Light management is of great importance in photovoltaic cells, as it determines the fraction of incident light entering the device. An optimal p-n junction combined with optimal light absorption can lead to a solar cell efficiency above the Shockley-Queisser limit. Here, we show how this is possible by studying photocurrent generation for a single core-shell p-i-n junction GaAs nanowire solar cell grown on a silicon substrate. At 1 sun illumination, a short-circuit current of 180 mA cm -2 is obtained, which is more than one order of magnitude higher than that predicted from the Lambert-Beer law. The enhanced light absorption is shown to be due to a light-concentrating property of the standing nanowire, as shown by photocurrent maps of the device. The results imply new limits for the maximum efficiency obtainable with III-V based nanowire solar cells under 1 sun illumination.N anowire-based solar cells hold great promise for third-generation photovoltaics and for powering nanoscale devices 1,2 . With the advent of third-generation photovoltaics, solar cells will become cheaper and more efficient than current devices. In particular, a cost reduction may be achieved by reducing material use through the fabrication of nanowire arrays and radial p-n junctions [3][4][5] . The geometry of nanowire crystals is expected to favour elastic strain relaxation, providing great freedom in the design of new compositional multijunction solar cells 6 grown on mismatched materials 7,8 . The efficiencies of nanostructured solar cells have increased over time and have now reached up to 13.8%, due to improvements in materials and new device concepts [9][10][11][12][13][14] .Light absorption in standing nanowires is a complex phenomenon, with a strong dependence on nanowire dimensions and the absorption coefficient of the raw materials [15][16][17][18] . In low-absorbing microwire arrays, such as those composed of silicon, light absorption is understood via ray optics or by calculation of the integrated local density of optical states of the nanowire film 19,20 . Interestingly, when these arrays stand on a Lambertian back-reflector, an asymptotic increase in light trapping for low filling factors (FFs) is predicted 19 . This is advantageous for improvement of the efficiency-to-cost ratio of solar cells and has led to the demonstration of microwire arrays exhibiting higher absorption than in the equivalent thickness of textured film 19,21,22 . The case for nanowires is quite different. Nanowire diameters are smaller than or comparable to the radiation wavelength. In this case, optical interference and guiding effects play a dominant role in relation to reflectivity and absorption spectra. For low-absorbing materials (for example, indirect bandgap materials such as silicon), waveguiding effects plays a key role 23,24 , whereas highly absorbing semiconductors (such as direct-bandgap GaAs) exhibit resonances that increase the total absorption several times. Nanowires lying on a substrate also exhibit such resonances, often described by Mi...

Continued development of high-efficiency multi-junction solar cells requires growth of latticemismatched materials. Today, the need for lattice matching both restricts the bandgap combinations available for multi-junctions solar cells and prohibits monolithic integration of high-efficiency III-V materials with low-cost silicon solar cells. The use of III-V nanowires is the only known method for circumventing this lattice-matching constraint, and therefore it is necessary to develop growth of nanowires with bandgaps 41.4 eV. Here we present the first gold-free gallium arsenide phosphide nanowires grown on silicon by means of direct epitaxial growth. We demonstrate that their bandgap can be controlled during growth and fabricate core-shell nanowire solar cells. We further demonstrate that surface passivation is of crucial importance to reach high efficiencies, and present a record efficiency of 10.2% for a core-shell single-nanowire solar cell. I mproving the cost/efficiency ratio of III-V-based multijunction cells can be done through efficiency enhancements, by adding additional junctions to the cell stack 1 or through the lowering of cost by replacing the expensive germanium substrate with silicon. Integrating III-V semiconductors and silicon requires overcoming their differences in lattice parameters and thermal expansion coefficient, as well as their polar/non-polar interfaces 2,3 . When constrained to a silicon-bottom cell, the optimum dualjunction solar cell, the simplest multi-junction solar cell, has a theoretical 1-sun peak efficiency between 33 and 43% (refs 4,5) when combined with a 1.7 eV bandgap top cell; this can be achieved with a III-V semiconductor consisting of GaAs 0.8 P 0.2.The small contact interface between the nanowire and the silicon substrate ensures that strain from lattice mismatch is relaxed within the first few monolayers 6 . Using the method of gallium (Ga)-assisted growth, gold-free perfect single crystal, gallium arsenide (GaAs) nanowires have been grown directly on silicon 7 . Higher bandgap gallium phosphide (GaP) 8 and gallium arsenide phosphide (GaAsP) 9,10 nanowires have also been grown, but only using gold as growth catalyst. Gold is incompatible with silicon 11 , and has been shown to incorporate into the III-V crystal 12 and degrade the optoelectronic properties of the nanowires 13 . In addition, a sparse array of nanowires can absorb almost all incoming light 14 , meaning that only minute amounts of the expensive III-V material is needed for making a nanowire top cell. Devices consisting of a contacted ensemble of free-standing nanowires have been exposed to temperature changes of up to 200 K, demonstrating that their strain-relieving ability is able to overcome the difference in thermal expansion 15 . To fully utilize their advantage with regards to non-lattice-matched growth, the nanowires themselves must also be able to function well as solar cells. ResultsGa-assisted GaAs 0.8 P 0.2 nanowire growth. High-quality GaAsP nanowires were grown without the use of a buffer la...

We realize the growth of self-catalyzed GaAsP nanowires (NWs) on silicon (111) substrates using solid-source molecular beam epitaxy. By optimizing the V/III and P/As flux ratios, as well as the Ga flux, high-crystal-quality GaAsP NWs have been demonstrated with almost pure zinc-blende phase. Comparing the growth of GaAsP NWs with that of the conventional GaAs NWs indicates that the incorporation of P has significant effects on catalyst nucleation energy, and hence the nanowire morphology and crystal quality. In addition, the incorporation ratio of P/As between vapor-liquid-solid NW growth and the vapor-solid thin film growth has been compared, and the difference between these two growth modes is explained through growth kinetics. The vapor-solid epitaxial growth of radial GaAsP shell on core GaAsP NWs is further demonstrated with room-temperature emission at ~710 nm. These results give valuable new information into the NW nucleation mechanisms and open up new perspectives for integrating III-V nanowire photovoltaics and visible light emitters on a silicon platform by using self-catalyzed GaAsP core-shell nanowires.

A quasi-3-fold composition symmetry has for the first time been observed in self-catalyzed III-V-V core-shell nanowires. In GaAsP nanowires, phosphorus-rich sheets on radial {110} planes originating at the corners of the hexagonal core were observed. In a cross section, they appear as six radial P-rich bands that originate at the six outer corners of the hexagonal core, with three of them higher in P content along ⟨112⟩A direction and others along ⟨112⟩B, forming a quasi-3-fold composition symmetry. We propose that these P-rich bands are caused by a curvature-induced high surface chemical potential at the small corner facets, which drives As adatoms away more efficiently than P adatoms. Moreover, their polarity related P content difference can be explained by the different adatom bonding energies at these polar corner facets. These results provide important information on the further development of shell growth in the self-catalyzed core-shell NW structure and, hence, device structure for multicomponent material systems.

The growth of self-catalyzed ternary core-shell GaAsP nanowire (NW) arrays on SiO2 patterned Si(111) substrates has been demonstrated by using solid-source molecular beam epitaxy. A high-temperature deoxidization step up to ∼ 900 °C prior to NW growth was used to remove the native oxide and/or SiO2 residue from the patterned holes. To initiate the growth of GaAsP NW arrays, the Ga predeposition used for assisting the formation of Ga droplets in the patterned holes, was shown to be another essential step. The effects of the patterned-hole size on the NW morphology were also studied and explained using a simple growth model. A lattice-matched radial GaAsP core-shell NW structure has subsequently been developed with room-temperature photoluminescence emission around 740 nm. These results open up new perspectives for integrating position-controlled III-V NW photonic and electronic structures on a Si platform.