Fast nanoscale imaging of strain in a multi-segment heterostructured nanowire with 2D Bragg ptychography.

Developing semiconductor devices requires a fast and reliable source of strain information with high spatial resolution and strain sensitivity. This work investigates the strain in an axially heterostructured 180 nm-diameter GaInP nanowire with InP segments of varying lengths down to 9 nm, simultaneously probing both materials. Scanning X-ray diffraction (XRD) is compared with Bragg projection ptychography (BPP), a fast single-projection method. BPP offers a sufficient spatial resolution to reveal fine details within the largest segments, unlike scanning XRD. The spatial resolution affects the quantitative accuracy of the strain maps, where BPP shows much-improved agreement with an elastic 3D finite element model compared with scanning XRD. The sensitivity of BPP to small deviations from the Bragg condition is systematically investigated. The experimental confirmation of the model suggests that the large lattice mismatch of 1.52% is accommodated without defects.

Modal analysis of resonant and non-resonant optical response in semiconductor nanowire arrays.

Nanowire array solar cells have reached efficiencies where it becomes feasible to talk about creating tandem solar cells in order to achieve even higher efficiencies. An example of such a tandem solar cell could be a nanowire array embedded in a membrane and integrated on top of a Si bottom cell. Such a system, however, requires understanding and control of its interaction with light, especially to make sure that the low energy photons are transmitted to the bottom cell. The dependence of the optical response of a nanowire array on the nanowire length, diameter, array pitch, materials surrounding the nanowires, and absorption coefficient of the nanowire material is very strong and possibly resonant, indicating the complexity of the optical response. In this work, we use an eigenmode-based analysis to reveal underlying physics that gives rise to observed resonant and non-resonant behavior. First, we show that an effective refractive index can be defined at long wavelengths, where only a single mode propagates. Second, we analyze the origin of the resonant reflection when the next optical mode becomes propagating and can be 'trapped' in the array and interact with the fundamental mode. Additionally, we define two simple boundaries for the wavelength range of the resonant response: the resonances can only occur if there is more than 1 propagating mode in the array, and they disappear if the 1st diffracted order is propagating in the top or bottom material. Such resonance effects could be detrimental for tandem solar cells. We thus provide recommendations for tuning the geometry of the array and the nanowire materials in order to push the resonant regime to the absorbing regime of the nanowire, where absorption in the nanowires dampens the resonances. Finally, this work demonstrates the strength of an eigenmode-based analysis of the optical response of periodic nanostructures in terms of simplifying the analysis of a complex system.

Nanobeam X-ray Fluorescence Dopant Mapping Reveals Dynamics of in Situ Zn-Doping in Nanowires.

The properties of semiconductors can be controlled using doping, making it essential for electronic and optoelectronic devices. However, with shrinking device sizes it becomes increasingly difficult to quantify doping with sufficient sensitivity and spatial resolution. Here, we demonstrate how X-ray fluorescence mapping with a nanofocused beam, nano-XRF, can quantify Zn doping within in situ doped III-V nanowires, by using large area detectors and high-efficiency focusing optics. The spatial resolution is defined by the focus size to 50 nm. The detection limit of 7 ppm (2.8 × 1017 cm-3), corresponding to about 150 Zn atoms in the probed volume, is bound by a background signal. In solar cell InP nanowires with a p-i-n doping profile, we use nano-XRF to observe an unintentional Zn doping of 5 × 1017 cm-3 in the middle segment. We investigated the dynamics of in situ Zn doping in a dedicated multisegment nanowire, revealing significantly sharper gradients after turning the Zn source off than after turning the source on. Nano-XRF could be used for quantitative mapping of a wide range of dopants in many types of nanostructures.

Spectrally resolved x-ray beam induced current in a single InGaP nanowire.

We demonstrate x-ray absorption fine structure spectroscopy (XAFS) detected by x-ray beam induced current (XBIC) in single n + -i-n + doped nanowire devices. Spatial scans with the 65 nm diameter beam show a peak of the XBIC signal in the middle segment of the nanowire. The XBIC and the x-ray fluorescence signals were detected simultaneously as a function of the excitation energy near the Ga K absorption edge at 10.37 keV. The spectra show similar oscillations around the edge, which shows that the XBIC is limited by the primary absorption. Our results reveal the feasibility of the XBIC detection mode for the XAFS investigation in nanostructured devices.

Growth kinetics of Ga x In(1-x)P nanowires using triethylgallium as Ga precursor.

Ga x In(1-x)P nanowire arrays are promising for various optoelectronic applications with a tunable band-gap over a wide range. In particular, they are well suited as the top cell in tandem junction solar cell devices. So far, most Ga x In(1-x)P nanowires have been synthesized by the use of trimethylgallium (TMGa). However, particle assisted nanowire growth in metal organic vapor phase epitaxy is typically carried out at relatively low temperatures, where TMGa is not fully pyrolysed. In this work, we developed the growth of Ga x In(1-x)P nanowires using triethylgallium (TEGa) as the Ga precursor, which reduced Ga precursor consumption by about five times compared to TMGa due to the lower homogeneous pyrolysis temperature of TEGa. The versatility of TEGa is shown by synthesis of high yield Ga x In(1-x)P nanowire arrays, with a material composition tunable by the group III input flows, as verified by x-ray diffraction measurements and photoluminescence characterization. The growth dynamics of Ga x In(1-x)P nanowires was assessed by varying the input growth precursor molar fractions and growth temperature, using hydrogen-chloride as in situ etchant. We observed a complex interplay between the precursors. First, trimethylindium (TMIn) inhibits Ga incorporation into the nanowires, resulting in higher In composition in the grown nanowires than in the vapor. Second, the growth rate increases with temperature, indicating a kinetically limited growth, which from nanowire effective binary volume growth rates of InP and GaP can be attributed to the synthesis of GaP in Ga x In(1-x)P. We observed that phosphine has a strong effect on the nanowire growth rate with behavior expected for a unimolecular Langmuir-Hinshelwood mechanism of pyrolysis on a catalytic surface. However, growth rates increase strongly with both TEGa and TMIn precursors as well, indicating the complexity of vapor-liquid-solid growth for ternary materials. One precursor can affect the decomposition of another, and each precursor can affect the wetting properties and catalytic activity of the metal particle.

Electrical and optical evaluation of n-type doping in In x Ga(1-x)P nanowires.

To harvest the benefits of III-V nanowires in optoelectronic devices, the development of ternary materials with controlled doping is needed. In this work, we performed a systematic study of n-type dopant incorporation in dense In x Ga(1-x)P nanowire arrays using tetraethyl tin (TESn) and hydrogen sulfide (H2S) as dopant precursors. The morphology, crystal structure and material composition of the nanowires were characterized by use of scanning electron microscopy, transmission electron microscopy and energy dispersive x-ray analysis. To investigate the electrical properties, the nanowires were broken off from the substrate and mechanically transferred to thermally oxidized silicon substrates, after which electron beam lithography and metal evaporation were used to define electrical contacts to selected nanowires. Electrical characterization, including four-probe resistivity and Hall effect, as well as back-gated field effect measurements, is combined with photoluminescence spectroscopy to achieve a comprehensive evaluation of the carrier concentration in the doped nanowires. We measure a carrier concentration of ∼1 × 1016 cm-3 in nominally intrinsic nanowires, and the maximum doping level achieved by use of TESn and H2S as dopant precursors using our parameters is measured to be ∼2 × 1018 cm-3, and ∼1 × 1019 cm-3, respectively (by Hall effect measurements). Hence, both TESn and H2S are suitable precursors for a wide range of n-doping levels in In x Ga(1-x)P nanowires needed for optoelectronic devices, grown via the vapor-liquid-solid mode.

Time-resolved photoluminescence characterization of GaAs nanowire arrays on native substrate.

Time-resolved photoluminescence (TRPL) measurements of nanowires (NWs) are often carried out on broken-off NWs in order to avoid the ensemble effects as well as substrate contribution. However, the development of NW-array solar cells could benefit from non-destructive optical characterization to allow faster feedback and further device processing. With this work, we show that different NW array and substrate spectral behaviors with delay time and excitation power can be used to determine which part of the sample dominates the detected spectrum. Here, we evaluate TRPL characterization of dense periodic as-grown GaAs NW arrays on a p-type GaAs substrate, including a sample with uncapped GaAs NWs and several samples passivated with AlGaAs radial shell of varied composition and thickness. We observe a strong spectral overlap of substrate and NW signals and find that the NWs can absorb part of the substrate luminescence signal, thus resulting in a modified substrate signal. The level of absorption depends on the NW-array geometry, making a deconvolution of the NW signal very difficult. By studying TRPL of substrate-only and as-grown NWs at 770 and 400 nm excitation wavelengths, we find a difference in spectral behavior with delay time and excitation power that can be used to assess whether the signal is dominated by the NWs. We find that the NW signal dominates with 400 nm excitation wavelength, where we observe two different types of excitation power dependence for the NWs capped with high and low Al composition shells. Finally, from the excitation power dependence of the peak TRPL signal, we extract an estimate of background carrier concentration in the NWs.

Absorption and transmission of light in III-V nanowire arrays for tandem solar cell applications.

III-V semiconductor nanowires are a platform for next-generation photovoltaics. An interesting research direction is to embed a nanowire array in a transparent polymer, either to act as a stand-alone flexible solar cell, or to be stacked on top of a conventional Si bottom cell to create a tandem structure. To optimize the tandem cell performance, high energy photons should be absorbed in the nanowires whereas low energy photons should be transmitted to and absorbed in the Si cell. Here, through optical measurements on 1.95 eV bandgap GaInP nanowire arrays embedded in a polymer membrane, we identify two mechanisms that could be detrimental for the performance of the tandem cell. First, the Au particles used in the nanowire synthesis can absorb >50% of the low-energy photons, leading to a <40% transmittance, even though the Au particles cover <15% of the surface area. The removal of the Au particles can recover the transmission of low energy photons to >80%. Second, after the removal of the Au particles, a 40% reflectance peak shows up due to resonant back-scattering of light from in-plane waveguide modes. To avoid the excitation of these optical modes in the nanowire array, we propose to limit the pitch of the nanowire array.