This application claims the priority benefit of China patent application serial no. 201910315604.8, filed on Apr. 19, 2019. The entirety of the above-mentioned patent application is hereby incorporated by reference herein and made a part of this specification.
The invention relates to a measurement and characterization research field of ultra-thin film optical properties, and particularly relates to a rapid measurement method for an ultra-thin film optical constant.
Along with rapid development of optoelectronic technology, etc., an application scope of thin films has gradually expanded, and many ultra-thin films with thickness of only tens or even a few nanometers have become a current research hotspot. Optical constants of ultra-thin films are very important in basic scientific research and design and optimization of nano-optical devices, and the optical constants of the ultra-thin films will change along with thickness and preparation conditions, etc., so that the information in existing literatures or databases cannot be simply used. Therefore, it is very important to achieve fast and accurate measurement of the ultra-thin film optical constants.
The optical constant measurement and characterization methods of ultra-thin films mainly include a photometric method, a prism coupling method, interferometry, ellipsometry, etc. The photometric method determines a thickness of the thin film based on a transmittance and a reflectance of the thin film measured by a spectrophotometer, and includes an envelope method and a full spectrum fitting method, etc., where the envelope method is the most commonly used one, but it generally requires a thicker thin film, which is not suitable for the ultra-thin films. The prism coupling method is a contact measurement method to determine a thickness and a refractive index of a thin film by placing a coupling prism on a sample surface of the thin film to introduce incident light into the measured thin film, and detecting and analyzing reflected light of different incident angles to determine a coupling angle of a waveguide film, where a measured thickness thereof cannot reach a scale range of the ultra-thin film. The interferometry is to determine a refractive index of thin films by using coherent light interference to form equal thickness interference fringes, which also has the same problem with that of the above methods. The ellipsometry measurement has advantages of non-destructive non-contact, high sensitivity and high precision, and its sensitivity to thickness may reach 0.01 nm, but the ellipsometry is an indirect measurement method, which requires computer fitting to obtain the thickness and optical constants (including a refractive index and an extinction coefficient) of the thin film. The ellipsometry measurement is an indirect measurement method, which detects geometric parameters and optical properties of a sample by measuring a change of a polarization state of light before and after the light is incident to the sample surface, and a measurement result needs to be fitted to an optical model by an algorithm to obtain the optical constants. Commonly used fitting methods include a point-to-point method and a oscillator model fitting method, where the point-to-point method is to give an initial value, and the optical constants of the ultra-thin film needs to be accurately estimated, otherwise it is easy to fall into a local optimal solution and cannot solve the correct optical constants; the oscillator model fitting method uses Lorenz oscillator, etc., and it is necessary to learn a knowledge of electronic transitions of the ultra-thin film in advance, and match measurement data to obtain the optical constants of the ultra-thin film. Regarding the ultra-thin film, properties such as electronic transitions thereof are often not well known, which leads to errors for a oscillator model fitting process. Therefore, to implement measurement of the ultra-thin film optical constants is a difficult point in the existing measurement technology.
In view of the above problems combined with the geometric properties of the ultra-thin film, some researchers have proposed a Taylor-expansion approximate direct calculation method based on an amplitude reflection coefficient ratio ρ, and in 2017, Peep Adamson of Estonia (A new ellipsometric approach for determining dielectric function of graphene in the infrared spectral region. Journal of Modern Optics, 2017, 64 (3): 272-279) performed a first-order approximation on the amplitude reflection coefficient ratio ρ of the ellipsometric parameters for graphene and similar materials on a transparent substrate, and by solving an approximate formula, calculation formulas of refractive index and extinction coefficient are obtained, and simulating calculation of graphene in an infrared band is performed; in 2018, Gwang-Hun Jung, et al. of Korea (Measuring the optical permittivity of two dimensional materials without a priori knowledge of electronic transitions [J]. Nanophotonics. 2018) adopted a similar method to perform first-order derivation on the amplitude reflection coefficient ratio ρ of p-light and s-light, and calculation formulas of refractive index and extinction coefficient of the ultra-thin film are obtained by solving the first-order equation, and by measuring and calculating two-dimensional materials such as molybdenum disulfide, tungsten disulfide and tungsten diselenide thin film on a sapphire substrate, it is verified that the method may calculate the optical constants of ultra-thin film more accurately in case of a longer wavelength band without a priori knowledge. The above two methods provide a new idea for determining the optical constants of the ultra-thin films, but there are also defects of limited calculation bands, and large errors occur in calculation of optical constants of a shorter wavelength range such as an ultraviolet band, etc.
In view of the above defects or improvement requirements of the existing technology, the invention provides a rapid measurement method for an ultra-thin film optical constant, by performing second-order Taylor expansion approximation on an amplitude reflection coefficient ratio, and by calculating and solving approximate formulas, the optical constant of the ultra-thin film is measured rapidly, which has advantages of fast measurement, accurate measurement, etc., and is adapted to rapid measurement and characterization of optical constants for arbitrary ultra-thin film.
In order to achieve the above purpose, the invention provides a rapid measurement method for an ultra-thin film optical constant, which includes following steps:
S1: using a p-light amplitude reflection coefficient rp and an s-light amplitude reflection coefficient rs of an incident light irradiating to an ultra-thin film to be measured to express an amplitude reflection coefficient ratio ρ of the ultra-thin film:
S2: performing a second-order Taylor expansion to
at df=0 while taking 2πdf/λ as a variable to obtain a second-order approximation form:
Where ρ0 is an amplitude reflection coefficient ratio of a substrate used by the ultra-thin film, df is a thickness of the ultra-thin film, λ is a wavelength of the incident light, and ρ′, ρ1″ and ρ2″ are all coefficients;
S3: performing merging, simplifying and substituting processing to the second-order approximation form for transforming the same into a one-variable quartic equation;
S4: solving the one-variable quartic equation to obtain a plurality of solutions of the optical constant of the ultra-thin film, and obtaining a correct solution through conditional judgment, where the correct solution is the optical constant of the ultra-thin film to be measured, so as to achieve the rapid measurement for the ultra-thin film optical constant.
Preferably, the p-light amplitude reflection coefficient rp is calculated according to a following equation:
Where nsub is an optical constant of the substrate used by the ultra-thin film, αinc is an incident angle of the incident light, n0 is an optical constant of a surrounding medium of the ultra-thin film, αtra is a refraction angle of the incident light transmitted to the substrate, df is a thickness of the ultra-thin film, λ is a wavelength of the incident light, and nf is an optical constant of the ultra-thin film to be measured.
Preferably, the s-light amplitude reflection coefficient rs is calculated according to a following equation:
Where nsub is an optical constant of the substrate used by the ultra-thin film, αinc is an incident angle of the incident light, n0 is an optical constant of the surrounding medium of the ultra-thin film, αtra is a refraction angle of the incident light transmitted to the substrate, df is a thickness of the ultra-thin film, λ is a wavelength of the incident light, and nf is an optical constant of the ultra-thin film to be measured.
Preferably, ρ′ is calculated according to a following equation:
Where n0 is an optical constant of the surrounding medium of the ultra-thin film, αinc is an incident angle of the incident light, nf is an optical constant of the ultra-thin film to be measured, nsub is an optical constant of the substrate used by the ultra-thin film, and αtra is a refraction angle of the incident light transmitted to the substrate.
Preferably, ρ1″ is calculated according to a following equation:
Where n0 is an optical constant of the surrounding medium of the ultra-thin film, αinc is an incident angle of the incident light, nf is an optical constant of the ultra-thin film to be measured, nsub is an optical constant of the substrate used by the ultra-thin film, and αtra is a refraction angle of the incident light transmitted to the substrate.
Preferably, ρ2″ is calculated according to a following equation:
Where n0 is an optical constant of the surrounding medium of the ultra-thin film, αinc is an incident angle of the incident light, nf is an optical constant of the ultra-thin film to be measured, nsub is an optical constant of the substrate used by the ultra-thin film, and αtra is a refraction angle of the incident light transmitted to the substrate.
Preferably, the step S3 of performing merging, simplifying and substituting processing to the second-order approximation form for transforming the same into the one-variable quartic equation includes:
S31: letting:
S32: simplifying the second-order approximation form into:
S33: expanding and simplifying the equation of the step S32 to obtain a one-variable quartic equation related to nf2:
para4·Nf4+para3·Nf3+para2·Nf2+para1·Nf+para0=0
Where Nf=nf2, para0, para1, para2, para3 and para4 are respectively a constant term, a one-order term coefficient, a quadratic term coefficient, a cubic term coefficient and a quartic term coefficient.
Preferably, the constant term para0, the one-order term coefficient para1, the quadratic term coefficient para2, the cubic term coefficient para3 and the quartic term coefficient para4 are represented as:
para0=BD2n04nsub4−CD2n04nsub6
para1=iADn02nsub2−2BD2n04nsub2−2BD2n02nsub4+2CD2n02nsub6
para2=−iADn02+BD2n04−iADnsub2+4BD2n02nsub2+2CD2n04nsub2+BD2nsub4−CD2n02nsub4−CD2nsub6−ρ+ρ0
para3=iAD−2BD2n02−CD2n04−2BD2nsub2−2CD2n02nsub2+CD2nsub4
para4=BD2+CD2n02
Preferably, the step S4 of obtaining the correct solution through conditional judgment includes: excluding optical constant solutions that do not satisfy physical conditions, and introducing remaining optical constant solutions satisfying the physical conditions into a Fresnel equation to calculate ellipsometric parameters of the ultra-thin film, and determining the correct solution according to a degree of fitness between the calculated ellipsometric parameters and ellipsometric parameters of the ultra-thin film obtained through the measurement.
In overall, compared with the prior art, the above technical scheme conceived by the invention has following technical advantages:
By performing Taylor second-order expansion to the amplitude reflection coefficient ratio ρ of the ultra-thin film (generally refers to a thin film material with a thickness less than 10 nm), a Taylor second-order equation is adapted to achieve an approximation of the amplitude reflection coefficient ratio ρ, at the same time, a non-linear equation that is originally unable to obtain analytical solutions is transformed into a one-variable quartic equation, so as to obtain the analytical solutions of the ultra-thin film optical constant through calculation. Compared with the existing methods for calculating the ultra-thin film optical constant, the method of the invention does not need to have a thorough understanding of the electronic transition of the material, and it does not need to estimate the initial value of the optical constant in a solving process. The method of the invention has no special limitation on the wavelength range and may be applied to the measurement of optical constants in a wider wavelength range. The method of the invention still has high measurement accuracy in the short wavelength range, accurate calculation results and small error, and which is very important for determination of the optical constants of the newly appeared ultra-thin films.
To make the aforementioned more comprehensible, several embodiments accompanied with drawings are described in detail as follows.
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
Reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings. It should be understood that the specific embodiments described herein are merely used for explaining the invention and are not intended to be limiting of the invention. Furthermore, the technical features involved in the various embodiments of the invention described below may be combined with each other as long as they do not conflict with each other.
As shown in
S1: obtaining a p-light amplitude reflection coefficient rp and an s-light amplitude reflection coefficient rs of a light source (incident light) incident to an ultra-thin film to be measured, and using rp and rs to express an amplitude reflection coefficient ratio
To be specific, the p-light amplitude reflection coefficient rp is calculated according to a following equation:
Where nsub is an optical constant of a substrate used by the ultra-thin film (with a thickness smaller than 10 nm), αinc is an incident angle of the incident light, n0 is an optical constant of a surrounding medium of the ultra-thin film, αtra is a refraction angle of the incident light transmitted to the substrate (a refraction angle of the incident light on the substrate), df is a thickness of the ultra-thin film, λ is a wavelength of the incident light, and nf is an optical constant of the ultra-thin film.
Further, the s-light amplitude reflection coefficient rs is calculated according to a following equation:
S2: performing a second-order Taylor expansion to
at df=0 while taking 2πdf/λ as a variable to obtain a second-order approximation form:
Where ρ0 is an amplitude reflection coefficient ratio of the bare substrate, df is a thickness of the ultra-thin film, λ is a wavelength of the incident light, and ρ′, ρ1″ and ρ2″ are respectively coefficients.
To be specific, ρ′ is calculated according to a following equation:
Where n0 is an optical constant of the surrounding medium of the ultra-thin film, αinc is an incident angle of the incident light, nf is an optical constant of the ultra-thin film, nsub is an optical constant of the substrate used by the ultra-thin film, and αtra is a refraction angle of the incident light transmitted to the substrate.
Further, ρ1″ is calculated according to a following equation:
Further, ρ2″ is calculated according to a following equation:
S3: performing merging, simplifying and substituting processing to the second-order approximation form to transform the same into a one-variable quartic equation, which includes following sub-steps:
S31: letting:
S32: introducing the above A-D to the second-order approximation form to obtain:
S33: expanding and simplifying the equation of the step S32 to obtain a one-variable quartic equation related to nf2: para4·Nf4+para3·Nf3+para2·Nf2+para1·Nf+para0=0, specifically:
Letting:
simplifying
to obtain:
para4·Nf4+para3·Nf3+para2·Nf2+para1·Nf+para0=0
Where, para0 is a constant term:
para0=BD2n04nsub4−CD2n04nsub6
para1 is a one-order term coefficient:
para1=iADn02nsub2−2BD2n04nsub2−2BD2n02nsub4+2CD2n02nsub6
para2 is a quadratic term coefficient:
para2=−iADn02+BD2n04−iADnsub2+4BD2n02nsub2+2CD2n04nsub2+BD2nsub4−CD2n02nsub4−CD2nsub6−ρ+ρ04
para3 is a cubic term coefficient:
para3=iAD−2BD2n02−CD2n04−2BD2nsub2−2CD2n02nsub2+CD2nsub4
para4 is a quartic term coefficient:
para4=BD2+CD2n02
S4: solving the one-variable quartic equation para4·Nf4+para3·Nf3+para2·Nf2+para1·Nf+para0=0 to obtain 8 solutions of the optical constant of the ultra-thin film, and obtaining a correct solution through conditional judgment, where the correct solution is the optical constant of the ultra-thin film to be measured, so as to achieve the rapid measurement for the ultra-thin film optical constant. To be specific, a Ferrari method is adopted to get 4 solutions for the one-variable quartic equation related to Nf, and after the square root, 8 solutions of nf is obtained.
To be specific, the conditional judgment is performed in a following method to obtain the correct solution:
S41: excluding optical constant solutions according to physical conditions:
A refractive index n and an extinction coefficient k are required to satisfy following physical conditions: n=Re(nf)>0 and k=−Im(nf)>0, where Re(nf) represents a real part of the optical constant nf, Im(nf) represents an imaginary part of the optical constant nf, the corresponding refractive index n (n=Re (nf)) and the extinction coefficient k (k=−Im (nf)) are obtained according to real parts and imaginary parts of each of the optical constant solutions, and then most of the 8 solutions are excluded according to aforementioned physical conditions;
S42: excluding the remaining optical constant solutions by using a Fresnel equation:
The remaining optical constant solutions are introduced into the Fresnel equation to calculate ellipsometric parameters of the ultra-thin film, and determining which one is the correct solution according to a degree of fitness between the calculated ellipsometric parameters and ellipsometric parameters of the ultra-thin film obtained through the measurement, so as to obtain the unique correct solution. To be specific, the ellipsometric parameters of the ultra-thin film obtained through calculation and the ellipsometric parameters of the ultra-thin film obtained through the measurement are compared, and the solution corresponding to the ellipsometric parameter with the highest degree of fitness is the correct solution.
Before the method of the invention is used to measure the ultra-thin film optical constant nf, following parameters are required to be determined: the surrounding medium of the ultra-thin film n0, the optical constant of the substrate used by the ultra-thin film nsub, the incident angle αinc of the incident light, the amplitude reflection coefficient ratio ρ0 of the substrate, the amplitude reflection coefficient ρ of the ultra-thin film, the thickness df of the ultra-thin film, the wavelength λ of the incident light and the refraction angle αtra of the incident light transmitted to the substrate.
To be specific, the optical constants of the thin film may vary along with a change of the wavelength, and measured wavelength ranges of different instruments are also different, so that an appropriate measurement wavelength range may be selected according to the measurement requirements and equipment conditions, for example, a single wavelength or spectrum measurement, and then the optical constant n0 of the surrounding medium and the optical constant nsub of the substrate used by the ultra-thin film in the measurement wavelength range may be obtained, and in general, the surrounding medium in measurement is air, i.e. n0=1. The optical constant of the substrate may be measured by an ellipsometer or other instrument, and if optical properties of the substrate are stable, known data in literatures may also be used. There is no specific requirement on the incident angle αinc of the incident light, which may be selected according to actual needs to ensure validity of the measured data, for example, 60°, 65° or 70°.
Regarding the amplitude reflection coefficient ratio ρ0 of the substrate, a calculation equation thereof is: ρ0=tan(ψsub)exp(iΔsub), and in the actual operation, the ellipsometric parameters of the substrate: an amplitude ratio Ψsub and a phase difference Δsub are obtained by using a general ellipsometer, an imaging ellipsometer, a Mueller matrix ellipsometer or other instruments capable of obtaining the ellipsometric parameter information of the sample, and after the ellipsometric parameters Ψsub and Δsub are obtained, the equation ρ0=tan(Ψsub)exp(iΔsub) is used to calculate the amplitude reflection coefficient ratio ρ0 of the substrate.
Regarding the amplitude reflection coefficient ratio ρ of the ultra-thin film in the final one-variable quartic equation, a calculation equation thereof is ρ=tan(Ψf)exp(iΔf), and in the actual operation, the ellipsometric parameters of the ultra-thin film: an amplitude ratio Ψf and a phase difference Δf are obtained by using a general ellipsometer, an imaging ellipsometer, a Mueller matrix ellipsometer or other instruments capable of obtaining the ellipsometric parameter information of the sample, and after the ellipsometric parameters Ψf and Δf are obtained, the equation ρ=tan(Ψf)exp(iΔf) is used to calculate the amplitude reflection coefficient ratio ρ of the ultra-thin film.
The thickness df of the ultra-thin film may be determined according to measurement approaches of AFM, SEM or the like. Regarding the wavelength λ of the incident light, a range thereof is determined according to an actual requirement. To be specific, the method of the invention may implement calculation of the optical constants of two-dimensional materials from an ultraviolet band to an infrared band, and implement calculation of the optical constants of ordinary ultra-thin films (with a thicknesses less than 10 nm) from a partial visible light band to the infrared band can be calculated. The refraction angle αtra of the incident light transmitted to the substrate is calculated according to a following equation:
n0 sin(αinc)=nsub sin(αtra)
An embodiments of the invention is provided below, and in the embodiment, a spectroscopic ellipsometer is used to measure a GaAs film with a thickness of 3 nm (df=3 nm) on a silicon substrate, and the optical constants of the ultra-thin film are rapidly calculated by introducing the ellipsometric parameters of the substrate and the thin film to an optical constant solving process.
First, various parameters are obtained, and the spectroscopic ellipsometer is adopted in the embodiment, the measurement wavelength range is Γ=[250, 1690] nm, and the optical constant n0 of the surrounding medium of the ultra-thin film and the optical constant nsub of the substrate in the wavelength range of [250, 1690] nm are obtained, and in the measurement, the surrounding medium is air n0=1, the substrate is made of silicon, optical constants of the silicon is relatively stable, and the optical constants of the silicon substrate are shown in
Then, the aforementioned obtained various parameters are introduced into the one-variable quartic equation para4·Nf4+para3·Nf3+para2·Nf2+para1·Nf+para0=0 to calculate the optical constants nf(λ) of the GaAs film. 8 optical constants of the GaAs film are obtained according to the above calculation process, and positive and negative of the refractive index and of the extinction coefficient are used to exclude 6 of the 8 solutions, and the remained two solutions (i.e. two sets of optical constants) are as shown in
In the aforementioned embodiment, the ellipsometer is adopted for measurement, for example, a laser ellipsometer is used to implement calculation of ultra-thin film single waveform optical constants. In the aforementioned calculation process, only the GaAs film on the silicon substrate is taken as an example for description, and for other types of ultra-thin films or different types of substrates, rapid measurement of optical constants may also be performed according to the same method.
In summary, in the rapid measurement method for the ultra-thin film optical constant, by performing Taylor second-order expansion to the amplitude reflection coefficient ratio ρ, a second-order equation is adapted to achieve an approximation of the original amplitude reflection coefficient ratio ρ, at the same time, a non-linear equation that is originally unable to obtain analytical solutions is transformed into a one-variable quartic equation, so as to obtain the analytical solutions of the ultra-thin film optical constant to achieve rapid measurement and calculation of the ultra-thin film optical constant.
It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed embodiments without departing from the scope or spirit of the invention, for example, to use other instruments capable of measuring polarization information, or replacing the type of the ultra-thin film or the substrate, etc. In view of the foregoing, it is intended that the invention covers modifications and variations provided they fall within the scope of the following claims and their equivalents.
Number | Date | Country | Kind |
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201910315604.8 | Apr 2019 | CN | national |
Number | Name | Date | Kind |
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5956147 | Jellison, Jr. | Sep 1999 | A |
9235668 | Poiroux | Jan 2016 | B1 |
20170115112 | Srocka | Apr 2017 | A1 |
Entry |
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Peep Adamson, “A new ellipsometric approach for determining dielectric function of graphene in the infrared spectral region,” Journal of Modern Optics, vol. 64, Issue 3, Sep. 7, 2016, pp. 1-9. |
Gwang-Hun Junga et al., “Measuring the optical permittivity of twodimensional materials without a priori knowledge of electronic transitions,” Journal of Nanophotonics, vol. 8, Issue 2, Sep. 29, 2018, pp. 263-270. |
Number | Date | Country | |
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20200333132 A1 | Oct 2020 | US |