Evolution of the Growth Mode and Its Consequences during Bulk Crystallization of GaN.

A detailed analysis of morphology of gallium nitride crystal growth obtained by ammonothermal and halide vapor phase epitaxy methods was carried out. The work was conducted to determine the source of triangular planar defects visible in X-ray topography as areas with locally different lattice parameters. It is shown that the occurrence of these defects is related to growth hillocks. Particular attention was paid to analyzing the manner and consequences of merging hillocks. In the course of the study, the nature of the mentioned defects and the cause of their formation were determined. It was established that the appearance of the defects depends on the angle formed between the steps located on the sides of two adjacent hillocks. A universal growth model is presented to explain the cause of heterogeneity during the merging of growth hillocks.

SERS performance of GaN/Ag substrates fabricated by Ag coating of GaN platforms.

The results of comparative studies on the fabrication and characterization of GaN/Ag substrates using pulsed laser deposition (PLD) and magnetron sputtering (MS) and their evaluation as potential substrates for surface-enhanced Raman spectroscopy (SERS) are reported. Ag layers of comparable thicknesses were deposited using PLD and MS on nanostructured GaN platforms. All fabricated SERS substrates were examined regarding their optical properties using UV-vis spectroscopy and regarding their morphology using scanning electron microscopy. SERS properties of the fabricated GaN/Ag substrates were evaluated by measuring SERS spectra of 4-mercaptobenzoic acid molecules adsorbed on them. For all PLD-made GaN/Ag substrates, the estimated enhancement factors were higher than for MS-made substrates with a comparable thickness of the Ag layer. In the best case, the PLD-made GaN/Ag substrate exhibited an approximately 4.4 times higher enhancement factor than the best MS-made substrate.

Influence of sandwich-type DNA construction strategy and plasmonic metal on signal generated by SERS DNA sensors.

The DNA biosensors are powerful tools in the gene mutation or pathogens detection. That is why there are a lot of DNA detection strategies and methods. Here we present the insight on a slightly overlooked DNA detection technique, surface-enhanced Raman scattering (SERS). The present work is a summary of the influence of the plasmonic metal of the SERS substrate and strategy of the sandwich-type biosensor construction, simply the placement of the Raman reporter and mismatches, on the SERS signal enhancement. We found that, although in general there is an increase in the intensity of the SERS signal when the distance between the Raman scatterer and the SERS-active surface decreases, for this type of DNA SERS sensor a greater intensity of the measured Raman signal is usually observed when the Raman reporter is farther away from the plasmonic substrate. This is probably caused by a significant change in the hybridisation efficiency for the different structures of the sensor analysed due to some steric hindrances.

Surface-enhanced Raman scattering used to study the structure of layers formed on metal surfaces from single-stranded DNA and 6-mercaptohexan-1-ol: influence of hybridization with the complementary DNA and influence of the metal substrate.

Capture single-stranded DNA with an attached alkanethiol linking moiety (capture HS-ssDNA) and 6-mercaptohexan-1-ol were chemisorbed on nanostructured GaN covered with sputtered layers of plasmonic metals (like silver and gold). The structure of the formed layer was determined by surface-enhanced Raman scattering (SERS) measurements. Hybridization with the target ssDNA, complementary to the chains of immobilized capture HS-ssDNA, induced changes in the conformation of the chains of chemisorbed ω-substituted alkanetiols (6-mercaptohexan-1-ol and the alkanethiol linking moiety of HS-ssDNA). Such changes are significantly larger in the case of experiments on silver than on gold and gold/silver SERS substrates. This means that silver substrates are significantly more promising for the SERS observation of such hybridization-induced rearrangements than the gold substrates previously used. Although the sputtered metal films have a nanograin structure, the nanostructuring of the GaN substrates plays an important role in the SERS-activity of this nanomaterial.

Large-Scale Defect Clusters with Hexagonal Honeycomb-like Arrangement in Ammonothermal GaN Crystals.

In this paper, we investigate, using X-ray Bragg diffraction imaging and defect selective etching, a new type of extended defect that occurs in ammonothermally grown gallium nitride (GaN) single crystals. This hexagonal "honeycomb" shaped defect is composed of bundles of parallel threading edge dislocations located in the corners of the hexagon. The observed size of the honeycomb ranges from 0.05 mm to 2 mm and is clearly correlated with the number of dislocations located in each of the hexagon's corners: typically ~5 to 200, respectively. These dislocations are either grouped in areas that exhibit "diameters" of 100-250 µm, or they show up as straight long chain alignments of the same size that behave like limited subgrain boundaries. The lattice distortions associated with these hexagonally arranged dislocation bundles are extensively measured on one of these honeycombs using rocking curve imaging, and the ensemble of the results is discussed with the aim of providing clues about the origin of these "honeycombs".

Fundamental Studies on Crystallization and Reaching the Equilibrium Shape in Basic Ammonothermal Method: Growth on a Native Lenticular Seed.

In this paper, a detailed investigation of the basic ammonothermal growth process of GaN is presented. By analyzing the crystallization on a native seed with a lenticular shape, thus with an intentionally varying off-cut, we wanted to answer some basic questions: (i) Which crystallographic planes play the most important role during growth (which planes are formed and which disappear)? (ii) What is the relationship between the growth rates in different crystallographic directions? (iii) What is the influence of the off-cut of the seed on the growth process? Two non-polar slices, namely, 12¯10 and 1¯100, as well as a 0001 basal plane slice of an ammonothermal crystal were analyzed. The examined planes were selectively etched in order to reveal the characteristic features of the growth process. The applied characterization methods included: optical microscopy with Nomarski contrast and ultraviolet illumination, X-ray topography and high-resolution X-ray diffraction, and secondary ion mass spectrometry. The obtained results allowed for creating a growth model of an ammonothermal GaN crystal on a lenticular seed. These findings are of great importance for the general understanding of the basic ammonothermal crystal growth process of GaN.

Investigation of organic monoradicals reactivity using surface-enhanced Raman spectroscopy.

Surface-enhanced Raman spectroscopy (SERS) and self-assembled monolayer (SAM) approaches were used to investigate the reactions of organic monoradicals with methanol. An attempt was made to generate monoradicals from thiophenols and phenylmethanethiols substituted with bromine, iodine, and nitro groups by irradiation with UV light. Monolayers of radical precursors were deposited on SERS substrates, which were then immersed in methanol and irradiated for 1 and/or 3, 6, 12 and 24 h in a UV photochemical reactor. Pre- and postreaction SERS spectra were obtained by using a confocal Raman microscope and compared with the spectra of expected products of the radical reaction with methanol. Our studies have shown that the efficiency of monoradical generation is highly dependent on the chemical structure of the precursor. In addition, it is shown that both the SERS substrate and experimental conditions used strongly influence the obtained results.

New strategy for the gene mutation identification using surface enhanced Raman spectroscopy (SERS).

An early and accurate diagnosis of a specific DNA mutations has a decisive role for effective treatment. Especially, when an immediate decision on treatment most needs to be made, the rapid and precise confirmation of clinical findings is vital. Herein, we show a new strategy for the gene mutation (BRAF c.1799T>A; p. V600E) identification using highly SERS-active and reproducible SERS substrate (photo-etched GaN covered with a thin layer of sputtered gold) and surface enhanced Raman scattering (SERS) spectroscopy. The detection is based on the conformation change (gauche → trans) of the alkanethiol linker modifying the capture DNA during the hybridization process. The value of the intensity ratio of the ν(C-S) bands of the trans and gauche conformer higher than 1.0 indicated the presence of mutation. The demonstrated new DNA SERS (bio)sensor is characterized by the low detection limit at the level of pg µL-1, wide analytical range from 6.75 pg µL-1 to 67.5 ng µL-1 and high selectivity. The proposed bioactive platforms, based on nanostructured GaN substrates modified with thiolated ssDNA (single stranded DNA) can be successfully used in the analysis of clinical samples.

Infrared Reflectance Analysis of Epitaxial n-Type Doped GaN Layers Grown on Sapphire.

Infrared (IR) reflectance spectroscopy is applied to study Si-doped multilayer n+/n0/n+-GaN structure grown on GaN buffer with GaN-template/sapphire substrate. Analysis of the investigated structure by photo-etching, SEM, and SIMS methods showed the existence of the additional layer with the drastic difference in Si and O doping levels and located between the epitaxial GaN buffer and template. Simulation of the experimental reflectivity spectra was performed in a wide frequency range. It is shown that the modeling of IR reflectance spectrum using 2 × 2 transfer matrix method and including into analysis the additional layer make it possible to obtain the best fitting of the experimental spectrum, which follows in the evaluation of GaN layer thicknesses which are in good agreement with the SEM and SIMS data. Spectral dependence of plasmon-LO-phonon coupled modes for each GaN layer is obtained from the spectral dependence of dielectric of Si doping impurity, which is attributed to compensation effects by the acceptor states.

Detection of Hepatitis B virus antigen from human blood: SERS immunoassay in a microfluidic system.

A highly sensitive immunoassay utilizing surface-enhanced Raman scattering (SERS) has been developed with a new Raman reporter and a unique SERS-active substrate incorporated into a microfluidic device. An appropriately designed Raman reporter, basic fuchsin (FC), gives strong SERS enhancement and has the ability to bind both the antibody and gold nanostructures. The fuchsin-labeled immuno-Au nanoflowers can form a sandwich structure with the antigen and the antibody immobilized on the SERS-active substrate based on Au-Ag coated GaN. Our experimental results indicate that this SERS-active substrate with its strong surface-enhancement factor, high stability and reproducibility plays a crucial role in improving the efficiency of SERS immunoassay. This SERS assay was applied to the detection of Hepatitis B virus antigen (HBsAg) in human blood plasma. A calibration curve was obtained by plotting the intensity of SERS signal of FC band at 1178cm(-1) versus the concentration of antigen. The low detection limit for Hepatitis B virus antigen was estimated to be 0.01IU/mL. The average relative standard deviation (RSD) of this method is less than 10%. This SERS immunoassay gives exact results over a broad linear range, reflecting clinically relevant HBsAg concentrations. It also exhibits high biological specificity for the detection of Hepatitis B virus antigen.