Revealing the Band-Edge Exciton Fine Structure of Single InP Nanocrystals.

We investigate the fundamental optical properties of single zinc-blende InP/ZnSe/ZnS nanocrystals (NCs) using frequency- and time-resolved magneto-photoluminescence spectroscopy. At liquid helium temperature, highly resolved spectral fingerprints are obtained and identified as the recombination lines of the three lowest states of the band-edge exciton fine structure. The evolutions of the photoluminescence spectra and decays under magnetic fields show evidence for a ground dark exciton level 0L with zero angular momentum projection along the NC main elongation axis. It lies 300 to 600 µeV below the ±1L bright exciton doublet, which is finely split by the NC shape anisotropy. These spectroscopic findings are well reproduced with a model of exciton fine structure accounting for shape anisotropy of the InP core. Our spectral fingerprints are extremely sensitive to the NC morphologies and unveil highly uniform shapes with prolate deviations of less than 3% from perfect sphericity.

Narrow Intrinsic Line Widths and Electron-Phonon Coupling of InP Colloidal Quantum Dots.

InP quantum dots (QDs) are the material of choice for QD display applications and have been used as active layers in QD light-emitting diodes (QDLEDs) with high efficiency and color purity. Optimizing the color purity of QDs requires understanding mechanisms of spectral broadening. While ensemble-level broadening can be minimized by synthetic tuning to yield monodisperse QD sizes, single QD line widths are broadened by exciton-phonon scattering and fine-structure splitting. Here, using photon-correlation Fourier spectroscopy, we extract average single QD line widths of 50 meV at 293 K for red-emitting InP/ZnSe/ZnS QDs, among the narrowest for colloidal QDs. We measure InP/ZnSe/ZnS single QD emission line shapes at temperatures between 4 and 293 K and model the spectra using a modified independent boson model. We find that inelastic acoustic phonon scattering and fine-structure splitting are the most prominent broadening mechanisms at low temperatures, whereas pure dephasing from elastic acoustic phonon scattering is the primary broadening mechanism at elevated temperatures, and optical phonon scattering contributes minimally across all temperatures. Conversely for CdSe/CdS/ZnS QDs, we find that optical phonon scattering is a larger contributor to the line shape at elevated temperatures, leading to intrinsically broader single-dot line widths than for InP/ZnSe/ZnS. We are able to reconcile narrow low-temperature line widths and broad room-temperature line widths within a self-consistent model that enables parametrization of line width broadening, for different material classes. This can be used for the rational design of more spectrally narrow materials. Our findings reveal that red-emitting InP/ZnSe/ZnS QDs have intrinsically narrower line widths than typically synthesized CdSe QDs, suggesting that these materials could be used to realize QDLEDs with high color purity.

Review: Quantum Dot Light-Emitting Diodes.

Quantum dot light-emitting diodes (QD-LEDs) are one of the most promising self-emissive displays in terms of light-emitting efficiency, wavelength tunability, and cost. Future applications using QD-LEDs can cover a range from a wide color gamut and large panel displays to augmented/virtual reality displays, wearable/flexible displays, automotive displays, and transparent displays, which demand extreme performance in terms of contrast ratio, viewing angle, response time, and power consumption. The efficiency and lifetime have been improved by tailoring the QD structures and optimizing the charge balance in charge transport layers, resulting in theoretical efficiency for unit devices. Currently, longevity and inkjet-printing fabrication of QD-LEDs are being tested for future commercialization. In this Review, we summarize significant progress in the development of QD-LEDs and describe their potential compared to other displays. Furthermore, the critical elements to determine the performance of QD-LEDs, such as emitters, hole/electron transport layers, and device structures, are discussed comprehensively, and the degradation mechanisms of the devices and the issues of the inkjet-printing process were also investigated.

Analysis of images supplied by Skincam® can record the changes of some scar features that occur over time. Comparisons with the assessments of dermatologist and patients' perception.

OBJECTIVE: The objective of the study was to assess in vivo the validity of a new imaging device in quantifying the scarring process over time and to compare its data with the expertise of dermatologist and patients' self-appraisals. MATERIALS AND METHODS: A total of 37 Korean women, aged 20-50 year, with closed scars of different types, were enrolled after a dermatological evaluation. All subjects applied daily a hydrating cream on their scars for 2 months. Images of scars at different times (Day 0, Day 28, and Day 56) were taken and further analyzed, yielding various parameters such as color, luminance, size, volume, and depth of each scar. A dermatologist visually graded, at each time point, the clinical aspect of the scar, and patients were asked to answer to some questions dealing with their self-examination of their scar. RESULTS: The changes in some scar features that occurred during the application period were quantified and statistically differed from the D0 baseline value. Scars became of reduced size, lighter (Increased luminance), less red, less deep, and less voluminous. Some of these parameters (volume, lightness, smoothness, texture regularity) were statistically different at D28 whereas some others (area, depth, redness) showed significant changes at D56 . Dermatologist expertise and patients' assessments were in high agreement. CONCLUSION: This methodological approach that uses a dedicated camera associated with image analysis, despite some inherent limits (size of the scar), appears as a valuable aid to surgeons in the management of scars, in the follow-up of a given procedure or treatment. Beyond scar management, this approach may be extended to other skin disorders such as acne.

Tuning Hot Carrier Dynamics of InP/ZnSe/ZnS Quantum Dots by Shell Morphology Control.

Isotropic InP/ZnSe/ZnS quantum dots (QDs) are prepared at a high reaction temperature, which facilitates ZnSe shell growth on random facets of the InP core. Fast crystal growth enables stacking faults elimination, which induces anisotropic growth, and as a result, improves the photoluminescence (PL) quantum yield by nearly 20%. Herein, the effect of the QD morphology on photophysical properties is investigated by observing the PL blinking and ultrafast charge carrier dynamics. It is found that hot hole trapping is considerably suppressed in isotropic InP QDs, indicating that the stacking faults in the anisotropic InP/ZnSe structures act as defects for luminescence. These results highlight the importance of understanding the correlation between QD shapes and hot carrier dynamics, and present a way to design highly luminescent QDs for further promising display applications.

Negative Trion Auger Recombination in Highly Luminescent InP/ZnSe/ZnS Quantum Dots.

Upon demonstrating self-luminescing quantum dot based light-emitting devices (QD-LEDs), rapid Auger recombination acts as one of the performance limiting factors. Here, we report the Auger processes of highly luminescent InP/ZnSe/ZnS QDs with different midshell structures that affect the performances of QD-LEDs. Transient PL measurements reveal that exciton-exciton binding energy is dependent on the midshell thickness, which implies that the intercarrier Coulomb interaction caused by the introduction of excess charges may come under the influence of midshell thickness which is in contrast with the nearly stationary single exciton behavior. Photochemical electron-doping and optical measurements of a single QD show that negative trion Auger recombination exhibits strong correlation with midshell thickness, which is supported by the dynamics of a hot electron generated in the midshell. These results highlight the role of excess electrons and the effects of engineered shell structures in InP/ZnSe/ZnS QDs, which eventually determine the Auger recombination and QD-LED performances.

Efficient and stable blue quantum dot light-emitting diode.

The visualization of accurate colour information using quantum dots has been explored for decades, and commercial products employing environmentally friendly materials are currently available as backlights1. However, next-generation electroluminescent displays based on quantum dots require the development of an efficient and stable cadmium-free blue-light-emitting device, which has remained a challenge because of the inferior photophysical properties of blue-light-emitting materials2,3. Here we present the synthesis of ZnSe-based blue-light-emitting quantum dots with a quantum yield of unity. We found that hydrofluoric acid and zinc chloride additives are effective at enhancing luminescence efficiency by eliminating stacking faults in the ZnSe crystalline structure. In addition, chloride passivation through liquid or solid ligand exchange leads to slow radiative recombination, high thermal stability and efficient charge-transport properties. We constructed double quantum dot emitting layers with gradient chloride content in a light-emitting diode to facilitate hole transport, and the resulting device showed an efficiency at the theoretical limit, high brightness and long operational lifetime. We anticipate that our efficient and stable blue quantum dot light-emitting devices can facilitate the development of electroluminescent full-colour displays using quantum dots.

Thermodynamic Investigation of Increased Luminescence in Indium Phosphide Quantum Dots by Treatment with Metal Halide Salts.

Increasing the quantum yields of InP quantum dots is important for their applications, particularly for use in consumer displays. While several methods exist to improve quantum yield, the addition of inorganic metal halide salts has proven promising. To further investigate this phenomenon, InP quantum dots dispersed in tetrahydrofuran were titrated with ZnCl2, ZnBr2, and InCl3. The optical properties were observed, and the reactions were studied by using quantitative 1H NMR and thermodynamic measurements from isothermal titration calorimetry. These measurements contradict the previously hypothesized reaction mechanism in which metal halide salts, acting as Z-type ligands, passivate undercoordinated anions on the surface of the quantum dots. This work provides evidence for a newly proposed mechanism wherein the metal halide salts undergo a ligand exchange with indium myristate. Thermodynamic measurements prove key to supporting this new mechanism, particularly in describing the organic ligand interactions on the surface. An Ising model was used to simulate the quantum dot surface and was fit by using thermodynamic and 1H NMR data. Together, these data and the proposed exchange mechanism provide greater insight into the surface chemistry of quantum dots.

Electrochemical Charging Effect on the Optical Properties of InP/ZnSe/ZnS Quantum Dots.

Semiconductor quantum dots (QDs) are spotlighted as a key type of emissive material for the next generation of light-emitting diodes (LEDs). This work presents the investigation of the electrochemical charging effect on the absorption and emission of the InP/ZnSe/ZnS QDs with different mid-shell thicknesses. The excitonic peak is gradually bleached during electrochemical charging, which is caused by 1Se (or 1Sh ) state filling when the electron (or hole) is injected into the InP core. Additional charges also lead to photoluminescence (PL) intensity reduction, however, it is greatly mitigated as the mid-shell thickness increases. Various PL measurements reveal that the PL reduction under electrochemical charging is attributed to the acoustic phonon-assisted Auger recombination. Here, the Auger recombination in QDs with a thick mid-shell is reduced under the electrochemically charged condition, indicating that QDs with larger volume are more stable emitters in charge-injecting devices such as LEDs. Furthermore, the negative and positive trion Auger recombination rate constants are estimated, respectively, via electrochemical charging. The negative trion Auger rate constants decrease with an increase in the mid-shell thickness increases, whereas the positive trion Auger rate constants are not heavily reliant on the mid-shell thickness.

Fundamental Limit of the Emission Linewidths of Quantum Dots: An Ab Initio Study of CdSe Nanocrystals.

The emission linewidth of a semiconducting nanocrystal (NC) significantly affects its performance in light-emitting applications, but its fundamental limit is still elusive. Herein, we analyze the exciton-phonon coupling (EPC) from Huang-Rhys (HR) factors using ab initio calculations and compute emission line shapes of CdSe NCs. When surface traps are absent, acoustic modes are found to dominate EPC. The computed linewidths are mainly determined by the size of NCs, being largely insensitive to the shape and crystal structure. Linewidths obtained in this work are much smaller than most measurements on homogeneous linewidths, but they are consistent with a CdSe/CdxZn1-xSe (core/shell) NC [Park, Y.-S.; Lim, J.; Klimov, V. I. Nat. Mater. 2019 18, 249-255]. Based on this comparison, it is concluded that the large linewidths in most experiments originated from internal fields by surface (or interface) traps or quasi-type II band alignment that amplifies EPC. Thus, the present results on NCs with ideal passivation provide the fundamental minimum of homogeneous linewidths, indicating that only the CdSe/CdxZn1-xSe NC has achieved this limit through well-controlled synthesis of shell structures. To further verify the role of internal fields, we model NCs with charged surface defects. We find that the internal field significantly increases HR factors and linewidths, in reasonable agreement with experiments on single cores. By revealing the fundamental limit of the emission linewidths of quantum dots, this work will pave the way for engineering quantum dots with an ultrasharp spectrum.

Highly efficient and stable InP/ZnSe/ZnS quantum dot light-emitting diodes.

Quantum dot (QD) light-emitting diodes (LEDs) are ideal for large-panel displays because of their excellent efficiency, colour purity, reliability and cost-effective fabrication1-4. Intensive efforts have produced red-, green- and blue-emitting QD-LEDs with efficiencies of 20.5 per cent4, 21.0 per cent5 and 19.8 per cent6, respectively, but it is still desirable to improve the operating stability of the devices and to replace their toxic cadmium composition with a more environmentally benign alternative. The performance of indium phosphide (InP)-based materials and devices has remained far behind those of their Cd-containing counterparts. Here we present a synthetic method of preparing a uniform InP core and a highly symmetrical core/shell QD with a quantum yield of approximately 100 per cent. In particular, we add hydrofluoric acid to etch out the oxidative InP core surface during the growth of the initial ZnSe shell and then we enable high-temperature ZnSe growth at 340 degrees Celsius. The engineered shell thickness suppresses energy transfer and Auger recombination in order to maintain high luminescence efficiency, and the initial surface ligand is replaced with a shorter one for better charge injection. The optimized InP/ZnSe/ZnS QD-LEDs showed a theoretical maximum external quantum efficiency of 21.4 per cent, a maximum brightness of 100,000 candelas per square metre and an extremely long lifetime of a million hours at 100 candelas per square metre, representing a performance comparable to that of state-of-the-art Cd-containing QD-LEDs. These as-prepared InP-based QD-LEDs could soon be usable in commercial displays.

The effects of discrete and gradient mid-shell structures on the photoluminescence of single InP quantum dots.

We investigated the dependence of the spectral diffusion and blinking behaviors of indium phosphide (InP) based core/shell/shell quantum dots (QDs) on their mid-shell compositions. We synthesized two types of core/shell/shell QDs having different mid-shell structures by controlling the shell thickness, the total sizes, and the selenium to sulfur ratios. The QDs with a discrete mid-shell (DS-QDs) exhibited a higher photoluminescence (PL) quantum yield (QY) and a narrower PL linewidth than the QDs with a gradient mid-shell (GS-QDs). By analyzing X-ray diffraction (XRD) patterns, and Raman spectra, we found that GS-QDs showed a larger lattice mismatch between the core and the shell than DS-QDs. Also, the spectral diffusion, PL blinking, Auger ionization efficiencies, and the lifetime blinking behavior on single QDs revealed that DS-QDs were nearly unaffected by the defect traps.

Trap Passivation in Indium-Based Quantum Dots through Surface Fluorination: Mechanism and Applications.

Treatment of InP colloidal quantum dots (QDs) with hydrofluoric acid (HF) has been an effective method to improve their photoluminescence quantum yield (PLQY) without growing a shell. Previous work has shown that this can occur through the dissolution of the fluorinated phosphorus and subsequent passivation of indium on the reconstructed surface by excess ligands. In this article, we demonstrate that very significant luminescence enhancements occur at lower HF exposure though a different mechanism. At lower exposure to HF, the main role of the fluoride ions is to directly passivate the surface indium dangling bonds in the form of atomic ligands. The PLQY enhancement in this case is accompanied by red shifts of the emission and absorption peaks rather than blue shifts caused by etching as seen at higher exposures. Density functional theory shows that the surface fluorination is thermodynamically preferred and that the observed spectral characteristics might be due to greater exciton delocalization over the outermost surface layer of the InP QDs as well as alteration of the optical oscillator strength by the highly electronegative fluoride layer. Passivation of surface indium with fluorides can be applied to other indium-based QDs. PLQY of InAs QDs could also be increased by an order of magnitude via fluorination. We fabricated fluorinated InAs QD-based electrical devices exhibiting improved switching and higher mobility than those of 1,2-ethanedithiol cross-linked QD devices. The effective surface passivation eliminates persistent photoconductivity usually found in InAs QD-based solid films.

Erratum: A comparison of postoperative emergence agitation between sevoflurane and thiopental anesthesia induction in pediatric patients (Korean J Anesthesiol 2015 Aug; 68(4): 373-378).

[This corrects the article on p. 373 in vol. 68, PMID: 26257850.].

A comparison of postoperative emergence agitation between sevoflurane and thiopental anesthesia induction in pediatric patients.

BACKGROUND: This study was performed to compare the incidence of emergence agitation (EA) between inhalation and intravenous anesthesia induction in children after sevoflurane anesthesia. METHODS: In this prospective and double-blind study, 100 children aged 3 to 7 years were enrolled. Subjects were randomly assigned to the sevoflurane (Group S) or thiopental (Group T) anesthesia induction groups. Anesthesia was induced using 8% sevoflurane and 4-6 mg/kg thiopental in Groups S and T, respectively. Anesthesia was maintained with nitrous oxide and sevoflurane. The children were evaluated at 5 and 20 min after arrival in the postanesthesia care unit (PACU) with a four-point agitation scale and the Pediatric Anesthesia Emergence Delirium scale. The incidence of EA and administration of the rescue agent were recorded. RESULTS: The incidence of EA was significantly lower in Group T compared to Group S at 5 min after PACU arrival (3/49 patients, 6% vs. 12/47 patients, 26%, P = 0.019). However, there was no difference between the two groups at 20 min after PACU arrival (23/49 vs. 19/47 patients in Group T vs. Group S, P = 0.425). The overall incidence of EA was 60% (28/47 patients) in Group S and 41% (20/49 patients) in Group T (P = 0.102). The number of children who received propofol as a rescue agent was significantly lower in Group T (Group S: 14/47 vs. Group T: 5/49, P = 0.031). CONCLUSIONS: Intravenous anesthesia induction with thiopental reduced the incidence of EA in the early PACU period compared to inhalation induction with sevoflurane in 3- to 7-year-old children undergoing sevoflurane anesthesia.

Modeling on the size dependent properties of InP quantum dots: a hybrid functional study.

Theoretical calculations based on density functional theory were performed to provide better understanding of the size dependent electronic properties of InP quantum dots (QDs). Using a hybrid functional approach, we suggest a reliable analytical equation to describe the change of energy band gap as a function of size. Synthesizing colloidal InP QDs with 2-4 nm diameter and measuring their optical properties was also carried out. It was found that the theoretical band gaps showed a linear dependence on the inverse size of QDs and gave energy band gaps almost identical to the experimental values.

Highly luminescent and photostable quantum dot-silica monolith and its application to light-emitting diodes.

A highly luminescent and photostable quantum dot-silica monolith (QD-SM) substance was prepared by preliminary surface exchange of the QDs and base-catalyzed sol-gel condensation of silica. The SM was heavily doped with 6-mercaptohexanol exchanged QDs up to 12 vol % (26 wt %) without particle aggregation. Propylamine catalyst was important in maintaining the original luminescence of the QDs in the SM during sol-gel condensation. The silica layer was a good barrier against oxygen and moisture, so that the QD-SM maintained its initial luminescence after high-power UV radiation (∼1 W) for 200 h and through the 150 °C LED encapsulant curing process. Green and red light-emitting QD-SMs were applied as color-converting layers on blue LEDs, and the external quantum efficiency reached up to 89% for the green QD-SM and 63% for the red one. A white LED made with a mixture of green and red QDs in the SM, in which the color coordinate was adjusted at (0.23, 0.21) in CIE1931 color space for a backlight application, showed an efficacy of 47 lm/W, the highest value yet reported.

Bright and stable alloy core/multishell quantum dots.

Color conversion: a quantum dot (QD) structure consisting of an alloy core (CdSe//ZnS) and multishells (CdSZnS) was prepared. The photoluminescence of the QDs could be tuned especially in the green-light region by controlling the thickness of the inner CdS shell. The alloy core/multishell (AC/MS) QDs showed a quantum efficiency of 100 % and a narrow spectrum width.