A high temperature in situ optical probe for colloidal nanocrystal synthesis.

We report on the fabrication and utilization of a robust high-temperature (>300 °C), adjustable-path-length, vacuum-tolerant, configurable, in situ optical probe, which interfaces with widely used chemical glassware via a 14/20 ground glass joint. This probe allows for high-speed reaction monitoring of colloidal semiconductor nanocrystal solutions at temperatures that were previously inaccessible. We demonstrate this capability by monitoring the hot-injection synthesis of CdSe quantum dots via UV-Vis absorption spectroscopy at 380 °C with a time resolution of ∼10 ms, with the primary limitation being the acquisition and data saving rate of the commercial spectrometer used. We further demonstrate that this probe can also be used for in situ photoluminescence measurements. This system is generally applicable to harsh solution environments where optical monitoring of reaction progress is desirable and/or necessary.

Colloidal Multi-Dot Nanorods.

Colloidal nanorod heterostructures consisting of multiple quantum dots within a nanorod (n-DNRs, where n is the number of quantum dots within a nanorod) are synthesized with alternating segments of CdSe "dot" and CdS "rod" via solution heteroepitaxy. The reaction temperature, time dependent ripening, and asymmetry of the wurtzite lattice and the resulting anisotropy of surface ligand steric hindrance are exploited to vary the morphology of the growing quantum dot segments. The alternating CdSe and CdS growth steps can be easily repeated to increment the dot number in unidirectional or bidirectional growth regimes. As an initial exploration of electron occupation effects on their optical properties, asymmetric 2-DNRs consisting of two dots of different lengths and diameters are synthesized and are shown to exhibit a change in color and an unusual photoluminescence quantum yield increase upon photochemical doping.

pH Tunable Patterning of Quantum Dots.

Patterning of quantum dots (QDs) is essential for many, especially high-tech, applications. Here, pH tunable assembly of QDs over functional patterns prepared by electrohydrodynamic jet printing of poly(2-vinylpyridine) is presented. The selective adsorption of QDs from water dispersions is mediated by the electrostatic interaction between the ligand composed of 3-mercaptopropionic acid and patterned poly(2-vinylpyridine). The pH of the dispersion provides tunability at two levels. First, the adsorption density of QDs and fluorescence from the patterns can be modulated for pH > ≈4. Second, patterned features show unique type of disintegration resulting in randomly positioned features within areas defined by the printing for pH ≤ ≈4. The first capability is useful for deterministic patterning of QDs, whereas the second one enables hierarchically structured encoding of information by generating stochastic features of QDs within areas defined by the printing. This second capability is exploited for generating addressable security labels based on unclonable features. Through image analysis and feature matching algorithms, it is demonstrated that such patterns are unclonable in nature and provide a suitable platform for anti-counterfeiting applications. Collectively, the presented approach not only enables effective patterning of QDs, but also establishes key guidelines for addressable assembly of colloidal nanomaterials.

Improving photovoltaic performance of light-responsive double-heterojunction nanorod light-emitting diodes.

Double heterojunction nanorods enable both electroluminescence and light harvesting capabilities within the same device structure, providing a promising platform for energy-scavenging displays and related applications. However, the efficiency of the photovoltaic mode remains modest for useful power conversion and may be challenging to improve without sacrificing performance in electroluminescence. Through a facile on-film partial ligand exchange with benzenethiol integrated into the device fabrication step, we achieve an average of more than threefold increase in power conversion efficiency while maintaining the maximum external quantum efficiency and the maximum luminance in the LED mode. The improved photovoltaic performance is mainly due to the increase in the short circuit current, which we attribute to the enhanced charge separation afforded by the partial ligand exchange. The recovery of the photoluminescence lifetime under the forward bias suggests that the hole traps introduced by benzenethiols are filled prior to reaching the voltage at which light emission begins, allowing LED performance to be maintained and possibly improved.

Design Principles of Colloidal Nanorod Heterostructures.

Anisotropic heterostructures of colloidal nanocrystals embed size-, shape-, and composition-dependent electronic structure within variable three-dimensional morphology, enabling intricate design of solution-processable materials with high performance and programmable functionality. The key to designing and synthesizing such complex materials lies in understanding the fundamental thermodynamic and kinetic factors that govern nanocrystal growth. In this review, nanorod heterostructures, the simplest of anisotropic nanocrystal heterostructures, are discussed with respect to their growth mechanisms. The effects of crystal structure, surface faceting/energies, lattice strain, ligand sterics, precursor reactivity, and reaction temperature on the growth of nanorod heterostructures through heteroepitaxy and cation exchange reactions are explored with currently known examples. Understanding the role of various thermodynamic and kinetic parameters enables the controlled synthesis of complex nanorod heterostructures that can exhibit unique tailored properties. Selected application prospects arising from such capabilities are then discussed.

Charging and Charged Species in Quantum Dot Light-Emitting Diodes.

Despite recent rapid advances in improving quantum dot light-emitting diodes, many fundamental aspects of the device operating mechanism remain unresolved. Through transient electroluminescence and time-resolved photoluminescence measurements, the effects of offset voltage on charging and charge transport are examined. First, capacitive charging occurs with a time constant of ∼500 ns, followed by electron transport through quantum dots with a mobility of ∼10-5 cm2 V-1 s-1. Hole injection then initiates an electroluminescence rise that is independent of offset voltage. The photoluminescence lifetime is also unaffected by the offset voltage, indicating no injection of charges into the quantum dots or on their surfaces prior to the voltage pulse. A slower equilibration to steady-state electroluminescence is dependent on the offset voltage, indicative of another charging process. Elemental mapping shows that ZnO deposition from solution can lead to the diffusion of charged species into the quantum dot layer, which may cause the slower process.

Accelerated screening of colloidal nanocrystals using artificial neural network-assisted autonomous flow reactor technology.

Colloidal semiconductor nanocrystals with tunable optical and electronic properties are opening up exciting opportunities for high-performance optoelectronics, photovoltaics, and bioimaging applications. Identifying the optimal synthesis conditions and screening of synthesis recipes in search of efficient synthesis pathways to obtain nanocrystals with desired optoelectronic properties, however, remains one of the major bottlenecks for accelerated discovery of colloidal nanocrystals. Conventional strategies, often guided by limited understanding of the underlying mechanisms remain expensive in both time and resources, thus significantly impeding the overall discovery process. In response, an autonomous experimentation platform is presented as a viable approach for accelerated synthesis screening and optimization of colloidal nanocrystals. Using a machine-learning-based predictive synthesis approach, integrated with automated flow reactor and inline spectroscopy, indium phosphide nanocrystals are autonomously synthesized. Their polydispersity for different target absorption wavelengths across the visible spectrum is simultaneously optimized during the autonomous experimentation, while utilizing minimal self-driven experiments (less than 50 experiments within 2 days). Starting with no-prior-knowledge of the synthesis, an ensemble neural network is trained through autonomous experiments to accurately predict the reaction outcome across the entire synthesis parameter space. The predicted parameter space map also provides new nucleation-growth kinetic insights to achieve high monodispersity in size of colloidal nanocrystals.

Mechanism of morphology variations in colloidal CuGaS2 nanorods.

Cu2-x S nanocrystals can serve as templates and intermediates in the synthesis of a wide range of nanocrystals through seeded growth, cation exchange, and/or catalytic growth. This versatility can facilitate and accelerate the search for environmentally benign nanocrystals of high performance with variable shapes, sizes, and composition. However, expanding the compositional space via Cu2-x S nanocrystals while achieving necessary uniformity requires an improved understanding of the growth mechanisms. Herein we address several unusual and previously unexplained aspects of the growth of CuGaS2 nanorods from Cu2-x S seeds as an example. In particular, we address the origin of the diverse morphologies which manifest from a relatively homogeneous starting mixture. We find that CuGaS2 nanorods start as Cu2-x S/CuGaS2 Janus particles, the majority of which have a {101̄2}/{101̄2} interface that helps to minimize lattice strain. We propose a mechanism that involves concurrent seed growth and cation exchange (CSC), where epitaxial growth of the Cu2-x S seed, rather than the anticipated catalytic or seeded growth of CuGaS2, occurs along with cation exchange that converts growing Cu2-x S to CuGaS2. This mechanism can explain the incorporation of the large number of anions needed to account for the order-of-magnitude volume increase upon CuGaS2 rod growth (which cannot be accounted for by the commonly assumed catalytic growth mechanism) and variations in morphology, including the pervasive tapering and growth direction change. Insights from the CSC growth mechanism also help to explain a previously puzzling phenomenon of regioselective nucleation of CuInSe2 on kinked CuGaS2 nanorods.

Highly luminescent double-heterojunction nanorods.

Anisotropic shape and band structure engineered into double-heterojunction nanorods (DHNRs) can improve and impart new optical/optoelectronic capabilities in colloidal quantum dot-based devices. However, the photoluminescence quantum yield of DHNRs, which is significantly lower than the near-ideal limit recently achieved in the state-of-the-art core/shell quantum dots, remains as their main limitation. Here, we examine how the photoluminescence of CdS/CdSe/ZnSe DHNRs is affected by (1) the length of the CdS seed nanorods, (2) the rod and tip diameter dependent variations in band offset, and (3) the CdSe-like islands on the sides of DHNRs that can result as a side-product of ZnSe shell growth. By understanding and optimizing these three key parameters, we demonstrate an improvement in the photoluminescence quantum yield up to 93% (up to 62% for excitation above CdS bandgap) while retaining useful shape anisotropy and the band structure design in DHNRs.

Efficient Type-II Heterojunction Nanorod Sensitized Solar Cells Realized by Controlled Synthesis of Core/Patchy-Shell Structure and CdS Cosensitization.

Here, we report the successful application of core/patchy-shell CdSe/CdSe xTe1- x type-II heterojunction nanorods (HNRs) to realize efficient sensitized solar cells. The core/patchy-shell structure designed to have a large type-II heterointerface without completely shielding the CdSe core significantly improves photovoltaic performance compared to other HNRs with minimal or full-coverage shells. In addition, cosensitization with CdS grown by successive ionic layer adsorption and reaction further improves the power conversion efficiency. One-diode model analysis reveals that the HNRs having exposed CdSe cores and suitably grown CdS result in significant reduction of series resistance. Investigation of the intercorrelation between diode quality parameters, diode saturation current density ( J0) and recombination order (ß = (ideality factor)-1) reveals that HNRs with open CdSe cores exhibit reduced recombination. These results confirm that the superior performance of core/patchy-shell HNRs results from their fine-tuned structure: photocurrent is increased by the large type-II heterointerface and recombination is effectively suppressed due to the open CdSe core enabling facile electron extraction. An optimized power conversion efficiency of 5.47% (5.89% with modified electrode configuration) is reported, which is unmatched among photovoltaics utilizing anisotropic colloidal heterostructures as light-harvesting materials.

Photoresist Contact Patterning of Quantum Dot Films.

Scalable and cost-effective protocols to pattern and integrate colloidal quantum dots (QDs) with high resolution have been challenging to establish. While their solubility can facilitate certain processes such as spin-casting into thin films, it also makes them incompatible with many conventional patterning techniques including photolithography that require solution processing. In this work, we present "photoresist (PR) contact patterning", a dry means to pattern QD films over large areas with high resolution while maintaining desired properties. Here, a PR layer on an elastomer substrate is patterned by conventional photolithography and used as a dry contact stamp to selectively peel off QDs in the contact regions, leaving behind a QD film with the negative of the PR pattern. Once patterned, QD films are readily transferred and integrated on foreign substrates by subsequent transfer printing processes. Patterned PR layers can also be transferred from elastomer substrates onto QD films and used as masking layers for subsequent deposition and patterning of additional materials, e. g., patterned metal electrodes or charge transport layers for QD-based devices. The study of the interfacial mechanics and energy of materials associated with PR contact patterning reveals why a lithographically patterned PR is superior for high-resolution QD film patterning. Applicability of PR contact patterning is demonstrated through the fabrication of red, green, and blue (RGB) QD light-emitting diode pixels. PR contact patterning presented in this work not only allows dry patterning of QD films but also enables high-resolution integration of functional multistack structures for future QD-based electronic and optoelectronic devices.

High-Performance Sub-Micrometer Channel WSe2 Field-Effect Transistors Prepared Using a Flood-Dike Printing Method.

Printing technology has potential to offer a cost-effective and scalable way to fabricate electronic devices based on two-dimensional (2D) transition metal dichalcogenides (TMDCs). However, limited by the registration accuracy and resolution of printing, the previously reported printed TMDC field-effect transistors (FETs) have relatively long channel lengths (13-200 µm), thus suffering low current-driving capabilities (≤0.02 µA/µm). Here, we report a "flood-dike" self-aligned printing technique that allows the formation of source/drain metal contacts on TMDC materials with sub-micrometer channel lengths in a reliable way. This self-aligned printing technique involves three steps: (i) printing of gold ink on a WSe2 flake to form the first gold electrode, (ii) modifying the surface of the first gold electrode with a self-assembled monolayer (SAM) to lower the surface tension and render the surface hydrophobic, and (iii) printing of gold ink close to the SAM-treated first electrode at a certain distance. During the third step, the gold ink would first spread toward the edge of the first electrode and then get stopped by the hydrophobic SAM coating, ending up forming a sub-micrometer channel. With this printing technique, we have successfully downscaled the channel length to ∼750 nm and achieved enhanced on-state current densities of ∼0.64 µA/µm (average) and high on/off current ratios of ∼3 × 105 (average). Furthermore, with our high-performance printed WSe2 FETs, driving capabilities for quantum-dot light-emitting diodes (LEDs), inorganic LEDs, and organic LEDs have been demonstrated, which reveals the potential of using printed TMDC electronics for display backplane applications.

Route to Improving Photovoltaics Based on CdSe/CdSexTe1-x Type-II Heterojunction Nanorods: The Effect of Morphology and Cosensitization on Carrier Recombination and Transport.

One-dimensionally elongated nanoparticles with type-II staggered band offset are of potential use as light-harvesting materials for photovoltaics, but only a limited attention has been given to elucidate the factors governing the cell performance obtainable from such materials. Herein, we describe a combined strategy to enhance charge collection from CdSe/CdSexTe1-x type-II heterojunction nanorods (HNRs) utilized as light harvesters for sensitized solar cells. By integrating morphology- and composition-tuned type-II HNRs into solar cells, factors that yield interfaces favorable both for the electron injection into TiO2 and hole transfer to electrolyte are examined. Furthermore, it is shown that a more efficient photovoltaic system results from cosensitization with CdS quantum dots (QDs) predeposited on a TiO2 scaffold, which improves charge collection from HNRs. Electrochemical impedance spectroscopy (EIS) analysis suggests that such a synergistically enhanced system benefits from the decreased recombination within HNRs and facilitated charge transport through the cosensitized TiO2 electrode, even with the activation of a recombination path presumably related to the photogenerated holes in CdS QDs.

Subfilamentary Networks Cause Cycle-to-Cycle Variability in Memristive Devices.

A major obstacle for the implementation of redox-based memristive memory or logic technology is the large cycle-to-cycle and device-to-device variability. Here, we use spectromicroscopic photoemission threshold analysis and operando XAS analysis to experimentally investigate the microscopic origin of the variability. We find that some devices exhibit variations in the shape of the conductive filament or in the oxygen vacancy distribution at and around the filament. In other cases, even the location of the active filament changes from one cycle to the next. We propose that both effects originate from the coexistence of multiple (sub)filaments and that the active, current-carrying filament may change from cycle to cycle. These findings account for the observed variability in device performance and represent the scientific basis, rather than prior purely empirical engineering approaches, for developing stable memristive devices.

Enhanced device lifetime of double-heterojunction nanorod light-emitting diodes.

Colloidal quantum dots (QDs) are emerging as solution-processable, high-performance materials for light-emitting diodes (LEDs). Understanding the failure mechanism(s) is of both fundamental and practical importance, yet little is known of how QD-LEDs fail. Here, we have carried out accelerated device lifetime measurements on double heterojunction nanorod- (DHNR) and QD-LEDs. A common dependence of device lifetime on the initial driving voltage is observed over more than two orders of magnitude range in the initial luminance. This behavior is independent of whether the emitting materials are DHNRs or QDs prepared under different conditions. Reducing the hole injection barrier by doping HTL allows lower voltage operation, leading to longer device lifetimes. DHNRs with a band structure that further lowers the hole injection barrier require even lower driving voltages and therefore lead to longer device lifetimes than core/shell QDs. At 1000 cd m-2, the DHNR-LED exhibits no significant degradation even after more than 200 h of continuous operation. QD-LEDs, on the other hand, are completely degraded in less than ∼100 h under the same initial luminance conditions. Hole accumulation/trapping leading to HTL degradation, which in turn deteriorates electroluminescence but not the photoluminescence, is suggested to be the main cause of degradation of both DHNR- and QD-LEDs.

Double-heterojunction nanorod light-responsive LEDs for display applications.

Dual-functioning displays, which can simultaneously transmit and receive information and energy through visible light, would enable enhanced user interfaces and device-to-device interactivity. We demonstrate that double heterojunctions designed into colloidal semiconductor nanorods allow both efficient photocurrent generation through a photovoltaic response and electroluminescence within a single device. These dual-functioning, all-solution-processed double-heterojunction nanorod light-responsive light-emitting diodes open feasible routes to a variety of advanced applications, from touchless interactive screens to energy harvesting and scavenging displays and massively parallel display-to-display data communication.

Quantifying redox-induced Schottky barrier variations in memristive devices via in operando spectromicroscopy with graphene electrodes.

The continuing revolutionary success of mobile computing and smart devices calls for the development of novel, cost- and energy-efficient memories. Resistive switching is attractive because of, inter alia, increased switching speed and device density. On electrical stimulus, complex nanoscale redox processes are suspected to induce a resistance change in memristive devices. Quantitative information about these processes, which has been experimentally inaccessible so far, is essential for further advances. Here we use in operando spectromicroscopy to verify that redox reactions drive the resistance change. A remarkable agreement between experimental quantification of the redox state and device simulation reveals that changes in donor concentration by a factor of 2-3 at electrode-oxide interfaces cause a modulation of the effective Schottky barrier and lead to >2 orders of magnitude change in device resistance. These findings allow realistic device simulations, opening a route to less empirical and more predictive design of future memory cells.

Metal Oleate Induced Etching and Growth of Semiconductor Nanocrystals, Nanorods, and Their Heterostructures.

Unexpected etching of nanocrystals, nanorods, and their heterostructures by one of the most commonly used metal precursors, metal oleates, is reported. Zn oleate is shown to etch CdS nanorods anisotropically, where the length decreases without a significant change in the diameter. Sodium oleate enhances the etch rate, whereas oleic acid alone does not cause etching, indicating the importance of the countercation on the rate of oleate induced etching. Subsequent addition of Se precursors to the partially etched nanorods in Zn oleate solution can lead to epitaxial growth of CdSe particles rather than the expected ZnSe growth, despite an excess amount of Zn precursors being present. The composition of this epitaxial growth can be varied from CdSe to ZnSe, depending on the amount of excess oleic acid or the reaction temperature. Similar tuning of composition can be observed when starting with collinear CdSe/CdS/CdSe rod/rod/rod heterostructures and spherical CdS (or CdSe/CdS core/shell) nanocrystals. Conversion of collinear rod/rod/rod structures to barbells and interesting rod growth from nearly spherical particles among other structures can also result due to the initial etching effect of metal oleates. These observations have important implications on our understanding of nanocrystal heterostructure synthesis and open up new routes to varying the composition and morphology of these materials.

Multilayer Transfer Printing for Pixelated, Multicolor Quantum Dot Light-Emitting Diodes.

Here, we report multilayer stacking of films of quantum dots (QDs) for the purpose of tailoring the energy band alignment between charge transport layers and light emitting layers of different color in quantum dot light-emitting diodes (QD LED) for maximum efficiency in full color operation. The performance of QD LEDs formed by transfer printing compares favorably to that of conventional devices fabricated by spin-casting. Results indicate that zinc oxide (ZnO) and titanium dioxide (TiO2) can serve effectively as electron transport layers (ETLs) for red and green/blue QD LEDs, respectively. Optimized selections for each QD layer can be assembled at high yields by transfer printing with sacrificial fluoropolymer thin films to provide low energy surfaces for release, thereby allowing shared common layers for hole injection (HIL) and hole transport (HTL), along with customized ETLs. This strategy allows cointegration of devices with heterogeneous energy band diagrams, in a parallelized scheme that offers potential for high throughput and practical use.