Incorporation Of Nanocrystals Research Articles

Quantum Dot to Nanorod Transition for Efficient White-Light-Emitting Diodes with Suppressed Absorption Losses

Colloidal nanocrystals have great potential for next-generation solid-state lighting due to their outstanding emission and absorption tunability via size and morphology, narrow emission linewidth, and high photoluminescence quantum yield (PLQY). However, the losses due to self- and interabsorption among multitudes of nanocrystals significantly decrease external quantum yield levels of light-emitting diodes (LEDs). Here, we demonstrate efficient white LEDs via CdSe/CdS dot to “dot-in-rod” transition that enabled a large Stokes shift of 780 meV and significantly reduced absorption losses when used in conjunction with near-unity PLQY ZnCdSe/ZnSe quantum dots (QDs) emitting at the green spectral range. The optimized incorporation of nanocrystals in a liquid state led to the white LEDs with an ultimate external quantum efficiency (EQE) of 42.9%, with a net increase of EQE of 10.3% in comparison with white LEDs using CdSe/CdS dots. Therefore, combinations of nanocrystals with different nanomorphologies hold high promise for efficient white LEDs.

Silymarin nanocrystals-laden chondroitin sulphate-based thermoreversible hydrogels; A promising approach for bioavailability enhancement

Hydrogels has gained tremendous interest as a controlled release drug delivery. However, currently it is a big challenge to attain high drug-loading as well as stable and sustained release of hydrophobic drugs. The poor aqueous solubility and low bioavailability of many drugs have driven the need for research in new formulations. This manuscript hypothesized that incorporation of nanocrystals of hydrophobic drug, such as silymarin into thermoreversible hydrogel could be a solution to these problems. Herein, we prepared nanocrystals of silymarin by antisolvent precipitation technique and characterized for morphology, particle size, polydispersity index (PDI) and zeta potential. Moreover, physical cross-linking of hydrogel formulations based on chondroitin sulphate (CS), kappa-Carrageenan (κ-Cr) and Pluronic® F127 was confirmed by Fourier transformed infrared spectroscopy (FT-IR). The hydrogel gelation time and temperature of optimized hydrogel was 14 ± 3.2 s and 34 ± 0.6 °C, respectively. The release data revealed controlled release of silymarin up to 48 h and in-vivo pharmacokinetic profiling was done in rabbits and further analyzed by high-performance liquid chromatography (HPLC). It is believed that the nanocrystals loaded thermoreversible injectable hydrogel system fabricated in this study provides high drug loading as well as controlled and stable release of hydrophobic drug for extended period.

Evaluation of waste chicken feather protein hydrolysate as a bio-based binder for particleboard production

The present study investigate the beneficiation potential of extracted keratin protein hydrolysate from chicken feather waste biomass as bio-adhesive for the production of particleboard. Chicken feathers were hydrolyzed using hybrid alkaline hydrolysis, and the obtained keratin protein fraction was used for bio-adhesive formulation. The formulated adhesive was employed for particleboard fabrication using the American National Standards Institute (A208.1) 1-L-1 grade specification. The quality of bio-adhesive and the particleboard mechanical strength performance were evaluated with Fourier transform infrared spectroscopy (FTIR), modulus of rupture (MOR), modulus of elasticity (MOE) and density. The FTIR spectra confirmed the amine, alkyl side chains and carboxylic groups of the amino acids in the unmodified keratin-based binder. The spectra revealed the covalent bonding between the azetidinium of the citric acid-based polyamide-epichlorohydrin cross-linking and the hydroxyl groups of the keratin protein hydrolysate. The fabricated particleboard's mechanical strength performance met the specification for the 1-L-1 grade of the American National Standards Institute (A208.1). The respective values obtained for modulus of rupture and modulus of elasticity of the panels made with unmodified keratin-based adhesive were 6, 5 and 1184, 34 ​MPa, respectively. The cellulose nanocrystals incorporation as a filler enhanced the formulated bio-adhesive static bending and bonding strength properties. Therefore, these findings demonstrate that keratin hydrolysate protein extracts from chicken feather waste could be considered as a potential feedstock for environmentally friendly wood composites bio-binder production.

Multilayer Heterostructures with Embedded CrSi<sub>2</sub> and β-FeSi<sub>2</sub> Nanocrystals on Si(111) Substrate: From the Formation to Photoelectric Properties

The studies are devoted to the development of the technology of multilayer incorporation of nanocrystals (NCs) of semiconductor chromium and iron disilicides with a layer density no less than 2x1010 cm-2, the establishment of the growth mechanism of heterostructures with two types of NCs, the determination of their crystalline quality and optical properties, as well as the creation and study of rectification and photoelectric properties of p-i-n diodes based on them. Morphologically smooth heterostructures with 6 embedded layers of CrSi2 nanocrystals and two types of embedded nanocrystals (with 4 layers of CrSi2 NCs and 2 layers of β-FeSi2 NCs) for optical studies and built-in silicon p-i-n diodes were grown for the first time. The possibility of optical identification of interband transitions in embedded nanocrystals in the photon energy range of 1.2 - 2.5 eV was determined from the reflection spectra and the strongest peaks in reflection from the integrated nanocrystals were determined: 2.0 eV for CrSi2 NCs and 1.75 eV for β-FeSi2 NCs. The created p-i-n diodes have a contact potential difference of 0.95 V, regardless of the type of embedded NCs. At 80 K, an absorption band (0.7 - 1.1 eV) was detected in the diodes, which was associated with carrier photo generation in the embedded CrSi2 and β-FeSi2 NCs. From the spectra of the photoresponse at 80 K, the band gap widths in the NCs were determined: 0.50 eV in CrSi2 and 0.70 eV in the superposition of the CrSi2 and β-FeSi2 NCs.

Incorporation of Cellulose Nanocrystals (CNC) derived from sawdust into polyamide thin-film composite membranes for enhanced water recovery

In this work, cellulose nanocrystals (CNC) derived from sawdust were successfully incorporated into a thin film composite membrane made from polyamide. The characteristics of unmodified and modified membranes were investigated using FT-IR, XRD, TGA, SEM, EDX, AFM and contact angle measurement. The membranes’ performances were evaluated using a dead-end test cell with sodium chloride (1500 ppm) and calcium chloride (2500 ppm) solutions. FT-IR and XRD analyses revealed that polymerization took place during the incorporation of the cellulose nanocrystals. From EDX analysis, it was found that incorporation of CNC into the membrane resulted in an increase in the oxygen content both at the atomic and mass levels. SEM and AFM images revealed dense and tight structures for both modified and unmodified membranes. The modified membrane was more hydrophilic and rougher than the unmodified membrane. The water flux was significantly increased (more than 23%) while maintaining high rejection rate values for sodium chloride (98.3 ± 0.8%) and calcium chloride (97.1 ± 0.5%). Furthermore, there was also an increase in the thermal stability of the membrane. The results, therefore, have shown a great prospect in the development of thin-film nanocomposite membranes using sawdust-derived cellulose nanocrystals incorporated in polyamide.

Luminescence relaxation dynamics for planar and rolled-up CdSe nanocrystals in a photonic-crystal matrix

Samples of inverted photonic-crystal films, containing planar and rolled-up (in the form of scrolls) CdSe nanocrystals, are studied. The transmission spectra of these structures are recorded. These spectra (along with the change in colour) confirm the incorporation of nanocrystals into the films. The photoluminescence decay dynamics is investigated. It is shown that the photonic-crystal matrix affects significantly the luminescence kinetics of nanostructures. The differences in the decay curves measured for nanocrystals in a photonic-crystal matrix and for their ensemble on a glass substrate are explained by the influence of the photonic-crystal stop band and the orientational effect of crystalline matrix, which orients anisotropic nanocrystals and prevents them from aggregation. The results obtained may be important for potential applications in optoelectronic devices.

Incorporating quantum dots for high efficiency and stable perovskite photovoltaics

Enhancing bulk perovskite photovoltaics by integrating perovskites and metal chalcogenide quantum dots.

Polymer nanocomposites functionalised with nanocrystals of zeolitic imidazolate frameworks as ethylene control agents

Ethylene (C2H4) management involves the usage of materials such as KMnO4 or processes such as ozone oxidation or combined photocatalysis/photochemistry. The ubiquity of C2H4, especially in an industrial context, necessitates a simpler and much more effective approach, and herein we propose the usage of tuneable polymer nanocomposites for the adsorption of C2H4 through the modification of the polymer matrices via the incorporation of nanocrystals of zeolitic imidazolate frameworks (nano-ZIFs). We demonstrate that the inclusion of ZIF-8 and ZIF-7 nanocrystals into polymeric matrices (Matrimid and polyurethane [PU]) yields robust nanocomposites that preserve the C2H4 adsorption/desorption capacity of nanocrystals while shielding it from degrading factors. We report new insights into the adsorption/desorption kinetics of the polymer and its corresponding nanocomposites, which can be tailored by exploiting the underlying polymeric molecular interactions. Importantly, we also elucidated the retention of the intrinsic structural framework dynamics of the nano-ZIFs even when embedded within the polymeric matrix, as evidenced from the breathing and gate-opening phenomena. Our findings pave the way for bespoke designs of novel polymer nanocomposites, which will subsequently impact the deployment of tailored nanomaterials for effective industrial applications.

Robust Hydrophobic and Hydrophilic Polymer Fibers Sensitized by Inorganic and Hybrid Lead Halide Perovskite Nanocrystal Emitters.

Advances in the technology and processing of flexible optical materials have paved the way toward the integration of semiconductor emitters and polymers into functional light emitting fabrics. Lead halide perovskite nanocrystals appear as highly suitable optical sensitizers for such polymer fiber emitters due to their ease of fabrication, versatile solution-processing and highly efficient, tunable, and narrow emission across the visible spectrum. A beneficial byproduct of the nanocrystal incorporation into the polymer matrix is that it provides a facile and low-cost method to chemically and structurally stabilize the perovskite nanocrystals under ambient conditions. Herein, we demonstrate two types of robust fiber composites based on electrospun hydrophobic poly(methyl methacrylate) (PMMA) or hydrophilic polyvinylpyrrolidone (PVP) fibrous membranes sensitized by green-emitting all-inorganic CsPbBr3 or hybrid organic-inorganic FAPbBr3 nanocrystals. We perform a systematic investigation on the influence of the nanocrystal-polymer relative content on the structural and optical properties of the fiber nanocomposites and we find that within a wide content range, the nanocrystals retain their narrow and high quantum yield emission upon incorporation into the polymer fibers. Quenching of the radiative recombination at the higher/lower bound of the nanocrystal:polymer mass ratio probed is discussed in terms of nanocrystal clustering/ligand desorption due to dilution effects, respectively. The nanocomposite's optical stability over an extended exposure in air and upon immersion in water is also discussed. The studies confirm the demonstration of robust and bright polymer-fiber emitters with promising applications in backlighting for LCD displays and textile-based light emitting devices.

Inductive co-crosslinking of cellulose nanocrystal/chitosan hydrogels for the treatment of vertebral compression fractures.

Vertebral compression fractures are a very common consequence of osteoporosis for which injection of a non-biodegradable, non-bioactive, mechanically-stiff polymer bone cement into the vertebral body is the most common treatment. Recently, there has been growing interest in using bioactive, degradable, and bone biomechanics-matching products as an alternative approach for treating these fractures. In this research, we focused on creating injectable, chitosan-based hydrogels that can convey mechanical strength similar to vertebral bone as well as possess inherent osteoinductivity. First, we investigated the effects of three different factors - 1) bioactive phosphate ionic crosslinking; 2) genipin covalent crosslinking; 3) mechanically reinforcing cellulose nanocrystal incorporation - on the material properties of chitosan-based hydrogels. Mesenchymal stem cells were then exposed to hydrogels with optimum mechanical properties and stability in order to assess the biological effects of the bioactive phosphate ionic crosslinker. Our results show that hydrogels with higher ionic and covalent crosslinking ratios supplemented with neutral cellulose nanocrystals possessed desirable compressive strength and stability. Also, the significant osteoinductivity of these composite hydrogels demonstrated their potential to function as an injectable system for the future treatment of vertebral compression fractures.

Thermal conductivity and tensile properties of tin oxide filled UPR/EPS composites with and without organic nanocrystal

Panel composite for building application made from waste expanded polystyrene (EPS) and unsaturated polyester (UPR) were fabricated and tested in this research for their tensile and thermal characteristics in determining its insulation properties. Research had been carried out to incorporate EPS into UPR with addition of two additives types which are tin oxide (SnO) stand alone, and tin oxide in combination with organic nanocrystals. The weight percentage of SnO had been varied from 0.1 to 2%, and the nanocrystals between 0.1 to 0.5%; both fabricated via casting and compression of the UPR/EPS composite. The testing performed are tensile properties by an Instron Universal Tensile Machine; and thermal conductivity test by using KD2 Pro hand-held thermal probe. It was found that, by using UPE/EPS, the additives affected the composites' thermal conductivity and tensile capabilities. For tensile strength, the control sample showed the highest tensile strength at 22.2 MPa. For thermal conductivity (k value), the lowest value was recorded by the 1% SnO stand alone at an approximate ~ 0.172 W/m.K. Via organic nanocrystal use fixed at 0.1%, the k value increases up to a certain point with increasing SnO. Addition of more SnO and nanocrystal incorporation had mostly increases its thermal conductivity and heat capacity. Heat capacity was also found to be at the lowest in the 1% SnO stand alone sample at 2.008 MJ/m3.K.

The role of cellulose nanocrystals incorporation route in waterborne polyurethane for preparation of electrospun nanocomposites mats

Electrospinning offers the possibility of obtaining fibers mats from polymer solutions. The use of environmentally-friendly waterborne polyurethane (WBPU) allows obtaining electrospun polyurethane mats in water medium. Furthermore, the incorporation of water dispersible nanoentities, like renewable cellulose nanocrystals (CNC), is facilitated. Therefore, in this work, a WBPU was synthesized and CNC were isolated for preparing WBPU–CNC dispersions nanocomposites with 1 and 3wt% of CNC following both the classical mixing by sonication, and the innovative in-situ route. The dispersions were used for obtaining electrospun mats assisted by poly(ethylene oxide) (PEO) as polymer template. Moreover, the extraction of PEO with water resulted in continuous WBPU–CNC mats, showing different properties respect to WBPU–CNC mats containing PEO. The effective addition of CNC led to more defined cylindrical morphologies and the two alternative incorporation routes induced to different CNC dispositions in the matrix, which modified fibers diameters, and thus, mats final properties.

Influence of In2O3 nanocrystals incorporation on sodium borosilicate glass and their nonlinear optical properties

To maintain the high transparency and superior properties of In2O3, In2O3 nanocrystals with various contents incorporation on sodium borosilicate glass have been successfully prepared by the sol-gel method. Microstructure results confirm that In2O3 nanocrystals with the average particle size of 18.5nm are incorporated in the glass. The UV–vis spectra show that these glasses are UV-absorbing and highly transparent in the visible region. The effect of In2O3 nanocrystals on the nonlinear optical properties is studied systematically using Z-scan measurement. Results demonstrate that the third-order nonlinear optical susceptibility χ(3) increases from 8.59×10−12 to 8.68×10−11esu with the contents of In2O3 enhanced from 0.5 to 1.5wt% in the glass.

Three-dimensional atomic mapping of hydrogenated polymorphous silicon solar cells

Hydrogenated polymorphous silicon (pm-Si:H) is a nanostructured material consisting of silicon nanocrystals embedded in an amorphous silicon matrix. Its use as the intrinsic layer in thin film p-i-n solar cells has led to good cell properties in terms of stability and efficiency. Here, we have been able to assess directly the concentration and distribution of nanocrystals and impurities (dopants) in p-i-n solar cells, by using femtosecond laser-assisted atom probe tomography (APT). An effective sample preparation method for APT characterization is developed. Based on the difference in atomic density between hydrogenated amorphous and crystalline silicon, we are able to distinguish the nanocrystals from the amorphous matrix by using APT. Moreover, thanks to the three-dimensional reconstruction, we demonstrate that Si nanocrystals are homogeneously distributed in the entire intrinsic layer of the solar cell. The influence of the process pressure on the incorporation of nanocrystals and their distribution is also investigated. Thanks to APT we could determine crystalline fractions as low as 4.2% in the pm-Si:H films, which is very difficult to determine by standard techniques, such as X-ray diffraction, Raman spectroscopy, and spectroscopic ellipsometry. Moreover, we also demonstrate a sharp p/i interface in our solar cells.

Dynamics of nanocubes embedding into polymer films investigated via spatially resolved plasmon modes.

Integration of nanoparticles into thin films is essential for the development of functional materials, studies of fundamental interfacial processes, and exploitation of inherent properties from the particles themselves. In this work, we systematically investigate the process of incorporation of silver nanocubes into thin polystyrene films at temperatures just above the polymer glass transition. The process of nanocrystal incorporation can be precisely monitored via far-field spectroscopy to observe the response of spatially resolved hybrid plasmon modes. Each plasmon resonance has a distinct dynamic range and maximum sensitivity forming a complementary set of nanorulers that operates over a distance comparable to the edge length of the cubes. The approach explored in this work is a general robust method for the development of long-range polychromatic nanorulers.

Ordering in Polymer Micelle-Directed Assemblies of Colloidal Nanocrystals.

Assembly of presynthesized nanocrystals by block copolymer micelles can be rationalized by the incorporation of nanocrystals into micellar coronas of constant width. As determined by quantitative analysis using small-angle X-ray scattering, high loading of small nanocrystals yields composites exhibiting order on two length scales, whereas intermediate loading of nanocrystals larger than the coronal width produces single nanocrystal networks. The resulting structures obey expectations of thermodynamically driven assembly on the nanocrystal length scale, whereas kinetically frozen packing principles dictate order on the polymer micelle length scale.

Incorporation of nanocrystals with different dimensionalities in hybrid TiO2/ P 3 HT solar cells

We investigate the effect of TiO 2 nanoparticles–nanospheres and nanorods–inserted in the poly(3-hexylthiophene) (P3HT) matrix of TiO 2 /P3HT inverted hybrid solar cells. X-ray diffraction, high-resolution transmission electron microscopy, small-angle x-ray scattering, photoluminescence, and photoelectrochemical experiments were employed to investigate the structure, morphology, and photoactivity of TiO 2 nanoparticles modified with 2-thiopheneacetic acid, mixed or not with P3HT. Both TiO 2 nanospheres and TiO 2 nanorods presented a good dispersion in the polymer matrix. The incorporation of TiO 2 nanospheres and nanorods has improved the photocurrent generation, and devices with efficiency values up to 1.35% were obtained. Our results reveal that the nanoscale morphology enables an enhanced interfacial area for exciton dissociation. In particular, the nanospheres contribute with their high specific area, and the nanorods contribute with their high aspect ratio.

Study of composition, heat treatment, and inorganic nanocrystal incorporation for hybrid-solar-cells performance

Hybrid solar cells were fabricated by blending [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and conjugate polymers, such as poly(3-hexyl thiophene) (P3HT) and poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]-dithiophene)-alt -4,7-(2,1,3-benzothiadiazole)] (PCPDTBT). The effects of solution composition, annealing, and the incorporation of inorganic semiconductor nanocrystals (NCs) on the performance of the device were investigated. The composite solution of a (PCBM:PCPDTBT) blend was optimized to control the surface morphology of the active layer. The composite films constructed with (PCBM:PCPDTBT) ratios of 1:1, 2:1, and 3:1 were studied, and results showed that the surface of the active layers were quite smooth. Heat treatment on the fabricated cell structure was also studied and was optimized to improve the device’s performance. To enhancement of the device’s efficiency, we added of semiconducting nanocrystals into the composite solution, which resulted in a maximum power conversion efficiency of 4.56% under AM1.5G simulated solar irradiation.

Improving carrier injection in colloidal CdSe nanocrystals by embedding them in a pseudomorphic ZnSe/ZnMgSe quantum well structure

The incorporation of colloidal nanocrystals in a high crystalline quality semiconductor matrix, the efficient carrier injection into the embedded nanocrystals and the fast optical response are key features for the fabrication of novel optoelectronic nanodevices based on colloidal nanostructures as active optical material. Using a novel growth approach, colloidal bare CdSe and core–shell CdSe/ZnS nanocrystals were monolithically incorporated in pseudomorphic ZnSe/ZnMgSe quantum wells in order to control and enhance the carrier transfer into the nanocrystals. The photoluminescence for bare CdSe nanocrystals incorporated in ZnSe/ZnMgSe quantum well structures is substantially enhanced in comparison to nanocrystals sandwiched in ZnSe epilayers, which we attribute to increased carrier injection into the embedded nanocrystals via the quantum well, resembling the function of a wetting layer in Stranski–Krastanov-grown quantum dots. Core–shell CdSe/ZnS nanocrystals embedded in quantum well structures do not show considerable PL modifications because the ZnS shell prevents the efficient carrier migration between the nanocrystal and the matrix. Systematic investigations of structural and optical properties by high-resolution x-ray diffraction, temperature-dependent photoluminescence and time-resolved emission are presented.

Tailoring the morphology and properties of waterborne polyurethanes by the procedure of cellulose nanocrystal incorporation

Polyurethane waterborne synthesis was performed using a two-step method, commonly referred to as a prepolymer method. Nanocomposites based on waterborne polyurethane and cellulose nanocrystals were prepared by the prepolymer method by altering the mode and step in which the nanofillers were incorporated during the polyurethane formation. The morphology, structural, thermal, and mechanical properties of the resulting nanocomposite films were evaluated by Fourier transform infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and tensile tests. FTIR results indicated that the degree of interaction between the nanofillers and the WPU through hydrogen bonds could be controlled by the method of cellulose nanocrystal incorporation. Data obtained from SAXS experiments showed that the cellulose nanocrystals as well as the step of the reaction in which they are added influenced the morphology of the polyurethane. The reinforcing effect of CNCs on the nanocomposites depends on their morphology.