Jonathan E. Halpert

Recent advances in micro-/nano-structured hollow spheres for energy applications: From simple to complex systems

Hollow micro-/nano-structured materials are now playing an important role in cutting edge innovations for energy conversion and storage technologies such as solar cells, fuel cells, lithium ion batteries and super capacitors. These materials show great promise in addressing growing environmental concerns for cleaner power sources at a time of increasing global demand for energy. In this perspective, we show that complex multi-shelled micro-/nano-materials show significant material advantages in many applications over conventional simple hollow structures. We also summarize the vast array of synthetic strategies used to create multi-shelled hollow structures, and discuss the possible application of these novel materials for power generation and storage. Finally, the emergent challenges and future developments of multi-shelled hollow structures are further discussed.

Quantum Dot Light-Emitting Devices with Electroluminescence Tunable over the Entire Visible Spectrum

Improvements in quantum dot light-emitting device (QD-LED) performance are achieved by the choice of organic charge transporting layers, by use of different colloidal QDs for the different parts of the visible spectrum, and by utilizing a recently demonstrated robust QD deposition method. Spectrally narrow electroluminescence of our QD-LEDs is tuned over the entire visible wavelength range from lambda = 460 nm (blue) to lambda = 650 nm (deep red). By printing close-packed monolayers of different QD types inside an identical QD-LED structure, we demonstrate that different color QD-LEDs with QDs of different chemistry can be fabricated on the same substrate. We discuss mechanisms responsible for efficiency increase for green (4-fold) and orange (30%) QD-LEDs as compared to previous reports and outline challenges associated with achieving high-efficiency blue QD-LEDs.

Accurate Control of Multishelled ZnO Hollow Microspheres for Dye-Sensitized Solar Cells with High Efficiency

A series of multishelled ZnO hollow microspheres with controlled shell number and inter-shell spacing have been successfully prepared by a simple carbonaceous microsphere templating method, whose large surface area and complex multishelled hollow structure enable them load sufficient dyes and multi-reflect the light for enhancing light harvesting and realize a high conversion efficiency of up to 5.6% when used in dye-sensitized solar cells.

A novel and highly efficient photocatalyst based on P25-graphdiyne nanocomposite.

Titania nanoparticles (P25) are successfully chemically bonded with graphdiyne (GD) nanosheets by a facile hydrothermal treatment, to form a novel nanocomposite photocatalyst. The as-prepared P25-GD nanocomposite exhibits higher photocatalytic activity for degrading methylene blue under UV irradiation than not only P25 and P25-carbon nanotube composite but also the current well-known P25-graphene composite photocatalysts. Moreover, P25-GD also shows considerable visible-light-driven photocatalytic activity, since the formation of chemical bonds between P25 and GD effectively decreases the bandgap of P25 and extends its absorbable light range. The photocatalytic activity of P25-GD can be adjusted by changing the content of GD in composites and the optimized value is about 0.6 wt%. Such a nanocomposite photocatalyst might find potential application in a wide range of fields including air purification and waste water treatment.

Alternating Current Driven Electroluminescence from ZnSe/ZnS:Mn/ZnS Nanocrystals

We present a novel technique for room temperature, solution-based fabrication of alternating current thin-film electroluminescent (AC-TFEL) devices using phosphor-doped nanocrystals. Synthesis for stable ZnSe/ZnS:Mn/ZnS nanocrystals that exhibit a quantum yield of 65 +/- 5% is outlined, and their electroluminescence is demonstrated in structures consisting of only wide band gap ceramic layers. Both the nanocrystal and the ceramic films have minimal absorption across the visible light spectrum, enabling us to demonstrate transparent AC-TFEL devices.

Selection of Metal Oxide Charge Transport Layers for Colloidal Quantum Dot LEDs

We investigate the effect of the electronic energy level positioning, conductivity, and morphology of metal oxide charge transport layers on the performance of light emitting devices (LEDs) that consist of a colloidally synthesized quantum dot (QD) luminescent film embedded between electron and hole injecting ceramic layers. We demonstrate that understanding of these material properties and their effect on charging processes in QDs enables the systematic design of higher efficiency QD-LEDs and excitation of QDs with different emission colors using the same device structure.

Air-Stable Operation of Transparent, Colloidal Quantum Dot Based LEDs with a Unipolar Device Architecture

We report a novel unipolar light-emitting device architecture that operates using direct-current, field-driven electroluminescence of colloidally synthesized quantum dots (QDs). This device architecture, which is based only on transparent ceramics and QDs, enables emission from different color QDs and, for the first time, constant QD electroluminescence during extended operation in air, unpackaged.

Effect of Carrier Thermalization Dynamics on Light Emission and Amplification in Organometal Halide Perovskites.

The remarkable rise of organometal halide perovskites as solar photovoltaic materials has been followed by promising developments in light-emitting devices, including lasers. Here we present unique insights into the processes leading to photon emission in these materials. We employ ultrafast broadband photoluminescence (PL) and transient absorption spectroscopies to directly link density dependent ultrafast charge dynamics to PL. We find that exceptionally strong PL at the band edge is preceded by thermalization of free charge carriers. Short-lived PL above the band gap is clear evidence of nonexcitonic emission from hot carriers, and ultrafast PL depolarization confirms that uncorrelated charge pairs are precursors to photon emission. Carrier thermalization has a profound effect on amplified stimulated emission at high fluence; the delayed onset of optical gain we resolve within the first 10 ps and the unusual oscillatory behavior are both consequences of the kinetic interplay between carrier thermalization and optical gain.

Granum‐Like Stacking Structures with TiO2–Graphene Nanosheets for Improving Photo‐electric Conversion

Solar energy is commonly considered to be one of the most important forms of future energy production. This is due to its ability to generate essentially free power, after installation, with low environmental impact. Green plants, meanwhile, exhibit a process for light-to-charge conversion that provides a useful model for using solar radiation efficiently. Granum, the core organ in photosynthesis consists of a stack of ~10-100 thylakoids containing pigments and electrons acceptors. Imitating the structure and function of granum, stacked structures are fabricated with TiO(2) /graphene nanosheets as the thylakoids unit, and their photo-electric effect is studied by varying the number of layers present in the film. The photo-electric response of the graphene composites are found to be 20 times higher than that of pure TiO(2) in films with 25 units stacked. Importantly, the cathodic photocurrent changes to anodic photocurrent as the thickness increases, an important feature of efficient solar cells which is often ignored. Here graphene is proposed to perform similarly to the b6f complex in granum, by separating charges and transporting electrons through the stacked film. Using this innovation, stacked TiO(2) /graphene structures are now able to significantly increase photoanode thickness in solar cells without losing the ability to conduct electrons.

Charge Dynamics in Solution-Processed Nanocrystalline CuInS2 Solar Cells.

We investigate charge dynamics in solar cells constructed using solution-processed layers of CuInS2 (CIS) nanocrystals (NCs) as the electron donor and CdS as the electron acceptor. By using time-resolved spectroscopic techniques, we are able to observe photoinduced absorptions that we attribute to the mobile hole carriers in the NC film. In combination with transient photocurrent and photovoltage measurements, we monitor charge dynamics on time scales from 300 fs to 1 ms. Carrier dynamics are investigated for devices with CIS layers composed of either colloidally synthesized 1,3-benzenedithiol-capped nanocrystals or in situ sol-gel synthesized thin films as the active layer. We find that deep trapping of holes in the colloidal NC cells is responsible for decreases in the open-circuit voltage and fill factor as compared to those of the sol-gel synthesized CIS/CdS cell.