Chemical and Physical Reduction of High Valence Ni States in Mesoporous NiO Film for Solar Cell Application

D’Amario, Luca; Jiang, Roger; Cappel, Ute B.; Gibson, Elizabeth A.; Boschloo, Gerrit; Rensmo, Håkan; Sun, Licheng; Hammarström, Leif; Tian, Haining

doi:10.1021/acsami.7b01532

Cited by 61 publications

(76 citation statements)

References 35 publications

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“…It has been confirmed that, as shown in Figure S4A in the Supporting Information, the solar cells with NiO x sputtered using a low oxygen partial pressure have a higher performance than those of the devices with NiO x sputtered using a high oxygen partial pressure. A possible reason is that the presence of excess Ni 3+ in the film sputtered from a high oxygen partial pressure may be responsible for the high rate of recombination, which has also been widely reported in the dye‐sensitized solar cells previously 42, 43, 44. However, further explanation of this improvement is needed, which is out of the scope of this paper.…”

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confidence: 89%

Overcoming the Limitations of Sputtered Nickel Oxide for High‐Efficiency and Large‐Area Perovskite Solar Cells

et al. 2017

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Perovskite solar cells (PSCs) are one of the promising photovoltaic technologies for solar electricity generation. NiOx is an inorganic p‐type semiconductor widely used to address the stability issue of PSCs. Although high efficiency is obtained for the devices employing NiOx as the hole transport layer, the fabrication methods have yet to be demonstrated for industrially relevant manufacturing of large‐area and high‐performance devices. Here, it is shown that these requirements can be satisfied by using the magnetron sputtering, which is well established in the industry. The limitations of low fill factor and short‐circuit current commonly observed in sputtered NiOx‐derived PSCs can be overcome through magnesium doping and low oxygen partial pressure deposition. The fabricated PSCs show a high power conversion efficiency of up to 18.5%, along with negligible hysteresis, improved ambient stability, and high reproducibility. In addition, good uniformity is also demonstrated over an area of 100 cm2. The simple and well‐established approach constitutes a reliable and scale method paving the way for the commercialization of PSCs.

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confidence: 89%

Overcoming the Limitations of Sputtered Nickel Oxide for High‐Efficiency and Large‐Area Perovskite Solar Cells

et al. 2017

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“…where the holes h + (NiO) localized on the NiO surface represent the defective Ni(III) sites of the pristine oxide [23,26]. This is equivalent to say that chemisorbed ERY induces the chemical conversion Ni(III) → Ni(II).…”

Section: Dyementioning

confidence: 99%

“…Moreover, FG introduces an additional peak of oxidation due to the electroactivity of the dye itself (see the comparison of the two traces in the left frame of Figure 3). where the holes h + (NiO) localized on the NiO surface represent the defective Ni(III) sites of the pristine oxide [23,26]. This is equivalent to say that chemisorbed ERY induces the chemical conversion Ni(III) → Ni(II).…”

Section: Dyementioning

confidence: 99%

“…The wide range of NiO applicability derives from the fact that NiO can constitute a functional material in both bulk [21] and nanostructured [22,23] versions. When nanostructured NiO is employed in the configuration of thin film (thickness, l < 10 µm) it displays photoelectrochemical activity in the presence of opportune redox mediators (e.g., the redox couple I − /I 3 − ) [24].…”

Section: Introductionmentioning

confidence: 99%

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Effect of Sensitization on the Electrochemical Properties of Nanostructured NiO

et al. 2018

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Screen-printed NiO electrodes were sensitized with 11 different dyes and the respective electrochemical properties were analyzed in a three-electrode cell with the techniques of cyclic voltammetry and electrochemical impedance spectroscopy. The dye sensitizers of NiO were organic molecules of different types (e.g., squaraines, coumarins, and derivatives of triphenyl-amines and erythrosine B), which were previously employed as sensitizers of the same oxide in dye-sensitized solar cells of p-type (p-DSCs). Depending on the nature of the sensitizer, diverse types of interactions occurred between the immobilized sensitizer and the screen-printed NiO electrode at rest and under polarization. The impedance data recorded at open circuit potential were interpreted in terms of two different equivalent circuits, depending on the eventual presence of the dye sensitizer on the mesoporous electrode. The fitting parameter of the charge transfer resistance through the electrode/electrolyte interface varied in accordance to the differences of the passivation action exerted by the various dyes against the electrochemical oxidation of NiO. Moreover, it has been observed that the resistive term R CT associated with the process of dark electron transfer between the dye and NiO substrate is strictly correlated to the overall efficiency of the photoconversion (η) of the corresponding p-DSC, which employs the same dye-sensitized electrode as photocathode.

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“…Such properties are in turn influenced by the modality with which the dye is anchored onto the surface, the chemisorption geometry being dependent on the nature of the sensitizer and on the surface properties of the semiconductor like morphology, chemical composition,,, and charge/potential distribution at the interface ,. In addition to that, the type of electronic interactions existing between the relevant orbitals of the sensitizer in the excited stateand the electronic structure of the nanostructured semiconductorare also of primary importance for the identification of the actual mechanism of electron transfer. In fact, the latter process can occur either via electron tunnelling or via the macro‐orbital obtained from the mixing of the molecular orbital(s) of the excited dye with the electronic surface states of the supporting semiconductor ,.…”

Section: Introductionmentioning

confidence: 99%

First Evidence of Electrode Reconstruction in Mesoporous NiO After Operation as Photocathode of Dye‐Sensitized Solar Cells

et al. 2018

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For the first time it is shown that the NiO films operating as photocathodes in dye‐sensitized solar cells (DSCs), alter their X‐ray diffraction (XRD) pattern upon occurrence of the photoelectrochemical reaction of reduction. In particular, it has been observed that mesoporous NiO sensitized with Fast Green (FG) presents splitting and broadening of its characteristic XRD peaks after device operation in p‐type DSC (p‐DSC) and tandem DSC (t‐DSC). The nature of the changes in the diffraction pattern of NiO does not vary with the magnitude of the current passing through the p‐DSC and the t‐DSC with NiO photocathodes. Such a combination of facts would indicate that the photoelectrochemical process of holes photoinjection mediated by the sensitizer is responsible of the structural variations in NiO photocathode. At a microscopic level, we attributed such modifications to the reconstruction of the NiO electrode following the realization of the dye‐mediated process of electron transfer with lattice deformation possibly due to the inclusion of the chemisorbed sensitizer in the oxide structure. This observation opens up a completely new direction of research in the field of DSC and analogous devices as far as the analysis and the understanding of the interactions dye/semiconductor in the common operative conditions of a DSC are concerned.

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Chemical and Physical Reduction of High Valence Ni States in Mesoporous NiO Film for Solar Cell Application

Cited by 61 publications

References 35 publications

Overcoming the Limitations of Sputtered Nickel Oxide for High‐Efficiency and Large‐Area Perovskite Solar Cells

Overcoming the Limitations of Sputtered Nickel Oxide for High‐Efficiency and Large‐Area Perovskite Solar Cells

Effect of Sensitization on the Electrochemical Properties of Nanostructured NiO

First Evidence of Electrode Reconstruction in Mesoporous NiO After Operation as Photocathode of Dye‐Sensitized Solar Cells

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