All‐inorganic lead halide perovskite nanocrystals (NCs) have great optoelectronic properties with promising applications in light‐emitting diodes (LEDs), lasers, photodetectors, solar cells, and photocatalysis. However, the intrinsic toxicity of Pb and instability of the NCs impede their broad applications. Shell‐coating is an effective method for enhanced environmental stability while reducing toxicity by choosing non‐toxic shell materials such as metal oxides, polymers, silica, etc. However, multiple perovskite NCs can be encapsulated within the shell material and a uniform epitaxial‐type shell growth of well‐isolated NCs is still challenging. In this work, lead‐free vacancy‐ordered double perovskite Cs2SnX6(X = Cl, Br, and I) shells are epitaxially grown on the surface of CsPbX3NCs by a hot‐injection method. The effectiveness of the non‐toxic double perovskite shell protection is demonstrated by the enhanced environmental and phase stability against UV illumination and water. In addition, the photoluminescence quantum yields (PL QYs) increase for the CsPbCl3and CsPbBr3NCs after shelling because of the type I band alignment of the core/shell materials, while enhanced charge transport properties obtained from CsPbI3/Cs2SnI6core/shell NCs are due to the efficient charge separation in the type II core/shell band alignment.
- Award ID(s):
- 1924412
- NSF-PAR ID:
- 10274330
- Date Published:
- Journal Name:
- Crystals
- Volume:
- 11
- Issue:
- 1
- ISSN:
- 2073-4352
- Page Range / eLocation ID:
- 51
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
null (Ed.)Colloidal semiconductor nanocrystals (NCs) represent a promising class of nanomaterials for lasing applications. Currently, one of the key challenges facing the development of high-performance NC optical gain media lies in enhancing the lifetime of biexciton populations. This usually requires the employment of charge-delocalizing particle architectures, such as core/shell NCs, nanorods, and nanoplatelets. Here, we report on a two-dimensional nanoshell quantum dot (QD) morphology that enables a strong delocalization of photoinduced charges, leading to enhanced biexciton lifetimes and low lasing thresholds. A unique combination of a large exciton volume and a smoothed potential gradient across interfaces of the reported CdS bulk /CdSe/CdS shell (core/shell/shell) nanoshell QDs results in strong suppression of Auger processes, which was manifested in this work though the observation of stable amplified stimulated emission (ASE) at low pump fluences. An extensive charge delocalization in nanoshell QDs was confirmed by transient absorption measurements, showing that the presence of a bulk-size core in CdS bulk /CdSe/CdS shell QDs reduces exciton–exciton interactions. Overall, present findings demonstrate unique advantages of the nanoshell QD architecture as a promising optical gain medium in solid-state lighting and lasing applications.more » « less
-
more » « less
Abstract Two-dimensional (2D) ternary materials recently generated interest in optoelectronics and energy-related applications, alongside their binary counterparts. To date, only a few naturally occurring layered 2D ternary materials have been explored. The plethora of benefits owed to reduced dimensionality prompted exploration of expanding non-layered ternary chalcogenides into the 2D realm. This work presents a templating method that uses 2D transition metal dichalcogenides as initiators to be converted into the corresponding ternary chalcogenide upon addition of copper, via a solution-phase synthesis, conducted in high boiling point solvents. The process starts with preparation of VSe2nanosheets, which are next converted into Cu3VSe4sulvanite nanosheets (NSs) which retain the 2D geometry while presenting an X-ray diffraction pattern identical with the one for the bulk Cu3VSe4. Both the scanning electron microscopy and transmission microscopy electron microscopy show the presence of quasi-2D morphology. Recent studies of the sulfur-containing sulvanite Cu3VS4highlight the presence of an intermediate bandgap, associated with enhanced photovoltaic (PV) performance. The Cu3VSe4nanosheets reported herein exhibit multiple UV–Vis absorption peaks, related to the intermediate bandgaps similar to Cu3VS4and Cu3VSe4nanocrystals. To test the potential of Cu3VSe4NSs as an absorber for solar photovoltaic devices, Cu3VSe4NSs thin-films deposited on FTO were subjected to photoelectrochemical testing, showing p-type behavior and stable photocurrents of up to ~ 0.036 mA/cm2. The photocurrent shows a ninefold increase in comparison to reported performance of Cu3VSe4nanocrystals. This proves that quasi-2D sulvanite nanosheets are amenable to thin-film deposition and could show superior PV performance in comparison to nanocrystal thin-films. The obtained electrical impedance spectroscopy signal of the Cu3VSe4 NSs-FTO based electrochemical cell fits an equivalent circuit with the circuit elements of solution resistance (Rs), charge-transfer resistance (Rct), double-layer capacitance (Cdl), and Warburg impedance (W). The estimated charge transfer resistance value of 300 Ω cm2obtained from the Nyquist plot provides an insight into the rate of charge transfer on the electrode/electrolyte interface.
-
Ultra-violet light emitting diodes (UV-LEDs) and lasers based on the III-Nitride material system are very promising since they enable compact, safe, and efficient solid-state sources of UV light for a range of applications. The primary challenges for UV LEDs are related to the poor conductivity of p-AlGaN layers and the low light extraction efficiency of LED structures. Tunnel junction-based UV LEDs provide a distinct and unique pathway to eliminate several challenges associated with UV LEDs1-4. In this work, we present for the first time, a reversed-polarization (p-down) AlGaN based UV-LED utilizing bottom tunnel junction (BTJ) design. We show that compositional grading enables us to achieve the lowest reported voltage drop of 1.1 V at 20 A/cm2 among transparent AlGaN based tunnel junctions at this Al-composition. Compared to conventional LED design, a p-down structure offers lower voltage drop because the depletion barrier for both holes and electrons is lower due to polarization fields aligning with the depletion field. Furthermore, the bottom tunnel junction also allows us to use polarization grading to realize better p- and n-type doping to improve tunneling transport. The epitaxial structure of the UV-LED was grown by plasma-assisted molecular beam epitaxy (PAMBE) on metal-organic chemical vapor deposition (MOCVD)-grown n-type Al0.3Ga0.7N templates. The transparent TJ was grown using graded n++-Al0.3Ga0.7N→ n++-Al0.4Ga0.6N (Si=3×1020 cm-3) and graded p++-Al0.4Ga0.6N →p++-Al0.3Ga0.7N (Mg=1×1020 cm-3) to take advantage of induced 3D polarization charges. The high number of charges at the tunnel junction region leads to lower depletion width and efficient hole injection to the p-type layer. The UV LED active region consists of three 2.5 nm Al0.2Ga0.8N quantum wells and 7 nm Al0.3Ga0.6N quantum barriers followed by 12 nm of p- Al0.46Ga0.64N electron blocking layer (EBL). The active region was grown on top of the tunnel junction. A similar LED with p-up configuration was also grown to compare the electrical performance. The surface morphology examined by atomic force microscopy (AFM) shows smooth growth features with a surface roughness of 1.9 nm. The dendritic features on the surface are characteristic of high Si doping on the surface. The composition of each layer was extracted from the scan by high resolution x-ray diffraction (HR-XRD). The electrical characteristics of a device show a voltage drop of 4.9 V at 20 A/cm2, which corresponds to a tunnel junction voltage drop of ~ 1.1 V. This is the best lowest voltage for transparent 30% AlGaN tunnel junctions to-date and is comparable with the lowest voltage drop reported previously on non-transparent (InGaN-based) tunnel junctions at similar Al mole fraction AlGaN. On-wafer electroluminescence measurements on patterned light-emitting diodes showed single peak emission wavelength of 325 nm at 100 A/cm2 which corresponds to Al0.2Ga0.8N, confirming that efficient hole injection was achieved within the structure. The device exhibits a wavelength shift from 330 nm to 325 nm with increasing current densities from 10A/cm2 to 100A/cm2. In summary, we have demonstrated a fully transparent bottom AlGaN homojunction tunnel junction that enables p-down reversed polarization ultraviolet light emitting diodes, and has very low voltage drop at the tunnel junction. This work could enable new flexibility in the design of future III-Nitride ultraviolet LEDs and lasers.more » « less
-
more » « less
Pyrazinacenes are next generation N-heteroacenes and represent a novel class of stable n-type materials capable of accepting more than one electron and displaying intriguing features, including prototropism, halochromism, and redox chromism. Astonishingly, despite a century since their discovery, there have been no reports on the conjugated polymers of pyrazinacenes due to unknown substrate scope and lack of pyrazinacene monomers that are conducive to condensation polymerization. Breaking through these challenges, in this work, we report the synthesis of previously undiscovered and highly coveted conjugated polymers of pyrazinacenes. In order to understand the intricacies of conjugation extension within the acene and along the polymer backbone, a series of electronically diverse four pyrazinacene conjugated polymers were synthesized. Polymers synthesis required optimizing a few synthetic steps along the 12-step synthetic pathway. The generated pyrazinacene monomers are not amenable to the popular condensation polymerizations involving Pd or Cu catalysts. Gratifyingly, Pd and Cu free dehydrohalogenation polymerization of the monomer with HgCl2 resulted in high molecular weight organometallic conjugated pyrazinacene polymers within a few minutes at room temperature. The dual role played by the Hg(II) during the polymerization, combined with the self-coupling of the RHgCl (intermediate), is at the core of successful polymerization. Notably, the self-coupling of intermediates challenges the strict stoichiometric balance typically required for step-growth polymerization and offers a novel synthetic strategy to generate high molecular weight conjugated polymers even with imbalanced monomer stoichiometries. A combination of electrochemical studies and DFT-B3LYP simulations indicated that the presence of the reduced pyrazine ring promotes interacene p-conjugation through the metal center, in contrast to completely oxidized tetrazaazaanthracene. The extension of conjugation results in ca. 2 eV lower reduction potential for polymers compared to the monomer, placing the LUMO energy levels of these polymers on par with some of the best-known n-type polymers. Also, the presence of NH protons in the pyrazinacene polymers show ionochromism and red-shift UV-vis absorption maximum by ca. 100 nm. This work not only shows a way to realize highly desirable and elusive pyrazinacene conjugated polymers but also paves the way for a library of n-type conjugated polymers that can undergo multi-electron reduction.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/cryst11010051
