InP Core Research Articles

Holographic imaging with a hard x-ray nanoprobe: ptychographic versus conventional phase retrieval.

We have performed near-field x-ray imaging with simultaneous object and probe reconstruction. By an advanced ptychographic algorithm based on longitudinal and lateral translations, full-field images of nanoscale objects are reconstructed with quantitative contrast values, along with the extended wavefronts used to illuminate the objects. The imaging scheme makes idealizing assumptions on the probe obsolete, and efficiently disentangles phase shifts related to the object from the imperfections in the illumination. We validate this approach by comparison to the conventional reconstruction scheme without simultaneous probe retrieval, based on the contrast transfer function algorithm. To this end, a set of semiconductor nanowires with controlled chemical composition (InP core, insulating SiO2 layer, and indium tin oxide cover) is imaged using the quasi-point source illumination realized by the hard x-ray nanofocus (26 nm×39 nm spot size) of the ID16A Nano-Imaging beamline at the European Synchrotron Radiation Facility.

Effect of Zinc Incorporation on the Performance of Red Light Emitting InP Core Nanocrystals.

This report presents a systematic study on the effect of zinc (Zn) carboxylate precursor on the structural and optical properties of red light emitting InP nanocrystals (NCs). NC cores were assessed using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), energy-dispersive X-ray spectroscopy (EDX), and high-resolution transmission electron microscopy (HRTEM). When moderate Zn:In ratios in the reaction pot were used, the incorporation of Zn in InP was insufficient to change the crystal structure or band gap of the NCs, but photoluminescence quantum yield (PLQY) increased dramatically compared with pure InP NCs. Zn was found to incorporate mostly in the phosphate layer on the NCs. PL, PLQY, and time-resolved PL (TRPL) show that Zn carboxylates added to the precursors during NC cores facilitate the synthesis of high-quality InP NCs by suppressing nonradiative and sub-band-gap recombination, and the effect is visible also after a ZnS shell is grown on the cores.

Emission wavelength control of self-catalytic InP/GaInAs/InP core–multishell nanowire on InP substrate grown by metal organic vapor phase epitaxy

InP nanowires and InP/GaInAs/InP core–multishell nanowires were successfully grown on an InP(111)B substrate by low-pressure metal organic vapor phase epitaxy (MOVPE) using an indium catalyst. The self-catalytic vapor–liquid–solid (VLS) mode was used to obtain high-quality nanowires in which a deposited indium droplet acts as the catalyst instead of a metal particle, as in the case of the conventional VLS mode. InP core nanowire structures dependent on growth temperature and preheating temperature were obtained. InP/GaInAs/InP core–multishell nanowire structures, densities, and optical properties were investigated at various flow rates of trimethylindium (TMI) during the growth of InP core nanowires and the growth time of the GaInAs shell layer was also studied. The growth volume and density of nanowires were mainly dependent on growth temperature and preheating temperature, respectively. The height of nanowires was dependent on the TMI flow rate in the InP core nanowire growth, and the thickness of GaInAs shell layer was controlled by adjusting the growth time of the GaInAs shell layer. The photoluminescence (PL) intensity increased with increasing nanowire height and the peak wavelength was controlled by adjusting the thickness of the GaInAs shell layer.

Beneficial effects of water in the colloidal synthesis of InP/ZnS core-shell quantum dots for optoelectronic applications.

We demonstrate that the presence of a small amount of water as an impurity during the hot-injection synthesis can significantly decrease the emission lines full width at half-maximum (FWHM) and improve the quantum yield (QY) of InP/ZnS quantum dots (QDs). By utilizing the water present in the indium precursor and solvent, we obtained InP/ZnS QDs emitting around 530 nm with a FWHM as narrow as 46 nm and a QY up to 45%. Without water, the synthesized QDs have emission around 625 nm with a FWHM of 66 nm and a QY of about 33%. Absorption spectra, XRD and XPS analyses revealed that when water is present, an amorphous phosphate layer is formed over the InP QDs and inhibits the QD growth. This amorphous layer favors the formation of a very thick ZnS shell by decreasing the lattice mismatch between the InP core and the ZnS shell. We further show the possibility to tune the emission wavelengths of InP/ZnS QDs by simply adjusting the amount of water present in the system while keeping all the other reaction parameters (i.e., precursor concentration, reaction temperature and time) constant. As an example of their application in light-emitting diodes (LEDs), the green and red InP/ZnS QDs are combined with a blue LED chip to produce white light.

Small-Size Effects on Electron Transfer in P3HT/InP Quantum Dots

The charge carrier photogeneration yield in hybrid polymer/nanocrystal solar cells strongly depends on the interplay between charge transfer across quantum dot (QD) organic capping layers and quantum confinement effects related to the QD size. Here we combine femtosecond transient spectroscopy and density functional theory (DFT) calculations to improve the understanding of charge transfer dynamics at P3HT/InP QD heterointerfaces as a function of core size (2.5 vs 4.5 nm) and length of the surface ligands (oleylamine vs pyridine). We find that, for large core QDs, the polaron generation yield in P3HT is enhanced by efficient exciton dissociation and charge transfer, and is limited by the length of the ligands. Conversely, for smaller size QDs, electron injection from P3HT to InP cores becomes inefficient due to the unfavorable interfacial energetics, even with short pyridine ligands. Thus, we suggest that both QD surface ligand functionalization and core size should be optimized simultaneously for the design of high-performance hybrid nanocrystal/polymer solar cells.

Simultaneous high-resolution scanning Bragg contrast and ptychographic imaging of a single solar cell nanowire.

Simultaneous scanning Bragg contrast and small-angle ptychographic imaging of a single solar cell nanowire are demonstrated, using a nanofocused hard X-ray beam and two detectors. The 2.5 µm-long nanowire consists of a single-crystal InP core of 190 nm diameter, coated with amorphous SiO2 and polycrystalline indium tin oxide. The nanowire was selected and aligned in real space using the small-angle scattering of the 140 × 210 nm X-ray beam. The orientation of the nanowire, as observed in small-angle scattering, was used to find the correct rotation for the Bragg condition. After alignment in real space and rotation, high-resolution (50 nm step) raster scans were performed to simultaneously measure the distribution of small-angle scattering and Bragg diffraction in the nanowire. Ptychographic reconstruction of the coherent small-angle scattering was used to achieve sub-beam spatial resolution. The small-angle scattering images, which are sensitive to the shape and the electron density of all parts of the nanowire, showed a homogeneous profile along the nanowire axis except at the thicker head region. In contrast, the scanning Bragg diffraction microscopy, which probes only the single-crystal InP core, revealed bending and crystalline inhomogeneity. Both systematic and non-systematic real-space movement of the nanowire were observed as it was rotated, which would have been difficult to reveal only from the Bragg scattering. These results demonstrate the advantages of simultaneously collecting and analyzing the small-angle scattering in Bragg diffraction experiments.

A Comparative Study of Absorption in Vertically and Laterally Oriented InP Core–Shell Nanowire Photovoltaic Devices

We have compared the absorption in InP core-shell nanowire p-i-n junctions in lateral and vertical orientation. Arrays of vertical core-shell nanowires with 400 nm pitch and 280 nm diameter, as well as corresponding lateral single core-shell nanowires, were configured as photovoltaic devices. The photovoltaic characteristics of the samples, measured under 1 sun illumination, showed a higher absorption in lateral single nanowires compared to that in individual vertical nanowires, arranged in arrays with 400 nm pitch. Electromagnetic modeling of the structures confirmed the experimental observations and showed that the absorption in a vertical nanowire in an array depends strongly on the array pitch. The modeling demonstrated that, depending on the array pitch, absorption in a vertical nanowire can be lower or higher than that in a lateral nanowire with equal absorption predicted at a pitch of 510 nm for our nanowire geometry. The technology described in this Letter facilitates quantitative comparison of absorption in laterally and vertically oriented core-shell nanowire p-i-n junctions and can aid in the design, optimization, and performance evaluation of nanowire-based core-shell photovoltaic devices.

Vapor–Solid growth of InP and Ga2O3 based composite nanowires

InP/Ga 2 O 3 core-shell nanowires were grown on Si substrate at 400 oC in the hydrazine (N 2 H 4 ) vapor diluted with 3 mol. % H 2 O. The crystalline InP and solid Ga served as source materials for the growth of nanowires. According to TEM and EDX data the nanowires consisted of wurtzite InP core with an amorphous Ga 2 O 3 shell. The minimum diameter of NWs was 14 nm, while the maximum lengths reached several micrometers. The twinned planes appeared in WZ InP core at increased nanowire diameters. Based on the obtained results and possible chemical reactions, the following mechanism was proposed for the growth of core-shell nanowires: pyrolytic decomposition of hydrazine caused the appearance of intermediate NH 2 , NH and H species in the vapor. At elevated temperatures the crystalline InP source was also dissociated to In droplets and phosphorus precursors. At source temperatures close to 600 oC, due to the interaction of In and Ga sources with water molecules and hydrazine decomposition products the volatile Ga 2 O and In 2 O were formed. These molecules reached the Si substrate which was heated to 400oC. The final chemical reaction involved Ga 2 O 3 , I 2 O 3 and phosphorus precursors. As a result of a spontaneous reaction the Ga 2 O 3 and InP phases were produced and segregated. The InP crystallized as a core while Ga 2 O 3 created the amorphous shell, because the growth temperature was insufficient for its crystallization.

Study of carrier concentration in single InP nanowires by luminescence and Hall measurements

The free electron carrier concentrations in single InP core–shell nanowires are determined by micro-photoluminescence, cathodoluminescence (CL) and Hall effect measurements. The results from luminescence measurements were obtained by solving the Fermi–Dirac integral, as well as by analyzing the peak full width at half maximum (FWHM). Furthermore, the platform used for Hall effect measurements, combined with spot mode CL spectroscopy, is used to determine the carrier concentrations at specific positions along single nanowires. The results obtained via luminescence measurements provide an accurate and rapid feedback technique for the epitaxial development of doping incorporation in nanowires. The technique has been employed on several series of samples in which growth parameters, such as V/III-ratio, temperature and dopant flows, were investigated in an optimization procedure. The correlation between the Hall effect and luminescence measurements for extracting the carrier concentration of different samples were in excellent agreement.

Growth of wurtzite GaP in InP/GaP core–shell nanowires by selective-area MOVPE

A GaP nanowire is promising from the viewpoint of device applications because when its crystal phase is changed from zinc blende (ZB) to wurtzite (WZ), its band gap changes from indirect to direct. GaP in the WZ phase is theoretically and experimentally shown to have the possibility of “green” emission. Here we report on the growth of WZ GaP in InP/GaP core–shell nanowires by selective-area metal–organic vapor-phase epitaxy (SA-MOVPE). WZ InP nanowires were used as a template for transferring the WZ structure to GaP. Transmission electron microscopy revealed that WZ GaP was grown on the sidewalls of the InP core in the lateral 〈−211〉 direction and that ZB GaP was grown on the top of the InP core in the axial 〈111〉A direction. A growth model for the different crystal structures of the GaP shell is proposed from the viewpoint of the growth direction. The WZ structure is “transferred” from the InP core to the GaP shell only when GaP grows in the direction perpendicular to the WZ stacking direction of the InP core. This so-called “crystal structure transfer” can also be applied to p- and n-doped GaP and is therefore promising for fabricating WZ-GaP-based light-emitting diodes.

Synthesis of Doped InP Core–Shell Nanowires Evaluated Using Hall Effect Measurements

InP core-shell nanowire pn-junctions doped with Zn and Sn have been investigated in terms of growth morphology and shell carrier concentration. The carrier concentrations were evaluated using spatially resolved Hall effect measurements and show improved homogeneity compared to previous investigations, attributed to the use of Sn as the n-type dopant. Anisotropies in the growth rate of different facets are found for different doping levels that in turn affects the migration of Sn and In on the nanowire surface. A route for increasing the In migration length to obtain a more homogeneous shell thickness is presented.

Thermal Stability of Colloidal InP Nanocrystals: Small Inorganic Ligands Boost High-Temperature Photoluminescence

We examine the stability of excitons in quantum-confined InP nanocrystals as a function of temperature elevation up to 800 K. Through the use of static and time-resolved spectroscopy, we find that small inorganic capping ligands substantially improve the temperature dependent photoluminescence quantum yield relative to native organic ligands and perform similarly to a wide band gap inorganic shell. For this composition, we identify the primary exciton loss mechanism as electron trapping through a combination of transient absorption and transient photoluminescence measurements. Density functional theory indicates little impact of studied inorganic ligands on InP core states, suggesting that reduced thermal degradation relative to organic ligands yields improved stability; this is further supported by a lack of size dependence in photoluminescence quenching, pointing to the dominance of surface processes, and by relative thermal stabilities of the surface passivating media. Thus, small inorganic ligands, which benefit device applications due to improved carrier access, also improve the electronic integrity of the material during elevated temperature operation and subsequent to high temperature material processing.

Interfacial Charge Separation and Recombination in InP and Quasi-Type II InP/CdS Core/Shell Quantum Dot-Molecular Acceptor Complexes

Recent studies of group II-VI colloidal semiconductor heterostuctures, such as CdSe/CdS core/shell quantum dots (QDs) or dot-in-rod nanorods, show that type II and quasi-type II band alignment can facilitate electron transfer and slow down charge recombination in QD-molecular electron acceptor complexes. To explore the general applicability of this wave function engineering approach for controlling charge transfer properties, we investigate exciton relaxation and dissociation dynamics in InP (a group III-V semiconductor) and InP/CdS core/shell (a heterostructure beween group III-V and II-VI semiconductors) QDs by transient absorption spectroscopy. We show that InP/CdS QDs exhibit a quasi-type II band alignment with the 1S electron delocalized throughout the core and shell and the 1S hole confined in the InP core. In InP-methylviologen (MV(2+)) complexes, excitons in the QD can be dissociated by ultrafast electron transfer to MV(2+) from the 1S electron level (with an average time constant of 11.4 ps) as well as 1P and higher electron levels (with a time constant of 0.39 ps), which is followed by charge recombination to regenerate the complex in its ground state (with an average time constant of 47.1 ns). In comparison, InP/CdS-MV(2+) complexes show similar ultrafast charge separation and 5-fold slower charge recombination rates, consistent with the quasi-type II band alignment in these heterostructures. This result demonstrates that wave function engineering in nanoheterostructures of group III-V and II-VI semiconductors provides a promising approach for optimizing their light harvesting and charge separation for solar energy conversion applications.

Optical characterization of InAs quantum wells and dots grown radially on wurtzite InP nanowires

Correlated micro-photoluminescence (μPL) and cathodoluminescence (CL) measurements are reported for single core–shell InP–InAs wurtzite nanowires grown using metal–organic vapor phase epitaxy. Samples covering a radial InAs shell thickness of 1–12 ML were investigated. The effective masses for the wurtzite material were determined from the transition energy dependence of the InAs shell thickness, using a model based on linear deformation potential theory. InP cores with segments of mixed zincblende and wurtzite, on which quantum dots nucleated selectively, were also investigated. Narrow peaks were observed by μPL and the spatial origin of the emission was identified with CL imaging.

The Optimization of InP/ZnS core/shell Nanocrystals and TiO2 Nanotubes for Quantum Dot Sensitized Solar Cells

ABSTRACTThe synthesis of InP/ZnS core/shell nanocrystals and TiO2 nanotubes and the optimization study to couple them together were explored for quantum dot sensitized solar cells. InP/ZnS nanocrystals have advantages of tunable optical properties and intrinsic nontoxicity. Highly luminescent InP/ZnS nanocrystals were produced by precursor-based colloidal synthesis for a photosensitizer. In order to improve on air stability, ZnS shell was grown on InP core. The emission peak was observed at 550 nm. Transmission electron microscopy (TEM) image shows that the nanocrystals highly crystalline and monodisperse. TiO2 nanotube is main inorganic material which is capable of harvesting light as well as being a prominent anode electrode in solar cells. The nanotubular form of TiO2 enhances charge transfer and reduces interfacial charge recombination. Free-standing TiO2 nanotubes were produced by anodization using ammonium fluoride. The free-standing nanotubes were formed under the condition that chemical dissolution speed which depends on fluoride concentration was faster than the speed of Ti oxidation. Electrophoretic deposition was carried out to couple the InP/ZnS nanocrystals with the TiO2 nanotubes. Under an optimized applied voltage condition, the current during the electrophoretic deposition decreased continuously with time. The amount of the deposited nanocrystals was estimated by calculation and the deposited nanocrystals on the TiO2 nanotubes were observed in the TEM.

Europium doped In(Zn)P/ZnS colloidal quantum dots

Chemically synthesised In(Zn)P alloy nanocrystals are doped with Eu(3+) ions using europium oleate as a molecular precursor and are subsequently covered with a ZnS shell. The presence of zinc in the synthesis of the InP core nanocrystals leads to the formation of an In(Zn)P alloy structure, making it possible to obtain stable fluorescence emission at 485 nm. We demonstrate by means of steady state and time resolved photoluminescence measurements that resonant energy transfer takes place from the In(Zn)P/ZnS host to the Eu(3+) dopant ions. It results in the characteristic phosphorescence lines of Eu(3+) originating from the transitions between the lowest-lying excited state (5)D0 to the (7)F(J) (J = 1, 2, 3, 4) ground states. The maximum phosphorescence efficiency is obtained for an initially applied Eu(3+) : In(3+) molar ratio of 0.3 : 1, resulting in a final doping level of approximately 4%.

InP/ZnS Nanocrystals: Coupling NMR and XPS for Fine Surface and Interface Description

Advanced (1)H, (13)C, and (31)P solution- and solid-state NMR studies combined with XPS were used to probe, at the molecular scale, the composition (of the core, the shell, and the interface) and the surface chemistry of InP/ZnS core/shell quantum dots prepared via a non-coordinating solvent strategy. The interface between the mismatched InP and ZnS phases is composed of an amorphous mixed oxide phase incorporating InPO(x) (with x = 3 and predominantly 4), In(2)O(3), and InO(y)(OH)(3-2y) (y = 0, 1). Thanks to the analysis of the underlying reaction mechanisms, we demonstrate that the oxidation of the upper part of the InP core is the consequence of oxidative conditions brought by decarboxylative coupling reactions (ketonization). These reactions occur during both the core preparation and the coating process, but according to different mechanisms.

Synthesis of blue emitting InP/ZnS quantum dots through control of competition between etching and growth

Blue (<480 nm) emitting Cd-free quantum dots (QDs) are in great demand for various applications. However, their synthesis has been challenging. Here we present blue emitting InP/ZnS core/shell QDs with a band edge emission of 475 nm and a full width at half maximum of 39 nm (215 meV) from their quantum confined states. The drastic temperature drop immediately after mixing of the precursors and holding them at a temperature below 150 °C was the critical factor for the synthesis of blue emitting QDs, because the blue QDs are formed by the etching of ultra-small InP cores by residual acetic acid below 150 °C. Etching was dominant at temperatures below 150 °C, whereas growth was dominant at temperatures above 150 °C. ZnS shells were formed successfully at 150 °C, yielding blue emitting InP/ZnS QDs. The colour of the InP/ZnS QDs depicted on the CIE 1931 chromaticity diagram is located close to the edge, indicating a pure blue colour compared to other InP-based QDs.

Solvothermal preparation and fluorescent properties of color-tunable InP/ZnS quantum dots

This work reports on the solvothermal preparation and optical properties of InP core and InP/ZnS core/shell quantum dots (QDs). InP QDs are synthesized using a phosphorus (P) source of tris(dimethylamino)phosphine (P(N(CH3)2)3) under the solvothermal conditions in the range of reaction temperature of 120–180°C and reaction time of 12h−1 week to tune their size. ZnS shelling is also solvothermally performed by varying the shell growth temperature from 180 to 220°C for 6h, and then respective InP and InP/ZnS QDs are subjected to the size-sorting procedure. Effects of the shelling temperature on the fluorescent attributes (emission peak wavelength, bandwidth, and quantum yield) of the resulting size-sorted InP/ZnS QD fractions are investigated. The qualitative information on the shell thickness as a function of shelling temperature is furthermore provided by x-ray diffraction and x-ray photoelectron spectroscopy.

Facilitating growth of InAs–InP core–shell nanowires through the introduction of Al

InAs nanowires were grown on GaAs substrates by the Au-assisted vapour–liquid–solid (VLS) method in a gas source molecular beam epitaxy (GSMBE) system. Passivation of the InAs nanowires using InP shells proved difficult due to the tendency for the formation of axial rather than core–shell structures. To circumvent this issue, AlxIn1−xAs or AlxIn1−xP shells with nominal Al composition fraction of x=0.20, 0.36, or 0.53 were grown by direct vapour–solid deposition on the sidewalls of the InAs nanowires. Characterisation by transmission electron microscopy revealed that the addition of Al in the shell resulted in a remarkable transition from the VLS to the vapour–solid growth mode with uniform shell thickness along the nanowire length. Possible mechanisms for this transition include reduced adatom diffusion, a phase change of the Au seed particle, and surfactant effects. The InAs–AlInP core-shell nanowires exhibited misfit dislocations, while the InAs–AlInAs nanowires with lower strain appeared to be free of dislocations.