Lateral Size-Dependent Spontaneous and Stimulated Emission Properties in Colloidal CdSe Nanoplatelets

Cataloged from PDF version of article.Here, we systematically investigated the spontaneous and stimulated emission performances of solution-processed atomically flat quasi-2D nanoplatelets (NPLs) as a function of their lateral size using colloidal CdSe core NPLs. We found that the photoluminescence quantum efficiency of these NPLs decreases with increasing lateral size while their photoluminescence decay rate accelerates. This strongly suggests that nonradiative channels prevail in the NPL ensembles having extended lateral size, which is well-explained by the increasing number of the defected NPL subpopulation. In the case of stimulated emission the role of lateral size in NPLs influentially emerges both in the single- and two-photon absorption (1PA and 2PA) pumping. In the amplified spontaneous emission measurements, we uncovered that the stimulated emission thresholds of 1PA and 2PA exhibit completely opposite behavior with increasing lateral size. The NPLs with larger lateral sizes exhibited higher stimulated emission thresholds under 1PA pumping due to the dominating defected subpopulation in larger NPLs. On the other hand, surprisingly, larger NPLs remarkably revealed lower 2PA-pumped amplified spontaneous emission thresholds. This is attributed to the observation of a "giant" 2PA cross-section overwhelmingly growing with increasing lateral size and reaching record levels higher than 10(6) GM, at least an order of magnitude stronger than colloidal quantum dots and rods. These findings suggest that the lateral size control in the NPLs, which is commonly neglected, is essential to high-performance colloidal NPL optoelectronic devices in addition to the vertical monolayer control

Inverted type-I CdS/CdSe core/crown colloidal quantum ring

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Low-threshold optical gain and lasing of colloidal nanoplatelets

Semiconductor nanocrystals, which are also known as colloidal quantum dots (CQDs), are highly attractive materials for high performance optoelectronic device applications such as lasers. With their size, shape and composition tunable electronic structure and optical properties, CQDs are highly desired for achieving full-color, temperature-insensitive, low-threshold and solution-processed lasers [1, 2]. However, due to their small size, they suffer from the nonradiative multiexciton Auger Recombination (AR), where energy of a bound electron-hole pair is transferred to a third particle of either an electron or a hole instead of radiative recombination. Therefore, CQDs having suppressed AR are strongly required for achieving high quality CQD-based lasers. To address this issue, CQDs having different size, shape and electronic structure have been synthesized and studied extensively [3-5]. Generally, suppression of AR and lower optical gain thresholds are achieved via reducing the wavefunction overlap of the electron and hole in a CQD. However, the separation of the electron and hole wavefunctions will dramatically decrease the oscillator strength and optical gain coefficient, which is highly critical for achieving high performance lasers. Therefore, colloidal materials with suppressed AR and high gain coefficients are highly welcomed. Here, we study optical gain performance of colloidal quantum wells [6] of CdSe-core and CdSe/CdS core/crown nanoplatelets (NPLs) that demonstrate remarkable optical properties with ultra-low threshold one- and two-photon optical pumping. As a result of their giant oscillator strength, superior optical gain and lasing performance are achieved from these colloidal NPLs with greatly enhanced gain coefficient [7]. © 2014 IEEE

Experimental Determination of the Absorption Cross-Section and Molar Extinction Coefficient of Colloidal CdSe Nanoplatelets

There has been a strong interest in solution-processed two-dimensional nanomaterials because of their great potential in optoelectronics. Here, the absorption cross-section and molar extinction coefficient of four and five monolayer thick colloidal CdSe nanoplatelets (NPLs) having various lateral sizes are reported. The absorption cross-section of these NPLs and their corresponding molar extinction coefficients are found to strongly depend on the lateral area. An excellent agreement is observed between the experimental results and the calculated values based on the small-particle light absorption model. With these optical properties, NPLs hold great promise for optoelectronic applications. © 2015 American Chemical Society

Anomalous spectral characteristics of ultrathin sub-nm colloidal CdSe nanoplatelets

We demonstrate high quantum yield broad photoluminescence emission of ultrathin sub-nanometer CdSe nanoplatelets (two-monolayer). They also exhibit polarization-characterized lateral size dependent anomalous heavy hole and light/split-off hole absorption intensities. © 2017 IEEE

Time-resolved photoluminescence study of CdSe/CdMnS/CdS core/multi-shell nanoplatelets

We used photoluminescence spectroscopy to resolve two emission features in CdSe/CdMnS/CdS and CdSe/CdS core/multi-shell nanoplatelet heterostructures. The photoluminescence from the magnetic sample has a positive circular polarization with a maximum centered at the position of the lower energy feature. The higher energy feature has a corresponding signature in the absorption spectrum; this is not the case for the low-energy feature. We have also studied the temporal evolution of these features using a pulsed-excitation/time-resolved photoluminescence technique to investigate their corresponding recombination channels. A model was used to analyze the temporal dynamics of the photoluminescence which yielded two distinct timescales associated with these recombination channels. The above results indicate that the low-energy feature is associated with recombination of electrons with holes localized at the core/shell interfaces; the high-energy feature, on the other hand, is excitonic in nature with the holes confined within the CdSe cores. © 2016 Author(s)

Near-Unity Emitting Copper-Doped Colloidal Semiconductor Quantum Wells for Luminescent Solar Concentrators

Doping of bulk semiconductors has revealed widespread success in optoelectronic applications. In the past few decades, substantial effort has been engaged for doping at the nanoscale. Recently, doped colloidal quantum dots (CQDs) have been demonstrated to be promising materials for luminescent solar concentrators (LSCs) as they can be engineered for providing highly tunable and Stokes-shifted emission in the solar spectrum. However, existing doped CQDs that are aimed for full solar spectrum LSCs suffer from moderately low quantum efficiency, intrinsically small absorption cross-section, and gradually increasing absorption profiles coinciding with the emission spectrum, which together fundamentally limit their effective usage. Here, the authors show the first account of copper doping into atomically flat colloidal quantum wells (CQWs). In addition to Stokes-shifted and tunable dopant-induced photoluminescence emission, the copper doping into CQWs enables near-unity quantum efficiencies (up to ≈97%), accompanied by substantially high absorption cross-section and inherently step-like absorption profile, compared to those of the doped CQDs. Based on these exceptional properties, the authors have demonstrated by both experimental analysis and numerical modeling that these newly synthesized doped CQWs are excellent candidates for LSCs. These findings may open new directions for deployment of doped CQWs in LSCs for advanced solar light harvesting technologies. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinhei

Time resolved photoluminescence study of magnetic CdSe/CdMnS/CdS core/multi-shell nanoplatelets

Colloidal semiconductor nanoplatelets (NPLs) are quasi 2D-nanostructures that are grown and processed inexpensively using a solution based method and thus have recently attracted considerable attention. We observe two features in the photoluminescence spectrum, suggesting two possible recombination channels. Their intensity ratio varies with temperature and two distinct temperature regions are identified; a low temperature region (10K < T < 90K) and a high temperature region (90K < T < 200K). This ratio increases with increasing temperature, suggesting that one recombination channel involves holes that are weakly localized with a localization energy of 0.043meV. A possible origin of these localized states are energy-variations in the xy-plane of the nanoplatelet. The presence of positive photoluminescence circular polarization in the magnetically-doped core/multi-shell NPLs indicates a hole-dopant exchange interaction and therefore the incorporated magnetic Manganese ions act as a marker that determines the location of the localized hole states.1 Time-resolved measurements show two distinct timescales (τfast and τslow) that can be modeled using a rate equation model. We identify these timescales as closely related to the corresponding recombination times for the channels. The stronger hole localization of one of these channels leads to a decreased electron-hole wave function overlap and thus a decreased oscillator strength and an increased lifetime. We show that we can model and understand the magnetic interaction of doped 2D-colloidal nanoplatelets which opens a pathway to solution processable spin controllable light sources. Copyright © 2017 SPIE

Magneto-optical studies of CdSe/CdMnS/CdS core/multi-shell colloidal nanoplatelets

We studied the photoluminescence (PL)) from CdSe/CdMnS/CdS core/multi-shell colloidal nanoplatelets, a versatile platform to study the interplay of optical properties and nanomagnetism. The photoluminescence (PL) exhibits σ+ polarization in the applied magnetic field. Our measurement detects the presence of even a single magnetic monolayer shell. The PLL consists of a higher and a lower energy component; the latter exhibits a circular polarization peak. The time-resolved PL (trPL) shows a red shift as function of time delay. At early (later) times the trPL spectra coincide with the high (low) energy PL component. A model is proposed to interpret these results. © 2016 SPIE

Type-II Colloidal Quantum Wells: CdSe/CdTe Core/Crown Heteronanoplatelets

Solution-processed quantum wells, also known as colloidal nanoplatelets (NPLs), are emerging as promising materials for colloidal optoelectronics. In this work, we report the synthesis and characterization of CdSe/CdTe core/crown NPLs exhibiting a Type-II electronic structure and Type-II specific optical properties. Here, based on a core-seeded approach, the CdSe/CdTe core/crown NPLs were synthesized with well-controlled CdTe crown coatings. Uniform and epitaxial growth of CdTe crown region was verified by using structural characterization techniques including transmission electron microscopy (TEM) with quantitative EDX analysis and X-ray diffraction (XRD). Also the optical properties were systematically studied in these Type-II NPLs that reveal strongly red-shifted photoluminescence (up to similar to 150 nm) along with 2 orders of magnitude longer fluorescence lifetimes (up to 190 ns) compared to the Type-I NPLs owing to spatially indirect excitons at the Type-II interface between the CdSe core and the CdTe crown regions. Photoluminescence excitation spectroscopy confirms that this strongly red-shifted emission actually arises from the CdSe/CdTe NPLs. In addition, temperature-dependent time-resolved fluorescence spectroscopy was performed to reveal the temperature-dependent fluorescence decay kinetics of the Type-II NPLs exhibiting interesting behavior. Also, water-soluble Type-II NPLs were achieved via ligand exchange of the CdSe/CdTe core/crown NPLs by using 3-mercaptopropionic acid (MPA), which allows for enhanced charge extraction efficiency owing to their shorter chain length and enables high quality film formation by layer-by-layer (LBL) assembly. With all of these appealing properties, the CdSe/CdTe core/crown heterostructures having Type-II electronic structure presented here are highly promising for light-harvesting applications