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At least 433 records · Page 24

Shock Damage Analysis in Serial Femtosecond Crystallography Data Collected at MHz X-ray Free-Electron Lasers

Serial femtosecond crystallography (SFX) data were recorded at the European X-ray free-electron laser facility (EuXFEL) with protein microcrystals delivered via a microscopic liquid jet. An XFEL beam striking such a jet may launch supersonic shock waves up the jet, compromising the oncoming sample. To investigate this efficiently, we employed a novel XFEL pulse pattern to nominally expose the sample to between zero and four shock waves before being probed. Analyzing hit rate, indexing rate, and resolution for diffraction data recorded at MHz pulse rates, we found no evidence of damage. Notably, however, this conclusion could only be drawn after careful identification and assimilation of numerous interrelated experimental factors, which we describe in detail. Failure to do so would have led to an erroneous conclusion. Femtosecond photography of the sample-carrying jet revealed critically different jet behavior from that of all homogeneous liquid jets studied to date in this manner.

36 MATERIALS SCIENCE↗

Characterization of Mn 5 Ge 3 Contacts on a Shallow Ge/SiGe Heterostructure

Mn 5 Ge 3 is a ferromagnetic phase of the Mn-Ge system that is a potential contact material for efficient spin injection and detection. Here, we investigate the creation of Mn 5 Ge 3 -based contacts on a Ge/SiGe quantum well heterostructure via solid-state synthesis. X-ray diffraction spectra fitting indicates the formation of Mn 5 Ge 3 -based contacts on bulk Ge and Ge/SiGe. High-resolution scanning transmission electron microscopy imaging and energy dispersive X-ray spectroscopy verify the correct Mn 5 Ge 3 -based phase formation. Schottky diode measurements, transmission line measurements, and Hall measurements reveal that Mn 5 Ge 3 -based contacts serve as good p-type contacts for Ge/SiGe quantum well heterostructures due to having a low Schottky barrier height of 0.10 eV (extracted from a Mn 5 Ge 3 /n-Ge analogue) and a contact resistance in the order of 1 kΩ. Furthermore, we show that these electrical characteristics have a gate-voltage dependence, thereby providing tunability.

36 MATERIALS SCIENCE↗

The Advanced Technology Large-Aperture Space Telescope (ATLAST) Technology Roadmap

We present the key technologies and capabilities that will enable a future, large-aperture ultravioletopticalinfrared (UVOIR) space observatory. These include starlight suppression systems, vibration isolation and control systems, lightweight mirror segments, detector systems, and mirror coatings. These capabilities will provide major advances over current and near-future observatories for sensitivity, angular resolution, and starlight suppression. The goals adopted in our study for the starlight suppression system are 10-10 contrast with an inner working angle of 40 milliarcsec and broad bandpass. We estimate that a vibration and isolation control system that achieves a total system vibration isolation of 140 dB for a vibration-isolated mass of 5000 kg is required to achieve the high wavefront error stability needed for exoplanet coronagraphy. Technology challenges for lightweight mirror segments include diffraction-limited optical quality and high wavefront error stability as well as low cost, low mass, and rapid fabrication. Key challenges for the detector systems include visible-blind, high quantum efficiency UV arrays, photon counting visible and NIR arrays for coronagraphic spectroscopy and starlight wavefront sensing and control, and detectors with deep full wells with low persistence and radiation tolerance to enable transit imaging and spectroscopy at all wavelengths. Finally, mirror coatings with high reflectivity ( 90), high uniformity ( 1) and low polarization ( 1) that are scalable to large diameter mirror substrates will be essential for ensuring that both high throughput UV observations and high contrast observations can be performed by the same observatory.

Telescope↗

A Future Large-Aperture UVOIR Space Observatory: Key Technologies and Capabilities

We present the key technologies and capabilities that will enable a future, large-aperture ultravioletopticalinfrared (UVOIR) space observatory. These include starlight suppression systems, vibration isolation and control systems, lightweight mirror segments, detector systems, and mirror coatings. These capabilities will provide major advances over current and near-future observatories for sensitivity, angular resolution, and starlight suppression. The goals adopted in our study for the starlight suppression system are 10-10 contrast with an inner working angle of 20 milliarcsec and broad bandpass. We estimate that a vibration and isolation control system that achieves a total system vibration isolation of 140 dB for a vibration-isolated mass of 5000 kg is required to achieve the high wavefront error stability needed for exoplanet coronagraphy. Technology challenges for lightweight mirror segments include diffraction-limited optical quality and high wavefront error stability as well as low cost, low mass, and rapid fabrication. Key challenges for the detector systems include visible-blind, high quantum efficiency UV arrays, photon counting visible and NIR arrays for coronagraphic spectroscopy and starlight wavefront sensing and control, and detectors with deep full wells with low persistence and radiation tolerance to enable transit imaging and spectroscopy at all wavelengths. Finally, mirror coatings with high reflectivity ( 90), high uniformity ( 1) and low polarization ( 1) that are scalable to large diameter mirror substrates will be essential for ensuring that both high throughput UV observations and high contrast observations can be performed by the same observatory.

Instrument↗

Luciola Hypertelescope Space Observatory

Luciola is a large (one kilometer) "multi-aperture densified-pupil imaging interferometer", or "hypertelescope" employing many small apertures, rather than a few large ones, for obtaining direct snapshot images with a high information content. A diluted collector mirror, deployed in space as a flotilla of small mirrors, focuses a sky image which is exploited by several beam-combiner spaceships. Each contains a pupil densifier micro-lens array to avoid the diffractive spread and image attenuation caused by the small sub-apertures. The elucidation of hypertelescope imaging properties during the last decade has shown that many small apertures tend to be far more efficient, regarding the science yield, than a few large ones providing a comparable collecting area. For similar underlying physical reasons, radio-astronomy has also evolved in the direction of many-antenna systems such as the proposed Low Frequency Array having hundreds of thousands of individual receivers . With its high limiting magnitude, reaching the mv=30 limit of HST when 100 collectors of 25cm will match its collecting area, high-resolution direct imaging in multiple channels, broad spectral coverage from the 1200 Angstrom ultra-violet to the 20 micron infra-red, apodization, coronagraphic and spectroscopic capabilities, the proposed hypertelescope observatory addresses very broad and innovative science covering different areas of ESA s Cosmic Vision program. In the initial phase, a focal spacecraft covering the UV to near IR spectral range of EMCCD photon-counting cameras ( currently 200 to 1000nm), will image details on the surface of many stars, as well as their environment, including multiple stars and clusters. Spectra will be obtained for each resel. It will also image neutron star, black-hole and micro-quasar candidates, as well as active galactic nuclei, quasars, gravitational lenses, and other Cosmic Vision targets observable with the initial modest crowding limit. With subsequent upgrade missions, the spectral coverage can be extended from 120nm to 20 microns, using four detectors carried by two to four focal spacecraft. The number of collector mirrors in the flotilla can also be increased from 12 to 100 and possibly 1,000. The imaging and spectroscopy of habitable exoplanets in the mid infra-red then becomes feasible once the collecting area reaches 6m2 , using a specialized mid infra-red focal spacecraft. Calculations ( Boccaletti et al., 2000) have shown that hypertelescope coronagraphy has unequalled sensitivity for detecting, at mid infra-red wavelengths, faint exoplanets within the exo-zodiacal glare. Later upgrades will enable the more difficult imaging and spectroscopy of these faint objects at visible wavelengths, using refined techniques of adaptive coronagraphy (Labeyrie. & Le Coroller, 2004). Together, the infra-red and visible spectral data carry rich information on the possible presence of life. The close environment of the central black-hole in the Milky Way will be imageable with unprecedented detail in the near infra-red . Cosmological imaging of remote galaxies at the limit of the known universe is also expected, from the ultra-violet to the near infra-red, following the first upgrade, and with greatly increasing sensitivity through successive upgrades. These areas will indeed greatly benefit from the upgrades, in terms of dynamic range, limiting complexity of the objects to be imaged, size of the elementary Direct Imaging Field , and limiting magnitude, approaching that of an 8-meter space telescope when 1000 apertures of 25cm are installed. Similar gains will occur for addressing fundamental problems in physics and cosmology, particularly when observing neutron stars and black holes, single or binary, including the giant black holes, with accretion disks and jets, in active galactic nuclei beyond the Milky Way. Gravitational lensing and micro-lensing patterns, including time-variable patterns and perhaps millisecond lensing flasheshich may be beamed by diffraction from sub-stellar masses at sub-parsec distances (Labeyrie, 1994) , will also be observable initially in the favourable cases, and upgrades will greatly improve the number of observable objects. The observability of gravitational waves emitted by binary lensing masses, in the form of modulated lensing patterns, is a debated issue ( Ragazzoni et al., 2003) but will also become addressable observationally. The technology readiness of Luciola approaches levels where low-orbit testing and stepwise implementation will become feasible in the 2015-2025 time frame. For the following decades beyond 2020, once accurate formation flying techniques will be mastered, much larger hypertelescopes such as the proposed 100km Exo-Earth Imager and the 100,000 km Neutron Star Imager should also become feasible. Luciola is therefore also seen as a precursor toward such very powerful instruments.

Labeyrie, Antoine↗

Normal incidence spectrophotometer using high density transmission grating technology and highly efficiency silicon photodiodes for absolute solar EUV irradiance measurements

New developments in transmission grating and photodiode technology now make it possible to realize spectrometers in the extreme ultraviolet (EUV) spectral region (wavelengths less than 1000 A) which are expected to be virtually constant in their diffraction and detector properties. Time dependent effects associated with reflection gratings are eliminated through the use of free standing transmission gratings. These gratings together with recently developed and highly stable EUV photodiodes have been utilized to construct a highly stable normal incidence spectrophotometer to monitor the variability and absolute intensity of the solar 304 A line. Owing to its low weight and compactness, such a spectrometer will be a valuable tool for providing absolute solar irradiance throughout the EUV. This novel instrument will also be useful for cross-calibrating other EUV flight instruments and will be flown on a series of Hitchhiker Shuttle Flights and on SOHO. A preliminary version of this instrument has been fabricated and characterized, and the results are described.

Ogawa, H. S.↗

Shape-persistent phthalocyanine cages

Phthalocyanine (Pc), an electro-redox active moiety, has many attractive properties stemming from its large aromatic system and ability to act as a catalyst in electrochemical reactions, such as the CO 2 reduction reaction (CO 2 RR). However, due to the synthetic challenge related to geometric requirements and poor solubility (strong aggregation), discrete shape-persistent cages consisting of site-isolated, readily accessible Pc moieties have not been available. Here, we report the synthesis of Zn- and Ni-metallated Pc-based molecular cages via one-step dynamic spiroborate linkage formation in high yields. The ZnPc cage structure is unambiguously elucidated at the atomic level by single-crystal X-ray diffraction. Moreover, owing to the site-isolated redox-active metal centers, readily accessible intrinsic cavity, and shape-persistent backbone, the Ni-metallated Pc (NiPc) cage exhibits high catalytic efficiency, selectivity, and stability, superior to the non-caged control molecules in electrocatalytic CO 2 RR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of Hierarchical Structure Formation in Merocyanine Photovoltaics

Merocyanines (MCs) are a versatile class of small-molecule dyes. Their optoelectronic properties are easily tunable by chemically controlling their donor–acceptor strength, and their structural properties can be tuned by simple side-chain substitution. This paper demonstrates a novel series of MCs featuring an indoline donor with varying hydrocarbon side-chain length (from 6 to 12 carbons) and a tert-butyl-thiazole acceptor, labeled InTBT. Bulk heterojunction organic photovoltaics are fabricated with a [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) acceptor and characterized. Films composed of I8TBT:PCBM and I9TBT:PCBM produced the highest power conversion efficiency of 4.5%, which suggests that the morphology is optimized by controlling the side-chain length. Hierarchical structure formation in InTBT:PCBM films is studied using grazing incidence X-ray diffraction (GIXRD), small-angle neutron scattering (SANS), and atomic force microscopy (AFM). When mixed with PCBM, InTBTs with ≤8 side-chain carbons form pure crystalline domains, while InTBTs with ≥9 side-chain carbons mix well with PCBM. SANS demonstrates that increasing side-chain length increases the InTBT-rich domain size. In addition, a branched hexyl–dodecyl side-chain IHDTBT:PCBM film was studied and found to exhibit the worst-performance organic photovoltaic (OPV) device. The large-branched side chain inhibited mixing between IHDTBT and PCBM resulting in large segregated phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multi-beam X-ray ptychography for high-throughput coherent diffraction imaging

X-ray ptychography is a rapidly developing coherent diffraction imaging technique that provides nanoscale resolution on extended field-of-view. However, the requirement of coherence and the scanning mechanism limit the throughput of ptychographic imaging. Herein, we propose X-ray ptychography using multiple illuminations instead of single illumination in conventional ptychography. Multiple locations of the sample are simultaneously imaged by spatially separated X-ray beams, therefore, the obtained field-of-view in one scan can be enlarged by a factor equal to the number of illuminations. We have demonstrated this technique experimentally using two X-ray beams focused by a house-made Fresnel zone plate array. Two areas of the object and corresponding double illuminations were successfully reconstructed from diffraction patterns acquired in one scan, with image quality similar with those obtained by conventional single-beam ptychography in sequence. Multi-beam ptychography approach increases the imaging speed, providing an efficient way for high-resolution imaging of large extended specimens.

47 OTHER INSTRUMENTATION↗

Inverse-designed metasurfaces with facile fabrication parameters

Abstract Optical metasurfaces are planar nanostructured devices that are industrially attractive in part because they utilize high-throughput microelectronic fabrication techniques for implementation. It is therefore critical to develop design paradigms that can balance the realization of highly efficient wavefront responses together with device manufacturability. We introduce a gradient-based design framework for freeform metasurfaces in which nanoscale elements are explicitly constrained to feature basic shapes, nearly uniform feature sizes, and exceptionally low aspect ratios. In spite of the apparent uniformity of the metasurface geometric features, the devices are able to utilize nonlocal near-field optical coupling to achieve highly efficient and extreme wavefront scattering beyond conventional design methodologies. Utilizing this approach, we design facile high-numerical-aperture devices such as beam deflectors and large-area metalenses capable of diffraction-limited focusing. We anticipate that these concepts can facilitate the design and integration of metasurfaces into monolithic optical systems.

Optics↗

Near, far, wherever you are: simulations on the dose efficiency of holographic and ptychographic coherent imaging

Different studies in X-ray microscopy have arrived at conflicting conclusions about the dose efficiency of imaging modes involving the recording of intensity distributions in the near (Fresnel regime) or far (Fraunhofer regime) field downstream of a specimen. A numerical study is presented on the dose efficiency of near-field holography, near-field ptychography and far-field ptychography, where ptychography involves multiple overlapping finite-sized illumination positions. Unlike what has been reported for coherent diffraction imaging, which involves recording a single far-field diffraction pattern, it is found that all three methods offer similar image quality when using the same fluence on the specimen, with far-field ptychography offering slightly better spatial resolution and a lower mean error. These results support the concept that (if the experiment and image reconstruction are done properly) the sample can be near or far; wherever you are, photon fluence on the specimen sets one limit to spatial resolution.

42 ENGINEERING↗

Towards time-resolved MicroED grid preparation using mix-and-inject gas dynamic virtual nozzles

Recent progress in gas dynamic virtual nozzle (GDVN) technologies in combination with high-brilliance synchrotron and X-ray free-electron lasers (XFELs) has allowed the visualization of protein dynamics in crystallo by mixing macromolecular protein crystals with a substrate using tunable mixing times on the order of milliseconds to seconds prior to serial X-ray diffraction data collection. This has become the method of choice for high-resolution structure determination of intermediate states. However, such experiments require large counts of crystals of proper sizes for high-resolution data collection, and premium beam times for screening efforts. Cryogenic microcrystal electron diffraction (MicroED) represents a complementary technique that may be a more accessible avenue for time-resolved nanocrystallography compared with serial X-ray diffraction experiments. MicroED can produce full diffraction datasets from just a few submicrometre-thick crystals, and the approach is more readily accessible, requiring standard cryogenic transmission electron microscopy (TEM) equipment available at many universities and institutes. Cryogenic MicroED, like other forms of cryo-EM, begins with rapidly freezing biological material on electron microscopy grids. In the case of MicroED, micro- to nano-crystals (<500 nm thick) are deposited onto electron microscopy grids and plunge-frozen for subsequent electron diffraction data collection. Here, we have incorporated GDVN technology developed originally for XFEL experiments into the freezing process as a first step towards time-resolved studies. We describe the limited deposition efficiency of the model MicroED protein proteinase K on TEM grids using GDVNs, preceding sample vitrification and successful MicroED data collection. We discuss both the initial results from such experiments and the methodological challenges in developing this approach into a reliable workflow for millisecond-to-second time-resolved structural studies of macromolecules. Our results promise a strategy to deposit crystals on grids using GDVNs and determine high-resolution structures by MicroED, constituting a first step towards development of time-resolved MicroED experiments.

MicroED↗

Second-Generation Design of Micro-Spec: A Medium-Resolution, Submillimeter-Wavelength Spectrometer-on-a-Chip

Micro-Spec (μ-Spec) is a direct-detection spectrometer which integrates all the components of a diffraction-grating spectrometer onto a ∼10-cm2 chip through the use of superconducting microstrip transmission lines on a single-crystal silicon substrate. A second-generation μ-Spec is being designed to operate with a spectral resolution of 512 in the submillimeter (500-1000 μm, 300-600 GHz) wavelength range, a band of interest for several spectroscopic applications in astrophysics. High altitude balloon missions would provide the first test bed to demonstrate the μ-Spec technology in a space-like environment and would be an economically viable venue for multiple observation campaigns. This work reports on the current status of the instrument design and will provide a brief overview of each instrument subsystem. Particular emphasis will be given to the design of the spectrometer's two-dimensional diffractive region, through which the light of different wavelengths is focused on the detectors along the focal plane. An optimization process is employed to generate geometrical configurations of the diffractive region that satisfy specific requirements on spectrometer size, operating spectral range, and performance. An optical design optimized for balloon missions will be presented in terms of geometric layout, spectral purity, and efficiency.

Cataldo, G.↗

Characterization of n-Type Iodine-Doped and Indium-Doped CdTe/Cd-Se-Te Thin Films Fabricated by Close-Spaced Sublimation Epitaxy

In this study, n-type CdTe thin films, specifically iodine-doped CdTe (CdTe:I), indium-doped CdTe (CdTe:In), and indium-doped Cd-Se-Te (CST:In), were synthesized using close-spaced sublimation epitaxy (CSSE). Characterization techniques secondary ion mass spectrometry (SIMS), electron backscatter diffraction (EBSD), Hall-effect measurements, and time-resolved photoluminescence (TRPL) were employed to analyze the chemical, structural, and electronic properties of these materials. The results indicated epitaxial single crystal CSSE films grew on the single crystal substrates, with carrier density ranging from 10^14 - 10^16 cm -3 , and after post-annealing, the minority-carrier lifetimes reach near the radiative limit. Additionally, a preliminary exploration of homojunction structures with an n- type (CdTe:In /CST:In /CdTe:I) /CdTe:P /Cu /Mo configuration was performed. The best device performance was achieved with CdTe:I including CdS aiding in band alignment, resulting in a power conversion efficiency (..eta..) of 2.61% with open circuit voltage (Voc) of 850 mV, fill factor (FF) of 47.8%, and short-circuit current (Jsc) of 6.44 mA/cm 2 . The observed low Jsc and efficiency may be attributed to a buried junction and a poor interface, due to dopant interdiffusion. Consequently, further investigations focusing on interface optimization, diffusion blocking, and reduced recombination through passivation, are crucial to enhancing the efficiency of CSSE CdTe homojunction devices in the future.

cadmium compounds↗

From Salt to Electronics: Heteroepitaxy and GaAs Solar Cells

This paper presents work on the heteroepitaxy of salts, specifically fluorides, on semiconductor and heteroepitaxy of semiconductor on salts. Fluorides layers are deposited on commercial Gallium Arsenide (GaAs) wafers followed by the heteroepitaxial growth of GaAs using metal organic chemical vapor deposition (MOCVD). The fluoride layers consist of 2 lattice-engineered layers of alkaline-earth compounds to match with GaAs, and are used to sandwich another alkaline-earth compound with higher water-solubility as sacrificial layer. The triple fluoride layers enable liftoff of free-standing semiconductor films which can be further transferred to desirable substrates. 2D-X-ray Diffraction (2D-XRD) measurements confirm epitaxial growth of both the fluorides and the subsequently grown GaAs films. Single junction (SJ) solar cell devices based on thus prepared films show a power conversion efficiency (PCE) of 10.3% under 1 sun illumination. After the completion of device fabrications, the GaAs film is lifted off from the substrate by a novel water-assisted epitaxial liftoff (H 2 O-ELO) technique and transferred to a cheaper substrate. The original GaAs wafer is recycled and reused twice. Devices based on reused substrates show no significant degradation in performance. Lastly, the semiconductor-salt-semiconductor scheme has great implications in high performance, flexible, and large area electronics.

14 SOLAR ENERGY↗

Room temperature sodium diffusion in sodium iron phosphate investigated with neutron scattering

Sodium iron phosphate, Na x FePO 4 , is currently one of the most promising cathode materials for sodium ion batteries. Here we employ a systematic approach using three neutron scattering techniques to investigate temperature dependent properties with a focus on the charge transfer processes. Two distinct Na + diffusive motions are observed with quasielastic neutron scattering, including room temperature motion. These processes correspond to rapid double jumps through extrinsic vacancy sites of ∼6 Å along with the more fundamental nearest neighbor jumps of 3.1 Å. Experimental observations of room temperature ionic diffusion are highly desirable, as the diffusion pathways are naturally well suited for efficient transport. Inelastic neutron scattering was used to probe the vibrational density of states that assist in the ionic and electronic (polaronic) transport processes, which are further supported with density functional theory. Neutron diffraction examines the disordering of the sodium sublattice upon transition to the solid-solution phase, which is believed to enhance the overall kinetics during sodium insertion/extraction. Finally, 57 Fe Mössbauer spectroscopy measurements probes polaron hopping and the local structural evolution that modifies the electron density surrounding the redox active iron sites. This study sheds light on the temperature induced atomic scale dynamics that occur in olivine Na x FePO 4 .

Novak, Eric [Swarthmore College, Swarthmore, PA (U↗

Efficient separation of xylene isomers by using a robust calcium-based metal–organic framework through a synergetic thermodynamically and kinetically controlled mechanism

Adsorptive separation of physically and chemically similar molecules and understanding the underlying host–guest interactions at the molecular level are of significant scientific and practical importance. Here we report the development of a novel calcium-based metal–organic framework, formulated as Ca 3 (Htcpp) 2 (H 4 tcpp = 2,3,5,6-tetrakis(4-carboxyphenyl)-pyrazine) featuring microporosity and high stability. This compound shows distinct adsorption behavior toward xylene isomers and is capable of separating them efficiently at an industrially relevant temperature. The selective adsorption is attributed to a synergetic thermodynamic and kinetic effect. Here, the host–guest interactions were probed directly by single-crystal X-ray diffraction analysis and the adsorption affinity was evaluated through computational molecular simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Prediction of chlorine and fluorine crystal structures at high pressure using symmetry driven structure search with geometric constraints

The high-pressure properties of fluorine and chlorine are not yet well understood because both are highly reactive and volatile elements, which have made conducting diamond anvil cell and x-ray diffraction experiments a challenge. Here, we use ab initio methods to search for stable crystal structures of both elements at megabar pressures. We demonstrate how symmetry and geometric constraints can be combined to efficiently generate crystal structures that are composed of diatomic molecules. Furthermore, our algorithm extends the symmetry driven structure search method by adding constraints for the bond length and the number of atoms in a molecule while still maintaining generality. As a method of validation, we have tested our approach for dense hydrogen and reproduced the known molecular structures of Cmca-12 and Cmca-4. We apply our algorithm to study chlorine and fluorine in the pressure range of 10 GPa–4000 GPa while considering crystal structures with up to 40 atoms per unit cell. We predict chlorine to follow the same series of phase transformations as elemental iodine from Cmca to Immm to Fm3¯m, but at substantially higher pressures. We predict fluorine to transition from a C2/c to Cmca structure at 70 GPa, to a novel orthorhombic and metallic structure with P42/mmc symmetry at 2500 GPa, and finally to its cubic analog form with Pm3¯n symmetry at 3000 GPa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗