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.     

Application of ETV-ICPMS in semiconductor process control

Submicron semiconductor manufacturing requires ultra-clean processes and materials to achieve high product yields. It is demonstrated that electrothermal evaporation (ETV) in a graphite furnace coupled with ICPMS offers a new possibility for a fast simultaneous analysis of eight elements with detection limits below 0.2 ng/g in conc. hydrofluoric acid and buffered oxide etch (ammonium fluoride/hydrogen fluoride mixture). ETV-ICPMS also comprises significant improvements in the analysis of metal contamination on silicon wafer surfaces with respect to currently used methods. The contaminants on the surface are usually analyzed by total reflexion X-ray fluorescence spectrometry (TXRF) or dissolved by HF vapour (vapour phase decomposition; VPD) or a mixture of hydrofluoric acid and hydrogen peroxide (droplet surface etching, DSE) and analyzed by GFAA or TXRF. ETV-ICPMS combines the advantages of both analytical methods: the multielemental advantage of TXRF and the possibility to analyze light elements like Al, Mg, Na which may not be analyzed by TXRF. With VPD/DSE-ETV-ICPMS detection limits between 0.2 and 2×10⁹ atoms cm^?2 on a 6″ wafer have been achieved in a simultaneous analysis of eight elements. The main advantage of ETV-ICPMS versus conventional ICPMS in both applications — chemical and surface analysis — is its capability to analyze Fe in the sub-ng/g range. As Fe is one of the most important impurities in semiconductor manufacturing ETV-ICPMS is much more useful for semiconductor applications than low-resolution ICPMS. For the present application potassium iodide was used as a modifier. It enhances the sensitivity by a factor of 3–4 and improves the reproducibility significantly.     

Method and mechanism of vapor phase treatment–total reflection X-ray fluorescence for trace element analysis on silicon wafer surface

Vapor phase treatment (VPT) is a pretreatment with hydrofluoric acid vapor to raise the sensitivity of total reflection X-ray fluorescence spectroscopy (TXRF) for trace metal analysis on silicon wafers. The International Organization for Standardization/Technical Committee 201/Working Group 2 (ISO/TC201/WG2) has been investigating the method to analyze 10⁹ atoms/cm² level of metallic contamination on the silicon wafer surface. Though VPT can enhance the TXRF signal intensity from the metallic contamination, it has turned out that the magnitude of the enhancement varies with the type of methods and the process conditions. In this study, approaches to increase TXRF intensity by VPT are investigated using a fuming chamber in an automated VPD instrument. Higher signal intensity can be obtained when condensation is formed on the sample surface in a humidifying atmosphere and with a decreasing stage temperature. Surface observations with SEM and AFM show that particles with ~ 4 μm in diameter are formed and unexpectedly they are dented from the top surface level.     

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.     

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 10⁸ 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 confidence with microdroplet standard reference.     

Semiconductor applications of nanoliter droplet methodology with total reflection x-ray fluorescence analysis

In this study, the nanoliter dried spot method was applied to semiconductor contamination analysis to enhance vapor phase decomposition processes with total reflection X-ray fluorescence detection. Nanoliter-sized droplets (10 and 50 nl) were deposited onto native silicon oxide wafer surfaces in a clean room environment from both single and multielemental standards containing various concentrations of iron in different matrices. Direct comparisons were made to droplets formed by conventional VPD with similar iron standards. Nanoliter dried spots could be reproducibly deposited and dried in air with typical drying times ranging from 20 s to 2 min depending on the nanoliter volume deposited, compared to VPD spots which have drying times ranging from tens of minutes to several hours. Both types of residues showed a linear relationship between Fe intensity and mass deposited. Variable angle experiments showed that both nanoliter and VPD deposits of single element standards were film-like in character, while residues formed from much more complex matrices and higher mass loadings were particulate in character. For the experimental conditions used in this study (30 kV, 100 mA), typical TXRF spectral Fe limits of detection were calculated to be on the order of picograms or ∼1×10¹⁰ atoms/cm² for a 0.8 cm² X-ray excitation beam area for both nanoliter dried spots and VPD spots prepared from single elemental standards. Calculated Fe detection limits for 200 mm diameter silicon wafers used in this study were in the ∼1×10⁸ atoms/cm² range. By using nanoliter sized droplets, the required sample volume is greatly reduced resulting in higher sample throughput than with conventional VPD methods.     

Trace analysis for 300 mm wafers and processes with total reflection X-ray fluorescence

Total reflection X-ray fluorescence (TXRF) is essential for 300-mm silicon wafer production and fabrication of semiconductor devices. The 300-mm TXRF enables non-destructive contamination analysis on wafers for process development and process control. The TXRF system shows a very stable continuous operation, which allows accurate trace and ultra trace analysis on the silicon surface. It is equipped with two excitation sources covering the requirements of very sensitive measurement and wide element range. The TXRF is a key technology for contamination control during wafer reclaim. For this purpose we show that the system is able to examine the wafers during different processing states of reclaim. The system sensitivity is influenced by the surface of the wafer. For important processing steps, e.g. double side polishing, the sensitivity is as good as for measurements on hazefree polished wafers. We show with TXRF that cross-contamination with copper during double side polishing is suppressed.     

Novel methods of TXRF analysis for silicon wafer surface inspection

TXRF became a standard, on-line inspection tool for controlling the cleanliness of polished Si wafers for semiconductor use. Wafer makers strive for an all-over metallic cleanliness of < 10¹⁰ atoms · cm^–2. The all-over cleanliness can be analyzed using VPD/TXRF. For VPD preparation and scanning we have developed an automatic system coupled with TXRF. With synchrotron radiation TXRF we were able to detect 13 fg of Ni in a residual microdroplet, i.e.10⁵ atoms · cm^–2. Received: 8 January 1998 / Revised: 13 July 1998 / Accepted: 30 July 1998     

Application of total reflection X-ray fluorescence in angle scan mode to establish the location of arsenic contamination in silicon and silicon oxide,respectively

Experiments have been carried out using total reflection X-ray fluorescence (TXRF) to determine the location of arsenic cross-contamination on or in silicon and silicon oxide, respectively, caused during argon-implantation. TXRF has been applied at varying angles of incidence — the so-called angle scan mode. By comparing the angle scan curves of implanted samples with those of a wafer, spin-coated with arsenic, at which arsenic is certainly located on top of the silicon surface, clear differences are observed. This indicates the presence of arsenic embedded in the subsurface. These observations are confirmed by Rutherford backscattering measurements, by modeling As-implantation profiles for low implantation energies as well as by step-by-step oxide etching followed by standard TXRF analysis. This fast and non-destructive application of TXRF angle scan appears a useful method for qualitative depth profiling.     

Some aspects of the high-temperature behavior of bismuth,strontium and barium on silicon surfaces studied by total reflection X-ray fluorescence spectrometry

Thin films of novel dielectric and ferroelectric materials, such as barium strontium titanate (BST) and strontium bismuth tantalate (SBT), which are scheduled for short-term implementation into standard microelectronic device technology, contain elements like Bi, Sr and Ba which may involve risks with regard to device yield and reliability. Therefore, the high-temperature behavior of bismuth, strontium and barium impurities on Si (100) substrates was studied. Intentionally contaminated Si substrates were annealed at 1000°C under different ambient (inert, oxidizing) by rapid thermal annealing (RTA) or in a furnace and analyzed by total reflection X-ray fluorescence spectrometry (TXRF), vapor phase decomposition/TXRF (VPD/TXRF) and electrolytic metal tracer (Elymat) technique. Ba and Sr are incorporated in the existing or growing oxide during rapid thermal annealing (RTA). Cross-contamination due to gas phase transport may occur in the case of Bi, in particular under N₂ atmosphere, but is of no concern in the case of Ba and Sr. All three contaminants do not exert an influence on the minority carrier lifetime on their own. The results illustrate that TXRF and VPD/TXRF are appropriate techniques for such studies.     

Vapor phase decomposition–droplet collection–total reflection X-ray fluorescence spectrometry for metallic contamination analysis on Ge wafers

Ge substrates are recently being reconsidered as a candidate material for the replacement of Si substrates in advanced semiconductor devices. The reintroduction of this material requires reengineering of the standard IC processing steps. In this paper, we present the extension of the methodology of vapor phase decomposition–droplet collection–total reflection X-ray fluorescence spectrometry (VPD–DC–TXRF) for metallic contamination analysis towards Ge substrates. A first step that asked for adaptation was the collection chemistry as the Ge wafers surface is not hydrophobic after the VPD treatment. The contact angle could be significantly increased using a concentrated HCl solution. This chemistry has been proved to perform well in the collection of metals from intentionally contaminated Ge wafers. A second step that needed optimization was the matrix removal method as a sample preparation step prior to the TXRF analysis. First, the upper limits of TXRF on Ge containing solutions have been characterized. The accuracy of TXRF is found to be acceptable for Ge contents lower than 1×10¹⁴ atoms (250 ppb in 50 μL) but decreases systematically with higher Ge contents. Fortunately, Ge can be volatilized at low temperatures as GeCl₄ by the addition of HCl. The parameters within this method have been investigated with respect to the removal of Ge and the recovery of metal traces. Finally, the full VPD–DC–TXRF method has been applied on intentionally contaminated Ge wafers and proved to be very accurate.     

Improvement of total reflection X-ray fluorescence analysis of low Z elements on silicon wafer surfaces at the PTB monochromator beamline for undulator radiation at the electron storage ring BESSY II

Several different total reflection X-ray fluorescence (TXRF) experiments were conducted at the plane grating monochromator beamline for undulator radiation of the Physikalisch-Technische Bundesanstalt (PTB) at the electron storage ring BESSY II, which provides photon energies between 0.1 and 1.9 keV for specimen excitation. The lower limits of detection of TXRF analysis were investigated for some low Z elements such as C, N, O, Al, Mg and Na in two different detection geometries for various excitation modes. Compared to ordinary XRF geometries involving large incident angles, the background contributions in TXRF are drastically reduced by the total reflection of the incident beam at the polished surface of a flat specimen carrier such as a silicon wafer. For the sake of an application-oriented TXRF approach, droplet samples on Si wafer surfaces were prepared by Wacker Siltronic and investigated in the TXRF irradiation chamber of the Atominstitut and the ultra-high vacuum TXRF irradiation chamber of the PTB. In the latter, thin C layer depositions on Si wafers were also studied.     

Considerations on the ideal sample shape for Total Reflection X-ray Fluorescence Analysis

Total Reflection X-ray Fluorescence analysis (TXRF) is widely used in semiconductor industry for the analysis of silicon wafer surfaces. Typically an external standard is used for the calibration of the spectrometer. This is sensitive to errors in quantification. For small sample amounts the thin film approximation is valid, absorption effects of the exciting and the detected radiation are neglected and the relation between sample amount and fluorescence intensity is linear. For higher total sample amounts deviations from linearity have been observed (saturation effect). These deviations are one of the difficulties for external standard quantification.A theoretical determination of the ideal TXRF sample shape is content of the presented work with the aim to improve the calibration process and therefore the quantification.The fluorescence intensity emitted by different theoretical sample shapes was calculated, whereby several parameters have been varied (excitation energy, density, diameter/height ratio of the sample). It was investigated which sample shape leads to the highest fluorescence intensity and exhibits the lowest saturation effect. The comparison of the different sample shapes showed that the ring shape matches the ideal TXRF sample shape best.     

Detection of metallic trace impurities on Si(100) surfaces with total reflection X-ray fluorescence (TXRF)

Summary The physical principles and analytical capabilities of TXRF are discussed and compared to other surface sensitive techniques. Metallic trace impurities on silicon surfaces are readily identified with detection limits down to 10¹¹ atoms/cm² (10^–4 monolayers). Other advantages are simple sample preparation and the possibility of analyzing insulating layers without charging problems. The method has been applied to quantify coverages of Fe, Ni, Cu and Au on Si(100) surfaces, deposited from intentionally doped solutions (NH₃/H₂O₂ and HF/NH₄F). It turns out that certain metal/solution combinations cause large surface coverages on the silicon wafer, even if the metal concentration in the solution is very low (g/kg range).

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Nachweis von metallischen Spurenverunreinigungen an Si(100)-Oberflächen mit der Totalreflexions-Röntgenfluorescenzanalyse (TXRF)

     

Synchrotron radiation induced total reflection X-ray fluorescence of low Z elements on Si wafer surfaces at SSRL — comparison of excitation geometries and conditions

The analysis of low Z elements, like Na and Al at ultra trace levels (<10¹⁰ atoms/cm²) on Si wafer surfaces is required by the semiconductor industry. Synchrotron radiation induced total reflection X-ray fluorescence analysis (SR-TXRF) is a promising method to fulfill this task, if a special energy dispersive detector with an ultra thin window is used. Synchrotron radiation is the ideal excitation source for TXRF of low Z elements due to its intense, naturally collimated and linearly polarized radiation with a wide spectral range down to low energies even below 1 keV. TXRF offers some advantages for wafer surface analysis such as non-destructive analysis and mapping capabilities. Experiments have been performed at the Stanford Synchrotron Radiation Lab (SSRL) using Beamline 3-4 (BL 3-4), a bending magnet beamline using white (<3 keV) and monochromatic radiation, as well as Beamline 3-3 (BL 3-3), using a crystal monochromator as well as a multilayer monochromator. A comparison of excitation–detection geometry was performed, using a side-looking detector with a vertically positioned wafer as well as a down-looking detector with a horizontally arranged wafer. The advantages and disadvantages of the various geometrical and excitation conditions are presented and the results compared. Detection limits are in the 100-fg range for Na, as determined with droplet samples on Si wafer surfaces.     

Calibration of reference materials for total-reflection X-ray fluorescence analysis by heavy ion backscattering spectrometry

Total-reflection X-ray fluorescence (TXRF) is widely used for the control of metallic contamination caused by surface preparation processes and silicon materials. At least three companies supply a variety of TXRF systems to the silicon integrated circuit (IC) community, and local calibration of these systems is required for their day to day operation. Differences in local calibration methods have become an issue in the exchange of information between IC manufacturers' different FABs (Fabrication Facility) and also between silicon suppliers and IC FABs. The question arises whether a universal set of fluorescence yield curves can be used by these different systems to scale system sensitivity from a single element calibration for calculation of elemental concentrations. This is emphasized by the variety of experimental conditions that are reported for TXRF data (e.g. different angles of incidence for the same X-ray source, different X-ray sources, etc.). It appears that an instrumental factor is required. We believe that heavy ion backscattering spectrometry (HIBS) provides a fundamental method of calibrating TXRF reference materials, and can be used in calculating this instrumental factor. In this paper we briefly describe the HIBS system at the Sandia National Laboratories HIBS User Facility and its application to the calibration of TXRF reference materials. We will compare HIBS and TXRF mapping capabilities and discuss the issues associated with the restrictions of some older TXRF sample stages. We will also discuss Motorola's cross-calibration of several TXRF systems using different elements as references.     

Applications of total reflection X-ray fluorescence spectrometry in trace element and surface analysis

Total reflection X-ray fluorescence spectrometry (TXRF) is presented as a genuine surface analytical technique. Its low information depth is shown to be the characteristic feature differentiating it from other energy dispersive X-ray fluorescence methods used for layer and surface analysis. The surface sensitivity of TXRF and its analytical capability together with the limitations of the technique are discussed here using typical applications including the contamination control of silicon wafers, thin layer analysis and trace element determination. For buried interfaces and implantation depth profiles in silicon a combination of TXRF and other techniques has been applied successfully. The TXRF method has the particular advantage of being calibrated without the need for standards. This feature is demonstrated for the example of the element arsenic.     

Feasibility study of SR‐TXRF‐XANES analysis for iron contaminations on a silicon wafer surface

The ability to chemically characterize the contamination on silicon wafers is of critical importance to the semiconductor industry. It provides information on possible unwanted chemical processes taking place on the wafer surface and helps in determining the true source of the contamination problem. This type of information is not readily accessible with standard laboratory equipment. Synchrotron radiation‐induced total reflection X‐ray fluorescence (SR‐TXRF) was combined with X‐ray absorption near‐edge structure (XANES) to determine the chemical state of Fe contaminations on a silicon wafer surface. Main purpose of the study was to test the method for a contamination issue as it could appear in a microelectronic VLSI production fab. Copyright © 2008 John Wiley & Sons, Ltd.     

Adaptation of a commercial total reflection X-ray fluorescence system for wafer surface analysis equipped with a new generation of silicon drift detector

Within the framework of a collaborative project, it is shown that commercial total reflection X-ray fluorescence (TXRF) systems used in laboratories can easily be upgraded with a silicon drift detector (SDD). SDDs have advantages when used with fully automatized wafer analyzers working under cleanroom conditions, because no liquid nitrogen is required as they are electrically cooled. The goal of this work was the integration of a KETEK 10 mm² SDD in an ATOMIKA 8030W wafer analyzer with special attention to maintain the high degree of automation of the system. An electronic device was designed to establish communication between the SDD and the TXRF electronic control system. The adapted system was tested and compared with the original setup using an 80 mm² Si(Li) detector. Multielement droplet samples on silicon wafers were analyzed and the results showed two times better detection limits for the Si(Li) detector for 1000 pg Ni in comparison to the SDD. Additionally, a RADIANT 50 mm² SDD (VORTEX) was tested which showed identical detection limits compared to the 80 mm² Si(Li) detector.     

Investigation of element distribution and homogeneity of TXRF samples using SR-micro-XRF to validate the use of an internal standard and improve external standard quantification

Total reflection X-ray fluorescence analysis (TXRF) offers a nondestructive qualitative and quantitative analysis of trace elements. Due to its outstanding properties TXRF is widely used in the semiconductor industry for the analysis of silicon wafer surfaces and in the chemical analysis of liquid samples. Two problems occur in quantification: the large statistical uncertainty in wafer surface analysis and the validity of using an internal standard in chemical analysis. In general TXRF is known to allow for linear calibration. For small sample amounts (low nanogram (ng) region) the thin film approximation is valid neglecting absorption effects of the exciting and the detected radiation. For higher total amounts of samples deviations from the linear relation between fluorescence intensity and sample amount can be observed. This could be caused by the sample itself because inhomogeneities and different sample shapes can lead to differences of the emitted fluorescence intensities and high statistical errors. The aim of the study was to investigate the elemental distribution inside a sample. Single and multi-element samples were investigated with Synchrotron-radiation-induced micro X-ray Fluorescence Analysis (SR-μ-XRF) and with an optical microscope. It could be proven that the microscope images are all based on the investigated elements. This allows the determination of the sample shape and potential inhomogeneities using only light microscope images. For the multi-element samples, it was furthermore shown that the elemental distribution inside the samples is homogeneous. This justifies internal standard quantification.