Electronic properties of clean unreconstructed 6H-SiC(0 0 0 1) surfaces studied by angle resolved photoelectron spectroscopy

The properties of the clean and unreconstructed 6H-SiC(0 0 0 1) and 6H-SiC surfaces were investigated by means of angle-resolved photoelectron spectroscopy (ARPES). These highly metastable surfaces were prepared by exposing hydrogen terminated surfaces to a high flux of synchrotron radiation. On both surfaces we find a band of surface states with 1 × 1 periodicity assigned to unsaturated Si and C dangling bonds located at 0.8 eV and 0.2 eV above the valence band maximum, respectively. Both states are located below the Fermi level. The dispersion of the surface bands amounts to 0.2 eV for the Si derived band and 0.7 eV for C derived band. It is suggested that the electronic properties of these surfaces are governed by strong correlation effects (Mott-Hubbard metal insulator transition). The results for the (0 0 0 1) surface are directly compared to Si-rich (√3 × √3)R30° reconstructed surface. Distinct differences in electronic structure of the (√3 × √3)R30° and 1 × 1 surfaces are observed.     

Hydrogen adsorption on GaAs(0 0 1)-c(4 × 4)

Exposure of the As-terminated GaAs(0 0 1)-c(4 × 4) reconstructed surface to atomic hydrogen (H) at different substrate temperatures (50-480 °C) has been studied by reflection high-energy electron diffraction (RHEED) and scanning tunnelling microscopy (STM). Hydrogen exposure at low temperatures (∼50 °C) produces a disordered (1 × 1) surface covered with AsH_x clusters. At higher temperatures (150-400 °C) exposure to hydrogen leads to the formation of mixed c(2 × 2) and c(4 × 2) surface domains with H adsorbed on surface Ga atoms that are exposed due to the H induced loss of As from the surface. At the highest temperature (480 °C) a disordered (2 × 4) reconstruction is formed due to thermal desorption of As from the surface. The results are consistent with the loss of As from the surface, either through direct thermal desorption or as a result of the desorption of volatile compounds which form after reaction with H.     

Structural and electronic properties of graphite layers grown on SiC(0 0 0 1)

Photoelectron spectroscopy, low-energy electron diffraction, and scanning probe microscopy were used to investigate the electronic and structural properties of graphite layers grown by solid state graphitization of SiC(0 0 0 1) surfaces. The process leads to well-ordered graphite layers which are rotated against the substrate lattice by 30°. On on-axis 6H-SiC(0 0 0 1) substrates we observe graphitic layers with up to several 100 nm wide terraces. ARUPS spectra of the graphite layers grown on on-axis 6H-SiC(0 0 0 1) surfaces are indicative of a well-developed band structure. For the graphite/n-type 6H-SiC(0 0 0 1) layer system we observe a Schottky barrier height of ?_B,n = 0.3 ± 0.1 eV. ARUPS spectra of graphite layers grown on 8° off-axis oriented 4H-SiC(0 0 0 1) show unique replicas which are explained by a carpet-like growth mode combined with a step bunching of the substrate.     

Zone specificity in low energy electron stimulated desorption of Cl from reconstructed Si(1 1 1)-7 × 7:Cl surfaces

Diffraction in electron stimulated desorption has revealed a propensity for Cl⁺ desorption from rest atom vs. adatom areas and unfaulted vs. faulted zones of Cl-terminated Si(1 1 1)-(7 × 7) surfaces. We associate the 15 eV ± 1 eV threshold with ionization of Si-Cl σ-bonding surface states and formation of screened two-hole states with Si 3s character. Similar specificity is observed from A and B reconstructions. This can be due to reduced screening in unfaulted regions and increased hole localization in Si back-bonds within faulted regions.     

Influence of the surface-termination of hexagonal SiC(0 0 0 1) on the temperature dependences of Ge growth modes and desorption

With the aim of comparing initial Ge adsorption and desorption modes on different surface terminations of 4H-SiC(0 0 0 1) faces, 3 × 3, √3×√3R30° (R3) and 6√3×6√3R30° (6R3) reconstructions, of decreasing Si surface richness, have been prepared by standard surface preparation procedures. They are controlled by reflection high energy electron diffraction (RHEED), low energy electron diffraction and photoemission. One monolayer of Ge has been deposited similarly at room temperature on each of these three surfaces, followed by the same set of isochronal heatings at increasing temperatures up to complete Ge desorption. At each step of heating, the structural and chemical status of the Ge ad-layer has been probed. Marked differences between the Si- (3 × 3 and R3) and C-rich (6R3) terminations have been obtained. Ge wetting layers are only obtained up to 400 °C on 3 × 3 and R3 surfaces in the form of a 4 × 4 reconstruction. The wetting is more complete on the R3 surface, whose atomic structure is the closest to an ideally Si-terminated 1 × 1 SiC surface. At higher temperatures, the wetting layer stage transiets in Ge polycrystallites followed by the unexpected appearance on the 3 × 3 surface of a more ordered Si island structure. It denotes a Si clustering of the initial Si 3 × 3 excess, induced by the presence of Ge. A phase separation mechanism between Si and Ge prevails therefore over alloying by Ge supply onto a such Si-terminated 3 × 3 surface. Conversely, no wetting is obtained on the 6R3 surface and island formation of exclusively pure Ge takes place already at low temperature. These islands exhibit a better epitaxial relationship characterized by Ge(1 1 1)//SiC(0 0 0 1) and Ge〈1 1 −2〉//SiC〈1 −1 0 0〉, ascertained by a clear RHEED spot pattern. The absence of any Ge-C bond signature in the X-ray photoelectron spectroscopy Ge core lines indicates a dominant island nucleation on heterogeneous regions of the surface denuded by the 6R3 graphite pavings. Owing to the used annealing cycles, the deposited Ge amount desorbs on the three surfaces at differentiated temperatures ranging from 950 to 1200 °C. These differences probably reflect the varying morphologies formed at lower temperature on the different surfaces. Considering all these results, the use of imperfect 6R3 surfaces appears to be suited to promote the formation of pure and coherent Ge islands on SiC.     

STM study of acetylene reaction with Si(1 1 1): observation of a carbon-induced Si(1 1 1)√3×√3R30° reconstruction

The first stages of acetylene reaction with the Si(1 1 1)7 × 7 reconstructed surface kept at 600 °C are studied by recording scanning tunneling microscopy (STM) images during substrate exposure at a C₂H₂ pressure of 2 × 10⁻⁴ Pa (2 × 10⁻² mbar). We observed the progressive substitution of the 7 × 7 reconstruction with a carbon induced Si(1 1 1)√3×√3R30° reconstruction characterized by an atomic distance of 0.75 ± 0.02 nm, very close to that of the silicon 7 × 7 adatoms. This means that a carbon enrichment of the silicon outermost layers occurs giving rise to the formation of a Si-C phase different from the √3×√3R30° reconstruction typical of Si terminated hexagonal SiC(0 0 0 1) surface with an atomic distance of 0.53 nm. To explain STM images, we propose a reconstruction model which involves carbon atoms in T₄ and/or S₅ sites, as occurring for B doped Si(1 1 1) surface. Step edges and areas around the silicon surface defects are the first regions involved in the reaction process, which spreads from the upper part of the step edges throughout the terraces. Step edges therefore, progressively flakes and this mechanism leads, for the highest exposures, to the formation of large inlets which makes completely irregular the straight edge typical of the Si(1 1 1)7 × 7 terraces. These observations indicate that there occurs an atomic diffusion like that driving the meandering effect. Finally, the formation of a few crystallites is shown also at the lowest acetylene exposures. This is the first STM experiment showing the possibility to have carbon incorporation in a Si(1 1 1) matrix for higher amounts than expected, at least up to 1/6 of silicon atomic layer.     

Density functional theory study of hydrogenation mechanism in Fe-doped Mg(0 0 0 1) surface

Using density functional theory (DFT) in combination with nudged elastic band (NEB) method, the dissociative chemisorptions and diffusion processes of hydrogen on both pure and Fe-doped Mg(0 0 0 1) surfaces are studied. Firstly, the dissociation pathway of H₂ and the relative barrier were investigated. The calculated dissociation barrier (1.08 eV) of hydrogen molecule on a pure Mg(0 0 0 1) surface is in good agreement with comparable experimental and theoretical studies. For the Fe-doped Mg(0 0 0 1) surface, the activated barrier decreases to 0.101 eV due to the strong interaction between the s orbital of H and the d orbital of Fe. Then, the diffusion processes of atomic hydrogen on pure and Fe-doped Mg(0 0 0 1) are presented. The obtained diffusion barrier to the first subsurface is 0.45 eV and 0.98 eV, respectively. Finally, Chou method was used to investigate the hydrogen sorption kinetic mechanism of pure MgH₂ and Mg mixed with 5 at.% Fe atoms composites. The obtained activation energies are 0.87 ± 0.02 and 0.31 ± 0.01 eV for H₂ dissociation on the pure surface and H atom diffusion in Fe-doped Mg surfaces, respectively. It suggests that the rate-controlling step is dissociation of H₂ on the pure Mg surface while it is diffusion of H atom in the Fe-doped Mg surface. And both of fitting data are matching well with our calculation results.     

Formation and hydrogenation of p(2 × 2)-N on Pt(1 1 1)

The formation of a well-ordered p(2 × 2) overlayer of atomic nitrogen on the Pt(1 1 1) surface and its reaction with hydrogen were characterized with reflection absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The p(2 × 2)-N overlayer is formed by exposure of ammonia to a surface at 85 K that is covered with 0.44 monolayer (ML) of molecular oxygen and then heating to 400 K. The reaction between ammonia and oxygen produces water, which desorbs below 400 K. The only desorption product observed above 400 K is molecular nitrogen, which has a peak desorption temperature of 453 K. The absence of oxygen after the 400 K anneal is confirmed with AES. Although atomic nitrogen can also be produced on the surface through the reaction of ammonia with an atomic, rather than molecular, oxygen overlayer at a saturation coverage of 0.25 ML, the yield of surface nitrogen is significantly less, as indicated by the N₂ TPD peak area. Atomic nitrogen readily reacts with hydrogen to produce the NH species, which is characterized with RAIRS by an intense and narrow (FWHM ∼ 4 cm⁻¹) peak at 3322 cm⁻¹. The areas of the H₂ TPD peak associated with NH dissociation and the XPS N 1s peak associated with the NH species indicate that not all of the surface N atoms can be converted to NH by the methods used here.     

Si epitaxial growth on LaAlO3(0 0 1)

We report on the growth of Si on c(2 × 2) reconstructed LaAlO₃(0 0 1) surfaces at high substrate temperature (700 °C) by molecular beam epitaxy. An initial Volmer-Weber mode is evidenced using reflection high energy electron diffraction (RHEED), X-ray photoelectron diffraction (XPD) and atomic force microscopy. After the deposition of a few monolayers, the islands coalesce. Using X-ray photoelectron spectroscopy, we demonstrate that Si islands exhibit an abrupt interface with the LaAlO₃ substrate without formation of silicate or silica. Finally, combined RHEED and XPD measurements show the epitaxial growth of Si with a unique Si(0 0 1)//LaAlO₃(0 0 1) and Si<1 0 0>//LAO<1 1 0> relationship.     

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.     

Clean reconstructed InAs(1 1 1) A and B surfaces using chemical treatments and annealing

Well-ordered clean InAs(1 1 1) A and B surfaces have been prepared using HCl-isopropanol solutions and characterized using low-energy electron diffraction and photoemission spectroscopy. The as-treated surfaces are covered by a layer containing arsenic and small amounts of InCl_x. Annealing induces desorption of the overlayer and reveals (2 × 2) and (1 × 1) structures on the A and B surfaces, respectively. For both surfaces, the surface components of the In 4d and As 3d reveal a charge transfer from the electropositive surface indium to the electronegative surface arsenic. The major advantage of this preparation method over conventional thermal cleaning is a significant reduction in the annealing temperature (≈250 °C) thereby avoiding anion evaporation.     

Behavior of the (0 0 0 1) surface of sapphire upon high-temperature annealing

Evolution of the (0 0 0 1) α-Al₂O₃ surface morphology upon annealing was studied using atomic force microscopy. The annealing protocol included temperatures of 1200 and 1500 °C and different time. Vicinal Al₂O₃ (0 0 0 1) surfaces annealed at 1200 °C exhibit initial localized step coalescence that evolves into terrace-and-step with island morphology that persists for several hours. Annealing at 1500 °C results in initial step coalescence on a global scale, and yields a terrace-and-step morphology with an indication of step bunching after longer annealing times.     

In-situ study on thermal decomposition of 1,3-disilabutane to silicon carbide on Si(1 0 0) surface

The intermediates of thermal decomposition of 1,3-disilabutane (SiH₃CH₂SiH₂CH₃, DSB) to form SiC on Si(1 0 0) surface were in situ investigated by reactive ion scattering (RIS), temperature programmed reactive ion scattering (TPRIS), temperature programmed desorption (TPD), and auger electron spectroscopy (AES). DSB as a single molecular precursor was exposed on Si(1 0 0) surface at a low temperature less than 100 K, and then the substrate was heated up to 1000 K. RIS, TPD, and AES investigations showed that DSB adsorbed molecularly and decomposed to SiC via some intermediates on Si(1 0 0) surface as substrate temperature increasing. Between 117 and 150 K molecularly adsorbed DSB desorbed partially and decomposed to CH₄Si₂, which is the first observation on Si(1 0 0) surface, and further decomposed to CH₄Si between 150 and 900 K. CH₄Si lost hydrogen and formed SiC over 900 K.     

Characterization of phosphorus-doped homoepitaxial (1 0 0) diamond films grown using high-power-density MWPCVD method with a conventional quartz-tube chamber

Phosphorus-doped n-type homoepitaxial diamond films have been successfully grown at high substrate temperatures (>1000 °C) on high-pressure/high-temperature-synthesized type-Ib single-crystalline diamond (1 0 0) substrates, by using a conventional microwave plasma chemical-vapor-deposition (CVD) system with high power densities. The deposition system employed in this work had an easily exchangeable 36 mm inner-diameter quartz-tube growth chamber. The homoepitaxial diamond films thus grown were characterized by means of Hall-effect measurements with an AC magnetic field, atomic force microscope observations and secondary ion mass spectrometry techniques. The dependences of the substrate temperature (≤1300 °C) and the P/C ratio in the source gas (≤9900 ppm) on the specimen features were investigated. The optimum substrate temperature deduced was ≈1160 °C, which was also applicable to the CVD growth of undoped homoepitaxial diamond layers. The n-type conductions with an activation energy ≈0.6 eV were observed for the specimens with amounts of the P atoms incorporated to ≈1.5 × 10¹⁸ cm⁻³ whereas the doping efficiencies changed from ≈0.06% to ≈0.92% with the growth condition. Possible origins for these results are discussed in relation to the growth mechanism.     

High resolution X-ray photoelectron spectroscopy study on initial oxidation of 4H-SiC(0 0 0 1)-(√3 × √3)R30° surface

An initial oxidation dynamics of 4H-SiC(0 0 0 1)-(√3 × √3)R30° surface has been studied using high resolution X-ray photoelectron spectroscopy and supersonic molecular beams. Clean 4H-SiC(0 0 0 1)-(√3 × √3)R30° surface was exposed to oxygen molecules with translational energy of 0.5 eV at 300 K. In the first step of initial oxidation, oxygen molecules are immediately dissociated and atomic oxygens are inserted into Si-Si back bonds to form stable oxide species. At this stage, drastic increase in growth rate of stable oxide species by heating molecular beam source to 1400 K was found. We concluded that this increase in growth rate of stable oxide is mainly caused by molecular vibrational excitation. It suggests that the dissociation barrier is located in the exit channel on potential energy hypersurface. A metastable molecular oxygen species was found to be adsorbed on a Si-adatom that has two oxygen atoms inserted into the back bonds. The adsorption of the metastable species is neither enhanced nor suppressed by molecular vibrational excitation.     

Observation of Si(1 0 0) surfaces annealed in hydrogen gas ambient by scanning tunneling microscopy

We investigated the cleaning process of Si(1 0 0) surfaces by annealing in H₂ gas ambient following chemical treatments by scanning tunneling microscopy. We observed the monohydride Si structure: Si(1 0 0):2 × 1-H on the surfaces annealed at 1000 °C in 2.5 × 10⁴ Pa H₂ gas ambient without conspicuous contaminants. On the sample annealed for 10 min or longer times, well-defined Si(1 0 0) structures with alternating S_A and S_B steps were observed, whereas the initial roughness still remained on the surfaces annealed for only 5 min.     

Morphology and photoluminescence of ultrasmall size of Ge quantum dots directly grown on Si(0 0 1) substrate

High density and ultrasmall size of Ge quantum dots (QDs) have been achieved directly on Si(0 0 1) (2 × 1) reconstruction surface. Their detailed morphology was observed by atomic force microscope (AFM) and shows that small pyramids, small domes, huts, and multi-headed large domes coexist in the film grown at 400 °C, while small domes and multi-headed large domes formed at 450 °C. Their low temperature photoluminescence (PL) showed that a very strong non-phonon (NP) peak with a large blue shift of 0.19 eV at 14 K, which can be attributed to their very high areal density, 5.2 × 10¹¹ cm⁻², and sub-10-nm mean size, 7.6 ± 2.3 nm.     

Investigation of hydrogen interaction with the Si(1 1 1)-7 × 7 surface by STM with Bi/W tips

The STM technique with a special Bi/W tip was used to study the interaction of hydrogen atoms with the Si(1 1 1)-7 × 7 surface. The reactivity of different room temperature (RT) adsorption sites, such as adatoms (A), rest atoms (R), and corner holes (CH) was investigated. The reactivity of CH sites was found to be ∼2 times less than that of R and A sites. At temperatures higher than RT, hydrogen atoms rearrange among A, R, and CH sites, with increased occupation of R sites (T <  300 °C). Further temperature increase leads to hydrogen desorption, where its surface diffusion plays an active role. We discuss one of the possible desorption mechanisms, with the corner holes surrounded by a high potential barrier. Hydrogen atoms have a higher probability to overcome the desorption barrier rather than diffuse either into or out of the corner hole. The desorption temperature of hydrogen from CH, R, and A sites is about the same, equal to ∼500 °C. Also it is shown that hydrogen adsorption on the CH site causes slight electric charge redistribution over neighbouring adatoms, namely, increases the occupation of electronic states on A sites in the unfaulted halves of the Si(1 1 1)-7 × 7 unit cell. Based on these findings, the indirect method of investigation with conventional W tips was suggested for adsorbate interaction with CH sites.     

Self-limited growth of Si on B atomic-layer formed Ge(1 0 0) by ultraclean low-pressure CVD system

Utilizing BCl₃ reaction on Ge(1 0 0) and subsequent Si epitaxial growth by SiH₄ reaction at 300 °C, B atomic-layer doping in Si/Ge(1 0 0) heterostructure was investigated. Cl atoms on the B atomic-layer formed Ge(1 0 0) scarcely affect upon the SiH₄ reaction. It is also found that Si atom amount deposited by SiH₄ reaction on Ge(1 0 0) is effectively enhanced by the existence of B atomic layer and the deposition rate tends to decrease at around 2-3 atomic layers which is three times larger than that in the case without B. The results of angle-resolved X-ray photoelectron spectroscopy show that most B atoms are incorporated at the heterointerface between the Si and Ge.     

Thermal stability of alkoxy monolayers grafted on Si(1 1 1)

Direct grafting of organic monolayers on Si is of prime interest in order to give specific properties to a silicon surface. However, for microelectronics applications, this possibility is hampered by the limited stability of the grafted layers. It has been previously established that alkyl layers attached to Si surfaces through Si-C bonds become unstable at 250-300 °C, by desorption of alkenes. Changing the nature of the bonding to the surface might allow one to circumvent this desorption pathway and increase the layer stability. In our work, decanol and decyl aldehyde are reacted with the Si(1 1 1)-H surface at ∼100 °C during 20 h in order to obtain alkoxy monolayers. FTIR measurements performed in ATR geometry show that the grafted molecule surface coverage is on the order of 33% after reaction with decanol and 50% after reaction with decyl aldehyde. Characterization by AFM essentially reveals that the morphology of the grafted surfaces is unaffected as compared to that of Si-H surfaces. However, the edges of the terraces at alcohol-grafted surfaces exhibit some pitting, probably due to the presence of water in the grafting liquid. Thermal stability studies show that alkoxy chains progressively disappear from the Si surface between 200 and 400 °C. From the CH₂/CH₃ ratio in the CH region (2760-3070 cm⁻¹), it appears that the chains undergo progressive dissociation by C-C bond breaking before their complete disappearance from the surface. Therefore, the thermal behaviour of alkoxy monolayers appears quite distinct from that of alkyl monolayers that tend to leave the surface in a much narrower temperature range (250-350 °C), essentially via breaking of the Si-C bonds.