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Solvent Templated Electrodeposition of Mesoporous Nickel Oxide Layers for

Solar Cell Application.

Article  in  ChemElectroChem · June 2017

DOI: 10.1002/celc.201700495

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 DOI: 10.1002/celc.201700495 Articles
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Solvent-Templated Electrodeposition of Mesoporous Nickel
5 Oxide Layers for Solar Cell Applications
6
7 Sana Koussi-Daoud,[a] Aurélien Planchat,[b] Adèle Renaud,[c] Yann Pellegrin,[b]
8 Fabrice Odobel,[b] and Thierry Pauporté*[a]
9
10
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Solvent engineering for the electrochemical preparation of solvent is included in the layer. After annealing at a sufficient
12
porous, thick, and adherent nickel oxide layers is investigated. temperature to eliminate DMSO, pores are released and
13
The deposition of this oxide is studied in pure aprotic dimethyl mesoporous films are formed. These solvent-templated electro-
14
sulfoxide (DMSO) medium and in DMSO/water mixtures through deposited layers have been applied in p-type dye-sensitized
15
the cathodic reduction of a nickel nitrate precursor. In pure solar cells (p-DSSCs) after sensitization by the P1 dye. For high
16
DMSO, the as-grown layers were a mixture of directly obtained water content (25 vol.%), the electrodeposited layers were non-
17
NiO and metallic nickel. On the other hand, in the presence of porous and were consequently unsuitable for p-DSSC applica-
18
water, b-Ni(OH)2 and Ni8 mixed layers were formed. In the tion.
19
absence of water or at low water contents, we show that the
20
21
22
23 1. Introduction using the same dye and the Tris(acetylacetonato)iron(II)/(II)
24 redox couple, published cells with an efficiency of 2.51 % and a
25 Dye-sensitized solar cells (DSSCs) have attracted considerable Jsc of 7.65 mA.cm@2.[16] Nickel oxide as a semiconductor with a
26 attention as one of the promising alternative to the conven- wide direct bandgap ranging between 3.6 and 3.8 eV at room
27 tional silicon solar cells due to their low production cost, nice temperature, has attracted a great attention for p-DSSC and
28 conversion efficiencies which are maintained under weak other advanced applications such as photocatalysis[17–20] and
29 indoor light and exhibit low dependence on the incidence UV-photodetectors.[21]
30 angle of light.[1–3] Currently, the most studied DSSCs are based Much higher performances than 2.51 % can be expected,
31 on the concept of electron injection from a dye, after excitation notably from the optimization of the oxide layer and then use
32 by light irradiation, into the conduction band of a n-type wide of new methods of preparation allowing a better control of the
33 bandgap semiconductor.[1] More recently, the DSSC concept morphological, electrical and optical properties of the layers.
34 was extended to the use of p-type semiconductor oxides The doctor blading and screen printing of nanoparticle pastes
35 combined to dyes.[4–12] In this case, holes are transferred from are the most popular techniques for preparing the photo-
36 the photoexcited sensitizer to the valence band of a p-type electrodes.[9–11,16,22] However, they give rise to layers containing
37 semiconductor.[10] Even if some alternative oxides such as many grain boundaries which are detrimental for charge
38 delafossites have given rise to promising results, especially in collection. Also limited alternative techniques have been
39 terms of solar cell open circuit voltage,[11–15] the record cells investigated such as hydrothermal growth[23] and spray.[24] To
40 actually implements NiO as oxide p-type semiconductor.[9,16] In the best of our knowledge, electrodeposition is a quasi-
41 2013 Powar et al implemented the PMI-6T-TPA dye combined unexplored synthesis technique for this application. As a
42 with a tris(1,2-diaminoethane) redox shuttle and achieved an versatile deposition technique, it can be used for the prepara-
43 efficiency of 1.30 % under one sun.[9] In 2015, the same group, tion of various oxide semiconductor layers with well-controlled
44 properties. It has the advantage of being i) well-suited for
45 scaling-up, ii) to produce homogeneous deposits on arbitrary
[a] Dr. S. Koussi-Daoud, Dr. T. Pauport8
46 Chimie ParisTech, PSL Research University
substrate shapes, iii) the morphology and size of electro-
47 CNRS, Institut de Recherche de Chimie Paris (IRCP) deposited structures can be tuned by manipulating the
48 11 rue P. et M. Curie, F-75005 Paris, France deposition parameters, iv) it is possible to precisely control the
E-mail: thierry.pauporte@chimie-paristech.fr
49 [b] A. Planchat, Dr. Y. Pellegrin, Dr. F. Odobel
deposition position by selective patterning of the substrate, v)
50 Universit8 LUNAM, Universit8 de Nantes the electrical contact between structures and substrate is
51 CNRS, Chimie et Interdisciplinarit8: SynthHse, Analyse excellent when the deposited layer is well-adherent, and vi)
Mod8lisation (CEISAM), UMR 6230
52 2 rue de la HoussiniHre, F-44322 Nantes cedex 03, France
there is a minimum inter-reaction or inter-diffusion between as-
53 [c] Dr. A. Renaud deposit and substrate due to the low deposition temperature/
54 Institut des Mat8riaux Jean Rouxel (IMN) annealing.
Universit8 de Nantes, CNRS
55 2 rue de la HoussiniHre, F-44322 Nantes cedex 3, France
The main drawback of the technique is that the layers
56 Supporting information for this article is available on the WWW under deposited in water electrolytes are composed of hydrated/
57 https://doi.org/10.1002/celc.201700495 hydroxide/oxyhydroxide nickel compounds that require a post-

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1 annealing treatment for the formation of pure NiO material. measure the effect of water on the electrochemical reduction
2 Moreover, these films are poorly adherents due to internal of nitrate. The CV curves are characterized by a cathodic wave
3 strains. In the present paper, we show that these drawbacks appearing at @0.4 V/SCE on the negative-going scan and
4 can be overcome by using novel solvents. We investigate the increasing in intensity with the overvoltage. In pure DMSO, an
5 preparation of nickel oxide layers in DMSO and DMSO/water aprotic solvent, the electrochemical reduction of NO3@, can be
6 based media by cathodic electroreduction of nickel nitrate written as Equation (1a)[25]:
7 followed by a post-deposition annealing treatment. Mesopo-
8 rous adherent layers of NiO containing some metallic nickel NO3 @ þ 2e@ ! NO2 @ þ O2@ ð1aÞ
9 have been prepared and tested for p-DSSC application.
10
Figure 1A shows that increasing the water content in the
bath increases the cathodic current.
11
12 2. Results and Discussion Due to the presence of protons, the reaction becomes
13 Equation (1b)[26]:
14 In this study, nitrate ions were used to act as a precursor of
15 oxygen for the formation of nickel oxide. Three different NO3 @ þ H2 O þ 2e@ ! NO2 @ þ 2OH@ ð1bÞ
16 electrolytic deposition baths, with various water contents, were
Figure 1B shows the cyclic voltammograms of solutions
17 first investigated by cyclic voltammetry (CV) to show the effect
containing 0.2 M Ni(NO3)2 in a solvent with various water
18 of water on the electroactivity of the system. Blank curves of
contents. The cathodic current wave was observed again and
19 baths containing 0.4 M KNO3 are shown in Figure 1A to
was of higher intensity. Moreover, the reverse current was
20
higher compared to the direct one. The electrode was observed
21
to darken upon the cathodic current exchange. The CV curves
22
show the deposition of a layer which favors the electrochemical
23
cathodic reaction.
24
25 Again the presence of water increased the cathodic current.
26 On the positive-going scan an anodic peak appeared. We have
27 observed that the electrode bleached upon the occurring
28 anodic reaction and then the oxidation of the deposited layer.
29 Moreover, large water content in the bath shifted the peak
30 towards more negative potentials. From the characterization of
31 the layers detailed below and our previous study of pure DMSO
32 medium,[27] the cathodic peak is assigned to the oxidation of
33 metallic nickel deposited upon the scan at the most negative
34 potentials. This reaction is favored by the presence of water
35 since the charge exchanged under the anodic peak increases
36 with the presence of water. For the nickel oxide deposition, the
37 applied overvoltage must be sufficiently high to allow the
38 production of O2@ and OH@ ions which will react at the
39 electrode surface with Ni2 + as follows [Eqs. (2) and (3)]:
40
41 Ni2þ þ O2@ ! NiO ð2Þ
42
Ni2þ þ 2OH@ ! NiðOHÞ2 $ NiO þ H2 O ð3Þ
43
44 On the other hand the applied potential must not be too
45 negative to avoid or limit the electrochemical reduction of Ni2 +
46 to metallic nickel (Ni8). Consequently, two applied potentials
47 were investigated: @0.85 V/SCE and @0.90 V/SCE. The current
48 transient curves measured for the various DMSO/water bath
49 mixtures are presented in Figure 2A and 2C. The curves are
50 characterized by a current increase upon the first 200 s prior to
51 reach a plateau. In agreement with the CV study, the current
52 was observed to increase with the overvoltage and the water
53 content. The latter is assigned to a higher reaction (1b) rate
54 compared to reaction (1a) and to the decrease of the viscosity
55 Figure 1. Cyclic voltammograms of electrolytes with various water contents
(FTO electrode, 10 mV.s@1, 90 8C). A) 0.4 M KNO3 solution, B) 0.2 M Ni(NO3)2. of the deposition solution with water content. The curves of
56 the electrochemical charge density are presented in Figure 2B
57

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15 Figure 2. Effect of electrolyte water content on current transient curves
upon layer deposition at A) @0.85 V/SCE and C) @0.90 V/SCE, and on charge
16 density transient curves at B) @0.85 V/SCE and D) @0.90 V/SCE. (Bath
17 temperature 90 8C; a) DMSO, b) DMSO_2 %H2O, and c) DMSO_25 %H2O).
18
19
20 and 2D for the two applied voltages. They show the continuous
21 growth of the layers and the increase of the electrical charge
22 exchanged with the applied overvoltage and the water content
23 of the bath.
24 The deposited layers were characterized by Raman spectro-
25 scopy before and after annealing. The spectra are shown in
26 Figure 3 for the layers deposited at @0.85 V/SCE and in
27 Figure S1 for the layers deposited at @0.90 V/SCE. After drying,
28 they varied in a large extent with the water content for the
29 synthesis. For pure DMSO solvent, two bands were observed at
30 505 cm@1 and 1030 cm@1. They are characteristics of NiO and
31 assigned to the 1LO and 2LO vibration modes, respectively.[28]
32 For 2 % of water, two bands were also found. They were much
33 less intense, centered at 315 cm@1 and 479 cm@1 and assigned
34 to the A1(T) and Eg(T) modes of b-Ni(OH)2, respectively.[29,30] The
35 DMSO_25 % H2O spectrum was characterized by two very weak
36 emission bands at 315 cm@1 and 820 cm@1 which are due to the
37 A1(T) and Eg(R) modes of b-Ni(OH)2, respectively. For the layers
38 deposited at @0.90 V/SCE, the Raman spectra of the dried layers
39 were very similar as shown in Figure S1 (Supporting Informa-
40 tion). In summary, NiO is directly deposited in the pure DMSO
41 medium whereas in the media with water, nickel hydroxide is
42 produced.
43 After annealing at 450 8C for 2 hours, we found intense
44 Raman bands for the layers prepared in the DMSO medium.
45 The first order transversal optical phonon (1TO) peak at about Figure 3. Raman spectra of the layers deposited at @0.85 V/SCE after drying
46 420 cm@1 could be observed as a shoulder of the 1LO band at 200 8C for 10 min (a) and after annealing at 450 8C for 2 h (b). A) DMSO
medium; B) DMSO_2 % H2O, and C) DMSO_25 % H2O.
47 (Figure 3A). The 1LO and 2LO bands became stronger. More-
48 over, the 2 M magnon band appeared at 1520 cm@1. The
49 magnon band is related to the antiferromagnetism properties
50 of NiO and its presence is the signature of a well-organized XPS spectra were recorded and compared to a reference
51 material.[31] For DMSO/H2O samples, the Raman emissions of the corresponding to a stoichiometric NiO compound (a pellet of
52 main NiO bands were present but were weaker due to a poorer Inframat NiO annealed at 900 8C during 1 h).[32] The wide range
53 organization. Similar spectra were recorded for the layers survey spectra are shown in Figure S2. Signals due to Ni, O, C, N
54 electrodeposited at @0.90 V/SCE (Figure S1, Supporting Infor- and S were detected. The C 1s spectra were used for calibration
55 mation). (Figure S3). The Ni 2p3/2 peaks of each sample are displayed in
56 Further characterizations were done to access the electronic Figure 4A. They were easily deconvoluted as classically reported
57 properties for the annealed films prepared in the three media. in the literature.[33,34] They are composed of 5 contributions, i. e.

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17 Figure 4. XPS spectra of Ni 2p3/2 (A) and O 1s (B) of layers prepared at
@0.85 V/SCE in DMSO, DMSO_2 %H2O, DMSO_25 %H2O media and annealed
18 2 h at 450 8C. The NiO reference spectra are also displayed..
19
20
21 two peaks at binding energies set to 853.9 eV and 855.6 eV
22 attributed to Ni2 +, and three satellite peaks at about 861.0 eV,
23 864.1 eV and 866.4 eV. The results of full Ni 2p3/2 contribution
24 deconvolution are gathered in Tables S1–S4. No peak at around
25 852.6 eV was observed which excludes the presence of Ni8 on
26 film surface and shows that the extreme outer surface of all the
27 annealed layers was oxidized.[33–35]
28 The presence of NiO on film surface was shown by XPS
29 measurements of the O 1s contribution (Figure 4B). The analysis
30 of the O 1s peaks (Tables S1–S3) reveals three contributions for
31 the layers at 529.6 eV, 531.4 eV and 532.1 eV. The first two are
32 assigned to the Ni@O and @OH bonds. The last contribution
33 was not found on the NiO reference spectrum and was
34 assigned to the S@O binding energy.[36] The sulfur traces is the
35 result of the sulfur remaining on the surface after the thermal
36 decomposition of DMSO. The presence of sulfur is confirmed
37 on the wide range survey spectra (Figure S2a) with two peaks
38 at 229 eV and 165.2 eV corresponding to S 2s and S 2p orbitals,
39 respectively.[37] Moreover, by quantitative comparison, a higher
40 hydroxide content was calculated for samples synthesized in
41 water condition namely DMSO_2 %H2O and DMSO_25 %H2O
Figure 5. XRD patterns of the layers deposited at @0.85 V/SCE after drying at
42 samples (Tables S2 and S3) compared to pure DMSO (Table S1). 200 8C for 10 min (a) and after annealing at 450 8C for 2 h (b). A) DMSO
43 The higher OH content in DMSO_2 % compared with DMSO_ medium; B) DMSO_2 % H2O; C) DMSO_25 % H2O. The starred peaks are
44 25 % should be due to the superior porosity of the first film assigned to the FTO substrate.

45 inducing a larger specific surface area. A close inspection of the

46 wide range survey also showed the presence of the N 1s peak
47 for the electrodeposited layers (Figure 2 Sb) and then traces of thermal annealing. For all the samples, the Ni peaks became
48 N in the layers due to nitrate. narrower. Moreover, new reflections appeared at 43.78 and
49 The structural properties of the deposited compounds were 63.38 for the samples prepared in DMSO (Figures 5A and S4A).
50 analyzed by X-ray diffraction (XRD). Figure 5 and Figure S4 They are indexed as the (200) and (220) planes of cubic NiO
51 show the diffraction patterns of rather thick materials (3–4 mm) (space group Fm-3m) (JCPDS card number 04–0835). A small
52 deposited in the various solvents at @0.85 V/SCE and @0.90 V/ peak at 31.58 is assigned to Ni2O3(002) reflection. The XRD
53 SCE, respectively. After drying, broad diffractions peaks were patterns of the annealed DMSO_2 % H2O layer had similar
54 observed, for the three deposition media, at about 44.68 and features but we noted that the NiO(200)/Ni(111) intensity ratio
55 53.38 which are assigned to the (111) and (200) planes of cubic was lower (Figures 5B and S4B). Additional diffraction peaks
56 metallic nickel (space group Fm-3m) (JCPDS card number 04- were found at 40.748, 47.98 and 68.578 which are assigned to
57 0850). The XRD patterns exhibited structural changes after the the (112), (203) and (312) reflections of monoclinic b-NiOOH

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1 (Space group C12/m1) (JCPDS card number 059-0464). These
2 peaks were also present on the patterns of the DMSO_25 %
3 H2O samples (Figure 5C and S4C). Moreover, the NiO(200)/
4 Ni(111) intensity ratio even decreased for the DMSO_25 % H2O
5 sample. In conclusion the layers prepared in the presence of
6 water were a mixture of several compounds, mainly Ni8, b-
7 NiOOH and NiO. Decreasing the water content in the electro-
8 deposition bath favors the production of NiO. The diffraction
9 peaks of nickel oxide/oxyhydroxide appeared with the anneal-
10 ing treatment due to the layer crystallization and oxidation.
11 Moreover the characterizations have shown that working in the
12 aprotic DMSO results in the higher NiO content.
13 In order to better understand the changes occurring in the
14 material upon annealing, the layers deposited at @0.85 V/SCE
15 were investigated by TG-DTA. The TG and DTA curves in
16 Figure S5 show a first weight loss along with an exothermic
17 peak between 240 and 340 8C. It is assigned to the elimination
18 of DMSO entrapped in the layer. We note that increasing water
19 content in the bath decreases the mass loss and suggests that
20 less DMSO is entrapped in the layer. A second weight gain is
21 found between 450 8C to 720 8C. It accompanies an exothermic
22 reaction. It can be assigned to the oxidation of the metallic
23 nickel initially present in the layer as shown by XRD. The full Figure 6. SEM images of electrodeposited annealed layers prepared in a,b)
pure DMSO, c,d) DMSO_2 %H2O, and e,f) DMSO_25 %H2O.
24 oxidation of Ni8 present in the layer to NiO upon the TG-DTA
25 analysis was confirmed by the XRD analysis of the powder
26 obtained after the experiment with a final annealing temper-
27 ature of 800 8C (Figure S6).
28 The morphologies before annealing of the layers prepared
29 at @0.85 V/SCE and @0.90 V/SCE are presented in Figure S7 and
30 S8, respectively. In DMSO, the films were made of large grains
31 with a 0.4–1.0 mm size which are composed of densely packed
32 nanocrystals. We noted that for a deposition at @0.85 V/SCE,
33 the grains were not fully merged and some uncovered FTO
34 substrate parts could be observed (Figure S7a). A similar aspect
35 was found in the case of DMSO_2 %H2O but the substrate was
36 then well-covered by the layer (Figures S7b and S8b). For
37 DMSO_25 % H2O, the substrate was well-covered and the large
38 grains were not observed. After annealing, the aspect of the
39 grains strikingly changed (Figure 6 and S9). It was observed Scheme 1. Molecular structure of P1 dye-sensitizer.

40 that DMSO and DMSO_2 %H2O samples, for the two different
41 potentials applied for the preparation, were mesoporous. The
42 TG-DTA curves (Figure S5) have shown that above 240 8C, tion, porosity generation and dye attachment on the oxide
43 DMSO entrapped in the layers is eliminated. The pores surface. The absorbance spectra of the annealed and sensitized
44 formation is explained by the full elimination by the thermal layers are shown in Figure 7A. Increasing the water content in
45 treatment of the DMSO remaining in the layer. Then the pores the NiO growth bath increases the absorbance in the red region
46 are released. These mesoporous layers are attractive for DSSC and the whole visible wavelength range due to the darkening
47 application which requires a large specific surface area available of the layer. Moreover, the absorption due to the dye decreases.
48 for the dye attachment. On the other hand, Figure 6, S7c and It shows a decrease of dye loading assigned to a reduction of
49 S8c show that the films deposited in DMSO_25 %H2O were the layer porosity.
50 made of aggregated small crystals. They did not look porous The solar cell performances of the samples prepared in pure
51 after annealing. This is in agreement with the poor DMSO DMSO electrolyte and annealed at 450 8C for 2 h are gathered
52 content of these layers (Figure S5C). in Table 1 and J-V curves are shown in Figure 7B. The power
53 The electrodeposited layers were integrated in p-DSSC conversion efficiency (PCE) was very low for the layers prepared
54 devices after their sensitization by the P1 dye presented in at @0.85 V/SCE. Low Jsc were recorded showing the poor
55 Schematic 1. The efficiency was negligible for the layers dried at sensitization of the layers by the dye and charge generation
56 200 8C or annealed at 300 8C for 1 h (not shown). Annealing at and collection efficiency at the photocathode. For the layers
57 high temperature is important for the DMSO solvent elimina- prepared at @0.90 V/SCE applied voltage, higher PCEs were

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1 Table 2. J-V curve parameters of p-DSSCs prepared with NiO layers
2 electrodeposited for 1000 s in DMSO/H2O media and annealed at 450 8C for
3 2 h (100 mW.cm@2 AM1.5G illumination).
4
5
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18 device efficiency, for layers prepared at @0.85 V/SCE, increased
19 from 0.0085 % to 0.039 %. The substrate coverage by NiO is an
20 important point for p-DSSC performances. In the presence of a
21 small amount of water, the prepared layer better-covered the
22 substrate and the contact zones between the electrolyte and
23 the FTO, where charge recombination occurs, were limited. It
24 resulted in a better Voc. Moreover, the Jsc was improved due to a
25 better sensitization of the layer. This is confirmed by the
26 comparison of the solar cell performances in the case of the
27 layers deposited at @0.90 V/SCE: layers prepared with and
28 without water are both porous and well-covering and it results
29 Figure 7. A) Absorbance per layer micrometer thickness curves of P1- in similar PCEs. We have noted that the DMSO_2 % H2O samples
30 sensitized NiO photoelectrode: a) DMSO, b) DMSO_2 %H2O, and c) DMSO_ contained more Ni8. This is detrimental for light transmission
25 %H2O. B) J-V curves of a) DMSO, E = @0.85 V/SCE; b) DMSO, E = @0.90 V/
31 but beneficial for the layer conductivity. It can also be noted
SCE; c) DMSO_2 %H2O E = @0.85 V/SCE; and d) DMSO_2 %H2O E = @0.90 V/
32 SCE. Full lines: under AM1.5G filtered 100 mW.cm@2 illumination; dashed that upon annealing, the surfaces of Ni8 is oxidized to NiO.
33 lines: dark current. Consequently, Ni8 in the photoelectrode must not be in contact
34 with the electrolyte and must not act as charge recombination
35 centers. Another difference between the DMSO and DMSO_
36 Table 1. J-V curve parameters of p-DSSCs prepared with NiO layers 2 %H2O cells is the presence of NiOOH in the latter. The
electrodeposited in pure DMSO medium and annealed at 450 8C for 2 h
37 (100 mW.cm@2 AM1.5G illumination). comparison of Table 1 and 2 suggests that it is favorable for the
38 Voc. In Table 2 is also reported the J-V characteristics of p-DSSCs
39 prepared using layers synthesized in a DMSO_25 %H2O me-
40 dium. The efficiency was very low. This is in line with the non-
41 porous character, low sensitization, of the layers and their high
42 Ni8 content even after their annealing. The former prevented
43 the adsorption of significant amounts of dye molecules on
44 nickel oxide and then a correct sensitization. In Table 3 are
45
46
Table 3. J-V characteristics of high efficiency p-DSSCs with P1 sensitizer
47
employing the iodide/triidide electrolyte (100 mW.cm@2 AM1.5G illumina-
48 tion).
49
50
51 observed. Higher Jsc were measured which must be due to the
52 better FTO coverage by these layers (Figure S7a, S8a and S9)
53 and to a better sensitization. The cell Voc and FF were also
54 slightly improved. The best cell PCE was 0.049 %.
55 In Table 2 are reported the performances of cells fabricated
56 with layers prepared in solutions containing water and J-V
57 curves are shown in Figure 7B. In the presence of 2 % H2O, the

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1 reported record performances of p-DSSC based on the P1 INVIA apparatus equipped with a microscope and a CCD detector.
2 dye.[22,38,39] NiO@P1 photocathode can reach efficiencies higher A 532 nm solid-state green laser was used for off-resonance
3 than 0.1 % and the best efficiency that can be found in the excitation with 10 mW power. The film surface of samples were
analyzed by X-ray photoelectron spectroscopy (XPS) technique.
4 literature is 0.17 %. The efficiencies recorded with the electro-
They were performed on a Kratos axis Nova spectrometer equipped
5 deposited NiO are lower but we note that the cell Voc was high with a Al Ka X-ray source (1486.6 eV) at 20 mA 15 kV (300 W). The
6 for this system. analyzed area was 700 V 300 mm2. The wide range survey spectra
7 were acquired at a pass energy of 80 eV corresponding to an all
8 over Fermi edge resolution of 0.89 : 0.02 eV with a 0.5 eV step. The
high resolution spectra of the C 1s, O 1s and Ni 2p were measured
9 3. Conclusions with a 0.1 eV step at Pass energy 20 eV (all over Fermi edge
10 resolution of 0.39 : 0.02 eV). The charge neutralizer system was
11 In conclusion we have developed an original STE technique for used during all the experiments to establish a steady state surface
12 the preparation of mesoporous and rather thick NiO layers. First potential. Data treatments were carried out using the CasaXPS[42]
13 a precursor layer containing nickel hydroxide/oxide and metallic software in its 2.3.18 version.[43] It consists in the peak fitting via the
14 nickel was prepared by electrodeposition. DMSO was used as a modeling of the background envelope by a Shirley function and
deconvolution of spectra with a Gaussian-Lorenzian GL(30) line
15 solvent and has been shown to act also as a templating agent
shape. The spectra energy was calibrated with the first deconvo-
16 to produce the porosity. Annealing of the layer at 450 8C was luted C 1s peak (attributed to the C@C bonding) rescale at 285 eV.
17 required to crystallize and oxidize the layer and to fully remove
TG-DTA measurements were conducted using a SETSYS evolution
18 the organic component. This step is shown very important for
16 apparatus from SETARAM. About 25 mg of deposit material was
19 the DMSO solvent elimination, porosity generation and dye scratched off from several electrodes for each measurement. The
20 attachment on the oxide surface and then for the use of these sample was heated from room temperature to 800 8C in air (1 bar,
21 layers for instance in p-type DSSCs. Adding water in the 30 mL.min@1). The temperature scan rate was 10 8C.min@1. Solar cells
22 electrolyte or using an applied potential of @0.90 V/SCE were prepared using the P1 (4-(bis-{4-[5-(2,2-dicyano-vinyl)
23 improved the layer coverage. On the other hand, water thiophene- 2-yl]phenyl}amino)benzoic acid, Dyenamo) dye shown
in Schematic 1).[38,44] After sensitization the photocathode was
24 decreases the layers porosity, their sensitization by the dye and
sealed to a platinized FTO/glass counter electrode using a Surlyn
25 then the final cell performance. The best PCE achieved was thermoplastic gasket (DuPont, 25 mm in thickness). Platinum
26 0.049 %. The present study on electrodeposited NiO layers for counter electrodes were prepared by depositing a few drops of an
27 p-DSSCs is promising with a noticeable rather high Voc value for isopropanol solution of hexachloroplatinic acid in distilled isopro-
28 this system but should require further optimization. panol (2 mg per mL) on FTO plates (TEC7, Solaronix). The space
29 between the two electrodes was filled by an electrolyte composed
of 1 M LiI and 0.1 M I2 in acetonitrile through a pre-drilled hole in
30
the counter-electrode. The cell had an active surface area of
31 Experimental Section 0.36 cm2. The J@V curves were recorded by a Keithley model 2400
32 source meter under illumination with an Oriel solar simulator
Chronoamperometry and cyclic voltammetry (CV) experiments
33 were conducted with a PGSTAT 30 potentiostat-galvanostat from filtered and calibrated to mimic AM 1.5G 100 mW.cm@2 conditions.
34 Autolab controlled by the NOVA software. For the cyclic voltamme-
35 try curves and the layer depositions, fluorine@doped tin oxide (FTO)
36 coated glass substrates (TEC-10, Pilkington) were used as a working Acknowledgements
electrode. The substrates were first cleaned with soap, rinsed with
37
distilled water, then sonicated 5 min in acetone and 5 min in
38 ethanol.[40] The working electrode surface area was 1.5 V 1.5 cm2 for Jonathan Hamon (IMN, Nantes, France) is acknowledged for XPS
39 layer characterization and was tape delimited to 0.6 V 0.6 cm2 for measurements. The authors thank Dr. Delphine Schaming (Itodys
40 the cell preparation. The substrate was placed vertically in the Laboratory, University Paris VII, France) for TG-DTA measurements.
41 three-electrode cell.[41] The counter-electrode was a platinum wire Dr. Stéphane Jobic and Dr. Laurent Cario (IMN, Nantes, France)
42 and the applied potential was controlled versus a saturated calomel are acknowledged for fruitful discussion on the data. The authors
reference electrode (SCE).
43 are grateful to the French National Agency for Research (ANR) for
44 The deposition bath was 0.2 M nickel nitrate hexahydrate its financial support through the POSITIF project (ANR-12-PRGE-
45 (Ni(NO3)2 · 6H2O) (Alfa Aesar, 98 %) dissolved under argon atmos- 0016) and to Pays de la Loire for the LUMOMAT project.
phere in three different solvents : pure DMSO, DMSO containing
46
2 vol.% of water and a 3 : 1 volume DMSO:H2O mixture. The
47 experiments were conducted at 90 8C. The solution was stirred
48 using a magnetic barrel rotated at 250 rpm. After deposition, the Conflict of Interest
49 layers were dried 10 min at 200 8C. The samples were annealed in a
50 Carbolite tubular furnace. The annealing temperature was reached The authors declare no conflict of interest.
51 using a ramp of 15 8C/min.
52 The morphology of the samples was examined with a high Keywords: NiO · electrodeposition · mesoporous · dye-
53 resolution Zeiss LEO 1530 scanning electron microscope (FE-SEM).
sensitized solar cells
54 The layer crystal structure was characterized by a PANalytical X-Pert
high-resolution X-ray diffractometer (XRD) operated at 45 kV and
55
40 mA and using CuKa radiation with l = 1.5406 Å. Raman scatter-
56 ing spectra were measured at room temperature with a Renishaw [1] A. Hagfeldt, G. Boschloo, L. C. Sun, L. Kloo, H. Pettersson, Chem. Rev.
57 2010, 110, 6595–6663.

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38
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