Transparent Intracellular Sensing Platform with Si Needles for Simultaneous Live Imaging.

Vertically ordered Si needles are of particular interest for long-term intracellular recording owing to their capacity to infiltrate living cells with negligible damage and minimal toxicity. Such intracellular recordings could greatly benefit from simultaneous live cell imaging without disrupting their culture, contributing to an in-depth understanding of cellular function and activity. However, the use of standard live imaging techniques, such as inverted and confocal microscopy, is currently impeded by the opacity of Si wafers, typically employed for fabricating vertical Si needles. Here, we introduce a transparent intracellular sensing platform that combines vertical Si needles with a percolated network of Au-Ag nanowires on a transparent elastomeric substrate. This sensing platform meets all prerequisites for simultaneous intracellular recording and imaging, including electrochemical impedance, optical transparency, mechanical compliance, and cell viability. Proof-of-concept demonstrations of this sensing platform include monitoring electrical potentials in cardiomyocyte cells and in three-dimensionally engineered cardiovascular tissue, all while conducting live imaging with inverted and confocal microscopes. This sensing platform holds wide-ranging potential applications for intracellular research across various disciplines such as neuroscience, cardiology, muscle physiology, and drug screening.

Coherent heteroepitaxial growth of I-III-VI2 Ag(In,Ga)S2 colloidal nanocrystals with near-unity quantum yield for use in luminescent solar concentrators.

Colloidal Ag(In,Ga)S2 nanocrystals (AIGS NCs) with the band gap tunability by their size and composition within visible range have garnered surging interest. High absorption cross-section and narrow emission linewidth of AIGS NCs make them ideally suited to address the challenges of Cd-free NCs in wide-ranging photonic applications. However, AIGS NCs have shown relatively underwhelming photoluminescence quantum yield (PL QY) to date, primarily because coherent heteroepitaxy has not been realized. Here, we report the heteroepitaxy for AIGS-AgGaS2 (AIGS-AGS) core-shell NCs bearing near-unity PL QYs in almost full visible range (460 to 620 nm) and enhanced photochemical stability. Key to the successful growth of AIGS-AGS NCs is the use of the Ag-S-Ga(OA)2 complex, which complements the reactivities among cations for both homogeneous AIGS cores in various compositions and uniform AGS shell growth. The heteroepitaxy between AIGS and AGS results in the Type I heterojunction that effectively confines charge carriers within the emissive core without optically active interfacial defects. AIGS-AGS NCs show higher extinction coefficient and narrower spectral linewidth compared to state-of-the-art heavy metal-free NCs, prompting their immediate use in practicable applications including displays and luminescent solar concentrators (LSCs).

Excitation Intensity-Dependent Quantum Yield of Semiconductor Nanocrystals.

One of the key phenomena that determine the fluorescence of nanocrystals is the nonradiative Auger-Meitner recombination of excitons. This nonradiative rate affects the nanocrystals' fluorescence intensity, excited state lifetime, and quantum yield. Whereas most of the above properties can be directly measured, the quantum yield is the most difficult to assess. Here we place semiconductor nanocrystals inside a tunable plasmonic nanocavity with subwavelength spacing and modulate their radiative de-excitation rate by changing the cavity size. This allows us to determine absolute values of their fluorescence quantum yield under specific excitation conditions. Moreover, as expected considering the enhanced Auger-Meitner rate for higher multiple excited states, increasing the excitation rate reduces the quantum yield of the nanocrystals.

Interface polarization in heterovalent core-shell nanocrystals.

The potential profile and the energy level offset of core-shell heterostructured nanocrystals (h-NCs) determine the photophysical properties and the charge transport characteristics of h-NC solids. However, limited material choices for heavy metal-free III-V-II-VI h-NCs pose challenges in comprehensive control of the potential profile. Herein, we present an approach to such a control by steering dipole densities at the interface of III-V-II-VI h-NCs. The controllable heterovalency at the interface is responsible for interfacial dipole densities that result in the vacuum-level shift, providing an additional knob for the control of optical and electrical characteristics of h-NCs. The synthesis of h-NCs with atomic precision allows us to correlate interfacial dipole moments with the NCs' photochemical stability and optoelectronic performance.

Surface state-induced barrierless carrier injection in quantum dot electroluminescent devices.

The past decade has witnessed remarkable progress in the device efficiency of quantum dot light-emitting diodes based on the framework of organic-inorganic hybrid device structure. The striking improvement notwithstanding, the following conundrum remains underexplored: state-of-the-art devices with seemingly unfavorable energy landscape exhibit barrierless hole injection initiated even at sub-band gap voltages. Here, we unravel that the cause of barrierless hole injection stems from the Fermi level alignment derived by the surface states. The reorganized energy landscape provides macroscopic electrostatic potential gain to promote hole injection to quantum dots. The energy level alignment surpasses the Coulombic attraction induced by a charge employed in quantum dots which adjust the local carrier injection barrier of opposite charges by a relatively small margin. Our finding elucidates how quantum dots accommodate barrierless carrier injection and paves the way to a generalized design principle for efficient electroluminescent devices employing nanocrystal emitters.

Tailoring the Electronic Landscape of Quantum Dot Light-Emitting Diodes for High Brightness and Stable Operation.

The charge injection imbalance into the quantum dot (QD) emissive layer of QD-based light-emitting diodes (QD-LEDs) is an unresolved issue that is detrimental to the efficiency and operation stability of devices. Herein, an integrated approach to harmonize the charge injection rates for bright and stable QD-LEDs is proposed. Specifically, the electronic characteristics of the hole transport layer (HTL) is delicately designed in order to facilitate the hole injection from the HTL into QDs and confine the electron overflow toward the HTL. The well-defined exciton recombination zone by the engineered QDs and HTL results in high performance with a peak luminance exceeding 410 000 cd/m2, suppressed efficiency roll-off characteristics (ΔEQE < 5% between 200 and 200 000 cd/m2), and prolonged operational stability. The electric and optoelectronic analyses reveal the charge carrier injection mechanism at the interface between the HTL and QDs and provides the design principle of QD heterostructures and charge transport layers for high-performance QD-LEDs.

Direct Photolithographic Patterning of Colloidal Quantum Dots Enabled by UV-Crosslinkable and Hole-Transporting Polymer Ligands.

Quantum dot (QD)-based displays call for nondestructive, high-throughput, and high-resolution patterning techniques with micrometer precision. In particular, self-emissive QD-based displays demand fine patterns of conductive QD films with uniform thickness at the nanometer scale. To meet these requirements, we functionalized QDs with photopatternable and semiconducting poly(vinyltriphenylamine-random-azidostyrene) (PTPA-N3-SH) ligands in which hole-transporting triphenylamine and UV-crosslinkable azide (-N3) groups are integrated. The hybridized QD films undergo chemical crosslinking upon UV irradiation without loss in the luminescence efficiency, enabling micrometer-scale QD patterns (pitch size down to ∼10 µm) via direct photolithography. In addition, the conjugated moieties in the ligands allow the crosslinked QD films to be used in electrically driven light-emitting diodes (LED). As the ultimate achievement, a patterned QD-LED was prepared with a maximum luminance of 11 720 cd m-2 and a maximum external quantum efficiency (EQE) of 6.25%. The present study offers a simple platform to fabricate conductive nanoparticle films with micrometer-scale patterns, and thus we anticipate that this system will expedite the realization of QD-based displays and will also be applicable to the manufacture of nanoparticles for other electronic devices.

"Positive Incentive" Approach To Enhance the Operational Stability of Quantum Dot-Based Light-Emitting Diodes.

Balanced charge injection promises high efficiency of quantum dot-based light-emitting diodes (QD-LEDs). The most widely used approach to realize charge injection balance impedes the injection rate of the dominant charge carrier with energetic barriers. However, these approaches often accompany unwanted outcomes (e.g., the increase in operation voltage) that sacrifice the operational stability of devices. Herein, a "positive incentive" approach is proposed to enhance the efficiency and the operational stability of QD-LEDs. Specifically, the supply of hole, an inferior carrier than its counterpart, is facilitated by adopting a thin fullerene (C60) interlayer at the interface between the hole injection layer (MoOX) and hole transport layer (4,4'-bis(9-carbazolyl)-1,1'-biphenyl). The C60 interlayer boosts the hole current by eliminating the universal energy barrier, lowers the operation voltage of QD-LEDs, and enhances the charge balance in the QD emissive layer within the working device. Consequently, QD-LEDs benefitting from the adoption of the C60 interlayer exhibit significantly enhanced device efficiency and operation stability. Grounded on the quantitative assessment of the charge injection imbalance within the QD emissive layer, the impact of electrical parameters of QD-LEDs on their optoelectronic performance and operational stability is also discussed.

Direct cation exchange of CdSe nanocrystals into ZnSe enabled by controlled binding between guest cations and organic ligands.

Zn chalcogenides are suitable candidates for blue-emitting fluorophores in light-emitting devices. In particular, the efforts to grow ZnSe nanocrystals (NCs) with fine control over size and shape via bottom-up approaches have faced challenges because of the slow decomposition of Zn precursors. In this study, we report direct cation exchange from CdSe NCs to ZnSe. Absorption spectroscopy and density functional theory (DFT) analysis reveal that the reactivity of cation exchange depends on the degree of complexation between organic ligands and Zn halides. We controlled the binding strength of Zn complexes by changing the organic ligands and halogen species that bind with Zn. Appropriate binding strength allows for the release of Zn ions and their facile incorporation into CdSe seed NCs. Under our experimental conditions, trioctylphosphine oxide (TOPO)-ZnI2 drives the efficient cation exchange reaction whereas TOPO-ZnCl2 induces no cation exchange of CdSe NCs. In addition, functional groups vary the binding strength between Zn and ligands. Oleylamine (OLAm)-ZnI2, which has a weaker ligand-ZnI2 binding than TOPO-ZnI2, breaks down the original morphologies of host CdSe NCs due to the very fast exchange rate. On the other hand, the TOPO-ZnI2 complex induces a mild exchange rate, leading to transformation into various morphologies such as CdSe nanorods (NRs) and nanoplatelets (NPLs) into CdSe/ZnSe heterostructures inaccessible via other synthesis methods. The incorporation of Zn into various morphologies of CdSe results in tunable optical transitions in blue-UV regions. The synthesis of heterostructured NCs in an elongated morphology is possible, opening opportunities in photocatalysis, light emitting diodes, and luminescent solar concentrators.

Threshold Voltage Control of Multilayered MoS2 Field-Effect Transistors via Octadecyltrichlorosilane and their Applications to Active Matrixed Quantum Dot Displays Driven by Enhancement-Mode Logic Gates.

In recent past, for next-generation device opportunities such as sub-10 nm channel field-effect transistors (FETs), tunneling FETs, and high-end display backplanes, tremendous research on multilayered molybdenum disulfide (MoS2 ) among transition metal dichalcogenides has been actively performed. However, nonavailability on a matured threshold voltage control scheme, like a substitutional doping in Si technology, has been plagued for the prosperity of 2D materials in electronics. Herein, an adjustment scheme for threshold voltage of MoS2 FETs by using self-assembled monolayer treatment via octadecyltrichlorosilane is proposed and demonstrated to show MoS2 FETs in an enhancement mode with preservation of electrical parameters such as field-effect mobility, subthreshold swing, and current on-off ratio. Furthermore, the mechanisms for threshold voltage adjustment are systematically studied by using atomic force microscopy, Raman, temperature-dependent electrical characterization, etc. For validation of effects of threshold voltage engineering on MoS2 FETs, full swing inverters, comprising enhancement mode drivers and depletion mode loads are perfectly demonstrated with a maximum gain of 18.2 and a noise margin of ≈45% of 1/2 VDD . More impressively, quantum dot light-emitting diodes, driven by enhancement mode MoS2 FETs, stably demonstrate 120 cd m-2 at the gate-to-source voltage of 5 V, exhibiting promising opportunities for future display application.

Unraveling the Origin of Operational Instability of Quantum Dot Based Light-Emitting Diodes.

We investigate the operational instability of quantum dot (QD)-based light-emitting diodes (QLEDs). Spectroscopic analysis on the QD emissive layer within devices in chorus with the optoelectronic and electrical characteristics of devices discloses that the device efficiency of QLEDs under operation is indeed deteriorated by two main mechanisms. The first is the luminance efficiency drop of the QD emissive layer in the running devices owing to the accumulation of excess electrons in the QDs, which escalates the possibility of nonradiative Auger recombination processes in the QDs. The other is the electron leakage toward hole transport layers (HTLs) that accompanies irreversible physical damage to the HTL by creating nonradiative recombination centers. These processes are distinguishable in terms of the time scale and the reversibility, but both stem from a single origin, the discrepancy between electron versus hole injection rates into QDs. Based on experimental and calculation results, we propose mechanistic models for the operation of QLEDs in individual quantum dot levels and their degradation during operation and offer rational guidelines that promise the realization of high-performance QLEDs with proven operational stability.

Ligand-Asymmetric Janus Quantum Dots for Efficient Blue-Quantum Dot Light-Emitting Diodes.

We present ligand-asymmetric Janus quantum dots (QDs) to improve the device performance of quantum dot light-emitting diodes (QLEDs). Specifically, we devise blue QLEDs incorporating blue QDs with asymmetrically modified ligands, in which the bottom ligand of QDs in contact with ZnO electron-transport layer serves as a robust adhesive layer and an effective electron-blocking layer and the top ligand ensures uniform deposition of organic hole transport layers with enhanced hole injection properties. Suppressed electron overflow by the bottom ligand and stimulated hole injection enabled by the top ligand contribute synergistically to boost the balance of charge injection in blue QDs and therefore the device performance of blue QLEDs. As an ultimate achievement, the blue QLED adopting ligand-asymmetric QDs displays 2-fold enhancement in peak external quantum efficiency (EQE = 3.23%) compared to the case of QDs with native ligands (oleic acid) (peak EQE = 1.49%). The present study demonstrates an integrated strategy to control over the charge injection properties into QDs via ligand engineering that enables enhancement of the device performance of blue QLEDs and thus promises successful realization of white light-emitting devices using QDs.

Performance Limits of Luminescent Solar Concentrators Tested with Seed/Quantum-Well Quantum Dots in a Selective-Reflector-Based Optical Cavity.

Luminescent solar concentrators (LSCs) can serve as large-area sunlight collectors for photovoltaic devices. An important LSC characteristic is a concentration factor (C), which is defined as the ratio of the output and the input photon flux densities. This parameter can be also thought of as an effective enlargement factor of a solar cell active area. On the basis of thermodynamic considerations, the C-factor can reach extremely high values that exceed those accessible with traditional concentrating optics. In reality, however, the best reported values of C are around 30. Here we demonstrate that using a new type of high-emissivity quantum dots (QDs) incorporated into a specially designed cavity, we are able to achieve the C of ∼62 for spectrally integrated emission and ∼120 for the red portion of the photoluminescence spectrum. The key feature of these QDs is a seed/quantum-well/thick-shell design, which allows for obtaining a high emission quantum yield (>95%) simultaneously with a large LSC quality factor (QLSC of ∼100) defined as the ratio of absorption coefficients at the wavelengths of incident and reemitted light. By incorporating the QDs into a specially designed cavity equipped with a top selective reflector (a Bragg mirror or a thin silver film), we are able to effectively recycle reemitted light achieving light trapping coefficients of ∼85%. The observed performance of these devices is in remarkable agreement with analytical modeling, which allows us to project that the applied approach should allow one to boost the spectrally integrated concentration factors to more than 100 by further improving light trapping and/or increasing QLSC.

Highly luminescent silica-coated CdS/CdSe/CdS nanoparticles with strong chemical robustness and excellent thermal stability.

We present facile synthesis of bright CdS/CdSe/CdS@SiO2 nanoparticles with 72% of quantum yields (QYs) retaining ca 80% of the original QYs. The main innovative point is the utilization of the highly luminescent CdS/CdSe/CdS seed/spherical quantum well/shell (SQW) as silica coating seeds. The significance of inorganic semiconductor shell passivation and structure design of quantum dots (QDs) for obtaining bright QD@SiO2 is demonstrated by applying silica encapsulation via reverse microemulsion method to three kinds of QDs with different structure: CdSe core and 2 nm CdS shell (CdSe/CdS-thin); CdSe core and 6 nm CdS shell (CdSe/CdS-thick); and CdS core, CdSe intermediate shell and 5 nm CdS outer shell (CdS/CdSe/CdS-SQW). Silica encapsulation inevitably results in lower photoluminescence quantum yield (PL QY) than pristine QDs due to formation of surface defects. However, the retaining ratio of pristine QY is different in the three silica coated samples; for example, CdSe/CdS-thin/SiO2 shows the lowest retaining ratio (36%) while the retaining ratio of pristine PL QY in CdSe/CdS-thick/SiO2 and SQW/SiO2 is over 80% and SQW/SiO2 shows the highest resulting PL QY. Thick outermost CdS shell isolates the excitons from the defects at surface, making PL QY relatively insensitive to silica encapsulation. The bright SiO2-coated SQW sample shows robustness against harsh conditions, such as acid etching and thermal annealing. The high luminescence and long-term stability highlights the potential of using the SQW/SiO2 nanoparticles in bio-labeling or display applications.

Multifunctional Dendrimer Ligands for High-Efficiency, Solution-Processed Quantum Dot Light-Emitting Diodes.

We present multifunctional dendrimer ligands that serve as the charge injection controlling layer as well as the adhesive layer at the interfaces between quantum dots (QDs) and the electron transport layer (ETL) in quantum dot light-emitting diodes (QLEDs). Specifically, we use primary amine-functionalized dendrimer ligands (e.g., a series of poly(amidoamine) dendrimers (PADs, also referred to PAMAM)) that bind to the surface of QDs by replacing the native ligands (oleic acids) and also to the surface of ZnO ETL. PAD ligands control the electron injection rate from ZnO ETL into QDs by altering the electronic energy levels of the surface of ZnO ETL and thereby improve the charge balance within QDs in devices, leading to the enhancement of the device efficiency. As an ultimate achievement, the device efficiency (peak external quantum efficiency) improves by a factor of 3 by replacing the native ligands (3.86%) with PAD ligands (11.36%). In addition, multibranched dendrimer ligands keep the QD emissive layer intact during subsequent solution processing, enabling us to accomplish solution-processed QLEDs. The approach and results in the present study emphasize the importance of controlling the ligands of QDs to enhance QLED performance and also offer simple yet effective chemical mean toward all-solution-processed QLEDs.

Colloidal Spherical Quantum Wells with Near-Unity Photoluminescence Quantum Yield and Suppressed Blinking.

Thick inorganic shells endow colloidal nanocrystals (NCs) with enhanced photochemical stability and suppression of photoluminescence intermittency (also known as blinking). However, the progress of using thick-shell heterostructure NCs in applications has been limited due to the low photoluminescence quantum yield (PL QY ≤ 60%) at room temperature. Here, we demonstrate thick-shell NCs with CdS/CdSe/CdS seed/spherical quantum well/shell (SQW) geometry that exhibit near-unity PL QY at room temperature and suppression of blinking. In SQW NCs, the lattice mismatch is diminished between the emissive CdSe layer and the surrounding CdS layers as a result of coherent strain, which suppresses the formation of misfit defects and consequently permits ∼100% PL QY for SQW NCs with a thick CdS shell (≥5 nm). High PL QY of thick-shell SQW NCs is preserved even in concentrated dispersion and in film under thermal stress, which makes them promising candidates for applications in solid-state lightings and luminescent solar concentrators.

Influence of External Pressure on the Performance of Quantum Dot Solar Cells.

We report the influence of post-treatment via the external pressure on the device performance of quantum dot (QD) solar cells. The structural analysis together with optical and electrical characterization on QD solids reveal that the external pressure compacts QD active layers by removing the mesoscopic voids and enhances the charge carrier transport along QD solids, leading to significant increase in JSC of QD solar cells. Increasing the external pressure, by contrast, accompanies reduction in FF and VOC, yielding the trade-off relationship among JSC and FF and VOC in PCE of devices. Optimization at the external pressure in the present study at 1.4-1.6 MPa enables us to achieve over 10% increase in PCE of QD solar cells. The approach and results show that the control over the organization of QDs is the key for the charge transport properties in ensemble and also offer simple yet effective mean to enhance the electrical performance of transistors and solar cells using QDs.

Influence of shell thickness on the performance of light-emitting devices based on CdSe/Zn1-X CdX S core/shell heterostructured quantum dots.

CdSe/Zn1-X CdX S core/shell heterostructured quantum dots (QDs) with varying shell thicknesses are studied as the active material in a series of electroluminescent devices. "Giant" CdSe/Zn1-X CdX S QDs (e.g., CdSe core radius of 2 nm and Zn1-X CdX S shell thickness of 6.3 nm) demonstrate a high device efficiency (peak EQE = 7.4%) and a record-high brightness (>100 000 cd m(-2) ) of deep-red emission, along with improved device stability.