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Cathodic electrochemiluminescence at double barrier Al/Al 2O 3/Al/Al 2O 3 tunnel emission electrodes
Abstract
Double insulating barrier tunnel emission electrodes were fabricated by adding a new pure aluminum layer upon oxidized aluminum electrodes by vacuum evaporation and thermally oxidizing the new aluminum layer in air at room temperature. Resulting Al/Al2O3/Al/Al2O3 electrodes allow the use of various aluminum alloys in the electrode body necessary for hardness or shaping ability of the electrode while obtaining the luminescence properties of pure aluminum oxide. During electrical excitation of luminescent labels by cathodic hot electron injection into aqueous electrolyte solution, the background noise is mainly based on high-field-induced solid-state electroluminescence and F-center luminescence of the outer aluminum oxide film. The more defect states and/or impurity centers the outer oxide film contains, the higher is the background emission intensity. The present electrode fabrication method provides a considerable improvement in signal-to-noise ratio for time-resolved electrochemiluminescence (TR-ECL) measurements when the original native oxide film of the electrode body contains luminescence centers displaying long-lived luminescence. The excellent performance of the present electrodes is demonstrated by extremely low-level detection of Tb(III) chelates, luminol, Pt(II) coproporphyrin and Tb(III) labels in an immunometric immunoassay by time-resolved electrochemiluminescence.
Optical techniques can afford a powerful characterization of the solid/liquid interface that is composed of an electrode immersed in an electrolyte. While a typical electrochemical measurement such as current intensity is averaged over the entire electrode surface, the access to surface heterogeneity can provide an increased level of information enabling to rationalize and optimize the performance of chemical or biochemical sensors. In this opinion paper, we will briefly review the different strategies developed to translate an electrochemical process into a luminescence signal. Also, several key examples will be selected and commented in order to highlight the key advantages of coupling electrochemistry with optical imaging, essentially fluorescence and electrochemiluminescence.
This paper presents a simple and inexpensive method to fabricate chemically and mechanically resistant hot electron-emitting composite electrodes on reusable substrates. In this study, the hot electron emitting composite electrodes were manufactured by doping a polymer, nylon 6,6, with few different brands of carbon particles (graphite, carbon black) and by coating metal substrates with the aforementioned composite ink layers with different carbon-polymer mass fractions. The optimal mass fractions in these composite layers allowed to fabricate composite electrodes that can inject hot electrons into aqueous electrolyte solutions and clearly generate hot electron-induced electrochemiluminescence (HECL). An aromatic terbium (III) chelate was used as a probe that is known not to be excited on the basis of traditional electrochemistry but to be efficiently electrically excited in the presence of hydrated electrons and during injection of hot electrons into aqueous solution. Thus, the presence of hot, pre-hydrated or hydrated electrons at the close vicinity of the composite electrode surface were monitored by HECL. The study shows that the extreme pH conditions could not damage the present composite electrodes. These low-cost, simplified and robust composite electrodes thus demonstrate that they can be used in HECL bioaffinity assays and other applications of hot electron electrochemistry.
A research on the effect of different buffers on the pH range of 6–10 on the thin oxide-covered surface of aluminum cathode has been conducted under the conditions corresponding with those generally used in bioaffinity assays or other determinations made by using aluminum probe based on time-resolved cathodic electrochemiluminoimmuno assay (tr-ECLIA or tr-CECLIA) detection. The experiments have been conducted on impedance and cathodic electrochemiluminescence (CECL) basis using a strong long lifetime having electroluminophore Tb(III)-1 chelate where the ligand 1 is 2,6-bis[N,N-bis(carboxymethyl)aminomethyl]-4-benzoylphenol and Ruthenium(II) tris(2,2′–bipyridine) (Ru(bpy)3²⁺) as the CECL model luminophores. The results point out that the natural oxide layer at the electrode surface does not essentially change as to its thickness but as to its resistance, it can be concluded that the best buffer in these luminophore determinations based on CECL and Al probe use is borate buffer adjusted to pH around 7–8 where the surface of aluminum has its neutral character. In the bioaffinity assays the meaning of the buffer seems to be more difficult to realize due to the complex character of the surface with plenty of different coatings and special handling steps but still with the aforementioned borate buffer the results were noticed to be the most stabile. The tests also pointed out that the character of the pure aluminum surface and the oxide layer above it without any other coatings could be strongly affected by the surrounding solution composition and in that way to the durability of the aluminum probe already during the quite short exposure times. The reported results are useful especially in the field of CECL based on aluminum probe use but could also in a certain extent to be utilized in a large scale of analysis considering the use of aluminum probes.
Hot electron-induced electrochemiluminescence (HECL) of calcein and calcein-Tb(III) complex was generated at oxide-covered aluminum electrode during cathodic pulse polarization. The excitation of calcein as a molecule or as a ligand is based on subsequent one-electron oxidation and reduction steps by oxidizing radicals and solvated electrons. During HECL excitation of calcein-Tb(III) solution a reaction product of the calcein is formed that also enables the photoexcitation of Tb(III) via the formed ligand derivative by ligand-sensitized mechanism. The determination of low concentrations of calcein with aluminum electrodes was complicated by a relatively strong background electroluminescence originating from the Al2O3-layer. Polyvinyl butyral-carbon black composite electrodes coated on brass were fabricated to solve this problem and a fifty-fold lower background emission was obtained for these novel composite electrodes in comparison to that of oxide-covered 99.9% pure aluminum electrodes. The obtained detection limits were 3.2·10⁻¹⁰ M for calcein and 6.4·10⁻⁹ M for calcein-Tb(III) at the present composite electrodes. These species could potentially be utilized as electrochemiluminescent labels in bioaffinity assays.
Tb(III) chelates exhibit intense hot electron-induced electrogenerated chemiluminescence during cathodic polarization of metal/polystyrene-graphite (M/PG) electrodes in fully aqueous solutions. The M/PG working electrode provides a sensitive means for the determination of aromatic Tb(III) chelates at nanomolar concentration levels with a linear log-log calibration curve spanning more than five orders of magnitude. The charge transport and other properties of these novel electrodes were studied by electrochemiluminescence measurements and cyclic voltammetry. The present composite electrodes can by utilized both under pulse polarization and DC polarization unlike oxide-coated metal electrodes which do not tolerate cathodic DC polarization. The present cost-effective electrodes could be utilized e.g. in immunoassays where polystyrene is extensively used as a solid phase for various bioaffinity assays by using electrochemiluminescent Tb(III) chelates or e.g. Ru(bpy)3²⁺as labels.
Various luminophores produce strong electrogenerated chemiluminescence during cathodic pulse polarization of the present insulating film-covered carbon paste electrodes in fully aqueous solutions. First electrodes made of a commercial conductive carbon paste were successfully utilized as working electrodes and their surface was characterized by ESCA. Then custom in-laboratory made improved composite electrodes were manufactured from the same insulating polymer and conducting carbon black particles. The relationship between the amount of carbon present on the composite electrode, in the bulk and on the surface, and the intensity of electrogenerated chemiluminescence was studied further. The overall performance of these composite electrodes makes them viable low-cost replacements for metal/insulator type electrodes such as oxide-coated silicon electrodes.
The heterogeneous immunoassay of thyroid stimulating hormone (TSH) was detected by the time-resolved cathodic electrochemiluminescence immunoassay (tr-CECLIA) method using magnetic beads as a mobile support. The magnetic beads coated with sandwich type TSH immunoassay were captured with a magnet for washing and detection processes. The time-resolved cathodic electrochemiluminescence (tr-CECL) signal of Tb(III) chelate label was generated by cathodic pulse polarization in the aluminum working electrode and platinum counter electrode system. The detection method causes injection of high energy electrons into the aqueous solution near the aluminum electrode and creates rigid simultaneous oxidative and reductive conditions that excitate the Tb(III) chelate used as a label luminophore in the heterogeneous sandwich type immunoassay of TSH in the surface of the magnetic beads. The limit of detection of the method was about 50 mIU L⁻¹. The precision of it was noticed to be good; the coefficient variation percentage was realized to be lower than 10 %. Unfortunately the limit of detection is not good enough for determination of analyte levels of very low concentrations for instance TSH in body fluids. The possible application areas of the method are in highly sophisticated micro or nano fluidic detection and sensor systems where the aspiration level of the analyte detection limit is not very high and the mobility and manageability and the large surface area of the magnetic beads can be utilized efficiently in separating, washing, moving, coating and detecting processes. In the case of tr-CECLIA the presented method makes possible to use multipurpose working electrodes instead of disposable ones.
Electrochemically induced luminescence (ECL) is an attractive analytical technique, which could be used for many applications. Introduction of reactants and/or removal of formed products both are very important issues in the most ECL-based systems. The introduction/removal of chemicals could be achieved by flow-through cells. Flow-through cells are not efficient in all designs of ECL systems. Therefore, rotating disk electrode (RDE) could be a valuable alternative, which could increase the efficiency of ECL-based devices. In this work, the RDE was used for the evaluation of electroluminescence of tris(2,2′-bipiridin)dichlorruthenium(II)hexahydrate ([Ru(bpy)3]²⁺), 5-Amino-2,3-dihydro-1,4-phthalazinedione (luminol), and N-(4-aminobuthyl)-N-ethyl-isoluminol (ABEI). Detection limits, optimal pH and potential values, and emission spectra were determined for each compound. Graphical abstract: [Figure not available: see fulltext.]
Hot electron induced cathodic electrochemiluminescence (ECL) was observed at screen printed carbon electrodes (SPCEs) during pulse polarization. The thin insulating film resulted from the printing inks was found to be suitable for generating hot electrons, which can further be converted to hydrated electrons and induce the subsequent luminescence. Compared with disposable Al/Al2O3 electrode, SPCEs show more stable and reproducible ECL in a wider pH range without background emission. A sensitive ECL method for determination of quercetin is proposed. The detection limit is 8.0×10−10 mol L−1(S/N=3), which is two magnitudes lower than that of common ECL method.
In this paper, a new niobate semiconductor photocatalyst Sr(0.4)H(1.2)Nb(2)O(6)·H(2)O (HSN) nanoparticle was applied to investigate the cathodic electrochemiluminescent (ECL) behavior of luminol for the first time. The results presented here demonstrated that there were two ECL peaks of luminol at the cathodic potential attributed to immobilization of HSN on the electrode surface. It is implied that HSN can be electrically excited and injected electrons into aqueous electrolytes from this electrode under a quite low potential that only excites luminol. A mechanism for this luminol-ECL system on HSN/GCE has been proposed. Additionally, this HSN/GCE has lots of advantages, such as high stability, good anti-interference ability, simple instrumentation, rapid procedure and ultrasensitive ECL response. It is envisioned that this HSN/GCE has further applications in biosensors.
In this chapter, we discuss the basics of cathodic hot electron-induced electrogenerated chemiluminescence (HECL). In the
applications of HECL, we discuss, e.g., the usable electrode materials and their advantages as well as the applicable solution
conditions in aqueous media. We also summarize the luminophore types excitable by this method and their usability as labels
in practical bioaffinity assay applications.
Electrogenerated luminescence of lanthanides is reviewed with emphasis on the electrochemiluminescence (ECL) of lanthanide chelates. Main application area of lanthanide chelates in this field is their use as electrochemiluminescent labels in bioaffinity assays such as in immunoassays or DNA probe assays. With lanthanide chelates as labels, hot electron-induced ECL at thin insulating film- coated cathodes outperforms ECL based on traditional electrochemistry at active metal electrodes. ECL excitation of lanthanide(III) chelates occurs normally by ligand-sensitized mechanisms wherein the ligand is first excited by redox reactions followed by energy transfer from ligand to the central ion, which finally emits by f–f transitions. Luminescent lanthanide ions can be excited at oxide-coated metal electrodes when these ions act as luminescence centers in the oxide film and/or at the oxide/electrolyte interface or as solvated in the close vicinity of the electrode surface. These ions typically show high field-induced solid-state electroluminescence when embedded inside of the oxide films and ECL at the surface of the electrode or in solution close to the electrode surface. These lanthanide-doped oxide films can be fabricated either by anodization of certain lanthanide-doped valve metals or from pure valve metals by anodization in lanthanide ion-containing anodization bath preferably with AC voltages. Some lanthanide ions can be electrically excited also in strongly acidic sulfuric acid solutions at platinum electrodes with mechanisms not known with certainty.
Cathodic electrochemiluminescence (ECL) is firstly observed at a carbon oxide covered glassy carbon (C/C(x)O(1-x)) electrode as a large cathodic pulse polarization is applied. This insulating carbon oxide (C(x)O(1-x)) film is constructed on a glassy carbon (GC) substrate by electrochemical oxidization in basic media. The film properties, such as the composition of carbon and oxygen, and the thickness as well, can be controlled by the potential and the duration in the oxidizing process. X-Ray photoelectron spectroscopy (XPS) studies show that carbonyl and carboxyl dominate at the oxidized surface, to which antibodies can be covalently bound. The specific immunoreaction between antigen (Ag) and antibody (Ab) resulted in a decrease in the ECL intensity, thus creating an interesting basis for the development of a label-free cathodic ECL immunosensor. As an example, human IgG (hIgG) was sensitively determined in the concentration range of 0.01-100 ng mL(-1), and the detection limit was ca. 1.0 pg mL (-1) (S/N = 3). In addition, the content of hIgG in human serum has been assayed by the developed immunosensor and a commercially available immune turbidimetry method, respectively, and consistent results were obtained. The prepared immunosensor provides a promising approach for the clinical determination of IgG levels in human serum, because it is simple, rapid, highly sensitive, specific, and without the need of tedious labeling operations.
Ruthenium(II) tris-(2,2′-bipyridine) chelate exhibits strong electrogenerated chemiluminescence during cathodic pulse polarization of oxide-covered aluminum electrodes in aqueous solutions. The present method is based on a tunnel emission of hot electrons into an aqueous electrolyte solution. The method allows the detection of ruthenium(II) tris-(2,2′-bipyridine) and its derivatives below nanomolar concentration levels and yields linear log-log calibration plots spanning several orders of magnitude of concentration. This method allows simultaneous excitation of derivatives of ruthenium(II) tris-(2,2′-bipyridine) and Tb(III)-chelates. The former label compounds have a luminescence lifetime of the order of microseconds, while the latter compounds generally have a luminescence lifetime of around 2 ms. Thus, the combined use of these labels easily provides the basis for two-parameter bioaffinity assays by either using wavelength or time discrimination or their combination.
This chapter discusses the reduction potentials involving inorganic free radicals in aqueous solution. Because free radicals are usually transients, knowing their thermodynamic properties is primarily useful in mechanistic studies. Thus, the useful redox couples associated with a given free radical correspond to plausible elementary steps in reaction mechanisms. All potentials are expressed against the normal hydrogen electrode (NHE). Apart from the NHE, the standard state for all solutes is the unit molar solution at 25 °C. This violates the usual convention for species, such as O2 that occur as gases, but because the rates of bimolecular reactions in solution are significant, the unit molar standard state is most convenient. The emphasis is on electron transfer reactions in which no bonds are formed or broken, electron transfer reactions in which concerted electron transfer and bond cleavage could occur, and certain atom transfer reactions. The chapter also presents a tabulation of ∆fG° values for all the radicals. A common approach in estimating the thermochemistry of aqueous free radicals is to use gas-phase data with approximations of solvation energies.
Kinetic data for the radicals H⋅ and ⋅OH in aqueous solution,and the corresponding radical anions, ⋅O− and eaq−, have been critically pulse radiolysis, flash photolysis and other methods. Rate constants for over 3500 reaction are tabulated, including reaction with molecules, ions and other radicals derived from inorganic and organic solutes.
Light emission from aluminium oxide during cathodic pulse-polarisation of oxide-covered aluminium in aqueous solution was observed to be strongly enhanced in the presence of peroxydisulfate ions. The spectrum of the light emission had a broad maximum between 400 and 450 nm being attributed to F-centre luminescence of aluminium oxide. The mechanism of the luminescence is associated with the two-step reduction of peroxydisulfate anions near the oxide-covered cathode where the first one-electronic reduction step occurs either (i) by tunnel-emission generated hydrated electrons or (ii) by trickling down the surface states to the energy level of peroxydisulfate ion or (iii) by direct heterogeneous electron transfer from the bottom of the aluminium oxide conduction band to peroxydisulfate ions during strong downward band bending induced by cathodic pulse-polarisation. The second step occurs by electrons from F- or F
+
-centres at the oxide/electrolyte interface. Transitions of aluminium oxide conduction band electrons to fill the sulfate radical-emptied electron trapping sites (oxygen vacancies) produces analogous F- and F
+
-centre luminescence to that occurring during photoluminescence and thermoluminescence of aluminium oxide. No enhancement of light emission was observed in the presence of hydrogen peroxide which is also reduced in a two-step process at oxide-covered aluminium electrode. This can be explained by the fact that the energy level of hydroxyl radical under the present conditions lies ca. 1 eV above, whereas the energy level of sulfate radical lies somewhat below the colour-centre sub-band of aluminium oxide. Therefore, the sulfate radical is a sufficiently strong oxidant but the hydroxyl radical is too weak an oxidant to abstract electrons from F- and F
+
-centres.
Hot electron injection into aqueous electrolyte solutions
from metal/insulator/metal/electrolyte and
metal/insulator/electrolyte tunnel junctions is considered
and the possibility of an electrochemical generation of
hydrated electrons is discussed. The hot electron-induced UV
electrochemiluminescence of (9-fluorenyl)methanol was used
to demonstrate the presence of highly energetic transient
species in aqueous solution at several
metal/insulator/electrolyte hot electron tunnel emitters.
These transient species cannot be produced electrochemically
in fully aqueous solutions at any active metal electrodes. A
detailed mechanism for the present electrochemiluminescence
is suggested.
An immunoanalytical method based on electrogenerated luminescence was developed in which the labelling compound is the terbium chelate of 2,6-bis[N,N-bis(carboxymethyl)aminomethyl]-4-benzoylphenol which is linked by a thioureido group to the antibody. The sandwich complex of the labelled antibody, antigen and antibody immobilized on the surface of an aluminium electrode is excited by an electrical pulse and, after a short delay from the end of the pulse, light emission is measured. The electroluminescence immunoassay is exemplified by the heterogeneous and homogeneous assays of human pancreatic phospholipase A2, for which both assay methods give a reasonably good linearity in the range 10–300 ng ml−1.
Ruthenium(II) tris-(2,2‘-bipyridine) chelate exhibits strong electrogenerated chemiluminescence during cathodic pulse polarization of oxide-covered aluminum electrodes in aqueous solutions. The present method is based on a tunnel emission of hot electrons into an aqueous electrolyte solution. The method allows the detection of ruthenium(II) tris-(2,2‘-bipyridine) and its derivatives below nanomolar concentration levels and yields linear log−log calibration plots spanning several orders of magnitude of concentration. This method allows simultaneous excitation of derivatives of ruthenium(II) tris-(2,2‘-bipyridine) and Tb(III)-chelates. The former label compounds have a luminescence lifetime of the order of microseconds, while the latter compounds generally have a luminescence lifetime of around 2 ms. Thus, the combined use of these labels easily provides the basis for two-parameter bioaffinity assays by either using wavelength or time discrimination or their combination.
Luminol exhibits strong electrogenerated chemiluminescence during cathodic pulse polarization of oxide-covered aluminum electrodes in aqueous solution. This electrogenerated chemiluminescence can be enhanced by the presence of dissolved oxygen or by the addition of other coreactants such as hydrogen peroxide, peroxydisulfate, or peroxydiphosphate ions. However, luminol detection is most sensitive in the presence of azide ions, which not only enhance the electrogenerated chemiluminescence intensity but also decrease the intrinsic electroluminescence of the thin aluminum oxide film on the electrodes mainly producing the blank emission. The present method is based on tunnel emission of hot electrons into an aqueous electrolyte solution and allows the detection of luminol, isoluminol, and its derivatives below nanomolar concentration levels. The linear logarithmic calibration range covers several orders of magnitude of concentration of luminol or N-(6-aminohexyl)-N-ethylisoluminol. Therefore, the above-mentioned labeling substances can be used as one of several available alternatives of simultaneous markers in multiparameter bioaffinity assays at disposable oxide-covered aluminum electrodes. The main advantage of the present electrochemiluminescence generation method is that luminescent compounds having very different photophysics and chemistry can be simultaneously excited, thus providing good possibilities for internal standardization and multiparameter bioaffinity assays.
Rate constants have been compiled for reactions of various inorganic radicals produced by radiolysis or photolysis, as well as by other chemical means in aqueous solutions. Data are included for the reactions of ⋅CO2−, ⋅CO3⋅-, O3, ⋅N3, ⋅NH2, ⋅NO2, NO3⋅, ⋅PO32-, PO4⋅2-, SO2⋅ -, ⋅SO3 -, SO4⋅-, ⋅SO5⋅-, ⋅SeO3⋅ -, ⋅(SCN)2⋅ -, ⋅CL2⋅-, ⋅Br2⋅ -, ⋅I2⋅ -, ⋅ClO2⋅, ⋅BrO2⋅, and miscellaneous related radicals, with inorganic and organic compounds. © 1988, American Institute of Physics for the National Institute of Standards and Technology. All rights reserved.
Some of the luminescent aromatic Tb(III) chelates can be excited at oxide-covered magnesium and n-ZnO:Al/MgO composite electrodes by cathodic pulse polarization in aqueous solution. This is based on the cathodic injection of hot electrons into the aqueous electrolyte solution and successive redox reactions in one-electron steps resulting in the excited states of the chelates. Due to the relatively long luminescence lifetime of multidentate Tb(III) chelates, these chelates can be very sensitively detected by time-resolved electrochemiluminescence (TR-ECL) measurements using the present working electrodes. Thus, metal or highly doped semiconductor electrodes coated by a thin MgO film lend themselves as nontransparent or in some cases, even optically transparent working electrodes for generation of free radicals and cathodic ECL in aqueous solution. The results suggest that also other even more efficient optically transparent composite tunnel emission electrodes than the present n-ZnO:Al/MgO electrodes could be constructed by coating n-ZnO:Al glass electrodes with other wide band gap insulating oxides.
Cathodic pulse polarisation of oxide-covered aluminium electrodes can generate electrochemiluminescence (ECL) from metalloporphyrins. This is based on the tunnel emission of hot electrons into aqueous electrolyte solution, which probably results in the generation of hydrated electrons as reducing mediators. These tunnel emitted electrons allow the production of highly reactive radicals, such as sulfate radicals from peroxodisulfate ions, which can induce strong redox luminescence from various organic chemiluminophores including metalloporphyrins. The work presented here illustrates the generation of ECL from platinum(II) coproporphyrin (PtCP) and its bovine serum albumin (BSA) conjugate. This allows the detection of these molecules below nanomolar concentrations and over several orders of magnitude of concentration. The relatively long luminescence lifetime of PtCP allows discrimination from the background ECL signal using time resolved measurements, leading to higher sensitivity and the detection of PtCP-BSA indicates the potential use of metalloporphyrins as labels in ECL-based bioassays such as immunoassays and DNA-binding assays.
Hot electron injection into aqueous electrolyte solution was studied with electrochemiluminescence and electron paramagnetic
resonance (EPR) methods. Both methods provide further indirect support for the previously proposed hot electron emission mechanisms
from thin insulating film-coated electrodes to aqueous electrolyte solution. The results do not rule out the possibility of
hydrated electron being as a cathodic intermediate in the reduction reactions at cathodically pulse-polarized thin insulating
film-coated electrodes. However, no direct evidence for electrochemical generation of hydrated electrons could be obtained
with EPR, only spin-trapping experiments could give information about the primary cathodic steps.
The luminescence lifetime of the electrochemiluminescence of luminol was studied at oxide-coated silicon and aluminum electrodes. In an undivided cell, the ECL was found to be produced only by cathodic processes, and luminol could be detected down to picomolar levels with time-resolved measurements
High amplitude cathodic pulse polarization of ultra thin oxide film-coated heavily doped silicon electrodes induces tunnel emission of hot electrons into aqueous electrolyte solution, which probably results in the generation of hydrated electrons in the vicinity of the electrode surface. The method allows the detection of tris (2,2'-bipyridine) ruthenium(II) chelate at subnanomolar concentration level. This paper shows that both n- and p-type heavily doped silicon electrodes can be used, illustrates the effect of oxide film thickness upon the silicon electrode on the intensity of ECL of tris (2,2'-bipyridine) ruthenium(II) and discusses the basic features of tris (2,2'-bipyridine) ruthenium(II) chelate-specific ECL at these electrodes. Thin oxide film-coated silicon electrodes provide a lower blank emission and a higher ECL intensity of the present ruthenium chelate than oxide-covered aluminium electrodes. This suggests that thin oxide film-coated silicon is a very promising working electrode material, especially in microanalytical systems made fully or partly of silicon. (c) 2004 Elsevier B.V. All rights reserved.
Low temperature (to 83 K) vacuum emission of hot electrons from silicon dioxide films is reported. This technique is specifically used to study the temperature dependence of the electronic distributions emerging into vacuum from very thin (50–60 Å) oxide layers where a significant number of the electrons have traveled through the insulator ballistically. The measured energy distributions of the emerging carriers are shown to reflect the temperature‐dependence of the distribution of the electron source in the silicon substrate at the abrupt interface with the silicon dioxide layer, particularly the Fermi tail, and possibly quantized levels in the silicon accumulation layer. The other features in the electron distributions are shown to be due to single phonon scattering of ballistic electrons in the silicon dioxide layer. Additionally, it is shown that as the oxide thickness is increased, the distribution broadens into its steady‐state characteristic, showing very little temperature dependence. All data are shown to be in good agreement with a temperature‐dependent, Monte Carlo simulation that includes the details of the electron source function at the interface of the silicon substrate and the oxide layer.
Leakage currents introduced in the low‐field, direct‐tunneling regime of thin oxides during high‐field stress are related to defects produced by hot‐electron transport in the oxide layer. From these studies, it is concluded that the ‘‘generation’’ of neutral electron traps in thin oxides is the dominant cause of this phenomenon. Other mechanisms due to anode hole injection or oxide nonuniformities are shown to be unrealistic for producing these currents. Exposure of thin oxides to atomic hydrogen from a remote plasma is shown to cause leakage currents similar to those observed after high‐field stress, supporting the conclusion that these currents are related to hydrogen‐induced defects. © 1995 American Institute of Physics.
The primary processes occurring at cathodically polarized oxide-covered aluminum electrode are discussed in detail. It is pointed out that more energetic cathodic processes can be induced in aqueous media at thin insulating film-coated electrodes than at any semiconductor or active metal electrode. It is proposed that tunnel emission of hot electrons with energies well above the level of the conduction band edge of water occur, and the thermalization and solvation of the emitted electrons can result in generation of hydrated electrons. The cathodically pulse-polarized oxide-covered aluminum also generates a strong oxidant (or oxidants) at the oxide/electrolyte interface, and it is proposed that this species is the hydroxyl radical which is generated either by cathodic high field-induced ejection of self-trapped holes as oxygen dianions (i.e. oxide radical ions) into the electrolyte solution, or by the action of anion vacancies and/or F+-centers as the primary oxidants capable of oxidizing hydroxide ions or the hydroxyl groups of the hydroxylated surface on the oxide film. These radicals, hydrated electrons/hydroxyl radicals, can act as mediating reductants/oxidants in reduction/oxidation of solutes. The formation of the primary species is monitored by electrochemiluminophores which cannot be cathodically excited at active metal electrodes in fully aqueous solutions, but which can be chemically excited in aqueous media in the simultaneous presence of highly reducing and highly oxidizing radicals.
Heterogeneous and homogeneous immunoassays of human thyroid stimulating hormone (hTSH) were developed on immunometric basis using aromatic Tb(III) chelates as electrochemiluminescent labels and varied types of disposable oxide-covered aluminum electrodes as the solid phase of the immunoassays. The long luminescence lifetime of the present labels allows the use of time-resolved electrochemiluminescence detection and provide the low detection limits of these labels and, thus, sensitive immunoassays. The primary antibody of immunometric immunoassays was coated upon aluminum oxide surface by physical absorption. In homogeneous immunoassays using 66 μl cell and 15 min incubation time, a linear calibration range of 0.25–324 μU/ml was obtained by applying only a single cathodic excitation pulse in the detection step of the assay.
A homogeneous immunoassay of T4 was developed using a semiautomatic electrochemiluminometer modified from a commercially available fluorometer. In addition, from the same analyte panel an immunometric immunoassay of TSH at similar disposable oxide-covered aluminum rake electrodes was studied using this instrument both on homogeneous and heterogeneous basis. Detection was based on hot electron-induced cathodic electrochemiluminescence utilizing a commercially available Tb(III) chelate label. The assays were reasonably sensitive and comparison was made with other older methods. Thus, it is possible to develop both non-competitive and competitive immunoassays based on detection of hot electron-induced ECL of the labels.
Photoluminescence spectra of thin-film aluminium oxide samples
on aluminium show spectral lines at ca. 330 and 420 nm that are attributed to
the F+ and F centers of aluminium oxide, respectively. Experimental results
reveal that the F centers are responsible for the intrinsic cathodic luminescence
of an oxide-covered aluminium electrode, too. The mechanism of the luminescence
is based on charge transfer reactions at the oxide/electrolyte interface.
Cathodic pulse polarisation of thin insulating film-coated electrodes enables the generation of electrochemiluminescence (ECL) by tunnel emission of hot electrons from the Fermi level of the conductor material of the conductor–insulator–aqueous electrolyte solution junction to the solutes at the vicinity of the electrode surface and probably also to the conduction band of water. The latter process can generate hydrated electrons as strongly reducing slightly longer-lived cathodic intermediates, which are known to be able to induce chemiluminescence (CL) of various types of luminophores having very different photophysical and chemical properties. The generation of the above-mentioned cathodic primary species provides good possibilities to use many types of luminophores as label molecules in sensitive immuno and DNA-probing assays. This paper introduces an electrochemiluminoimmunoassay (ECLIA) for human thyroid stimulating hormone (hTSH) at oxide-coated n-silicon electrodes and demonstrates the suitability of silicon electrodes covered with thermally grown silicon dioxide film as disposable working electrodes (WEs) in sensitive time-resolved ECL (tr-ECL) measurements in aqueous solution. The label chelate can be detected almost down to picomolar level and the calibration curve of the chelate covers more than five orders of magnitude of chelate concentration. Also the calibration curve of the immunometric hTSH assay was found to be linear over a wide range of hTSH concentration, the detection limit of the hormone being below 1 mU l−1 (4 pmol l−1).
A detailed theoretical study of impact-ionization-related transport phenomena in SiO2 thin films is presented. The Boltzmann transport equation is integrated by the Monte Carlo method using acoustic-phonon-scattering rates derived from photoinduced electron transmission experiments. It is shown that these empirical scattering rates necessitate the inclusion of impact ionization at fields F>Fiith=7 MV/cm because phonon scattering alone can no longer stabilize the electron energy distribution below the ionization energy of 9 eV. However, even above Fiith, acoustic-phonon scattering is found to considerably delay the heating of electrons, leading to a wide dark space in which impact ionization cannot take place or is strongly reduced. Therefore, the electron multiplication factors m(F,tox) decrease rapidly with decreasing oxide thickness, tox, for tox=25 nm. The field and thickness dependence of the measured positive charge buildup (hole trapping) near the Si/SiO2 interface can be quantified in terms of impact ionization in the oxide film. The calculated carrier multiplication, however, cannot fully account for the substrate hole currents and the hole trapping measured in thinner oxides, tox
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