Solar Energy Materials & Solar Cells 161 (2017) 449–459

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Solar Energy Materials & Solar Cells
journal homepage: www.elsevier.com/locate/solmat

All-oxide solar cells based on electrodeposited Cu2O absorber and atomic MARK
layer deposited ZnMgO on precious-metal-free electrode
Jatinder Kaura,c, Ole Bethgec, Rachmat Adhi Wibowoa, Neha Bansala, Martin Baucha,

Raad Hamidb, Emmerich Bertagnollic, Theodoros Dimopoulosa,
a
AIT Austrian Institute of Technology, Energy Department, Photovoltaic Systems, Giefinggase 6, 1210 Vienna, Austria
b
AIT Austrian Institute of Technology, Mobility Department, Electric Drive Technologies, Giefinggase 2, 1210 Vienna, Austria
c
Vienna University of Technology, Institute for Solid State Electronics, Floragasse 7, 1040 Vienna, Austria

A R T I C L E I N F O A BS T RAC T

Keywords: All-oxide solar cells based on electrodeposited p-type Cu2O absorber and atomic layer deposited n-type ZnMgO
All-oxide solar cells are investigated. The introduced solar cell architecture is free of precious metals that are usually employed as
Cuprous oxide electrodes in Cu2O solar cells and is composed almost exclusively of oxide layers. Firstly, a detailed investigation
Magnesium-doped zinc oxide is made on the potentiostatic electrodeposition of the absorber layer on the sputtered, highly conductive and
Electrodeposition
reflective Cr/ITO (ITO: tin-doped indium oxide) electrode. The focus is set on adjusting the deposition
Atomic layer deposition
Band alignment
parameters to obtain Cu2O layers, which are void-free and with large grains. A multi-textured film is obtained
with prominent (111), (200) and (220) reflections. The absorber has a bandgap of 1.93 eV and a rough,
antireflective surface. Next, the n-type ZnMgO layer has been investigated and a linear relation of the optical
bandgap (3.2–3.9 eV) versus Mg content was found. The valence band maximum levels have been extracted
from X-Ray photoelectron spectroscopy and the band alignment of the Cu2O/ZnMgO was evaluated. Solar cells
employing ZnMgO films with ~10 at% Mg show best photovoltaic performance, whereas for larger Mg contents
a dramatic decrease of the performance takes place, presumably due to excessive, deep-level defects, leading to
tunnel recombination. Best cells show short circuit current density of 6.8 mA/cm2, open circuit voltage of
550 mV, fill factor of 45% and power conversion efficiency of 1.67%.

1. Introduction semiconductor, due to a high concentration of negatively-charged
copper vacancies [3]. Its direct bandgap of about 2 eV is quite large
All-oxide solar cells are considered a high-potential, low-cost option for an ideal match of the solar spectrum, but still allows for a
for future large-scale deployment of photovoltaics (PV). The most theoretical maximum power conversion efficiency of about 20% for a
prominent of oxide semiconductors that can be used as light absorber single junction cell under AM1.5 illumination [4]. Its bandgap makes
in PV cells is cuprous oxide (Cu2O). Although its PV property was Cu2O attractive as top cell absorber in tandem architectures and an
recognized as early as the 1920s [1], the technological advancements ideal candidate for intermediate bandgap solar cells. Cu2O features a
towards a Cu2O-based solar cell were for long time very limited. In the high absorption coefficient for energies above the bandgap (103 up to
last years, Cu2O attracts increased attention, driven on one hand by the more than 105 cm-1) [5], high majority carrier mobilities (in the range
need for abundant and environment-friendly materials for PV and on of 100 cm2/Vs) [6,7] and large minority carrier diffusion length (up to
the other hand by the newly introduced technological approaches for several micrometers) [8,9]. Early investigations showed that Cu2O
solar cell fabrication. In recent studies, Cu2O appears as one of the Schottky barrier-type solar cells lead to poor PV performance [8] and
most intriguing inorganic absorbers for abundant and affordable suggested the need for heterojunction or homojunction architectures.
electricity supply, based on the requirements of adequate material Since the n-type doping of Cu2O is extremely difficult due to the dopant
supply and lowest cost-per-watt [2]. self-compensation [10], research efforts focused inevitably on hetero-
Apart from its abundance and non-toxicity, Cu2O can be prepared junctions solar cells. To obtain high power conversion efficiency (PCE)
by non-vacuum techniques, such as thermal oxidation of Cu sheets and in heterojunction solar cells, the appropriate energy band alignment at
electrochemical deposition (ECD). Cuprous oxide is a native p-type the p/n interface is of paramount importance, as well as keeping the


Corresponding author.
E-mail address: theodoros.dimopoulos@ait.ac.at (T. Dimopoulos).

http://dx.doi.org/10.1016/j.solmat.2016.12.017
Received 21 October 2016; Received in revised form 7 December 2016; Accepted 9 December 2016
Available online 29 December 2016
0927-0248/ © 2016 Elsevier B.V. All rights reserved.

Further. almost exclusively composed of metal oxide semiconduc. doping of ZnO with Mg was shown to be an efficient means to modify the The purging time was for all deposition cycles kept at 30 s. Na-doped Cu sheets and a MgF2 antireflection layer [20]. The power conversion structural characterization. band structure of the Zn1−xMgxO material. To this end. Reflection was measured grown Zn1−xMgxO films. To circumvent this.06% [24].5×2. 2. For some substrate [7]. An impressive open and nitrogen (N2) were used as Zn metal precursor. at 13° angle of ties of the ECD-Cu2O/ALD-Zn1−xMgxO heterojunction are then inves.47 W/cm2 and 1 µbar record efficiency of 8. in content of the n-type layer. oxidant and circuit voltage of ~1. employing at a power density of 0. The measured signal was referenced tigated with focus on the energy band alignment. high throughput and roll-to-roll compatible. Finally. coated with dielectric) in the range discusses the PV performance of the solar cells as a function of the Mg from 330 nm to 550 nm and to a thick.5 was reached by easily up-scalable.5 cm2 and 1 mm-thick energy-intensive preparation at temperatures exceeding 1000 °C and microscopy slides (Menzel-Gläser) were used.97% through the Savannah 100 ALD reactor. 150 nm Au-coated substrate. reported efficiency Optik) or silicon wafer pieces with native oxide (Silicon Materials Si- of 4.J.18] and later 5. 0. were reduced and the efficiency increased to 3.9 eV.1% with a PLD. the precursors were kept at room temperature. a large number of n-type layers and deposition techniques have been investigated [11–19]. For the combination with electrodeposited Cu2O [27]. Total (direct plus diffuse) 450 . X-Ray Diffraction (XRD) measurements efficiency of 0. Zn1−xMgxO layers were already successfully applied as buffer and window layers in chalcogenide solar cells and also in thermally The layer thickness values were determined either by step height oxidized Cu2O cells. The H2O and DEZn rise to reduced open circuit voltage values [26]. the demand remains to The Cu2O absorber was electrodeposited using an AUTOLAB obtain efficient solar cells with thin film absorbers. The proper. Diethylzinc (DEZn). layers were obtained by Scanning Electron Microscopy (SEM. combined with ALD-grown Zn1−xMgxO voltage. The Cr and ITO targets were sputtered grown. Only recently the efficiency was considerably increased to 2. silicon oxide glass (Plan and appropriate ZnO doping with Mg. which was stirred for several and from solutions of low-cost chemical reagents. as mentioned before. for which grain sizes up The investigated solar cell architecture is: glass/Cr/ITO/Cu2O/ to the mm range can be achieved with correspondingly large charge Zn1−xMgxO/AZO. The samples were optically char- architecture. The content of Mg may attain values up to x≈0.2 V was reached in the latter case. while (CpEt)2Mg at 85 °C. The gradually adding NaOH in the solution.62O/Cu2O:Na heterojunction solar cells [21]. as a function of the Mg content. using a Cu Ka source cell with device structure FTO/Zn1-xMgxO/Cu2O/Ag.21 to electrochemically analyze the diffractogramms.28% permanent mild stirring at the reaction temperature of 50 °C prior to [22]. Zn1-xMgxO (0≤x≤0. giving ((CpEt)2Mg) precursor and water were used. Direct Cu2O absorber on the new type of electrode is presented in detail. highest power conversion efficiencies were achieved for bulk. formed by atomic reservoir and connected to the working electrode (WE) of the potentio- layer deposition (ALD) and a substrate-type of solar cell [23]. Nevertheless. The sheet resistance was measured with the four-point. respectively. holder was kept at 25 °C during the deposition process.1% was very recently achieved for MgF2/Al-doped Ar pressure. PCE of more than 2% was ultrasonic bath for 5 min at 60 °C in a Hellmanex III-solution. 2. ECD of Cu2O has a large purified and deionized Milli-Q water was prepared. In contrast to the existing literature.1. An aqueous solution with reagent-grade demand and low fabrication cost.38Ge0. By decreasing the deposition temperature of the n. ZnO has the lowest cost.2 M potential as it takes place close to room temperature (about 50–60 °C) of CuSO4×5H2O and 3 M lactic acid. J. In 2006.025Ga 0. having low material potentiostat/galvanostat.06. However impressive these results may be. the paper to a calibrated mirror (aluminum. From all the aforementioned n-type layers. The precursor vapors were alternately pulsed result of an optimized band alignment at the heterojunction. The optimization of the electrochemical deposition of the meter (FTIR). Through optimization of the thermal oxidation process experiments (will be specified in the text). Even better results were sputter system (DC magnetron sputtering) was used for the deposition reported by the same group.65% the immersion of the Cr/ITO-coated glass substrate vertically in the by employing an amorphous tin-doped ZnO layer. thermally oxidized Cu2O absorber cells. defects at the heterojunction interface reference electrode (RE).1) based solar were realized in Bragg-Brentano geometry. A pH of 12. To this 2. The AZO target was sputtered at 1. Characterization mother material.49 W/cm2 and at Ar pressure of 5 and 2 µbar. In addition.13) films analysis using a profilometer (KLA-Tencor—Alpha-Step IQ). but For the deposition of MgO. Lactic acid was used to stabilize maximum achieved efficiency of solar cells with thin film. Kaur et al. These were cleaned in process duration of several hours.38% through the use of Ga2O3 n-layer [19].71% was obtained for the Zn1-xMgxO (x=0. bis-(ethylcyclopentadienyl)-magnesium features a high conduction band misalignment with Cu2O of ~0. highest PCE for ECD-grown Cu2O cells reached 3.3% [17. Zeiss This paper presents for the first time the properties of ECD Cu2O SUPRA 40) using an in-lens detector and 5 kV beam acceleration cells.3 without modification of the crystal structure of the 2. where precious metals are probe technique (Süss MicroTec probes connected to an Agilent 4156 C used as electrodes. the The Zn1−xMgxO layers were deposited using a Cambridge Nanotech. A Leybold Univex 450C modular prepared by pulsed laser deposition (PLD). acterized using a Bruker Vertex 70 Fourier transform infrared spectro- tor layers. The applied deposition potentials were referenced to an Ag/AgCl type layer from 120 °C to 70 °C. Finally. Wollam Co. additionally equipped with a visible light source. the range from 550 nm to 1100 nm. deionized water (H2O) implementation of an ALD Ga2O3 layer [25]. thermally oxidized cells demand SnO2 and AZO for ZnO doped with 2 wt% Al2O3 (targets from Materion excessive material use (as they are produced from Cu sheets) and Advanced Chemicals Inc). The target-substrate distance was 10 cm and the substrate ZnO/Zn0. ECD-grown the Cu (II) ions at bath pH > 7. As substrates.). Solar Energy Materials & Solar Cells 161 (2017) 449–459 defect density at the heterojunction interface as low as possible. to the sample holder without sample (air). at a base pressure of 1 mbar and at substrate temperature of 150 °C.A. Experimental details end. where ITO stands for In2O3 doped with 10 wt% carrier mobilities. ITO and AZO layers.975O). optical and electronic properties of the ALD. in-line. reaching an efficiency of 6. respectively. Surface and cross section images of the deposited Cu2O were investigated by Buonassisi et al. of the Cr. with the A513QA accessory of the spectrometer. The aqueous solution was heated under Cu2O in combination with ZnO remained for long limited at 1. incidence and un-polarized light. with Au stat. [28]. then achieved by sputter-depositing a thin ZnO layer on a bulk Cu2O 5 min in ultrapure water before finally being dried with air. of the substrate-type. layers. as transmittance was measured for normal incident light and referenced well as the structural. ECD is hours until all grains were fully dissolved. n-type aluminum gallium oxide (Al 0. Minami et al. being mainly the purging gas. or by grown by metal-organic chemical vapor deposition (MOCVD) were used in ellipsometry measurements (alpha-SE. A platinized titanium mesh was used as the counter electrode as bottom electrode. this paper presents precious-metal-free solar cell semiconductor parameter analyzer). containing 0. Finally. the band (X’PERT (PRO) POWDER) and the software X’Pert Highscore Plus to offset values of PLD Zn1-xMgxO with x=0. Fabrication Up to now. Mat) were used as substrates instead. (CE).2.

reaction (2Cu2++2OH-+2e-→Cu2O+H2O). The The ECD of Cu2O was performed at solution volume of 200 ml peak assigned to the Cr is marked with the hash key (#).5G illumination (Agilent 4156 C semiconduc. F=96485. Results and discussion reduction and oxidation reactions at the electrode progress at the same rates.7 eV [32]. It is known. E. for use in optoelectronic devices [36]. (400). 2). The Cr/ITO electrode obtain Eeq=−190 mV (marked in Fig. leading to dense and stable nucleation sites and good quality. electrochemical cell was recorded. Peak positions were flowing deionized water to wash residual salts and unreacted products determined by using Gaussian-Lorentzian line shape fits of the analyz. from the surface. Cr adheres strongly on the glass substrate. alternatively written as: ln| solar cells in the literature [30. Indeed. 2 we plot the quantity ln|j|. The lack of specific texture for the ITO layer is expected. (123). (440) and (622) planes (JCPDS 01-089-4598). since the sputter deposition takes place without substrate heating to foster layer crystallization. The cross section and surface SEM images of the substrate (Fig. j|=ln|j0|-(αF/RT) η. Further. The XRD measurement (Fig. It also binds strongly to the ITO. It supports the con- ductivity of the ITO layer (which is deposited without substrate heating) and it has a relatively high work function of 4. This means that the film's growth will be finally determined by how fast the mass is transported to the electrode. A GaP and a Si detector law: d=MQ/nFAρ. A the surface of the electrodeposited surface in tron spectroscopy (XPS) using Al (1486. For large. Cr is. 3. shown to form stable interfaces with oxides [35] and has been employed as an interfacial layer to increase the adhesion between ITO and Al. To obtain. 1. without stirring. sample was removed from the solution and thoroughly rinsed in 9 detector. therefore. All spectra obtained by XPS measurements (Phoibos 150 MCD. Cr increases the electrode's reflectance in the visible wavelength region. After the deposition. through the Faraday's integration sphere accessory for the Vertex 70. 451 . d. 1) shows a dominant peak from the (222) planes’ reflection of ITO's cubic structure (symmetry group Ia-3) and secondary peaks from the (211). where M is the molecular weight of Cu2O (143. with Eeq being the equilibrium (or reversible) potential. it is an inexpensive material. The Cu2O absorber (p-type layer) Fig. The deposition was interrupted when a certain charge. the use of electrodes with extremely low resistance (such as thick Au) permits high current densities to be readily supplied even for very low cathodic potential during the potentiostatic electrodeposi- tion. The transmittance and reflectance were measured with a teflon (PTFE) charge is related to the targeted film thickness.23.2). Firstly. Cr was chosen as a buffer layer for a number of reasons.31]. Solar Energy Materials & Solar Cells 161 (2017) 449–459 shape and defect-rich deposits (as discussed in Section 3. 1) illustrate the compactness and low roughness of the Cr/ITO electrode. respectively. however. as a function of the applied electrode potential. The activation overpotential is defined as η=(E-Eeq). n=2 is the number of electrons involved per electrochemical 1100 nm.J. Cross section and plane view SEM images of the Cr/ITO electrode. In addition.2. thus enhancing the light path in the absorber layer. used to that mass-transport-controlled growth leads to poorly-defined grain determine the deposition potential for the Cu2O layer.09 were used to record spectra in the range of 330–550 nm and 550– gr/mol). the potential was ramped from 0 to samples.6 eV) as an X-ray radiation cm2 and ρ=6 gr/cm3 the density of Cu2O. SPECS) were calibrated for the C 1s. The Cr/ITO electrode's sheet resistance of 17 Ω/□ is low enough for a solar cell electrode and yet quite substantial to allow control over the current flow during the electrodeposition of Cu2O. which are predominantly used in high-efficiency Cu2O Volmer equation: |j|=|j0| exp[-(αF/RT) η]. has been recorded by AUTOLAB's analog charge integrator. 2). the Faraday constant. Even if indium is relatively rare. as an oxygen-active element. together with the X-ray diffractogram. Semi-logarithmic current density versus electrode potential curve. for which the 3. Peaks assigned to the ITO are marked with an asterisk (*). according to the Butler- cious metals. compact films [34]. The mean specular reflectance of the Cr/ITO electrode in the window 350–650 nm is 0. 2. Furthermore. where j is the current density. In Fig. appropriate for an anode. negative values of overpotential (|η|≥50 mV) the current The Cr(20 nm)/ITO(160 nm) electrode does not contain any pre- density increases exponentially with E (Fig. Kaur et al. 1. Q. the source.5 eV [33]. tor parameter analyzer). a more substantial electrode resistance can be of advantage. Current-density vs voltage (j-V) characteristics were obtained −1 V at a rate of 10 mV/sec and the current flowing through the in dark and under AM1.1. Fig.33289 C/mol is The surface analysis of the layers was realized by X-ray photoelec. indeed. growth that is controlled by the charge transfer to the electrode and not by the mass-transport.41. For the Cr/ITO-coated substrate and the used electrolyte we 3. The XRD peaks of ITO and the (110) peak of the Cr layer (JCPDS 01-085-1336) are marked in Fig. which is appropriate for a hole- selective electrode. ITO has a high work function of ~4. j0 is the exchange current density its cost is far lower compared to that of Au or Ag. ing tool Casa XPS from Neal Fairly (VAMAS Processing Software) [29] To determine suitable potentiostatic deposition conditions for the and consistency of the XPS setup was controlled by using Au reference absorber on the specific substrate. In this equation.

84. 2 yields α=0. Fig. Solar Energy Materials & Solar Cells 161 (2017) 449–459 (the reaction rate at the equilibrium potential). The slope of the linear fit of the aspect ratio (AR) of 1. as dictated by differences in the energy between the different Fig. defined for a single rate-determining step according to the coalescence. where jmax and tmax are the maximum current density and the time instant that this maximum is obtained. 3(a) shows the evolution of the current density as a function of facets [38]. The (reaction) temperature.3144598 J/ giving rise to irregular island growth. High nucleation density is. 3.42 V. i. N. during Cu2O deposition as a function of the deposition time. required to achieve in lowering the free energy barrier for the electrochemical reaction to small critical thickness for coalescence. Kaur et al.42 V. This potential was used for our reported that activation-control leads to well-defined islands of the further investigation. j. for E=−0.J. therefore. In the mixed-control region (i. void-free films at relatively low electrode from the bulk electrolyte. quantity (j/jmax) versus (t/tmax). The inset shows the dimensionless quantity (j/jmax) versus (t/tmax). (a) Evolution of the current density. as well as the grain size of the film. Indeed. where jmax and tmax are the maximum Fig. respectively. the dcrit can be estimated from the relation: experimental data shown in Fig. It is mixed-control region. 2 shows that for thicknesses. the deposition (mol K) is the universal gas constant and T=323 K (50 °C) is the bath rate and the nucleation density. This value represents dcrit=(2√N)-1 and the average grain size at coalescence is approximately the fraction of the electrode-electrolyte interfacial potential that assists N-1/2 [39].and the electrode start to appear and we enter the region of mixed-control. increase with the overpotential.e. t. allowing compact and thin take place. Points A-F mark the deposition times where the absorber layer was imaged by SEM. For an island latest IUPAC assessment [37]. the electrode reaction is controlled by the electrical charge transfer at In view of the above. deposit. On the other hand. dcrit. On the other hand. (ii) large grain size and (iii) high deposition rate.42 V deposition potential. R=8. (c) Temporal evolution of the Cu2O grain size. large grain sizes. are achieved for low nucleation density. as limitations due to mass transport to the corresponding to the transition between the activation. (b) Plane view SEM images of the absorber obtained for the deposition times marked by points A-F. The inset plots the dimensionless values) the island formation is disturbed by mass-transport limitations.42 V the rate of current optimum potential to combine these attributes would be the one increase slows down. t. −0. α is the dimensionless cathodic charge transfer nucleation density determines the minimum film thickness for island coefficient. For point E the white arrows mark voids in the film. absorbers. as extracted from the SEM images. The potential values more negative than −0. which are desired for The Butler–Volmer equation holds for the potential regime where improved electrical properties. 452 . the value of the deposition potential should be the electrode (activation-control) and not by the mass transfer to the chosen so as to obtain: (i) compact.e. at higher overpotential deposition time. for −0.

Pure MgO and ZnO films were also texture as a function of the film thickness was also reported in the prepared as references. we can deduce that. 5.J. For The Zn1−xMgxO layers were deposited either on plain substrates or the 2000 s deposition.3. Table 1. for t/tmax < 1 the transient (through the OH-) that favors the growth of planes with largest oxygen curve follows the model of Scharifker and Hills [40] for instantaneous density.e. the two reflections alternate in importance. 6 shows XPS spectra for the Zn and Mg peaks.5 µm was to the expression [45]: chosen. a Cu2O thickness of 2. signifying a faster overlap of the absorber.2% For t/tmax > 1 the experimental current declines much faster than between the Au(111) and the Cu2O(111) favors a highly textured predicted from the above expression. extracting the optical band gap is to simply determine the wavelength clusters of nuclei at close proximity merge to single islands at later at which the extrapolations of the “base line” (1) and the absorption stages of the deposition. the island density decreases from edge (2) cross [43]. Apart from these two peaks.e. 3(c) plots the grain size as a function of time. The precise atomic concentration of Mg in the ZnO films. The number of super-cycles is repeated n times to obtain planes is also significant. The total of 8 cycles defines the so-called times. The Mg concentration in ZnO was the grains of the deposited film are well-faceted. the growth of specular reflectance is much lower than the integrated one. Kaur et al. Firstly. xXPS =x . In the Films with increasing Mg concentration were prepared. The crystal structure of the Cu2O deposits was investigated by XRD. 453 . Which texture is finally induced to the Cu2O film is determined by the respectively. beginning of the growth. GPCMgO+(n ·GPCZnO ) (1) The obtained diffractograms for different deposition times are shown in Fig. For thicker Fig. 1 h. Due to respectively. as deter- literature for electrodeposition on Ni/Si and Au/Si substrates [41]. 4. From the SEM Cr(20 nm)/ITO(160 nm)/Cu2O(2. For the solar cells. The current transient provides insight regarding the the high pH value of the solution there is large supply of oxygen growth evolution of the Cu2O film. also plays an important role in the final texture. the lateral grain growth slows down due to steric hindrance.12 nm/cycle for ZnO and MgO.5 µm) are shown in Fig.14 and 0. combined effect of the solution pH value and the used substrate. The oxide growth per cycle (GPC). with low density of controlled by varying the number of MgO cycles during ALD. mined by ellipsometry. described by the equation: nevertheless. was 0. By measuring the lateral dimension of an ensemble of This method yields a value of EG=1. The substrate. for the integrated reflectance as shown in Fig. The images. because the Cu2O absorber takes place through instantaneous nucleation and of the very pronounced absorber roughness. i. corresponding to a deposition time of approx. The Zn2p core level exhibits two peaks. no voids could be observed. with the (111) finally dominating over the (200) for large deposition followed by one cycle of MgO. the strongest peaks stem where xGPC is the Mg concentration and n the number of ZnO cycles. A similar alternation of the Cu2O prominent the required film thickness. ( j / jmax )2 = [1. R. SEM the (200) or (220). As an example. was determined by XPS.2564(t / tmax )]}2 a highly (111) textured film is obtained with the (200) plane reflection practically vanishing. the one stemming from the (220) super-cycle. 5. On the other hand. Integrated and specular reflectance spectra of the glass/Cr/ITO/Cu2O sample films the (111) texture prevails. Solar Energy Materials & Solar Cells 161 (2017) 449–459 current density and the time instant that this maximum is obtained. on top of the absorber by using ALD. Due to this. In the value extracted earlier for a similarly prepared Cu2O film [44]. of the sample: glass/ deposition process. marked as points A-F in Fig. 4. Using the same solution for the electrodeposition of Cu2O on Au (111) substrate. according structural defects.9542⋅(t / tmax )−1]⋅{1 − exp [−1. until t~600 s. Most importantly. From the very early deposition stage. corresponding to the Fig. shown in Fig. its initial value. i. the (111) planes of the cubic Cu2O [42]. Indeed. indeed. Voids in the film can still be observed in the 1500 s SEM image (voids marked with arrows). 3D islands. certain crystal orientations favoring the Cu2O (111) growth and others In order to understand the growth evolution of the Cu2O film. Fig. Subsequently. in good agreement with the grains. the grain size increases almost linearly with time. images of the deposits were taken at different time instances of the The specular and integrated reflectance. 3(a). GPCMgO xGPC = . nucleation with subsequent island overlap. the ITO electrode is poly-textured with diffusion layers of the growing Cu2O particles. The most direct way of growth of cubic. 5. the ratio 7:1 stands for seven cycles of ZnO. 3(b). grains with dimensions up to ~2700 nm are 3. showing the alternation between the (111) and (200) as prominent textures. as shown in course of the deposition. The nuclei do not grow independently.93 eV. Fig. with the extraction of the optical bandgap of the absorber. the small lattice mismatch of ~4. X-ray diffractograms obtained for different times of Cu2O electrodeposition. The Zn1−xMgxO (n-type layer) measured after 2000 s deposition. from the (111) and (200) plane reflections (ICCD 01-077-0199).

461 0. for the rest of the paper the XPS. unit cell. 6). A linear fit yields: binding energy to higher values (~350–400 meV) for Zn1−xMgxO EG=3. Kaur et al. Solar Energy Materials & Solar Cells 161 (2017) 449–459 Table 1 The Mg concentration as calculated from the oxides GPC (xGPC ) and from the XPS measurements (xXPS ). The ratio of the corrected peak areas Zn1−xMgxO films were measured and analyzed.06 1304.coordinated Zn atoms. are shown in Table 1. the Mg1s Additionally to the lower electron negativity of Mg compared to Zn.07 eV) energies is observed for the Zn doublet peak (~100 meV) for (Fig. with the corresponding change of confirms that Zn appears only in the Zn2+ oxidation state within the the Mg coordination number from octahedral to tetrahedral. there are two tetrahedrally. The binding energies of the Zn2p3/2 (E Zn2p3/2 ) and Mg1s (EMg1s ) peaks for each film are also shown.16. due to the widening of the optical band gap. the samples with varying x .333 1021.69 5:1 0.072 0.109 0. as spectra for the 20 nm-thick films of various Mg concentrations. whereas a much less significant shift to lower x agrees with the literature reports for films prepared by a variety of Fig.088 1022.13 eV) and Zn2p3/2 (1022.94 1304. In the hexagonal wurtzite ZnO (hν–EG).84 7:1 0.70 1:1 0. The observed linear dependence of the bandgap on compared to MgO.01 1304.19+2.40 spin-orbit doublet Zn2p1/2 (1045. On the other hand. while the transmittance increases with x derived Mg concentration will be used.79. films are highly transparent.163 1022. while A is a other hand.7 eV [46] was not observed.40 eV) and no metallic Mg peak (1303 eV) [46] was observed.05 1304. for photon energies above transfer degree for the tetrahedral than for the octahedral coordination the bandgap (inset of Fig. [48] for Mg-doped ZnO films. The Mg atomic shift of the Zn 2p core level is due to the nearest neighbor effect only concentration in the films was extracted with the following procedure: and therefore less significant. h and ν are the optical absorption coefficient. resulting in the observed binding energy shift of the Mg1s core level The positions of the Zn2p3/2 and Mg1s peaks for the investigated towards higher energies. 6 show a considerable shift of the Mg 1s x for both 20 and 100 nm-thick films in Fig. This suggests the substitutional incor- with a binding energy of 1021. The EG values were The doping of ZnO with Mg modifies the atomic configuration and extracted by using Tauc plots [49].J. which poration of Mg into the ZnO lattice. four octahedrally coordinated Mg atoms constitute the constant and the exponent n has the value 2 for direct bandgap cubic MgO unit cell. As the coordination of Zn does not change. 6. and 18. respectively. Metallic Zn Zn1−xMgxO compared to ZnO. XPS detection limit of ~1019 atoms/cm3. where α. On the Planck's constant and photon frequency.80 MgO 1 1 – 1304. The XPS spectra in Fig. based on the relation: (αhν)n=A gradually tunes the electronic structure. with a higher intercept of the data fit to the Tauc relation.89 1304.73 3:1 0.35x eV. 8.107 1021. which The optical transmittance spectra of 20 and 100 nm-thick are 11.1 – 11:1 0. These results agree with the findings of firstly the Mg1s.140 1022. ZnO/MgO cycles xGPC xXPS E Zn2p3/2 (eV) EMg1s (eV) ZnO 0 0 1022. Fig.146 0. 9. in accordance to the ZnO wurtzite structure [46]. (1304. Zn2p1/2 and Zn2p3/2 peak areas were calculated and Achary et al. The net charge transfer from the cation to the semiconductors. then divided with the respective relative sensitive factors (RSF). The Zn2p and Mg1s core level peaks with varying Mg concentration. 7 presents the Mg/(Mg+Zn) yields the Mg atomic concentration of the films. 454 .222 0. The bandgap value is extracted from the hv-axis anion depends on the cation coordination number. Thereafter. 7).91 [47]. The EG values are plotted as a function of [48]. core level measured for the MgO film exhibits one intense peak this alters the potential of core electrons due to screening effects. The presented in Table 1.

In ZnO. The diffractograms for the 20 nm-thick films (VBM) position of Mg-doped ZnO downwards as compared to undoped show only an extremely weak ZnO (002) peak for x ≤0. as shown in Fig.53 and 952. Further. used for the 20 and 100 nm-thick films. a weaker peak stems from the (100) amount of Mg incorporated into the ZnO crystal is very large. due to the The structural properties of the ALD Zn1−xMgxO films were absence of Mg d electrons. The bandgap increase in Zn1−xMgxO is related to the modification of the valence and conduction band structure. techniques [50–53].J. Kaur et al. ZnO deposition. The undoped ZnO has the wurtzite crystal structure.ZnO binary system includes (002) peak becomes gradually weaker. conduction band mostly forms from cation s states [53–55]. the lattice parameter from 5. The peak obtained at 934.33 [50]. promoting interface recombination [24].210 Å for ZnO to 5.136 Å for x=0. On the other hand. The ECD-Cu2O/ALD-Zn1−xMgxO interface The surface of the ECD Cu2O film was characterized by XPS measurements before and after the ALD of the n-layer (with a thickness of 3 nm). XRD measurements of the Zn1−xMgxO films for varying Mg concentration. The Cu2O film shows two main peaks at 932. the experimental solid solubility x ≥0.4 eV corresponding to the 2p3/2 and 2p1/ 1+ 2 levels of Cu state (Cu2O). The reduction Fig. For x < 0. Mg solubility in ALD films is comparable to that of PLD or sputtering. as no satellite peaks or shoulder peak at 934.163. along with the Tauc plots for the extraction of the optical bandgap values. a cubic phase is dominant in the films [50]. until it almost disappears for less than 4 at% of Mg [58]. the valence band maximum of Zn1−xMgxO for varying x. 8. Due to the layer-by-layer growth. the position of state without definite increase of band gap is found. 0. the the conduction band upwards C [56]. as described by Kraut et al. This shifts the valence band maximum investigated by XRD.43 a mixed comparison of the intensities of the main peaks. with the resulting gradual shrinkage of the c-axis temperature during deposition. the p-d coupling strength decreases. substrate. 10(a)) and the VBM were determined by linear extrapolation of the leading edges of the spectra to the base line (Fig. The broad satellite peaks near 940–944 eV originate from the CuO phase. structure is transformed from the wurtzite to the cubic one [50. On the other hand. the (100) texture dominates. However.163. the top of the valence band is dominated by the coupling of anion p with cation p and semicore d orbitals. the MgO . This layer would affect the solar cell efficiency. 11(a).33. For all Mg-containing films.33 to x < 0. The solubility limit indicating the substitutional incorporation of the small ionic radius depends on the type of fabrication method. 9.2 eV is attributed to Cu2+ (CuO). which shifts the bottom of lization being visible for low Mg content. and the Mg2+ into Zn2+ sites. Transmittance spectra of 20 nm-thick Zn1−xMgxO films with different Mg concentrations.163.2 eV are visible anymore. the Zn 4s state in the conduction band are therefore amorphous/nanocrystalline with the onset of crystal- decreases with increasing the Mg content. while MgO is cubic. the plane reflection and finally the (110) and (101) peaks are also visible. 11(a)) before the ALD shows the presence of a CuO layer. 10(b)). formed due to the absorber exposure to air. When a ZnO layer is deposited by ALD on the top of the absorber. 10(b). 100 nm-thick films show well-defined ZnO peaks (Fig. as demonstrated from the increase of band gap is exhibited and for x > 0. single phase wurtzite structure with linear the Mg-doped films are less crystalline. was extracted.4. If the ZnO has a strong (002) texture. the (110) and (101) peaks are not limit of MgO into ZnO by PLD (pulse laser deposition) is as high as significantly modified for x ≤0. whereas the bottom of the Fig. 7.107. Besides. A similar reduction behavior of CuO to Cu2O by DEZ 455 . The XPS valence band spectra were obtained (Fig. 3. while the According to the phase diagram. On the other hand. which is a characteristic of materials having a d9 configuration in the ground state [60].57]. [59]. The bandgap as a function of the Mg concentration with values extracted for the of the CuO layer is attributed to the DEZ ALD precursor. The films ZnO. doping. For still higher Mg the (002) peak is shifted to higher 2θ values with increasing x. The obtained XPS spectrum (Fig. Solar Energy Materials & Solar Cells 161 (2017) 449–459 Fig. Compared to the undoped ZnO. the CuO on the surface is reduced. These values are shown in Fig. 9). When ZnO is doped with Mg.

XPS measurements ΔECBO = ΔEVBO + (EGZn1− x Mgx O − EGCu2 O ) were conducted to extract the VBM for the Cu2O absorber (Fig. (Fig. HET HET HET Applying the same linear extrapolation method of the leading edge to where ∆ECL =(EZn 2p3/2 − ECu2p3/2 ) is the energy separation between the baseline. [24] and Hoye et al.58 1.107. It relations [59]: is also important to note that the position of the core level peaks for the HET Zn1− x Mgx O Zn1− x Mgx O Cu2 O Cu2 O bare absorber do not change when the ZnO layer is deposited atop ∆EVBO =[∆ECL + (EZn 2p3/2 − EVBM ) − (ECu 2p3/2 − EVBM )].088 2. In addition to the core level peaks.140 2. Zn1− x Mgx O Zn1− x Mgx O Cu2 O Cu2 O The valence and the conduction band offset values. 10. Fig. 12). The band offset values of the Cu2O x=0.49 1.28].05 x=0.J. respectively. were extracted from the therefore conclude that the heterojunction interface is free from CuO. XPS spectra of the Cu2p3/2 and Cu2p1/2 core level for the bare Cu2O surface and for Cu2O capped with 3 nm ALD ZnO. 11(b)). The values are shown in Table 2. 11. of the heterojunction.02eV was yielded. (a) XPS spectrum for the determination of the VBM for a film with x =0. (b) Zoom-in the region of the spectra used for the VBM determination.47 eV were reported [62. Table 2 The core level peaks for the heterojunctions are practically in the same The calculated valence and conduction band offsets for the Cu2O/Zn1−xMgxO hetero. Solar Energy Materials & Solar Cells 161 (2017) 449–459 Fig.22 A type II Cu2O/ Zn1−xMgxO heterojunction (staggered gap) is x=0. measurements). has been reported by Lee et al.10 heterojunction with pure and doped ZnO have been studied in the x=0. We can ∆ECBO .61 1. Kaur et al.16 formed in every case (Fig. [61]. a VBM=0. 11(a)). Zn2p3/2 and Cu2p3/2 core levels for the heterojunction. respectively. Due to this.7 to 2. VBO values from 1. positions as for the pure materials (within the accuracy of the XPS junction for the different Mg concentrations.0 to 1.94 literature.63. the ∆EVBO and ∆ECBO can be extracted from the VBM values and the bandgaps of the Zn1−xMgxO and the Cu2O/ Zn1−xMgxO ∆EVBO (eV) ∆ECBO (eV) Cu2O.54 1. ∆EVBO and (EZn 2p3/2 −EVBM ) and (ECu 2p3/2 − EVBM ) are the VBM energies with reference to the core level peaks in Zn1−xMgxO and Cu2O.66 0. through the linear extrapolation of the leading edges to the base line.8 eV and CBO values from 1.23.107 2. x=0 2.163 2. The calculated band offset values 456 .

A cross section SEM image of the cell is shown in Fig.5. it was shown that a large-grain ( > 2 µm) minimum moves upwards with the Mg concentration. which attains a maximum value of only ~45%.5 µm)/Zn1−xMgxO(20 nm)/ AZO(800 nm). as discussed in the introduction [19–21]. fill-factor (FF) and power conversion efficiency (η) as a function of the Mg content of the n-layer.107. These states can provide a tunneling recombination path for the carriers in the solar cell.140 the correspond- ing values are 172 and 78 Ω cm2. Further increase of the Mg content in the n-type film has a dramatically negative influence on the cell performance. Nevertheless. even for the shift of the electrodeposition potential at the onset of the mixed-control 300 mV (x=0. with the efficiency decreasing to 0. whereas the increase of the series resistance could originate from an additional barrier created at the Zn1−xMgxO/AZO interface. The reduction of the optical losses in the doped films also contributes to the increase of jsc. a FF of 55% would have increased the efficiency to the level above 2%. The PV performance is very similar for x=0. Conclusions Fig. On the 457 . 13.67% for x=0. Indeed. Carrier transport through deep-level defects could account for the low shunt resistance. based on electrodeposited Cu2O absorber and atomic layer deposited Zn1−xMgxO on a precious-metal-free Cr/ITO bottom electrode and AZO top in this work lie within the reported ranges. with the structure: glass/Cr(20 nm)/ITO(160 nm)/Cu2O (2. determined by the pH of the solution and the texture of the ITO electrode. At the same time. since the CB alignment should improve with increasing x. offer a more appropriate alignment. the Ga2O3. by setting carrier recombination in solar cells. we anticipate a and void-free absorber film can be deposited at considerable growth corresponding increase of the open circuit voltage and decrease of the rate under potentiostatic mode on the introduced electrode. the Voc presents a significant increase compared to the pure ZnO case. The obtained Cu2O film has a mixed (111) and (200) texture.65]. Indeed. Kaur et al. Besides. It has been shown that in Zn1−xMgxO layers the deep level defect states increase with the Mg content. Characteristically. AlxGa1−xO and ZnxGe1−xO n-layers. although the bandgap of the Zn1−xMgxO layer can be widely adjusted through the Mg content.248. It should be noted here that the FF. 4. other regime. decreasing the efficiency. 13(b).103. Solar Energy Materials & Solar Cells 161 (2017) 449–459 3.248.163).163 and 0. also the jsc and the FF are improved. For x=0. in order to reduce the series resistance. In view of these limitations. In conclusion. the effect of the bandgap widening is shared between the valence and the conduction band of the Zn1−xMgxO. First. such as the Ga2O3.J. provide a better matching to the Cu2O absorber. One of the possibilities to increase the FF would be to use additional metal fingers on the front AZO contact. the paper introduced an all-oxide solar cell. In Fig. From the observation of the j-V curves we can say that the degradation is accompanied by an increase of the series resistance and decrease of the shunt resistance in the cells. as demonstrated from pronounced defect-related luminescence. 14 we plot the open circuit voltage (Voc). for the best performing cell (x=0. From the measured PV performance of the cells and the hetero- junction characterization we can say that. giving rise to an increase in the efficiency from η=0. from 360 to 550 mV. 13(a).9% for x=0 to η=1. 12. Schematic energy band diagram of the Cu2O/Zn1−xMgxO type II heterojunction.140 and to practically null for Fig.1% for x=0.103) the shunt and series resistance are 500 and 24 Ω cm2 respectively.103. Indeed. This increase can be to a large extent attributed to the improved conduction band alignment at the Cu2O/Zn1−xMgxO heterojunction with the resulting reduction of recombination losses. while for the cell with x=0. short circuit current density (jsc). is a significant limitation to the overall cell performance. Illuminated j-V characteristics of the solar cells with varying x. the desired effect of improving the heterojunction band alignment is not as significant as we would wish. The illuminated current-density-voltage (j-V) curves are shown in Fig. the CB misalignment remains large. The absorber surface is rough and low reflective. with x=0–0. As the conduction band transparent electrode. Such a behavior is not expected from the point of view of energy band structure. attributed to Mg interstitials or oxygen vacancies [64. oxides. the Mg content cannot be considerably increased without detrimental effects on the cell efficiency. x=0. Solar cell characterization Complete solar cells were fabricated.

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