Reflectance Measurements Research Articles

Kvačekite, NiSbSe, a new selenide mineral from Bukov, Czech Republic

Abstract Kvačekite is a new mineral species discovered in a sample collected from the now abandoned Bukov uranium mine, western Moravia, Czech Republic. It occurs as rare anhedral grains, up to 15 μm in size, associated with nickeltyrrellite, tyrrellite, berzelianite, hakite-(Zn), hakite-(Cd), eucairite, clausthalite, and gold in calcite gangue. In reflected light, kvačekite is white with a faint yellowish shade; bireflectance, pleochroism and anisotropy are absent. Internal reflections were not observed. Reflectance values for the four COM wavelengths for kvačekite in air [R (%) (λ in nm)] are: 54.9 (470); 53.5 (546); 52.6 (589); and 52.2 (650). The empirical formula, based on electron-microprobe analyses (EPMA), is (Ni0.95Cu0.04Co0.03)Σ1.02Sb1.00(Se0.97S0.01)Σ0.98. The ideal formula is NiSbSe, which requires (in wt.%) Ni 22.63, Sb 46.93, Se 30.44, total 100.00. Kvačekite is cubic, P213, with unit-cell parameters a = 6.09013(13) Å, V = 225.881(15) Å3 and Z = 4. The strongest reflections in the X-ray powder diffraction pattern of synthetic kvačekite [d, Å (I) hkl] are: 3.0458 (11) 200; 2.7242 (100) 201, 210; 2.4867 (71) 211; 1.8632(39) 311; 1.6277(29) 321, 312; and 1.3290 (13) 421. Given the similarity with ullmannite, NiSbS, the crystal structure was refined from the powder X-ray diffraction data starting from those atomic coordinates using the synthetic analogue of kvačekite. Its crystal structure is formed by corner-sharing [NiSb3Se3] octahedra which form a three-dimensional network. The identity of the natural kvačekite and synthetic cubic NiSbSe were confirmed by a study of their chemical composition, reflectance measurements, Raman spectroscopy and electron back-scattered diffraction (EBSD) measurements on the mineral. Kvačekite is named after Milan Kvaček (1930–1993), a prominent Czech mineralogist. The mineral and its name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2023-095).

Speckle Noise Reduction via Linewidth Broadening for Planetary Laser Reflectance Spectrometers

The low obliquity of the Moon leads to challenging solar illumination conditions at the poles, especially for passive reflectance measurements aimed at determining the presence and extent of surface volatiles. A nascent alternate method is to use active laser illumination sources in either a multispectral or hyperspectral design. With a laser spectral source, however, the achievable reflectance precision may be limited by speckle noise resulting from the interference effects of a coherent beam interacting with a rough surface. Here, we have experimentally tested the use of laser linewidth broadening to reduce speckle noise and, thus, increase reflectance precision. We performed a series of speckle imaging tests with near-infrared laser sources of varying coherence, compared them to both theory and speckle pattern simulations, and measured the reflectance precision using calibrated targets. By increasing the laser linewidth, we observed a reduction in speckle contrast and the corresponding increase in reflectance precision, which was 80% of the theoretical improvement. Finally, we discuss methods of laser linewidth broadening and spectral resolution requirements for planetary laser reflectance spectrometers.

Fabrication and evaluation of a spatially resolved fiber-optic probe for diffuse reflectance measurement for noninvasive diabetic foot ulcer diagnosis perspective

Fabrication and evaluation of a spatially resolved fiber-optic probe for diffuse reflectance measurement for noninvasive diabetic foot ulcer diagnosis perspective

In-Line Chemical Composition Monitoring for the Injection Molding Process of Biodegradable Polymer Blends Using Simultaneous Measurement of Near-Infrared Diffuse Reflectance and Transmission Spectra.

In the processing of polymer blends and composites, in-line near-infrared (NIR) spectroscopy enables monitoring of the composition and its composite uniformity and contributes to rapid process development and quality control. However, in the injection molding process, the study of the composition of polymer materials has been delayed due to high-pressure conditions. Our research group developed NIR probes for transmission and diffuse reflectance measurements that can withstand high-pressure and temperature conditions up to 130 MPa and 200 °C. In this research, transmission and diffuse reflectance spectra were measured inline during the injection molding process of polymer blends of poly(lactic acid) and polybutylene succinate adipate. The intensity of each polymer band in the second-derivative spectra exhibited a monotonic increase or decrease in response to changes in the blend ratio. Using transmission and diffuse reflectance spectra as explanatory variables of the partial least squares regression model simultaneously, the model showed high estimation accuracy for the entire region of the blend ratio. Finally, this model was applied to monitor the polymer changeover operation, and the change in the blend ratio in the molded product was successfully estimated in line.

Hybrid graphene-high-aspect ratio plasmonic nanograting systems

One-dimensional plasmonic nanogratings (1D-PNGs) with high aspect ratios and narrow grooves promise enhanced coupling for hybrid graphene systems with the localized surface plasmon of the metallic grating and graphene surface plasmons. However, both the fabrication of the 1D-PNG and the application of graphene to it are difficult. We developed 1D-PNGs with a high aspect ratio of 15 and narrow grooves of 100 nm in width using the tapered mold method and a dry graphene-transfer procedure. Raman spectroscopy measurements showed that monolayer graphene was successfully transferred onto the 1D-PNGs, and the graphene was strongly doped with Au in the 1D-PNGs. Graphene on narrow grooves (free-standing graphene) demonstrated an almost identical p-doping level to graphene on Au because the narrow groove width allowed sufficient doping by Au for graphene on grooves. Reflectance measurements showed that the 1D-PNGs exhibited polarization- and wavelength-selective absorption at infrared (IR) wavelengths, and the effect of graphene blue-shifted the absorption peak wavelength induced by the surface plasmon resonance of 1D-PNGs. Numerical calculations agree well with these experimental results and indicate that the electric field strongly localizes on graphene in the grooves. Moreover, the doping level tunes the absorption wavelength owing to the coupling with graphene plasmons and the surface plasmon resonance of 1D-PNGs. This could provide electrical tunability to the graphene plasmons. Our fabrication procedure produced hybrid graphene-1D-PNGs with high aspect ratios and narrow groove systems for IR wavelengths. This system can contribute to developing high-performance electrically tunable graphene-based IR photodetectors, tunable IR emitters/absorbers, and biological sensors.

Preparation of a Lignin-Based Cationic Flocculant and Its Application in Kaolin Suspension Treatment.

The preparation of an environmentally friendly and efficient flocculant for solid-liquid separation in industrial wastewater is highly important. In this study, a novel cationic flocculant (AL-g-PAMA) was synthesized by a thermal initiation method using alkali lignin (AL) as the main chain and acrylamide (AM) and methacrylamido propyl trimethyl ammonium chloride (MAPTAC) as the grafted side chains. The structure, thermal stability, and surface morphology of the copolymers were investigated by various characterization methods. The results indicated the successful synthesis of AL-g-PAMA. AL-g-PAMA was applied to improve solid-liquid separation in kaolin suspensions. The results showed that AL-g-PAMA had excellent flocculation-sedimentation and dewatering efficiency. When the dosage of AL-g-PAMA #5 was 600.0 g/t(s), the thickness of the compressed layer was 2.2 cm, the floc settling velocity was 24.1 cm/min, and the transmittance of the supernatant was 84.0%. The moisture content of the filter cake decreased from 55.0% to 43.4% after treatment with AL-g-PAMA #5. The results of zeta potential and focused beam reflectance measurement (FBRM) analysis indicated that bridging and electroneutralization were the main flocculation mechanisms. Therefore, this study extends the potential for using lignin as a bioflocculant and provides a feasible approach to efficiently purify high-turbidity wastewater.

Fundamental Properties of Sub-THz Reflected Waves for Water Content Estimation of Reinforced Concrete Structures

Water plays a significant role in the deterioration of reinforced concrete buildings; therefore, it is essential to evaluate the water content of the cover concrete. This study explores a novel non-destructive method for assessing the water content using sub-terahertz (sub-THz) waves. Among the four frequencies selected to evaluate the water content, an increase in reflectance was observed as the unit volume water content increased, and smaller data scatter was confirmed as the frequency increased. The derived empirical equation can classify the corrosion risk of the rebar environment based on the water content obtained using reflectance measurements. In other words, it can contribute to the diagnosis of the building integrity associated with rebar corrosion.

Engineering electrically tunable TiN/SiO2 epsilon-near-zero metamaterials

Electrically tunable TiN/SiO2/TiN epsilon-near-zero photonic structures with various parameters were fabricated using the reactive DC magnetron sputtering approach. Effective medium approximation was used to predict the optical permittivity of a multilayered TiN/SiO2 metamaterial and guide the design/fabrication. Experimental reflectance measurements for tunable TiN/SiO2/TiN structures were obtained using the ellipsometer technique in the visible and near-infrared spectral ranges. Results show that reflectance for biased (12 V) and un-biased bulk TiN/SiO2/TiN structure changes up to ∼ 2% with the spectral shift at the ENZ spectral point ∼ 10 nm for samples with an optimal SiO2 dielectric layer (thickness d=10 nm). Reflectance measurements for multilayered tunable TiN/SiO2/TiN structures show strong variation in reflectance change for s- polarized light at epsilon-near-zero wavelengths due to applied voltage (12 V). We expect that the results of this research study of the tunable TiN/SiO2/TiN epsilon-near-zero photonic structures will potentially be useful for the photonic density of states engineering, surface sensing, and metamaterial-based super-resolution imaging.

Investigation of the homogeneity of particle suspension

The homogeneity of particle suspension has attracted more attention in the fields of rehydrating milk beverages. This work focus on size characterization of the floating, sticking (on the wall), suspended and settling particles involving both online and offline sizing techniques. Focused Beam Reflectance Measurement (FBRM) is a powerful online technique that is capable for measuring and analysing chord length distribution (CLD) of the suspended particles in liquid. It has been widely used in terms of monitoring size evolution of crystallization and sedimentation processes. In this work, a new approach that involves FBRM probe to measure the particle size distribution has been developed. The probe is placed at three different height levels in a standard container after one hour of free sedimentation. The results suggest that the finest fraction is dominant at all three heights but the percentage of it decreases with an increase of larger particles when looking at the bottom. Besides, all the floating, sticking and settling particles are collected and analysed, and the particle size distributions (PSDs) are obtained and compared using the offline sizing techniques, such as optical microscope and Camsizer. In the results, the suspended particle is the smallest one followed by the sticking and the floating particles, while the settling particle is the largest. However, for the sticking particles sticking on the wall, a great number of agglomerates is found during the test due to adhesion force, indicating that the size distribution might be overestimated. Based on the results, the target particle size range that can be stably suspended in the model suspension was selected by eliminating the unfavourable fractions.

Chemical sensing of common microorganisms found in biopharmaceutical industries using MIR laser spectroscopy and multivariate analysis.

Mid-infrared laser spectroscopy was used to investigate common bacteria encountered in biopharmaceutical industries. The study involved the detection of bacteria using quantum cascade laser spectroscopy coupled to a grazing angle probe (QCL-GAP). Substrates similar to surfaces commonly used in biopharmaceutical industries were used as support media for the samples. Reflectance measurements were assisted by Multivariate Analysis (MVA) to assemble a powerful spectroscopic technique with classification and identification resources. The species analyzed, Staphylococcus aureus, Staphylococcus epidermidis, and Micrococcus luteus, were used to challenge the technique's capability to discriminate from microorganisms of the same family. Principal Components Analysis and Partial Least Squares-Discriminant Analysis differentiated between the bacterial species, using QCL-GAP-MVA as the reference. Spectral differences in the bacterial membrane were used to determine if these microorganisms were present in the samples analyzed. Results herein provided effective discrimination for the bacteria under study with high sensitivity and specificity.

Optical characterization of a fiber Fabry-Perot cavity: precision measurement of intra-cavity loss, transmittance, and reflectance

We propose and demonstrate a method for characterizing the individual mirror parameters of a fiber Fabry–Perot cavity (FFPC). By measuring the reflection and transmission spectra of the FFPC with an incident laser propagating from the two mirrors of the FFPC and considering several normal or unique losses, the transmittance, reflectance, and intra-cavity loss of the individual mirrors can be determined. Due to the intrinsic limitation of cavity length, traditional powerful methods, such as the cavity ring-down technique, are not applicable to FFPCs for characterizing the parameters of individual mirrors. This scheme provides a dependable method for assessing FFPC mirrors and provides a significant capability for the implementation of strong-coupling cavity quantum electrodynamics based on FFPCs.

Laboratory VIS–NIR reflectance measurements of heated Vesta regolith analogs: Unraveling the spectral properties of the pitted impact deposits on Vesta

AbstractPitted impact deposits on Vesta show higher reflectance and pyroxene absorption band strengths compared to their immediate surroundings and other typical Vestan materials. We investigated whether heating to different temperatures for different durations of Vestan regolith analog materials can reproduce these spectral characteristics using mixtures of HEDs, the carbonaceous chondrite Murchison, and terrestrial analogs. We find no consistent spectral trend due merely to temperature increases, but observed that the interiors of many heated samples show both higher reflectance and pyroxene band I strength than their heated surfaces. With electron probe microanalysis, we additionally observe the formation of hematite, which could account for the higher reflectance. The presence of hematite indicates oxidation occurring in the sample interiors. In combination with heat, this might cause the increase of pyroxene band strengths through migration of iron cations. The effect grows larger with increasing temperature and duration, although temperature appears to play the more dominant role. A higher proportion of Murchison or the terrestrial carbonaceous chondrite analog within our mixtures also appears to facilitate the onset of oxidation. Our observations suggest that both the introduction of exogenic material on Vesta as well as the heating from impacts were necessary to enable the process (possibly oxidation) causing the observed spectral changes.

Intensification of organic pollutant degradation under visible light irradiation using ZnO nanostructured photocatalysts doped with praseodymium

Zinc oxide nanostructures doped with praseodymium (ZnO:Pr) at varying Pr content (0.05 % to 1.0 % w/w) were synthesized using the electrospinning-calcination technique. Comprehensive morphological and structural characterizations were conducted through SEM, XRD, and XPS analyses. In addition, diffuse reflectance and photoluminescence spectroscopy measurements were performed to assess the optical properties of materials. The produced photocatalysts (ZnO:Pr) were then employed for the degradation of methylene blue dye and oxytetracycline under visible-light irradiation. ZnO:Pr(0.1 %) demonstrated the best photocatalytic performance against methylene blue showing a pseudo-first-order rate constant of k = 3.630 × 10-2 min−1. Investigation of oxytetracycline photodegradation with ZnO:Pr(0.1 %) revealed a pseudo-second-order rate constant of ks = 1.165 × 10-1 L mg−1 min−1, resulting in a reaction half-life (τ½) of approximately 1 min under optimal conditions. Total organic carbon and mass spectrometry analyses highlighted mineralization and identified the main reaction intermediates, respectively, for the oxytetracycline photodegradation. The photodegradation mechanism of oxytetracycline was proposed by the photocatalytic degradation measurements in the presence of scavengers such as hydroquinone and isopropanol. These nanostructures exhibited robust photocatalytic activity over multiple cycles, demonstrating excellent stability. This study underlines the promising potential of ZnO:Pr(0.1 %) as an efficient photocatalyst able to intensify the photodegradation of organic pollutants.

Nanomechanical behavior, adhesion and wear resistance of tin oxide coatings for biomedical applications

AbstractThis study investigates the properties of tin oxide coatings employed in biomedical applications. The films were deposited on a clean glass substrate, preheated at 450 °C, applying the spray pyrolysis technique as the latter produces crystallized thin films without the need for further heat treatment. X‐ray diffraction analysis showed that tin oxide films had a tetragonal structure characterized by a preferential orientation (111). The measurements of reflectance and transmittance revealed a wide optical band gap of 4.0 eV. Nanoindentation tests showed that the tin oxide coating, with a hardness of 5.9 GPa and a Young's modulus of 78 GPa, exhibited elastic‐plastic behavior. In addition, tribological tests indicated that tin oxide coating had a very low coefficient of friction (μ=0.06), high wear resistance (wear rate 2.10−5 mm3 N−1 m−1) and good adhesion to the substrate (critical adhesion load of 5.55 N). It was also noticed that tin oxide thin films had antibacterial activity due to their nanocrystalline impurities. These properties make tin oxide perfectly acceptable for biomedical applications.

Catalog of Ultraviolet Bright Stars: Strategies for UV Occultation Measurements, Planetary Illumination Modeling, and Sky Map Analyses Using Hybrid IUE-Kurucz Spectra

Ultraviolet spectroscopy is a powerful method to study planetary surface composition through reflectance measurements, atmospheric composition through stellar/solar occultations, transits of other planetary bodies, and direct imaging of airglow and auroral emissions. The next generation of ultraviolet spectrographs (UVS) on board ESA’s Jupiter Icy Moons Explorer and NASA’s Europa Clipper missions will perform such measurements of Jupiter and its moons in the early 2030s. This work presents a compilation of a detailed UV stellar catalog, named Catalog of Ultraviolet Bright Stars (CUBS), of targets with high intensity in the 50–210 nm wavelength range with applications relevant to planetary spectroscopy. These applications include (1) planning and simulating occultations, including calibration measurements; (2) modeling starlight illumination of dark, nightside planetary surfaces primarily lit by the sky; and (3) studying the origin of diffuse Galactic UV light as mapped by existing data sets from Juno-UVS and others. CUBS includes observations from the International Ultraviolet Explorer (IUE) and additional information from the SIMBAD database. We have constructed model spectra at 0.1 nm resolution for almost 90,000 targets using interpolated Kurucz models (which have a resolution of 1 nm) and, when available, IUE spectra. CUBS also includes robust checks for agreement between the Kurucz models and the IUE data. We also present a tool for which our catalog can be used to identify the best candidates for stellar occultation observations, with applications for any UV instrument. We report on our methods for producing CUBS and discuss plans for its implementation during ongoing and upcoming planetary missions.

Combined experimental and first principles look into (Ce, Mo) doped BiVO4

Here we investigated the effects of Ce and Mo doping on hydrothermally synthesized bismuth vanadate BiVO4 nanoparticles (NPs). The existence of monoclinic scheelite and tetragonal zircon phases of NPs was validated from Rietveld refinement of the powdered X-ray diffraction, room temperature Raman, and Fourier-transform infrared spectroscopy. The co-doping of Bi and V sites with respective Ce and Mo dopants in a mixed tetragonal zircon and monoclinic scheelite phases of BiVO4 lattice was corroborated from high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. The photoluminescence measurements revealed enhancement of photo-generated carrier recombination in (Ce, Mo) co-doped BiVO4 NPs which may have hampered its photocatalytic efficiency in degrading the methylene blue dye. The simulations based on Hubbard U corrected density functional theory (DFT+U) suggest that Mo and Ce co-doping introduced deep impurity states which may have facilitated the photo-generated carrier recombination detrimental to photocatalytic performance. The UV-vis diffuse reflectance measurements provided evidence for the presence of these defect states. In summary, this work may have presented a comprehensive experimental analysis of (Ce, Mo) doped BiVO4 supported by DFT simulations.

RF sputtered metal oxide layers as ARCs to improve photovoltaic performance of commercial monocrystalline solar cell

The rf-sputtered ZnO, MgO and Al2O3 transition metal oxide nano layers were developed as efficient antireflection coatings (ARCs) on commercial monocrystalline silicon (m-Si) photovoltaic cells. Wavelength dependence reflectance measurements show minimal reflectance (i.e., ∼1.3–2.0%) between 350 and 800 nm wavelength regions affirming antireflection behavior of oxide layers. The phase formation studies of these oxide layers display the crystalline phase however the presence of non-crystalline phase is noted in Al2O3 diffractogram pattern. Cross section microstructure characterization carried out using scanning electron microscopy (SEM) to know the ARC layer thickness illustrates MgO, ZnO and Al2O3 layers with coating thickness around 85 nm, 87 nm and 77 nm respectively. Also, the thickness of antireflection coatings computed using wavelength dependent refractive index measurement is consistent with cross section microstructure images. Photon to energy conversion (PEC) of ARC coated device under 1 sun condition display 1.99%, 1.07% and 0.39% improvement in efficiencies compared with commercial m-Si-solar cell endorsing suitability of selected transition metal oxides as efficient ARC materials. The external quantum efficiency (EQE) measurements show notable improvement in efficiency for MgO, ZnO and Al2O3 coated devices reaffirming their usability as efficient ARC materials on commercial m-Si-solar cells.

Spectral Analysis of Pink Mealy Bug Damaged Mulberry Plants Using Hyperspectral Radiometry

Mulberry (Morus spp.) foliage forms a sole food to silkworms, Bombyx mori L. Its quality plays a pivotal role in superior silk fiber production. Like any other plants, mulberry is susceptible to detrimental diseases and infested by insect pests. Many sucking pests cause damage to mulberry among which, pink mealybug causes severe damage leading to significant loss in mulberry leaf yield (12-25 %). Conventional approaches to assess and manage damage caused by pink mealybugs demand substantial manpower and expertise, resulting in time-consuming and inefficient processes. However, leveraging modern tools and technologies like remote sensing has emerged as a remarkably effective strategy for crop protection and management.Specifically, hyperspectral remote sensing proves invaluable by furnishing insights into the biophysical and biochemical traits of crops. This is achieved through the recording of narrow wave bands that reflect specific plant characteristics. The main objectives were to understand the spectral reflectance characteristics of healthy and pink mealy bug damaged mulberry crops, to identify the optimal spectral bands and vegetative indices for detecting pink mealy bug damage in mulberry and to explore the feasibility of estimating pest damage levels based on the spectral properties of mulberry crops. Top of FormAt the mulberry garden of the Department of Sericulture, Tamil Nadu Agricultural University (TNAU), Coimbatore, studies were conducted on spectral analysis of pink mealy bug damaged mulberry plants using hyperspectral radiometry during 2018. In this trial, at 15-day intervals during the active damage stage, the percentage damage was observed in plots infested with pink mealy bugs and those that were healthy. Measurements of spectral reflectance across various wavelengths and vegetation indices (VIs) were taken using a hyperspectral radiometer. The analysis included evaluating the sensitivity of different spectral bands and VIs to pink mealybug damage, along with employing correlation and regression analyses between the extent of pest damage and the VIs. The findings revealed distinct differences in the spectral reflectance profiles of mulberry plants compared to their healthy counterparts. Typically, affected plants exhibited increased reflectance in the red (620–680 nm) and green (520–590 nm) bands and reduced near-infrared (NIR) reflectance (770–860 nm). The average values of the Normalized Difference Vegetation Index (NDVI), Green Red Vegetation Index (GRVI), and Ratio Vegetation Index (RVI) were significantly lower in the pink mealybug-damaged plants across all measurements. Notably, red reflectance demonstrated the greatest sensitivity to pink mealybug-induced damage. The study highlighted the Simple Ratio (SR) index as particularly effective for identifying pest damage. Damage estimation by pink mealybugs was refined using linear regression models based on spectral indices, specifically NDVI, RVI, and GRVI. The correlation intensity analysis pinpointed the green region at 516.73 nm as showing the most significant negative correlation (r = -0.02), whereas the highest positive correlation with pink mealybug damage was observed in the NIR region (r = 0.77), underscoring the precise wavelengths and indices most indicative of pest impact. Thus, using hyperspectral radiometry identification of damage caused by pink mealy bug possible, through analysis of spectral bands and indices.

Structural, Optical and Optoelectrical Properties of CuAlSnS4 Thin Films

The present study used chemical deposition to deposit thin copper aluminum tin sulfide (CATS4) layers onto clean glass substrates. X-ray diffraction analysis was utilized to explore the crystalline structure of the CATS4 films, which refers to the CATS4 films having a cubic crystal structure. Energy-dispersive X-ray analysis showed the presence of Cu, Al, Sn, and S peaks in the CATS4 films, and their atomic ratio is close to 1:1:1:4. Spectrophotometric measurements of optical transmittance and reflectance spanning the 400–2500 nm spectral range were performed to describe the optical properties of the CATS4 layers. The CATS4 films demonstrated a direct energy gap transition between 1.42 and 1.31 eV. Further, increasing the layer thickness enhanced the refractive index and Urbach energy of the CATS4 films. The inspected CATS4 films showed better optoelectrical properties with increasing thickness, including improved optical conductivity, optical resistivity, optical carrier concentration, relaxation time, and optical mobility. Increasing the thickness of the CATS4 films increased their nonlinear optical indices. Additionally, the hot probe apparatus verified the p-type semiconducting characteristics of CATS4 films.

Syntheses, Crystal Structures, and Electronic Structures of Quaternary Group IV-Selenide Semiconductors.

Early transition-metal chalcogenides have garnered recent attention for their optoelectronic properties for solar energy conversion. Herein, the first Zr-/Hf-chalcogenides with a main group cation, Ba9Hf3Sn2Se19 (1) and Ba8Zr2SnSe13(Se2) (2), have been synthesized. The structure of 1 is formed from isolated SnSe44- tetrahedra and distorted HfSe6 octahedra. The latter condense via face-sharing trimeric motifs that are further vertex-bridged into chains of 1∞[Hf(1)2Hf(2)Se11]10-. The structure of 2 is comprised of SnSe44- tetrahedra, Se22- dimers, and face-sharing dimers of distorted ZrSe6 octahedra. These represent the first reported examples of Hf-/Zr-chalcogenides exhibiting face-sharing octahedra with relatively short Hf-Hf and Zr-Zr distances. Their preparation in high purity is inhibited by their low thermodynamic stability, with calculations showing small calculated ΔUdec values of +7 and +9 meV atom-1 for 1 and 2, respectively. Diffuse reflectance measurements confirm the semiconducting nature of 1 with an indirect band gap of ∼1.4(1) eV. Electronic structure calculations show that the band gap absorptions arise from transitions between predominantly Se-4p valence bands and mixed Hf-5d/Sn-5p or Zr-4d/Sn-5p conduction bands. Optical absorption coefficients were calculated to be more than ∼105 cm-1 at greater than 1.8 eV. Thus, promising optical properties are demonstrated for solar energy conversion within these synthetically challenging chemical systems.