Wet KOH etching of freestanding AlN single crystals

We investigated defect-selective wet chemical etching of freestanding aluminum nitride (AlN) single crystals and polished cuts in a molten NaOH–KOH eutectic at temperatures ranging from 240 to 400 °C. Due to the strong anisotropy of the AlN wurtzite structure, different AlN faces get etched at very different etching rates. On as-grown rhombohedral and prismatic facets, defect-related etching features could not be traced, as etching these facets was found to mainly emphasize features present already on the un-etched surface. On nitrogen polar basal planes, hexagonal pyramids/hillocks exceeding 100 μm in diameter may form within seconds of etching at 240 °C. They sometimes are arranged in lines and clusters, thus we attribute them to defects on the surface, presumably originating in the bulk material. On aluminum polar basal planes, the etch pit density which saturates after approx. 2–3 min of total etching time at 350 °C equals the density of a certain type of dislocations (presumably screw dislocations) threading the surface. Smaller etch pits form around annealed indentations, in the vicinity of some bigger etch pits after repeated etching, and sometimes also isolated on the surface area. Although alternate explanations exist, we attribute these etch pits to threading mixed and edge dislocations. This paper features etching parameters optimized for different planes and models on the formation of etching features especially on the polar faces. Finally, the issue of reliability and reproducibility of defect detection and evaluation by wet chemical etching is addressed.     

GaN-based lasers on SiC: influence of mirror reflectivity on L–I characteristics

The influence of the mirror reflectivity on the L–I characteristics of GaN-based lasers has been studied. A cleaved, Al-coated fiber is used as an external micro-mirror to control the reflectance of the end facets allowing for a continuous adjustment of mirror losses of a particular laser. In contrast to other methods, this eliminates all ambiguities usually arising from the comparison of different or differently coated devices. An increase in the single facet external quantum efficiency by 45% is observed for uncoated lasers and simultaneously, the threshold current is reduced by 12%. Internal losses of approximately 20–30 cm⁻¹ are derived from the differential quantum efficiency variation depending on the particular device under investigation.     

High-resolution imaging of 1:1 [0 0 0 1] ordered a-plane Al0.3Ga0.7N

We report the observation of ordering in Al_0.3Ga_0.7N as part of an epitaxial lateral overgrowth (ELO) of GaN carried out using (1 1 2¯ 2) GaN templates grown by metal-organic chemical vapor deposition on m-plane sapphire. Transmission electron microscopy showed that the crystalline quality of the ELO GaN was greatly improved when the ELO SiO₂ mask was patterned along the [1 1 2¯ 0]_sapphire direction. The ELO GaN wings had an inclined columnar shape with smooth (0 0 0 1) and (1 1 2¯ 0) facets. Layers of 1:1 [0 0 0 1] ordered a-plane Al_0.3Ga_0.7N were observed on the a-plane GaN facets by high-resolution transmission electron microscopy and high-angle annular-dark-field scanning transmission electron microscopy. However, no ordering was observed for c-plane Al_0.3Ga_0.7N layers grown at the same time on the c-plane GaN facets.     

Selective-controlled synthesis of one-dimensional strontium phosphates

Anorthic SrHPO₄ nanobelts and hexagonal Sr₁₀O(PO₄)₆ nanorods were obtained by a simple hydrothermal method without adding any surfactant as template. The as-synthesized products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). TEM and HRTEM observations of the products revealed that the as-prepared SrHPO₄ nanobelts and Sr₁₀O(PO₄)₆ hexagonal nanorods are single crystals with their preferential growth direction along the normal of (1 0 0) and (0 0 1) planes, respectively.     

Evolution of ordered one-dimensional and two-dimensional InAs/InP quantum dot arrays on patterned InP (1 0 0) and (3 1 1)B substrates by self-organized anisotropic strain engineering

The formation of ordered InAs/InP quantum dot (QD) arrays is demonstrated on patterned InP (1 0 0) and (3 1 1)B substrates by the concept of self-organized anisotropic strain engineering in chemical beam epitaxy (CBE). On shallow- and deep stripe-patterned InP (1 0 0) substrates, depending on the stripe orientation, the linear one-dimensional InAs QD arrays are rotated away from their natural direction due to the presence of vicinal stepped sidewall planes modifying the self-organization process, coexisting with QD free steep side facets on the deep-patterned substrates. On shallow- and deep-patterned InP (3 1 1)B substrates only QD free side facets form with flat top and bottom areas, not affecting the natural ordering of the two-dimensional InAs QD arrays. On the deep-patterned substrates a row of dense QDs forms on top along the side facets due to their slow-growing behavior. The optical properties of the QD arrays on the patterned substrates are not degraded compared to those of arrays formed on planar substrates for both InP (1 0 0) and (3 1 1)B substrates showing the potential of self-organized anisotropic strain engineering combined with step engineering for the creation of advanced complex QD arrays and networks.     

Anisotropic vapor phase growth of Ga2O3 crystalline nanobelts

Ga₂O₃ nanobelts were synthesized by gas reaction at high temperature in the presence of oxygen in ammonia. X-ray diffraction and chemical microanalysis revealed that the nanostructures were Ga₂O₃ with the monoclinic structure. Electron microscopy study indicated the nanobelts were single crystalline with broad (0 1 0) crystallographic planes. The nanostructures grew anisotropically with the growth direction of . Statistical analysis of the anisotropic morphology of the nanobelts and electron microscopy investigation of the nanobelt tips indicated that both vapor–solid and vapor–liquid–solid mechanisms controlled the growth process. The anisotropic nature of crystallographic morphology is explained in terms of surface energy.     

Template free-solvothermaly synthesized copper selenide (CuSe,Cu2−xSe, β-Cu2Se and Cu2Se) hexagonal nanoplates from different precursors at low temperature

Nonstoichiometric (Cu_2−xSe) and stoichiometric (CuSe, β-Cu₂Se and Cu₂Se) copper selenide hexagonal nanoplates have been synthesized using different general and convenient copper sources, e.g. copper chloride, copper sulphate, copper nitrate, copper acetate, elemental copper with elemental selenium, friendly ethylene glycol and hydrazine hydrate in a defined amount of water at 100 °C within 12 h adopting the solvothermal method. Phase analysis, purity and morphology of the product have been well studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray diffraction (EDAX) techniques. The structural and compositional analysis revealed that the products were of pure phase with corresponding atomic ratios. SEM, TEM and HRTEM analyses revealed that the nanoplates were in the range 200–450 nm and the as-prepared products were uniform and highly crystallized. The nanoplates consisted of {0 0 1} facets of top–bottom surfaces and {1 1 0} facets of the other six side surfaces. This new approach encompasses many advantages over the conventional solvothermal method in terms of product quality (better morphology control with high yield) and reaction conditions (lower temperatures). Copper selenide hexagonal nanoplates obtained by the described method could be potential building blocks to construct functional devices and solar cell. This work may open up a new rationale on designing the solution synthesis of nanostructures for materials possessing similar intrinsic crystal symmetry. On the basis of the carefully controlled experiments mentioned herein, a plausible formation mechanism of the hexagonal nanoplates was suggested and discussed. To the best of our knowledge, this is the first report on nonstoichiometric (Cu_2−xSe) as well as stoichiometric (CuSe, β-Cu₂Se and Cu₂Se) copper selenide hexagonal nanoplates with such full control of morphologies and phases by this method under mild conditions.     

Electron microscopy studies of epitaxial MgB2 superconducting thin films grown by in situ reactive evaporation

The morphology and chemistry of epitaxial MgB₂ thin films grown using reactive Mg evaporation on different substrates have been characterized by transmission electron microscopy methods. For polycrystalline alumina and sapphire substrates with different surface planes, an MgO transition layer was found at the interface region. No such layer was present for films grown on MgO and 4-H SiC substrates, and none of the MgB₂ films had any detectable oxygen incorporation nor MgO inclusions. High-resolution electron microscopy revealed that the growth orientation of the MgB₂ thin films was closely related to the substrate orientation and the nature of the intermediary layer. Electrical measurements showed that very low resistivities (several μΩ cm at 300 K) and high superconducting transition temperatures (38 to 40 K) could be achieved. The correlation of electrical properties with film microstructure is briefly discussed.     

Synthesis and characterization of type-II textured tungsten disulfide thin films by vdWR process with Pb interfacial layer as texture promoter

The growth of type-II textured tungsten disulfide (WS₂) thin films by solid state reaction between the spray deposited WO₃ and gaseous sulfur vapors with Pb interfacial layer has been studied. X-ray diffraction (XRD) technique is used to measure the degree of preferred orientation ‘S’ and texture of WS₂ films. Scanning electron microscopy (SEM) and transmission electron microscopy techniques have been used to examine the microstructure and morphology. The electronic structure and chemical composition were studied using X-ray photoelectron spectroscopy (XPS). The use of Pb interfacial layer for the promotion of type-II texture in WS₂ thin films is successfully demonstrated. The presence of (0 0 3 l), (where l=1, 2, 3, …) family of planes in the XRD pattern indicates the strong type-II texture of WS₂ thin films. The crystallites exhibit rhombohedral (3R) structure. The large value of ‘S’ (1086) prompts the high degree of preferred orientation as well. The stratum of crystallites with their basal plane parallel to the substrate surface is seen in the SEM image. The EDS and XPS analyses confirm the tungsten to sulfur atomic ratio as 1:1.75. We purport that Pb interfacial layer enhances type-II texture of WS₂ thin films greatly.     

Studies of the facetting of the polished (100) face of CaF2

The present paper deals with studies of the facetting of the polished (1 0 0) surface of CaF₂ during annealing and growth in UHV using low energy electron diffraction (LEED), atomic force microscopy (AFM), and transmission electron microscopy (TEM). First morphological modifications of the polished surfaces become visible at temperatures of T=874 K. Surfaces annealed at T=974 K exhibit a micro-roughening with pyramidal protrusions and corresponding depressions. LEED studies indicate the evolution of {1 1 1} facets. Reflexes from the (1 0 0) surface are not seen. After growth of about 660 monolayers of CaF₂ at T=1093 K and a saturation ratio S=33 from the vapor phase, larger pyramid-like or hip roof-like crystallites are developed. The results of AFM height profiles as well as of the LEED investigations indicate again the formation of {1 1 1} facets as proved by their angles of 54.7 ^o with the base (1 0 0) surface. This shows that the crystallites are homoepitaxially grown on the underlying CaF₂ substrate.     

Chemical vapor transport of zinc sulfide

Crystals of cubic zinc sulfide with different isotopic compositions have been grown by iodine vapor transport for basic research purposes (vibrational, electronic, and thermodynamic properties). The synthesis reaction in sulfur vapor was found to be controlled by solid-state diffusion of zinc atoms through a ZnS passivation layer. Crystals up to 5 mm in length were grown from small amounts of source material. The presence of argon reduced the nucleation density and favored the formation of facets.     

Molecular dynamics simulation of the crystallization of a liquid gold nanoparticle

Molecular dynamics simulation of the crystallization behavior of a liquid gold (Au) nanoparticle, about 4 nm in diameter, on cooling has been carried out based on the modified embedded-atom-method potential. With decreasing cooling rate, the final structure of the particle changes from amorphous to crystalline via icosahedron-like structure. While the outer shell of the icosahedron-like particle shows crystalline feature with {1 1 1}-like facets, the inner core remains amorphous. It is found that the structure of the fully crystallized particle is polycrystalline face-centered cubic (fcc). The fcc structure of the gold nanoparticle is proved energetically the most stable form.     

Pattern formation mechanism of a periodically faceted interface during crystallization ofSi

We investigated the pattern formation mechanism of a periodically faceted crystal–melt interface during the crystallization of Si by in situ observation. It was directly proved that spacing between the reentrants of adjacent zigzag facets increases with the unification of adjacent facets when a facet with a higher growth velocity catches up with the one with a lower growth velocity. The spacing becomes stable after unification, and the stable spacing was found to increase with increase in growth velocity. The experimental results was discussed by taking the negative temperature gradient in front of the growth interface into account.     

Surface analysis of different oriented GaAs substrates annealed under bismuth flow

Several orientations of GaAs substrates, including (1 0 0), (4 1 1), (1 1 1) and (5 1 1) have been annealed in a metalorganic vapour phase epitaxy (MOVPE) horizontal reactor at different annealing temperatures and under different trimethyl-bismuth (TMBi) flux. Surface morphology of the annealed GaAs substrates was investigated by means of scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results show islands formation on all the studied samples. The density and size of Bi islands vary greatly with annealing temperature and TMBi flow. For different substrate orientations, the activation energies were deduced from Arrhenius plot of island density. Except for (5 1 1) oriented GaAs, all the studied orientations show the same activation energy of 1.8 eV. For low annealing temperature 420 °C, and under different Bi flux, each oriented substrate shows a specific behaviour. For higher temperatures 700 °C and above Bi islands are totally removed and the substrates are smooth. Surface change of (1 0 0) oriented GaAs substrate was in situ monitored by laser reflectometry.     

Bi20TiO32 nanocones prepared from Bi–Ti–O mixture by metalorganic decomposition method

Bi₂₀TiO₃₂ in the form of nanocones are reported for the first time, which have been found during the formation of Bi₂Ti₂O₇ nanocrystals. Bi₂₀TiO₃₂ nanocones were prepared by metalorganic decomposition technique. From X-ray patterns, it was found that Bi₂₀TiO₃₂ is a metastable phase, and can transform gradually into Bi₂Ti₂O₇ phase with the annealing time increasing at a temperature of 550°C. The image of field emission scanning electron microscopy shows that the lengths of the nanocones are up to several micrometers and the diameters of cusps range from 20 to 200 nm. The studies of transmission electron microscopy show that the nanocones are crystalline Bi₂₀TiO₃₂. The growth mechanism of Bi₂₀TiO₃₂ nanocones has been proposed, which is similar to the vapor–liquid–solid growth mechanism.     

Reactions at the liquid silicon/silica glass interface

Experiments have been carried out to determine the nature and origin of the spots growing on silica glass surfaces in contact with liquid silicon during CZ–Si crystal growth. Silica glass ampoules were filled with silicon and tempered between 5 min and 40 h at a temperature (1693 K) slightly above the melting point of silicon. Cross sections of the ampoules with solidified silicon have been examined by scanning electron microscopy and optical polarization microscopy. In addition cross sections from commercial silica glass crucibles used in the Czochralski process or dipped into the silicon melt were investigated with the same methods. At the silicon/silica glass interface different reaction zone morphologies were detected. A solution-precipitation mechanism is suggested for the fast lateral growth of the reaction zone, which is proposed to consist of small cristobalite crystals embedded in a silica glass matrix.     

Mechanochemical metathesis synthesis and characterization of nano-structured MnV2O6·xH2O (x=2, 4)

A solid-state metathesis approach for the synthesis of hydrated MnV₂O₆·xH₂O (x=2, 4) materials driven by mechanochemical activation energy has been demonstrated. The metathesis pathway of forming the desired product is confirmed by the presence of high lattice energy by-product such as NaCl. The structural, optical, and chemical properties of the synthesized materials are examined by powder X-ray diffraction, X-ray photoelectron spectroscopy, thermo gravimetric analysis, scanning electron microscopy, transmission electron microscopy, and diffused reflectance measurements in the UV–vis range. The valence state of Mn and V was determined to be +2 and +5, respectively, for the title compounds and the bandgap values determined showed these materials are likely to be semiconductors.     

Epitaxial growth of tin oxide film on TiO2(1 1 0) using molecular beam epitaxy

Growth of tin oxide thin films using molecular beam epitaxy in a pyrolyzed nitrogen dioxide atmosphere on a titanium dioxide (1 1 0) substrate was investigated using X-ray photoelectron spectroscopy (XPS), electron diffraction, and atomic force microscopy (AFM). Properties of deposited films were studied for their dependence on substrate temperature and oxidation gas pressure. Analyses using XPS data revealed that tin atoms were fully oxidized to Sn⁴⁺ and SnO₂ films were grown epitaxially in deposition conditions of substrate temperatures of 627 K or higher and NO₂ pressure greater than 3×10⁻³ Pa. At a substrate temperature of 773 K, a smooth surface with atomic steps was visible in the SnO₂ films, but above or below this temperature, fine grains with crystal facets or porous structures appeared. At pressures of 8×10⁻⁴ to 3×10⁻⁴ Pa, the randomly oriented SnO phase was dominantly grown. Further decreasing the pressure, the Sn metal phase, which was epitaxially crystallized at less than 500 K, was also grown.     

The growth of Pd thin films on a 6H-SiC(0 0 0 1) substrate

Pd thin films, grown on Si-rich 6H-SiC(0 0 0 1) substrates, were studied by atomic force microscopy, electron diffraction and high-resolution transmission electron microscopy. It is concluded that the growth is successful only when all the growth process takes place at room temperature. Under these conditions a very good epitaxial growth of Pd is achieved, despite the large misfit (about 8.6%) between Pd and the substrate and the existence of a semi-amorphous layer between the thin film and the substrate. A large number of twins appear in these films.     

Selective area growth of GaN microstructures on patterned (1 1 1) and (0 0 1) Si substrates

Selective MOVPE growth of GaN microstructure on silicon substrates has been investigated using SiO₂ mask having circular or stripe window. In case of (0 0 1)substrate, grooves with (1 1 1) facets at the sides were made by using the etching anisotropy of a KOH solution. On the (1 1 1) facets of patterned silicon substrate (or on the as opened window region of (1 1 1) substrate), growth of wurtzite GaN was performed, of which the c-axis is oriented along the 1 1 1 axis of silicon. The photoluminescence and X-ray diffraction analysis were performed to characterize the single crystal to reveal the effect of the growth conditions of the intermediated layer and the microstructure.