Building Quantum Dots into Solids with Well‐Defined Shapes

Quantum dots (QDs) chemically synthesized in solution at a higher temperature (85 °C) were built in situ into a variety of three‐dimensional (3D) close‐packed QD ensembles (QD solids) with well‐defined shapes: needles, disks, rods, spheres, bundles, stars, ribbons, and transition structures (TSs). Design strategies using a novel cold‐treatment (–25 to 0 °C) process immediately following the synthesis of the QDs provided control over these shapes, independently from the II–VI materials used. Transformation occurred between different shapes by the rearrangement of the QDs within the QD ensembles. The QD solids were characterized by advanced electron microscopy and photoluminescence spectroscopy. The cold treatment strategy is versatile and has been applied to several II–VI QDs (CdS, ZnS, and CdSe) and may be extended to other QD systems and other chemical approaches.     

Interaction of CdSe/ZnS quantum dots: Among themselves and with matrices

Photoluminescence (PL) of CdSe/ZnS quantum dots (QDs) deposited on Si, fused silica, Au film, shows red-shift; and blue-shift whenever two peaks are present, particularly on silica nanospheres. The red-shift with increasing density of QDs is attributed to interaction between QDs with PL emerging from the lower bonding state, and the second peak is attributed to molecular complexes on the surface of QD interacting with its surrounding matrices. The second peak is too weak to be detected on Si wafer with native oxide. The couplings between QD/QD and QDs/silica spheres via the molecular complexes are explained with a simple model. We also demonstrate that the band-gap of photonic crystals consisting of silica spheres can be stabilized by dehydration, annealing at high temperatures up to 1000 °C.     

Exceptional Catalytic Nature of Quantum Dots for Photocatalytic Hydrogen Evolution without External Cocatalysts

The catalytic nature of semiconducting quantum dots (QDs) for photocatalytic hydrogen (H₂) evolution can be thoroughly aroused, not because of coupling with external cocatalysts, but through partially covering controlled amount of ZnS shell on the surface. Specifically, CdSe QDs, with an optimal coverage of ZnS (≈46%), can produce H₂ gas with a constant rate of ≈306.3 ± 21.1 µmol mg^?1 h^?1 during 40 h, thereby giving a turnover number of ≈(4.4 ± 0.3) × 10⁵, which is ≈110‐fold to that of unmodified CdSe QDs under identical conditions. The performance of H₂ evolution is comparable to or even better than the commonly used external cocatalysts, e.g., metal complexes, noble metals assisted photosystems. Mechanistic insights indicate that the dramatically enhanced activity and stability of bare QDs for photocatalytic H₂ production are derived from (i) inhibiting exciton annihilation at trap states, (ii) preventing the photo‐oxidation of core frameworks, and (iii) retaining tunneling efficiencies of photogenerated electrons and holes to reactive sites with partial ZnS coverage.     

Improving the Power Conversion Efficiency of Organic Solar Cell by Blending with CdSe/ZnS Core–Shell Quantum Dots

We have blended poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) with CdSe/ZnS core–shell quantum dots (QDs) as the active layer to produce organic solar cells (OSC). The size of the CdSe/ZnS core–shell QDs was determined to be about 4 nm using transmission electron microscopy. The OSC were characterized by measuring the absorption spectra, current–voltage characteristics, and external quantum efficiency (EQE) spectra. The samples doped with 0.5 wt.% CdSe/ZnS core–shell QDs exhibited higher power conversion efficiency (PCE) than samples doped with other concentrations of QDs. The PCE of the OSC increases from 2.10% to 2.38% due to an increase of the short circuit current density (J _sc) from 6.00 mA/cm² to 6.25 mA/cm². The open circuit voltage (V _oc) was kept constant when comparing OSC that were undoped and doped with 0.5 wt.% CdSe/ZnS core–shell QDs. These CdSe/ZnS core–shell QDs can increase optical absorption as well as provide extra exciton dissociation and additional electric pathways in hybrid OSC.     

Cover Picture: Highly Fluorescent Poly(dimethylsiloxane) for On‐Chip Temperature Measurements (Adv. Funct. Mater. 2/2009)

This work describes a convenient method to generate a poly(dimethylsiloxane) (PDMS) composite containing ZnO quantum dots (QDs) for whole‐chip temperature measurements. This composite is highly fluorescent and very sensitive to temperature changes (0.4 nm °C⁻¹, compared to 0.1 nm °C⁻¹ in commonly used CdSe QDs). It also shows extremely high fluorescent stability under various conditions over long time without phase separation or fluorescent changes. Both merits make this composite an ideal material for sensing temperature changes on microfluidic chips. The bonding between the QDs and PDMS is studied by comparing PDMS composites with ZnO QDs of different sizes, and a model is given to elucidate the high stability of this composite.     

Rapid and Controllable Digital Microfluidic Heating by Surface Acoustic Waves

Fast and controllable surface acoustic wave (SAW) driven digital microfluidic temperature changes are demonstrated. Within typical operating conditions, the direct acoustic heating effect is shown to lead to a maximum temperature increase of about 10 °C in microliter water droplets. The importance of decoupling droplets from other on‐chip heating sources is demonstrated. Acoustic‐heating‐driven temperature changes reach a highly stable steady‐state value in ≈3 s, which is an order of magnitude faster than previously published. This rise time can even be reduced to ≈150 ms by suitably tailoring the applied SAW‐power excitation profile. Moreover, this fast heating mechanism can lead to significantly higher temperature changes (over 40 °C) with higher viscosity fluids and can be of much interest for on‐chip control of biological and/or chemical reactions.     

Targeting Cooling for Quantum Dots in White QDs‐LEDs by Hexagonal Boron Nitride Platelets with Electrostatic Bonding

Although quantum dots (QDs) show excellent advantages in flexible wavelength‐tuning and high color rendering capability in white light‐emitting diodes (WLEDs) lighting and display applications, the less‐than‐one quantum efficiency inevitably gives rise to a non‐negligible heat generation problem, which induces high‐temperature quenching issues of QDs and severely hinders their potential applications. Efficient heat dissipation for these nanoscale QDs is challenging since these nanoparticle “heat sources” are usually embedded in a low‐thermal conductivity polymer matrix. In this work, this problem is attempted by targeting cooling of the QDs in the silicone matrix by electrostatically bonding the hexagonal boron nitride (hBN) platelets onto QDs without sacrificing the optical performance of WLEDs. The red‐emissive QDs/hBN composites are mixed with yellow‐emissive phosphor to fabricate QDs/hBN‐WLEDs. Due to the effective heat transfer channels established by the QDs/hBN in the silicone, the heat could be dissipated efficiently to ambient air, and the working temperature of WLEDs is reduced by 22.7 °C at 300 mA. The QDs/hBN‐WLEDs still maintain a high luminous efficiency of 108.5 lm W^?1 and a high color rendering index of Ra > 95, R9 > 90, showing that the present strategy can improve heat dissipation without sacrificing the optical performance.     

Luminescent high temperature sensor based on the CdSe/ZnS quantum dot thin film

A high temperature sensor based on the multi-parameter temperature dependent characteristic of photoluminescence （PL） of quantum dot （QD） thin film is demonstrated by depositing the CdSe/ZnS core/shell QDs on the SiO2 glass substrates. The variations of the intensity, the peak wavelength and the full width at half maximum （FWHM） of PL spectra with temperature are studied experimentally and theoretically. The results indicate that the peak wavelength of the PL spectra changes linearly with temperature, while the PL intensity and FWHM vary exponentially for the tem- perature range from 30 ℃ to 180 ℃. Using the obtained temperature dependent optical parameters, the resolution of the designed sensor can reach 0.1 nm/℃.     

Influence of crystallinity of as-deposited Ge film on formation of quantum dot in carbon-mediated solid-phase epitaxy

The influence of crystallinity of as-deposited Ge films on Ge quantum dot (QD) formation via carbon (C)-mediated solid-phase epitaxy (SPE) was investigated. The samples were fabricated by solid-source molecular beam epitaxy (MBE). Ge/C/Si structure was formed by sequential deposition of C and Ge at deposition temperature (T_D) of 150–400 °C, and it was heat-treated in the MBE chamber at 650 °C. In the case of amorphous or a mixture of amorphous and nano-crystalline Ge film grown for T_D ≤250 °C, density of QDs increased with increasing T_D due to the increase of C-Ge bonds in Ge layer. Ge QDs with diameter of 9.2±2.1 nm were formed in the highest density of 8.3×10¹¹ cm⁻² for T_D =250 °C. On the contrary, in the case of polycrystalline Ge film for T_D ≥300 °C, density of QDs decreased slightly. This is because C incorporation into Ge layer during SPE was suppressed due to the as-crystallized columnar grains. These results suggest that as-deposited Ge film in a mixture of amorphous and nano-crystalline state is suitable to form small and dense Ge QDs via C-mediated SPE.     

Biological reaction signal enhancement in porous silicon Bragg mirror based on quantum dots fluorescence

In this paper, we mainly study the preparation of an optical biosensor based on porous silicon (PSi) Bragg mirror and its feasibility for biological detection. The quantum dot (QD) labeled biotin was pipetted onto streptavidin functionalized PSi Bragg mirror samples, the affinity reaction between QD labeled biotin and streptavidin in PSi occurred, so the QDs were indirectly connected to the PSi. The fluorescence of QD enhanced the signal of biological reactions in PSi. The performance of the sensor is verified by detecting the fluorescence of the QD in PSi. Due to the fluorescence intensity of the QDs can be enhanced by PSi Bragg mirror, the sensitivity of the PSi optical biosensor will be improved.     

Aqueous synthesis of highly monodispersed thiol-capped CdSe quantum dots based on the electrochemical method

A facile green approach is developed to control the growth regime in the aqueous synthesis of CdSe semiconductor quantum dots (QDs) based on the electrochemistry method. The low growth temperature and slow injection of Se precursors are used to prolong the diffusion controlled stage and thus suppress the Ostwald ripening during nanocrystal growth. The experimental results show that a low concentration of Se precursor would definitely influence the growth procedure. The narrow absorption peaks in the UV–visible absorption spectra, as well as transmission electron microscopy images indicate that the as-prepared CdSe QDs have a good monodispersity. The high-resolution transmission electron microscopy (HRTEM) images and powder X-ray diffraction (XRD) pattern suggest that the as-prepared QDs have high crystallinity and cubic structure. The QDs exhibit high fluorescence QYs of about 30% without any postpreparative treatment over a broad spectral range of 560–660 nm, which could be further broadened by long-term refluxing. The current work suggests that the electrochemical method is an attractive approach to the synthesis of high-quality II–VI semiconductor QDs at a large scale.     

Electron microscopy of GaAs Structures with InAs and as quantum dots

An electron-microscopy study of GaAs structures, grown by molecular-beam epitaxy, containing two coupled layers of InAs semiconductor quantum dots (QDs) overgrown with a thin buffer GaAs layer and a layer of low-temperature-grown gallium arsenide has been performed. In subsequent annealing, an array of As nanoinclusions (metallic QDs) was formed in the low-temperature-grown GaAs layer. The variation in the microstructure of the samples during temperature and annealing conditions was examined. It was found that, at comparatively low annealing temperatures (400–500°C), the formation of the As metallic QDs array weakly depends on whether InAs semiconductor QDs are present in the preceding layers or not. In this case, the As metallic QDs have a characteristic size of about 2–3 nm upon annealing at 400°C and 4–5 nm upon annealing at 500°C for 15 min. Annealing at 600°C for 15 min in the growth setup leads to a coarsening of the As metallic QDs to 8–9 nm and to the formation of groups of such QDs in the area of the low-temperature-grown GaAs which is directly adjacent to the buffer layer separating the InAs semiconductor QDs. A more prolonged annealing at an elevated temperature (760°C) in an atmosphere of hydrogen causes a further increase in the As metallic QDs’ size to 20–25 nm and their spatial displacement into the region between the coupled InAs semiconductor QDs.     

Formation and characterization of self-organized CdSe quantum dots

We have investigated the formation and characteristic of self-organized CdSe quantum dots (QDs) on ZnSe(001) surfaces with the use of photoluminescence (PL) and transmission electron microscopy (TEM). Coherent CdSe QDs are naturally formed on ZnSe surfaces, when the thickness of CdSe layers is around 2 ML. The plan-view TEM images exhibit that CdSe QDs have a relatively narrow distribution of QD size, and that the density of CdSe QDs is about 10¹⁰ cm⁻². The base structure of the CdSe dot is rhombic, which has the long axis of about 20 nm in length along direction. The temperature dependence of macro-PL spectra reveals that the behavior of self-organized CdSe QDs is quite different from that of ZnCdSe quantum well (QW), resulting from characteristic features of zero-dimensional structures of QDs. Moreover, the macro-PL results suggest the existence of QW-like continuous state lying over QD states. Micro-PL measurements show several numbers of high-resolved sharp lines from individual CdSe QDs. The linewidth broadening with temperature depends on peak energy position of the QDs. The linewidths of lower energy lines, corresponding to larger size QDs, are more temperature dependent.     

Precisely Encoded Barcodes Using Tetrapod CdSe/CdS Quantum Dots with a Large Stokes Shift for Multiplexed Detection

A serious obstacle to the construction of high‐capacity optical barcodes in suspension array technology is energy transfer, which can prompt unpredictable barcode signals, limited barcode numbers, and the need for an unfeasible number of experimental iterations. This work reports an effective and simple way to eliminate energy transfer in multicolor quantum dots (QDs)‐encoded microbeads by incorporating tetrapod CdSe/CdS QDs with a large Stokes shift (about 180 nm). Exploiting this unique feature enables the facile realization of a theoretical 7 × 7‐1 barcoding matrix combining two colors and seven intensity levels. As such, microbeads containing tetrapod CdSe/CdS QDs are demonstrated to possess a powerful encoding capacity which allows for precise barcode design. The ability of the Shirasu porous glass membrane emulsification method to easily control microbead size facilitates the establishment of a 3D barcode library of 144 distinguishable barcodes, indicating the enormous potential to enable large‐scale multiplexed detection. Moreover, when applied for the multiplexed detection of five common allergens, these barcodes exhibit superior detection performance (limit of detection: 0.01–0.02 IU mL^?1) for both spiked and patient serum samples. Therefore, this new coding strategy helps to expand barcoding capacity while simultaneously reducing the technical and economic barriers to the optical encoding of microbeads for high‐throughput multiplexed detection.     

Highly Efficient Quantum‐Dot‐Sensitized Solar Cell Based on Co‐Sensitization of CdS/CdSe

Cadmium sulfide (CdS) and cadmium selenide (CdSe) quantum dots (QDs) are sequentially assembled onto a nanocrystalline TiO₂ film to prepare a CdS/CdSe co‐sensitized photoelectrode for QD‐sensitized solar cell application. The results show that CdS and CdSe QDs have a complementary effect in the light harvest and the performance of a QDs co‐sensitized solar cell is strongly dependent on the order of CdS and CdSe respected to the TiO₂. In the cascade structure of TiO₂/CdS/CdSe electrode, the re‐organization of energy levels between CdS and CdSe forms a stepwise structure of band‐edge levels which is advantageous to the electron injection and hole‐recovery of CdS and CdSe QDs. An energy conversion efficiency of 4.22% is achieved using a TiO₂/CdS/CdSe/ZnS electrode, under the illumination of one sun (AM1.5,100 mW cm^?2). This efficiency is relatively higher than other QD‐sensitized solar cells previously reported in the literature.     

Optical and electrical simulation of hybrid solar cell based on conjugated polymer and size-tunable CdSe quantum dots: Influence of the QDs size

The photovoltaic performance of hybrid solar cell based on poly(3-hexylthiophene) (P3HT) and size-tunable CdSe quantum dots is analyzed by combination of optical and electrical simulations. The employed optical and electrical models describe the dependency of solar cell characteristics on CdSe QDs diameter and active layer thickness. The device performance improvement is observed by increasing CdSe QDs diameter from 2.3 nm to 8.3 nm. The short circuit current density (Jsc) shows significant ascending trend by QDs diameter which is due to electron mobility (μ_n) and absorption range enhancement. However, the maximum achievable open circuit voltage (V_OC) decreases by QDs size growth, V_OC shows ascending trend with CdSe QDs diameter increase, because of the higher dissociation probability and lesser recombination rate for larger nanocrystals. As the electron mobility proportionally increases by CdSe QDs size, the performance dependency on the charge mobility is studied. Results show that by growing the size of CdSe QDs, charge extraction is dominant in the competition between recombination rate increase and charge extraction increase.     

Enhanced Photocurrent Generation in Proton‐Irradiated “Giant” CdSe/CdS Core/Shell Quantum Dots

Group II–VI quantum dots (QDs) possess tunable electrical and optical properties that make them very attractive for high‐tech applications and power generation. The effects of proton irradiation on both the structural and physical properties of “giant” CdSe/CdS core–shell QDs (g‐CS QDs) are investigated. These experiments shed light on photoelectron delocalization in g‐CS QDs, where current linkages and strong variations in optical emission result from the spatial extension of the photoelectron wavefunctions over the conduction bands of CdSe and CdS. Monte Carlo simulations of ion–matter interactions show that the damaging rates can be set from the energy of impinging protons to promote the formation of structural defects in the core or shell. The formation of nanocavities is demonstrated after irradiation doses higher than ≈10¹⁷ H⁺ cm^?2, while a continuous decrease in luminescence intensity is observed for increasing proton fluencies. This feature is accompanied by a concomitant lifetime decrease marking the rise of nonradiative phenomena and the occurrence of greater photocarrier transfers between CdS and CdSe. Current‐to‐voltage characterizations evidence that proton implantation can be implemented to enhance the photocurrent generation in g‐CS QDs. This increase is attributed to the delocalization of photoelectrons in the CdS shell, whose improvement is found to promote electron–hole pair separation.     

Annealing temperature dependent structural and optical properties of electrodeposited CdSe thin films

Cadmium selenide films were synthesized using simple electrodeposition method on indium tin oxide coated glass substrates. The synthesized films were post annealed at 200 °C, 300 °C and 400 °C. X-ray diffraction of the films showed the hexagonal structure with crystallite size <3 nm for as deposited films and 3–25 nm for annealed films. The surface morphology of films using field emission scanning electron microscopy showed granular surface. The high resolution transmission electron microscopy of a crystallite of the film revealed lattice fringes which measured lattice spacing of 3.13 Å corresponding to (002) plane, indicating the lattice contraction effect, due to small size of CdSe nanocrystallite. The calculation of optical band gap using UV–visible absorption spectrum showed strong red-shift with increase in crystallite size, indicating to the charge confinement in CdSe nanocrystallite.     

Improved performance of CdSe/ZnS quantum dot light-emitting diodes through doping with small molecule CBP

The poor film formation of CdSe/ZnS quantum dots (QDs) during spin-coating makes a substantial impact on the device performance of quantum dot light-emitting diodes (QLEDs). This work proposes a method to improve the morphology of the quantum dot light-emitting layer (EML) by adding small organic molecular 4,4''-Bis(9H-carbazol-9-yl) biphenyl (CBP) into the layer. Its surface roughness reduces from 6.21 nm to 2.71 nm, which guarantees a good contact between hole transport layer (HTL) and EML. Consequently, the CdSe/ZnS QDs:CBP based QLED achieves maximum external quantum efficiency (EQE) of 5.86%, and maximum brightness of 10 363 cd/m2. It is demonstrated that the additive of small organic molecules could be an effective way to improve the brightness and the efficiency of QLEDs.     

<Emphasis Type="Italic">In Situ</Emphasis> Study of Reduction Process of CuO Paste and Its Effect on Bondability of Cu-to-Cu Joints

A bonding method utilizing redox reactions of metallic oxide microparticles achieves metal-to-metal bonding in air, which can be alternative to lead-rich high-melting point solder. However, it is known that the degree of the reduction of metallic oxide microparticles have an influence on the joint strength using this bonding method. In this paper, the reduction behavior of CuO paste and its effect on Cu-to-Cu joints were investigated through simultaneous microstructure-related x-ray diffraction and differential scanning calorimetry measurements. The CuO microparticles in the paste were gradually reduced to submicron Cu₂O particles at 210–250°C. Subsequently, Cu nanoparticles were generated instantaneously at 300–315°C. There was a marked difference in the strengths of the joints formed at 300°C and 350°C. Thus, the Cu nanoparticles play a critical role in sintering-based bonding using CuO paste. Furthermore, once the Cu nanoparticles have formed, the joint strength increases with higher bonding temperature (from 350°C to 500°C) and pressure (5–15 MPa), which can exceed the strength of Pb-5Sn solder at higher temperature and pressure.