Qualitative and quantitative studies of the oxidation of polycrystalline copper (Cu) thin films upon exposure
to ambient air conditions for long periods (on the order of several months) are reported in this work. Thin
films of Cu, prepared by thermal evaporation, were analyzed by means of X-ray photoelectron spectroscopy
(XPS) to gain an understanding on the growth mechanism of the surface oxide layer. Analysis of high-resolution Cu LMM, Cu2p3/2, and O1s spectra was used to follow the time dependence of individual oxide
overlayer thicknesses as well as the overall oxide composite thickness. Transmission electron microscopy
(TEM) and spectroscopic ellipsometry (SE) were used to confirm the results obtained from XPS measurements.
Three main stages of copper oxide growth were observed: (a) the formation of a Cu2O layer, most likely due
to Cu metal ionic transport toward the oxide−oxygen interface, (b) the formation of a Cu(OH)2 metastable
overlayer, due to the interactions of Cu ions with hydroxyl groups present at the surface, and (c) the
transformation of the Cu(OH)2 metastable phase to a more stable CuO layer. These three stages were found
to occur simultaneously and to be mutually dependent on each other. The findings of this study may provide
guidance in choosing the optimal conditions to fabricate and store copper-based ultra-large-scale integrated
(ULSI) circuits.
The critical dose for graphitization of diamond as a result of ion implantation induced damage (boron and arsenic) and subsequent thermal annealing is determined by combining secondary ion mass spectroscopy measurements, chemical etching of the graphitized layer, and TRIM simulations. Li ions are implanted as a deep marker to accurately determine the position of the graphite/diamond interface. The damage density threshold, beyond which graphitization occurs upon annealing, is found to be 1022 vacancies/cm3. This value is checked against published data and is shown to be of general nature, independent of ion species or implantation energy.
We present a detailed study of the evolution with annealing temperature (in an oxygen environment) of the morphological and structural properties of thin erbium oxide (Er2O3) films evaporated in an electron beam gun system. The electrical characteristics of metal-oxide-semiconductor structures are also described. Atomic force microscope and x-ray difractometry were used to map out the morphology and crystalline nature of films ranging in thickness from 4.5 to 100 nm. High-resolution cross-sectional transmission electron microscopy imaging and Auger electron spectroscopy reveal three sublayers: an outer dense nanocrystalline Er2O3 layer, a middle transition layer and amorphous SiO2 film placed close to the Si substrate. The effective dielectric constant depends on the thickness and the annealing temperature. A 1–2.8 nm interfacial SiO2 layer as well as an ErO inclusion with low polarizability are formed during the deposition and the annealing process has a profound effect on the dielectric constant and the leakages. The minimum effective oxide thickness is 2.4–2.8 nm and in the thinnest films we obtained a leakage current density as low as 1–5×10−8 A/cm2 at an electric field of 1 MV/cm. We observe a shift of the flatband voltage to the positive side and significant lowering of the positive charge down to ∼1×1010 cm−2. For a 4.5 nm film, the maximum total breakdown electric field was approximately 1×107 V/cm.
Copper (Cu) has been extensively used as an interconnect material for microelectronic devices because of its high electrical and thermal conductivity and excellent electromigration resistance. However, the formation of relatively rough Cu surfaces ( approximately 5 nm roughness) and Cu-oxide layers upon exposure to air still hinders their reliable application in a wide range of fields. In this article, we show the potential values of highly stable and ultrasmooth polycrystalline bare Cu obtained by simple annealing and chemical modification for a wide range of Cu-based electronic devices. The morphological properties and oxidation behavior of annealed Cu surfaces, before and after coating by self-assembled monolayers of terephthalic acid (TPA), were examined upon exposure to ambient air conditions ( approximately 110 days). Thin films of polycrystalline Cu, deposited on top of an adhesion layer of tantalum nitride (TaN) and annealed for 8 h at 580 degrees C under 2 x 10(-7) Torr, provided ultrasmooth Cu surfaces (R(rms) = 0.15-1.1 nm for fresh samples) and had a stable Cu-oxide layer after 65 days ( approximately 3.5 nm). These observations were perceived to be superior to nonannealed polycrystalline Cu samples. Coating fresh (oxide-free) samples of ultrasmooth Cu with TPA molecules created a closely packed monolayer with a standing-up phase configuration and molecular coverage of approximately 90%. The TPA-coated Cu surface has not shown any detectable oxidation during the first 2 weeks of exposure. The protection efficiency of this layer was found to be superior to those reported earlier on polycrystalline Cu surfaces. The oxidation mechanisms of both annealed and nonannealed Cu surfaces are presented and discussed.
Additive–metal interactions can induce additive migration to the organic/electrode interface to spontaneously form interlayers that affect the metal work function and enhance OPV device performance.
Interfacial interactions between thermally evaporated metal atoms and a polymer can induce its segregation to the polymer blend/metal interface. This segregation effectively modifies the surface composition, originally directed by surface energy considerations during film formation, and can be utilized to enhance device performances as demonstrated here for polymer solar cells.
The possibility of carbon nitride formation by low-energy nitrogen ion irradiation of graphite was investigated by in situ x-ray photoelectron spectroscopy. Room-temperature and hot 500-eV N+2 implantations were performed with saturation doses for which a constant nitrogen concentration was obtained. Analysis of the N(1s) core level line indicates the existence of three different carbon–nitrogen bonding states in the room-temperature implanted layer. Annealing experiments up to 500 °C revealed a slight, gradual decrease of nitrogen concentration in the implanted layer accompanied by a partial redistribution of the nitrogen bonding states. Hot nitrogen implantations at 300 and 500 °C resulted in a predominant population of the more covalent, with higher N(1s) binding energy, nitrogen bonding state. Such a distribution of carbon–nitrogen chemical bonds could not have been obtained by annealing of the room-temperature implanted layer. These results may be of importance in finding a way to produce the elusive β-C3N4 phase by ion beam assisted deposition.
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