Invented by Jean-Marc Girard, Peng Zhang, Antonio Sanchez, Manish Khandelwal, Gennadiy ITOV, Reno PESARESI, Grigory Nikiforov, David Orban, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Market for Si-Containing Film Forming Precursors
The market for Si-containing film forming precursors is expected to grow at a CAGR of 7.5% from 2020 to 2025. The increasing demand for electronic devices, solar cells, and coatings is driving the growth of this market. The Asia-Pacific region is the largest market for Si-containing film forming precursors, followed by North America and Europe.
The major players in the Si-containing film forming precursors market are DowDuPont, Shin-Etsu Chemical Co., Ltd., Momentive Performance Materials Inc., Gelest Inc., and Wacker Chemie AG. These companies are investing in research and development to improve the properties of their precursors and to develop new applications.
Methods of Using Si-Containing Film Forming Precursors
Si-containing film forming precursors can be used in various methods, including chemical vapor deposition (CVD), atomic layer deposition (ALD), and spin coating. CVD is a popular method for depositing thin films of Si-containing materials. In this method, the precursor is vaporized and then deposited on a substrate, where it reacts to form a thin film. ALD is another method that is used to deposit thin films of Si-containing materials. In this method, the precursor is alternately exposed to a substrate, where it reacts to form a thin film.
Spin coating is a simple and cost-effective method for depositing thin films of Si-containing materials. In this method, the precursor is dissolved in a solvent and then deposited on a substrate by spinning it at high speeds. The solvent evaporates, leaving behind a thin film.
Si-containing film forming precursors are also used in the production of solar cells. In this application, the precursor is used to deposit a thin film of silicon on a substrate, which is then used to produce a solar cell. Si-containing precursors are preferred in this application due to their high reactivity and low toxicity.
The market for Si-containing film forming precursors is growing due to the increasing demand for electronic devices, solar cells, and coatings. Si-containing precursors are preferred due to their unique properties, such as high thermal stability, low toxicity, and high reactivity. The major players in this market are investing in research and development to improve the properties of their precursors and to develop new applications. Si-containing film forming precursors can be used in various methods, including CVD, ALD, and spin coating. These methods are used to deposit thin films of Si-containing materials for various applications.
The LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude invention works as follows
Methods for halogenation of a hydrosilazane include contacting the hydrosilazane with a halogenating agent in a liquid phase to produce the halosilazane having a formula\n(SiHa(NR2)bXc)(n+2)Nn(SiH(2?d)Xd)(n?1),\nwherein each a, b, c is independently 0 to 3; a+b+c=3; d is 0 to 2 and n?1; wherein X is selected from a halogen atom selected from F, Cl, Br or I; each R is selected from H, a C1-C6 linear or branched, saturated or unsaturated hydrocarbyl group, or a silyl group [SiR?3]; further wherein each R? “Methods for halogenation of a hydrosilazane include contacting the hydrosilazane with a halogenating agent in a liquid phase to produce the halosilazane having a formulan(SiHa(NR2)bXc)(n+2)Nn (SiH(2?d)Xd)(n?1),nwherein each a, b, c is independently 0 to 3; a+ a
Background for Si-containing Film Forming Precursors and Methods of Using the Same
Trisilylamine is a molecule that has a high Si concentration and the formula N(SiH3)3. TSA can be used as a silicon nitride (T) precursor at low temperatures (see, for example, U.S. Pat. No. No. 7,192,626) as well as for a flowable CVD precursor (see, for example, U.S. Pat. No. No. 8,846,536, US2014/0057458, or U.S. Patent. No. 8,318,584). TSA is a versatile precursor for thin film deposition (with low T and carbon-free capabilities), but its applicability in thermal ALD was limited. No. No.
US2014/0363985 A1 discloses amino-silylamines used for forming a silicon-containing thin-film having a generic formula of R1R2R3Si?N(SiR4R5?NR6R7)2, wherein R1 to R5 are each independently hydrogen, halogen, (C1-C7)alkyl, (C2-C7)alkenyl, (C2-C7)alkynyl, (C3-C7)cycloalkyl or (C6-C12)aryl. US2014/0158580A is a description of an alkoxysilylamine with a TSA like structure. U.S. Pat. No. No. 7,122,222 utilizes a Si?C-bond free hydrazinosilane precursor [R1 2N?NH]nSi (R2)4?n] for depisting SiN, SiO2 or SiON films. Silazane compounds N? As a coating gas, (SiR1R2R3)mR4?m disclosed in the WO2013/058061 is used. In U.S. Pat. No. No. Patents similar to U.S. Pat. Nos. 5,663,398A, 5,332,853A, 5,340,507A, EP 525881 A1, etc.
Experimentally, methods for preparing inorganic halogenated silazanes or halosilazane were demonstrated. However, they are restricted in different ways.
Cradock et al. (?Reactions between Tin(iv), Chloride and Silyl Compounds. Part 1. Part 1. Trans. : Inorg. Chem. (1975) p. 1624-8) disclosed TSA-Clx (x=1-3) compounds that were prepared from SnCl4 and TSA:\n(SiH3)3N+SnCl4? (SiH3-xClx)3N+SnCl2+HCl (x=1-3).\nHowever, as the HCl byproduct cleaved Si?N bonds, the reaction suffered from the lack of selectivity and the major product was found to be MCS. The yields for mono-, bi-, and tris chlorinated TSA, were respectively 20, 15 and 10%.
Reaction occurred in the presence AlCl3 catalyst and was used to synthesize aminosilanes(SiH2NR2)2NH as per Gi et. al. To WO2018182305A1. The patent does not disclose any evidence for (SiH2Cl), the proton resonance, or the N?H group. Neither was there any FT-IR evidence for N?H for the aminosilanes (SiH2NR2)2NH that were prepared by the aminolysis reaction from (SiH2Cl). The reaction apparently has low selectivity as the reported yield of bis(ethylmethylaminosilyl)amine prepared from (SiH2Cl)2NH intermediate is 33%. According to WO2015135698 by Hoppe et. al., the disilylamine, (SiH3)2NH, is unstable, producing TSA or ammonia, or reactive towards the SiH3Cl that was used in the above synthesis.
U.S. Pat. No. No. Preparation of monohalogenated TSA-derivatives was disclosed. The invention suggests that halogenated TSA-Hal can be synthesized by mixing dihalosilane SiH2X2 and monohalosilane SiH3X in a tubular flow reactor. The patent does not provide any examples of the production of TSA Hal or optimization conditions, so it is impossible to make any judgments about the yield and selectivity. Stock et al., as an example, have all cited earlier references that suggest the proposed method could yield a large amount of side-products. (?Siliconhydrides X. Nitrogen-containing compounds?, Stock, Alfred; Somieski, Karl; Ber, B: Abhandlungen (1921), 54B, 740-58), Zhang et al. CN 102173398A, JP1917728 C3 Matsumoto et.al.,JP1777774 C3 Matsumoto et.al.,JP3516815B2 Nakajima et.al., U.S. Pat. No. 4,397,828 A to Seyferth et al., WO 9119688 A1 to Delaet, state that interaction of SiH2X2 and ammonia produces a solid chlorine free polymer and proceeds according to the reaction: 3NH3+H2SiCl2?2NH4Cl+[SiH2(NH)]x.
The US 2013/0209343A1 to Korolev discloses the fact that monochlorosilane of higher purity produces more TSA through reaction with ammonia. Application of impure SiH3Cl results in a mixture of TSA, TSA, TSA, and TSA oligomers. However, it was not disclosed what impurity causes formation of chlorinated compound.
The reaction produced large amounts of polymeric material contaminated with NH4Cl. The reaction produced large quantities of polymeric material contaminated by NH4Cl, from which it was impossible to recover the desired amine compound (SiH3SiH2)3N.
Pflugmacher et al. “Pflugmacher et al. The fully chlorinated (Cl3Si3N) homologue is a volatile liquid and can be produced by reacting SiCl4 with N2 in glow discharge tubes. Anon (IP.com Journal 2013, 13(1B), 8 IP.COM DISCLOSURE NUMBER: IPCOM000224804D), proposed to synthesize the (Cl3Si3N) directly from ammonia and tetrachlorosilane. However, A. Stock (Hydrides Of Boron And Silicon, Cornell University Press Ithaca, N.Y. 1933) and Richetto, et al. Richetto (K. C. S.); Silva, C. R. M. ; Baldacin (S. A.), Materials Science Forum, (2003), 416-418, (Advanced Powder Technology III), p. 688-692, stated that the interaction between SiCl4 & ammonia produced only polymeric solids.
All of these disclosures aside, halogenated aminosilanes were not prepared or used commercially in the period.
Catalysts were applied to the halogenated aminosilanes in an attempt to increase yields. The organic silanes have been chlorinated using various chlorocarbons with the presence of highly acidic catalysers such as HCl or B(C6F5)3, and AlCl3 (refer J. Am. Chem. Soc., 1963, 85 (16), pp 2430-2433; J. Am. Chem. Soc., 1969, vol. 91, p. 7076; Appl. Organometal. Chem., 2018; 32:e4442). These substrates have been shown to trigger disilative coupling or break the Si?N bond of hydrosilazanes without carbon, such as TSA. (See U.S. Pat. Appl. Publ. Publ.
Pongkittiphan et al. have reported a catalysis example by Palladium to promote the chlorination by C2Cl6 of iPr3SiH. (?Hexachloroethane – a Highly Efficient Resagent for Synthesis of Chlorosilanes From Hydrosilanes?” Veerachai, Pongkittiphan Emmanuel A. Theodorakis and Warinthorn, Chavasiri, Tetrahedron Letters (2009) 50(36),5080-5082. The examples given below, comparing TSA chlorination using C2Cl6 or Pd/C, reveal that the method is not suitable for the hydrosilazanes described here: in all examples, halosilazanes are yielded below 5%.
By A. Stock (?Hydrides of Boron and Silicon? Stock, Cornell University Press Ithaca, N.Y. 1933), Halogens Hal2 violently oxidize hydrosilazanes inorganic with the formation of H-Hal, which also breaks Si?N bonds. Stock also reveals H-Hal by itself or with catalysts in “Hydrides Of Boron And Silicon”, by A. Stock, Cornell University Press Ithaca, N.Y. 1933), would cleave the Si?N bonds in hydrosilazanes.
Transition metal halogenides SnCl4, CuCl2, HgBr2, PdCl2 etc. (e.g., Dalt. Trans. : Inorg. Chem. Journal of Organometallic Chemistry, 2003, vol. 686, p. 3; J. Am. Chem. Soc., v.80 (1958), p. 5083.) This would result in the cleavage of Si?N bonds and/or the formation of polymeric materials.
Cradock and colleagues have disclosed the existence of halogenides of non-metals such as P, As B, S, and others. (?Reactions between Tin(iv), Chloride and Silyl Compounds. Part 1. Reactions With Inorganic Silyl Compounds? Stephen Cradock and E. A. V. Ebsworth; Journal of the Chemical Society Dalton Transactions Inorganic Chemistry (1975), p.1624-8), Kunai et.al. A Kunai and J Ohshita (2003, Journal of Organometallic Chemistry, Vol. 686, 3) and Herbert et al. (?Reactions between Triethylsilane, Diethylsilane, and Inorganic Halides? ; Herbert H. Anderson; J. Am. Chem. Soc., 1958, vol. “80, p.5083) causes cleavages of S?N bond in aminosilanes or disilazanes in accordance with the prior art.
?Hydrogen-Halogen? Moedritzer et al. have revealed the redistribution of various Si compounds when Lewis acidlbase catalysers are present. The Redistribution Equilibria Of Silanic Hydrogen With Chlorine On Methylsilicon Moisturities, K. Moedritzer & J. Van Wazer, J. Organomet. Chem. 12 (1968), p.69-77. Whitmore’s “Hydrogen Halogen Exchange Reactions with Triethylsilane” is also a good reference. F. C. Whitmore and E. W. Pietrusza in J. Am. Chem. Soc., 1947, vol. 69, p. 2108). These catalysts would cause desilylative coupling, as shown in the examples of comparison.
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