Stability of Cs2NaBiBr6 and Cs2NaBiCl6.

Bismuth-based halide perovskites are nontoxic alternatives to widely studied lead-based perovskites for optoelectronic applications. Here, we synthesized Cs2NaBiCl6 thin films and attempted to synthesize Cs2NaBiBr6 using physical vapor deposition. While Cs2NaBiCl6 forms a stable cubic structure with a 3.4 eV band gap and could be synthesized successfully, Cs2NaBiBr6 does not form and is unstable with respect to dissociation into Cs3-xNaxBi2Br9 and Cs3-xNaxBiBr6. Furthermore, the close X-ray diffraction patterns of Cs3-xNaxBi2Br9 and Cs2NaBiBr6 raise doubts about the previous reports of the latter's formation based on X-ray diffraction alone.

Controlled p-Type Doping of Pyrite FeS2.

Pyrite FeS2 has extraordinary potential as a low-cost, nontoxic, sustainable photovoltaic but has underperformed dramatically in prior solar cells. The latter devices focus on heterojunction designs, which are now understood to suffer from problems associated with FeS2 surfaces. Simpler homojunction cells thus become appealing but have not been fabricated due to the historical inability to understand and control doping in pyrite. While recent advances have put S-vacancy and Co-based n-doping of FeS2 on a firm footing, unequivocal evidence for bulk p-doping remains elusive. Here, we demonstrate the first unambiguous and controlled p-type transport in FeS2 single crystals doped with phosphorus (P) during chemical vapor transport growth. P doping is found to be possible up to at least ∼100 ppm, inducing ∼1018 holes/cm3 at 300 K, while leaving the crystal structure and quality unchanged. As the P doping is increased in crystals natively n-doped with S vacancies, the majority carrier type inverts from n to p near ∼25 and ∼55 ppm P, as detected by Seebeck and Hall effects, respectively. Detailed temperature- and P-doping-dependent transport measurements establish that the P acceptor level is 175 ± 10 meV above the valence band maximum, explain details of the carrier inversion, elucidate the relative mobility of electrons and holes, reveal mid-gap defect levels, and unambiguously establish that the inversion to p-type occurs in the bulk and is not an artifact of hopping conduction. Such controlled bulk p-doping opens the door to pyrite p-n homojunctions, unveiling new opportunities for solar cells based on this extraordinary semiconductor.

Transformations and Environmental Impacts of Copper Zinc Tin Sulfide Nanoparticles and Thin Films.

Quaternary chalcogenide copper zinc tin sulfide (CZTS) nanoparticles are used to make the p-type absorber layer in CZTS solar cells, which are considered more benign alternatives to those based on cadmium telluride (CdTe) and less expensive than copper indium gallium selenide. CZTS has an ideal band gap and a high absorption coefficient for solar radiation, making the nanoparticles an attractive option for photovoltaic cells. In this work, we explore the toxicity of CZTS nanoparticles using an environmentally relevant bacterial model Shewanella oneidensis MR-1. This study also focuses on understanding the stability of CZTS-based thin films and their direct interaction with bacterial cells. Bacterial cell viability, stability of nanoparticles and thin films, as well as mechanisms of toxicity were evaluated using various analytical tools. The CZTS nanoparticle suspensions show significant acute toxic effects on bacterial cells, but long-term (72 h) exposure of bacterial cells to CZTS-based thin films (made from nanoparticles) do not exhibit similar detrimental impacts on bacterial viability. This result is compelling because it suggests that CZTS nanomaterials will have minimal unintended toxicity as long as they are incorporated into a stable film structure.

Stability of the Halide Double Perovskite Cs2AgInBr6.

Cs2AgInBr6 is among the lead-free halide perovskites of interest, predicted by first-principles calculations to be stable with a direct band gap, but there has been only one report of its synthesis. Herein we report the formation of Cs2AgInBr6 thin films through thermal evaporation of CsBr, AgBr, and InBr3 and subsequent annealing between 130 °C and 250 °C. Cs2AgInBr6 appears stable in this temperature range. However, Cs2AgInBr6 thin films are thermodynamically unstable at room temperature, remaining cubic only long enough to be characterized but not long enough to be useful for practical devices. Cs2AgInBr6 decomposed into Cs2AgBr3, Cs3In2Br9, AgBr, and InBr3 upon cooling from 130 °C to 250 °C to room temperature. This conclusion did not depend on illumination, film thickness, annealing environment, or details of the film formation, pointing to an intrinsic thermodynamic instability of the material. Optical absorption measurements may be interpreted as Cs2AgInBr6 having a direct band gap of 1.57 ± 0.1 eV.

Chemically Induced Magnetic Dead Shells in Superparamagnetic Ni Nanoparticles Deduced from Polarized Small-Angle Neutron Scattering.

Advances in the synthesis and characterization of colloidal magnetic nanoparticles (NPs) have yielded great gains in the understanding of their complex magnetic behavior, with implications for numerous applications. Recent work using Ni NPs as a model soft ferromagnetic system, for example, achieved quantitative understanding of the superparamagnetic blocking temperature-particle diameter relationship. This hinged, however, on the critical assumption of a ferromagnetic NP volume lower than the chemical volume due to a non-ferromagnetic dead shell indirectly deduced from magnetometry. Here, we determine both the chemical and magnetic average internal structures of Ni NP ensembles via unpolarized, half-polarized, and fully polarized small-angle neutron scattering (SANS) measurements and analyses coupled with X-ray diffraction and magnetometry. The postulated nanometric magnetic dead shell is not only detected but conclusively identified as a non-ferromagnetic Ni phosphide derived from the trioctylphosphine commonly used in hot-injection colloidal NP syntheses. The phosphide shell thickness is tunable via synthesis temperature, falling to as little as 0.5 nm at 170 °C. Temperature- and magnetic field-dependent polarized SANS measurements additionally reveal essentially bulk-like ferromagnetism in the Ni core and negligible interparticle magnetic interactions, quantitatively supporting prior modeling of superparamagnetism. These findings advance the understanding of synthesis-structure-property relationships in metallic magnetic NPs, point to a simple potential route to ligand-free stabilization, and highlight the power of the currently available suite of polarized SANS measurement and analysis capabilities for magnetic NP science and technology.

High photoluminescence quantum yield near-infrared emission from a lead-free ytterbium-doped double perovskite.

When excited by photons with energies greater than 2.2 eV, the bandgap energy, Yb-doped Cs2AgBiBr6 thin films synthesized via physical vapor deposition emit strong near-infrared luminescence centered at ∼1.24 eV via the Yb3+ 2F5/2 → 2F7/2 electronic transition. Robust, reproducible, and stable photoluminescence quantum yields (PLQY) as high as 82.5% are achieved with Cs2AgBiBr6 films doped with 8% Yb. This high PLQY indicates facile and efficient energy transfer from the perovskite host, Cs2AgBiBr6, to Yb, making Cs2AgBiBr6 the most promising lead-free down-conversion material.

Metal-insulator transition in a semiconductor nanocrystal network.

Many envisioned applications of semiconductor nanocrystals (NCs), such as thermoelectric generators and transparent conductors, require metallic (nonactivated) charge transport across an NC network. Although encouraging signs of metallic or near-metallic transport have been reported, a thorough demonstration of nonzero conductivity, σ, in the 0 K limit has been elusive. Here, we examine the temperature dependence of σ of ZnO NC networks. Attaining both higher σ and lower temperature than in previous studies of ZnO NCs (T as low as 50 mK), we observe a clear transition from the variable-range hopping regime to the metallic regime. The critical point of the transition is distinctly marked by an unusual power law close to σ ∝ T 1/5. We analyze the critical conductivity data within a quantum critical scaling framework and estimate the metal-insulator transition (MIT) criterion in terms of the free electron density, n, and interparticle contact radius, ρ.

Lead-free double perovskites Cs2InCuCl6 and (CH3NH3)2InCuCl6: electronic, optical, and electrical properties.

Searching for alternatives to lead-containing metal halide perovskites, we explored the properties of indium-based inorganic double perovskites Cs2InMX6 with M = Cu, Ag, Au and X = Cl, Br, I, and of its organic-inorganic hybrid derivative MA2InCuCl6 (MA = CH3NH3+) using computation within Kohn-Sham density functional theory. Among these compounds, Cs2InCuCl6 and MA2InCuCl6 were found to be potentially promising candidates for solar cells. Calculations with different functionals provided the direct band gap of Cs2InCuCl6 between 1.05 and 1.73 eV. In contrast, MA2InCuCl6 exhibits an indirect band gap between 1.31 and 2.09 eV depending on the choice of exchange-correlation functional. Cs2InCuCl6 exhibits a much higher absorption coefficient than that calculated for c-Si and CdTe, common semiconductors for solar cells. Even MA2InCuCl6 is predicted to have a higher absorption coefficient than c-Si and CdTe across the visible spectrum despite the fact that it is an indirect band gap material. The intrinsic charge carrier mobilities for Cs2InCuCl6 along the L-Γ path are predicted to be comparable to those for MAPbI3. Finally, we carried out calculations of the band edge positions for MA2InCuCl6 and Cs2InCuCl6 to offer guidance for solar cell heterojunction design and optimization. We conclude that Cs2InCuCl6 and MA2InCuCl6 are promising semiconductors for photovoltaic and optoelectronic applications.

Transport Evidence for Sulfur Vacancies as the Origin of Unintentional n-Type Doping in Pyrite FeS2.

Pyrite FeS2 has long been considered a potential earth-abundant low-cost photovoltaic material for thin-film solar cells but has been plagued by low power conversion efficiencies and open-circuit voltages. Recent efforts have identified a lack of understanding and control of doping, as well as uncontrolled surface conduction, as key roadblocks to the development of pyrite photovoltaics. In particular, while n-type bulk behavior in unintentionally doped single crystals and thin films is speculated to arise from sulfur vacancies (VS), proof remains elusive. Here, we provide strong evidence, from extensive electronic transport measurements on high-quality crystals, that VS are deep donors in bulk pyrite. Otherwise identical crystals grown via chemical vapor transport under varied S vapor pressures are thoroughly characterized structurally and chemically, and shown to exhibit systematically different electronic transport. Decreased S vapor pressure during growth leads to reduced bulk resistivity, increased bulk Hall electron density, reduced transport activation energy, onset of positive temperature coefficient of resistivity, and approach to an insulator-metal transition, all as would be expected from increased VS donor density. Impurity analyses show that these trends are uncorrelated with metal impurity concentration and that extracted donor densities significantly exceed total impurity concentrations, directly evidencing a native defect. Well-controlled, wide-range n-doping of pyrite is thus achieved via the control of VS concentration, with substantial implications for photovoltaic and other applications. The location of the VS state within the gap, the influence of specific impurities, unusual aspects to the insulator-metal transition, and the influence of doping on surface conduction are also discussed.

Quantum confinement in few layer SnS nanosheets.

Orthorhombic tin monosulfide (SnS) consists of layers of covalently bound Sn and S atoms held together by weak van der Waals forces and is a stable two-dimensional material with potentially useful properties in emerging applications such as valleytronics. Large-scale sustainable synthesis of few-layer (e.g., 1-10 layers) SnS is a challenge, which also slows progress in understanding their properties as a function of number of layers. Herein we describe solvothermal synthesis of SnS in water or ethylene glycol. The latter yields a flower-like morphology where the petals are SnS nanoplates and sonication and separation of these flowers via differential centrifugation yields 1-10 layer SnS nanoplates. The direct optical absorption edges of these SnS nanoplates blue-shift due to quantum confinement from 1.33 to 1.88 eV as the thickness (number of layers) is decreased from ∼5 nm (10 layers) to ∼2 nm (4 layers).

Variable range hopping conduction in ZnO nanocrystal thin films.

Zinc oxide (ZnO) nanocrystal films are of interest for new applications in thin film transistors and as transparent conductive oxides. Previous work has concentrated on achieving highly conductive, metallic films. This work focusses on the less explored insulating to semi-insulating regime, which enables obtaining deeper insights into the roles of surface states and defect states trapped at the nanocrystal interfaces. We examine the effects of various post-deposition treatments including controlled dosing with ultraviolet light, filling the voids between nanocrystals with a matrix material deposited by atomic layer deposition, and thermal annealing of the nanocrystal films. Both Mott and Efros-Shklovskii variable range hopping are observed depending on the carrier concentration in the nanocrystals. Using the above post-treatments to transition the films between the two conduction mechanisms enables determining the Fermi level density of states and the electron localization length. To interpret our results, we propose a model based on the assumption of nanocrystals consisting of quasi-neutral cores surrounded by shells depleted by surface OH trap states. The model suggests that the primary source of the increased conductivity in ZnO nanocrystal films based on post-treatments is an increase in the ability to tunnel between nanocrystals due to a reduction of the distance between the quasi-neutral nanocrystal cores.

Functionalization of Cadmium Selenide Quantum Dots with Poly(ethylene glycol): Ligand Exchange, Surface Coverage, and Dispersion Stability.

Semiconductor quantum dots synthesized using rapid mixing of precursors by injection into a hot solution of solvents and surfactants have surface ligands that sterically stabilize the dispersions in nonpolar solvents. Often, these ligands are exchanged to disperse the quantum dots in polar solvents, but quantitative studies of quantum dot surfaces before and after ligand exchange are scarce. We studied exchanging trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO) ligands on as-synthesized CdSe quantum dots dispersed in hexane with a 2000 g/mol thiolated poly(ethylene glycol) (PEG) polymer. Using infrared spectroscopy we quantify the absolute surface concentration of TOP/TOPO and PEG ligands per unit area before and after ligand exchange. While 50-85% of the TOP/TOPO ligands are removed upon ligand exchange, only a few are replaced with PEG. Surprisingly, the remaining TOP/TOPO ligands outnumber the PEG ligands, but these few PEG ligands are sufficient to disperse the quantum dots in polar solvents such as chloroform, tetrahydrofuran, and water. Moreover, as-synthesized quantum dots once easily dispersed in hexane are no longer dispersible in nonpolar solvents after ligand exchange. A subtle coverage-dependent balance between attractive PEG-solvent interactions and repulsive TOP/TOPO-solvent interactions determines the dispersion stability.

ZnO Nanocrystal Networks Near the Insulator-Metal Transition: Tuning Contact Radius and Electron Density with Intense Pulsed Light.

Networks of ligand-free semiconductor nanocrystals (NCs) offer a valuable combination of high carrier mobility and optoelectronic properties tunable via quantum confinement. In principle, maximizing carrier mobility entails crossing the insulator-metal transition (IMT), where carriers become delocalized. A recent theoretical study predicted that this transition occurs at nρ3 ≈ 0.3, where n is the carrier density and ρ is the interparticle contact radius. In this work, we satisfy this criterion in networks of plasma-synthesized ZnO NCs by using intense pulsed light (IPL) annealing to tune n and ρ independently. IPL applied to as-deposited NCs increases ρ by inducing sintering, and IPL applied after the NCs are coated with Al2O3 by atomic layer deposition increases n by removing electron-trapping surface hydroxyls. This procedure does not substantially alter NC size or composition and is potentially applicable to a wide variety of nanomaterials. As we increase nρ3 to at least twice the predicted critical value, we observe conductivity scaling consistent with arrival at the critical region of a continuous quantum phase transition. This allows us to determine the critical behavior of the dielectric constant and electron localization length at the IMT. However, our samples remain on the insulating side of the critical region, which suggests that the critical value of nρ3 may in fact be significantly higher than 0.3.

Copper-Zinc-Tin-Sulfide Thin Films via Annealing of Ultrasonic Spray Deposited Nanocrystal Coatings.

Thin polycrystalline films of the solar absorber copper-zinc-tin-sulfide (CZTS) were formed by annealing coatings deposited on molybdenum-coated soda lime glass via ultrasonic spraying of aerosol droplets from colloidal CZTS nanocrystal dispersions. Production of uniform continuous nanocrystal coatings with ultrasonic spraying requires that the evaporation time is longer than the aerosol flight time from the spray nozzle to the substrate such that the aerosol droplets still have low enough viscosity to smooth the impact craters that form on the coating surface. In this work, evaporation was slowed by adding a high boiling point cosolvent, cyclohexanone, to toluene as the dispersing liquid. We analyzed, quantitatively, the effects of the solvent composition on the aerosol and coating drying dynamics using an aerosol evaporation model. Annealing coatings in sulfur vapor converts them into polycrystalline films with micrometer size grains, but the grains form continuous films only when Na is present during annealing to enhance grain growth. Continuous films are easier to form when the average nanocrystal size is 15 nm: using larger nanocrystals (e.g., 20 nm) sacrifices film continuity.

Nonthermal Plasma Synthesis of Nanocrystals: Fundamental Principles, Materials, and Applications.

Nonthermal plasmas have emerged as a viable synthesis technique for nanocrystal materials. Inherently solvent and ligand-free, nonthermal plasmas offer the ability to synthesize high purity nanocrystals of materials that require high synthesis temperatures. The nonequilibrium environment in nonthermal plasmas has a number of attractive attributes: energetic surface reactions selectively heat the nanoparticles to temperatures that can strongly exceed the gas temperature; charging of nanoparticles through plasma electrons reduces or eliminates nanoparticle agglomeration; and the large difference between the chemical potentials of the gaseous growth species and the species bound to the nanoparticle surfaces facilitates nanocrystal doping. This paper reviews the state of the art in nonthermal plasma synthesis of nanocrystals. It discusses the fundamentals of nanocrystal formation in plasmas, reviews practical implementations of plasma reactors, surveys the materials that have been produced with nonthermal plasmas and surface chemistries that have been developed, and provides an overview of applications of plasma-synthesized nanocrystals.

Nonequilibrium-Plasma-Synthesized ZnO Nanocrystals with Plasmon Resonance Tunable via Al Doping and Quantum Confinement.

Metal oxide semiconductor nanocrystals (NCs) exhibit localized surface plasmon resonances (LSPRs) tunable within the infrared (IR) region of the electromagnetic spectrum by vacancy or impurity doping. Although a variety of these NCs have been produced using colloidal synthesis methods, incorporation and activation of dopants in the liquid phase has often been challenging. Herein, using Al-doped ZnO (AZO) NCs as an example, we demonstrate the potential of nonthermal plasma synthesis as an alternative strategy for the production of doped metal oxide NCs. Exploiting unique, thoroughly nonequilibrium synthesis conditions, we obtain NCs in which dopants are not segregated to the NC surfaces and local doping levels are high near the NC centers. Thus, we achieve overall doping levels as high as 2 × 10(20) cm(-3) in NCs with diameters ranging from 12.6 to 3.6 nm, and for the first time experimentally demonstrate a clear quantum confinement blue shift of the LSPR energy in vacancy- and impurity-doped semiconductor NCs. We propose that doping of central cores and heavy doping of small NCs are achievable via nonthermal plasma synthesis, because chemical potential differences between dopant and host atoms-which hinder dopant incorporation in colloidal synthesis-are irrelevant when NC nucleation and growth proceed via irreversible interactions among highly reactive gas-phase ions and radicals and ligand-free NC surfaces. We explore how the distinctive nucleation and growth kinetics occurring in the plasma influences dopant distribution and activation, defect structure, and impurity phase formation.

Phase Stability and Stoichiometry in Thin Film Iron Pyrite: Impact on Electronic Transport Properties.

The use of pyrite FeS2 as an earth-abundant, low-cost, nontoxic thin film photovoltaic hinges on improved understanding and control of certain physical and chemical properties. Phase stability, phase purity, stoichiometry, and defects, are central in this respect, as they are frequently implicated in poor solar cell performance. Here, phase-pure polycrystalline pyrite FeS2 films, synthesized by ex situ sulfidation, are subject to systematic reduction by vacuum annealing (to 550 °C) to assess phase stability, stoichiometry evolution, and their impact on transport. Bulk probes reveal the onset of pyrrhotite (Fe(1-δ)S) around 400 °C, rapidly evolving into the majority phase by 425 °C. This is supported by X-ray photoelectron spectroscopy on (001) crystals, revealing surface Fe(1-δ)S formation as low as 160 °C, with rapid growth near 400 °C. The impact on transport is dramatic, with Fe(1-δ)S minority phases leading to a crossover from diffusive transport to hopping (due to conductive Fe(1-δ)S nanoregions in an FeS2 matrix), followed by metallicity when Fe(1-δ)S dominates. Notably, the crossover to hopping leads to an inversion of the sign, and a large decrease in magnitude of the Hall coefficient. By tracking resistivity, magnetotransport, magnetization, and structural/chemical parameters vs annealing, we provide a detailed picture of the evolution in properties with stoichiometry. A strong propensity for S-deficient minority phase formation is found, with no wide window where S vacancies control the FeS2 carrier density. These findings have important implications for FeS2 solar cell development, emphasizing the need for (a) nanoscale chemical homogeneity, and (b) caution in interpreting carrier types and densities.

Formation of Copper Zinc Tin Sulfide Thin Films from Colloidal Nanocrystal Dispersions via Aerosol-Jet Printing and Compaction.

A three-step method to create dense polycrystalline semiconductor thin films from nanocrystal liquid dispersions is described. First, suitable substrates are coated with nanocrystals using aerosol-jet printing. Second, the porous nanocrystal coatings are compacted using a weighted roller or a hydraulic press to increase the coating density. Finally, the resulting coating is annealed for grain growth. The approach is demonstrated for making polycrystalline films of copper zinc tin sulfide (CZTS), a new solar absorber composed of earth-abundant elements. The range of coating morphologies accessible through aerosol-jet printing is examined and their formation mechanisms are revealed. Crack-free albeit porous films are obtained if most of the solvent in the aerosolized dispersion droplets containing the nanocrystals evaporates before they impinge on the substrate. In this case, nanocrystals agglomerate in flight and arrive at the substrate as solid spherical agglomerates. These porous coatings are mechanically compacted, and the density of the coating increases with compaction pressure. Dense coatings annealed in sulfur produce large-grain (>1 µm) polycrystalline CZTS films with microstructure suitable for thin-film solar cells.

High electron mobility in thin films formed via supersonic impact deposition of nanocrystals synthesized in nonthermal plasmas.

Thin films comprising semiconductor nanocrystals are emerging for applications in electronic and optoelectronic devices including light emitting diodes and solar cells. Achieving high charge carrier mobility in these films requires the identification and elimination of electronic traps on the nanocrystal surfaces. Herein, we show that in films comprising ZnO nanocrystals, an electron acceptor trap related to the presence of OH on the surface limits the conductivity. ZnO nanocrystal films were synthesized using a nonthermal plasma from diethyl zinc and oxygen and deposited by inertial impaction onto a variety of substrates. Surprisingly, coating the ZnO nanocrystals with a few nanometres of Al2O3 using atomic layer deposition decreased the film resistivity by seven orders of magnitude to values as low as 0.12 Ω cm. Electron mobility as high as 3 cm(2) V(-1) s(-1) was observed in films comprising annealed ZnO nanocrystals coated with Al2O3.

Plasma synthesis of stoichiometric Cu2S nanocrystals stabilized by oleylamine.

Nonthermal plasmas can produce high quality nanocrystals in a continuous process without requiring solvents. A nonthermal plasma process is demonstrated to synthesize stoichiometric Cu2S nanocrystals, which show no signs of oxidation by spectrophotometry after 2 months in the ambient when stabilized with oleylamine and dispersed in toluene.