Zhilong Zhang

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.

Air-stable PbS quantum dots synthesized with slow reaction kinetics via a PbBr2 precursor

PbS quantum dots have been synthesized using a PbBr2 precursor and the halide content has been examined. Slower reaction kinetics for quantum dots growth relative to the use of PbCl2 was observed for PbBr2, giving a possible route to increased control over quantum dot size with in situ passivation. Unambiguous determination of the surface conditions of nanomaterials is still a developing area of science, pushing the limits of current microscopy and analytical techniques. Contributions to a rigorous form of nanomaterial surface analysis are made here using X-ray photoelectron spectroscopy to analyse bonding in detail. Atomic resolution TEM is applied to produce energy dispersive X-ray spectroscopy maps with state of the art resolution. This analysis has been applied to air-stable halide terminated PbS nanoparticles, which is a nanomaterial of central importance for quantum confined solar cell applications. Chemical analysis from X-ray photoelectron spectroscopy is consistent with Br surface termination and high resolution energy dispersive X-ray spectroscopy (EDS) maps also show a positive spatial correlation for Br with quantum dot location. An observed excess Br content is attributed to the presence of bromine terminated PbS quantum dots nuclei in the final colloid.

Ab initio calculation of halide ligand passivation on PbSe quantum dot facets

The passivation and charge compensation provided by inorganic halide ligands on low index facets of lead selenide (PbSe) nanocrystals has been studied using density functional theory to produce projected densities of states (PDOS), bond lengths and to perform Bader analysis. The calculations were made using a grid-based planar augmented wave code with a localized double zeta potential basis and the generalized gradient approximation. Surface energies of halide ligands bonded onto surface Pb atoms show trends that are consistent with the increased electronegativity of the species, with iodine having the lowest binding energy of the halides investigated. Different densities of iodine ligands lead to different levels of passivation with a continuous widening of the bandgap on particular facets for increasing levels of coverage. In particular, the (111) plane shows a clear recovery of surface layer back to bulk property and widening of bandgap when the ligands cover most Pb atoms on the surfaces. Additionally, a possible increase of carrier conductance along with the increase of ligand density has been found using Bader analysis. Relative increases in the conductance for large halide atoms stem from the measurable increases to electronic states near the top of the valence band in these p-type semiconductors. The passivation is observed to increase along with the s-type character of the electron density at the surface, suggesting that a higher degree of symmetry in the electron density accompanies the reduction in defect levels.

Enhanced performance via partial lead replacement with calcium for a CsPbI3 perovskite solar cell exceeding 13% power conversion efficiency

Cesium metal halides are potential light-harvesting materials for use in the top cells of multi-junction devices due to their suitable bandgaps and good thermal stabilities. In particular, CsPbI3 has a bandgap of 1.7 eV, which is suitable for perovskite/Si tandem cells. However, the desirable black phase for CsPbI3 is not stable because Cs is too small to support the PbI6 octahedra. Also, there is room for improvement in terms of cell performance. Herein, we partially replace Pb2+ with Ca2+ in the CsPbI3 precursor, producing multiple benefits. Firstly, more uniform films with larger grains are produced from CsPbI3 with Ca2+, due to the reduction in the size of the colloids in the precursor solution with Ca2+. This morphology improvement provides better contact at the interface between the perovskite and the hole transport layer. In addition, it is found that the surface of the film is modified by the formation of a Ca rich oxide layer, providing a surface passivation effect. Finally, incorporation of Ca increases the band gap, leading to an increase in output voltage. The best CsPbI3 solar cell using 5% Ca2+ substitution in the precursor achieves a stabilised efficiency of 13.3%, and maintains 85% of its initial efficiency for over 2 months with encapsulation.

Investigation of anti-solvent induced optical properties change of cesium lead bromide iodide mixed perovskite (CsPbBr3-xIx) quantum dots

Cesium lead halide (CsPbX3, X=Cl, Br, I) perovskites are a new material system that has attracted a lot of research focus. Its tunable band gap and better thermal stability than organic lead halide perovskite give it the potential for applications in optoelectronic devices such as light-emitting diodes and solar cells. Here we have synthesized CsPbBr3-xIx perovskite quantum dots (QDs) via a solution process, and then have selected three different anti-solvents to purify the product. A significant effect on optical properties of CsPbBr3-xIx was found after the centrifugation process. Up to a ∼40nm shift was observed in mixed halide CsPbBr3-xIx QDs in both absorbance and PL spectra after purification while there was no obvious change in pure CsPbBr3 when it was subjected to the same purification steps. XPS analysis shows that the Br:I ratio of the CsPbBr3-xIx QDs had changed as a result of exposure to the anti-solvent, causing the change of the band gap and shift of the spectra. It is also shown that iodine can be removed more easily than bromine during the anti-solvent purification. Ab-initio simulations of small CsPbBr3-xIx atomic clusters suggest that exposed Cs ions on Cs-terminated facets are the first species to be attacked by hydrophilic molecules, likely dragging halide ions into solution with them to maintain overall charge neutrality in the material. Charge carrier recombination rates were found to be unchanged and all samples maintained a good PL quantum yield which was more than 44%.

Theoretical investigation of carrier transfer by an optical contacting scheme for optoelectronic application

As a promising charge carrier transfer scheme, optical coupling could potentially improve the performance of an optoelectronic device for energy harvesting based on well developed nanotechnology. By extracting carriers optically, the functional features of the nano-structured material could be better used by minimizing the concerns about its electrical properties. In this paper, we present a rigorous electromagnetic model to analyze the optical carrier transfer problem. The flow of the energy is analyzed carefully by the photon transfer spectrum, and the photon emitters (electron-hole pairs) are assumed in a thermal equilibrium described by Bose-Einstein distribution. The result shows that an energy selective carrier transfer can be optically achieved at the device level by integrating the emitter and receiver into a nano-optical resonator, where both the photon emission and absorption are significantly amplified by a near-field coupling around the resonant frequency. General design and optimization schemes in practice are addressed by examining the influence of the photonic design and an energy dependent emissivity of the emitter, which can be used to develop the optical contacting concept further.

Hot carrier solar cell absorbers: materials, mechanisms and nanostructures

The hot carrier cell aims to extract the electrical energy from photo-generated carriers before they thermalize to the band edges. Hence it can potentially achieve a high current and a high voltage and hence very high efficiencies up to 65% under 1 sun and 86% under maximum concentration. To slow the rate of carrier thermalisation is very challenging, but modification of the phonon energies and the use of nanostructures are both promising ways to achieve some of the required slowing of carrier cooling. A number of materials and structures are being investigated with these properties and test structures are being fabricated. Initial measurements indicate slowed carrier cooling in III-Vs with large phonon band gaps and in multiple quantum wells. It is expected that soon proof of concept of hot carrier devices will pave the way for their development to fully functioning high efficiency solar cells.

MgCl 2 passivated ZnO electron transporting layer to improve PbS quantum dot solar cells

The unique tunable bandgaps and straightforward synthesis of colloidal quantum dots make them promising low-cost materials for photovoltaics. High-performance colloidal quantum dot solar cells rely on good-quality electron transporting layers (ETLs) to make carrier selective contacts. Despite extensive use of n-type oxides as ETLs, a detailed understanding of their surface and interface states as well as mechanisms to improve their optical properties are still under development. Here, we report a simple procedure to produce MgCl2 passivated ZnO nanoparticles ETLs that show improved device performance. The MgCl2 treated ZnO electron transporting layers boost the PbS colloidal quantum dot cell efficiency from 6.3% to 8.2%. The cell exhibits reduced defects leading to significant improvements of both FF and J sc. This low-temperature MgCl2 treated ZnO electron transporting layer may be applied in solution processed tandem cells as a promising strategy to further increase cell efficiencies.

Ab initio calculation of transport properties between PbSe quantum dots facets with iodide ligands

The transport properties between Lead Selenide (PbSe) quantum dots decorated with iodide ligands has been studied using density functional theory (DFT). Quantum conductance at each selected energy levels has been calculated along with total density of states and projected density of states. The DFT calculation is carried on using a grid-based planar augmented wave (GPAW) code incorporated with the linear combination of atomic orbital (LCAO) mode and Perdew Burke Ernzerhof (PBE) exchange-correlation functional. Three iodide ligand attached low index facets including (001), (011), (111) are investigated in this work. P-orbital of iodide ligand majorly contributes to density of state (DOS) at near top valence band resulting a significant quantum conductance, whereas DOS of Pb p-orbital shows minor influence. Various values of quantum conductance observed along different planes are possibly reasoned from a combined effect electrical field over topmost surface and total distance between adjacent facets. Ligands attached to (001) and (011) planes possess similar bond length whereas it is significantly shortened in (111) plane, whereas transport between (011) has an overall low value due to newly formed electric field. On the other hand, (111) plane with a net surface dipole perpendicular to surface layers leading to stronger electron coupling suggests an apparent increase of transport probability. Apart from previously mentioned, the maximum transport energy levels located several eVs (1 ~2 eVs) from the edge of valence band top.

Selective optical contacting for solar spectrum management

Solar spectrum management using up/down conversion is an important method to improve the photovoltaic energy conversion efficiency. It asks for a monochromatic luminescence absorption at the band edge of the photovoltaic device to reduce both the sub-band-gap and over-band-gap energy losses. Here, we demonstrate an energy selective optical contacting concept to improve the luminescence transfer efficiency for spectrum management. By increasing both the luminescence emission and re-absorption ability through photonic resonance, an efficient photon transfer channel could be established between the luminescence emitter and the photovoltaic component in a near-field region. This concept is not only able to compensate the insufficient band edge absorption ability of the photovoltaic device, but also to break the far-field limitation of luminescence radiation. The energy selection on the optical spectrum naturally imposed by the mode resonance is also helpful to improve the monochromaticity of the luminescence yield. In this paper, a photonic crystal cavity is used to realize the optical contacting concept between a thin silicon film and spectrum converter. The optical power and photon flux transferred between different components are calculated analytically using the electromagnetic Green’s function. The corresponding radiative dipole moment is estimated by the fluctuation-dissipation theorem. The example shows an over 80 times enhancement in the luminescence absorbance by the silicon layer, illustrating the great potential of this concept to be applied on nano-structured photovoltaic devices.