XPS investigation of ion beam induced conversion of GaAs(0 0 1) surface into GaN overlayer

For the advance of GaN based optoelectronic devices, one of the major barriers has been the high defect density in GaN thin films, due to lattice parameter and thermal expansion incompatibility with conventional substrates. Of late, efforts are focused in fine tuning epitaxial growth and in search for a low temperature method of forming low defect GaN with zincblende structure, by a method compatible to the molecular beam epitaxy process. In principle, to grow zincblende GaN the substrate should have four-fold symmetry and thus zincblende GaN has been prepared on several substrates including Si, 3C-SiC, GaP, MgO, and on GaAs(0 0 1). The iso-structure and a common shared element make the epitaxial growth of GaN on GaAs(0 0 1) feasible and useful. In this study ion-induced conversion of GaAs(0 0 1) surface into GaN at room temperature is optimized. At the outset a Ga-rich surface is formed by Ar⁺ ion bombardment. Nitrogen ion bombardment of the Ga-rich GaAs surface is performed by using 2-4 keV energy and fluence ranging from 3 × 10¹³ ions/cm² to 1 × 10¹⁸ ions/cm². Formation of surface GaN is manifested as chemical shift. In situ core level and true secondary electron emission spectra by X-ray photoelectron spectroscopy are monitored to observe the chemical and electronic property changes. Using XPS line shape analysis by deconvolution into chemical state, we report that 3 keV N₂⁺ ions and 7.2 × 10¹⁷ ions/cm² are the optimal energy and fluence, respectively, for the nitridation of GaAs(0 0 1) surface at room temperature. The measurement of electron emission of the interface shows the dependence of work function to the chemical composition of the interface. Depth profile study by using Ar⁺ ion sputtering, shows that a stoichiometric GaN of 1 nm thickness forms on the surface. This, room temperature and molecular beam epitaxy compatible, method of forming GaN temperature can serve as an excellent template for growing low defect GaN epitaxial overlayers.     

Adsorption and thermal reaction of short-chain alkanethiols on GaAs(1 0 0)

By means of temperature-programmed desorption (TPD) and X-ray photoemission spectroscopy (XPS) with synchrotron radiation, we investigated the adsorption and thermal decomposition of alkanethiols (RSH, R = CH₃, C₂H₅, and C₄H₉) on a GaAs(1 0 0) surface. All chemisorbed alkanethiols can deprotonate to form thiolates below 300 K via dissociation of the sulfhydryl hydrogen (-SH). Two types of thiolates species are observed on GaAs(1 0 0), according to adsorption on surface Ga and As sites. The thiolates adsorbed on a Ga site preferentially recombine with surface hydrogen to desorb as a molecular thiol at 350-385 K. The thiolate on the As site exhibits greater thermal stability and undergoes mainly dissociation of the C-S bond at ∼520 K, independent of the alkyl chain length. The decomposition of CH₃S either directly desorbs CH₃ or transfers the CH₃ moiety onto the surface. The surface CH₃ further evolves directly from the surface at 665 K. The dissociations of C₂H₅S and C₄H₉S yield surface C₂H₅ and C₄H₉, which further decompose to desorb C₂H₄ and C₄H₈, respectively, via β-hydride elimination. The complete decomposition of alkanethiol leads to the formation of surface S without deposition of carbon. Adsorption of CH₃SSCH₃ results in the formation of surface CH₃S at initial exposures via scission of the S−S bond. Compared with the adsorption of CH₃SH, the CH₃S on the Ga site exhibits greater thermal stability because surface hydrogen is absent. At a high exposure, CH₃SSCH₃ can absorb molecularly on the surface and decompose to desorb CH₃SCH₃ via formation of a CH₃SS intermediate.     

Optimization of VI/II pressure ratio in ZnTe growth on GaAs(0 0 1) by molecular beam epitaxy

ZnTe epilayers were grown on GaAs(0 0 1) substrates by molecular beam epitaxy (MBE) at different VI/II beam equivalent pressure (BEP) ratios (R_VI/II) in a wide range of 0.96-11 with constant Zn flux. Based on in situ reflection high-energy electron diffraction (RHEED) observation, two-dimensional (2D) growth mode can be formed by increasing the R_VI/II to 2.8. The Te/Zn pressure ratios lower than 4.0 correspond to Zn-rich growth state, while the ratios over 6.4 correspond to Te-rich one. The Zn sticking coefficient at various VI/II ratios are derived by the growth rate measurement. The ZnTe epilayer grown at a R_VI/II of 6.4 displays the narrowest full-width at half-maximum (FWHM) of double-crystal X-ray rocking curve (DCXRC) for (0 0 4) reflection. Atomic force microscopy (AFM) characterization shows that the grain size enlarges drastically with the R_VI/II. The surface root-mean-square (RMS) roughness decreases firstly, attains a minimum of 1.14 nm at a R_VI/II of 4.0 and then increases at higher ratios. It is suggested that the most suitable R_VI/II be controlled between 4.0 and 6.4 in order to grow high-quality ZnTe epitaxial thin films.     

Growth and annealing of zinc-blende CdSe thin films on GaAs (0 0 1) by molecular beam epitaxy

CdSe thin films have been grown on GaAs (0 0 1) substrates by molecular beam epitaxy (MBE). The effects of substrate temperature and annealing treatment on the structural properties of CdSe layers were investigated. The growth rate slightly decreases due to the accelerated desorption of Cd from CdSe surface with an increase in the temperature. The sample grown at 260 °C shows a polycrystalline structure with rough surface. As the temperature increases over 300 °C, crystalline CdSe (0 0 1) epilayers with zinc-blende structure are achieved and the structural quality is improved remarkably. The epilayer grown at 340 °C displays the narrowest full-width at half-maximum (FWHM) from (0 0 4) reflection in double-crystal X-ray rocking curve (DCXRC) and the smallest root-mean-square (RMS) roughness of 0.816 nm. Additionally, samples fabricated at 320 °C were annealed in air for 30 min to study the films’ thermal stability. X-ray diffraction (XRD) results indicate that the zinc-blende structure remains unchanged when the annealing temperature is elevated to 460 °C, meaning a good thermal stability of the cubic CdSe epilayers.     

Phosphorus incorporation during InP(0 0 1) homoepitaxial growth by solid source molecular beam epitaxy

The incorporation behaviour of phosphorus (P₂) during growth by molecular beam epitaxy of InP thin films on InP(0 0 1) substrates has been studied in situ by reflection high energy electron diffraction. The incorporation coefficient of P₂ decreases from 0.94 at 360 °C to 0.54 at 470 °C. This behaviour is attributed to the increasing fraction of the incident P₂ flux that desorbs from the surface at higher temperatures and does not contribute to layer growth. The low- and temperature-dependent incorporation coefficients imply the need for high P₂:In flux ratios and low substrate temperatures for the preparation of smooth InP epitaxial layers.     

Morphology and optical properties of p-type porous GaAs(1 0 0) layers made by electrochemical etching

Porous GaAs layers were formed by electrochemical etching of p-type GaAs(1 0 0) substrates in HF solution. A surface characterization has been performed on p-type GaAs samples using X-ray photoelectron spectroscopy (XPS) technique in order to get information about the chemical composition, particularly on the surface contamination. According to the XPS spectra, the oxide layer on as-received porous GaAs substrates contains As₂O₃, As₂O₅ and Ga₂O₃. Large amount of oxygen is present at the surface before the surface cleaning.Compared to untreated GaAs surface, room temperature photoluminescence (PL) investigations of the porous layers reveal the presence of two PL bands: a PL peak at ∼871 nm and a “visible” PL peak at ∼650-680 nm. Both peak wavelengths and intensities varied from sample to sample depending on the treatment that the samples have undergone. The short PL wavelength at 650-680 nm of the porous layers is attributed to quantum confinement effects in GaAs nano-crystallites. The surface morphology of porous GaAs has been studied using atomic force microscopy (AFM). Nano-sized crystallites were observed on the porous GaAs surface. An estimation of the mean size of the GaAs nano-crystals obtained from effective mass theory and based on PL data was close to the lowest value obtained from the AFM results.     

Growth process of β-FeSi2 epitaxial film on Si(1 1 1) by molecular beam epitaxy

We have reported a one step growth of a high quality β-FeSi₂ epitaxial film on hydrogen terminated Si(1 1 1) by using molecular beam epitaxy (MBE) without template layer or post-growth annealing. In the present work, the growth process was studied by analyzing X-ray diffraction (XRD) spectra, reflective high energy electron diffraction (RHEED) and atomic force microscopy (AFM) observations on the samples grown with different growth times from 10 s to 1 h. A phase transformation from γ-FeSi₂ to β-FeSi₂ was confirmed existing in the crystal film growth, as well as the growth mode changing from three-dimensional (3D) to two-dimensional (2D) mode.     

Surface reactions of 2-iodopropane on GaAs(1 0 0)

The surface reactions of 2-iodopropane ((CH₃)₂CHI) on gallium-rich GaAs(1 0 0)-(4 × 1), was studied by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). CH₃CHICH₃ adsorbs molecularly at 120 K but dissociates below room temperature to form chemisorbed 2-propyl ((CH₃)₂CH) and iodide (I) species. Thermal activation causes desorption of the molecular species at 240 K, and this occurs in competition with the further reactions of the (CH₃)₂CH and I chemisorbed species. Self-coupling of the (CH₃)₂CH results in the formation of 2,3-dimethylbutane ((CH₃)₂CH-CH(CH₃)₂) at 290 K. β-Hydride elimination in (CH₃)₂CH yields gaseous propene (CH₃CHCH₂) at 550 K while reductive elimination reactions of (CH₃)₂CH with surface hydrogen yields propane (CH₃CH₂CH₃) at 560 K. Recombinative desorption of the adsorbed hydrogen as H₂ also occurs at 560 K. We observe that the activation barrier to carbon-carbon bond formation with 2-propyls on GaAs(1 0 0) is much lower than that in our previous investigations involving ethyl and 1,1,1-trifluoroethyl species where the β-elimination process was more facile. The difference in the surface chemistry in the case of 2-propyl species is attributable to its rigid structure resulting from the bonding to the surface via the second carbon atom, which causes the methyl groups to be further away from the surface than in the case of linear ethyl and 1,1,1-trifluoroethyl species. The β-hydride and reductive elimination processes in the adsorbed 2-propyl species thus occurs at higher temperatures, and a consequence of this is that GaI desorption, which is expected to occur in the temperature range 550-560 K becomes suppressed, and the chemisorbed iodine leaves the surface as atomic iodine.     

XPS study of SnTe(1 0 0) oxidation by molecular oxygen

The interaction between the (1 0 0) surface of SnTe single crystal and molecular oxygen was studied by means of X-ray photoelectron spectroscopy (XPS). Analysis of the obtained spectra shows that the mechanism of surface oxidation does not change in the range of oxygen exposure 10⁸-10¹³ L. During the oxidation an additional component shifted 1.1 eV towards higher binding energies appears in the Sn 3d spectra. The Te 3d_5/2 spectra fitting reveals two additional components with binding energies close to Te⁰ and Te⁺⁴. The dependence of the additional components fraction in both Sn 3d and Te 3d_5/2 spectra on the oxygen exposure is semi-logarithmic. On the base of the experimental data two possible mechanisms are proposed.     

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.     

Etching reaction of methylchloride molecule on the GaAs (0 0 1)-2 × 4 surface

Adsorption process of methylchloride (CH₃Cl) on the GaAs (0 0 1)-2 × 4 surface was studied by a scanning tunnelling microscopy (STM) measurement. The arsenic rich 2 × 4 surface, which was prepared by molecular beam epitaxy (MBE), was exposed to a supersonic molecular beam of CH₃Cl with a kinetic energy of 0.06 eV. New bright spots appeared on the CH₃Cl exposed surface. They were largely observed at the “B-type” step edge and divided into two types according to their locations. It was suggested that new spots were due to weakly adsorbed CH₃Cl molecules without any dissociation. The adsorption mechanism of CH₃Cl molecule was also studied by an ab initio Hartree-Fock calculation, which explained the experimental results well.     

Surface chemistry of NO and NO2 on the Pt(1 1 0)-(1 × 2) surface: A comparative study

The surface chemistry of NO and NO₂ on clean and oxygen-precovered Pt(1 1 0)-(1 × 2) surfaces were investigated by means of high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). At room temperature, NO molecularly adsorbs on Pt(1 1 0), forming linear NO(a) and bridged NO(a). Coverage-dependent repulsive interactions within NO(a) drive the reversible transformation between linear and bridged NO(a). Some NO(a) decomposes upon heating, producing both N₂ and N₂O. For NO adsorption on the oxygen-precovered surface, repulsive interactions exist between precovered oxygen adatoms and NO(a), resulting in more NO(a) desorbing from the surface in the form of linear NO(a). Bridged NO(a) experiences stronger repulsive interactions with precovered oxygen than linear NO(a). The desorption activation energy of bridged NO(a) from oxygen-precovered Pt(1 1 0) is lower than that from clean Pt(1 1 0), but the desorption activation energy of linear NO(a) is not affected by the precovered oxygen. NO₂ decomposes on Pt(1 1 0)-(1 × 2) surface at room temperature. The resulted NO(a) (both linear NO(a) and bridged NO(a)) and O(a) repulsively interact each other. Comparing with NO/Pt(1 1 0), more NO(a) desorbs from NO₂/Pt(1 1 0) as linear NO(a), and both linear NO(a) and bridged NO(a) exhibit lower desorption activation energies. The reaction pathways of NO(a) on Pt(1 1 0), desorption or decomposition, are affected by their repulsive interactions with coexisting oxygen adatoms.     

Layer-resolved photoelectron diffraction from Si(0 0 1) and GaAs(0 0 1)

Photoelectron diffraction in the layer-resolved mode brings more detailed information about local atomic arrangement than is obtained in the standard mode. This is demonstrated in crystals with diamond and zinc-blende structures, both for unpolarized photon excitation as well as for circularly polarized excitation. The full angular distributions of photoemission intensities are evaluated for large atomic clusters representing ideally truncated surfaces of Si(0 0 1) and GaAs(0 0 1). Highly structured layer-resolved patterns enable a more detailed understanding of the standard mode outcomes. Photoelectron intensities from atomic layers placed at different depths under the crystal surface provide direct evidence about electron attenuation and its anisotropy in crystals.     

Surface etching induced by Ce silicide formation on Si(1 0 0)

We investigate the temperature-dependent surface etching process induced by Ce silicide on Si(1 0 0) using scanning tunneling microscopy and X-ray photoelectron spectroscopy. We found that step edges on the Si(1 0 0) surface are gradually roughened due to the formation of Ce silicide as a function of substrate temperature. Unlike the Si(1 1 1) surface, however, terrace etching also occurs in addition to step roughening at 500 °C. Moreover, we found that Si(1 0 0) dimers are released and formed dimer vacancy lines because bulk diffusion of Ce silicide into Si(1 0 0) surface occurs the defect-induced strain at higher temperature (∼600 °C).     

Stability of MgO(1 1 1) films grown on 6H-SiC(0 0 0 1) by molecular beam epitaxy for two-step integration of functional oxides

Crystalline magnesium oxide (MgO) (1 1 1), 20 Å thick, was grown by molecular beam epitaxy (MBE) on hydrogen cleaned hexagonal silicon carbide (6H-SiC). The films were further heated to 740 °C and 650 °C under different oxygen environments in order to simulate processing conditions for subsequent functional oxide growth. The purpose of this study was to determine the effectiveness and stability of crystalline MgO films and the MgO/6H-SiC interface for subsequent heteroepitaxial deposition of multi-component, functional oxides by MBE or pulsed laser deposition processes. The stability of the MgO films and the MgO/6H-SiC interface was found to be dependent on substrate temperature and the presence of atomic oxygen. The MgO films and the MgO/6H-SiC interface are stable at temperatures up to 740 °C at 1.0 × 10⁻⁹ Torr for extended periods of time. While at temperatures below 400 °C exposure to the presence of active oxygen for extended periods of time has negligible impact, exposure to the presence of active oxygen for more than 5 min at 650 °C will degrade the MgO/6H-SiC interface. Concurrent etching and interface breakdown mechanisms are hypothesized to explain the observed effects. Further, barium titanate was deposited by MBE on bare 6H-SiC(0 0 0 1) and MgO(1 1 1)/6H-SiC(0 0 0 1) in order to evaluate the effectiveness of the MgO as a heteroepitaxial template layer for perovskite ferroelectrics.     

GaAs（100）表面氧化的XPS 研究

用X射线光电子能谱仪 (XPS)研究了砷化镓 (GaAs)晶片在空气中的热氧化和在紫外光 臭氧激发下的氧化反应 .分析了氧化层中的微观化学构成、表面化学计量比以及表面氧化层的厚度等 .研究表明 ,两种氧化方法的氧化过程不同 ,在砷化镓表面形成的氧化膜的厚度以及组成也不同 ,热氧化下氧化层主要由Ga2 O3、As2 O3、As2 O5 以及少量元素As组成 ,而且表面明显富镓 ;紫外光激发下生成的氧化物主要为Ga2 O3 和As2 O3 ,镓砷比与本体一致 .讨论了可能的反应机理 ,紫外光不仅将氧分子激发为激发态氧原子 ,增加了氧的反应活性 ;同时也激发了GaAs材料的价电子 ,使其更容易被氧化     

Growth of epitaxial thin Pd(1 1 1) films on Pt(1 1 1) and oxygen-terminated FeO(1 1 1) surfaces

Thin Pd films (1-10 monolayers, ML) were deposited at 35 K on a Pt(1 1 1) single crystal and on an oxygen-terminated FeO(1 1 1) monolayer supported on Pt(1 1 1). Low energy electron diffraction, Auger electron spectroscopy, and Kr and CO temperature programmed desorption techniques were used to investigate the annealing induced changes in the film surface morphology. For growth on Pt(1 1 1), the films order upon annealing to 500 K and form epitaxial Pd(1 1 1). Further annealing above 900 K results in Pd diffusion into the Pt(1 1 1) bulk and Pt-Pd alloy formation. Chemisorption of CO shows that even the first ordered monolayer of Pd on Pt(1 1 1) has adsorption properties identical to bulk Pd(1 1 1). Similar experiments conducted on FeO(1 1 1) indicate that 500 K annealing of a 10 ML thick Pd deposit also yields ordered Pd(1 1 1). In contrast, annealing of 1 and 3 ML thick Pd films did not result in formation of continuous Pd(1 1 1). We speculate that for these thinner films Pd diffuses underneath the FeO(1 1 1).     

Surface preparation effect of GaAs(110) substrates on the ZnSe epitaxial layer grown by molecular beam epitaxy

The effect of the surface preparation of the GaAs(110) substrate on the ZnSe epitaxial layer grown by molecular beam epitaxy (MBE) was investigated by means of etch-pit density (EPD) measurements, surface morphology observation, and reflection high-energy electron diffraction (RHEED) analysis. The ZnSe epitaxial layer grown on a GaAs(110) surface prepared by cleaving the (001)-oriented wafer in ultrahigh vacuum (UHV) showed about 5×10⁴ cm^-2 of EPD. This value is much lower than that observed from both the samples grown on the mechanically polished surface with and without a GaAs buffer layer. Due to the non-stoichiometric surface after thermal evaporation of the surface oxide, three-dimensional growth can easily occur on the mechanically polished GaAs(110) substrate. These results suggest that the stoichiometric and atomically flat substrate surface is essential for the growth of low-defect ZnSe epitaxial layers on the GaAs(110) non-polar surface. Received: 21 August 1998 / Accepted: 19 October 1998 / Published online: 28 April 1999     

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.     

The growth and structure of titanium dioxide films on a Re(1 0 −1 0) surface: Rutile(0 1 1)-(2 × 1)

Titanium dioxide films were grown on Re(1 0 −1 0) by Ti vapor deposition in oxygen at T = 830 K and studied by means of low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), low-energy ion scattering (LEIS) and X-ray diffraction (XRD). The Ti oxide stoichiometry was determined by XPS as Ti:O = 1:2, with the Ti oxidation state (4+). The TiO₂ growth was monitored by means of LEED as a function of film thickness. Extending the coverage from the submonolayer into the multilayer regime gives rise to a p(2 × 2) pattern, a (poorly ordered) (1 × 1), and, finally, a stable (2 × 2) structure, the latter being associated with a homogeneous TiO₂ phase. For normal electron incidence, the (2 × 2) LEED pattern exhibits systematically extinguished beams at (n ± 1/2, 0) positions, indicating a glide mirror plane. The pg(2 × 2) structure could be explained by both a rutile(0 1 1)-(2 × 1) reconstructed surface and a bulk truncated brookite(0 0 1) surface. Faceting phenomena, i.e. running LEED spots, observed with thin TiO₂ films point to the formation of a rutile(0 1 1)-(2 × 1) surface with two domains and {0 1 1}-(2 × 1) facets and rule out the brookite alternative. Confirmation of this assignment was obtained by an XRD analysis performed at the Berlin synchrotron facility BESSY.