Studies of the rearrangement‐energy in electrode kinetics at SnO<sub>2</sub>‐electrodes

Memming, R.; Möllers, F.

doi:10.1002/bbpc.19720760604

Cited by 86 publications

(6 citation statements)

References 12 publications

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“…This figure is given for the case when the electrode was polarized at --0.35V in 0.5M H2SO4. If one takes into consideration the distribution function of unoccupied electron states in the hydrogen electrode (18,19), hydronium ions must find a distribution probability in the energies equal to or higher than the lowest level of the surface states. Therefore, the electron transfer from the surface states to hydronium ions in the electrolyte must occur in the energy region covering the entire surface state.…”

Section: Resultsmentioning

confidence: 99%

Extension of Spectral Response of p‐Type Gallium Phosphide Electrodes by Metal Adatoms

Yoneyama

Mayumi

Tamura

1978

J. Electrochem. Soc.

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The spectral response of p-type GaP electrodes was successfully extended to longer wavelengths by depositing a monolayer of any of several kinds of metal such as gold, silver, palladium, or copper onto the electrode surface and then cathodically polarizing the electrode under illumination. The shape, but not the magnitude, of the developed photocurrent spectra, which covered wavelengths between 600 and 1400 nm, were independent of the kind of metal chosen. Impregnated hydrogen seemed to be responsible for the enhanced photocurrent spectra. Pb-0.27 PdC12 9 2H20 16, NI-I4C1 30, NH~OH 30 10.36 -0.40 KAg(CN)2 100, I~CO~ 45 12.51 -0.23 KAu(CN)2 170,

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Section: Resultsmentioning

confidence: 99%

Extension of Spectral Response of p‐Type Gallium Phosphide Electrodes by Metal Adatoms

Yoneyama

Mayumi

Tamura

1978

J. Electrochem. Soc.

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“…The separation between Wox and WRed is essential 2~, where ~ is the solvent reorganizational energy during electron transfer. The values estimated for several couples by Memming et al (5) have been used in Fig. 8.…”

Section: Discussionmentioning

confidence: 99%

“…Processes involving elimination or diminution of charge of ions are usually associated with an increase of volume of the system due to decrease or removal of the electrostriction in the over-all reaction. Examples in homogeneous processes are redox reactions, ionpair association, and the reverse of quaternization of tertiary amines (Menschutkin reaction) (1,4,5). In the latter case, it is known that the decrease of electrostriction in the over-all reaction is accompanied by a positive volume of activation, as may be expected.…”

Section: Introductionmentioning

confidence: 90%

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Semiconductor Electrodes: XIV . Electrochemistry and Electroluminescence at n‐Type in Aqueous Solutions

Noufi

Kohl

Frank

et al. 1978

J. Electrochem. Soc.

102

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The electrochemical behavior of single crystal n-TiO2 was investigated in aqueous solutions. Charge transfer at the semiconductor/electrolyte interface was probed with several redox couples with standard redox potentials spanning a wide range. Most reductions occurred at potentials close to Vfb, the flatband potential and the current-voltage behavior suggested involvement of surface states in the charge transfer process. Evidence for the adsorption of phosphate ion and its effect on the reduction of Fe (CN)68-is also presented. Electroluminescence was observed during reduction of S2Os 2-at wavelengths longer than 700 nm, suggesting the existence of intermediate levels.The electrochemical behavior of n-TiO2 has been the subject of several recent investigations including a previous report in this series (1), which utilized an aprotic solvent, acetonitrile (ACN), and which postulated that electron transfer can occur via intermediate levels or surface states within the bandgap region. Studies in aqueous solutions with TiO2 (2) and other semiconductors (3, 4) have also investigated the mechanism of charge transfer of added redox couples at the semiconductor/solution interface. Although not as many Nernstian, one-electron redox couples are available in aqueous, as compared to nonaqueous solutions, the relative location of the energy levels of TiO2 at the semiconductor/solution interface (i.e., the fiatband potential) can be changed in aqueous solutions by relatively large amounts by changing the solution pH. This provides another variable for investigating the band structure. This approach has previously been used to study SiC (4) and SnO2 (5).In the present study the semiconductor/solution interface was investigated by several techniques. Electron transfer reactions of couples, including some with standard redox potential well positive of those used in a previous study (2), were investigated at different pH's. To probe the existence and role of intermediate levels within the bandg~ap, electroluminescence of the n-TiO2 semiconductor caused by electron-hole recombination from minority carrier injection from the electrolyte was studied. Hole injection into n-type semiconductors leading to radiative recombination has previously been demonstrated for GaP (6), SnO2, ZnO, CdS, and GaAs (7).In addition a study of the space charge capacitance, Csc, as a function of potential, E, was undertaken in an * Electrochemical Society Student Member.

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“…However, the reorganization energy would be normally distributed from 1 to 2 eV for simple hydrated ions according to their ionic radius and specific hydrated structure. 28 This reorganization energy affects the detailed state density function of the redox couple and the level where the redox couple and the metal electrode are in equilibrium. Therefore, the large difference of the reorganization energy between the ideal and the real situations is likely to result in a P30 ECS Journal of Solid State Science and Technology, 2 (1) P26-P30 (2013) mismatch between the hypothesis and the experimental results.…”

Section: Equationmentioning

confidence: 99%

Effect of Oxidizers on Chemical Mechanical Planarization of Ruthenium with Colloidal Silica Based Slurry

Cui

Park

2012

ECS J. Solid State Sci. Technol.

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We investigated effect of oxidizers on chemical mechanical planarization (CMP) of ruthenium (Ru). Several commonly used oxidizers with different standard reduction potentials were used in the Ru CMP test, and their corrosion behaviors and states of surface oxidation were analyzed. We found that Ru only had a high polishing rate with slurries containing sodium periodate and sodium hypochlorite. We also observed that Ru film underwent severe pitting corrosion with these slurries, and formed a porous RuO 3 /RuO 2 oxide layer. Ru film was unable to achieve high corrosion current density as well as form a porous RuO 3 /RuO 2 oxide layer except for these two oxidizers. Both the corrosion and oxidation (formation of RuO 3 /RuO 2 layer) processes influenced the Ru polishing rate, but the oxidation process was assumed to play a more decisive role in the Ru CMP. The mechanism for the types of oxidizers in Ru corrosion and oxidation processes is discussed and explained through a diagram of the equilibrium electronic band of Ru metal electrodes and oxidizers in an aqueous solution.Metal chemical mechanical planarization (CMP) has become one of the most important constituents in the field of CMP since the first application tungsten (W) metallization in 1989 by IBM. 1 Most research has mainly focused on investigating the catalytic role of ferric and ferrous ions in slurry that contains hydrogen peroxide (H 2 O 2 ) in W CMP. 2-4 Copper (Cu) with its lower resistivity and better electromigration has been adopted as the material for metallization instead of aluminum to reduce resistance-capacitance delay as the device design rule shrinks under the 0.1 μm technology node. 5 Since then, a worldwide boom in research on Cu CMP slurry started, and has even continued for over two decades to the present day due to the complexity of Cu CMP slurry and emerging new applications of Cu metallization like that in through-silicon via. Considering the soft mechanical hardness and corrosion susceptible property of Cu, the Cu CMP slurry overwhelmingly concentrated on chelating and corrosion inhibiting chemistry in slurry containing H 2 O 2 . 6-10 Up until now, H 2 O 2 has been preferentially used as the oxidizer in metal CMP slurry because of its powerful oxidizing capability, clean nature (metal ion free), and reasonable price. The development of CMP slurry for mechanically hard and chemically inactive metals like tantalum (Ta) and ruthenium (Ru) has gradually evolved with the growing development of new memories and new applications in conventional memories. However, H 2 O 2 has been confronted with problems in achieving moderate polishing rates with these metals. Other ionic substances have inevitably been investigated as oxidizers in CMP slurries for such metals. Du et al. and Pettit et al. investigated the role of iodate ions as oxidizers in Ta CMP. 11,12 Ceric ammonium nitrate (CAN) was first used as the oxidizer in a highly acidic Ru CMP slurry (pH < 1). 13 Except for CAN, periodate ions have been widely studied as effective oxidizers in th...

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Studies of the rearrangement‐energy in electrode kinetics at SnO₂‐electrodes

Cited by 86 publications

References 12 publications

Extension of Spectral Response of p‐Type Gallium Phosphide Electrodes by Metal Adatoms

Extension of Spectral Response of p‐Type Gallium Phosphide Electrodes by Metal Adatoms

Semiconductor Electrodes: XIV . Electrochemistry and Electroluminescence at n‐Type in Aqueous Solutions

Effect of Oxidizers on Chemical Mechanical Planarization of Ruthenium with Colloidal Silica Based Slurry

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Studies of the rearrangement‐energy in electrode kinetics at SnO2‐electrodes

Cited by 86 publications

References 12 publications

Extension of Spectral Response of p‐Type Gallium Phosphide Electrodes by Metal Adatoms

Extension of Spectral Response of p‐Type Gallium Phosphide Electrodes by Metal Adatoms

Semiconductor Electrodes: XIV . Electrochemistry and Electroluminescence at n‐Type in Aqueous Solutions

Effect of Oxidizers on Chemical Mechanical Planarization of Ruthenium with Colloidal Silica Based Slurry

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Studies of the rearrangement‐energy in electrode kinetics at SnO₂‐electrodes