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AgxSe (x > 2) colloidal quantum dots (CQDs) have recently emerged as a promising environmentally friendly material contender for mid- and long-wave infrared optoelectronics, leveraging their intraband transition (1Se-1Pe). However, multicarrier interactions in CQDs, particularly Auger recombination, have profound implications on the optoelectronic properties of the materials and their potential in device applications. Understanding the intraband excited-state dynamics in n-doped AgxSe is therefore essential for the assessment and successful implementation of this material platform in devices. We, herein, investigate the carrier dynamics of AgxSe in both solution and thin-film states using a femtosecond mid-infrared transient absorption spectrometer. Our observations reveal that the multicarrier Auger process depends on the degree of doping in AgxSe CQDs and accelerates when the Fermi energy (EF) level approaches the 1Pe state. The calculated intraband Auger coefficients (CA) are measured to be on the order of â¼10-28 cm6 s-1, significantly larger compared to analogous n-doped HgS/Se CQDs.
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CsPbI3 perovskite quantum dots (QDs) could achieve pure-red emission by reducing their size, but the increased exciton binding energy (EB) and surface defects for the small-sized QDs (SQDs) cause severe Auger and trap recombinations, thus worsening their electroluminescence (EL) performance. Herein, we utilize the dangling bonds of the SQDs as a driving force to accelerate KI dissolution to solve its low solubility in nonpolar solvents, thereby allowing K+ and I- to bond to the surface of SQDs. The EB of the SQDs was decreased from 305 to 51 meV because of the attraction of K+ to electrons, meanwhile surface vacancies were passivated by K+ and I-. The Auger and trap recombinations were simultaneously suppressed by this difunctional ligand. The SQD-based light-emitting diode showed a stable pure-red EL peak of 639 nm, an external quantum efficiency of 25.1% with low roll-off, and a brightness of 5934 cd m-2.
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Auger recombination is a pivotal process for semiconductor nanocrystals (NCs), significantly affecting charge carrier generation and collection in optoelectronic devices. This process depends mainly on the NCs' electronic structures. In our study, we investigated Auger recombination dynamics in manganese (Mn2+)-doped CsPbI3 NCs using transient absorption (TA) spectroscopy combined with theoretical and experimental structural characterization. Our results show that Mn2+ doping accelerates Auger recombination, reducing the biexciton lifetime from 146 to 74 ps with increasing Mn doping concentration up to 10%. This accelerated Auger recombination in Mn-doped NCs is attributed to increased band edge wave function overlap of excitons and a larger density of final states of Auger recombination due to Mn orbital involvement. Moreover, Mn doping reduces the dielectric screening of the excitons, which also contributes to the accelerated Auger recombination. Our study demonstrates the potential of element doping to regulate Auger recombination rates by modifying the materials' electronic structure.
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The metal halide perovskite nanocrystals exhibit a remarkable tolerance to midgap defect states, resulting in high photoluminescence quantum yields. However, the potential of these nanocrystals for applications in display devices is hindered by the suppression of biexcitonic emission due to various Auger recombination processes. By adopting single-particle photoluminescence spectroscopy, herein, we establish that the biexcitonic quantum efficiency increases with the increase in the number of facets on cesium lead bromide perovskite nanocrystals, progressing from cube to rhombic dodecahedron to rhombicuboctahedron nanostructures. The observed enhancement is attributed mainly to an increase in their surface polarity as the number of facets increases, which reduces the Coulomb interaction of charge carriers, thereby suppressing Auger recombination. Moreover, Auger recombination rate constants obtained from the time-gated photon correlation studies exhibited a discernible decrease as the number of facets increased. These findings underscore the significance of facet engineering in fine-tuning biexciton emission in metal halide perovskite nanocrystals.
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Auger electrons (AEs) represent an intriguing topic in the field of radionuclide therapy. They are emitted by several radionuclides commonly used in nuclear medicine (indium-111, iodine-123, iodine-125), allowing for highly localized energy deposition and thus exerting a radiotoxic effect on specific cellular and sub-cellular targets. However, due to their short range in matter, AEs have had limited use in therapeutic applications so far. In recent years, the synthesis of various radiopharmaceuticals capable of binding to the enzyme poly(ADP-ribose) polymerase 1 has reignited interest in this type of therapy, laying the groundwork for a theranostic approach based on radionuclides emitting AEs. The enzyme PARP-1 operates enzymatically in close proximity to DNA that represents the prime target of radionuclide therapies. Following this trend, several PARP-targeted radiopharmaceuticals for AE-based theranostics have been developed. We provide an updated overview of preclinical studies focused on the applications of this new theranostic approach in glioblastoma, breast, prostate and ovarian carcinoma, and pancreatic adenocarcinoma.
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Nuclear DNA is the canonical target for biological damage induced by Auger electrons (AE) in the context of targeted radionuclide therapy (TRT) of cancer, but other subcellular components might also be relevant for this purpose, such as the energized mitochondria of tumor cells. Having this in mind, we have synthesized novel DOTA-based chelators carrying a prostate-specific membrane antigen (PSMA) inhibitor and a triphenyl phosphonium (TPP) group that were used to obtain dual-targeted 111In-radioconjugates ([111In]In-TPP-DOTAGA-PSMA and [111In]In-TPP-DOTAGA-G3-PSMA), aiming to promote a selective uptake of an AE-emitter radiometal (111In) by PSMA+ prostate cancer (PCa) cells and an enhanced accumulation in the mitochondria. These dual-targeted 111In-radiocomplexes are highly stable under physiological conditions and in cell culture media. The complexes showed relatively similar binding affinities toward the PSMA compared to the reference tracer [111In]In-PSMA-617, in line with their high cellular uptake and internalization in PSMA+ PCa cells. The complexes compromised cell survival in a dose-dependent manner and in the case of [111In]In-TPP-DOTAGA-G3-PSMA to a higher extent than observed for the single-targeted congener [111In]In-PSMA-617. µSPECT imaging studies in PSMA+ PCa xenografts showed that the TPP pharmacophore did not interfere with the excellent in vivo tumor uptake of the "golden standard" [111In]In-PSMA-617, although it led to a higher kidney retention. Such kidney retention does not necessarily compromise their usefulness as radiotherapeutics due to the short tissue range of the Auger/conversion electrons emitted by 111In. Overall, our results provide valuable insights into the potential use of mitochondrial targeting by PSMA-based radiocomplexes for efficient use of AE-emitting radionuclides in TRT, giving impetus to extend the studies to other AE-emitting trivalent radiometals (e.g., 161Tb or 165Er) and to further optimize the designed dual-targeting constructs.
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Neoplasias da Próstata , Masculino , Humanos , Neoplasias da Próstata/diagnóstico por imagem , Neoplasias da Próstata/radioterapia , Neoplasias da Próstata/metabolismo , Glutamato Carboxipeptidase II/metabolismo , Antígenos de Superfície/metabolismo , Radioisótopos , Compostos Radiofarmacêuticos , Mitocôndrias/metabolismo , Linhagem Celular TumoralRESUMO
Radionuclide therapy employing alpha emitters holds great potential for personalized cancer treatment. However, certain challenges remain when designing alpha radiopharmaceuticals, including the lack of stability of used radioconjugates due to nuclear decay events. In this work, ultrasmall silver telluride nanoparticles with a core diameter of 2.1 nm were prepared and radiolabeled with lead-212 using a chelator-free method with a radiolabeling efficiency of 75%. The results from the in vitro radiochemical stability assay indicated a very high retention of bismuth-212 despite the internal conversion effects originating from the decay of 212Pb. To further evaluate the potential of the nanoparticles, they were radiolabeled with indium-111, and their cell uptake and subcellular distribution were determined in 2D U87 cells, showing accumulation in the nucleus. Although not intentional, it was observed that the indium-111-radiolabeled nanoparticles induced efficient tumor cell killing, which was attributed to the Auger electrons emitted by indium-111. Combining the results obtained in this work with other favorable properties such as fast renal clearance and the possibility to attach targeting vectors on the surface of the nanoparticles, all well-known from the literature, these ultra-small silver telluride nanoparticles provide exciting opportunities for the design of theragnostic radiopharmaceuticals.
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Deep defects in the long-wave infrared (LWIR) HgCdTe heterostructure photodiode were measured via deep-level transient spectroscopy (DLTS) and photoluminescence (PL). The n+-P+-π-N+ photodiode structure was grown by following the metal-organic chemical vapor deposition (MOCVD) technique on a GaAs substrate. DLTS has revealed two defects: one electron trap with an activation energy value of 252 meV below the conduction band edge, located in the low n-type-doped transient layer at the π-N+ interface, and a second hole trap with an activation energy value of 89 meV above the valence band edge, located in the π absorber. The latter was interpreted as an isolated point defect, most probably associated with mercury vacancies (VHg). Numerical calculations applied to the experimental data showed that this VHg hole trap is the main cause of increased dark currents in the LWIR photodiode. The determined specific parameters of this trap were the capture cross-section for the holes of σp = 10-16-4 × 10-15 cm2 and the trap concentration of NT = 3-4 × 1014 cm-3. PL measurements confirmed that the trap lies approximately 83-89 meV above the valence band edge and its location.
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Efficient Auger recombination (AR) presents a significant challenge for the advancement of colloidal quantum dot (QD)-based devices involving multiexcitons. Here, the AR dynamics of near-infrared Ag2Se QDs were studied through transient absorption experiments. As the QD radius increases from 0.9 to 2.5 nm, the biexciton lifetime (τ2) of Ag2Se QDs increases from 35 to 736 ps, which is approximately 10 times longer than that of comparable-sized CdSe and PbSe QDs. A qualitative analysis based on observables indicates that the slow Auger rate is primarily attributed to the low density of the final states. The biexciton lifetime and triexciton lifetime (τ3) of Ag2Se QDs follow R3 and R2.6 dependence, respectively. Moreover, the ratio of τ2/τ3 is â¼2.3-3.2, which is markedly lower than the value expected from statistical scaling (4.5). These findings suggest that environmentally friendly Ag2Se QDs can serve as excellent candidates for low-threshold lasers and third-generation photovoltaics utilizing carrier multiplication.
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Time-resolved analysis of photon cross-correlation function g(2)(τ) is applied to photoluminescence (PL) of individual submicrometer size MAPbI3 perovskite crystals. Surprisingly, an antibunching effect in the long-living tail of PL is observed, while the prompt PL obeys the photon statistics typical for a classical emitter. We propose that antibunched photons from the PL decay tail originate from radiative recombination of detrapped charge carriers which were initially captured by a very limited number (down to one) of shallow defect states. The concentration of these trapping sites is estimated to be in the range 1013-1016 cm-3. In principle, photon correlations can be also caused by highly nonlinear Auger recombination processes; however, in our case it requires unrealistically large Auger recombination coefficients. The potential of the time-resolved g(2)(0) for unambiguous identification of charge rerecombination processes in semiconductors considering the actual number of charge carries and defects states per particle is demonstrated.
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A thorough understanding of the photocarrier relaxation dynamics in semiconductor quantum dots (QDs) is essential to optimize their device performance. However, resolving hot carrier kinetics under high excitation conditions with multiple excitons per dot is challenging because it convolutes several ultrafast processes, including Auger recombination, carrier-phonon scattering, and phonon thermalization. Here, we report a systematic study of the lattice dynamics induced by intense photoexcitation in PbSe QDs. By probing the dynamics from the lattice perspective using ultrafast electron diffraction together with modeling the correlated processes collectively, we can differentiate their roles in photocarrier relaxation. The results reveal that the observed lattice heating time scale is longer than that of carrier intraband relaxation obtained previously using transient optical spectroscopy. Moreover, we find that Auger recombination efficiently annihilates excitons and speeds up lattice heating. This work can be readily extended to other semiconductor QDs systems with varying dot sizes.
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BACKGROUND: The existence of voids within the mineral trioxide aggregate (MTA) composition is one of the factors that can influence the treatment outcome. The primary objective of this study was to quantitatively assess and compare the MTA orthograde obturation quality in severe curved root canals using two different MTA compaction techniques: manual compaction with K-file, or Auger technique using micro-computed tomography (micro-CT) imaging. METHODS: For this study, 26 mandibular first molar teeth with severely curved mesiobuccal root canals were selected. These samples were randomly divided into two groups. All root canals were instrumented using ProTaper Gold rotary files up to the F3 file at the working length. In one group, OrthoMTA was compacted using a stainless steel K-file, while in the other group, the Auger technique was employed for compaction into the root canals. Once the MTA had completely set, the filled root canals were subjected to scanning using a high-resolution micro-CT scanner. The porosity volume was determined as a percentage in relation to the overal volume of the canal, and the collected data were subjected to analysis using SPSS software, with the significance level set at P < 0.05. RESULTS: The two techniques had no significant difference in open, closed, and total mean porosity. In both groups, the mean of open porosity was significantly more than closed porosity. CONCLUSIONS: According to the results of the present study, neither of these two techniques is preferred to the other, and factors such as working time, etc., can be considered to choose the more appropriate clinical technique.
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Compostos de Alumínio , Compostos de Cálcio , Cavidade Pulpar , Combinação de Medicamentos , Óxidos , Materiais Restauradores do Canal Radicular , Obturação do Canal Radicular , Silicatos , Microtomografia por Raio-X , Microtomografia por Raio-X/métodos , Silicatos/uso terapêutico , Óxidos/uso terapêutico , Compostos de Cálcio/uso terapêutico , Compostos de Alumínio/uso terapêutico , Obturação do Canal Radicular/métodos , Humanos , Materiais Restauradores do Canal Radicular/uso terapêutico , Cavidade Pulpar/diagnóstico por imagem , Dente Molar/diagnóstico por imagem , Preparo de Canal Radicular/métodos , PorosidadeRESUMO
Decreasing perovskite nanocrystal size increases radiative recombination due to the quantum confinement effect, but also increases the Auger recombination rate which leads to carrier imbalance in the emitting layers of electroluminescent devices. Here, we overcome this trade-off by increasing the exciton effective mass without affecting the size, which is realized through the trace Cd2+ doping of formamidinium lead bromide perovskite nanocrystals. We observe an ~2.7â times increase in the exciton binding energy benefiting from a slight distortion of the [BX6]4- octahedra caused by doping in the case of that the Auger recombination rate is almost unchanged. As a result, bright color-saturated green emitting perovskite nanocrystals with a photoluminescence quantum yield of 96 % are obtained. Cd2+ doping also shifts up the energy levels of the nanocrystals, relative to the Fermi level so that heavily n-doped emitters convert into only slightly n-doped ones; this boosts the charge injection efficiency of the corresponding light-emitting diodes. The light-emitting devices based on those nanocrystals reached a high external quantum efficiency of 29.4 % corresponding to a current efficiency of 123â cd A-1, and showed dramatically improved device lifetime, with a narrow bandwidth of 22â nm and Commission Internationale de I'Eclairage coordinates of (0.20, 0.76) for color-saturated green emission for the electroluminescence peak centered at 534â nm, thus being fully compliant with the latest standard for wide color gamut displays.
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The innate inverse Auger effect within bulk silicon can result in multiple carrier generation. Observation of this effect is reliant upon low high-energy photon reflectance and high-quality surface passivation. In the photovoltaics industry, metal-assisted chemical etching (MACE) to afford black silicon (b-Si) can provide a low high-energy photon reflectance. However, an industrially feasible and cheaper technology to conformally passivate the outer-shell defects of these nanowires is currently lacking. Here, a technology is introduced to infiltrate black silicon nanopores with a simple and vacuum-free organic passivation layer that affords millisecond-level minority carrier lifetimes and matches perfectly with existing solution-based processing of the MACE black silicon. Advancements such as the demonstration of an excellent passivation effect whilst also being low reflectance provide a new technological route for inverse Auger multiple carrier generation and an industrially feasible technical scheme for the development of the MACE b-Si solar cells.
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Triple-negative breast cancer (TNBC) has a high risk for recurrence and metastasis. We studied the effectiveness of Auger electron (AE) radioimmunotherapy (RIT) with antiepidermal growth factor receptor (EGFR) panitumumab conjugated with DOTA complexed to 111In ([111In]In-DOTA-panitumumab) for preventing metastatic progression after local treatment of 231/LM2-4 Luc+ human TNBC tumors in the mammary fat pad of NRG mice. Prior to RIT, the primary tumor was resected, and tumor margins were treated with X-irradiation (XRT; 5 days × 6 Gy/d). RIT was administered 1 day post-XRT by intravenous injection of 26 MBq (15 µg) or 2 × 10 MBq (15 µg each) separated by 7 d. These treatments were compared to tumor resection with or without XRT combined with DOTA-panitumumab (15 µg) or irrelevant [111In]In-DOTA-IgG2 (24 MBq; 15 µg), and efficacy was evaluated by Kaplan-Meier survival curves. The effect of [111In]In-DOTA-panitumumab (23 MBq; 15 µg) after tumor resection without local XRT was also studied. Tumor resection followed by XRT and RIT with 26 MBq [111In]In-DOTA-panitumumab significantly increased the median survival to 35 d compared to tumor resection with or without XRT (23-24 d; P < 0.0001). Local treatment with tumor resection and XRT followed by 2 × 10 MBq of [111In]In-DOTA-panitumumab, DOTA-panitumumab, or [111In]In-DOTA-IgG2 did not significantly improve median survival (26 days for all treatments). RIT alone with [111In]In-DOTA-panitumumab postresection of the tumor without XRT increased median survival to 29 days, though this was not significant. Despite significantly improved survival in mice treated with tumor resection, XRT, and RIT with [111In]In-DOTA-panitumumab, all mice eventually succumbed to advanced metastatic disease by 45 d post-tumor resection. SPECT/CT with [111In]In-DOTA-panitumumab, PET/MRI with [64Cu]Cu-DOTA-panitumumab F(ab')2, and PET/CT with [18F]FDG were used to detect recurrent and metastatic disease. Uptake of [111In]In-DOTA-panitumumab at 4 d p.i. in the MFP tumor was 26.8 ± 9.7% ID/g and in metastatic lymph nodes (LN), lungs, and liver was 34.2 ± 26.9% ID/g, 17.5 ± 6.0% ID/g, and 9.4 ± 2.4%ID/g, respectively, while uptake in the lungs (6.0 ± 0.9% ID/g) and liver (5.2 ± 2.9% ID/g) of non-tumor-bearing NRG was significantly lower (P < 0.05). Radiation-absorbed doses in metastatic LN, lungs, and liver were 9.7 ± 6.1, 6.4 ± 2.1, and 10.9 ± 2.7 Gy, respectively. In conclusion, we demonstrated that RIT with [111In]In-DOTA-panitumumab combined with tumor resection and XRT significantly improved the survival of mice with recurrent TNBC. However, the aggressive nature of 231/LM2-4 Luc+ tumors in NRG mice may have contributed to the tumor recurrence and progression observed.
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Neoplasias de Mama Triplo Negativas , Humanos , Animais , Camundongos , Panitumumabe , Neoplasias de Mama Triplo Negativas/tratamento farmacológico , Neoplasias de Mama Triplo Negativas/radioterapia , Radioimunoterapia , Receptores ErbB/metabolismo , Tomografia por Emissão de Pósitrons combinada à Tomografia Computadorizada , Elétrons , Imunoglobulina GRESUMO
Current therapeutic approaches to cancer are not fully effective, and so development of more effective treatment is needed. Auger-electron therapy and photodynamic therapy have attracted marked attentions as a promising strategy in cancer treatment. In this study, we synthesized [125I]BH-2/BH-2, which comprised Hoechst and 2,6-diiodo-substituted BODIPY, and evaluated its usefulness as a bi-modal agent for Auger-electron/photodynamic therapy by comparison with the previously reported compound [125I]BH/BH. [125I]BH-2 was obtained at a 13% radiochemical yield. [125I]BH-2 showed similar uptake into the nucleus to [125I]BH, suggesting that Hoechst can function as a nuclear localization tag. HeLa cell viabilities were reduced in both cells exposed to [125I]BH-2 and [125I]BH. γ-H2AX foci in HeLa cells exposed to [125I]BH-2 or [125I]BH were increased in a dose-dependent manner, indicating that DNA double-strand breaks may have occurred. No significant difference was observed between [125I]BH-2 and [125I]BH at these investigations. For PDT application, BH-2 showed a higher singlet oxygen quantum yield (ΦΔ) and caused superior photo-induced cytotoxicity in HeLa cells compared with BH. These results suggest that bi-modal [125I]BH-2/BH-2 can cause anti-tumor effects with Auger-electron and photodynamic therapy.
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Neoplasias , Fotoquimioterapia , Humanos , Células HeLa , Elétrons , Radioisótopos do Iodo , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/químicaRESUMO
Nucleophilic copper-mediated radioiodination (CMRI) of organoboronic precursors with radioiodides is a promising method of radioiodination. The previously reported CMRI has demonstrated its great potential and scope of labeling for the radiosynthesis of radioiodine-labeled compounds. However, the reported protocols (using a small amount/volume of radioactivity) are practically not reproducible in large-scale CMRI, in which the radioactivity was usually provided in a bulk alkaline solution. A large amount of water and a strong base are incompatible with CMRI. To overcome these issues in large-scale CMRI, we have developed a simple protocol for large-scale CMRI. The bulk water was removed under a flow of inert gas at 110°C, and the strong base (i.e., NaOH) was neutralized with an acid, pyridinium p-toluenesulfonate or p-toluenesulfonic acid. In the model reactions of [123 I]KX-1, a PARP-1 radioligand for Auger radiotherapy, radiochemical conversions were significantly improved after neutralization of the base, and the addition of additional acids was tolerated and favorable for the reactions. Using this protocol, [123 I]KX-1 was radiosynthesized from 20 mCi (0.74 GBq) of [123 I]iodide in high radiochemical yields, high radiochemical purity, and high molar activity. This protocol should be applicable to the radiosynthesis of other compounds with radioiodine via CMRI.
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Cobre , Radioisótopos do Iodo , Compostos Radiofarmacêuticos , ÁguaRESUMO
The continuous and concerted development of colloidal quantum dot light-emitting diodes over the past two decades has established them as a bedrock technology for the next generation of displays. However, a fundamental issue that limits the performance of these devices is the quenching of photoluminescence due to excess charges from conductive charge transport layers. Although device designs have leveraged various workarounds, doing so often comes at the cost of limiting efficient charge injection. Here we demonstrate that high-field terahertz (THz) pulses can dramatically brighten quenched QDs on metallic surfaces, an effect that persists for minutes after THz irradiation. This phenomenon is attributed to the ability of the THz field to remove excess charges, thereby reducing trion and nonradiative Auger recombination. Our findings show that THz technologies can be used to suppress and control such undesired nonradiative decay, potentially in a variety of luminescent materials for future device applications.
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Colloidal semiconductor nanocrystals offer bandgap tunability, high photoluminescence quantum yield, and colloidal processing of benefit to optoelectronics, however rapid nonradiative Auger recombination (AR) deleteriously affects device efficiencies at elevated excitation intensities. AR is understood to transition from temperature-dependent behavior in bulk semiconductors to temperature-independent behavior in zero-dimensional quantum dots (QDs) as a result of discretized band structure that facilitates satisfaction of linear momentum conservation. For nanoplatelets (NPLs), two-dimensional morphology renders prediction of photophysical behaviors challenging. Here, we investigate and compare the temperature dependence of excited-stated lifetime and fluence-dependent emission of CdSe NPLs and QDs. For NPLs, upon temperature reduction, biexciton lifetime surprisingly decreases (even becoming shorter lived than trion emission) and emission intensity increases nearly linearly with fluence rather than saturating, consistent with dominance of radiative recombination rather than AR. CdSe NPLs thus differ fundamentally from core-only QDs and foster increased utility of photogenerated excitons and multiexcitons at low temperatures.
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Compostos de Cádmio , Compostos de Selênio , Aceleração , Compostos de Cádmio/química , Recombinação Genética , Compostos de Selênio/química , TemperaturaRESUMO
Auger recombination and thermalization time are detrimental in reducing the gain threshold of optically pumped semiconductor nanocrystal (NC) lasers for future on-chip nanophotonic devices. Here, we report the design strategy of facet engineering to reduce the gain threshold of amplified spontaneous emission by manyfold in NCs of the same concentration and edge length. We achieved this hallmark result by controlling the Auger recombination rates dominated by processes involving NC volume and thermalization time to the emitting states by optimizing the number of facets from 6 (cube) to 12 (rhombic dodecahedron) and 26 (rhombicuboctahedrons) in CsPbBr3 NCs. For instance, we demonstrate a 2-fold reduction in Auger recombination rates and thermalization time with increased number of facets. The gain threshold can be further reduced â¼50% by decreasing the sample temperature to 4 K. Our systematic studies offer a new method to reduce the gain threshold that ultimately forms the basis of nanolasers.