Tania Paskova

In Situ Chemical Functionalization of Gallium Nitride with Phosphonic Acid Derivatives during Etching

In situ functionalization of polar (c plane) and nonpolar (a plane) gallium nitride (GaN) was performed by adding (3-bromopropyl) phosphonic acid or propyl phosphonic acid to a phosphoric acid etch. The target was to modulate the emission properties and oxide formation of GaN, which was explored through surface characterization with atomic force microscopy, X-ray photoelectron spectroscopy, photoluminescence (PL), inductively coupled plasma-mass spectrometry, and water contact angle. The use of (3-bromopropyl) phosphonic acid and propyl phosphonic acid in phosphoric acid demonstrated lower amounts of gallium oxide formation and greater hydrophobicity for both sample sets, while also improving PL emission of polar GaN samples. In addition to crystal orientation, growth-related factors such as defect density in bulk GaN versus thin GaN films residing on sapphire substrates were investigated as well as their responses to in situ functionalization. Thin nonpolar GaN layers were the most sensitive to etching treatments due in part to higher defect densities (stacking faults and threading dislocations), which accounts for large surface depressions. High-quality GaN (both free-standing bulk polar and bulk nonpolar) demonstrated increased sensitivity to oxide formation. Room-temperature PL stands out as an excellent technique to identify nonradiative recombination as observed in the spectra of heteroepitaxially grown GaN samples. The chemical methods applied to tune optical and physical properties of GaN provide a quantitative framework for future novel chemical and biochemical sensor development.

Electron band bending of polar, semipolar and non-polar GaN surfaces

The magnitudes of the surface band bending have been determined by X-ray photoelectron spectroscopy for polar, semipolar, and non-polar surfaces of wurtzite GaN crystals. All surfaces have been prepared from crystalline GaN samples grown by the hydride-vapour phase epitaxy and separated from sapphire substrates. The Ga 3d core level peak shifts have been used for band bending determination. Small band bending magnitudes and also relatively small difference between the band bendings of the surfaces with opposite polarity have been found. These results point to the presence of electron surface states of different amounts and types on surfaces of different polarity and confirm the important role of the electron surface states in compensation of the bound surface polarity charges in wurtzite GaN crystals.

Dielectric response functions of the (0001¯), (101¯3) GaN single crystalline and disordered surfaces studied by reflection electron energy loss spectroscopy

Polar GaN(0001¯) (1×1), semipolar GaN(101¯3) surfaces prepared in NH3 vapor, and their disordered counterparts are investigated by reflection electron energy loss spectroscopy (REELS) and low-energy electron diffraction. The REELS spectra are measured in a range of polar angles at electron kinetic energies of 200 and 1000 eV. The electron energy loss function is determined from the REELS within the framework of the semiclassical approach. Good agreement between experimental and theoretical functions is achieved at all angles for the disordered GaN surfaces and for the ordered surfaces measured at a kinetic energy of 1000 eV. The agreement is worse for the crystals measured at 200 eV, which is explained by the coherent scattering contributions at low energies. The optical constants of the GaN surfaces are derived from the computed dielectric functions: the optical properties of the (0001¯) and (101¯3) surfaces are similar, except for differences in bandgap values, which may be due to observed steps on the ...

Comparison of the Stability of Functionalized GaN and GaP

Surface functionalization via 1u2009H,1u2009H,2u2009H,2H-perfluoro octanephosphonic acid was done in the presence of phosphoric acid to provide a simplified surface passivation technique for gallium nitride (GaN) and gallium phosphide (GaP). In an effort to identify the leading causes of surface instabilities, hydrogen peroxide was utilized as an additional chemical modification to cap unsatisfied bonds. The stability of the surfaces was studied in an aqueous environment and subsequently characterized. A physical characterization was carried out to evaluate the surface roughness and water hydrophobicity pre and post stability testing via atomic force microscopy and water goniometry. Surface-chemistry changes and solution leaching were quantified by X-ray photoelectron spectroscopy and inductively coupled plasma mass spectrometry. The results indicate a sensitivity to hydroxyl terminated species for both GaN and GaP under aqueous environments, as the increase of the degree of leaching was more significant for hydrogen peroxide treated samples. The results support the notion that hydroxyl species act as precursors to gallium oxide formation and lead to subsequent instability in aqueous solutions.

Surface Characterization of Gallium Nitride Modified with Peptides before and after Exposure to Ionizing Radiation in Solution

An aqueous surface modification of gallium nitride was employed to attach biomolecules to the surface. The modification was a simple two-step process using a single linker molecule and mild temperatures. The presence of the peptide on the surface was confirmed with X-ray photoelectron spectroscopy. Subsequently, the samples were placed in water baths and exposed to ionizing radiation to examine the effects of the radiation on the material in an environment similar to the body. Surface analysis confirmed degradation of the surface of GaN after radiation exposure in water; however, the peptide molecules successfully remained on the surface following exposure to ionizing radiation. We hypothesize that during radiation exposure of the samples, the radiolysis of water produces peroxide and other reactive species on the sample surface. Peroxide exposure promotes the formation of a more stable layer of gallium oxyhydroxide which passivates the surface better than other oxide species.

Biomolecular Gradients via Semiconductor Gradients: Characterization of Amino Acid Adsorption to InxGa1–xN Surfaces

The band gap of indium gallium nitride can be tuned by varying the compositional ratio of indium to gallium, spanning the entire visible region and extending into the near-infrared and near-ultraviolet. This tunability allows for device optimization specific to different applications, including as a biosensor or platform for studying biological interactions. However, these rely on chemically dependent interactions between the device surface and the biostructures of interest. This study presents a material gradient of changing In:Ga composition and the subsequent evaluation of amino acid adsorption to this surface. Arginine is adsorbed to the surface in conditions both above and below the isoelectric point, providing insight to the role of electrostatic interactions in interface formation. These electrostatics are the driving force of the observed adsorption behaviors, with protonated amino acid demonstrating increased adsorption as a function of native surface oxide buildup. We thus present a gradient inorganic substrate featuring varying affinity for amino acid adhesion, which can be applied in generating gradient architectures for biosensors and studying cellular behaviors without application of specialized patterning processes.

Polarity of semipolar wurtzite crystals: X-ray photoelectron diffraction from GaN{101¯1} and GaN{202¯1} surfaces

Polarity of semipolar GaN(101¯1)u2009(101¯1¯) and GaN(202¯1)u2009(202¯1¯) surfaces was determined with X-ray photoelectron diffraction (XPD) using a standard MgKα source. The photoelectron emission from N 1s core level measured in the a-plane of the crystals shows significant differences for the two crystal orientations within the polar angle range of 80–100° from the 〈0001〉 normal. It was demonstrated that XPD polar plots recorded in the a-plane are similar for each polarity of the GaN{101¯1} and GaN{202¯1} crystals if referred to 〈0001〉 crystal axes. For polarity determinations of all important GaN{h0h¯l} semipolar surfaces, the above given polar angle range is suitable.

Effect of etching with cysteamine assisted phosphoric acid on gallium nitride surface oxide formation

In-situ functionalization of polar GaN was performed by adding cysteamine to a phosphoric acid etchant in order to study its effect on photoluminescence and oxide formation on the surfaces. The functionalization was characterized by atomic force microscopy, x-ray photoelectron spectroscopy, photoluminescence (PL), and water contact angle measurements. Two sets of polar GaN samples with different dislocation densities were evaluated, thin GaN layers residing on sapphire and thick free-standing GaN separated from sapphire substrate aiming to reveal the effect of material quality on in-situ functionalization. The addition of cysteamine to the phosphoric acid solution was found to result in: (i) decreased surface roughness, (ii) no change to hydrophobicity, (iii) decreased oxygen content especially at high-temperature treatments. The effect of the in-situ functionalization on the PL efficiency was more pronounced in the free-standing sample than in the film residing on the sapphire, which was attributed to a ...

Anisotropic thermal conductivity of β-Ga2O3 at elevated temperatures: Effect of Sn and Fe dopants

The thermal conductivity of undoped, Sn-doped, and Fe-doped beta-Ga2O3 bulk crystals was measured by the 3 omega technique in the temperature range of 295-410 K. A unique approach for extracting th ...

Recombination and diffusion processes in polar and nonpolar bulk GaN investigated by time-resolved photoluminescence and nonlinear optical techniques

Optically-injected carrier dynamics were investigated in bulk polar and nonpolar GaN in 1015-to-1020 cm-3 carrier density range, exploring single- and two-photon photoexcitation conditions. The excitation decay and recombination rates were monitored by time-resolved photoluminescence and free-carrier absorption techniques, while diffusivity was investigated by light-diffraction on transient grating technique. Carrier dynamics in c- and m-plane thick freestanding HVPE GaN revealed nearly linear increase of carrier lifetime with temperature in the 80 - 800 K range whereas the bipolar carrier diffusivity decreased with temperature. This feature suggests that the measured long lifetime values of 40-50 ns at RT result from diffusion-governed carrier flow to interface defects at GaN hexagons, which act as centers of nonradiative recombination. The fast PL transients under carrier injection to submicrometer thick layer were fitted by using the determined diffusivity and lifetime values and revealed a strong impact of vertical carrier diffusion, surface recombination, and reabsorption processes. Radiative and nonradiative emission rates were analyzed by various optical techniques to discriminate contribution of excitons and free carriers at various temperatures and injected carrier densities.