Generalised optical printing of photocurable metal chalcogenides

Optical three-dimensional (3D) printing techniques have attracted tremendous attention owing to their applicability to mask-less additive manufacturing, which enables the cost-effective and straightforward creation of patterned architectures. However, despite their potential use as alternatives to traditional lithography, the printable materials obtained from these methods are strictly limited to photocurable resins, thereby restricting the functionality of the printed objects and their application areas. Herein, we report a generalised direct optical printing technique to obtain functional metal chalcogenides via digital light processing. We developed universally applicable photocurable chalcogenidometallate inks that could be directly used to create 2D patterns or micrometre-thick 2.5D architectures of various sizes and shapes. Our process is applicable to a diverse range of functional metal chalcogenides for compound semiconductors and 2D transition-metal dichalcogenides. We then demonstrated the feasibility of our technique by fabricating and evaluating a micro-scale thermoelectric generator bearing tens of patterned semiconductors. Our approach shows potential for simple and cost-effective architecturing of functional inorganic materials

Large-Scale Synthesis of Highly Luminescent InP@ZnS Quantum Dots Using Elemental Phosphorus Precursor

Department of Chemical EngineeringColloidal quantum dots can control the bandgap by controlling the particle size, and are capable of solution processing, which is cost competitive, and has a narrow half width of the emission wavelength. Using these characteristics, it is possible to utilize various kinds of LED, solar cell, and bio imaging. Among them, indium phosphide (InP) quantum dots have a bandgap capable of emitting light in the near-infrared region from the visible light region, and are less toxic to humans and the environment than cadmium-based quantum dots, and are attracting attention as next generation light emitting materials. However, the limited choice and high cost of P precursors have a negative impact on their practical applicability. In this work, I report the large-scale synthesis of highly luminescent InP@ZnS QDs from an elemental P precursor (P4), which was simply synthesized via the sublimation of red P powder. The size of the InP QDs was controlled by varying the reaction parameters such as the reaction time and temperature, and the type of In precursors. This way, the photoluminescence properties of the synthesized InP@ZnS QDs could be easily tuned across the entire visible range, while their quantum yield could be increased up to 60% via the optimization of reaction conditions. Furthermore, possible reaction pathways for the formation of InP QDs using the P4 precursor have been investigated with nuclear magnetic resonance spectroscopy and it was demonstrated that the direct reaction of P4 precursor with In precursor produces InP structures without the formation of intermediate species. The large-scale production of InP@ZnS QDs was demonstrated by yielding more than 6 g of QDs per one-batch reaction. In the case of InP using different precursor P except the Tris(Trimethylsilyl) phosphine ((TMS)3P) there has been a problem that the size distribution is poor. Two kinds of P precursors with different reactivities were used to separate the nucleation and growth processes and to induce growth along the Lamer mechanism to produce uniform particles. For this, (TMS)3P and DEAP were used as fast reacting P precursors, and P4 was used as a slow reacting P precursor. Through this, the possibility of uniform particle formation was observed. I strongly believe that the newly developed approach bears the potential to be widely used for manufacturing inexpensive high-quality QD emitters.ope

Surface Engineering of All-Inorganic Nanocrystals for Electronic and 3D Printing Applications

Department of Materials Science and Engineeringclos

Synthesis of inorganic-organic two-dimensional CdSe slab-diamine quantum nets

Porous semiconductors attract great interest due to their unique structural characteristics of high surface area as well as their intrinsic optical and electronic properties. In this study, synthesis of inorganic-organic 2D CdSe slabs‐diaminooctane (DAO) porous quantum net structures is demonstrated. It is found that the hybrid 2D CdSe‐DAO lamellar structures are disintegrated into porous net structures, maintaining an ultrathin thickness of ≈1 nm in CdSe slabs. Furthermore, the CdSe slabs in quantum nets show the highly shifted excitonic transition in the absorption spectrum, demonstrating their strongly confined electronic structures. The possible formation mechanism of this porous structure is investigated with the control experiments of the synthesis using n‐alkyldiamines with various hydrocarbon chain lengths and ligand exchange of DAO with oleylamine. It is suggested that a strong van der Waals interaction among long chain DAO may exert strong tensile stress on the CdSe slabs, eventually disintegrating slabs. The thermal decomposition of CdSe‐DAO quantum nets is further studied to form well‐defined CdSe nanorods. It is believed that the current CdSe‐DAO quantum nets will offer a new type of porous semiconductors nanostructures under a strong quantum‐confinement regime, which can be applied to various technological areas of catalysts, electronics, and optoelectronics

Molybdenum and Tungsten Sulfide Ligands for Versatile Functionalization of All-Inorganic Nanocrystals

We report a strategy toward the synthesis of colloidal nanocrystals capped with inorganic molybdenum and tungsten sulfide ligands. MoS4 2- and WS4 2- thiometalates were utilized to replace organic ligands capping a wide range of nanocrystals such as metals, semiconductors, and well-conserved primary properties of nanocrystals in polar media. Especially, MoS4 2-- and WS4 2--capped CdSe nanocryatals showed the dramatic enhancement of photoluminescence properties by the photo-oxidation treatment, which originated from the preferential formation of MoSxOy layers on the CdSe surface. The highest quantum yield reached up to 51%. Furthermore, we studied the charge-transport properties of MoS4 2--capped PbS nanocryatals by the fabrication of a field-effect transistor and photodetectors. Finally, MoS4 2-- and WS4 2--capped nanocrystals were used for the production of two-dimensional MoS2 and WS2 thin layers on nanostructures by heat treatment. Such versatility of these thiometalate ligands offers an additional degree of control over the functionality of nanocrystals for optoelectronic and catalytic applications.clos

Polyphosphide Precursor for Low-Temperature Solution-Processed Fibrous Phosphorus Thin Films

Crystalline red phosphorus has very recently emerged as a stable and cost-effective semiconductor material. However, despite its potentiality in electronics and optoelectronics, the widespread application of this material is still hampered by the limited synthetic route of the ampoule-based chemical vapor deposition that critically requires mineralizing agents. To address this issue, we report the chemical synthesis of soluble polyphosphide precursors that serve as inks for the solution-processed fabrication of crystalline fibrous phosphorus thin films. The purified polyphosphide precursor formed crystalline fibrous phosphorus via thermal annealing at a temperature as low as 250 ??C without any mineralizing agents. This anionic polyphosphide functioned as a surface-capping ligand for nanoparticles including metals, semiconductors, and magnets. Therefore, the study investigates the possibility of solution-processed fibrous phosphorus thin films as active channel layers in field-effect transistors as well as photodetectors and demonstrates their initial performances on the charge-transport and photoresponsive characteristics of these devices. The effect of semiconducting PbS nanoparticles embedded in the fibrous phosphorus thin films on device performance was also studied. The synthesized polyphosphide precursor offers a vast opportunity for the facile preparation of crystalline red phosphorus and chemical design of nanoparticles

Colloidal Synthesis of Te-Doped Bi Nanoparticles: Low-Temperature Charge Transport and Thermoelectric Properties

Electronically doped nanoparticles formed by incorporation of impurities have been of great interest because of their controllable electrical properties. However, the development of a strategy for n-type or p-type doping on sub-10 nm-sized nanoparticles under the quantum confinement regime is very challenging using conventional processes, owing to the difficulty in synthesis. Herein, we report the colloidal chemical synthesis of sub-10 nm-sized tellurium (Te)-doped Bismuth (Bi) nanoparticles with precisely controlled Te content from 0 to 5% and systematically investigate their low-temperature charge transport and thermoelectric properties. Microstructural characterization of nanoparticles demonstrates that Te ions are successfully incorporated into Bi nanoparticles rather than remaining on the nanoparticle surfaces. Low-temperature Hall measurement results of the hot-pressed Te-doped Bi-nanostructured materials, with grain sizes ranging from 30 to 60 nm, show that the charge transport properties are governed by the doping content and the related impurity and nanoscale grain boundary scatterings. Furthermore, the low-temperature thermoelectric properties reveal that the electrical conductivity and Seebeck coefficient expectedly change with the Te content, whereas the thermal conductivity is significantly reduced by Te doping because of phonon scattering at the sites arising from impurities and nanoscale grain boundaries. Accordingly, the 1% Te-doped Bi sample exhibits a higher figure-of-merit ZT by ???10% than that of the undoped sample. The synthetic strategy demonstrated in this study offers the possibility of electronic doping of various quantum-confined nanoparticles for diverse applications

Monomeric MoS42--Derived Polymeric Chains with Active Molecular Units for Efficient Hydrogen Evolution Reaction

Molybdenum sulfides have attracted widespread attention as promising nonprecious-metal catalysts for the hydrogen evolution reaction (HER). Since the MoS2 edge was proposed as a major active site, molecular and polymeric analogues to the MoS2 edge have been widely explored as the HER catalysts. In particular, amorphous MoSx coordination polymers have been considered as active HER catalysts because they are rich in unsaturated Mo-S coordination, which is the characteristic of the active MoS2 edge. Herein, we report that the simple monomeric thiomolybdate (MoS4 2-) could adopt a polymeric chain structure, which exhibited high HER activity; its turnover frequency surpassed those of dimeric [Mo2S12]2-- and trimeric [Mo3S13]2--derived MoSx catalysts. This high HER activity of monomeric MoS4 2- is attributed to the polymerization of MoS4 2- anions, generating active molecular analogues that comprise monomeric S2- sites bridging Mo(V) and Mo(IV). Density functional theory calculations of possible polymeric chain structures identified the Mo(IV)Mo(V)2(S2 2-)2(S2-)5 unit as the most plausible structure that best matched the experimentally deduced structure. The Gibbs free energy for hydrogen adsorption on the bridging S2- (??-S2-) site in Mo(IV)Mo(V)2(S2 2-)2(S2-)5 was found to be -0.05 eV, which is close to the thermoneutral state. Combined analyses by resonance Raman spectroscopy and extended X-ray absorption fine structure suggested the role of Mo-oxo (Mo???Ox) species to generate the active Mo(V)-(??-S2-)-Mo(IV) center for effective hydrogen adsorption

Controlled Grafting of Colloidal Nanoparticles on Graphene through Tailored Electrostatic Interaction

Nanoparticle/graphene hybrid composites have been of great interest in various disciplines due to their unique synergistic physicochemical properties. In this study, we report a facile and generalized synthesis method for preparing nanoparticle/exfoliated graphene (EG) composites by tailored electrostatic interactions. EG was synthesized by an electrochemical method, which produced selectively oxidized graphene sheets at the edges and grain boundaries. These EG sheets were further conjugated with polyethyleneimine to provide positive charges at the edges. The primary organic ligands of the colloidal nanoparticles were exchanged with Cl- or MoS42- anions, generating negatively charged colloidal nanoparticles in polar solvents. By simple electrostatic interactions between the EG and nanoparticles in a solution, nanoparticles were controllably assembled at the edges of the EG. Furthermore, the generality of this process was verified for a wide range of nanoparticles, such as semiconductors, metals, and magnets, on the EG. As a model application, designed composites with size-controlled FeCo nanoparticle/EG were utilized as electromagnetic interference countermeasure materials that showed a size-dependent shift of the frequency ranges on the electromagnetic absorption properties. The current generalized process will offer great potential for the large-scale production of well-designed graphene nanocomposites for electronic and energy applications

Simultaneous improvement in electrical and thermal properties of interface-engineered BiSbTe nanostructured thermoelectric materials

Over the past decade, nanostructuring has become the core of thermoelectric (TE) material research because it creates numerous internal interfaces that provide an effective way to tune the electrical and/or thermal properties of TE materials. Herein, we report a synthesis of interface-engineered BiSbTe nanostructured TE materials by introducing chemically synthesized molecular Te-n(2-) polyanions into BiSbTe particles, from which BiSbTe nanostructured materials with high-density Te interfacial layers are prepared in thin films and sintered pellets. These Te layers form the contact potential well at the BiSbTe-Te junction to realize energy dependent carrier scattering and scatter phonons effectively, thus resulting in simultaneous improvement in the electrical and thermal properties to increase the ZT value well above 1.3 +/- 0.14 that is increased by 40% compared to bulk BiSbTe. The findings of current study can open up new chemical design spaces for interface-engineered electronic and TE materials.clos