Electromechanical conversion efficiency of GaN NWs: critical influence of the NW stiffness, the Schottky nano-contact and the surface charge effects.

The piezoelectric nanowires (NWs) are considered as promising nanomaterials to develop high-efficient piezoelectric generators. Establishing the relationship between their characteristics and their piezoelectric conversion properties is now essential to further improve the devices. However, due to their nanoscale dimensions, the NWs are characterized by new properties that are challenging to investigate. Here, we use an advanced nano-characterization tool derived from AFM to quantify the piezo-conversion properties of NWs axially compressed with a well-controlled applied force. This unique technique allows to establish the direct relation between the output signal generation and the NW stiffness and to quantify the electromechanical coupling coefficient of GaN NWs, which can reach up to 43.4%. We highlight that this coefficient is affected by the formation of the Schottky nano-contact harvesting the piezo-generated energy, and is extremely sensitive to the surface charge effects, strongly pronounced in sub-100 nm wide GaN NWs. These results constitute a new building block in the improvement of NW-based nanogenerator devices.

Investigation of the effect of the doping order in GaN nanowire p-n junctions grown by molecular-beam epitaxy.

We analyse the electrical and optical properties of single GaN nanowire p-n junctions grown by plasma-assisted molecular-beam epitaxy using magnesium and silicon as doping sources. Different junction architectures having either a n-base or a p-base structure are compared using optical and electrical analyses. Electron-beam induced current (EBIC) microscopy of the nanowires shows that in the case of a n-base p-n junction the parasitic radial growth enhanced by the magnesium (Mg) doping leads to a mixed axial-radial behaviour with strong wire-to-wire fluctuations of the junction position and shape. By reverting the doping order p-base p-n junctions with a purely axial well-defined structure and a low wire-to-wire dispersion are achieved. The good optical quality of the top n nanowire segment grown on a p-doped stem is preserved. A hole concentration in the p-doped segment exceeding 1018 cm-3 was extracted from EBIC mapping and photoluminescence analyses. This high concentration is reached without degrading the nanowire morphology.

Improvement of carrier collection in Si/a-Si:H nanowire solar cells by using hybrid ITO/silver nanowires contacts.

Optoelectronic devices based on high aspect ratio nanowires bring new challenges for transparent electrodes, which can be well addressed by using hybrid structures. Here we demonstrate that a composite contact to radial junction nanowire solar cells made of a thin indium-tin oxide (ITO) layer and silver nanowires greatly improves the collection of charge carriers as compared to a single thick ITO layer by reducing the series resistance losses while improving the transparency. The optimization is performed on p-i-n solar cells comprising of dense non-vertical nanowires with a p-doped c-Si core and an ultra-thin a-Si:H absorption layer grown by plasma-enhanced chemical vapor deposition on glass substrates. The optimal hybrid contact developed in this work is demonstrated to increase the solar cell conversion efficiency from 4.3% to 6.6%.

Nanoscale electrical analyses of axial-junction GaAsP nanowires for solar cell applications.

Axial p-n and p-i-n junctions in GaAs0.7P0.3 nanowires are demonstrated and analyzed using electron beam induced current microscopy. Organized self-catalyzed nanowire arrays are grown by molecular beam epitaxy on nanopatterned Si substrates. The nanowires are doped using Be and Si impurities to obtain p- and n-type conductivity, respectively. A method to determine the doping type by analyzing the induced current in the vicinity of a Schottky contact is proposed. It is demonstrated that for the applied growth conditions using Ga as a catalyst, Si doping induces an n-type conductivity contrary to the GaAs self-catalyzed nanowire case, where Si was reported to yield a p-type doping. Active axial nanowire p-n junctions having a homogeneous composition along the axis are synthesized and the carrier concentration and minority carrier diffusion lengths are measured. To the best of our knowledge, this is the first report of axial p-n junctions in self-catalyzed GaAsP nanowires.

Investigation of GaN nanowires containing AlN/GaN multiple quantum discs by EBIC and CL techniques.

In this work, nanoscale electrical and optical properties of n-GaN nanowires (NWs) containing GaN/AlN multiple quantum discs (MQDs) grown by molecular beam epitaxy are investigated by means of single wire I(V) measurements, electron beam induced current microscopy (EBIC) and cathodoluminescence (CL) analysis. A strong impact of non-intentional AlN and GaN shells on the electrical resistance of individual NWs is put in evidence. The EBIC mappings reveal the presence of two regions with internal electric fields oriented in opposite directions: one in the MQDs region and the other in the adjacent bottom GaN segment. These fields are found to co-exist under zero bias, while under an external bias either one or the other dominates the current collection. In this way EBIC maps allow us to locate the current generation within the wire under different bias conditions and to give the first direct evidence of carrier collection from AlN/GaN MQDs. The NWs have been further investigated by photoluminescence and CL analyses at low temperature. CL mappings show that the near band edge emission of GaN from the bottom part of the NW is blue-shifted due to the presence of the radial shell. In addition, it is observed that CL intensity drops in the central part of the NWs. Comparing the CL and EBIC maps, this decrease of the luminescence intensity is attributed to an efficient charge splitting effect due to the electric fields in the MQDs region and in the GaN base.

Nanoscale investigation of a radial p-n junction in self-catalyzed GaAs nanowires grown on Si (111).

One obstacle for the development of nanowire (NW) solar cells is the challenge to assess and control their nanoscale electrical properties. In this work a top-cell made of p-n GaAs core/shell NWs grown on a Si(111) substrate by Molecular Beam Epitaxy (MBE) is investigated by high resolution charge collection microscopy. Electron Beam Induced Current (EBIC) analyses of single NWs have validated the formation of a homogeneous radial p-n junction over the entire length of the NWs. The radial geometry leads to an increase of the junction area by 38 times with respect to the NW footprint. The interface between the NWs and the Si(111) substrate does not show any electrical loss, which would have led to a decrease of the EBIC signal. Single NW I-V characteristics present a diodic behavior. A model of the radial junction single NW is proposed and the electrical parameters are estimated by numerical fitting of the I-Vs and of the EBIC map. Solar cells based on NW arrays were fabricated and analyzed by EBIC microscopy, which evidenced the presence of a Schottky barrier at the NW/ITO top contact. Improvement of the top contact quality is achieved by thermal annealing at 400 °C, which strongly reduces the parasitic Schottky barrier.

Optimization of the optical coupling in nanowire-based integrated photonic platforms by FDTD simulation.

The optimized design of a photonic platform based on a nanowire light emitting diode (LED) and a nanowire photodetector connected with a waveguide is proposed. The light coupling efficiency from the LED to the detector is optimized as a function of the geometrical parameters of the system using the finite difference time domain simulation tool Lumerical. Starting from a design reported in the literature with a coupling efficiency of only 8.7%, we propose an optimized photonic platform with efficiency reaching 65.5%.

High Piezoelectric Conversion Properties of Axial InGaN/GaN Nanowires.

We demonstrate for the first time the efficient mechanical-electrical conversion properties of InGaN/GaN nanowires (NWs). Using an atomic force microscope equipped with a modified Resiscope module, we analyse the piezoelectric energy generation of GaN NWs and demonstrate an important enhancement when integrating in their volume a thick In-rich InGaN insertion. The piezoelectric response of InGaN/GaN NWs can be tuned as a function of the InGaN insertion thickness and position in the NW volume. The energy harvesting is favoured by the presence of a PtSi/GaN Schottky diode which allows to efficiently collect the piezo-charges generated by InGaN/GaN NWs. Average output voltages up to 330 ± 70 mV and a maximum value of 470 mV per NW has been measured for nanostructures integrating 70 nm-thick InGaN insertion capped with a thin GaN top layer. This latter value establishes an increase of about 35% of the piezo-conversion capacity in comparison with binary p-doped GaN NWs. Based on the measured output signals, we estimate that one layer of dense InGaN/GaN-based NW can generate a maximum output power density of about 3.3 W/cm². These results settle the new state-of-the-art for piezo-generation from GaN-based NWs and offer a promising perspective for extending the performances of the piezoelectric sources.

Flexible inorganic light emitting diodes based on semiconductor nanowires.

The fabrication technologies and the performance of flexible nanowire light emitting diodes (LEDs) are reviewed. We first introduce the existing approaches for flexible LED fabrication, which are dominated by organic technologies, and we briefly discuss the increasing research effort on flexible inorganic LEDs achieved by micro-structuring and transfer of conventional thin films. Then, flexible nanowire-based LEDs are presented and two main fabrication technologies are discussed: direct growth on a flexible substrate and nanowire membrane formation and transfer. The performance of blue, green, white and bi-color flexible LEDs fabricated following the transfer approach is discussed in more detail.

Flexible Photodiodes Based on Nitride Core/Shell p-n Junction Nanowires.

A flexible nitride p-n photodiode is demonstrated. The device consists of a composite nanowire/polymer membrane transferred onto a flexible substrate. The active element for light sensing is a vertical array of core/shell p-n junction nanowires containing InGaN/GaN quantum wells grown by MOVPE. Electron/hole generation and transport in core/shell nanowires are modeled within nonequilibrium Green function formalism showing a good agreement with experimental results. Fully flexible transparent contacts based on a silver nanowire network are used for device fabrication, which allows bending the detector to a few millimeter curvature radius without damage. The detector shows a photoresponse at wavelengths shorter than 430 nm with a peak responsivity of 0.096 A/W at 370 nm under zero bias. The operation speed for a 0.3 × 0.3 cm2 detector patch was tested between 4 Hz and 2 kHz. The -3 dB cutoff was found to be ∼35 Hz, which is faster than the operation speed for typical photoconductive detectors and which is compatible with UV monitoring applications.

Flexible White Light Emitting Diodes Based on Nitride Nanowires and Nanophosphors.

We report the first demonstration of flexible white phosphor-converted light emitting diodes (LEDs) based on p-n junction core/shell nitride nanowires. GaN nanowires containing seven radial In0.2Ga0.8N/GaN quantum wells were grown by metal-organic chemical vapor deposition on a sapphire substrate by a catalyst-free approach. To fabricate the flexible LED, the nanowires are embedded into a phosphor-doped polymer matrix, peeled off from the growth substrate, and contacted using a flexible and transparent silver nanowire mesh. The electroluminescence of a flexible device presents a cool-white color with a spectral distribution covering a broad spectral range from 400 to 700 nm. Mechanical bending stress down to a curvature radius of 5 mm does not yield any degradation of the LED performance. The maximal measured external quantum efficiency of the white LED is 9.3%, and the wall plug efficiency is 2.4%.

Substrate-Free InGaN/GaN Nanowire Light-Emitting Diodes.

We report on the demonstration of substrate-free nanowire/polydimethylsiloxane (PDMS) membrane light-emitting diodes (LEDs). Metal-organic vapour-phase epitaxy (MOVPE)-grown InGaN/GaN core-shell nanowires were encapsulated into PDMS layer. After metal deposition to p-GaN, a thick PDMS cap layer was spin-coated and the membrane was manually peeled from the sapphire substrate, flipped upside down onto a steel holder, and transparent indium tin oxide (ITO) contact to n-GaN was deposited. The fabricated LEDs demonstrate rectifying diode characteristics. For the electroluminescence (EL) measurements, the samples were manually bonded using silver paint. The EL spectra measured at different applied voltages demonstrate a blue shift with the current increase. This shift is explained by the current injection into the InGaN areas of the active region with different average indium content.

Color control of nanowire InGaN/GaN light emitting diodes by post-growth treatment.

Core/shell InGaN/GaN nanowire light emitting diodes (LEDs) based on vertically standing single nanowires and nanowire arrays were fabricated and extensively characterized. The emission of single wire LEDs with the same conformal contact geometry as the array device exhibits the same broadening as the array LED electroluminescence, which proves an excellent wire-to-wire homogeneity. The electroluminescence spectra present two peaks corresponding to the m-plane InGaN quantum well (blue emission) and to an In-rich region at the m-plane-semipolar plane junction (green emission), in agreement with structural characterizations. Modification of the contact layout and a post-growth plasma treatment enable strongly suppressing the unwanted green electroluminescence while increasing the intensity in the blue spectral range for the same injected electrical power. Electron beam induced current mapping proves the inhibition of the electrical activity of the top part of the nanowire after plasma treatment. Inductively coupled plasma etching of the In-rich region permits one to completely remove the green emission for all injection currents, but loss of intensity in the blue spectral range is observed. Selectively contacting the m-plane and plasma treatment of the top part of the nanowire appear as a viable solution for controlling the color of core/shell nanowire LEDs with an inhomogeneous indium composition.

Flexible Light-Emitting Diodes Based on Vertical Nitride Nanowires.

We demonstrate large area fully flexible blue LEDs based on core/shell InGaN/GaN nanowires grown by MOCVD. The fabrication relies on polymer encapsulation, nanowire lift-off and contacting using silver nanowire transparent electrodes. The LEDs exhibit rectifying behavior with a light-up voltage around 3 V. The devices show no electroluminescence degradation neither under multiple bending down to 3 mm curvature radius nor in time for more than one month storage in ambient conditions without any protecting encapsulation. Fully transparent flexible LEDs with high optical transmittance are also fabricated. Finally, a two-color flexible LED emitting in the green and blue spectral ranges is demonstrated combining two layers of InGaN/GaN nanowires with different In contents.

First demonstration of plasmonic GaN quantum cascade detectors with enhanced efficiency at normal incidence.

We have designed, fabricated and measured the first plasmon-assisted normal incidence GaN/AlN quantum cascade detector (QCD) making use of the surface plasmon resonance of a two-dimensional nanohole Au array integrated on top of the detector absorption region. The spectral response of the detector at room temperature is peaked at the plasmon resonance of 1.82 µm. We show that the presence of the nanohole array induces an absolute enhancement of the responsivity by a factor of ~30 over that of the bare device at normal incidence and by a factor of 3 with respect to illumination by the 45° polished side facet. We show that this significant improvement arises from two phenomena, namely, the polarization rotation of the impinging light from tangential to normal induced by the plasmonic structure and from the enhancement of the absorption cross-section per quantum well due to the near-field optical intensity of the plasmonic wave.

Nanometer scale spectral imaging of quantum emitters in nanowires and its correlation to their atomically resolved structure.

We report the spectral imaging in the UV to visible range with nanometer scale resolution of closely packed GaN/AlN quantum disks in individual nanowires using an improved custom-made cathodoluminescence system. We demonstrate the possibility to measure full spectral features of individual quantum emitters as small as 1 nm and separated from each other by only a few nanometers and the ability to correlate their optical properties to their size, measured with atomic resolution. The direct correlation between the quantum disk size and emission wavelength provides evidence of the quantum confined Stark effect leading to an emission below the bulk GaN band gap for disks thicker than 2.6 nm. With the help of simulations, we show that the internal electric field in the studied quantum disks is smaller than what is expected in the quantum well case. We show evidence of a clear dispersion of the emission wavelengths of different quantum disks of identical size but different positions along the wire. This dispersion is systematically correlated to a change of the diameter of the AlN shell coating the wire and is thus attributed to the related strain variations along the wire. The present work opens the way both to fundamental studies of quantum confinement in closely packed quantum emitters and to characterizations of optoelectronic devices presenting carrier localization on the nanometer scale.

Investigation of the electronic transport in GaN nanowires containing GaN/AlN quantum discs.

We report the investigation of electronic transport in GaN nanowires containing GaN/AlN quantum discs (QDiscs). The nanowires were grown by plasma-assisted molecular beam epitaxy and contacted by electron-beam lithography. Three nanowire samples containing QDiscs are analyzed and compared to a reference binary n-i-n GaN nanowire sample. The current-voltage measurements on single nanowires show that if the QDiscs are covered with a lateral GaN shell, the current mainly flows through the shell close to the lateral surface and the wire conductivity is extremely sensitive to the environmental conditions. On the contrary, if no GaN shell is present, the current flows through the QDisc region and a reproducible negative differential resistance related to electron tunneling through the QDiscs can be observed for temperatures up to 250 K. The demonstration of the resonant tunneling in GaN/AlN superlattices is of major importance for the development of nitride-based far-infrared quantum cascade lasers operating at high temperature.