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Polycrystalline ZnTe thin film on silicon synthesized by pulsed laser deposition and

subsequent pulsed laser melting

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2016 Mater. Res. Express 3 036403

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 Mater. Res. Express 3 (2016) 036403 doi:10.1088/2053-1591/3/3/036403

PAPER

Polycrystalline ZnTe thin film on silicon synthesized by pulsed laser

RECEIVED
4 August 2015
deposition and subsequent pulsed laser melting
REVISED
24 December 2015
ACCEPTED FOR PUBLICATION
Menglei Xu1,2,3, Kun Gao1,2, Jiada Wu4, Hua Cai4, Ye Yuan1,2, S Prucnal1, R Hübner1, W Skorupa1,
20 January 2016 M Helm1,2 and Shengqiang Zhou1
PUBLISHED
1
Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Institute of Ion Beam Physics and Materials Research, Bautzner Landstrasse 400,
7 March 2016 D-01328 Dresden, Germany
2
Technische Universität Dresden, D-01062 Dresden, Germany
3
KU Leuven, B-3000 Leuven, Belgium
4
Department of Optical Science and Engineering, Fudan University, Shanghai 200433, People’s Republic of China
E-mail: menglei.xu@kuleuven.be

Keywords: ZnTe, pulsed laser deposition, pulsed laser melting, cyrstallization, low temperature process

Abstract
ZnTe thin films on Si substrates have been prepared by pulsed laser deposition and subsequent pulsed
laser melting (PLM) treatment. The crystallization during PLM is confirmed by Raman scattering,
x-ray diffraction and room temperature photoluminescence (PL) measurements. The PL results show
a broad peak at 574 nm (2.16 eV), which can be assigned to the transitions from the conduction band
to the acceptor level located at 0.145 eV above the valence band induced by zinc-vacancy ionization.
Our work provides an applicable approach to low temperature preparation of crystalline ZnTe
thin films.

1. Introduction

The II-VI semiconductor ZnTe has attracted considerable attention because of its potential to realize various
optoelectronic devices. Applications of ZnTe have been reported in fabricating terahertz (THz) wave emitters
and detectors [1, 2], light emitting diodes (LED) in the green spectral range [3, 4], multi-junction solar cells [5],
and photonic digitizing [6].
In order to realize ZnTe-based optoelectronic devices, preparation of high-quality ZnTe thin films is
essential. So far, ZnTe thin films have been prepared on various substrates including GaAs [7, 8], Au-coated Cu
[9], glass [10, 11], and ZnTe [12, 13] through different techniques, such as molecular beam epitaxy [7],
electrochemical deposition [9], radio frequency magnetron sputtering [10], metal-organic chemical vapor
deposition [12, 13], and pulsed laser deposition (PLD) [8, 11]. The motivation of incorporating optoelectronics
with Si-based technology requires the growth of ZnTe on Si substrate [6, 14, 15]. However, the synthesis of ZnTe
on Si is still challenging due to the significant lattice mismatch of 11%.
In this study, PLD followed by pulsed laser melting (PLM) is adopted to prepare polycrystalline ZnTe on
(001) oriented Si substrate at temperatures below 80 °C. The crystallization induced by PLM treatment has been
confirmed by Raman spectroscopy, x-ray diffractometer (XRD), and room temperature photoluminescence
(PL) measurements. The XRD patterns exhibit the polycrystalline nature of the ZnTe thin films. Presented
approach can be also applied to the synthesis of polycrystalline ZnOxTe1−x and ZnSxTe1−x on Si substrate at low
temperature.

2. Experimental details

Amorphous ZnTe thin films were deposited on polished (001) Si substrate by PLD. A bulk ZnTe target was
mounted on a rotating stage. The Si substrate was positioned parallel to the target surface at a distance of 40 mm.
A Q-switched Nd: YAG laser was utilized to ablate the ZnTe target (wavelength: 532 nm, pulse duration: 5 ns,

© 2016 IOP Publishing Ltd

Mater. Res. Express 3 (2016) 036403 M Xu et al

Figure 1. Room temperature Raman spectra from as-grown ZnTe and ZnTe treated by PLM with different laser energy fluences. The
spectra are vertically shifted for better visibility.

repetition rate: 10 Hz). The laser beam was focused on the target to a 1.2 mm2 spot with an energy fluence of
4 J cm−2. The bombardment of the species from the pulsed laser ablated plasma results in a slight temperature
rise (not more than 80 °C) of the substrate during the film growth. Other detailed descriptions of the experiment
have been provided elsewhere [16–18]. After deposition, the samples were processed by PLM. A coherent XeCl
excimer laser (Coherent COMPexPRO201) with a wavelength of 308 nm and a pulse duration of 28 ns was
uniformized by a fly-eye homogenizer and focused onto a 5×5 mm2 square spot [19]. The samples were
irradiated by one laser pulse with various energy fluences ranging from 0.1 to 0.3 J cm−2.
Raman spectra of the as-deposited and PLM-treated samples were recorded at room temperature in
backscattering configuration by a liquid-nitrogen-cooled charge coupled device (CCD). A Nd: YAG laser with a
wavelength of 532 nm was utilized as the excitation source. The crystallographic properties were studied using a
Bruker D8 XRD (θ-2θ scans) with Cu Kα emission. Room temperature PL measurements were taken using a
continuous 405 nm blue laser as the exciting light source. The luminescence was dispersed by a Jobin Yvon Triax
550 monochromator and then recorded by a Si photomultiplier (Hamamatsu H7732-10). A filter (RG 430) was
applied in the collecting light path, which indicates light with wavelength below 430 nm was cut off. The surface
morphology was analyzed using secondary electrons in a Hitachi S-4800 scanning electron microscope (SEM)
operated at an accelerating voltage of 10 kV.

3. Results and discussion

3.1. Raman
Raman spectra of the as-grown and PLM-treated ZnTe samples are illustrated in figure 1. No obvious peaks are
observed for as-grown ZnTe, whereas the longitudinal optical (LO) phonon modes of ZnTe are resolvable for
samples processed by PLM. The silence of Raman active modes from the as-deposited samples indicates an
amorphous structure. The appearance of the LO phonon modes suggests that the crystallization occurs during
PLM treatment. For the sample processed by PLM with the laser energy fluence of 0.3 J cm−2, peaks at about 203
and 406 cm−1 can be assigned to the first order 1LO and the second order 2LO phonon mode of ZnTe,
respectively. A significant redshift of the 1LO mode is observed for the PLM-treated samples compared to the
usual value of 206 cm−1 [20]. It has been reported that the phonon mode of a crystal under tensile strain is lower
than the strain-relaxed one [21]. However, the tensile strain induced by different thermal expansion coefficients
of ZnTe and Si cannot change the phonon behavior to such a significant scale. So the redshift of 1LO phonon
modes can be partially related to the imperfect crystallinity. The 1LO phonon mode shifts from 201 to 203 cm−1
by increasing PLM laser energy fluence from 0.1 to 0.3 J cm−2, which supports our hypothesis. On the other
hand, the composition fluctuation could be another reason to induce the redshift of the 1LO mode.
In addition, a peak appears at 267 cm−1 for the PLM-treated ZnTe samples, which is absent in bulk ZnTe
[22]. This peak can be assigned to the tellurium-specific mode since the formation of Te aggregates can be
induced by laser irradiation [23]. The minimum laser energy fluence of 0.1 J cm−2 used in our work is larger than
the threshold of laser-induced formation of Te aggregates, which was reported by Wiedemeier et al [24].

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Mater. Res. Express 3 (2016) 036403 M Xu et al

Figure 2. XRD patterns of ZnTe treated by PLM with different laser energy fluences, as well as the as-grown ZnTe for comparison. The
patterns are vertically shifted for a better visibility.

Table 1. Assignment of XRD peaks of ZnTe after PLM

treatment with different energy fluences. XRD data from
literature are listed for comparison [28].

XRD Peak 2θ (0.1/0.2/0.3 J cm−2) Reference

ZnTe(111) 25.5°/25.3°/25.5° 25.3°

ZnTe(220) 42.5°/42.2°/42.2° 41.8°
ZnTe(311) 49.7°/49.9°/49.6° 49.5°

Figure 3. Normalized room temperature PL spectra of ZnTe treated by PLM with different laser energy fluences, as well as the as-
grown ZnTe for comparison.

3.2. X-ray diffraction

As illustrated in figure 2, no characteristic diffraction maxima of crystalline ZnTe are observed for as-grown
ZnTe. Bragg reflections appear only for samples after PLM treatment. The peaks at about 2θ=25°, 42°, and 49°
are assigned to the 111, 220, and 311 reflections of cubic ZnTe, respectively, which indicates a polycrystalline
structure of the thin films after PLM process. The peaks at 27.5° and 38.4° can be assigned to the 101 and 102
diffraction maxima of crystalline Te, respectively [25–27]. Hence, the XRD patterns further verify the formation
of crystalline ZnTe after PLM treatment, which is consistent with the Raman results. A list of the peak positions
for ZnTe processed by different PLM conditions is given in table 1. In addition, the Bragg peak positions
according to ICDD-PDF card 15–746 are listed for reference [28].

3.3. Room temperature photoluminescence

The normalized room temperature PL spectra of the as-grown and PLM-treated ZnTe samples are depicted in
figure 3. Small peak visible in all presented PL spectra at about 405 nm is due to the imperfect filtering of the
exciting laser by the RG 430 filter. Peaks at 432 and 442 nm with shoulder at 467 nm are observed for PLM-
treated and as-grown ZnTe, respectively. Those luminescences may originate from non-stoichiometric

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Mater. Res. Express 3 (2016) 036403 M Xu et al

Figure 4. SEM surface micrographs: (a) as-grown ZnTe, and PLM-treated ZnTe with laser energy fluences of (b) 0.1 J cm−2, (c)
0.2 J cm−2, and (d) 0.3 J cm−2.

ZnxTeyOz, which are consistent with the bandgaps of ZnxTeyOz alloys [29, 30]. The oxide layer formed during
sample exposure to the air after deposition is amorphous in the as-grown sample. PLM process leads to the
recrystallization of the as-grown ZnTe layer and the oxide layer simultaneously. Therefore, the blue shift of the
blue emission peaks from 442 to 432 nm is attributed to the recrystallization of ZnxTeyOz layer. Recently, similar
phenomenon was observed in ZnO films synthesized by PLD and subsequent flash lamp annealing [31]. The
thickness of the naturally grown oxide is expected to be not more than 5 nm. Therefore, its presence was not
detected by either Raman spectroscopy or XRD.
The green emission peaks have been observed for PLM-treated ZnTe samples, corresponding to the ZnTe
bandege. The strong well resolved luminescence peaking at 574 nm (2.16 eV) was revealed for the sample
processed by PLM with the energy fluence of 0.1 J cm−2. This relatively broad peak can be assigned to the
transitions from the conduction band to the acceptor level at 0.145 eV above the valence band induced by zinc-
vacancy ionization [32]. An increase of the PLM laser energy fluence results in a slight blue shift of the green
emission, which is an indication of the improvement of the crystal quality of synthesized films. Both Raman and
XRD results indicate that no crystalline ZnTe is formed after PLD, which can explain the absence of green PL
emission for the as-grown ZnTe.

3.4. Surface morphology

Top-view SEM micrographs of ZnTe are shown in figure 4. The surface of the as-grown ZnTe is smooth.
Compact grains of the PLM-treated ZnTe are observed, as depicted in figures 4(b) and (c). The grain size is
strongly dependent on the laser energy fluence. In the low fluence range (0.1 J and 0.2 J cm−2), the SEM
micrographs indicate an increase in the average grain size with increasing PLM laser fluence. However, the
microstructure becomes dramatically different for ZnTe processed with high PLM laser energy fluence of
0.3 J cm−2 (see figure 4(d)). A transition from nano-crystalline thin film to a more 3-D-like structure was
observed. This phenomenon can be attributed to complete melting and recrystallization for ZnTe processed by
high PLM laser energy fluence. Similar results have been reported in the case of recrystallization of amorphous Si
thin films using PLM [33].

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Mater. Res. Express 3 (2016) 036403 M Xu et al

4. Conclusion

ZnTe thin films on (001) oriented Si substrate were prepared by PLD followed by PLM treatment. The post PLM
process results in the formation of polycrystalline ZnTe thin films. Raman, XRD, and PL analyses confirm the
crystalline structure of the PLM treated ZnTe. Note that during PLM, the substrate has been kept at room
temperature. This low temperature process opens possibilities to prepare polycrystalline ZnTe-based thin films
on various kinds of substrates including flexible plastic substrates with a low melting point.

Acknowledgments

The authors would like to thank Elfi Christalle and Jörg Grenzer for their help with the SEM and XRD
measurements, respectively. Menglei thanks Yanda Ji for his careful discussion on XRD results. The work is
financially supported by the Helmholtz-Gemeinschaft Deutscher Forschungszentren (HGF-VH-NG-713).

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