GaN Nanocrystals Research Articles

In-plane and out-of-plane domain orientation dispersions in 1 to 3 monolayers epitaxial WS2 and MoS2 films on GaN(0001) film/sapphire(0001)

Transition-metal dichalcogenides and their heterostructures have attractive potential applications in electronics and optoelectronics. Wafer scale 1 to 3 monolayers WS2 and MoS2 ultrathin films on GaN/sapphire substrates were grown by metal organic chemical vapor deposition. Azimuthal reflection high-energy electron diffraction (ARHEED) was used to characterize the long-range order of these TMDC ultrathin films. The RHEED patterns of WS2 and MoS2 show stripes and arcs but the MoS2 on GaN shows sharp spots in addition to stripes and arcs. The 2D map constructed from ARHEED patterns shows that WS2 is epitaxial and has an in-plane domain orientation dispersion. For the MoS2 on GaN/sapphire substrate, the 2D map shows concentric continuous rings for each diffraction order of MoS2 and GaN indicating that the in-plane MoS2 domain orientation and GaN nanocrystals are random. The out-of-plane orientation dispersion of MoS2 on the GaN substrate is larger than that of WS2 on the GaN substrate. The observations of stripes, arcs, and spots from RHEED patterns and the 2D maps reveal the deviation of ultrathin epitaxial films from its perfect epitaxy, especially the TMDC domain orientation dispersion over a large area. These rich findings from 2D maps broaden the application of ARHEED in more than one monolayer thick 2D materials.

Preparation of GaN Nanocrystals with Single Ag Cores

Preparation of GaN Nanocrystals with Single Ag Cores

Circumventing the ammonia-related growth suppression for obtaining regular GaN nanowires by HVPE

Selective area growth by hydride vapor phase epitaxy of GaN nanostructures with different shapes was investigated versus the deposition conditions including temperature and ammonia flux. Growth experiments were carried out on templates of GaN on sapphire masked with SiN x . We discuss two occurrences related to axial and radial growth of GaN nanowires. A growth suppression phenomenon was observed under certain conditions, which was circumvented by applying the cyclic growth mode. A theoretical model involving inhibiting species was developed to understand the growth suppression phenomenon on the masked substrates. Various morphologies of GaN nanocrystals were obtained by controlling the competition between the growth and blocking mechanisms as a function of the temperature and vapor phase composition. The optimal growth conditions were revealed for obtaining regular arrays of ∼5 μm long GaN nanowires.

Laser synthesis route for production of GaN nanocrystals for optical sensor protection

Laser synthesis route for production of GaN nanocrystals for optical sensor protection

A promising InGaAsN photoanode protected by multifunctional GaN nanocrystal for efficient photoelectrochemical water splitting

Photoelectrochemical (PEC) water splitting is one of the most promising techniques to produce sustainable hydrogen fuels. However, the sluggish oxygen evolution reaction (OER) kinetics and poor stability occurring on photoanodes greatly limit its practical application. In this work, a photoanode semiconductor using high-quality InGaAsN film was innovatively introduced to enhance PEC water oxidation. Further, GaN nanocrystal was deposited on InGaAsN photoanode to accelerate the transportation of photogenerated carriers and improve the photostability against electrolyte. Arising to the high light transparence of GaN and the favorable band alignment between GaN and InGaAsN, InGaAsN/GaN photoanode exhibited the enhanced light absorption and improved charge transfer and separation efficiency. As a result, the optimized InGaAsN/GaN photoanode showed a high photocurrent density of ∼120 mA cm−2 at 0.5 V vs. reversible hydrogen electrode (RHE) and an applied bias photo-to-current efficiency (ABPE) of over 6%. This study reveals that InGaAsN will be expected to be utilized in long-term and high-efficiency PEC cells.

Synthesis of Colloidal GaN and AlN Nanocrystals in Biphasic Molten Salt/Organic Solvent Mixtures under High-Pressure Ammonia.

Group III nitrides are of great technological importance for electronic devices. These materials have been widely manufactured via high-temperature methods such as physical vapor transport (PVT), chemical vapor deposition (CVD), and hydride vapor phase epitaxy (HVPE). The preparation of group III nitrides by colloidal synthesis methods would provide significant advantages in the form of optical tunability via size and shape control and enable cost reductions through scalable solution-based device integration. Solution syntheses of III-nitride nanocrystals, however, have been scarce, and the quality of the synthesized products has been unsatisfactory for practical use. Here, we report that incorporating a molten salt phase in solution synthesis can provide a viable option for producing crystalline III-nitride nanomaterials. Crystalline GaN and AlN nanomaterials can be grown in a biphasic molten-salt/organic-solvent mixture under an ammonia atmosphere at moderate temperatures (less than 300 °C) and stabilized under ambient conditions by postsynthetic treatment with organic surface ligands. We suggest that microscopic reversibility of monomer attachment, which is essential for crystalline growth, can be achieved in molten salt during the nucleation and the growth of the III-nitride nanocrystals. We also show that increased ammonia pressure increases the size of the GaN nanocrystals produced. This work demonstrates that use of molten salt and high-pressure reactants significantly expands the chemical scope of solution synthesis of inorganic nanomaterials.

The Surface Morphology Evolution of GaN Nucleation Layer during Annealing and Its Influence on the Crystal Quality of GaN Films

The surface morphology evolution of GaN nucleation layer (NL) after different annealing time has been investigated by atomic force microscope. The surface morphologies of GaN NL after different annealing time are island-like. It is observed that for 0-min annealing time sample nucleation islands (NIs) are high density and small in size which results in high dislocation density GaN films, while the samples with longer annealing time have low density and large size NIs which results in low dislocation density GaN films. The crystal structure of GaN NLs after different annealing time investigated by high-resolution X-ray diffraction indicates GaN NL is polycrystalline. During annealing, GaN nanocrystals misaligned with sapphire gradually disappear and GaN nanocrystals aligned with sapphire survive and grow up. Thus, the GaN NL surface has different NIs’ densities and sizes after different annealing time. The NL annealing time can effectively control the density and size of the NIs and further determine the GaN films crystal quality.

GaN nanocrystals obtained by Ga and N implantations and thermal treatment under N2 into SiO2/Si and SiNx/Si wafers

The formation of GaN nanocrystals in SiO2/Si and SiNx/Si dielectric layers implanted with Ga + and N + ions, followed by annealing at 950 °C for 60–120 min in N2, has been studied by high resolution transmission electron microscopy (HRTEM), synchrotron radiation X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) technique at the Ga K-edge, as well as by Rutherford Backscattering spectrometry (RBS), X-Ray photoelectron spectroscopy (XPS), Raman spectroscopy (RS) and Scanning electron microscopy (SEM). The effect of the dielectric matrix, of the gas annealing environment (N2) and of the annealing time at 950 °C have been investigated. GaN nanocrystals implanted near the surface are observed in SiO2/Si only. The hexagonal wurtzite crystalline structure was confirmed by HRTEM, XRD and Raman spectroscopy. However, the synthesis process is multiphasic as elemental Ga0 nanoparticles at larger depths and Ga2O3 rods (~200–300 nm) on the surface were formed in addition to implanted h-GaN, as shown by TEM, XAFS, SEM, XPS and Raman spectroscopy. Moreover, Ga atoms are always remaining on some vacant Si sites in the SiO2 matrix. The local environment around Ga is quite different in the SiNx matrix, as seen by XAFS. This difference can be explained by the gallium and nitrogen diffusions which are much faster in the case of the SiO2 matrix, as shown by RBS profiles. Results are discussed in close comparison with existing literature.

Enhancing crystal quality and optical properties of GaN nanocrystals by tuning pH of the synthesis solution

Abstract Gallium nitride nanocrystals as a wide bandgap semiconductor material for optoelectronic applications can be synthesized using chemical methods. In this research using co-precipitation and nitridation processes gallium nitride nanocrystals have been synthesized, and by tuning pH of the synthesis solution at the co-precipitation step, crystal quality and optical property of the resultant gallium nitride nanocrystals have been enhanced. Gallium nitride nanocrystal samples were synthesized using solutions with pH values of 2.1, 4.8, 7.8, and 9.0, and then nitridation at 950 °C under the flow of ammonia gas. The synthesized nanocrystal samples were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and photoluminescence techniques. The XRD data show that the nanocrystals have hexagonal wurtzite crystal structure, and using Scherer’s equation the sizes of the synthesized nanocrystals are 23.6, 26.6, 19.7, and 10.4 nm for the samples synthesized using the solutions with pH values of 2.1, 4.8, 7.8, and 9.0 respectively. The sizes of the nanocrystals obtained from SEM images are larger than the values obtained using Scherer’s equation, due to the aggregation of nanocrystals. EDX spectra show that pH of the synthesis solution affects the elemental stoichiometry of the gallium nitride nanocrystals. We obtained better stoichiometry for the nanocrystal sample synthesized using solution with the pH of 4.8. Photoluminescence spectra show that for this sample the emission intensity is higher than the others.

Highly Efficient Excitonic Recombination of Non-polar (11overline{2}0) GaN Nanocrystals for Visible Light Emitter by Hydride Vapour Phase Epitaxy

While non-polar nanostructured-GaN crystals are considered as a prospective material for the realization of futuristic opto-electronic application, the formation of non-polar GaN nanocrystals (NCs) with highly efficient visible emission characteristics remain unquestionable up to now. Here, we report the oxygen-incorporated a-plane GaN NCs with highly visible illumination excitonic recombination characteristics. Epitaxially aligned a-plane NCs with average diameter of 100 nm were formed on r-plane sapphire substrates by hydride vapor phase epitaxy (HVPE), accompanied by the oxygen supply during the growth. X-ray photoemission spectroscopy measurements proved that the NCs exhibited Ga-O bonding in the materials, suggesting the formation of oxidized states in the bandgap. It was found that the NCs emitted the visible luminescence wavelength of 400‒500 nm and 680‒720 nm, which is attributed to the transition from oxygen-induced localized states. Furthermore, time-resolved photoluminescence studies revealed the significant suppression of the quantum confined Stark effect and highly efficient excitonic recombination within GaN NCs. Therefore, we believe that the HVPE non-polar GaN NCs can guide the simple and efficient way toward the nitride-based next-generation nano-photonic devices.

Size control of GaN nanocrystals formed by ion implantation in thermally grown silicon dioxide

The growth of GaN nanocrystals in an amorphous SiO2 matrix by sequential Ga and N implantation and rapid thermal annealing is reported. The effect of the implantation and annealing conditions on the distribution of the implanted ions, as well as the size, static disorder, and stability of the grown GaN nanocrystals, is studied by means of transmission electron microscopy, Rutherford backscattering spectrometry, Raman scattering, and extended X-ray absorption fine structure spectroscopies. It is found that the optimum temperature range for the post-implantation annealing of the nanocrystals, with a size that ranges from about 3 to 12 nm, is 1000–1100 °C. Higher temperatures result in the dissociation of the nanocrystals and out-diffusion of N and Ga, whereas lower temperatures are insufficient for the growth of GaN nanocrystals. Annealing for 30–90 s is optimum in order to avoid considerable loss of N and Ga. However, upon annealing at higher temperatures within the optimum range, up to 1100 °C, or for longer times, up to 120 s, larger GaN nanocrystals are grown and/or lower static disorder is observed.

Forming the GaN Nanocrystals on the Graphene-Like g-AlN and g-Si3N3 Surface

The formation of GaN nanocrystals on the graphene-like AlN (g-AlN) modification and graphene-like (g-Si3N3) silicon nitride by ammonia molecular beam epitaxy has been investigated. It has been found that the GaN growth on the g-Si3N3 surface leads to the formation of misoriented nanocrystals. During the GaN growth on the g-AlN surface, the epitaxial growth of similarly oriented GaN quantum dots of the graphite-like modification has been observed. The lattice parameters and energy structure of two graphite-like GaN modifications with the alternating AB (graphite structure) and AA+ (hexagonal boron nitride structure) layers have been calculated.

Low temperature selective growth of GaN single crystals on pre-patterned Si substrates

We report on a hybrid method for fabrication of arrays of GaN nanocrystals by low-temperature UHV selective growth on pre-patterned silicon substrates covered by native oxide. Patterning of the substrates was performed by using a gallium focused ion beam (FIB). To get GaN nanocrystals at specific positions, Ga droplets were created at FIB patterned sites by evaporation of Ga atoms at 280 °C substrate temperature first, and then modified by their post-nitridation using an ultra-low energy (50 eV) nitrogen ion–beam at a sample temperature of 200 °C. To get larger arrays of GaN nanocrystals (≈150 nm and 200 nm in diameter), such a sequential process was repeated in several cycles at slightly modified operation conditions. The quality of the nanocrystals was checked by measurement of their photoluminescence properties which proved the occurrence of the peak of a band edge emission at around 367 nm (3.38 eV).

Upconversion emission of the GaN nanocrystals doped with rare earth ions

The crystalline powders of GaN doped with pairs of rare earth ions Er3+-Yb3+ or Ho3+-Yb3+, were synthesized with using the combustion and ammonolysis procedures. Spectroscopic properties of the investigated GaN nanosized samples were measured and analyzed. As excitation sources, the laser diodes operating at 808 and 975 nm were used. The upconversion emissions in the visible range were observed for used laser excitations. The upconversion emission properties depend on the synthesis conditions and the concentration ratio of the doped lanthanide ions.

Nanowire-Seeded Growth of Single-Crystalline (010) β-Ga2 O3 Nanosheets with High Field-Effect Electron Mobility and On/Off Current Ratio.

2D β-Ga2 O3 nanosheets, as fundamental materials, have great potential in next generations of ultraviolet transparent electrodes, high-temperature gas sensors, solar-blind photodetectors, and power devices, while their synthesis and growth with high crystalline quality and well-controlled orientation have not been reported yet. The present study demonstrates how to grow single-crystalline ultrathin quasi-hexagonal β-Ga2 O3 nanosheets with nanowire seeds and proposes a hierarchy-oriented growth mechanism. The hierarchy-oriented growth is initiated by epitaxial growth of a single-crystalline β-Ga2 O3 nanowire on a GaN nanocrystal and followed by homoepitaxial growth of quasi-hexagonal (010) β-Ga2 O3 nanosheets. The undoped 2D (010) β-Ga2 O3 nanosheet field effect transistor has a field-effect electron mobility of 38 cm2 V-1 s-1 and an on/off current ratio of 107 with an average subthreshold swing of 150 mV dec-1 . The from-nanowires-to-nanosheets technique paves a novel way to fabricate nanosheets, which has great impact on the field of nanomaterial synthesis and growth and the area of nanoelectronics as well.

Формирование нанокристаллов GaN на поверхности графеноподобных g-AlN и g-Si-=SUB=-3-=/SUB=-N-=SUB=-3-=/SUB=-

In this work, the GaN nanocrystals formation on a graphene-like modification of AlN (g-AlN) and graphene-like silicon nitride (g-Si3N3) by ammonia molecular beam epitaxy was studied. The GaN growth on the g-Si3N3 surface was found to result in the misoriented nanocrystals formation. With the GaN growth on the g-AlN surface, epitaxial growth of the equally oriented GaN quantum dots with graphite-like modification was observed. The lattice parameters and the energy structure of two GaN graphite-like modifications with alternating layers AB (graphite structure) and AA’ (hexagonal boron nitride structure) were calculated. This work was supported by the Russian Foundation for Basic Research (№ 17-02-00947-Бел_а and 18-52-00008-а). This work was supported by the Belarusian Republican Foundation for Basic Research in the framework of the joint project Ф18Р-234.

A simple synthesis of Ga2O3 and GaN nanocrystals

A simple top-down strategy to α-Ga2O3 and GaN nanocrystals is developed and the morphology-dependent optical properties of α-Ga2O3 crystals are established.

Mild preparation and high fluorescence emission efficiency of europium-doped gallium nitride nanocrystals and first-principles density functional theoretical analysis of optical properties

Eu:GaN nanocrystals have strong fluorescence emission and efficient energy transfer by means of DFT simulations. SiO2 coating improves the fluorescence quantum yield.

Magnetic Properties of Pure and Doped Gallium Nitride Nanocrystals.

In the present paper, Ga(1− x) Co(x) N, Ga(1− x) Ni(x) N and Ga(1− x) Tb(x) N (0 ≤ x ≤ 0.1) nanocrystals have been synthesized by a facile solvothermal method. Crystallographic characterization of synthesized materials has been done using powder X-ray diffraction technique. Recorded diffraction patterns reveal the formation of wurtzite (hexagonal) structured GaN nanocrystals. Electron microscopic studies have been carried for the detailed topographical and morphological analyses of synthesized nanomaterials. Recorded electron micrographs indicate the formation of nearly mono-disperse nanoparticles, having average size ˜4 nm. Magnetic measurements of doped nanocrystals revealed ferromagnetic behavior at room temperature however pure GaN is diamagnetic at room temperature.

Alignment control and atomically-scaled heteroepitaxial interface study of GaN nanowires.

Well-aligned GaN nanowires are promising candidates for building high-performance optoelectronic nanodevices. In this work, we demonstrate the epitaxial growth of well-aligned GaN nanowires on a [0001]-oriented sapphire substrate in a simple catalyst-assisted chemical vapor deposition process and their alignment control. It is found that the ammonia flux plays a key role in dominating the initial nucleation of GaN nanocrystals and their orientation. Typically, significant improvement of the GaN nanowire alignment can be realized at a low NH3 flow rate. X-ray diffraction and cross-sectional scanning electron microscopy studies further verified the preferential orientation of GaN nanowires along the [0001] direction. The growth mechanism of GaN nanowire arrays is also well studied based on cross-sectional high-resolution transmission electron microscopy (HRTEM) characterization and it is observed that GaN nanowires have good epitaxial growth on the sapphire substrate following the crystallographic relationship between (0001)GaN∥(0001)sapphire and (101[combining macron]0)GaN∥(112[combining macron]0)sapphire. Most importantly, periodic misfit dislocations are also experimentally observed in the interface region due to the large lattice mismatch between the GaN nanowire and the sapphire substrate, and the formation of such dislocations will favor the release of structural strain in GaN nanowires. HRTEM analysis also finds the existence of "type I" stacking faults and voids inside the GaN nanowires. Optical investigation suggests that the GaN nanowire arrays have strong emission in the UV range, suggesting their crystalline nature and chemical purity. The achievement of aligned GaN nanowires will further promote the wide applications of GaN nanostructures toward diverse high-performance optoelectronic nanodevices including nano-LEDs, photovoltaic cells, photodetectors etc.