Coherent X-ray Spectroscopy Elucidates Nanoscale Dynamics of Plasma-Enhanced Thin-Film Growth.

Sophisticated thin film growth techniques increasingly rely on the addition of a plasma component to open or widen a processing window, particularly at low temperatures. Taking advantage of continued increases in accelerator-based X-ray source brilliance, this real-time study uses X-ray Photon Correlation Spectroscopy (XPCS) to elucidate the nanoscale surface dynamics during Plasma-Enhanced Atomic Layer Deposition (PE-ALD) of an epitaxial indium nitride film. Ultrathin films are synthesized from repeated cycles of alternating self-limited surface reactions induced by temporally separated pulses of the material precursor and plasma reactant, allowing the influence of each on the evolving morphology to be examined. During the heteroepitaxial 3D growth examined here, sudden changes in the surface structure during initial film growth, consistent with numerous overlapping stress-relief events, are observed. When the film becomes continuous, the nanoscale surface morphology abruptly becomes long-lived with a correlation time spanning the period of the experiment. Throughout the growth experiment, there is a consistent repeating pattern of correlations associated with the cyclic growth process, which is modeled as transitions between different surface states. The plasma exposure does not simply freeze in a structure that is then built upon in subsequent cycles, but rather, there is considerable surface evolution during all phases of the growth cycle.

Atomic Layer Deposition as the Enabler for the Metastable Semiconductor InN and Its Alloys.

Indium nitride (InN) is a low-band-gap semiconductor with unusually high electron mobility, making it suitable for IR-range optoelectronics and high-frequency transistors. However, the development of InN-based electronics is hampered by the metastable nature of InN. The decomposition temperature of InN is lower than the required growth temperature for most crystal growth techniques. Here, we discuss growth of InN films and epitaxial layers by atomic layer deposition (ALD), a growth technique based on self-limiting surface chemical reactions and, thus, inherently a low-temperature technique. We describe the current state of the art in ALD of InN and InN-based ternary alloys with GaN and AlN, and we contrast this to other growth technologies for these materials. We believe that ALD will be the enabling technology for realizing the promise of InN-based electronics.

Development of solar-blind photodetectors based on Si-implanted ß-Ga(2)O(3).

ß-Ga(2)O(3) films grown on Al(2)O(3) by a metalorganic chemical vapor deposition technique were used to fabricate a solar-blind photodetector with a planar photoconductor structure. The crystal structure and quality of the ß-Ga(2)O(3) films were analyzed using X-ray diffraction and micro-Raman spectroscopy. Si ions were introduced into the ß-Ga(2)O(3) thin films by ion implantation method and activated by an annealing process to form an Ohmic contact between the Ti/Au electrode and the ß-Ga(2)O(3) film. The electrical conductivity of the ß-Ga(2)O(3) films was greatly improved by the implantation and subsequent activation of the Si ions. The photoresponse properties of the photodetectors were investigated by analyzing the current-voltage characteristics and the time-dependent photoresponse curves. The fabricated solar-blind photodetectors exhibited photoresponse to 254 nm wavelength, and blindness to 365 nm light, with a high spectral selectivity.

Electron backscatter diffraction study of hexagonal boron nitride growth on Cu single-crystal substrates.

Hexagonal boron nitride (h-BN) is an important material for the development of new 2D heterostructures. To enable this development, the relationship between crystal growth and the substrate orientation must be explored and understood. In this study, we simultaneously grew h-BN on different orientations of Cu substrates to establish the impact of substrate structure on the growth habit of thin h-BN layers. The substrates studied were a polycrystalline Cu foil, Cu(100), Cu(110), and Cu(111). Fourier transform grazing-incidence infrared reflection absorption spectroscopy (FT-IRRAS) was used to identify h-BN on copper substrates. X-ray photoelectron spectroscopy (XPS) was used to determine the effective thickness of the h-BN. Scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD) were used to measure the morphology of the films and postgrowth crystal structure of the Cu substrates, respectively. Combining the SEM and EBSD images allowed for the correlation between h-BN film coverage and the crystal structure of Cu. It was found that the growth rate was inversely proportional to the surface free energy of the Cu surface, with Cu(111) having the most h-BN surface coverage. The Cu foil predominately crystallized with a (100) surface orientation, and likewise had a film coverage very close to the Cu(100).

Formation of Thick Dense Yttrium Iron Garnet Films Using Aerosol Deposition.

Aerosol deposition (AD) is a thick-film deposition process that can produce layers up to several hundred micrometers thick with densities greater than 95% of the bulk. The primary advantage of AD is that the deposition takes place entirely at ambient temperature; thereby enabling film growth in material systems with disparate melting temperatures. This report describes in detail the processing steps for preparing the powder and for performing AD using the custom-built system. Representative characterization results are presented from scanning electron microscopy, profilometry, and ferromagnetic resonance for films grown in this system. As a representative overview of the capabilities of the system, focus is given to a sample produced following the described protocol and system setup. Results indicate that this system can successfully deposit 11 µm thick yttrium iron garnet films that are  > 90% of the bulk density during a single 5 min deposition run. A discussion of methods to afford better control of the aerosol and particle selection for improved thickness and roughness variations in the film is provided.

Chemical etching behaviors of semipolar (11̄22) and nonpolar (11̄20) gallium nitride films.

Wet chemical etching using hot KOH and H3PO4 solutions was performed on semipolar (11̄22) and nonpolar (11̄20) GaN films grown on sapphire substrates. An alternating KOH/H3PO4/KOH etch process was developed to control the orientation of the facets on the thin-film surface. The initial etch step in KOH produced c- and m-plane facets on the surface of both semipolar (11̄22) and nonpolar (11̄20) GaN thin-films. A second etch step in H3PO4 solution additionally exposed a (̄1̄12̄2) plane, which is chemically stable in H3PO4 solution. By repeating the chemical etch with KOH solution, the m-plane facets as seen in the original KOH etch step were recovered. The etching methods developed in our work can be used to control the surface morphologies of nonpolar and semipolar GaN-based optoelectronic devices such as light-emitting diodes and solar cells.

Magneto-optical fingerprints of distinct graphene multilayers using the giant infrared Kerr effect.

The remarkable electronic properties of graphene strongly depend on the thickness and geometry of graphene stacks. This wide range of electronic tunability is of fundamental interest and has many applications in newly proposed devices. Using the mid-infrared, magneto-optical Kerr effect, we detect and identify over 18 interband cyclotron resonances (CR) that are associated with ABA and ABC stacked multilayers as well as monolayers that coexist in graphene that is epitaxially grown on 4H-SiC. Moreover, the magnetic field and photon energy dependence of these features enable us to explore the band structure, electron-hole band asymmetries, and mechanisms that activate a CR response in the Kerr effect for various multilayers that coexist in a single sample. Surprisingly, we find that the magnitude of monolayer Kerr effect CRs is not temperature dependent. This unexpected result reveals new questions about the underlying physics that makes such an effect possible.

GaN-based ultraviolet light-emitting diodes with AuCl3-doped graphene electrodes.

We demonstrate AuCl3-doped graphene transparent conductive electrodes integrated in GaN-based ultraviolet (UV) light-emitting diodes (LEDs) with an emission peak of 363 nm. AuCl3 doping was accomplished by dipping the graphene electrodes in 5, 10 and 20 mM concentrations of AuCl3 solutions. The effects of AuCl3 doping on graphene electrodes were investigated by current-voltage characteristics, sheet resistance, scanning electron microscope, optical transmittance, micro-Raman scattering and electroluminescence images. The optical transmittance was decreased with increasing the AuCl3 concentrations. However, the forward currents of UV LEDs with p-doped (5, 10 and 20 mM of AuCl3 solutions) graphene transparent conductive electrodes at a forward bias of 8 V were increased by ~48, 63 and 73%, respectively, which can be attributed to the reduction of sheet resistance and the increase of work function of the graphene. The performance of UV LEDs was drastically improved by AuCl3 doping of graphene transparent conductive electrodes.

Single n-GaN microwire/p-Silicon thin film heterojunction light-emitting diode.

The emission and waveguiding properties of individual GaN microwires as well as devices based on an n-GaN microwire/p-Si (100) junction were studied for relevance in optoelectronics and optical circuits. Pulsed photoluminescence of the GaN microwire excited in the transverse or longitudinal direction demonstrated gain. These n-type GaN microwires were positioned mechanically or by dielectrophoretic force onto pre-patterned electrodes on a p-type Si (100) substrate. Electroluminescence from this p-n point junction was characteristic of a heterostructure light-emitting diode. Additionally, waveguiding was observed along the length of the microwire for light originating from photoluminescence as well as from electroluminescence generated at the p-n junction.

Epitaxial graphene nucleation on C-face silicon carbide.

The initial stages of epitaxial graphene growth were studied by characterization of graphene formed in localized areas on C-face 6H-SiC substrates. The graphene areas were determined to lie below the level of the surrounding substrate and showed different morphologies based on size. Employing electron channeling contrast imaging, the presence of threading screw dislocations was indicated near the centers of each of these areas. After the graphene was removed, these dislocations were revealed to lie within the SiC substrate. These observations suggest that screw dislocations act as preferred nucleation sites for graphene growth on C-face SiC.

Nanostructured n-ZnO / thin film p-silicon heterojunction light-emitting diodes.

Electroluminescence (EL) was obtained from a p-Si (100) thin film/nanostructured n-ZnO heterojunction diode fabricated by a simple dielectrophoresis (DEP) method. The Si substrate was pre-patterned with electrodes and an insulating separation layer by a standard photolithographic process. ZnO nanostructures were formed by a simple solution chemistry and subsequently transferred to the pre-patterned substrate. Application of the DEP force at a frequency of 100 kHz and 6 V peak-to-peak voltage allowed precise positioning of the ZnO nanostructures at the edge of the metal electrodes. The physically formed p-Si (100) thin film/nanostructured n-ZnO heterojunction displayed multi-color emission from the ZnO near band edge as well as emission from defective states within the ZnO band gap.

Transparent conductive graphene electrode in GaN-based ultra-violet light emitting diodes.

We report a graphene-based transparent conductive electrode for use in ultraviolet (UV) GaN light emitting diodes (LEDs). A few-layer graphene (FLG) layer was mechanically deposited. UV light at a peak wavelength of 368 nm was successfully emitted by the FLG layer as transparent contact to p-GaN. The emission of UV light through the thin graphene layer was brighter than through the thick graphene layer. The thickness of the graphene layer was characterized by micro-Raman spectroscopy. Our results indicate that this novel graphene-based transparent conductive electrode holds great promise for use in UV optoelectronics for which conventional ITO is less transparent than graphene.

Quantum linear magnetoresistance in multilayer epitaxial graphene.

We report the first observation of linear magnetoresistance (LMR) in multilayer epitaxial graphene grown on SiC. We show that multilayer epitaxial graphene exhibits large LMR from 2.2 K up to room temperature and that it can be best explained by a purely quantum mechanical model. We attribute the observation of LMR to inhomogeneities in the epitaxially grown graphene film. The large magnitude of the LMR suggests potential for novel applications in areas such as high-density data storage and magnetic sensors and actuators.

Photopolymerization of self-assembled monolayers of diacetylenic alkylphosphonic acids on group-III nitride substrates.

This paper describes the fabrication and characterization of photopolymerizable alkylphosphonate self-assembled monolayers (SAMs) on group-III nitride substrates including GaN and Al(x)Ga(1-x)N (AlGaN; x = 0.2 and 0.25). Contact angle goniometry, visible absorption spectroscopy, and atomic force microscopy were used to assess the formation, desorption, and photopolymerization of SAMs of diacetylenic alkylphosphonic acids (CH(3)(CH(2))(n)-C[triple bond]C-C[triple bond]C-(CH(2))(m)PO(OH)(2); (m, n) = (3, 11), (6, 8), and (9, 5)). As with GaN substrates (Ito, T.; Forman, S. M.; Cao, C.; Li, F.; Eddy, C. R., Jr.; Mastro, M. A.; Holm, R. T.; Henry, R. L.; Hohn, K.; Edgar, J. H. Langmuir 2008, 24, 6630-6635), alkylphosphonic acids formed SAMs on UV/O(3)-treated AlGaN substrates from their toluene solutions in contrast to other primary substituted hydrocarbons with a terminal -COOH, -NH(2), -OH, or -SH group. Diacetylenic alkylphosphonate SAMs on group-III nitrides could be polymerized by UV irradiation (254 nm), as indicated by the appearance of a visible absorption band around 640 nm and also by their significantly reduced desorption from the surface in a 0.1 M aqueous NaOH solution. A longer UV irradiation time was required to maximize the photopolymerization of a SAM having a diacetylene group close to the terminal phosphonate moiety, probably because of the hindrance of the topochemical polymerization due to the limited flexibility of the cross-linking moieties on an atomically rough substrate surface.

Conductance anisotropy in epitaxial graphene sheets generated by substrate interactions.

We present the first microscopic transport study of epitaxial graphene on SiC using an ultrahigh vacuum four-probe scanning tunneling microscope. Anisotropic conductivity is observed that is caused by the interaction between the graphene and the underlying substrate. These results can be explained by a model where charge buildup at the step edges leads to local scattering of charge carriers. This highlights the importance of considering substrate effects in proposed devices that utilize nanoscale patterning of graphene on electrically isolated substrates.

Polarization fields in III-nitride nanowire devices.

Control of the polarization fields is the most important parameter in designing III-nitride thin-film devices, and herein we show that the polarization fields may be equally, if not more, important in devising III-nitride nanowire devices. One common approach to produce III-nitride nanowires is via a vapor-liquid-solid approach that, in general, yields nanowires with the major (growth) axis in the <1120> direction. The cross section of this wire is an isosceles triangle with two {1101} facets and one {0001} facet. In this work, we analyze the polarization fields that arise in two distinct sets of crystal planes that can manifest in this triangular nanowire geometry: (0001), (1101), (1101) or (0001), (1101), (1101). Calculations show that the polarization field at the {0001} facet is much larger than at the two opposing {1101} facets, although the sign of the field at each facet has a complicated dependence on the orientation and structure of the nanowire. An undoped nanowire transistor was fabricated that displayed p-type operation based solely on polarization-induced hole carriers at the (0001) AlGaN/GaN interface, consistent with our field calculations.

Technique for the dry transfer of epitaxial graphene onto arbitrary substrates.

To make graphene technologically viable, the transfer of graphene films to substrates appropriate for specific applications is required. We demonstrate the dry transfer of epitaxial graphene (EG) from the C-face of 4H-SiC onto SiO(2), GaN and Al(2)O(3) substrates using a thermal release tape. Subsequent Hall effect measurements illustrated that minimal degradation in the carrier mobility was induced following the transfer process in lithographically patterned devices. Correspondingly, a large drop in the carrier concentration was observed following the transfer process, supporting the notion that a gradient in the carrier density is present in C-face EG, with lower values being observed in layers further removed from the SiC interface. X-ray photoemission spectra collected from EG films attached to the transfer tape revealed the presence of atomic Si within the EG layers, which may indicate the identity of the unknown intrinsic dopant in EG. Finally, this transfer process is shown to enable EG films amenable for use in device fabrication on arbitrary substrates and films that are deemed most beneficial to carrier transport, as flexible electronic devices or optically transparent contacts.

Correlating Raman spectral signatures with carrier mobility in epitaxial graphene: a guide to achieving high mobility on the wafer scale.

We report a direct correlation between carrier mobility and Raman topography of epitaxial graphene (EG) grown on silicon carbide (SiC). We show the Hall mobility of material on SiC(0001) is highly dependent on thickness and monolayer strain uniformity. Additionally, we achieve high mobility epitaxial graphene (18100 cm(2)/(V s) at room temperature) on SiC(0001) and show that carrier mobility depends strongly on the graphene layer stacking.

Self-assembled monolayers of alkylphosphonic acid on GaN substrates.

In this paper we describe the formation and characterization of self-assembled monolayers of octadecylphosphonic acid (ODPA) on epitaxial (0001) GaN films on sapphire. By immersing the substrate in its toluene solution, ODPA strongly adsorbed onto UV/O 3-treated GaN to give a hydrophobic surface. Spectroscopic ellipsometry verified the formation of a well-packed monolayer of ODPA on the GaN substrate. In contrast, adsorption of other primarily substituted hydrocarbons (C n H 2 n+1 X; n = 16-18; X = -COOH, -NH 2, -SH, and -OH) offered less hydrophobic surfaces, reflecting their weaker interaction with the GaN substrate surfaces. A UV/O 3-treated N-polar GaN had a high affinity to the -COOH group in addition to ODPA, possibly reflecting the basic properties of the surface. These observations suggested that the molecular adsorption was primarily based on hydrogen bond interactions between the surface oxide layer on the GaN substrate and the polar functional groups of the molecules. The as-prepared ODPA monolayers were desorbed from the GaN substrates by soaking in an aqueous solution, particularly in a basic solution. However, ODPA monolayers heated at 160 degrees C exhibited suppressed desorption in acidic and neutral aqueous solution maybe due to covalent bond formation between ODPA and the surface. X-ray photoelectron spectroscopy provided insight into the effect of the UV/O 3 treatment on the surface composition of the GaN substrate and also the ODPA monolayer formation. These results demonstrate that the surface of a GaN substrate can be tailored with organic molecules having an alkylphosphonic acid moiety for future sensor and device applications.