InGaAs量子点的自发发射及光增益

研究了InGaAs量子点材料自发发射、放大自发发射及光增益特性.实验发现InGaAs量子点材料随着注入电流密度的增加,其自发发射及放大自发发射光谱峰蓝移,表现出明显的能带填充现象.由于量子点材料尺寸及形状等存在一定的分布,在光谱中没有明显的对应量子点激发态的谱峰.由单程增益放大自发发射得到了量子点材料在不同注入电流密度下的光增益谱.结果表明存在由于量子点大小分布造成的量子点态非均匀展宽引起的增益峰蓝移和增益谱展宽现象.     

Magnetic/Fluorescent Barcodes Based on Cadmium‐Free Near‐Infrared‐Emitting Quantum Dots for Multiplexed Detection

Magnetic/fluorescent barcodes, which combine quantum dots (QDs) and superparamagnetic nanoparticles in micrometer‐sized host microspheres, are promising for automatic high‐throughput multiplexed biodetection applications and “point of care” biodetection. However, the fluorescence intensity of QDs sharply decreases after addition of magnetic nanoparticles (MNPs) due to absorption by MNPs, and thus, the encoding capacity of QDs becomes more limited. Furthermore, the intrinsic toxicity of cadmium‐based QDs, the most commonly used QD in barcodes, has significant risks to human health and the environment. In this work, to alleviate fluorescence quenching and intrinsic toxicity, cadmium‐free NIR‐emitting CuInS₂/ZnS QDs and Fe₃O₄ MNPs are successfully incorporated into poly(styrene‐co‐maleic anhydride) microspheres by using the Shirasu porous glass membrane emulsification technique. A “single‐wavelength” encoding model is successfully constructed to guide the encoding of NIR QDs with wide emission spectra. Then, a “single‐wavelength” encoding combined with size encoding is used to produce different optical codes by simply changing the wavelength and the intensity of the QDs as well as the size of the barcode microspheres. 48 barcodes are easily created due to the greatly reduced energy transfer between the NIR‐emitting QDs and MNPs. The resulting bifunctional barcodes are also combined with a flow cytometer using one laser for multiplexed detection of five tumor markers in one test. Assays based on these barcodes are significantly more sensitive than non‐magnetic and traditional ELISA assays. Moreover, validating experiments also show good performance of the bifunctional barcodes‐based suspension array when dealing with patient serum samples. Thus, magnetic/fluorescent barcodes based on NIR‐emitting CuInS₂/ZnS QDs are promising for multiplexed bioassay applications.     

Surface Chemistry Routes to Modulate the Photoluminescence of Graphene Quantum Dots: From Fluorescence Mechanism to Up‐Conversion Bioimaging Applications

The bandgap in graphene‐based materials can be tuned from 0 eV to that of benzene by changing size and/or surface chemistry, making it a rising carbon‐based fluorescent material. Here, the surface chemistry of small size graphene (graphene quantum dots, GQDs) is tuned programmably through modification or reduction and green luminescent GQDs are changed to blue luminescent GQDs. Several tools are employed to characterize the composition and morphology of resultants. More importantly, using this system, the luminescence mechanism (the competition between both the defect state emission and intrinsic state emission) is explored in detail. Experiments demonstrate that the chemical structure changes during modification or reduction suppresses non‐radiative recombination of localized electron‐hole pairs and/or enhances the integrity of surface π electron network. Therefore the intrinsic state emission plays a leading role, as opposed to defect state emission in GQDs. The results of time‐resolved measurements are consistent with the suggested PL mechanism. Up‐conversion PL of GQDs is successfully applied in near‐IR excitation for bioimaging.     

Efficient Near‐Infrared Light‐Emitting Diodes based on In(Zn)As–In(Zn)P–GaP–ZnS Quantum Dots

Near‐infrared (NIR) lighting plays an increasingly important role in new facial recognition technologies and eye‐tracking devices, where covert and nonvisible illumination is needed. In particular, mobile or wearable gadgets that employ these technologies require electronic lighting components with ultrathin and flexible form factors that are currently unfulfilled by conventional GaAs‐based diodes. Colloidal quantum dots (QDs) and emerging perovskite light‐emitting diodes (LEDs) may fill this gap, but generally employ restricted heavy metals such as cadmium or lead. Here, a new NIR‐emitting diode based on heavy‐metal‐free In(Zn)As–In(Zn)P–GaP–ZnS quantum dots is reported. The quantum dots are prepared with a giant shell structure, enabled by a continuous injection synthesis approach, and display intense photoluminescence at 850 nm with a high quantum efficiency of 75%. A postsynthetic ligand exchange to a shorter‐chain 1‐mercapto‐6‐hexanol (MCH) affords the QDs with processability in polar solvents as well as an enhanced charge‐transport performance in electronic devices. Using solution‐processing methods, an ITO/ZnO/PEIE/QD/Poly‐TPD/MoO₃/Al electroluminescent device is fabricated and a high external quantum efficiency of 4.6% and a maximum radiance of 8.2 W sr^?1 m^?2 are achieved. This represents a significant leap in performance for NIR devices employing a colloidal III–V semiconductor QD system, and may find significant applications in emerging consumer electronic products.     

Saturated and Multi‐Colored Electroluminescence from Quantum Dots Based Light Emitting Electrochemical Cells

Novel light emitting electrochemical cells (LECs) are fabricated using CdSe‐CdS (core‐shell) quantum dots (QDs) of tuned size and emission blended with polyvinylcarbazole (PVK) and the ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIM‐PF₆). The performances of cells constructed using sequential device layers of indium tin oxide (ITO), poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS), the QD/PVK/IL active layer, and Al are evaluated. Only color saturated electroluminescence from the QDs is observed, without any other emissions from the polymer host or the electrolyte. Blue, green, and red QD‐LECs are prepared. The maximum brightness (≈1000 cd m^‐2) and current efficiency (1.9 cd A^‐1) are comparable to polymer LECs and multilayer QD‐LEDs. White‐light QD‐LECs with Commission Internationale d'Eclairage (CIE) coordinates (0.33, 0.33) are prepared by tuning the mass ratio of R:G:B QDs in the active layer and voltage applied. Transparent QD‐LECs fabricated using transparent silver nanowire (AgNW) composites as the cathode yield an average transmittance greater than 88% over the visible range. Flexible devices are demonstrated by replacing the glass substrates with polyethylene terephthalate (PET).     

Superior Micro‐Supercapacitors Based on Graphene Quantum Dots

Graphene quantum dots (GQDs) have attracted tremendous research interest due to the unique properties associated with both graphene and quantum dots. Here, a new application of GQDs as ideal electrode materials for supercapacitors is reported. To this end, a GQDs//GQDs symmetric micro‐supercapacitor is prepared using a simple electro‐deposition approach, and its electrochemical properties in aqueous electrolyte and ionic liquid electrolyte are systematically investigated. The results show that the as‐made GQDs micro‐supercapacitor has superior rate capability up to 1000 V s^?1, excellent power response with very short relaxation time constant (τ₀ = 103.6 μs in aqueous electrolyte and τ₀ = 53.8 μs in ionic liquid electrolyte), and excellent cycle stability. Additionally, another GQDs//MnO₂ asymmetric supercapacitor is also built using MnO₂ nanoneedles as the positive electrode and GQDs as the negative electrode in aqueous electrolyte. Its specific capacitance and energy density are both two times higher than those of GQDs//GQDs symmetric micro‐supercapacitor in the same electrolyte. The results presented here may pave the way for a new promising application of GQDs in micropower suppliers and microenergy storage devices.     

Distributed Feedback Lasers Based on Thiophene/Phenylene Co‐Oligomer Single Crystals

Organic crystals have great potential for the applications in laser devices. This article presents an effective approach for fabrication of distributed feedback single crystal lasers. With the laser interference ablation method, high quality grating structures have been fabricated on the organic single‐crystalline thin film materials. The relationship between the depth, periodicity, and laser fluence is discussed. The optical properties, such as photoluminescence, and diffractive properties are studied in detail. With the appropriate period, strong laser emission has been observed from these devices. Distributed feedback lasing is demonstrated from the laser interference ablated organic single crystals for the first time.     

Light‐Emitting Electrochemical Cells Based on Color‐Tunable Inorganic Colloidal Quantum Dots

Large‐area, ultrathin light‐emitting devices currently inspire architects and interior and automotive designers all over the world. Light‐emitting electrochemical cells (LECs) and quantum dot light‐emitting diodes (QD‐LEDs) belong to the most promising next‐generation device concepts for future flexible and large‐area lighting technologies. Both concepts incorporate solution‐based fabrication techniques, which makes them attractive for low cost applications based on, for example, roll‐to‐roll fabrication or inkjet printing. However, both concepts have unique benefits that justify their appeal. LECs comprise ionic species in the active layer, which leads to the omission of additional organic charge injection and transport layers and reactive cathode materials, thus LECs impress with their simple device architecture. QD‐LEDs impress with purity and opulence of available colors: colloidal quantum dots (QDs) are semiconducting nanocrystals that show high yield light emission, which can be easily tuned over the whole visible spectrum by material composition and size. Emerging technologies that unite the potential of both concepts (LEC and QD‐LED) are covered, either by extending a typical LEC architecture with additional QDs, or by replacing the entire organic LEC emitter with QDs or perovskite nanocrystals, still keeping the easy LEC setup featured by the incorporation of mobile ions.     

Evidence for Edge‐State Photoluminescence in Graphene Quantum Dots

For a practical realization of graphene‐based logic devices, the opening of a band gap in graphene is crucial and has proven challenging. To this end, several synthesis techniques, including unzipping of carbon nanotubes, chemical vapor deposition, and other bottom‐up fabrication techniques have been pursued for the bulk production of graphene nanoribbons (GNRs) and graphene quantum dots (GQDs). However, only limited progress has been made towards a fundamental understanding of the origin of strong photoluminescence (PL) in GQDs. Here, it is experimentally shown that the PL is independent of the functionalization scheme of the GQDs. Following a series of annealing experiments designed to passivate the free edges, the PL in GQDs originates from edge‐states, and an edge‐passivation subsequent to synthesis quenches the PL. The results of PL studies of GNRs and carbon nano‐onions are shown to be consistent with PL being generated at the edge sites of GQDs.     

Electrical‐Polarization‐Induced Ultrahigh Responsivity Photodetectors Based on Graphene and Graphene Quantum Dots

Hybrid quantum dot–graphene photodetectors have recently attracted substantial interest because of their remarkable performance and low power consumption. However, the performance of the device greatly depends on the interfacial states and photogenerated screening field. As a consequence, the sensitivity is limited and the response time is relatively slow. In order to circumvent these challenges, herein, a composite graphene and graphene quantum dot (GQD) photodetector on lead zirconate titanate (Pb(Zr_0.2Ti_0.8)O₃) (PZT) substrates has been designed to form an ultrasensitive photodetector over a wide range of illumination power. Under 325 nm UV light illumination, the device shows sensitivity as high as 4.06 × 10⁹ A W^?1, which is 120 times higher than reported sensitivity of the same class of devices. Plant derived GQD has a broad range of absorptivity and is an excellent candidate for harvesting photons generating electron–hole pairs. Intrinsic electric field from PZT substrate separates photogenerated electron–hole pairs as well as provides the built‐in electric field that causes the holes to transfer to the underlying graphene channel. The composite structure of graphene and GQD on PZT substrate therefore produces a simple, stable, and highly sensitive photodetector over a wide range of power with short response time, which shows a way to obtain high‐performance optoelectronic devices.     

Robust and Stable Ratiometric Temperature Sensor Based on Zn–In–S Quantum Dots with Intrinsic Dual‐Dopant Ion Emissions

Dual emission quantum dots (QDs) have attracted considerable interest as a novel phosphor for constructing ratiometric optical thermometry because of its self‐referencing capability. In this work, the exploration of codoped Zn–In–S QDs with dual emissions at ≈512 and ≈612 nm from intrinsic Cu and Mn dopants for ratiometric temperature sensing is reported. It is found that the dopant emissions can be tailored by adjusting the Mn‐to‐Cu concentration ratios, enabling the dual emissions in a tunable manner. The energy difference between the conduction band of the host and Cu dopant states is considered as the key for the occurrence of Mn ion emission. The as‐constructed QD ratiometric temperature sensor exhibits a totally robust stability with a fluctuation of ≈I_Cu/I_tot versus times lower than 1% and almost no hysteresis in cycles over a broad window of 100–320 K. This discovery represents that the present cadmium‐free, intrinsic dual‐emitting codoped QDs can open a new door for the synthesis of novel QDs with stable dual emissions, which poise them well for challenging applications in optical nanothermometry.     

Single‐Electron Tunneling through Molecular Quantum Dots in a Metal‐Insulator‐Semiconductor Structure

A sigle‐electron tunneling (SET) in a metal‐insulator‐semiconductor (MIS) structure is demonstrated, in which C₆₀ and copper phthalocyanine (CuPc) molecules are embedded as quantum dots in the insulator layer. The SET is found to originate from resonant tunneling via the energy levels of the embedded molecules, (e.g., the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO)). These findings show that the threshold voltages for SET are tunable according to the energy levels of the molecules. Furthermore, SET is observable even near room temperature. The results suggest, together with the fact that these properties are demonstrated in a practical device configuration, that the integration of molecular dots into the Si‐MIS structure has considerable potential for achieving novel SET devices. Moreover, the attempt allows large‐scale integration of individual molecular functionalities.     

All‐Inorganic Bismuth‐Based Perovskite Quantum Dots with Bright Blue Photoluminescence and Excellent Stability

Lead halide perovskite quantum dots (QDs) possess color‐tunable and narrow‐band emissions and are very promising for lighting and display applications, but they suffer from lead toxicity and instability. Although lead‐free Bi‐based and Sn‐based perovskite QDs (CsSnX₃, Cs₂SnX₆, and (CH₃NH₃)₃Bi₂X₉) are reported, they all show low photoluminescence quantum yield (PLQY) and poor stability. Here, the synthesis of Cs₃Bi₂Br₉ perovskite QDs with high PLQY and excellent stability is reported. Via a green and facile process using ethanol as the antisolvent, as‐synthesized Cs₃Bi₂Br₉ QDs show a blue emission at 410 nm with a PLQY up to 19.4%. The whole series of Cs₃Bi₂X₉ (X = Cl, Br, and I) QDs by mixing precursors can cover the photoluminescence emission range from 393 to 545 nm. Furthermore, Cs₃Bi₂Br₉ QDs show excellent photostability and moisture stability due to the all‐inorganic nature and the surface passivation by BiOBr, which enables the one‐pot synthesis of Cs₃Bi₂Br₉ QD/silica composite. A lead‐free perovskite white light‐emitting diode is fabricated by simply combining the composite of Cs₃Bi₂Br₉ QD/silica with Y₃Al₅O₁₂ phosphor. As a new member of lead‐free perovskite QDs, Cs₃Bi₂Br₉ QDs open up a new route for the fabrication of optoelectronic devices due to their excellent stability and photophysical characteristics.     

Tumor‐Targeted Multimodal Optical Imaging with Versatile Cadmium‐Free Quantum Dots

The rapid development of fluorescence imaging technologies requires concurrent improvements in the performance of fluorescent probes. Quantum dots have been extensively used as an imaging probe in various research areas because of their inherent advantages based on unique optical and electronic properties. However, their clinical translation has been limited by the potential toxicity especially from cadmium. Here, a versatile bioimaging probe is developed by using highly luminescent cadmium‐free CuInSe₂/ZnS core/shell quantum dots conjugated with CGKRK (Cys–Gly–Lys–Arg–Lys) tumor‐targeting peptides. This probe exhibits excellent photostability, reasonably long circulation time, minimal toxicity, and strong tumor‐specific homing property. The most important feature of this probe is that it shows distinctive versatility in tumor‐targeted multimodal imaging including near‐infrared, time‐gated, and two‐photon imaging in different tumor models. In a glioblastoma mouse model, the targeted probe clearly denotes tumor boundaries and positively labels a population of diffusely infiltrating tumor cells, suggesting its utility in precise tumor detection during surgery. This work lays a foundation for potential clinical translation of the probe.     

PbS/CdS/ZnS Quantum Dots: A Multifunctional Platform for In Vivo Near‐Infrared Low‐Dose Fluorescence Imaging

Over the past decade, near‐infrared (NIR)‐emitting nanoparticles have increasingly been investigated in biomedical research for use as fluorescent imaging probes. Here, high‐quality water‐dispersible core/shell/shell PbS/CdS/ZnS quantum dots (hereafter QDs) as NIR imaging probes fabricated through a rapid, cost‐effective microwave‐assisted cation exchange procedure are reported. These QDs have proven to be water dispersible, stable, and are expected to be nontoxic, resulting from the growth of an outer ZnS shell and the simultaneous surface functionalization with mercaptopropionic acid ligands. Care is taken to design the emission wavelength of the QDs probe lying within the second biological window (1000–1350 nm), which leads to higher penetration depths because of the low extinction coefficient of biological tissues in this spectral range. Furthermore, their intense fluorescence emission enables to follow the real‐time evolution of QD biodistribution among different organs of living mice, after low‐dose intravenous administration. In this paper, QD platform has proven to be capable (ex vivo and in vitro) of high‐resolution thermal sensing in the physiological temperature range. The investigation, together with the lack of noticeable toxicity from these PbS/CdS/ZnS QDs after preliminary studies, paves the way for their use as outstanding multifunctional probes both for in vitro and in vivo applications in biomedicine.