X-ray photoelectron spectroscopy (XPS) is a quantitative spectroscopic technique that measures the elemental composition, empirical formula, chemical

state and electronic state of the elements that exist within a material. XPS spectra are obtained by irradiating a material with a beam of X-rays while simultaneously measuring the kinetic energy and number of electrons that escape from the top 1 to 10 nm of the material being analyzed. XPS requires ultra high vacuum (UHV) conditions. XPS is a surface chemical analysis technique that can be used to analyze the surface chemistry of a material in its "as received" state, or after some treatment, for example: fracturing, cutting or scraping in air or UHV to expose the bulk chemistry, ion beam etching to clean off some of the surface contamination, exposure to heat to study the changes due to heating, exposure to reactive gases or solutions, exposure to ion beam implant, exposure to ultraviolet light.

XPS is also known as ESCA, an abbreviation for Electron Spectroscopy for Chemical Analysis. XPS detects all elements with an atomic number (Z) of 3 (lithium) and above. It cannot detect hydrogen (Z = 1) or helium (Z = 2) because the diameter of these orbitals is so small, reducing the catch probability to almost zero. Detection limits for most of the elements are in the parts per thousand range. Detection limits of parts per million (ppm) are possible, but require special conditions: concentration at top surface or very long collection time (overnight). XPS is routinely used to analyze inorganic compounds, metal alloys, semiconductors, polymers, elements, catalysts, glasses, ceramics, paints, papers, inks, woods, plant parts, make-up, teeth, bones, medical implants, bio-materials, viscous oils, glues, ion modified materials and many others.

XPS is used to measure:

elemental composition of the surface (top 110 nm usually) empirical formula of pure materials elements that contaminate a surface chemical or electronic state of each element in the surface uniformity of elemental composition across the top surface (or line profiling or mapping) uniformity of elemental composition as a function of ion beam etching (or depth profiling)

XPS can be performed using either a commercially built XPS system, a privately built XPS system or a synchrotron-based light source combined with a custom designed electron analyzer. Commercial XPS instruments in the year 2005 used either a highly focused 20 to 200 micrometer beam of monochromatic aluminium K X-rays or a broad 1030 mm beam of non-monochromatic (polychromatic) magnesium Xrays. A few, special design, XPS instruments can analyze volatile liquids or gases, materials at low or high temperatures or materials at roughly 1 torr vacuum, but there are relatively few of these types of XPS systems. Because the energy of an X-ray with particular wavelength is known, the electron binding energy of each of the emitted electrons can be determined by using an equation that is based on the work of Ernest Rutherford (1914):

where Ebinding is the binding energy (BE) of the electron, Ephoton is the energy of the X-ray photons being used, Ekinetic is the kinetic energy of the electron as measured by the instrument and is the work function of the spectrometer (not the material).

Physics

A typical XPS spectrum is a plot of the number of electrons detected (sometimes per unit time) (Y-axis, ordinate) versus the binding energy of the electrons detected (X-axis, abscissa). Each element produces a characteristic set of XPS peaks at characteristic binding energy values that directly identify each element that exist in or on the surface of the material being analyzed. These characteristic peaks correspond to the electron configuration of the electrons within the atoms, e.g., 1s, 2s, 2p, 3s, etc. The number of detected electrons in each of the characteristic peaks is directly related to the amount of element within the area (volume) irradiated. To generate atomic percentage values, each raw XPS signal must be corrected by dividing its signal intensity (number of electrons detected) by a "relative sensitivity factor" (RSF) and normalized over all of the elements detected. To count the number of electrons at each kinetic energy value, with the minimum of error, XPS must be performed under ultra-high vacuum (UHV) conditions because electron counting detectors in XPS instruments are typically one meter away from the material irradiated with X-rays. It is important to note that XPS detects only those electrons that have actually escaped into the vacuum of the instrument. The photo-emitted electrons that have escaped into the vacuum of the instrument are those that originated from within the top 10 to 12 nm of the material. All of the deeper photo-emitted electrons, which were generated as the X-rays penetrated 1 5 micrometers of the material, are either recaptured or trapped in various excited states within the material. For most applications, it is, in effect, a non-destructive technique that measures the surface chemistry of any material. The main components of a commercially made XPS system include:

A source of X-rays An ultra-high vacuum (UHV) stainless steel chamber with UHV pumps An electron collection lens An electron energy analyzer Mu-metal magnetic field shielding An electron detector system A moderate vacuum sample introduction chamber Sample mounts A sample stage A set of stage manipulators

Monochromatic aluminium K-alpha X-rays are normally produced by diffracting and focusing a beam of non-monochromatic X-rays off of a thin disc of natural, crystalline quartz with a <1010> orientation. The resulting wavelength is 8.3386 angstroms (0.83386 nm) which corresponds to a photon energy of 1486.7 eV. The energy width of the monochromated X-rays is 0.16 eV, but the common electron energy analyzer (spectrometer) produces an ultimate energy resolution on the order of 0.25 eV which, in effect, is the ultimate energy resolution of most commercial systems. When working under practical, everyday conditions, high energy resolution settings will produce peak widths (FWHM) between 0.40.6 eV for various pure elements and some compounds. Non-monochromatic magnesium X-rays have a wavelength of 9.89 angstroms (0.989 nm) which corresponds to a photon energy of 1253 eV. The energy width of the non-monochromated X-ray is roughly 0.70 eV, which, in effect is the ultimate energy resolution of a system using non-monochromatic X-rays. Non-monochromatic X-ray sources do not use any crystals to diffract the X-rays which allows all primary X-rays lines and the full range of high energy Bremsstrahlung X-rays (112 keV) to reach the surface. The typical ultimate high energy resolution (FWHM) when using this source is 0.91.0 eV, which includes with the spectrometer-induced broadening, pass-energy settings and the peak-width of the non-monochromatic magnesium X-ray source.

[edit] Uses and capabilities

XPS is routinely used to determine:

What elements and the quantity of those elements that are present within the top 1-12 nm of the sample surface What contamination, if any, exists in the surface or the bulk of the sample Empirical formula of a material that is free of excessive surface contamination The chemical state identification of one or more of the elements in the sample The binding energy of one or more electronic states The thickness of one or more thin layers (18 nm) of different materials within the top 12 nm of the surface The density of electronic states

[edit] Capabilities of advanced systems

Measure uniformity of elemental composition across the top the surface (or line profiling or mapping) Measure uniformity of elemental composition as a function of depth by ion beam etching (or depth profiling) Measure uniformity of elemental composition as a function of depth by tilting the sample (or angle resolved XPS)

[edit] Chemical States from XPS analyses

The ability to produce Chemical State information from the topmost 1-12 nm of any surface makes XPS a unique and invaluable tool for understanding the chemistry of any surface either, as received, or after physical or chemical treatment(s). Because modern systems use monochromatic X-ray sources, XPS measurements leave the surface free of any degradation with few exceptions. Chemical state analysis of the surface of polymers readily reveals the presence or absence of the chemical states of carbon known as: carbide (C 2-), hydrocarbon (C-C), alcohol (C-OH), ketone (C=O), organic ester (COOR), carbonate (CO3), fluoro-hydrocarbon (CF2-CH2), trifluorocarbon (CF3). Chemical state analysis of the surface of a silicon wafer readily reveals the presence or absence of the chemical states of silicon known as: n-doped silicon, p-doped silicon, silicon suboxide (Si2O), silicon monoxide (SiO), Si2O3, silicon dioxide (SiO2).

Industries that use XPS

Adhesion Agriculture Automotive Battery Biotechnology Canning Catalyst Ceramic Chemical Computer Cosmetics Electronics Environmental

Fabrics Food Fuel cells Geology Glass Laser Lighting Lubrication Magnetic memory Mineralogy Mining Nanotechnology Nuclear

Packaging Paper and wood Plating Polymer and plastic Printing Recording Semiconductor Steel Textiles Thin-film coating Welding

Quantitative accuracy

XPS is widely used to generate empirical formula because it readily yields excellent quantitative accuracy from homogeneous solid state materials Quantitative accuracy depends on several parameters such as: signal-to-noise ratio, peak intensity, accuracy of relative sensitivity factors, correction for electron transmission function, surface volume homogeneity, correction for energy dependency of electron mean free path, and degree of sample degradation due to analysis. Under optimum conditions, the quantitative accuracy of the atomic percent (at%) values calculated from the Major XPS Peaks is 90-95% for each major peak. If a high level quality control protocol is used, the accuracy can be further improved. Under routine work conditions, where the surface is a mixture of contamination and expected material, the accuracy ranges from 80-90% of the value reported in atomic percent values. The quantitative accuracy for the weaker XPS signals, that have peak intensities 10-20% of the strongest signal, are 60-80% of the true value.

[edit] Analysis time

110 minutes for a survey scan that measures the amount of all elements, 1 10 minutes for high energy resolution scans that reveal chemical state differences, 1 4 hours for a depth profile that measures 4 5 elements as a function of etched depth (usual final depth is 1,000 nm)

[edit] Detection limits

0.11.0 at% (0.1 at% = 1 part per thousand = 1000 ppm). (Ultimate detection limit for most elements is approximately 100 ppm, which requires 816 hours.)

[edit] Measured area

Measured area depends on instrument design. The minimum analysis area ranges from 10 to 200 micrometres. Largest size for a monochromatic beam of X-rays is 15 mm. Non-monochromatic beams are 1050 mm in diameter. Spectroscopic image resolution levels of 200 nm or below has been achieved on latest imaging XPS instruments using synchrotron radiation as X-ray source.

[edit] Sample size limits

Older instruments accept samples: 11 to 33 cm. Present systems can accept samples up to 3030 cm.[citation
needed]

[edit] Degradation during analysis

Depends on the sensitivity of the material to the wavelength of X-rays used, the total dose of the X-rays, the temperature of the surface and the level of the vacuum. Metals, alloys, ceramics and most glasses are not measurably degraded by either non-monochromatic or monochromatic X-rays. Some, but not all, polymers, catalysts, certain highly oxygenated compounds, various inorganic compounds and fine organics are degraded by either monochromatic or non-monochromatic X-ray sources. Non-monochromatic X-ray sources produce a significant amount of high energy Bremsstrahlung X-rays (1 15 keV of energy) which directly degrade the surface chemistry of various materials. Non-monochromatic Xray sources also produce a significant amount of heat (100 to 200 C) on the surface of the sample because the anode that produces the X-rays is typically only 1 to 5 cm (2 in) away from the sample. This level of heat, when combined with the Bremsstrahlung X-rays, acts synergistically to increase the amount and rate of degradation for certain materials. Monochromatic X-ray sources, because they are far away (50 100 cm) from the sample, do not produce any heat effects. Monochromatic X-ray sources are monochromatic because the quartz monochromator system diffracted the Bremsstrahlung X-rays out of the X-ray beam which means the sample only sees one X-ray energy, for example: 1.486 keV if aluminium K-alpha X-rays are used.

Because the vacuum removes various gases (e.g. O2, CO) and liquids (e.g. water, alcohol, solvents) that were initially trapped within or on the surface of the sample, the chemistry and morphology of the surface will continue to change until the surface achieves a steady state. This type of degradation is sometimes difficult to detect.

[edit] Materials routinely analyzed by XPS

Inorganic compounds, metal alloys, semiconductors, polymers, pure elements, catalysts, glasses, ceramics, paints, papers, inks, woods, plant parts, make-up, teeth, bones, human implants, biomaterials, viscous oils, glues, ion modified materials Organic chemicals are not routinely analyzed by XPS because they are readily degraded by either the energy of the X-rays or the heat from non-monochromatic X-ray sources.
[edit] Charge compensation techniques

Low-voltage electron beam (1-20 eV) (or electron flood gun) UV lights Low-voltage argon ion beam with low-voltage electron beam (1-10 eV) Aperture masks Mesh screen with low-voltage electron beams

[edit] Sample preparation

Sample handling Sample cleaning Sample mounting

[edit] Peak identification

The identification of peaks in any survey spectrum is possible because Prof. Kai Siegbahn improved the energy resolution of his XPS instrument to the point that observed signals were both tall and narrow with respect to the energy range measured (0-1400 eV).[citation needed] In the course of improving his XPS instruments, he collected spectra from pure conductive elements. That collection of spectra yielded peaks with energies (reported as BEs) that are characteristic for each specific element. The number of peaks produced by a single element varies from 1 to more than 20. Tables of binding energies (BEs) that identify the shell and spin-orbit of each peak produced by a given element are included with modern XPS instruments, and can be found in various handbooks [citations] and websites [citations]. Because these experimentally determined BEs are characteristic of specific elements, they can be directly used to identify experimentally measured peaks of a material with unknown elemental composition. Before beginning the process of peak identification, the analyst must determine if the BEs of the unprocessed survey spectrum (0-1400 eV) have or have not been shifted due to a positive or negative surface charge. This is most often done by looking for two peaks that due to the presence of carbon and oxygen. {tbc}
[edit] Charge referencing insulators

Charge referencing is needed when a sample suffers either a positive (+) or negative (-) charge induced shift of experimental BEs. Charge referencing is needed to obtain meaningful BEs from both wide-scan, high sensitivity (low energy resolution) survey spectra (0-1100 eV), and also narrow-scan, chemical state (high energy resolution) spectra. Charge induced shifting causes experimentally measured BEs of XPS peaks to appear at BEs that are greater or smaller than true BEs. Charge referencing is performed by adding or subtracting a "Charge Correction

Factor" to each of the experimentally measured BEs. In general, the BE of the hydrocarbon peak of the C (1s) XPS signal is used to charge reference (charge correct) all BEs obtained from non-conductive (insulating) samples or conductors that have been deliberately insulated from the sample mount. Charge induced shifting is normally due to: a modest excess of low voltage (-1 to -20 eV) electrons attached to the surface, or a modest shortage of electrons (+1 to +15 eV) within the top 1-12 nm of the sample caused by the loss of photo-emitted electrons. The degree of charging depends on various factors. If, by chance, the charging of the surface is excessively positive, then the spectrum might appear as a series of rolling hills, not sharp peaks as shown in the example spectrum. The C (1s) BE of the hydrocarbon species (moieties) of the "Adventitious" carbon that appears on all, airexposed, conductive and semi-conductive materials is normally found between 284.5 eV and 285.5 eV. For convenience, the C (1s) of hydrocarbon moieties is defined to appear between 284.6 eV and 285.0 eV. A value of 284.8 eV has become popular in recent years. However, some recent reports indicate that 284.9 eV or 285.0 eV represents hydrocarbons attached on metals, not the natural native oxide.[citation needed] The 284.8 eV BE is routinely used as the "Reference BE" for charge referencing insulators. When the C (1s) BE is used for charge referencing, then the charge correction factor is the difference between 284.8 eV and the experimentally measured C (1s) BE of the hydrocarbon moieties. When using a monochromatic XPS system together with a low voltage electron flood gun for charge compensation the experimental BEs of the C (1s) hydrocarbon peak is often 4-5 eV smaller than the reference BE value (284.8 eV). In this case, all experimental BEs appear at lower BEs than expected and need to be increased by adding a value ranging from 4 to 5 eV. Non-monochromatic XPS systems are not usually equipped with a low voltage electron flood gun so the BEs will normally appear at higher BEs than expected. It is normal to subtract a charge correction factor from all BEs produced by a non-monochromatic XPS system. Conductive materials and most native oxides of conductors should never need charge referencing. Conductive materials should never be charge referenced unless the topmost layer of the sample has a thick non-conductive film.
[edit] Peak-fitting

The process of peak-fitting high energy resolution XPS spectra is still a mixture of art, science, knowledge and experience. The peak-fit process is affected by instrument design, instrument components, experimental settings (aka analysis conditions) and sample variables. Most instrument parameters are constant while others depend on the choice of experimental settings. Before starting any peak-fit effort, the analyst performing the peak-fit needs to know if the topmost 15 nm of the sample is expected to be a homogeneous material or is expected to be a mixture of materials. If the top 15 nm is a homogeneous material with only very minor amounts of adventitious carbon and adsorbed gases, then the analyst can use theoretical peak area ratios to enhance the peak-fitting process. Variables that affect or define peak-fit results include:

FWHMs Chemical Shifts Peakshapes Instrument design factors Experimental settings Sample factors

[edit] FWHMs When using high energy resolution experiment settings on an XPS equipped with a monochromatic Al Kalpha X-ray source, the FWHM of the major XPS peaks range from 0.3 eV to 1.7 eV. The following is a simple summary of FWHM from major XPS signals:

Main metal peaks (e.g. 1s, 2p3, 3d5, 4f7) from pure metals have FWHMs that range from 0.30 eV to 1.0 eV Main metal peaks (e.g. 1s, 2p3, 3d5, 4f7) from binary metal oxides have FWHMs that range from 0.9 eV to 1.7 eV The O (1s) peak from binary metal oxides have FWHMs that, in general, range from 1.0 eV to 1.4 eV The C (1s) peak from adventitious hydrocarbons have FWHMs that, in general, range from 1.0 eV to 1.4 eV

[edit] Chemical Shifts Chemical shift values depend on the degree of electron bond polarization between nearest neighbor atoms. A specific chemical shift is the difference in BE values of one specific chemical state versus the BE of the pure element.

Peaks derived from peak-fitting a raw chemical state spectrum are due to the presence of different chemical states.

X-ray fluorescence (XRF) is the emission of characteristic "secondary" (or fluorescent) X-rays from a material that has been excited by bombarding with high-energy X-rays or gamma rays. The phenomenon is widely used for elemental analysis and chemical analysis, particularly in the investigation of metals, glass, ceramics and building materials, and for research in geochemistry, forensic science and archaeology.

When materials are exposed to short-wavelength X-rays or to gamma rays, ionization of their component atoms may take place. Ionization consists of the ejection of one or more electrons from the atom, and may occur if the atom is

exposed to radiation with an energy greater than its ionization potential. X-rays and gamma rays can be energetic enough to expel tightly held electrons from the inner orbitals of the atom. The removal of an electron in this way renders the electronic structure of the atom unstable, and electrons in higher orbitals "fall" into the lower orbital to fill the hole left behind. In falling, energy is released in the form of a photon, the energy of which is equal to the energy difference of the two orbitals involved. Thus, the material emits radiation, which has energy characteristic of the atoms present. The term fluorescence is applied to phenomena in which the absorption of radiation of a specific energy results in the re-emission of radiation of a different energy (generally lower). Characteristic radiation

Each element has electronic orbitals of characteristic energy. Following removal of an inner electron by an energetic photon provided by a primary radiation source, an electron from an outer shell drops into its place. There are a limited number of ways in which this can happen, as shown in figure 1. The main transitions are given names: an LK transition is traditionally called K, an MK transition is called K, an ML transition is called L, and so on. Each of these transitions yields a fluorescent photon with a characteristic energy equal to the difference in energy of the initial and final orbital. The wavelength of this fluorescent radiation can be calculated from Planck's Law:

The fluorescent radiation can be analysed either by sorting the energies of the photons (energy-dispersive analysis) or by separating the wavelengths of the radiation (wavelength-dispersive analysis). Once sorted, the intensity of each characteristic radiation is directly related to the amount of each element in the material. This is the basis of a powerful technique in analytical chemistry. Figure 2 shows the typical form of the sharp fluorescent spectral lines obtained in the wavelength-dispersive method (see Moseley's law).
Primary radiation

In order to excite the atoms, a source of radiation is required, with sufficient energy to expel tightly held inner electrons. Conventional X-ray generators are most commonly used, because their output can readily be "tuned" for the application, and because higher power can be deployed relative to other techniques. However, gamma ray sources can be used without the need for an elaborate power supply, allowing an easier use in small portable instruments. When the energy source is a synchrotron or the X-rays are focused by an optic like a polycapillary, the X-ray beam can be very small and very intense. As a result, atomic information on the sub-micrometre scale can be obtained. X-ray generators in the range 2060 kV are used, which allow excitation of a broad range of atoms. The continuous spectrum consists of "bremsstrahlung" radiation: radiation produced when high-energy electrons passing through the tube are progressively decelerated by the material of the tube anode (the "target"). A typical tube output spectrum is shown in figure 3.
[edit] Dispersion

In energy dispersive analysis, the fluorescent X-rays emitted by the material sample are directed into a solidstate detector which produces a "continuous" distribution of pulses, the voltages of which are proportional to the incoming photon energies. This signal is processed by a multichannel analyser (MCA) which produces an accumulating digital spectrum that can be processed to obtain analytical data. In wavelength dispersive analysis, the fluorescent X-rays emitted by the material sample are directed into a diffraction grating monochromator. The diffraction grating used is usually a single crystal. By varying the angle of incidence and take-off on the crystal, a single X-ray wavelength can be selected. The wavelength obtained is given by the Bragg Equation:

where d is the spacing of atomic layers parallel to the crystal surface.

[edit] Detection

In energy dispersive analysis, dispersion and detection are a single operation, as already mentioned above. Proportional counters or various types of solid-state detectors (PIN diode, Si(Li), Ge(Li), Silicon Drift Detector SDD) are used. They all share the same detection principle: An incoming X-ray photon ionises a large number of detector atoms with the amount of charge produced being proportional to the energy of the incoming photon. The charge is then collected and the process repeats itself for the next photon. Detector speed is obviously critical, as all charge carriers measured have to come from the same photon to measure the photon energy correctly (peak length discrimination is used to eliminate events that seem to have been produced by two X-ray photons arriving almost simultaneously). The spectrum is then built up by dividing the energy spectrum into discrete bins and counting the number of pulses registered within each energy bin. EDXRF detector types vary in resolution, speed and the means of cooling (a low number of free charge carriers is critical in the solid state detectors): proportional counters with resolutions of several hundred eV cover the low end of the performance spectrum, followed by PIN diode detectors, while the Si(Li), Ge(Li) and Silicon Drift Detectors (SDD) occupy the high end of the performance scale. In wavelength dispersive analysis, the single-wavelength radiation produced by the monochromator is passed into a photomultiplier, a detector similar to a Geiger counter, which counts individual photons as they pass through. The counter is a chamber containing a gas that is ionised by X-ray photons. A central electrode is charged at (typically) +1700 V with respect to the conducting chamber walls, and each photon triggers a pulse-like cascade of current across this field. The signal is amplified and transformed into an accumulating digital count. These counts are then processed to obtain analytical data.
[edit] X-ray intensity

The fluorescence process is inefficient, and the secondary radiation is much weaker than the primary beam. Furthermore, the secondary radiation from lighter elements is of relatively low energy (long wavelength) and has low penetrating power, and is severely attenuated if the beam passes through air for any distance. Because of this, for high-performance analysis, the path from tube to sample to detector is maintained under high vacuum (around 10 Pa residual pressure). This means in practice that most of the working parts of the instrument have to be located in a large vacuum chamber. The problems of maintaining moving parts in vacuum, and of rapidly introducing and withdrawing the sample without losing vacuum, pose major challenges for the design of the instrument. For less demanding applications, or when the sample is damaged by a vacuum (e.g. a volatile sample), a helium-swept X-ray chamber can be substituted, with some loss of low-Z (Z = atomic number) intensities.

Chemical analysis
The use of a primary X-ray beam to excite fluorescent radiation from the sample was first proposed by Glocker and Schreiber in 1928.[1] Today, the method is used as a non-destructive analytical technique, and as a process control tool in many extractive and processing industries. In principle, the lightest element that can be analysed is beryllium (Z = 4), but due to instrumental limitations and low X-ray yields for the light elements, it is often difficult to quantify elements lighter than sodium (Z = 11), unless background corrections and very comprehensive inter-element corrections are made.

Energy dispersive spectrometry

In energy dispersive spectrometers (EDX or EDS), the detector allows the determination of the energy of the photon when it is detected. Detectors historically have been based on silicon semiconductors, in the form of lithium-drifted silicon crystals, or high-purity silicon wafers.
Si(Li) detectors

These consist essentially of a 35 mm thick silicon junction type p-i-n diode (same as PIN diode) with a bias of 1000 V across it. The lithium-drifted centre part forms the non-conducting i-layer, where Li compensates the residual acceptors which would otherwise make the layer p-type. When an X-ray photon passes through, it causes a swarm of electron-hole pairs to form, and this causes a voltage pulse. To obtain sufficiently low conductivity, the detector must be maintained at low temperature, and liquid-nitrogen must be used for the best resolution. With some loss of resolution, the much more convenient Peltier cooling can be employed.[2]

[edit] Wafer detectors

More recently, high-purity silicon wafers with low conductivity have become routinely available. Cooled by the Peltier effect, this provides a cheap and convenient detector, although the liquid nitrogen cooled Si(Li) detector still has the best resolution (i.e. ability to distinguish different photon energies).
[edit] Amplifiers

The pulses generated by the detector are processed by pulse-shaping amplifiers. It takes time for the amplifier to shape the pulse for optimum resolution, and there is therefore a trade-off between resolution and count-rate: long processing time for good resolution results in "pulse pile-up" in which the pulses from successive photons overlap. Multi-photon events are, however, typically more drawn out in time (photons did not arrive exactly at the same time) than single photon events and pulse-length discrimination can thus be used to filter most of these out. Even so, a small number of pile-up peaks will remain and pile-up correction should be built into the software in applications that require trace analysis. To make the most efficient use of the detector, the tube current should be reduced to keep multi-photon events (before discrimination) at a reasonable level, e.g. 520%.
[edit] Processing

Considerable computer power is dedicated to correcting for pulse-pile up and for extraction of data from poorly resolved spectra. These elaborate correction processes tend to be based on empirical relationships that may change with time, so that continuous vigilance is required in order to obtain chemical data of adequate precision.

[edit] Usage

EDX spectrometers are superior to WDX spectrometers in that they are smaller, simpler in design and have fewer engineered parts. They can also use miniature X-ray tubes or gamma sources. This makes them cheaper and allows miniaturization and portability. This type of instrument is commonly used for portable quality control screening applications, such as testing toys for Lead (Pb) content, sorting scrap metals, and measuring the lead content of residential paint. On the other hand, the low resolution and problems with low count rate and long dead-time makes them inferior for high-precision analysis. They are, however, very effective for high-speed, multi-elemental analysis. Field Portable XRF analysers currently on the market weigh less than 2 kg, and have limits of detection on the order of 2 parts per million of Lead (Pb) in pure sand.
Wavelength dispersive spectrometry

In wavelength dispersive spectrometers (WDX or WDS), the photons are separated by diffraction on a single crystal before being detected. Although wavelength dispersive spectrometers are occasionally used to scan a wide range of wavelengths, producing a spectrum plot as in EDS, they are usually set up to make measurements only at the wavelength of the emission lines of the elements of interest. This is achieved in two different ways:

"Simultaneous" spectrometers have a number of "channels" dedicated to analysis of a single element, each consisting of a fixed-geometry crystal monochromator, a detector, and processing electronics. This allows a number of elements to be measured simultaneously, and in the case of high-powered instruments, complete high-precision analyses can be obtained in under 30 s. Another advantage of this arrangement is that the fixed-geometry monochromators have no continuously moving parts, and so are very reliable. Reliability is important in production environments where instruments are expected to work without interruption for months at a time. Disadvantages of simultaneous spectrometers include relatively high cost for complex analyses, since each channel used is expensive. The number of elements that can be measured is limited to 1520, because of space limitations on the number of monochromators that can be crowded around the fluorescing sample. The need to accommodate multiple monochromators means that a rather open arrangement around the sample is required, leading to relatively long tube-sample-crystal distances, which leads to lower detected intensities and more scattering. The instrument is inflexible, because if a new element is to be measured, a new measurement channel has to be bought and installed. "Sequential" spectrometers have a single variable-geometry monochromator (but usually with an arrangement for selecting from a choice of crystals), a single detector assembly (but usually with more than one detector arranged in tandem), and a single electronic pack. The instrument is programmed to move through a sequence of wavelengths, in each case selecting the appropriate X-ray tube power, the appropriate crystal, and the appropriate detector arrangement. The length of the measurement program is essentially unlimited, so this arrangement is very flexible. Because there is only one monochromator, the tube-sample-crystal distances can be kept very short, resulting in minimal loss of detected intensity. The obvious disadvantage is relatively long analysis time, particularly when many elements are being analysed, not only because the elements are measured in sequence, but also because a certain amount of time is taken in readjusting the monochromator geometry between measurements. Furthermore, the frenzied activity of the monochromator during an analysis program is a challenge for mechanical reliability. However, modern sequential instruments can achieve reliability almost as good as that of simultaneous instruments, even in continuous-usage applications.

[edit] Sample presentation

In order to keep the geometry of the tube-sample-detector assembly constant, the sample is normally prepared as a flat disc, typically of diameter 2050 mm. This is located at a standardized, small distance from the tube window. Because the X-ray intensity follows an inverse-square law, the tolerances for this placement and for the flatness of the surface must be very tight in order to maintain a repeatable X-ray flux. Ways of obtaining sample discs vary: metals may be machined to shape, minerals may be finely ground and pressed into a tablet, and glasses may be cast to the required shape. A further reason for obtaining a flat and

representative sample surface is that the secondary X-rays from lighter elements often only emit from the top few micrometres of the sample. In order to further reduce the effect of surface irregularities, the sample is usually spun at 520 rpm. It is necessary to ensure that the sample is sufficiently thick to absorb the entire primary beam. For higher-Z materials, a few millimetres thickness is adequate, but for a light-element matrix such as coal, a thickness of 3040 mm is needed.

Monochromators

The common feature of monochromators is the maintenance of a symmetrical geometry between the sample, the crystal and the detector. In this geometry the Bragg diffraction condition is obtained. The X-ray emission lines are very narrow (see figure 2), so the angles must be defined with considerable precision. This is achieved in two ways:

Flat crystal with Soller collimators

The Soller collimator is a stack of parallel metal plates, spaced a few tenths of a millimetre apart. To improve angle resolution, one must lengthen the collimator, and/or reduce the plate spacing. This arrangement has the advantage of simplicity and relatively low cost, but the collimators reduce intensity and increase scattering, and reduce the area of sample and crystal that can be "seen". The simplicity of the geometry is especially useful for variable-geometry monochromators.

Curved crystal with slits

The Rowland circle geometry ensures that the slits are both in focus, but in order for the Bragg condition to be met at all points, the crystal must first be bent to a radius of 2R (where R is the radius of the Rowland circle), then ground to a radius of R. This arrangement allows higher intensities (typically 8-fold) with higher resolution (typically 4-fold) and lower background. However, the mechanics of keeping Rowland circle geometry in a variable-angle monochromator is extremely difficult. In the case of fixed-angle monochromators (for use in simultaneous spectrometers), crystals bent to a logarithmic spiral shape give the best focusing performance. The manufacture of curved crystals to acceptable tolerances increases their price considerably.

[edit] Analysis Lines

The spectral lines used for chemical analysis are selected on the basis of intensity, accessibility by the instrument, and lack of line overlaps. Typical lines used, and their wavelengths, are as follows: element line Li Be B C N O F Ne Na Mg Al Si P S Cl Ar K Ca Sc Ti V Cr Mn Fe Co K K K K K K wavelength wavelength wavelength wavelength element line element line element line (nm) (nm) (nm) (nm) 22.8 11.4 6.76 4.47 3.16 2.362 Ni Cu Zn Ga Ge As Se Br Kr Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te K1 0.1658 K1 0.1541 K1 0.1435 K1 0.1340 K1 0.1254 K1 0.1176 K1 0.1105 K1 0.1040 K1 0.09801 K1 0.09256 K1 0.08753 K1 0.08288 K1 0.07859 K1 0.07462 K1 0.07094 K1 0.06751 K1 0.06433 K1 0.06136 K1 0.05859 K1 0.05599 K1 0.05357 L1 0.3772 L1 0.3600 L1 0.3439 L1 0.3289 I Xe Cs Ba La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Re Os Ir L1 0.3149 L1 0.3016 L1 0.2892 L1 0.2776 L1 0.2666 L1 0.2562 L1 0.2463 L1 0.2370 L1 0.2282 L1 0.2200 L1 0.2121 L1 0.2047 L1 0.1977 L1 0.1909 L1 0.1845 L1 0.1784 L1 0.1727 L1 0.1672 L1 0.1620 L1 0.1570 L1 0.1522 L1 0.1476 L1 0.1433 L1 0.1391 L1 0.1351 Pt Au Hg Tl Pb Bi Po At Rn Fr Ra Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No L1 0.1313 L1 0.1276 L1 0.1241 L1 0.1207 L1 0.1175 L1 0.1144 L1 0.1114 L1 0.1085 L1 0.1057 L1 0.1031 L1 0.1005 L1 0.0980 L1 0.0956 L1 0.0933 L1 0.0911 L1 0.0888 L1 0.0868 L1 0.0847 L1 0.0828 L1 0.0809 L1 0.0791 L1 0.0773 L1 0.0756 L1 0.0740 L1 0.0724

K1,2 1.832 K1,2 1.461 K1,2 1.191 K1,2 0.989 K1,2 0.834 K1,2 0.7126 K1,2 0.6158 K1,2 0.5373 K1,2 0.4729 K1,2 0.4193 K1,2 0.3742 K1,2 0.3359 K1,2 0.3032 K1,2 0.2749 K1 0.2504 K1 0.2290 K1 0.2102 K1 0.1936 K1 0.1789

Other lines are often used, depending on the type of sample and equipment available.
[edit] Crystals

The desirable characteristics of a diffraction crystal are:

High diffraction intensity High dispersion Narrow diffracted peak width High peak-to-background Absence of interfering elements Low thermal coefficient of expansion

Stability in air and on exposure to X-rays Ready availability Low cost

Crystals with simple structure tend to give the best diffraction performance. Crystals containing heavy atoms can diffract well, but also fluoresce themselves, causing interference. Crystals that are water-soluble, volatile or organic tend to give poor stability. Commonly used crystal materials include LiF (lithium fluoride), ADP (ammonium dihydrogen phosphate), Ge (germanium), graphite, InSb (indium antimonide), PE (tetrakis-(hydroxymethyl)-methane: pentaerythritol), KAP (potassium hydrogen phthalate), RbAP (rubidium hydrogen phthalate) and TlAP (thallium(I) hydrogen phthalate). In addition, there is an increasing use of "layered synthetic microstructures", which are "sandwich" structured materials comprising successive thick layers of low atomic number matrix, and monatomic layers of a heavy element. These can in principle be custommanufactured to diffract any desired long wavelength, and are used extensively for elements in the range Li to Mg. Properties of commonly used crystals Properties of commonly used crystals

material LiF LiF LiF ADP Ge graphite InSb PE KAP RbAP Si TlAP YB66 6 nm LSM

plane 200 220 420 101 111 001 111 002 1010 1010 111 1010 400 -

d (nm) 0.2014 0.1424 0.0901 0.5320 0.3266 0.3354 0.3740 0.4371 1.325 1.305 0.3135 1.295 0.586 6.00

min (nm) 0.053 0.037 0.024 0.139 0.085 0.088 0.098 0.114 0.346 0.341 0.082 0.338 1.566

max (nm) 0.379 0.268 0.169 1.000 0.614 0.630 0.703 0.821 2.490 2.453 0.589 2.434 11.276

intensity +++++ +++ ++ + +++ ++++ ++++ +++ ++ ++ ++ +++ +++

thermal durability expansion +++ ++ ++ ++ + + + +++++ ++ ++ + ++ + +++ +++ +++ ++ +++ +++ +++ + ++ ++ +++ ++ ++

Detectors

Detectors used for wavelength dispersive spectrometry need to have high pulse processing speeds in order to cope with the very high photon count rates that can be obtained. In addition, they need sufficient energy resolution to allow filtering-out of background noise and spurious photons from the primary beam or from crystal fluorescence. There are four common types of detector:

gas flow proportional counters sealed gas detectors scintillation counters semiconductor detectors

Gas flow proportional counters are used mainly for detection of longer wavelengths. Gas flows through it continuously. Where there are multiple detectors, the gas is passed through them in series, then led to waste. The gas is usually 90% argon, 10% methane ("P10"), although the argon may be replaced with neon or helium where very long wavelengths (over 5 nm) are to be detected. The argon is ionised by incoming X-ray photons, and the electric field multiplies this charge into a measurable pulse. The methane suppresses the formation of fluorescent photons caused by recombination of the argon ions with stray electrons. The anode wire is typically tungsten or nichrome of 2060 m diameter. Since the pulse strength obtained is essentially proportional to the ratio of the detector chamber diameter to the wire diameter, a fine wire is needed, but it must also be strong enough to be maintained under tension so that it remains precisely straight and concentric with the detector. The window needs to be conductive, thin enough to transmit the X-rays effectively, but thick and strong enough to minimize diffusion of the detector gas into the high vacuum of the monochromator chamber. Materials often used are beryllium metal, aluminised PET film and aluminised polypropylene. Ultra-thin windows (down to 1 m) for use with low-penetration long wavelengths are very expensive. The pulses are sorted electronically by "pulse height selection" in order to isolate those pulses deriving from the secondary X-ray photons being counted. Sealed gas detectors are similar to the gas flow proportional counter, except that the gas does not flow through it. The gas is usually krypton or xenon at a few atmospheres pressure. They are applied usually to wavelengths in the 0.150.6 nm range. They are applicable in principle to longer wavelengths, but are limited by the problem of manufacturing a thin window capable of withstanding the high pressure difference. Scintillation counters consist of a scintillating crystal (typically of sodium iodide doped with thallium) attached to a photomultiplier. The crystal produces a group of scintillations for each photon absorbed, the number being proportional to the photon energy. This translates into a pulse from the photomultiplier of voltage proportional to the photon energy. The crystal must be protected with a relatively thick aluminium/beryllium foil window, which limits the use of the detector to wavelengths below 0.25 nm. Scintillation counters are often connected in series with a gas flow proportional counter: the latter is provided with an outlet window opposite the inlet, to which the scintillation counter is attached. This arrangement is particularly used in sequential spectrometers.

Semiconductor detectors can be used in theory, and their applications are increasing as their technology improves, but historically their use for WDX has been restricted by their slow response (see EDX).

Extracting analytical results

At first sight, the translation of X-ray photon count-rates into elemental concentrations would appear to be straightforward: WDX separates the X-ray lines efficiently, and the rate of generation of secondary photons is proportional to the element concentration. However, the number of photons leaving the sample is also affected by the physical properties of the sample: so-called "matrix effects". These fall broadly into three categories:

X-ray absorption X-ray enhancement sample macroscopic effects

All elements absorb X-rays to some extent. Each element has a characteristic absorption spectrum which consists of a "saw-tooth" succession of fringes, each step-change of which has wavelength close to an emission line of the element. Absorption attenuates the secondary X-rays leaving the sample. For example, the mass absorption coefficient of silicon at the wavelength of the aluminium K line is 50 m/kg, whereas that of iron is 377 m/kg. This means that a given concentration of aluminium in a matrix of iron gives only one seventh of the count rate compared with the same concentration of aluminium in a silicon matrix. Fortunately, mass absorption coefficients are well known and can be calculated. However, to calculate the absorption for a multi-element sample, the composition must be known. For analysis of an unknown sample, an iterative procedure is therefore used. It will be noted that, to derive the mass absorption accurately, data for the concentration of elements not measured by XRF may be needed, and various strategies are employed to estimate these. As an example, in cement analysis, the concentration of oxygen (which is not measured) is calculated by assuming that all other elements are present as standard oxides. Enhancement occurs where the secondary X-rays emitted by a heavier element are sufficiently energetic to stimulate additional secondary emission from a lighter element. This phenomenon can also be modelled, and corrections can be made provided that the full matrix composition can be deduced. Sample macroscopic effects consist of effects of inhomogeneities of the sample, and unrepresentative conditions at its surface. Samples are ideally homogeneous and isotropic, but they often deviate from this ideal. Mixtures of multiple crystalline components in mineral powders can result in absorption effects that deviate from those calculable from theory. When a powder is pressed into a tablet, the finer minerals concentrate at the surface. Spherical grains tend to migrate to the surface more than do angular grains. In machined metals, the softer components of an alloy tend to smear across the surface. Considerable care and ingenuity are required to minimize these effects. Because they are artifacts of the method of sample preparation, these effects can not be compensated by theoretical corrections, and must be "calibrated in". This means that the calibration materials and the unknowns must be compositionally and mechanically similar, and a given calibration is applicable only to a limited range of materials. Glasses most closely approach the ideal of homogeneity and isotropy, and for accurate work, minerals are usually prepared by dissolving them in a borate glass, and casting them into a flat disc or "bead". Prepared in this form, a virtually universal calibration is applicable. Further corrections that are often employed include background correction and line overlap correction. The background signal in an XRF spectrum derives primarily from scattering of primary beam photons by the sample surface. Scattering varies with the sample mass absorption, being greatest when mean atomic number is low. When measuring trace amounts of an element, or when measuring on a variable light matrix, background correction becomes necessary. This is really only feasible on a sequential spectrometer. Line overlap is a common problem, bearing in mind that the spectrum of a complex mineral can contain several hundred measurable lines. Sometimes it can be overcome by measuring a less-intense, but overlap-free line, but in certain instances a correction is inevitable. For instance, the K is the only usable line for measuring sodium, and it overlaps the zinc L (L2-M4) line. Thus zinc, if present, must be analysed in order to properly correct the sodium value.

Hitungan x-ray
lambda= 0,7107 A (hkl) d_hkl (A) ao (110) (200) (211) (220) (310) (222) (321) (400) 2,02632511 1,43278417 1,17006722 1,01302956 0,90591153 0,82692751 0,76598148 0,71699483 2,8657 2,8657 2,8657 2,8657 2,8657 2,8657 2,8657 2,8657

Peak 2-teta (deg) 1 20,2 2 28,72 3 35,36 4 41,07 5 46,19 6 50,9 7 55,28 8 59,42

teta sin^2teta sin^2teta/0.0308 h^2+k^2+l^2 (rad) 0,1763 0,0308 1,0 2 0,2506 0,0615 2,0 4,0 0,3086 0,0922 3,0 6,0 0,3584 0,1230 4,0 8,0 0,4031 0,1539 5,0 10,0 0,4442 0,1847 6,0 12,0 0,4824 0,2152 7,0 14,0 0,5185 0,2456 8,0 16,0