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At least 91 records · Page 5

Surface-Induced Deprotonation of Thiol Ligands Impacts the Optical Response of CdS Quantum Dots

Cadmium chalcogenide quantum dots (QDs) passivated by thiol-based ligands exhibit several advantages in their applications in lighting, sensing, and imaging technologies. However, their emission is sensitive to thiol concentrations, pH conditions, and temperatures. Using calculations based on the density functional theory, we identify conditions for thiol/thiolate equilibrium at the CdS QD surface that either eliminate or introduce optically inactive hole trap states favoring or disfavoring the emission. Our calculations indicate much weaker interactions between the QD and protonated species (thiols), compared to their deprotonated counterparts (thiolates). Additionally, the surface of CdS QD facilitates the partial deprotonation of thiols, leading to the formation of an additional stable networking conformation where the proton is shared between the ligand and the QD surface. Thiolates strongly reduce the optical intensity of low-energy transitions in CdS QDs, contributing thiolate-localized hole trap states at the QD band gap. However, networking between the thiols and the surface, as well as the presence of native ligands such as primary amines, stabilize such trap states brightening the lowest optical transitions. This explains the increased emission of thiol-passivated QDs at lower concentrations in neutral or acidic solutions. Surface-mediated bias toward deprotonated species and their contribution to optically inactive states also rationalizes irreversible emission quenching and bleaching in the CdSe/CdS QDs exposed to high temperatures or intensive laser pulse.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vapor-Phase Heteroatom Incorporation into Semiconductive Molecular-Scale Magic-Size Clusters

Magic-size metal chalcogenide clusters of molecular size exhibit well-defined structure and unique properties that might be further expanded with the incorporation or substitution of a second metal. Here, we report the postmodification of magic-size clusters synthesized in polymer thin films via exposure to volatile metal organic precursors commonly utilized for atomic layer deposition. Exposure of In 6 S 6 (CH 3 ) 6 clusters to dimethylcadmium results in exposure-dependent incorporation of Cd 2+ , which extends the optical absorbance of the clusters into the visible spectrum. The mechanism for Cd 2+ incorporation is consistent with Cd 2+ replacement of In 3+ that includes methyl ligand removal to maintain charge neutrality. Even for clusters embedded in a polymer matrix, ligand loss leads to sintering and transformation into larger nanoscale aggregates with zinc blende-type structure. The extent of Cd incorporation can be modulated by varying the process temperature and volatile metal organic exposure as well as the choice of volatile metal organic precursor. A computational thermodynamic analysis of heteroatom incorporation for several metals and chemistries reveals that both the stability of the substituted cluster and the favorability of reaction byproducts jointly determine the favorability of cation incorporation.

atomic layer deposition↗

Quantum oscillations from networked topological interfaces in a Weyl semimetal

Layered transition metal chalcogenides are promising hosts of electronic Weyl nodes and topological superconductivity. MoTe 2 is a striking example that harbors both noncentrosymmetric T d and centrosymmetric T’ phases, both of which have been identified as topologically nontrivial. Applied pressure tunes the structural transition separating these phases to zero temperature, stabilizing a mixed T d –T’ matrix that entails a network of interfaces between the two nontrivial topological phases. Here, we show that this critical pressure range is characterized by distinct coherent quantum oscillations, indicating that the difference in topology between topologically nonvtrivial T d and T’ phases gives rise to an emergent electronic structure: a network of topological interfaces. A rare combination of topologically nontrivial electronic structures and locked-in transformation barriers leads to this counterintuitive situation, wherein quantum oscillations can be observed in a structurally inhomogeneous material. These results further open the possibility of stabilizing multiple topological phases coexisting with superconductivity.

36 MATERIALS SCIENCE↗

Crystalline Order Yet Glass-Like Heat Transport Driven by Hidden Local Distortions as the Structural Origin of Ultralow Thermal Conductivity in AgErTe 2

Given their rich chemical diversity and the interplay among the p-, d-, and f-orbitals of chalcogens, transition metals, and lanthanides, respectively, rare-earth transition-metal chalcogenides exhibit a wide variety of structural, magnetic, and transport phenomena. As a result, they form a particularly appealing platform for investigating structure–property relationships, emergent electronic and magnetic behaviors, and thermal transport. Here we investigate AgErTe 2 as a model system to understand phonon-glass behavior in ordered crystalline solids, which establishes the design principles for thermal barrier coatings and next-generation thermoelectrics. The local bonding asymmetry and lattice softness suppress the inherently low lattice thermal conductivity, resembling the characteristics of amorphous materials. This suppression is significantly influenced by local off-centering of Ag atoms, which breaks lattice periodicity while maintaining global crystallinity. The presence of antibonding states just below the Fermi level, arising from Ag 4d and Te 5p orbital interactions, leads to lattice softening and destabilizes ideal tetrahedral coordination, resulting in a pseudo Jahn–Teller distortion. Furthermore, the coexistence of weaker, more polarizable Ag–Te bonds and stronger Er–Te bonds creates a complex vibrational landscape enriched with low-frequency modes and enhanced phonon scattering. A pronounced disparity in interatomic force constants gives rise to highly localized, low-energy optical phonons linked to Ag rattling. These flat vibrational modes exhibit strong coupling with transverse acoustic phonons, resulting in ultrashort phonon lifetimes and mean free paths approaching interatomic distances. These features collectively enhance phonon scattering across a broad range of length and energy scales. This work offers a framework for engineering suppressed thermal conductivity in crystalline systems without the introduction of alloying elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insulator–metal transition in CrSiTe 3 triggered by structural distortion under pressure

van der Waals solids are well known to host remarkable phase diagrams with competing phases, unusual energy transfer processes, and elusive states of matter. Among this class of materials, chalcogenides have emerged as the most flexible and relevant platforms for unraveling charge–structure–function relationships. In order to explore the properties of complex chalcogenides under external stimuli, we measured the far infrared spectroscopic response of CrSiTe 3 under extreme pressure–temperature conditions. Analysis of the 368 cm –1 Si–Te stretching mode and the manner in which it is screened by the closure of the indirect gap reveals that the insulator–metal transition takes place immediately after the structural phase transition—once the mixed phase aspect of the lattice distortion is resolved. At the same time, the two-phase region associated with the structural transition widens with decreasing temperature, and the slope of the insulator–metal transition under pressure is consistent with increasing entropy. These trends completely revise the character of the temperature–pressure phase diagram as well as the relationship between the structural and insulator–metal transitions, leading to a critical nexus of activity that may hide a quantum critical point and allow superconductivity to emerge.

36 MATERIALS SCIENCE↗

Ultrafine Interwoven Dendritic Cu 2 Se/CuFeSe 2 Composites with Enhanced Thermoelectric Performance

As an effort to develop high-performance and stable copper chalcogenide thermoelectrics, several (1-x)Cu 2 Se/(x)CuFeSe 2 composites were successfully synthesized via a one-step solid-state transformation of CuSe 2 template. Uniform ultrafine dendritic structures consisting of interweaving Cu 2 Se and CuFeSe 2 nanofibers were observed in samples with low Fe content (0.05 ≤ x ≤ 0.1). Increasing the Fe content to x = 0.5 led to phase segregation into Cu 2 Se-rich region with embedded CuFeSe 2 fine structures interwoven with CuFeSe 2 -rich region containing Cu 2 Se nanofibers. The formation of such an entwined dendritic structure is believed to arise from the temperature-dependent solubility of CuFeSe 2 in the Cu 2 Se matrix. The dynamic dissolution of CuFeSe 2 into the Cu 2 Se at high temperatures leads to temperature-dependent doping of the Cu 2 Se matrix, enabling drastic enhancements of thermoelectric power factor at high temperatures. As a result, such a strategy is expected to be a powerful tool for properties modulation in thermoelectric materials.

36 MATERIALS SCIENCE↗

Anisotropic topological surface states in thin-film monoclinic Ag 2 Se

Silver chalcogenide systems have recently attracted significant attention due to their promising topological insulating properties. Here we conducted systematic low-temperature local scanning tunneling microscopy/spectroscopy and first-principles studies on the surface states of monoclinic Ag 2 Se thin films grown using molecular beam epitaxy. Through the use of quasi-particle interference patterns, we have observed evidence for topological surface states on the selenium-terminated surfaces with different types of defect densities. The results of ab initio calculations confirm the existence of nontrivial topological surface states in the monoclinic Ag 2 Se structure, for which such properties have not been previously reported. The energy dispersion determined using voltage-dependent standing wave patterns suggests that these topological states have an anisotropic Dirac cone structure. In conclusion, this discovery may lead to new applications for monoclinic Ag 2 Se in the rapidly growing fields of nanoelectronics and spintronics.

36 MATERIALS SCIENCE↗

Embedding PbS Quantum Dots (QDs) in Pb-Halide Perovskite Matrices: QD Surface Chemistry and Antisolvent Effects on QD Dispersion and Confinement Properties

Hybrid materials of metal chalcogenide colloidal quantum dots (QDs) embedded in metal halide perovskites (MHPs) have led to composites with synergistic properties. Here, we investigate how QD size, surface chemistry, and MHP film formation methods affect the resulting optoelectronic properties of QD/MHP “dot-in-matrix” systems. We monitor the QD absorption and photoluminescence throughout synthesis, ligand exchange, and transfer into the MHP ink, and we characterize the final QD/MHP films via electron microscopy and transient absorption. In addition, we are the first to globally map how PbS QDs are distributed on the micrometer scale within these dot-in-matrix systems, using three-dimensional (3D) tomography time-of-flight secondary ion mass spectrometry. The surface chemistry imparted during synthesis directly affects the optical properties of the dot-in-matrix composites. Pb-halide passivation leads to QD/MHP dot-in-matrix samples with optical properties that are well-described by a theoretical model, based on a Type I finite-barrier heterostructure between the PbS QD and the MHP matrix. Samples without Pb-halide passivation show complicated size-dependent behavior, indicating a transition from a Type I heterostructure between the PbS QD wells and MHP barriers for small-sized QDs to PbS QDs that are electronically decoupled from the MHP matrix for larger QDs. Furthermore, the choice in perovskite antisolvent crystallization method leads to a difference in the spatial QD distribution within the perovskite matrix, differences in carrier lifetime, and photoluminescence shifts of up to 180 meV for PbS in methylammonium lead iodide. This work establishes an understanding of such emerging synergistic systems relevant for technologies such as photovoltaics, infrared emitters and detectors, and other unexplored technological applications.

92 SC - Basic Energy Sciences (BES) (SC-22)↗

Understanding the thermally activated charge transport in NaPb m SbQ m+2 (Q = S, Se, Te) thermoelectrics: weak dielectric screening leads to grain boundary dominated charge carrier scattering

Many thermoelectric materials feature irregular electrical conductivity with thermally activated transport below ~600 K and metallic behavior at high temperatures, despite possessing degenerate carrier concentrations. The suppression of the electrical conductivity ultimately degrades the thermoelectric performance on the cold side and limits the device energy conversion efficiency. As such, establishing the origin of the low temperature scattering and developing strategies to mitigate its effect are paramount issues. To date, the correct microscopic description of the low temperature carrier scattering remains an open issue, and there is little work addressing why some thermoelectric materials are more susceptible to the deleterious behavior. Here, we use the promising thermoelectric alloys of PbQ and NaSbQ 2 (Q = S, Se, Te) as model systems to address these concerns. We directly show the thermally activated transport stems from the scattering of charge carriers by the grain boundaries (GBs), and that the expected metallic electrical conductivity is recovered by preparing large grained samples with reduced densities of GBs. We furthermore study the electrical properties NaPb m SbSe m+2 as a function of NaSbSe 2 fraction, as well as those of the chalcogenide analogues, PbTe–NaSbTe 2 and PbS–NaSbS 2 , and demonstrate that the strength of GB scattering can be understood by utilizing simple chemical principles. By considering the polarizability of the host atoms, we directly relate the magnitude of GB scattering to the relative degree of charge carrier screening in each material, and demonstrate that GB scattering is strongest in the ionic NaSbQ 2 -rich compounds and weakest in more polarizable PbQ-rich phases. We finally show how these chemical arguments elegantly explain the strong GB scattering in numerous other thermoelectric materials. By uniting the deleterious charge transport properties exhibited by many different compounds into a common picture, we discuss how our work gives design principles for proper microstructure engineering in emerging thermoelectric materials.

36 MATERIALS SCIENCE↗

Improving charge transport in integrated MoO 3 /C electrode materials for water-in-salt energy storage systems by incorporating oxygen vacancies

Improvements in the charge storage properties of α-MoO 3 used as an electrode with a 30m ZnCl 2 water-in-salt electrolyte have been achieved by enhancements in electron and ion transport enabled by an inventive synthesis route. Electron transport was improved through the integration of MoO 3 with dopamine-derived carbon via a chemical preintercalation route, and enhanced ion transport was achieved by incorporating oxygen vacancies in MoO 3 structure through ethanol 2 reduction under hydrothermal conditions. Here, the presence of carbon was confirmed by corresponding D and G bands observed in Raman spectroscopy measurements. The presence of oxygen vacancies was proven through correlated XPS, TGA, Raman spectroscopy and XRD analyses, with the introduction of oxygen vacancies leading to an expanded interlayer region. Four-point probe measurements provided evidence of increased electronic conductivity due to the incorporation of carbon, and cyclic voltammetry-based charge storage mechanism analyses revealed increases in ion transport kinetics due to oxygen vacancy formation. Tuning the oxygen vacancy concentration is critical, as excessive concentrations of these point defects leads to structural instability and poor capacity retention. This work demonstrates the combined potential of carbon and oxygen vacancies in moderate concentrations to enhance the charge storage properties of transition metal oxides. The strategies developed in this study offer a path to the development of promising materials for high-rate, high-capacity, and long-duration electrochemical energy storage technologies.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Influence of metal organic framework glasses on thermoelectric properties of AgSb 0.96 Zn 0.04 Te 2 alloy

In recent years, a significant number of chalcogenides-based thermoelectric (TE) materials have been investigated theoretically and experimentally. However, the efficiency of TE materials is often limited by physical and chemical stability issues. Therefore, it is crucial to identify additive materials that can reduce thermal conductivity and improve the efficiency of crystalline TE materials. One well-known approach to lower thermal conductivity is introducing porosity into the material structure, which helps scatter phonon energy. Metal-organic framework (MOF) crystalline materials, known for their porosity and physical and chemical stability, offer unique advantages in TE applications. In this study, we investigate the influence of 20 weight% amorphous Zeolitic Imidazolate Framework (ZIF)-62 to p-type AgSb 0.96 Zn 0.04 Te 2 (ASTZ), a well-known TE material. We synthesized composites, ASTZ, ASTZ-Zn, and ASTZ-Co, by sintering ASTZ with amorphous ZIF-62(Zn) and ZIF-62(Co) respectively. The addition of amorphous ZIF-62(Zn) leads to a significant enhancement in the Seebeck coefficient of ASTZ increasing from 151 µV/K to 229 µV/K at 586K. Moreover, the thermal conductivity of the ASTZ TE materials drops drastically from 0.491 Wm -1 K -1 to around 0.22 Wm -1 K -1 at 623K with the addition of either amorphous ZIF-62(Zn) or ZIF-62(Co). Remarkably, ASTZ containing amorphous ZIF-62(Zn) achieves a maximum thermoelectric figure of merit (zT max ) of approximately 0.078 at 573K, surpassing any MOF-based thermoelectric material reported to date. In conclusion, these findings highlight the potential of amorphous ZIF-62 as an effective additive for enhancing the properties of thermoelectric materials.

36 MATERIALS SCIENCE↗

Ultralow Thermal Conductivity and Thermoelectric Properties of Rb 2 Bi 8 Se 13

Complex bismuth chalcogenides are narrow band gap semiconductors with intrinsic low thermal conductivity, which exhibit high potential as highly efficient thermoelectric materials. Here, we assess the basic thermoelectric properties of polycrystalline Rb 2 Bi 8 Se 13 in the temperature range 300-823 K as well as performance-optimizing strategies. We find that the as-made bulk samples are single phase with the monoclinic crystal structure (P2 1 /m) and crystallize in layer morphology. The pristine sample exhibits an exceedingly low lattice thermal conductivity of 0.6- 0.46 W·m -1 ·K -1 at 300-823 K, which derives from strong lattice anharmonicity, large Grüneisen parameters, and low phonon velocities induced by the complex crystal structure with heavy atom Bi and a large unit cell. Here, the Cl doping successfully enhances the carrier concentration in Rb 2 Bi 8 Se 13 with a negligible impact on the electronic band structure, displaying common doping behaviors. Se vacancy, on the contrary, leads to n-type doping and enhances the effective mass and power factors more significantly. Consequently, a maximum ZT of ~0.75 at 823 K for the 0.3% Se-vacancy-doped sample is obtained.

36 MATERIALS SCIENCE↗

MoS 2 -supported Au 31 for CO hydrogenation: A first-principle study

While the basal plane of single-layer molybdenum disulphide (MoS 2 ) is inert, attempts have been made to functionalize it chemically through the creation of defects and/or addition of dopants. With nanoparticles as dopants, the authors present density functional theory-based calculations of the hydrogenation of CO on a 31-atom, bilayer Au cluster supported on single-layer MoS 2 (Au31/MoS 2 ). Not surprisingly, the adsorption and reaction of all species involved in the hydrogenation occur at the edges of the cluster—the regions at which the interaction between MoS 2 and the Au cluster is tracked to be the strongest. The authors find two possible mechanisms that lead to the formation of methanol: (1) CO* → CHO* → CH 2 O* → CH 3 O* → CH 3 OH* and (2) CO* → CHO* → HCOH* → CH2OH* → CH3OH*, where * indicates the adsorbed species. Detailed analysis of the reaction pathways, however, does not result in favoring one mechanism over the other. Rather, both mechanisms are facile. In addition, the rate-limiting step in each mechanism is found to be the formation of the formyl radical group (CO* + H* → CHO*).

2D materials↗

Band Gap Engineering and Metastable Phase Discovery in Cu 2 BaSnS 4– x Se x Nanocrystals via Topotactic Anion Exchange

Earth-abundant multinary inorganic chalcogenides, such as Cu 2 BaSnS 4–x Se x (CBTSSe), have emerged as promising absorbers for next-generation solar cells. However, accessing colloidal CBTSSe nanocrystals, including metastable polymorphs with more favorable optoelectronic properties, remains a critical synthetic challenge. Herein, we report the first use of topotactic anion exchange to access metastable crystal structures in soft chemistry syntheses. By varying the stoichiometry of selenium precursors, we directly synthesize Cu 2 BaSnS 4–x Se x (0 ≤ x ≤ 4) nanocrystals with a broad band gap tunability of 1.51–2.04 eV. At x = 4, a new metastable trigonal phase of Cu 2 BaSnSe 4 is isolated. This phase arises via an in-situ topotactic anion exchange from sulfur-rich Cu 2 BaSnS 4–x Se x intermediates, while retaining both the cation sublattice and overall nanocrystal morphology. The trigonal Cu 2 BaSnSe 4 exhibits a nearly direct band gap that is 280 meV lower than its thermodynamically stable orthorhombic counterpart, aligning more closely with the optimal band gap for single-junction solar cells. In contrast, a post-synthetic anion exchange route leads to the thermodynamically preferred orthorhombic polymorph, pointing to the critical nature of the in-situ transformation. Our findings open a versatile pathway for both polymorphic and morphological control in colloidal nanocrystals, expanding the synthetic design space for new optoelectronic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultralow Thermal Conductivity, Multiband Electronic Structure and High Thermoelectric Figure of Merit in TlCuSe

The entanglement of lattice thermal conductivity, electrical conductivity, and Seebeck coefficient complicates the process of optimizing thermoelectric performance in most thermoelectric materials. Semiconductors with ultralow lattice thermal conductivities and high power factors at the same time are scarce but fundamentally interesting and practically important for energy conversion. In this work, an intrinsic p-type semiconductor TlCuSe that has an intrinsically ultralow thermal conductivity (0.25 W m -1 K -1 ), a high power factor (11.6 μ W cm -1 K -2 ), and a high figure of merit, ZT (1.9) at 643 K is described. The weak chemical bonds, originating from the filled antibonding orbitals p-d* within the edge-sharing CuSe 4 tetrahedra and long Tl-Se bonds in the PbClF-type structure, in conjunction with the large atomic mass of Tl lead to an ultralow sound velocity. Strong anharmonicity, coming from Tl + lone-pair electrons, boosts phonon-phonon scattering rates and further suppresses lattice thermal conductivity. The multiband character of the valence band structure contributing to power factor enhancement benefits from the lone-pair electrons of Tl + as well, which modify the orbital character of the valence bands, and pushes the valence band maximum off the Gamma-point, increasing the band degeneracy. The results provide new insight on the rational design of thermoelectric materials.

36 MATERIALS SCIENCE↗

Transmission Electron Microscopy Study on the Effect of Thermal and Electrical Stimuli on Ge2Te3 Based Memristor Devices

Memristor devices fabricated using the chalcogenide Ge 2 Te 3 phase change thin films in a metal-insulator-metal structure are characterized using thermal and electrical stimuli in this study. Once the thermal and electrical stimuli are applied, cross-sectional transmission electron microscopy (TEM) and X-ray energy-dispersive spectroscopy (XEDS) analyses are performed to determine structural and compositional changes in the devices. Electrical measurements on these devices showed a need for increasing compliance current between cycles to initiate switching from low resistance state (LRS) to high resistance state (HRS). The measured resistance in HRS also exhibited a steady decrease with increase in the compliance current. High resolution TEM studies on devices in HRS showed the presence of residual crystalline phase at the top-electrode/dielectric interface, which may explain the observed dependence on compliance current. XEDS study revealed diffusion related processes at dielectric-electrode interface characterized, by the separation of Ge 2 Te 3 into Ge- and Te- enriched interfacial layers. This was also accompanied by spikes in O level at these regions. Furthermore, in-situ heating experiments on as-grown thin films revealed a deleterious effect of Ti adhesive layer, wherein the in-diffusion of Ti leads to further degradation of the dielectric layer. This experimental physics-based study shows that the large HRS/LRS ratio below the current compliance limit of 1 mA and the ability to control the HRS and LRS by varying the compliance current are attractive for memristor and neuromorphic computing applications.

Shallcross, Austin↗

Vapor Infiltration Synthesis of Indium Sulfide Magic Size Cluster

The energetically favorable formation of atomically precise clusters, known as magic size clusters, in the solution phase enables a precision nanoscale synthesis with exquisite uniformity. Here, we report the synthesis of magic size clusters via vapor infiltration of atomic layer deposition precursors directly in a polymer thin film. Sequential infiltration of trimethylindium vapor and hydrogen sulfide gas into poly(methyl methacrylate) leads to the formation of clusters with uniform properties consistent with a magic size cluster-In 6 S 6 (CH 3 ) 6 . While an increase in cluster size might be expected with additional sequential infiltration cycles of the reactive In and S precursors, uniform properties consistent with magic size clusters form in multiple polymers under a range of processing conditions. Ultraviolet-visible absorption spectra of In 6 S 6 (CH 3 ) 6 are largely independent of the number of sequential infiltration cycles and exhibit air stability, both of which are attributed to an energetically favorable synthetic pathway that is evaluated with density functional theory.

atomic layer deposition↗

Influence of surface adsorption on MoS 2 memtransistor switching kinetics

Sulfur-deficient polycrystalline two-dimensional (2D) molybdenum disulfide (MoS 2 ) memtransistors exhibit gate-tunable memristive switching to implement emerging memory operations and neuromorphic computing paradigms. Grain boundaries and sulfur vacancies are critical for memristive switching; however, the underlying physical mechanisms are not fully understood. Furthermore, the adsorption of water and gaseous species strongly perturbs electronic transport in monolayer MoS 2 , and little work has been done to explore the influence of surface interactions on defect-related kinetics that produces memristive switching. Here, we study the switching kinetics of back-gated MoS 2 memtransistors using current transient measurements in a controlled atmosphere chamber. Here, we observe that adsorbed water molecules lead to suppression of the electronic trap-filling processes concomitant with the resistive switching process, resulting in altered kinetics of the resistive switching. Additionally, using the transient response from “bunched” drain voltage pulse trains performed as a function of temperature, we extract the energy of the affected trap state and find that it places the trap roughly midgap [E T = E C – 0.7 (±0.4) eV]. Our results highlight the importance of controlling for surface interactions that may affect switching kinetics in 2D memtransistors, synaptic transistors, and related memory devices.

36 MATERIALS SCIENCE↗