Complex organosulfur molecules on comet 67P: Evidence from the ROSINA measurements and insights from laboratory simulations.

The ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) instrument aboard the Rosetta mission revolutionized our understanding of cometary material composition. One of Rosetta's key findings is the complexity of the composition of comet 67P/Churyumov-Gerasimenko. Here, we used ROSINA data to analyze dust particles that were volatilized during a dust event in September 2016 and report the detection of large organosulfur species and an increase in the abundances of sulfurous species previously detected in the coma. Our data support the presence of complex sulfur-bearing organics on the surface of the comet. In addition, we conducted laboratory simulations that show that this material may have formed from chemical reactions that were initiated by the irradiation of mixed ices containing H2S. Our findings highlight the importance of sulfur chemistry in cometary and precometary materials and the possibility of characterizing organosulfur materials in other comets and small icy bodies using the James Webb Space Telescope.

Mid- and long-wave infrared point spectrometer (MLPS): a miniature space-borne science instrument.

The mid- and long-wave infrared point spectrometer (MLPS) is an infrared point spectrometer that utilizes unique technologies to meet the spectral coverage, spectral sampling, and field-of-view (FOV) requirements of many future space-borne missions in a small volume with modest power consumption. MLPS simultaneously acquires high resolution mid-wave infrared (∼2-4 µm) and long-wave infrared (∼5.5-11 µm) measurements from a single, integrated instrument. The broadband response of MLPS can measure spectroscopically resolved reflected and thermally emitted radiation from a wide range of targets and return compositional, mineralogic, and thermophysical science from a single data set. We have built a prototype MLPS and performed end-to-end testing under vacuum showing that the measured spectral response and the signal-to-noise ratio (SNR) for both the mid-wave infrared (MIR) and long-wave infrared (LIR) channels of MLPS agree with established instrument models.

Miniature high-speed, low-pulse-energy picosecond Raman spectrometer for identification of minerals and organics in planetary science.

The motivation behind time-resolved Raman spectroscopy for planetary surface exploration is (1) to provide comprehensive identification of minerals (nearly all rock-forming minerals and weathering products) and many organics of prime importance including fossilized carbonaceous materials; (2) to do so ensuring that it is possible to characterize even the most sensitive materials that would be altered by current state-of-the-art pulsed lasers (e.g., dark minerals, organics). These goals are accomplished here using a lightweight, high-speed (MHz) pulsed (<100ps) Raman spectrometer based on a high-speed microchip laser combined with a single photon avalanche diode detector array. Using a Mars analog sample set and an automated grid sampling technique, we demonstrate consistent identification of major minerals and kerogen detection at ∼≥1% by volume, without losses typically associated with the two biggest problems: fluorescence interference and sample damage. Despite improvements, we find that time-resolved Raman spectroscopy is still limited by the availability of a suitable laser and detector. As technology advances and such devices become available, we expect that this technique will hold an important place in Raman spectroscopy for both commercial and planetary science applications. We also discuss the utility of Raman point mapping for planetary science (e.g., in comparison with other common techniques like infrared reflectance spectroscopy) and conclude that the choice of technique must be planetary mission-specific; one must consider whether incurring the time to map single microscopic points is worthwhile, and how many points would be sufficient to gain the required information to characterize the surface.

Vectorized magnetometer for space applications using electrical readout of atomic scale defects in silicon carbide.

Magnetometers are essential for scientific investigation of planetary bodies and are therefore ubiquitous on missions in space. Fluxgate and optically pumped atomic gas based magnetometers are typically flown because of their proven performance, reliability, and ability to adhere to the strict requirements associated with space missions. However, their complexity, size, and cost prevent their applicability in smaller missions involving cubesats. Conventional solid-state based magnetometers pose a viable solution, though many are prone to radiation damage and plagued with temperature instabilities. In this work, we report on the development of a new self-calibrating, solid-state based magnetometer which measures magnetic field induced changes in current within a SiC pn junction caused by the interaction of external magnetic fields with the atomic scale defects intrinsic to the semiconductor. Unlike heritage designs, the magnetometer does not require inductive sensing elements, high frequency radio, and/or optical circuitry and can be made significantly more compact and lightweight, thus enabling missions leveraging swarms of cubesats capable of science returns not possible with a single large-scale satellite. Additionally, the robustness of the SiC semiconductor allows for operation in extreme conditions such as the hot Venusian surface and the high radiation environment of the Jovian system.

Miniaturized time-resolved Raman spectrometer for planetary science based on a fast single photon avalanche diode detector array.

We present recent developments in time-resolved Raman spectroscopy instrumentation and measurement techniques for in situ planetary surface exploration, leading to improved performance and identification of minerals and organics. The time-resolved Raman spectrometer uses a 532 nm pulsed microchip laser source synchronized with a single photon avalanche diode array to achieve sub-nanosecond time resolution. This instrument can detect Raman spectral signatures from a wide variety of minerals and organics relevant to planetary science while eliminating pervasive background interference caused by fluorescence. We present an overview of the instrument design and operation and demonstrate high signal-to-noise ratio Raman spectra for several relevant samples of sulfates, clays, and polycyclic aromatic hydrocarbons. Finally, we present an instrument design suitable for operation on a rover or lander and discuss future directions that promise great advancement in capability.

Delta-doped electron-multiplied CCD with absolute quantum efficiency over 50% in the near to far ultraviolet range for single photon counting applications.

We have used molecular beam epitaxy (MBE) based delta-doping technology to demonstrate nearly 100% internal quantum efficiency (QE) on silicon electron-multiplied charge-coupled devices (EMCCDs) for single photon counting detection applications. We used atomic layer deposition (ALD) for antireflection (AR) coatings and achieved atomic-scale control over the interfaces and thin film materials parameters. By combining the precision control of MBE and ALD, we have demonstrated more than 50% external QE in the far and near ultraviolet in megapixel arrays. We have demonstrated that other important device performance parameters such as dark current are unchanged after these processes. In this paper, we briefly review ultraviolet detection, report on these results, and briefly discuss the techniques and processes employed.

Fast single-photon avalanche diode arrays for laser Raman spectroscopy.

We incorporate newly developed solid-state detector technology into time-resolved laser Raman spectroscopy, demonstrating the ability to distinguish spectra from Raman and fluorescence processes. As a proof of concept, we show fluorescence rejection on highly fluorescent mineral samples willemite and spodumene using a 128×128 single-photon avalanche diode (SPAD) array with a measured photon detection efficiency of 5%. The sensitivity achieved in this new instrument architecture is comparable to the sensitivity of a technically more complicated system using a traditional photocathode-based imager. By increasing the SPAD active area and improving coupling efficiency, we expect further improvements in sensitivity by over an order of magnitude. We discuss the relevance of these results to in situ planetary instruments, where size, weight, power, and radiation hardness are of prime concern. The potential large-scale manufacturability of silicon SPAD arrays makes them prime candidates for future portable and in situ Raman instruments spanning numerous applications where fluorescence interference is problematic.

Ultraviolet antireflection coatings for use in silicon detector design.

We report on the development of coatings for a charged-coupled device (CCD) detector optimized for use in a fixed dispersion UV spectrograph. Because of the rapidly changing index of refraction of Si, single layer broadband antireflection (AR) coatings are not suitable to increase quantum efficiency at all wavelengths of interest. Instead, we describe a creative solution that provides excellent performance over UV wavelengths. We describe progress in the development of a coated CCD detector with theoretical quantum efficiencies (QEs) of greater than 60% at wavelengths from 120 to 300 nm. This high efficiency may be reached by coating a backside-illuminated, thinned, delta-doped CCD with a series of thin film AR coatings. The materials tested include MgF(2) (optimized for highest performance from 120-150 nm), SiO(2) (150-180 nm), Al(2)O(3) (180-240 nm), MgO (200-250 nm), and HfO(2) (240-300 nm). A variety of deposition techniques were tested and a selection of coatings that minimized reflectance on a Si test wafer were applied to functional devices. We also discuss future uses and improvements, including graded and multilayer coatings.

Time-resolved Raman spectroscopy for in situ planetary mineralogy.

Planetary mineralogy can be revealed through a variety of remote sensing and in situ investigations that precede any plans for eventual sample return. We briefly review those techniques and focus on the capabilities for on-surface in situ examination of Mars, Venus, the Moon, asteroids, and other bodies. Over the past decade, Raman spectroscopy has continued to develop as a prime candidate for the next generation of in situ planetary instruments, as it provides definitive structural and compositional information of minerals in their natural geological context. Traditional continuous-wave Raman spectroscopy using a green laser suffers from fluorescence interference, which can be large (sometimes saturating the detector), particularly in altered minerals, which are of the greatest geophysical interest. Taking advantage of the fact that fluorescence occurs at a later time than the instantaneous Raman signal, we have developed a time-resolved Raman spectrometer that uses a streak camera and pulsed miniature microchip laser to provide picosecond time resolution. Our ability to observe the complete time evolution of Raman and fluorescence spectra in minerals makes this technique ideal for exploration of diverse planetary environments, some of which are expected to contain strong, if not overwhelming, fluorescence signatures. We discuss performance capability and present time-resolved pulsed Raman spectra collected from several highly fluorescent and Mars-relevant minerals. In particular, we have found that conventional Raman spectra from fine grained clays, sulfates, and phosphates exhibited large fluorescent signatures, but high quality spectra could be obtained using our time-resolved approach.