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reflectance spectroscopy

M. Nowak,1,a B. Kauch,2 and P. Szperlich1

1

Institute of Physics, Silesian University of Technology, ul. Krasiskiego 8, 40-019 Katowice, Poland

Department of Biophysics, Agricultural University SGGW, ul. Nowoursynowska 159, 02-776 Warsaw, Poland

Received 11 December 2008; accepted 2 March 2009; published online 21 April 2009

Twelve methods of determining energy band gap Eg of semiconductors using diffuse reflectance

spectroscopy have been applied in investigations of sonochemically produced antimony sulfoiodide

SbSI consisting of nanowires. It has been proved that the best method of determining Eg is based

on simultaneous fitting of many mechanisms of absorption to the spectral dependence of Kubelka

Munk function evaluated from the diffuse reflectance data. It allows determining the values of

indirect forbidden Eg, the Urbach energy, and the constant absorption/scattering of the examined

semiconductor. 2009 American Institute of Physics. DOI: 10.1063/1.3103603

Optical absorption spectra have been extensively used as

one of the most important tools for probing the energy gaps

Eg and band structures of semiconductors.1 There are several methods for measuring them. These include diffuse reflectance spectroscopy DRS. When a material, consisting

of many particles, or nanoparticles, is illuminated, some of

the impinging radiation penetrates the sample and some is

reflected from its surface. The portion that penetrates the

sample is scattered at a large number of points in its path as

well as it is transmitted through the particles a number of

times. Only the part of this radiation that is returned to the

surface of the sample and comes back out is considered to be

diffuse reflection.2

DRS is a suitable, not destructive, and simple method of

investigation, especially important in examinations of porous, nanocrystalline materials and gels.3 It is impossible to

examine such materials applying specular reflection and it is

also extremely difficult to determine the path length in an

optical transmittance of them. The following factors are related to high spectral quality of diffuse reflectance: dilution

of the sample with a nonabsorbing matrix ensures a deeper

penetration of the incident beam into the sample, which increases the contribution of the scattered component in the

spectrum and minimizes the specular reflection component;

and smaller particles improve the quality of DRS spectra.

However, there is no one reliable method for determining Eg while applying the DRS. The already used methods of

DRS investigations have been applied in this paper to determine Eg of ultrasonically prepared nanowires of antimony

sulfoiodide SbSI. The SbSI being a semiconducting ferroelectric has an unusually large number of interesting properties that have been reviewed in a few monographs but they

are still investigated see the literature in, e.g., Ref. 3.

The SbSI xerogel consisting of nanowires was prepared

sonochemically from the elements Sb, S, and I. The used

experimental set up and the applied procedure were the same

as described in Ref. 3. Characterization of the xerogel was

done using powder x-ray diffraction, scanning electron microscopy, energy dispersive x-ray analysis, high-resolution

a

0034-6748/2009/804/046107/3/$25.00

diffraction. Description of the used equipment and the results

of investigations were given in Ref. 3.

The DRS measurements were carried out on a spectrophotometer SP-2000 equipped with an integrating sphere

ISP-REF Ocean Optics Inc.. Spectra were recorded at temperature of 293 K in the mode of exclusion of specular reflectance. The standard WS-1 Ocean Optics Inc. was used

as a reference. The spectrum of diffuse reflectance signal the

ratio Rd = Idiffuse / Istandard of intensities of radiation reflected in

diffuse manner from the sample and from the known standard of SbSI xerogel has been presented in Fig. 1. It corresponds to the ideal diffuse reflectance spectrum consisting of

the following: the nearly flat, low absorbance region at small

photon energies h Rd in this region can be dominated by

reflection and scattering due to the high refractive index of

the investigated material; the abrupt decrease in Rd when

radiation becomes more intensively absorbed with increasing

h it corresponds to an onset of transmission near the optical absorption edge, and; the also nearly flat, strong absorbance region at high h.

There are at least eleven methods in determining Eg using DRS. Method 1 see, e.g., Ref. 4: the onset of the linear

increase in diffuse reflectance with decreasing h Fig. 1a

in the supplementary material5 was taken as a measure of

Eg. Method 2 see, e.g., Refs. 4 and 6: the intersection of

straight-line extrapolations below and above the high photon

energy knee of the spectral characteristics of Rd Fig. 1b in

the supplementary material5 was used to determine Eg.

Method 3 see, e.g., Ref. 7: similarly to the case of

optical transmittance, the diffuse reflectance data were transformed in the so-called absorbance

A = d = log

Istandard

= logRd,

Idiffuse

where d is absorption path length and represents absorption coefficient of radiation. The Eg was derived as the intersection point between lines that extrapolate the absorbances

in the small h range and at the linear absorption edge Fig.

2 in the supplementary material5.

Method 4 see, e.g., Ref. 8: the Eg was determined by

the intersection point Fig. 3a in the supplementary

80, 046107-1

046107-2

TABLE I. Comparison of the values of energy gap of SbSI nanowires determined using different techniques of diffusive reflection spectroscopy.

Eg

eV

Munk function calculated for the DRS data of SbSI nanowires. Solid

curve represents the least square fitted theoretical dependence for the sum of

indirect forbidden absorption without excitons and phonon statistics, Urbach

ruled absorption, and constant absorption term description in the text, values of the fitted parameters are given in Table II.

linear portion of the absorption edge of so-called Kubelka

Munk function known as re-emission function, too2

FKMRdh =

1 Rdh2 h

=

,

2Rdh

S

where S is the scattering factor. In some cases, S is approximately equal to unity for very small participles or it is

constant e.g., when thickness of the sample is much bigger

than the individual participle see, e.g., Refs. 4 and 812.

Method 5 see, e.g., Ref. 9: sometimes, also in the small h

range, FKM has values much larger than zero.9 Therefore, Eg

was determined as the intersection point between lines that

extrapolate FKM values in the small h range and at the linear

absorption edge Fig. 3b in the supplementary material5.

Method 6 see, e.g., Refs. 4 and 8: the Eg was determined as

the energy coordinate of the point on the low energy side of

FKM curve at which the linear increase starts Fig. 3c in the

supplementary material5. However, this method is very

ambiguousit is difficult to determine uncertainty of Eg

value. Method 7 see, e.g., Ref. 10: The Eg was evaluated as

the intersection point between lines that extrapolate FKM values in the high h range and at the linear absorption edge

Fig. 3d in the supplementary material5.

Method 8 see, e.g., Ref. 10: some more information

about Eg can be obtained by McLean analysis of the absorption edge. The threshold of continuous optical absorption can

be explained by the quantum mechanical perturbation theory

of electron-photon interaction. For different transition

mechanisms, it has been proved that along the sharp absorption edge, the energy of incident photons, and Eg of a semiconductor can have, i.e., such simple relations as

n = A1h Eg

3a

hn = A2h Eg,

3b

or

where index n depends on the interband transition mechanism. The values of n equal 2 or 2/3 imply a direct allowed

or direct forbidden transition, respectively. If n = 1 / 2 or

n = 1 / 3, the interband transition is indirect allowed or indirect

forbidden, respectively. Generally the best fitting for differ-

No. of the

method

2.234

2.111

2.08

11

2.05

2.04

1.981

1.971

1.921

1.901

1.821

1.811

12

1.761

10

Eg using the DRS

The intersection of the straight-line extrapolation

below and above the high photon energy knee

of the FKM curve

The intersection of the straight-line extrapolation

below and above the high photon energy knee

of the curve of diffuse reflectance

Maximum of numerical derivative of

KubelkaMunk reemission function

The onset of linear increase in reflectance

with decreasing photon energy h

The onset of linear increase in FKM function

with increasing photon energy

The intersection of the straight-line extrapolations

below and above the small photon energy knee

of the FKM curve;

The intersection point between the photon energy

axis and the line extrapolated from the linear

portion of the absorption edge in a plot

of FKM function

The intersection point between the line that

extrapolates A = logRd values in the small

h range and the line extrapolated from the

linear portion of the absorption edge in the

A vs h eV plot

The intersection of the straight-line extrapolations

below and above the small photon energy knee

of the FKM1/3 curve

The intersection point between the h axis and

the line extrapolated from the linear portion

of the absorption edge in a plot of

FKM1/3 function

Multi absorption fitting of the KubelkaMunk

reemission function

The intersection point between the h axis

and the line extrapolated from the linear portion

of the absorption edge in a plot of

lnRmax Rmin / Rd Rminn function n = 1 / 3

in the investigated material or the absorption mechanism

cited in literature was taken into account. Since indirect forbidden band gap exists in SbSI single crystals,13 in this paper

FKM1/3 values were plotted versus h Fig. 4a in the supplementary material5. The intersection of the fitting straight

line with h axis gave the value of Eg. Method 9 see, e.g.,

Ref. 11: the Eg was determined by the intersection of the

straight-line extrapolations below and above the small h

knee of FKM1/3 curve Fig. 4b in the supplementary

material5.

Method 10 see, e.g., Ref. 10: the Eg was obtained

from the intersection point between h axis and the line extrapolated from the linear portion of the absorption edge

Fig. 5 in the supplementary material5 in a plot of

lnRmax Rmin / Rd Rminn function where Rmax and Rmin

are maximum and minimum values of diffusive reflectance,

Rd is the reflectance at a given h, and n = 1 / 3 for indirect

forbidden transition.

Method 11 see, e.g., Ref. 12: the value of Eg was obtained from the maximum of a numerical derivative of FKM

with respect to h Fig. 6 in the supplementary material5.

The values of Eg of SbSI nanowires derived using the

presented above DRS methods are in a very large range

from 2.23 to 1.76 eV Table I. It must be underlined that

only methods 8, 9, and 10 are based on theoretical dependences that include explicitly Eg. Methods 1, 2, and 7 are

046107-3

knee of the reflectance spectra as it is in the case of the

transmittance one.

It must also be noted that the values of Eg determined

from the intersections of h axis and the extrapolations of

some functions i.e., in methods 8 and 10, can be influenced

by the absolute value of the appropriate function in the small

h range, e.g., due to strong free carriers absorption or high

value of refractive index of the investigated material. As a

result, too small a value of the determined Eg can be obtained. In order to avoid it, Eg13 = 1.801 eV was calculated

from the intersection of the straight-line extrapolations below

and above the small h knee of the lnRmax Rmin / Rd

Rminn curve Fig. 5 in the supplementary material5.

However, one can see that a more reliable method of investigations is needed.

Since not only various mechanisms of absorption of

electromagnetic radiation can be observed in semiconductors, nevertheless some of them can coexist in the same

spectral range. Therefore another way for fitting the spectral

dependence of the KubelkaMunk function has been suggested. In this method, the following least square function

has been minimized as follows:

n

2 = FKMhi B jhi

i=1

various mechanisms of light absorption, and B is the proportionality factor. Some 32 of the known mechanisms of absorption in semiconductors have been considered.

Figure 1 presents the spectrum of FKM of the investigated SbSI nanowires and the least square fitted theoretical

dependence appropriate for the sum of indirect forbidden absorption without excitons and phonon statistics 1, Urbach

ruled absorption 2, and constant absorption term

3 = A0 see reference cited in Ref. 3

1 = A60h EgIf3

2 = AU exp

h

,

EU

for h EgIf ,

5a

5b

the Urbach energy, and A60 and AU are constant parameters.

The constant absorption term A0 is an attenuation coefficient

that is considered as the sum of the scattering and absorption

independent of h near the absorption edge.

The fitting presented in Fig. 1 is rather good. Values of

the fitted parameters are given in Table II.

It is clear to see that the best approach to determine Eg

using DRS is to perform the multiabsorption fitting of the

KubelkaMunk function method 12 because it allows to

determine not only Eg and the main mechanism of absorption, but also gives information on the coexisting phenomena

Table II. The value Eg12 = EgIf = 1.811 eV of the indirect

forbidden energy band gap of SbSI nanowires, which was

determined using this method, is close to the value evaluated

for powdered SbSI single crystals EgIf = 1.7931 eV.3 It is

Eg12 = EgIf, the Urbach energy EU and the other parameters of SbSI nanowires with the data of powdered SbSI single crystals Ref. 3 that were

determined from the fitting of the spectrum of KubelkaMunk function.

Values obtained for

Parameter

SbSI nanowires

Powdered bulk

single crystals of SbSIa

B A60, 1 / eV3 m

EgIf, eV

B AU, 1/m

EU, eV

B A0, 1/m

45.2824

1.811

2.796 104

0.5717

0.04881

35.2027

1.7931

2.527 109

0.1035

0.014117

Reference 3.

reported in the literature: 1.82 eV at 301 K,14 for the light

polarized in direction of the c-axis of the SbSI, i.e., in the

direction of growth of the SbSI nanowires.3 The optical energy gap for light polarized in perpendicular direction is

slightly bigger.14

The penetration depth of the incident radiation is determined by properties of the sample and its surface as well as

by the angle of incidence of the incoming photons. Therefore, it is extremely difficult to determine the path length and

absorption coefficient of light in the diffuse reflectance experiment. However, it seems to be less important for determining of Eg using the spectral dependence of the Kubelka

Munk function than in the case of optical transmittance

measurements.

This paper was partially supported by the MNiSzW

Poland under Contract No. N N507 1577 33.

J. I. Pankove, Optical Processes in Semiconductors Prentice-Hall, New

Jersey, 1971.

2

B. Philips-Invernizzi, D. Dupont, and C. Caze, Opt. Eng. 40, 1082 2001.

3

M. Nowak, P. Szperlich, . Bober, J. Szala, G. Moskal, and D. Str,

Ultrason. Sonochem. 15, 709 2008.

4

F. Jahan, M. H. Islam, and B. E. Smith, Sol. Energy Mater. Sol. Cells 37,

283 1995.

5

See EPAPS Document No. E-RSINAK-80-007904 for the complete set of

figures that present elaboration of the experimental data using different

methods. For more information on EPAPS, see http://www.aip.org/

pubservs/epaps.html.

6

H. Hanmei, M. Maosong, Y. Baojun, Z. Xuanjun, L. Qiaowei, Y. Weichao,

and Q. Yitai, J. Cryst. Growth 258, 106 2003.

7

J. Llanos, C. Mujica, and A. Buljan, J. Alloys Compd. 316, 146 2001.

8

F. Zhou, K. Kang, T. Maxisch, G. Ceder, and D. Morgan, Solid State

Commun. 132, 181 2004.

9

R. Patschke, X. Zhang, D. Singh, J. Schindler, C. R. Kannewurf, N.

Lowhorn, T. Tritt, G. S. Nolas, and M. G. Kanatzidis, Chem. Mater. 13,

613 2001.

10

G. A. Martinez-Castanon, M. G. Sanchez-Loredo, H. J. Dorantes, J. R.

Martinez-Mendoza, G. Ortega-Zarzosa, and F. Ruiz, Mater. Lett. 59, 529

2005.

11

A. Escobedo Morales, E. Sanches Mora, and U. Pal, Rev. Mex. Fis. S53,

18 2007.

12

O. Raymond, H. Villavicencio, V. Petranovskii, and J. M. Siqueiros,

Mater. Sci. Eng., A 360, 202 2003.

13

M. Nowak, P. Szperlich, A. Kidawa, M. KJpiska, P. Gorczycki, and B.

Kauch, Proc. SPIE 5136, 172 2003.

14

V. M. Fridkin, Ferroelectric Semiconductors Consultants Bureau, New

York, 1980.

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