Direct Nitridation of Silicon Substrates

Frieser, R. G.

doi:10.1149/1.2410895

Cited by 26 publications

(13 citation statements)

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“…A peak at 610 cm-' identified as the phonon absorption of the silicon substrate was observed, but no absorption interpreted as Si-O bonds was found in this spectrum. The 865 and 895 cm-' peaks are due to the stretching vibration of Si-N bonds and seem to be almost the same as the peak described by Frieser (2). However, a peak at 920 cm-', higher than our measurement, results for Si-N bonds was reported by Ito et al (4).…”

Section: Resultssupporting

confidence: 88%

“…In spite of these advantages, the silicon nitride film deposited on silicon wafers by LPCVD cannot be used for the gate dielectric film of MOSFET because it was interfacial instabilities between the silicon nitride and the silicon substrafe. Many attempts at achieving direct nitridation and forming the silicon nitride film have already been made (2,3). Ito et aL reported that uniform amorphous silicon nitride films could be obtained from the reaction of silicon in an ammonia ambient and applied to the LSI device fabrication (4).…”

Section: Progress In Mosmentioning

confidence: 99%

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Growth Mechanism of Silicon Plasma Anodic Nitridation

Hirayama¹,

Matsukawa²,

Arima³

et al. 1985

J. Electrochem. Soc.

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Nitridation of silicon was performed in a temperature range of 680~176 by 13.56 MHz RF oscillation in nitrogenhydrogen plasma. Growth kinetics and activation energy of nitridation were investigated. The relationship between nitridation time (t) and nitrided film thickness (xn) was found to be xn (2 -0.00695Vd~) = 0.86 x 10-% External dc voltage (V~D on plasma nitridation was effective in obtaining a high growth rate of nitrided film on silicon. Activation energy for the plasma anodic nitridation of silicon (0.25 eV) was twice as large as the value of plasma nitridation without an external dc voltage. The role of hydrogen in plasma nitridation was also studied with quadrupole mass spectroscopy. Progress in MOSVLSI densification requires a large capacitance in a small capacitor area (I). Therefore, the direct nitridation of silicon may be one of the most attractive techniques for the device fabrication process. Compared with the widely used silicon dioxide film, silicon nitride film has a higher dielectric constant. The silicon nitride film is chemically stable and is also much better as a diffusion barrier for impurities and metals. In spite of these advantages, the silicon nitride film deposited on silicon wafers by LPCVD cannot be used for the gate dielectric film of MOSFET because it was interfacial instabilities between the silicon nitride and the silicon substrafe. Many attempts at achieving direct nitridation and forming the silicon nitride film have already been made (2, 3). Ito et aL reported that uniform amorphous silicon nitride films could be obtained from the reaction of silicon in an ammonia ambient and applied to the LSI device fabrication (4). However, these films were very thin because of the slow diffusion of nitridant species through the nitrided film. To improve the low growth rate, plasma nitridation and plasma anodic nitridation were attempted. A high reaction rate was given by the plasmaexited reactive species compared with the thermal reaction. Plasma anodic nitridation was expected to give an enhanced growth rate, similar to that in the case of the anodic oxidation of silicon (5). Also, the reaction temperature could be decreased below the temperature of the thermodynamical limit beause the plasma reaction forms reactive species.In this paper, the growth mechanism of plasma anodic nitridation will be investigated. To prevent the contamination of oxygen and hydro-oxygen, we used highly purified hydrogen and nitrogen for our experiment. ExperimentalThe vacuum system, gas sources, and experimental arrangements for achieving the plasma anodic nitridation of silicon are shown in Fig. i. They are the same as those used in the earlier study (6). Nitrogen plasma was generated at a pressure range from 0.5 to 2.0 torr by an RF oscillator whose frequency was 13.56 MHz. Anodization voltage applied between the anode and the ground level was supplied by an external dc supply. The nitridation experiments were performed in a temperature range from 680 ~ to 920~ Boron-doped n-type (100)-oriented CZ silicon ...

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Section: Resultssupporting

confidence: 88%

Section: Progress In Mosmentioning

confidence: 99%

Growth Mechanism of Silicon Plasma Anodic Nitridation

Hirayama¹,

Matsukawa²,

Arima³

et al. 1985

J. Electrochem. Soc.

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“…Chemical reaction between nitrogen and silicon has been reported at temperatures of 1100°C and above. 13,14 Our experiments are conducted below this temperature threshold, and our data do not show the formation of silicon nitride. H439 Electrochemical and Solid-State Letters, 12 ͑12͒ H437-H440 ͑2009͒ H439…”

Section: H438mentioning

confidence: 68%

Experimental Investigation of Silicon Surface Migration in Low Pressure Nonreducing Gas Environments

Kant

Ferralis

Provine

et al. 2009

Electrochem. Solid-State Lett.

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Silicon migration in four nonreducing gas ambients of helium, neon, argon, and nitrogen at a low pressure ͑10 −3 Torr͒ and in an ultrahigh vacuum ͑10 −9 Torr͒ is studied by monitoring the effect on microfabricated trench structures after a 5 min anneal at 1000°C in each environment. The measurements of the trench corner curvature are used to extract the relative migration rates for each ambient. The migration rate has no ambient gas dependence for the noble gases at 10 −3 Torr and has pressure dependence in the 10 −3 -10 −9 Torr range.

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“…In addition to their use as oxidation masks, (CVD) silicon nitride films are used as dual dielectric gate and surface passivation films. Silicon nitride films have also been considered for use as dielectric films in MIS devices and as a result, several studies have been made of the growth of such films by direct nitridation of silicon in nitrogen or ammonia (3)(4)(5)(6)(7). In order, there-fore, to learn how to grow such films and to investigate the reasons for the oxidation resistance, their growth and oxidation as well as chemical composition have been determined and are reported in this work.…”

mentioning

confidence: 99%

Thermal Nitridation of Silicon in Ammonia Gas: Composition and Oxidation Resistance of the Resulting Films

Murarka¹,

Chang²,

Adams³

1979

J. Electrochem. Soc.

123

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Thermal nitridation of silicon in ammonia or ammonia‐argon mixtures at temperatures between 900° and 1200°C has resulted in the formation of oxynitride films that are oxidation resistant. Typical film thicknesses were 50–60Å after nitridation for 3–16 hr at 1100°C in pure ammonia. The temperature of nitridation and the ammonia content in the ambient had little effect on the final film thickness. The growth kinetics followed a rapid initial increase for 1–3 hr, with no significant increase thereafter. The nitrogen content of the film increased with increasing ammonia content of the annealing ambient and with the temperature and time of treatment. The nitrogen fraction false{Nfalse} varied from 0.30 to 0.65 (1.00 for pure silicon nitride). Etch rates of films with false{Nfalse}≅0.6 were 20–22 Å/min in 7:1 BHF. These films were resistant to dry and wet oxidations at temperatures below 1200° and 1000°C, respectively; for example, a film grown for 40 min in pure ammonia at 1100°C inhibited substrate oxidation for nearly 3 hr at 1100°C in dry oxygen. The oxidation resistance increased with the nitrogen content, and oxidation proceeded in three steps. The first was a rapid substitution of nitrogen with oxygen, until false{Nfalse} decreased to 0.20. In the second, at 0.20>false{Nfalse}>0.10 , the film was most resistant to oxygen diffusion, and about 70% of the total oxidation resistance time was accounted for by the film in this composition range. In the third, below false{Nfalse}≅0.10 , false{Nfalse} again decreased rapidly. The film lost its oxidation resistance near false{Nfalse}≅0.01 or less.

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Direct Nitridation of Silicon Substrates

Abstract: not Available.

Cited by 26 publications

References 0 publications

Growth Mechanism of Silicon Plasma Anodic Nitridation

Growth Mechanism of Silicon Plasma Anodic Nitridation

Experimental Investigation of Silicon Surface Migration in Low Pressure Nonreducing Gas Environments

Thermal Nitridation of Silicon in Ammonia Gas: Composition and Oxidation Resistance of the Resulting Films

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