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Plasma-enhanced atomic layer deposition (PEALD) enables the epitaxial growth of ultrathin indium nitride (InN) films at significantly reduced process temperatures and with greater control of layer thickness compared to other growth methods. However, the reliance on plasma-surface interactions increases the complexity of the growth process. A detailed understanding of the relationship between the plasma properties and the growth kinetics is therefore required to guide the tuning of growth parameters. We present an in situ investigation of the early-stage PEALD growth kinetics of epitaxial InN within three different plasma regimes using grazing incidence small-angle x-ray scattering (GISAXS). The GISAXS data are supported by diagnostic studies of the plasma species generation in the inductively coupled plasma source as a function of the relative concentrations of the nitrogen/argon gas mixture used in the growth process. The growth mode is found to be correlated to the production of nitrogen species in the plasma, with high concentrations of the atomic N species promoting Volmer–Weber growth (i.e., island growth) and low concentrations promoting Stranski–Krastanov growth (i.e., layer-plus-island growth). The critical thickness for island formation, island center-to-center distance, and island radius are found to increase with ion flux. Furthermore, the island center-to-center distance and areal density are observed to change only during plasma exposure and to continue changing with exposure even after the methylindium adlayer is believed to have fully reacted with the plasma. Our results demonstrate the potential to control the growth kinetics during PEALD of epitaxial films by intentionally accessing specific regimes of plasma species generation.

The surface topological evolution during the growth of indium nitride (InN) by plasma-assisted atomic layer epitaxy (ALEp) on gallium nitride (GaN) (0001) substrates was studied using in situ real-time grazing incidence small-angle x-ray scattering (GISAXS) for 180, 250, and 320 °C growth temperatures. The GISAXS data reveal that the ALEp growth of InN on GaN in this temperature range proceeds in a Stranski–Krastanov mode, in which the 2D–3D transition occurred after 2.3 monolayers for 180 °C, 1 monolayer for 250 °C, and 1.5 monolayers for 320 °C. The corresponding initial island center-to-center distances were 7.4, 11.6, and 11.7 nm. Additionally, island coarsening was observed to increase with temperature. After 200 growth cycles, the mean island diameters were 3.9, 5.6, and 7.0 nm, and the mean island center-to-center distances were 8.6, 13.7, and 17.1 nm for 180, 250, and 320 °C growth temperatures, respectively. For the 320 °C growth, the mean island shape was observed to gradually evolve from relatively mounded to cylindrical. These results are supported by atomic force microscopy and specular x-ray reflectivity.

In situ and in vacuo surface studies of in situ and ex situ GaN substrate preparation were conducted to advance fundamental understanding of GaN surface preparation for low temperature atomic layer epitaxial growth. Grazing incidence small angle x-ray scattering (GISAXS) information is complemented with in vacuo x-ray photoelectron spectroscopy and ex situ atomic force microscopy studies to assess different ex situ sample preparation methods to produce the most suitable GaN surface for epitaxy. The authors have determined that a UV-ozone exposure followed by an HF dip produces the cleanest and smoothest GaN surface. They have further determined with GISAXS that subjecting the optimum surface to the established low temperature emulated gallium flash-off atomic level process (ALP) eliminates the need for any nitridation ALP. These ex situ and in situ cleaning preparations result in clean, highly-ordered surfaces that should provide an ideal substrate for high quality crystalline epitaxial films.In situ and in vacuo surface studies of in situ and ex situ GaN substrate preparation were conducted to advance fundamental understanding of GaN surface preparation for low temperature atomic layer epitaxial growth. Grazing incidence small angle x-ray scattering (GISAXS) information is complemented with in vacuo x-ray photoelectron spectroscopy and ex situ atomic force microscopy studies to assess different ex situ sample preparation methods to produce the most suitable GaN surface for epitaxy. The authors have determined that a UV-ozone exposure followed by an HF dip produces the cleanest and smoothest GaN surface. They have further determined with GISAXS that subjecting the optimum surface to the established low temperature emulated gallium flash-off atomic level process (ALP) eliminates the need for any nitridation ALP. These ex situ and in situ cleaning preparations result in clean, highly-ordered surfaces that should provide an ideal substrate for high quality crystalline epitaxial films.

In situ synchrotron x-ray studies were employed to develop a fundamental understanding of the low temperature atomic level processes (ALPs) for GaN substrates to develop in situ methods for preparation of epitaxy ready surfaces. An emulated gallium flash-off (GFO) ALP, followed by a hydrogen clean ALP, and a subsequent nitridation ALP are studied as a function of temperature and number of cycles. The results demonstrate that ideal GFO ALP results are achieved at a higher temperature, 500 °C, and that only ten GFO ALP cycles are needed to remove the surface oxide and result in an ordered GaN surface. Continued GFO ALP cycles at 500 °C roughen the GaN surface. GFO ALP executed at 400 °C only roughens the surface, while executing the GFO ALP at 250 °C causes uneven surface features presumably due to the incomplete removal of the oxide. The hydrogen clean ALP generally roughens the surface at all three temperatures after 30 cycles of the GFO ALP. Further, the nitridation ALP executed after 30 cycles of the GFO ALP, at any of the above temperatures, has little effect since the surface of the GaN has been roughened beyond recovery. These results provide insight into optimal GaN substrate surface preparation at temperatures consistent with the low temperature atomic layer epitaxy process.

The authors present an in situ study of the effect of nitrogen plasma pulse time on the temporal evolution of the surface morphology of InN growth on a-plane sapphire at 250 °C by plasma assisted atomic layer epitaxy (ALEp). The growth surface evolution was monitored in real-time using grazing incidence small angle x-ray scattering (GISAXS) measurements at an x-ray incidence angle of 0.8°. Nitrogen plasma pulse time (tp) was varied between 15 and 30 s in 5-s steps, and for all tp, the near specular scattering broadens and correlated peaks develop and evolve along the Yoneda Wing (YW). For tp ≥ 20 s, a YW with one correlated length scale evolves. At the end of the growth, the longest correlated length scale is 16.54 nm for tp = 25 s. Porod analysis of GISAXS intensity at high qy for tp = 25 s shows the formation of mounded shapes at the early stage of nucleation that transitioned to cylinders after about 3 unit cells of InN growth. Additionally, at tp = 25 s, the growth rate is highest with root mean square surface roughness and carbon impurity levels at or below atomic force microscopy and x-ray photoelectron spectroscopy sensitivity limits, respectively. At tp 30 s, it appears that trimethylindium precursor molecules start to decompose, resulting in higher carbon content in the film. Thus, the nature of GISAXS correlated length scale directly correlates with the material quality. Additional ex situ characterizations reveal an electron mobility of 6–31 cm2/V s for a 3–5 nm thick InN film on a-plane sapphire, which is similar to the reported value of 30 cm2/V s for a 1300 nm thick InN film grown by molecular beam epitaxy directly on sapphire. Thus, the combination of in situ synchrotron x-ray analysis and ex situ characterization is a powerful approach to develop understanding of the growth mechanisms of ALEp of III-N materials in order to improve the quality by reducing impurities and broaden material applications.The authors present an in situ study of the effect of nitrogen plasma pulse time on the temporal evolution of the surface morphology of InN growth on a-plane sapphire at 250 °C by plasma assisted atomic layer epitaxy (ALEp). The growth surface evolution was monitored in real-time using grazing incidence small angle x-ray scattering (GISAXS) measurements at an x-ray incidence angle of 0.8°. Nitrogen plasma pulse time (tp) was varied between 15 and 30 s in 5-s steps, and for all tp, the near specular scattering broadens and correlated peaks develop and evolve along the Yoneda Wing (YW). For tp ≥ 20 s, a YW with one correlated length scale evolves. At the end of the growth, the longest correlated length scale is 16.54 nm for tp = 25 s. Porod analysis of GISAXS intensity at high qy for tp = 25 s shows the formation of mounded shapes at the early stage of nucleation that transitioned to cylinders after about 3 unit cells of InN growth. Additionally, at tp = 25 s, the growth rate is highest with root mean squar...

The temporal evolution of high quality indium nitride (InN) growth by plasma-assisted atomic layer epitaxy (ALEp) on a-plane sapphire at 200 and 248 °C was probed by synchrotron x-ray methods. The growth was carried out in a thin film growth facility installed at beamline X21 of the National Synchrotron Light Source at Brookhaven National Laboratory and at beamline G3 of the Cornell High Energy Synchrotron Source, Cornell University. Measurements of grazing incidence small angle x-ray scattering (GISAXS) during the initial cycles of growth revealed a broadening and scattering near the diffuse specular rod and the development of scattering intensities due to half unit cell thick nucleation islands in the Yoneda wing with correlation length scale of 7.1 and 8.2 nm, at growth temperatures (Tg) of 200 and 248 °C, respectively. At about 1.1 nm (two unit cells) of growth thickness nucleation islands coarsen, grow, and the intensity of correlated scattering peak increased at the correlation length scale of 8.0 a...

Wide bandgap semiconducting nitrides have found wide-spread application as light emitting and laser diodes and are under investigation for further application in optoelectronics, photovoltaics, and efficient power switching technologies. Alloys of the binary semiconductors allow adjustments of the band gap, an important semiconductor material characteristic, which is 6.2 eV for aluminum nitride (AlN), 3.4 eV for gallium nitride, and 0.7 eV for (InN). Currently, the highest quality III-nitride films are deposited by metalorganic chemical vapor deposition and molecular beam epitaxy. Temperatures of 900 °C and higher are required to deposit high quality AlN. Research into depositing III-nitrides with atomic layer epitaxy (ALEp) is ongoing because it is a fabrication friendly technique allowing lower growth temperatures. Because it is a relatively new technique, there is insufficient understanding of the ALEp growth mechanism which will be essential to development of the process. Here, grazing incidence small...

The authors have investigated the early stages of indium island formation and growth by vapor phase deposition on room temperature sapphire using real-time grazing incidence small angle x-ray scattering (GISAXS), followed by ex-situ atomic force microscopy and scanning electron microscopy. The results are consistent with the formation and coalescence of hemispherical islands, as described by Family and Meakin. Monte Carlo simulations of systems of coalescing islands were used to supplement and quantify the results of GISAXS, and a good agreement is seen between the data and the simulations.

Atomic layer deposition (ALD) is a thin film deposition technique that has been studied with a variety of in situ techniques. By exploiting the high photon flux and energy tunability of synchrotron based x-rays, a variety of new in situ techniques become available. X-ray reflectivity, grazing incidence small angle x-ray scattering, x-ray diffraction, x-ray fluorescence, x-ray absorption spectroscopy, and x-ray photoelectron spectroscopy are reviewed as possible in situ techniques during ALD. All these techniques are especially sensitive to changes on the (sub-)nanometer scale, allowing a unique insight into different aspects of the ALD growth mechanisms.

The authors report on the growth, structure, and emission properties of AlGaN double heterostructures having a graded-index-separate-confinement-heterostructure design. These devices were grown on the Si-face of 6H-SiC substrates by plasma-assisted molecular-beam epitaxy. The active region of the device consists of 75-nm thick Al0.72Ga0.28N film, confined by two 50-nm thick compositionally graded AlxGa1−xN films (x = 1–0.8 and x = 0.8–1) and two AlN cladding layers. X-ray diffraction and transmission electron microscopy provide evidence that the compositionally graded AlGaN layer may also be serving as a strain transition buffer, by blocking threading defects in the vicinity of the AlN/AlGaN heterointerface. Polarization dependent photoluminescence studies indicate that the emission from these structures at 257 nm is transverse magnetic polarized. Simulation studies indicate that the vertical confinement of the optical mode in these structures is 32.5% and simulations of the band structure indicate the formation of a p-n junction resulting from polarization-induced doping. Electron-beam pumping of these structures provides evidence of the onset of stimulated emission at room temperature.

Effects of seed atoms on the formation of nanodots on silicon surfaces during normal incidence Ar+ ion bombardment at room temperature are studied with real-time grazing-incidence small-angle x-ray scattering (GISAXS), real-time wafer curvature stress measurements and ex situ atomic force microscopy. Although Si surfaces remain smooth during bombardment at room temperature, when a small amount of Mo atoms is supplied to the surface during ion bombardment, the development of correlated structures (“dots”) is observed. Stress measurements show that initially a compressive stress develops during bombardment, likely due to amorphization of the surface and insertion of argon. However, seeding causes a larger tensile stress to develop with further bombardment, possibly due to the formation of higher density regions around the Mo seed atoms on the surface. Detailed fits of the GISAXS evolution during nanostructure growth show that the instability is larger than predicted by the Bradley-Harper theory of curvature...