In situpassivation of GaxIn(1-x)P nanowires using radial AlyIn(1-y)P shells grown by MOVPE.

GaxIn(1-x)P nanowires with suitable bandgap (1.35-2.26 eV) ranging from the visible to near-infrared wavelength have great potential in optoelectronic applications. Due to the large surface-to-volume ratio of nanowires, the surface states become a pronounced factor affecting device performance. In this work, we performed a systematic study of GaxIn(1-x)P nanowires' surface passivation, utilizing AlyIn(1-y)P shells grownin situby using a metal-organic vapor phase epitaxy system. Time-resolved photoinduced luminescence and time-resolved THz spectroscopy measurements were performed to study the nanowires' carrier recombination processes. Compared to the bare Ga0.41In0.59P nanowires without shells, the hole and electron lifetime of the nanowires with the Al0.36In0.64P shells are found to be larger by 40 and 1.1 times, respectively, demonstrating effective surface passivation of trap states. When shells with higher Al composition were grown, both lifetimes of free holes and electrons decreased prominently. We attribute the acceleration of PL decay to an increase in the trap states' density due to the formation of defects, including the polycrystalline and oxidized amorphous areas in these samples. Furthermore, in a separate set of samples, we varied the shell thickness. We observed that a certain shell thickness of approximately ∼20 nm is needed for efficient passivation of Ga0.31In0.69P nanowires. The photoconductivity of the sample with a shell thickness of 23 nm decays 10 times slower compared with that of the bare core nanowires. We concluded that both the hole and electron trapping and the overall charge recombination in GaxIn(1-x)P nanowires can be substantially passivated through growing an AlyIn(1-y)P shell with appropriate Al composition and thickness. Therefore, we have developed an effectivein situsurface passivation of GaxIn(1-x)P nanowires by use of AlyIn(1-y)P shells, paving the way to high-performance GaxIn(1-x)P nanowires optoelectronic devices.

Gain and bandwidth of InP nanowire array photodetectors with embedded photogated InAsP quantum discs.

Here we report on the experimental results and advanced self-consistent real device simulations revealing a fundamental insight into the non-linear optical response of n+-i-n+ InP nanowire array photoconductors to selective 980 nm excitation of 20 axially embedded InAsP quantum discs in each nanowire. The optical characteristics are interpreted in terms of a photogating mechanism that results from an electrostatic feedback from trapped charge on the electronic band structure of the nanowires, similar to the gate action in a field-effect transistor. From detailed analyses of the complex charge carrier dynamics in dark and under illumination was concluded that electrons are trapped in two acceptor states, located at 140 and 190 meV below the conduction band edge, at the interface between the nanowires and a radial insulating SiOx cap layer. The non-linear optical response was investigated at length by photocurrent measurements recorded over a wide power range. From these measurements were extracted responsivities of 250 A W-1 (gain 320)@20 nW and 0.20 A W-1 (gain 0.2)@20 mW with a detector bias of 3.5 V, in excellent agreement with the proposed two-trap model. Finally, a small signal optical AC analysis was made both experimentally and theoretically to investigate the influence of the interface traps on the detector bandwidth. While the traps limit the cut-off frequency to around 10 kHz, the maximum operating frequency of the detectors stretches into the MHz region.

Embedded sacrificial AlAs segments in GaAs nanowires for substrate reuse.

We report on the use of a sacrificial AlAs segment to enable substrate reuse for nanowire synthesis. A silicon nitride template was deposited on a p-type GaAs substrate. Then a pattern was transferred to the substrate by nanoimprint lithography and reactive ion etching. Thermal evaporation was used to define Au seed particles. Metalorganic vapour phase epitaxy was used to grow AlAs-GaAs NWs in the vapour-liquid-solid growth mode. The yield of synthesised nanowires, compared to the number expected from the patterned template, was more than 80%. After growth, the nanowires were embedded in a polymer and mechanically removed from the parent substrate. The parent substrate was then immersed in an HCl:H2O (1:1) mixture to dissolve the remaining stub of the sacrificial AlAs segment. The pattern fidelity was preserved after peeling off the nanowires and cleaning, and the semiconductor surface was flat and ready for reuse. Au seed particles were then deposited on the substrate by use of pulse electrodeposition, which was selective to the openings in the growth template, and then nanowires were regrown. The yield of regrowth was less optimal compared to the first growth but the pattern was preserved. Our results show a promising approach to reduce the final cost of III-V nanowire based solar cells.

High Responsivity of InP/InAsP Nanowire Array Broadband Photodetectors Enhanced by Optical Gating.

High-performance photodetectors operating in the near-infrared (0.75-1.4 µm) and short-wave infrared (1.4-3.0 µm) portion of the electromagnetic spectrum are key components in many optical systems. Here, we report on a combined experimental and theoretical study of square millimeter array infrared photodetectors comprising 3 million n+-i-n+ InP nanowires grown by MOVPE from periodically ordered Au seed particles. The nominal i-segment, comprising 20 InAs0.40P0.60 quantum discs, was grown by use of an optimized Zn doping to compensate the nonintentional n-doping. The photodetectors exhibit bias- and power-dependent responsivities reaching record-high values of 250 A/W at 980 nm/20 nW and 990 A/W at 532 nm/60 nW, both at 3.5 V bias. Moreover, due to the embedded quantum discs, the photoresponse covers a broad spectral range from about 0.70 to 2.5 eV, in effect outperforming conventional single InGaAs detectors and dual Si/Ge detectors. The high responsivity, and related gain, results from a novel proposed photogating mechanism, induced by the complex charge carrier dynamics involving optical excitation and recombination in the quantum discs and interface traps, which reduces the electron transport barrier between the highly doped n+ contact and the i-segment. The experimental results obtained are in perfect agreement with the proposed theoretical model and represent a significant step forward toward understanding gain in nanoscale photodetectors and realization of commercially viable broadband photon detectors with ultrahigh gain.

Effect of hydrogen chloride etching on carrier recombination processes of indium phosphide nanowires.

Introduction of in situ HCl etching to an epitaxial growth process has been shown to suppress radial growth and improve the morphology and optical properties of nanowires. In this paper, we investigate the dynamics of photo-generated charge carriers in a series of indium phosphide nanowires grown with varied HCl fluxes. Time resolved photo-induced luminescence, transient absorption and time resolved terahertz spectroscopy were employed to investigate charge trapping and recombination processes in the nanowires. Since the excitation photons generate charges predominantly in less than a half length of the nanowires, we can selectively assess the charge carrier dynamics at their top and bottom. We found that the photoluminescence decay is dominated by the decay of the mobile hole population due to trapping, which is affected by the HCl etching. The hole trapping rate is in general faster at the top of the nanowires than at the bottom. In contrast, electrons remain highly mobile until they recombine non-radiatively with the trapped holes. The slowest hole trapping as well as the least efficient non-radiative recombination was recorded for etching using the HCl molar fraction of χHCl = 5.4 × 10-5.

Three-Dimensional Imaging of Beam-Induced Biasing of InP/GaInP Tunnel Diodes.

Electron holographic tomography was used to obtain three-dimensional reconstructions of the morphology and electrostatic potential gradient of axial GaInP/InP nanowire tunnel diodes. Crystal growth was carried out in two opposite directions: GaInP-Zn/InP-S and InP-Sn/GaInP-Zn, using Zn as the p-type dopant in the GaInP but with changes to the n-type dopant (S or Sn) in the InP. Secondary electron and electron beam-induced current images obtained using scanning electron microscopy indicated the presence of p-n junctions in both cases and current-voltage characteristics measured via lithographic contacts showed the negative differential resistance, characteristic of band-to-band tunneling, for both diodes. Electron holographic tomography measurements confirmed a short depletion width in both cases (21 ± 3 nm) but different built-in potentials, Vbi, of 1.0 V for the p-type (Zn) to n-type (S) transition, and 0.4 V for both were lower than the expected 1.5 V for these junctions if degenerately doped. Charging induced by the electron beam was evident in phase images which showed nonlinearity in the surrounding vacuum, most severe in the case of the nanowire grounded at the p-type Au contact. We attribute their lower Vbi to asymmetric secondary electron emission, beam-induced current biasing, and poor grounding contacts.

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.

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.

Intersubband Quantum Disc-in-Nanowire Photodetectors with Normal-Incidence Response in the Long-Wavelength Infrared.

Semiconductor nanowires have great potential for realizing broadband photodetectors monolithically integrated with silicon. However, the spectral range of such detectors has so far been limited to selected regions in the ultraviolet, visible, and near-infrared regions. Here, we report on the first intersubband nanowire heterostructure array photodetectors exhibiting a spectrally resolved photoresponse from the visible to long-wavelength infrared. In particular, the infrared response from 3 to 20 µm is enabled by intersubband transitions in low-bandgap InAsP quantum discs synthesized axially within InP nanowires. The intriguing optical characteristics, including unexpected sensitivity to normal incident radiation, are explained by excitation of the longitudinal component of optical modes in the photonic crystal formed by the nanostructured portion of the detectors. Our results provide a generalizable insight into how broadband nanowire photodetectors may be designed and how engineered nanowire heterostructures open up new, fascinating opportunities for optoelectronics.

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.

Carrier Recombination Processes in Gallium Indium Phosphide Nanowires.

Understanding of recombination and photoconductivity dynamics of photogenerated charge carriers in GaxIn1-xP NWs is essential for their optoelectronic applications. In this letter, we have studied a series of GaxIn1-xP NWs with varied Ga composition. Time-resolved photoinduced luminescence, femtosecond transient absorption, and time-resolved THz transmission measurements were performed to assess radiative and nonradiative recombination and photoconductivity dynamics of photogenerated charges in the NWs. We conclude that radiative recombination dynamics is limited by hole trapping, whereas electrons are highly mobile until they recombine nonradiatively. We also resolve gradual decrease of mobility of photogenerated electrons assigned to electron trapping and detrapping in a distribution of trap states. We identify that the nonradiative recombination of charges is much slower than the decay of the photoluminescence signal. Further, we conclude that trapping of both electrons and holes as well as nonradiative recombination become faster with increasing Ga composition in GaxIn1-xP NWs. We have estimated early time electron mobility in GaxIn1-xP NWs and found it to be strongly dependent on Ga composition due to the contribution of electrons in the X-valley.

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.

InxGa1-xP Nanowire Growth Dynamics Strongly Affected by Doping Using Diethylzinc.

Semiconductor nanowires are versatile building blocks for optoelectronic devices, in part because nanowires offer an increased freedom in material design due to relaxed constraints on lattice matching during the epitaxial growth. This enables the growth of ternary alloy nanowires in which the bandgap is tunable over a large energy range, desirable for optoelectronic devices. However, little is known about the effects of doping in the ternary nanowire materials, a prerequisite for applications. Here we present a study of p-doping of InxGa1-xP nanowires and show that the growth dynamics are strongly affected when diethylzinc is used as a dopant precursor. Specifically, using in situ optical reflectometry and high-resolution transmission electron microscopy we show that the doping results in a smaller nanowire diameter, a more predominant zincblende crystal structure, a more Ga-rich composition, and an increased axial growth rate. We attribute these effects to changes in seed particle wetting angle and increased TMGa pyrolysis efficiency upon introducing diethylzinc. Lastly, we demonstrate degenerate p-doping levels in InxGa1-xP nanowires by the realization of an Esaki tunnel diode. Our findings provide insights into the growth dynamics of ternary alloy nanowires during doping, thus potentially enabling the realization of such nanowires with high compositional homogeneity and controlled doping for high-performance optoelectronics devices.