Extended abstract of a paper presented at Microscopy and Microanalysis 2013 in Indianapolis, Indiana, USA, August 4 – August 8, 2013.

Methods using X-ray fluorescence have been developed to identify cometary material captured in aerogel during the NASA Stardust mission to Comet 81P/Wild 2. These analytical methods are necessitated by the levels of trace contaminants present in the aerogel. The cometary material disaggregates during deceleration in the aerogel, so fluorescence mapping of the entire track (which can be several millimeters long) is necessary. Distinguishing those pixels which have cometary material and aerogel from those which have only cometary material can be very challenging. We have chosen a “dual threshold” method, with some pixels clearly having only aerogel (plus contaminants) and other pixels clearly having cometary and aerogel material. Between these two threshold levels is a set of pixels which cannot be easily ascribed to one or the other. By leaving these pixels out of the analysis, the estimate of cometary material is improved.

There are factors present in cleanroom air that may lead to contamination prior to processing. These factors need to be better understood in order to meet tomorrow's requirement for atomically clean surfaces prior to gate oxidation. This paper identifies the conditions that initiate room temperature oxidation of fluoride prepared hydrogen passivated silicon surfaces by using X-ray Photoelectron Spectroscopy (XPS). Possible oxidation factors investigated include lighting conditions and ambient gases. Both Hx-Si(100) and H-Si(111)(1X1) surfaces do not oxidize in dark conditions and in 450nm wavelength lighting conditions for both humid and dry air ambients. These surfaces do oxidize in dry air and humid air when the surface is exposed to shorter wavelengths of light. Wavelength dependence for oxidation on both surfaces is confirmed. In addition, the level of oxidation observed depends on the surface orientation in humid air but not in dry air.

Trace metal contamination during wet cleaning processes on silicon wafer surfaces is a detrimental effect that impairs device performance and yield. Determining the chemical state of deposited impurities helps in understanding how silicon surfaces interact with chemical species in cleaning solutions. However, since impurity concentrations of interest to the semiconductor industry are so low, conventional techniques such as x-ray photoelectron spectroscopy cannot be applied. Nonetheless, chemical information on trace levels of contaminants can be determined with x-ray absorption near edge spectroscopy (XANES) in a grazing incidence geometry. In this study, silicon samples were dipped in ultra pure water (UPW) and 2% hydrofluoric (HF) solutions with copper concentrations of 5 and 1000 ppb, respectively. These samples were then analyzed using XANES in fluorescence yield mode to determine the oxidation state of deposited copper contaminants. It was found that copper impurities on the silicon surface from HF solution were metal in character while copper impurities deposited from the spiked UPW solution were deposited as an oxide. These results show that XANES can provide information on the chemical state of trace impurities even at surface concentrations below a few thousandths of a monolayer.

Synchrotron Radiation has become an important tool for the analysis of silicon surfaces in both fundamental and applied problems with techniques ranging from x-ray scattering to fluorescence. Applications that have been studied include the analysis of ultra-low levels of impurities on silicon wafer surfaces using the total external x-ray fluorescence technique (TXRF), measurement of silicon wafer surface roughness using crystal truncation rod scattering, measurement of the stress and defects associated with isolation trenches used in the fabrication of integrated circuits, and the study of transient enhanced diffusion in implanted silicon using x-ray diffuse scattering.

As the dimensions of integrated circuits become smaller and smaller, the thickness of the gate oxide is being reduced to a level where it has become necessary to control the process to virtually atomic levels. With oxide thicknesses less than 100 Angstroms, surface impurities can have deleterious affects on the oxide properties.

Synchrotron-based total-reflection x-ray fluorescence(SR-TXRF) has been developed as a leading technique for measuring wafer cleanliness. It holds advantages over other techniques in that it is non-destructive and allows mapping of the surface. The highest sensitivity observed thus far is 3x108 atoms/cm 2 (- 3fg) for 1000 second count time. Several applications of SR-TXRF are presented which take advantage of the energy tunability of the synchrotron source or the mapping capability.

This work describes recent progress in implementation and applications of synchrotron radiation total reflection x-ray fluorescence (SR-TXRF) to measure trace metals on wafer surfaces. To date, we have achieved state-of-the-art transition metal sensitivity of 3×108 atoms/cm2 (˜3fg) for 1000 sec. counting time for impurities which have an monolayer-like distribution on the surface and <1fg for droplet-like impurities. Recent instrumentation breakthroughs include reduction of detector parasitic backgrounds (particularly Cu) to below our present detection limit, 150 and 200mm whole-wafer handling, wafer-mapping capability and a cleanroom mini-environment. With these upgrades, measurements were made of wafers from various steps in the integrated circuit fabrication process. These results demonstrate that synchtron radiation brings TXRF into a new and useful regime. Further developments are underway to increase throughput and access for broader application.

Cesiation of type IIB diamond (110) crystals was studied using a combination of ultraviolet photoemission spectroscopy, x-ray photoemission spectroscopy, and low energy electron diffraction. The diamond (110) crystal was hydrogen treated by exposure to a hydrogen microwave discharge. Although cesium was largely unreactive with the hydrogenated diamond surface, cesiation yielded a large enhancement in the secondary electron yield of the diamond surface and the negative electron affinity (NEA) condition. An increase in the downwards band bending of approximately 0.75-0.9 eV was inferred from the shift in the valence band edge following cesiation. In addition, (lx 1) LEED patterns were observed at all cesium coverages. Exposure of the cesiated diamond surface to molecular oxygen significantly reduced the NEA peak (relative to the secondary electron background); however, recovery of the NEA peak was observed when the molecular oxygen source was removed.

Two complementary techniques are used to study the electrical transport properties related to the use of diamonds as materials for ionizing radiation detectors. Transient photoconductivity using soft x-rays is used to probe the first few microns of the material, while ionizing particle-excited conductivity is used to probe the entire bulk of the material (1 millimeter). Both techniques measure the mean drift distance of free carriers, or the collection distance d. In addition, transient photoconductivity is able to extract the lifetimes and mobilities of the excited carriers. The collection distance measured by the two methods are in agreement, suggesting the material is homogeneous. At an applied field of 10 kV/cm, d is 25 to 30 microns, and, up to a field of 25 kV/cm, d has not saturated. The lifetime varies between 100 and 600 ps, and the mobility varies between 1000 and 4000 cm2/V-s, the range due to natural variations from sample to sample. The primary defects limiting the lifetime are believed to be nitrogen impurities and dislocations.

The epitaxial growth of Ge on Si using Te as a surfactant has been studied with high resolution photoemission, low energy electron diffraction and cross-sectional transmission electron microscopy. The growth mode of Ge on Si changed from Stranski-Krastanov (S-K) to layer-by-layer mode when 1/4 ML Te atoms were on the surface. During the growth, Te atoms segregated to the top of the surface. If the growth temperature is too high (above ∼450°C), the Te coverage was less than that necessary to keep the layer-by-layer growth, and the growth mode of Ge on Si is still S-K.

The valence band and the Si 2p core level of electrochemically etched light emitting porous silicon samples prepared with different etching parameters and upon thermal annealing have been studied. The core level shows appreciable broadening as chemical etching time increases. Upon annealing, the core level linewidth decreases and the valence band develops spectral features. The photoluminescence intensity, also, decreases upon annealing. However, impurity species are found to be present only in trace amounts. Our data is consistent with a photoluminescence mechanism involving a silicon species that degrades, decomposes, or desorbs upon annealing.

A photoelectron microscope operating with a retarding field analyzer has been used to exploit core level energy shifts due to band bending in order to directly image Fermi level variations on n- and p-type cleaved GaAs(110) surfaces. Fermi level maps resolved to better than 10 um indicate lateral variations in the surface Fermi level which are often quite abrupt. In agreement with earlier, lower resolution work [1], Fermi level topography is found to be highly correlated with surface roughness as characterized by SEM, optical microscope and stylus profi lometer. The largest defect derived pinnings encountered to date resut in the Fermi level lying 0.5 eV above the VBM for both n- and p-type GaAs. Low coverage In evaporations have the. effect of reducing Fermi level contrast as Fermi levels in formerly unpinned regions move into the gap.

X-ray absorption fine structure, Auger electron spectroscopy and low energy electron diffraction have been used to study the evolution of the lattice constant and the degree of intermixing of thin (∼5 Å) silicon films grown on the germanium(111) surface by solid phase epitaxy. Our results indicate that as the system is annealed, the silicon intermixes with the germanium at elevated temperatures to form a pseudomorphic Si-Ge alloy with the germanium bulk lattice constant. We further observe a splitting of the ‘white line’ Is absorption edge in crystalling Si, SiGe and dilute (<10% silicon) SiGe. The measured splittings agree with band structure calculations for Si, SiGe, and Ge, respectively, indicating that the density of conduction band states of SiGe behaves as the interpolation between the states of Si and Ge. Qualitatively, our spectra may be interpreted in terms of a one electron picture without invoking many body excitonic effects. The absorption edge of amorphous silicon is also presented and the features of the density of states due to long versus short range order are extracted.

The thermal behavior of Te implanted, laser annealed GaAs was investigated by helium backscattering spectroscopy and transmission electron microscopy in order to correlate structural changes with the two stage reduction in the carrier concentration due to post laser anneal heating above 200°C. The activation energy for stage one which occurs in the range 200–400°C was determined to be approximately 1.3 eV. Post laser anneal heating at 450°C caused no observable structural changes. On the other hand, 850°C post laser anneal heating induced the formation of precipitates and dislocation loops as well as narrowing the channeling half-angle of Te by about 11%.