1. Characterizing Thin Films

The refractive index (n) and extinction coefficient (k) are related to the interaction between a material and incident light, and are associated with refraction and absorption (respectively). They can be considered as the “fingerprint of the material". Thin film material coatings on various substrates provide important functionalities for the microfabrication industry, and the n, k, as well as the thickness, t, of these thin film constituents must be measured and controlled to allow for repeatable manufacturing.

The Forouhi–Bloomer dispersion equations for n and k were originally expected to apply to semiconductors and dielectrics, whether in amorphous, polycrystalline, or crystalline states. However, they have been shown to describe the n and k spectra of transparent conductors,^[1] as well as metallic compounds.^{[2][3][4][5][6][7][8][9][10][11]} The formalism for crystalline materials was found to also apply to polymers,^[12][13][14] which consist of long chains of molecules that do not form a crystallographic structure in the classical sense.

Other dispersion models that can be used to derive n and k, such as Tauc-Lorentz, can be found in the literature.^[15][16] Two well-known models—Cauchy and Sellmeier—provide empirical expressions for n valid over a limited measurement range, and are only useful for non-absorbing films where k=0. Consequently, the Forouhi–Bloomer formulation has been used for measuring thin films in various applications.^{[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]}

In the following discussions, all variables of photon energy, E, will be described in terms of wavelength of light, λ, since experimentally variables involving thin films are typically measured over a spectrum of wavelengths. The n and k spectra of a thin film cannot be measured directly, but must be determined indirectly from measurable quantities that depend on them. Spectroscopic reflectance, R(λ), is one such measurable quantity. Another, is spectroscopic transmittance, T(λ), applicable when the substrate is transparent. Spectroscopic reflectance of a thin film on a substrate represents the ratio of the intensity of light reflected from the sample to the intensity of incident light, measured over a range of wavelengths, whereas spectroscopic transmittance, T(λ), represents the ratio of the intensity of light transmitted through the sample to the intensity of incident light, measured over a range of wavelengths; typically, there will also be a reflected signal, R(λ), accompanying T(λ).

The measurable quantities, R(λ) and T(λ) depend not only on n(λ) and k(λ) of the film, but also on film thickness, t, and n(λ) and k(λ) of the substrate. For a silicon substrate, the n(λ) and k(λ) values are known and are taken as a given input. The challenge of characterizing thin films involves extracting t, n(λ) and k(λ) of the film from the measurement of R(λ) and/or T(λ). This can be achieved by combining the Forouhi–Bloomer dispersion equations for n(λ) and k(λ) with the Fresnel equations for the reflection and transmission of light at an interface^[17] to obtain theoretical, physically valid, expressions for reflectance and transmittance. In so doing, the challenge is reduced to extracting the five parameters A, B, C, E_g, and n(∞) that constitute n(λ) and k(λ), along with film thickness, t, by utilizing a nonlinear least squares regression analysis^[18][19] fitting procedure. The fitting procedure entails an iterative improvement of the values of A, B, C, E_g, n(∞), t, in order to reduce the sum of the squares of the errors between the theoretical R(λ) or theoretical T(λ) and the measured spectrum of R(λ) or T(λ).

Besides spectroscopic reflectance and transmittance, spectroscopic ellipsometry can also be used in an analogous way to characterize thin films and determine t, n(λ) and k(λ).

2. Measurement Examples

The following examples show the versatility of using the Forouhi–Bloomer dispersion equations to characterize thin films utilizing a tool based on near-normal incident spectroscopic reflectance. Near-normal spectroscopic transmittance is also utilized when the substrate is transparent. The n(λ) and k(λ) spectra of each film are obtained along with film thickness, over a wide range of wavelengths from deep ultraviolet to near infrared wavelengths (190–1000 nm).

In the following examples, the notation for theoretical and measured reflectance in the spectral plots is expressed as “R-theor” and “R-meas”, respectively.

Below are schematics depicting the thin film measurement process:

https://handwiki.org/wiki/index.php?curid=1659535

The Forouhi–Bloomer dispersion equations in combination with Rigorous Coupled-Wave Analysis (RCWA) have also been used to obtain detailed profile information (depth, CD, sidewall angle) of trench structures. In order to extract structure information, polarized broadband reflectance data, Rs and Rp, must be collected over a large wavelength range from a periodic structure (grating), and then analyzed with a model that incorporates Forouhi–Bloomer dispersion equations and RCWA. Inputs into the model include grating pitch and n and k spectra of all materials within the structure, while outputs can include Depth, CDs at multiple locations, and even sidewall angle. The n and k spectra of such materials can be obtained in accordance with the methodology described in this section for thin film measurements.

Below are schematics depicting the measurement process for trench structures. Examples of trench measurements then follow.

https://handwiki.org/wiki/index.php?curid=1982680

2.1. Example 1: Amorphous Silicon on Oxidized Silicon Substrate (a-Si/SiO₂/Si-Sub)

Ex. 1: Reflectance spectra collected over 190–1000nm wavelength range for an amorphous silicon film (a-Si) on an oxidized silicon substrate (SiO₂/Si-Sub) plus the n(λ) and k(λ) spectra of the a-Si film. The film thickness was found to be 1147nm. The thicknesses of a-Si and SiO₂ films, plus the n(λ) and k(λ) spectra of the a-Si were all simultaneously determined. The n(λ) and k(λ) spectra of the SiO₂ film was held fixed.

Ex. 1: Amorphous materials typically exhibit one broad maximum in their n(λ) and k(λ) spectra. As a material transitions from the amorphous state to the fully crystalline state, the broad maximum sharpens up and other sharp peaks start to appear in the n(λ) and k(λ) spectra. This is demonstrated for the case of amorphous silicon progressing to poly-silicon and further progressing to crystalline silicon.

Example 1 shows one broad maximum in the n(λ) and k(λ) spectra of the a-Si film, as is expected for amorphous materials. As a material transitions toward crystallinity, the broad maximum gives way to several sharper peaks in its n(λ) and k(λ) spectra, as demonstrated in the graphics.

When the measurement involves two or more films in a stack of films, the theoretical expression for reflectance must be expanded to include the n(λ) and k(λ) spectra, plus thickness, t, of each film. However, the regression may not converge to unique values of the parameters, due to the non-linear nature of the expression for reflectance. So it is helpful to eliminate some of the unknowns . For example, the n(λ) and k(λ) spectra of one or more of the films may be known from the literature or previous measurements, and held fixed (not allowed to vary) during the regression. To obtain the results shown in Example 1, the n(λ) and k(λ) spectra of the SiO₂ layer was fixed, and the other parameters, n(λ) and k(λ) of a-Si, plus thicknesses of both a-Si and SiO₂ were allowed to vary.

2.2. Example 2: 248 nm Photoresist on Silicon Substrate (PR/Si-Sub)

Ex. 2: Reflectance spectra collected over the 190–1000nm wavelength range for a photoresist film on silicon substrate, plus the n(λ) and k(λ) spectra of the photoresist. The film thickness was found to be 498nm. The thickness and the n(λ) and k(λ) spectra of the photoresist were all simultaneously determined.

Polymers such as photoresist consist of long chains of molecules which do not form a crystallographic structure in the classic sense. However, their n(λ) and k(λ) spectra exhibit several sharp peaks rather than a broad maximum expected for non-crystalline materials. Thus, the measurement results for a polymer are based on the Forouhi–Bloomer formulation for crystalline materials. Most of the structure in the n(λ) and k(λ) spectra occurs in the deep UV wavelength range and thus to properly characterize a film of this nature, it is necessary that the measured reflectance data in the deep UV range is accurate.

The figure shows a measurement example of a photoresist (polymer) material used for 248 nm micro-lithography. Six terms were used in the Forouhi–Bloomer equations for crystalline materials to fit the data and achieve the results.

2.3. Example 3: Indium Tin Oxide on Glass Substrate (ITO/Glass-Sub)

Ex. 3: Reflectance and transmittance spectra in 190–1000nm range for an uncoated glass substrate. Note that T = 0 for the glass substrate in the DUV, indicating absorption in this range of the spectrum. It is found that the value of k(λ) in the deep UV wavelength range is of the order of k = 3x10⁻⁴, and this small non-zero value is consistent with T = 0 in the deep UV.

Ex. 3: Reflectance and transmittance spectra in 190–1000nm range of ITO deposited on the glass substrate described above, plus the n(λ) and k(λ) spectra of the ITO film. ITO thickness of 133nm and its n(λ) and k(λ) spectra were simultaneously determined by fitting measured reflectance and transmittance spectra to theoretical expressions of these quantities using the Forouhi–Bloomer equations.

Indium tin oxide (ITO) is a conducting material with the unusual property that it is transparent, so it is widely used in the flat panel display industry. Reflectance and transmittance measurements of the uncoated glass substrate were needed in order to determine the previously unknown n(λ) and k(λ) spectra of the glass. The reflectance and transmittance of ITO deposited on the same glass substrate were then measured simultaneously, and analyzed using the Forouhi–Bloomer equations.

As expected, the k(λ) spectrum of ITO is zero in the visible wavelength range, since ITO is transparent. The behavior of the k(λ) spectrum of ITO in the near-infrared (NIR) and infrared (IR) wavelength ranges resembles that of a metal: non-zero in the NIR range of 750–1000 nm (difficult to discern in the graphics since its values are very small) and reaching a maximum value in the IR range (λ>1000 nm). The average k value of the ITO film in the NIR and IR range is 0.05.

2.4. Example 4: Multi-Spectral Analysis of Germanium (40%)–Selenium (60%) Thin Films

Ex. 4: Multi-spectral analysis was used to analyze the reflectance spectra of a Ge₄₀Se₆₀ film deposited on two different substrates: both silicon and oxidized-silicon substrates. The measurements yielded a single n(λ) and k(λ) spectra of Ge₄₀Se₆₀. A thickness of 33.6 nm for Ge₄₀Se₆₀ on the oxidized silicon substrate was found, while a thickness of 34.5 nm of Ge₄₀Se₆₀ on the silicon substrate was found. In addition the thickness of the oxide layer was determined to be 166nm.

When dealing with complex films, in some instances the parameters cannot be resolved uniquely. To constrain the solution to a set of unique values, a technique involving multi-spectral analysis can be used. In the simplest case, this entails depositing the film on two different substrates and then simultaneously analyzing the results using the Forouhi–Bloomer dispersion equations.

For example, the single measurement of reflectance in 190–1000 nm range of Ge₄₀Se₆₀/Si does not provide unique n(λ) and k(λ) spectra of the film. However, this problem can be solved by depositing the same Ge₄₀Se₆₀ film on another substrate, in this case oxidized silicon, and then simultaneously analyzing the measured reflectance data to determine:

• Thickness of the Ge₄₀Se₆₀/Si film on the silicon substrate as 34.5nm,
• Thickness of the Ge₄₀Se₆₀/Si film on the oxidized silicon substrate as 33.6nm,
• Thickness of SiO₂ (with n and k spectra of SiO₂ held fixed), and
• n and k spectra, in 190–1000 nm range, of Ge₄₀Se₆₀/Si.

2.5. Example 5: Complex Trench Structure

Ex. 5: A trench structure consisting of various films and complex profile. The Poly-Si film was measured on a blanket area of the sample and its n and k spectra were determined based on the Forouhi–Bloomer dispersion equations. A fixed table of values for the n and k spectra of the SiO₂ and Si₃N₄ films was utilized. With the n and k spectra of these films at hand, and utilizing Rigorous Coupled Wave Analysis (RCWA), film thicknesses, various depths (heights) inside the trench, and CDs are then determined. https://handwiki.org/wiki/index.php?curid=1561880

Ex. 5: Measured Rs and Rp reflectance collected on the Complex Trench Structure. https://handwiki.org/wiki/index.php?curid=1575798

The trench structure depicted in the adjacent diagram repeats itself in 160 nm intervals, that is, it has a given pitch of 160 nm. The trench is composed of the following materials:

Accurate n and k values of these materials are necessary in order to analyze the structure. Often a blanket area on the trench sample with the film of interest is present for the measurement. In this example, the reflectance spectrum of the poly-silicon was measured on a blanket area containing the poly-silicon, from which its n and k spectra were determined in accordance with the methodology described in this article that utilizes the Forouhi–Bloomer dispersion equations. Fixed tables of n and k values were used for the SiO₂ and Si₃N₄ films.

Combining the n and k spectra of the films with Rigorous Coupled-Wave Analysis (RCWA) the following critical parameters were determined (with measured results as well):