Terahertz charge transport dynamics in 3D graphene networks with localization and band regimes.

Terahertz steady-state and time-resolved conductivity and permittivity spectra were measured in 3D graphene networks assembled in free-standing covalently cross-linked graphene aerogels. Investigation of a transition between reduced-graphene oxide and graphene controlled by means of high-temperature annealing allowed us to elucidate the role of defects in the charge carrier transport in the materials. The THz spectra reveal increasing conductivity and decreasing permittivity with frequency. This contrasts with the Drude- or Lorentz-like conductivity typically observed in various 2D graphene samples, suggesting a significant contribution of a relaxational mechanism to the conductivity in 3D graphene percolated networks. The charge transport in the graphene aerogels exhibits an interplay between the carrier hopping among localized states and a Drude contribution of conduction-band carriers. Upon photoexcitation, carriers are injected into the conduction band and their dynamics reveals picosecond lifetime and femtosecond dephasing time. Our findings provide important insight into the charge transport in complex graphene structures.

Direct-Indirect Nature of the Bandgap in Lead-Free Perovskite Nanocrystals.

With record efficiencies achieved in lead halide perovskite-based photovoltaics, urgency has shifted toward finding alternative materials that are stable and less toxic. Bismuth-based perovskite materials are currently one of the most promising candidates among those alternatives. However, the band structures of these materials, including the nature of the bandgaps, remain elusive due to extremely low photoluminescence quantum yield (PLQY) and scattering issues in their thin-film form. Here, we reveal the specific nature of the material's electronic transitions by realizing monodisperse colloidal nanocrystals (NCs) of hexagonal-phase Cs3Bi2X9 perovskites, which afford well-resolved PL features. Interestingly, the PL profile exhibits a dual-spectral feature at room temperature with comparable intensities, based on which we propose an exciton recombination process involving both indirect and direct transitions simultaneously-an observation further supported by temperature-dependent and density functional theory (DFT) calculations. Our findings provide experimental and theoretical insights into the nature of the bandgaps in bismuth halide materials-essential information for assessing their viability in solar cells and optoelectronics.

Direct versus ligand-exchange synthesis of [PtAg28(BDT)12(TPP)4]4- nanoclusters: effect of a single-atom dopant on the optoelectronic and chemical properties.

Heteroatom doping of atomically precise nanoclusters (NCs) often yields a mixture of doped and undoped products of single-atom difference, whose separation is extremely difficult. To overcome this challenge, novel synthesis methods are required to offer monodisperse doped NCs. For instance, the direct synthesis of PtAg28 NCs produces a mixture of [Ag29(BDT)12(TPP)4]3- and [PtAg28(BDT)12(TPP)4]4- NCs (TPP: triphenylphosphine; BDT: 1,3-benzenedithiolate). Here, we designed a ligand-exchange (LE) strategy to synthesize single-sized, Pt-doped, superatomic Ag NCs [PtAg28(BDT)12(TPP)4]4- by LE of [Pt2Ag23Cl7(TPP)10] NCs with BDTH2 (1,3-benzenedithiol). The doped NCs were thoroughly characterized by optical and photoelectron spectroscopy, mass spectrometry, total electron count, and time-dependent density functional theory (TDDFT). We show that the Pt dopant occupies the center of the PtAg28 cluster, modulates its electronic structure and enhances its photoluminescence intensity and excited-state lifetime, and also enables solvent interactions with the NC surface. Furthermore, doped NCs showed unique reactivity with metal ions - the central Pt atom of PtAg28 could not be replaced by Au, unlike the central Ag of Ag29 NCs. The achieved synthesis of single-sized PtAg28 clusters will facilitate further applications of the LE strategy for the exploration of novel multimetallic NCs.

Doping-Induced Anisotropic Self-Assembly of Silver Icosahedra in [Pt2Ag23Cl7(PPh3)10] Nanoclusters.

Atomically precise self-assembled architectures of noble metals with unique surface structures are necessary for prospective applications. However, the synthesis of such structures based on silver is challenging because of their instability. In this work, by developing a selective and controlled doping strategy, we synthesized and characterized a rod-shaped, charge-neutral, diplatinum-doped Ag nanocluster (NC) of [Pt2Ag23Cl7(PPh3)10]. Its crystal structure revealed the self-assembly of two Pt-centered Ag icosahedra through vertex sharing. Five bridging and two terminal chlorides and 10 PPh3 ligands were found to stabilize the cluster. Electronic structure simulations corroborated structural and optical characterization of the cluster and provided insights into the effect of the Pt dopants on the optical properties and stability of the cluster. Our study will open new avenues for designing novel self-assembled NCs using different elemental dopants.

Comprehensive Study of All-Solid-State Z-Scheme Photocatalytic Systems of ZnO/Pt/CdZnS.

We have investigated a Z-scheme based on a ZnO/Pt/CdZnS photocatalyst, active in the presence of a complex medium composed of acetic acid and benzyl alcohol, the effects of which on the catalyst stability and performance are studied. Transmission electron microscopy images showed uniformly dispersed sub-nanometer Pt particles. Inductively coupled plasma and X-ray photoelectron spectroscopy analyses suggested that Pt is sandwiched between ZnO and CdZnS. An apparent quantum yield (AQY) of 34% was obtained over the [ZnO]4/1 wt %Pt/CdZnS system at 360 nm, 2.5-fold higher than that of 1%Pt/CdZnS (14%). Furthermore, an AQY of 16% was observed using [ZnO]4/1 wt %Pt/CdZnS, which was comparable to that of 1 wt %Pt/CdZnS (10%) at 460 nm. On the basis of these results, we proposed a charge transfer mechanism, which was confirmed through femtosecond transient absorption spectroscopy. Finally, we identified the two main factors that affected the stability of the catalyst, which were the sacrificial reagent and the acidic pH.

Engineering Interfacial Charge Transfer in CsPbBr3 Perovskite Nanocrystals by Heterovalent Doping.

Since compelling device efficiencies of perovskite solar cells have been achieved, investigative efforts have turned to understand other key challenges in these systems, such as engineering interfacial energy-level alignment and charge transfer (CT). However, these types of studies on perovskite thin-film devices are impeded by the morphological and compositional heterogeneity of the films and their ill-defined surfaces. Here, we use well-defined ligand-protected perovskite nanocrystals (NCs) as model systems to elucidate the role of heterovalent doping on charge-carrier dynamics and energy level alignment at the interface of perovskite NCs with molecular acceptors. More specifically, we develop an in situ doping approach for colloidal CsPbBr3 perovskite NCs with heterovalent Bi3+ ions by hot injection to precisely tune their band structure and excited-state dynamics. This synthetic method allowed us to map the impact of doping on CT from the NCs to different molecular acceptors. Using time-resolved spectroscopy with broadband capability, we clearly demonstrate that CT at the interface of NCs can be tuned and promoted by metal ion doping. We found that doping increases the energy difference between states of the molecular acceptor and the donor moieties, subsequently facilitating the interfacial CT process. This work highlights the key variable components not only for promoting interfacial CT in perovskites, but also for establishing a higher degree of precision and control over the surface and the interface of perovskite molecular acceptors.

Pure crystal orientation and anisotropic charge transport in large-area hybrid perovskite films.

Controlling crystal orientations and macroscopic morphology is vital to develop the electronic properties of hybrid perovskites. Here we show that a large-area, orientationally pure crystalline (OPC) methylammonium lead iodide (MAPbI3) hybrid perovskite film can be fabricated using a thermal-gradient-assisted directional crystallization method that relies on the sharp liquid-to-solid transition of MAPbI3 from ionic liquid solution. We find that the OPC films spontaneously form periodic microarrays that are distinguishable from general polycrystalline perovskite materials in terms of their crystal orientation, film morphology and electronic properties. X-ray diffraction patterns reveal that the film is strongly oriented in the (112) and (200) planes parallel to the substrate. This film is structurally confined by directional crystal growth, inducing intense anisotropy in charge transport. In addition, the low trap-state density (7.9 × 1013 cm-3) leads to strong amplified stimulated emission. This ability to control crystal orientation and morphology could be widely adopted in optoelectronic devices.

pH-Induced Surface Modification of Atomically Precise Silver Nanoclusters: An Approach for Tunable Optical and Electronic Properties.

Noble metal nanoclusters (NCs) play a pivotal role in bridging the gap between molecules and quantum dots. Fundamental understanding of the evolution of the structural, optical, and electronic properties of these materials in various environments is of paramount importance for many applications. Using state-of-the-art spectroscopy, we provide the first decisive experimental evidence that the structural, electronic, and optical properties of Ag44(MNBA)30 NCs can now be tailored by controlling the chemical environment. Infrared and photoelectron spectroscopies clearly indicate that there is a dimerization between two adjacent ligands capping the NCs that takes place upon lowering the pH from 13 to 7.

Shape-Tunable Charge Carrier Dynamics at the Interfaces between Perovskite Nanocrystals and Molecular Acceptors.

Hybrid organic/inorganic perovskites have recently emerged as an important class of materials and have exhibited remarkable performance in photovoltaics. To further improve their device efficiency, an insightful understanding of the interfacial charge transfer (CT) process is required. Here, we report the first direct experimental observation of the tremendous effect that the shape of perovskite nanocrystals (NCs) has on interfacial CT in the presence of a molecular acceptor. A dramatic change in CT dynamics at the interfaces of three different NC shapes, spheres, platelets, and cubes, is recorded. Our results clearly demonstrate that the mechanism of CT is significantly affected by the NC shape. More importantly, the results demonstrate that complexation on the NC surface acts as an additional driving force not only to tune the CT dynamics but also to control the reaction mechanism at the interface. This observation opens a new venue for further developing perovskite NCs-based applications.

Porous-Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis.

A number of permanently porous polymers containing Ru(bpy)n photosensitizer or a cobaloxime complex, as a proton-reduction catalyst, were constructed via one-pot Sonogashira-Hagihara (SH) cross-coupling reactions. This process required minimal workup to access porous platforms with control over the apparent surface area, pore volume, and chemical functionality from suitable molecular building blocks (MBBs) containing the Ru or Co complexes, as rigid and multitopic nodes. The cobaloxime molecular building block, generated through in situ metalation, afforded a microporous solid that demonstrated noticeable catalytic activity toward hydrogen-evolution reaction (HER) with remarkable recyclability. We further demonstrated, in two cases, the ability to affect the excited-state lifetime of the covalently immobilized Ru(bpy)3 complex attained through deliberate utilization of the organic linkers of variable dimensions. Overall, this approach facilitates construction of tunable porous solids, with hybrid composition and pronounced chemical and physical stability, based on the well-known Ru(bpy)nor the cobaloxime complexes.

Real-Space Mapping of Surface Trap States in CIGSe Nanocrystals Using 4D Electron Microscopy.

Surface trap states in copper indium gallium selenide semiconductor nanocrystals (NCs), which serve as undesirable channels for nonradiative carrier recombination, remain a great challenge impeding the development of solar and optoelectronics devices based on these NCs. In order to design efficient passivation techniques to minimize these trap states, a precise knowledge about the charge carrier dynamics on the NCs surface is essential. However, selective mapping of surface traps requires capabilities beyond the reach of conventional laser spectroscopy and static electron microscopy; it can only be accessed by using a one-of-a-kind, second-generation four-dimensional scanning ultrafast electron microscope (4D S-UEM) with subpicosecond temporal and nanometer spatial resolutions. Here, we precisely map the collective surface charge carrier dynamics of copper indium gallium selenide NCs as a function of the surface trap states before and after surface passivation in real space and time using S-UEM. The time-resolved snapshots clearly demonstrate that the density of the trap states is significantly reduced after zinc sulfide (ZnS) shelling. Furthermore, the removal of trap states and elongation of carrier lifetime are confirmed by the increased photocurrent of the self-biased photodetector fabricated using the shelled NCs.

Gold Doping of Silver Nanoclusters: A 26-Fold Enhancement in the Luminescence Quantum Yield.

A high quantum yield (QY) of photoluminescence (PL) in nanomaterials is necessary for a wide range of applications. Unfortunately, the weak PL and moderate stability of atomically precise silver nanoclusters (NCs) suppress their utility. Herein, we accomplished a ≥26-fold PL QY enhancement of the Ag29 (BDT)12 (TPP)4 cluster (BDT: 1,3-benzenedithiol; TPP: triphenylphosphine) by doping with a discrete number of Au atoms, producing Ag29-x Aux (BDT)12 (TPP)4 , x=1-5. The Au-doped clusters exhibit an enhanced stability and an intense red emission around 660 nm. Single-crystal XRD, mass spectrometry, optical, and NMR spectroscopy shed light on the PL enhancement mechanism and the probable locations of the Au dopants within the cluster.

Real-Space Visualization of Energy Loss and Carrier Diffusion in a Semiconductor Nanowire Array Using 4D Electron Microscopy.

A breakthrough in the development of 4D scanning ultrafast electron microscopy is described for real-time and space imaging of secondary electron energy loss and carrier diffusion on the surface of an array of nanowires as a model system, providing access to a territory that is beyond the reach of either static electron imaging or any time-resolved laser spectroscopy.

Templated Atom-Precise Galvanic Synthesis and Structure Elucidation of a [Ag24Au(SR)18](-) Nanocluster.

Synthesis of atom-precise alloy nanoclusters with uniform composition is challenging when the alloying atoms are similar in size (for example, Ag and Au). A galvanic exchange strategy has been devised to produce a compositionally uniform [Ag24Au(SR)18](-) cluster (SR: thiolate) using a pure [Ag25(SR)18](-) cluster as a template. Conversely, the direct synthesis of Ag24Au cluster leads to a mixture of [Ag(25-x)Au(x)(SR)18](-), x=1-8. Mass spectrometry and crystallography of [Ag24Au(SR)18](-) reveal the presence of the Au heteroatom at the Ag25 center, forming Ag24Au. The successful exchange of the central Ag of Ag25 with Au causes perturbations in the Ag25 crystal structure, which are reflected in the absorption, luminescence, and ambient stability of the particle. These properties are compared with those of Ag25 and Ag24Pd clusters with same ligand and structural framework, providing new insights into the modulation of cluster properties with dopants at the single-atom level.

Air-Stable Surface-Passivated Perovskite Quantum Dots for Ultra-Robust, Single- and Two-Photon-Induced Amplified Spontaneous Emission.

We demonstrate ultra-air- and photostable CsPbBr3 quantum dots (QDs) by using an inorganic-organic hybrid ion pair as the capping ligand. This passivation approach to perovskite QDs yields high photoluminescence quantum yield with unprecedented operational stability in ambient conditions (60 ± 5% lab humidity) and high pump fluences, thus overcoming one of the greatest challenges impeding the development of perovskite-based applications. Due to the robustness of passivated perovskite QDs, we were able to induce ultrastable amplified spontaneous emission (ASE) in solution processed QD films not only through one photon but also through two-photon absorption processes. The latter has not been observed before in the family of perovskite materials. More importantly, passivated perovskite QD films showed remarkable photostability under continuous pulsed laser excitation in ambient conditions for at least 34 h (corresponds to 1.2 × 10(8) laser shots), substantially exceeding the stability of other colloidal QD systems in which ASE has been observed.

To what extent can charge localization influence electron injection efficiency at graphene-porphyrin interfaces?

Controlling the electron transfer process at donor-acceptor interfaces is a research direction that has not yet seen much progress. Here, with careful control of the charge localization on the porphyrin macrocycle using ß-cyclodextrin as an external cage, we are able to improve the electron injection efficiency from cationic porphyrin to graphene carboxylate by 120%. The detailed reaction mechanism is also discussed.

Ultrafast electron injection at the cationic porphyrin-graphene interface assisted by molecular flattening.

The steady-state and femtosecond (fs) time-resolved data clearly demonstrate that the charge transfer (CT) process at the porphyrin-graphene carboxylate (GC) interfaces can be tuned from zero to very sufficient and ultrafast by changing the electronic structure of the meso unit and the redox properties of the porphyrin cavity.