Analysis of low Z elements on Si wafer surfaces with synchrotron radiation induced total reflection X-ray fluorescence at SSRL, Beamline 3-3: comparison of droplets with spin coated wafers

The unique properties of synchrotron radiation, such as high incident flux combined with low divergence, its linear polarization and energy tunability, make it an ideal excitation source for total reflection X-ray fluorescence (TXRF) spectroscopy in order to non-destructively detect trace impurities of transition metals on Si wafer surfaces. When used with a detector suitable for the determination of low energy radiation this technique can be extended to the detection of low-Z elements, such as Al, Na and Mg. Experiments have been performed at SSRL Beamline 3-3, a bending magnet beamline using monochromatic radiation from a double multilayer monochromator. The wafer was mounted vertically in front of the detector, which was aligned along the linear polarization vector of the incoming synchrotron radiation. This configuration allows the detector to accept a large solid angle as well as to take advantage of the reduced scattered X-ray intensity emitted in the direction of the linear polarization vector. A comparison between droplet samples and spin coated samples was done, in order to compare the capabilities of vapor phase decomposition (VPD-TXRF) with conventional SR-straight-TXRF. Detection limits in the range of 50 fg corresponding to 2E10 atoms/cm² have been obtained for Na. The spin coated samples, prepared from solutions containing an equal amount of Na, Mg and Al showed an unexpected result when performing a scan of the angle of incidence of the incoming X-rays suggesting a different adsorption behavior of the elements in a multielement solution on the wafer surface. The observation of this behavior is important because the spin coating technique is the standard method for the preparation of surface standards in semiconductor quality control. This effect could be characteristic of the Na, Mg, Al solution used, but the angle dependence of the fluorescence signal of a standard should always be investigated before using the standard for calibration of the apparatus and quantification.     

Synchrotron Stories from Stanford—From a Parking Lot to First Beam

Our journey in synchrotron radiation started in July 1972 when we joined a group at Stanford led by Seb Doniach and Bill Spicer to build a “Pilot Project” to test the feasibility of performing X-ray photoemission experiments on the newly commissioned SPEAR storage ring at SLAC. The SPEAR ring was expressly built for high-energy physics using colliding electron and positron beams (ultimately discovering the existence of quarks and garnering two Nobel prizes). As a result, anything we did could not interfere with the high-energy physics experiments.     

Direct measurement of valence-charge asymmetry by x-ray standing waves

By monitoring valence-photoelectron emission under condition of strong x-ray Bragg reflection, we have determined that a majority of GaAs valence charge resides on the anion sites of this heteropolar crystal, in quantitative agreement with the GaAs bond polarity as calculated from the Hartree-Fock term values. In contrast, the valence-charge distribution in Ge is found to be symmetric. In both cases, the valence emission is found to be closely coupled to the atomic cores.     

Three‐dimensional imaging of chemical phase transformations at the nanoscale with full‐field transmission X‐ray microscopy

The ability to probe morphology and phase distribution in complex systems at multiple length scales unravels the interplay of nano‐ and micrometer‐scale factors at the origin of macroscopic behavior. While different electron‐ and X‐ray‐based imaging techniques can be combined with spectroscopy at high resolutions, owing to experimental time limitations the resulting fields of view are too small to be representative of a composite sample. Here a new X‐ray imaging set‐up is proposed, combining full‐field transmission X‐ray microscopy (TXM) with X‐ray absorption near‐edge structure (XANES) spectroscopy to follow two‐dimensional and three‐dimensional morphological and chemical changes in large volumes at high resolution (tens of nanometers). TXM XANES imaging offers chemical speciation at the nanoscale in thick samples (>20 µm) with minimal preparation requirements. Further, its high throughput allows the analysis of large areas (up to millimeters) in minutes to a few hours. Proof of concept is provided using battery electrodes, although its versatility will lead to impact in a number of diverse research fields.     

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.     

Ad-atom interactions with III-V semiconductor surfaces

Photoemission techniques (core level, valence band and partial yield spectroscopies) using synchrotron radiation as the excitation source have been applied to study the changes in the surface electronic structure of the (110) cleavage face of III-V semiconductor surfaces as a function of different ad-atom coverages. In this paper we concentrate on Au overlayers on GaSb and in particular address the problem of the mechanism for Fermi level pinning and the formation of Schottky barrier heights. It appears that the Fermi level pinning is fully established at a small fraction of a monolayer coverage. Core level spectroscopy gives evidence for a strong metal-semiconductor interaction leading to decomposition of GaSb at the interface. The experimental results form the basis for proposing a new model for the Schottky barrier based on defect states at the interface.     

Oxygen adsorption and the surface electronic structure of GaAs (110)

The surface electronic structure of cleaved GaAs (110) is found to be very sensitive to small amounts of adsorbed oxygen. For example, adsorbing oxygen on only a few percent of the surface Ga or As atomic sites can produce changes of a factor of two in the surface electronic structure. Thus, long range effects must be involved, and these are associated with rearrangement of the surface atoms.