Search NASA⌕ Search

SEARCH · Search NASA

Results for “chalcopyrite”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Mineralogy-dependent sulfide oxidation via polysulfide and thiosulfate pathways during weathering of mixed-sulfide bearing mine waste rock

Tracking the S oxidation pathway in sulfide-bearing mine waste-rock piles is complicated by variations in water content, O 2 and Fe 3+ concentrations, microbial diversity, mineralogy, the occurrence of a variety of S species associated with incomplete oxidation, and nonlinear coupling between physicochemical processes. Synchrotron-based S K-edge X-ray absorption near edge structure (XANES) spectroscopy facilitates the identification and quantification of S species (i.e., S 2– , $S_{2}O_{2}^{2–}$, S 8 , $S_{2}O_{3}^{2–}$, and $S_{2}O_{4}^{2–}$) in a weathered mine waste-rock pile containing pyrite, sphalerite, galena, pyrrhotite, and chalcopyrite. Mineralogy-dependent polysulfide and thiosulfate pathways both affect the S oxidation within the waste-rock pile. Currently, the polysulfide pathway, with S 8 as the intermediate S species, generates high concentrations of dissolved metals (from the rapid oxidation of monosulfides including sphalerite, galena, pyrrhotite, and chalcopyrite). As these monosulfides are depleted, the thiosulfate pathway of pyrite oxidation, including intermediate oxidation products (i.e., S 8 and $S_{2}O_{3}^{2–}$), will become the dominant oxidation pathway, resulting in the potential for generation of additional acidic drainage. This information highlights the importance of identifying the sulfide-mineral oxidation reaction pathways when attempting to estimate acid generation potential, and when developing remediation strategies for the storage and management of sulfide-bearing waste rock.

58 GEOSCIENCES↗
DOE OSTI2020

Observation of [VCu1–Ini2+VCu1–] Defect Triplets in Cu-Deficient CuInS2

Copper indium disulfide (CuInS2) is a semiconductor with a direct energy band gap of 1.53 eV, an optimal value for highly efficient thin-film solar cells. But it has reached only ~ 11 % power conversion efficiency, far less than the theoretically achievable value of ~ 30 %. The cause of this low performance is not understood. A single crystal grown from 1 mol% Cu-deficient melt was studied, using atomic resolution high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) and electron dispersive spectroscopy (EDS). While the bulk crystal is exactly stoichiometric CuInS2, it contains nanometer-thick, structurally coherent, Cu-deficient interphases that form along rotational twin boundaries in the {112} plane. Transition zones from bulk crystal to interphase are observed, where In is seen to move from its normal site InIn in the chalcopyrite structure to a tetrahedral interstitial site Ini, while Cu remains in its normal CuCu position. Two InIn rows of the bulk crystal merge into one row of Ini, causing excess Ini in the interphase. The concentrations of CuCu and Ini reflect a ratio of Cu vacancies, VCu, to excess Ini of ~ 2. Their relative lattice positions, and the high electrical resistivity of the crystal, suggests that VCu and excess Ini ‘precipitate’ as self-compensating, electrically neutral, [VCu1- Ini2+ VCu1-] defect triplets. This is the first atomic-level observation of the ordered defect that has been invoked as the basic structural modifier in chalcopyrite compound homologs. The interphases introduce an optical gap of 1.47 eV. Electron trapping in band tail states, evident from a photoconductivity exponent of 0.54, is the likely cause of an unusually low electron mobility of 0.1 cm2V-1s-1. The overall result is that making CuInS2 slightly copper-poor inserts nanometer-thick layers of the interphase into the bulk crystal. This study shows that apparently conflicting results of the effect of Cu deficiency on CuInS2 thin-film solar cells may be resolved by analyzing structure and composition at nanometer spatial resolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Molecular Coatings Improve the Selectivity and Durability of CO 2 Reduction Chalcogenide Photocathodes

The quest for solar-driven conversion of carbon dioxide to chemicals and fuels hinges upon the identification of an efficient, durable, and selective photocathode. Chalcogenide p-type semiconductors exemplified by chalcopyrite Cu(In,Ga)Se 2 (CIGS) have been effectively deployed as photocathodes. However, selectivity toward CO 2 reduction and durability of the commonly used CdS adlayer remain primary challenges. Here, we demonstrate that for the wide band gap CuGa 3 Se 5 chalcopyrite absorber these challenges are well addressed by an organic coating generated in situ from an N,N'-(1,4-phenylene)bispyridinium ditriflate salt in the electrolyte. The molecular additive provides a 30-fold increase in selectivity toward CO2R products compared to the unmodified system and lowers Cd corrosion at least 10-fold. This dual functionality highlights the promise of hybrid solid-state-molecular photocathodes for enabling durable and efficient solar fuel systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Evidence of Reversible Oxidation at CuInSe2 Grain Boundaries

Effects related to alkali metal doping and grain boundaries have puzzled the chalcopyrite photovoltaics community for a long time. This study is the first to report reversible oxidation of grain boundaries in CuInSe2 thin films. The phenomenon is observed in sodium-doped films, but not in undoped ones. Cathodoluminescence imaging, secondary ion mass spectrometry and Kelvin probe force microscopy analyses are performed on CuInSe2 thin films before and after exposure to vacuum. The findings suggest the existence of yet unidentified solid-gas equilibria. Resolving the nature of such reactions will provide new insights into the mechanism of alkali metal doping and passivation in chalcopyrite solar cells.

14 SOLAR ENERGY↗
DOE OSTI2021

Optical Characterization of Defects in High-Efficiency (Ag,Cu)(In,Ga)Se2

We applied time-resolved photoluminescence (TRPL) spectroscopy to study optimized chalcopyrite (Ag,Cu)(In,Ga)Se2 thin films. The device shows power conversion efficiency of 18.7%. The metastable defect VSe-VCu within ACIGS at EV+0.98 eV is detected in sub-bandgap TRPL excitation spectra. TRPL lifetime of 50 ns is limited by the density of mid-gap defects such as CuGa or CuIn. The similarity of TRPL dynamics before and after light soaking indicates the optimized ACIGS thin film is less metastable because the density of VCu-VSe defect is reduced to below 10^15 cm^-3. This study indicates that ACIGS has improved cell efficiency and reliability characteristics.

41 EE - Solar Energy Technologies Office (EE-4S)↗
DOE OSTI2021

Large-Scale Synthesis of Semiconducting Cu(In,Ga)Se2 Nanoparticles for Screen Printing Application

During the last few decades, the interest over chalcopyrite and related photovoltaics has been growing due the outstanding structural and electrical properties of the thin-film Cu(In,Ga)Se2 photoabsorber. More recently, thin film deposition through solution processing has gained increasing attention from the industry, due to the potential low-cost and high-throughput production. To this end, the elimination of the selenization procedure in the synthesis of Cu(In,Ga)Se2 nanoparticles with following dispersion into ink formulations for printing/coating deposition processes are of high relevance. However, most of the reported syntheses procedures give access to tetragonal chalcopyrite Cu(In,Ga)Se2 nanoparticles, whereas methods to obtain other structures are scarce. Herein, we report a large-scale synthesis of high-quality Cu(In,Ga)Se2 nanoparticles with wurtzite hexagonal structure, with sizes of 10–70 nm, wide absorption in visible to near-infrared regions, and [Cu]/[In + Ga] ≈ 0.8 and [Ga]/[Ga + In] ≈ 0.3 metal ratios. The inclusion of the synthesized NPs into a water-based ink formulation for screen printing deposition results in thin films with homogenous thickness of ≈4.5 µm, paving the way towards environmentally friendly roll-to-roll production of photovoltaic systems.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Vacuum-Healing of Grain Boundaries in Sodium-Doped CuInSe 2 Solar Cell Absorbers

Alkali metal doping and grain boundaries (GB) have been at the center of attention within the Cu(In,Ga)(S,Se) 2 photovoltaics community for years. This study provides the first experimental evidence that the GB of sodium-doped CuInSe 2 thin films may undertake reversible oxidation even at room temperature, whereas undoped films may not. The findings are corroborated by cathodoluminescence imaging, secondary ion mass spectrometry, and Kelvin probe force microscopy on air-exposed films subsequently subject to vacuum. A thermochemical assessment identifies the likely solid-gas equilibria involved. These reactions open new research questions with respect to the beneficial role played by alkali metal dopants in chalcopyrite solar cells and may steer the community toward new breakthroughs.

14 SOLAR ENERGY↗
DOE OSTI2022

Large-Area (Ag,Cu)(In,Ga)Se 2 Thin-Film Solar Cells with Increased Bandgap and Reduced Voltage Losses Realized with Bulk Defect Reduction and Front-Grading of the Absorber Bandgap

The 1.24 eV bandgap, 18.8% power conversion efficiency Ag-alloyed chalcopyrite (Ag,Cu)(In,Ga)Se 2 (ACIGS) solar cells are characterized to relate voltage and efficiency improvements to electro-optical (EO) characteristics. Shockley-Read-Hall recombination center defect density, identified and characterized through deep level transient spectroscopy and time-resolved photoluminescence (TRPL), is reduced through potassium and copper treatment optimization. Concomitantly, longer minority carrier lifetimes are achieved, which increases open-circuit voltage (V OC ). Near-conduction band defects associated in earlier studies with light-induced current instability are also mitigated. Analysis of charge-carrier dynamics after single- and two-photon excitation is used to separate recombination at the front interface and in the absorber bulk. From TRPL decay simulations, the authors estimate ranges of key solar cell material characteristics: bulk carrier lifetime T bulk = 110-210 ns, charge-carrier mobility u = 110-160 cm 2 V -1 s -1 , and front interface recombination velocity S front = 700-1050 cm s -1 . This lowest-reported S front for ACIGS absorbers originates from the notched conduction band grading, which also makes the impact of the back interface recombination negligible. It is suggested in the results that solar cell performance enhancements can be made most readily with two distinct strategies: improving device architecture and reducing semiconductor defect densities. Using these approaches, power conversion efficiency in large-area solar cells is improved by 1.1% absolute.

14 SOLAR ENERGY↗
DOE OSTI2021

Colloidal metal transport in soils developing on historic coal mine spoil

Chemical weathering of pyrite via oxidative dissolution is well-known for generating Fe(III)-bearing colloids at acid mine drainage (AMD) sites; however, the potential for physical weathering of pyrite-bearing materials and subsequent release and transport of colloidal pyrite and associated trace metals has not been studied. Here, we monitored the colloidal metal transport in soil developing on abandoned coal mine spoil with a history of AMD generation to systematically study the contribution of colloids to base and trace metal transport and determine the elemental and mineralogical composition of colloids. Additionally, we collected soil pore water using lysimeters with a pore size of approximately 1.3 μm and centrifugation was used to separate the colloids from aqueous fractions. Metal concentrations of Na, Ca, Mg, K, Si, Al, Mn, Fe, Cu, and Zn were analyzed. Our results show only 14% of the total Al and Cu were present in colloidal fractions whereas 23%, 43%, and 54% of Fe, Mn, and Zn were transported in the colloidal phase, respectively. In contrast, all base metals were primarily present in the aqueous concentration with a small fraction (<10%) present in the colloidal phase. The colloidal fractions of the base metals were inferred to be associated with the concentration of clay colloids. The release of colloids exhibited possible sensitivity toward weather conditions such as alternating high temperatures and rainfall during summer (May–July) compared to fall (August–November). The morphology, elemental, and mineral composition of colloids were determined by a scanning electron microscopy equipped with energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Colloids were dominated by phyllosilicates (biotite, muscovite, and kaolinite) with minor quartz and feldspars. Other minerals phases identified in colloidal fractions were hematite, goethite, arsenopyrite, and chalcopyrite. Colloids consisting of Fe, S, and O with structures resembling framboidal pyrite were identified, which is consistent with the non-silicates minerals identified by XRD. Our study suggests that the physical weathering of pyrite in the mine spoil can generate colloidal pyrite, which is mobilized and transported by soil pore water. Our results also indicate that these pyritic colloids are associated with toxic trace metals including Cu, Mn, and Zn. Colloid mobilization is also impacted by changes in temperature and precipitation, where clay mobilization afer rain events is favored. Further, sudden spikes in aqueous and/or colloidal concentrations may be the result of local heterogeneity within soils developing on mine spoil, indicating that further field-based work is necessary to better characterize pore-scale processes that control aqueous and colloid transport at similar sites to have a better understanding of potential contaminant transport from mine spoil systems.

58 GEOSCIENCES↗
DOE OSTI2021

Copper transformation, speciation, and detoxification in anoxic and suboxic freshwater sediments

The complex chemistry of copper (Cu) in freshwater sediments at low concentrations is not well understood. We evaluated the transformation processes of Cu added to freshwater sediments under suboxic and anoxic conditions. Freshwater sediments from three sources in Michigan with different characteristics (Spring Creek, River Raisin, and Maple Lake) were spiked with 30 or 60 mg kg -1 Cu and incubated under a nitrogen atmosphere. After 28-d, each treatment subset was amended with organic matter (OM) to promote anoxic conditions and evaluate its effects on Cu speciation. OM addition triggered a shift from suboxic to anoxic conditions, and sequential extractions showed that Cu accordingly shifted from acid-soluble to oxidizable fractions. Extended X-ray absorption fine-structure (EXAFS) spectroscopy revealed that Cu sulfides dominated all anoxic samples except for Spring Creek 30 mg kg -1 , where Cu(I) was predominantly complexed to thiol groups of OM. Covellite and chalcopyrite (CuFeS 2 ) were the predominant Cu species in nearly all anoxic samples, as determined by Raman spectroscopy, scanning electron microscopy, and X-ray absorption near-edge structure (XANES) spectroscopy. Copper reduction also occurred under suboxic conditions: for two of three sediments, around 80% had been reduced to Cu(I), while the remaining 20% persisted as Cu(II) complexed to OM. However, in the third coarsest (i.e., Spring Creek), around 50% of the Cu had been reduced, forming Cu(I)-OM complexes, while the remainder was Cu(II)-OM complexes. Toxicity tests showed that survival of H. azteca and D. magna were significantly lower in suboxic treatments. Anoxic sediments triggered a near-complete transformation of Cu to sulfide minerals, reducing its toxicity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Tunable structural, morphological and optical properties of undoped, Mn, Ni and Ag-doped CuInS 2 thin films prepared by AACVD

The preparation of high-quality copper indium sulphide, CuInS 2 photo-absorber material with tunable properties for efficient, low-cost, thin film solar cells using scalable methods remains a challenge. In order to address this, high quality off-stoichiometric undoped and Mn, Ni and Ag-doped CuInS 2 (CIS) thin films have been deposited onto glass substrates by aerosol-assisted chemical vapour deposition (AACVD) using metal diethyldithiocarbamate precursors at temperatures of 350, 400 and 450 °C. Data from powder X-ray diffraction (p-XRD), Raman spectroscopy and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) suggest a correlation of morphology and composition of tetragonal phase (chalcopyrite and copper-gold-type) sulphur-deficient microcrystalline CIS thin films. For undoped thin films, near-infrared optical absorption and emission with tunable band gap between 1.32 and 1.42 eV are likely associated with donor-acceptor pairs involving deep or shallow electronic states such as sulphur vacancies (V S •• ), indium-copper anti-sites (In Cu •• ) and indium interstitials (In i ••• ) as donors and copper vacancies (V Cu ') as acceptors. Whilst Mn-doped thin films exhibit minimal tunable properties, Ni and Ag-doped films exhibit tunable morphology, composition and near-infrared absorption for small dopant content. Here, though further studies are required to explore the defect chemistry, these results show the utility of AACVD in tuning structural, morphological and optical properties of undoped, Mn, Ni and Ag-doped CIS thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ligand-Mediated Phase Control in Colloidal AgInSe 2 Nanocrystals

Synthetic studies of colloidal nanoparticles that crystallize in metastable structures represent an emerging area of interest in the development of novel functional materials, as metastable nanomaterials may exhibit unique properties when compared to their counterparts that crystallize in thermodynamically preferred structures. Herein, we demonstrate how phase control of colloidal AgInSe 2 nanocrystals can be achieved by performing reactions in the presence, or absence, of coordinating ligands that can act as cation exchange mediators (i.e., oleylamine or 1-dodecanethiol). These coordinating ligands play a crucial role in formation of metastable AgInSe 2 nanocrystals, as they mediate in-situ topotactic conversion of an orthorhombic Ag2Se intermediate to a metastable orthorhombic phase of AgInSe 2 . We pro-vide a detailed mechanistic crystal chemistry description of this process to structurally elucidate how the orthorhombic phase of AgInSe 2 forms. Density functional theory calculations suggest that the metastable orthorhombic phase of AgInSe 2 is metastable by a small margin, at 10 meV/atom above the thermodynamic ground state. In the absence of oleylamine or 1-dodecanethiol, Ag 2 Se nanocrystal intermediates convert through kinetically slow, non-topotactic conversion processes to yield the thermodynamically preferred chalcopyrite structure of AgInSe 2 . Furthermore, on the basis of these discoveries, we offer new insight into the prediction of novel metastable multinary nanocrystal phases that do not exist on bulk phase diagrams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Wide Band Gap Chalcogenide Semiconductors

Wide band gap semiconductors are essential for today’s electronic devices and energy applications because of their high optical transparency, controllable carrier concentration, and tunable electrical conductivity. The most intensively investigated wide band gap semiconductors are transparent conductive oxides (TCOs), such as tin-doped indium oxide (ITO) and amorphous In–Ga–Zn–O (IGZO), used in displays and solar cells, carbides (e.g., SiC) and nitrides (e.g., GaN) used in power electronics, and emerging halides (e.g., γ-CuI) and 2D electronic materials (e.g., graphene) used in various optoelectronic devices. Compared to these prominent materials families, chalcogen-based (Ch = S, Se, Te) wide band gap semiconductors are less heavily investigated but stand out because of their propensity for p-type doping, high mobilities, high valence band positions (i.e., low ionization potentials), and broad applications in electronic devices such as CdTe solar cells. This manuscript provides a review of wide band gap chalcogenide semiconductors. First, we outline general materials design parameters of high performing transparent semiconductors, as well as the theoretical and experimental underpinnings of the corresponding research methods. We proceed to summarize progress in wide band gap (EG > 2 eV) chalcogenide materials—namely, II–VI MCh binaries, CuMCh 2 chalcopyrites, Cu 3 MCh 4 sulvanites, mixed-anion layered CuMCh(O,F), and 2D materials—and discuss computational predictions of potential new candidates in this family, highlighting their optical and electrical properties. Then, we finally review applications—for example, photovoltaic and photoelectrochemical solar cells, transistors, and light emitting diodes—that employ wide band gap chalcogenides as either an active or passive layer. Overall, by examining, categorizing, and discussing prospective directions in wide band gap chalcogenides, this Review aims to inspire continued research on this emerging class of transparent semiconductors and thereby enable future innovations for optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Electronic and Thermal Properties of the Cation Substitution-Derived Quaternary Chalcogenide CuInSnSe 4

Quaternary chalcogenides continue to be of interest for a variety of technological applications, with physical properties stemming from their structural complexity and stoichiometric variation. In certain structure types, partial vacancies on specific lattice positions present an opportunity to investigate electrical and thermal properties in light of these lattice defects. In this work, we investigated the structural, thermal, and electronic properties of CuInSnSe 4 , a material that belongs to a relatively unexplored class of quaternary chalcogenides with a defect adamantine crystal structure. First-principles calculations together with experimental measurements revealed a chalcopyrite-like structure with inherent vacancies and characteristic s–p and p–d orbital hybridizations in the electronic structure of the material. Cation disorder and lattice anharmonicity result in very low thermal conductivity with values significantly lower than those for related compositions. In conclusion, this work reveals the fundamental physical properties of a previously uninvestigated quaternary chalcogenide and may aid investigations of similar as well as other quaternary chalcogenide compositions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Pressure-Induced Multidimensional Assembly and Sintering of CuInS 2 Nanoparticles into Lamellar Nanosheets with Band Gap Narrowing

Two-dimensional (2D) nanomaterials have fascinating structural, electrical, and optical properties, especially strong excitonic effects due to decreased dielectric screening. However, constructing 2D ultrathin nanomaterials, with the exception of layered materials, remains a challenge. In this work, we successfully realize oriented attachment on guiding one-dimensional chalcopyrite CuInS 2 nanocrystal (NC) formation and 2D assembly into lamellar nanosheets by applying pressure-driven sintering of zero-dimensional CuInS2 nanoparticles (NPs). We discuss the atomic-level mechanism of such phenomena and illustrate a pressure-driven processing diagram that reveals the sintering process of NPs coordinated by pressure and structural transformation. Optical measurements exhibit that the band gap has a narrowing by 0.21 eV compared with the initial 2.03 eV upon decompression to ambient conditions. Our findings represent a significant step forward in gaining an in-depth understanding of the pressure-driven morphology engineering of nanomaterials and provide a promising strategy to prepare 2D NCs, thereby greatly increasing the choice of materials for various applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Using resonant energy X-ray diffraction to extract chemical order parameters in ternary semiconductors

II–IV–V 2 materials, ternary analogs to III–V materials, are emerging for their potential applications in devices such as LEDs and solar cells. Controlling cation ordering in II–IV–V 2 materials offers the potential to tune properties at nearly fixed compositions and lattice parameters. While tuning properties at a fixed lattice constant through ordering has the potential to be a powerful tool used in device fabrication, cation ordering also creates challenges with characterization and quantification of ordering. In this work, we investigate two different methods to quantify cation ordering in ZnGeP 2 thin films: a stretching parameter calculated from lattice constants , and an order parameter determined from the cation site occupancies ( S ). We use high resolution X-ray diffraction (HRXRD) to determine and resonant energy X-ray diffraction (REXD) to extract S . REXD is critical to distinguish between elements with similar Z -number ( e.g. Zn and Ge). We found that samples with a corresponding to the ordered chalcopyrite structure had only partially ordered S values. The optical absorption onset for these films occurred at lower energy than expected for fully ordered ZnGeP 2 , indicating that S is a more accurate descriptor of cation order than the stretching parameter. Since disorder is complex and can occur on many length scales, metrics for quantifying disorder should be chosen that most accurately reflect the physical properties of interest.

36 MATERIALS SCIENCE↗