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Article
Band Alignment Engineering at CuO/ZnO Heterointerfaces
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Sebastian Siol, Jan C. Hellmann, S. David Tilley, Michael Grätzel, Jan


Morasch, Jonas Deuermeier, Wolfram Jaegermann, and Andreas Klein
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b07325 • Publication Date (Web): 25 Jul 2016
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Band Alignment Engineering at Cu2O/ZnO Heterointerfaces
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6 Sebastian Siol1*+, Jan C. Hellmann1, S. David Tilley2&, Michael Graetzel2, Jan Morasch1,
7 Jonas Deuermeier3, Wolfram Jaegermann1, and Andreas Klein1*
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9 1
Technische Universität Darmstadt, Institute of Materials Science,
10 Surface Science Division, Petersenstrasse 32, 64287 Darmstadt, Germany
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12 2
Ecole Polytechnique Fédérale de Lausanne (EPFL), Institut des Sciences et Ingénierie Chimiques,
13 Laboratory of Photonics and Interfaces, Station 6, CH-1015 Lausanne, Switzerland
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i3N/CENIMAT, Universidade NOVA de Lisboa and CEMOP/UNINOVA, Department of Materials
16 Science, Faculty of Science and Technology, Campus de Caparica, 2829-516 Caparica, Portugal
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18 & Present Address: University of Zurich, Department of Chemistry, Winterthurerstrasse 190, 8057 Zurich,
19 Switzerland
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21 + Present Address: National Renewable Energy Laboratory, 15013 Denver West Pkwy, 80401 Golden, CO,
22 USA
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24 *E-mail: siol.sebastian@gmail.com, aklein@surface.tu-darmstadt.de
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27 Keywords: Band alignment, Cu2O, ZnO, XPS, Interface experiment, Fermi level pinning,
28 Band Offset
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33 Abstract
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35 Energy band alignments at heterointerfaces play a crucial role in defining the
36 functionality of semiconductor devices, yet the search for material combinations with
37 suitable band alignments remains a challenge for numerous applications. In this work we
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demonstrate how changes in deposition conditions can dramatically influence the
40 functional properties of an interface, even within the same material system. The energy
41 band alignment at the heterointerface between Cu2O and ZnO was studied using
42 photoelectron spectroscopy with stepwise deposition of ZnO onto Cu2O and vice versa. A
43 large variation of energy band alignment depending on the deposition conditions of the
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substrate and the film is observed, with valence band offsets ranging from ΔEVB = 1.45 –
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46 2.7 eV. The variation of band alignment is accompanied by the occurrence or absence of
47 band bending in either material. It can therefore be ascribed to a pinning of the Fermi
48 level in ZnO and Cu2O, which can be traced back to oxygen vacancies in ZnO and to
49 metallic precipitates in Cu2O, respectively. The intrinsic valence band offset for the
50 interface, which is not modified by Fermi level pinning, is derived as ΔEVB ≈ 1.5 eV,
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being favorable for solar cell applications.
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Introduction
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6 The energy band alignment between two semiconductors is characterized by the
7 discontinuities in the valence band maximum EVBM and the conduction band minimum
8 energies ECBM at the interface1. These discontinuities are the basis for a large number of
9 modern opto-electronic devices as they enable controlled quantum confinement of charge
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carriers and generation of interfacial two dimensional electron gases for high mobility
12 transistors2. A popular example for the relevance of energy band alignments are thin film
13 compound semiconductor solar cells such as Cu(In,Ga)Se2 or CdTe3, where suitable
14 energy band discontinuities at the interfaces are required in order to enable transfer of
15 photo generated charge carriers4–6. In recent years the term Band Alignment Engineering
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has been used to describe the new research paradigm of purposefully altering the band
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18 alignment at heterointerfaces to enable desired functionality7–10. Even though significant
19 progress has been made in the prediction of energy band alignments, a generally
20 applicable model for quantitative predictions has yet to be developed11,12.
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22 Energy band alignment of covalently bonded semiconductors like Si and III-V
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compounds are governed by induced interface dipoles, which result in an alignment of
25 charge neutrality levels 1,13–15. For semiconductors with more ionic type of bonding, the
26 density of induced interface states is expected to be lower 13,16. A large variation of
27 Schottky barrier heights with both high and low work function oxide contact materials
28 (RuO2, ϕ = 6.1 eV; In2O3:Sn (ITO), ϕ = 4.5 eV) has been explicitly demonstrated, for
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example, for a number of semiconducting oxides like (Ba,Sr)TiO3 and Pb(Zr,Ti)O3 17,18.
31 Experimental determinations of valence band discontinuities ΔEVB of a number of
32 semiconducting oxides using photoelectron spectroscopy indicate weak Fermi level
33 pinning for defect free interfaces. In these cases the energy band alignment can be
34 understood in terms of the orbital contributions to the valence bands19–23. However,
35 defects are often formed during interface formation, which can lead to a considerable
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37 modification of energy band alignment and/or Schottky barrier heights22,24–29. This is also
38 true for Cu2O, where the presence of metallic Cu or CuO can lead to a modification of
39 band alignment30–32.
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41 No strong dependence of band alignment on the details of the interface structure is
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expected, if the alignment is governed by charge neutrality levels or orbital contributions
44 to the valence bands, since both are bulk properties. But a variation may be expected in
45 dependence on atomic reconstruction for interfaces between materials with different
46 polarity1,33,34. However, except for a few examples (see e.g. 35), a significant variation of
47 energy band alignment, which can be related to intrinsic interface properties, has not yet
48 been demonstrated.
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51 Materials availability and toxicity issues motivated the search for alternative materials for
52 photovoltaic solar energy conversion36–38. Among them, semiconducting oxides have
53 recently been considered 39,40.
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Currently, the most successful oxide solar cells are based on heterostructures of Cu2O. In
57 2011 reports of Cu2O/ZnO solar cells with efficiencies of up to 3.8% led to a renewed
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interest in the material for photovoltaic applications41,42. In recent years the conversion
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5 efficiencies Cu2O based solar cells could be improved significantly. Utilization of
6 alternative buffer layers led to much higher efficiencies of 5.3% with Ga2O343,44 and 8.1%
7 with Zn1−xGexO 45, respectively. Here the main improvement is due to a reduction of the
8 conduction band offset, which leads to an increase in open circuit voltage45.
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11 Cu2O is one of the oldest known semiconducting materials 42,46. It crystallizes as cubic
12 cuprite with a lattice constant of a = 4.27 Å and has a direct band gap of 2.17 eV47. Its
13 common p-type conductivity originates from copper vacancies with an ionization energy
14 of 0.28 eV48. ZnO has a direct band gap of 3.3 eV and crystallizes in hexagonal wurtzite
15 structure with lattice constants of a = 3.25Å and c = 5.20 Å47. ZnO is intrinsically doped
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n-type, though it is still unsettled which defect causes this doping 49–51. Different values
18 for the valence band offset at Cu2O/ZnO have been reported 52–54. Several groups have
19 reported on successfully altering the band alignment of Cu2O/ZnO heterointerfaces55–57.
20 However, the mechanisms, leading to the different band alignments, have not yet been
21 completely identified.
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24 In this work the origin of this phenomenon is systematically investigated. A strong
25 dependence of the energy band alignment at the oxide heterointerface between Cu2O and
26 ZnO on the preparation of the layers is reported. The observed variation can be directly
27 related to tiny differences in the chemical composition of the layers, which lead to
28 various concentration of metallic precipitates for Cu2O or oxygen vacancies for ZnO.
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A dependence of band alignment on defect properties has been shown previously for
31 various oxide/metal 25,29,58 and oxide/semiconductor interfaces 37,59–62. In the present case,
32 the assignment becomes evident from the different magnitude of surface potential
33 changes in the layers, which are prohibited in the case of larger defect concentrations.
34 The results presented in this contribution therefore do not only explain the variation of
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ΔEVB at the Cu2O/ZnO interfaces reported in this work and in the literature, they also
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37 provide a general strategy to control the energy band alignment at oxide heterointerfaces.
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40 Experiment
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Band alignment and band bending (BB) during interface formation are obtained from X-
44 ray photoelectron spectroscopy (XPS) performed in the Darmstadt Integrated System for
45 Materials Research (DAISY-MAT)63, which combines a Physical Electronics PHI 5700
46 multi technique surface analysis system with several thin film deposition chambers by a
47 vacuum transfer system. XPS measurements were performed using monochromatic Al
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Kα radiation with an energy of 1486.6 eV and an overall energy resolution of less than
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50 0.4 eV as derived from the Gaussian broadening of the Fermi edge of a sputter cleaned
51 Ag foil, which is also used for binding energy (BE) calibration. For ultraviolet
52 photoelectron spectroscopy (UPS) measurements a He(I) discharge lamp (hν = 21.2 eV)
53 is used as excitation source.
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The interface properties were studied using increasing film thickness of ZnO on Cu2O
57 and vice versa. Interface experiments with films deposited by magnetron sputtering were
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performed in-situ in the DAISY-MAT without breaking vacuum between individual
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5 deposition and analysis steps using a single sample. Atomic layer deposition (ALD) and
6 electrodeposition (ED) growth were performed ex-situ with mail transfer of samples in
7 ambient atmosphere. In this case, each film thickness corresponds to a separate sample. A
8 summary of the performed experiments is given in Table S1. Due to a non-negligible
9 photo voltage upon illumination no work functions and hence no values for the interface
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dipole could be obtained by UPS measurements. A small potential drop over the interface
12 due to x-ray induced photo voltage might occur during regular XPS measurements.
13 Performing calibration measurements on bulk samples, this photo voltage could be
14 identified to be smaller than VPh < 0.10 eV. Overall this adds to the uncertainty of the
15 measurements but does not change the overall conclusion of this study.
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18 ZnO layers were deposited either by magnetron sputtering (MS) or ALD, and Cu2O films
19 by reactive magnetron sputtering or ED, respectively. MS-Cu2O was deposited at room
20 temperature. The stoichiometry of the films can be controlled by changing the argon- to
21 oxygen fluxes, which were adjusted using mass flow controllers. The ZnO layers were
22 likewise deposited via RF-magnetron sputtering using a ceramic ZnO target at room
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temperature or 300°C. A change of defect concentration was further achieved by adding
25 up to 3 % oxygen to the process gas.
26 The atomic ratios have been calculated via XPS measurements by evaluating the area
27 under curve values for the Cu 2p3/2, Zn 2p3/2 and O 1s spectra taking into account the
28 respective sensitivity factors. Additional experiments were performed using
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electrodeposited Cu2O. The ED of Cu2O was performed at EPFL as described in 64, and
31 interfaces with ALD ZnO and ZnO:Al were investigated by preparation of several
32 samples with different ZnO or ZnO:Al thickness. The experimental details for the ALD
33 of ZnO and ZnO:Al are given in the supporting information.
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37 Results
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39 In this contribution the band alignments for several Cu2O/ZnO heterointerfaces are
40 presented (see Table 1). To determine the band alignments of the respective Cu2O/ZnO
41 interfaces, XPS measurements were carried out while successively depositing ZnO on a
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thick layer of Cu2O or vice versa. The depositions were carried out as described in the
44 experimental section with the deposition parameters supplied in Table S1. For each
45 experiment survey spectra were taken for each deposition step to check the sample for
46 contamination.
47 Special attention was given to the stoichiometry of the Cu2O layers, which was verified
48 by checking the Cu 2p3/2 and Cu LMM spectra, respectively. In the Cu 2p region
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50 characteristic shake up satellites would indicate the presence of Cu2+ (CuO, as well as
51 Cu(OH)2)20. In the copper Auger spectra a shoulder at binding energies of 568 eV would
52 be visible if elemental copper is embedded in the film. While no metallic Cu or CuO
53 could be identified for the in-situ samples, ex-situ samples prepared by ED showed trace
54 amounts of surface oxidation.
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57 The following discussion describes in an exemplary manner how the band alignment is
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determined from the photoelectron (PE) spectra, following a commonly practiced
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5 procedure as described in65. First XPS measurements are carried out while successively
6 depositing the Film material on a thick layer of the Substrate material (see Table 1). XPS
7 measurements are performed after every deposition step to determine the evolution of
8 binding energies with increasing film thickness. Since the evolution of the valence band
9 maximum cannot be precisely determined for steps of intermediate coverage, core level
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binding energies were measured of Zn 2p3/2 and O 1s as well as Cu 2p3/2 and CuLMM,
12 respectively (a exemplary set of photo emission spectra is shown in Figure S1). For the
13 determination of the band alignment the peak positions of substrate- as well as film-
14 specific photoemission lines have to be considered. The binding energies of the core level
15 spectra were determined by fitting using Wavemetrics IGOR Pro software. The position
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of the valence band maximum was determined by a linear extrapolation of the low
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18 binding energy edge of the valence band emission.
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From the evolution of core level binding energies over film thickness the band diagram
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5 can be extracted. A display of this evolution of core level BE for all discussed interface
6 experiments is given in Figure 1.
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Figure 1: Evolution of the core level BE as well as the valence band maximum (VBM)
46 with increasing film thickness for the individual interface experiments discussed in this
47 study. The core level binding energies are normalized to the VBM in the bulk of the
48 respective material. Interface experiments A-D were carried out in-situ. Experiments E-G
49 were prepared ex-situ.
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Based on the evolution of the core level BE for each material the surface potential
54 changes can be determined, respectively. The surface potential changes in the substrate
55 ΔEBE-sub add to any surface band bending, which might be present prior to deposition.
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57 To determine the band bending in the growing film (BBfilm), the deposition induced
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surface potential change (ΔEBE-sub) has to be subtracted from the shift of the film-specific
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5 core level binding energies (ΔEBE-film), since it has to be taken into account that a change
6 in the substrate’s electric potential causes a shift of all core level binding energies:
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8 BBfilm = ΔEBE-film – ΔEBE-sub. (1)
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The valence band offset at the interface is calculated using the BE difference of the Cu
12 2p3/2 and Zn 2p3/2 peaks at intermediate coverage (ΔBE) as well as the BE of the Cu 2p3/2
13 (BECu2p3/2-VBM) and Zn 2p3/2 (BEZn2p3/2-VBM) core levels with respect to the valence band
14 maximum.
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ΔEVB = BECu2p3/2-VBM – BEZn2p3/2-VBM + ΔBE (2)
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19 Using ΔEVB and the band gaps from literature (Eg = 2.1 eV for Cu2O and Eg = 3.3 eV for
20 ZnO) the conduction band offset can be determined as
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22 ΔECB = 2.1 eV + ΔEVB - 3.3 eV (3)
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25 The band offsets as well as the magnitude of the substrate surface potential changes
26 ΔEBE-sub and the band bending in the film for all interface experiments are listed in Table
27 1. The typical uncertainty in the determination of these values is on the order of ± 0.1 eV.
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30 Table 1: Investigated interfaces. Shown are the substrate (Sub) and the film material, as
31 well as the respective deposition method (MS: RF-magnetron sputtering, ED:
32 electrodeposition, ALD: atomic layer deposition). Depending on the EVBM, different
33 substrate surface potential changes ΔEBE-sub and film band bending BBfilm can be
34 observed. The magnitude of the BB is related to the variation of the valence band offsets
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∆EVB.
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38 # Sub EVBM ΔEBE-sub Film EVBM BBfilm ∆EVB
39 A MS-Cu2O 0.25 0.5 MS-ZnO 2.8 0.1 1.9
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B MS-ZnO 2.75 0.55 MS-Cu2O 0.21 0.35 1.6
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42 C MS-Cu2O 0.45 0.0 MS-ZnO 2.6 0.6 1.6
43 MS-Cu2O
D MS-ZnO 2.44 0.5 0.48 0.1 1.45
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45 E ED-Cu2O 0.26 0.55 MS-ZnO 2.86 -0.15 2.15
46 F ED-Cu2O 0.41 0.0 ALD-AZO 3.4 0.3 2.7
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48 G ED-Cu2O 0.30 0.3 ALD-ZnO 3.3 0.25 2.5
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50 Besides the deposition method of the respective layers (MS: RF-magnetron sputtering,
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ED: electrodeposition, ALD: atomic layer deposition) the values for valence band offset
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53 ΔEVB, substrate surface potential changes ΔEBE-sub and film band bending BBfilm are listed
54 for every experiment. Additionally the energy values for the valence band maxima EVBM
55 for the substrate as well as the thick film are given.
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32 Figure 2: Energy band diagrams for the 7 interface experiments carried out in this study.
33 Shown are the respective Fermi level (EF), the band gap (Eg), substrate surface potential
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change (ΔEBE-sub), film band bending (BBfilm), as well as the valence band offset (∆EVB)
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36 and conduction band offset for the interface (∆ECB). Experiments A-D were carried out
37 in-situ. Interface experiments E-G were prepared ex-situ. Surface band bending in the
38 substrate and the film are neglected.
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40 With these values the band diagram for the ZnO/Cu2O-interface can be drawn.
41 Figure 2 shows the band diagrams for all seven interface experiments that were carried
42 out for this study.
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46 Discussion
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48 For this work a total of seven interface experiments was carried out. The results are given
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in the previous section. Looking at the values in Table1 a broad range of valence band
51 offsets (VBO) can be observed. Dependence of energy band alignment on sample
52 preparation has been observed at a few hetero interfaces, in particular if oxide
53 semiconductors are involved20,54,59,62.
54 In the case of the Cu2O/ZnO heterointerfaces investigated in this study, the development
55 of the valence band discontinuity depends strongly on the valence band maximum in the
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57 bulk of both substrate and film as well as on the occurrence of band bending in the
58 respective materials. For layers deposited via RF-magnetron sputtering the magnitude of
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band bending can be controlled by changing the oxygen partial pressure during
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5 deposition. Cu2O layers that have been deposited using 4.0% oxygen (Exp. A-B) show a
6 band bending of up to 0.5 eV whereas for 3.7% oxygen (Exp. C-D) no band bending can
7 be observed. Taking into account the differences in intrinsic doping, which arise from the
8 alternating deposition parameters for layers prepared under more oxidizing conditions,
9 Fermi levels in the range of 0.2 eV-0.8 eV can be achieved at the interface whereas for
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layers prepared under a more reducing atmosphere the Fermi level seems to be pinned at
12 around 0.5 eV.
13 Aside from the intrinsic doping the deposition conditions directly affect the materials
14 stoichiometry (see Table S1). The Fermi level pinning effect observed for CuxO layers
15 with atomic Cu/O ratios of x > 2 (Exp. C & D) can tentatively be explained by a large
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density of Cu2O/Cu-Schottky barriers at internal interfaces spread throughout the
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18 material, which are commonly known to promote Fermi level pinning66. This way the
19 Fermi level in Cu2O adopts a value of EF - EVB = (0.5 ± 0.1) eV. The barrier height could
20 be confirmed by performing Cu/Cu2O in-situ interface experiments58. A schematic
21 illustration of this pinning mechanism is displayed in Figure 3.a.
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37 Figure  3:  a)  Schematic  illustration  of  the  Fermi  level  pinning  mechanism  in  Cu-­‐rich  
38 Cu2O  layers.  Shown  are  the  work  functions  (Φ)  and  band  gaps  (Eg)  of  Cu  and  Cu2O,  
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respectively.  If  the  distance  d  between  two  interfaces  becomes  significantly  smaller  
41 than  the  space  charge  region  W  of  the  interface,  the  EVBM  will not reach the bulk value
42 in the areas between the contacts. b) Correlation between the (bulk) EVBM  of  the  Cu2O  
43 layers  discussed  in  this  study  and  their  respective  band  bending  at  the  interface  
44 with  ZnO.
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48 Figure 3.b displays the correlation between intrinsic doping and observed band bending.
49 For CuxO-layers with atomic Cu/O ratios of x ≤ 2 (EVBM < 0.4 eV) band bending of up to
50 0.55 eV can be observed. For these layers a limitation of the Fermi level through
51 formation of point defects can be observed. Here the Fermi levels are found to be in the
52 range of 0.2 - 0.8 eV. The lower limit corresponds well to the charging of copper vacancy
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defect states whereas the upper limit is in accordance with a discontinuity of formation
55 energy for copper interstitials67. For the ex-situ prepared layers of experiments E-G, this
56 stoichiometry is not as easily accessible since adsorbates on the sample’s surface falsify
57 the values for the oxygen content. Nevertheless the big discrepancy in band bending
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between the experiments can be explained by the different methods for the ZnO-
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5 deposition. The highest band bending can be observed for the case of magnetron
6 sputtered ZnO (Exp. E) whereas no band bending is obtained for the ALD preparation of
7 ZnO:Al (Exp. F) on top of the electrodeposited Cu2O. It has been shown in the literature
8 how, depending on the choice of precursors, the substrates surface can be reduced during
9 ALD-deposition62,31. As opposed to the ZnO deposition via magnetron sputtering this
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may result in an increased density of Cu-precipitates at the junction.
12 For ZnO the restriction of the Fermi level shift within the band gap due to contact
13 formation can be traced back to oxygen vacancies and is most pronounced for ZnxO
14 layers that have been deposited in pure argon atmosphere and exhibit a stoichiometry of x
15 ≥ 1.2 (Exp. A & E). For these layers, that naturally show an abundance of oxygen
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vacancies, the Fermi level seems to be pinned to values of EF > 2.5 eV, which
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18 corresponds well to the charging point for oxygen vacancies as reported in the
19 literature50,27.
20 For the case of a pinned Fermi level in ZnO, taking into account the observed restrictions
21 for the Fermi level in Cu2O of 0.2<EF<0.8, the smallest achievable VBO ΔEVB-Min is
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ΔEVB-Min = EF-ZnO-pinned – EF-Cu2O-Max = 2.5 eV-0.8 eV = 1.7 eV. (4)
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26 For a case where the Fermi level is pinned in both materials this value increases to
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28 ΔEVB-Min = EF-ZnO-pinned – EF-Cu2O-pinned = 2.5 eV-0.5 eV = 2 eV. (5)
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32 The band alignment at the Cu2O/ZnO heterointerface has been thoroughly discussed in
33 literature. Simple predictions based on the electron affinity rule (EAR) indicate a large
34 valence band offset of 2.2 eV as well as conduction band offset of 1.0 eV68. Few
35 experimental values have been reported, mostly acquired via sputter depth profiles using
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37 photoelectron spectroscopy on ex-situ prepared heterointerfaces. The values for the VBO
38 range from 2.17 eV to 2.91 eV for intrinsic ZnO53,54. However in 2011 Ichimura et al.
39 predicted a theoretical value for the valence band offset based on first principle
40 calculations. Depending on the choice of unit cell for the interface the VBO was
41 determined to be 1.3 eV or 1.6 eV respectively. Also, their interface experiments carried
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out on electrodeposited ZnO/Cu2O heterointerfaces revealed a lower VBO of 1.7 eV52.
44 Taking into account the results of this work it can be concluded that the valence band
45 discontinuity at the junction can reach values as low as ΔEVB ≈ 1.5 eV which corresponds
46 to a conduction band discontinuity of ΔEVB ≈ 0.3 eV. Experimental results that predict
47 larger offsets on the other hand can be explained through a restriction of the of accessible
48 Fermi level position by a reduced band bending in the respective materials, caused by
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50 high defect concentrations.
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52 Brandt et al. investigated the influence of the conduction band offset (CBO) on the open
53 circuit voltage of Cu2O based devices69. In this study it was concluded, that the maximum
54 open circuit voltage can be achieved if the CBO is in the range of ± 0.2 eV, whereas
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larger CBO offsets lead to lower open circuit voltages. Even though the CBO for the
57 ZnO/Cu2O interface presented in this work can reach values close to this range, it is also
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apparent that the band alignment is highly sensitive to the bulk defect chemistry of both
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5 materials. An alternative buffer layer material with smaller electron affinity like the
6 aforementioned Ga2O3 or Zn1−xGexO  is  therefore  expected  to  lead  to  better  results.
7
8 Overall, the discrepancies in band alignments as observed in this work highlight how
9 important the preparation process is on the functional properties of the hetero interface.
10
11 Besides differences in stoichiometry or the chemical environment during the deposition
12 process other process parameters like deposition sequence can have a tremendous impact
13 on the band alignment of the interface. This is transferrable to other materials systems. A
14 comprehensive series of interface experiments as presented in this study can offer design
15 principles on how to purposefully alter important interface properties.
16
17
18 In the case of the Cu2O/ZnO interface a small conduction band offset, which are required
19 for high solar cell efficiency, has to be targeted. According to our results, this requires an
20 energy band alignment as shown in Figure 2, B-D. The critical issue enabling the low
21 conduction band offset is a Fermi energy at the interface, which is only 2 eV above the
22 valence band maximum at the ZnO surface. A high concentration of oxygen vacancies in
23
24 ZnO would restrict the Fermi energy at > 2.5 eV50,27 and must therefore be avoided.
25 Possible surface potential changes in Cu2O cannot fully compensate for a too high Fermi
26 level in ZnO, as evident from the situation sketched in Figure 2, A. However,
27 stoichiometric or slightly oxidized Cu2O, which enables a higher Fermi in the Cu2O, will
28 reduce the conduction band offset.
29
30
31 The recipe for manipulating energy band alignments at oxide heterojunctions depends
32 very much on the details of the defect properties of the materials involved. The
33 concentrations and charge transition energies of the defects determine the limits of the
34 Fermi energy and thereby the range of energy band alignment. In principle, a pinning of
35 the Fermi energy can be achieved by any defect with a charge transition energy inside the
36
37 energy gap. Both intrinsic defects, but also impurities, including hydrogen, can be
38 therefore be utilized to manipulate the energy band alignment.
39
40 Summary and Conclusion
41
42
43
With the renewed interest in Cu2O based devices for photovoltaic applications awareness
44 has been raised to the issue of band alignment at the Cu2O/ZnO heterointerface. Several
45 experiments have been conducted to determine the band alignment whereas a strong
46 discrepancy regarding the respective valence band offsets can be observed. Interface
47 experiments, carried out utilizing various deposition techniques and parameters, indicate
48
that key features of the band alignment, such as VBO or band bending, can be controlled
49
50 by adjusting the deposition conditions and thus the electronic properties of the respective
51 layers in contact to each other. The biggest band bending in either ZnO and Cu2O have
52 been observed for samples prepared under sufficiently oxidizing conditions reaching a
53 maximum of 0.55 eV in Cu2O and 0.6 eV in ZnO respectively resulting in valence band
54 offsets as low as ΔEVB ≈ 1.5 eV. Such an alignment corresponds to a low conduction
55
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band offset ΔECB, which is desirable for solar cell applications. The limitation of the band
57 bending in Cu2O and ZnO can be assigned to the occurrence of metallic Cu precipitates
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in Cu2O and to oxygen vacancies in ZnO, both being abundant for reducing deposition
4
5 conditions. These observations highlights how the occurrence of bulk defects in two
6 oxides forming a heterojunction can dramatically alter their band alignments by adding
7 restrictions to the Fermi level position in the respective materials. In other words, the
8 ability to carefully control bulk defects and the understanding of the respective
9 limitations for the Fermi level in two materials forming a heterojunction can provide a
10
11
novel toolset for band alignment engineering that is transferrable to other material
12 systems and technologies.
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19
20 Acknowledgements
21
22 This work was supported by German Ministry for Education and Research (BMBF)
23
24
under contract number 03SF0358A, the European Commission FP7 project All-
25 Oxide PV, and the Swiss Federal Office for Energy (PECHouse Competence Center, contract
26 number SI/500090–02).
27
28
29
Corresponding author
30
31
32 Correspondence to Sebastian Siol (siol.sebastian@googlemail.com) and Andreas Klein
33 (aklein@surface.tu-darmstadt.de)
34
35
36 Supporting information
37
38
39 Experimental details regarding the deposition parameters for the in-situ interface
40 experiments, Experimental details regarding the atomic layer deposition of ZnO for the
41 ex-situ studies, Exemplary set of detailed photoemission spectra.
42
43
44
45
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