Advanced Ceramics / Raw and Processed Materials

Silicon Nitride Synthesis

Silicon nitride offers solutions to problems faced in industries that require high-temperature, high-strength materials and very small allowable tolerances.

April 1, 2013
/ Print / Reprints /
/ Text Size+

Silicon nitride (Si3N4) is a naturally formed material created during the development of the earth due to the ammonia-rich atmosphere, silicon-rich crust and high

Jump to:
Direct Nitridation
Diimide Decomposition
Carbothermal Reduction
Forming and Heat Treatment
Bonding Phase

temperatures.Silicon nitride was first developed synthetically in 1859 by Deville and Wöhler, resulting in a patent filed in Germany.1

Development lay dormant until 1953, however, when the synthesis process was rediscovered (and again patented) by the Carborundum Co. in Niagara Falls.1-3 This rediscovery of silicon nitride yielded solutions to problems faced in industries that required high-temperature, high-strength materials and very small allowable tolerances.

Silicon nitride has two different phases: the low-temperature (α) phase and the high-temperature (β) phase.4 Both phases are of the hexagonal crystal structure.5 The phase transition from α to β occurs between the temperatures of 1400 and 1600°C, depending on impurity (alumina) concentration.5,6 It has been observed that additions of alumina reduce the activation energy of the phase transformation.6

In addition to the α and β phases, a fiber or whisker phase has also been detected.1,5 These whiskers are a volatile phase that generally forms on the specimens or furnace wall. The formation is due to poor gas flow rate and/or impurities in the nitriding atmosphere.5

Decomposition or oxidation of Si3N4 can occur at a variety of different temperatures depending on atmosphere chemistry.5,7 It has been demonstrated that at 1700°C, Si3N4 will start to decompose to Si(l,g) and N2(g); at 1880°C, the pressure of dissociated N2(g) reaches 1 bar.1,7

Three common commercial routes can be used to produce Si3N4:1,6,7

• Direct nitridation1-5,7,8

• Diimide decomposition1,5,7,9

• Carbothermal reduction1,7

Direct Nitridation

Direct nitridation is the most well understood Si3N4 synthesis process. The reaction is as follows:1,2,7

3Si + 2N2 --> Si3N4 + Heat (at ~1400°C)          (1)

The highly exothermic (~ 725 kJ/mole at 1400°C) nature of direct nitridation, coupled with the melting point of silicon (1414°C), makes temperature control during the direct nitridation process important.1,2,5,10 If the temperature reaches the melting point of silicon before an adjacent layer of Si3N4 has completely enveloped the silicon particle surface, the silicon particles will fuse together and the liquid silicon will not wet the partial coating of silicon nitride.1,2,5 The liquid silicon will therefore coalesce into globules larger than the original silicon particles and reduce the effective surface area for the direct nitridation reaction.5

Direct nitridation results in a theoretical weight gain of 66.67% of the weight of silicon metal; however, empirical evidence shows the weight gain of a fully nitrided part to be approximately 60% due to volitization of silicon during the process.2

The kinetics of the direct nitridation reaction can be improved through the use of catalysts. The most substantial impurity in silicon is iron, which is introduced in the milling process.1-3,8 It has been demonstrated that the iron impurity acts to catalyze the nitriding reaction by removal of the SiO2 film formed on each silicon particle. It is thought that a eutectic melt is formed with the approximate chemistry of ferrosilite (FeSiO3).1

Another additive introduced to aid in the nitridation process is fluorine, typically added as CaF2 or BaF2.1-3,8 The optimal fluorine addition is currently unknown; 1 wt% (relative to silicon) is typically added. It has been demonstrated, however, that the concentration should not exceed 5 wt% (relative to silicon).

Diimide Decomposition

The starting reactants for diimide decomposition are silicon tetracholoride (SiCl4) and ammonia (typically gas or liquid state).1,5,9 Combining these two components results in a reaction that will occur at temperatures greater than or equal to 0°C:

SiCl4(l) + 6NH3 --> Si(NH)2(s) + 4NH4Cl(s) + Heat (at 0°C)   (2)

The initial reaction for diimide decomposition is an extremely exothermic reaction that needs to be carefully monitored for safety reasons.7 When ammonia is used in excess, the additional compound formed will contain excess amide (NH) groups, which upon heating will reduce the compound to a less complex, more stable form (i.e., the product described in Equation 2).9 To form extremely pure Si(NH)2, a sol-gel route is used:9

• SiCl4 is treated with ammonia

• The resulting particles are dissolved in water

• A fluorine containing salt is added, causing the solution to gel

• Supernatant is filtered from the gel

• The gel is dissolved in a mineral acid

• The resulting solution is filtered

• NaOH(aq) is added to re-precipitate the gel in a pure form

• The gel is removed and washed in water

The produced gel is then heated to approximately 1000°C in a N2 atmosphere for approximately 30 minutes, resulting in a decomposition to amorphous Si3N4:1,5,9

Si(NH)2 --> Si3N4(amorphous) (at 1000°C)        (3)

The amorphous phase developed can be converted to the alpha phase via further heating to ~1450°C (in N2).1,5

Carbothermal Reduction

Carbothermal reduction was first patented in Germany in 1896. During the rediscovery of Si3N4 in the 1950s, it was again patented by the Carborundum Co. in 1955.1 Carbothermal reduction has been described as the most commercially viable method for making Si3N4.1,7 Carbothermal reduction is also the most commonly used method due to the safety of the process; all reactants and products are non-toxic and environmentally safe, and the reaction is endothermic in nature:7

3SiO2 + 6C + 2N2 + Heat --> α-Si3N4 + 6CO (at 1450-1500°C) (4)

The carbothermal reduction process can be divided into three steps:7

• Preparation of the raw material

• Reaction

• Carbon removal

The raw material fabrication generally requires all particles to have a high surface area for an increased reaction rate. Typically, a fumed silica (amorphous) powder is used and mixed with carbon in a specific ratio. Increasing the ratio of C:SiO2 generally increases the rate of Si3N4 formation up to a maximum point (as dictated by Equation 4).

The reaction is observed to occur at a temperature between 1450-1500°C. Below 1450°C, the reaction kinetics are extremely slow, and above 1500°C another reaction resulting in the formation of SiC is thermodynamically more stable.7

Similar to the other methods of silicon nitride production, the partial pressure of oxygen is an important parameter; in addition, for carbothermal reduction, the partial pressure of CO is important. If the partial pressure of oxygen is too great, the oxygen in the atmosphere, rather than the supplied SiO2, will react with the carbon reactant to form carbon monoxide. Hoffman suggests the partial pressure of oxygen must be kept below 2 x 10-20 to ensure the carbothermal reduction.7 A 98.5% conversion of SiO2 to Si3N4 has been demonstrated with the carbothermal reduction reaction (see Equation 4) by heat treating in N2 at 1470°C for six hours.7

The carbon removal step removes excess carbon and oxygen from the prepared silicon nitride to increase the purity. This is carried out by leaking in atmospheric air during the cooling range of 600-850°C. The cooling rate is slowed during this process to have the temperature hold at 600-850°C for one to eight hours.

Forming and Heat Treatment

The most common method of forming and subsequently sintering silicon nitride is hot pressing with an addition of MgO; however, due to current advances, pressure-less sintering is achievable.1 To densify a silicon nitride compact without introducing high pressures, additions of yttria (Y2O3) and alumina (Al2O3) must be included.6,7 The compacts can then be sintered without an increase in pressure at a temperature of 1750°C; however, the maximum rate of densification occurs between the temperatures of 1450-1500°C. The total shrinkage and temperature at which densification begins depends on the production route for the silicon nitride powders used.7

Heat treatment of Si3N4 powders requires an N2 atmosphere or vacuum due to the sensitivity of the Si3N4 to impurities in the atmosphere.3,5,8 Contamination of the atmosphere by H2O, O2 or H2 has significant effects on the products being heat treated.1 Removal of impurity gases, specifically oxygen, is difficult in commercial production. If the silicon metal is still present (not yet reacted to form Si3N4) with oxygen or water vapor present, the silicon metal will oxidize to SiO2, resulting in the formation of a glassy phase upon cooling.

The formation of silicon oxide due to the presence of H2O and/or O2 can be visually detected by a “glaze” on the surface of the Si3N4 products.5 The presence of oxygen and/or water vapor will also have an adverse effect on the already formed Si3N4, possibly causing the silicon nitride to oxidize (forming Si2N2O) or result in the dissociation of silicon nitride (with the former reaction more thermodynamically stable):1

2Si3N4 + 1.5O2 --> 3Si2N2O + N2, ΔG1227°C = -1063 kJ/mole    (5)

Si3N4 + 3O2 --> SiO2 + 2N2, ΔG1227°C = -802 kJ/mole      (6)

The activation energy (Q) for the oxidation of silicon nitride (see Equation 5) at temperature in the range of 1000-1400°C is approximately 486 kJ/mole, whereas for the oxidation of silicon metal, Q = 112 kJ/mole in the same temperature range. In contrast, it has been demonstrated that a small amount (0.2%) of H2 gas present during nitriding leads to an increase in weight gain, implying more complete nitridation of the silicon particles.5

Bonding Phase

The Si3N4 bonding phase may be formed in-situ during proprietary heat treatment processes using all three methods of forming silicon nitride. Through these processes, very large (weighing up to 900 lbs) industrial Si3N4-bonded silicon carbide parts have been produced with tight tolerances, typically ± 0.04 in. 

For more information, contact the author at (518) 436-1263 or, or visit

Visit to listen to our podcast with the author!


1. Riley, F.L., “Silicon Nitride and Related Materials,” J. Am. Ceram. Soc., 83 [2] 245-65, 2000.

2. Nicholson, K.C., “Silicon Nitride-Bonded Refractory Oxide Bodies and Method of Making,” U.S. Pat. 2636828, April 28, 1953.

3. Nicholson, K.C., “Manufacture of Silicon Nitride-Bonded Articles,” U.S. Pat. 2618565, November 18, 1953.

4. Thompson, D.S., and Pratt, P.L., “The Structure of Silicon Nitride,” Science of Ceramics, Vol. 3, edited by Stewart, G.H., Academic Press, New York, 1967, pp. 33-51.

5. Popper, P., and Ruddlesden, A.C., “The Preparation, Properties and Structure of Silicon Nitride,” Trans. Br. Ceram. Soc., 60 603-26 (1961).

6. van Dijen, F.K., Kerber, A., Vogt, U., Pfeifer, W., and Schulze, M., “A Comparative Study of Three Silicon Nitride Powders, Obtained by Three Different Syntheses,” Silicon Nitride ’93, Vol. 89-91, Edited by Hoffmann, M.J., Becher, P.F., and Petzow, G., 1994, pp. 19-28.

7. Hofmann, H., Vogt, U., Kerber, A., and v. Dijen, F.K., “Silicon Nitride Powder from Carbothermal Reaction,” Silicon Nitride Ceramics: Scientific and Technological Advances, Edited by Chen, I.W., Becher, P.F., Mitomo, M., Petzow, G., and Yen, T.S., Materials Research Society, Pittsburgh, 1993, pp. 105-20.

8. Atkinson, A., Moulson, A.J., and Roberts, E.W., “Nitridation of High-Purity Silicon,” J. Am. Ceram. Soc., 59 [7-8] 285-9, 1976.

9. Sowa, F.J., “Production of Metallic Nitrides,” U.S. Pat. 2606815, August 12, 1952.

 10. CRC Handbook of Chemistry and Physics, 82nd ed., Edited by Lide, D.R., CRC Press, New York, NY, 2002. 

Did you enjoy this article? Click here to subscribe to Ceramic Industry Magazine.

You must login or register in order to post a comment.



Image Galleries

October 2014 Issue Highlights

Our October 2014 issue is now available!


Manufacturing Day 2014

Manufacturing Day organizers share their insights with Managing Editor Kelsey Seidler.

More Podcasts

Ceramic Industry Magazine

CI January 2015 cover

2015 January

It's our annual Materials Handbook issue, with the ever-popular "Raw & Manufactured Materials Overview" article! Check it out today.

Table Of Contents Subscribe

Personal Smartphones

Do you use your personal smartphone or other device to complete tasks for your job?
View Results Poll Archive


M:\General Shared\__AEC Store Katie Z\AEC Store\Images\Ceramics Industry\handbook of advanced ceramics.gif
Handbook of Advanced Ceramics Machining

Ceramics, with their unique properties and diverse applications, hold the potential to revolutionize many industries, including automotive and semiconductors.

More Products

Clear Seas Research

Clear Seas ResearchWith access to over one million professionals and more than 60 industry-specific publications,Clear Seas Research offers relevant insights from those who know your industry best. Let us customize a market research solution that exceeds your marketing goals.


facebook_40px twitter_40px  youtube_40pxlinkedin_40google+ icon 40px


CI Data Book July 2012

Ceramic Industry's Directories including Components, Equipment Digest, Services, Data Book & Buyers Guide, Materials Handbook and much more!