Surface and Thin Film Analysis: Principles, Instrumentation, Applications Edited by H. Bubert and H.

Jenett Copyright # 2002 Wiley-VCH Verlag GmbH ISBNs: 3-527-30458-4 (Hardback); 3-527-60016-7 (Electronic)
4.9 UVVisIR Ellipsometry (ELL)
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water molecules. Despite the power of SFG in surface investigations, applications are still limited by the shortage of powerful tunable mid-infrared lasers and by the experimental expense.

4.9 UVVisIR Ellipsometry (ELL)

Bernd Gruska and Arthur Rseler

4.9.1 Principles

Ellipsometry is a method of measuring the film thickness, refractive index, and extinction coefficient of single films, layer stacks, and substrate materials with very high sensitivity. Rough surfaces, interfaces, material gradients and mixtures of different materials can be analyzed. Film thicknesses between 0.1 nm and 100 mm can be measured, depending on the spectral range used for the analysis and the homogeneity of the thicker films. Thicknesses < 1 mm can be determined with a sensitivity better than 0.01 nm. Thicknesses in the micron-range can be analyzed with sensitivity typically better than 1 nm. The refractive index of a film or a substrate material can be measured with a sensitivity better than 5 6 104, the best available for non-invasive optical measurement methods, especially for thin films. The extinction coefficient can be measured with almost the same sensitivity, which corresponds to a lower limit of 10100 cm1 for the absorption coefficient of the material. The number of measurable layers of a stack is limited only by the optical contrast between the different layers. In practice stacks of ten layers and more can be analyzed by ellipsometry. Further advantages of ellipsometry compared with other metrological methods are the non-invasive and non-destructive character of the optical method, the low energy entry into the sample, the direct measurement of the dielectric function of materials, and the possibility of making the measurement in any kind of optical transparent environment. The principal of measurement is shown schematically in Fig. 4.61. Linear polarized light is reflected from a sample surface which must be flat and sufficiently reflecting. The state of polarization of the incident light is changed, by reflection, into ellipti-

Fig. 4.61. Principle of measurement in ellipsometry.

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cally polarized light. The properties measured by ellipsometry are tan_, the amplitude ratio of the resolved components of the electric field vector of the reflected light parallel to and perpendicular to the plane of incidence, and cos_, the phase difference between the two components. Unambiguous determination of the phase angle, D, over the whole data range between 08 and 3608 is possible using a retarder to direct circular polarized light as incident light in a second measurement tanC and sin D are determined. Information about the properties of the sample are contained in the complex ratio, r, of the Fresnel coefficients of reflection of the parallel (rP) and perpendicular (rS) incident plane polarized electrical field vectors. r rP rS (4.31)

The fundamental equation of ellipsometry [4.311]: r tan C eiD (4.32)

describes the connection between the measured quantities C and D and the sample properties contained in the coefficients of reflection, and hence in r. In principal this complex equation can be solved analytically for pure substrates only. Each other more complex structure requires optical modeling of the sample and fitting of the calculated ratio, r, to the measured quantities C and D. C and D are always correct quantities assuming the ellipsometer is working correctly. Film thickness, refractive index, extinction coefficient and other properties are calculated quantities based on a model. The choice of the correct optical model for the sample is a fundamental assumption for correct values of all the properties calculated. The thickness of a film influences the interference of light waves reflected from the front and back of the film, and hence the reflectance. The thickness of an absorbing film can, therefore, be measured only as long as there is still a contribution of from the back of the film to the reflectance of the sample. Typical measurable thicknesses of metallic layers are < 50 nm. Ellipsometric measurements depends on the incident angle, f, because of the angular dependence of the coefficients of reflection rS and rP. Large differences between both quantities are found for angles >508, where rP has a local minimum at the socalled Brewster angle. This angle is between 50 and 608 for transparent materials and >708 for almost all absorbing materials. Ellipsometric measurements close to the Brewster angle of the substrate are especially sensitive for very thin layers on top of the substrate. Multiple angle measurements are suitable for confirming optical models of sample structure. Two measured ellipsometric angles C and D at a fixed wavelength and a fixed angle of incidence enable calculation of a maximum of two other properties, e. g. the film thickness and refractive index of a transparent layer. Multiple angle measurements increase the number of measured quantities and hence the number of properties which can be determined for a specific sample, although even under these condi-

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tions the number of measurable properties will typically be no larger than 45. Wavelength-dependent ellipsometric measurements (spectroscopic ellipsometry) further increase the number of measurable properties, and hence the complexity of the analyzable sample structure. Spectroscopic ellipsometry enables measurement of the dispersion of the refractive index and the extinction coefficient of materials, and the analysis of more complex sample structures (e. g. multilayer stacks, interfaces, material gradients, material compositions) on the basis of parameterized dielectric functions which drastically reduce the number of unknown properties compared with the number of measured ellipsometric angles. Spectroscopic ellipsometry is sensitive to the dielectric functions of the different materials used in a layer stack. But it is not a compositional analytical technique. Combination with one of the compositional techniques, e. g. AES or XPS and with XTEM, to furnish information about the vertical structure, can provide valuable additional information enabling creation of a suitable optical model for an unknown complex sample structure.
4.9.2 Instrumentation

The basic configuration of each ellipsometer is very simple: light source, polarizer, sample, polarizer, detector. Advanced configurations use a phase shift device (retarder) before or after the sample. There is a large number of possibilities in which a specific ellipsometer can be realized. The main differences consist in the way the light is polarized and the way the state of polarization of the reflected light is detected. The light source can be monochromatic (lasers), white light (xenon arc lamp, deuterium lamp, halogen lamp) with a monochromator, or silicon carbide rods (glowbars used mainly for infrared ellipsometry). Photomultiplier tubes (vacuum UV), silicon photodiodes (UVVis), Ge- or InGaAs photodiodes (near IR), MCT (HgCdTe), or DTGS detectors (mid-MIR) are used as broadband detectors. They must be operated with a monochromator if a white light source is used. Fast spectroscopic ellipsometers use photometers and diode arrays as detectors. This enables simultaneous detection of multiple wavelengths, rather than sequential detection. State-of-the-art ellipsometry in the infrared spectral range (approximately 0.8100 mm wavelength) uses modulated white light from an FTIR instrument and broadband detectors to measure the reflected light. Intensity spectra are generated by Fourier transformation of the detected signal. Ellipsometric measurements are performed at a fixed angle of incidence. Each ellipsometer configuration can be operated in a discrete wavelength or spectroscopic (i. e. variable angle of incidence) manner. Null ellipsometers are among the oldest configurations. In these a revolving polarizer and a revolving compensator are used to change the state of polarization of the incident light and a revolving polarizer (analyzer) is used to analyze the reflected light. The angular position of the optical elements is changed until the intensity of the light on the detector is zero. This configuration is one of the most accurate but also the slowest, even if automated.

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Rotating element ellipsometers have a continuously rotating element (1040 Hz frequency of revolution) which enables automated acquisition and faster measurement. Most of the instruments used nowadays have this configuration. The polarizer (rotating polarizer ellipsometer, RPE) or analyzer (rotating analyzer ellipsometer, RAE) can be used as the rotating element. The detector signal is measured as function of time and is then Fourier-analyzed to obtain the ellipsometric angles C and D. The RPE configuration has the advantage that any detector (photomultiplier tube, monochromator) polarization sensitivity does not influence the measurement. The state of polarization of the detected light is fixed by the fixed analyzer position. The disadvantage is the sensitivity to residual polarized light of the light beam incident on the rotating polarizer. The RAE configuration has the advantage of being insensitive to any residual polarization of the light source (laser, white light source with monochromator), but errors can occur as a result of the polarization sensitivity of the detector (photomultiplier tube). If polarization-insensitive Si photodiodes are used as detectors this configuration is most often used for discrete wavelength ellipsometers. Single wavelength ellipsometers are typically equipped with a quarter-wave plate (compensator) which can be moved into the light beam. The linearly polarized light is changed into circularly polarized (in general elliptically polarized) light after passing through the quarter-wave plate. The measured ellipsometric angle, D, is thereby shifted by 908 ; it can be determined in the whole data range of 03608, and the large uncertainty of D is removed when the value of D is close to 08 or 1808. Spectroscopic ellipsometers that measure D in the whole data range require an achromatic compensator with a phase shift close to 908 over a large spectral range. The compensator can be located between polarizer and sample or between sample and analyzer. Step scan polarizer/analyzer (SSP/SSA) and continuously rotating element configurations are used for diode-array- or FTIR-based ellipsometers. With the SSP or SSA modes complete intensity spectra are measured at several angle positions of the revolving polarizer/analyzer. The acquisition time varies between seconds (UV-Vis) and minutes (IR), depending on the intensity of the incident beam and the reflectance of the sample. The measurements are rapid compared with the monochromator based configurations and the positioning of the revolving element is highly exact. The continuously rotating element configuration is used for very fast spectroscopic ellipsometers measuring complete ellipsometric spectra in less than 100 ms. For such instruments the intensity at each wavelength (pixel of the diode array) is accumulated over a 458 revolution angle of the rotating element. A few instruments have a continuously rotating compensator and fixed polarizer and analyzer. The advantage of this configuration is insensitivity to residual polarization of the light source or to polarization sensitivity of the detector. The disadvantage is the large effect of a small misalignment of the rotating achromatic compensator on the performance of the instrument. Polarization modulation ellipsometers use a photo-elastic modulator to modulate the state of polarization of the incident beam. Polarizer and analyzer are fixed during the measurement. Fourier analysis of the time dependent signal gives the ellipso-

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metric parameters C and D. The advantages of this configuration are the very high measuring speed (typical modulation frequency 50 kHz) for discrete wavelengths and the lack of moving parts. The ellipsometric angle, D, can be measured over the whole range of 03608. Disadvantages are the frequent calibration of the instrument owing to the high temperature-dependence of the polarization modulator and the limited measurement speed for complete spectra. The infrared ellipsometer is a combination of a Fourier-transform spectrometer (FTS) with a photometric ellipsometer. One of the two polarizers (the analyzer) is moved step by step in four or more azimuths, because the spectrum must be constant during the scan of the FTS. From these spectra, the tanC and cosD spectra are calculated. In this instance only D is determined in the range 01808, with severely reduced accuracy in the neighborhood of 08 and 1808. This problem can be overcome by using a retarder (compensator) with a phase shift of approximately 908 for a second measurement cosD and sinD are thereby measured independently with the full D information [4.315]. In a second kind of infrared ellipsometer a dynamic retarder, consisting of a photoelastic modulator (PEM), replaces the static one. The PEM produces a sinusoidal phase shift of approximately 40 kHz and supplies the detector exit with signals of the ground frequency and the second harmonic. From these two frequencies and two settings of the polarizer and PEM the ellipsometric spectra are determined [4.316]. This ellipsometer system is mainly used for rapid and relative measurements.
4.9.3 Applications 4.9.3.1 UVVisNIR Spectral Range Spectroscopic ellipsometry in the UVVisNIR is mainly used for the characterization of new materials (e. g. photoresist, polymers, low-k dielectrics, semiconductors, composed material), the analysis of multilayer stacks (e. g. low-k and AR layer stacks on architecture glass, flat panel applications, silicon IC technology, optoelectronic devices, photonic devices), qualification of a large number of deposition processes for production and R&D applications, and in-situ monitoring of growth and deposition processes. Spectral range and speed of the measurement are key features which strongly force the use of spectroscopic ellipsometers for R&D and for production surveillance. The availability of spectroscopic ellipsometers in the spectral range 1402.3 mm enables many applications in metrology. Ellipsometry in the vacuum UV (< 190 nm) enables the analysis of materials for the next generation lithography (photoresist, AR coatings) at the latest exposure wavelengths (157 nm and 193 nm). The short wavelengths increase the sensitivity of ellipsometric measurements of ultra thin films (< 10 nm). New prospects are expected for the analysis of thin metallic and dielectric layers. In the UV most of the materials of interest, e. g. Si, polysilicon, SiGe, GaAs, and other semiconductor materials, are strongly absorbing; this enables surface-sensitive measurements, Surface roughness, native oxide covering, material composition, and structural properties can be analyzed.

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4 Photon Detection Fig. 4.62. Measured ellipsometric spectra of an a-Si/SiN multilayer stack (seven layers) on GaAs.

The Vis-NIR spectral range is mainly used to measure the thickness of single films and layer stacks. Many materials (dielectrics, semiconductors, polymers) are transparent in this spectral range. The analysis of complex layer stacks often requires a knowledge of the dielectric function of each material in the stack or parameterized dispersion models to reduce the number of unknown parameters. The Cauchy formula is often used for transparent layers, the DrudeLorentz formula works well for metals and infrared active materials, the Leng formula [4.312] can be used for semiconductor materials, and the Tauc-Lorentz formula [4.313] works best for amorphous materials. The general Gaussian-broadened polynomial superposition (GBPS) parametric dispersion model [4.314] can be broadly applied to most materials, including crystalline and amorphous semiconductors, metals, and organic compounds. Fig. 4.62 shows measured ellipsometric spectra of an a-Si/SixNy multilayer deposited on GaAs. Four layers of SixNy and three layers of a-Si were deposited alternately. The dispersion of each layer material was measured on single films. Film thicknesses of 78 nm for a-Si and 145 nm for SixNy were determined for the different layers of the layer stack, by use of appropriate parameterized dispersion models for each material. Other typical multilayer applications are dielectric stacks on silicon, spectral selective mirrors stacks, or Bragg reflectors for laser devices. Ellipsometric measurements in the NIR are often used to determine the thickness and refractive index of thicker dielectric films and semiconductor stacks based on InP and GaAs, which are transparent in this spectral region. For highly sensitive ellipsometric measurement of film thickness and refractive index the wavelength and film thickness used should not differ much. Fig. 4.63 shows ellipsometric spectra obtained from a 2.5 mm thick SiO2 layer on silicon measured between the wavelengths 350 nm and 2.3 mm. The higher sensitivity in the near-infrared spectral range is obvious. The growing number of applications of 1.55 mm semiconductor lasers has resulted in the use of near-infrared ellipsometers for control and monitoring of AR coatings on laser facets. Laterally inhomogeneous films and patterned structures of microelectronic and optoelectronic applications require small measuring spots. Today's measurements in 50 mm 6 50 mm areas are standard for -spot spectroscopic ellipsometers used in fablines. Areas more than ten times smaller can be analyzed by use of discrete-wavelength ellipsometers equipped with laser-light sources.

4.9 UVVisIR Ellipsometry (ELL) Fig. 4.63. Measured and calculated ellipsometric spectra from a 2.5 mm thick SiO2 layer on Si.

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4.9.3.2 Infrared Ellipsometry Infrared ellipsometry is typically performed in the mid-infrared range of 400 to 5000 cm1, but also in the near- and far-infrared. The resonances of molecular vibrations or phonons in the solid state generate typical features in the tanC and D spectra in the form of relative minima or maxima and dispersion-like structures. For the isotropic bulk calculation of optical constants refractive index n and extinction coefficient k is straightforward. For all other applications (thin films and anisotropic materials) iteration procedures are used. In ellipsometry only angles are measured. The results are also absolute values, obtained without the use of a standard. Two types of resonance must be distinguished in the infrared, that of strong and weak oscillators. The strong oscillator is characterized by a region in which the refractive index is < 1 for wave numbers higher than the oscillator frequency; this is usually observed for inorganic compounds with reststrahlen bands (n, k spectrum of quartz glass, see Fig. 4.67 b, below). Weak oscillators, typically organic compounds, always have refractive indexes >1 (Fig. 4.64 a). The optical constants of these spectra are calculated by use of relationships derived for metal optics [4.317]. From ellipsometrically determined optical constants other experimental configurations can be calculated. Figure 4.64 b shows the transmission spectrum calculated from the spectra in Fig. 4.64 a; this is now is suitable for direct comparison with library spectra.

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4 Photon Detection Fig. 4.64. (a) Bulk spectrum of polycarbonate n and k ; (b) with n, k calculated transmission spectrum for a thickness of 1 m.

The spectra from strong oscillators have special features which are different from those from metallic and dielectric substrates. Different structures in tanC and D are observed on a metallic substrate, dependent on the thickness of the film (Fig. 4.65). For very thin films up to approximately 100 nm the Berreman effect is found near the position of n = k and n < 1 with a shift to higher wavenumbers in relation to the oscillator frequency. This effect decreases with increasing thickness (d 6 approx. 100 nm) and is replaced by excitation of a surface wave at the boundary of the dielectric film and metal. The oscillator frequency (TO mode) can now also be observed. On metallic substrates for thin films (d ^ approx. 2 mm) only the z-component of the electric field is relevant. With thin films on a dielectric substrate the oscillator frequency and the Berreman effect are always observed simultaneously, because in these circumstances all three components of the electric field are possible (Fig. 4.66).

Fig. 4.65. Different spectral features of tanC for a strong model oscillator at 1000 cm1 on a metal substrate. The TO mode (1000 cm1), Berreman effect (1050 cm1), and excitation of a surface wave (1090 cm1) are seen for different thicknesses 1, 5, 10, 50, 100, 500, and 1000 nm.

4.9 UVVisIR Ellipsometry (ELL) Fig. 4.66. tanC spectra for the same oscillator as in Fig. 4.65 for a silicon substrate thicknesses 1, 5, 10, 50, and 100 nm.

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The relative slopes of tanC (maximum or minimum), D, and reflectivity for the parallel component depend on the position relative to the Brewster angle (greater or lower). Thicker films on both types of substrate lead to dominant interferences. Double and buried layers are readily detected by infrared ellipsometry if the film material is characterized by reststrahlen bands. The response is observed at the position

Fig. 4.67. (a) tanC and d spectrum of (4 nm) on a silicon substrate, (b) SiO2 a double layer of SiO2 (6 nm) and Si3N4 spectrum for comparison.

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of the Berreman effect (Figs 4.67 a and b for SiO2 and Si3N4 layers, and the SiO2 spectrum for comparison) and also by the TO mode for greater thicknesses. The thinnest film was observed by the H-terminated silicon surface with a thickness of 0.2 nm [4.318]. Determination of the optical constants and the thickness is affected by the problem of calculating three results from two ellipsometric values. This problem can be solved by use of the oscillator fit in a suitable wavenumber range or by using the fact that ranges free from absorption always occur in the infrared. In these circumstances the thickness and the refractive index outside the resonances can be determined by the algorithm of Reinberg [4.317], for example. With this result only two data have to be calculated. It is usually possible to investigate very thin films (up to the subnanometer range) by use of infrared wavelengths, which are much greater than the thickness of the film (a factor of 10 000) because of the interference optics of the strong oscillator (Berreman effect).

4.10 Other Photon-detecting Techniques

John C. Rivire
4.10.1 Appearance Potential Methods

Appearance potential methods all depend on detecting the threshold of ionization of a shallow core level and the fine structure near the threshold; they differ only in the way in which detection is performed. In all of these methods the primary electron energy is ramped upward from near zero to whatever is appropriate for the sample material, while the primary current to the sample is kept constant. As the incident energy is increased, it passes through successive thresholds for ionization of core levels of atoms in the surface. An ionized core level, as discussed earlier, can recombine by emission either of a characteristic X-ray photon or of an Auger electron.
4.10.1.1 Soft X-ray Appearance Potential Spectroscopy (SXAPS) In SXAPS the X-ray photons emitted by the sample are detected, normally by letting them strike a photosensitive surface from which photoelectrons are collected, but also with the advent of X-ray detectors of increased sensitivity by direct detection. Above the X-ray emission threshold from a particular core level the excitation probability is a function of the densities of unoccupied electronic states. Because two electrons are involved, incident and the excited, the shape of the spectral structure is proportional to the self-convolution of the unoccupied state densities.