Quantitative determination of oxygen in silicon by combination of FTIR-spectroscopy,inert gas fusion analysis and secondary ion mass spectroscopy

Analytical and Bioanalytical Chemistry - VLSI devices are almost exclusively fabricated on Czochralski (CZ) silicon containing high concentrations of interstitially dissolved oxygen ([Oi] ∼...     

Accurate calibration of TXRF using microdroplet samples

TXRF has been applied in combination with VPD to the analysis of trace impurities in the native oxide layer of Si wafer surfaces down to the range of 10(8) atoms. cm(-2). Proper quantification of VPD/TXRF data requires calibration with microdroplet standard reference wafers. The precision of calibration function has been evaluated and found to allow quantification at a high level of 3 sigma confidence with microdroplet standard reference.     

Quo Vadis total reflection X-ray fluorescence?

The multielement trace analytical method ‘total reflection X-ray fluorescence’ (TXRF) has become a successfully established method in the semiconductor industry, particularly, in the ultra trace element analysis of silicon wafer surfaces. TXRF applications can fulfill general industrial requirements on daily routine of monitoring wafer cleanliness up to 300 mm diameter under cleanroom conditions. Nowadays, TXRF and hyphenated TXRF methods such as ‘vapor phase decomposition (VPD)-TXRF’, i.e. TXRF with a preceding surface and acid digestion and preconcentration procedure, are automated routine techniques (‘wafer surface preparation system’, WSPS). A linear range from 10⁸ to 10¹⁴ [atoms/cm²] for some elements is regularly controlled. Instrument uptime is higher than 90%. The method is not tedious and can automatically be operated for 24 h/7 days. Elements such as S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Br, Sn, Sb, Ba and Pb are included in the software for standard peak search. The detection limits of recovered elements are between 1×10¹¹ and 1×10⁷ [atoms/cm²] depending upon X-ray excitation energy and the element of interest. For the determination of low Z elements, i.e. Na, Al and Mg, TXRF has also been extended but its implementation for routine analysis needs further research. At present, VPD-TXRF determination of light elements is viable in a range of 10⁹ [atoms/cm²]. Novel detectors such as silicon drift detectors (SDD) with an active area of 5 mm², 10 mm² or 20 mm², respectively, and multi-array detectors forming up to 70 mm² are commercially available. The first SDD with 100 mm² (!) area and integrated backside FET is working under laboratory conditions. Applications of and comparison with ICP-MS, HR-ICP-MS and SR-TXRF, an extension of TXRF capabilities with an extremely powerful energy source, are also reported.     

Routine analysis of ultra pure water by ICP-MS in the low- and sub-ng/L level

The chemical analysis with inductively coupled plasma-mass spectrometry (ICP-MS) can help to examine the purity of ultra pure water (UPW) down to 10 part per trillion (ng/L) and lower. For a proper determination of a high number of samples per week the analysis must be divided into two parts: the routine analysis and the reference water analysis. The routine analysis is done by direct measurement of the ultra pure water samples. Applying a standard addition method under particular clean conditions, the reference water analysis leads to the definition of the accurate zero. A quick evaluation scheme is also presented for the reference water analysis. The method is tested for its fitness for application by examining LOD (for relevant element < 2 ng/L), reproducibility and linearity of calibration. The ICP-MS was optimized according to the methodology of G. Taguchi to improve reproducibility and LOD.     

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.     

Determination of nanogram amounts of sulphide by release of radioactive iodide

Two variants of a technique for determination of ng-amounts of sulphide ions in liquid samples are presented. They are based on the replacement of radioactively labelled iodide from silver iodide by sulphide. In the first variant, suitable for small sample volumes, the labelled silver iodide is fixed on a filter paper disc which is then shaken with the solution to be analysed until equilibrium is attained. In the second variant, suitable for sample volumes up to 300 ml, the sample solution is passed through a filter paper disc carrying labelled silver iodide or through a labelled silver iodide precipitate. The amount of sulphide is determined from the activity of the released radioiodide by comparison with standards which have been processed in the same way. The method is applicable to sulphide amounts greater than 5 ng and concentrations greater than 0.2 ppM. The interference by many common accompanying anions and cations has been investigated.     

Ultra-trace analytical monitoring of silicon wafer surfaces by capillary electrophoresis

Several methods are presented for the routine ultra-trace analytical monitoring of inorganic and organic anions and cations on the surface and in the native oxide of silicon wafers--the wafer-surface water-extraction method, the vapor-phase-decomposition method, and the re-dissolving method. Electrokinetic injection, sample stacking, and electrolyte composition were, therefore, optimized and made robust. For electrokinetic injection with transient isotachophoretic preconcentration a linear range of 0.05 to 0.5 micromol L(-1) was obtained; for sample stacking the linear range was 0.5 to 10 micromol L(-1), even in the presence of up to 750 micromol L(-1) hydrofluoric acid. Inorganic anions and monovalent carboxylic acids are predominately dissolved in the aqueous layer on the wafer surface whereas dicarboxylic acids are chemically bonded to the silanol groups and form esters.     

Analysis of organic contaminants on Si wafers with TXRF-NEXAFS

Organic contamination is starting to play an important role in the production and quality control of Si wafers. For the traceability of the source of contamination, information on the chemical binding conditions is very valuable. A near edge X-ray absorption fine structure (NEXAFS) investigation is the natural development of total reflection X-ray fluorescence (TXRF) analysis of the wafer surfaces able to solve the problem of speciation. The plane grating monochromator beamline for undulator radiation of the Physikalisch-Technische Bundesanstalt at the electron storage ring BESSY II, which provides photon energies between 30 eV and 1.9 keV for the specimen excitation, is an ideal excitation source for TXRF-NEXAFS experiments that require a high resolving power and a sufficient photon flux for trace analysis of low Z elements. The contaminants have been diluted and deposited as droplets on wafer pieces thoroughly cleaned after the cutting. The K edges of C, N, O have been examined. Some discrepancies have been found in the analysis of the same compounds in two different beamtimes; molecular orientation is pointed to as the cause for the difference in magnitude of the resonances. The unintentional contamination has been identified as mainly composed of aliphatic chains.     

Industrial applications of instrumental neutron activation analysis

Neutron activation analysis is shown as a useful diagnostic technique in semiconductor industry. A better acceptance of the method for applications in industry has been achieved through a specialized analytical service. Its main application is the characterization of high purity silicon in all stages of production. Irradiation of large sample volumes allowes a very sensitive detection of impurities in silicon with detection limits down to 10^–16 g/g. Other applications discussed are the analysis of silicon carbide, quartz, pure water and titanium. Special techniques described are autoradiography, depth profiling and surface analysis. In semiconductor process technology NAA was used to monitor contamination of silicon wafers.