The effect of hydrogen chemisorption on GaAs(100) and GaAs(1̄1̄1̄)

The interaction of hydrogen with the polar (100) and (1̄1̄1̄) surfaces of GaAs has been studied with LEED, angle-resolved photoemission and core level spectroscopy. It was found that the properties of the hydrogen-covered surface were independent of the composition of the initial surface. The core levels also showed an increase in the surface As concentration for initially Ga-rich surfaces. Angle-resolved photoemission results for GaAs(100) and GaAs(100):H are presented and the dispersion of a hydrogen-induced state is shown.     

LEED-Auger characterization of GaAs during activation to negative electron affinity by the adsorption of Cs and O

A combination of low energy electron diffraction (LEED) and Auger electron spectroscopy (AES) has been used to study the formation of the negative electron affinity (NEA) condition on surfaces of p-type, degenerate, (100) and (111) GaAs. Activation to NEA is achieved by adsorbing Cs and O onto atomically clean GaAs in repetitive cycles of first Cs and then O. Before activation, the clean GaAs surfaces exhibit their characteristic LEED patterns. However, once obtained, there is no significant correlation between the quality of these LEED patterns and the final activation. The adsorption of both Cs and O during activation to NEA is amorphous. Auger measurements have shown that the first photoemission maximum occurs after the adsorption of about a half monolayer of Cs. The initial O adsorption occurs on the GaAs surface between the Cs atoms. The adsorbed O interacts strongly with Cs at any stage during the activation. Peak photosensitivities, after completion of the Cs and O adsorptions, were in the range 400 to 1100 $\text{μA}\text{lumen}$. The final activation does not correlate with the quantity of Cs and O on the surface. The temperature dependence of the photosensitivity of NEA GaAs (100) activated at ?170°C has a broad maximum at about ?50°C and a subsidiary maximum at about 160°C. In addition, the photoemission at ?170°C can be either increased or decreased by having heated the sample up to 200°C, even though no Cs or O desorption has taken place. These results can be traced to changes in work function rather than to changes in bulk properties. While the LEED patterns from clean GaAs show no structural changes with temperature, such changes are observed when Cs is on the surface. It is suggested that changes both in photoemission and in LEED patterns are due to the temperature-induced mobility of Cs on GaAs. An atomic model for the NEA surface is discussed in terms of a layer of Cs and O atoms about 10 Å thick on the GaAs.     

Selective photon-stimulated desorption of hydrogen from GaAs surfaces

Photon-stimulated desorption of H(+) from hydrogenated GaAs (110) and (100) surfaces was studied as a function of photon energy. Distinct peaks, observed around As 3d core-level binding energy for desorption from the GaAs (100) surface and in the As 3d and Ga 3p region for desorption from the GaAs (110) surface, show a striking similarity with the fine structure (spin-orbit splitting) measured in the photoemission from As 3d and Ga 3p levels. These results provide clear evidence for direct desorption processes and represent a basis for selective modification of hydrogenated GaAs surfaces.     

Leed,aes and photoemission measurements of epitaxially grown GaAs(001), (111)A and (1̄1̄1̄)B surfaces and their behaviour upon cs adsorption

Epitaxially grown GaAs(001), (111) and (1?1?1?) surfaces and their behaviour on Cs adsorption are studied by LEED, AES and photoemission. Upon heat treatment the clean GaAs(001) surface shows all the structures of the As-stabilized to the Ga-stabilized surface. By careful annealing it is also possible to obtain the As-stabilized surface from the Ga-stabilized surface, which must be due to the diffusion of As from the bulk to the surface. The As-stabilized surface can be recovered from the Ga-stabilized surface by treating the surface at 400°C in an AsH₃ atmosphere. The Cs coverage of all these surfaces is linear with the dosage and shows a sharp breakpoint at 5.3 × 10¹⁴ atoms cm^?2. The photoemission reaches a maximum precisely at the dosage of this break point for the GaAs(001) and GaAs(1?1?1?) surface, whereas for the GaAs(111) surface the maximum in the photoemission is reached at a higher dosage of 6.5 × 10¹⁴ atoms cm^?2. The maximum photoemission from all surfaces is in the order of 50μA Im^?1 for white light (T = 2850 K). LEED measurements show that Cs adsorbs as an amorphous layer on these surfaces at room temperature. Heat treatment of the Cs-activated GaAs (001) surface shows a stability region of 4.7 × 10¹⁴ atoms cm^?2 at 260dgC and one of 2.7 × 10¹⁴ atoms cm^?2 at 340°C without any ordering of the Cs atoms. Heat treatment of the Cs-activated GaAs(111) crystal shows a gradual desorption of Cs up to a coverage of 1 × 10¹⁴ atoms cm^?2, which is stable at 360°C and where LEED shows the formation of the GaAs(111) (√7 × √7)Cs structure. Heat treatment of the Cs-activated GaAs(1?1?1?) crystal shows a stability region at 260°C with a coverage of 3.8 × 10¹⁴ atoms cm^?2 with ordering of the Cs atoms in a GaAs(1?1?1?) (4 × 4)Cs structure and at 340°C a further stability region with a coverage of 1 × 10¹⁴ at cm^?2 with the formation of a GaAs(1?1?1?) (√21 × √21)Cs structure. Possible models of the GaAs(1?1?1?) (4 × 4)Cs, GaAs(1?1?1?)(√21 × √21)Cs and GaAs(111) (√7 × √7)Cs structures are given.     

Atomic reconstructions and electronic states on the GaAs(001) surface with the adsorbed Sb and Cs layers

In experiments on the adsorption and thermal desorption of Cs on GaAs(001) surfaces with various atomic reconstructions and compositions including those enriched in the cation (gallium) and in the anions (arsenic and antimony), the correlation in the behavior of the atomic structure and the surface electronic states, which determine the band bending, has been established. The cesium adsorption on the anion-rich surfaces results in both the similar disordering of the atomic structure and in the close dose dependences of the band bending, while the adsorption on the Ga-rich surface is ordered and results in the qualitatively different dose dependence, which has several maxima and minima. In the Cs desorption and the subsequent adsorption-desorption cycles, the stabilizing effect of Sb on the atomic structure and the electronic states of the Cs/Sb/GaAs(001) surface has been revealed.     

The electronic properties of the Cs/GaAs(100) interface and the formation of metastable Cs clusters

The method of threshold photoemission spectroscopy is used to investigate the electronic properties of the ultrafine gallium-enriched Cs/GaAs(100) interface. The rearrangement of the spectrum of surface photo-emission as a function of Cs coating, as well as the temperature dependence of the spectrum, enable one to identify two phases of adsorption with strong (Cs-Ga) and weak (Cs-Cs) bonds. In the first phase of adsorption with the coating of approximately 0.3 monolayers, two surface bands are detected which are due to the local interaction of cesium adatoms with gallium dimers. It is found that the transition from the first to the second phase of adsorption occurs with the Cs coating of approximately 0.7 monolayers, which corresponds to the saturation of all dangling bonds of gallium on the gallium-enriched GaAs(100) surface. In the second phase of adsorption with the coating of more than 0.7 monolayers, a number of additional photoemission singularities are observed in the spectra, whose emergence is associated with the formation of metastable Cs formations. Photoemission peaks at 1.9 and 2.17 eV may be associated with the excitation of quasi-two-and/or quasi-three-dimensional Cs clusters, and the peaks at 2.05, 2.4, and 2.78 eV may be associated with the excitation of an interface plasmon and of surface and bulk Cs plasmons, respectively.     

Anomalous mobility of strongly bound surface species: Cl on GaAs(001)-c(8 x 2)

Although strongly bound chemisorbates at low coverage readily diffuse on metal surfaces at 300 K, they generally do not diffuse on semiconductor surfaces because of a large corrugation in the adsorbate-surface interaction potential. Chlorine chemisorbed on the Ga-rich GaAs(001)-c(8x2) surface has anomalously fast diffusion even though the chemisorption state is tightly bound and highly specific. Simple Hartree-Fock total energy calculations suggest that this diffusion of strongly bound adsorbates can occur at 300 K because there are multiple nearly degenerate adsorbate sites.     

The study of vicinal GaAs( 100) surfaces by PAX

The adsorption of xenon at low temperatures on both GaAs(100) and vicinal surfaces has been studied using ultraviolet photoemission spectroscopy. The Xe 5p peaks show a characteristic shift to lower binding energy with surface As-depletion. Additional weak emission features seen on the vicinal planes, shifted by around 0.45 eV to higher binding energy, are attributed to Xe adsorbed at the step sites on such surfaces.     

Hydrogen chemisorption on cleavage faces of III–V compounds

In this paper a number of experimental results dealing with the study of the electronic properties of H-exposed III–V semiconductor cleavage surfaces will be reviewed. The principal aim of the paper is to show how surface sensitive spectroscopies like electron energy loss spectroscopy (EELS) and ultraviolet photoemission spectroscopy (UPS) can be used to investigate these systems. The paper is focused on GaAs(1 1 0):H. GaAs(1 1 0) is one of the most widely investigated and better known semiconductor surfaces: this system can be taken as a case study for the interaction of H with III–V semiconductor cleavage surfaces. The paper is divided into two parts. In the first part EELS and UPS are used and combined to get information about the surface valence states. In the second part core level (CL) photoemission results are presented and discussed.

Combining theory with the above results, a unified picture of the H interaction with the (1 1 0) surface of GaAs comes out. H atoms chemisorb at the early stages along the dangling bond directions of the ideal not relaxed surface, removing the surface relaxation and introducing at the same time defects at the surface.

At the same time the interaction with H produces a Ga enrichment at the surface ascribed to As desorption.     

Angular-resolved photoemission from GaAs(110) surfaces with adsorbed Al

GaAs(110) surfaces with adsorbed Al were studied by a combination of angular-resolved valence band photoemission, Ga 3d core level photoemission, low energy electron loss spectroscopy and Auger electron spectroscopy. At room temperature Al is adsorbed on top of GaAs. After heat treatment the compound AlAs is formed at the surface, which is used as a substrate for Ga adsorption to form the inverted structure of the system GaAs + Al.     

利用飞秒双光子光电子发射研究GaAs(100)的自旋动力学过程

超短激光技术的发展为研究材料中的超快光动方学过程提供了重要的实验手段，也使得人们 能够更为深入地研究电子的自旋动力学行为.GaAs(100)表面由于费米钉扎而会导致能带弯曲 ，位于该区域的电子及其自旋特性将会明显不同于体相材料中的情况.利用时间分辨和自旋 分辨的双光子光电子发射技术研究了p型掺杂GaAs(100)表面的电子极化动力学过程.结果表 明，由费米钉扎而引起的能带弯曲明显影响电子的自旋弛豫过程，从实验上观察到了GaAs(1 00)表面能带弯曲区域的电子自旋翻转时间存在近2个量级的差异(从几纳秒到几十皮秒)，基 于电子-自旋交换相互作用的BAP机理在自旋弛豫过程中起着主导作用. 关键词： 光物理 自旋极化 双光子光电子发射 砷化镓     

GaAs(0 0 1) surface reconstructions: geometries, chemical bonding and optical properties

We re-examine the GaAs(0 0 1) surface by means of first-principles calculations based on a real-space multigrid method. The c(4×4),(2×4) and (4×2) surface reconstructions minimize the surface energy for anion-rich, stoichiometric and cation-rich surfaces, respectively. Structural models proposed in the literature to explain the Ga-rich GaAs(0 0 1) (4×6) surface are dismissed on energetic grounds. The electronic properties of the novel ζ(4×2) structure are discussed in detail. We calculate the reflectance anisotropy of the energetically most favoured surfaces. A strong influence of the surface geometry on the optical anisotropy is found.     

Electron-stimulated desorption of potassium and cesium atoms from oxidized molybdenum surfaces

The electron-stimulated desorption (ESD) yields and energy distributions for potassium (K) and cesium (Cs) atoms have been measured from K and Cs layers adsorbed at 300 K on oxidized molybdenum surfaces with various degrees of oxidation. The measurements were carried out using a time-of-flight method and surface ionization detector. The ESD appearance threshold for K and Cs atoms is independent of the molybdenum oxidation state and is close to the oxygen 2s level ionization energy of 25 eV. Additional thresholds for both K and Cs atoms are observed at about 40 and 70 eV in ESD from layers adsorbed on an oxygen monolayer-covered molybdenum surface; they are associated with resonance processes involving Mo 4p and 4s excitations. The ESD energy distributions for K and Cs atoms consist of single peaks. The most probable kinetic energy of atoms decreases in going from cesium to potassium and with increasing adsorbed metal concentration; it lies in the energy range around 0.35 eV. The K and Cs atom ESD energy distributions from adlayers on an oxygen monolayer-covered molybdenum surface are extended toward very low kinetic energies. The data can be interpreted by means of the Auger stimulated desorption model, in which neutralization of adsorbed alkali-metal ions occurs after filling of holes created by incident electrons in the O 2s, Mo 4s or Mo 4p levels.     

Spectroscopy of image-potential states by two-photon photoemission

Unoccupied electronic states in solids and at solid surfaces are usually studied by inverse photoemission. An alternative method is two-photon photoemission. It is superior in resolution but limited to states of sufficiently long lifetime below the vacuum level. So far this method has mainly been applied to image-potential states on metal surfaces. On Ag(111) and Cu(111) a narrow surface state below the Fermi level serves as the initial state, which results in a pronounced resonance in the two-photon photoemission. Ni(111) shows similar results. In the resonance the image-potential state is so highly populated that electron-electron interaction leads to an Auger-type process. Nevertheless, the system is not so greatly disturbed as to show deviations from the one-photon photoemission results concerning the occupied states. Ag(100) and Cu(100) have a smooth continuum of initial states. Consequently, no resonance occurs. The binding energy does not depend on the material but changes with surface orientation: it is about 0.80 eV at the (111) surfaces and about 0.55 eV at the (100) surfaces. The effective mass is free electron like except on Ag(111), where it is 30% heavier. The lifetime on Ag(100) is about 20 fs. The agreement with theory is excellent in some cases and only fair in others.     

Photoemission studies of the electronic structure of III–V semiconductor surfaces

The photoemission technique using synchroton radiation in the photon energy range 5–450 eV has been applied to the study of the electronic structure of some III–V semiconductor surfaces, prepared by cleavage in situ under ultrahigh vacuum conditions, ? 10^?11 Torr. For p-type GaAs(110), the Fermi level is pinned at the top of the valence band and thus no filled surface states extend into the band-gap. The situation is more complicated for n-type GaAs(110), where band bending easily can be introduced by extrinsic effects (impurities, cleavage quality, etc.) and push the Fermi level down to about midgap. Chemical shifts of inner core levels (3d for Ga and As) are used to obtain information on the bonding site of oxygen on the (110) surface. GaAs(110) can be exposed to atmospheric pressure of molecular oxygen without breaking the bonds between the surface atoms and the bulk. Oxygen is predominantly bonded to the As atoms on the surface. The oxidation behavior is strikingly different for GaSb(110) with formation of gallium and antimony oxides on the surface directly upon oxygen exposure. Heavier oxidation of GaAs(110) and breaking of the surface bonds will also be reported.     

The electronic structure of alkali-metal layers on semiconductor surfaces

Alkali-metal layers on semiconductor surfaces are model systems for metal-semiconductor contacts, Schottky barriers, and metallization processes. The strong decrease of the work function as a function of alkali-metal coverage is also technically made use of. Recently, however, interest in these systems is growing owing to ongoing controversial discussions about questions like: Is the adsorbate system at monolayer coverage metallic or semiconducting, and does the metallization take place in the alkali overlayer or in the top layer of the semiconductor? Is the bonding ionic or covalent? What ist the absolute coverage at saturation? What are the adsorption sites? Do all alkali metals behave similar on the same semiconductor surface? We try to answer some of the questions for Li, Na, K and Cs on Si(111)(2×1), K and Cs on Si(111)(7×7) and on GaAs(110), and Na and K on Si(100)(2×1) employing the techniques of direct and inverse photoemission.     

Electronic properties of cesium ultrathin coatings on the Ga-rich GaAs(100) surface

The cesium submonolayer coatings on the Ga-rich GaAs(100) surface at different coverages have been investigated by threshold photoemission spectroscopy. The electronic spectra of surface states and the ion-ization energies are analyzed. At a cesium coverage of about one-half the monolayer, the spectrum exhibits two narrow adsorption-induced bands below the Fermi level. This indicates that cesium atoms interacting with gallium dimers occupy two nonequivalent positions. It is found that the gallium broken bonds are saturated at the cesium coverage of ～0.7 monolayer, and the adsorption bonding is predominantly covalent in character. At the coverages close to the monolayer, broad bands with energies of 1.9, 2.05, and 2.4 eV have been observed for the first time. These bands can be associated with the excitation of cesium islands, cesium clusters, and surface cesium plasmon, respectively. The results obtained suggest two adsorption stages characterized by the formation of strong and weak bonds.     

Surface states at the clean surfaces of cleaved Si(111) and GaAs(110)

A combination of ellipsometric data on the electronic transitions from occupied to unoccupied surface states and published photoemission data on the energy distribution of the occupied surface states has been used to construct models of the surface states densities at the cleaved Si (111) and GaAs (110) surfaces.     

Electronic surface properties of uhv-cleaved III–V compounds

Combined CPD and photoemission measurements were performed on uhv-cleaved surfaces of the III–V compounds InAs, GaSb, GaAs and GaP with moderate p-type and n-type dopings. Except for n-type GaP these materials show practically no band bending. N-type GaP exhibits surface Fermi level stabilization at 0.55 eV below the conduction band edge. This is ascribed to an intrinsic empty surface state band in the forbidden zone. On the basis of our experiments together with available data from literature we propose an empirical model for the (110) plane of III–V compounds containing In or Ga as metal and Sb, As or P as non-metal atoms from which the lower edge of the empty surface state band can be predicted. The model indicates that for any of these compounds except for GaP no empty surface state band exist in the band gap on the (110) surface.