be developed that would permanently and reliably attach a sapphire fiber to platinum. Brazing a sapphire fiber to a platinum shell. The fiber-optic probe assembly consists of a 0.015-in.-diameter sapphire fiber attached to a 0.25-in.-long, 0.059-in.-diameter platinum shell. Because of the small size of this assembly, electron beam brazing was chosen instead of conventional vacuum brazing. The advantage of the electron beam is that it can generate a localized heat source in a vacuum. Gold reactive braze was used to join the sapphire fiber and the platinum. Consequently, the sapphire fiber was not affected by the total heat needed to braze the components together.
The Genesis Solar Wind Sample Re-turn Mission used a variety of materials as solar wind (SW) collectors. “Sapphire”, which is single crystal corundum, was ~6.7% of the collector material flown. But, a much higher percentage of Genesis sapphire collectors (SAP) survived the crash of the sample-return capsule as SAP is chemically inert, physically tough, and hard (MOHS 9, by definition). In fact, 39 sapphire fragments of bulk SW collector having areas ≥60 sq mm are available in JSC’s Genesis online catalog, whereas only 1 similarly sized silicon fragment is available (accessed 1/1/2020). In spite of the ease of accessing larger fragments, sapphire has not been popular among Genesis re-searchers because it is an electrical insulator (making SIMS more difficult) and its chemical inertness, high melting point and high hardness precludes the use of many mass-spectroscopic techniques. Recently, as alternative techniques for measuring Genesis samples are developed (e.g., synchrotron TXRF, INAA, laser ablation mass spectroscopy), more researchers are choosing to analyze sapphire. Thus, a number of researchers are actively studying how to best remove contamination from the Genesis sapphire surfaces. This report extends the task in Schmeling et al. that used polishing compounds to remove contamination from Genesis sapphire and focuses on contaminants (welded silicon, aluminum) that current chemical methods find recalcitrant.
The use of single-crystal sapphire optical fibers has been considered to extend fiber-optic sensing to the extreme temperature (>1000 °C) environments encountered in nuclear applications. However, before these sapphire fiber–based sensors can be deployed, their optical transmission and dimensional stability (which impacts drift of some sensors) must be characterized under representative testing conditions. Data regarding the optical transmission of sapphire following high-dose neutron irradiation at temperatures >100 °C is extremely limited. This work provides measurements of optical density (i.e., attenuation) and directional dimensional changes in bulk single-crystal sapphire materials irradiated to a fast neutron fluence of 2.4 × 10 21 n/cm 2 (3.5 displacements per atom) at temperatures ranging from 95 to 688 °C. Optical density measured after irradiation at 95 and 298 °C showed ultraviolet and visible absorption bands corresponding to known defect centers and temperature trends that were generally consistent with previous ex situ and in situ measurements made at much lower neutron fluence. However, optical density measured after irradiation at 688 °C was as much as two orders of magnitude higher, indicating that the fundamental mechanism for radiation-induced attenuation changes at this irradiation temperature. Additional analysis and comparison with previous works suggest that the attenuation may result from void formation, leading to increased Rayleigh scattering losses in the material and increased swelling that would also result in drift of Bragg grating-based sensors in sapphire fibers. These results pose serious questions regarding the feasibility of sapphire fiber–based sensors for high-temperature nuclear applications.
Since natural coloured sapphire ({alpha}-Al{sub 2}O{sub 3}) commands a high gem stone market price there is a need for a reliable method of identifying artificially coloured sapphire that has an inherently lower value. Diffusing beryllium into sapphire at high temperatures results in a coloured stone virtually indistinguishable from a natural one. Beryllium can occur naturally in sapphire but at levels of <1 ppma. Beryllium diffused sapphire typically contains >10 ppma, which is difficult to determine in a non destructive way. It is possible to utilize nuclear reaction analysis techniques to determine the beryllium content in a macroscopically non destructive way. Kinematically ideal reactions are Be(p,{alpha}) and Be(p,d) which, for Ep = 0.5 to 0.9 MeV, exhibit distinct reaction product signatures well separated from other proton induced reactions in aluminium or oxygen. Due to the lack of comprehensive cross section data for the Be(p,{alpha}) and Be(p,d) reactions in the energy range of interest, a series of measurements were made at the Van de Graaff accelerator facility at Necsa to create a new data base. A further outcome of these measurements was a deviation in reported values for the non-Rutherfordian proton back-scatter cross section. These new data bases, which extend to Ep = 2.6MeV, can now facilitate a procedure for determining beryllium content in sapphire.