Sander A. Mann

Extreme light absorption in thin semiconductor films wrapped around metal nanowires.

Metallic and dielectric nanostructures have highly tunable resonances that have been used to increase light absorption in a variety of photovoltaic materials and device structures. Metal nanowires have also emerged as a promising candidate for high-performance transparent electrodes for local contacts. In this Letter we propose combining these electrical and optical functions. As a first step, we use rigorous solutions to Maxwells equations to demonstrate theoretically extreme absorption in semiconductor thin films wrapped around metal nanowires. We show that there are two key principles underlying this extraordinary light trapping effect: (1) maximizing the absorption of each individual resonance by ensuring it is critically coupled and (2) increasing the total number of degenerate resonances. Inserting a metal core into a semiconductor nanowire creates such a degeneracy: polarization-dependent Mie resonances are transformed into polarization-independent Fabry-Pérot-like resonances. We demonstrate that, by reducing the polarization sensitivity and increasing the number of critically coupled modes, this hybrid coaxial nanowire geometry substantially outperforms solid semiconducting nanowires, even though the semiconductor volume is significantly reduced. These results suggest that metal nanowires with semiconductor shells might be ideal building blocks for photovoltaic and solar fuel applications.

Indirect to direct bandgap transition in methylammonium lead halide perovskite

Methylammonium lead iodide perovskites are considered direct bandgap semiconductors. Here we show that in fact they present a weakly indirect bandgap 60 meV below the direct bandgap transition. This is a consequence of spin–orbit coupling resulting in Rashba-splitting of the conduction band. The indirect nature of the bandgap explains the apparent contradiction of strong absorption and long charge carrier lifetime. Under hydrostatic pressure from ambient to 325 MPa, Rashba splitting is reduced due to a pressure induced reduction in local electric field around the Pb atom. The nature of the bandgap becomes increasingly more direct, resulting in five times faster charge carrier recombination, and a doubling of the radiative efficiency. At hydrostatic pressures above 325 MPa, MAPI undergoes a reversible phase transition resulting in a purely direct bandgap semiconductor. The pressure-induced changes suggest epitaxial and synthetic routes to higher efficiency optoelectronic devices.

Dielectric particle and void resonators for thin film solar cell textures.

Using Mie theory and Rigorous Coupled Wave Analysis (RCWA) we compare the properties of dielectric particle and void resonators. We show that void resonators-low refractive index inclusions within a high index embedding medium-exhibit larger bandwidth resonances, reduced peak scattering intensity, different polarization anisotropies, and enhanced forward scattering when compared to their particle (high index inclusions in a low index medium) counterparts. We evaluate amorphous silicon solar cell textures comprising either arrays of voids or particles. Both designs support substantial absorption enhancements (up to 45%) relative to a flat cell with anti-reflection coating, over a large range of cell thicknesses. By leveraging void-based textures 90% of above-bandgap photons are absorbed in cells with maximal vertical dimension of 100 nm.

Direct imaging of hybridized eigenmodes in coupled silicon nanoparticles

High-index dielectric nanoparticles support leaky geometrical resonances in the visible spectral range with large interaction cross sections, and find applications in nanoscale optoelectronic devices and surface coatings. Coupling between such resonant nanoparticles in close proximity can give rise to enhanced directionality and confinement. Here, we combine dark-field (DF) scattering spectroscopy with cathodoluminescence (CL) imaging spectroscopy to study hybridization of resonant modes in coupled silicon nanoparticles and directly image the modal field profiles of these hybridized eigenmodes. The DF measurements show a strong influence of the gap size on the scattering spectrum as a result of hybridization. Using finite-element modeling we calculate the eigenmodes of the dimer and identify the hybridized eigenmodes in the scattering spectrum. CL imaging spectroscopy is used to directly map the modal field profiles of single particles and dimer structures with deep-subwavelength spatial resolution. Detailed comparison with eigenmode calculations shows that the measured modal field profiles correspond to the hybridized symmetric electric and antisymmetric magnetic bonding modes. We study dimers composed of large dielectric bars to explore the ability of CL imaging to map highly complex hybridized field profiles inside resonant nanostructures. Our results demonstrate the ability to characterize the complex resonant properties of coupled nanostructures, paving the way for more complex applications and devices based on resonant dielectric nanoparticles.

Nanoscale Spatial Coherent Control over the Modal Excitation of a Coupled Plasmonic Resonator System

We demonstrate coherent control over the optical response of a coupled plasmonic resonator by high-energy electron beam excitation. We spatially control the position of an electron beam on a gold dolmen and record the cathodoluminescence and electron energy loss spectra. By selective coherent excitation of the dolmen elements in the near field, we are able to manipulate modal amplitudes of bonding and antibonding eigenmodes. We employ a combination of CL and EELS to gain detailed insight in the power dissipation of these modes at the nanoscale as CL selectively probes the radiative response and EELS probes the combined effect of Ohmic dissipation and radiation.

Resonant Nanophotonic Spectrum Splitting for Ultrathin Multijunction Solar Cells.

We present an approach to spectrum splitting for photovoltaics that utilizes the resonant optical properties of nanostructures for simultaneous voltage enhancement and spatial separation of different colors of light. Using metal–insulator–metal resonators commonly used in broadband metamaterial absorbers we show theoretically that output voltages can be enhanced significantly compared to single-junction devices. However, the approach is general and works for any type of resonator with a large absorption cross section. Due to its resonant nature, the spectrum splitting occurs within only a fraction of the wavelength, as opposed to traditional spectrum splitting methods, where many wavelengths are required. Combining nanophotonic spectrum splitting with other nanophotonic approaches to voltage enhancements, such as angle restriction and concentration, may lead to highly efficient but deeply subwavelength photovoltaic devices.

Solution-phase epitaxial growth of quasi-monocrystalline cuprous oxide on metal nanowires

The epitaxial growth of monocrystalline semiconductors on metal nanostructures is interesting from both fundamental and applied perspectives. The realization of nanostructures with excellent interfaces and material properties that also have controlled optical resonances can be very challenging. Here we report the synthesis and characterization of metal–semiconductor core–shell nanowires. We demonstrate a solution-phase route to obtain stable core–shell metal–Cu2O nanowires with outstanding control over the resulting structure, in which the noble metal nanowire is used as the nucleation site for epitaxial growth of quasi-monocrystalline Cu2O shells at room temperature in aqueous solution. We use X-ray and electron diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, photoluminescence spectroscopy, and absorption spectroscopy, as well as density functional theory calculations, to characterize the core–shell nanowires and verify their structure. Metal–semiconductor core–shell nanowires offer several potential advantages over thin film and traditional nanowire architectures as building blocks for photovoltaics, including efficient carrier collection in radial nanowire junctions and strong optical resonances that can be tuned to maximize absorption.

Quantifying losses and thermodynamic limits in nanophotonic solar cells

Nanophotonic engineering shows great potential for photovoltaics: the record conversion efficiencies of nanowire solar cells are increasing rapidly and the record open-circuit voltages are becoming comparable to the records for planar equivalents. Furthermore, it has been suggested that certain nanophotonic effects can reduce costs and increase efficiencies with respect to planar solar cells. These effects are particularly pronounced in single-nanowire devices, where two out of the three dimensions are subwavelength. Single-nanowire devices thus provide an ideal platform to study how nanophotonics affects photovoltaics. However, for these devices the standard definition of power conversion efficiency no longer applies, because the nanowire can absorb light from an area much larger than its own size. Additionally, the thermodynamic limit on the photovoltage is unknown a priori and may be very different from that of a planar solar cell. This complicates the characterization and optimization of these devices. Here, we analyse an InP single-nanowire solar cell using intrinsic metrics to place its performance on an absolute thermodynamic scale and pinpoint performance loss mechanisms. To determine these metrics we have developed an integrating sphere microscopy set-up that enables simultaneous and spatially resolved quantitative absorption, internal quantum efficiency (IQE) and photoluminescence quantum yield (PLQY) measurements. For our record single-nanowire solar cell, we measure a photocurrent collection efficiency of >90% and an open-circuit voltage of 850 mV, which is 73% of the thermodynamic limit (1.16 V).

Opportunities and Limitations for Nanophotonic Structures To Exceed the Shockley–Queisser Limit

Nanophotonic engineering holds great promise for photovoltaics, with several recently proposed approaches that have enabled efficiencies close to the Shockley-Queisser limit. Here, we theoretically demonstrate that suitably designed nanophotonic structures may be able to surpass the 1 sun Shockley-Queisser limit by utilizing tailored directivity of the scattering response of nanoparticles. We show that large absorption cross sections do not play a significant role in the efficiency enhancement, and on the contrary, directivity enhancement constitutes the nanoscale equivalent to concentration in macroscopic photovoltaic systems. Based on this principle, we discuss fundamental limits to the efficiency based on directivity bounds and a number of approaches to get close to these limits. We also highlight that, in practice, achieving efficiencies above the Shockley-Queisser limit is strongly hindered by whether high short-circuit currents can be maintained. Finally, we discuss how our results are affected by the presence of significant nonradiative recombination, in which case both directivity and photon escape probability should be increased to achieve voltage enhancement.

Au-Cu2O core-shell nanowire photovoltaics

Semiconductor nanowires are among the most promising candidates for next generation photovoltaics. This is due to their outstanding optical and electrical properties which provide large optical cross sections while simultaneously decoupling the photon absorption and charge carrier extraction length scales. These effects relax the requirements for both the minority carrier diffusion length and the amount of semiconductor needed. Metal-semiconductor core-shell nanowires have previously been predicted to show even better optical absorption than solid semiconductor nanowires and offer the additional advantage of a local metal core contact. Here, we fabricate and analyze such a geometry using a single Au-Cu2O core-shell nanowire photovoltaic cell as a model system. Spatially resolved photocurrent maps reveal that although the minority carrier diffusion length in the Cu2O shell is less than 1 μm, the radial contact geometry with the incorporated metal electrode still allows for photogenerated carrier collection...