Accepted Manuscript

Title: XRD Raman analysis and optical properties of CuS

nanostructured film

Author: T. Hurma S. Kose

PII: S0030-4026(16)30292-3
DOI: http://dx.doi.org/doi:10.1016/j.ijleo.2016.04.019
Reference: IJLEO 57502

To appear in:

Received date: 4-2-2016

Accepted date: 11-4-2016

Please cite this article as: T.Hurma, S.Kose, XRD Raman analysis and optical properties
of CuS nanostructured film, Optik - International Journal for Light and Electron Optics
http://dx.doi.org/10.1016/j.ijleo.2016.04.019

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XRD Raman analysis and optical properties of CuS nanostructured film

T. Hurmaa*, S. Koseb
a
Department of Physics, Anadolu University, TR-26470, Eskisehir, Turkey
b
Department of Physics, Eskisehir Osmangazi University, TR-26480, Eskisehir, Turkey.

Corresponding author: Tel.: +90 222 3350580; Fax: +90 222 3204910

E-mail address: tulayhurma@gmail.com (T. Hurma)

Abstract

Raman spectroscopy and X-ray diffraction (XRD) methods were applied to determine the

phase composition and crystal quality of CuS nanostructured film grown by spray pyrolysis.

The film has polycrystalline structure with preferential growth along the (101) plane. The

grain size for the film was found to be lower than 20 nm. The very sharp Raman peak around

470 cm-1 in the high frequency region was identified as the S–S stretching mode of S2 ions at

the 4e sites. Other Raman peaks were around 266 cm-1, 118 cm-1 and 68 cm-1 in the low

frequency region due to CuS phase. Particles of nanometric size show low wavenumber

vibrational modes that can be observed by Raman spectroscopy. Optical properties were

obtained from UV-vis absorption, transmittance and reflectance spectra of the nanostructured

CuS film. The optical constants of the film such as refractive index, extinction coefficient

and, optical conductivity were investigated. The film was found to be p-type by using hot

probe method.

Keywords: CuS nanostructured film; XRD; Raman; Optical constants

1. Introduction

Chalcogenite semiconductor materials are being studied extensively for their various

applications in science and technology. The control over size and morphology of nanometer

and micrometer sized semiconductor materials represents great challenge in implementing the

design of novel functional devices due to their sizes or shape dependent properties [1].

Nanocrystalline copper sulfide (CuS NCs) is such a p-type semiconductor which regularly

exhibits at least five stable phases with different Cu:S molar ratios (CuxS). Copper sulphide

forms five stable phases at room temperature: covellite (CuS), anilide (Cu1.75S), digenite

(Cu1.8S), djurleite (Cu1.95S) and chalcocite (Cu2S) [2] with a crystal structure varying from

orthogonal to hexagonal [3]. Copper sulfide films are interesting absorber materials with their

film solar cells with ideal optical characteristics. Copper sulfide thin films maintain

transmittance in the infrared region, low reflectance in the visible region and relatively high

reflectance in the near infrared region [4] which has been used in many applications,

including solar control coatings, solar energy conversion, electronic and low-temperature gas

sensor applications [5–8]. In particular, the band gap of CuxS has values ranging from 1.2 eV

for the “copper rich” phase Cu2S to 2 eV for “copper deficient” CuS [9, 10]. Real-time XRD

experiments have already been performed during the growth of the CuS film and given an

insight into the bulk processes. But one of the most efficient optical methods suitable for the

determination of phase composition of different materials including nanoscale CuS is Raman

spectroscopy. Within the scope of the Raman scattering process of a crystal, an incident

photon from a laser can absorb or emit a phonon of the crystal, and then scatter into the

surroundings at all directions [11]. With Raman spectroscopy, a laser photon is scattered by a

sample molecule and loses (or gains) energy during the process. The amount of energy loss is
seen as a change in energy (wavelength) of the irradiating photon. This energy loss is

characteristic for a particular bond in the molecule. Raman can be best thought of as

producing a precise spectral fingerprint, unique to a molecule or indeed an individual

molecular structure. The group theoretical analysis predicts eight Raman active phonon

modes for CuS: 2A1g, 2E1g, and 4E2g. Three intense phonon modes around 20, 60, and 475

cm−1 and three weaker bands at 115, 140, and 265 cm−1 are typically observed in the Raman

spectra of CuS. The modes around 20 and 475 cm−1 are assigned to vibrational modes from

the covalent S−S bonds [12]. Particles of nanometric size show low wavenumber vibrational

modes that can be observed by Raman spectroscopy [13]. In this study, Raman spectroscopy

and other experimental techniques, such as X-ray diffraction, scanning electron microscopy

(SEM) and UV-vis spectra have been used in order to achieve an accurate knowledge on the

crystalline properties of the CuS NCs film.

2. Experimental details

CuS NCs film has been produced by spraying the aqueous solution of 25 ml CuCl2.2H2O

and 75 ml of SC(NH2)2. Totally 100 ml of solution was sprayed onto glass substrates that had

been previously heated for 15 min. Substrate temperature was kept constant at 300±5 ◦C using

Fluke 62 max infrared thermometer. The ultrasonic spray-head to substrate distance was

approximately 30 cm. Detailed description of the experimental technique is given elsewhere

[14]. The flow rate of solution which was controlled with a flow meter and carrier gas

pressure during spraying was adjusted to be 5 ml min-1 and 0.2 kg cm-2, respectively. Nitrogen

was used as the carrier gas. P-type conductivity of the film was verified by the well-known

hot probe method. XRD and Raman spectroscopy were used to evaluate crystalline phase. For

XRD measurements X-ray powder diffractometer (BRUKER D8 Advance) was used. The

XRD pattern was scanned in 2θ range of 20°–70°. The film was mounted on rotating sample
holders (15 rpm). The Raman spectrum of the film was recorded in 0-2000 cm-1 range on a

Bruker Senterra Dispersive Raman instrument using laser excitation with the wavelength of

632.8 nm. For the optical measurements of CuS film, we used a double beam Shimadzu 2450

UV-spectrophotometer with an integrating sphere in 200-900 nm wavelength range. The

surface morphology of the film was characterized using ZEISS Ultra plus model field

emission scanning electron microscopy (FESEM).

3. Results and discussion

3.1. X-ray diffraction analysis and SEM images

The crystallinity and the preferred crystal orientation of the CuS NCs film were analyzed

by the XRD method. Fig. 1 shows the diffraction pattern of the film. The XRD result suggests

that the CuS NCs film has polycrystalline structure. There is basically one high intensity

diffraction peak around at 2θ=28,46ᵒ which is related to lattice planes of (101) (PDF 06-0464)

the hexagonal phase of the CuS covellite structure [15]. The other peak appeared with lower

intensities around at 2θ=47ᵒ is related with the lattice planes of (107) the CuS covellite

structure [16]. We note that two extra peaks appeared with very weak intensities around

2θ=32,49ᵒ and 2θ=55,3ᵒ which might be due to minor presence of Cu2-xS (0,6≤x≤1) phases

and this finding can confirm Raman results. The presence of these minor phases is generally

attributed to a sun of internal origins obeying the thermodynamics of solid solutions, to defect

chemistry and the thermal gradient which plays an important role as described elsewhere [17].

The crystallite size was calculated by using the well- known Scherrer equation with the peak

corresponding to the (101) plane to be 20 nm. Figure 2 shows SEM image of the film, which

supports the nanocrystallite and particle size estimated from the SEM data. SEM image shows

the surface morphology of the nanostructured CuS film. Film has mostly the “coral-like”

porous structure.
3.2. Raman analysis

Atomic vibration modes of CuS NCs film were studied using the Raman spectroscopy.

Raman spectroscopy provides an in situ method for identifying surface species, and spatial

variations in composition, provided the layer is >5 nm as the detection limit of this technique.

The integration of Raman spectroscopy with potentiodynamic techniques provides a powerful

tool to assist in understanding that complex system. Fig. 3 shows the Raman spectrum of CuS

NCs film in the frequency region of 0-2000 cm-1. The very sharp Raman peak around 470

cm-1 in the high frequency region was identified as the S–S stretching mode of S2 ions at the

4e sites [18]. The S-S stretch band was the dominant feature of the spectrum from the surface

when the potential was increased into the region in which covellite CuS is formed. The sharp

peak reveals that the lattice atoms are aligned in the periodic array. This result shows that

Raman spectroscopy can distinguish between copper sulfides with and without S-S bonding.

As shown in Fig.3, the Raman spectrum revealed other peaks around 266 cm-1, 118 cm-1 and

68 cm-1 in the low frequency region due to CuS phase [12,18]. Particles of nanometric size

show low wavenumber vibrational modes that can be observed by Raman spectroscopy [13].

The position and intensity of these Raman bands appearing in the low-frequency region

depend on the size of nanoparticles. In addition to this, extra peak at 322 cm-1 can be assigned

to the Cu2-xS (0,6≤x≤1) phonon mode. Raman method is very sensitive to the presence of

this defect phase.

3.4. Optical properties

The absorbance and transmittance spectra of the film were measured in the range of 200–900

nm, as shown in Fig. 4. The optical absorption in the ultraviolet region is larger than those in

the visible region. The transmittance decreased abruptly in short wavelengths. A sharp

decrease in the transmittance was observed at around 500 nm. The average transmittance

value determined for film was 38%. The film has relatively high absorption coefficient

between 104-105 cm-1 in the visible and the near-IR spectral range. The optical band gap was

estimated to be 2.22 eV, which was exhibiting a considerable blue shift due to quantum size

effects. The refractive index of the film was calculated by the following relation [19]:

1 R  4R
n  k2 (1)
1 R  1  R 2

where n is the refractive index, k (=αλ/4π) is extinction coefficient and R is the reflectance.

The refractive index and extinction coefficient values of the films are given in Fig. 5-6

respectively. Refractive index value was decreased to a lower value at 250 nm and gradually

increased again with increasing photon energy. Refractive index of the film is high around the

wavelength of 700 nm and a gradual fall was observed in 700-900 nm wavelength range.

Extinction coefficient of the film is high around 300 nm wavelength and a gradual fall was

observed in 400-550 nm wavelength range. Extinction coefficient increased again in the

wavelength range of 550-900 nm. The decrease in extinction coefficient with increase in

wavelength show that the fraction of light is lost due to scattering and consequently

absorbance decreases [20]. The value of optical conductivity is related to the absorption

coefficient (α), speed of light (c) and the refractive index (n) by the following expression [21].

nc
 (2)
4

A plot of film's optical conductivity (σ) as a function of photon energy (hν) is given in Figure

7. It is revealed from the figure and observed that the optical conductivity increased by the
photon energy up to 4.0 eV, exhibiting a peak value equal to 4.25 × 1012 S−1 for the 4.0 eV

photon energy and gradually decreased due to an increase in the photon energy within 4.0 to

5.62 eV range. Increase in the optical conductivity up to 4.0 eV can be attributed to an

increase in the absorption coefficient in this region, and a decrease in the real part of optical

conductivity within the energy range from 4.0 to 5.62 eV can be attributed to a decrease in the

absorption coefficient within this energy region. The described features make the CuS NCs

film a suitable candidate for absorber layer in solar cells. The film thickness has an important

effect on optical properties. So, in this study, the micrometers of film thickness play an

important role on optical properties of the film.

4. Conclusion

CuS nanostructure film was prepared on glass substrate. Raman Spectroscopy and X-Ray

Diffraction (XRD) methods have been chosen to study the structural properties of the film.

The XRD pattern of the film showed that CuS film is polycrystalline in nature and strongly

oriented along the (101) direction. The very sharp Raman peak around 470 cm-1 in the high

frequency region was identified as the S–S stretching mode. The S-S stretch mode was the

dominant feature of the spectrum from the surface when the potential was increased for the

region in which covellite CuS is formed. The Raman bands in the low-frequency region are

attributed to acoustic modes associated with vibration of the individual nanoparticle as a

whole. Hot probe method showed that the CuS sample exhibited a p-type conductivity. All the

films have relatively high absorption coefficients between 104-105 cm-1 in the visible and the

near-IR spectral range. The refractive index, extinction coefficient and optical conductivity

were calculated for the film.

Acknowledgement

We would like to thank Mrs. Özge Bağlayan for the Raman spectroscopy, Mrs. Seval Aksoy

for SEM, UV-vis measurements and Mrs. Büşra Avcı for XRD measurements.

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Figure Captions

Fig. 1. XRD pattern of the CuS NCs film.

Fig. 2. SEM image of the CuS NCs film.

Fig. 3. Raman spectrum of the CuS NCs film.

Fig. 4. Absorbance (a) and transmittance (b) spectra of the CuS NCs film.
Fig. 5. Variation of refractive index of the film with wavelength.

Fig. 6. Variation of extinction coefficient of the film with wavelength.

Fig. 7. Variation of optical conductivity of the film with photon energy.