Low-temperature noninjection approach to homogeneously-alloyed PbSe(x)S(1-x) colloidal nanocrystals for photovoltaic applications

Homogeneously alloyed PbSe(x)S(1-x) nanocrystals (NCs) with their excitonic absorption peaks in wavelength shorter than 1200 nm were developed for photovoltaic (PV) applications. Schottky-type solar cells fabricated with our PbSe?.?S?.? NCs as their active materials reached a high power conversion efficiency (PCE) of 3.44%, with an open circuit voltage (V(oc)) of 0.49 V, short circuit photocurrent (J(sc)) of 13.09 mA/cm2, and fill factor (FF) of 0.54 under Air Mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm2. The syntheses of the small-sized colloidal PbSe(x)S(1-x) NCs were carried out at low temperature (60 °C) with long growth periods (such as 45 min) via a one-pot noninjection-based approach in 1-octadecene (ODE), featuring high reaction yield, high product quality, and high synthetic reproducibility. This low-temperature approach employed Pb(oleate)? as a Pb precursor and air-stable low-cost thioacetamide (TAA) as a S source instead of air-sensitive high-cost bis(trimethylsilyl)sulfide ((TMS)?S), with n-tributylphosphine selenide (TBPSe) as a Se precursor instead of n-trioctylphosphine selenide (TOPSe). The reactivity difference of TOPSe made from commercial TOP 90% and TBPSe made from commercial TBP 97% and TBP 99% was addressed with in situ observation of the temporal evolution of NC absorption and with 31P nuclear magnetic resonance (NMR). Furthermore, the addition of a strong reducing/nucleation agent diphenylphosphine (DPP) promoted the reactivity of the Pb precursor through the formation of a Pb-P complex, which is much more reactive than Pb(oleate)?. Thus, the reactivity of TBPSe was increased more than that of TAA. The larger the DPP-to-Pb feed molar ratio, the more the Pb-P complex, the higher the Se amount in the resulting homogeneously alloyed PbSe(x)S(1-x) NCs. Therefore, the use of DPP allowed reactivity match of the Se and S precursors and led to sizable nucleation at low temperature so that long growth periods became feasible. The present study brings insight into the formation mechanism of monomers, nucleation/growth of colloidal composition-tunable NCs, and materials design and synthesis for next-generation low-cost and high-efficiency solar cells.     

Synthesis of nano-sized PbSe from octeno-1,2,3-selenadiazole

Reaction between trioctylphosphine selenide (TOPSe), generated from an organo-selenium compound, i.e. octeno-1,2,3-selenadiazole in tri-octylphosphine (TOP), and lead acetate has resulted formation of PbSe nano-crystals (cubes). TOPSe generated from the current method is first of its kind approach and is a novel concept. Characteristic absorption bands between 1.8-2.1 μm in near infra-red spectrum (NIR) are observed from sonicated PbSe crystals. X-ray diffraction (XRD) pattern revealed rock-salt crystal structure of PbSe with crystallite size of less than 10 nm. Observations made by scanning electron microscopy (SEM) revealed well-defined particles of the cubical crystals. XPS analysis showed that nano-crystals of PbSe were prone to air-oxidation due to ‘not-so-efficient’ capping.     

Raman scattering for the size of CdSe and CdS nanocrystals and comparison with other techniques

The sizes of the ensembles of CdSe regular nanocrystals (RNCs), CdSe magic-sized nanocrystals (MSNCs), and CdS RNCs were investigated by Raman scattering. The nanocrystal ensembles were synthesized via wet-chemistry approaches. The size distribution increases from CdSe MSNCs (2.26 nm), to CdSe RNCs (3.52 nm), and to CdS RNCs (3-8 nm and 4-10 nm). The sizes derived from Raman spectra are compared with those from other characterization tools such as UV/vis spectroscopy and transmission electron microscopy (TEM). The present study suggests that Raman scattering is an alternative and reliable technique for the determination of nanocrystal size and size distribution.     

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.     

CdSe Magic-Sized Nuclei,Magic-Sized Nanoclusters and Regular Nanocrystals: Monomer Effects on Nucleation and Growth

Colloidal semiconductor quantum dots (QDs) have been well appreciated for their potential in nanophotonics with an unprecedented impact in various areas, including light emitting diodes (LEDs) and solar cells. There is an outstanding demand on the control of size and size distribution for the various applications, with rational design supported by fundamental understanding of nucleation and growth. This Research News introduces recent advances in the synthesis of colloidal CdSe magic-sized nuclei (MSN) exhibiting sharp bandgap emission, with a model proposed to illustrate the nature of monomers and their degree of supersaturation (DS) affecting the formation of various CdSe MSN, magic-sized nanoclusters (MSCs), and regular nanocrystals (RNCs). Also, this model addresses tuning the CdSe RNCs into the CdSe MSN with the presence of cadmium acetate (Cd(OAc)₂) affecting the nature of the monomers.     

Low-temperature approach to high-yield and reproducible syntheses of high-quality small-sized PbSe colloidal nanocrystals for photovoltaic applications

Small-sized PbSe nanocrystals (NCs) were synthesized at low temperature such as 50-80 °C with high reaction yield (up to 100%), high quality, and high synthetic reproducibility, via a noninjection-based one-pot approach. These small-sized PbSe NCs with their first excitonic absorption in wavelength shorter than 1200 nm (corresponding to size < ～3.7 nm) were developed for photovoltaic applications requiring a large quantity of materials. These colloidal PbSe NCs, also called quantum dots, are high-quality, in terms of narrow size distribution with a typical standard deviation of ～7-9%, excellent optical properties with high quantum yield of ～50-90% and small full width at half-maximum of ～130-150 nm of their band-gap photoemission peaks, and high storage stability. Our synthetic design aimed at promotion of the formation of PbSe monomers for fast and sizable nucleation with the presence of a large number of nuclei at low temperature. For formation of the PbSe monomer, our low-temperature approach suggests the existence of two pathways of Pb-Se (route a) and Pb-P (route b) complexes. Either pathway may dominate, depending on the method used and its experimental conditions. Experimentally, a reducing/nucleation agent, diphenylphosphine, was added to enhance route b. The present study addresses two challenging issues in the NC community, the monomer formation mechanism and the reproducible syntheses of small-sized NCs with high yield and high quality and large-scale capability, bringing insight to the fundamental understanding of optimization of the NC yield and quality via control of the precursor complex reactivity and thus nucleation/growth. Such advances in colloidal science should, in turn, promote the development of next-generation low-cost and high-efficiency solar cells. Schottky-type solar cells using our PbSe NCs as the active material have achieved the highest power conversion efficiency of 2.82%, in comparison with the same type of solar cells using other PbSe NCs, under Air Mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm(2).     

Sequential synthesis of type II colloidal CdTe/CdSe core-shell nanocrystals

Colloidal type II CdTe/CdSe nanocrystals were synthesized by sequential addition of a tri-n-octylphosphine telluride (TOPTe)/TOP solution and several shell-precursor solutions to a CdO/TOP solution; the shell-precursor solutions consisted of CdO and TOPSe in TOP. For the growth of the CdTe core, the TOPTe/TOP solution was swiftly added to the CdO/TOP solution at a higher temperature (300 degrees C) than the growth temperature (250 degrees C). For the growth of the CdSe shell, in contrast, the CdO/TOPSe/TOP solution was slowly added to the CdTe/TOP solution at a lower temperature than the growth temperature (200-240 degrees C). The temporal evolution of the optical properties of the growing core-shell nanocrystals was monitored in detail. During the growth of the CdSe shell, the core-shell nanocrystals exhibited interesting changes in photoluminescence (PL) properties. The highest PL efficiency (approximately 38 %) was detected from core-shell nanocrystals with a CdSe shell thickness of 0.4-0.5 nm (indicated by TEM); the formation of the first monolayer is proposed. Our synthetic approach is well suited to a practical realization of engineering materials with bandgaps in the near-IR and IR spectral ranges.     

Nanocrystals of PbSe core, PbSe/PbS, and PbSe/PbSxS(1-x) core/shell as saturable absorbers in passively Q-switched near-infrared lasers

The saturable optical absorption properties of PbSe core nanocrystals (NCs), and their corresponding PbSe/PbScore/shell and PbSe/PbSexS(1-x) core/alloyed-shell NCs, were examined at lambda = 1.54 microm. Saturation intensities of approximately 100 MW/cm2 were obtained. The NCs act as passive Q switches in near-infrared pulsed lasers. Q-switched output pulse energies up to 3 mJ, with a pulse duration of 40-55 ns were demonstrated. Analysis of the optical transmission versus pulse light intensity was carried out according to a model that includes ground-state as well as excited-state absorption. For pulses approximately 10 ns long, the NCs act as fast saturable absorbers. The theoretical fits yield a ground-state absorption cross section of 10-16-10-15 cm2, an excited-state absorption cross section of sigma(es) is congruent to 10(-16) cm2, and an effective lifetime of tau(eff) is congruent to 5 x 10(-12) s.     

A mild phosphine-free synthesis of alkylamine-capped CdSe nanocrystals

A new phosphine-free approach has been developed to synthesize high-quality cadmium selenide (CdSe) nanocrystals with cubic zinc-blende structure, by using the highly reactive selenium (Se) precursor at milder temperature than that used in the traditional phosphine route. This Se precursor was obtained from the reduction of Se powder by sodium borohydride in N,N-dimetbylformamide, in the absence of phosphine. Without the addition of other long-chain coordinating substances in this approach, the alkylamines such as dodecylamine (DDA) and octylamine (OA) were used as reaction solvents, and they also acted as surface capping reagents to produce DDA-capped and OA-capped CdSe NCs, respectively. The rapid nucleation and slow growth were observed by ultraviolet-visible absorption spectrum. The resulting OA-capped CdSe NCs grew faster compared with DDA-capped CdSe NCs under the same other conditions. These as-synthesized CdSe nanocrystals showed relatively narrow size distribution and high photoluminescence quantum efficiency (up to 9.4% for OA-capped CdSe NCs). This mild approach is low cost, relatively low danger and high production yield (approximately 80%), indicating that it is very effective for the phosphine-free synthesis of alkylamine-capped CdSe nanocrystals.     

Facile synthesis of CdSe nanocrystals for bulk-heterojunction solar cells

Oleic acid (OA)-capped cadmium selenide (CdSe) nanocrystals (NCs) have been synthesized via a new high-scale route. X-ray diffraction and transmission electron microscopy confirmed that rod-like hexagonal (wurtzite) CdSe NCs with an average size of 10 nm were obtained via this new route. The obtained CdSe NCs were treated individually with pyridine and tert-butylamine (t-BA) for ligand exchange. Fourier transform infrared spectra of the as-synthesized and treated CdSe NCs confirmed the removal of OA ligands from the surface of CdSe NCs after treatments with pyridine and t-BA. Bulk-heterojunction (BHJ) solar cell devices were prepared using untreated and surface treated CdSe NCs blended with poly (3-hexylthiophene-2,5-diyl) (P3HT) polymer. BHJ solar cell devices made from P3HT:(surface treated CdSe NCs) blends showed greater improvement in photovoltaic performances compared to P3HT:(untreated CdSe NCs) blend. The improvement in photovoltaic performances was due to the increase of electron mobility in P3HT:(CdSe NCs) blends after surface treatment of CdSe NCs.     

Lead selenide nanowire growth by vapor-liquid-solid mechanism under mask during plasma processing

Data on the formation of lead selenide (PbSe) nanowires under a stencil mask during the processing of epitaxial PbSe films in high-density inductively coupled plasma (ICP) of low-pressure argon RF discharge are presented. The nanowires were studied by high-resolution scanning electron microscopy and energy-dispersive X-ray spectroscopy. A physical model is proposed that explains the local formation of PbSe nanowires in terms of their catalytic growth according to the vapor-liquid-solid mechanism.     

Ultrabright PbSe magic-sized clusters

We present the synthesis and characterization of novel, ultrasmall PbSe magic-sized nanoclusters (MSCs). Unlike the syntheses of high-quality semiconductor nanoparticles, the MSC synthesis is straightforward, occurring at room temperature in air over several hours. MSCs have core diameters <2 nm and fluoresce in the near-infrared (900 nm) with remarkable quantum efficiencies consistently greater than 50%. The relatively slow growth of MSCs allows for a significant scale up of reaction volumes. Transfer to aqueous solvents has also been demonstrated, establishing MSCs as a potential new fluorophore for applications in biological imaging.     

Hydrothermal synthesis of cuboidal PbSe microcrystals via an EDTA reduction route

Cuboidal lead selenide (PbSe) microcrystals have been successfully synthesized via a novel EDTA reduction route in which EDTA molecules serve as both chelating reagent and reductant. Hereafter EDTA is the abbreviation for ethylenediaminetetraacetic acid tetrasodium salt dihydrate (C₁₀H₁₂N₂Na₄O₈·2H₂O). The unique cuboidal PbSe microcrystals have eight symmetric arms along the < 111> directions. The edge of a cuboidal PbSe microcrystal extends outwards from its core with a tiny cubic center leaving step-like faces. The whole synthetic system provides an appropriate crystal growth environment for the formation of these microcrystals. Furthermore cuboidal PbSe microcrystals with different concave faces can be obtained at different reaction stages.     

Doping effect on the kinetics and mechanism of thermal oxidation of polycrystalline PbSe layers

We have shown that the thermal oxidation (473–773 K) of polycrystalline lead selenide layers, undoped and doped with bismuth, cadmium, tin, and chlorine, has similar effects on their electrical properties, microstructure, and phase composition. The rate of oxygen diffusion and the formation kinetics of oxide phases depend on the nature and concentration of donors in the as-deposited layers; with decreasing doping level, oxygen diffuses more rapidly. In contrast to the diffusional mechanism of oxygen incorporation and gradual micro-structural changes in undoped and PbSe〈Bi〉 layers, iodine doping gives rise to drastic structural changes, including encapsulation of PbSe grains, which are accompanied by the formation of lead oxyselenites and almost instantaneous oxygen incorporation into the surface layer of the PbSe crystallites. Moreover, iodine is shown to catalyze the formation of dielectric oxide phases, reducing the temperature of this process and resulting in high photosensitivity compared to undoped PbSe layers.     

室温生物诱导合成硒化铅纳米半导体

以醋酸铅和硒代硫酸钠作为反应物, 蛋壳薄膜作为生物活性载体, 设计一种在生物活性材料参与下室温原位合成硒化铅纳米团簇的新方法. 利用蛋膜上特定周期性分布的大分子与无机前驱体离子之间的螯合作用和电荷作用, 引导和控制硒化铅微晶在蛋膜载体上的形成、聚集和分布, 成功制得结晶完善且在蛋膜上均匀分布的具有规则形状的硒化铅纳米团簇. 紫外-可见光谱和荧光光谱分析表明所制备的硒化铅纳米粒子具有均匀的小尺寸, 表现为明显的量子尺寸效应.     

Effects of 1,9-dibromnonane on the structural,photophysical properties and stability of cesium lead bromide perovskite nanocrystals

The CsPbBr_3@Cs_4PbBr_6 nanocrystals(NCs) could be synthesized by multiple Cs-oleate injections as adding the 1,9-dibromnonane in the reaction solution. The 1,9-dibromnonane could provide Br-ions and the rich Br-ions effectively restrain the generation of Cs Br. The Cs_4 PbBr_6 wrapped around the Cs Pb Br_3 NCs and the size of crystalline grain was increased with increasing the Cs-oleate as excess oleylamine. The quantum yield for 14 S4 DN reached to 99.3% due to the decrease of defects and the surface passivation of Cs_4 PbBr_6. There are more oleylammonium bromide on the surface of Cs Pb Br_3 NCs as synthesized with1,9-dibromnonane. The ligand shell and the surface passivation of Cs_4 PbBr_6 restrained the decomposition of surface, consequently improved the stability of moisture and light for Cs Pb Br_3 NCs. When the CsPbBr_3@Cs_4PbBr_6 NCs were immersed in water under UV light(365 nm) for 2 h, the PL intensity could retain 90.4%, while the 11 S1(traditional Cs Pb Br_3 NCs) was only 10.9%. It indicated the stability of moisture and light for Cs Pb Br_3 NCs were greatly improved, because Cs_4 PbBr_6 NCs effectively passivated the surface of Cs Pb Br_3 NCs and restrained the generation of traps states.     

Lead Selenide (PbSe) Colloidal Quantum Dot Solar Cells with >10% Efficiency

Low‐cost solution‐processed lead chalcogenide colloidal quantum dots (CQDs) have garnered great attention in photovoltaic (PV) applications. In particular, lead selenide (PbSe) CQDs are regarded as attractive active absorbers in solar cells due to their high multiple‐exciton generation and large exciton Bohr radius. However, their low air stability and occurrence of traps/defects during film formation restrict their further development. Air‐stable PbSe CQDs are first synthesized through a cation exchange technique, followed by a solution‐phase ligand exchange approach, and finally absorber films are prepared using a one‐step spin‐coating method. The best PV device fabricated using PbSe CQD inks exhibits a reproducible power conversion efficiency of 10.68%, 16% higher than the previous efficiency record (9.2%). Moreover, the device displays remarkably 40‐day storage and 8 h illuminating stability. This novel strategy could provide an alternative route toward the use of PbSe CQDs in low‐cost and high‐performance infrared optoelectronic devices, such as infrared photodetectors and multijunction solar cells.     

A New Passivation Route Leading to Over 8% Efficient PbSe Quantum‐Dot Solar Cells via Direct Ion Exchange with Perovskite Nanocrystals

Colloidal quantum dots (QDs) are promising candidate materials for photovoltaics (PV) owing to the tunable bandgap and low‐cost solution processability. Lead selenide (PbSe) QDs are particularly attractive to PV applications due to the efficient multiple‐exciton generation and carrier transportation. However, surface defects arising from the oxidation of the PbSe QDs have been the major limitation for their development in PV. Here, a new passivation method for chlorinated PbSe QDs via ion exchange with cesium lead halide (Br, I) perovskite nanocrystals is reported. The surface chloride ions on the as‐synthesized QDs can be partially exchanged with bromide or iodide ions from the perovskite nanocrystals, hence forming a hybrid halide passivation. Consistent with the improved photoluminescence quantum yield, the champion PV device fabricated with these PbSe QDs achieves a PCE of 8.2%, compared to 7.3% of that fabricated with the untreated QDs. This new method also leads to devices with excellent air‐stability, retaining at least 93% of their initial PCEs after being stored in ambient conditions for 57 d. This is considered as the first reported PbSe QD solar cell with a PCE of over 8% to date.     

Optical properties and luminescence dynamics of Eu3+-doped terbium orthophosphate nanophosphors

The development of luminescent inorganic nanocrystals (NCs) doped with rare-earth (RE) ions has attracted increasing interest owing to their distinct optical properties and versatile applications in time-resolved bioassays, multiplex biodetection, DNA hybridization and bioimaging. Hexagonal TbPO4:Eu3+ NCs (10-30 nm) were synthesized via a facile hydrothermal method assisted with oleic acid (OA) surfactants, which exhibit tunable emissions from green to red by varying the concentration of Eu3+. The Tb3+-to-Eu3+ energy transfer efficiency observed reaches up to 94%. Different from their bulk counterparts, a new interface-state band (316 nm) in addition to the commonly observed spin-forbidden 4f-5d transition band (265 nm) of Tb3+ was found to be dominant in the excitation spectrum of NCs due presumably to the formation of surface TbPO4/OA complexes, which provides an additional excitation antenna in practical utilization. Two kinds of luminescence sites of Eu3+ in TbPO4 NCs, with the site symmetry of C2 or C1, were identified based on the emission spectra at 10 K and room temperature. Furthermore, the photoluminescence (PL) dynamics of Tb3+ ions in pure TbPO4 NCs have been revealed. Compared to the exponential PL decay in bulk counterparts induced by very fast energy migration, the non-exponential decay from 5D4 of Tb3+ in TbPO4 NCs is mainly attributed to the diffusion-limited energy migration due to more rapid energy transfer from Tb3+ to defects than the energy migration among Tb3+.