The influence of the chemical composition of silicon nitride films on their thermal oxidation parameters

Chramova, L.V.; Smirnova, T. P.; Ayupov, B. M.; Belyĭ, V. I.

doi:10.1016/0040-6090(81)90032-8

Cited by 14 publications

(5 citation statements)

References 9 publications

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“…Further insight into the nature of the oxidized SiNx surface is provided by the specular reflectance infrared spectrum of a 45 Å SiNx film, Figure . The two major absorption bands at 1160 and 880 cm -1 are attributed to the stretching vibrations of SiO 2 and the in-plane Si−N. − The presence of both absorption bands in the infrared has been attributed to the existence of two locally separate phases, i.e., Si 3 N 4 and SiO 2 , within silicon nitride films. , Figure also shows the presence of a smaller, sharp absorption band at 3750 cm -1 , which is due to the O−H stretching vibration of the silanol Si−OH group existing as the free, geminal, and vicinal functional groups 4 The reflectance infrared spectrum of the sputtered SiNx (45 Å) film.…”

Section: Resultsmentioning

confidence: 99%

Intermolecular Interactions between a Monomolecular Hydroxyl-Terminated Perfluoropolyether Film and the Sputtered SiNx Surface

Waltman¹,

Yen²,

White³

et al. 2004

Chem. Mater.

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The intermolecular interactions at the interface between a monomolecular hydroxyl-terminated perfluoropolyether (PFPE) liquid and an amorphous silicon nitride (SiNx) film were investigated using contact angle goniometry, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The results demonstrate that the surface of the sputtered SiNx film is highly oxidized (SiO2) and contain hydroxyl groups (SiOH) that are capable of attractive interactions with the hydroxyl end groups of the PFPE. The attractive interactions lead to a lowering of the polar surface energy with increasing PFPE coverage up to a monolayer. Ab initio quantum chemical computations on model dimers provide the energetic details associated with the PFPE/surface interactions. The primary source of the attractive, adhesive interactions in the PFPE/SiNx system stems from hydrogen bonding between the PFPE and SiNx hydroxyl groups. The binding energy is computed to be approximately −4 kcal/mol. Both the SiNx surface nitrogen and oxygen atoms in the Si3N and Si−O−Si local geometries are weakly basic and hence incapable of providing strong adhesive interaction sites for the PFPE hydroxyl end groups. The results on the kinetics of the adhesive interactions between the hydroxyl-terminated PFPE and the SiNx surface demonstrate a nonclassical time-dependent rate coefficient, k(t) ∝ k o t - h . With increasing temperature, the temporal dependence is observed to change from h = 0.5 (lower temperature) to h = 1.0 (higher temperature), which is interpreted as a two-dimensional melting transition from a solidlike to a liquidlike confined film. Under ambient conditions, adsorbed water competes with PFPE for surface bonding sites on the polar SiNx surface, leading to a significantly reduced level of adhesion for the hydroxyl-terminated PFPE.

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Section: Resultsmentioning

confidence: 99%

Intermolecular Interactions between a Monomolecular Hydroxyl-Terminated Perfluoropolyether Film and the Sputtered SiNx Surface

Waltman¹,

Yen²,

White³

et al. 2004

Chem. Mater.

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“…Silicon nitride (Si x N 4 ) is a material commonly used in microelectronic industry for its strong mechanical resistance and its insulator and chemical barrier properties. − Because of its biocompability, Si x N 4 also finds application in biomedical and biosensor fields. − In comparison with silicon, it offers the extra advantage of a low optical refractive index, , which is favorable for several detection schemes in the biochip context . Such a material can be easily obtained as thin films by (plasma-enhanced) chemical vapor deposition ((PE)-CVD) − or by reactive magnetron sputtering. − When exposed to atmosphere, silicon nitride is covered by a native oxynitride layer − which needs to be removed for some applications. One method to remove the native oxynitride is to use wet etching solutions.…”

Section: Introductionmentioning

confidence: 99%

Etching and Chemical Control of the Silicon Nitride Surface

Brunet

Aureau

Chantraine

et al. 2017

ACS Appl. Mater. Interfaces

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Silicon nitride is used for many technological applications, but a quantitative knowledge of its surface chemistry is still lacking. Native oxynitride at the surface is generally removed using fluorinated etchants, but the chemical composition of surfaces still needs to be determined. In this work, the thinning (etching efficiency) of the layers after treatments in HF and NHF solutions has been followed by using spectroscopic ellipsometry. A quantitative estimation of the chemical bonds found on the surface is obtained by a combination of infrared absorption spectroscopy in ATR mode, X-ray photoelectron spectroscopy, and colorimetry. Si-F bonds are the majority species present at the surface after silicon nitride etching; some Si-OH and a few Si-NH bonds are also present. No Si-H bonds are present, an unfavorable feature for surface functionalization in view of the interest of such mildly reactive groups for achieving stable covalent grafting. Mechanisms are described to support the experimental results, and two methods are proposed for generating surface SiH species: enriching the material in silicon, or submitting the etched surface to a H plasma treatment.

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“…12 In comparison to the thermal oxidation of silicon, the oxidation rate of silicon nitride is much lower and the activation energy for silicon oxide formation is higher. 12,18 The rate of thermal dry oxidation of silicon nitride films is influenced by the presence of hydrogen in the silicon nitride films. [13][14][15][16][17] The silicon oxynitride intermediate layer, which is formed in between the silicon nitride and the external silicon oxide layers, is responsible for the superior oxidation resistance of silicon nitride.…”

Section: Introductionmentioning

confidence: 99%

“…It has been reported that when silicon nitride is oxidized, in addition to silicon oxide formation, a silicon oxynitride intermediate phase is formed. 18 Hydrogen in silicon nitride films may accelerate the oxidation process by dissolving oxidants in the growing silicon oxide film in the form of OH groups. It is generally believed that the thermal oxidation of silicon is controlled by oxygen diffusion through the amorphous silicon oxide network.…”

Section: Introductionmentioning

confidence: 99%

Chemical bonding and interdiffusion in scaled down SiO2∕Si3N4∕SiO2 stacks with top oxide formed by thermal ed copyoxidation

Saraf¹,

Edrei²,

Akhvlediani³

et al. 2006

Journal of Vacuum Science &Amp; Technology B: Microelectronics and Nanometer Structures Processing, Measurement, and Phenomena

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Articles you may be interested inWet oxidation of nitride layer implanted with low-energy Si ions for improved oxide-nitride-oxide memory stacks Appl. Phys. Lett. 90, 263513 (2007); 10.1063/1.2752769 Effect of oxidation on the chemical bonding structure of PECVD SiN x thin films Hafnium interdiffusion studies from hafnium silicate into siliconThe influence of thermal oxidation on the composition of silicon nitride films in SiO 2 /Si 3 N 4 / SiO 2 stacks for advanced nonvolatile memories is reported. X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry analyses lead to the conclusion that wet thermal ͑pyrogenic͒ oxidation of silicon nitride enhances the incorporation of oxygen into the silicon nitride layer and creates a silicon oxynitride layer. In the oxynitride layer formed by wet oxidation, O is mostly bonded to N, whereas in the native oxynitride at the silicon nitride surface, O is preferentially bonded to Si. Dry oxidation ͑1200°C͒ results in an even higher amount of oxygen incorporation into the silicon nitride layer as compared with the pyrogenic process. After both pyrogenic and dry oxidation, hydrogen concentration decreases in the bulk of the silicon nitride layer. Following wet oxidation, hydrogen was found to accumulate at the surface layers of the grown oxynitride film. Oxygen penetration into the nitride layer was found to be higher in thinner nitride layers. The peculiarities of hydrogen distribution were not affected by the thickness of the nitride layer.

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The influence of the chemical composition of silicon nitride films on their thermal oxidation parameters

Cited by 14 publications

References 9 publications

Intermolecular Interactions between a Monomolecular Hydroxyl-Terminated Perfluoropolyether Film and the Sputtered SiNx Surface

Intermolecular Interactions between a Monomolecular Hydroxyl-Terminated Perfluoropolyether Film and the Sputtered SiNx Surface

Etching and Chemical Control of the Silicon Nitride Surface

Chemical bonding and interdiffusion in scaled down SiO2∕Si3N4∕SiO2 stacks with top oxide formed by thermal ed copyoxidation

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