Matthew J. Greaney

Synthesis and Characterization of Wurtzite-Phase Copper Tin Selenide Nanocrystals

A new wurtzite phase of copper tin selenide (CTSe) was discovered, and the resulting nanocrystals were synthesized via a facile solution-phase method. The wurtzite CTSe nanocrystals were synthesized with dodecylamine and 1-dodecanethiol as coordinating solvents and di-tert-butyl diselenide ((t)Bu(2)Se(2)) as the selenium source. Specific reaction control (i.e., a combination of 1-dodecanethiol with (t)Bu(2)Se(2)) was proven to be critical in order to obtain this new phase of CTSe, which was verified by powder X-ray diffraction and selected area electron diffraction. The wurtzite CTSe nanocrystals possess an optical and electrochemical band gap of 1.7 eV and display an electrochemical photoresponse indicative of a p-type semiconductor.

Improving Open Circuit Potential in Hybrid P3HT:CdSe Bulk Heterojunction Solar Cells via Colloidal tert-Butylthiol Ligand Exchange

Organic ligands have the potential to contribute to the reduction potential, or lowest unoccupied molecular orbital (LUMO) energy, of semiconductor nanocrystals. Rationally introducing small, strongly binding, electron-donating ligands should enable improvement in the open circuit potential of hybrid organic/inorganic solar cells by raising the LUMO energy level of the nanocrystal acceptor phase and thereby increasing the energy offset from the polymer highest occupied molecular orbital (HOMO). Hybrid organic/inorganic solar cells fabricated from blends of tert-butylthiol-treated CdSe nanocrystals and poly(3-hexylthiophene) (P3HT) achieved power conversion efficiencies of 1.9%. Compared to devices made from pyridine-treated and nonligand exchanged CdSe, the thiol-treated CdSe nanocrystals are found to consistently exhibit the highest open circuit potentials with V(OC) = 0.80 V. Electrochemical determination of LUMO levels using cyclic voltammetry and spectroelectrochemistry suggest that the thiol-treated CdSe nanocrystals possess the highest lying LUMO of the three, which translates to the highest open circuit potential. Steady-state and time-resolved photoluminescence quenching experiments on P3HT:CdSe films provide insight into how the thiol-treated CdSe nanocrystals also achieve greater current densities in devices relative to pyridine-treated nanocrystals, which are thought to contain a higher density of surface traps.

Nickel oxide particles catalyze photochemical hydrogen evolution from water-nanoscaling promotes p-type character and minority carrier extraction

Nickel(II) oxide (NiO) is an important wide gap p-type semiconductor used as a hole transport material for dye sensitized solar cells and as a water oxidation electrocatalyst. Here we demonstrate that nanocrystals of the material have increased p-type character and improved photocatalytic activity for hydrogen evolution from water in the presence of methanol as sacrificial electron donor. NiO nanocrystals were synthesized by hydrolysis of Ni(II) nitrate under hydrothermal conditions followed by calcination in air. The crystals have the rock salt structure type and adopt a plate-like morphology (50-90 nm × 10-15 nm). Diffuse reflectance absorbance spectra indicate a band gap of 3.45 eV, similar to bulk NiO. Photoelectrochemical measurements were performed at neutral pH with methylviologen as electron acceptor, revealing photo-onset potentials (Fermi energies) of 0.2 and 0.05 eV (NHE) for nanoscale and bulk NiO, respectively. Nano-NiO and NiO-Pt composites obtained by photodepositon of H2PtCl6 catalyze hydrogen evolution from aqueous methanol at rates of 0.8 and 4.5 μmol H2 h(-1), respectively, compared to 0.5 and 2.1 μmol H2 h(-1) for bulk-NiO and NiO-Pt (20 mg of catalyst, 300 W Xe lamp). Surface photovoltage spectroscopy of NiO and NiO-Pt films on Au substrates indicate a metal Pt-NiO junction with 30 mV photovoltage that promotes carrier separation. The increased photocatalytic and photoelectrochemical performance of nano-NiO is due to improved minority carrier extraction and increased p-type character, as deduced from Mott-Schottky plots, optical absorbance, and X-ray photoelectron spectroscopy data.

Direct Spectroscopic Evidence of Ultrafast Electron Transfer from a Low Band Gap Polymer to CdSe Quantum Dots in Hybrid Photovoltaic Thin Films

Ultrafast transient absorption spectroscopy is used to study charge transfer dynamics in hybrid films composed of the low band gap polymer PCPDTBT and CdSe quantum dots capped with tert-butylthiol ligands. By selectively exciting the polymer, a spectral signature for electrons on the quantum dots appears on ultrafast time scales (≲ 65 fs), which indicates ultrafast electron transfer. From this time scale, the coupling between the polymer chains and the quantum dots is estimated to be J ≳ 17 meV. The reduced quantum dot acceptors exhibit an unambiguous spectral bleach signature, whose amplitude allows for the first direct calculation of the absolute electron transfer yield in a hybrid solar cell (82 ± 5%). We also show that a limitation of the hybrid system is rapid and measurable geminate recombination due to the small separation of the initial charge pair. The fast recombination is consistent with the internal quantum efficiency of the corresponding solar cell. We therefore have identified and quantified a main loss mechanism in this type of third generation solar cell.

Chalcogenol Ligand Toolbox for CdSe Nanocrystals and Their Influence on Exciton Relaxation Pathways

We have employed a simple modular approach to install small chalcogenol ligands on the surface of CdSe nanocrystals. This versatile modification strategy provides access to thiol, selenol, and tellurol ligand sets via the in situ reduction of R2E2 (R=tBu, Bn, Ph; E=S, Se, Te) by diphenylphosphine (Ph2PH). The ligand exchange chemistry was analyzed by solution NMR spectroscopy, which reveals that reduction of the R2E2 precursors by Ph2PH directly yields active chalcogenol ligands that subsequently bind to the surface of the CdSe nanocrystals. Thermogravimetric analysis, FT-IR spectroscopy, and energy dispersive X-ray spectroscopy provide further evidence for chalcogenol addition to the CdSe surface with a concomitant reduction in overall organic content from the displacement of native ligands. Time-resolved and low temperature photoluminescence measurements showed that all of the phenylchalcogenol ligands rapidly quench the photoluminescence by hole localization onto the ligand. Selenol and tellurol ligands exhibit a larger driving force for hole transfer than thiol ligands and therefore quench the photoluminescence more efficiently. The hole transfer process could lead to engineering long-lived, partially separated excited states.

Tandem and triple-junction polymer:nanocrystal hybrid solar cells consisting of identical subcells.

Tandem and triple-junction polymer:nanocrystal hybrid solar cells with identical subcells based on P3HT:CdSe nanocrystal bulk heterojunctions (BHJs) are reported for the first time showing 2-fold and 3-fold increases of open-circuit voltage (VOC), respectively, relative to the single-junction cell. A combination of nanocrystalline ZnO and pH-neutral PEDOT:PSS is used as the interconnecting layer, and the thicknesses of subcells are optimized with the guidance of optical simulations. As a result, the average power conversion efficiency (PCE) exhibits a significant increase from 2.0% (VOC = 0.57 V) in single-junction devices to 2.7% (champion 3.1%, VOC = 1.28 V) in tandem devices and 2.3% (VOC = 1.98 V) in triple-junction devices.

Deconvoluting contributions of photoexcited species in polymer-quantum dot hybrid photovoltaic materials

Abstract. Ultrafast transient absorption spectroscopy is used in conjunction with spectroelectrochemistry and chemical doping experiments to study the photogeneration of charges in hybrid bulk heterojunction (BHJ) thin films composed of 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) and CdSe nanocrystals. Chemical doping experiments on hybrid and neat PCPDTBT:CdSe thin films are used to deconvolute the spectral signatures of the transient states in the near infrared. We confirm the formation and assignment of oxidized species in chemical doping experiments by comparing the spectral data to that from spectroelectrochemical measurements on hybrid and neat PCPDTBT:CdSe BHJ thin films. The deconvolution procedure allows extraction of the polaron populations in the neat polymer and hybrid thin films.

Ultrafast electron transfer from low band gap conjugated polymer to quantum dots in hybrid photovoltaic materials

Ultrafast transient absorption spectroscopy is used in conjunction with chemical doping experiments to study the photo-generation of charges in hybrid thin films composed of PCPDTBT and CdSe quantum dots. We show how we use chemical doping experiments to de-convolute the spectral signatures of the transient states in the near infrared.