J Mater Sci: Mater Electron

DOI 10.1007/s10854-017-7685-9

Comparative study of multilayered ZnO/TiO2/ZnO and ­TiO2/

ZnO/TiO2 thin films prepared by sol–gel dip coating method
M. I. Khan1 · Muhammad Saleem2,3 · K. A. Bhatti4 · Rabia Qindeel5 ·
Hayat Saeed Althobaiti5 · Noorah Alonizan5

Received: 1 June 2017 / Accepted: 10 August 2017

© Springer Science+Business Media, LLC 2017

Abstract The aim of this research work is to represent the 1 Introduction

comparative study of ZnO/TiO2/ZnO (ZTZ) and T ­ iO2/ZnO/
TiO2 (TZT) thin films deposited by sol–gel dip coating on In recent years, thin film technology has gained significant
FTO substrates. After deposition, the films were annealed at consideration because of its potential applications in opti-
500 °C for 1 h. Structural, surface morphology, optical and cal, electronic and optoelectronic devices. In spite of the
electrical properties of these films were studied by X-ray fact that utilization of single layer thin films have ascended;
diffractrometer (XRD), Raman spectra, atomic force micro- many applications demand multilayer thin films that join the
scope (AFM), photoluminescence spectra (PL) and four properties of different materials. Mostly, the multilayer films
point probe technique respectively. XRD and Raman spectra are used in the design of optical reflectors, computer disks,
confirmed the anatase, brookite phases of T ­ iO2 and cubic anti-reflecting coating and solar cells [1]. Results showed
phase of ZnO. AFM confirmed the formation of nano parti- that the coupled semiconductors have larger optical and elec-
cles with average sizes of 18.4 and 47.2 nm of TZT and ZTZ trical properties as compared to a single semiconductor due
films respectively. According to PL spectra, both the multi- to synergistic role of two semiconductors [2–4].
layer films slowdown the electron hole recombination rate The performance of device which is based on ZnO and
and enhances the optoelectronic properties of the materials. ­TiO2 thin films is directly connected to the quality of crys-
Also it showed the peaks in the visible region of spectrum. talline structure of ZnO thin films first. In Comparison
The four point probe results showed that the average sheet with ZnO, T ­ iO2 has similar energy band gap approximately
resistivity of the films is 450 and 120 (ohm-m) respectively. 3.2 eV [5]. Both have outstanding properties and large appli-
cations in material science therefore take much attention of
researchers. However, the intrinsic characteristics of both
* M. I. Khan semiconductors are different as one has direct energy band
[email protected] gap (ZnO) and other has indirect energy band gap (­ TiO2) [6].
Muhammad Saleem Up to now, plethora of techniques has been employed to
[email protected] fabricate ZnO and T ­ iO2 thin films such as sol–gel process
1
Department of Physics, The University of Lahore,
[5], spray pyrolysis [7] and chemical vapour deposition [8].
Lahore 53700, Pakistan Among all the process, sol–gel dip coating is a low cost,
2
Department of Physics, COMSATS Institute of Information
environmental friendly, easy to handle and large area deposi-
Technology, Lahore 54000, Pakistan tion technique [9]. To the best of our knowledge, there is no
3
Department of Basic Sciences and Humanities, Khawaja
comparative study on multilayer ZnO/TiO2/ZnO (ZTZ) and
Fareed University of Engineering and Information ­TiO2/ZnO/TiO2 (TZT) films on FTO substrate. Therefore, in
technology, Rahim Yar Khan, Pakistan this study, multi-layers ZnO/TiO2/ZnO and ­TiO2/ZnO/TiO2
4
Department of Physics, Laser and Optronics Center, UET, have been synthesized using sol–gel dip-coating route for the
Lahore 54800, Pakistan comparative study of their crystalline structure, morphology
5
Department of Physics and Astronomy, College of Science, (surface roughness), optical and electrical properties.
King Saud University, Riyadh 11451, Saudi Arabia

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 J Mater Sci: Mater Electron

2 Experimental section at room temperature and excited by the 365 nm line of an

ozone-free xenon arc lamp, employing a Horiba JobinYvon
2.1 Preparation of ZnO and ­TiO2 solutions Fluoromax-3 Fluorescence Spectrometer Four point probe
technique (KIETHLEY Instrument) is used to study the elec-
For the preparation of samples, following chemicals were trical properties. This instrument has measure voltage of
purchased and used without further purification: titanium 1–120 nV, current source of 6220 DC and source current of
dioxide nano powder (­ TiO2, chemical purity 99.5%), zinc 2 nA to 105 mA. The thickness of the films was measured
acetate dihydrate [Zn(CH3COO)2·2H2O, chemical purity by surface perfilometer (AMBIOS).
99.5%] (ZAD), diethyleneglycol ­(C 4 H 10 O 3 , chemical
purity 99.5%) (DEG), 2-methoxyethanol [(CH3O(CH2)2)
OH, chemical purity 99.5%] (2-ME), monoethanolamine 3 Results and discussion
[((HOCH2CH2)NH2), chemical purity 99.5%] (MEA) and
ethanol ­(C2H6O, chemical purity 99.95%),all of them from 3.1 XRD analysis
Fluka.
The steps involved in this experiment were as follows: Figure 1 showed the XRD micrograph of TZT and ZTZ mul-
tilayer thin films annealed at 500 °C. The graph is measured
1. 2.4 g of ZAD was placed in flat-bottom 250 ml conical at the scanning range from ­20o to ­80o. The peaks obtained
flask. at the angles of 25.3, 38.0 and 48.1 degrees corresponding
2. 50 ml of solvent (2-ME) was added to the conical flask. to (101), (004) and (200) planes of reflections respectively,
3. The solution was stirred at 60 °C for 30 by using mag- confirmed the anatase phase of T ­ iO2 according to standard
netic stirrer. card number PDF#21-1272. These results are in good agree-
4. After stirring for 30 min at 60 °C the stabilizer (MEA) ment with the results of Wang et al. [10]. The peaks obtained
was added drop wise under constant stirring for 90 min at the angles of 26.4, 52.0 and 65.0 degrees, corresponding
at 60 °C. The solution was then aged for 24 h. to (111), (204) and (213) planes of reflections respectively,
5. The procedure for the preparation of T­ iO2 solution was confirms the brookite phase of T ­ iO2, according to standard
the same as discussed above, 2.4 g of ­TiO2 powder was card number PDF # 29-1360. Meanwhile the peaks obtained
added in 50 ml solvent (ethanol) and 5 ml stabilizer at the angles of 33.5 and 61.3 corresponding to (200) and
(DEG). This mixture was stirred for 72 h at 60 °C to (220) planes of reflections respectively, confirms the cubic
yield a homogeneous and milky white solution of ­TiO2. phase of ZnO according to PDF # 65-2880. Therefore, it
can be suggested that the multilayer films of ­TiO2 and ZnO
annealed at 500 °C consists of anatase and brookite T ­ iO2
2.2 Preparation of ZTZ and TZT thin films particles and cubic ZnO particles. In addition, most diffrac-
tion peaks in the XRD pattern are sharp, which further indi-
ZTZ and TZT multilayered thin films were deposited by cated that the particles of T
­ iO2 and ZnO in the composites
sol–gel dip coating at a withdrawal speed of 100 mm min−1. films have high crystallinity. The results are also identified
Prior to the film deposition two pieces of FTO (fluorine- with literature [10, 11].
doped ­SnO2) glass substrate were cleaned with acetone and
ethyl alcohol for 30 min, respectively. Films were depos- 3.2 AFM analysis
ited three times using dip coating technique. The films were
dried at 100 °C for 20 min in vacuum oven. Finally, the films Figure 2a, b showed the AFM images of TZT and ZTZ thin
were annealed at 500 °C for 1 h. films deposited by “sol–gel dip coating technique”. The
The crystallinity and phases of the ZnO/TiO2/ZnO (ZTZ) particles are clearly seen and are homogenous. The aver-
and ­TiO2/ZnO/TiO2 (TZT) films were studied by using a age particle size of TZT and ZTZ films is 18.4 and 47.2 nm
Bruker D8 X-ray diffractometer (XRD) with operating con- respectively. In TZT thin film, the thickness of T ­ iO2 first
ditions of 40 KV and 100 mA, with CuKα radiation wave- layer, ZnO second layer and T­ iO2 third layer is 71.54, 50.45
length of λ = 1.5406 Å. Data was collected from 20° to 70° and 68.75 nm respectively. In ZTZ thin film, the thick-
at a scanning speed of 40 min−1. The surface morphology of ness of ZnO first layer, T
­ iO2 second layer and ZnO third
films was carried out by “Field Emission Scanning Electron layer are 51.57, 70.64 and 48.96 nm respectively. The total
Microscopy (FE-SEM, Nova-400)”. The optical absorption thickness of TZT and ZTZ films are approximately 190.74
spectra were recorded by using a “UV–Vis double beam and 171.17 nm respectively. The distribution of particles
spectrophotometer” (Agilent 8453 spectro-photometer) at is affected by incorporation of ­TiO2 with ZnO and also on
room temperature in the wavelength range 200–1100 nm. the deposition temperature [12]. The electrical properties of
Photoluminescence (PL) measurements were performed films depended on the particle size [13]. The large particle

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J Mater Sci: Mater Electron

Fig. 1  XRD pattern of TZT TZT

and ZTZ films
4 ZTZ

B (204)
A (004)
B (111)
ZTZ Film
3

Z (200)

B (213)
A (101)

Z (220)
Intensity (a.u.)
2

A (200)
1
TZT Film

0
20 30 40 50 60 70

Angle 2θ (degree)

Fig. 2  AFM images of a TZT

and b ZTZ thin films

sizes reduce the grain boundaries which improved the sur- 3.3 PL analysis
face contact between particles. Therefore, electrons can
easily move from grain to grain which enhance the electri- Photoluminescence spectra at room temperature of TZT and
cal properties [14]. As ZTZ film has large particle size as ZTZ films are explained in Fig. 4. Both the films exhibited
compared to TZT film therefore the electrical conductivity the PL emission peaks at 550–800 nm. The PL emission
of ZTZ is larger than TZT. The increase in grain size of ZTZ ­ i4+–OH, when
could be attributed to the surface state like T
support I-V characteristic in Fig. 5 and reported resistivity excited with light having energies larger than the band gap
is decreased as compared to TZT film. of the samples [16, 17]. Generally, visible luminescence is
Film inner structure, crystallinity, texture and morphol- produced due to structural defects which are related to the
ogy are strongly dependent to roughness evolution The sur- deep-level emissions, like interstitial oxygen (yellow emis-
face roughness profile of TZT and ZTZ films is shown in sion at 580–620 nm) and oxygen vacancy (green emission
Fig. 3. The average roughness of TZT film is 0.29 which is at 500–540 nm) [18, 19].
higher than ZTZ film which has 0.23 roughness. The low Both the films exhibit the yellow, red and near infrared
roughness indicates the enhancement of crystalline quality emissions at 580, 705 and 783 nm respectively. A yellow
[15]. Therefore, ZTZ film shows high crystallinity as com- emission peak at 580 nm is attributed to the recombination
pared to TZT film. of a photo electron and hole in the valence band [16, 20, 21].

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 J Mater Sci: Mater Electron

TZT 15000

ZTZ Raman spectra of TZT and ZTZ films

0.30
tzt
ztz
0.25
10000

Intensit (a.u)
0.20

5000
Z (µm)

0.15

0.10

0
0.05

250 500 750 1000 1250 1500 1750 2000

0.00 Wavelength (nm)
0 2 4 6 8 10

X (µm)
Fig. 5  Raman spectra of TZT and ZTZ films

Fig. 3  Surface roughness profile of TZT and ZTZ thin films

that a lower rate of recombination of excited holes and
electrons [25]. As ZTZ film has low PL emission peaks as
30 compared to TZT films, it indicated that the electron hole
PL spectra of TZT and ZTZ thin films recombination rate of ZTZ is lower as compared to TZT
TZT
25
ZTZ
film which is suitable for the formation of DSSC. Won et al.
[18] have shown that pure T ­ iO2 film has negligible lumini-
20
cence in the visible region of spectrum. Hence, our results
PL Intensity ×103 (a.u)

15
are interested because the peaks are showing in the visible
region of spectrum.
10

5 3.4 Raman analysis

0
Raman spectroscopy, is a very sensitive tool to measure the
crystal structure and phase of T­ iO2 and ZnO without damag-
-5
550 600 650 700 750 800 ing the material [26].
Wavelength (nm) The nature of chemical binding of ZnO lies between ionic
and covalent. The bonds ionicity between Zn and O atoms
Fig. 4  PL spectra of TZT and ZTZ films are very large (about 0.62 on the Phillips scale), therefore,
these are denoted as ­Zn2+ and ­O2− ions, respectively. In
ambient conditions, its hexagonal wurtzite structure is ther-
The peak intensity of TZT film is higher at the wave- modynamically stable. When ZnO is deposited on cubic sub-
lengths of 580 and 783 nm than ZTZ film. strate then it can also exhibit zinc-blende structure, respec-
The reason of this increase in intensity is attributed to tively [27].
the trapping of electrons in defect levels of ­TiO2 during the It can be seen from Fig. 5 that the remarkable Raman
crystallization and nucleation of T­ iO2 nanocrystalline [22, shifts appeared at 396, 514.9, 639, 797, and 1099 cm−1. The
23]. The NIR luminescence appeared at 783 nm is due to the appearance of peaks, 396, 514.9, 639 and 797 cm−1 con-
trapped electrons recombine with free holes [24]. There are firmed ­Eg, ­B1g, ­A1g and Eg phonon vibrational modes of
small peaks at the wavelengths 684, 696 and 715 nm. These anatase ­TiO2 phase in lattice respectively [27–31]. Similarly,
small peaks represent the defects between the valence and a characteristic peak is appeared at 1035 cm−1 confirmed
conduction bands. Therefore it slows down the electron hole the 2LO mode of phonon vibration in the ZnO lattice [32].
recombination rate and enhances the optoelectronic proper- Thus, the presence of all corresponding ZnO and ­TiO2
ties of the materials. peaks in the Raman scattering indicate that the ­TiO2/ZnO
When excited electrons and holes are recombine then they thin-film exist as a mixed crystalline structure of both
give PL spectra. Therefore, the lower PL intensity showed materials.

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J Mater Sci: Mater Electron

tzt 500

0.06 ztz
450

0.05 400

Average resistivity (Ω-m)

350
0.04

300
Current (A)

0.03
250

0.02 200

150
0.01

100
TZT ZTZ
0.00
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 Number of Films
Voltage (V)
Fig. 7  Average sheet resistivity of TZT and ZTZ films
Fig. 6  I–V measurement of TZT and ZTZ films

appears to be due to synergistic effects at the interface.

3.5 Four point probe analysis Another possible reason for the rise in conductivity with
number of layers may also be related with variations in the
Figure 6 shows the Current–Voltage measurement of TZT properties of heterojunction composite film [39].
and ZTZ films with supply voltage ranging from 0 to 1.6 V. Hence, the multilayer films of ZTZ and TZT deposited by
The results showed that the obtained I–V curve for both sol–gel spin coating and annealed at 500 °C exhibiting the
films is almost linear. This means that both films exhibit high conductivity is possibly can be used in DSSC.
ohmic behavior. From Fig. 6a, it is cleared that ZTZ film has
high I-V value as compared to TZT. The reason is that ZnO
has high electron mobility as compared to ­TiO2.
However, Schottky response is produced due to some fac- 4 Conclusion
tors, as shown in Fig. 6. These factors may be due to metal
contacts or the barrier between ZnO/TiO2 interface and also The highly conductive multilayer thin films of ZTZ and TZT
due to the defects on the ZnO/TiO2 interface [14]. have been successfully deposited by using low cost sol–gel
From the I–V graph, the reported sheet resistivity and dip coating method. After deposition all the films were
conductivity is calculated by using the following relation annealed at 500 °C. XRD and Raman confirmed both the
[5, 33, 34] to examine the electrical behavior of ZTZ and ­TiO2 and ZnO particles present in the films. AFM showed
TZT films the particles sizes of TZT and ZTZ films are 18.4 and
47.2 nm respectively.ZTZ film has low PL emission peaks as
𝜌=
𝜋 V
. =
1
(1) compared to TZT film. This indicated that the electron hole
ln 2 I 𝜎 recombination rate of ZTZ is lower than TZT film which
where I, V 𝜌 and 𝜎 are the current, applied voltage, resistivity is suitable for the formation of DSSC. The presence of PL
and conductivity respectively. peaks in the visible region of spectrum indicate that the vis-
The calculated sheet resistivity of TZT and ZTZ films ible light can excite the electrons and improve the efficiency
are 450 and 120 (ohm-m) respectively, as shown in Fig. 7. of DSSCs. Electrical resistivity of TZT and ZTZ films are
The sheet resistivity of ZTZ is smaller than TZT film. This 450 and 120 (ohm-m) respectively. This is the lower cal-
decrease in sheet resistivity showed the higher concentration culated sheet resistivity of T ­ iO2 thin film. Therefore, it is
of electrons in the multilayer films [35, 36]. Moreover, in suggested that the multilayer films deposited by sol–gel dip
multilayer films, the particle size is increased due to reduce coating technique and annealed at 500 °C are good for the
lattice mismatching. This increment in particle size reduces working electrode of DSSC.
the grain boundaries that produce better electron mobility
Acknowledgements This project is partially supported by “King
in the multilayer thin films which reduce resistivity [37, 38].
Saud University, Deanship of Scientific Research, College of Science
The increase of conductivity is primarily attributed due to Research Center”, Saudi Arabia where a part of the experiment was
increase in number of charge carrier with thickness, which carried out.

13
 J Mater Sci: Mater Electron

References 20. J. Barber, Biological solar energy. Philos. Trans. R. Soc. London
A 365(1853), 1007–1023 (2007)
21. Y.-H. Su et al., Surface plasmon resonance of layer-by-layer gold
1. M. Kitui et al., Optical properties of T ­ iO2 based multilayer thin
nanoparticles induced photoelectric current in environmentally-
films: application to optical filters. Int. J. Thin Films Sci. Technol.
friendly plasmon-sensitized solar cell. Sci. Appl. Light 1(6), e14
1, 17–21 (2015)
(2012)
2. T. Georgakopoulos et al., On the transient photoconductivity
22. D. Zhao et al., High-efficiency solution-processed planar perovs-
behavior of sol–gel ­TiO2/ZnO composite thin films. J. Non-Cryst.
kite solar cells with a polymer hole transport layer. Adv. Energy
Solids 410, 135–141 (2015)
Mater. 5(6), 1–5 (2014)
3. X. Qin, L. Cui, G. Shao, Preparation of ZnO–Zn2 ­TiO4 sol com-
23. E.D. Kosten et al., Highly efficient GaAs solar cells by limiting
posite films and its photocatalytic activities. J. Nanomater. 2013,
light emission angle. Light 2(1), e45 (2013)
19 (2013)
24. X. Wang et al., Trap states and carrier dynamics of TiO 2 studied
4. C.C. Pei, W.W.-F. Leung, Photocatalytic degradation of Rhoda-
by photoluminescence spectroscopy under weak excitation condi-
mine B by T ­ iO2/ZnO nanofibers under visible-light irradiation.
tion. Phys. Chem. Chem. Phys. 12(26), 7083–7090 (2010)
Sep. Purif. Technol. 114, 108–116 (2013)
25. J. Gong et al., Review on dye-sensitized solar cells (DSSCs):
5. M. Khan et al., Investigations of the structural, morphological and
advanced techniques and research trends. Renew. Sustain. Energy
electrical properties of multilayer ZnO/TiO2 thin films, deposited
Rev. 68, 234–246 (2017)
by sol–gel technique. Res. Phys. 6, 156–160 (2016)
26. K. Pan et al., Facile fabrication of hierarchical T
­ iO2 nanobelt/ZnO
6. C. Firdaus et al., Characterization of ZnO and ZnO: ­TiO2 thin
nanorod heterogeneous nanostructure: an efficient photoanode for
films prepared by sol-gel spray-spin coating technique. Proc. Eng.
water splitting. ACS Appl. Mater. Interfaces 5(17), 8314–8320
41, 1367–1373 (2012)
(2013)
7. O. Vigil et al., Influence of post-thermal annealing on the proper-
27. B. O’regan, M. Grfitzeli, A low-cost, high-efficiency solar cell
ties of sprayed cadmium–zinc oxide thin films. Appl. Surf. Sci.
based on dye-sensitized. Nature 353(6346), 737–740 (1991)
161(1), 27–34 (2000)
28. F. Gong et al., In situ growth of Co0. 85Se and Ni0. 85Se on con-
8. K. Haga et al., ZnO thin films prepared by remote plasma-
ductive substrates as high-performance counter electrodes for dye-
enhanced CVD method. J. Cryst. Growth 214, 77–80 (2000)
sensitized solar cells. J. Am. Chem. Soc. 134(26), 10953–10958
9. L. Li et al., The effects of Cu-doped T ­ iO2 thin films on hyperpla-
(2012)
sia, inflammation and bacteria infection. Appl. Sci. 5(4), 1016–
29. L. Song et al., Spray deposition of titania films with incorporated
1032 (2015)
crystalline nanoparticles for all-solid-state dye-sensitized solar
10. L. Wang et al., Preparation, characterization, and photocatalytic
cells using P3HT. Adv. Funct. Mater. 26, 1498–1506 (2016)
activity of ­TiO2/ZnO nanocomposites. J. Nanomater. 2013, 15
30. L. Zhang, Z.S. Wang, Enhancing the performance of dye-sensi-
(2013)
tized solar cells with a gold-nanoflowers box. Chemistry 11(22),
11. R. Wang et al., Functionalized ZnO@ ­TiO2 nanorod array film
3283–3289 (2016)
loaded with ZnIn 0.25 Cu 0.02 S 1.395 solid-solution. Synthesis,
31. S.-S. Kim, J.-H. Yum, Y.-E. Sung, Improved performance of a
characterization and enhanced visible light driven water splitting.
dye-sensitized solar cell using a T ­ iO2/ZnO/Eosin Y electrode.
Nanoscale 7(25), 11082–11092 (2015)
Solar Energy Mater. Solar Cells 79(4), 495–505 (2003)
12. R. Hussin, C. Kwang-Leong, H.H. Xiang, Fabrication of mul-
32. M. Grätzel, Conversion of sunlight to electric power by nanocrys-
tilayer ZnO/TiO2/ZnO thin films with enhancement of optical
talline dye-sensitized solar cells. J. Photochem. Photobiol. A
properties by atomic layer deposition (ALD). Appl. Mech. Mater.
164(1), 3–14 (2004)
465(2), 916–921 (2014)
33. M. Khan et al., Characterizations of multilayer ZnO thin films
13. M. Rani, S. Tripathi, A comparative study of nanostructured ­TiO2,
deposited by sol-gel spin coating technique. Res. Phys. 7, 651–655
ZnO and bilayer T ­ iO2/ZnO dye-sensitized solar cells. J. Electron.
(2017)
Mater. 44(4), 1151 (2015)
34. M. Khan et al., Structural, electrical and optical properties of
14. I. Saurdi, M.H. Mamat, M. Rusop, Electrical and structural prop-
multilayer ­TiO2 thin films deposited by sol–gel spin coating. Res.
erties of ZnO/TiO2 nanocomposite thin films by rf magnetron
Phys. 7, 1437–1439 (2017)
co-sputtering. in Advanced Materials Research (Trans Tech Pub-
35. F. De Angelis et al., Absorption spectra and excited state energy
lications, Zurich, 2013)
levels of the N719 dye on T ­ iO2 in dye-sensitized solar cell models.
15. A. Fujishima, Electrochemical photolysis of water at a semicon-
J. Phys. Chem. C 115(17), 8825–8831 (2011)
ductor electrode. Nature 238, 37–38 (1972)
36. A.J. Frank, N. Kopidakis, J. van de Lagemaat, Electrons in nano-
16. W. Nie et al., High-efficiency solution-processed perovskite solar
structured ­TiO2 solar cells: transport, recombination and photo-
cells with millimeter-scale grains. Science 347(6221), 522–525
voltaic properties. Coord. Chem. Rev. 248(13), 1165–1179 (2004)
(2015)
37. S. Xue et al., Effects of annealing on optical properties of Zn-
17. A. Kubacka, M. Fernández-García, G. Colón, Advanced nano-
implanted ZnO thin films. J. Alloys Compd. 458(1), 569–573
architectures for solar photocatalytic applications. Chem. Rev.
(2008)
112(3), 1555–1614 (2012)
38. J. Chang, M.-H. Hon, The effect of deposition temperature on the
18. W.S. Choi et al., Optical and structural properties of ZnO/TiO2/
properties of Al-doped zinc oxide thin films. Thin Solid Films
ZnO multi-layers prepared via electron beam evaporation. Vac-
386(1), 79–86 (2001)
uum 83(5), 878–882 (2009)
39. S.A. Shah et al., Multilayer Si/Ge thin films with quantum confine-
19. N.S. Lewis, D.G. Nocera, Powering the planet: chemical chal-
ment effects for photovoltaic applications. Appl. Surf. Sci. 296,
lenges in solar energy utilization. Proc. Natl. Acad. Sci. 103(43),
185–188 (2014)
15729–15735 (2006)

13