1120-46-3Relevant academic research and scientific papers
Control of PbSe nanorod aspect ratio by limiting phosphine hydrolysis
Boercker, Janice E.,Foos, Edward E.,Placencia, Diogenes,Tischler, Joseph G.
, p. 15071 - 15076 (2013)
The aspect ratio and yield of PbSe nanorods synthesized by the reaction of Pb-oleate with tris(diethylamino)phosphine selenide are highly sensitive to the presence of water, making it critical to control the amount of water present in the reaction. By car
Structural characterization of self-assembled multifunctional binary nanoparticle superlattices
Shevchenko, Elena V.,Talapin, Dmitri V.,Murray, Christopher B.,O'Brien, Stephen
, p. 3620 - 3637 (2006)
Nanocrystals of different size and functionality (e.g., noble metals, semiconductors, oxides, magnetic alloys) can be induced to self-assemble into ordered binary superlattices (also known as opals or colloidal crystals), retaining the size tunable properties of their constituents. We have built a variety of binary superlattices from monodisperse PbS, PbSe, CoPt3, Fe2O3, Au, Ag, and Pd nanocrystals, mixing and matching these nanoscale building blocks to yield multifunctional nanocomposites (metamaterials). Superlattices with AB, AB2, AB3, AB 4, AB5, AB6, and AB13 stoichiometry with cubic, hexagonal, tetragonal, and orthorhombic symmetries have been identified. Assemblies with the same stoichiometry can be produced in several polymorphous forms by tailoring the particle size and deposition conditions. We have identified arrays isostructural with NaCl, CuAu, AlB2, MgZn 2, MgNi2, Cu3Au, Fe4C, CaCu 5, CaB6, NaZn13, and cub-AB13 compounds emphasizing the parallels between nanoparticle assembly and atomic scale crystal growth and providing confidence that many more structures will follow. Recently, we have demonstrated that electrical charges on sterically stabilized nanoparticles in addition to such parameters as particle size ratio and their concentrations can provide the formation of a much broader pallet of binary nanoparticle superlattices as compared with the limited number of possible superlattices formed by hard noninteracting spheres. In this contribution, we demonstrate a large variety of different binary superlattices, provide their detailed structural characterization, and discuss the role of energetic and kinetic factors in the cocrystallization process. We found that Coulomb, van der Waals, charge-dipole, dipole-dipole, and other interactions can contribute equally to cocrystallization, allowing superlattice formation to be dependent on a number of tunable parameters. We present binary superlattices as a new class of materials with a potentially unlimited library of constituents over a wide range of tunable structures.
Colloidal Nanocrystals as a Platform for Rapid Screening of Charge Trap Passivating Molecules for Metal Halide Perovskite Thin Films
Alpert, Matthew R.,Niezgoda, J. Scott,Chen, Alexander Z.,Foley, Benjamin J.,Cuthriell, Shelby,Yoon, Lucy U.,Choi, Joshua J.
, p. 4515 - 4526 (2018)
Charge recombination at surface trap sites is a significant impediment to metal halide perovskite (MHP) thin film-based optoelectronic devices. To passivate the surface charge traps, chemical treatments with molecules that bind to the MHP thin film surfaces can be employed. However, the current approaches to test the trap passivation efficacy of molecules on thin film surface suffer from limited through-put and low statistical significance. Here, we demonstrate the use of colloidal MHP nanocrystals (NCs) as an experimental platform for high-throughput screening of charge trap passivating molecules for MHP thin films. Using CsPbX3 (X = Br, I) NCs, over 20 molecules were rapidly screened for their surface trap passivation efficacy. Our approach identified trin-butylphosphine (TBPh) as a superb charge trap passivating molecule on MHP surfaces. TBPh treatment brings the photoluminescence quantum yield of CsPbBr3 NCs to near unity and also results in superior surface trap passivation of MHP thin films, even when compared to a previously reported treatment with pyridine. Our work highlights the benefits of utilizing the high surface area-to-volume ratio of NCs for the accelerated study of surface trap passivation using molecular treatment and then translating the findings to bulk semiconductors. This approach is broadly applicable to a wide range of semiconductors as long as they can be synthesized into NCs.
Role of organosulfur compounds in the growth and final surface chemistry of PbS quantum dots
McPhail, Martin R.,Weiss, Emily A.
, p. 3377 - 3384 (2014)
This paper describes the mechanism by which reaction of sulfur with 1-octadecene (ODE) induces a change in the shape of PbS quantum dots (QDs), synthesized from the S/ODE precursor and lead(II) oleate, from cubic to hexapodal by altering the ligand chemistry of the growing QDs. 1H NMR and optical spectroscopies indicate that extended heating of sulfur and ODE at 180 °C produces a series of organosulfur compounds with optical transitions in the visible region and that the binding of organosulfur ligands to the growing QD induces a preferential growth at the 100 faces (over the 111 faces) and, therefore, a hexapodal geometry for the particles. The study shows that S/ODE can be made a more reliable precursor by reducing the temperature and duration of the sulfur dissolution step and that any metal sulfide QD synthesis using elemental sulfur heated to high temperatures should take steps to reduce the in situ yield of organosulfur byproducts by avoiding olefinic solvents.
Steric-hindrance-driven shape transition in PbS quantum dots: Understanding size-dependent stability
Choi, Hyekyoung,Ko, Jae-Hyeon,Kim, Yong-Hyun,Jeong, Sohee
, p. 5278 - 5281 (2013)
Ambient stability of colloidal nanocrystal quantum dots (QDs) is imperative for low-cost, high-efficiency QD photovoltaics. We synthesized air-stable, ultrasmall PbS QDs with diameter (D) down to 1.5 nm, and found an abrupt transition at D ≈ 4 nm in the a
Simultaneous ligand and cation exchange in PbSe/CdSe nanocrystal films
Treml,Yang,Wise,Hanrath
, p. 69 - 74 (2016)
Trap states formed at the surface of colloidal semiconductor nanocrystals can have deleterious impact on performance in emerging optoelectronic applications. To mitigate surface traps in nanocrystal thin films we investigated simultaneous surface passivation and ligand exchange for PbSe nanocrystal films via treatment with a cadmium acetate solution. We show that a kinetically limited surface cation exchange produces a thin CdxPb1 -xSe shell that effectively passivates the nanocrystal surface as confirmed by increased photoluminescence intensity and photoluminescence lifetime. Ligand exchange to acetate ligands is confirmed via Fourier transform infrared spectroscopy and grazing incidence small angle X-ray scattering. We studied the impact of the cadmium acetate treatment on interparticle coupling and found that the reduced interparticle spacing and limited shell thickness leads to increased F?rster resonant energy transfer in nanocrystal films. Simultaneous cation/ligand exchange enables the production of heterostructured nanocrystal films with properties like Quasi-Type II nanocrystals synthesized in solution.
Quantum confinement-tunable ultrafast charge transfer at the PbS quantum dot and phenyl-C61-butyric acid methyl ester interface
El-Ballouli, Alaa O.,Alarousu, Erkki,Bernardi, Marco,Aly, Shawkat M.,Lagrow, Alec P.,Bakr, Osman M.,Mohammed, Omar F.
, p. 6952 - 6959 (2014)
Quantum dot (QD) solar cells have emerged as promising low-cost alternatives to existing photovoltaic technologies. Here, we investigate charge transfer and separation at PbS QDs and phenyl-C61-butyric acid methyl ester (PCBM) interfaces using a combination of femtosecond broadband transient absorption (TA) spectroscopy and steady-state photoluminescence quenching measurements. We analyzed ultrafast electron injection and charge separation at PbS QD/PCBM interfaces for four different QD sizes and as a function of PCBM concentration. The results reveal that the energy band alignment, tuned by the quantum size effect, is the key element for efficient electron injection and charge separation processes. More specifically, the steady-state and time-resolved data demonstrate that only small-sized PbS QDs with a bandgap larger than 1 eV can transfer electrons to PCBM upon light absorption. We show that these trends result from the formation of a type-II interface band alignment, as a consequence of the size distribution of the QDs. Transient absorption data indicate that electron injection from photoexcited PbS QDs to PCBM occurs within our temporal resolution of 120 fs for QDs with bandgaps that achieve type-II alignment, while virtually all signals observed in smaller bandgap QD samples result from large bandgap outliers in the size distribution. Taken together, our results clearly demonstrate that charge transfer rates at QD interfaces can be tuned by several orders of magnitude by engineering the QD size distribution. The work presented here will advance both the design and the understanding of QD interfaces for solar energy conversion.
3D assembly of all-inorganic colloidal nanocrystals into gels and aerogels
Sayevich, Vladimir,Cai, Bin,Benad, Albrecht,Haubold, Danny,Sonntag, Luisa,Gaponik, Nikolai,Lesnyak, Vladimir,Eychmüller, Alexander
, p. 6334 - 6338 (2016)
We report an efficient approach to assemble a variety of electrostatically stabilized all-inorganic semiconductor nanocrystals (NCs) by their linking with appropriate ions into multibranched gel networks. These all-inorganic non-ordered 3D assemblies benefit from strong interparticle coupling, which facilitates charge transport between the NCs with diverse morphologies, compositions, sizes, and functional capping ligands. Moreover, the resulting dry gels (aerogels) are highly porous monolithic structures, which preserve the quantum confinement of their building blocks. The inorganic semiconductor aerogel made of 4.5 nm CdSe colloidal NCs capped with I- ions and bridged with Cd2+ ions had a large surface area of 146 m2 g-1. An assembly approach for a variety of electrostatically stabilized all-inorganic semiconductor nanocrystals is based on their linking with appropriate ions into multibranched gel networks. The resulting aerogels are highly porous monolithic structures, which preserve the quantum confinement of their building blocks.
Spontaneous multielectron transfer from the surfaces of PbS quantum dots to tetracyanoquinodimethane
Knowles, Kathryn E.,Malicki, Michal,Parameswaran, Radha,Cass, Laura C.,Weiss, Emily A.
, p. 7264 - 7271 (2013)
This paper describes an investigation of the interfacial chemistry that enables formation of a multielectron ground-state charge-transfer (CT) complex of oleate-coated PbS quantum dots (QDs) and tetracyanoquinodimethane (TCNQ) in CHCl3 dispersions. Thermodynamically spontaneous electron transfer occurs from sulfur ions on the surfaces of the QDs (radius = 1.6 nm) to adsorbed TCNQ molecules and creates indefinitely stable ion pairs that are characterized by steady-state visible and mid-infrared absorption spectroscopy of reduced TCNQ and by NMR spectroscopy of the protons of oleate ligands that coat the QDs. The combination of these techniques shows that (i) each QD reduces an average of 4.5 TCNQ molecules, (ii) every electron transfer event between the QD and TCNQ occurs at the QD surface, (iii) sulfur ions on the surfaces of the QDs (and not delocalized states within the QDs) are the electron donors, and (iv) some TCNQ molecules adsorb directly to the surface of the QDs while others adsorb upon displacement of oleate ligands.
Two-phase approach to high-quality, oil-soluble, near-infrared-emitting PbS quantum dots by using various water-soluble anion precursors
Deng, Dawei,Cao, Jie,Xia, Junfei,Qian, Zhiyu,Gu, Yueqing,Gu, Zhongze,Akers, Walter John
, p. 2422 - 2432 (2011)
Colloidal PbS quantum dots (QDs) with tunable photoemission throughout the near-infrared (NIR) region (ca. 750-1000 nm) were synthesized by a two-phase approach. Here, oil-soluble lead oleate formed by a reaction of lead acetate and oleic acid (OA, the capping agent) in n-decane at 130 °C was used as lead precursor, and water-soluble Na2S, thioacetamide (TAA), and thiourea, each having a different reactivity, were used as sulfur sources. When an n-decane solution of lead precursor and an aqueous solution of sulfur precursor were mixed at the appointed temperature, oil-soluble, near-infrared-emitting PbS QDs were achieved. In this study, we investigated the influence of the reactivity of water-soluble sulfur sources on the synthesis of PbS QDs. The morphology and crystal structure of the as-prepared PbS QDs were characterized by (high-resolution) transmission electron microscopy (TEM), selected area electron diffraction (SAED), and X-ray diffraction (XRD).
