Colloidal CdSe nanocrystals from tri-n-octylphosphine: Part II: control of growth rate for high quality and large-scale production by tuning Cd-to-Se stoichiometry

Colloidal CdSe nanocrystals were synthesized in reaction media consisting of tri-n-octylphosphine (TOP) without addition of other species; the single-step approach used cadmium oxide (CdO) and TOPSe as Cd and Se sources, respectively. The temporal evolution of the optical properties of the growing TOP-capped CdSe nanocrystals was monitored for a couple of hours, showing that there are two distinguishable stages of growth: an early stage (less than 5 minutes) and a later stage; the growth kinetics of the two stages is a function of the Cd-to-Se precursor molar ratios. A rational choice of 2-6Cd-to-1Se molar ratio was found, based on the temporal evolution of the photoluminescent (PL) efficiency (studied as PL intensity and sensitivity to the media of dispersion, and non-resonant Stokes shifts). For a 2Cd-to-1Se synthesis, the growth in size was slow in the early stages and became fast in the later stages; this fast-later-stage feature could be suppressed by going to a synthesis with a 4-6Cd-to-1Se mole ratio: the nanocrystals between 0.5-60 min growth time exhibit very much similar optical properties, with less than 19 nm redshift of bandgap absorption and emission occurring. Thus, the synthetic route developed here, with a rational 4-6Cd-to-1Se molar ratio, enables us to produce high-quality CdSe nanocrystals on a large-scale with a high degree of synthetic reproducibility. The insights gained facilitate a deeper understanding of the concept of what constitutes high-quality nano-crystals: high PL efficiency resulting from a low growth rate, which can be thoroughly and readily investigated by the red-shift rate of the band-gap peak positions; in addition, the insights gained help us to define a proper synthetic approach for large-scale production with high-quality product.     

In-situ observation of nucleation and growth of PbSe magic-sized nanoclusters and regular nanocrystals

In-situ observation of the temporal evolution of the absorption of PbSe nanocrystals (NCs) via a low-temperature noninjection approach is presented. Based on a model reaction of lead oleate (Pb(OA)(2) ) and n-trioctylphosphine selenide (TOPSe) in 1-octadecene at 35-80 °C, the use of commercially available TOP (90 or 97%) in affecting the formation of the NCs is explored. TOPSe solutions made from TOP 90% exhibited higher reactivity than those made from TOP 97%. (31)P NMR spectroscopy detected no dioctylphosphine selenide (DOPSe) but some DOP in ≈1.0 M TOPSe/TOP solution (made from TOP 90%), as well as no diphenylphosphine selenide (DPPSe) when DPP was added to the ≈1.0 M solution. Hence, it is proposed that, for the formation of PbSe monomers, an indirect pathway dominates with the formation of a Pb-P complex/intermediate, which results from the activation of Pb(OA)(2) by a phosphine compound (such as DPP, DOP, or TOP) and in turn reacts with TOPSe. With the use of TOP 90% and the addition of secondary phosphine DPP, the formation of PbSe magic-sized nanoclusters (MSNCs) and regular NCs (RNCs) is investigated. With proper tuning of the synthesis conditions, the formation of various PbSe MSNCs versus RNCs is monitored in situ with versus without the addition of DPP, or at different reaction temperatures but otherwise identical synthetic formulation and reaction parameters. Accordingly, the degree of supersaturation (DS) of the PbSe monomer affecting the development of these PbSe MSNCs versus RNCs is proposed; the higher the DS, the more the MSNCs are favored. Also, surface-determined cluster-cluster aggregation is proposed to be the growth mechanism for both the RNCs and MSNCs. For the former, quantized growth is followed by continuous growth. For the latter, the sizes of the magic-sized families are calculated.     

不同温度下硒化镉(CdSe)量子点的生长及荧光性研究

研究了以氧化镉（CdO）和硒（Se）粉为前驱体,在三辛基膦（TOP）和油酸中合成无机半导体量子点（quantum dots, QDs）CdSe.研究了在不同的反应温度下粒子的生长,通过紫外吸收光谱（UV-Vis）、荧光发射光谱（PL）、透射电子显微镜（TEM）等手段跟踪反应过程并对样品性能进行了表征.实验结果表明,反应温度和反应时间对量子点的生长和荧光性能有很大的影响.     

A surfactant-free recipe for shape-controlled synthesis of CdSe nanocrystals

We described surfactant-free recipes for the synthesis of CdSe nanocrystals (NCs) with well-controlled morphologies at a relatively low temperature. Dot-, rod-, tetrapod-and sphere-shaped CdSe NCs were prepared with trioctylphosphine oxide (TOPO) as a non-equilibrium solvent and trioctylphosphine selenide (TOPSe) and cadmium carboxylates as Se and Cd precursors, respectively. It was found that the morphology and stacking pattern of the CdSe NCs were related to the preparation conditions such as the concentration of the injected TOPSe(monomer concentration), reaction temperature and chain length of the cadmium carboxylate precursors. At a reaction temperature of 240?°C, CdSe NCs with a tetrapod selectivity of up to 85% were obtained in the presence of cadmium myristate under high concentrated TOPSe injection, and the in situ-formed myristic acid supplied the best acidic ligand with optimal amount to stabilize the anisotropic growth of the tetrapods. The intentional addition of more myristic acid in the reaction system would block the growth pathway of the tetrapods. Using cadmium laurate, cadmium palmitate and cadmium stearate as the cadmium precursors would reduce the formation of the tetrapods, showing the very low selectivity of the tetrapods.     

High quality zinc-blende CdSe nanocrystals synthesized in a hexadecylamine–oleic acid–paraffin liquid mixture

Safe, common, and low-cost compounds were used as solvents for the non-tri-n-octylphosphine (TOP) synthesis of high quality CdSe nanocrystals (NCs) in open air. In oleic acid–paraffin liquid system, CdSe nanocrystals in the less common zinc-blende (ZB, cubic) crystal structure have been obtained. The effects of adding n-hexadecylamine (HDA) to different solutions were discussed. Stable, highly homogeneous and luminescent CdSe nanocrystals were formed by adding n-hexadecylamine to Cd solution rather than to Se solution. Without any size sorting, the size distribution of the nanocrystals can be readily controlled and the highest photoluminescence (PL) quantum efficiency (QE) of the nanocrystals was up to 20–30%.     

Hybrid Au-CdSe and Ag-CdSe nanoflowers and core-shell nanocrystals via one-pot heterogeneous nucleation and growth

A general approach, based on heterogeneous nucleation and growth of CdSe nanostructures on Au or Ag nanocrystals, for the synthesis of Au-CdSe and Ag-CdSe hybrid nanostructures is developed. The new approach provides a versatile one-pot route for the synthesis of hybrid nanoflowers consisting of a gold or silver core and multipod CdSe rods or an intact CdSe shell with controlled thickness, depending on the nucleation and growth parameters. At lower growth temperatures such as 150 °C, the CdSe clusters are adsorbed on the surface of the metal cores in their surface defects, then multiple arms and branches form, resulting in nanoflower-shaped hybrid structures. Increasing the size of the metal core through the choice of the reducing and capping agents results in an improvement of the interface between the metal and CdSe domains, producing core-shell structures. The growth temperature appears to be the most important factor determining the nature of the interface between the metal and CdSe domains. At relatively high temperatures such as 300 °C, the formation of large, faceted Au cores creates preferential growth sites for the CdSe nanocrystalline shell, thus resulting in well-defined Au-CdSe core-shell structures with large interfaces between the Au and CdSe domains. The present approach is expected to foster systematic studies of the electronic structures and optical properties of the metal-semiconductor hybrid materials for potential applications in photovoltaic and nanoelectronic devices.     

巯基包覆CdSe和CdSe/CdS核壳纳米晶的水相合成与表征

利用水相合成的方法制备了巯基包覆的具有较高荧光量子产率的CdSe和CdSe／CdS纳米晶．水相合成方法的优点是原料低廉、安全可靠和重复性高，缺点是纳米晶的尺寸分布较宽，发光效率不是很高．采用X-射线粉末衍射、吸收和荧光等光谱手段对纳米晶的平均尺度、粒径分布、晶体结构及发光特性进行了表征。在77K到300K的温度范围内，随着温度降低，CdSe纳米晶的发光峰逐渐蓝移，而CdSe／Cds纳米晶发光峰位基本不随温度变化而变化．此外，在325nm激光辐照下，CdSe／CdS纳米晶的荧光寿命比CdSe纳米晶延长了6倍左右，稳定性大幅度提高．以上结果表明，核壳结构的CdSe／CdS纳米晶具有较高的发光效率和良好的稳定性，具有广阔的应用前景．     

CdSe/Cd(x)Zn1-xS core/shell nanocrystals: core morphology and luminescent property

CdSe cores with rod (an aspect ratio of 1.8, d-5 nm) and spherical (an aspect ratio of 1, d-5 nm) morphologies were fabricated by two kinds of organic approaches through adjusting growth processes. Because of large difference of size and morphology, two kinds of cores revealed different absorption spectra. However, these cores exhibited almost same photoluminescence (PL) spectra with a red-emitting PL peak of around 625 nm. This is ascribed that they have a similar size in diameter. A graded Cd(x)Zn1-xS shell of larger band gap was grown around CdSe rods and spheres using oleic acid as a capping agent. Based on the growth kinetics of CdS and ZnS, interfacial segregation was created to preferentially deposit CdS near the core, providing relaxation of the strain at the core/shell interface. For spherical CdSe cores, the homogeneous deposition of the Cd(x)Zn1-xS shell created spherical core/shell nanocrystals (NCs) with a size of 7.1 nm in diameter. In the case of using CdSe cores with rod morphology, the anisotropic aggregation behaviors of CdS monomers on CdSe rods led to the size (approximately 10 nm in diameter) of spherical CdSe/Cd(x)Zn1-xS core/shell NCs with a small difference to the length of the CdSe rod (approximately 8.9 nm). The resulting spherical core/shell NCs created by the rod and spherical cores exhibited almost same PL peak wavelength (652 and 653 nm for using rod and spherical cores, respectively), high PL efficiency up to 50%, and narrow PL spectra (36 and 28 nm of full with at half maximum of PL spectra for the core/shell NCs with CdSe spheres and rods, respectively). These core/shell NCs provide an opportunity for the study of the evolution of PL properties as the shape of semiconductor NCs.     

Preparation of a ZnS shell on CdSe quantum dots using a single-molecular ZnS precursor

A simple synthetic route to the preparation of a thin ZnS shell on CdSe quantum dot cores from the air-stable, single-molecular precursor zinc diethyldithiocarbamate, Zn(S(2)CNEt(2))(2), in the three-component solvent system octadec-1-ene/oleylamine/tri-n-octylphosphine (ODE/OLA/TOP) is presented. The one-pot synthesis proceeds through heating of the solution of CdSe cores and the amount of crystalline Zn(S(2)CNEt(2))(2) corresponding to a shell thickness of two monolayers of ZnS to 110-120 °C for 1-2 h. The role of the surfactants OLA and TOP and the significance of the temperature and the amount of Zn(S(2)CNEt(2))(2) have been investigated with optical absorption and luminescence spectroscopy. We show that the presence of both OLA and TOP is crucial for the low-temperature growth and that the amount of precursor corresponding to two monolayers of ZnS results in the highest quality of core/shell CdSe/ZnS quantum dots.     

Hydrothermal synthesis and photocatalytic activity of CdO2 nanocrystals

CdO(2) nanocrystals with different sizes were synthesized via the hydrothermal reaction of 3CdSO(4).8H(2)O and H(2)O(2) in 1.25-6.25 vol.% ammonia solutions at 100-140 degrees C for 12h. The resultant products were characterized by powder X-ray diffraction, transmission electron microscope, thermal gravimetric and differential scanning calorimetry, and UV-vis absorption spectra. It was concluded that the resultant products were pure cubic phase CdO(2) nanocrystals, and they would decompose at temperatures higher than 180 degrees C. In addition, degradation of methyl orange in aqueous solution (20.0mg/l) was carried out with the CdO(2) nanocrystals as photocatalyst under ultraviolet light irradiation. The experimental results showed that even a little amount (0.2g) of as-prepared CdO(2) nanocrystals could catalyze degradation of 500 ml methyl orange solution above 99% after 5h of illumination, and smaller size made for higher photocatalytic activity of CdO(2) nanocrystals.     

Colloidal synthesis and air-annealing of CdSe nanorods for the applications in hybrid bulk hetero-junction solar cells

TOP/TOPO-capped CdSe nanorods were synthesized by colloidal route process using hexylphosphonic acid as a ligand and CdO as a Cd precursor, and the influence of thermal annealing in air on the morphology, crystal structure and optical properties of CdSe nanorods has been elucidated by XRD, TEM and PL analysis. It was observed that as-synthesized CdSe nanorods of ∼ 4-5 nm diameters and ∼ 20 nm lengths go through solid state morphology transformation upon annealing at 350 °C in air atmosphere, forming the nanorods with bullet shape with one side pointed and the other side having a blunt hexagon with the average diameter of ∼ 12 nm and length of ∼ 25 nm. The annealed CdSe nanorods showed improved PL emissions without the shift of peak positions, indicating significant improvement of the crystallinity and optoelectronic properties of nanorods caused by reduction of defects.     

Preparation and characterization of CdSe nanoparticles in the presence of Triocytlphosphine as solvent and capping agent

Triocytlphosphine (TOP)-capped CdSe nanoparticles (NPs) have been successfully prepared by the one-pot solution growth method at 240 °C under argon atmosphere. In particular, The TOP used in this process as the single coordinating solvent is favorable for probing capping mechanism of CdSe NPs surface. The growth process and characterization of CdSe NPs were determined by photoluminescence (PL) spectroscopy, X-ray diffraction (XRD), Transmission electron microscopy (TEM), Ultraviolet-visible (UV-Vis) spectroscopy and Fourier transform infrared spectroscopy (FTIR). Results demonstrated the TOP-capped CdSe NPs to be well dispersed and uniform in shape and the diameter of the particle was confined within 8 nm. PL measurement showed the near band-edge luminescence of the final product.     

Study on the photoluminescence character of water-soluble CdSe nanocrystals under ambient conditions

Water soluble, thioglycolic acid (TGA) modified CdSe nanocrystals (NCs) have been prepared in aqueous media by the reaction between Cd2+ and NaHSe. Although initially these quantum dots (QDs) display photoluminescence (PL) with very low quantum yields (QY), upon prolonged exposure to ambient light, a strong PL enhancement by illumination is observed which leads to water soluble QDs with high luminescence. This result may have important application potential in biological or other fields. The primary reason for the luminescence enhancement is concluded to be the incorporation of sulfide ions from TGA into the lattice of CdSe NCs and the subsequent formation of alloy structures. Moreover, the CdSe/CdS core-shell structured QDs synthesized in aqueous solutions also consolidate this conclusion.     

One-pot/three-step synthesis of zinc-blende CdSe/CdS core/shell nanocrystals with thick shells

A one-pot/three-step synthetic scheme was developed for phase-pure epitaxy of CdS shells on zinc-blende CdSe nanocrystals to yield shells with up to sixteen monolayers.The key parameters for the epitaxy were identified,including the core nanocrystal concentration,solvent type/composition,quality of the core nanocrystals,epitaxial growth temperature,type/concentration of ligands,and composition of the precursors.Most of these key parameters were not influential when the synthetic goal was thin-shell CdSe/CdS core/shell nanocrystals.The finalized synthetic scheme was reproducible at an almost quantitative level in terms of the crystal structure,shell thickness,and optical properties.     

Effects of reaction temperature on size and optical properties of CdSe nanocrystals

We report experimental results on the reaction temperature dependence of luminescence properties in size-controlled CdSe nanocrystals. Such reaction temperature dependent property is also sizedependent. The diameter of the CdSe nanocrystals is tuned from 4–11.0 nm by varying the reaction temperatures. The growth process and characterization of CdSe nanocrystals are determined by photoluminescence (PL) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, X-ray photoelectron spectrometry (XPS), X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The influence of reaction conditions on the growth of CdSe nanocrystals demonstrates that low reaction temperature is favourable for the formation of high quality CdSe nanocrystals.     

Facile synthesis of straight and branched CdTe nanowires using CdO as precursor

High-quality colloidal CdTe nanowires (NWs) containing both straight and branched ones were controllably prepared via a solution-based approach, using a low melting Bi nanoparticles as catalysts, CdO and tributylphosphine telluride (TBP-Te) as precursors, and a tri-n-octylphosphine oxide/tri-n-octylphosphine (TOPO/TOP) mixture as solvent. The resulting straight CdTe NWs have typical diameters below 20 nm accompanying with lengths exceeding 10 microm. In the case of branched CdTe NWs, tripod, V-shaped and y-shaped morphologies are obtained by decreasing the apparent Cd/Te molar ratio. It is found that, as the surface capping ligands, di-n-octylphosphinic acid (DOPA) is superior to decylphosphonic acid (DPA) in the reproducible growth of high-quality CdTe NWs. Since highly toxic dimethylcadmium, a cadmium precursor widely used in literatures, is replaced by CdO and the amount of the TOPO/TOP solvent mixture is significantly reduced, a relative safe and economical synthetic approach of high-quality colloidal CdTe NWs with controllable morphology is thus presented.     

Hybrid epitaxial-colloidal semiconductor nanostructures

We present a growth technique which combines wet-chemical growth and molecular beam epitaxy (MBE) to create complex semiconductor nanostructures with nanocrystals as active optical material. The obtained results show that wet-chemically prepared semiconductor nanocrystals can be incorporated in an epitaxally grown crystalline cap layer. As an exemplary system we chose CdSe nanorods and CdSe(ZnS) core-shell nanocrystals in ZnSe and discuss the two limits of thin (d approximately 2R) and thick (d>2R) ZnSe cap layers of thickness d for CdSe nanorods and nanodots of radii R between 2 and 4 nm. In contrast to the strain-induced CdSe/ZnSe Stranski-Krastanow growth of a quantum dot layer in a semiconductor heterostructure, the technique proposed here does not rely on strain and thus results in additional degrees of freedom for choosing composition, concentration, shape, and size of the nanocrystals. Transmission electron microscopy and X-ray diffractometry show that the ZnSe cap layer is of high crystalline quality and provides all parameters for a consecutive growth of Bragg structures, waveguides, or diode structures for electrical injection.     

Synthesis, morphology, and optical properties of colloidal CdTe/CdSe and CdTe/CdS nanoheterostructures based on CdTe tetrapods

We report the synthesis of colloidal CdTe/CdSe and CdTe/CdS nanoheterostructures based on CdTe tetrapods with a CdSe or CdS shell. The shell growth takes place on the lateral faces of the tetrapod legs, whereas the leg length remains essentially unchanged. Both the CdSe and CdS shell growth shifts the luminescence of the nanoheterostructures to the near-IR range, up to 850 nm, with a quantum yield of up to 20%. Analysis of the kinetics of the shift of the excitonic absorption band during nanoheterostructure growth suggests that the growth rate of CdS exceeds that of CdSe. The variation of the luminescence wavelength with shell thickness is compared to numerical modeling results.     

Highly Stable,Near‐Unity Efficiency Atomically Flat Semiconductor Nanocrystals of CdSe/ZnS Hetero‐Nanoplatelets Enabled by ZnS‐Shell Hot‐Injection Growth

Colloidal semiconductor nanoplatelets (NPLs) offer important benefits in nanocrystal optoelectronics with their unique excitonic properties. For NPLs, colloidal atomic layer deposition (c‐ALD) provides the ability to produce their core/shell heterostructures. However, as c‐ALD takes place at room temperature, this technique allows for only limited stability and low quantum yield. Here, highly stable, near‐unity efficiency CdSe/ZnS NPLs are shown using hot‐injection (HI) shell growth performed at 573 K, enabling routinely reproducible quantum yields up to 98%. These CdSe/ZnS HI‐shell hetero‐NPLs fully recover their initial photoluminescence (PL) intensity in solution after a heating cycle from 300 to 525 K under inert gas atmosphere, and their solid films exhibit 100% recovery of their initial PL intensity after a heating cycle up to 400 K under ambient atmosphere, by far outperforming the control group of c‐ALD shell‐coated CdSe/ZnS NPLs, which can sustain only 20% of their PL. In optical gain measurements, these core/HI‐shell NPLs exhibit ultralow gain thresholds reaching ≈7 µJ cm^?2. Despite being annealed at 500 K, these ZnS‐HI‐shell NPLs possess low gain thresholds as small as 25 µJ cm^?2. These findings indicate that the proposed 573 K HI‐shell‐grown CdSe/ZnS NPLs hold great promise for extraordinarily high performance in nanocrystal optoelectronics.