Metal-Solvent Complex Formation at the Surface of InP Colloidal Quantum Dots.

The surface chemistry of colloidal semiconductor nanocrystals (QDs) profoundly influences their physical and chemical attributes. The insulating organic shell ensuring colloidal stability impedes charge transfer, thus limiting optoelectronic applications. Exchanging these ligands with shorter inorganic ones enhances charge mobility and stability, which is pivotal for using these materials as active layers for LEDs, photodetectors, and transistors. Among those, InP QDs also serve as a model for surface chemistry investigations. This study focuses on group III metal salts as inorganic ligands for InP QDs. We explored the ligand exchange mechanism when metal halide, nitrate, and perchlorate salts of group III (Al, In Ga), common Lewis acids, are used as ligands for the conductive inks. Moreover, we compared the exchange mechanism for two starting model systems: InP QDs capped with myristate and oleylamine as X- and L-type native organic ligands, respectively. We found that all metal halide, nitrate, and perchlorate salts dissolved in polar solvents (such as n-methylformamide, dimethylformamide, dimethyl sulfoxide, H2O) with various polarity formed metal-solvent complex cations [M(Solvent)6]3+ (e.g., [Al(MFA)6]3+, [Ga(MFA)6]3+, [In(MFA)6]3+), which passivated the surface of InP QDs after the removal of the initial organic ligand. All metal halide capped InP/[M(Solvent)6]3+ QDs show excellent colloidal stability in polar solvents with high dielectric constant even after 6 months in concentrations up to 74 mg/mL. Our findings demonstrate the dominance of dissociation-complexation mechanisms in polar solvents, ensuring colloidal stability. This comprehensive understanding of InP QD surface chemistry paves the way for exploring more complex QD systems such as InAs and InSb QDs.

Disorder and Halide Distributions in Cesium Lead Halide Nanocrystals as Seen by Colloidal 133Cs Nuclear Magnetic Resonance Spectroscopy.

Colloidal nuclear magnetic resonance (cNMR) spectroscopy on inorganic cesium lead halide nanocrystals (CsPbX3 NCs) is found to serve for noninvasive characterization and quantification of disorder within these structurally soft and labile particles. In particular, we show that 133Cs cNMR is highly responsive to size variations from 3 to 11 nm or to altering the capping ligands on the surfaces of CsPbX3 NCs. Distinct 133Cs signals are attributed to the surface and core NC regions. Increased heterogeneous broadening of 133Cs signals, observed for smaller NCs as well as for long-chain zwitterionic capping ligands (phosphocholines, phosphoethanol(propanol)amine, and sulfobetaines), can be attributed to more significant surface disorder and multifaceted surfaces (truncated cubes). On the contrary, capping with dimethyldidodecylammonium bromide (DDAB) successfully reduces signal broadening owing to better surface passivation and sharper (001)-bound cuboid shape. DFT calculations on various sizes of NCs corroborate the notion that the surface disorder propagates over several octahedral layers. 133Cs NMR is a sensitive probe for studying halide gradients in mixed Br/Cl NCs, indicating bromide-rich surfaces and chloride-rich cores. On the contrary, mixed Br/I NCs exhibit homogeneous halide distributions.

Unblocking Ion-occluded Pore Channels in Poly(triazine imide) Framework for Proton Conduction.

Poly(triazine imide) or PTI is an ordered graphitic carbon nitride hosting Å-scale pores attractive for selective molecular transport. AA'-stacked PTI layers are synthesized by ionothermal route during which ions occupy the framework and occlude the pores. Synthesis of ion-free PTI hosting AB-stacked layers has been reported, however, pores in this configuration are blocked by the neighboring layer. The unavailability of open pore limits application of PTI in molecular transport. Herein, we demonstrate acid treatment for ion depletion which maintains AA' stacking and results in open pore structure. We provide first direct evidence of ion-depleted open pores by imaging with the atomic resolution using integrated differential phase-contrast scanning transmission electron microscopy. Depending on the extent of ion-exchange, AA' stacking with open channels and AB stacking with closed channels are obtained and imaged for the first time. The accessibility of open channels is demonstrated by enhanced proton transport through ion depleted PTI.

Nanosegregation in arene-perfluoroarene π-systems for hybrid layered Dion-Jacobson perovskites.

Layered hybrid perovskites are based on organic spacers separating hybrid perovskite slabs. We employ arene and perfluoroarene moieties based on 1,4-phenylenedimethylammonium (PDMA) and its perfluorinated analogue (F-PDMA) in the assembly of hybrid layered Dion-Jacobson perovskite phases. The resulting materials are investigated by X-ray diffraction, UV-vis absorption, photoluminescence, and solid-state NMR spectroscopy to demonstrate the formation of layered perovskite phases. Moreover, their behaviour was probed in humid environments to reveal nanoscale segregation of layered perovskite species based on PDMA and F-PDMA components, along with enhanced stabilities of perfluoroarene systems, which is relevant to their application.

Vanadium complexes with N-heterocyclic vinylidene ligands.

The preparation and the structural characterization of vanadium complexes with terminal and bridging N-heterocyclic vinylidene ligands is reported. The synthesis of the complexes was enabled by utilization of diazoolefins as ligand precursors. Structural data and theoretical results show that N-heterocyclic vinylidenes can act as 6e- donor ligands, leading to strong metal-carbon interactions.

Enhanced Room-Temperature Ionic Conductivity of NaCB11H12 via High-Energy Mechanical Milling.

The body-centered cubic (bcc) polymorph of NaCB11H12 has been stabilized at room temperature by high-energy mechanical milling. Temperature-dependent electrochemical impedance spectroscopy shows an optimum at 45-min milling time, leading to an rt conductivity of 4 mS cm-1. Mechanical milling suppresses an order-disorder phase transition in the investigated temperature range. Nevertheless, two main regimes can be identified, with two clearly distinct activation energies. Powder X-ray diffraction and 23Na solid-state NMR reveal two different Na+ environments, which are partially occupied, in the bcc polymorph. The increased number of available sodium sites w.r.t. ccp polymorph raises the configurational entropy of the bcc phase, contributing to a higher ionic conductivity. Mechanical treatment does not alter the oxidative stability of NaCB11H12. Electrochemical test on a symmetric cell (Na|NaCB11H12|Na) without control of the stack pressure provides a critical current density of 0.12 mA cm-2, able to fully charge/discharge a 120 mA h g-1 specific capacity positive electrode at the rate of C/2.

Solid-State NMR and NQR Spectroscopy of Lead-Halide Perovskite Materials.

Two- and three-dimensional lead-halide perovskite (LHP) materials are novel semiconductors that have generated broad interest owing to their outstanding optical and electronic properties. Characterization and understanding of their atomic structure and structure-property relationships are often nontrivial as a result of the vast structural and compositional tunability of LHPs as well as the enhanced structure dynamics as compared with oxide perovskites or more conventional semiconductors. Nuclear magnetic resonance (NMR) spectroscopy contributes to this thrust through its unique capability of sampling chemical bonding element-specifically (1/2H, 13C, 14/15N, 35/37Cl, 39K, 79/81Br, 87Rb, 127I, 133Cs, and 207Pb nuclei) and locally and shedding light onto the connectivity, geometry, topology, and dynamics of bonding. NMR can therefore readily observe phase transitions, evaluate phase purity and compositional and structural disorder, and probe molecular dynamics and ionic motion in diverse forms of LHPs, in which they can be used practically, ranging from bulk single crystals (e.g., in gamma and X-ray detectors) to polycrystalline films (e.g., in photovoltaics, photodetectors, and light-emitting diodes) and colloidal nanocrystals (e.g., in liquid crystal displays and future quantum light sources). Herein we also outline the immense practical potential of nuclear quadrupolar resonance (NQR) spectroscopy for characterizing LHPs, owing to the strong quadrupole moments, good sensitivity, and high natural abundance of several halide nuclei (79/81Br and 127I) combined with the enhanced electric field gradients around these nuclei existing in LHPs as well as the instrumental simplicity. Strong quadrupole interactions, on one side, make 79/81Br and 127I NMR rather impractical but turn NQR into a high-resolution probe of the local structure around halide ions.

Bulk and Nanocrystalline Cesium Lead-Halide Perovskites as Seen by Halide Magnetic Resonance.

Lead-halide perovskites increasingly mesmerize researchers because they exhibit a high degree of structural defects and dynamics yet nonetheless offer an outstanding (opto)electronic performance on par with the best examples of structurally stable and defect-free semiconductors. This highly unusual feature necessitates the adoption of an experimental and theoretical mindset and the reexamination of techniques that may be uniquely suited to understand these materials. Surprisingly, the suite of methods for the structural characterization of these materials does not commonly include nuclear magnetic resonance (NMR) spectroscopy. The present study showcases both the utility and versatility of halide NMR and NQR (nuclear quadrupole resonance) for probing the structure and structural dynamics of CsPbX3 (X = Cl, Br, I), in both bulk and nanocrystalline forms. The strong quadrupole couplings, which originate from the interaction between the large quadrupole moments of, e.g., the 35Cl, 79Br, and 127I nuclei, and the local electric-field gradients, are highly sensitive to subtle structural variations, both static and dynamic. The quadrupole interaction can resolve structural changes with accuracies commensurate with synchrotron X-ray diffraction and scattering. It is shown that space-averaged site-disorder is greatly enhanced in the nanocrystals compared to the bulk, while the dynamics of nuclear spin relaxation indicates enhanced structural dynamics in the nanocrystals. The findings from NMR and NQR were corroborated by ab initio molecular dynamics, which point to the role of the surface in causing the radial strain distribution and disorder. These findings showcase a great synergy between solid-state NMR or NQR and molecular dynamics simulations in shedding light on the structure of soft lead-halide semiconductors.

Lead-Halide Scalar Couplings in 207Pb NMR of APbX3 Perovskites (A = Cs, Methylammonium, Formamidinium; X = Cl, Br, I).

Understanding the structure and dynamics of newcomer optoelectronic materials - lead halide perovskites APbX3 [A = Cs, methylammonium (CH3NH3+, MA), formamidinium (CH(NH2)2+, FA); X = Cl, Br, I] - has been a major research thrust. In this work, new insights could be gained by using 207Pb solid-state nuclear magnetic resonance (NMR) spectroscopy at variable temperatures between 100 and 300 K. The existence of scalar couplings 1JPb-Cl of ca. 400 Hz and 1JPb-Br of ca. 2.3 kHz could be confirmed for MAPbX3 and CsPbX3. Diverse and fast structure dynamics, including rotations of A-cations, harmonic and anharmonic vibrations of the lead-halide framework and ionic mobility, affect the resolution of the coupling pattern. 207Pb NMR can therefore be used to detect the structural disorder and phase transitions. Furthermore, by comparing bulk and nanocrystalline CsPbBr3 a greater structural disorder of the PbBr6-octahedra had been confirmed in a nanoscale counterpart, not readily captured by diffraction-based techniques.

Colloidal-ALD-Grown Core/Shell CdSe/CdS Nanoplatelets as Seen by DNP Enhanced PASS-PIETA NMR Spectroscopy.

Ligand exchange and CdS shell growth onto colloidal CdSe nanoplatelets (NPLs) using colloidal atomic layer deposition (c-ALD) were investigated by solid-state nuclear magnetic resonance (NMR) experiments, in particular, dynamic nuclear polarization (DNP) enhanced phase adjusted spinning sidebands-phase incremented echo-train acquisition (PASS-PIETA). The improved sensitivity and resolution of DNP enhanced PASS-PIETA permits the identification and study of the core, shell, and surface species of CdSe and CdSe/CdS core/shell NPLs heterostructures at all stages of c-ALD. The cadmium chemical shielding was found to be proportionally dependent on the number and nature of coordinating chalcogen-based ligands. DFT calculations permitted the separation of the the 111/113Cd chemical shielding into its different components, revealing that the varying strength of paramagnetic and spin-orbit shielding contributions are responsible for the chemical shielding trend of cadmium chalcogenides. Overall, this study points to the roughening and increased chemical disorder at the surface during the shell growth process, which is not readily captured by the conventional characterization tools such as electron microscopy.

Zeolite-Templated Carbon as the Cathode for a High Energy Density Dual-Ion Battery.

Dual-ion batteries (DIBs) are electrochemical energy storage devices that operate by the simultaneous participation of two different ion species at the anode and cathode and rely on the use of an electrolyte that can withstand the high operation potential of the cathode. Under such conditions at the cathode, issues associated with the irreversible capacity loss and the formation of solid-electrolyte interphase at the surface of highly porous electrode materials are far less significant than at lower potentials, permitting the exploration of high surface area, permanently porous framework materials as effective charge storage media. This concept is investigated herein by employing zeolite-templated carbon (ZTC) as a cathode in a dual-ion battery based on a potassium bis(fluorosulfonyl)imide (KFSI) electrolyte. Anion (FSI-) insertion within the pore network during electrochemical cycling is confirmed by NMR spectroscopy, and the maximum charge capacity is found to be proportional to surface area and micropore volume by comparison to other microporous carbon materials. Full cells based on ZTC as the cathode exhibit both high specific energy (up to 176 Wh kg-1, 79.8 Wh L-1) and high specific power (up to 3945 W kg-1, 1095 W L-1), stable cycling performance over hundreds of cycles, and reversibility within the potential range of 2.65-4.7 V versus K/K+.

Size-Dependent Fault-Driven Relaxation and Faceting in Zincblende CdSe Colloidal Quantum Dots.

Surface chemistry and core defects are known to play a prominent role in governing the photophysical properties of nanocrystalline semiconductors. Nevertheless, investigating them in small nanocrystals remains a complex task. Here, by combining X-ray scattering techniques in the wide- and small-angle regions and using the Debye scattering equation (DSE) method of analysis, we unveil a high density of planar defects in oleate-terminated zincblende (ZB) CdSe colloidal quantum dots (QDs) and size-dependent faceting within a square-cuboid morphology. Atomistic models of faulted ZB nanocrystals, based on the probabilistic stacking of CdSe layers in cubic and hexagonal sequences, and data analysis point to the preferential location of faults near the center of nanocrystals. By finely modeling faulting and morphological effects on the X-ray scattering pattern, a relaxation of the Cd-Se bond distance parallel to the stacking direction, up to +3% (2.71 Å) with respect to the reference bulk value (2.63 Å), is detected, at the cubic/hexagonal transitions. The smallest nanocrystals show cubic {100} facets; {111} facets appear above 4 nm and progressively extend at larger sizes. These structural and morphological features likely vary depending on the synthesis conditions; nevertheless, since planar defects are nearly ubiquitous in CdSe QDs, the modeling approach here presented has a general validity. This work also points to the great potential of combining small- and wide-angle X-ray scattering and DSE-modeling techniques in gaining important knowledge on atomic-scale defects of semiconductor nanocrystals, underpinning the comprehension of the impact of structural defectiveness on the exciting properties of these QDs.

High-energy-density dual-ion battery for stationary storage of electricity using concentrated potassium fluorosulfonylimide.

Graphite dual-ion batteries represent a potential battery concept for large-scale stationary storage of electricity, especially when constructed free of lithium and other chemical elements with limited natural reserves. Owing to their non-rocking-chair operation mechanism, however, the practical deployment of graphite dual-ion batteries is inherently limited by the need for large quantities of electrolyte solutions as reservoirs of all ions that are needed for complete charge and discharge of the electrodes. Thus far, lithium-free graphite dual-ion batteries have employed moderately concentrated electrolyte solutions (0.3-1 M), resulting in rather low cell-level energy densities of 20-70 Wh kg-1. In this work, we present a lithium-free graphite dual-ion battery utilizing a highly concentrated electrolyte solution of 5 M potassium bis(fluorosulfonyl)imide in alkyl carbonates. The resultant battery offers an energy density of 207 Wh kg-1, along with a high energy efficiency of 89% and an average discharge voltage of 4.7 V.

Resolving the Core and the Surface of CdSe Quantum Dots and Nanoplatelets Using Dynamic Nuclear Polarization Enhanced PASS-PIETA NMR Spectroscopy.

Understanding the surface of semiconductor nanocrystals (NCs) prepared using colloidal methods is a long-standing goal of paramount importance for all their potential optoelectronic applications, which remains unsolved largely because of the lack of site-specific physical techniques. Here, we show that multidimensional 113Cd dynamic nuclear polarization (DNP) enhanced NMR spectroscopy allows the resolution of signals originating from different atomic and magnetic surroundings in the NC cores and at the surfaces. This enables the determination of the structural perfection, and differentiation between the surface and core atoms in all major forms of size- and shape-engineered CdSe NCs: irregularly faceted quantum dots (QDs) and atomically flat nanoplatelets, including both dominant polymorphs (zinc-blende and wurtzite) and their epitaxial nanoheterostructures (CdSe/CdS core/shell quantum dots and CdSe/CdS core/crown nanoplatelets), as well as magic-sized CdSe clusters. Assignments of the NMR signals to specific crystal facets of oleate-terminated ZB structured CdSe NCs are proposed. Significantly, we discover far greater atomistic complexity of the surface structure and the species distribution in wurtzite as compared to zinc-blende CdSe QDs, despite an apparently identical optical quality of both QD polymorphs.

Colloidal Bismuth Nanocrystals as a Model Anode Material for Rechargeable Mg-Ion Batteries: Atomistic and Mesoscale Insights.

At present, the technical progress of secondary batteries employing metallic magnesium as the anode material has been severely hindered due to the low oxidation stability of state-of-the-art Mg electrolytes, which cannot be used to explore high-voltage (>3 V versus Mg2+/Mg) cathode materials. All known electrolytes based on oxidatively stable solvents and salts, such as Mg(ClO4)2 and Mg bis(trifluoromethanesulfonimide), react with the metallic magnesium anode, forming a passivating layer at its surface and preventing the reversible plating and stripping of Mg. Therefore, in a near-term effort to extend the upper voltage limit in the exploration of future candidate Mg-ion battery cathode materials, bismuth anodes have attracted considerable attention due to their efficient magnesiation and demagnesiation alloying reaction in such electrolytes. In this context, we present colloidal Bi nanocrystals (NCs) as a model anode material for the exploration of cathode materials for rechargeable Mg-ion batteries. Bi NCs demonstrate a stable capacity of 325 mAh g-1 over at least 150 cycles at a current density of 770 mA g-1, which is among the most-stable performance of Mg-ion battery anode materials. First-principles crystal structure prediction methodologies and ex situ X-ray diffraction measurements reveal that the magnesiation of Bi NCs leads to the simultaneous formation of the low-temperature trigonal structure, α-Mg3Bi2, and the high-temperature cubic structure, ß-Mg3Bi2, which sheds insight into the high stability of this reversible alloying reaction. Furthermore, small-angle X-ray scattering measurements indicate that although the monodispersed, crystalline nature of the Bi NCs is indeed disturbed during the first discharge step, no notable morphological or structural changes occur in the following electrochemical cycles. The cost-effective and facile synthesis of colloidal Bi NCs and their remarkably high electrochemical stability upon magnesiation make them an excellent model anode material with which to accelerate progress in the field of Mg-ion secondary batteries.

High-performance thermoelectric nanocomposites from nanocrystal building blocks.

The efficient conversion between thermal and electrical energy by means of durable, silent and scalable solid-state thermoelectric devices has been a long standing goal. While nanocrystalline materials have already led to substantially higher thermoelectric efficiencies, further improvements are expected to arise from precise chemical engineering of nanoscale building blocks and interfaces. Here we present a simple and versatile bottom-up strategy based on the assembly of colloidal nanocrystals to produce consolidated yet nanostructured thermoelectric materials. In the case study on the PbS-Ag system, Ag nanodomains not only contribute to block phonon propagation, but also provide electrons to the PbS host semiconductor and reduce the PbS intergrain energy barriers for charge transport. Thus, PbS-Ag nanocomposites exhibit reduced thermal conductivities and higher charge carrier concentrations and mobilities than PbS nanomaterial. Such improvements of the material transport properties provide thermoelectric figures of merit up to 1.7 at 850 K.

Host-guest chemistry for tuning colloidal solubility, self-organization and photoconductivity of inorganic-capped nanocrystals.

Colloidal inorganic nanocrystals (NCs), functionalized with inorganic capping ligands, such as metal chalcogenide complexes (MCCs), have recently emerged as versatile optoelectronic materials. As-prepared, highly charged MCC-capped NCs are dispersible only in highly polar solvents, and lack the ability to form long-range ordered NC superlattices. Here we report a simple and general methodology, based on host-guest coordination of MCC-capped NCs with macrocyclic ethers (crown ethers and cryptands), enabling the solubilization of inorganic-capped NCs in solvents of any polarity and improving the ability to form NC superlattices. The corona of organic molecules can also serve as a convenient knob for the fine adjustment of charge transport and photoconductivity in films of NCs. In particular, high-infrared-photon detectivities of up to 3.3 × 10(11) Jones with a fast response (3 dB cut-off at 3 kHz) at the wavelength of 1,200 nm were obtained with films of PbS/K3AsS4/decyl-18-crown-6 NCs.

Structure of Colloidal Quantum Dots from Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy.

Understanding the chemistry of colloidal quantum dots (QDs) is primarily hampered by the lack of analytical methods to selectively and discriminately probe the QD core, QD surface and capping ligands. Here, we present a general concept for studying a broad range of QDs such as CdSe, CdTe, InP, PbSe, PbTe, CsPbBr3, etc., capped with both organic and inorganic surface capping ligands, through dynamic nuclear polarization (DNP) surface enhanced NMR spectroscopy. DNP can enhance NMR signals by factors of 10-100, thereby reducing the measurement times by 2-4 orders of magnitude. 1D DNP enhanced spectra acquired in this way are shown to clearly distinguish QD surface atoms from those of the QD core, and environmental effects such as oxidation. Furthermore, 2D NMR correlation experiments, which were previously inconceivable for QD surfaces, are demonstrated to be readily performed with DNP and provide the bonding motifs between the QD surfaces and the capping ligands.