Shape‐ and Trap‐Controlled Nanocrystals for Giant‐Performance Improvement of All‐Inorganic Perovskite Photodetectors

In the last few years, all‐inorganic perovskite CsPbBr₃ nanocrystals (NCs) have attracted tremendous attention for its high carrier mobility, long carrier diffusion length, excellent visible light absorption, and more importantly superior air stability. In fact, photodetectors (PDs) are designed and fabricated using the CsPbBr₃ NCs with very high performance. Herein, by optimizing the NC shape, size, and surface passivation, the CsPbBr₃ PDs are developed with an even higher performance. It is found that the PDs based on CsPbBr₃ nanoribbons show the best photoresponse among all common NC structures synthesized. Moreover, it is found that 6,6‐phenyl‐C61‐butyric acid ethyl ester can be used to passivate defects on the CsPbBr₃ nanoribbon surface and shows the charge transfer. As a result, the device displays superior photoresponsivity (R = 18.4 A W⁻¹), excellent signal‐to‐noise ratio, as high as 10⁴, and a very sharp rise/decay time (8.7/3.5 ms). The method demonstrated may offer an attractive strategy to improve sensitivity for all‐inorganic perovskite PDs in general.     

Synthesis of NIR‐Emitting InAs‐Based Core/Shell Quantum Dots with the Use of Tripyrazolylarsane as Arsenic Precursor

Tris(3,5‐dimethylpyrazolyl)arsane (1) is introduced as a low‐cost and convenient to handle arsenic precursor for the straight forward synthesis of InAs quantum dots (QDs). Transamination of 1 with the solvent oleylamine (OLAH) gives trioleylarsane (As(OLA)₃) which in the presence of the reducing agents diisobutylaluminum hydride (DIBAL‐H) or trioleylphosphane (P(OLA)₃) yields InAs QDs via a typical hot injection approach. The size of the obtained InAs core QDs are tuned by varying the reaction time, the amount of the applied reducing agent, or even more effectively by changing the indium and/or zinc halide precursors, InX₃, and ZnX₂ (Cl, Br, or I). Passivation of the resulting InAs particles with a protective ZnS or ZnSe shell results in improved photoluminescence of the core/shell QDs covering a spectral range between 600 and 1150 nm.     

Self-Assembly of Chiral Nematic Liquid Crystalline Phases of AgNR@SiO2@Cysteine@CsPbBr3 Hybrid Nanorods with Plasmon-Dependent Photoluminescence

The direct synthesis of a chiral nematic liquid crystalline phase of AgNR@SiO₂@cysteine@CsPbBr₃ hybrid nanorods (HNRs) is reported. The circular dichroism spectra can be divided into three components: (1) the interband absorption–enhanced optical activity of structural arrangement of cysteine (cys) molecules, 200–320 nm, (2) the chiral nematic liquid crystalline arrangement of the Ag nanorods (AgNRs), 350–450 nm, and (3) the exciton adsorption edge of the perovskite, 500–550 nm. The polarizing optical microscope images indicate that the chiroptical response of perovskite arises from chiral nematic crystalline arrangement rather than cys-induced electronic coupling between a chiral ligand and otherwise achiral perovskite quantum dots (QDs). The luminescent intensity of CsPbBr₃ QDs in AgNR@SiO₂@cys@CsPbBr₃ HNRs is boosted 87-fold due to the local surface plasmon resonance field enhancement effect. Furthermore, the high-performance green light emitting diode is constructed employing AgNR@SiO₂@cys@CsPbBr₃ complexes, which exhibit excellent luminescent properties. This work contributes insights into structure–property relationships and this strategy promisingly provides guidance for the other inorganic chiral semiconductor suprastructures.     

A reaction cell for time‐resolved in situ XAS studies during wet chemical synthesis: the Cu2(OH)3Cl case

The use of in situ time‐resolved dispersive X‐ray absorption spectroscopy (DXAS) to monitor the formation of Cu₂(OH)₃Cl particles in an aqueous solution is reported. The measurements were performed using a dedicated reaction cell, which enabled the evolution of the Cu K‐edge X‐ray absorption near‐edge spectroscopy to be followed during mild chemical synthesis. The formed Cu₂(OH)₃Cl particles were also characterized by synchrotron‐radiation‐excited X‐ray photoelectron spectroscopy, X‐ray diffraction and scanning electron microscopy. The influence of polyvinylpyrrolidone (PVP) on the electronic and structural properties of the formed particles was investigated. The results indicate clearly the formation of Cu₂(OH)₃Cl, with or without the use of PVP, which presents very similar crystalline structures in the long‐range order. However, depending on the reaction, dramatic differences were observed by in situ DXAS in the vicinities of the Cu atoms.     

Efficient Quantum Dot Light-Emitting Diodes Based on Well-Type Thick-Shell CdxZn1−xS/CdSe/CdyZn1−yS Quantum Dots

Device grade quantum dots (QDs) require QDs ensembles to retain their original superior optical properties as in solution. QDs with thick shells are proven effective in suppressing the inter-dot interaction and preserving the emission properties for QDs solids. However, lattice strain–induced defects may form as the shell grows thicker, resulting in a notable photoluminescence quenching. Herein, a well-type Cd_xZn_1−xS/CdSe/Cd_yZn_1−yS QDs is proposed, where ternary alloys CdZnS are adopted to match the lattice parameter of intermediate CdSe by separately adjusting the x and y parameters. The resultant thick-shell Cd_0.5Zn_0.5S/CdSe/Cd_0.73Zn_0.27S QDs reveal nonblinking properties with a high PL QY of 99% in solution and 87% in film. The optimized quantum dot light-emitting diodes (QLEDs) exhibit a luminance of 31547.5 cd m⁻² at the external quantum efficiency maximum of 21.2% under a bias of 4.0 V. The shell thickness shows great impact on the degradation of the devices. The T₅₀ lifetime of the QLEDs with 11.2 nm QDs reaches 251 493 h, which is much higher than that of 6.5 and 8.4 nm QDs counterparts. The performances of the well-type thick-shell QLEDs are comparable to state-of-the-art devices, suggesting that this type of QDs is a promising candidate for efficient optoelectronic devices.     

Thermal and Tribological Properties of Fullerene‐Containing Composite Systems. Part 3. Features of the Mechanism of Thermal Degradation of Poly‐(N‐Vinyl‐Pyrrolidone) and Its Compositions with Fullerene C60

By mass‐spectrometric thermal analysis (MTA) the thermochemical features of poly(N‐vinyl pyrrolidone) (PVP) and its compositions with fullerene C₆₀ were studied. The mechanism of PVP thermal degradation was investigated; in particular the nature of the low‐temperature degradation (between 75 and 300°C) accompanied by output of pyrrolidone was explained as well as the influence of fullerene C₆₀ on this mechanism. It was shown that during thermal degradation of copolymer PVP‐C₆₀, there is a disappearance of the low‐temperature peaks of the output of pyrrolidone that is interpreted as an increase of the thermal stability of N‐vinyl‐pyrrolidone fragments in this product in comparison with their thermal stability in pure PVP.     

Multicolor Light‐Emitting Diodes with MoS2 Quantum Dots

Molybdenum disulfide (MoS₂) quantum dots (QDs) are known for their excitation‐wavelength‐dependent photoluminescent (PL) properties. However, the mechanism of this phenomenon is still unclear. Here, small size MoS₂ QDs with a narrow size distribution are synthesized. Based on the decay study and PL dynamics, a reasonable radiation model is presented to understand the special PL properties, i.e., the carrier recombination in the localized surface defect states generated the PL. Accordingly, this optical property is used to fabricate multicolor light‐emitting devices with the same MoS₂ QDs. The emission color covers the full visible spectrum from blue to red, only by adjusting the thickness of the down‐conversion QD layers.     

InAs/AlAs quantum dots with InGaAs insertion layer: dependence of the indium composition and the thickness

We have systematically studied the effect of an In_xGa_1−xAs insertion layer (IL) on the optical and structural properties of InAs quantum dot (QD) structures. A high density of 9.6×10¹⁰ cm⁻² of InAs QDs with an In_0.3Ga_0.7As IL has been achieved on a GaAs (1 0 0) substrate by metal organic chemical vapor deposition. A photoluminescence line width of 25 meV from these QDs has been obtained. We attribute the high density and high uniformity of these QDs to the use of the IL. Our results show that the InGaAs IL is useful for obtaining high-quality InAs QD structures for devices with a 1.3 μm operation.     

Effect of deposition period on structural and optical properties of InGaAs/GaAs quantum dots formed by InAs/GaAs short-period superlattices

Structural and optical properties of In_0.5Ga_0.5As/GaAs quantum dots (QDs) grown at 510 °C by atomic layer molecular beam epitaxy technique are studied as a function of n repeated deposition of 1-ML-thick InAs and 1-ML-thick GaAs. Cross-sectional images reveal that the QDs are formed by single large QDs rather than closely stacked InAs QDs and their shape is trapezoidal. In the image, existence of wetting layers is not clear. In 300 K-photoluminescence (PL) spectra of InGaAs QDs (n=5), 4 peaks are resolved. Origin of each peak transition is discussed. Finally, it was found that the PL linewidths of atomic layer epitaxy (ALE) QDs were weakly sensitive to cryostat temperatures (16–300 K). This is attributed to the nature of ALE QDs; higher uniformity and weaker wetting effect compared to SK QDs.     

Hydrophilic Cu3BiS3 Nanoparticles for Computed Tomography Imaging and Photothermal Therapy

Hydrophilic Cu₃BiS₃ nanoparticles (NPs) have been prepared using the thermal decomposition of precursor complexes in oily‐mixed solvent followed by coating the produced Cu₃BiS₃ NPs with polyvinylpyrrolidone (PVP). The resulting Cu₃BiS₃/PVP NPs remain stable in aqueous solutions over a long period of time, and meanwhile, they show low in vitro cytotoxicity and negligible toxicity to mice in vivo. Cu₃BiS₃/PVP NPs could operate as an efficient dual‐modal contrast agent to simultaneously enhance X‐ray computed tomography imaging and photothermal imaging of tumor model in vivo. Moreover, highly efficient ablation of cancer cells both in vitro and in vivo has been successfully achieved by combining Cu₃BiS₃/PVP NPs with near‐infrared (NIR) laser irradiation. All of the positive results in this study highlight that Cu₃BiS₃/PVP NPs could serve as a promising platform for cancer diagnosis and therapy.     

Study of InAs/GaAs quantum dots grown by MOVPE under the safer growth conditions

InAs quantum dots (QDs) have been formed on GaAs (001) substrate by metal-organic vapor phase epitaxy (MOVPE) under the safer growth conditions: using tertiarybutylarsine (TBA) to replace AsH₃ as the arsenic source and replacing hydrogen by pure nitrogen as the carrier gas. Effects of growth conditions on the QD formation have been investigated. It is observed that the wetting layer is stabilized with some material being transferred to form the QDs due to the strain relaxation process during the QD formation. Dot size dispersion becomes broader when the post-growth interruption is more than 20 s. Compared with normal one-step grown QDs, dot density increases greatly by 213% after employing two-step deposition for QD growth. This is explained by considering the indium-flux-dependent nucleation density at step 1 and kinetically self-limiting growth at step 2. The two photoluminescence (PL) emission peaks, 1.203 μm and 1.094 μm, from the two-step grown QDs are attributed to E1–HH1 and E1–LH1 transitions of the QDs, respectively. The measured results agree well with those received by an 8 k·p theoretical calculation. The narrow PL linewidth of ~50 nm shows high quality of the QDs. This paves the way to develop safer MOVPE process, using TBA/N₂ instead of AsH₃/H₂, to grow QDs for device application.     

High-Throughput Robotic Synthesis and Photoluminescence Characterization of Aqueous Multinary Copper–Silver Indium Chalcogenide Quantum Dots

The feasibility of a high-throughput robot-assisted synthesis of complex Cu_1-xAg_xInS_ySe_1-x (CAISSe) quantum dots (QDs) by spontaneous alloying of aqueous glutathione-capped Ag–In–S, Cu–In–S, Ag–In–Se, and Cu–In–Se QDs is demonstrated. Both colloidal and thin-film core CAISSe and core/shell CAISSe/ZnS QDs are produced and studied by high-throughput semiautomated photoluminescence (PL) spectroscopy. The silver-copper-mixed QDs reveal clear evidence of a band bowing effect in the PL spectra and higher average PL lifetimes compared to the counterparts containing silver or copper only. The photophysical analysis of CAISSe and CAISSe/ZnS QDs indicates a composition-dependent character of the nonradiative recombination in QDs. The rate of this process is found to be lower for mixed copper-silver-based QDs compared to Cu- or Ag-only QDs. The combination of the band bowing effect and the suppressed nonradiative recombination of CAISSe QDs is beneficial for their applications in photovoltaics and photochemistry. The synergy of high-throughput robotic synthesis and a high-throughput characterization in this study is expected to grow into a self-learning synthetic platform for the production of metal chalcogenide QDs for light-harvesting, light-sensing, and light-emitting applications.     

Ab Initio Simulation of Charge Transfer at the Semiconductor Quantum Dot/TiO2 Interface in Quantum Dot‐Sensitized Solar Cells

Quantum dot‐sensitized solar cells (QDSSCs) have emerged as a promising solar architecture for next‐generation solar cells. The QDSSCs exhibit a remarkably fast electron transfer from the quantum dot (QD) donor to the TiO₂ acceptor with size quantization properties of QDs that allows for the modulation of band energies to control photoresponse and photoconversion efficiency of solar cells. To understand the mechanisms that underpin this rapid charge transfer, the electronic properties of CdSe and PbSe QDs with different sizes on the TiO₂ substrate are simulated using a rigorous ab initio density functional method. This method capitalizes on localized orbital basis set, which is computationally less intensive. Quite intriguingly, a remarkable set of electron bridging states between QDs and TiO₂ occurring via the strong bonding between the conduction bands of QDs and TiO₂ is revealed. Such bridging states account for the fast adiabatic charge transfer from the QD donor to the TiO₂ acceptor, and may be a general feature for strongly coupled donor/acceptor systems. All the QDs/TiO₂ systems exhibit type II band alignments, with conduction band offsets that increase with the decrease in QD size. This facilitates the charge transfer from QDs donors to TiO₂ acceptors and explains the dependence of the increased charge transfer rate with the decreased QD size.     

Tunable and High Photoluminescence Quantum Yield from Self‐Decorated TiO2 Quantum Dots on Fluorine Doped Mesoporous TiO2 Flowers by Rapid Thermal Annealing

Herein a novel approach is reported to achieve tunable and high photoluminescence (PL) quantum yield (QY) from the self‐grown spherical TiO₂ quantum dots (QDs) on fluorine doped TiO₂ (F‐TiO₂) flowers, mesoporous in nature, synthesized by a simple solvothermal process. The strong PL emission from F‐TiO₂ QDs centered at ≈485 nm is associated with shallow and deep traps, and a record high PL QY of ≈5.76% is measured at room temperature. Size distribution and doping of F‐TiO₂ nanocrystals (NCs) are successfully tuned by simply varying the HF concentration during synthesis. During the post‐growth rapid thermal annealing (RTA) under vacuum, the arbitrary shaped F‐TiO₂ NCs transform into spherical QDs with smaller sizes and it shows dramatic enhancement (≈163 times) in the PL intensity. Electron spin resonance (ESR) and X‐ray photoelectron spectroscopy (XPS) confirm the high density of oxygen vacancy defects on the surface of TiO₂ NCs. Confocal fluorescence microscopy imaging shows bright whitish emission from the F‐TiO₂ QDs. Low temperature and time resolved PL studies reveal that the ultrafast radiative recombination in the TiO₂ QDs results in highly efficient PL emission. A highly stable, biologically inert, and highly fluorescent TiO₂ QDs/flowers without any capping agent demonstrated here is significant for emerging applications in bioimaging, energy, and environmental cleaning.     

Mn-including InAs quantum dots fabricated by Mn implantation

Mn-including InAs quantum dots (QDs) were fabricated by Mn-ion implantation and subsequent annealing. The optical, compositional, and structural properties of the treated samples were analyzed by photoluminescence (PL) and microscopy. Energy dispersive X-ray (EDX) results indicate that Mn ions diffused from the bulk GaAs into the InAs QDs during annealing, and the diffusion appears to be driven by the strain in the InAs QDs. The temperature dependence of the PL of Mn-including InAs QD samples exhibits QDs PL characteristics. At the same time, the heavy Mn-including InAs QD samples have ferromagnetic properties and high T_c.     

Influence of the built-in electric field on luminescent properties in self-formed single-GaN/AlxGa1−xN quantum dots

Based on the framework of effective-mass approximation and variational approach, the luminescent properties are investigated theoretically in self-formed wurtzite GaN/Al_xGa_1−xN single-quantum dots (QDs). Considering the three-dimensional (3D) confinement of electron and hole pair and the strong built-in electric field effects, the exciton binding energy, the emission wavelength and the oscillator strength are calculated with and without the built-in electric field in detail. The results elucidate that the strong built-in electric field has a significant influence on luminescent properties of GaN/Al_xGa_1−xN QDs.     

Giant permittivity of three phase polymer nanocomposites obtained by modifying hybrid nanofillers with polyvinylpyrrolidone

In this work, the combination of graphene decorated with graphene quantum dots (G-D-GQDs) and barium titanate (BaTiO₃) nanoparticles filled poly (vinyledene fluoride) (PVDF) nanocomposites are prepared using solvent casting method. The modification of G-D-GQDs and BaTiO₃ nanoparticles with polyvinyl pyrrolidone (PVP) show finer dispersion in PVDF matrix as compared to unmodified G-D-GQDs and BaTiO₃ nanoparticles in PVDF matrix. XRD of PVDF nanocomposites shows the formation of α and β form of PVDF crystals. The incorporation of the combination of PVP modified BaTiO₃ nanoparticles and G-D-GQDs in PVDF matrix show a decrease in crystallization temperature (T_c), percent crystallinity (X_c) and increase in thermal stability as compared to unmodified PVDF/BaTiO₃/G-D-GQDs nanocomposites, due to interaction of PVP modified nanoparticles with PVDF. Further, the incorporation of the combination of 20 wt.% BaTiO₃ nanoparticles and 3 wt.% G-D-GQDs in PVDF matrix show a giant dielectric constant. The giant dielectric constant is achieved due to accumulation of more charges across conductor-insulator interface, more numbers of microcapacitor formed and enhanced interfacial compatibility between BaTiO₃/G-D-GQDs with PVDF through PVP. The loss tangent (tan δ) of PVP modified G-D-GQDs and BaTiO₃ nanoparticles and its PVDF nanocomposites is low due to lower leakage current, which make the material suitable for various applications.     

All‐optical modulation based on silicon quantum dot doped SiOx:Si‐QD waveguide

All‐optical modulation based on silicon quantum dot doped SiO_x:Si‐QD waveguide is demonstrated. By shrinking the Si‐QD size from 4.3 nm to 1.7 nm in SiO_x matrix (SiO_x:Si‐QD) waveguide, the free‐carrier absorption (FCA) cross section of the Si‐QD is decreased to 8 × 10⁻¹⁸ cm² by enlarging the electron/hole effective masses, which shortens the PL and Auger lifetime to 83 ns and 16.5 ps, respectively. The FCA loss is conversely increased from 0.03 cm⁻¹ to 1.5 cm⁻¹ with the Si‐QD size enlarged from 1.7 nm to 4.3 nm due to the enhanced FCA cross section and the increased free‐carrier density in large Si‐QDs. Both the FCA and free‐carrier relaxation processes of Si‐QDs are shortened as the radiative recombination rate is enlarged by electron–hole momentum overlapping under strong quantum confinement effect. The all‐optical return‐to‐zero on‐off keying (RZ‐OOK) modulation is performed by using the SiO_x:Si‐QD waveguides, providing the transmission bit rate of the inversed RZ‐OOK data stream conversion from 0.2 to 2 Mbit/s by shrinking the Si‐QD size from 4.3 to 1.7 nm.     

Luminescence of CsPbBr3-like quantum dots in CsBr single crystals

Luminescence and decay kinetics of the Pb²⁺ aggregates in CsBr host crystals were measured in the 4–300 K temperature interval and in 10⁻¹⁰–10⁻³ time scale. Their emission properties are similar to those of CsPbBr₃ bulk crystal showing a subnanosecond free exciton emission in the 520–540 nm spectral region and slower trapped exciton emission in the 530–580 nm spectral region. An efficient energy exchange between the free and trapped exciton states is shown by the temperature dependencies of emission spectra. The quantum size effect is demonstrated in the high energy shift and broadening of the absorption and emission spectra and an estimate of the size of the CsPbBr₃-like aggregates is provided. Independent evidence of the presence of the CsPbBr₃ and Cs₄PbBr₆ aggregated phases in the CsBr host was obtained by X-ray structural studies.     

Bright all-solution-processed CsPbBr3 perovskite light emitting diodes optimized by quaternary ammonium salt

Perovskite light-emitting diodes (PeLEDs) prepared by the all-solution-process are gradually coming into view due to their low cost and flexible production process. However, the performance of CsPbBr₃ device is limited by the high non-radiative recombination losses due to incomplete surface coverage and grain defects. Here a quaternary ammonium salt, tetrabutylammonium hexafluorophosphate (TBA-PF₆) was simultaneously introduced into perovskite emission layers (CsPbBr₃) and electron transport layer (TPBi (1,3,5-Tris(1-phenyl-1H-benzimidazol-2-yl) benzene) dissolved in ethyl acetate). As a result, the morphology and luminescence of CsPbBr₃ films were improved, and the energy level of TPBi was more conducive to charge transport. Consequently, the maximum luminance and current efficiency of the modified green-emitting PeLEDs are improved. Furthermore, the optimized device had an operating life of more than 20 min at an initial luminance of 1230 cd/m². This work provides a simple and easy method to be scaled up for the development of low-cost all-solution-processed PeLEDs.