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8 ARTICLE
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11 Complex dielectrics transformation of UV-vis diffused reflectance
12
13
spectra for estimating optical band-gap energies and materials
14 classification
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Received 00th January 20xx,

15 Accepted 00th January 20xx
16 Prince George and Pradip Chowdhury*a
DOI: 10.1039/x0xx00000x
17
In this work, a complex dielectrics transformation of the UV-vis diffused reflectance spectra is proposed to estimate the
18

Analyst Accepted Manuscript

www.rsc.org/
optical band-gap energies of an array of materials classified as semi-conductors, conductors and insulators and the results
19
are compared with the more common Kubelka-Munk (K-M) transformation. The results show a close match between the
20
proposed method and the Tauc model based on K-M transformation within ca. 0.16-7.07% variation. The proposed
21
method based on well established dielectrics transformation is unique in a way to estimate band-gap energy when there
22
remains unresolved or multiple absorption peaks in the diffused reflectance spectra. Importantly, the complex dielectrics
23
transformation method as well distinguishes the class of the materials which is paramount important to validate and
24
substantiate the band-gap energy values.
25
26 model, but with percentage error of 20%10. However, if the
27 Introduction absorption peaks are not well resolved, even the use of
28 secondary derivative does not assure the exact approximation
29 The most fundamental parameter that classifies a
of band gap energy which might lead to inaccurate conclusions8.
30 semiconductor material is its optical band gap energy (Eg). The
In dielectrics transformation, the optical constants such as
31 simplest and commonly used technique employed is UV-vis
refractive index (n), extinction coefficient (k) and reflectivity of
32 diffused reflectance spectroscopy (DRS), a non-destructive
a semiconductor material can be converted into functions with
33 method for band gap determination. Band gap engineering is a
the real and imaginary parts of the complex dielectric function
34 powerful technique for the design of new semiconductor
(ε) with spectral dependence11. This enables comparison with
35 materials, finding various applications in solid state devices1,2 to
models of classical dipole oscillators and the approximated
36 photo catalysts3,4. Two important mathematical models have
oscillator characteristics fits well for entire bulk material as its
37 been formulated for the determination of band gap energy: The
spatially independent7,12. Even though some literature studies
38 Tauc model and Cody model. Both of these models take into
have reported 200% error in using the imaginary part of
39 account the density of states (DOS) of the material being
refractive index to determine the absorption coefficient due the
40 responsible for the spectral dependence of the absorption
action of the incident light beam10 and subsequently various
41 coefficient5,6. The assumption that the optical matrix has
corrective methods to minimize the errors in diffused
42 constant elements (in case of Cody model), the dipole elements
reflectance studied have been proposed in published
43 in the optical matrix is independent of photon energy while in
literature13. Various empirical relations have been correlated
44 the Tauc model, the momentum elements is independent of
with the resonance frequency of oscillators with the band gap
45 photon energy for the absorption edge7 and it provides
energy14–16. Most have been employed in the fabrication of
46 information about the optical band gap8. Various methods and
optical waveguide in optoelectronic materials. The empirical
47 approximation techniques are available in determining the
relation suggested by Moss et.al. relates the refractive index
48 absorption peak to ascertain the onset of absorption. The
and band gap energy was the first of its kind fitting wide range
49 absorbance determination from diffused reflectance spectra
of materials15. While there exist various sub models such as
50 gives direct information of absorption edge (where other thin
Ravindra and Reddy’s empirical relationships14. The
51 film parameters such as film thickness has to be accounted
mathematical basis for the above mentioned models has been
52 for)8,9. Kubelka-Munk (K-M) transform, approximates for the
described by Penn model and was further expanded by Herve
53 absorption coefficient, converting into a single parameter
et al., based on covalent and ionic bonds within the material12.
54
55 The K-M transformation of reflectance data is the most
56 a. Department of Chemical Engineering, National Institute of Technology Rourkela,
commonly employed technique used in Tauc model to estimate
57 Rourkela, Odisha, India.
† Footnotes relating to the title and/or authors should appear here. optical band-gap energy of a semi-conductor material.
58 Electronic Supplementary Information (ESI) available: [details of any supplementary However, if the material property is unknown (whether or not
59 information available should be included here]. See DOI: 10.1039/x0xx00000x
60

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3 conductor, semi-conductor or insulator), any onset of Synthesis of MOFs View Article Online

4 absorption edge in the Tauc plot would essentially lead to some DOI: 10.1039/C8AN02257G

5 value of band-gap energy with incorrect information on the The synthesis of MOFs such as MIL-53(Fe), and its cation and
6 material property. Additionally, if there is unresolved multiple anion doped derivatives; MIL-125(Ti) and Amino functionalized
7 absorption peaks or edges in the Tauc plot (a common feature MIL-125(Ti) were carried out using microwave routes in
8 with hybrid polyfunctional materials e.g. metal organic Monowave 300 (Anton Parr) reactor. The synthesis recipes and
9 frameworks (MOFs)), an exact assessment on the point at which post-synthesis treatments are detailed in the supporting
10 the tangent should be drawn remains inconclusive, leading to information.
11 multiple results in band-gap energy estimation17. Additionally,
MOFs, which have shown promise as potential photocatalysts Synthesis of α-Fe2O3
12
13 are susceptible to different post-synthetic treatments with
The synthesis of -Fe2O3 was carried out following the
14 varying physical properties and the exact nature of the Tauc plot
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prescribed stoichiometry of Chaudhari et al18 and the detailed

15 might as well show different trends in terms of absorption
description is given in the supporting information.
16 edge/peak positions within the experimental wavelength range.
17 Synthesis of Emeraldine
18 This work is a first of its kind in screening and analyzing a wide

Analyst Accepted Manuscript

19 array of conventional and novel semi-conductor, conductor and The synthesis of Emeraldine followed the reaction
20 insulator materials to estimate their optical band-gap energies stoichiometry proposed by Gomes et al.19
21 and simultaneously classifying the materials properties. A
22 complex dielectrics transformation of the UV-vis diffused Synthesis of Graphene Oxide (GO)
23 reflectance spectra is proposed for the aforementioned
24 objectives. The standard K-M transformation results are The synthesis of GO was carried out following the modified
25 compared with the proposed dielectrics protocol to analyze the Hummer Method20 as detailed in literature.
26 deviation.
Characterization
27
28 UV-vis diffused reflectance studies were carried out for a total
29 Experimental
number of 21 samples representative of semi-conductor,
30 conductor and insulator type of materials using JASCO V-750
31 Materials spectrophotometer. The spectral data were collected within the
32 range between 200-700 nm. The spectral bandwidth of the
Chemicals/reagents of analytical grade viz. Titanium dioxide
33 instrument was set at 4.0 nm with a scan rate of 400 nm/min.
[TiO2, Fisher Scientific, India], Zirconium Oxide [ZrO2, Fisher
34 The recorded spectral data interval was set at 1.0 nm.
Scientific, India], Tungsten (III) Oxide [WO3, Otto Chime, India],
35
Zinc Oxide [ZnO, Fisher Scientific, India], Alumina [Al2O3, Fisher
36 The reflectance data were processed using SPECTRA MANAGER
Scientific, India], Magnesia [MgO, Fisher Scientific, India], Silica
37 2.0 (JASCO) software. The refractive indices and extinction
[SiO2, Fisher Scientific, India], Graphite [C, Fisher Scientific,
38 spectra of the reflectance data was obtained applying Kramers–
India], Anhydrous Iron (III) Chloride [FeCl3, RFCL Ltd, India],
39 Kronig transformation.
Lithium Acetate di hydrate [CH3COOLi.2H2O, Loba Chemie
40
Private Limited, India], Anhydrous Sodium Acetate [CH3COONa,
41 Theory
Fisher Scientific, India], Anhydrous Potassium Acetate
42
[CH3COOK, Fisher Scientific, India], Sodium Sulfide [Na2S, Fisher Diffused reflectance method to measure the optical band-gap
43
Scientific, India],Titanium isopropoxide [C12H28O4Ti, Otto of materials with internal inhomogeneity is a common
44
Chime, India],1,4-benzene dicarboxylic acid (commonly known technique where the propagation of light through
45
as terephthalic acid) [C8H6O4, Sigma Aldrich, India], 2-amino- inhomogeneous media leads to light-scattering along its path21.
46
1,4-benzene dicarboxylic acid (commonly known as amino In this research article, two most commonly employed
47
terephthalic acid) [C8H7O4N, Sigma Aldrich, India], N, N- techniques viz. Kubelka-Munk (K-M) and dielectric transforms
48
dimethyl formamide [C3H7NO, Merck Specialities Private for the estimation of optical band gap energies of myriad
49
Limited, India], Urea [CON2H4, Fisher Scientific, India], Aniline different materials are discussed.
50
[C6H7N2, Fisher Scientific, India],Ammonium persulphate (APS)
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[(NH4)2S2O8, Fisher Scientific, India] and Hydrochloric acid (37%) Kubelka-Munk (K-M) transformation
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[HCl, Merck Specialities Private Limited, India] were procured
53
from respective vendors and used without further purification. In Kubelka-Munk (K-M) model, the geometric particularities of
54
55 the inhomogeneous medium are adjusted into a single
56 parameter, the scattering coefficient ‘s’21,22. The diffuse
Methods
57 reflectance 𝑅∞ is given as:
Synthesis of materials
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7 The diffused reflectance is then solved for k/s yielding the K-M
8 transform23. The complex transformation of dielectric functions is presented
9
in polar coordinate system thereby enabling spatial
10
independence. This reduces Penn model into a two parameter
11
model with spatial independence (hence an infinite
12
The scattering coefficient s is, in fact, dominated by particle size inhomogeneous medium).
13
and refractive index of the sample. It is not a strong function of
14
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the wavelength or the absorption coefficient (α), and hence the

15
K-M model considers it a constant. In reality, the scattering
16
coefficient does vary slowly with wavelength. Hence, K-M
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transform for measurable spectroscopic observations is The dispersion-dissipation plot reflects the optical
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Analyst Accepted Manuscript

approximately proportional to the absorption coefficient (α) of characteristics of the material.
19
the sample. The following absorption coefficient (α) expression
20
is then derived also known as Tauc equation5,24as: At,
21
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25 A plot between ℎ𝜐 (the energy of the light) on the X axis and the
quantity (αhυ)1/n on the Y axis, where α is the absorption
26
coefficient of the material is necessary. The value of the
27
exponent n denotes the nature of the transition and β denotes
28 the band edge parameter. The resulting plot has a distinct linear
29 regime which denotes the onset of absorption. Thus,
30 extrapolating this linear region onto the X axis gives the optical
31 band gap energy of the material (𝐸𝑔).
32
33
34 Dielectrics transformation
35
36 Kramers–Kronig transformation (K-K transformation) is used for
37 obtaining the absorption coefficient of the material and
38 refractive index from diffused reflectance spectra25.
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48 Figure 1: Process algorithm for the estimation of optical band gap via dielectrics model
49 The phase shift angle of the sample is given by
50 On applying the Tauc equation, the resulting equation becomes:
51
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55 A plot between the quantities 1/ℎ𝜐 (the energy of the light) on
56 The conversion of extinction coefficient 𝑘(𝜐)of the material and the Y axis and the quantity 𝑛(𝜐)2 on the X axis is necessary. The
57 refractive index𝑛(𝜐) spectra into complex dielectric functions of resulting plot has a distinct linear regime which denotes the
58 frequency/wavelength (εcomplex) gives: onset of absorption. Thus, extrapolating this linear region onto
59 the Y axis gives the energy of the optical band gap of the
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3 material (1/𝐸𝑔).The detailed mathematical protocol is detailed transition), MCT (metal charge transitions) andView IVCT (inter
Article Online

4 in Figure 1.The mathematical derivations are detailed in the valance charge transition) superimposingDOI: with10.1039/C8AN02257G
each other in the
supporting information. diffused reflectance spectra26–28. Hence, the interpretation of
5
6 the exact linear regime signifying the onset of absorption is a
7 difficult decision as it may lead to varying values of optical band-
Results and discussion
8 gap of the same material. It is also observed that additional
9 The Tauc plots as presented in Figure 2(A, B and D) show the problems with hybrid materials surfaces when the absorption
10 details of optical band gap (𝑬𝒈) values of different class of peak is not well resolved. On a different note Figure 2C shows
11 materials studied in this work viz. insulators, common the Tauc plots for a class of inorganic and organic materials
12 semiconductors, hybrid materials (such as metal organic those are conducting in nature either due to free electrons or
13 frameworks (MOFs)). The Kubelka-Munk (K-M) model was used polarons19.
14
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48 Figure 2: Tauc plots of various material samples modelled via K-M Model A) Insulators B) Semiconductors C) Organic and Inorganic Optical conductors and D) Hybrid materials (MOFs)
49
50
for estimation of values. For both regular insulators and semi- The presence of distinct absorption edges for these materials
51
conductor materials (Figure 2 A and B), the estimation of optical can be misleading as it would lead to erroneous interpretation
52
bang energies can easily be interpreted because of the presence on the class of materials i.e. either semi-conductors or
53
54 of distinct absorption edge (due to distinct levels in electronic insulators rather than conductors.
55 transition states) in representative samples. However, in case of
56 hybrid materials like MOFs, as can be seen from the Figure 2D,
57 there exists multiple absorption peaks or edges in the plots of
58 the representative investigated samples. This is largely due to
59 various electronic transitions of LMCT (ligand to metal charge
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Figure 3: Dispersion-Dissipation Vs Energy Plot of various investigated materials modelled via dielectrics model A) Insulator B) Semi-conductor and C) Conductor
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28 Figure 4: Hypothesised electron transition schematic for the onset of absorption edge A) Insulator and semi-conductor B) Conductors
29
30
31 This aspect is essentially more important for unknown intercept on the y axis gives the inverse of band gap energy and
32 materials. This particular aspect of materials classification matches well with Tauc model and standard data available in
33 during estimating optical band-gap energy of a sample can’t be literature for the representative materials. The details of rest of
34 directly interpreted from the regular Tauc plot. This the materials can be found in the supporting information.
35 necessitates further resolving the equations in a different
36 domain using Dielectrics model. Table 1: Detailed comparison of various material samples (such as insulators) band gap
energy with K-M model and Dielectrics model
37
38 In case of dielectrics model, the complex representation of
39 dielectric functions in polar coordinates following the protocol Optical Band-gap Percentage
40 discussed in Fig 1 with energy of the photon as the X axis energy (eV) Difference (%)
Sl.
Material Sample
41 distinguishes the nature of the materials as demonstrated in no
K-M Dielectrics
42 Figure 3(A, B and C). Insulators and semiconductors (Figure 3A model Model
43 and B) show discontinuity and undergoes a phase shift of 180◦
44 at →-90◦which is very similar to dispersion–dissipation plot as 1 Alumina (α-Al2O3) 3.74 3.79 1.33
45 reported elsewhere and was explained due to polarization29.
46 Here, the phase shift can be hypothesised due to dominating
47 2 Magnesia (MgO) 3.87 3.83 1.04
absorption coefficient with increase in energy, thus showing the
48
absorption edge23.In Figure 3C, the dispersion–dissipation to
49
energy plot is shown for a conductor. The continuity in the plot 3 Silica (SiO2) 3.77 3.78 0.26
50
with no phase shift is observed along with an absence of any
51
52 absorption edge. The hypothesised schematic representation of
Terephthalic acid
electron transitions for the representative samples are shown 4 3.57 3.6 0.84
53 (BDC)
54 in Figure 4.
55 2-amino-terephthalic
5 acid (NH -BDC) 2.56 2.61 1.93
56 Following the protocol as explained in Figure 1, for insulators 2

57 and semiconductors, a plot between 1/hυ (the energy of the

58 light) on the Y axis and the quantity 𝒏(𝝊)𝟐 on the X axis is
59 constructed as shown in Figure 5A and B respectively. The
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3 Table 2: Detailed comparison of various material sample’s (such as semiconductors) The scope of this present work was further View extended by
Article Online

4
band gap energy with K-M model and Dielectrics model comparing the band-gap energy values DOI: determined from the
10.1039/C8AN02257G
presented models with other experimental techniques like
5
electrochemical methods (X-ray photoelectron spectroscopy
6 Sl. Material Optical Band-gap Percentage
(XPS)/ultraviolet photoelectron spectroscopy (UPS), cyclic
7 no Sample energy (eV) Difference (%)
voltammetry/electrochemical impedance spectroscopy)) and
8 theoretical models (ab-initio, empirical/semi-empirical and DFT
K-M Dielectrics
9 model Model (density functional theory)) for the common materials available
10 in literature. The detailed table is shown in the supporting
11 Titanium information (Table S1). There is a close match between the
12 1 dioxide (TiO2) 3.1 3.26 5.03 values in band-gap energies of the current study and reported
13 literature, validating its feasibility. Importantly, conducting
14 materials that have shown metallic properties and zero band
2 Zirconia (ZrO2)
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3.73 3.67 1.62 gaps in DFT studies30-37 is also corroborated well from the
15
present dispersion-dissipation plots (as represented Figure 3C
16 Haematite (α-
and Figures 1 J-L of the supporting information).
17 3 Fe2O3) 1.7 1.76 3.47
18

Analyst Accepted Manuscript

Tungsten
19 Meanwhile, in case of hybrid materials such as MOFs, the
20 4 oxide (WO3) 2.47 2.65 7.03 observations for the nature of the material and optical band gap
21 were consistent with both Tauc and dielectrics models. The
Zinc oxide
22 detailed plots of dispersion–dissipation and 𝒏(𝝊)𝟐 vs 𝟏/𝑬 of
5 (ZnO) 3.18 3.19 0.31
23 various MOFs (such as MIL-125 (Ti),NH2-MIL-125(Ti),MIL-53(Fe),Li-
24 MIL-53(Fe),Na-MIL-53(Fe),K-MIL-53(Fe),S-MIL-53(Fe) )are shown in
the supporting information. The corresponding comparison of
25
optical band gap energies evaluated via both K-M and dielectrics
26
models alongside percentage errors are tabulated in Table 3. The
27 percentage difference between to K-M and dielectrics models
28 ranged from 0.8-4.92%, within a confidence level of 97%.
29
Table 3: Detailed comparison of various hybrid materials (such as MOFs semiconductors)
30 band gap energy with K-M model and Dielectrics model
31
32 Optical Band-gap energy
33 Sl. (eV)
34 no Material Sample
35 Percentage
36 Difference (%)
37
K-M Dielectrics
38 model Model
39
40
41 1 MIL-53(Fe) 1.93 1.996 3.36
42
43
2 Li-MIL-53(Fe) 1.81 1.894 4.54
44
45
46 3 Na-MIL-53(Fe) 1.88 1.953 3.81
47
48
49 4 K-MIL-53(Fe) 1.88 1.967 4.52
50 Figure 5:n(υ)2 Vs 1/E plot for material samples in Figure 3 for optical band gap
determination A) Magnesium Oxide (MgO) B) Titanium dioxide (TiO2) 5 S-MIL-53(Fe) 2.5 2.48 0.8
51
52
Table 1 and 2 gives a comparative assessment of optical band
53 6 MIL-125(Ti) 3.17 3.33 4.92
gap energy values estimated from both K-M model and the
54
dielectrics model. Among the various materials analysed, the
55
percentage difference between K-M and dielectrics model 7 NH2-MIL-125(Ti) 2.62 2.657 1.4
56
57 ranged from 0.26-7.03%, within a confidence level of 96%.
58
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3 transition from semiconductor to conductors View
in Article
caseOnline
of
4 multifunctional materials. DOI: 10.1039/C8AN02257G

5
6
Conclusions
7
8
9 This work successfully demonstrated a complex dielectrics
10 transformation of the UV-vis diffused reflectance spectra to
11 estimate the optical band-gap energies of an array of semi-
12 conductor, conductor and insulator materials and the results
13 showed close comparison with Kubelka-Munk (K-M)
14 transformation (within ca. 0.16-7.07% variation). The proposed
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method based on well-established dielectrics transformation

15
was effective in estimating optical band-gap energy when there
16
remained unresolved or multiple absorption peaks in the
17 diffused reflectance spectra, a characteristic common to hybrid
18

Analyst Accepted Manuscript

poly-functional materials like MOFs. The proposed method as
19 well distinguished the class of the materials, an important
20 condition to validate and substantiate the band-gap energy
21 values.
22
23
24 Conflicts of interest
25 “There are no conflicts to declare”.
26
27
28 References
29
30 1 A. Sitt, I. Hadar and U. Banin, Nano Today, 2013, 8, 494–
31 513.
32 2 T. Okubo, K. Himoto, K. Tanishima, S. Fukuda, Y. Noda, M.
33 Nakayama, K. Sugimoto, M. Maekawa and T. Kuroda-sowa,
Figure 6: Comparison of optical band gap before and after solvent processing A) K-M
34 , DOI:10.1021/acs.inorgchem.7b02923.
modelled Tauc plot B) n(υ)2Vs 1/E plot for hybrid material (case MIL-53(Fe))
35 3 H. Huang, X. Li, J. Wang, F. Dong, P. K. Chu, T. Zhang and Y.
36 Zhang, ACS Catal., 2015, 5, 4094–4103.
37 One of the major advantages of dielectrics model over K-M 4 F. Dong, T. Xiong, Y. Sun, L. Lu, Y. Zhang, H. Zhang, H.
38 model is found to be in its accuracy in selecting the onset of
Huang, Y. Zhou and Z. Wu, Appl. Catal. B Environ., 2017,
39 absorption edge especially when there exists multiple or
219, 450–458.
40 unresolved absorption peaks in K-M domain. Also, for hybrid
materials like MOFs, it was observed that the onset of 5 R. Raciti, R. Bahariqushchi, C. Summonte, A. Aydinli, A.
41 Terrasi and S. Mirabella, J. Appl. Phys., 2017, 121, 234304.
absorption edge/peak and their positioning differs with post-
42 6 C. Rotaru, S. Nastase and N. Tomozeiu,phys. stat. sol.
synthesis treatments. The details are shown in Figure 6A and B
43 (a),1999, 171, 365 .
for a representative MOF viz. MIL-53 (Fe). As can be seen from
44 Figure 6A, DMF and water wash led to different profiles in the 7 B. Gu, N. H. Kwong and R. Binder, Phys. Rev. B, 2013, 87,
45 K-M domain. The optical band gaps for DMF wash was 125301.
46 estimated to be 2.557 eV whereas for water wash the value was 8 U. P. AE Morales, ES Mora, Rev. Mex. F´ISICA, 2007, 53, 18–
47 1.967 eV. The uncertainty of the absorption edge is clearly 22.
48 resolved in dielectrics domain as shown in Figure 6B. Since 9 J. C. S. Costa, R. J. S. Taveira, C. F. R. A. C. Lima, A. Mendes
49 there exist complex levels of electron interactions, the selection
and L. M. N. B. F. Santos, Opt. Mater. (Amst)., 2016, 58,
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