The Relation Between Performance and Stability of Cd‐Chalcogenide/Polysulfide Photoelectrochemical Cells: I . Model and the Effect of Photoetching

Tenne, Reshef; Müller, Norbert; Mirovsky, Y.; Lando, D.

doi:10.1149/1.2119834

Cited by 31 publications

(17 citation statements)

References 13 publications

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“…We have earlier shown that one 416-nm nanosecond pulse can excite aqueous p-benzoquinone (BQ) to the Tx state, and generate the resonance Raman spectra of that state.5 We now report higher resolution spectra in the 1600-cm"1 region, and attempt a vibrational assignment for BQ-h4, BQ-d4, and the methyl derivative MeBQ (Toluquinone). Our purpose is to understand the changes in (1) Trommsdorf, . P. J. Chem.…”

Section: Introductionmentioning

confidence: 99%

Resonance Raman investigation of the .pi. antibonding distribution in excited triplet aqueous p-benzoquinone

Rossetti¹,

Beck²,

Brus³

1983

J. Phys. Chem.

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The time-resolved resonance Raman spectra of triplet p-benzoquinone in water have been investigated at 266, 315,355, and 416 nm. Recent improvements in the apparatus are described. The C-C ring stretch (Wilson's 8a) and the symmetric C--O stretch are tentatively identified, using the isotopic shift for ring deuteration and comparison with the semiquinone radical anion. The symmetric carbonyl stretch at 1496 cm-' is unusally high for an nlr* excited state. The C=C ring stretch at 1552 cm-' is unusually low for a quinoid type species. These results indicate that there is a* antibonding density on the ring as well as on the carbonyl groups. Comparison is made with previous So -T1 vibronic electronic absorption studies in neon matrices.(7) Beck, S. M.; Brus, L. E.

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Section: Introductionmentioning

confidence: 99%

Resonance Raman investigation of the .pi. antibonding distribution in excited triplet aqueous p-benzoquinone

Rossetti¹,

Beck²,

Brus³

1983

J. Phys. Chem.

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“…Polysulfide solution modification can have significant effects on CdX]Sx = PEa performance. Photoelectrode operating lifetime has been shown to increase with increasing concentration of polysulfide in the electrolyte (2,3). However, these studies were performed in polysulfide electrolyte containing added alkali hydroxide, which was shown recently to be detrimental to CdX/S7 PEC photovoltage, photocurrent, and solar-to-electrical energy conversion efficiency (4).…”

mentioning

confidence: 99%

The High Aqueous Solubility of K 2 S and Its Effect on Bulk and Photoelectrochemical Characteristics of Cd ( SeTe ) / S x = Cells: I . Polysulfide Variation at Constant Sulfur/Sulfide Ratio

Licht

Manassen

Hodes

1986

J. Electrochem. Soc.

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The aqueous solubility of K2S is measured to be 5.6, 8.9, and 11.3m at 0°, 25°, and 72°C, respectively. The high K2S solubility, compared to that of Na2S , is discussed. An increase in potassium sulfide concentration in polysulfide solutions containing a fixed ratio of dissolved sulfur to alkali sulfide is shown to: (i) modify the distribution of polysulfide species in solution, (ii) increase the solution‐absorbance of light, (iii) negatively shift the redox potential, (iv) increase the calculated disproportionation‐limited lifetime of the solution, and (v) decrease potassium ion activity. Thin film normalCdfalse(normalSeTefalse) photoelectrochemical solar cells were investigated with polysulfide electrolytes containing 0.5 normalto 8.5m K2S . At either lower or higher sulfide concentrations, photocurrent, fill factor, and conversion efficiency are depressed. A relative gain in efficiency >30% is achieved with electrolytes of intermediate concentration containing 1 to 2m potassium sulfide.

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“…The very occurrence of a positive temperature dependence of the short-circuit photocurrent indicates that not all photogenerated holes are used for oxidation of sulfide. In the case of Cd chalcogenides, it was argued that such a mismatch between hole flux and electrochemical reaction flux will lead to self-oxidation of the semiconductor and thus to instability (25,26). As we will see in the following section, this is not so for the CuInX2/polysulfide systems.…”

Section: Effect Of Polysulfide Composition On 1-17 Character-mentioning

confidence: 93%

Ternary Chalcogenide‐Based Photoelectrochemical Cells: IV . Further Characterization of the Polysulfide Systems

Cahen

Dagan

Mirovsky

et al. 1985

J. Electrochem. Soc.

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The photoelectrochemistry of n-CuInS2 and CuInSe2 in polysulfide electrolyte is studied with particular emphasis on the pretreatments of the electrodes and on their output stability. The use of Cd doping, (photoelectro)chemical etching, and mild air oxidation all were found to improve electrode performance. The effect of air oxidation was reproducible only for the diselenide, where it improved the fill factor and, because of a negative shift of the flatband potential, the open-circuit voltage. Optimized cells showed, at elevated temperatures, conversion efficiencies around 5 and 7.5% for the sulfide and selenide, respectively. The positive temperature dependence of the photo-I-V characteristics at both low and high illumination intensities, the existence of optimal polysulfide solution compositions, the linear dependence of the photocurrent on the light intensity, and the effects of temperature, solution composition, and initial current density on the photocurrent decrease during the first minute of operation of the cells, are ascribed to limitations of the charge-transfer process across the solid/liquid interface. Thermally activated rates of ad-and desorption of sulfur containing solution species on the semiconductor surface and/or the presence of adsorption-induced electronic states in the bandgap are postulated as causes for this behavior. Notwithstanding these limitations the cells are resistant to photocorrosion, after the initial decrease is arrested, in contrast to what is known for similar Cd-chalcogenide-based systems. We suggest that this stability, which persists under load and at high light intensities, is due to the strength and character of the bonds in CuIn-dichalcogenides, or to the presence of a top layer of indium oxide in which recombination will take place, or to both.

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The Relation Between Performance and Stability of Cd‐Chalcogenide/Polysulfide Photoelectrochemical Cells: I . Model and the Effect of Photoetching

Cited by 31 publications

References 13 publications

Resonance Raman investigation of the .pi. antibonding distribution in excited triplet aqueous p-benzoquinone

Resonance Raman investigation of the .pi. antibonding distribution in excited triplet aqueous p-benzoquinone

The High Aqueous Solubility of K 2 S and Its Effect on Bulk and Photoelectrochemical Characteristics of Cd ( SeTe ) / S x = Cells: I . Polysulfide Variation at Constant Sulfur/Sulfide Ratio

Ternary Chalcogenide‐Based Photoelectrochemical Cells: IV . Further Characterization of the Polysulfide Systems

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