Toward Water-Resistant, Tunable Perovskite Absorbers Using Peptide Hydrogel Additives.

In recent years, hydrogels have been demonstrated as simple and cheap additives to improve the optical properties and material stability of organometal halide perovskites (OHPs), with most research centered on the use of hydrophilic, petrochemical-derived polymers. Here, we investigate the role of a peptide hydrogel in passivating defect sites and improving the stability of methylammonium lead iodide (MAPI, CHNHPbI) using closely controlled, X-ray photoelectron spectroscopy (XPS) techniques under realistic pressures. Optical measurements reveal that a reduction in the density of defect sites is achieved by incorporating peptide into the precursor solution during the conventional one-step MAPI fabrication approach.

Elucidating the Mechanism of Self-Healing in Hydrogel-Lead Halide Perovskite Composites for Use in Photovoltaic Devices.

Since the emergence of organometal halide perovskite (OMP) solar cells, there has been growing interest in the benefits of incorporating polymer additives into the perovskite precursor, in terms of both photovoltaic device performance and perovskite stability. In addition, there is interest in the self-healing properties of polymer-incorporated OMPs, but the mechanisms behind these enhanced characteristics are still not fully understood. Here, we study the role of poly(2-hydroxyethyl methacrylate) (pHEMA) in improving the stability of methylammonium lead iodide (MAPI, CHNHPbI) and determine a mechanism for the self-healing of the perovskite-polymer composite following exposure to atmospheres of differing relative humidity, using photoelectron spectroscopy.

Structural investigations into colour-tuneable fluorescent InZnP-based quantum dots from zinc carboxylate and aminophosphine precursors.

Fluorescent InP-based quantum dots have emerged as valuable nanomaterials for display technologies, biological imaging, and optoelectronic applications. The inclusion of zinc can enhance both their emissive and structural properties and reduce interfacial defects with ZnS or CdS shells. However, the sub-particle distribution of zinc and the role this element plays often remains unclear, and it has previously proved challenging to synthesise Zn-alloyed InP-based nanoparticles using aminophosphine precursors.

Spiers Memorial Lecture: prospects for photoelectron spectroscopy.

An overview is presented of recent advances in photoelectron spectroscopy, focussing on advances in and time-resolved measurements, and in extending the sampling depth of the technique. The future prospects for each are considered. Progress in the last few years has been remarkable, aided by substantial advances in photon sources, environmental cells and in analyser and detection technology.

Characterization of buried interfaces using Ga Kα hard X-ray photoelectron spectroscopy (HAXPES).

The extension of X-ray photoelectron spectroscopy (XPS) to measure layers and interfaces below the uppermost surface requires higher X-ray energies and electron energy analysers capable of measuring higher electron kinetic energies. This has been enabled at synchrotron radiation facilities and by using lab-based instruments which are now available with sufficient sensitivity for measurements to be performed on reasonable timescales. Here, we detail measurements on buried interfaces using a Ga Kα (9.

Surface band bending and carrier dynamics in colloidal quantum dot solids.

Band bending in colloidal quantum dot (CQD) solids has become important in driving charge carriers through devices. This is typically a result of band alignments at junctions in the device. Whether band bending is intrinsic to CQD solids, is band bending present at the surface-vacuum interface, has previously been unanswered.

Role of Alkali Cations in Stabilizing Mixed-Cation Perovskites to Thermal Stress and Moisture Conditions.

Perovskite solar cells (PSCs) based on organic-inorganic hybrid perovskites containing a small fraction of substituted alkali-metal cations have shown remarkable performance and stability. However, the role of these cations is unclear. The thermal- and moisture-induced degradation of FACsPbI and (FACs)RbPbI (where FA represents formamidinium, , = 0.

Surface and Interface Chemistry in Colloidal Quantum Dots for Solar Applications Studied by X-Ray Photoelectron Spectroscopy.

Control of the surface and interface chemistry of colloidal quantum dots (CQDs) is critical to achieving a product with good air stability and high performing optoelectronic devices. Through various surface passivation treatments, vast improvements have been made in fields such as CQD photovoltaics; however devices have not currently reached commercial standards. We show how X-ray photoelectron spectroscopy (XPS) can provide a better understanding of exactly how surface treatments act on CQD surfaces, and the effect of surface composition on air stability and device performance.

Influence of Multistep Surface Passivation on the Performance of PbS Colloidal Quantum Dot Solar Cells.

The performance of devices containing colloidal quantum dot (CQD) films is strongly dependent on the surface chemistry of the CQDs they contain. Multistep surface treatments, which combine two or more strategies, are important for creating films with high carrier mobility that are well passivated against trap states and oxidation. Here, we examine the effect of a number of these surface treatments on PbS CQD films, including cation exchange to form PbS/CdS core/shell CQDs, and solid-state ligand-exchange treatments with Cl, Br, I, and 1,2-ethanedithiol (EDT) ligands.

The passivating effect of cadmium in PbS/CdS colloidal quantum dots probed by nm-scale depth profiling.

Achieving control of the surface chemistry of colloidal quantum dots (CQDs) is essential to fully exploit their properties in solar cells, but direct measurement of the chemistry and electronic structure in the outermost atomic layers is challenging. Here we probe the surface oxidation and passivation of cation-exchanged PbS/CdS core/shell CQDs with sub nm-scale precision using synchrotron-radiation-excited depth-profiling photoemission. We investigate the surface composition of the topmost 1-2.

In situ investigation of degradation at organometal halide perovskite surfaces by X-ray photoelectron spectroscopy at realistic water vapour pressure.

Near-ambient-pressure X-ray photoelectron spectroscopy enables the study of the reaction of in situ-prepared methylammonium lead iodide (MAPI) perovskite at realistic water vapour pressures for the first time. We show that MAPI decomposes directly to PbI, HI and NH without formation of methylammonium iodide, allowing us to distinguish between alternative mechanisms for the atmospheric degradation reaction.

Surface properties of nanocrystalline PbS films deposited at the water-oil interface: a study of atmospheric aging.

Nanocrystalline thin films of PbS are obtained in a straightforward reaction by precipitation at the interface between toluene (containing a Pb precursor) and water (containing Na2S). Lead thiobiuret [Pb(SON(CN(i)Pr2)2)2] and lead diethyldithiocarbamate [Pb(S2CNEt2)2] precursors are used. The films are characterized by X-ray diffraction and electron microscopy, revealing typical particle sizes of 10-40 nm and preferred (200) orientation.

Near-unity quantum yields from chloride treated CdTe colloidal quantum dots.

Colloidal quantum dots (CQDs) are promising materials for novel light sources and solar energy conversion. However, trap states associated with the CQD surface can produce non-radiative charge recombination that significantly reduces device performance. Here a facile post-synthetic treatment of CdTe CQDs is demonstrated that uses chloride ions to achieve near-complete suppression of surface trapping, resulting in an increase of photoluminescence (PL) quantum yield (QY) from ca.

Dynamics in next-generation solar cells: time-resolved surface photovoltage measurements of quantum dots chemically linked to ZnO (101[combining macron]0).

The charge dynamics at the surface of the transparent conducting oxide and photoanode material ZnO are investigated in the presence and absence of light-harvesting colloidal quantum dots (QDs). The time-resolved change in surface potential upon photoexcitation has been measured in the m-plane ZnO (101[combining macron]0) using a laser pump-synchrotron X-ray probe methodology. By varying the oxygen annealing conditions, and hence the oxygen vacancy concentration of the sample, we find that dark carrier lifetimes at the ZnO surface vary from hundreds of μs to ms timescales, i.

Electronic and surface properties of PbS nanoparticles exhibiting efficient multiple exciton generation.

Ultrafast transient absorption measurements have been used to study multiple exciton generation in solutions of PbS nanoparticles vigorously stirred to avoid the effects of photocharging. The threshold and slope efficiency of multiple exciton generation are found to be 2.5 ± 0.

Controlled synthesis of tuned bandgap nanodimensional alloys of PbS(x)Se(1-x).

Truly alloyed PbS(x)Se(1-x) (x = 0-1) nanocrystals (∼5 nm in size) have been prepared, and their resulting optical properties are red-shifted systematically as the sulfur content of the materials increases. Their optical properties are discussed using a modified Vegard's approach and the bowing parameter for these nanoalloys is reported for the first time. The alloyed structure of the nanocrystals is supported by the energy-filtered transmission electron microscope images of the samples, which show a homogeneous distribution of sulfur and selenium within the nanocrystals.

Electronic properties of the interface between p-CuI and anatase-phase n-TiO2 single crystal and nanoparticulate surfaces: a photoemission study.

We present a study of the growth of the p-type inorganic semiconductor CuI on n-type TiO2 anatase single crystal (101) surfaces and on nanoparticulate anatase surfaces using synchrotron radiation photoemission spectroscopy. Core level photoemission data obtained using synchrotron radiation reveal that both the substrate (TiO2) and the overlayer (CuI) core levels shift to a lower binding energy to different degrees following the growth of CuI on TiO2. Valence band photoemission data show that the valence band maximum of the clean substrate differs from that of the dosed surface which may be interpreted qualitatively as due to the introduction of a new density of states within the band gap of TiO2 as a result of the growth of CuI.

Resonant photoemission from complex cuprates and nickelates.

Synchrotron-excited resonant-photoemission measurements at rare-earth 4d --> 4f and transition-metal 3p --> 3d thresholds have been carried out using a variety of complex cuprates and nickelates on stations 6.1 (grazing-incidence monochromator) and 6.2 (toroidal-grating monochromator) at the SRS CLRC Daresbury Laboratory.

The k-space components of a photoelectron from an arbitrarily oriented crystal face.

A standard rotational matrix method is described for determining the k-space components of photoelectrons emitted from a crystal surface, which is arbitrarily oriented with respect to the experimental frame. This simplifies the analysis of angle-resolved photoemission data from a crystal surface not aligned to the experimental chamber axes.