Research article Topical Sections

Study of oxide/metal/oxide thin films for transparent electronics and solar cells applications by spectroscopic ellipsometry

  • A comprehensive study of a class of Oxide/Metal/Oxide (Oxide = ITO, AZO, TiO2 and Bi2O3, Metal = Au) thin films was done by correlating the spectrophotometric studies with the ellispometric models. Films were deposited by successive sputtering from metallic targets In:Sn, Zn:Al, Ti and Bi in reactive atmosphere (for the oxide films) and respective inert atmosphere (for the metallic Au interlayer films) on glass substrates. The measurements of optical constants n—the refractive index and k—the extinction coefficient, at different incident photon energies for single oxide films and also for the three layers films oxide/metal/oxide samples were made using the spectroscopic ellipsometry (SE) technique. The ellipsometry modelling process was coupled with the recorded transmission spectra data of a double beam spectrophotometer and the best fitting parameters were obtained not only by fitting the n and k experimental data with the dispersion fitting curves as usual is practiced in the most reported data in literature, but also by comparing the calculated the transmission coefficient from ellipsometry with the experimental values obtained from direct spectrophotometry measurements. In this way the best dispersion model was deduced for each sample. Very good correlations were obtained for the other different thin films characteristics such as the films thickness, optical band gap and electrical resistivity obtained by other measurements and calculation techniques. The ellipsometric modelling, can hence give the possibility in the future to predict, by ellipsometric simulations, the proper device architecture in function of the preferred optical and electrical properties.

    Citation: Mihaela Girtan, Laura Hrostea, Mihaela Boclinca, Beatrice Negulescu. Study of oxide/metal/oxide thin films for transparent electronics and solar cells applications by spectroscopic ellipsometry[J]. AIMS Materials Science, 2017, 4(3): 594-613. doi: 10.3934/matersci.2017.3.594

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  • A comprehensive study of a class of Oxide/Metal/Oxide (Oxide = ITO, AZO, TiO2 and Bi2O3, Metal = Au) thin films was done by correlating the spectrophotometric studies with the ellispometric models. Films were deposited by successive sputtering from metallic targets In:Sn, Zn:Al, Ti and Bi in reactive atmosphere (for the oxide films) and respective inert atmosphere (for the metallic Au interlayer films) on glass substrates. The measurements of optical constants n—the refractive index and k—the extinction coefficient, at different incident photon energies for single oxide films and also for the three layers films oxide/metal/oxide samples were made using the spectroscopic ellipsometry (SE) technique. The ellipsometry modelling process was coupled with the recorded transmission spectra data of a double beam spectrophotometer and the best fitting parameters were obtained not only by fitting the n and k experimental data with the dispersion fitting curves as usual is practiced in the most reported data in literature, but also by comparing the calculated the transmission coefficient from ellipsometry with the experimental values obtained from direct spectrophotometry measurements. In this way the best dispersion model was deduced for each sample. Very good correlations were obtained for the other different thin films characteristics such as the films thickness, optical band gap and electrical resistivity obtained by other measurements and calculation techniques. The ellipsometric modelling, can hence give the possibility in the future to predict, by ellipsometric simulations, the proper device architecture in function of the preferred optical and electrical properties.


    1. Introduction

    ITO (Indium Tin Oxide) is a critical raw material mostly used as transparent electrode [1,2,3,4,5,6] in many applications such as plastic electronics, flexible solar cells, screens, etc. The huge development of these technologies and the limited resources of Indium require the replacement or the reduction of the necessary quantity ITO for such kind of applications [7,8,9,10,11,12,13,14,15,16].

    We showed in our previous studies [17] that the quantity of ITO can be divided by four if the ITO films (150 nm) are replaced by ITO (20 nm)/metal (7 nm)/ITO (20 nm) films by maintaining the same figures of merit of the electrodes as that one's of single layer films. Moreover, subsequent studies of Kubis [18] and Berny [19] show the excellent mechanical properties and robustness of these films for large scale applications.

    At present the research on founding alternative transparent conducting films for the replacement of ITO is mostly done by many experimental trials. Ellipsometry is a non-destructive, non-invasive non-contact, very precise, reproducible and very sensitive technique for study the ultra-thin films. Spectroscopic ellipsometry (SE) provides a widely applicable method for determining accurate characterization of optical and electrical transport properties of thin films multi-layers structures, in particularly when the multilayer of device structure, is of critical importance to their effective implementation [20,21].

    However, the difficulty consists to discern between two or more ellipsometric models which both fits well the same data. In the most reported data in literature, the ellispometric models studied are considered enough good if the experimental data of the global refractive index (n) and extinction coefficient (k) fits well with the dispersion curves. Nevertheless we remarked for a large number of our experiments and data, that models which fits well with the experimental data for the global n and k they are not necessarily consistent with the other optical parameters, such as the transmission or reflection coefficient.

    The purpose of this article is to provide a comprehensive study of the spectroscopic ellipsometric measurements of single oxide films and oxide/metal/oxide multi-layers thin film using a two-modulator generalized ellipsometer by continuing the study much further than usual given in literature and by also comparing the calculated the transmission coefficient from ellipsometry with the experimental values obtained from direct spectrophotometry measurements. This procedure allows establishing in a more accurate way the best dispersion model for each sample.

    Given the fact that the characterization of optical and electrical properties of transparent oxide thin films such as ITO, ZnO:Al (Aluminium doped Zinc Oxide—AZO), TiO2, Bi2O3 or multi-layers thin films Oxide/Au/Oxide of the above mentioned oxide is of considerable interest in multiple applications [22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43], we compare the results of multiple techniques for correlating all these properties.

    The good correlations obtained between the electrical and optical properties determined experimentally by different techniques and the electrical and optical characteristics obtained by theoretical ellipsometric simulations, indicate that high accurate ellipsometric modelling approach, can give the possibility in the future to predict the appropriate device architecture in function of the desired optical and electrical properties.


    2. Materials and Method

    The oxide thin films were deposited on glass substrates by sputtering in reactive atmosphere using In:Sn (90%:10%), Zn:Al (98%:2%), Ti and Bi metallic targets from Kurt Lesker and respectively Mateck for the last two. The gold interlayer thin film for the oxide/metal/oxide multi-layers films was deposited in argon atmosphere. The substrates were placed in a vertical target-substrate configuration onto a rotating disk kept at room temperature. The target-substrate distance was of about 70 mm. The deposition parameters are given in Table 1. The deposition rates were 12 nm/min for ITO films, 10 nm/min for AZO films, 7.5 nm/min for TiO2 thin films, 30 nm/min for Bi2O3 thin films and 30 nm/min for gold films. The optimized values of the films thickness were chosen in correlation with literature data and in the range for which we obtained, after many trials, simultaneously good optical and electrical properties. The glass substrate thickness was of 1.1 mm and the refractive index n = 1.52.

    Table 1. Samples deposition conditions.
    Layer Target composition Atmosphere conditions Target–Substrate distance (cm) Deposition current (mA) Pressure (10−2 mbar) Depositiontime (s)
    ITO In 90%, Sn 10% Reactive atm. 7 30 2 160
    Au Au 100% Argon atm. 7 30 1 14
    ITO In 90%, Sn 10% Reactive atm. 7 30 2 160
    ZnO Zn 98%, Al 2% Reactive atm. 7 100 2 160
    Au Au 100% Argon atm. 7 30 1 14
    ZnO Zn 98%, Al 2% Reactive atm. 7 100 2 160
    TiO2 Ti 100% Reactive atm. 7 100 2 160
    Au Au 100% Argon atm. 7 30 1 14
    TiO2 Ti 100% Reactive atm. 7 100 2 160
    Bi2O3 Bi 100% Reactive atm. 7 30 2 160
    Au Au 100% Argon atm. 7 30 1 14
    Bi2O3 Bi 100% Reactive atm. 100 30 2 160
     | Show Table
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    Films thickness measurements were done by profilometry using a Dektak profilometer and as well by ellipsometry. The total thickness of oxide/metal/oxide multi-layer structures ranged between 60 and 300 nm.

    Samples structures were investigated by X-ray diffraction (XRD) using D8 Advance Brucker diffractometer CuKα 1.2 (λ = 1.5406 Å), equipped with a linear Vantec super speed detector and by scanning electron microscopy (SEM) using a JEOL microscope.

    Optical properties studied were made on single layer oxide thin film and also oxide/Au/oxide three layers films. The investigations of optical properties were made by spectroscopic ellipsometry (SE) technique using a UVVISELTM ellipsometer from Horiba Jobin Yvon, with a 75 W high discharge Xe lamp in the spectral range from 260 to 2100 nm. All the spectra were recorded at room temperature, at an incident angle of 70°. The configuration chosen for the modulator (M), analyzer (A) and polarizer (P) positions were: M = 0°, A = 45° respectively. After the relatively fast recording of ψ and Δ spectra, the next step was the construction of an appropriate optical model for the samples in order to fit the experimental values. These investigations were coupled with the recording of absorption/transmission spectra using a double beam spectrophotometer LAMBDA 950 UV/Vis/NIR spectrophotometer in the same spectral range from 260 to 2100 nm.


    3. Results and Discussions

    Figure 1 present the architecture of the studied samples oxide and oxide/metal/oxide deposited on glass substrates and Figure 2 present the SEM micrographs for single oxide layers (named here bottom layer) and then of subsequently oxide layers of the structure oxide/Au/oxide (named top layer). Surfaces are smooth and, generally, small differences were observed between the surface morphology of bottom oxide layer and top oxide layer.

    Figure 1. Studied samples architecture.
    Figure 2. SEM micrograph of oxide single layer (bottom layer) and oxide/metal/oxide samples bottom and top layer: (a) ITO/Au/ITO, (b) AZO/Au/AZO, (c) TiO2/Au/TiO2, (d) Bi2O3/Au/Bi2O3.

    The apparently phase-separation like morphology for the TiO2/Au/TiO2 sample can be attributed to the fact that the top TiO2 film is very thin, much thinner, compared to the other samples, hence due to the scanning electron microscopy penetration depth, the top image of the three layer sample, the partially image of the gold layer can be visible through the top layer. From other analysis like AFM (not shown here), we did not remark significant differences on the morphology of the top oxide layer compared to the bottom layer.

    Figures 3(a–d) show the X-ray diffraction patters of as deposited oxide single layers films and oxide/metal/oxide films. As one can see all single oxide layers are amorphous. The oxide/metal/oxide layers are also amorphous except AZO/Au/AZO sample which shows small peak corresponding to (002) crystalline plane of ZnO zincite (JCPDS card No. 003-0752), this indicating a preponderantly microcrystalline growth with the (002) plane parallel to the substrate surface. For TiO2/Au/TiO2 the peak appearing in the XRD pattern (Figure 3c) corresponds to Au (100) crystalline plane (JCPDS card No. 00001-1172). For Bi2O3 and Bi2O3/Au/Bi2O3 samples, the strongest line corresponds to the (201) plane of the β-Bi2O3 phase according to JCPDS card No. 00-027-0050.

    Figure 3. XRD diffraction patterns for (a) ITO single layer and ITO/Au/ITO three layer sample, (b) AZO single layer and AZO/Au/AZO three layer sample, (c) TiO2 and TiO2/Au/TiO2, (d) Bi2O3 and Bi2O3/Au/Bi2O3.

    In ellipsometry, the variation of the amplitude and the phase difference between the perpendicular (p) and the parallel (s) components of the reflected light polarized, with respect to the plane of incidence, are measured. In general, reflection causes a change in the relative phase of p and s waves and in the ratio of their amplitudes. According to the fundamental equation of ellipsometry the relation between the ellipsometric angles ψ and Δ is given by [44]:

    tanψexp(iΔ)=RpRs (1)

    where, Rp/Rs is the complex ratio of the Fresnel reflection coefficients. ψ—measure the amplitude ratio and Δ—measure the relative phase change.

    The measured ellipsometric spectra are fitted by minimizing the squared difference χ2 between the measured and calculated values of the ellipsometric parameters Is and Ic. Is and Ic are given by:

    Is=sin2ψsinΔ (2)
    Ic=sin2ψcosΔ (3)

    and

    χ2=[1(2NP)]Ni[(IexpsiIcalsi)2+(IexpciIcalci)2] (4)

    where, N is the number of data points and P the number of model parameters [45]. A fit is considered enough good if χ2 < 10. Ellipsometry is an indirect method. The difficulty is that one that is not sufficient to obtain a good fit of ψ and Δ spectra with very low values of χ2. Many dispersion models can fits well and the difficulty is to know what model is the most suitable. That means that once a model is tested and a good fit is obtained the results should be compared with other data measurements and the model should be improve until a good coherence between all the data is obtained. For this reason we conduct our study furthermore than usually presented in literature, by comparing the transmittance spectra calculated from ellipsometry with the transmittance spectra obtained by direct measurements from spectrophotometry.

    The refractive index and extinction coefficient for a bulk (substrate) material are related to ψ and Δ by the following formula and can be calculated directly by separating the real and imaginary part of this equation and solving the two equation system [46].

    ˜ε=ε1+iε2=˜n2=(n+ik)2=sin(θ)2[1+tan(θ)2(1tan(ψ)eiΔ1+tan(ψ)eiΔ)2] (5)

    The DeltaPsi2 software of Horiba Jobin Yvon allows to fit the spectra of ψ and Δ, Is and Ic by minimizing the values of χ2. The software calculates also a "global" refractive index and a "global" extinction coefficient of the samples including the substrate + layer (s) and allows to calculate the global transmittance (T%) and reflectance (R%). The individual refractive index, n, and individual extinction coefficient, k, for each layer should be extracted from the model on the basis of the dispersion formula which gives the best fit.

    The direct measurement of n and k on the basis of Eq. (5) can be compared with the theoretical values given by the known dispersions models (Adachi-Forouhi, Cauchy, Tauc-Lorentz, Kato-Adachi, Sellmeier, etc.) of different materials from the data basis of the DeltaPsi2 software, and good fits between the measured n and k and calculated n (n-fit) and k (k-fit) can be obtained, for more than one dispersion model.

    The theoretical spectral transmittance (T) and reflectance (R) of a thin film deposited on a substrates are functions of n, k, d and λ, where d is the film thickness and λ the wavelength of incident light. The certainty of the appropriate model is achieved when the calculated values T, R and d coincides with the direct measured values of Tex, Rex and dex, from spectrophotometry for Tex, Rex and profilometry, SEM or other methods for dex [47]:

    T(n,k,d,λ)=Tex
    R(n,k,d,λ)=Rex
    d=dex (6)

    Figure 4 depicts the experimental and best fitted spectra of ψ and Δ and Figure 5 gives the experimental and calculated values for the "global" refractive index for all the samples: single oxide layers and three layers oxide/metal/oxide films deposited on glass substrates. The optimization of the models was done by comparing the calculated transmittance coefficient from ellipsometry model with the experimental values obtained from spectrophotometry (Figure 6). From curves given in Figure 4 and Figure 5, we remark a very good fit between the calculated data (lines) and experimental values (dots) but the optimization was done on the basis of successive comparison with the transmittance spectra obtained by spectrophotometry. Figure 6 presents the best fits of the calculated transmittance spectra from ellipsometry with transmittance spectra obtained by spectrophotometry.

    Figure 4. Best fits between the experimental measurements of ellipsometric angles and (dots) and calculated values (line) using the ellipsometry models given in Figure 7.
    Figure 5. Samples global refractive index n, for single layer oxide on glass and three layers oxide/metal/oxide layers on glass substrate (experimental—dots and fit—line).
    Figure 6. Transmission coefficient from spectrophotometric experimental data and ellipsometric calculations models for single and three layers samples.

    If the thickness d of a film, its refractive index n, and extinction coefficient k are known, it is possible to derive its reflectance R and transmittance T. Basic equations have been derived by Heavens [48] and are detailed for a single layer on a substrate of refractive index n1 and extinction coefficient k1 in [49]. In the same way calculations can be made for samples with multiple layers. A computer solution can also be carried out by successive approximations using Newton's method [3,49,50]. The DeltaPsi2 software allows such calculations and gives the values of the transmission and reflection coefficients.

    Figure 7 indicates the dispersion models used in each case. The formulas of dispersion models are: based on the sum of the single and double Lorentz and Drude classical oscillators for ITO films, in agreement with [51,52,53]:

    ε=ε+(εsε)ω2tω2tω2+iΓ0ω+ω2pω2+iΓDω+2j=1fjω20jω20jω2+iγjω (7)
    Figure 7. Ellipsometric models.

    In agreement with [54] the best dispersion model founded for Al:ZnO doped films corresponds to Kato-Adachi dispersion model:

    ε=ε+ε1+ε2+ε3+ε4
    ε1=A0E1.5021+χ1χχ2
    ε2=B1ξ2ln(1ξ2)
    ε3=B1XE1EiΓ1
    ε4=C1(EE2)2iEE2Γ2
    χ=E+iΓ0E0 (8)

    The new amorphous dispersion formula for TiO2 is a rewriting of original Forouhi-Bloomer formula [55]:

    n(ω)=n+B(ωωj)+C(ωωj)2+Γ2j
    k(ω)={fj(ωωg)2(ωωj)2+Γ2j,ω>ωg0,ωωg

    where

    B=fjΓj[Γ2j(ωjωg)2]
    C=2fjΓj(ωjωg) (9)

    Tauc-Lorentz for Bi2O3films [50,51]:

    ε=ε1+ε2where:
    ε2={1EAE0C(EEg)2(E2E20)2+C2E2,E>Eg0,EEg
    ε1=ε+2πPEgξε2(ξ)ξ2E2dξ (10)

    Drude:

    ε=ω2pω2+iΓDω (11)

    The dispersion models parameters corresponding hence to the best fit of the experimental data are given in Tables 2Tables 6.

    Table 2. Ellipsometric fitting parameters for ITO films.
    Sample Layer ITO/Dispersion model: double Lorentz + Drude χ2
    ε εs ωt ωp Γ0 Γd
    ITO 2.21 3.08 5.45 0.51 1.64 -0.37 4.57
    ITO/Au/ITO 2.23 3.38 3.96 1.85 6.64 0.60 7.35
     | Show Table
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    Table 3. Ellipsometric fitting parameters for AZO films.
    Sample Layer AZO/Dispersion model: Kato-Adachi χ2
    ε E0
    (eV)
    A0
    (eV)
    Γ0
    (cm−1)
    E1
    (eV)
    B1
    (eV)
    B1·X Γ1
    (cm−1)
    E2
    (eV)
    C
    (eV)
    Γ2
    (cm−1)
    AZO 4.86 2.09 20.70 1.08 3.71 1.78 0.33 0.26 6.65 3.72 −0.48 1.42
    AZO/Au/AZO 1.54 3.31 13.05 −0.001 3.49 0.15 0.59 0.37 5.90 2.53 2.38 3.98
     | Show Table
    DownLoad: CSV
    Table 4. Ellipsometric fitting parameters for TiO2 films.
    Sample Layer TiO2/Dispersion model: New Amorphous χ2
    n ωg fj ωj Γj
    TiO2 1.18 3.58 0.91 3.95 0.80 0.56
    TiO2/Au/TiO2 1.59 3.67 0.56 4.85 0.89 3.51
     | Show Table
    DownLoad: CSV
    Table 5. Ellipsometric fitting parameters for Bi2O3 films.
    Sample Layer Bi2O3/Dispersion model: Tauc-Lorentz χ2
    Osc. Eg (eV) ε A (eV) E0 (eV) C (eV)
    Bi2O3 1 3.08 2.60 120.13 3.68 1.54 15.39
    Bi2O3/Au/Bi2O3 1 3.17 2.48 138.39 3.79 1.67 6.38
     | Show Table
    DownLoad: CSV
    Table 6. Ellipsometric fitting parameters for Au films.
    Sample Layer Au/Dispersion model: Tauc-Lorentz + Drude χ2
    Osc. Eg (eV) n A (eV) E0 (eV) C (eV) ωp (cm−1) Γ (cm−1)
    ITO/Au/ITO 1 3.16 2.4 −958 3.06 0.26 14.18 −35.56 7.35
    2 182 2.25 11.45
    3 32.96 −518 −4374
    AZO/Au/AZO 1 1.96 1.9 15.65 4.22 0.92 7.42 3.12 3.98
    2 −148.89 2.11 12.50
    3 3.56 3.84 0.33
    TiO2/Au/TiO2 1 2.26 2.01 233.51 2.27 0.203 6.10 0.172 3.51
    2 94.25 2.14 12.52
    3 −74.47 −3.41 27.85
    Bi2O3/Au/Bi2O3 1 1.60 3.16 8.14 1.65 −1.06 5.29 0.10 6.38
    2 279.50 2.12 12.65
    3 40.59 3.92 −4.23
     | Show Table
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    Table 7 gives the thickness values for single and three layer samples. We remark a good correlation between the values obtained by profilometry and ellipsometry for the samples for which the transmission curves in Figure 6 (ITO/Au/ITO, AZO and Bi2O3) obtained by the two techniques are closer.

    Table 7. Thin films thickness values determined by profilometry measurements and ellipsometry calculations.
    No. Sample d (nm) profilometry d (nm) ellipsometry χ2
    1 ITO 45 ± 2 86 ± 2 4.57
    2 AZO 40 ± 2 46 ± 3 1.42
    3 TiO2 25 ± 2 17 ± 3 0.56
    4 Bi2O3 120 ± 2 124 ± 2 15.39
    5 ITO/Au/ITO 45 ± 2/7 ± 2/45 ± 2 45 ± 2/9 ± 2/43 ± 3 7.35
    6 AZO/Au/AZO 40 ± 2/10 ± 2/40 ± 2 27 ± 1/14 ± 2/22 ± 1 3.98
    7 TiO2/Au/TiO2 30 ± 2/7 ± 2/30 ± 2 21 ± 8/3 ± 2/16 ± 3 3.51
    8 Bi2O3/Au/Bi2O3 120 ± 2/10 ± 2/120 ± 2 141 ± 3/7 ± 1/149 ± 2 6.38
     | Show Table
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    As confirmed, ellipsometry analysis is performed from fitting using an optical model. Nevertheless, an optical model used in ellipsometry analysis simply represents an approximated sample structure, and obtained results are not necessarily correct even when the fit is sufficiently good. This is the greatest disadvantage of the ellipsometry technique and accordingly, ellipsometry results must be justified by using other measurement methods [50]. The novelty of this paper consist in refining the modelling of optical properties by additionally fitting the transmission coefficients by two different techniques, moreover than the usual method presented in literature, which consist only on the fit of experimental ψ and Δ angles. By this deeper analysis of the optical models we can see that even after refining by this procedure and very good fits of ψ and Δ angles, or effective n and k coefficients, the fits for transmission coefficients by comparing the data from ellipsometry and spectrophotometry are not perfect. The differences observed between the transmission coefficient curves obtained by ellipsometry calculations and direct spectrophotometry measurements in Figure 6. for ITO, TiO2 or Bi2O3/Au/Bi2O3 are coherent with the differences observed between the thickness values measured directly by profilometry and those calculated from ellipsometry and indicate the limits the optical models. However, once an analytical method is established, it becomes possible to perform high-precision characterization using spectroscopic ellipsometry. From this study, it can be considered that a good optical model can be established when the calculated curves of transmission coefficient obtained by ellipsometry coincides with the experimental values obtained by spectrophotometry and not only when good fits between experimental data and calculated values are obtained for the angles ψ and Δ angles, or effective n and k coefficients. The parameter which is most critically subject of errors, in the case of ellipsometry models calculations, is the films thickness, especially in the case of very thin films.

    The dispersion curves of n and k of single layer oxides were extracted from these models and depicted in Figure 8.

    Figure 8. Refractive index and extinction coefficient for single oxide films.

    The obtained values are in good agreement with the data obtained by other authors for ITO [56], AZO [57], TiO2 [58] and Bi2O3 [59].

    The absorption coefficient was calculated using the formula [3]:

    α(λ)=1dln[1R(λ)T(λ)] (12)

    The plot of (hνα)n versus photon energy gives information about energy of the indirect (n = 1/2) or direct transitions (n = 2), respectively. By using the Eq. (12):

    α(hν)=Ahν(hνEg)1/n (13)

    For the direct allowed transition, (hνα)2 versus photon energy, was plotted for ITO and AZO (Figure 9a and 9b). The intercept on the abscissa gives the value of the direct band gap [3]. The optical band gap values obtained (eV) are very close to the values quoted in literature [3,9].

    Figure 9. Optical gap calculations from spectrophotometry measurements.

    The values for indirect band transitions for TiO2 [60] and Bi2O3 [61] were determined from the linear extrapolation of (hνα)1/2 = f (hν) curves towards the intersection with the x-axis (Figure 9c and 9d).

    The values of the optical band gaps determined from spectrophotometry data and ellipsometry calculations are given in Table 8. Good correlations between the calculations by the two methods were obtained.

    Table 8. Oxide thin films optical band gap values determined by spectrophotometry measurements and ellipsometry calculations.
    No. Sample Eg (eV) Spectrophotometry Eg (eV) Ellipsometry
    1 ITO 3.80 4.20
    2 AZO 3.48 3.48
    3 TiO2 3.20 3.58
    4 Bi2O3 2.81 3.08
     | Show Table
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    Single oxide layers films are high resistive due to the size effect as a consequence of their low thickness. The oxide/Au/oxide films have a good electrical conductivity due to the Au interlayer film. The electrical resistivity is of 8 × 10−4 Ω·cm for ITO/Au/ITO, 2 × 10−3 Ω·cm for AZO/Au/AZO, 7 × 10−3 Ω·cm for TiO2/Au/TiO2, 3 × 10−2 Ω·cm for Bi2O3/Au/Bi2O3.

    The total (sheet) resistance of the multi-layer is a combination of the resistances of three consecutive layers [62]:

    1R=1Rox+1Rm+1Rox (14)

    Hence:

    R=RoxRmRox+2Rm=Rm1+2RmRox (15)

    If we note p = Rm/Rox

    R=Rm1+2p (16)

    Generally Rox>>Rmp0

    RRm (17)

    According to Drude's theory in metals the plasma frequency is given by [63]:

    ω2p=4πne2ε0εme (18)

    where n is the carriers concentration, me* is the effective mass of charge carriers, ε and ε0 represent the dielectric constants of medium and free space. On the other hand the electrical conductivity is given by:

    σ=ne2τme (19)

    where τ is the mean value of the relaxation time, hence from the Eq. (18) and Eq. (19) it results that:

    ω2p=4πσε0ετ (20)

    Figure 10 presents the values of ω2p obtained from the ellipsometric models (see Table 6) in function of the measured electrical conductivity in direction parallel to the substrate for the oxide/metal/oxide samples. We remark a linear dependence in agreement with Eq. (20). The resistance of single oxide layer of TiO2 and Bi2O3 is higher than the resistance of individual ITO an AZO layers. In conclusion, the condition Rox >> Rm is better verified for TiO2/Au/TiO2 and Bi2O3/Au/Bi2O3 which is coherent with the fact that for these samples the points (ω2p,σ) are closer to the linear dependence expressed by Eq. (20).

    Figure 10. The values of ωp2 (ωp = 2πfp, fp—plasma frequency) obtained from the ellipsometric models (Table 6) in function of the measured electrical conductivity in direction parallel to the substrate for the oxide/metal/oxide samples.

    4. Conclusions

    A complete study of the optical and electrical properties of single oxide layer and oxide/metal/oxide (Oxide = ITO, AZO, TiO2 and Bi2O3, Metal = Au) three layers was done by spectrophotometry, ellipsometry and four probe electrical measurements. At our best knowledge, the multi-layer structure Bi2O3/Au/Bi2O3 was studied for the first time. Oxide films were deposited by reactive sputtering and all are amorphous and have a transmission coefficient higher than 80%. The improvement of the developed optical models was done by refining the fittings, not only, between the measured and the calculated values for the ψ and Δ angles, but also by comparing the calculated values of the transmission coefficient from ellipsometric models with the experimental values of the transmission coefficient determined from spectrophotometry, and also by other correlations of specific parameters measured by other methods. This procedure allows to better establish the validity of the different optical models in function of the correlations obtained for different thin films characteristics such as the films thickness, transmission coefficient, optical band gap and electrical resistivity obtained by different techniques. The best dispersion models for n(λ) and k(λ) were hence established by the correlations of data obtained by spectrophotometry and ellipsometry. The global and individual refractive index and global and individual extinction coefficients were calculated. This approach also shows how the ellipsometric modelling can be improved, with maybe the possibility, in the future to predict, by ellipsometric simulations, the suitable device architecture in function of the desired optical and electrical properties.


    Conflict of Interest

    The authors declare that there is no conflict of interest regarding the publication of this manuscript.


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