Quantum Dots Interface Research Articles

Design, modeling, and fabrication of high frequency Oersted lines for electron spin manipulation in silicon based quantum devices

Coherent manipulation of electron spins is one of the central challenges of silicon-based quantum computing efforts. Electron spin resonance (ESR) lines, or Oersted lines, allow 10–60 GHz radio frequency (RF) pulses to induce an electromagnetic field that drives Rabi oscillations in a quantum dot interface. The frequency of these Rabi oscillations is directly proportional to the strength of the induced electromagnetic field. We outline a methodology for the design of a printed circuit board and an ESR line that is able to transmit an RF pulse in the 40 GHz regime and induce an oscillating magnetic field onto a qubit device. We propose and implement a novel design by coupling a second symmetrical Oersted line in the opposing direction of the first to act as an antenna for the purpose of monitoring power and magnetic field strength at the embedded device interface.

Construction of 0-dimensional silver quantum dot/MoSe2@MXene/3-dimensional porous copper foam composite electrodes with heterogeneous interfaces for synergistic electrocatalytic degradation of antibiotics

This study proposes a novel and efficient Ag quantum dots (QDs)/MoSe2@two-dimensional transition metal carbide/nitride (MXene)/copper foam (CF) composite electrode to address the challenge of electrocatalytic degradation of antibiotics in water. The electrode formed a unique electron donor–acceptor system by loading Ag QDs and heterostructured nanosheets on CF, significantly facilitating charge transfer and segregation at the interface. The catalytically active sites at the edges and defective locations of MoSe2 in conjunction with the two-dimensional MXene structure, which formed an efficient electron transfer channel, promoted the electron transfer from the interior to the surface and accelerated the hydrogen adsorption and reduction reactions. Moreover, the charge redistribution at the interface of Ag QDs and MoSe2@MXene formed interfacial dipoles, increasing the active sites on the catalyst surface and promoting the generation of cathodic atomic hydrogen (H*). Under optimal conditions, the degradation rate of tigecycline (TGC) reached as high as 90.1 % ± 2.4 % within 60 min. The anode-generated OH and HClO, along with the cathode-generated H, further promoted the degradation of TGC through co-catalysis. The degradation pathways were analyzed using density-functional theory (DFT) calculations and liquid chromatography-mass spectrometry (LC-MS) techniques. Moreover, toxicity analysis of the degradation products was carried out to ensure the safety of the treated wastewater discharge. A reflux continuous effluent reactor was also designed to achieve high degradation efficiency and low energy consumption after stable operation, laying the foundation for industrial applications. This technology provides new ideas for the design of green, efficient, stable, and low-consumption electrocatalytic reactors and contributes to a sustainable future environment.

(Invited) Photophysical Properties and Photodynamics in CdSe Quantum Dots as Photocatalysts and Photosensitizers

Interactions between dye molecules and the semiconductor quantum dots (QDs) has a strong effect on both solar-to-electrical and solar-to-chemical energy conversion processes. In both types of applications, the charge transfer from the photoexcited QD to the molecule play a crucial role. Applying DFT-based non-adiabatic molecular dynamics, we have revealed ultrafast hole transfer (~10 fs) from the CdSe QD to the Ru(II) dye, following by a slow component (~100 fs) associated with the redistribution of population throughout QD states. The ultrafast interfacial QD-to-dye hole transfer is rationalized by strong non-adiabatic couplings between the QD surface states and the high frequency vibrational modes of isocyanide ligands in the dye. We also have studied the effect of the complex heterostructures of Janus QDs, where a half of the QD is made from CdSe and another half is from PbSe forming an interface along a specific crystalline direction. Our calculations show that the Pb-enriched (111) crystalline direction of the interface enhances optical response of the QDs. The hole relaxation is much slower than the electron relaxation, followed by the hole transfer to the dye. The hole transfer is sensitive to the polarity of the environment, rather than the ways of dye’s attachment to the surface. We also found that in nonstoichiometric QDs, a loss of a passivating ligand affects the electronic structure in the same way as injection of an electron in Cd-rich QDs or hole injection in Se-rich QDs. Moreover, electron injection to the Se-rich QDs results in highly optically active redshifted transitions associated with the introduced charge. Overall, our calculations provide atomistic insights into QD-to-molecule charge transfer, giving researchers an additional handle for enhancing QD photophysical properties by means of the QD stoichiometry, interface structure, and QD-molecule engineering.

High‐Performance Perovskite Solar Cell via Chirality‐Engineered Graphene Quantum Dot Interface Passivation

High‐Performance Perovskite Solar Cell via Chirality‐Engineered Graphene Quantum Dot Interface Passivation

Potassium Iodide Doping for Vacancy Substitution and Dangling Bond Repair in InP Core-Shell Quantum Dots.

This work highlights the novel approach of incorporating potassium iodide (KI) doping during the synthesis of In0.53P0.47 core quantum dots (QDs) to significantly reduce the concentration of vacancies (i.e., In vacancies; VIn-) within the bulk of the core QD and inhibit the formation of InPOx at the core QD-Zn0.6Se0.4 shell interfaces. The photoluminescence quantum yield (PLQY) of ~97% and full width at half maximum (FWHM) of ~40 nm were achieved for In0.53P0.47/Zn0.6Se0.4/Zn0.6Se0.1S0.3/Zn0.5S0.5 core/multi-shell QDs emitting red light, which is essential for a quantum-dot organic light-emitting diode (QD-OLED) without red, green, and blue crosstalk. KI doping eliminated VIn- in the core QD bulk by forming K+-VIn- substitutes and effectively inhibited the formation of InPO4(H2O)2 at the core QD-Zn0.6Se0.4 shell interface through the passivation of phosphorus (P)-dangling bonds by P-I bonds. The elimination of vacancies in the core QD bulk was evidenced by the decreased relative intensity of non-radiative unpaired electrons, measured by electron spin resonance (ESR). Additionally, the inhibition of InPO4(H2O)2 formation at the core QD and shell interface was confirmed by the absence of the {210} X-ray diffraction (XRD) peak intensity for the core/multi-shell QDs. By finely tuning the doping concentration, the optimal level was achieved, ensuring maximum K-VIn- substitution, minimal K+ and I- interstitials, and maximum P-dangling bond passivation. This resulted in the smallest core QD diameter distribution and maximized optical properties. Consequently, the maximum PLQY (~97%) and minimum FWHM (~40 nm) were observed at 3% KI doping. Furthermore, the color gamut of a QD-OLED display using R-, G-, and B-QD functional color filters (i.e., ~131.1%@NTSC and ~98.2@Rec.2020) provided a nearly perfect color representation, where red-light-emitting KI-doped QDs were applied.

Modulation of charge transfer at the pentacene/graphene quantum dot interface by localized surface plasmonic resonance

We, for the first time, quantified localized surface plasmon resonance (LSPR)-induced charge transfer, and tuned charge carrier concentration in field-effect transistors (FETs) by incorporating silver nanoparticles (Ag NPs) at the pentacene/graphene quantum dot (GQD) interface. This resulted in a significant threshold voltage shift under illumination at a resonance frequency of 450 nm, primarily due to LSPR-induced charge transfer at the Ag NP/GQD interface. Further, the formation of an Ag NP-induced interface dipole in the dark accumulated holes in the pentacene layer in the absence of the gate electric field. Our research not only contributes to a deeper understanding of the interplay between plasmonics and semiconductor physics but also paves the way for new applications in electronics and photonics.

Negative corona discharge strategy for efficient quantum dot light-emitting diodes.

In colloid quantum dot light-emitting diodes (QLEDs), the control of interface states between ZnO and quantum dots (QDs) plays a vital role. We present a straightforward and efficient method using a negative corona discharge to modify the QD film, creating a dipole moment at the interface of QDs and magnesium-doped ZnO (ZnMgO) for balanced charge carrier distribution within the QDs. This process boosts external quantum efficiencies in red, green, and blue QLEDs to 17.71%, 14.53%, and 9.04% respectively. Notably, optimized devices exhibit significant enhancements, especially at lower brightness levels (1000 to 10,000 cd·m-2), vital for applications in mobile displays, TV screens, and indoor lighting.

The influence of ligands passivation on strength of Fermi level pinning in the quantum dots interface

PbS quantum dots capped by ethanedithiol (PbS QD-EDT) and tetrabutylammonium iodide (PbS QD-TBAI) and supported by different substrates were examined in terms of Fermi level pinning (FLP), gap states, and electron and hole barriers (Φe and Φh, respectively) using ultraviolet and low-energy inverse photoemission spectroscopy. The former analysis showed that TBAI and EDT differed in their ability to induce gap-state passivation, with the corresponding energy difference determined as 4.0 eV. Two FLP regimes were identified: at substrate work function (Фsub) < 4.0 eV, both ligands showed perfect FLP (S ≈ 0 for holes and electrons), whereas at Фsub > 4.0 eV, the pinning strength of PbS QD-EDT (S of Фb,h and Фb,e = 0.19 and 0.24, respectively) exceeded that of PbS QD-TBAI (S of Фb,h and Фb,e = 0.53 and 0.57, respectively). Thus, the gap states were more effectively passivated in the case of PbS QD-TBAI. Our results indicate the importance of considering FLP strength when working with high-work-function substrates for the design of optimized QD-based devices.

Optimizing ZnO–Quantum Dot Interface with Thiol as Ligand Modification for High‐Performance Quantum Dot Light‐Emitting Diodes (Small 13/2024)

Optimizing ZnO–Quantum Dot Interface with Thiol as Ligand Modification for High‐Performance Quantum Dot Light‐Emitting Diodes (Small 13/2024)

Doping‐Induced Performance Improvement in ReS2 Field Effect Transistors: Exploring a Heterostructure with In2O3 Quantum Dots

AbstractRhenium disulfide (ReS2) is a type of transition metal dichalcogenides (TMDs) that has potential electronic and photoelectrical applications. However, limited research has been conducted on improving its electrical properties and understanding the effect of doping on ReS2‐based devices. In this study, the enhanced electrical and photoelectrical performance of a 2D/0D heterostructure constructed by decorating the In2O3 quantum dots (QDs) on a multilayer ReS2 field‐effect transistor (FET) is reported. The In2O3 QDs are characterized by using a transmission electron microscope, optical absorption, and photoluminescence spectroscopy. The n‐doping effects with improved mobility are clearly observed, which is attributed to the electron transfer induced by the relatively high conduction band level of In2O3 QDs. Owing to the channel migration of ReS2 and traps at the ReS2/In2O3 QDs interface, additional performance improvements are observed, including reduced contact resistance, improved subthreshold swing, and increased photoresponsivity; however, the photoresponse speed is decreased. In summary, the findings suggest a novel mixed‐dimensional heterostructure for enhancing the performance of ReS2 transistors and provide insights into doping‐induced channel migration for 2D materials.

Localized surface plasmon resonance-induced charge carrier localization at the silver nanoparticle/graphene quantum dot interface

We report a novel investigation into the effects of localized surface plasmon resonance (LSPR) on charge carrier localization and dynamics, utilizing a test structure where pentacene is layered over a graphene quantum dot (GQD) film. To induce LSPR, we strategically embedded silver nanoparticles (Ag NPs) between the pentacene and GQD films. This configuration led to a notable shift in the threshold voltage when the structure was illuminated at a resonance frequency of 450 nm. This shift is primarily attributed to the LSPR-induced charge transfer occurring at the interface between the Ag NPs and the GQD film. Remarkably, following the discontinuation of illumination, there was a noticeable and gradual release of electrons previously localized at the Ag NP/GQD interface. This phenomenon demonstrated effective retention of electrons at the interface, which subsequently led to an enhancement in the field-effect transistor (FET) mobility. This enhancement in the FET mobility is likely due to the diminished Coulombic interaction between the localized electrons and the mobile hole carriers within the pentacene channel.“

Enhancement and Broadening of the Internal Electric Field of Hole-Transport-Layer-Free Perovskite Solar Cells by Quantum Dot Interface Modification.

Hole-transport-layer-free perovskite solar cells have attracted strong interest due to their simple structure and low cost, but charge recombination is serious. Built-in electric field engineering is an intrinsic driver to facilitate charge separation transport and improve the efficiency of photovoltaic devices. However, the enhancement of the built-in electric field strength is often accompanied by the narrowing of the space charge region, which becomes a key constraint to the performance improvement of the device. Here, we propose an effective regulation method, the component engineering of quantum dots, to enhance the strength of the built-in electric field and broaden the range of space charge. By using all inorganic CsPbBrxI3-x (x = 0, 1, 2, 3) quantum dot interface modification to passivate the defects of MAPbI3 perovskite films, the regulation law of quantum dot components on the work function of perovskite films was revealed, and the mechanism of their influence on the internal electric field intensity and space charge region distribution was further clarified, thereby fundamentally solving the serious problem of charge recombination. As directly observed by electron-beam-induced current (EBIC), the introduction of CsPbBr2I quantum dots can effectively enhance the interfacial electric field intensity, widening the space charge region from 160 to 430 nm. Moreover, the efficiency of the hole-free transport layer perovskite solar cells modified by CsPbBr2I quantum dots was also significantly enhanced by 1.5 times. This is an important guideline for electric field modulation and efficiency improvement within photovoltaic devices with other simplified structures.

Promoted Charge Extraction in All-Inorganic CsPbBr3 Perovskite Solar Cells by a CsPbX3 (X = Br and I) Quantum Dot Interface Layer

Promoted Charge Extraction in All-Inorganic CsPbBr₃ Perovskite Solar Cells by a CsPbX₃ (X = Br and I) Quantum Dot Interface Layer

In situ growth MoS2 quantum dots as promising interface materials for silicon solar cells

The carrier selectivity at interface is one key factor to improve the performance of silicon solar cells. Here, Molybdenum disulfide (MoS2) quantum dots were successfully synthesized by one-step in situ plasma enhanced atom layer deposition. A transmission electron microscope was employed to investigate nano-size scaled as well as growth mechanism of the crystalline MoS2 quantum dots. MoS2 quantum dots with additional molybdenum-oxygen (Mo–O) bonding were prepared by co-reactant plasma processing, which exhibited photo-generated carrier selectivity as promising interface materials for silicon heterojunction solar cells. Our results indicated their carrier selectivity of electron-blocking and hole-transporting at interface was attributable to unique quantum effects and tunneling effects. A photovoltaic conversion efficiency 23% was achieved by a sample silicon solar cell combined with MoS2 quantum dots interface materials. Because the interface engineering is well-defined, and the synthesis is low-cost, this bottom-up strategy provides a potential advance in design and construction of innovative and highly efficient photovoltaic devices.

The radiation intensity of optical transitions in the germanium/silicon nanosystems

It is shown that utilization of electron transitions between quasistationary exciton states of spatially separated electron (in spherical germanium quantum dot (QD) core) and hole (localized ot the QD interface with silicon matrix) can provide up to four times enhancement of the radiative intensity against the similar ones among stationary exciton states.

Using host-guest interactions at the interface of quantum dots to load drug molecules for biocompatible, safe, and effective chemo-photodynamic therapy against cancer.

Combining photodynamic therapy (PDT) and chemotherapy (CHT) by loading an anti-cancer drug and a photosensitizer (PS) into the same delivery nanosystem has been proposed as an effective approach to achieve synergistic effects for a safe cancer treatment. However, exploring an ideal delivery nanosystem has been challenging, because the noncovalent interactions must be maintained between the multiple components to produce a stable yet responsive nanostructure that takes into account the encapsulation of drug molecules. We addressed this issue by engineering the interfacial interaction between Ag2S quantum dots (QDs) using a pillararene derivative to direct the co-self-assembly of the entire system. The high surface area-to-volume ratio of the Ag2S QDs provided ample hydrophobic space to accommodate the anti-drug molecule doxrubicine. Moreover, Ag2S QDs served as PSs triggered by 808 nm near-infrared (NIR) light and also as carriers for high-efficiency delivery of drug molecules to the tumor site. Drug release experiments showed smart drug release under the acidic microenvironments (pH 5.5) in tumor cells. Additionally, the Ag2S QDs demonstrated outstanding PDT ability under NIR light, as confirmed by extracellular and intracellular reactive oxygen species generation. Significant treatment efficacy of the chemo-photodynamic synergistic therapy for cancer using the co-delivery system was demonstrated via in vitro and in vivo studies. These findings suggest that our system offers intelligent control of CHT and PDT, which will provide a promising strategy for constructing hybrid systems with synergistic effects for advanced applications in biomedicine, catalysis, and optoelectronics.

Study of the Interfacial Oxidation of InP Quantum Dots Synthesized from Tris(dimethylamino)phosphine.

InP quantum dots (QDs) are the most competitive in terms of environmentally friendly QDs. However, the synthesis of InP QDs requires breakthroughs in low-cost and safe phosphorus precursors such as tri(dimethylamino)phosphine [(DMA)3P]. It is found that even if the oxygen is completely avoided, there are still oxidation state defects at the core/shell interface of InP QDs. Herein, the record-breaking (DMA)3P-based red InP QDs were synthesized with the assist of HF processing to eliminate the InPOx defect and improve the fluorescence efficiency. The maximum photoluminescence quantum yield was 97.7%, which is the highest of the red InP QDs synthesized by the aminophosphine. The external quantum efficiency and brightness of the QD light-emitting diode device are also improved accordingly from 0.6% and 1276 cd·m-2 to 3.5% and 2355 cd·m-2, respectively.

Efficient hole extraction with Eu3+-doped CsPbBr3 QD interface modification for HTL-free CH3NH3PbI3:Na perovskite solar cells

Hole transport layer free perovskite solar cells (HTL-Free PSCs) have attracted extensive attention due to their advantages of simple structure and low cost. However, due to the serious energy level mismatch caused by the direct contact between the perovskite layer and the opposite electrode, the space for improving the efficiency of HTL-Free PSCs is greatly limited. We use Eu3+ doped CsPbBr3 quantum dots (QD) to modify the interface between MAPbI3:Na layer and C electrode, and study its effect on the surface defect passivation, interface energy level arrangement and carrier transport behavior in the device. It was found that compared with the interfacial modification of CsPbBr3 QD alone, the interfacial modification of CsPbBr3:Eu QD could effectively solve the problem of energy level mismatch in HTL-Free PSCs, resulting in a remarkable improvement of conversion efficiency from 9.01 % to 12.95 %. Furthermore, electron beam induced current (EBIC) was used to prove that CsPbBr3:Eu QD interface modification significantly improved the hole collection ability. This provides an experimental basis and theoretical guidance for the optimization of the efficiency of other types of transport layer free photovoltaic devices.

Tailoring Charge Separation at Meticulously Engineered Conjugated Polymer/Perovskite Quantum Dot Interface for Photocatalyzing Atom Transfer Radical Polymerization.

In stark contrast to conventional organic ligand-capped counterparts, the ability to create stable metal halide perovskite nanocrystals strongly tethered with conjugated polymers (CPs) represents an important endeavor toward tailoring charge carrier dynamics at their interface that critically underpins applications of this unique class of all semiconducting, organic-inorganic nanomaterials for optoelectronics. This, however, has yet to be largely explored. Herein, we report, for the first time, the unraveling of efficient charge separation at judiciously designed CP/perovskite quantum dot (QD) interface for photoinduced atom transfer radical polymerization (p-ATRP). Such scrutiny is rendered by in situ crafting an array of monodisperse, highly stable, CP-ligated perovskite QDs with precisely controlled dimensions of each constituent via capitalizing on unimolecular, amphiphilic starlike block copolymers as nanoreactors. The intimate and permanent surface tethering of CPs imparts remarkable thermal, photo, and polar solvent stabilities of CP-ligated perovskite QDs. More importantly, they manifest efficient interfacial charge separation with a profound dependence on the length of ligated CPs and the size of perovskite QDs. The outstanding structural stabilities and charge separation characteristic enable CP-ligated perovskite QDs as robust photocatalysts for p-ATRP of a wide selection of monomers with stable and controllable reaction kinetics, also depending crucially on the length of CPs and the size of perovskite QDs. In principle, an exciting variety of CP-ligated, uniform perovskite QDs with virtually unlimited material choice of both markedly improved stabilities and tunable electronic band alignments can be readily accessed by exploiting the amphiphilic starlike block copolymer nanoreactor strategy for use in photodetectors, sensors, and LEDs, among other areas.

Ultrasound-aided synthesis of gold-loaded boron-doped graphene quantum dots interface towards simultaneous electrochemical determination of guanine and adenine biomolecules

To acquire substantial electrochemical signals of guanine-GUA and adenine-ADE present in deoxyribonucleic acid-DNA, it is critical to investigate innovative electrode materials and their interfaces. In this study, gold-loaded boron-doped graphene quantum dots (Au@B-GQDs) interface was prepared via ultrasound-aided reduction method for monitoring GUA and ADE electrochemically. Transmission electron microscopy-TEM, Ultraviolet–Visible spectroscopy-UV–Vis, Raman spectroscopy, X-ray photoelectron spectroscopy-XPS, cyclic voltammetry-CV, and differential pulse voltammetry-DPV were used to examine the microstructure of the fabricated interfaceand demonstrate its electrochemical characteristics. The sensor was constructed by depositing the as-prepared Au@B-GQDs as a thin layer on a glassy carbon-GC electrode by the drop-casting method and carried out the electrochemical studies. The resulting sensor exhibited a good response with a wide linear range (GUA = 0.5–20 μM, ADE = 0.1–20 μM), a low detection limit-LOD (GUA = 1.71 μM, ADE = 1.84 μM), excellent sensitivity (GUA = 0.0820 µAµM−1, ADE = 0.1561 µAµM−1) and selectivity with common interferents results from biological matrixes. Furthermore, it seems to have prominentselectivity, reproducibility, repeatability, and long-lastingstability. The results demonstrate that the fabricated Au@B-GQDs/GC electrode is a simple and effective sensing platform for detecting GUA and ADE in neutral media at low potential as it exhibited prominent synergistic impact and outstanding electrocatalytic activity corresponding to individual AuNPs and B-GQDs modified electrodes.