XPS, electric and photoluminescence-based analysis of the GaAs (1 0 0) nitridation

In this paper, nitridation process of GaAs (1 0 0) substrates was studied in-situ using X-ray photoelectron spectroscopy (XPS) and ex-situ by means of electrical method I-V and photoluminescence surface state spectroscopy (PLS³) in order to determine chemical, electrical and electronic properties of the elaborated GaN/GaAs interfaces.The elaborated structures were characterised by I-V analysis. The saturation current I_S, the ideality factor n, the barrier height Φ_Bn and the serial resistance R_S are determined.The elaborated GaN/GaAs structures are also exhibited a high PL intensity at room temperature. From the computer-aided analysis of the power-dependent PL efficiency measurements (PLS³ technique), the value of the interface state density N_SS(E) close to the mid-gap was estimated to be in the range of 2-4 × 10¹¹ eV⁻¹ cm⁻², indicating a good electronic quality of the obtained interfaces.Correlation among chemical, electronic and electrical properties of the GaN/GaAs interface was discussed.     

Study of S ion-assisted sulfurization of n-GaAs (1 0 0) surface

The chemical structure and site location of sulfur atoms on n-GaAs (1 0 0) surface treated by bombardment of S⁺ ions over their energy range from 10 to 100 eV have been studied by X-ray photoelectron spectroscopy and low energy electron diffraction. The formation of Ga-S and As-S species on the S⁺ ion bombarded n-GaAs surface is observed. An apparent donor doping effect is observed for the n-GaAs by the 100 eV S⁺ ion bombardment. It is found that the S⁺ ions with higher energy are more effective in the formation of Ga-S species, which assists the n-GaAs (1 0 0) surface in reconstruction into an ordered (1 × 1) structure upon subsequent annealing. The treatment is further extended to repair Ar⁺ ion damaged n-GaAs (1 0 0) surface. It is found that after a n-GaAs (1 0 0) sample is damaged by 150 eV Ar⁺ ion bombardment, and followed by 50 eV S⁺ ion treatment and subsequent annealing process, finally an (1 × 1) ordering GaAs (1 0 0) surface with low surface states is obtained.     

The CuGaSe2(0 0 1) surface: A (4 × 1) reconstruction

We report on the formation of a stable (4 × 1) reconstruction of the chalcopyrite CuGaSe₂(0 0 1) surface. Using Ar⁺ ion-bombardment and annealing of epitaxial CuGaSe₂ films grown on GaAs(0 0 1) substrates it was possible to obtain flat, well-ordered surfaces showing a clear (4 × 1) reconstruction. The cleanliness and structure were analyzed in situ by AES and LEED. AES data suggest a slight Se-enrichment and Cu-depletion upon surface preparation. Our results demonstrate that (0 0 1) surfaces of the Cu-III-VI₂(0 0 1) material can show stable, unfacetted surfaces.     

Computational study of adsorption, diffusion, and dissociation of precursor species on the GaN (0 0 0 1) surface during GaN MOCVD

The adsorption, diffusion, and dissociation of precursor species, MMGa (monomethylgallium) and NH₃, on the GaN (0 0 0 1) surface have been investigated using the DFT (density functional theory) calculation combined with a GaN (0 0 0 1) surface cluster model. The energetics of NH₃(ad) dissociation on the surface proposed of NH₃(ad) via NH₂(ad) to NH(ad) was facile with small activation barriers. A combined analysis with surface diffusion of adatoms demonstrated Ga(ad) and NH(ad) become primary reactant species for 2D film growth, and N(ad) develops into a nucleation center. Our studies suggest the control of NH₃(ad) dissociation are essential to improve epitaxial film quality as well as Ga-rich condition. In addition, the adsorbability of H(ad)s resulted from NH₃(ad) dissociation were found to influence on the surface chemistry during film growth.     

Epitaxial SiC formation induced by medium energy ions on Si(1 1 1) at room temperature

In the search for silicon technology compatible substrate for III-nitride epitaxy, we present a proof-of-concept for forming epitaxial SiC layer on Si(1 1 1). A C/Si interface formed by ion sputtering is exposed to 100-1500 eV Ar⁺ ions, inducing a chemical reaction to form SiC, as observed by core-level X-ray photoelectron spectroscopy (XPS). Angle dependent XPS studies shows forward scattering feature that manifest the epitaxial SiC layer formation, while the valence band depicts the metal to insulator phase change.     

New reconstruction-stoichiometry correlation for GaAs(0 0 1) surface treated by atomic hydrogen

The structure, stoichiometry and electronic properties of the GaAs(0 0 1)-(2 × 4)/c(2 × 8) surface treated by cycles of atomic hydrogen (AH) exposure and subsequent annealing in UHV were studied with the aim of preparing the Ga-rich surface at low temperatures. Low energy electron diffraction showed reproducible structural transformations in each cycle: AH adsorption at the (2 × 4)/c(2 × 8) surface led to the (1 × 4) structure at low AH exposure and to a (1 × 1) surface at higher AH exposure with subsequent restoration of the (2 × 4)/c(2 × 8) structure under annealing at 450 °C. The cycles of AH treatment preserved the atomic flatness of the GaAs(1 0 0) surface, keeping the mean roughness on to about 0.15 nm. The AH treatment cycles led to the oscillatory behavior of 3dAs/3dGa ratio with a gradual decrease to the value characteristic for the Ga-rich surface. Similar oscillatory variations were observed in the work function. The results are consistent with the loss of As from the surface as a result of the desorption of volatile compounds which are formed after reaction with H. The prepared Ga-rich GaAs(0 0 1) surface showed the stability of the (2 × 4)/c(2 × 8) structure up to the annealing temperature of 580 °C.     

Damage formation in Ge during Ar and He implantation at 15 K

Ar⁺ and He⁺ ions were implanted into Ge samples with (1 0 0), (1 1 0), (1 1 1) and (1 1 2) orientations at 15 K with fluences ranging from 1×10¹¹ to 1×10¹⁴ cm⁻² for the Ar⁺ ions and fluences ranging from 1×10¹² to 6×10¹⁵ cm⁻² for the He⁺ ions. The Rutherford backscattering (RBS) technique in the channelling orientation was used to study the damage built-up in situ. Implantation and RBS measurements were performed without changing the target temperature. The samples were mounted on a four axis goniometer cooled by a close cycle He cryostat. The implantations were performed with the surface being tilt 7° off the ion beam direction to prevent channelling effects. After each 300 keV Ar⁺ and 40 keV He⁺ implantation, RBS analysis was performed with 1.4 MeV He⁺ ions.For both the implantation ions, there is about no difference between the values found for the damage efficiency per ion for the four different orientations. This together with the high value (around 5 times higher than that found in Si), gives rise to the assumption of amorphous pocket formation per incident ion, i.e. direct impact amorphization, already at low implantation fluences. At higher fluences, when collision cascades overlap, there is a growth of the already amorphized regions.     

An ab initio-based approach to phase diagram calculations for GaN(0 0 0 1) surfaces

Surface phase diagrams of GaN(0 0 0 1)-(2 × 2) and pseudo-(1 × 1) surfaces are systematically investigated by using our ab initio-based approach. The phase diagrams are obtained as functions of temperature T and Ga beam equivalent pressure p_Ga by comparing chemical potentials of Ga atom in the vapor phase with that on the surface. The calculated results imply that the (2 × 2) surface is stable in the temperature range of 700-1000 K at 10⁻⁸ Torr and 900-1400 K at 10⁻² Torr. This is consistent with experimental stable temperature range for the (2 × 2). On the other hand, the pseudo-(1 × 1) phase is stable in the temperature range less than 700 K at 10⁻⁸ Torr and less than 1000 K at 10⁻² Torr. Furthermore, the stable region of the pseudo-(1 × 1) phase almost coincides with that of the (2 × 2) with excess Ga adatom. This suggests that Ga adsorption or desorption during GaN MBE growth can easily change the pseudo-(1 × 1) to the (2 × 2) with Ga adatom and vice versa.     

GaN/LiNbO3 (0 0 0 1) interface formation calculated from first-principles

The stable adsorption sites for both Ga and N ions on the ideal and on the reconstructed LiNbO₃ (0 0 0 1) surface are determined by means of first-principle total energy calculations. A single N layer is found to be more strongly bound to the substrate than a single Ga layer. The adsorption of a GaN monolayer on the polar substrate within different orientations is then modeled. On the basis of our results, we propose a microscopic model for the GaN/LiNbO₃ interface. The GaN and LiNbO₃ (0 0 0 1) planes are parallel, but rotated by 30° each other, with in-plane epitaxial relationship [1 0 0]_GaN‖ [1 1  0]_LiNbO3. In this way the (0 0 0 1) plane lattice mismatch between GaN and LiNbO₃ is minimal and equal to 6.9% of the GaN lattice constant. The adsorbed GaN and the underlying LiNbO₃ substrate have parallel c-axes.     

XPS study of the formation of ultrathin GaN film on GaAs(1 0 0)

The nitridation of GaAs(1 0 0) surfaces has been studied using XPS spectroscopy, one of the best surface sensitive techniques. A glow discharge cell was used to produce a continuous plasma with a majority of N atomic species. We used the Ga3d and As3d core levels to monitor the chemical state of the surface and the coverage of the species. A theoretical model based on stacked layers allows to determine the optimal temperature of nitridation. Moreover, this model permits the determination of the thickness of the GaN layer. Varying time of nitridation from 10 min to 1 h, it is possible to obtain GaN layers with a thickness between 0.5 nm and 3 nm.     

The effect of preadsorbed K on the size distribution of Au nanoparticles on TiO2(1 1 0) surface

The effect of K on the morphology of Au nanoparticles deposited on TiO₂(1 1 0) surface is investigated by STM-STS and AES methods. For comparison, the enhanced concentration of oxygen defect sites generated by Ar⁺ bombardment was also studied. It was found that both the K additive and the oxygen defect sites induce a pronounced decrease in the average size of the Au nanoparticles evolved at 320 K. On the clean TiO₂(1 1 0) the average size of Au particles is 4.3 nm at approximately monolayer coverage of gold, while in the presence of K or oxygen vacancies this value decreased to 2.5 nm. In spite of the reduced average diameter detected at room temperature, the mean size of the Au nanoparticles increased significantly from 2.5 nm up to 7 nm on the effect of annealing at 500-700 K for K precoverages of 0.3-1 ML. For the clean and the Ar⁺ pretreated TiO₂(1 1 0) surfaces the mean size of the Au particles changed only slightly on the effect of the same thermal treatments.     

Hydroxylated α-Al2O3 (0 0 0 1) surfaces and metal/α-Al2O3 (0 0 0 1) interfaces

X-ray photoelectron spectroscopy was applied to study the hydroxylation of α-Al₂O₃ (0 0 0 1) surfaces and the stability of surface OH groups. The evolution of interfacial chemistry of the α-Al₂O₃ (0 0 0 1) surfaces and metal/α-Al₂O₃ (0 0 0 1) interfaces are well illustrated via modifications of the surface O1s spectra. Clean hydroxylated surfaces are obtained through water- and oxygen plasma treatment at room temperature. The surface OH groups of the hydroxylated surface are very sensitive to electron beam illumination, Ar⁺ sputtering, UHV heating, and adsorption of reactive metals. The transformation of a hydroxylated surface to an Al-terminated surface occurs by high temperature annealing or Al deposition.     

Self-assembled InAs island formation on GaAs (1 1 0) by metalorganic vapor phase epitaxy

Formation of self-assembled InAs 3D islands on GaAs (1 1 0) substrate by metal organic vapor phase epitaxy has been investigated. Relatively uniform InAs islands with an average areal density of 10⁹ cm⁻²are formed at 400 ° C using a thin InGaAs strain reducing (SR) layer. No island formation is observed without the SR layer. Island growth on GaAs (1 1 0) is found to require a significantly lower growth temperature compared to the more conventional growth on GaAs (1 0 0) substrates. In addition, the island height is observed to depend only weakly on the growth temperature and to be almost independent of the V/III ratio and growth rate. Low-temperature photoluminescence at 1.22 eV is obtained from the overgrown islands.     

GaN nucleation on (0 0 0 1)-sapphire via ion-induced nitridation of gallium

The growth of epitaxial GaN films on (0 0 0 1)-sapphire has been investigated using X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED). In order to investigate the mechanism of the growth in detail, we have focused on the nitridation of pre-deposited Ga layers (droplets) using ion beam-assisted molecular beam epitaxy (IBA-MBE). Comparative analysis of XPS core-level spectra and LEED patterns reveals, that nitride films nucleate as epitaxial GaN islands. The wetting of the surface by GaN proceeds via reactive spreading of metallic Ga, supplied from the droplets. The discussed growth model confirms, that excess of metallic Ga is beneficial for GaN nucleation.     

Surface treatments toward obtaining clean GaN(0 0 0 1) from commercial hydride vapor phase epitaxy and metal-organic chemical vapor deposition substrates in ultrahigh vacuum

We studied processes of cleaning GaN(0 0 0 1) surfaces on four different types of wafers: two types were hydride vapor phase epitaxy (HVPE) free-standing substrates and two types were metal-organic chemical vapor deposition (MOCVD) films grown on these HVPE substrates and prepared by annealing and/or Ar ion sputtering in ultra high vacuum. We observed the surfaces through treatments using in situ low-energy electron diffraction (LEED), reflection high-energy electron diffraction (RHEED), scanning tunneling microscopy (STM), and Auger electron spectroscopy, and also using ex situ temperature programmed desorption, X-ray photoelectron spectroscopy, X-ray diffraction, and secondary ion mass spectrometry. For HVPE samples, we obtained relatively clean surfaces under optimized three-step annealing conditions (200 °C for 12 h + 400 °C for 1 h + 500 °C for 5 min) without sputtering, after which the surface contamination of oxide and carbide was reduced to ∼20% of that before annealing. Clear GaN(0 0 0 1)1×1 patterns were obtained by LEED and RHEED. STM images showed flat terraces of ∼10 nm size and steps of ∼0.5 nm height. Upon annealing the HVPE-GaN samples at a much higher temperature (C), three-dimensional (3D) islands with facets were formed and the surface stoichiometry was broken down with the desorption of nitrogen in the form of ammonia, since the samples include hydrogen as an impurity. Ar⁺ sputtering was effective for removing surface contamination, however, postannealing could not recover the surface roughness but promoted the formation of 3D islands on the surface. For MOCVD/HVPE homoepitaxial samples, the surfaces are terminated by hydrogen and the as-introduced samples showed a clear 1×1 structure. Upon annealing at 500-600 °C, the surface hydrogen was removed and a 3×3 reconstruction structure partially appeared, although a 1×1 structure was dominant. We summarize the structure differences among the samples under the same treatment and clarify the effect of crystal quality, such as dislocations, the concentration of hydrogen impurities, and the residual reactant molecules in GaN films, on the surface structure.     

Desorption of chemisorbed Carbon on Mo(1 0 0) by noble gas ion sputtering: Validation of ground test measurements of ion engine lifetimes

We report desorption cross section measurements for one monolayer of chemisorbed carbon on a Mo(1 0 0) surface induced by sputtering with noble gas ions (Ne⁺, Ar⁺, Xe⁺) at different incident angles, ion energies, and substrate temperatures. Desorption cross sections were determined by using low-energy ion scattering (LEIS) to monitor the increase of the signal from the Mo substrate. A monolayer of p(1 × 1) carbon adatoms on the Mo(1 0 0) surface was created by dosing ethylene (C₂H₄) to the substrate at 800 K, and characterized by Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). We find that the carbon desorption cross section increases with increasing mass and energy of the impinging ions, and there is a maximum value for the desorption cross section at an incident angle for the ions of 30° from the surface plane. The desorption cross section also increases up to a substrate temperature of 300 °C. Values for the carbon desorption cross section for carbon adatoms on Mo(1 0 0) by 400-eV Xe⁺ ion sputtering are about 2 × 10⁻¹⁵ cm², which is one order of magnitude higher than those for bulk carbon samples. This information is particularly important for evaluation of ion-engine lifetimes from ground-test measurements in which contaminant carbon is deposited on Mo accelerator grids, potentially altering the sputtering rate of the Mo. Our measurements show that monolayer amounts of carbon on Mo have desorption cross sections that are two orders of magnitude higher than estimates of what would be required to reduce the Mo erosion rate, and thus ground-test measurements can be used with confidence to predict ion-engine wear in space, from this perspective.     

Fourfold in-plane magnetic anisotropy in epitaxial Fe(1 1 0)/Cu(0 0 1) and Fe(1 1 0)/Ni(0 0 1) bilayers

Epitaxial Fe(1 1 0) films with thicknesses of 100-800 nm on Cu(0 0 1) and Ni(0 0 1) buffer layers grown on MgO(0 0 1) substrates have been fabricated. These films contain Fe(1 1 0) crystallites which are in the Pitsch orientation relationship. Magnetization and the fourfold in-plane magnetic anisotropy constants of these films have been determined by torque measurements. All the samples under study are characterized by a fourfold magnetic anisotropy with easy axes parallel to the [1 0 0] and [0 1 0] directions of Cu(0 0 1) and Ni(0 0 1) layers. The measured values of the constant for Fe(1 1 0)/Cu(0 0 1) are found to depend on deposition temperature; a maximum value of (2.5±0.1)×10⁵ erg/cm³ is reached after annealing at 600 °С. The in-plane torque measurements on Fe(1 1 0)/Ni(0 0 1) bilayers obtained at 300 °С, on the other hand, exhibit a constant value of (2.7±0.1)×10⁵ erg/cm³. Assuming an exchange interaction between the Fe(1 1 0) crystallites, which are in the Pitsch orientation relationship, the fourfold in-plane magnetic anisotropy has been calculated as 2.8×10⁵ erg/cm³. The deviations of the experimental values from the predicted one may be explained by the formation of a polycrystalline phase within the Fe(1 1 0) layer and a partial disorientation of the epitaxial crystallites.     

Characterization of crystal lattice constant and dislocation density of crack-free GaN films grown on Si(1 1 1)

GaN have sphalerite structure (Cubic-GaN) and wurtzite structure (hexagonal GaN). We report the H-GaN epilayer with a LT-AlN buffer layer has been grown on Si(1 1 1) substrate by metal-organic chemical vapor deposition (MOCVD). According to the FWHM values of 0.166° and 14.01 cm⁻¹ of HDXRD curve and E₂ (high) phonon of Raman spectrum respectively, we found that the crystal quality is perfect. And based on the XRD spectrum, the crystal lattice constants of Si (a = 5.3354 ?) and H-GaN (a_epi = 3.214 ?, c_epi = 5.119 ?) have been calculated for researching the tetragonal distortion of the sample. These results indicate that the GaN epilayer is in tensile strain and Si substrate is in compressive strain which were good agreement with the analysis of Raman peaks shift. Comparing with typical values of screw-type (D_screw = 7 × 10⁸ cm⁻²) and edge-type (D_edge = 2.9 × 10⁹ cm⁻²) dislocation density, which is larger than that in GaN epilayers growth on SiC or sapphire substrates. But our finding is important for the understanding and application of nitride semiconductors.     

Effect of 100 MeV Ni ion irradiation on MOCVD grown n-GaN

Metal-organic chemical vapor deposition (MOCVD) grown n-type Gallium nitride (GaN) has been irradiated with 100 MeV Ni⁹⁺ ions at room temperature. Atomic force microscopy (AFM) images show the nano-clusters' formation upon irradiation and the irradiated GaN surface roughness increases with the increasing ion fluences. High-resolution X-ray diffraction (HR-XRD) analysis reveals the formation of Ga₂O₃ due to the interface mixing of GaN/Al₂O₃ upon irradiation. FWHM values of GaN (0 0 0 2) increases due to the lattice disorder. Photoluminescence studies show reduced band edge emission and yellow luminescence (YL) intensity with the increasing ion fluences. Change in the band gap energy between 3.38 and 3.04 eV was measured by UV-visible optical absorption spectrum on increasing the ion fluences.     

Surface morphology of Mn implanted Ge(1 0 0): A systematic investigation as a function of the implantation substrate temperature

Ge (1 0 0) wafers were implanted with 100 keV Mn⁺ ions with a dose of 2 × 10¹⁶ ions/cm² at different temperatures, ranging from 300 to 573 K. The surface morphology of implanted samples, analyzed with scanning electron microscopy and atomic force microscopy measurements, reveals for the 300-463 K implant temperature range the formation of a surface swelled and porous film, containing sponge-like structures. On the contrary, samples implanted in the 513-573 K temperature range present an atomically flat surface, with a roughness less than 1 nm, indicating that crystalline order has been preserved. X-ray photoemission spectroscopy depth profiling measurements indicate the presence of adsorbed oxygen in the porous layer of lower-temperature implanted samples, as well the presence of a large Mn concentration below the expected end of range for impinging ions. Mn and O concentrations at anomalously great depths are maximum in the 413 K implanted sample, indicating that the phenomenon of ion beam induced porosity is best favored at a well defined temperature.