KCN Chemical Etch For Interface Engineering in Cu2Znsnse4 Solar Cells

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KCN Chemical Etch for Interface Engineering in Cu2ZnSnSe4 Solar Cells
Article in ACS Applied Materials & Interfaces · June 2015

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Article
KCN Chemical Etch for Interface Engineering in Cu2ZnSnSe4 Solar Cells
Marie Buffiere, Guy Brammertz, Sylvester Sahayaraj, Maria Batuk, Samira Khelifi, Denis
Mangin, Abdelaziz El Mel, Ludovic Arzel, Joke Hadermann, Marc Meuris, and Jef Poortmans
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 03 Jun 2015
Downloaded from http://pubs.acs.org on June 5, 2015
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Page 1 of 36 ACS Applied Materials & Interfaces
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KCN Chemical Etch for Interface Engineering in
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12 Cu2ZnSnSe4 Solar Cells
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17 Marie Buffière1,2,9*, Guy Brammertz4,5, Sylvester Sahayaraj2,4,5, Maria Batuk6, Samira Khelifi7,
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19 Denis Mangin8, Abdel-Aziz El Mel3, Ludovic Arzel3, Joke Hadermann6, Marc Meuris4,5 and Jef
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Poortmans1,2,4
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25 1 imec- partner in Solliance, Kapeldreef 75, 3001 Leuven, Belgium
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27 2 Department of Electrical Engineering (ESAT), KU Leuven, Kasteelpark Arenberg 10, 3001
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29 Heverlee, Belgium
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32 3 Institut des Matériaux Jean Rouxel, Université de Nantes, CNRS, 2 rue de la Houssinière B.P.
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34 32229, 44322 Nantes cedex 3, France
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36 4 imec division IMOMEC - partner in Solliance, Wetenschapspark 1, 3590 Diepenbeek, Belgium
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5 Institute for Material Research (IMO) Hasselt University, Wetenschapspark 1, 3590 Diepenbeek,
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41 Belgium
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43 6 Electron Microscopy for Materials Science (EMAT), University of Antwerp, Groenenborgerlaan
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45 171, 2020 Antwerp, Belgium
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7 Electronics and Information Systems department (ELIS), University of Gent, Sint-
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50 Pietersnieuwstraat 41, 9000 Gent, Belgium
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52 8 Institut Jean Lamour, Université de Lorraine, Parc de Saurupt, CS 50840, 54011 Nancy, France
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54 9 Qatar Environment and Energy Research Institute (QEERI) Qatar Foundation, Doha, Qatar
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57 * Corresponding author : marie.buffiere@outlook.com
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ABSTRACT. The removal of secondary phases from the surface of the kesterite crystals is one
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6 of the major challenges to improve the performances of Cu2ZnSn(S,Se)4 (CZTSSe) thin film
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8 solar cells. In this contribution, the KCN/KOH chemical etching approach, originally developed
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for the removal of CuxSe phases in Cu(In,Ga)(S,Se)2 thin films, is applied to CZTSe absorbers
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13 exhibiting various chemical compositions. Two distinct electrical behaviors were observed on
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15 CZTSe/CdS solar cells after treatment: (i) the improvement of the fill factor (FF) after 30 s of
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18 etching for the CZTSe absorbers showing initially a distortion of the electrical characteristic; (ii)
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20 the progressive degradation of the FF after long treatment time for all Cu-poor CZTSe solar cell
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22 samples. The first effect can be attributed to the action of KCN on the absorber, that is found to
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25 clean the absorber free surface from most of the secondary phases surrounding the kesterite
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27 grains (e.g., Se0, CuxSe, SnSex, SnO2, Cu2SnSe3 phases, excepting the ZnSe-based phases). The
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second observation was identified as a consequence of the preferential etching of Se, Sn and Zn
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32 from the CZTSe surface by the KOH solution, combined with the modification of the alkali
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34 content of the absorber. The formation of a Cu-rich shell at the absorber/buffer layer interface,
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37 leading to the increase of the recombination rate at the interface, and the increase in the doping
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39 of the absorber layer after etching are found to be at the origin of the deterioration of the FF of
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41 the solar cells.
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45 KEYWORDS. Kesterite, CZTSe, KCN, surface, selective etching, photovoltaic.
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5 INTRODUCTION
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Considered as a promising technology for substituting Cu(In,Ga)(S,Se)2 (CIGSSe) and CdTe
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11 photovoltaic devices due to its low-toxic and earth-abundant constituent elements,
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13 Cu2ZnSn(S,Se)4 (CZTSSe) thin film solar cells have attracted increasing attention during the last
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16 decade, achieving recently a record efficiency of 12.7 %.1-3 CZTSSe compounds are p-type
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18 semiconductors, with high absorption coefficients (>104 cm-1) and a direct band gap that can be
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20 easily tuned from 1 to 1.5 eV depending on the [S]/([S]+[Se]) ratio.4-6 Thanks to these unique
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23 properties, CZTSSe technology was considered as a promising candidate for a wide range of
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25 applications.7-9 However, the limited control of the composition and the microstructure observed
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so far in such materials -due to the limited stability of the kesterite compound10- could be
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30 considered as a bottleneck for its industrial implementation. Various secondary phases, such as
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32 Zn(S,Se), Cux(S,Se), Sn(S,Se)x or Cu2Sn(S,Se)3, can be formed during the processing of the
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absorber layer and eventually hinder the electrical performances of the devices.11-14 This is
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37 particularly the case when the CZTSSe layers are prepared under Sn-rich ([Zn]/[Sn]< 1) and Cu-
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39 rich ([Cu]/(Sn]+[Zn])> 1) conditions, which enhance the formation of low band gap Sn(S,Se) or
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42 Cu2Sn(S,Se)3 and p-type degenerated Cux(S,Se) secondary phases. As a consequence, the best
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44 CZTSSe solar cells (i.e., efficiency > 5 %) have been prepared under Cu-poor
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46 ([Cu]/([Sn]+[Zn])~ [0.7;0.95]) and Zn-rich ([Zn]/[Sn]~ [1.0;1.25]) conditions;1-3,15-17 in such
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49 case, the Zn excess is found to form Zn-rich secondary phases mainly located at the grain
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51 boundaries and at the free surface of the CZTSSe grains.18,19 In most cases, however, the
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CZTSSe layer is found to also contain some residue of the other secondary phases, even if their
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56 formation was prevented by using optimal precursor compositions and synthesis conditions.18
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Applying a chemical wet etching step is the classical route to selectively remove the secondary
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6 phases that could be present on the surface of CZTSSe thin films (i.e., at the p/n junction in the
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8 CZTSSe-CdS-ZnO solar cell structure). Different specific procedures were previously developed
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to etch each of the identified secondary phases. While the immersion of the CZTSSe samples in
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13 hot HCl solution (10 wt.%) is adapted to remove ZnS compounds at the surface of the absorber
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15 layer,20 (NH4)2S treatment (22 wt.%) is found to efficiently etch Sn(S,Se) clusters formed due to
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18 a stoichiometric deviation or by condensation.21 Br2/MeOH (1 wt.%) was reported to remove
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20 Cu−Sn−Se-related secondary phases.22 However, the most common etching approach used so far
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22 in literature is based on KCN solution.22-25 The KCN treatment has been originally developed for
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25 CIGSSe thin films and is used for the selective removal of Cu-rich phases such as Cux(S,Se) that
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27 are known to induce shunting issues in the devices.26 Concerning CZTSSe compounds, the
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standard KCN etching process consists in dipping the as-synthesized CZTSSe layer for 2
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32 minutes in a 5-10 wt.% KCN aqueous solution containing KOH for safety reasons.27 Timmo et
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34 al. have shown that such KCN treatment applied to CZTSSe mono-grains mainly dissolves Cu,
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37 Sn and chalcogens.28 Photoemission studies reported by Bär et al. confirmed that KCN
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39 preferentially etches Cu and, to a lesser degree, Sn, from CZTS surface, leading to an increase in
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41 the surface band gap.29 In a previous work, we have shown that using a KCN etching step can
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44 help recovering a decent minority carrier lifetime for air-exposed CZTSe samples.30 However,
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46 the necessity of such chemical treatment to prepare high efficiency kesterite solar cells is still
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48 open to discussion. To provide more elements to answer this question, here we report on the
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51 impact of the nominal composition of the absorber and of the KCN etching duration on the
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53 properties of CZTSe solar cells. A detailed analysis, consisting of chemical, physical and
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electrical measurements, was carried out on the devices.
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RESULTS AND DISCUSSION
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7 Impact of the standard wet KCN treatment on CZTSe thin films. The chemical composition
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9 and the microstructure of different CZTSe layers before and after a standard KCN treatment (i.e.,
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11 carried out for 120 s at 20 oC using a 5 wt.% KCN aqueous solution in 0.5 wt.% KOH) were first
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14 studied. For this purpose, four CZTSe thin films were synthesized using different Cu precursor
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16 layer thicknesses (101 nm (sample code: Cu101), 117 nm (sample code: Cu117), 133 nm
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(sample code: Cu133) and 149 nm (sample code: Cu149)), while the thicknesses of the CuSn and
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21 Zn layers were kept constant (see supporting information, section I.A). Figure 1(a-h) shows top
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23 view secondary electron microscopy (SEM) images of these CZTSe samples before (left column)
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26 and after KCN treatment (right column). The EDS analysis of the samples is presented in Figure
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28 1(i). As expected, increasing the Cu content in the precursor films results in a linear increase in
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30 the [Cu]/([Zn]+[Sn]) ratio of the CZTSe films, from 0.62 to 0.98. It also leads to the
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33 modification of the [Zn]/[Sn] ratio (that varies between 0.94 and 1.19), as the initial Cu content
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35 may influence the formation of volatile secondary phases such as SnSe and Zn. As a
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37 consequence, different CZTSe surface morphologies were obtained. Concerning the as-grown
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40 samples, some features are visible on the surface of the CZTSe thin films, such as droplets of
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42 secondary phases with a size ranging between a few and hundreds of nanometers (Fig. 1(a,b)) as
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well as nano-needles of elemental Se (Fig. 1(d)) that can originate from either the stoichiometric
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47 deviation during the growth or the condensation of the gaz phases. In case of sample Cu133, the
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49 light gray areas visible on Fig. 1(c) are due to the presence of ZnSe at the surface of the
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52 material.31 After KCN etching, most of these in-homogeneities were removed, except in case of
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54 sample Cu133. In case of the most Cu-poor CZTSe sample (Cu101), large holes were observed
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56 (Fig. 1(e)) that may originate from the removal of large crystals of secondary phases. This
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assumption is supported by the change in the overall composition of the Cu101 CZTSe layer
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6 after etching (i.e., the film is less rich in Sn), while the [Cu]/([Zn]+[Sn]) and [Zn]/[Sn] ratios
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8 remain quasi-constant for the other samples. Raman spectroscopy and X-ray diffraction analysis
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performed on these samples also confirmed that the Cu101 thin film has its overall structure
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13 modified after exposure to KCN due to the removal of secondary phases, such as Cu2SnSe3,
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15 SnxSe and CuxSe (see supporting information, section II.A).
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55 Figure 1. Top view SEM images of CZTSe layers with different initial Cu contents before (a-d)
56 and after (e-h) dipping in KCN solution for 120 s. The evolution of the [Zn]/[Sn] and the
57 [Cu]/([Zn]+[Sn]) ratios of the samples as found by EDS at 20 kV is plotted in panel i.
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Inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis was performed
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6 on the KCN solutions after different etching durations (30, 60, 200 and 600 s) applied to the
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8 Cu117 sample (Figure 2(a)). The ICP-AES measurements revealed the removal of Se, Sn and, in
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less extend, Zn from the absorber layer. The proportion in Se: Sn: Zn remains relatively constant
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13 (atomic ratio close to 3: 1: 1) for the different immersion durations. Furthermore, the etching
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15 rates of these elements are quasi-linear (taking into account the error bars). As the etched amount
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18 after 600 s could not be explained only by the etching of the secondary phases (according to the
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20 XRD diagram of the Cu117 sample, see supporting information), one can conclude that these Se,
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22 Sn and Zn atoms present in the solutions are the products of a preferential etching of the CZTSe
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25 phase. It is important to mention that a negligible amount of Cu was detected in the solutions.
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27 This appears to be in contradiction with the previous reports on the impact of KCN on CZTS thin
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films29 and CZTSSe monograins28; this might be related to the different nature of the kesterite
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32 samples considered in our study compared to literature (i.e., relatively low amount of CuxSe
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34 phase). The etched amounts suggest that the free surfaces of the CZTSe crystals should become
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37 more Cu-rich after a long KCN etching. Figure 2(b) shows that the preferential etching of Se, Sn
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39 and Zn from the CZTSe free surfaces can be confirmed for other CZTSe samples (Cu101 and
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41 Cu133). In order to better understand the underlying mechanisms of this preferential etching
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44 process, ICP-AES measurements were also performed on KOH solution (0.5 wt.%) and pure de-
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46 ionized water (DIW) samples in which the Cu117 sample was immersed for 120 s. As similar
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48 etched amounts of Se, Sn and Zn were found in the KCN/KOH and KOH solutions (while only
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51 0.2 ppm of Se was measured in the DIW sample), it can be concluded that the preferential
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53 etching of these elements during the KCN treatment is a consequence to the presence of KOH in
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the solution. This could be due to the presence of stable hydroxide-based complex ions with Sn
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and Zn, that can be easily formed due to their relatively high oxidation states in CZTSe (+IV and
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49 Figure 2. (a) Evolution of the chemical concentrations of Cu, Zn, Sn and Se as found by ICP-
50 AES measurements performed on the KCN solution samples after different immersion times of
51 Cu117 CZTSe sample; (b) Comparison between the chemical concentrations of Cu, Zn, Sn and
52 Se in the etchant solutions after 120 s of immersion time of the Cu101, Cu117 and Cu133 CZTSe
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samples in KCN/KOH, KOH or DIW.
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To assess the effect of the KCN/KOH etching on the chemical surface structure in detail, X-ray
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6 photoelectron spectroscopy (XPS) analyses were performed on the samples (Cu101, Cu117,
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8 Cu133 and Cu149) before and after a KCN treatment of 120 s (Fig. 3(a-l)). The high-resolution
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scans of the Sn 3d5/2 XPS lines show that, for all the samples, the FWHM of the signal decreases
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13 after etching in KCN due to the vanishing of a high binding energy (BE) contribution to the
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15 signal (as clearly observed for the sample Cu149, where this contribution leads to the formation
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18 of a shoulder at 487.5 eV). Most probably, this contribution may originate from Sn-based
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20 secondary phases which were etched from the absorber surface upon exposure to KCN, in
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22 agreement with the SEM images of the cleaned surfaces obtained after treatment (Fig. 1). In the
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25 meantime, the O 1s and Se 3d spectra also shows multiple contributions to the XPS signals
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27 (except in the case of the sample Cu 117). For the O 1s signal, the two contributions located at
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530.3 and 531.6 eV are simultaneously reduced after treatment. For the Se 3d spectra, the
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32 additional contributions seem to be reduced while the one coming from the CZTSe/ZnSe
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34 material is enhanced. Therefore, this Sn-based secondary phases can be SnO2 or/and SnSe2
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37 compounds, since it contains Sn with an oxidation state similar to the one present in the CZTSe
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39 phase (i.e., very close BE values) and that no additional Cu or Zn contribution can be extracted
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41 from the XPS signals. In case of the Cu101, Cu133 and Cu149 samples, as the intensity of the O
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44 1s signal decreases while the one of Se 3d peaks increases after KCN, the decrease of the
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46 FWMH of the Sn 3d XPS peaks can be explained by the partial removal of SnO2. For the sample
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48 Cu117, the Sn 3d5/2 signal can also be fitted with two contributions; however, in this particular
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51 case, it is the intensity of the low BE contribution at 486.3 eV attributed to the CZTSe phase that
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53 slightly decreases after treatment. This might be due to the preferential etching of Sn detected by
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ICP-AES, that become more visible as this sample contains few secondary phases (according to
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the low oxygen content and the Se 3d signals that can be fitted with only one contribution for
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6 each peak). The comparative analysis of the samples before and after KCN treatment also reveals
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8 that, in our case, the Cu content at the surface of the absorber slightly increases after the KCN
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treatment, except in the case of the Cu117 for which the Cu content stays rather constant (see
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13 supporting information, part II.B). This would mean that the preferential etching of Sn, Zn and
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15 Se does not necessarily take place at the top surface of the absorber. Indeed, as many voids are
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18 usually observed at the back contact/absorbers interfaces and as the etching solution could easily
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20 penetrates these voids, the preferential etch might also take place in this region of the absorber.
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22 The low amount of Cu measured on all the CZTSe surfaces has been already reported
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25 elsewhere32 and could be compared to the Cu-depletion observed at the surface of CIGSe
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27 absorbers.33 We also observed that the Zn content measured before and after KCN etching is
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quite similar. The sample Cu133 shows a high Zn and Se concentration with a ratio close to 1;
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32 this confirms the presence of a large amount of ZnSe at the surface of such absorber that is not
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34 removed after treatment. The KCN etch is also found to remove the Na accumulated at the
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Figure 3. Sn 3d5/2, Se 3d and O 1s XPS peaks recorded on Cu101, Cu117, Cu133 and Cu149
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Influence of the KCN treatment duration on CZTSe solar cells. In this section we investigate
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6 the impact of the KCN/KOH etch on the electrical performances of CZTSe-CdS-ZnO solar cells
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8 prepared with the Cu101, Cu117, Cu133 and Cu149 absorber layers. In Figure 4(a-d), the I-V
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curves measured on four series of solar cells are presented; for each series the same CZTSe
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13 absorber etched for different durations in KCN (i.e. 0 s, 30 s, 120 s or 300 s) was used. It can be
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15 clearly remarked that the impact of the KCN etch on the solar cell performances depends on the
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18 chemical composition of the CZTSe absorber. For the most Cu-poor sample (Fig. 4(a)), the Jsc is
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20 improved after 30 s of KCN etch, resulting in an improvement of the efficiency of the device.
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22 When increasing the treatment duration, a kink appears on the I-V curve leading, at first, to a
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25 decrease in the Voc and the FF, and then in the Jsc of the device. Considering our previous
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27 observation on the effect of KOH and KCN on the chemical composition at the CZTSe surface,
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we suggest that the improvement of the Jsc in the case of the Cu101 sample is due to the removal
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32 of the secondary phases, while the KOH would be responsible for the progressive degradation of
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34 the FF when increasing the treatment duration, likely due to the preferential etching of Se, Sn
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37 and Zn from the surfaces of the absorber. In the case of the sample Cu117 (Fig. 4(b)), an
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39 improvement of the efficiency is also revealed after 30 s of KCN etch, mainly due to the
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41 improvement in the FF, as the kink present on the as-grown reference sample disappears after
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44 treatment. Here again, increasing the KCN etching duration to 120 s and then to 300 s leads to a
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46 distortion in the I-V curve, which increase as increasing the treatment time. In this case, the
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48 origin of the improvement of the efficiency after 30 s of treatment is less obvious, as this
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51 absorber contains a low amount of secondary phases. However, it cannot be excluded that
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53 secondary phases are present around the voids at the back/absorber interfaces forming a barrier
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to the holes transport, and could be etched by the KCN solution. Complementary electrical
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results obtained on CZTSe solar cells showing initially a large I-V distortion and treated in KCN
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6 (without KOH) or in KOH (without KCN) tend to confirm that the FF improvement is due to the
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8 KCN, while KOH degrades the FF (see supporting information, section II.E).
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For the series using the Cu133 absorber (Fig. 4(c)), the KCN etch quickly leads to a drastic
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13 decrease of all the electrical parameters due to a very strong distortion of the characteristic. This
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15 might be due to the particular surface of this sample, which contains a large amount of ZnSe
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18 phase. As the KCN/KOH does not affect this phase, the action of the etchant will be focused on
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20 the small domains of CZTSe accessible to the solution. Therefore, the preferential etching of Se,
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22 Sn and Zn is concentrated on these areas and severely affect the properties of the p/n junction.
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25 Finally, the as-grown reference sample using the most Cu-rich absorber (Cu149, Fig. 4(d)) is
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27 found to be shunted, likely due to the presence of CuxSe phases. Therefore, the KCN treatment
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carried out on this type of absorber slightly improves the efficiency of the devices.
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56 Figure 4. I-V curves of CZTSe-CdS-ZnO solar cells prepared from (a) Cu101, (b) Cu117, (c)
57 Cu133 and (d) Cu149 treated in KCN for different durations (0, 30, 120 and 300 s).
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5 Furthermore, more detailed electrical characterizations were performed on the Cu101 solar
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7 cells with different treatment durations. Figure 5(a) shows the doping profile derived from Mott-
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9 Schottky plot of capacitance-voltage (C-V) measurements. It can be seen that the doping of the
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12 CZTSe absorber increases by one order of magnitude when increasing the immersion time in the
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14 KCN/KOH solution from 0 s to 300 s, therefore decreasing the apparent space charge region
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16
(SCR) width in the absorber. The external quantum efficiency (EQE) spectra of these solar cells
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19 measured without intentional light bias reveal that the maximum EQE value (at 500 nm)
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21 increases after 30 s of treatment, and decreases after a longer treatment duration. This evolution
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of the shape of the EQE can be due to the modification of the SCR width. When using light bias,
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26 the collection of the photoelectron is improved on the whole wavelength range (giving Jsc values
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28 close to the one measured by I-V), showing the presence of a light sensitive barrier. Finally, I-V
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31 measurements as a function of the temperature (I-V-T) show that the extrapolation of the qVoc
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33 value progressively decreases as the etching duration increases from 0 s to 300 s, meaning that
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35 the main location of the limiting recombination mechanisms is moving from bulk to interface.
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49 Figure 5. Doping profile derived from Mott-Schottky plot (a), EQE spectra (b) and evolution of
50 the Voc as a function of temperature (c) measured on Cu101 solar cells using different durations
51 of KCN etch (0, 30, 120 and 300 s).
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In order to determine the physical origins of these electrical phenomena, complete devices were
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6 analyzed by scanning transmission electron microscopy (STEM) and secondary ions mass
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8 spectroscopy (SIMS). At first, STEM-EDS mapping was carried out on the Cu101 solar cells
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synthesized with and without a standard KCN treatment. Figure 6(a,c) show HAADF-STEM
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13 images of both samples. In both cases, the thickness of the CZTSe layers varies from 900 nm to
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15 ~1.15 µm and consists of large (~ 800 nm) densely packed grains of an irregular shape. Large
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18 holes were observed at the CZTSe/Mo interface, as already reported.18 However, the grain
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20 boundaries of the non-treated sample are more visible, meaning that they likely contain more
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22 chemical and structural non-homogeneity. According to the EDS maps acquired on this sample
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25 (Fig. 6(c)), this specimen contains a lot of inclusions of secondary phases, mainly located at the
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27 grain boundaries and close to the interfaces. Within the CZTSe layer, we found some inclusions
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of ZnSe randomly distributed within the CZTSe layer (as indicated with the blue arrows on Fig.
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32 6). The Zn:Se atomic ratio in these areas is very close to 1:1. There are also large inclusions of
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34 the ternary CuxSnSey phases (indicated with pink circles). An average Cu:Sn:Se ratio measured
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37 from four areas is 32:16:52. Some tiny CuxSe clusters were also observed (as pointed out on Fig.
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39 6(c) with green arrows). No SnSex phases could be detected on this specimen at the surface
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41 region of the sample; this may appear in contradiction with our XPS results, but could be due to
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44 the very small area measured by STEM compared to XPS. The CZTSe/Mo interface shows not
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46 only inclusions of ZnSe and CuxSnSey, but also CuxSe and ZnxSnSey (see supporting
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48 information, section II.C). We also observed that the CdS layer on top of the CZTSe layer is not
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51 completely uniform, with some area contaminated with Cu (likely originating from the CuxSe
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53 phase). The Cu101 CZTSe absorber seems more homogeneous after KCN treatment (Fig. 6(d)),
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as only ZnSe inclusions located at the back interface could be observed. However, a layer as thin
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as ~ 20 nm was found to surround the free surface of the bottom CZTSe grains (indicated with a
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6 yellow arrow). The EDS maps recorded on this area show that this layer mainly contains Cu, Cd
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8 and S, in different proportions depending on the analyzed area (see supporting information,
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section II.C). This layer could have been formed first during the KCN etch, then during the
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13 deposition of the n-type CdS buffer layer, through the pinholes in the CZTSe film observed after
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15 KCN etching (Fig. 1(e)). Also, a continuous Cu-rich layer is formed at the CZTSe/CdS interface;
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18 this is in good agreement with the previous ICP-AES and XPS results, showing that this Cu-rich
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20 layer is formed during the chemical treatment. Therefore, despite the quality improvement of the
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22 kesterite absorber, the degradation of the CZTSe/CdS interface due to the Cu-rich interlayer
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25 and/or the presence of a thin Cu:Cd:S layer at the free surface of the CZTSe grains could be
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27 responsible for the distortion of the electrical characteristics of the CZTSe solar cells revealed
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after treatment. When increasing the etching time, this effect becomes more visible as a thicker
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32 Cu-rich interlayer/capping layer can be formed. This supposition is in good agreement with most
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34 of literature reporting on CZTSe and CIGSe solar cells, which show that the distortion of I-V
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37 curves in thin film solar cells can be explained by interface issues (e.g., presence of a potential
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39 barrier in the region of the heterojunction).34,35 This barrier may be responsible for the increase in
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41 the photo-carrier recombination rate observed at the interface when increasing the treatment
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44 duration. Furthermore, it is well known that the CdS compound itself is a photosensitive
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46 material, for which the doping depends on the illumination conditions.36 By extrapolation, the
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48 mixed Cu:Cd:S compound could also be photosensitive; this would explain the difference in the
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51 EQE spectra measured with and without light bias.
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29 Figure 6. HAADF-STEM images and the corresponding overlaid RGB images of the Cu-K, Zn-
30 K, Sn-L, Se-K, Cd-L and Mo-K EDS dynamic maps recorded on a Cu101 solar cell prepared
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without (a-c) and with (b-d) a KCN treatment for 120 s.
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36 Additionally, SIMS measurements were performed on the 4 samples using the Cu117
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38
absorber. The concentrations in alkali atoms (Na, K), which originally diffuse from the glass
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40 23 39
41 substrate during the annealing stage, were followed. Figure 7 shows the Na and K SIMS
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43 depth profiles through the Cu117 solar cells synthesized without and with 30 s, 120 s or 300 s of
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KCN etch. All the alkali profiles measured on the samples exhibit a V-shape profile. Indeed, as
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48 our kesterite absorbers can be considered as porous structures due to the large amount of holes at
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50 the back side of the absorbers, the surface-to-bulk ratio of the CZTSe thin films is relatively high
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53 and the apparent “bulk” of the absorber contains some voids. In CZTSe polycrystalline thin
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55 films, Na (and likely K) atoms are mainly located at the free surface and grain boundaries.38 As
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57 the KCN solution could easily interpenetrate the porous CZTSe structure and modify the alkali
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content on the free surfaces (and eventually at the grain boundaries) of the absorber, the Na/K
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6 concentrations is found to be proportional to the surface/bulk ratio as a function of the analysis
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8 depth. After 30 s of treatment, the Na concentration in the CZTSe layer appears to remain similar
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to the one measured without etching. As the KCN etch duration increases from 30 s to 300 s, the
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13 Na content in the absorber decreases by two orders of magnitude. It can be also remarked that the
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15 K content increases after KCN treatment; the extra-potassium atoms measured in the absorber
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18 may originate either from KCN or KOH present in the etching solution. The modification of both
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20 Na and K contents in the absorber as a function of the treatment time could eventually contribute
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22 to a change of doping in the absorber.37 This change of doping could also be at the origin of the
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25 vanishing of the initial kink after 30 s of treatment observed for this sample. Also, according to
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27 the SIMS profiles, it seems that both Na and K concentrations mainly change at the back side of
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the absorber after KCN treatment, where the S content was found to slightly increases (see
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32 supporting information, section II.D) due to the formation of the Cu:Cd:S layer. Therefore, the
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34 appearance of the kink could be also due to the modification of the alkali content at the free
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37 CZTSe surface close to the Mo back contact and/or at the CZTSe/CdS interface.
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39
as-grown
Secondary Ion Count Rate (cps)
40 Na
41 7 Front Cu117)
Absorber (Cu101) Back
10 K
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43 10
6 KCN, 30 s
44 Na
K
45 5
10
46 KCN, 120 s
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48 10 K
49 3
50 10 KCN, 300 s
Na
51 K
52 250 500 750 1000 1250 1500
53 Sputtering time (s)
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55 Figure 7. 23Na and 39K SIMS depth profiles recorded through Cu101 solar cells synthesized
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without and with 30 s, 120 s, 300 s of KCN etch.
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6 CONCLUSION
7
8 In summary, the effect of the standard wet KCN/KOH treatment on the properties of the
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interfaces in CZTSe solar cells was investigated. From the physical characterization of the
12
13 samples, the KCN treatment is found to selectively etch most of the secondary phases that can be
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15 formed at the free surface of the CZTSe thin films (i.e., Se0, CuxSe, CuxSnSey, SnSe2 and SnO2)
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18 except ZnSe, while the KOH present in the KCN solution, added in general for safety reasons,
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20 preferentially reacts with the Se, Sn and Zn of the CZTSe phase leading to an increase in the Cu
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22 content at the surface of the CZTSe absorber. The etching solution was also found to modify the
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25 alkali content (Na, K) content of the absorber, while the bulk concentrations in Cu, Zn, Sn and
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27 Se remain constant (except in case of large amount of secondary phases). As a consequence, two
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distinct phenomena were observed on the electrical characteristic of the CZTSe solar cells: (i) the
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32 improvement of the efficiency after only 30 s of treatment, for the devices showing initially a
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34 distortion of the I-V curve; (ii) the progressive decrease in the FF of the solar cells when
35
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37 increasing the treatment duration. This later observation is a consequence of the increase of the
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39 doping of the absorber combined with the presence of a barrier at the p/n junction that increase
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41 the recombination rate at this interface, likely due to the degradation of the free surface of the
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44 CZTSe grains that become more Cu-rich. Therefore, it is recommended to limit the duration of
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46 the KCN treatment to 30 s and/or to reduce the concentration of KOH in solution for the
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48 processing of high efficiency CZTSe solar cells.
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51
52
53 ASSOCIATED CONTENT
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Supporting Information. Experimental methods, characterization techniques and further
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6 physical and electrical characterization of the devices. This material is available free of charge
7
8 via the Internet at http://pubs.acs.org.
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12 AUTHOR INFORMATION
13
14
Corresponding Author. mbuffiere@qf.org.qa
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17 Author Contributions
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20 The manuscript was written through contributions of all authors. All authors have given approval
21
22 to the final version of the manuscript.
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24
25
26 Notes
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28 The authors declare no competing financial interests.
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35 ACKNOWLEDGMENT
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37
This research is partially funded by the Flemish government, Department Economy, Science and
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40 Innovation. We would like to acknowledge Flamac at Gent for the sputter-deposition of the
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42 metal layers. AGC is acknowledged for providing SLG/Mo substrates
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47
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11 S. Red-blue Effect in CIGS Devices Revisited Thin Solid Films, 2013, 535, 302-306.
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16 Khelifi, S.; Meuris, M.; Poortmans, J. Spectral Current-voltage Analysis of Kesterite Solar Cells J.
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Phys. D. Appl. Phys., 2014, 47, 175101.
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22 (36) Pudov, A.O.; Kanevce, A.; Al-Thani, H.A.; Sites, J.R.; Hasoon, F. S. Secondary Barriers in
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24 CdS-CuIn1-xGaxSe2 Solar Cells, J. Appl. Phys., 2005, 97, 064901 .
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27 (37) Li, J.V.; Kuciauskas, D.; Young, M.R.; Repins, I.L. Effects of Sodium Incorporation in Co-
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29 Evaporated Cu2ZnSnSe4 Thin-Film Solar Cells Appl. Phys. Lett., 2013, 102, 163905.
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32 (38) Schwarz, T.; Cojocaru-Mirédin, O.; Choi, P.; Mousel, M.; Redinger, A.; Siebentritt, S.; Raabe, D.
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Atom Probe study of Cu2ZnSnSe4 Thin-films prepared by Co-evaporation and Post-deposition Annealing
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37 Appl. Phys. Lett., 2013, 102, 042101.
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40 TABLE OF CONTENT
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123x190mm (150 x 150 DPI)
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KCN Chemical Etch For Interface Engineering in Cu2Znsnse4 Solar Cells

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KCN Chemical Etch for Interface Engineering in Cu2ZnSnSe4 Solar Cells

Article in ACS Applied Materials & Interfaces · June 2015

M. Buffière Guy Brammertz

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Sylvester Sahayaraj Maria Batuk

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6 60 (a) Cu101 Cu101 16 (e) Cu101 290 (i) Cu101

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