AiClJ Proceedings of the

"International Conference on Advanced Nanomaterials & Emerging Engineering Technologies" (ICANMEET-20J3)

I organized by Sathyabama University, Chennai, India in association with DRDO, New Delhi, India, 24th _26tl" July, 2013
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Band Gap Variation in Copper Nitride Thin Films

. #3
#1
*2
Guruprasad Sahoo ,S. R. Meher ,Mahaveer K. Jam
Department ofPhysics, Indian Institute of Technology Madras
Chennai - 600036, India

School ofAdvanced Sciences, VIT University

Vellore - 632014, India

19uruprasad@physics.iitm.ac.in
3mkj@physics.iitm.ac.in
2samirmeher@gmail.com
Abstract- Copper nitride thin films have been prepared by

were passed into the chamber maintaining the total flow rate

pulsed direct current reactive magnetron sputtering. Structural,

at 40 sccm. By using the throttle valve the deposition pressure

morphological and optical properties of the as-deposited films

was fixed at 10 mTorr. The pulsed DC power, pulse frequency,

have been studied. X-ray diffraction analysis shows that the films

pulse width and substrate-target distance were kept constant at

are polycrystalline single phase of CU3N. Prominent growth

20 W, 5 kHz, 2 f.ts and 80

along (tOO) plane is observed for higher nitrogen flow rate

grown at various Nz flow rate and deposition time. The

whereas growth along

(111)

plane is observed for relatively lower

nitrogen flow rate. The band gap of this material changes from

1.02

to

1.40

eV by varying the nitrogen flow rate and deposition

time.

respectively. The films were

structural characterization of the films was carried out using

Panalylical X'Pert Pro X-ray diffractometer with a Cu
1.5406

A)

Ka (A

radiation. The Raman spectra were collected by

Jobin-Yvon HR 800 Raman spectrometer equipped with an

Keywords- Copper nitride, thin film, sputtering, band gap.

I.

mm

excitation source of 488 nm Ar ion laser. The thickness of the

INTRODUCTION

films (shown in table I) was measured using the Filmetrics

Copper nitride (Cu3N) has a cubic anti-Re03 type structure

F20 spectrophotometer. The surface morphology was studied

with lattice parameter 3.814

A and space group Ohi (Pm3m). It

is a stable compound at room temperature, but starts to

decompose into copper (Cu) and nitrogen (Nz) at 100 - 470C
[1]-[4]. Its low decomposition temperature and discriminating

using FEI Quanta FEG 200 scanning electron microscope

(SEM) and the transmission spectra in the wavelength range
300-2500 nm were recorded using a Jasco UV-VIS-NIR
spectrophotometer.

optical properties compared to Cu attract appreciable attention

III. RESULTS AND DISCUSSION

to be used in optical data storage devices, by generating

microscopic Cu spots on CU3N film by local heating [1], [3].

A)

Structural and Morphological Characterization

Its low band gap favours its future applications as barrier

material in spin tunnel junctions [5] and organic-inorganic

(a)

solar cells [6]. The band gap value of this material has been
theoretically calculated to be 0.9 eV, whereas experimentally
observed in the range of 0.8-1.9 eV [2], [5], [7]. This indicates
that the actual composition and microstructure of the material
and, thus, its band gap depends on the growth processes and
40

experimental conditions. Various techniques such as reactive

20 (deg.)

direct current (DC) sputtering [8], radio frequency magnetron

sputtering [2], molecular beam epitaxy [5], etc., are reported
in literature to prepare CU3N thin films. In this report, we have
used pulsed DC reactive magnetron sputtering to prepare
CU3N films and have studied the variation in the band gap
ofthis

material

by

varying

nitrogen

(Nz)

flow

rate

and

deposition time. Sputtering has been proven to be an industrial

40

20 (deg.)

viable technique for growing structurally uniform and good

quality films. Further, nitrification of the target surface could

Fig. 1 The XRD of Thin films

be avoided by pulsing nature of the power supply.

The X-ray diffraction (XRD) patterns of the films grown at

N2 flow rates of 30 and 40 sccm (Ar flow rate 10 and 0 sccm

II. PAGE LAYOUT

CU3N thin films were grown

respectively) with different deposition time of 5 - 20 minutes

by pulsed DC reactive

magnetron sputtering using a 50 mm diameter copper target in

the presence N2 and argon (Ar) plasma. A base vacuum of
5
1 x 10. Torr was created inside the chamber. N2 and Ar gases

978-1-4799-1379-4/13/$31.002013 IEEE

are shown in Fig. I. The films show polycrystalline single

phase of CU3N.

It is observed that at lower deposition time

the peaks are not clearly identified and with increase in the
deposition time these are well intensified. Thickness of the

540

Proceedings of the
1&:iLl]
organized by Sathyabama University, Chennai, India in association with DRDO, New Delhi, India, 24th _26tl" July, 2013

"International Conference on Advanced Nanomaterials & Emerging Engineering Technologies" (ICANMEET-20J3)

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films deposited for low time is very less and hence the

flow rate of 40 sccm. This gives a clear indication of decrease

intensity of the diffracted rays becomes very poor to be

in copper content and increase in nitrogen content in the film

significantly identified. The films prepared at N2 flow rate of

prepared at higher N2 flow rate.

40 sccm show preferential growth along (100) plane whereas

those prepared at N2 flow rate of 30 sccm show growth along

A)

Optical properties

(111) plane. This is because of the increased nitrogen content

Fig. 1 XRD patterns of the CUJN films grown for different deposition time
at N, flow rates of (a) 30 seem and (b) 40 seem
in the former case. With decrease in Nz flow rate below 30
sccm, presence of metallic copper has been observed (not
shown in figure). The average crystallite size, D for the films
has been calculated using Scherrer's semi-empirical formula,

D=
where A

1.5406

A and j3

0.9-1

films are highly transparent in the IR region and undergo inter

band transition in the visible region. The band gap values are
calculated from the transmission spectra using Tauc's plot
[13] for indirect transition as given below:
a =

(1)

peose
=

The transmission spectra of the films grown for 20 minutes

at Nz flow rates of 30 and 40 sccm are shown in Fig. 4(a). The

In(1 / T)

(2)

B-b. B is the observed full width

(3)

at half maximum and b is the instrumental broadening

determined from nano-crystalline silicon diffraction line. The
crystallite size is found to be decreased with decrease in
thickness as shown in table I.
The Raman spectra of the films deposited for 20 minutes at
Nz flow rates of 30 and 40 sccm are shown in Fig. 2. This
l
shows a broad peak at 650 cm' along with a small shoulder
l
peak at 510 cm' for the film grown at 40 sccm Nz flow rate.
These peaks are found to be broader for the film grown at 30
sccm Nz flow rate. Theoretical analysis predicts that the
optically active lattice vibrations are 2Flu+ 1F2u [9], [10]. The
Flu modes are active only in the infra-red (IR) spectra and the
F2u mode is inactive both in IR and Raman spectra. Thus no

where,

a is the absorption coefficient,

d is the film thickness,

Eg

T is the transmittance,

is the indirect band gap and A is a

constant. The indirect optical energy gap

(Eg) is determined by

(ahv/2 versus hv and extrapolating the

full line to the abscissa of hv as shown in Fig. 4(b). The fitting
plotting the curve of

has been carried out at two different regions and the two

Eg - Ep
Ep is the energy of the phonon involved in

points at which the lines touch the abscissa represent

and

Eg + Ep,

where

the indirect transition process. The band gap values along with
the phonon energy of the films deposited for different times
are given in table I. It shows that with decrease in the

vibrational modes are Raman active for a perfect cubic CU3N.

However experimental results show the presence of Raman
l
peaks at 220 and 634 cm' for CU3N thin films [11], at 212
l
l
cm' for CU3N nano rods and at 277 cm' for CU3N powder
[12]. Raman peaks in our sample are different from above
reports and may arise because of defects or disorders, or
oxygen impurities in the system.

Olil1m

Fig. 3 SEM images of the films grown at N2 flow rates of (a) 30 seem and (b)
40 seem (deposition time 20 mins.)
deposition time (or thickness) band gap starts to decrease and
then increases. Decrease in thickness of the film leads to
increase in disorders. Unsaturated bonds are the reason for
400

600

aoo

"W'ave ......her (."..-1)

such disorders and they produce localized states in the

11000

forbidden region which cause decrease in the band gap.

Fig. 2 Raman spectra of the CUJN films grown at N, flow rates of 30 and
40 seem (deposition time 20 mins.)
The SEM images of films grown for 20 minutes at Nz flow
rates of 30 and 40 sccm show uniformly distributed grains

However further decrease in thickness leads to increase in

band gap may be because of quantum size effect. Moreover,
the films deposited at 30 sccm N2 flow rate have lower band
gap than the films grown at 40 sccm N2 flow rate because of

(Fig. 3). The energy dispersive spectroscopy (EDS) reveals

82.7 and 17.3 atomic% of Cu and N respectively for the film
deposited at N2 flow rate of 30 sccm whereas 78.4 and 21.6

atomic% of Cu and N respectively for the film deposited at N2

541

 organized
Proceedings of the
by Sathyabama University, Chennai, India in association with DRDO, New Delhi, India, 24th _26tl" July, 2013
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ABLE I THICKNESS, CRYSTALLITE SIZE, BAND GAP AND PHONON ENERGY OF THE FILMS PREPARED FOR DIFFERENT DEPOSITION TIME AT N2 FLOW RATES
"International Conference on Advanced Nanomaterials & Emerging Engineering Technologies" (ICANMEET-20J3)

OF 40 AND 30 SCCM

Nz Flow Rate

Deposition Time

Approximate

Crystallite Size

Band Gap

(seem)

(mins.)

Thickness (nm)

(nm)

(eV)

40

20

516

17.3

10

287

10.7

20

538
424

15

143

30

11.5

418

15

7.3
16.0

12.4

312

10
5

[3]

films is found to vary from 1.02 to 1.40 eV by varying the N2

flow rate and deposition time.

[4]

,-___________--,

10

[5]

_10
o

[6]

r::::
as
t:

E40

r::::

f!
1-20

[7]

5GD

(b)

t5GO

tDGO

2IIGII

[8]

25DD

Wavelength (II1II)

[9]
[10]
[II]
[12]
2

O+---_.----r-
t.o

t.5

." (eV)

2.0

2.5

[13]

Fig. 4 (a) Transmission spectra of the films deposited for 20 mins. at N, flow
rates of 30 and 40 sccm (b) corresponding (ahv)'"2 vs. hv plot
IV. CONCLUSIONS
We have prepared CU3N thin films by pulsed DC reactive
magnetron sputtering at different nitrogen flow rate and
deposition time. Increase in Nz flow rate leads to increase in
nitrogen content in the film. The band gap is found to be
varied from 1.02 to 1.40 eV by varying N2 flow rate and
deposition time.
REFERENCES

[I]
[2]

1.35

l.l9

1.38
1.15

1.02

1.12

l.l5

170

higher copper content. Hence the band gap of the CU3N thin

(a)

1.40

M. Asano, K. Umeda, and A. Tasaki, "Cu1N thin film for a new light
recording media," Jpn. J Appl. Phys., vol. 29, pp. 1985-1986, Oct.
1990.
G.H. Yue, P.X. Yan, J.Z. Liu, M.X. Wang, M. Li, and X.M. Yuan,
"Copper nitride thin film prepared by reactive radio-frequency
magnetron sputtering," J Appl. Phys., vol. 98, pp. 103506 1-7, Nov.
2005.

542

Phonon Energy

115

(meV)

145

225
110

185
160
140

260

T. Maruyama, and T. Morishita, "Copper nitride and tin nitride thin

films for write-once optical recording media," Appl. Phys. Lett., vol.
69, pp. 890-891, Aug. 1996.
L. Maya, "Deposition of crystalline binary nitride films of tin, copper,
and nickel by reactive sputtering," J Vac. Sci. Techno!. A., vol. II, pp.
604-608, May. 1993.
D. M. Borsa, S. Grachev, C. Presura, and D. O. Boerma, "Growth and
properties of Cu,N films and Cu1N/y'- Fe.N bilayers," App!. Phys.
Lett., vol. 80, pp. 1823-1825, Mar. 2002.
C. Navio, M. J. Capitan, J. Alvarez, F. Yndurain, and R. Miranda,
"Intrinsic surface band bending in Cu1N(100) ultrathin films," Phys.
Rev. 8., vol. 76, pp. 085105 1- 8, Aug. 2007.
U. Hahn, and W. Weber, "Electronic structure and chemical-bonding
mechanism of Cu,N, Cu,NPd, and related Cu (I) compounds," Phys.
Rev. 8., vol. 53, pp. 12684-12693, May. 1996.
F. Hadian , A. Rahmati , H. Movla , and M. Khaksar, "Reactive DC
magnetron sputter deposited copper nitride nano-crystalline thin films:
Growth and characterization," Vacuum., vol. 86, pp. 1067-1072, Feb.
2012.
M. Ishii, T. Tanaka, T. Akahane, and N. Tsuda, "Infrared transmission
spectra of metallic Re03," J Phys. Soc. Japan., vol. 41, pp. 908-912,
Sep. 1976.
W. Yu, J. Zhao, and C. ,lin, "Simultaneous softening of Cu,N phonon
modes along the T2 line under pressure: A first-principles calculation,"
Phys. Rev. 8., vol. 72, pp. 214116 1-7, Dec. 2005.
A. Fallberg, M. Ottosson, and J. Carlsson, " Phase stability and oxygen
doping in the Cu-N-O system," J Cryst. Growth., vol. 312, pp. 17791784, Mar. 2010.
Z. Ying, FLY Lam, Y. ZiFeng, and H. XiJun, "Fabrication of copper
(I) nitride nanorods within SBA-15 by metal organic chemical vapor
deposition," Sci. China Ser. E: Techn. SCi., vol. 52, pp. 352-356, Feb.
2009.
1. Tauc, R. Grigorovici, and A. Vancu, "Optical properties and
electronic structure of amorphous germanium," Phys. Status Solidi B.,
vol. 15, pp. 627-637, Mar. 1966.