Infrared optical oscillation response from Nb on SiO2 ultrathin films

R. Villagómez

CICESE Campus Monterrey. Ángel M. Villarreal 425 Col. Chepevera, C.P. 64030 Monterrey, N. L. México. CP 64030
rvillago@cicese.mx

Abstract: Observation of oscillations in the infrared reflectance from Nb ultra thin films deposited on α-type
SiO2 substrates are presented in this letter. P-polarized reflectance (Rp) measurements are made using a tunable p-
polarized CO2 waveguide laser using wavelengths from the p-branch (9.4 to 9.7)µm. and R-branch (10.0 to
10.4)µm. Nb/SiO2 ultra thin films were assembled by a conventional RF sputtering technique and tailored
thicknesses were deposited from 5.5 to 55Å. Because of the strong influence from the chosen substrate, IR
reflectivity was fitted to the optical response of our metal-substrate system by using the three-oscillator model and
numerical calculations on the basis of the local field calculation for a single metallic quantum well. Although
quantum size effects are well studied in semiconductor compounds, there are only few studies of this effect in
metallic films where the present investigation has its most important contribution.

Key words: Thin films, optical properties, Surfaces

PACs: 78.66.-w ,78.20.-e

1. Introduction
When a metallic thin film has a very small thickness in one direction, say the z direction, the classical Fresnel formalism breaks
down and its optical properties has to be analyzed within a quantum mechanical scheme. The component of the electron wave
vectors in the z direction becomes quantized, giving rise to Quantum Size Effects (QSE) mainly observed as fine oscillations
superimposed on the optical (reflectance, transmission, absorption or electrical dc-conductivity) response of the system under
investigation. In the making of thin or ultra thin films on insulating or semi-insulating substrates (SiO2, Si, etc.), it is well known
that, as a rule, metallic films grow by building up three dimensional nuclei (so called islands) for thicknesses less than a critical
value, say: d* where thin films do not become continuous before reaching the right value, d*, which strongly depends upon the
chosen metal [6], the substrate condition, and evaporation process used to form the thin film. At first sight, QSE fail to be
observable when the average substrate surface roughness has a large scale, therefore we carefully select substrates with low scale
surface roughness. In 1966, Ogrin [1] reports, the observation of the so-called QSE for electrons in Bi films. In that report, Ogrin
study the thickness dependence of Bi films resistivity (ρ) with temperature. Although Bi films thicknesses were in the range from
20 nm to 160 nm (thick classical films), he was able to foresee oscillations in his results and named them as: Quantum Size Effects.
Later on Alieva [4] published the first experimental evidence of the reflectivity fluctuations on metallic ultrathin films, where he
reports an oscillatory behavior with an oscillating period of about 6Å at λ~10µm. Short after, Silberberg [5] reported the first
calculations on the optical properties of metallic quantum wells using the simple square well model. In his studies, he calculated the
absorption coefficient, choosing an external driving field frequency in such a way that only interband transitions were allowed.
As reported by Alieva, on the fact that the optical conductivity and DC conductivity of Nb super-thin films exhibit an
oscillatory behavior with an oscillating period of about 6Å at λ~10µm. In contrast to our experimental results, they measured the
oscillations and obtained a period value quite larger to our present results. The most recent work from Rogacheva, et. al.[10] reports
oscillations of the transport properties associated with quantum size effects due to electron confinement in the PbSe ultrathin films
so called “quantum wells”. In what follows we will present results of QSE observed, as fine oscillations in the infrared reflectance
spectra from Nb quantum wells. Also, we observe how the corresponding peaks and valleys of the oscillations are preserved on both
quantum well spectra while these oscillations are completely absent for the bare substrate experimental spectra as predicted on the
basis of a self-consistent local field calculation, as reported by Keller and Liu [7] for the case where only intraband transitions
(diamagnetic case) dominate (see Fig. 1a solid line). Although it is not our main purpose to discuss theoretical considerations (for
details see [7]), the aforementioned numerical calculations are made to show there might be a good correlation with our
experimental findings under this theoretical assumptions.

1
2. The Nb quantum well

Having a Nb film between two identical barrier layers [7,8] guarantee a symmetric square well. In this situation we shall
assume the conduction electrons of the Nb film are placed in a one-dimensional square well potential of height -Vo= -9.31 eV, εF =
5.32 eV (the Fermi energy) and d as the film thickness. Under this scheme, conduction electrons exhibit free particle behavior in the
x-y plane. For the QW bound states (E<0), and using the low temperature limit [7], the appropriate conduction-electron density in a
quantum well can be written as [7]:

M 2

∑ ϕ ( z) ( ε - ε n )Θ(ε F - ε n )
m
n( z) = , (1)
π h2 n
n F

where ϕn and εn are the wave functions and the energy Eigen values of the n´th state and Θ is the Heavyside step function. The
summation in (1) runs over the occupied Eigen states of the well. M is the upper most bound at which the summation is truncated.
The Nb/QW energy eigenvalue spectrum of the bound states is calculated by solving the transcendental equation:

2
⎛ k⊥ ⎞
cos 2
( 1
2 k ⊥ d) = ⎜ 0 ⎟
⎝ k⊥ ⎠
, (2)

1 2
and k = ⎡ 2m (ε + V )⎤ , the plus sign inside the square root is due to we are considering negative V0. Once the
1 2
with k0 = ⎛⎜ 2mV0 ⎞⎟
⊥ ⊥ ⎢ h2 n 0 ⎥
⎝ h ⎠
2
⎣ ⎦
energy Eigen values are calculated, the wave functions may be obtained [7]. From the fundamental integral equations of the local
field in a quantum well [7], it immediately appears that, for the p-polarized local field, the reflection coefficient is given in terms of
its correction factor Kxx as:

rp − Kxx
~
rp = , (3)
1 − Kxx
with

e 2τ q⊥o (1 − rp )n( z )
K xx = . (4)
2i mε oω (i + ωτ )

∫ ϕ ( z ) dz = 1 due to the normalization of the wave functions for all n. Here, the wave vectors
2
In eq. 4, one takes the integral
QW

[
are given as: q ⊥o = (ω c0 ) 2 − q||2 ] with q|| = (ω c0 ) sin θ and θ the angle of incidence. From eq. 4 one can see that the only fitting
1 2

parameter can be the relaxation time τ because of its phenomenological nature.

3. Substrate considerations

The optical properties for silicon dioxide (SiO2) type α (crystalline) or glass are well established in many papers and
handbooks, nevertheless, there may exists deviations from experimental data and the optical constants reported. To be self-
consistent with our real time measurements one ought to find experimentally the optical properties for the substrate in use. In order
to be reliable with the fitting procedure, the first step forward is the collection of data to determine the optical constants from the
substrate. The main concern here is the substrate optical response dielectric function ε( ω) which can be written for a system of N
oscillators by the Four-Parameter Semi quantum (FPSQ) model described by Gervais et al. [2], as:

2
 Ω2jLO − ω2 + iγ jLOω
ε( ω) = ε∞ ∏ , (5)
j Ω2jTO − ω2 + iγ jTOω

where ω is the applied field frequency, Ωj and γj are the corresponding frequencies and damping constant for the longitudinal and
transverse optical modes in the crystal. The fundamental goal here is to find their values to fit the experimental reflectivity spectra
in the range of frequencies used. Table 1 shows, the appropriate values that fit our actual “bare” substrate used in our experiments.
For p-polarized laser radiation taken for the frequency range of 9.2 µm to 10.4 µm and taking the high-frequency dielectric constant
as: ε∞ = 2.383, the following fit parameters shown in Table I, were obtained.

Table 1 Parameters used to fit the reflectivity spectra (p-polarization) for SiO2, using three oscillators.

Transverse modes Longitudinal modes

j ΩjTO (cm-1) γjTO (cm-1) ΩjLO (cm-1) γjLO (cm-1)

1 480.2 10.1 569.5 8.7

2 776.7 6.8 792.2 18.1
3 1069.9 65.5 1223.2 12.1

Figure 1 underline the reflectance spectra for our calculated values using the local field calculations as described above. For
these calculations we use SiO2 (α-type) as substrate upon which the growth of the Nb took place. In our calculations, the external
field was p-polarized at wavelength range from 7.6 µm to 10.6 µm incident to an angle of θ = 7°. The model program was written in
FORTRAN code using the MS Power Station software.

0.5

70 Å
0.3
Rp

0.2 45 Å

30 Å
0.1
10 Å

5Å

0Å
0.0
7.6 8.1 8.6 9.1 9.6 10.1 10.6
λ (µm)

Fig. 1. Wavelength dependence reflectance spectra for Nb/QW using the local field calculation for thicknesses from 5Å to 70Å. Thickness
d=0Å represent the bare substrate. The calculations are based on the substrate fitting parameters shown on table I

4. Experimental results and discussion

In order to have a symmetric quantum well structure, the fabrication process is set to include two barrier layers, one between
the substrate and the metal ultra thin film and another on the top of it. We have seen experimentally that these barrier layers do not
affect R, therefore the geometry for a square well potential is still valid. Performing a deposition test for the barrier layers (Al2O3)
and the metal ultrathin film, we controlled the quantum well deposition rate. The results from this preliminary test show an error of
less than 5% on the deposition rate for the samples. The procedure, for the quantum well preparation, has been described earlier by
Villagómez et al.[9]. Our optical setup includes a tunable CO2 laser from Edinburgh Instruments, a Soleil-babinet compensator,
along with a ZnSe polarizer with a 45o retarder. Bandwidth resolution for our scanning IR optical setup is about ∆ν = 1.256 x 105
THz which is experimentally measured. Pyroelectric detectors for our normalized measurements where designed to be integrated to
a lock-in amplifier (Stanford Research). All the system was computer controlled along with a stepper motor with a mechanical
3
transmission of 1:1000 ratio directly put to scan the laser wavelengths of the laser and a second stepper motor to scan sample-to-
sample into the working area. Quantum well preparation was accomplished by using the RF-Sputtering technique with a
SPUTRON-II system from Balzers Inc. SiO2 substrates were carefully selected with a small surface roughness scale. The symmetric
quantum wells are produced using Al-oxide (Al2O3) as barrier layers. To determine the deposition rate of the barrier layers (Al2O3),
a sapphire target was RF-sputtered for about 40 minutes. Thereafter its thickness was measured by ellipsometry with an accuracy of
1Å. The same procedure, as mentioned for the barrier layers, was used to determine the Nb layer deposition rate. The time taken for
deposition of these metallic films was 80 minutes and their thickness was measured using an interference microscope with an
accuracy of 5%. The RF-power on the targets was 200 Watts having high stability on the rate of deposition during the whole
process. With this technique, a set of 15 individual ultrathin films made for thicknesses between 5.5Å and 55.0Å. Measurements of
the reflection coefficient for niobium ultrathin films were made at room temperature. The optical constants for the substrate have
been estimated by using the FPSQ model. The fitting parameters are the transverse and longitudinal mode frequencies and damping
factors as given in Table I. In this case, measurements of the bare substrate reflection coefficient were taken with wavelength
dependence. Although fitting experimental data could be done, there are wavelength gaps between the actual regular lasing bands
from the CO2 laser. This situation may lead to a bit of uncertainty in our results but still there is enough data generated in this actual
wavelengths windows to be able to fulfill the conditions for evaluating the Fourier transform using these data to have the oscillation
period within a true experimental sureness to perceive the oscillating structure on R for the Nb/SiO2 quantum wells. To be
consistent in our measurements, we collect experimental reflectance values from bare substrates where we could notice a smooth
curve following, with high accuracy, the calculated tendency from the local field calculation. The model value for the metallic thin
film thickness was set to d=0 Å, representing the bare substrate. No oscillations were seen. Figure 2 depicts the Nb/SiO2
wavelength reflectivity response for our Nb ultrathin films. Solid lines in Figure 2a and 2b are the fit obtained by using the
formalism described in previous sections (see fig. 1) and the use of the relaxation time τ, from equation 4, as a phenomenological
fitting parameter. The best fitting value found here was τ=0.97 fs.
Next, as shown in Figure 1, we calculate the local field, as in reference 3, using the numerical calculations on the Nb/SiO2 QW
presented by Keller and Liu [7]. The difference between Keller and Liu calculations and the presented here is that we use real time
experimental data to model the optical response for our experimental substrate (see Figure 1).This explains why the maximum value
for R is not larger than the 50% of that of Keller and Liu. Both calculations revels the convergence of the reflectivity around 9.2
µm. The experimental error was measured to be less than 2% Therefore, all measurements represented in figure2, are depicted using
symbol size of the order of the error bar. As an achievement, a systematic oscillatory behavior observed by repeated measurements
for this 55Å ultrathin film is clearly seen. Also, we could be able to see these oscillations from other samples made for different
thickness film, for which we will discuss elsewhere. Followed by repeated systematic measurements, it was observed that the
reflectivity, from each individual ultrathin film, follows the same up and down tendency, with a slight change on the local
amplitude. This suggests evidence for the existence of periodic oscillations when wavelength dependence measurements are
performed in the IR region. These oscillations are considered to be due to quantum size effects even when they may have different
natural precedence. Reflectivity spectra was taken for Nb thickness d: 0 (Substrate), 5.5, 6.5, 7.2, 8.8, 10.5, 12.1, 13.2, 13.8, 15.4,
16.5, 19.8, 23.1, 26.4, 27.7 and 55 Å. As a permanent remark, one has to bare in mind the existence of a critical thickness d* for a
metal, in the case for Nb, d*~32Å [6]. Therefore, for our 5.5Å sample, we can state that QSE come from an amorphous film while
for our 55Å sample, QSE come form a “quasi-isotropic” one. Isotropic Nb films are considered with metallic thin film thickness
larger or equal to approximately 300Å where QSE are completely smeared out.

a) b)
0.5 0.36
τ = 0.97 fsec

0.32
τ = 0.97 fsec
Rp

0.28
Rp

0.4

0.24

0.2
0.3 10.18 10.22 10.26 10.3 10.34
9.46 9.5 9.54 9.58 9.62
λ (µµ) λ(µm)

Fig. 2 Experimental reflectance optical response for a 55Å Nb/QW deposited on a Si02 substrate. Solid line in a) and on b) are the calculated
Rp by using the FPSQ model and the local field calculation with the relaxation time τ = 0.97 fs.

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 To go with for our final discussion here, we extend our conducting measurements by analyzing the reflectivity spectra with
thickness dependence. In this case, the set of Nb ultra thin films were tailored only for thicknesses values less than d* for Nb [8].
For this purpose, we collect the reflectivity spectra for the following well thickness d: 0 (Substrate), 5.5, 6.5, 7.2, 8.8, 10.5, 12.1,
13.2, 13.8, 15.4, 16.5, 19.8, 23.1, 26.4, 27.7 and 55 Å. Figure 3 shows the reflectivity spectra as measured for λ = 9.526µm. Open
symbols represent the averaged over 30 measurements on each experimental data point while the solid line is an interpolation for
those points. One interesting result is the periodic oscillatory behavior, previously reported [4] where the fact that the optical
conductivity and DC conductivity of Nb super-thin films exhibit an oscillatory behavior with an oscillating period of about 6Å at
λ~10µm. In our results these oscillations are evident, and after some data processing, using data interpolation and discrete Fourier
transformation, the period of the reflectivity is found to be PNb/SiO2 = 2.7Å.

0.46

0.44

0.42
Rp

0.40

0.38

0.36
5 10.75 16.5 22.25 28
d (Å)

Fig. 3. Thickness dependence reflectance for Nb/QW. Solid line is drawn to guide the eye and amplify the oscillatory behavior on the Rp
spectra. Reflectance values are normalized to 1 and the set wavelength to λ = 9.526µm.

5. Conclusions

We have shown that systematic oscillation in the IR optical response from Nb ultrathin films are clearly observed. These
oscillations may be attributed by quantum size effects (QSE) in ultra thin metallic films of Nb deposited on SiO2 substrates are seen
as pronounced fine oscillations in the reflectance spectra at the infrared spectral region. In addition to previous results, we have
measured the Nb/QW oscillation period as PNb/SiO2 = 2.7Å, which in turn have to be taken into account for having the correct value
of the dielectric constant of Nb/QW. We did model, upon our experimental data, the substrate optical response dielectric function
ε( ω) using the most general form for a system of N-oscillators by the Four-Parameter Semi Quantum (FPSQ) model. It has also
been shown that QSE exist in a well-defined fashion for metallic quantum wells by experimental evidence on the p-polarized IR
reflectivity with wavelength dependence. Although, on the basis of the local field calculations, QSE can not be modeled, it is clearly
shown, indeed, that the local field reflectance calculations follow up the experimental data without the oscillations. As a final
remark the generalized behavior of the optical response of the Nb/SiO2 quantum wells is very influenced by the optical response of
the substrate, here we claim the convergence of the wavelength dependence reflectivity to the chosen substrate resonance at
9.201µm.

References
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8. R. Villagómez , Ph. D. Thesis, Institute of Physics, Aalborg University 1996.
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