Problems and contradictions in galvanoluminescence, a critical review

Ikonopisov, S.

doi:10.1016/0013-4686(75)85015-8

Cited by 64 publications

(20 citation statements)

References 75 publications

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“…However, these characteristics are not directly related to physical parameters such as pKa, viscosity, water content, or the ionic conductivity of the ILs. Ikonopisov reported that in an aqueous solution V B is correlated with the logarithm of electrolyte conductivity, 43 but for the ILs there are no physical properties that can directly explain the V H value.…”

Section: Resultsmentioning

confidence: 99%

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Anodization Behavior of Aluminum in Ionic Liquids with a Small Amount of Water

et al. 2013

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We investigated the anodic oxidation of aluminum in ionic liquids (ILs) by the constant-voltage rising rate (C-V) method and constant-current density (C-C) method, with characterization by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The structure of the oxide layer and the reaction efficiency varied with the type of IL, the applied voltage, the forming method, and the water content. A homogeneous Al 2 O 3 film with a superior dielectric property was formed by the C-V method (100 mV/s) in 1-butyl-3-methylimidazolium benzoate (BMIm-BEN, water content 0.81 wt%) at 40 V. Although a homogeneous barrier-type Al 2 O 3 film was also formed in 1-butyl-3-methylimidazolium mandelate (BMIm-MAN, water content 0.34 wt%) at 40 V, some anion species existed in the film, and its jump-voltage characteristics was inferior to that of the film formed in BMIm-BEN. The relative permittivity of the film formed in BMIm-BEN was almost equal to that of the Al 2 O 3 film formed in adipate (1.0 wt%) aqueous solution, but the dielectric constant of the film formed in BMIm-MAN was 1.5 times larger. In contrast, a heterogeneous porous Al 2 O 3 film containing a large amount of anion molecules was formed in 1-ethyl-3-methylimidazolium acetate (EMIm-ACE, water content 0.79 wt%) at 40 V. Since the source of oxygen for anodic oxidation is the small amount of water in the ILs, the water content strongly affected the characteristics of the formed Al 2 O 3 layer.

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Section: Resultsmentioning

confidence: 99%

“…4,7,40,43,44 The electron avalanche mechanism occurs as follows. (1) (4) This process is repeated to produce an electron avalanche.…”

Section: Resultsmentioning

confidence: 99%

Anodization Behavior of Aluminum in Ionic Liquids with a Small Amount of Water

et al. 2013

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“…Galvanoluminescence (GL) is a common name for light appearing at one of the electrodes in an electrolytic solution during anodization [11,12]. Since the discovery of GL at the end of XIX century, it has been investigated by many authors, but explanations of the nature and the mechanism of GL are still not completely resolved because of complex environment and many experimental parameters that dictate the intensity and spectral distribution of GL [13].…”

Section: Introductionmentioning

confidence: 99%

Luminescence properties of oxide films formed by anodization of aluminum in 12-tungstophosphoric acid

Stojadinović

Vasilić

Petković

et al. 2010

Electrochimica Acta

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“…The main drop of the potential is at the oxide interlayer where the electric field intensity is high [7]. At as low electric field intensity as 105 V/m, the high-energy electrons can cause the galvanoluminescence of the oxides [8]. For the electrons to have, under the action of the electric field, the acceleration necessary for breaking down the wide-band oxide, their energy must be higher than 3Eg/2 (Eg is the width of the forbidden band).…”

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Simulation of synthesis of oxide-ceramic coatings in discharge channels of a metal-electrolyte system

Klapkiv¹

1999

Mater Sci

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The formation of oxide-ceramic coatings on rectifying metals in the metal-electrolyte system under the action of an external electric field includes several stages. The first stage consists in the formation of the primary oxide film according to the electrochemical mechanism. The electrochemical activity of the rectifying metals decreases in the row Mg, A1, Ti, Nb, Ta, and these metals remain at the beginning of the passivity row. A characteristic feature of the anodic behavior of the rectifying metals is the absence of the active region of dissolution, which is due to their electronic structure. In the metal-electrolyte systems, they give off their d-electrons and transform into ions with rearranged d-levels. These ions react with the oxygen dissolved in electrolyte, OH radicals, or water, forming surface oxide films. Anodic oxide films are amorphous and poreless, and they have ionic conductivity and high electrical resistance. They are classified [1] as n-semiconductors with a wide forbidden band. The electrons are not transferred through the passive layers on the rectifying metals [2,3]. The only reaction on the anode at a voltage of up to 100 V is the anodic growth of oxide. In this case, the overvoltage of the oxide formation is less than the voltage of the decomposition of the electrolyte. When the latter is reached, the injection of electrons into the oxide layer takes place, and oxygen begins to evolve on the anode [4]. This corresponds to the beginning of the second stage of the formation of the spark discharge channel in the metal-oxide-electrolyte system. The mechanisms of breakdown and the parameters of the discharge channel can be different [5,6], depending on the material of the electrode and the nature of the interelectrode space. In the case of realization of the spark discharge in the metal-oxide-electrolyte system under the action of a direct-current electric field, the metal serves as an anode, and the electrolyte serves as a cathode. The interelectrode space consists of the oxide and the double electric layer on the oxide-electrolyte boundary. The main drop of the potential is at the oxide interlayer where the electric field intensity is high [7]. At as low electric field intensity as 105 V/m, the high-energy electrons can cause the galvanoluminescence of the oxides [8]. For the electrons to have, under the action of the electric field, the acceleration necessary for breaking down the wide-band oxide, their energy must be higher than 3Eg/2 (Eg is the width of the forbidden band). These electrons have energy sufficient for ionizing the atoms, which results in the appearance of new electrons. When the coefficient of reproduction exceeds unity, electronic avalanche arises. The ionized atoms that remain behind the avalanche create a practically stationary spatial charge which decelerates the electrons. Since, as was mentioned above, the potential drop is localized mainly in the oxide, and the oxides of the rectifying metals show the properties of wide-band semiconductors of n-type, for determining...

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Problems and contradictions in galvanoluminescence, a critical review

Cited by 64 publications

References 75 publications

Anodization Behavior of Aluminum in Ionic Liquids with a Small Amount of Water

Anodization Behavior of Aluminum in Ionic Liquids with a Small Amount of Water

Luminescence properties of oxide films formed by anodization of aluminum in 12-tungstophosphoric acid

Simulation of synthesis of oxide-ceramic coatings in discharge channels of a metal-electrolyte system

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