METHOD FOR REFERENCING A NEAR-FIELD MEASUREMENT WITH DRIFT AND FLUCTUATION CORRECTION
20230280369 · 2023-09-07
Inventors
- Ivan MALOVICHKO (Haar, DE)
- Florian HUTH (Haar, DE)
- Alexander A. GOVYADINOV (Haar, DE)
- Marcus DIEM (Haar, DE)
Cpc classification
G01Q60/22
PHYSICS
International classification
Abstract
The present invention relates to a method for referencing a near-field measurement, e.g. in a scanning probe microscope.
Claims
1. Method for referencing a near-field measurement of a sample in a scattering type near field microscope comprising a probe and a sample, which method comprises the steps of a) providing a modulation of the probe-sample distance z(t)=z.sub.0−A*cos(φ(t)) having an offset distance z.sub.0, phase φ(t), such that φ(t)=0 corresponds to the smallest probe-sample distance, and at a modulation frequency
σ.sub.rbg=Σ.sub.nA.sub.n*σ.sub.n (II) wherein coefficients A.sub.n of the respective frequencies n*Ω are to be chosen such that the relative contribution of the scattering signal for |φ(t)|<ε, wherein ε≤π, to the σ.sub.rbg is made small over an oscillation cycle; d) determining the near field signal σ.sub.NF of a position of the sample using at least one harmonic of the modulation frequency Ω at a frequency m*Ω, m being an integer equal to or larger than 0, and e) determining the referenced near-field signal σ.sub.NFref of the position of the sample using the calculated reference background σ.sub.rbg as a reference.
2. The method according to claim 1, wherein in step e) the amplitude and/or the phase of the near field signal σ.sub.NFref is determined using the calculated reference background σ.sub.bg as an amplitude and/or phase reference.
3. The method according to claim 1, wherein in step c) the contribution of the scattering signal for |φ(t)|<ε, wherein ε≤π to the total scattering signal S over an oscillation cycle (|φ(t)|≤π) is made small by determining the coefficients A.sub.n such that
r=√{square root over (|∫.sub.−ε.sup.+εH.sup.2(φ)dφ|)}/√{square root over (|∫.sub.−π.sup.+πH.sup.2(φ)dφ|)}<δ,
wherein
H(φ)=Σ.sub.nA.sub.n cos(nφ) (II) and δ=0.1, preferably δ=0.01 and most preferably δ=0.001.
4. The method according to claim 3, wherein the coefficients A.sub.n are found by nullifying all derivatives of function H(φ) up to the order
5. The method according to claim 1, wherein M=3, or M≥4.
6. The method according to claim 1, wherein in step d) the near field signal σ.sub.NF is determined using any single σ.sub.n of step b).
7. The method according to claim 1, wherein in step d) the near field signal σ.sub.NF is determined using a linear combination σ.sub.NF=Σ.sub.nB.sub.n*σ.sub.n.
8. The method according to claim 1, wherein step d) is conducted before step c).
9. The method according to claim 1, wherein the offset distance z.sub.0 is provided a modulation, i.e. z.sub.0=z.sub.0(t).
10. The method according to claim 1, wherein the value of the probe-sample distance z(t) used corresponds to any combination of the following quantities: the voltage applied to an actuator regulating the probe-sample distance, the vertical position Z of the sample or the probe as obtainable from a Z-position sensor, or a value obtained from AFM detection system readout, such as quadrant diode or piezoelectric sensor, or value corresponding to time t if the probe-sample distance z(t) predictably depends on time, e.g. in case of an oscillating probe.
11. The method according to claim 1, wherein the amplitude of the probe-sample distance z(t) is at least 0.1 nm, preferably at least 10 nm or 100 nm.
12. The method according to claim 1, wherein the referenced near-field signal of the sample σ.sub.NFref is determined for a plurality of probe or sample positions and steps b) to e) are conducted for each sample position for which the near-field σ.sub.NFref is determined, or wherein steps b) to e) are conducted at least once before, after or during one scan of the sample.
13. The method according to claim 1, wherein the scattering type near field microscope comprises a wavelength tunable light source and steps a) to e) of claim 1 are conducted for a plurality of different illumination wavelengths.
14. The method according to claim 1, wherein in step b) the σ.sub.n are determined by interferometric detection, such as Homodyne, Heterodyne, Pseudoheterodyne, Quadrature Homodyne, Self-Homodyne, High Speed holography, Phase Shifting or nano-FTIR, or by non-interferometric detection, or by self-detection technique.
15. The method according to claim 1, wherein the scattering type near field microscope comprises a wavelength tunable light source and an asymmetric interferometer operated in the while light position.
16. The method according to claim 1, wherein in step d) the near-field signal σ.sub.NF is determined using at least one background contaminated σ.sub.m, wherein preferably m<2, and the reference background σ.sub.rbg.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
[0036] The invention relates to a method for referencing a near-field measurement of a sample in a scattering type near field microscope comprising a probe and a sample, which method comprises the steps a) to e).
[0037] The scanning probe microscope used in the methods of the invention comprises an oscillating cantilever probe, a sample and a source of electromagnetic radiation. Suitable systems are known in the art, e.g. from US 2012/0204296 A1, which is included herein by reference.
[0038] Step a) comprises providing a modulation of the probe-sample distance z(t)=z.sub.0−A*cos(φ(t)) having an offset distance z.sub.0, phase φ(t), such that φ(t)=0 corresponds to the smallest probe-sample distance, and a modulation frequency
[0039] In general, any oscillating movement could be expressed in the following form:
z(t)=z.sub.0−A*cos(φ), where φ=φ(t) (1)
where A is the amplitude and φ is the phase of the oscillation. In a preferred embodiment a cantilevered AFM probing tip is oscillating substantially vertically with a frequency Ω, typically Ω is about 5 Hz to about 1000 kHz, preferably 200-300 kHz, as known in homodyne, pseudo heterodyne, nano-FTIR and other setups that utilize the high-harmonic demodulation technique for the background suppression. For such harmonic-oscillations (tapping mode case) one could substitute φ(t)=Ωt+ϕ.sub.0:
z(t)=z.sub.0−A*cos(Ωt+ϕ.sub.0) (2)
where ϕ.sub.0 is an arbitrary phase offset and z.sub.0 is the offset distance.
[0040] Preferably, the amplitude of the probe-sample distance z(t) is at least 0.1 nm, preferably at least 10 nm or 100 nm.
[0041] Probes to be used in the method according to the present invention are probes comprising a cantilever and a tip, which are known in the art for AFM or for scanning near-field optical microscopy (s-SNOM). These probes typically comprise a cantilever which carries the tip on one of its ends, the other end of the cantilever is typically mounted onto a larger base to simplify mounting and replacement of the probe. The radius of curvature of the tip is typically below about 100 nm, preferably below about 50 nm, most preferably below about 20 nm, however, tips with curvature radii as large as 750 nm are also known and suitable to be used for some s-SNOM applications [Maissen et al, ASC Photonics, 6, 1279 (2019)]. The tips of the cantilevers may be metalized. Suitable probes are commercially available, e.g. from nanoSensors™ or MikroMasch.
[0042] In a preferred embodiment cantilevered probes are used. In an alternative embodiment a tuning fork, preferably oscillating vertically or in sheer force mode, could be utilized as probe. In yet another embodiment a hybrid technology where a cantilevered probe is attached to a tuning fork can be used.
[0043] In yet another embodiment the AFM probing tip could perform non-harmonic periodic vertical movement, such as jumping, linear or zigzag approach and retraction (as in Peak Force and other non-resonant measurement modes).
[0044] In an alternative embodiment, the offset distance z.sub.0 is provided with a modulation, i.e. z.sub.0=z.sub.0(t).
[0045] In one embodiment, the value of the probe-sample distance z(t) used corresponds to any combination of the following quantities: the voltage applied to an actuator regulating the probe-sample distance, the vertical position Z of the sample or the probe as obtainable from a Z-position sensor, or a value obtained from AFM detection system readout, such as quadrant diode or piezoelectric sensor, or value corresponding to time t if the probe-sample distance z(t) predictably depends on time, e.g. in case of an oscillating probe.
[0046] Step b) comprises measuring the scattering signal S of the probe, and determining σ.sub.n for different n as the scattering signal S demodulated at frequencies n*Ω, n being an integer equal to or larger than 0, wherein σ.sub.n is determined for at least N different frequencies n*A, and N being at least 2. Preferably, N=3, or N≥4, the latter being most preferred.
[0047] Step c) comprises calculating a reference background σ.sub.rbg as a linear combination of σ.sub.n according to equation (II)
σ.sub.rbg=Σ.sub.nA.sub.n*σ.sub.n (II)
wherein coefficients A.sub.n of the respective frequencies n*Ω are to be chosen such that the relative contribution of the scattering signal for |φ(t)|<ε, wherein ε≤π, to the σ.sub.rbg is made small over an oscillation cycle, preferably smaller than 10%, even more preferably below 1% and most preferred below 0.1%.
[0048] Light scattered from the probing tip when it is in a closest-proximity to the sample surface during its movement contains the information about the optical near-field interaction between the probing tip and the sample and constitutes the near-field contribution to the scattering signal, which is the main object of interest for s-SNOM measurements. Detection of this light allows for achieving the nanoscale spatial resolution about 10-20 nm. Light scattered from the probe when it is at distant segments of the motion trajectory contains mostly scattering from the tip shaft and long-distance probe-sample interaction, which corresponds to the background contributions. Traditionally, this contribution is discarded. The general idea of current invention is to recover this background and to use it to solve the problems known in the art as discussed above.
[0049] In a preferred embodiment the background information is collected simultaneously with the near-field contribution, thus allowing for the compensation of even the parasitical physical effects that are changing in time during the course of s-SNOM measurements.
[0050] The mathematical basis for the findings of the present invention is discussed in more detail in the following:
[0051] As typically described before in the art (Ocelic, 2007), the total tip scattered field E.sub.sca consist of E.sub.nf that is associated with near-field interaction between the tip and the sample surface and unavoidable background E.sub.bg resulting from scattering off the tip shaft or distant sample positions:
E.sub.sca=E.sub.nf+E.sub.bg (3)
[0052] Because the tip oscillates, the scattered field is modulated:
E.sub.sca=Σ.sub.n=0.sup.∞(E.sub.nf,n+E.sub.bg,n)cos(nφ) (4)
[0053] For interferometric detection, the detector is also illuminated by the reference field, E.sub.ref and the combined power is measured:
I.sub.det=k.sub.u|E.sub.sca+E.sub.ref|.sup.2 (5)
where k.sub.u is a proportionality constant whose value depends on the illumination power, detector responsivity and the transfer function of the measurements setup.
[0054] Substituting Eq. (4) into Eq. (5) and decomposing I.sub.det into a Fourier series, equaling the Fourier coefficients of the same order and assuming that E.sub.ref>>E.sub.bg (the reference field can in principle be made arbitrarily high) gives:
u.sub.n=k.sub.u(E.sub.sca,nE*.sub.ref+E*.sub.sca,nE.sub.ref),for n>0 (6)
[0055] It is convenient to rewrite Eq. (6) as
u.sub.n=k.sub.us.sub.ns.sub.ref cos(ϕ.sub.n−ψ.sub.ref), (7)
or in complex-valued form:
u.sub.n=Re(U.sub.n)=Re(k.sub.us.sub.ns.sub.refs.sub.ne.sup.i(ϕ.sup.
where s.sub.n and s.sub.ref are the amplitudes and ϕ.sub.n and ψ.sub.ref are the phases of the scattered and reference fields, respectively. Re denotes the real part.
[0056] By using one of the techniques known in the art (e.g. Pseudo Heterodyne, Phase shifting, High Speed Holography, nano-FTIR, Quadrature Homodyne, etc.), one can extract both the amplitude |U.sub.n|=k.sub.us.sub.ns.sub.ref and the phase arg(U.sub.n)=ϕ.sub.n−ψ.sub.ref from the detector readings. To further eliminate k.sub.u, r.sub.ref and ψ.sub.ref a second measurement on a reference material with known optical properties is typically performed in the art followed by the normalization procedure:
where a complex valued scattering coefficient σ.sub.n=s.sub.n exp(iϕ.sub.n) has been defined.
[0057] The main purpose of the normalization procedure Eq. (8) is to eliminate the unknown factors, such as the transmissivity of the microscope setup, responsivity of the detector, illumination power, reference beam phase and amplitude. For sufficiently high demodulation order (n≥2) the background contribution σ.sub.bg,n is much smaller than the near-field contribution σ.sub.nf,n to σ.sub.n: σ.sub.bg,n<<σ.sub.nf,n. Thus, η.sub.n measures the local optical properties of the materials:
and is often called in the art as near-field contrast. These contrast could be related to the optical properties of the sample material at different locations on the sample (material contrast), or to the optical properties of the sample material at the same location but different illumination frequencies (spectral contrast).
[0058] The normalization procedure according to Eq. (8) utilized in the art requires an additional reference measurement and is susceptible to the physical effects not constant in time, especially for long measurements. In an alternative approach, the normalization to the reference measurement could be replaced by normalization to the demodulated detector signal measured at 0-th harmonic (Craig et al., 2013):
[0059] Such normalization is capable of canceling out the unknown k.sub.u, r.sub.ref and ψ.sub.ref, including the physical factors that are not constant in time. It could also eliminate the need for a reference measurement; however, it also decreases the material or the spectral contrast. Indeed, it is known in the art that all demodulation orders, including m=0 contain the near-field (see
[0060] The present invention discloses an approach that completely eliminates the necessity for a separate reference measurement, yet is capable of retaining the near-field contrast both in s-SNOM spectra and in s-SNOM images. This is achieved by reconstructing the complex-valued background σ.sub.bg from the standard s-SNOM detector readings and using this reconstructed background as a reference measurement in the normalization procedure. This is achieved as described in step c) of the method of the invention.
[0061] In general, σ.sub.rbg can be written as:
σ.sub.rbg=Σ.sub.nA.sub.nσ.sub.n (11)
[0062] The coefficients A.sub.n need to be chosen in such a way that σ.sub.rbg contains a minimum to no near-field signal, i.e. pure background without the contribution emanating from the near-field hotspot directly below the tip apex.
[0063] To demonstrate how A.sub.n coefficients could be found, Eq. (6) can be first rewritten as:
u.sub.n=k.sub.u(E.sub.nf,nE*.sub.ref+E*.sub.nf,nE.sub.ref+E.sub.bg,nE*.sub.ref+E*.sub.bg,nE.sub.ref) (12)
where star represents the complex conjugation. By multiplying both parts by A.sub.n and summing over all n, one arrives at:
Σ.sub.nA.sub.nu.sub.n=k.sub.u(ξ.sub.bgE*.sub.ref+ξ*.sub.bgE.sub.ref)+k.sub.u(ξ.sub.nfE*.sub.ref+ξ*.sub.nfE.sub.ref) (13)
where
ξ.sub.bg=Σ.sub.nA.sub.nE.sub.bg,n (13a)
ξ.sub.nf=Σ.sub.nA.sub.nE.sub.nf,n (13b)
[0064] Coefficients A.sub.n need to be selected in such a way that |ξ.sub.bg|/|ξ.sub.nf|>>1. This can be done by considering a portion of the AFM tip trajectory for which E.sub.nf=E.sub.nf(φ)<<E.sub.bg. This trajectory corresponds to the oscillation phase φ(t).Math.[−ε,ε] in Eq. (1), where ε is a free constraint parameter that defines the near-field region. Using the explicit expressions for the Fourier coefficients E.sub.nf,n (note that E.sub.nf(φ) is a symmetric function over each period):
E.sub.nf,n=∫.sub.−π.sup.+πE.sub.nf(φ)cos(nφ)dφ (14)
and applying the Cauchy-Schwarz inequality, the magnitude of ξ.sub.nf in Eq. (13b) can be evaluated:
|ξ.sub.nf|=|Σ.sub.nA.sub.nE.sub.nf,n|=|∫.sub.−π.sup.+πE.sub.nf(φ)Σ.sub.nA.sub.n cos(nφ)dφ|˜|∫.sub.−ε.sup.+εE.sub.nf(φ)Σ.sub.nA.sub.n cos(nφ)dφ|≤√{square root over (|∫.sub.−ε.sup.+εE.sub.nf.sup.2(φ)dφ|)}√{square root over (|∫.sub.−ε.sup.+ε(Σ.sub.nA.sub.n cos(nφ)).sup.2dφ|)}=G√{square root over (|∫.sub.−ε.sup.+εH.sup.2(φ)dφ|)} (15)
where G and H are defined as:
G=√{square root over (|∫.sub.−ε.sup.−εE.sub.nf.sup.2(φ)dφ|)} (16)
and
H(φ)=Σ.sub.nA.sub.n cos(nφ) (17)
[0065] Eq. (15) shows that H(φ) acts as a filter function that constraints the upper value of ξ.sub.nf by scaling the near-field-related functional G. Therefore, by making H(φ) small one can minimize the relative contribution of near field in Eq. (13). Since H(φ) doesn't depend on the sample properties or experimental conditions, this minimization can be performed independently from the s-SNOM measurements using standard analytical, semi-analytical or numerical methods.
[0066] Thus, preferably, in step c) the contribution of the scattering signal for |φ(t)|<ε, wherein ε≤π to the total scattering signal S over an oscillation cycle is made small by determining the coefficients A.sub.n such that
r=√{square root over (|∫.sub.−ε.sup.+εH.sup.2(φ)dφ|)}/√{square root over (|∫.sub.−π.sup.+πH.sup.2(φ)dφ|)}<δ,
and δ=0.1, more preferably δ=0.01 and most preferably δ=0.001.
[0067] In practice, the detector signal is always measured until some maximum demodulation order M, i.e. A.sub.n are only available for n=
[0068] Thus, in a preferred embodiment, the coefficients A.sub.n are found by nullifying all derivatives of function H(φ) up to the order 2(M−1) at φ=0
[0069] It is to be noted that all derivatives of the odd order 2p+1 are identically null since H is a symmetric function. This way, in order to find A.sub.n that maximize the background-to-nearfield ratio |ξ.sub.bg|/|ξ.sub.nf| one needs to solve the following linear system of equations:
[0070] This system is formally determined and can be solved. The solution yields a Taylor series expansion of the function H(φ) in the nearest proximity to the sample surface:
H(φ)=O(φ.sup.2M),φε[−ε,ε]
[0071] The functions H(φ) corresponding to the solution of Eq. (19) in the region φ∈[−π,π] are plotted in
|ξ.sub.nf|<G√{square root over (|∫.sub.−ε.sup.+εO(ϕ.sup.4m)dφ|)}˜GO(ε.sup.2M+0.5) (20)
[0072] In a preferred embodiment, the minimization of the function H(φ) is performed analytically using Taylor expansion.
[0073] It can be shown that the minimization of ξ.sub.nf maximizes the background to near-field ratio |Ξ.sub.bg|/|ξ.sub.nf|. Indeed, the dominant contribution to ξ.sub.bg in Eq. (13a) comes from E.sub.bg,1. This follows from the fact that for small (compared to the illumination wavelength) tapping amplitudes the background is nearly linear in the tip-sample distance, yielding exponentially small amplitudes for higher-order Fourier coefficients (see
|ξ.sub.bg|/|ξ.sub.nf|=Σ.sub.nA.sub.nE.sub.bg,n/|ξ.sub.nf|˜E.sub.bg,1/|ξ.sub.nf| (21)
where we have again assumed that A.sub.1=1 without the loss of generality.
[0074] In another embodiment, minimization of H(φ) could performed with A.sub.0 set to unity. Direct substitution of the resulting function H(φ) into Eq. (18) yields the following system of equations:
[0075] This system is also formally determined and yields a set of coefficients A.sub.l. The corresponding function H(φ) are shown in
[0076] In an alternative embodiment any arbitrary number of coefficients A.sub.n could be set to zero (for example because the corresponding σ.sub.n are unavailable) and the solution for the remaining coefficients is found according to Eq. (18).
[0077] The method of the invention further comprises the steps of d) determining the near field signal aw of a position of the sample using at least one harmonic of the modulation frequency Ω at a frequency m*Ω, m being an integer equal to or larger than 0, and e) determining the referenced near-field signal σ.sub.NFref of the position of the sample using the calculated reference background σ.sub.rbg as a reference.
[0078] Eq. (21) proves that the higher M is taken—the higher is the background-to-nearfield ratio |.Math..sub.bg|/|ξ.sub.nf| in the Eq. (13). Since the σ.sub.n are related to u.sub.n, it follows that coefficients A.sub.n provide filtering of the near-field contribution from the reconstructed background σr.sub.rbg defined by Eq. (11). Thus, normalizing s-SNOM measurements to σ.sub.rbg according to
does not reduce the near-field contrast as much as the normalization according to Eq. (10). This is particularly important, since such normalization preserves to greater extend the relative contrast between materials, assuming that the background stays constant over the area of interest. This allows for putting measurements η.sub.n into prospective by comparing them to the measurements, η.sub.n.sup.ref on some reference material with known optical properties, as typically done in s-SNOM for quantitative analysis:
[0079] Since reconstructing the background σ.sub.rbg does not require additional measurements, it contains the same reference phase and multiplicative factors such as the illumination power and transfer function of the imaging setup as σ.sub.n. Thus, these factors cancel out upon normalization according to Eq. (22). This includes the unpredictable changes in the reference beam (phase and/or magnitude) upon tuning an illumination source. Thus, the present invention enables a true reference-free point-spectroscopy with wavelength-tunable sources as illustrated in
[0080] The normalization according to Eq. (22) also eliminates the time-dependent physical effects, related to the interferometer drift and mismatch of the dispersion and absorption in different interferometer arms, including mechanical noise and random fluctuations. Thus, the current invention significantly improves the signal quality and the stability over course of longer measurements.
[0081] It is also to be noted that despite describing the invention in the context of oscillating tip motion, the described method also applies for non-periodic tip motion. Indeed, any motion can be viewed as a single cycle of some oscillation described by Eq. (1), and the whole mathematical formalism as developed above still applies. Particular, the disclosed method can still be applied for measurements that record, e.g. a single approach curve without tip tapping, etc.
[0082] In an alternative embodiment at least one approach curve is recorded (i.e. scattered signal is sampled as a function of tip-sample distance) followed by the described background reconstruction using the Fourier series representation of the approach curve.
[0083] In a preferred embodiment the background is found according to Eq. (11), where the coefficients A, are found by solving Eq. (19). In another embodiment, the coefficients A, are found using Eq. (21a). Yet in another embodiment, the coefficients are found by other analytical, semi-analytical or numerical methods, such as linear and nonlinear regression, least squares or other methods of mathematical optimization with aim of minimizing the near-field contribution in Eq. (13).
[0084] In an alternative embodiment the reconstruction of background is obtained by scaling the detector signal I.sub.det with some weighting coefficients that are dependent on the instantaneous probe-sample distance. Particularly, the time-gated measurements can be used to collect the near-field-free signal and to use as a reference for the near-field measurements. Since the corresponding near-field interaction is stronger for small probe-sample distances, the higher background-to-nearfield separation ratio could be achieved with a proper choice of weighting coefficients or/and with proper time-gating.
[0085] It is to be noted that the normalization according to Eq. (22) can be applied to a single harmonic or several harmonics of the detector signal σ.sub.n. Moreover, it can be applied to any linear combination σ.sub.NF of several harmonics:
σ.sub.NF=ΣB.sub.nσ.sub.n(*)
with the same benefit of canceling unknown multiplicative factors and fluctuations in σ.sub.NF.
[0086] In preferred embodiments, in step d) the near field signal σ.sub.NF is determined using any single σ.sub.n of step b), and/or in step d) the near field signal σ.sub.NF is determined using a linear combination σ.sub.NF=Σ.sub.nB.sub.n*σ.sub.n. In one embodiment, step d) is conducted before step c).
[0087] Preferably, the referenced near-field signal of the sample σ.sub.NFref is determined for a plurality of probe or sample positions and steps b) to e) are conducted for each sample position for which the near-field σ.sub.NFref is determined, or wherein steps b) to e) are conducted at least once before, after or during one scan of the sample.
[0088] In one preferred embodiment, in step b) the an are determined by interferometric detection, such as Homodyne, Heterodyne, Pseudoheterodyne, Quadrature Homodyne, Self-Homodyne, High Speed holography, Phase Shifting or nano-FTIR, or by non-interferometric detection, or by self-detection technique.
[0089] In a preferred embodiment, multiple harmonics n of the detector signal are measured simultaneously.
[0090] In one embodiment, the scattering type near field microscope comprises a wavelength tunable light source and steps a) to e) are conducted for a plurality of different illumination wavelengths.
[0091] In one preferred embodiment, the scattering type near-field microscope comprises a wavelength tunable light source and an asymmetric interferometer operated in the while light position (WLP), which is known in the art, and in particular as defined in EP3268748 A1. Namely, there is an interferometer integrated in the optical path of the light source, comprising a beam splitter splitting the light of the light source into two optical light paths, the reference light path and the signal light path, wherein the reference light path does not contain the probe, and the signal light path comprises the probe, and the reference and the signal light paths are superimposed at the detector, and the difference of the lengths of the two optical paths can be adjusted to be at most 1000 μm.
[0092] Using WLP reduces the changes in phase upon small changes in the illumination wavelength or fluctuations in the relative pathlength between two interferometer arms. In an alternative embodiment, the interferometer is operated outside of the white light position, e.g. the difference of the lengths of the two optical paths can be adjusted to be at least 1000 μm or more.
[0093] In a preferred embodiment the quantum cascade laser is utilized as an illumination source. In another embodiment, the optical parametric oscillator is utilized as a source of illumination.
[0094] In an alternative embodiment, a free electron laser (FEL) is used as a source of illumination. FEL is known for poor pulse to pulse stability, which makes referencing to another measurement even more problematic. The benefits of this invention are applicable for the utilization of FEL sources in s-SNOM.
[0095] The invention is further illustrated by the following Example.
[0096] Point spectroscopy was performed on a SiO.sub.2 sample using pseudo-heterodyne (PsHet) detection technique as also described in EP 1770714. In PsHet, the position of the reference mirror is modulated harmonically with amplitude γ, yielding a phase modulation of the reference beam. The modulation frequency F is chosen to be much lower than the tip vibration frequency (typically ˜300 Hz), so that
E.sub.ref=r.sub.Re.sup.iψ.sup.
[0097] This modulation leads to the appearance of sidebands in the frequency spectrum of the detector signal, as illustrated in
where J.sub.m is the Bessel function of the first kind.
[0098] The complex-valued scattering-coefficient σ.sub.n can be recovered for example, from the detector-signal sideband amplitudes u.sub.n,1 and u.sub.n,2 by setting γ=2.63:
describes the light source spectral properties and total optical transmissibility of the system, which depend on the reference beam, illumination wavelength, power, etc.
[0099] The results of our measurements using a wavelength-tunable IR source (Mircat QCL) are shown in
[0100] In contrast, the spectrum C in
[0101] For comparison, a raw spectrum A recorded on SiO.sub.2 without any normalization is also shown in
[0102] Another example presented in
Elimination of the Indirect Illumination
[0103] The incident electric field E.sub.in illuminating the AFM probing tip can be decomposed into a direct E.sub.dir and an indirect E.sub.ind parts (see
[0104] The indirect illumination results in a nonlocal multiplicative factor in the near-field signal:
σ.sub.n=(1+R).sup.2s.sub.n exp(iϕ.sub.n) (26)
where R describes the relative strength of the reflection compared to the direct illumination. Since this prefactor can vary from one sample location to another—it is not completely cancelled out by the typical normalization according to Eq. 9 utilized in the art. However, this prefactor is constant for all demodulation harmonics, provided that they are measured simultaneously. Therefore, the indirect illumination is also contained in the reconstructed background, i.e. σ.sub.rbg∝(1+R).sup.2 and is cancelled out by the normalization to σ.sub.rbg according to Eq. (22). That is, this invention solves another major problem of s-SNOM known in the art.
[0105] In a preferred embodiment, a pseudoheterodyne detection is employed. In another embodiment, high-speed holography as known in the art is employed. In yet another preferred embodiment, phase shifting technique as known in the art is utilized. In an alternative embodiment the quadrature homodyne detection is utilized or any other amplitude- and/or phase-resolved technique that returns harmonics of the demodulated detector signal as known in the art.
Application for Nano-FTIR and Broadband Sources.
[0106] In nano-FTIR measurements a broadband light source is used, whose spectral properties could be described by a complex-valued spectral density S(k), where k=2π/λ is the free-space wavenumber. The detector measures the total power I.sub.det, which is the spectral power at the detector, S.sub.det, integrated over the whole source spectrum:
I.sub.n=∫.sub.0.sup.+∞|S.sub.det(k)|.sup.2dk:
I.sub.n∝∫.sub.0.sup.+∞{S.sub.sca,nS.sub.ref*+S.sub.sca,n*S.sub.ref}dk,for n>0 (27)
where S.sub.sca,n and S.sub.ref are the spectral densities of the total scattered field and the reference, respectively. As before, the reference being much stronger than the scattering is assumed.
[0107] For the nano-FTIR detection, the length of the reference beam is varied linearly by translating the reference mirror and the detector power is recorded as a function of the mirror position. This mirror translation yields a linear shift of the reference beam phase. Thus, S.sub.ref(k)=s.sub.ref(k)e.sup.ikx, where x is the pathlength accumulated due to the mirror translation. The mirror translation is done in such a way that the reference phase variations are much slower than the probe-oscillating frequency, i.e.
By writing Eq. (27) in the complex form we can obtain:
I.sub.n(x)=∫.sub.−∞.sup.+∞β(k)σ.sub.n(k)e.sup.ikxdk (28)
where β(k) is the complex-valued responsivity function that describes the light-source spectral properties and the total optical transmissibility of the system, which are typically not known. The σ.sub.n=S.sub.sca,n/S.sub.in is the complex-valued scattering coefficient (S.sub.in is the spectral power incident upon the tip). This scattering coefficient is the sum of the near-field and background scattering coefficients, σ.sub.n=σ.sub.nf,n+σ.sub.bg,n and can be found using the Fourier transform of Eq. (28):
where [I.sub.det,n](k) denotes the Fourier transform of the detector signal I.sub.det,n(x). As known in the art in nano-FTIR spectroscopy the unknown function β(k) can be removed by normalizing σ.sub.n(k) to that obtained from a reference measurement performed on an area with known optical properties, yielding the nano-FTIR spectrum of the sample material. For sufficiently high demodulation harmonic the background is fully suppressed and the normalization according to Eq. (9) yields:
[0108] As was described before and as it is known in the art, the drawback of this normalization is the necessity of making an additional reference measurement (which sometimes even requires changing the sample) and the susceptibility to various parasitic physical effects as discussed in the art.
[0109] The method of the present invention allows avoiding the necessity of the independent reference measurement. Instead, a background spectrum can be recovered for each spectral component k:
σ.sub.rbg(k)=Σ.sub.nA.sub.nσ.sub.n(k) (31)
and used for the normalization of σ.sub.n(k) according to Eq. (22):
[0110] The coefficients A.sub.n are once again found to ensure the best suppression of the near-field contribution possible with the available data.
[0111] The benefit of the using the reconstructed background as a reference in nano-FTIR measurements is that it intrinsically includes all the noise and power fluctuations happening over the course of measurements of I.sub.n(x) on both slow and fast time scales compared to the sampling rate, thus allowing for its suppression and elimination. In addition, the normalization according to Eq. (32) compensates the “indirect illumination” effects related to the spectral variation of the far-field reflection from the sample surface. For example, when a sample comprises a film with thickness on a micrometer scale, illumination by IR light leads to periodic oscillations in the far-field reflection spectrum due to Fabry-Perot resonances in the film that illuminates the tip. These oscillations are transferred to an through the multiplicative prefactor (1+R).sup.2 in the Eq. (26), which in turn cancels out upon the normalization to σ.sub.rbg.
[0112] In a preferred embodiment a nano-FTIR detection principle is utilized, where the AFM probing tip together with the sample is placed into one arm of an (asymmetric) interferometer and the detector signal is recorded as a function of reference mirror position.
[0113] In an alternative embodiment, a symmetric interferometer with the sample located outside of the interferometer is utilized.
[0114] In a preferred embodiment, the reference mirror is translated linearly and the Fourier transformation is applied to the recorded detector signal to obtain spectra.
[0115] In an alternative embodiment, the reference path length x is modulated harmonically or non-harmonically and the appropriate transformation is applied to obtain the spectrum σ.sub.n(k).
[0116] In an alternative embodiment the time domain spectroscopy (TDS) is used for detection.
[0117] In yet another embodiment the electrooptical sampling (Eisele et al., 2014) or all electronic detection (Liewald et al., 2018) is utilized for the detection of the scattered field.
[0118] In a preferred embodiment a broadband, preferably supercontinuum, laser source is utilized. In another preferred embodiment a synchrotron radiation is used as an illumination source. In yet another embodiment a thermal source, such as glowbar or plasma or laser driven plasma is utilized. In yet another embodiment the radiation from a photoconductive antenna is utilized.
Application to Self-Detection
[0119] The method was illustrated above using s-SNOM setups that have a dedicated detector for recording the tip-scattered light. The same principles, however, can be applied for set-ups that utilize the laser source as a detector itself—so called self-detection s-SNOM (see Giordano et al., 2018). In self-detection s-SNOM setups the laser cavity and the external cavity formed between the laser source and the tip-sample system act as an interferometer that controls the interference pattern in the laser gain medium depending on the length of the external cavity (controlled by a delay stage). In turn, the interference pattern varies the voltage across the gain medium, which serves as the detector. When used with the high-harmonic demodulation technique, the result of the measurements are the demodulation harmonics which can be used to reconstruct the background and further apply the method of this invention described in the context of the interferometric s-SNOM. Importantly, the method applies to both amplitude measurements and amplitude- and phase-resolved measurements, which can be obtained by combining self-detection with e.g. PsHet or high speed holography principles for extracting amplitude and phase of the backscattered signal.
[0120] In a preferred embodiment, a quantum cascade laser is used as the illumination (and detection) source.
[0121] In a preferred embodiment, the length of the external cavity is changed linearly, harmonically or non-harmonically with the corresponding mathematical transformation/filtering to obtain amplitude and phase of the scattered signal.
Application to Non-Interferometric Techniques
[0122] Reconstructing the background from the demodulation harmonics as described above for interferometric s-SNOM could be also beneficial for non-interferometric detection s-SNOM schemes, as demonstrated below. In non-interferometric measurements the detector records the scattering power without reference:
I.sub.det∝|E.sub.sca|.sup.2=|E.sub.nf+E.sub.bg|.sup.2 (33)
[0123] It can be shown, for n>0
u.sub.n∝(E.sub.nf,nE*.sub.bg,0+E*.sub.nf,nE.sub.bg,0) (34)
where we have only retained the strongest background contribution arising from E.sub.bg,0 (see
[0124] This expression is completely analogous to Eq. (6) and can also be rewritten as:
u.sub.n=k.sub.us.sub.nb.sub.0 cos(ϕ.sub.n−ψ.sub.0) (35)
where b.sub.0 and ψ.sub.0 stand for the amplitude and phase of the background demodulated at the 0.sup.th harmonic, i.e. σ.sub.bg,0=b.sub.0 exp(iψ.sub.0).
[0125] Assuming that the ratio between the amplitude of the 0.sup.th harmonic and the 1.sup.st harmonic of the background stays constant for different measurements, the reconstructed background σ.sub.bg is indicative of σ.sub.bg,0 (see Eq. (21)) and the normalization according to Eq. (22) would return η.sub.n such that |η.sub.n|∝s.sub.n, i.e. measures the amplitude of the near-field. It is to be noted that all benefits described in the context of interferometric s-SNOM are also valid, such as the elimination of time-dependent and time-independent parasitic effects.
Extraction of Near Field from Lower Demodulation Orders
[0126] As described in the art, the demodulated signal in lower harmonics is contaminated by the additive background. Since the background is generally unknown, these harmonics (n<2) are usually not utilized for the sample analysis in s-SNOM despite having stronger near-field signal (see
[0127] In a preferred embodiment, evaluation is performed comprising the following 3 steps. At step 1 the reconstructed background is calculated according to step c) of the present invention. At step 2, the reconstructed background is subtracted from the optical signal measured at the first demodulation harmonic. At step 3, the result of step 2 is normalized to the reconstructed background. In an alternative embodiment, the reconstructed background is used to obtain the vertical dependence of the background signal on tip height. Subsequent simulated demodulation returns a more accurate representation of the E.sub.rbg,1, which is then subtracted from E.sub.1 to obtain the near-field contribution E.sub.nf,1. Subsequent normalization according to Eq. (22) eliminates the remaining multiplicative constants.
Types of Illumination Sources
[0128] In the preferred embodiment the illumination source is a source of infrared (IR) radiation. In an alternative embodiment, the illumination is provided by an X-Ray, UV, Visible, Near-Infrared, THz or sub-THz light source. In a preferred embodiment the sources is a tunable single wavelength source. In an alternative embodiment, the source is a broadband source. The inventions applies to continuous-wave (CW) and pulsed light sources.
[0129] In one embodiment the power of the electromagnetic radiation source is harmonically modulated.
[0130] Preferably, the measurements of the dielectric properties of the sample with the method of the invention are performed for a plurality of spatial positions on the sample and/or for a plurality of wavelengths of the electromagnetic radiation.
REFERENCES
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