Colloidal semiconductor nanocrystals are promising materials for classical and quantum light sources due to their versatile chemistry and efficient photoluminescence (PL) properties. While visible emitters are well-established, the pursuit of excellent (near-)infrared sources continues. One notable candidate in this regard are photoluminescent two-dimensional (2D) PbS nanoplatelets (NPLs) exhibiting excitonic emission at 720 nm (1.7 eV) directly tying to the typical emission range limit of CdSe NPLs. Here, we present the first comprehensive analysis of low-temperature PL from this material class. Ultrathin 2D PbS NPLs exhibit high crystallinity confirmed by scanning transmission electron microscopy, and revealing Moire patterns in overlapping structures. At 4K, we observe unique PL features in single PbS NPLs, including narrow zero-phonon lines with line widths down to 0.6 meV and a linear degree of polarization up to 90 dominant emission source with a 2.3 ns decay time. Sub-meV spectral diffusion and no immanent blinking over minutes is observed, as well as discrete spectral jumps without memory effects. These findings advance the understanding and underpin the potential of colloidal PbS NPLs for optical and quantum technologies.
Colloidal semiconductor nanocrystals are promising materials for classical and quantum light sources due to their efficient photoluminescence (PL) and versatile chemistry. While visible emitters are well-established, excellent (near-infrared) sources are still being pursued. We present the first comprehensive analysis of low-temperature PL from two-dimensional (2D) PbS nanoplatelets (NPLs). Ultrathin 2D PbS NPLs exhibit high crystallinity confirmed by scanning transmission electron microscopy, revealing Moire patterns in overlapping NPLs. At 4 K, unique PL features are observed in single PbS NPLs, including narrow zero-phonon lines with line widths down to 0.6 meV and a linear degree of polarization up to 90%. Time-resolved measurements identify trions as the dominant emission source with a 2.3 ns decay time. Sub-meV spectral diffusion and no inherent blinking over minutes are observed, as well as discrete spectral jumps without memory effects. These findings advance the understanding and underscore the potential of colloidal PbS NPLs for optical and quantum technologies.
Near-infrared emitting colloidal two-dimensional (2D) PbX (X = S, Se) nanoplatelets (NPLs) have emerged as interesting materials with strong size quantization in the thickness dimension. They act as model systems for efficient charge carrier multiplication and hold potential as intriguing candidates for fiber-based photonic quantum applications. However, synthetic access to the third family member, 2D PbTe, remains elusive due to challenging precursor chemistry. Here, we report a direct synthesis for 2D PbTe NPLs with tunable photoluminescence [PL, 910-1460 nm (1.36-0.85 eV), PL quantum yields 1-15%], based on aminophosphine precursor chemistry. Ex situ transamination of tris(dimethylamino)phosphine telluride with octylamine is confirmed by P-31 nuclear magnetic resonance and yields a reactive tellurium precursor for the formation of 2D PbTe NPLs at temperatures as low as 0 degrees C. The PL position of the PbTe NPLs is tunable by controlling the Pb/Te ratio in the reaction. Grazing-incidence wide-angle X-ray scattering confirms the 2D geometry of the NPLs and the formation of superlattices. The importance of a postsynthetic passivation of PbTe NPLs by PbI2 to ensure colloidal stability of the otherwise oxygen-sensitive samples is supported by X-ray photoelectron spectroscopy. Our results expand and complete the row of lead chalcogenide-based 2D NPLs, opening up new ways for further pushing the optical properties of 2D NPLs into the infrared and toward technologically relevant wavelengths.
In this work, thin composite films of zeolitic imidazolate frameworks (ZIFs) and colloidal two-dimensional (2D) CdSe/CdS nanoplatelet emitters with minimal scattering are formed by cycled growth and yield highly transparent coatings while retaining the strong and narrow photoluminescence of the nanoplatelets at 546 nm (FWHM: 25 nm) in a solid-state composite structure. The porous ZIF matrix acts as functional encapsulation for the nanoplatelet emitters which is shown by the adsorption of the guest molecules water and ethanol by the ZIF and sensed by a reversable change in the photoluminescence of the embedded nanoplatelets. Additionally, the transmittance of the composite films surpasses the values of uncoated glass substrates at UV-Vis wavelengths where the nanoplatelets show no absorption, rendering it a photoluminescent antireflective coating. The fast formation of smooth films without pre-polymerizing the colloidal nanoplatelet emitters provides a powerful tool for application-oriented photoluminescence-based gas sensing in the composites.
The shells of walnuts (WS) are major refuse in the global fruits and nuts trade. This, otherwise discarded, lignin-rich material can be carbonized to biochar—a value-added product with environmental applications such as carbon sequestration, soil amelioration, and pollutant adsorption. These applications are dictated by structural and chemical characteristics of the biochar carbon. Conventional controlled pyrolysis (CPy) of biomass is cost-intensive and technically too complex for widespread adoption, especially in emerging economies. Here, walnut shell biochar (BWS0) is derived through uncontrolled pyrolysis (UCPy) in a pyrolysis oven and further hybridized as magnetic biochar through ex-situ chemical co-precipitation. The physico-chemical characteristics of biochar and its water-extractable fractions are comprehensively investigated to understand their carbon structure and environmental applicability. The sp 2 amorphous carbon sequestered in BWS0 is 0.84 kg CO2 /kg biomass with a BET (N 2 ) surface area of 292 m 2 /g and is comparable to biochar from CPy in terms of carbon structure. The polyaromatic hydrocarbons present are only trace amounts of naphthalene, biphenyl, and phenanthrene. The magnetization decreases porosity of BWS0 while greatly facilitating its separation from aqueous media. BWS0 is suitable for adsorption of cations (between pH 2.8 and 9.45) and hydrophobic pollutants with only 19 mg L −1 fouling from their intrinsic dissolved organic carbon. In combination with fast-release N, P fertilizers, BWS0 (C/N of 24.8) is suitable for application in hydrophilic soils at higher loading rates. The results suggest an avenue where WS biochar can also be prepared via UCPy for direct environmental applications. Future investigations into soil incubation and adsorption tests are recommended. Graphical abstract
Colloidal 2D semiconductor nanoplatelets are highly efficient light emitters, which exhibit large absorption and emission cross sections, and constitute promising laser gain media. However, if dispersed in solutions, such nanoplatelets lack a suitable optical platform for scalable and application-oriented integration into optical setups such as lasers. Here, we demonstrate the first successful integration of solution-processed 2D CdSe/CdS Core/Crown nanoplatelets in m-scale liquid core optical fibers. We compare the nanoplatelets' spectroscopic properties before and after filling them into the fibers and find that spontaneous emission is shifted and broadened. We even observe a first evidence of stimulated emission at high excitation energies. In conclusion, liquid core fibers constitute a novel and scalable platform for optical integration of nanoplatelets for applications as novel, highly reconfigurable laser gain medium.
Stable jet electrospinning (SJES) is a special form of optical fiber generation that prevents chaotic fiber whipping typical for conventional electrospinning procedures. Incorporation of highly emissive semiconductor nanoplatelets (NPLs) in such fibers has very high potential in optical data transmission, optological circuits, fiber lasers, solar light concentrators and many other fields because NPLs exhibit strongly directed emission from their surface plane due to various in-plane transition dipole moments. However, potential orientation control of 2D-NPLs in SJES is entirely unknown as electric fields and various mechanical forces contribute in a complex manner simultaneously. Here, the observation of counter-intuitive yet very beneficial orientation of rectangular CdSe/CdS 2D-NLP in SJES perpendicular to the fiber drawing axis is reported. Scanning electron microscopy, 3D-single particle excitation polarization microscopy, 3D-photogoniometry, polarized emission spectroscopy and small angle X-ray scattering (SAXS) demonstrate aggregation free perpendicular alignment of the NPLs in poly(methyl methacrylate) (PMMA) fibers, resulting in dominant emission in directions parallel to the fiber. It is suggested that the observed vertical alignment is due to normal forces resulting from viscoelastic expansion when the polymer solution leaves the cannula (Barus effect) and that using such perpendicular nano-emitter alignment forces allows for the generation of novel materials also beyond fibers.
Two-dimensional (2D) semiconductor nanoplatelets (NPLs) are strongly photoluminescent materials with interesting properties for optoelectronics. Especially their narrow photoluminescence paired with a high quantum yield is promising for light emission applications with high color purity. However, retaining these features in solid-state thin films together with an efficient encapsulation of the NPLs is a challenge, especially when trying to achieve high-quality films with a defined optical density and low surface roughness. Here, we show photoluminescent polymer-encapsulated inorganic-organic nanocomposite coatings of 2D CdSe/CdS NPLs in poly(diallyldimethylammonium chloride) (PDDA) and poly(ethylenimine) (PEI), which are prepared by sequential layer-by-layer (LbL) deposition. The electrostatic interaction between the positively charged polyelectrolytes and aqueous phase-transferred NPLs with negatively charged surface ligands is used as a driving force to achieve self-assembled nanocomposite coatings with a well-controlled layer thickness and surface roughness. Increasing the repulsive forces between the NPLs by increasing the pH value of the dispersion leads to the formation of nanocomposites with all NPLs arranging flat on the substrate, while the surface roughness of the 165 nm (50 bilayers) thick coating decreases to Ra = 14 nm. The photoluminescence properties of the nanocomposites are determined by the atomic layer thickness of the NPLs and the 11-mercaptoundecanoic acid ligand used for their phase transfer. Both the full width at half-maximum (20.5 nm) and the position (548 nm) of the nanocomposite photoluminescence are retained in comparison to the colloidal CdSe/CdS NPLs in aqueous dispersion, while the measured photoluminescence quantum yield of 5% is competitive to state-of-the-art nanomaterial coatings. Our approach yields stable polymer-encapsulated CdSe/CdS NPLs in smooth coatings with controllable film thickness, rendering the LbL deposition technique a powerful tool for the fabrication of solid-state photoluminescent nanocomposites.
Colloidal two-dimensional (2D) lead chalcogenide nanoplatelets (NPLs) represent highly interesting materials for near- and short wave-infrared applications including innovative glass fiber optics exhibiting negligible attenuation. In this work, we demonstrate a direct synthesis route for 2D PbSe NPLs with cubic rock salt crystal structure at low reaction temperatures of 0 °C and room temperature. A lateral size tuning of the PbSe NPLs by controlling the temperature and by adding small amounts of octylamine to the reaction leads to excitonic absorption features in the range of 1.55-1.24 eV (800-1000 nm) and narrow photoluminescence (PL) reaching the telecom O-, E- and S-band (1.38-0.86 eV, 900-1450 nm). The PL quantum yield of the as-synthesized PbSe NPLs is more than doubled by a postsynthetic treatment with CdCl2 (e.g. from 14.7% to 37.4% for NPLs emitting at 980 nm with a FWHM of 214 meV). An analysis of the slightly asymmetric PL line shape of the PbSe NPLs and their characterization by ultrafast transient absorption and time-resolved PL spectroscopy reveal a surface trap related PL contribution which is successfully reduced by the CdCl2 treatment from 40% down to 15%. Our results open up new pathways for a direct synthesis and straightforward incorporation of colloidal PbSe NPLs as efficient infrared emitters at technologically relevant telecom wavelengths.
Preparation of low density monolithic and free-standing organic-inorganic hybrid aerogels of various properties is demonstrated using green chemistry from a biosafe natural source (flaxseed mucilage) and freeze-casting and subsequent freeze drying. Bio-aerogels, luminescent aerogels, and magneto-responsive aerogels are obtained by combination of the flaxseed mucilage with different types of nanoparticles. Moreover, the aerogels are investigated as possible drug release systems using curcumin as a model. Various characterization techniques like thermogravimetric analysis, nitrogen physisorption, electron microscopy, UV/Vis absorption, and emission spectroscopy, bulk density, and mechanical measurements, as well as in vitro release profile measurements, are employed to investigate the obtained materials. The flaxseed-inspired organic-inorganic hybrid aerogels exhibit ultra-low densities as low as 5.6 mg cm(-3) for 0.5% (w/v) the mucilage polymer, a specific surface area of 4 to 20 m(2) g(-1), high oil absorption capacity (23 g g(-1)), and prominent compressibility. The natural biopolymer technique leads to low cost and biocompatible functional lightweight materials with tunable properties (physicochemical and mechanical) and significant potential for applications as supporting or stimuli responsive materials, carriers, reactors, microwave- and electromagnetic radiation protective (absorbing)-materials, as well as in drug delivery and oil absorption.
Colloidal 2D PbSe nanoplatelets (NPLs) are promising near-and short wave-infrared emitters for optoelectronic applications at telecommunication wavelengths. However, their photoluminescence quantum yield (PLQY) is limited by the ubiquitous presence of surface-related trap states. Here, we apply a treatment of colloidal PbSe NPLs with different metal halides (MX2, M = Zn, Cd, Pb; X = F, Cl, Br, I) to improve their emission brightness. A surface passivation of the NPLs by PbI2 leads to the best results with a strongly increased PLQY (27% for PbSe NPLs emitting at 0.98 eV (1265 nm) and up to 61% for PbSe NPLs emitting at 1.25 eV (989 nm)). Simultaneously, the full width at half-maximum of the NPL photoluminescence decreased by 10% after the treatment. X-ray photoelectron spectroscopy and complementary surface treatment of PbSe NPLs with organic halides reveal the combined passivating role of both X-type binding halides X- and Z-type binding metal halides MX2 in enhancing the optical properties of the PbSe NPLs. Our results emphasize the potential of 2D PbSe NPLs for efficient emission tailored for the application in fiber optics.
Colloidal two-dimensional (2D) lead chalcogenide nanoplatelets (NPLs) represent highly interesting materials for near- and short wave-infrared applications including innovative glass fiber optics exhibiting negligible attenuation. In this work, we demonstrate a direct synthesis route for 2D PbSe NPLs with cubic rock salt crystal structure at low reaction temperatures of 0 °C and room temperature. A lateral size tuning of the PbSe NPLs by controlling the temper-ature and by adding small amounts of octylamine to the reaction leads to excitonic absorption features in the range of 800 – 1000 nm (1.6 – 1.3 eV) and narrow photoluminescence (PL) seamlessly covering the broadband infrared spec-tral window of 900 – 1450 nm (1.4 – 0.9 eV). The PL quantum yield of the as-synthesized PbSe NPLs is more than doubled by a postsynthetic treatment with CdCl2 (e.g. from 14.7 % to 37.4 % for NPLs emitting at 980 nm with a FWHM of 214 meV). An analysis of the slightly asymmetric PL line shape of the PbSe NPLs and their characterization by ultrafast transient absorption and time-resolved PL spectroscopy reveal a surface trap related PL contribution which is successfully reduced by the CdCl2 treatment from 40 % to 15 %. Our results open up new pathways for a direct synthesis and straightforward incorporation of colloidal PbSe NPLs as efficient infrared emitters at technologi-cally relevant telecommunication wavelengths.
Colloidal PbS nanoplatelets (NPLs) are highly interesting materials for near-infrared optoelectronic applications. We use ultrafast transient optical absorption spectroscopy to study the characteristics and dynamics of photoexcited excitons in ultrathin PbS NPLs with a cubic crystal structure. NPLs are synthesized at near room temperature from lead oleate and thiourea precursors; they show an optical absorption onset at 680 nm (1.8 eV) and photoluminescence at 720 nm (1.7 eV). By postsynthetically treating PbS NPLs with CdCl2, their photoluminescence quantum yield is strongly enhanced from 1.4% to 19.4%. The surface treatment leads to an increased lead to sulfur ratio in the structures and associated reduced nonradiative recombination. Additionally, exciton-phonon interactions in pristine and CdCl2 treated NPLs at frequencies of 1.96 and 2.04 THz are apparent from coherent oscillations in the transient absorption spectra. This study is an important step forward in unraveling and controlling the optical properties of IV-VI semiconductor NPLs.
Different techniques that enable the selective microstructure design of aerogels without the use of additives are presented. For this, aerogels were prepared from platinum nanoparticle solutions using the cryoaerogelation method, and respective impacts of different freezing times, freezing media, and freezing temperatures were investigated with electron microscopy as well as inductively coupled plasma optical emission spectroscopy. The use of lower freezing temperatures, freezing media with higher heat conductivities, and longer freezing periods led to extremely different network structures with enhanced stability. In detail, materials were created in the shape of lamellar, cellular, and dendritic networks. So far, without changing the building blocks, it was not possible to create the selective morphologies of resulting aerogels in cryoaerogelation. Now, these additive-free approaches enable targeted structuring and will open up new opportunities in the future cryoaerogel design.
Single wall carbon nanotubes (SWCNT) fluoresce in the near infrared (NIR) and have been assembled with biopolymers such as DNA to form highly sensitive molecular sensors. They change their fluorescence when they interact with analytes. Despite the progress in engineering of these sensors the underlying mechanisms are still not understood. Here, we identify processes and rate constants that explain the photophysical signal transduction by exploiting sp3 quantum defects in the sp2 carbon lattice of SWCNTs. As a model system we use ssDNA coated (6,5)-SWCNTs, which increase their NIR emission (E11, 990 nm) up to + 250 % in response to the important neurotransmitter dopamine. In contrast, SWCNTs coated with DNA but with a low number of NO2-Aryl sp3 quantum defects decrease both their E11 (-35%) and defect related E11* emission (- 50%) at 1130 nm. Consequently, the interaction with the analyte does not change the radiative exciton decay pathway alone. Furthermore, the fluorescence response of pristine SWCNTs increases with SWCNT length, suggesting that exciton diffusion is affected. The quantum yield of pristine (6,5)-SWCNTs increases in response to the analyte from 0.6 % to 1.3 % and points to a change in non-radiative rate constants. These experimental results are explained by a Monte Carlo simulation of exciton diffusion, which supports a change of two non-radiative decay pathways together with an increase of exciton diffusion (3 rate constant model). The combination of such SWCNTs with defects and without defects enables the assembly of ratiometric sensors with opposing responses at different wavelengths. In summary, we demonstrate how perturbation of a system with quantum defects reveals the photophysical mechanism and reverses optical responses.
Sustainable agroindustry has presented many challenges related to waste management. Most of its residues are lignocellulosic biomass materials with great application potential due to their chemical composition, hence the use of biomass-derived carbon materials in energy storage has received growing interest in recent years. In this work, highly micro-porous carbonaceous materials using the endocarp of the coffee fruit or coffee husk (CH) as precursor are obtained. Specifically, three different activating agents (KOH, K2CO3, and steam) to derive activated carbons (ACs) with good capacitive properties are tested. The properties of ACs such as surface chemistry, texture, crystal graphite size, and order in the carbonaceous structure are assessed and compared. The capacitive behavior inherent to the activation routes is also characterized by means of Cyclic Voltammetry (CV), Galvanostatic Charge/Discharge (GCD) and Electrochemical Impedance Spectroscopy (EIS). The obtained specific capacitance values range from 106 to 138 F g-1 for a discharge current of 0.5 A g-1. These results nominate coffee husk as a good precursor of carbonaceous materials suitable for energy storage.