Journal of Luminescence 215 (2019) 116642

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Photoluminescence of Cu2O nanostructured in stressed thin films induced by T

temperature
G. Martínez-Saucedoa, C.G. Torres-Castanedob, S. Arias-Cerónc, R. Castanedo-Péreza,*,
G. Torres-Delgadoa, O. Zelaya-Ángeld
a
Centro de Investigación y de Estudios Avanzados del I.P.N., Unidad Querétaro, Querétaro, 76230, Querétaro, Mexico
b
Department of Materials Science and Engineering, Northwestern University, Evanston, IL, 60208, USA
c
SEES-Depto. de Ingeniería Eléctrica, Centro de Investigación y de Estudios Avanzados del I.P.N., A.P. 14-740, Ciudad de México, 07360, Mexico
d
Depto. de Física, Centro de Investigación y de Estudios Avanzados del I.P.N., A.P. 14-740, Ciudad de México, 07360, Mexico

ARTICLE INFO ABSTRACT

Keywords: Cu2O nanostructured films were prepared by the dip-coating method with average crystallite size of 10 ± 1 nm.
Cu2O thin films The photoluminescence of Cu2O was studied for different temperatures in the 70–300 K interval. The range of
Low-T photoluminescence wavelengths analyzed was 360–1000 nm. Two photoluminescence systems were used, with an excitation line of
Dip coating 325 nm He–Cd and 488 nm Ar laser, at different power. Several interband and excitonic transitions at energies in
Stressed films
the 1.8–2.8 eV interval were identified for Cu2O where an intensity shift toward lower energies was observed as
Cu2O thermal expansion coefficient
the temperature was increased. The difference of the thermal expansion coefficients (α) between the Cu2O and
Excitons
the soda-lime substrate induces change from compressive to tensile stress within the 70–300 K interval. This
change is a consequence that α value for Cu2O is negative and for soda lime is positive in that temperature
region. Raman spectra as a function of temperature, show a frequency shift for all modes studied and α values of
thin film Cu2O were estimated from these shifts at 77 and 280 K. The stress (σ) on the Cu2O film was calculated
considering the decrease of the temperature in this interval. The effect of this stress on the energy band structure
is related to the shift of the PL bands.

1. Introduction pioneer works of Frerichs et al. (1959) [12] and Vorobiev et al. (1961)
[13] up to date, little advance has been obtained, however, in very
Cuprous oxide (Cu2O) is a semiconductor material, which has recent works [14,15], by means of heterojunctions with other semi-
gained a lot of interest since the seventies of the last century [1], be- conductors, light emitting Cu2O based devices have been fabricated.
cause of its various technological applications. Interest in Cu2O as a Therefore, efficient electro-optical devices based on cuprous oxide seem
semiconductor grew with the fabrication of rectifier devices for the first to be a close goal.
time by L.O. Grondahl in 1920 [2]. Most of the research carried out to The optical, electrical, thermal and magnetic properties of cuprous
date on the applications of Cu2O has been focussed on low cost ter- oxide make Cu2O a very interesting material. Cu2O is a compound
restrial solar cell design and fabrication. Despite the moderate con- semiconductor whose fundamental properties depend a lot on the
version efficiencies (η) reached to date (~8.1%) [3], efforts continue to growth technique and the preparation conditions [11]. The band gap
push efficiencies towards the theoretical maximum η = 20% for energy and photoluminescent (PL) properties experience notable
homojunction solar cells [4]. In recent years, other technological ap- changes due to different characteristics: particle size, stress, mor-
plications for Cu2O have been reported, for instance, in the preparation phology, annealing, doping, etc., which are partially a consequence of
of photocatalysts [5], batteries [6], antibacterials [7], detectors [8], the crystalline conditions and some non-understood properties of the
among others. The ferromagnetic and luminescent properties of Cu2O lattice [16,17]. Currently, subjects like Bose-Einstein excitons con-
are also topics of intense research [9], since in the former, results in- densation [18] and Giant-Rydberg excitons [19] occupy the attention of
dicate that lattice defects enhance ferromagnetism [10]. Concerning many researchers because of their important repercussions on the
light emission, the main problem is the weak luminescent efficiency, knowledge of the structural properties of Cu2O. The advances on the
probably due to forbidden transitions in the material [11]. From fundamental physical and chemical properties of Cu2O, will contribute

*
Corresponding author.,
E-mail addresses: [email protected], [email protected] (R. Castanedo-Pérez).

https://doi.org/10.1016/j.jlumin.2019.116642
Received 26 January 2019; Received in revised form 11 July 2019; Accepted 24 July 2019
Available online 26 July 2019
0022-2313/ © 2019 Elsevier B.V. All rights reserved.
G. Martínez-Saucedo, et al. Journal of Luminescence 215 (2019) 116642

Fig. 1. (Top) Diffractogram for 20 ≤ 2θ ≤ 80° of the Cu2O film treated with
rapid thermal annealing at 425 °C in vacuum. (Bottom). Standard diffraction
Fig. 3. Optical transmittance in the 400–800 nm (1.5–3.0 eV) interval of the
reflections of Cu2O. The inset exhibits the 100% intensity reflection of CuO,
Cu2O film. The inset illustrates the Tauc's method employed to calculate the
Cu4O3, Cu3O2 and Cu2O oxides. CuO: PDF #48–1548. Cu2O: PDF #05–0667.
direct forbidden transitions band gap (Eg1) and the direct band gap (Eg2).
Cu4O3: PDF #49–1839.

temperature for 10 s. X-Ray diffraction (XRD) characterization was

performed with a Rigaku D/Max 2100 diffractometer with
Kα1 = 1.54 Å. Crystallite mean size (CS) was estimated with Scherrer's
formula using Jade 5® analysis software, calibrated with a Si standard.
Film thickness was determined with a Dektak II profilometer. Optical
absorbance measurements were performed with a Cary-5000 (Agilent
Technologies) spectrophotometer in the 350–1300 nm range. As both
sides of the substrate are film-coated, only the film exposed to the va-
cuum during the RTA was characterized. The film at the back side was
removed with a 10% HCl solution previously to the transmittance and
absorbance measurements. Morphological properties were determined
by scanning electron microscopy (SEM) using a JEOL electron probe
microanalyzer model JXA-8530 F. PL spectra were obtained employing
two different measurements systems: (a) HeCd-laser (Omnichrome–-
Series 56) λexc = 325 nm, cylindrical lens of 0.5 mm × 0.15 mm and
power = 15 mW, with a Ag–Cs–O photodetector. (b) Horiba Labram HR
Evolution spectrometer, Ar laser λexc = 488 nm, X50 lens,
power = 20 mW and provided with a Si detector. Raman measurements
Fig. 2. SEM image at 100,000X of the Cu2O sample after RTA at 425 °C for 10 s.
Uniform surface constituted of nanocrystalline clusters.
were performed with a Horiba Aramis Raman spectrometer, solid-state
laser λexc = 473 nm, X50 lens, power = 7.91 mW and utilizing a Si
detector. PL and Raman spectra were obtained at different temperatures
to the understanding of the electronic transitions in the band structure, in the 70–300 K range.
which will be useful for the fabrication of more efficient electro-optical
devices. In this work the photoluminescence as a function of tempera-
ture of Cu2O nanostructured thin films, prepared by the dip-coating 3. Results and discussion
method on soda-lime substrates is reported. The difference of the sub-
strate-Cu2O thermal expansion coefficients, which introduces stress on The diffractogram of the CuO film after the RTA treatment is shown
the thin film, along with phase transformation in the material at critical in Fig. 1. Only the Cu2O cuprite crystalline phase was detected. The full
temperatures, may originate notable alterations on the PL emission transformation from CuO to Cu2O was verified by other techniques in a
spectra. previous work [20]. The inset in Fig. 1 shows the diffractogram in the
35.2° ≤ 2θ ≤ 37.6° interval where no contribution of other Cu-based
2. Experimental oxides to the Cu2O films is observed from the XRD measurements (at
2θ ~ 36°, 100% intensity is reported for all the four oxides) [21]. From
Cupric oxide (CuO) films were initially deposited on glass substrates this XRD data and by using Scherrer's formula, an average crystalline
(soda-lime Velab®) at room temperature (RT) by the dip-coating grain size of 10 ± 1 nm was estimated. Fig. 2 illustrates the SEM image
method; the preparation process was described previously [20]. Rapid of surface of the sample after RTA, where a uniform texture of nano-
thermal annealing (RTA) treatments were performed in a closed crystalline clusters is obtained. The optical transmittance is about 70%
chamber at a vacuum pressure of ~1 × 10−5 Torr. For heating, the after the absorption band edge, as exhibited in Fig. 3. The inset shows
sample was placed between two graphite plates which absorb radiation Tauc's method employed to calculate the forbidden direct transitions
generated by halogen lamps. One side of the sample is resting on the band gap (Eg1), and the direct allowed transition band gap (Eg2). For Eg1
graphite plate and the other is exposed to the vacuum. An initial de- calculation (αhν)2/3 versus hν was plotted (here α is the optical ab-
gassing treatment stage in the chamber was applied to the sample at sorption coefficient, d the thickness, and hν the photon energy), and for
200 °C for 5 min. After that, the samples were rapidly heated at 425 °C Eg2, (αhν)2 versus hν was used. The intersection of the extrapolated
through a non-conventional heating ramp of 5 °C/s. Once the anneling straight line with the energy axis indicates that Eg1 = 2.37 ± 0.03 eV
temperature (TA) set-point was reached, the sample remained at this and Eg2 = 2.58 ± 0.05 eV. In this case, Eg2 is larger than Eg1 as

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G. Martínez-Saucedo, et al. Journal of Luminescence 215 (2019) 116642

Fig. 4. a) Photoluminescence spectra a) with λexc = 488 nm and b) (λexc = 325 nm), for all temperatures (70–300 K interval).

reported in the literature [22,23]. The increase of Eg1 and Eg2 with blue exciton series of Cu2O, (E7) ~2.6 eV to the limit of the blue exciton
respect to the reported values is mainly attributed to quantum con- series interband transitions ( +7 → 8 ) and (E8) ~2.8 eV to the limit of the
finement effects [24]. indigo exciton series interband transitions ( +8 → 8 ) [11].
Cu2O luminescence is expected to be of low-intensity due to the The intensity values of the PL maxima and the integrated intensity
symmetry of the electron band which does not allow a dipole transition of spectra as a function of temperature are displayed in Fig. 7. Both
between the valence band (VB) maximum and the conduction band parameters show a very similar decrease as temperature increases,
(CB) minimum [11]. Nevertheless several processes have been em- which could be an indication that the PL intensity decay for all the
ployed to overcome this barrier in Cu2O, for instance stress [25], temperature values is originated, in general, by the same processes for
quantum confinement [26], doping [27], applied electric field [28], etc. all the emission wavelengths studied. In general, the intensity di-
The energy symmetry and degeneracy of the bands due to the distortion minishes because of the increasing of the non-radiative electron-hole
produced by the stress change in such a way that the transitions be- recombination rate when temperature increases, like the case of InGaN/
tween the VB maximum and the CB minimum become dipole allowed GaN quantum wells [34] and Si nanocrystals [35].
[25,26]. Before the discussion about band position in the energy axis as the
PL spectra measured at different temperatures in the 490–1000 nm temperature varies from 70 to 300 K, a thermal analysis of the materials
and in the 360–950 nm range are shown in Fig. 4a and b, respectively. will be considered. The thermal expansion coefficient of the Cu2O oxide
The first spectra were obtained using λexc = 488 nm as an excitation in bulk (αCu2O) [36] and soda-lime substrate (αsub) [37] vs temperature
line and the second at λexc = 325 nm. Both figures show a shift of the is shown in Fig. 8. Observe that αCu2O has a negative value and positive
central maxima intensity of some emissions for several temperatures, in for the αsub in the entire interval 12 ≤ T ≤ 300 K. It has been reported
comparison with others. In general, there is an increase in PL intensity that αCu2O becomes positive just above RT. This means that from 12 K
as the temperature is lowered. Fig. 5a–f shows the deconvolution Cu2O is always compressed with respect to the lattice volume at RT, and
method used for the exact determination of each band center, at three at T ~70 K the compression starts to diminish for Cu2O. The soda-lime
temperatures. Gaussian curves were used for the fitting. Fig. 5g and h swells along all the 12–300 K interval. In this way, the Cu2O film is
shows an overlapping of the PL signal emitted by the soda-lime glass subjected, besides its own compression, to the influence of the tensile
substrate and the PL signal of the Cu2O thin film deposited over the stress from the substrate. From T > ~70 K, |α|sub > |α|Cu2O, then the
substrate. The PL emission for the soda-lime glass substrate is shown in substrate always has a larger tensile stress than the compressive one for
Fig. 5i and j where the same deconvolution method was used. Several Cu2O. For the-film, which is not detached from the glass, the tensile
emission peak values were determined for the soda-lime glass substrate, strain on Cu2O dominates the compressive one. On the other hand,
at 1.53, 1.63 and 1.77 eV for λexc = 488 nm, and at 2.04, 2.23 and Young's modulus of Cu2O films is larger than the one of soda-lime glass
2.95 eV for λexc = 325 nm. Emission peak values assigned to the Cu2O [38,39]. All these combined properties may contribute for the enabling
film at low temperature are labeled as E1-E8 in Fig. 6a and b. of forbidden to allowed transitions in Cu2O [25,26].
The identification of these eight PL emissions, according to the lit- For the estimation of the stress intensity levels on the layers due to
erature, are associated with the following radiative transitions: (E1) temperature changes, the α value of the Cu2O thin film was calculated.
~1.9 eV to the formation of exciton-defect complexes [29], (E2) ~2.0 eV Raman spectroscopy has been reported as a practical and non-destructive
to phonon-assisted direct recombination of ortho-excitons [11,30–33] technique for estimating α in thin film materials such as graphene [40].
and (E3) ~ 2.2 eV to the fundamental direct forbidden band gap energy Raman measurements of the Cu2O thin film and soda-lime glass substrate
transition of Cu2O [11]. Transitions (E4, E5) ~ 2.3 eV to the limit of the at room temperature are shown in Fig. 9a. Several vibrational modes
green exciton series of Cu2O which corresponds to interband transition with different symmetries of Cu2O are identified: (T2u) ~ 90 cm−1,
( +8 → +6 ), where splitting of the valence band is present due to spin-orbit (Eu) ~ 110 cm−1, (T1u) ~ 145 cm−1, (2Eu) ~ 220 cm−1 and
−1
interactions [11]. Transition (E6) ~ 2.4 eV to excitonic transitions in the (T1u) ~ 618 cm [11]. Raman spectra of Cu2O for some temperature

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G. Martínez-Saucedo, et al. Journal of Luminescence 215 (2019) 116642

Fig. 7. Integrated area and maximum intensity from all photoluminescence

spectra shown in Fig. 4.

Fig. 5. Gaussian deconvolution used to determine the center of the emission

lines at specific temperatures. (a–f) Cu2O/soda-lime glass substrate, (g–h)
Comparison between Cu2O/soda-lime glass and soda-lime glass PL signals, (i–j)
soda-lime glass substrate.

Fig. 8. Thermal expansion coefficients (α) of the bulk Cu2O ( ) and of the soda-
lime glass substrate ( ) taken from the literature, and those estimated for Cu2O
thin films in the present work (✰).

values are shown in Fig. 9b. The shift of maximum values of the T1u
mode is plotted in the inset as a function of temperature. A shift in fre-
cuency T (Tm ) can be observed as temperature varies, where for thin
films Yoon et al. has deduced the following equation [40]:

T (Tm ) = E
T (Tm ) + A
T (Tm ) + S
T (Tm ) (1)
Fig. 6. PL emission energies (E1-E8) identified for Cu2O thin films at low where E
corresponds to the shift caused by thermal expansion of the
T
temperature and obtained at a) λexc = 488 nm and b) λexc = 325 nm. crystal lattice, T to an anaharmonicity effect and T to the stress
A S

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G. Martínez-Saucedo, et al. Journal of Luminescence 215 (2019) 116642

Tm Tm

T (Tm ) = T (0)exp 3 Cu2 O dTm sub Cu2 O dTm

0 0 (7)

By a numerical solution, the experimental value for Cu2 O was es-

timated at 77 K and 280 K using approximate values reported for and
sub [36,37]. For 280 K the α value for quartz was used since there is no
data available for soda-lime glass, although the values between both
materials are very similar. The values estimated for Cu2 O are shown in
Fig. 8 (✰). It has been determined that these values are approximate to
those that have been previously reported for Cu2O bulk [36], and the
tendency to decrease under compression as temperature rises above
77 K towards RT has been confirmed.
Since the Cu2O thin film experiences stress levels when it is cooled,
the strain was estimated from Cu2 O and sub values:

l (T ) = l 0 T ( sub Cu2 O ) (8)

where l 0 represents the initial lenght of the sample (5 mm) and l (T ) is

the length difference between the thin film and the substrate, if each
were considered as a separate system. Assuming that strain is only
elastic and, using the reported Young's modulus ECu2 O
(98.5 ± 6.9 GPa) [38] the stress on the thin film ( Cu2 O ) is given by:

Cu2 O = ECu2 O T ( sub Cu2 O ) (9)

The stress experienced by the Cu2O thin film deposited on soda-lime

glass substrate, when T decreases from 280 to 77 K was estimated to be
Cu2 O = 111.7 MPa .
The hν-energy position of the center of the E1 to E8 PL-bands is
depicted in Fig. 10. Observe that, the hν position does not follow a
monotonic behavior but the bands experience irregular changes as T
Fig. 9. a) Raman measurements of both, Cu2O thin film/glass and soda-lime increases, mainly in the central part of the T-interval. In general for all
glass substrate (Sub.) at room temperature, b) Temperature dependence of the PL bands, there is a shift to lower hν values as temperature increases.
Cu2O T1u mode and change in Raman shift (inset). This shift in energy is directly related to the decrease of the band gap as
the interatomic distance in the lattice grows, when the temperature is
increased.
produced by differences in αCu2O and αsub. The T term may be ne-
A
Note that generally, the curves suffer abrupt changes around
glected since the temperature interval that is studied is below the Debye T = 160 and 220 K, this fact is caused by transitions of Cu2O at these
temperature ΘD(T) for Cu2O, thus, its contribution is very low [41,42]. temperatures. Some transitions are: Rhöler and coworkers report
A second term may be employed for T (Tm ) where T (0) is ex- changes in the Cu–Cu disorder exactly at these two temperatures [44].
trapolated from the data plotted on the inset of Fig. 9b (641.53 cm−1) Chen et al. found antiferromagnetic to ferromagnetic transition in Cu2O
which corresponds to the Raman frequency at 0 K [43]: at 160 K [45]. Möller [46] and coworkers report desorption of water
molecules from the Cu2O surface at 155 K, which has been associated
T (Tm ) = T (0) T (Tm ) (2)
with changes in the hydrophilic properties of the surface. All these
Eq. (1) can be rewritten as: Cu2O characteristics around these T values can be associated with
changes in the lattice and/or electronic structure.
T (0) T (Tm ) =[ T (0)
E
T (Tm )] [ T (0)
S
T (Tm )] (3)

For the E
T and S
T terms the following expressions are given [40]: 4. Conclusions

Tm
The influence of compressive and tensile stress on the photo-
E
T (Tm ) = T (0)exp 3 Cu2 O dTm luminescence of nanostructured films of Cu2O for different luminescent
0 (4) emissions in the 360–1000 nm wavelength interval was studied. The
stress on the Cu2O films was induced by the temperature variation of
Tm the PL measurements in the 70–300 K range. In this T interval, the Cu2O
S
T (Tm ) = sub Cu2 O dTm suffers strains because of the difference of the thermal expansion
0 (5) coefficients between Cu2O and the soda-lime substrate. The stress also
contributes for direct forbidden transitions to allowed ones. Raman
where represents Grüneisen parameter for Cu2O and the biaxial
spectroscopy was used for the quantification of stress parameters for
stress coefficient of the T1u mode where:
thin films such as α. In addition, the Cu2O lattice experiences remark-
= 2 T (0) (6) able changes in the Cu2O atomic framework which, in turn, produce
noticeable alterations in the electronic transitions at about 160 and
Combining Ecs. 3–5 the following expression is obtained: 220 K, which are reflected in the luminescent emissions spectra.

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G. Martínez-Saucedo, et al. Journal of Luminescence 215 (2019) 116642

Fig. 10. hν-position centers of the PL E bands as a function of temperature, for the E1-E8 emissions.

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