Full-Spectrum White-Light Emission from Triple Self-Trapped Excitons in Hybrid Mixed-Metal Halides.

Low-dimensional metal halides with broadband emissions are expected to serve as downconversion luminescent materials for solid-state lighting (SSL). However, efficiently generating full-spectrum white-light emission with a high color-rendering index (CRI) in single-phase emitters remains a challenge. Here, we report a novel zero-dimensional (0D) hybrid mixed-metal halide (TPA)2CuAgI4 (TPA = tetrapropylammonium), in which individual [CuAgI4]2- dimers are completely isolated and surrounded by the organic cations TPA+. Cu+ and Ag+ share the same crystallographic site in [CuAgI4]2- dimers with the same statistical probability. Upon photoexcitation, single crystals exhibit a full-spectrum white-light emission with a full width at half-maximum (fwhm) of up to 314 nm and a high quantum efficiency of 46.8%. Detailed photophysical studies and theoretical calculations reveal that the ultra-broadband emission of (TPA)2CuAgI4 originates from the radiative recombination of red-, green-, and blue-emitting self-trapped excitons in [CuAgI4]2- dimers. In addition, (TPA)2CuAgI4 nanocrystals were successfully synthesized and exhibited optical properties similar to those of single-crystal counterparts. Finally, a prototype ultraviolet (UV)-pumped white-light-emitting diode (WLED) and a composite thin film employing this new white-light emitter produces a well-distributed full-spectrum white light with a high CRI of 91.4 and a warm correlated color temperature (CCT) of 4135 K, indicating the potential application of this white-light emitter in SSL. These results provide a new perspective for designing superior single-phase white-light emitters.

Realizing Near-Unity Quantum Efficiency of Zero-Dimensional Antimony Halides through Metal Halide Structural Modulation.

Zero-dimensional (0D) organic metal halides have attracted significant attention because of their exceptional structure tunability and excellent optical characteristics. However, controllable synthesis of a desirable configuration of metal halide species in a rational way remains a formidable challenge, and how the unique crystal structures affect the photophysical properties are not yet well understood. Here, a reasonable metal halide structural modulation strategy is proposed to realize near-unity photoluminescence quantum efficiency (PLQE) in 0D organic antimony halides. By carefully controlling the reaction conditions, both 0D (C12H28N)2SbCl5 and (C12H28N)SbCl4 with different metal halide configurations can be prepared. (C12H28N)2SbCl5 with pyramid-shaped [SbCl5]2- species exhibits yellow emission with a near-unity PLQE of 96.8%, while (C12H28N)SbCl4 with seesaw-shaped [SbCl4]- species is not emissive at room temperature. Theoretical calculations indicate that the different photophysical properties of these two crystals can be attributed to the different symmetries of their crystal structures. (C12H28N)2SbCl5 adopts a triclinic structure with P-1 symmetry, while (C12H28N)SbCl4 possesses a monoclinic structure with P21/c symmetry, which has an inversion center, and thus the optical transitions between their band-edge states give a minimal dipole intensity because of their similar parity character. In addition, we also successfully synthesized (C12H28N)2SbCl5 nanocrystals for the first time, which are particularly appealing for their solution processibility and excellent optical properties. Furthermore, (C12H28N)2SbCl5 nanocrystals flexible composite film shows bright yellow emission under ß-ray excitation, suggesting a strong potential of (C12H28N)2SbCl5 for ß-ray detection.

Highly Luminescent Zero-Dimensional Organic Copper Halides for X-ray Scintillation.

The present work reports highly efficient flexible and reabsorption-free scintillators based on two zero-dimensional (0D) organic copper halides (TBA)CuX2 (TBA = tetrabutylammonium cation; X = Cl, Br). The (TBA)CuX2 exhibit highly luminescent green and sky-blue emissions peaked at 510 and 498 nm, with large Stokes shifts of 224 and 209 nm and high photoluminescence quantum yields (PLQYs) of 92.8% and 80.5% at room temperature for (TBA)CuCl2 and (TBA)CuBr2 single crystals (SCs), respectively. Interestingly, above room temperature, their PLQYs increase with temperature and reach near unity at 320 and 345 K for (TBA)CuCl2 and (TBA)CuBr2, respectively. The excellent properties originate from self-trapped excitons (STEs) in individual [CuX2]- quantum rods, which is demonstrated by the temperature-dependent PL, ultrafast transient absorption (TA) combined with density functional theory (DFT) calculations. The (TBA)CuX2 scintillators show bright radioluminescence (RL), impressive linear response to dose rate in a broad range, and high light yields. Their potential application in X-ray imaging is demonstrated by using (TBA)CuX2 composite scintillation screens. Importantly, flexible scintillators are demonstrated to be superior than flat ones for imaging nonplanar objects by conformally coating, which produce accurate images with negligible distortion.

Efficient Dual-Band White-Light Emission with High Color Rendering from Zero-Dimensional Organic Copper Iodide.

Broad-band white-light emissions from organic-inorganic lead halide hybrids have attracted considerable attention in energy-saving solid-state lighting (SSL) applications. However, the toxicity of lead in these hybrids hinders their commercial prospects, and the low photoluminescence quantum yields (PLQYs) cannot meet the requirements for efficient lighting. Here, we report a highly efficient dual-band white-light emission from organic copper iodide, (C16H36N)CuI2, which exhibits a high PLQY of 54.3% and excellent air stability. The single-crystalline (C16H36N)CuI2 possesses a unique zero-dimensional (0D) structure, in which the isolated [Cu2I4]2- dimers are periodically embedded in the wide band gap organic framework of C16H36N+. This perfect 0D structure can cause significant quantum confinement and strong electron-phonon coupling, which contributes to efficient emissions from self-trapped excitons (STEs). Photophysical studies revealed the presence of two self-trapped emitting states in [Cu2I4]2- dimers, whose populations are highly sensitive to the temperature that governs the molecular environment for [Cu2I4]2- dimers and the thermal activation energy of STEs. An ultraviolet (UV) excited white light-emitting diode fabricated using this single-phase white-light emitter exhibits a high color rendering index (CRI) of 78. The new material provides a promising emitter, having a high PLQY and a high CRI simultaneously, for SSL and display applications.

Efficiently Passivated PbSe Quantum Dot Solids for Infrared Photovoltaics.

Infrared (IR) solar cells are promising devices for significantly improving the power conversion efficiency of common solar cells by harvesting the low-energy IR photons. PbSe quantum dots (QDs) are superior IR photon absorbing materials due to their strong quantum confinement and thus strong interdot electronic coupling. However, the high chemical activity of PbSe QDs leads to etching and poor passivation in ligand exchange, resulting in a high trap-state density and a high open circuit voltage (VOC) deficit. Here we develop a hybrid ligand co-passivation strategy to simultaneously passivate the Pb and Se sites; that is, halide anions passivate the Pb sites and Cd cations passivate the Se sites. The cation and anion hybrid passivation substantially improves the quality of PbSe QD solids, giving rise to an excellent trap-state control and prolonged carrier lifetime. A high VOC and a high short circuit current density (JSC) are achieved simultaneously in the IR QD solar cells based on this hybrid ligand treatment. Finally, a IR-PCE of 1.31% under the 1100-nm-filtered solar illumination is achieved in the PbSe QD solar cells, which is the highest IR-PCE for PbSe QD IR solar cells at present. Additionally, the PbSe QD devices show a high external quantum efficiency of 80% at ∼1295 nm.

Towards chirality control of graphene nanoribbons embedded in hexagonal boron nitride.

The integrated in-plane growth of graphene nanoribbons (GNRs) and hexagonal boron nitride (h-BN) could provide a promising route to achieve integrated circuitry of atomic thickness. However, fabrication of edge-specific GNRs in the lattice of h-BN still remains a significant challenge. Here we developed a two-step growth method and successfully achieved sub-5-nm-wide zigzag and armchair GNRs embedded in h-BN. Further transport measurements reveal that the sub-7-nm-wide zigzag GNRs exhibit openings of the bandgap inversely proportional to their width, while narrow armchair GNRs exhibit some fluctuation in the bandgap-width relationship. An obvious conductance peak is observed in the transfer curves of 8- to 10-nm-wide zigzag GNRs, while it is absent in most armchair GNRs. Zigzag GNRs exhibit a small magnetic conductance, while armchair GNRs have much higher magnetic conductance values. This integrated lateral growth of edge-specific GNRs in h-BN provides a promising route to achieve intricate nanoscale circuits.

Efficient and Reabsorption-Free Radioluminescence in Cs3Cu2I5 Nanocrystals with Self-Trapped Excitons.

Radioluminescent materials (scintillators) are widely applied in medical imaging, nondestructive testing, security inspection, nuclear and radiation industries, and scientific research. Recently, all-inorganic lead halide perovskite nanocrystal (NC) scintillators have attracted great attention due to their facile solution processability and ultrasensitive X-ray detection, which allows for large area and flexible X-ray imaging. However, the light yield of these perovskite NCs is relatively low because of the strong self-absorption that reduces the light out-coupling efficiency. Here, NCs with self-trapped excitons emission are demonstrated to be sensitive, reabsorption-free scintillators. Highly luminescent and stable Cs3Cu2I5 NCs with a photoluminescence quantum yields of 73.7%, which is a new record for blue emission lead-free perovskite or perovskite-like NCs, is produced with the assistance of InI3. The PL peak of the Cs3Cu2I5 NCs locates at 445 nm that matches with the response peak of a silicon photomultiplier. Thus, Cs3Cu2I5 NCs are demonstrated as efficient scintillators with zero self-absorption and extremely high light yield (≈79 279 photons per MeV). Both Cs3Cu2I5 NC colloidal solution and film exhibit strong radioluminescence under X-ray irradiation. The potential application of Cs3Cu2I5 NCs as reabsorption-free, low cost, large area, and flexible scintillators is demonstrated by a prototype X-ray imaging with a high spatial resolution.

Isolating hydrogen in hexagonal boron nitride bubbles by a plasma treatment.

Atomically thin hexagonal boron nitride (h-BN) is often regarded as an elastic film that is impermeable to gases. The high stabilities in thermal and chemical properties allow h-BN to serve as a gas barrier under extreme conditions. Here, we demonstrate the isolation of hydrogen in bubbles of h-BN via plasma treatment. Detailed characterizations reveal that the substrates do not show chemical change after treatment. The bubbles are found to withstand thermal treatment in air, even at 800 °C. Scanning transmission electron microscopy investigation shows that the h-BN multilayer has a unique aligned porous stacking nature, which is essential for the character of being transparent to atomic hydrogen but impermeable to hydrogen molecules. In addition, we successfully demonstrated the extraction of hydrogen gases from gaseous compounds or mixtures containing hydrogen element. The successful production of hydrogen bubbles on h-BN flakes has potential for further application in nano/micro-electromechanical systems and hydrogen storage.

Controlled synthesis of brightly fluorescent CH3NH3PbBr3 perovskite nanocrystals employing Pb(C17H33COO)2 as the sole lead source.

Organometal halide perovskite nanocrystals hold vast potential for application in photovoltaics, light emitting diodes, low-threshold lasers, and photodetectors due to their size-tunable bandgap energies and photoluminescence as well as excellent electron and hole mobilities. However, the synthesis of such nanocrystals typically suffers from poor structural stability in solution and the coexistence of lamellate nanocrystals (nanoplatelets) and spherical nanocrystals (nanoparticles). Here we show that the pure nanoparticle morphology of CH3NH3PbBr3 nanocrystals can be realized by employing lead oleate (Pb(C17H33COO)2) as the sole lead source and controlled using short- and long-chain mixed alkyl ammonium. These nanocrystals are monodispersed (2.2 ± 0.4 nm in diameter), highly fluorescent (with a quantum yield approaching 85%), and highly stable in the solution (for more than 30 days). Comparative studies reveal that the shape of CH3NH3PbBr3 nanocrystals is strongly dependent on the lead source, PbBr2 and Pb(C17H33COO)2, and evolves as a function of the ratio of short- and long-chain alkyl ammoniums in the precursors. At an optimal short to long-chain alkyl ammonium ratio of 4 : 6, the growth of CH3NH3PbBr3 nanoplatelets can be selectively suppressed with Pb(C17H33COO)2 as the sole lead source, enhancing the overall photoluminescence quantum yield of the produced CH3NH3PbBr3 nanocrystals. This work reveals important new insights for controlled synthesis of perovskite nanocrystals with pure crystal shape and significantly improved photoluminescence properties and stability.

Comparison of photoemission characteristics between square and circular wire array GaAs photocathodes.

Two types of negative electron affinity gallium arsenide (GaAs) wire array photocathodes were fabricated by reactive ion etching and inductively coupled plasma etching of bulk GaAs material. High density GaAs wire arrays with high periodicity and good morphology were verified using scanning electron microscopy, and photoluminescence spectra confirmed the wire arrays had good crystalline quality. Reflection spectra showed that circular GaAs wire arrays had superior light trapping compared with square ones. However, after Cs/O activation, the square GaAs wire array photocathodes showed enhanced spectral response. The integral sensitivity of the square wire array photocathodes was approximately 2.8 times that of the circular arrays.

Oriented graphene nanoribbons embedded in hexagonal boron nitride trenches.

Graphene nanoribbons (GNRs) are ultra-narrow strips of graphene that have the potential to be used in high-performance graphene-based semiconductor electronics. However, controlled growth of GNRs on dielectric substrates remains a challenge. Here, we report the successful growth of GNRs directly on hexagonal boron nitride substrates with smooth edges and controllable widths using chemical vapour deposition. The approach is based on a type of template growth that allows for the in-plane epitaxy of mono-layered GNRs in nano-trenches on hexagonal boron nitride with edges following a zigzag direction. The embedded GNR channels show excellent electronic properties, even at room temperature. Such in-plane hetero-integration of GNRs, which is compatible with integrated circuit processing, creates a gapped channel with a width of a few benzene rings, enabling the development of digital integrated circuitry based on GNRs.

[Removal of Cd from Soil by Aspergillus fumigatus in a Semi-solid Culture].

A method was proposed to remove Cd from contaminated soils by a semi-solid culture containing Aspergillus fumigatus that have a strong resistance to Cd. The removal efficiencies of Cd in different simulated Cd pollution levels were studied and the changes in Cd adsorption and the enrichment in Aspergillus fumigatus were measured. The results showed that Aspergillus fumigatus could remove some Cd from the soil in the semi-solid culture system. When the concentration of Cd was 10 mg·kg-1, the total removal rate of Cd was up to 31%. Meanwhile, the dry weight of Aspergillus fumigatus and the pH of the system were studied during the culture process. The results showed that the dry weight decreased with the increase in culture time and Cd concentration, the maximum decrease rate of dry weight was 64%. The removal efficiency was the best when the pH was varied from 5.6 to 6.0. The changes in different extraction fractions for Cd showed that the main fractions of Cd removed by Aspergillus fumigatus were the acid-soluble fraction and the reducible fraction and the oxidizable fraction of Cd remained essentially unchanged before and after the culturing. The proposed method would provide valuable information for the remediation of heavy metal-contaminated soil by fungi.

[Effects on Physico-chemical Parameters of Glycoside Hydrolase Family 6 Genes During Composting of Agricultural Waste].

Polymerase chain reaction denaturing gradient gel electrophoresis (PCR-DGGE) was used to study the changes of glycoside hydrolase family 6 (GH6 family) genes during the composting of agricultural waste. In addition, a redundancy analysis (RDA) and Monte Carlo permutation test were applied to determine the relationship between the changes to the GH6 family genes and physico-chemical parameters. According to the relative magnitudes of the influence caused by these different parameters on the changes to GH6 family genes, the eight-ranked physico-chemical parameters were pH > pile temperature > total nitrogen (TN) > total organic matter (TOM) > C/N ratio > moisture content > ambient temperature > water soluble carbon (WSC). The eight physico-chemical parameters, which explained 83.1% of the variation of GH6 family genes, confirmed that these parameters had important effects on the GH6 family genes changes. The pH (P=0.002), pile temperature (P=0.004), and TN (P=0.004) had the most significant impacts on these changes. These three significant factors explained 24.92%, 15.57%, and 15.04% of the variation of GH6 family genes, respectively. There were different dominant species which contain GH6 family genes in different stages of composting. The diversity and abundance of GH6 family genes demonstrated these fluctuation trends. The t-value biplots based on the RDA showed that these three significant factors had either positive or negative correlations with the dynamic changes of GH6 family genes and the microbial species contained within GH6 family genes can be generally be divided into five types. The microbial community changes are reflected by the No. 4 to No. 10 bands and these had a significant positive correlation with pile temperature and a significant negative correlation with pH and TN. The microbial community changes reflected by the No. 20 to No. 23 bands had a significant positive correlation with pH and TN.

Dynamics of graded-composition and graded-doping semiconductor nanowires under local carrier modulation.

Scanning photocurrent microscopy is a powerful tool for investigating charge transfer and internal fields, which strongly influence carrier statics and dynamics in semiconductor nanowires. We performed comprehensive numerical modeling of the carrier dynamics of graded-composition and graded-doping AlGaAs nanowires to achieve a greater understanding of these nanowires. The simulation results indicated that the built-in electric field changes the shape of the scanning photocurrent microscopy profiles, which helped us to judge the dopant level, Al composition range and doping type of the material. The simulation results also assess the potential of the scanning photocurrent techniques in graded-doping and graded-composition nanowire properties.

Quantum dot PbS(0.9)Se(0.1)/TiO2 heterojunction solar cells.

We report on photovoltaic cells based on ternary PbS(0.9)Se(0.1) quantum dots utilizing a heterojunction type device configuration. The best device shows an AM 1.5 power conversion efficiency of 4.25%. Furthermore, this ternary PbS(x)Se(1-x) quantum dot heterojunction device has a peak external quantum efficiency above 100% at 2.76 eV, approximately 2.7× the bandgap energy. The ternary quantum dots combine the higher short circuit currents of the binary PbSe system with the higher open circuit voltages of the binary PbS system.