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DOE OSTI2021

In situ inorganic conductive network formation in high-voltage single-crystal Ni-rich cathodes

High nickel content in LiNi x Co y Mn z O 2 (NCM, x ≥ 0.8, x + y + z = 1) layered cathode material allows high specific energy density in lithium-ion batteries (LIBs). However, Ni-rich NCM cathodes suffer from performance degradation, mechanical and structural instability upon prolonged cell cycling. Although the use of single-crystal Ni-rich NCM can mitigate these drawbacks, the ion-diffusion in large single-crystal particles hamper its rate capability. Herein, we report a strategy to construct an in situ Li 1.4 Y 0.4 Ti 1.6 (PO 4 ) 3 (LYTP) ion/electron conductive network which interconnects single-crystal LiNi 0.88 Co 0.09 Mn 0.03 O 2 (SC-NCM88) particles. The LYTP network facilitates the lithium-ion transport between SC-NCM88 particles, mitigates mechanical instability and prevents detrimental crystalline phase transformation. When used in combination with a Li metal anode, the LYTP-containing SC-NCM88-based cathode enables a coin cell capacity of 130 mAh g -1 after 500 cycles at 5 C rate in the 2.75-4.4 V range at 25 °C. Tests in Li-ion pouch cell configuration (i.e., graphite used as negative electrode active material) demonstrate capacity retention of 85% after 1000 cycles at 0.5 C in the 2.75-4.4 V range at 25 °C for the LYTP-containing SC-NCM88-based positive electrode.

25 ENERGY STORAGE↗

DOE OSTI2023

Crystal Growth and Characterization of Europium-Doped Rubidium Calcium Bromide Scintillators

National security strategies like gamma spectroscopy and high-energy X-ray radiography are limited, in part, by the scintillator used, prompting research into novel materials with improved properties. In this paper, Eu 2+ activated rubidium calcium bromide scintillators were grown via the vertical Bridgman method with a range of dopant concentrations. Light yield, energy resolution, and the afterglow of Rb 4 CaBr 6 :Eu and RbCaBr 3 :Eu improved with increasing Eu 2+ concentration, and scintillation decay time increased. The highest light yields of Rb 4 CaBr 6 :Eu and RbCaBr 3 :Eu were 71000 and 45000 ph/MeV, respectively.

36 MATERIALS SCIENCE↗

NASA NTRS1999

Innovative, Inexpensive Etching Technique Developed for Polymer Electro- Optical Structures

Electro-optic, polymer-based integrated optic devices for high-speed communication and computing applications offer potentially significant advantages over conventional inorganic electro-optic crystals. One key area of integrated optical technology--primary processing and fabrication--may particularly benefit from the use of polymer materials. However, as efforts concentrate on the miniaturization of electro-integrated circuit pattern geometries, the ability to etch fine features and smoothly sloped sidewalls is essential to make polymers useful for electro-integrated circuit applications. There are many existing processes available to etch polymer materials, but they all yield nearly vertical sidewalls. Vertical sidewalls are too difficult to reliably cover with a metal layer, and incomplete metalization degrades microwave performance, particularly at high frequency. However, obtaining a very sloped sidewall greatly improves the deposition of metal on the sidewall, leading to low-loss characteristics, which are essential to integrating these devices in highspeed electro-optic modulators. The NASA Lewis Research Center has developed in-house an inexpensive etching technique that uses a photolithography method followed by a simple, wet chemical etching process to etch through polymer layers. In addition to being simpler and inexpensive, this process can be used to fabricate smoothly sloped sidewalls by using a commercial none rodible mask: Spin-On-Glass. A commercial transparent material, Spin-On-Glass, uses processes and equipment similar to that for photoresist techniques.

Nguyen, Hung D.↗

DOE OSTI2024

Study of electro-physical properties of CsPbBr3 perovskite single crystals

Methods have been developed for the synthesis and growth of lead halide perovskites CsPbBr3, which can be used as detectors of optical, X-ray and gamma-radiation. Single crystals of these compounds were grown by the Bridgman method. The melt temperature was 580 °C, the gradient at the crystallization front was 5 K/cm, and the ampoule lowering speed was 3 mm/hour. In this work, the electro-physical properties of the inorganic perovskite CsPbBr3 were investigated. Crystals for research were cut from the beginning and end of the ingot. The optical absorption spectra were measured depending on the crystal thickness and temperature, the differential resistivity dif and the product  were determined from the I-V characteristics. It was established that dif practically does not change for samples made from the beginning and the end of the ingot, and is dif  21010 Ωcm at 100 V and 293 K.

Sklyarchuk, V.↗

DOE OSTI2023

Ultrahigh‐Flux X‐ray Detection by a Solution‐Grown Perovskite CsPbBr 3 Single‐Crystal Semiconductor Detector

Abstract Solution‐processed perovskites are promising for hard X‐ray and gamma‐ray detection, but there are limited reports on their performance under extremely intense X‐rays. Here, a solution‐grown all‐inorganic perovskite CsPbBr 3 single‐crystal semiconductor detector capable of operating at ultrahigh X‐ray flux of 10 10 photons s −1 mm −2 is reported. High‐quality solution‐grown CsPbBr 3 single crystals are fabricated into detectors with a Schottky diode structure of eutectic gallium indium/CsPbBr 3 /Au. A high reverse‐bias voltage of 1000 V (435 V mm − 1 ) can be applied with a small and stable dark current of ≈60–70 nA (≈9–10 nA mm − 2 ), which enables a high sensitivity larger than 10 000 µC Gy air −1 cm − 2 and a simultaneous low detection limit of 22 nGy air s − 1 . The CsPbBr 3 semiconductor detector shows an excellent photocurrent linearity and reproducibility under 58.61 keV synchrotron X‐rays with flux from 10 6 to 10 10 photons s − 1 mm − 2 . Defect characterization by thermally stimulated current spectroscopy shows a similar low defect density of a synchrotron X‐ray and a lab X‐ray irradiated device. Solid‐state nuclear magnetic resonance spectroscopy suggests that the excellent performance of the solution‐grown CsPbBr 3 single crystal may be associated with its good short‐range order, comparable to the spectrometer‐grade melt‐grown CsPbBr 3 .

Pan, Lei↗

DOE OSTI2021

Metal Halide Scaffolded Assemblies of Organic Molecules with Enhanced Emission and Room Temperature Phosphorescence

Ionically bonded organic metal halide hybrids have emerged as versatile multicomponent material systems exhibiting unique and useful properties. The unlimited combinations of organic cations and metal halides lead to the tremendous structural diversity of this class of materials, which could unlock many undiscovered properties of both organic cations and metal halides. Here we report the synthesis and characterization of a series benzoquinolinium (BZQ) metal halides with a general formula (BZQ)Pb 2 X 5 (X = Cl, Br), in which metal halides form a unique two-dimensional (2D) structure. These BZQ metal halides are found to exhibit enhanced photoluminescence and stability as compared to the pristine BZQ halides, due to the scaffolding effects of 2D metal halides. Optical characterizations and theoretical calculations reveal that BZQ + cations are responsible for the emissions in these hybrid materials. Changing the halide from Cl to Br introduces heavy atom effects, resulting in yellow room temperature phosphorescence (RTP) from BZQ + cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2001

Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

Day, Delbert E.↗

NASA NTRS2003

Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

This flight definition project has the specific objective of investigating the kinetics of nucleation and crystal growth in high temperature inorganic oxide, glass forming melts in microgravity. It is related to one1 of our previous NASA projects that was concerned with glass formation for high temperature containerless melts in microgravity. The previous work culminated in two experiments which were conducted aboard the space shuttle in 1983 and 1985 and which consisted of melting (at 1500 C) and cooling levitated 6 to 8 mm diameter spherical samples in a Single Axis Acoustic Levitator (SAAL) furnace. Compared to other types of materials, there have been relatively few experiments, 6 to 8, conducted on inorganic glasses in space. These experiments have been concerned with mass transport (alkali diffusion), containerless melting, critical cooling rate for glass formation, chemical homogeneity, fiber pulling, and crystallization of glass forming melts. One of the most important and consistent findings in all of these experiments has been that the glasses prepared in microgravity are more resistant to crystallization (better glass former) and more chemically homogeneous than equivalent glasses made on earth (1g). The chemical composition of the melt appears relatively unimportant since the same general results have been reported for oxide, fluoride and chalcogenide melts. These results for space-processed glasses have important implications, since glasses with a higher resistance to crystallization or higher chemical homogeneity than those attainable on earth can significantly advance applications in areas such as fiber optics communications, high power laser glasses, and other photonic devices where glasses are the key functional materials. The classical theories for nucleation and crystal growth for a glass or melt do not contain any parameter that is directly dependent upon the g-value, so it is not readily apparent why glasses prepared in microgravity should be more resistant to crystallization than equivalent glasses prepared on earth. Similarly, the gravity-driven convection in a fluid melt is believed to be the primary force field that is responsible for melt homogenization on earth. Thus, it is not obvious why a glass prepared in space, where gravity-driven convection is ideally absent, would be more chemically homogeneous than a glass identically prepared on earth. The primary objective of the present research is to obtain experimental data for the nucleation rate and crystal growth rate for a well characterized silicate melt (lithium disilicate) processed entirely in space (low gravity) and compare these rates with the nucleation and crystal growth rates for a similar glass prepared identically on earth (1g).

Day, Delbert E.↗

DOE OSTI2020

Single crystal structure, vibrational spectroscopy, gas sorption and antimicrobial properties of a new inorganic acidic diphosphates material (NH 4 ) 2 Mg(H 2 P 2 O 7 ) 2 • 2 H 2 O

We report on the successful synthesis of diammonium magnesium dihydrogendiphosphate (V) dihydrate compound (NH 4 ) 2 Mg(H 2 P 2 O 7 ) 2 •2H 2 O using a wet chemical route. Single crystal X-ray diffraction analysis and micro Raman spectroscopy are employed to characterize the compound. We demonstrate, using a multidisciplinary approach, that this compound is ideal for carbon dioxide (CO 2 ) capture in addition to other anthropogenic gasses. We show here -from both an experimental as well as from a density functional theory (DFT) calculations routes- the potential for adopting this compound into domestic air-conditioning units (ACUs). From these experiments, the resistance to bacterial growth is also investigated, which is critical for the adoption of this compound in ACUs. Our compound exhibits a higher methane (CH 4 ) sorptivity as compared to CO 2 at 25 °C and 45 °C under pressures up to 50 bars. Furthermore, DFT electronic structure calculations are used to compute the main structural and electronic properties of the compound, taking into consideration the characteristics of the identified pores as a function of the progressive CO 2 vs. CH 4 loadings. Finally, the antibacterial assay reveals a strong antibacterial activity against the tested Gram-positive and Gram-negative bacteria, with a large zone of inhibition against the tested E. Coli, S. Aureus and K. Pneumonia

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Demonstration of Energy-Resolved γ-Ray Detection at Room Temperature by the CsPbCl 3 Perovskite Semiconductor

The detection of gamma-rays at room temperature with high-energy resolution using semiconductors is one of the most challenging applications. The presence of even the smallest amount of defects is sufficient to kill the signal generated from gamma-rays which makes the availability of semiconductors detectors a rarity. Lead halide perovskite semiconductors exhibit unusually high defect tolerance leading to outstanding and unique optoelectronic properties and are poised to strongly impact applications in photoelectric conversion/detection. Here we demonstrate for the first time that large size single crystals of the all-inorganic perovskite CsPbCl 3 semiconductor can function as a high-performance detector for gamma-ray nuclear radiation at room temperature. CsPbCl 3 is a wide-gap semiconductor with a bandgap of 3.03 eV and possesses a high effective atomic number of 69.8. We identified the two distinct phase transitions in CsPbCl 3 , from cubic (Pm-3m) to tetragonal (P4/mbm) at 325 K and finally to orthorhombic (Pbnm) at 316 K. Despite crystal twinning induced by phase transitions, CsPbCl 3 crystals in detector grade can be obtained with high electrical resistivity of similar to 1.7 X 10 9 Ω∙cm. The crystals were grown from the melt with volume over several cubic centimeters and have a low thermal conductivity of 0.6 W m -1 K -1 . The mobilities for electron and hole carriers were determined to similar to 30 cm 2 /(V s). Using photoemission yield spectroscopy in air (PYSA), we determined the valence band maximum at 5.66 +/- 0.05 eV. Under gamma-ray exposure, our Schottky-type planar CsPbCl 3 detector achieved an excellent energy resolution (similar to 16% at 122 keV) accompanied by a high figure-of-merit hole mobility-lifetime product (3.2 x 10 -4 cm 2 /V) and a long hole lifetime (16 mu s). The results demonstrate considerable defect tolerance of CsPbCl 3 and suggest its strong potential for gamma-radiation and X-ray detection at room temperature and above.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Rb 4 CuSb 2 Cl 11 and Rb 2 In 0.91(0.2) Sb 0.09 Cl 5 ·H 2 O: Wide Band Gap 0D Metal Halide Semiconductors

Herein, we report the discovery, structural and photophysical characterization of a new zero-dimensional (0D) lead-free all-inorganic halide, Rb 4 CuSb 2 Cl 11 , which adopts a new structure type. Single-crystal X-ray diffraction (SCXRD) shows that the structure consists of isolated, distorted seesaw [SbCl 4 ] − and trigonal planar [CuCl 3 ] 2− units, separated by Rb + cations that provide charge balance. Optoelectronic measurements and density functional theory (DFT) calculations indicate an indirect band gap of 2.89 eV, making it a candidate for wide-bandgap optoelectronic applications. Electrical resistivity was measured at 1.29 × 10 10 Ω·cm, and the trap-state density (n trap ) was found to be 7.44 × 10 10 cm −3 . Attempts to synthesize substitution analogs of Rb 4 CuSb 2 Cl 11 led to the synthesis of Rb 2 In 0.91(0.2) Sb 0.09 Cl 5 ·H 2 O, which was erroneously reported as Rb 2 SbCl 5 O in a previous study. Rb 2 In 0.91(0.2) Sb 0.09 Cl 5 ·H 2 O adopts a vacancyordered perovskite structure and exhibits broad-band yellow emission under UV excitation. The measured photoluminescence quantum yield (PLQY) for Rb 2 In 0.91 (0.2)Sb 0.09 Cl 5 ·H 2 O is 18.2%. These findings add to the growing class of quaternary metal halides with multiple cation and anion compositions, expanding the chemical phase space for the discovery of new materials with functional properties.

Crystal structure↗

DOE OSTI2024

Coupled Gel/Seeded Growth of Cs2AgBiBr6 Single Crystals for Radiation Detection

Abstract— The all-inorganic lead free Cs2AgBiBr6 perovskite represents a highly promising environment-friendly radiation detector material. The first attempt to grow Cs2AgBiBr6 single crystals using the unique gel growth method is reported in this study. This technique enables controlled reagent diffusion in a gel medium at room temperature, fostering the growth of visible single crystals. It offers advantages over conventional methods, leading to fewer equilibrium and non-equilibrium defects and simplified execution. Interestingly, the as-grown crystals exhibited variations in size and colors within the gel matrix, indicating the influence of Bi solutes in Bi-poor and Bi-rich Cs2AgBiBr6 crystals. Once the crystals were confirmed by powder xray diffraction, a series of comprehensive material characterizations was performed. The resistivity of Cs2AgBiBr6 single crystals was measured at 1.12x107 Ω•cm. Trap density analysis yielded a value of 2.82 x1010 cm-3. The charge carrier mobility was determined to be 32.9 cm2V-1S-1, suggesting the suitability for radiation detector applications. Additional growth optimization is going on and further characterization will be reported during the presentation. Our work helps accelerate the development of lead-free perovskite materials toward radiation detector applications.

James, Ralph B.↗

NASA NTRS1991

Interpretation of DTA experiments used for crystal nucleation rate determinations

An analysis is presented of two schemes which have been proposed for the determination of the temperature dependence of homogeneous crystal nucleation rates in glasses via DTA measurements. The first method is based upon the postulate that the inverse of the temperature at which the DTA crystallization rate is maximum, will increase monotonically as the number density of nucleated particles increases. The secone method is based on the observation that the intensity at T(p) (peak height) increases as T(p) grows. The validity of both of these methods is assessed for inorganic glasses for two specific crystal growth models.

Weinberg, Michael C.↗

DOE OSTI2021

Multicolor Photonic Pigments for Rotation-Asymmetric Mechanochromic Devices

Photonic crystals are extensively explored to replace inorganic pigments and organic dyes as coloring elements in printing, painting, sensing, and anti-counterfeiting due to their brilliant structural colors, chemical stability, and environmental friendliness. However, most existing photonic-crystal-based pigments can only display monochromatic colors once made, and generating multicolors has to start with designing different building blocks. In this work, a novel photonic pigment featuring highly tunable structural colors in the entire visible spectrum, made by the magnetic assembly of monodisperse nanorods into body-centered-tetragonal photonic crystals, is reported. Their prominent magnetic and crystal anisotropy makes it efficient to generate multicolors using one photonic pigment by magnetically controlling the crystal orientation. Further, the combination of angle-dependent diffraction and magnetic orientation control enables the design of rotation-asymmetric photonic films that display distinct patterns and encrypted information in response to rotation. The efficient multicolor generation through precise orientational control makes this novel photonic pigment promising in developing high-performance structural-colored materials and optical devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

The mechanism driving a solid–solid phase transition in a biomacromolecular crystal

A solid-solid phase transition (SSPT) occurs between distinguishable crystalline forms. Because of its importance in application and theory in material science and condensed matter physics, SSPT has been studied most extensively in metallic alloys, inorganic salt or small organic molecular crystals, but much less so in biomacromolecular crystals. In general, the mechanism of SSPT at atomic and molecular levels is not well understood. Here, we describe the ordered molecular rearrangements in biomacromolecular crystals of the adenine riboswitch (riboA) aptamer using real-time serial crystallography and solution atomic force microscopy (AFM). The large, ligand-induced conformational changes drive the initial phase transition from the apo unit cell (AUC) to the trans unit cell 1 (TUC1). During this transition, coaxial stacking of P1 duplexes becomes the dominant packing interface, whereas P2-P2 interactions are almost completely disrupted, resulting in “floating” layers of molecules. The coupling points in TUC1 and their local conformational flexibility allow the molecules to reorganize to achieve the more densely packed and energetically favorable bound unit cell (BUC). Our study thus reveals the interplay between the conformational changes and the crystal phases—the underlying mechanism that drives the phase transition. Using polarized video microscopy (PVM) to monitor the SSPT in small crystals at high ligand concentration, we have identified the time window during which the major conformational changes take place, and simulated the in crystallo kinetics. Together, these results provide the spatiotemporal information necessary for informing time-resolved crystallography (TRX) experiments. Moreover, this study illustrates a practical approach to characterize SSPT in transparent crystals.

36 MATERIALS SCIENCE↗

NASA NTRS2008

New Techniques in Characterization of Ferroelectric Materials

Two new techniques have been developed to characterize Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) based ferroelectric single crystals: (i) electro-thermal imaging, and (ii) single crystal x-ray diffraction in the transmission mode. (i) Electro-thermal imaging is a remote sensing technique that can detect the polarization direction and poling state of a whole crystal slice. This imaging technique utilizes an IR camera to determine the field induced temperature change and does not require any special or destructive sample preparation. In the resulting images it is possible to distinguish regions of 180 deg domains. This powerful technique can be used remotely during poling to determine the poling state of the crystal to avoid over-poling that can result in inferior properties and/or cracking of the crystals. Electro-thermal imaging produced the first direct observations of polarization rotation. Under bipolar field, the domains near the corners were the first to switch direction. As the field increased above the coercive field, domains at the center part of the crystals switched direction. (ii) X-ray diffraction in the transmission mode has long been used in structure determination of organic crystals and proteins; however, it is not used much to characterize inorganic systems. 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 single crystals were examined by this XRD technique for the first time, and a never-before-seen super-lattice was revealed with a doubling of the unit cell in all three directions, giving a cell volume eight times that of a traditional perovskite unit cell. The significance of the super-lattice peaks increased with poling, indicating a structural contribution to ordering. Lack of such observations by electron diffraction in the transmission electron microscope examinations suggests the presence of a bulk effect.

Sehirlioglu, Alp↗

DOE OSTI2021

Remarkably Weak Anisotropy in Thermal Conductivity of Two-Dimensional Hybrid Perovskite Butylammonium Lead Iodide Crystals

Two-dimensional (2D) hybrid organic-inorganic perovskites consisting of alternating organic and inorganic layers are a new class of layered structures. They have attracted increasing interest for photovoltaic, optoelectronic, and thermoelectric applications, where knowing their thermal transport properties is critical. In this study, we carry out both experimental and computational studies on thermal transport properties of 2 D butylammonium lead iodide crystals and find their thermal conductivity is ultralow (below 0.3 W m( -1 ) K -1 ) with very weak anisotropy (around 1.5) among layered crystals. Further analysis reveals that the unique structure with the preferential alignment of organic chains and complicated energy landscape leads to moderately smaller phonon lifetimes in the out-of-plane direction and comparable phonon group velocities in in-plane and out-of-plane directions. These new findings may guide the future design of novel hybrid materials with desired thermal conductivity for various applications.

2D hybrid perovskite↗

DOE OSTI2021

High-efficiency perovskite photovoltaic modules achieved via cesium doping

Perovskite solar modules have been attracting increasing attention due to their market potential, yet publications concerned with theintrinsic scale-up potential of different perovskite compositions remain relatively scarce. On the other hand, while great success is being made towards improving the power conversion efficiency (PCE) of perovskite solar cells (PSCs) by cesium cation (Cs + ) doping of the perovskite, more attention is being paid to the perovskite phase stabilization effect of Cs + doping, and less to other properties that are critical to understand and futher improve the PSC's. In this work, moderately-Cs-doped MAPbI 3 was employed as a model perovskite material in order to exclude the phase stabilization effect. Our systematic study revealed the influence of Cs + in organic-inorganic hybrid perovskites on the crystal structure, crystallization process, trap state density, band structure and charge (i.e., ions or photo-carriers) transport. Markedly, it has been observed that Cs + doping can greatly increase the carrier diffusion length in the perovskite films, thus improving the potential to scale-up PSC's.The PCE of small area devices (0.09 cm 2 ) was increased to 21.72% from 19.73%, with decreased hysteresis behavior and increased operational stability (T85 = 1000 h) after Cs + doped, where T85 refers to the retention of 85% of the initial PCE. Moreover, a PCE of 21.08% was obtained for a Cs + -containing perovskite module with an active area > 30 cm 2 , which demonstrates a better "reproducibility" than the reference sample (MAPbI3-based perovskite modules, PCE = 18.26%).

14 SOLAR ENERGY↗