JP2018519233A - Preparation of Si-H containing iodosilane by halide exchange reaction - Google Patents

Abstract

A method of synthesizing a Si—H containing iodosilane, such as diiodosilane or pentaiododisilane, utilizing a halide exchange reaction is disclosed. [Selection] Figure 1

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is a benefit of US Patent Application No. 62 / 338,882, filed May 19, 2016, which is hereby incorporated by reference in its entirety for all purposes. Is an insistence.

  A method of synthesizing a Si—H containing iodosilane, such as diiodosilane or pentaiododisilane, utilizing a halide exchange reaction is disclosed.

Halosilane chemical products have found many uses in industry. In particular, iodosilane precursors such as diiodosilane (SiH ₂ I ₂ ) have been used to deposit various silicon-containing films for use in semiconductor manufacturing processes.

Emeleus et al. Disclose the synthesis of diiodosilane (SiH ₂ I ₂ ) by reaction of silane (SiH ₄ ), hydrogen iodide (HI), and aluminum iodide (AlI ₃ ). Derivatives of monosilane. Part II. The Ido compounds: Emeleus, H .; J. et al. Maddock, A .; G. Reid C .; , J .; Chem. Soc. 1941, 353-358). On page 354 of the document, the reaction produces the desired reaction product SiH ₂ I ₂ along with iodosilane (SiH ₃ I), triiodosilane (SiHI ₃ ), and tetraiodosilane (SiI ₄ ).

Keinan et al. Show that reacting iodine with phenylsilane at a molar ratio of 1: 1 at −20 ° C. in the presence of trace amounts of ethyl acetate produces 1 mole of SiH ₂ I ₂ and 1 mole of benzene. Disclosure. J. et al. Org. Chem. , Vol. 52, no. 22, 1987, pp. 4846-4851. Although selective to SiH ₂ I ₂ over other possible iodosilanes (ie, SiH ₃ I, SiHI ₃ , and SiI ₄ ), this method produces a known human carcinogenic benzene and is therefore commercialized. Is difficult to realize. Despite this drawback, it still remains the preferred synthetic route for diiodosilane production.

  Impurities from these synthetic methods, such as hydrogen iodide and / or iodine, may degrade the resulting product iodosilane. Current industrial practices are described in Eaborn, 'Organicicon Compounds. Part II. 'A Conversion Series for Organosilicate Halides, Pseudohalides, and Sulphides', 1950, J. Am. Chem. Soc. , 3077-3089 and Beilstein 4, IV, 4009, using antimony, silver, or copper powder / pellet additives to stabilize these products. Although the addition of copper can stabilize the product, it can also introduce impurities (Cu) that can adversely affect the electrical properties of the deposited film.

The so-called Finkelstein reaction is an S _N 2 reaction (nucleophilic substitution bimolecular reaction) involving the exchange of one halogen atom for another. Although the halide exchange is an equilibrium reaction, the reaction can be completed by utilizing a different soluble halide salt or by using a large excess of halide salt. Smith et al. (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience.

  For example, the synthesis of iodotrimethylsilane (TMS-I) by the reaction of chlorotrimethylsilane with lithium iodide in chloroform or sodium iodide in acetonitrile has been reported (Formula 4). Handbook of Reagents for Organic Synthesis, Reagents for Silicon-Mediated Organic Synthesis, Iodotrimethylsilane, Wiley 2011, p. 325.

  Si-Cl is reactive to the exchange of iodine by this route, but R groups such as alkyl or aryl groups are not reactive. On the other hand, it has been found that Si-H bonds are usually more reactive than Si-Cl bonds. Chemistry and Technology of Silicones, Academic Press, 1968, p. 50. In response, one skilled in the art would expect the exchange of both H and Cl atoms of any Si-H containing halosilane by a Finkelstein reaction.

  There remains a need for a commercially viable synthesis and supply of stable Si-H containing iodosilanes, such as diiodosilanes, suitable for use in the semiconductor industry.

A method of synthesizing a Si-H containing iodosilane is disclosed. The Si-H containing iodosilane has the formula Si _w H _x R _y I _z (1)
N (SiH _a R _b I _c ) ₃ (2), or (SiH _m R _n I _o ) ₂ —CH ₂ (3)
(Wherein w is 1 to 3, x + y + z = 2w + 2, x is 1 to 2w + 1, y is 0 to 2w + 1, z is 1 to 2w + 1, and each a is independently 0 to 3 Each b is independently 0-3, each c is independently 0-3, a + b + c = 3, provided that at least one a and at least one c are 1, and each m Is independently 0-3, each n is independently 0-3, each o is independently 0-3, and at least one m and at least one o is 1, m + n + o = 3 and each R is independently a C1-C12 hydrocarbyl group, Cl, Br, or ER ′ ₃ group, where each E is independently Si or Ge, and each R ′ is independently H or a C1-C12 hydrocarbyl group). Formula _{Si w H x R y X z} , N (SiH a R b X c) 3, or in _{(SiH m R n X o)} 2 -CH 2 ( wherein, X is Cl or Br, and w, x , Y, z, a, b, c, m, n, and o are as defined above, can be represented by the formula MI, where M = Li, Na, K, Rb, or by reacting with an alkali metal halide reactant having a a) cs, MX and _{Si w H x R y I z} , n (SiH a R b I c) 3, or _{(SiH m R n I o)} 2 -CH A mixture with ₂ is produced. SiH-containing Yodoshiran having the formula _{Si w H x R y I z} , N (SiH a R b I c) 3, or _{(SiH m R n I o)} 2 -CH 2 may be isolated from the mixture. Alternatively, the halosilane reactant may be mixed with an alkali metal halide reactant to produce Si _w H _x I _z , N (SiH _a R _b I _c ) ₃ or (SiH _m R _n I _o ) ₂ —CH ₂ and MX. A mixture is produced. The mixture is filtered to produce a Si—H containing iodosilane having the formula Si _w H _x I _z , N (SiH _a R _b I _c ) ₃ , or (SiH _m R _n I _o ) ₂ —CH ₂ . Any of the methods of the present disclosure may include one or more of the following aspects:
R is not Cl or Br;
R is a Cl to C12 hydrocarbyl group;
R is ₃ ER 'groups;
M = Li;
Y = 0
Z = 2 to 2w + 1;
Adding a solvent to the reaction process;
The solvent is Si-H containing iodosilane;
The solvent is an alkane;
The solvent is propane, butane, pentane, hexane, heptane, chloromethane, dichloromethane, chloroform, carbon tetrachloride, methylene chloride, acetonitrile, and combinations thereof;
The solvent is pentane;
And isolating step, the mixture was filtered, and separating the MX from Si-H containing Yodoshiran having the formula _{Si w H x R y I z} ;
The halosilane reactant is SiH ₂ Cl ₂ ;
The halosilane reactant is Si ₂ HCl ₅ ;
The halosilane reactant is (SiH ₃ ) ₂ N (SiH ₂ Cl);
The alkali metal halide reactant is LiI;
· Si-H-containing Yodoshiran has the formula _{Si w H x R y I z} (1);
The Si-H containing iodosilane has the formula SiH _x I _{4-x where} x = 1-3;
The Si—H containing iodosilane is SiHI ₃ ;
The Si—H containing iodosilane is SiH ₂ I ₂ ;
The Si—H containing iodosilane is SiH ₃ I;
· SiH-containing Yodoshiran the formula _{SiH x R y I 4-x} -y ( wherein a x = 1 to 2, a y = 1~2, x + y is less than or equal to 3, and each R is independently C1-C12 hydrocarbyl group, Cl, Br, or ER'3 group, wherein each E is independently Si or Ge, and each R 'is independently H or C1-C12 hydrocarbyl group) Having:
The Si—H containing iodosilane is MeSiHI ₂ ;
The Si—H containing iodosilane is MeSiH ₂ I;
The Si—H containing iodosilane is Me ₂ SiHI;
The Si—H containing iodosilane is EtSiHI ₂ ;
The Si—H containing iodosilane is EtSiH ₂ I;
The Si—H containing iodosilane is Et ₂ SiHI;
The Si—H containing iodosilane is ClSiHI ₂ ;
The Si—H containing iodosilane is ClSiH ₂ I;
The Si—H containing iodosilane is Cl ₂ SiHI;
The Si—H containing iodosilane is BrSiHI ₂ ;
The Si—H containing iodosilane is BrSiH ₂ I;
The Si-H containing iodosilane is Br ₂ SiHI;
The Si—H containing iodosilane is H ₃ SiSiHI ₂ ;
The Si—H containing iodosilane is H ₃ SiSiH ₂ I;
The Si—H containing iodosilane is (H ₃ Si) ₂ SiHI;
The Si—H containing iodosilane is H ₃ GeSiHI ₂ ;
The Si—H containing iodosilane is H ₃ GeSiH ₂ I;
The Si—H containing iodosilane is (H ₃ Ge) ₂ SiHI;
The Si—H containing iodosilane is Me ₃ SiSiHI ₂ ;
The Si—H containing iodosilane is Me ₃ SiSiH ₂ I;
The Si—H containing iodosilane is (Me ₃ Si) ₂ SiHI;
The Si—H containing iodosilane is Me ₃ GeSiHI ₂ ;
The Si—H containing iodosilane is Me ₃ GeSiH ₂ I;
The Si—H containing iodosilane is (Me ₃ Ge) ₂ SiHI;
The Si—H containing iodosilane is Me ₂ HSiSiHI ₂ ;
The Si—H containing iodosilane is Me ₂ HSiSiH ₂ I;
The Si—H containing iodosilane is (Me ₂ HSi) ₂ SiHI;
The Si—H containing iodosilane is Me ₂ HGeSiHI ₂ ;
The Si—H containing iodosilane is Me ₂ HGeSiH ₂ I;
The Si—H containing iodosilane is (Me ₂ HGe) ₂ SiHI;
· Si-H-containing Yodoshiran has the formula _{Si 2 H x I 6-x} ( wherein, is x = 1 to 5);
The Si—H containing iodosilane is Si ₂ HI ₅ ;
The Si—H containing iodosilane is Si ₂ H ₂ I ₄ ;
The Si—H containing iodosilane is Si ₂ H ₃ I ₃ ;
The Si—H containing iodosilane is Si ₂ H ₄ I ₂ ;
The Si—H containing iodosilane is Si ₂ H ₅ I;
Si-H containing iodosilane has the formula Si ₂ H _x R _y I _6-xy (where x = 1-4, y = 1-4, x + y is 5 or less, and each R Are independently C1-C12 hydrocarbyl groups, Cl, Br, or ER′3 groups, where each E is independently Si or Ge, and each R ′ is independently H or C1-C12 hydrocarbyl group. Have)
The Si—H containing iodosilane is MeSi ₂ HI ₄ ;
The Si—H containing iodosilane is MeSi ₂ H ₂ I ₃ ;
The Si—H containing iodosilane is MeSi ₂ H ₃ I ₂ ;
The Si—H containing iodosilane is MeSi ₂ H ₄ I;
The Si—H containing iodosilane is Me ₂ Si ₂ HI ₃ ;
The Si—H containing iodosilane is Me ₂ Si ₂ H ₂ I ₂ ;
The Si—H containing iodosilane is Me ₂ Si ₂ H ₃ I;
The Si—H containing iodosilane is Me ₃ Si ₂ HI ₂ ;
The Si—H containing iodosilane is Me ₃ Si ₂ H ₂ I;
The Si—H containing iodosilane is Me ₄ Si ₂ HI;
The Si—H containing iodosilane is EtSi ₂ HI ₄ ;
The Si—H containing iodosilane is EtSi ₂ H ₂ I ₃ ;
The Si—H containing iodosilane is EtSi ₂ H ₃ I ₂ ;
The Si—H containing iodosilane is EtSi ₂ H ₄ I;
The Si—H containing iodosilane is Et ₂ Si ₂ HI ₃ ;
The Si—H containing iodosilane is Et ₂ Si ₂ H ₂ I ₂ ;
The Si—H containing iodosilane is Et ₂ Si ₂ H ₃ I;
The Si—H containing iodosilane is Et ₃ Si ₂ HI ₂ ;
The Si—H containing iodosilane is Et ₃ Si ₂ H ₂ I;
The Si—H containing iodosilane is Et ₄ Si ₂ HI;
The Si—H containing iodosilane is ClSi ₂ HI ₄ ;
The Si—H containing iodosilane is ClSi ₂ H ₂ I ₃ ;
The Si—H containing iodosilane is ClSi ₂ H ₃ I ₂ ;
The Si—H containing iodosilane is ClSi ₂ H ₄ I;
The Si—H containing iodosilane is Cl ₂ Si ₂ HI ₃ ;
The Si—H containing iodosilane is Cl ₂ Si ₂ H ₂ I ₂ ;
The Si—H containing iodosilane is Cl ₂ Si ₂ H ₃ I;
The Si—H containing iodosilane is Cl ₃ Si ₂ HI ₂ ;
The Si—H containing iodosilane is Cl ₃ Si ₂ H ₂ I;
The Si—H containing iodosilane is Cl ₄ Si ₂ HI;
The Si—H containing iodosilane is BrSi ₂ HI ₄ ;
The Si—H containing iodosilane is BrSi ₂ H ₂ I ₃ ;
The Si—H containing iodosilane is BrSi ₂ H ₃ I ₂ ;
The Si—H containing iodosilane is BrSi ₂ H ₄ I;
The Si—H containing iodosilane is Br ₂ Si ₂ HI ₃ ;
The Si—H containing iodosilane is Br ₂ Si ₂ H ₂ I ₂ ;
The Si—H containing iodosilane is Br ₂ Si ₂ H ₃ I;
The Si—H containing iodosilane is Br ₃ Si ₂ HI ₂ ;
The Si—H containing iodosilane is Br ₃ Si ₂ H ₂ I;
The Si—H containing iodosilane is Br ₄ Si ₂ HI;
The Si—H containing iodosilane is H ₃ SiSi ₂ HI ₄ ;
The Si—H containing iodosilane is H ₃ SiSi ₂ H ₂ I ₃ ;
The Si—H containing iodosilane is H ₃ SiSi ₂ H ₃ I ₂ ;
The Si—H containing iodosilane is H ₃ SiSi ₂ H ₄ I;
The Si—H containing iodosilane is (H ₃ Si) ₂ Si ₂ HI ₃ ;
The Si—H containing iodosilane is (H ₃ Si) ₂ Si ₂ H ₂ I ₂ ;
The Si—H containing iodosilane is (H ₃ Si) ₂ Si ₂ H ₃ I;
The Si—H containing iodosilane is (H ₃ Si) ₃ Si ₂ HI ₂ ;
The Si—H containing iodosilane is (H ₃ Si) ₃ Si ₂ H ₂ I;
The Si—H containing iodosilane is (H ₃ Si) ₄ Si ₂ HI;
The Si—H containing iodosilane is H ₃ GeSi ₂ HI ₄ ;
The Si—H containing iodosilane is H ₃ GeSi ₂ H ₂ I ₃ ;
The Si—H containing iodosilane is H ₃ GeSi ₂ H ₃ I ₂ ;
The Si—H containing iodosilane is H ₃ GeSi ₂ H ₄ I;
The Si—H containing iodosilane is (H ₃ Ge) ₂ Si ₂ HI ₃ ;
The Si—H containing iodosilane is (H ₃ Ge) ₂ Si ₂ H ₂ I ₂ ;
The Si—H containing iodosilane is (H ₃ Ge) ₂ Si ₂ H ₃ I;
The Si—H containing iodosilane is (H ₃ Ge) ₃ Si ₂ HI ₂ ;
The Si—H containing iodosilane is (H ₃ Ge) ₃ Si ₂ H ₂ I;
The Si—H containing iodosilane is (H ₃ Ge) ₄ Si ₂ HI;
The Si—H containing iodosilane is Me ₃ SiSi ₂ HI ₄ ;
The Si—H containing iodosilane is Me ₃ SiSi ₂ H ₂ I ₃ ;
The Si—H containing iodosilane is Me ₃ SiSi ₂ H ₃ I ₂ ;
The Si—H containing iodosilane is Me ₃ SiSi ₂ H ₄ I;
The Si—H containing iodosilane is (Me ₃ Si) ₂ Si ₂ HI ₃ ;
The Si—H containing iodosilane is (Me ₃ Si) ₂ Si ₂ H ₂ I ₂ ;
The Si—H containing iodosilane is (Me ₃ Si) ₂ Si ₂ H ₃ I;
The Si—H containing iodosilane is (Me ₃ Si) ₃ Si ₂ HI ₂ ;
The Si—H containing iodosilane is (Me ₃ Si) ₃ Si ₂ H ₂ I;
The Si—H containing iodosilane is (Me ₃ Si) ₄ Si ₂ HI;
The Si—H containing iodosilane is Me ₃ GeSi ₂ HI ₄ ;
The Si—H containing iodosilane is Me ₃ GeSi ₂ H ₂ I ₃ ;
The Si—H containing iodosilane is Me ₃ GeSi ₂ H ₃ I ₂ ;
The Si—H containing iodosilane is Me ₃ GeSi ₂ H ₄ I;
The Si—H containing iodosilane is (Me ₃ Ge) ₂ Si ₂ HI ₃ ;
The Si—H containing iodosilane is (Me ₃ Ge) ₂ Si ₂ H ₂ I ₂ ;
The Si—H containing iodosilane is (Me ₃ Ge) ₂ Si ₂ H ₃ I;
The Si—H containing iodosilane is (Me ₃ Ge) ₃ Si ₂ HI ₂ ;
The Si—H containing iodosilane is (Me ₃ Ge) ₃ Si ₂ H ₂ I;
The Si—H containing iodosilane is (Me ₃ Ge) ₄ Si ₂ HI;
The Si—H containing iodosilane is Me ₂ HSiSi ₂ HI ₄ ;
The Si—H containing iodosilane is Me ₂ HSiSi ₂ H ₂ I ₃ ;
The Si—H containing iodosilane is Me ₂ HSiSi ₂ H ₃ I ₂ ;
The Si—H containing iodosilane is Me ₂ HSiSi ₂ H ₄ I;
The Si—H containing iodosilane is (Me ₂ HSi) ₂ Si ₂ HI ₃ ;
The Si—H containing iodosilane is (Me ₂ HSi) ₂ Si ₂ H ₂ I ₂ ;
The Si—H containing iodosilane is (Me ₂ HSi) ₂ Si ₂ H ₃ I;
The Si—H containing iodosilane is (Me ₂ HSi) ₃ Si ₂ HI ₂ ;
The Si—H containing iodosilane is (Me ₂ HSi) ₃ Si ₂ H ₂ I;
The Si—H containing iodosilane is (Me ₂ HSi) ₄ Si ₂ HI;
The Si—H containing iodosilane is Me ₂ HGeSi ₂ HI ₄ ;
The Si—H containing iodosilane is Me ₂ HGeSi ₂ H ₂ I ₃ ;
The Si—H containing iodosilane is Me ₂ HGeSi ₂ H ₃ I ₂ ;
The Si—H containing iodosilane is Me ₂ HGeSi ₂ H ₄ I;
The Si—H containing iodosilane is (Me ₂ HGe) ₂ Si ₂ HI ₃ ;
The Si—H containing iodosilane is (Me ₂ HGe) ₂ Si ₂ H ₂ I ₂ ;
The Si—H containing iodosilane is (Me ₂ HGe) ₂ Si ₂ H ₃ I;
The Si—H containing iodosilane is (Me ₂ HGe) ₃ Si ₂ HI ₂ ;
The Si—H containing iodosilane is (Me ₂ HGe) ₃ Si ₂ H ₂ I;
The Si—H containing iodosilane is (Me ₂ HGe) ₄ Si ₂ HI;
· Si-H-containing Yodoshiran has the formula _{Si 3 H x I 8-x} ( wherein, is x = 1 to 8);
The Si—H containing iodosilane is Si ₃ H ₇ I;
The Si—H containing iodosilane is Si ₃ H ₆ I ₂ ;
The Si—H containing iodosilane is Si ₃ H ₅ I ₃ ;
The Si—H containing iodosilane is Si ₃ H ₄ I ₄ ;
The Si—H containing iodosilane is Si ₃ H ₃ I ₅ ;
The Si—H containing iodosilane is Si ₃ H ₂ I ₆ ;
The Si—H containing iodosilane is Si ₃ HI ₇ ;
The Si-H containing iodosilane is of the formula N (SiH _a I _c ) ₃ , where each a is independently 0-3, provided that at least one a and at least one c are 1. Each c is independently 0-3);
The Si—H containing iodosilane is N (SiH ₃ ) ₂ (SiH ₂ I);
The Si—H containing iodosilane is N (SiH ₃ ) ₂ (SiHI ₂ );
The Si—H containing iodosilane is N (SiH ₃ ) (SiH ₂ I) ₂ ;
The Si—H containing iodosilane is N (SiH ₃ ) (SiHI ₂ ) ₂ ;
The Si—H containing iodosilane is N (SiHI ₂ ) ₂ (SiH ₂ I);
The Si—H containing iodosilane is N (SiHI ₂ ) (SiH ₂ I) ₂ ;
The Si—H containing iodosilane is N (SiH ₂ I) ₃ ;
The Si—H containing iodosilane is N (SiHI ₂ ) ₃ ;
Si-H containing iodosilane is represented by the formula N (SiH _a R _b I _c ) ₃ (wherein each a is independently 0-3, each b is independently 0-3, and each c is independently 0 ~ 3, a + b + c = 3, and each R is independently a C1-C12 hydrocarbyl group, Cl, Br, or ER'3 group, where each E is independently Si or Ge; And each R ′ is independently H or a C1-C12 hydrocarbyl group, wherein (a) at least one x, at least one y, and at least one z are 1, and (b) at least one Provided that Si is bonded to both H and I);
The Si—H containing iodosilane is N (SiH ₃ ) ₂ (SiMeHI);
The Si—H containing iodosilane is N (SiH ₂ Me) ₂ (SiMeHI);
The Si—H containing iodosilane is N (SiHMe ₂ ) ₂ (SiMeHI);
The Si—H containing iodosilane is N (SiMe ₂ H) ₂ (SiH ₂ I);
The Si—H containing iodosilane is N (SiMe ₃ ) ₂ (SiH ₂ I);
The Si—H containing iodosilane is N (SiMe ₂ H) ₂ (SiHI ₂ );
The Si—H containing iodosilane is N (SiMe ₃ ) ₂ (SiHI ₂ );
· SiH-containing Yodoshiran has the formula _{(SiH m R n I o)} 2 -CH 2 (3);
The Si—H containing iodosilane has the formula (SiH _x I _y ) ₂ CH ₂ , where each x is independently 0-3, provided that at least one x and at least one y are 1. And each y is independently 0-3);
The Si—H containing iodosilane is (SiH ₂ I) ₂ —CH ₂ ;
The Si—H containing iodosilane is (SiHI ₂ ) ₂ —CH ₂ ;
The Si—H containing iodosilane is (SiH ₂ I) —CH ₂ — (SiH ₃ );
The Si—H containing iodosilane is (SiHI ₂ ) —CH ₂ — (SiH ₃ ); or The Si—H containing iodosilane is (SiH ₂ I) —CH ₂ — (SiHI ₂ ).

A Si-containing film forming composition containing any of the Si-H containing iodosilanes listed above is also disclosed. The composition for forming a Si-containing film of the present disclosure includes one or more of the following aspects:
The Si-containing film forming composition contains from about 99% v / v to about 100% v / v of one Si-H containing iodosilane;
The Si-containing film-forming composition contains about 99.5% v / v to about 100% v / v of one Si—H containing iodosilane;
The Si-containing film-forming composition contains about 99.97% v / v to about 100% v / v of one Si-H containing iodosilane;
The Si-containing film-forming composition contains about 0 ppbw to about 100 ppbw Cu;
The Si-containing film-forming composition contains about 0 ppbw to about 100 ppbw of Ag;
The Si-containing film-forming composition contains from about 0 ppbw to about 100 ppbw Sb;
The Si-containing film-forming composition contains about 0 ppbw to about 50 ppbw Cu;
The Si-containing film-forming composition contains about 0 ppbw to about 50 ppbw of Ag;
The Si-containing film-forming composition contains about 0 ppbw to about 50 ppbw Sb;
The Si-containing film-forming composition contains about 0 ppbw to about 10 ppbw Cu;
The Si-containing film-forming composition contains about 0 ppbw to about 10 ppbw Ag; or The Si-containing film-forming composition contains about 0 ppbw to about 10 ppbw Sb.

A Si-containing film forming composition transfer apparatus, comprising an inlet pipe and an outlet pipe, and comprising a canister containing any of the Si-containing film forming compositions disclosed above A composition transfer device is also disclosed. The apparatus of the present disclosure may include one or more of the following aspects:
The end of the inlet tube end is located above the surface of the Si-containing film-forming composition and the end of the outlet tube is located below the surface of the Si-containing film-forming composition;
The end of the inlet tube is located below the surface of the Si-containing film-forming composition and the end of the outlet tube is located above the surface of the Si-containing film-forming composition;
-Further comprising diaphragm valves at the inlet and outlet;
The inner surface of the canister is glass;
The inner surface of the canister is passivated stainless steel;
The canister is a light-resistant glass with a light-resistant coating on the outer surface of the canister;
The inner surface of the canister is aluminum oxide;
-Further comprising one or more barrier layers on the inner surface of the canister;
-Further comprising 1-4 barrier layers on the inner surface of the canister;
-Further comprising one or two barrier layers on the inner surface of the canister;
Each barrier layer comprises a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a silicon carbonitride layer, a silicon oxycarbonitride layer, or a combination thereof;
• Each barrier layer is 1-100 nm thick; or • Each barrier layer is 2-10 nm thick.

Notation and Naming Certain abbreviations, symbols and terms are used throughout the following specification and claims, including the following:

  In this specification, the indefinite article “one (a)” or “one” means one or more.

  As used herein, the term “approximately” or “about” means ± 10% of a specified value.

As used herein, the term “independently” when used in connection with the description of an R group is independently selected from other R groups in which the subject R group has the same or different subscript or superscript. It should be understood to mean that it is independently selected from any additional species of the same R group. For example, in the formula MR ¹ _x (NR ² R ³ ) _{(4-x) where} x is 2 or 3, two or three R ¹ groups are the same as each other or R ² or R ³ May, but need not be the same. Further, unless otherwise specified, it should be understood that the values of the R groups when used in different formulas are independent of each other.

  As used herein, the term “hydrocarbyl group” means a functional group containing carbon and hydrogen, and the term “alkyl group” means a saturated functional group containing only carbon and hydrogen atoms. The hydrocarbyl group may be saturated or unsaturated. Any term means a linear, branched or cyclic group. Examples of linear alkyl groups include, but are not limited to, methyl groups, ethyl groups, n-propyl groups, n-butyl groups, and the like. Examples of branched alkyl groups include, but are not limited to, iso-propyl and t-butyl. Examples of the cyclic alkyl group include, but are not limited to, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like.

  As used herein, the term “aryl” means an aromatic ring compound in which one hydrogen atom is removed from the ring. As used herein, the term “heterocycle” means a cyclic compound having atoms of at least two different elements as elements of the ring.

  As used herein, the abbreviation “Me” means a methyl group, the abbreviation “Et” means an ethyl group, the abbreviation “Pr” means any propyl group (ie, n-propyl or isopropyl), and the abbreviation “IPr” means isopropyl group, abbreviation “Bu” means any butyl group (n-butyl, iso-butyl, t-butyl, sec-butyl), abbreviation “tBu” means tert-butyl group. The abbreviation “sBu” means sec-butyl group, the abbreviation “iBu” means iso-butyl group, the abbreviation “Ph” means phenyl group, and the abbreviation “Am” means any amyl group ( iso-amyl, sec-amyl, tert-amyl), and the abbreviation “Cy” means a cyclic alkyl group (cyclobutyl, cyclopentyl, cyclohexyl, etc.).

As used herein, the acronym “HCDS” means hexachlorodisilane, the acronym “PCDS” means pentachlorodisilane, the acronym “OCTS” means n-octyltrimethoxysilane, and the acronym “TSA”. "Means trisilylamine or N (SiH ₃ ) ₃ .

  As used herein, the term “iodosilane” means a molecule that contains at least one Si—I bond, regardless of other bonds on Si or the backbone of the molecule. More generally, “halosilane” refers to a molecule that contains at least one Si—X containing bond (where X is a halogen atom), regardless of other bonds on Si or the backbone of the molecule.

  As used herein, the term “Si—H containing” means a molecule that contains at least one Si—H bond, regardless of other bonds on Si or the backbone of the molecule.

As used herein, the term “coordinating solvent” means any solvent that donates an electron pair, such as a solvent containing an OH group or an NH ₃ group. Typical coordinating solvents include amines, phosphines, ethers, and ketones.

  In this specification, the acronym “LCD-TFT” means a liquid crystal display thin film transistor, the acronym “MIM” means metal-insulator-metal, the acronym “DRAM” means dynamic random access memory, The acronym “FeRAM” means ferroelectric random access memory, the acronym “sccm” means standard cubic centimeter per minute, and the acronym “GCMS” means gas chromatography mass spectrometry.

  In this specification, standard abbreviations for elements from the periodic table of elements are used. It should be understood that an element may be referred to by these abbreviations (eg, Si means silicon, N means nitrogen, O means oxygen, C means carbon, etc.).

  Any and all ranges listed herein include their endpoints regardless of whether the term “include all” is used (ie, X = 1 to 4 is X = 1, X = 4, and X = including any number in between).

  For a further understanding of the nature and objects of the present invention, reference should be made to the following detailed description taken together with the accompanying figures.

1 is a schematic diagram of an apparatus capable of performing the synthesis method of the present disclosure. FIG. 6 is a schematic diagram of another apparatus capable of performing the synthesis method of the present disclosure. 1 is a side sectional view of an embodiment of a transfer device 1 for a composition for forming a Si-containing film. It is a sectional side view of 2nd Embodiment of the transfer apparatus 1 of the composition for Si containing film formation. 1 is a side cross-sectional view of an exemplary embodiment of a solid precursor sublimation apparatus 100 for sublimating a solid Si-containing film forming composition. _{6 is} a gas chromatography / mass spectrum (GC / MS) graph of the reaction product SiH ₂ I ₂ of Example 5. FIG. It is a GC / MS graph of the reaction mixture of Example 7 after stirring for 90 minutes.

formula:
Si _w H _x R _y I _z (1)
N (SiH _a R _b I _c ) ₃ (2), or (SiH _m R _n I _o ) ₂ —CH ₂ (3)
(Wherein w is 1 to 3, x + y + z = 2w + 2, x is 1 to 2w + 1, y is 0 to 2w + 1, z is 1 to 2w + 1, and each a is independently 0 to 3 Each b is independently 0-3, each c is independently 0-3, a + b + c = 3, provided that at least one a and at least one c are 1, and each m Is independently 0-3, each n is independently 0-3, each o is independently 0-3, and at least one m and at least one o is 1, m + n + o = 3 and each R is independently a C1-C12 hydrocarbyl group, Cl, Br, or ER ′ ₃ group, where each E is independently Si or Ge, and each R ′ is independently H or a C1-C12 hydrocarbyl group)
Disclosed is a method for synthesizing a Si-H containing iodosilane having:

These compounds such as diiodosilane (SiH ₂ I ₂ ) or pentaiododisilane (Si ₂ HI ₅ ) contain highly reactive Si—H groups, and organic protecting groups when y or b or n is 0. There is no at all. As a result, these silicon hydrides are susceptible to nucleophilic attack of silicon hydride from coordinating solvents. For example, Keinan et al. , J .; Org. Chem. 1987, 52, 4846-4851 (demonstrating catalytic deoxygenation of alcohols and ethers with iodotrimethylsilane, carbonyl conjugate addition reaction, and α-alkoxymethylation of ketones). That is, since the final product can react with the solvent, great care must be taken in selecting an appropriate solvent when using a solvent. This can cause product degradation and side reactions. This also limits the selection of suitable solvents for synthesis.

The Finkelstein-type S _N 2 reaction typically relies on the respective solubility and insolubility of the reagents and salt by-products to serve as the driving force for the reaction. For example, iodotrimethylsilane (TMS-I) can be synthesized by reaction of chlorotrimethylsilane with an alkali metal iodide salt (see Reaction Scheme 4 above) in a suitable solvent such as chloroform or acetonitrile. In this specific example, chlorotrimethylsilane (TMS-Cl) and sodium iodide salt have some solubility in these solvents, but no by-product sodium chloride. Precipitation of sodium chloride as a by-product contributes to the driving force of the reaction.

Si _w H _x R _y I _z (eg, SiH ₂ I ₂ or Si ₂ HI ₅ ), N (SiH _a R _b I _c ) ₃ (eg, N (SiH ₃ ) ₂ (SiH ₂ I)), or ( _{SiH m R n I o) 2} -CH 2 ( _{e.g., (SiH 2 I) -CH 2} - synthesis of _(SiH 3)), since the reactivity of the SiH bond, halogen exchange (scrambling) and side reactions Can result. Coordinating solvents can make such halogen recombination and side reactions serious. The reaction between dichlorosilane (DCS) and lithium iodide produces diiodosilane in the absence of solvent at ambient temperature (see Example 3 below). Non-coordinating solvents (for example, n-pentane and chloroform) are useful when filtering the by-product lithium chloride salt. Non-coordinating solvents can also facilitate the reaction through improved mixing (ie, dilution of the reaction product) and suppression of side reactions (heat exchange medium). Suitable non-coordinating solvents include hydrocarbons (pentane, hexane, cyclohexane, heptane, octane, benzene, toluene, etc.) and chlorinated aliphatic hydrocarbons (chloromethane, dichloromethane, chloroform, carbon tetrachloride, etc.), Examples include acetonitrile. However, the use of chlorinated solvents is a less attractive option because chlorinated solvents are usually strictly regulated (permissions are required) and may be carcinogenic. The solvent should be selected to have a sufficient boiling point difference with the desired product, and such boiling point difference is typically> 20 ° C, preferably> 40 ° C.

Typical Si—H containing iodosilane reaction products include, but are not limited to:
SiH _x I _4-x such as SiHI ₃ , SiH ₂ I ₂ , or SiH ₃ I, where x = 1-3;
_{· MeSiHI 2, MeSiH 2 I,} Me 2 SiHI, EtSiHI 2, EtSiH 2 I, Et 2 SiHI, ClSiHI 2, ClSiH 2 I, Cl 2 SiHI, BrSiHI 2, BrSiH 2 I, Brl 2 SiHI, H 3 SiSiHI 2, H ₃ SiSiH ₂ I, (H ₃ Si) ₂ SiHI, H ₃ GeSiHI ₂ , H ₃ GeSiH ₂ I, (H ₃ Ge) ₂ SiHI, Me ₃ SiSiHI ₂ , Me ₃ SiSiH ₂ I, (Me ₃ Si) ₂ SiHI, Me ₃ GeSiHI ₂ , Me ₃ GeSiH ₂ I, (Me ₃ Ge) ₂ SiHI, Me ₂ HSiSiHI ₂ , Me ₂ HSiSiH ₂ I, (Me ₂ HSi) ₂ SiHI, Me ₂ HGeSiH ₂ , Me ₂ HGeSiH ₂ , (Me ₂ HGe) ₂ SiH _x R _y I _4- xy, such as SiHI (wherein x = 1 to 2, y = 1 to 2, x + y is 3 or less, and each R is independently C1 to C2 C12 hydrocarbyl groups, Cl, Br, or ER′3 groups, where each E is independently Si or Ge, and each R ′ is independently H or a C1-C12 hydrocarbyl group);
Si ₂ H _x-6 I _x such as Si ₂ HI ₅ , Si ₂ H ₂ I ₄ , Si ₂ H ₃ I ₃ , Si ₂ H ₄ I ₂ , or Si ₂ H ₅ I where x = 1 X is preferably 5 (ie, Si ₂ HI ₅ );
MeSi ₂ HI ₄ , MeSi ₂ H ₂ I ₃ , MeSi ₂ H ₃ I ₂ , MeSi ₂ H ₄ I, Me ₂ Si ₂ HI ₃ , Me ₂ Si ₂ H ₂ I ₂ , Me ₂ Si ₂ H ₃ I, Me ₃ Si ₂ HI ₂ , Me ₃ Si ₂ H ₂ I, Me ₄ Si ₂ HI, EtSi ₂ HI ₄ , EtSi ₂ H ₂ I ₃ , EtSi ₂ H ₃ I ₂ , EtSi ₂ H ₄ I, Et ₂ Si ₂ HI ₃ , Et ₂ Si ₂ H ₂ I ₂ , Et ₂ Si ₂ H ₃ I, Et ₃ Si ₂ HI ₂ , Et ₃ Si ₂ H ₂ I, Et ₄ Si ₂ HI, ClSi ₂ HI ₄ , ClSi ₂ H ₂ I ₃ , ClSi ₂ H ₃ I ₂ , ClSi ₂ H ₄ I, Cl ₂ Si ₂ HI ₃ , Cl ₂ Si ₂ H ₂ I ₂ , Cl ₂ Si ₂ H ₃ I, Cl ₃ Si ₂ HI ₂ , Cl ₃ S i ₂ H ₂ I, Cl ₄ Si ₂ HI, BrSi ₂ HI ₄ , BrSi ₂ H ₂ I ₃ , BrSi ₂ H ₃ I ₂ , BrSi ₂ H ₄ I, Br ₂ Si ₂ HI ₃ , Br ₂ Si ₂ H ₂ I ₂ , Br ₂ Si ₂ H ₃ I, Br ₃ Si ₂ HI ₂ , Br ₃ Si ₂ H ₂ I, Br ₄ Si ₂ HI, H ₃ SiSi ₂ HI ₄ , H ₃ SiSi ₂ H ₂ I ₃ , H ₃ SiSi ₂ H ₃ I ₂ , H ₃ SiSi ₂ H ₄ I, (H ₃ Si) ₂ Si ₂ HI ₃ , (H ₃ Si) ₂ Si ₂ H ₂ I ₂ , (H ₃ Si) ₂ Si ₂ H ₃ I , (H ₃ Si) ₃ Si ₂ HI ₂ , (H ₃ Si) ₃ Si ₂ H ₂ I, (H ₃ Si) ₄ Si ₂ HI, H ₃ GeSi ₂ HI ₄ , H ₃ GeSi ₂ H ₂ I ₃ , H ₃ GeSi ₂ H ₃ I ₂ , H ₃ GeSi ₂ H ₄ I, (H ₃ Ge) ₂ Si ₂ HI ₃ , (H ₃ Ge) ₂ Si ₂ H ₂ I ₂ , (H ₃ Ge) ₂ Si ₂ H ₃ I, (H ₃ Ge) ₃ Si ₂ HI ₂ , (H ₃ Ge) ₃ Si ₂ H ₂ I, (H ₃ Ge) ₄ Si ₂ HI, Me ₃ SiSi ₂ HI ₄ , Me ₃ SiSi ₂ H ₂ I ₃ , Me ₃ SiSi ₂ H ₃ I ₂ , Me ₃ SiSi ₂ H ₄ I, (Me ₃ Si) ₂ Si ₂ HI ₃ , (Me ₃ Si) ₂ Si ₂ H ₂ I ₂ , (Me ₃ Si) ₂ Si ₂ H ₃ I, (Me ₃ Si) ₃ Si ₂ HI ₂ , (Me ₃ Si) ₃ Si ₂ H ₂ I, (Me ₃ Si) ₄ Si ₂ HI, Me ₃ GeSi ₂ HI ₄ , Me ₃ GeSi ₂ H ₂ I ₃ , Me ₃ GeSi ₂ H ₃ I _{2, Me} 3 GeSi ₂ H _{I, (Me 3 Ge) 2} Si 2 HI 3, (Me 3 Ge) 2 Si 2 H 2 I 2, (Me 3 Ge) 2 Si 2 H 3 I, (Me 3 Ge) 3 Si 2 HI 2, ( Me ₃ Ge) ₃ Si ₂ H ₂ I, (Me ₃ Ge) ₄ Si ₂ HI, Me ₂ HSiSi ₂ HI ₄ , Me ₂ HSiSi ₂ H ₂ I ₃ , Me ₂ HSiSi ₂ H ₃ I ₂ , Me ₂ HSiSi ₂ H ₄ I, (Me ₂ HSi) ₂ Si ₂ HI ₃ , (Me ₂ HSi) ₂ Si ₂ H ₂ I ₂ , (Me ₂ HSi) ₂ Si ₂ H ₃ I, (Me ₂ HSi) ₃ Si ₂ HI _{2 , (Me 2 HSi) 3 Si} 2 H 2 I, (Me 2 HSi) 4 Si 2 HI, Me 2 HGeSi 2 HI 4, Me 2 HGeSi 2 H 2 I 3, Me 2 HGeSi 2 H 3 I 2, _{e 2 HGeSi 2 H 4 I,} (Me 2 HGe) 2 Si 2 HI 3, (Me 2 HGe) 2 Si 2 H 2 I 2, (Me 2 HGe) 2 Si 2 H 3 I, (Me 2 HGe) 3 _{Si 2 HI 2, (Me 2} HGe) 3 Si 2 H 2 I, (Me 2 HGe) 4 Si 2 Si 2 H such or HI _{x R y I 6-x-} y ( where, x = 1 to 4 Y = 1-4, x + y is 5 or less, and each R is independently a C1-C12 hydrocarbyl group, Cl, Br, or ER′3 group, where each E is independently Si or Ge, and each R ′ is independently H or a C1-C12 hydrocarbyl group);
_{· Si 3 H 7 I, Si} 3 H 6 I 2, Si 3 H 5 I 3, Si 3 H 4 I 4, Si 3 H 3 I 5, Si 3 H 2 I 6, Si 3 HI 7 Si 3 such as H _x-8 I _{x where} x = 1-7;
N (SiH ₃ ) ₂ (SiH ₂ I), N (SiH ₃ ) ₂ (SiHI ₂ ), N (SiH ₃ ) (SiH ₂ I) ₂ , N (SiH ₃ ) (SiHI ₂ ) ₂ , N (SiHI) ₂ ) N (SiH _x I _y ) ₃ such as ₂ (SiH ₂ I), N (SiHI ₂ ) (SiH ₂ I) ₂ , N (SiH ₂ I) ₃ , or N (SiHI ₂ ) ₃ Each x is independently 0-3, and each y is independently 0-3, provided that at least one x and at least one y are 1);
N (SiH ₃ ) ₂ (SiMeHI), N (SiH ₂ Me) ₂ (SiMeHI), N (SiHMe ₂ ) ₂ (SiMeHI), N (SiMe ₂ H) ₂ (SiH ₂ I), N (SiMe ₃ ) ₂ (SiH ₂ I), N (SiMe ₂ H) ₂ (SiHI ₂ ), N (SiMe ₃ ) ₂ (SiHI ₂ ), etc. N (SiH _x R _y I _z ) ₃ (wherein each x is independent 0 to 3, each y is independently 0 to 3, each z is independently 0 to 3, x + y + z = 3, and each R is independently a C1 to C12 hydrocarbyl group, Cl, Br, or ER′3 group, wherein each E is independently Si or Ge, and each R ′ is independently H or a C1-C12 hydrocarbyl group, but (a) at least one x , At least one y, and at least one Z is 1 and (b) provided that at least one Si is bonded to both H and I); or (SiH ₂ I) ₂ —CH ₂ , (SiHI _{2) 2 -CH 2, (SiH} 2 I) -CH 2 - , such as _{(SiHI 2) - (SiH 3} ), (SiHI 2) -CH 2 - (SiH 3), or _{(SiH 2 I)} -CH ₂ (SiH _x I _y ) ₂ CH ₂ , wherein each x is independently 0-3, and each y is independently 0-0, provided that at least one x and at least one y are 1. 3);
~ Can be mentioned.

Si-H containing iodosilanes are synthesized by reacting the corresponding halosilane with an alkali metal halide as shown:
_{Si w H x R y X z} + nMI → Si w H x R y I z + nMX (6)
N (SiH _a R _b X _c ) ₃ + nMI → N (SiH _a R _b I _c ) ₃ + nMX (7)
_{(SiH m R p X o)} 2 -CH 2 + nMI → (SiH m R p I o) 2 -CH 2 + nMX (8)
(W = 1-3, x = 1-2w + 1, y = 0-2w + 1, z = 1-2w + 1, x + y + z = 2w + 2, each a is independently 0-3 Each b is independently 0-3, each c is independently 0-3, a + b + c = 3, provided that at least one a and at least one c are 1, and each m Is independently 0-3, each p is independently 0-3, each o is independently 0-3, and at least one m and at least one o is 1, m + n + o = 3, n = 1-4, X = Br or Cl, M = Li, Na, K, Rb, or Cs, preferably Li, and each R is independently a C1-C12 hydrocarbyl. Group, Cl, Br, or ER′3 group, where each E is independently Si or Ge and each R ′ is independently H or a C1-C12 hydrocarbyl group). Alkali metal salts (ie, MI) may be used in excess or deficiency, depending on the desired degree of halogen exchange. However, excess MI will favor complete replacement of the halide on the halosilane with iodide and will reduce the amount of chlorine or bromine impurities contained in the reaction product. Those skilled in the art will know the reaction stoichiometry for making partially iodinated molecules such as SiH ₂ ICl, SiHClI ₂ , Si ₂ HCl ₄ I, SiH ₂ IBr, SiHBrI ₂ , Si ₂ HBr ₄ I, etc. Will adjust.

As mentioned above, the salt driven reaction determines which reagent should be used. However, unlike the prior art Finkelstein reaction, lithium iodide and lithium chloride show little or no solubility in hydrocarbons or fluorocarbons. For example, aliphatic, aromatic, or reaction of SiCl ₂ H ₂ and 2 moles of lithium iodide in a chlorinated hydrocarbon, the main product and the salt by-product SiI ₂ H ₂ and 2 moles, respectively Lithium chloride will be formed. During this reaction, both LiI and LiCl remain solid. Li and Cl form a hard acid / base pair, while LiI has a hard / soft acid / base mismatch. As a result, Applicants believe that the formation of insoluble LiCl can provide the driving force for the reaction. However, the generation of SiH ₂ I ₂ itself can partially solubilize LiI and help drive the reaction. As a result, it may be beneficial to add the desired product, Si—H containing iodosilane, to the original reaction mixture.
SiH ₂ Cl ₂ (g or l) + 2LiI (s) → SiH ₂ I ₂ (l) + 2LiCl (s) (9)
Here, g is a gas, l is a liquid, and s is a solid. In some cases for the synthesis of halogen exchange products, other alkali metal salts such as sodium iodide (NaI) are useful. However, NaI is less reactive than lithium iodide in an equivalent solvent and typically requires a coordinating solvent to proceed with any reaction at an industrially suitable reaction rate. I will. However, the coordinating solvent is selected to minimize adverse effects on product synthesis and / or yield.

In another example, the reaction of Si ₂ Cl ₅ H with 5 moles of sodium iodide in a chlorinated hydrocarbon such as chloroform is performed using Si ₂ I ₅ H and 5 moles as the main product and salt by-product, respectively. Of sodium chloride. The production of NaCl is the driving force for the reaction.
Si ₂ HCl ₅ (l) + 5NaI (s) → Si ₂ HI ₅ (l) + 5NaCl (s) (10)
One skilled in the art will recognize that the use of less reactive NaI or another alkali metal halide and / or another solvent may be required for competition between Si-Si bond cleavage and halogen exchange. . Product yield could be further maximized by optimizing the reaction parameters, such as removing all salt by-products as the reaction proceeds to further prevent halogen exchange and side reactions.

  The examples below demonstrate synthetic methods of the present disclosure using inorganic halosilane reactants, but those skilled in the art will recognize that organic Si-R groups are less reactive than Si-X and Si-H, It will be appreciated that the synthetic methods of the present disclosure are likely to remain unaffected.

Halosilane and alkali metal halide reactants are commercially available. Alternatively, the halosilane reactant may be a corresponding fully halogenated silane (ie, Si _x R _y X _{2x + 2-y} , N (SiR _b X _3-b ) ₃ , or (SiR _n X _3-n ) ₂ −. CH ₂ ) can be synthesized by reduction with a standard reducing agent (lithium aluminum hydride (eg, LiAlH ₄ ), NaBH ₄ etc.). In another alternative, the halosilane reactant can be obtained from Morrison et al. , J .; Organomet. Chem. , 92, 2, 1975, 163 to 168, the corresponding silane in toluene at a temperature in the range of 0 ° C. to reflux for 1 to 12 hours [ie, Si _x R _y H _{2x + 2-y} , N (SiH _a R _{3 -a) 3,} or _{(SiH m R 3-m)} 2 -CH 2] with a halogenating agent (N- chloro - bromo, or - can be synthesized by reacting such succinimide) of iodine . The form of the reactant is not critical (ie, solid, liquid, or gas), but one skilled in the art will give more reaction sites for reactants with a larger surface area, resulting in more efficient You will recognize that a good response is obtained. For example, typically finer particle powders provide more reactive sites than solid beads or lumps.

The water content of the reactants and all solvents should be minimized to prevent the formation of the by-product siloxane (ie, Si—O—Si). Preferably, the moisture content ranges from about 0% w / w to about 0.001% w / w (10 ppmw). If necessary, the reaction is prepared by refluxing over P ₂ O ₅ , treatment with molecular sieves, or heating under vacuum (eg, anhydrous LiI is calcined at 325 ° C. for more than 8 hours under vacuum. Can be dried prior to synthesis using standard techniques.

The reaction vessel is made of a material that is compatible with the reactants and products, is covered with such material, or is processed into such material. Typical materials include passivated stainless steel, glass, perfluoroalkoxyalkane (PFA), and polytetrafluoroethylene (PTFE). The container may be covered with a jacket or placed in a heating or cooling bath. The reaction vessel may include a stirring mechanism made of a compatible material, such as a glass stirring shaft, a PTFE paddle stirrer, and / or a stainless steel impeller coated with PTFE. The reaction vessel may also include a plurality of “injection ports”, pressure gauges, and diaphragm valves. The reaction vessel is designed to perform the synthesis under an inert atmosphere such as N ₂ or a noble gas. Precautions may be taken to minimize exposure of the reactants and reaction mixture to light, such as covering all transparent glassware with tin foil. For the synthesis of SiH ₂ I ₂ , glass products that are amber colored are not suitable because the iron oxide coating can contaminate the product. Also, the reaction vessel, agitation mechanism, and any other associated equipment (such as a Schlenk line or glove box) can be used to air and standard air using standard drying techniques such as vacuum, inert gas flow, oven drying, etc. It is necessary not to have moisture.

As described above with respect to the reactants and as shown in the examples below, the reaction vessel and any and all components that come into contact with the reactants and products should have a high purity. A high purity reaction vessel is typically a vessel that is compatible with the Si—H containing iodosilane and does not contain impurities that can react with or contaminate the Si—H containing iodosilane. A typical example of such a high purity container is a stainless steel canister with low surface roughness and mirror finish. Low surface roughness and mirror finish are typically obtained by mechanical polishing and optionally additional electropolishing. High purity typically uses (a) a washing step with dilute acid (HF, HNO ₃ ), followed by (b) high purity deionized water to ensure complete removal of trace amounts of acid. Obtained by a process including rinsing and subsequent (c) drying of the container. Deionized water (DIW) rinses are typically performed until the resistivity of the rinse water reaches 100 μS / cm, preferably less than 25 μS / cm. The drying step includes a purge step using an inert gas such as He, N ₂ , Ar (preferably N ₂ or Ar), a vacuum step for promoting degassing from the surface by reducing the pressure in the container, It may include heating the container, or any combination thereof.

The gas used for the purge is semiconducting grade, i.e. free of contaminants such as traces of moisture and oxygen (<1 ppm, preferably <10 ppb) and particles (<5 particles per liter @ 0.5 μm) It needs to be a thing. The drying process may include another purging procedure in which a constant gas flow flows through the vessel, and a vacuuming process. Alternatively, the drying step may be performed by constantly flowing a purge gas while maintaining the inside of the container at a low pressure. The efficiency and endpoint of canister drying can be assessed by measuring trace H ₂ O levels in the gas exiting the vessel. With an inflow gas having less than 10 ppb H ₂ O, the effluent gas has a moisture content in the range of about 0 ppm to about 10 ppm, preferably in the range of about 0 ppm to about 1 ppm, more preferably in the range of about 0 ppb to about 200 ppb. It should be. It is known that heating the vessel during the purge and vacuum steps accelerates drying, and the vessel is typically maintained at a temperature in the range of about 40 ° C to about 150 ° C.

After washing and drying, the container of such a high purity, less than 1E-6std ^cm 3 / s, preferably should have a total amount of leakage of ^{<1E-8std cm 3 / s} .

  Optionally, the container may have an internal coating or plating to further reduce the risk of corrosion of the container or to further improve the stability of the product in the container. Exemplary coatings include those shown by Silcotek (https://www.silcotek.com) or those disclosed in US Patent Application Publication No. 2016/046408. The vessel may be passivated by exposure to a silylating agent such as silane, disilane, monochlorosilane, hexamethyldisilazane before the reaction and / or before the Si—H containing iodosilane is introduced.

  Those skilled in the art will recognize suppliers for system components that are used to perform the disclosed methods. Some customization of the components may be required based on the desired temperature range, pressure range, local regulations, and the like. Exemplary equipment suppliers include Buchi Glass Uster AG, Shandong Chemsta Machinery Manufacturing Co. Ltd .. , Jiangsu Shajiabang Chemical Equipment Co., Ltd. Ltd. and the like. As explained above, the component is preferably made from a corrosion-resistant material such as glass, steel that is internally coated with glass, or steel with a corrosion-resistant liner.

  An alkali metal halide is placed in a high purity reactor free of air and moisture. An optional solvent that does not decompose or react with the final product before or after addition of the alkali metal halide may be added as a heat exchange medium and / or as a mixing aid and / or product extraction. Typical solvents include C3-C20 alkanes such as propane, butane, pentane, etc., or chlorinated hydrocarbons such as chloromethane, dichloromethane, chloroform, carbon tetrachloride, etc., and mixtures thereof. As described above, the target Si—H containing iodosilane may be used as a solvent. The alkali metal halide salt can be dissolved in the solvent. However, depending on the reactants, the solubility of the salt may not be an important factor. For example, as shown in Example 5 below, lithium iodide in pentane reacts with dichlorosilane in a solid-liquid reaction. The reaction mixture may be stirred to facilitate contact between the reactants. Alternatively, as shown in Example 3 below, the reaction may proceed without a solvent.

  The halosilane may be added to the reactor as a gas, as a liquid (condensation), or in solution, through the headspace, or by subsurface addition. The halosilane may be in gaseous form and may be added to the headspace above the lithium iodide / solvent mixture. Alternatively, the gaseous form of the halosilane may be condensed using a condenser and added directly to the lithium iodide / solvent mixture. In another alternative, halosilane in liquid form may be added from the top of the reactor using a conduit plumbed to the reactor. In another alternative, the gaseous or liquid form may be added below the surface of the iodine / solvent mixture using a reactor with a dip tube plugged inside the salt / solvent mixture. Good. In the examples below, dichlorosilane condensation was performed to facilitate transfer of reagents more rapidly.

Depending on the product distribution required, the halosilane may be added in excess, in stoichiometric amounts, or in sub-stoichiometric amounts. An excess of halosilane relative to the metal iodide salt results in partial substitution of the halide with iodine on the halosilane, wherein the compound of formula Si _w H _x R _y I _z where at least one R is Cl or Will be possible). Excess metal iodide salt will favor the complete substitution of iodide on the halosilane (ie, the absence of R = Cl or Br).

  Alternatively, the halosilane may be added into the reactor prior to the addition of the alkali metal halide. The mechanism of addition of the halosilane and alkali metal halide described above remains the same regardless of whether the reactants are added to the reactor first or second.

  The halosilane / alkali metal halide mixture may be agitated to facilitate contact between the reactants. The reaction may be exothermic. In the examples below, the reaction mixture is stirred for a time sufficient to complete the reaction at ambient temperature (ie, about 20 ° C. to about 26 ° C.). In the examples below, heating was not required, but it could be an option to accelerate the reaction. One skilled in the art can determine the most appropriate temperature range depending on the individual kinetics of each halosilane. For example, halosilanes with partial hydrocarbyl substitution may require higher reaction temperatures than halosilanes without hydrocarbyl substituents due to steric hindrance caused by hydrocarbyl groups.

The progress of the reaction can be followed using, for example, gas chromatography or in-situ probes (such as FTIR or RAMAN probes), which are commercially available. For stoichiometric excess of a metal iodide salt, the major reaction product is _{Si w H x R y I z} + nMX, and a small amount of _{Si w H x R y X z} , and MI, and a solvent, the intermediate reaction The product Si _w H _x R _y (IX) _z (including both z and I). For example, a reaction mixture of SiH ₂ I ₂ may include a reaction product SiH ₂ I ₂ , a reaction by-product LiCl, a small amount of residual SiCl ₂ H ₂ and / or reactant LiI, a solvent, and an intermediate reaction product. ClSiH ₂ I may be included.

  The stirred mixture may be filtered to remove any solid impurities and by-product salts. Typical filters include glass frit filters or polymer frit filters.

  Alternatively, if the salt by-product dissolves in the solvent, the stirred mixture may be filtered to remove the solid by-product prior to further processing. Filtering agents such as anhydrous diatomaceous earth may be used to improve the process. Typical filters include glass frit filters or polymer frit filters.

  In some cases, additional processing of the filtrate may be necessary. For example, if the filtrate yields a heterogeneous suspension of solid material, to obtain Si-H containing iodosilane by a flash distillation process that removes some or all unwanted reaction by-products or impurities, It may then be distilled through a short pass column. Alternatively, the Si-H containing iodosilane, the reaction product, may be isolated from the filtrate by a distillation column or by heating the filtrate to about the boiling point of the non-organic silicon hydride, the reaction product. In another alternative, both a flash step and a distillation column may be required. One skilled in the art will recognize that the boiling point of the warmed stirred mixture changes as the reaction product, Si-H containing iodosilane, is isolated from the warmed stirred mixture and adjusts the recovery temperature accordingly. I will. Because of the large mass of iodine relative to Br or Cl, all unreacted halosilanes tend to be more volatile than the resulting product and can be evacuated through a distillation column. One skilled in the art will recognize that the exhausted halosilane can be recovered for later use or exhaust.

  The disclosed method can convert from about 40% mol / mol to about 99% mol / mol halosilane into the reaction product, Si—H containing iodosilane. The isolated reaction product, Si—H containing iodosilane, typically has a purity in the range of about 50% mol / mol to about 99% mol / mol.

  The reaction product, Si—H containing iodosilane, may be further purified by distillation, sublimation, or recrystallization. Suitable distillation methods include atmospheric fractional distillation, or batch fractional distillation, or vacuum fractional distillation. Batch fractional distillation may be performed at low temperature and low pressure. Alternatively, the reaction product, Si—H containing iodosilane, is separated by two distillations in order to separate the reaction product, Si—H containing iodosilane, from both low and high boiling impurities. It may be purified by continuous distillation through a column. The purified Si-H-containing iodosilane, which is a reaction product, can be used as a composition for forming a Si-containing film.

  The composition for forming a Si-containing film is about 97% mol / mol to about 100% mol / mol, preferably about 99% mol / mol to about 100% mol / mol, more preferably about 99.5% mol / mol. Having a purity in the range of about 100% mol / mol, more preferably about 99.97% mol / mol to about 100% mol / mol. The composition for forming a Si-containing film preferably has a metal contaminant (e.g., at least Ag, Al, Ca, Cr, Cu, Fe, Mg, Mo, Ni, K) between the detection limit and 100 ppbw. , Na, Sb, Ti, Zn, etc.). The concentration of X (where X = Cl, Br, or I) in the Si-containing film forming composition may range from about 0 ppmw to about 100 ppmw, more preferably from about 0 ppmw to about 10 ppmw. .

As shown in the examples below, the purified product can be analyzed by gas chromatography mass spectrometry (GCMS). The structure of the product can be confirmed by ¹ H, ¹³ C, and / or ²⁹ Si NMR.

  As detailed above and in the examples below, the Si-containing film-forming composition must be stored in a clean dry storage container that does not react with it to maintain its purity. .

  FIG. 1 is an exemplary system suitable for performing the method of the present disclosure. Air can be removed from various parts of the system (eg, reactor 1, vessel 8, boiler 6) by an inert gas 9 such as nitrogen or argon. The inert gas 9 can also function for pressurization of the solvent 11 that allows the transfer of the solvent 11 to the reactor 1. Nitrogen, cold ethanol, acetone / dry ice mixture, or heat transfer agent (such as monoethylene glycol (MEG)) is used to cool various parts of the system (eg, reactor 1, distillation column 27, condenser 57). May be used.

  Reactor 1 can be maintained at the desired temperature by jacket 2. The jacket 2 has an inlet 21 and an outlet 22. The inlet 21 and outlet 22 may be connected to a heat exchanger / cooling device 23 and / or a pump (not shown) to obtain recirculation of cooling of the fluid. Alternatively, if the batch size is small enough and the mixing time is short enough, the jacket 2 may not require the inlet 21 and outlet 22 since the hot fluid may be cold enough for the duration of the reaction. In another alternative, as mentioned above, jacketed temperature control may not be required and these four components are removed from the system (ie 2, 21, 22, and 23). .

  Reactants (a solvent such as pentane stored in vessel 11 and a halosilane such as ethyldichlorosilane stored in vessel 24) are added to reactor 1 via lines 14 and 25, respectively. The solvent and halosilane may be added to the reactor 1 by a liquid metering pump (not shown) such as a diaphragm pump, peristaltic pump, or syringe pump. Alkali metal halides such as LiI stored in the container 13 may be added to the reactor 1 by natural flow or suspended in a solvent compatible with Si-H-containing iodosilane which is a reaction product. May then be introduced into the reactor in the same manner as the solvent and halosilane (ie, via line 16). The reactants can be mixed in the reactor by an impeller 17a rotated by a motor 17b to form a mixture 26. Preferably, the mixing is performed under an inert atmosphere at about atmospheric pressure. A temperature sensor (not shown) may be used to monitor the temperature of the reactor 1 contents.

After the addition is complete, the progress of the reaction can be followed using, for example, gas chromatography. After the reaction is complete, the mixture 26 can be removed from the reactor 1 through the filter 3 and into the vessel 4 by means of a drain 19. The main reaction products are ethyldiiodosilane (EtSiHI ₂ ), which is liquid at standard temperature and pressure, and LiCl, which is solid at standard temperature and pressure, with trace amounts of impurities, LiI and EtSiICH. In this embodiment, the reactor 1 would most likely be located above the filter 3 in order to take full advantage of gravity. For example, since MX reaction by-products (X = Cl, Br) such as LiCl (not shown) are suspended in the mixture 26, clogging of the reactor 1 does not become a problem.

  The filtered stirred mixture (filtrate) (not shown) may be collected in a container (not shown) and carried to a new location before the next processing step is performed. Alternatively, the filtrate may be immediately transferred to the still pot 4 in order to isolate the reaction product from the filtrate using the heater 28. The filtrate is warmed by the heater 28. The volatile solvent is pushed out from the distillation column 27 and the outlet 43 by heating. The isolated reaction product is then collected in the container 8.

  Again, the container 8 may be moved to a new location before the next processing step is performed. The isolated reaction product may be transferred from the vessel 8 to the boiler 6 for further purification, if necessary. The boiler 6 is heated by the heater 29. The isolated reaction product is purified by fractional distillation using distillation column 53, condenser 57, and reflux distributor 54. The purified reaction product is collected in the recovery tank 7. The collection tank 7 includes an exhaust port 60.

  FIG. 2 is another exemplary system suitable for performing the method of the present disclosure. In this alternative, the reactor 1 also functions as the still pot 4 of FIG. This embodiment may be useful for the synthesis of large batches of Si-H containing iodosilanes. After thorough mixing, the cooling medium (not shown) in the jacket 2 is replaced by a heating medium (not shown). One skilled in the art will recognize that “replacement” of the cooling medium is not necessary if the cooling medium can also function as both a heating medium and a cooling medium (eg, MEG). Instead, the temperature of the medium can be changed, for example, by the heat exchanger 23.

  The volatile solvent can be separated from the mixture 26 through the distillation column 27 and the exhaust port 43. Thereafter, the Si—H-containing iodosilane is recovered in the container 8. The remaining solvent / salt mixture can be removed from the reactor 1 by drain 19 while recovering the salt on the filter 3. Again, the container 8 may be moved to a new location before the next processing step is performed. The Si—H containing iodosilane may be transferred from the vessel 8 to the boiler 6 for further purification as required. The boiler 6 is heated by the heater 29. The Si—H containing iodosilane is purified by fractional distillation using a distillation column 53, a condenser 57, and a reflux distributor 54. The purified Si—H containing iodosilane is collected in the recovery tank 7. The collection tank 7 includes an exhaust port 60.

  The reaction supplies halosilanes, optionally diluted with a solvent, with metal iodides, optionally suspended in the solvent, and passes them through the reactor through a controlled residence time and temperature. In some cases, it may be carried out in a continuous reactor. The flow of each reagent may be controlled by a metering pump such as a peristaltic pump. The reaction mixture can then be collected in a receiving vessel and separated as in the batch synthesis example above. Alternatively, the solid fraction may be removed in the line using, for example, a centrifugal pump (commercially available). The product can also be separated from the solvent (s) by continuously feeding the filtered fraction to a continuous distillation unit.

The advantages of the synthetic method of the present disclosure are as follows:
A catalyst-free process that helps reduce cost, contamination, and product isolation problems;
Most of the side reactions associated with prior art reactions using iodine, a reactant that produces lower and higher order iodosilanes as impurities, are essentially eliminated;
Does not produce HX intermediate reaction products that can contribute to side reactions and increased impurity profiles, and the resulting products do not require prior art Ag, Cu, or Sb stabilizers;
Many starting materials are not expensive and are readily available;
A one-step one-pot reaction;
The method may be solvent-free;
Simple purification;
A small reaction exotherm;
Can be performed at ambient temperature (ie, about 20 ° C. to about 26 ° C.); and • Waste generation is minimal and environmentally friendly.

All of the above are advantageous from the perspective of developing scalable industrial processes. Furthermore, the resulting product is more stable than products produced using the X ₂ or HX-based reactants. As a result, a purity level suitable for the semiconductor industry of the reaction product is maintained without using stabilizers such as Cu that can adversely affect the electrical properties of the deposited film.

  A method of using the composition for forming a Si-containing film of the present disclosure for the vapor deposition method is also disclosed. The disclosed method provides for the use of a Si-containing film forming composition for the deposition of silicon-containing films. The disclosed method may be useful in the manufacture of semiconductors, solar cells, LCD-TFT, or flat panel type devices. The method includes introducing a vapor of the Si-containing film-forming composition of the present disclosure into a reactor in which a substrate is disposed, and depositing at least a portion of the Si—H-containing iodosilane of the present disclosure by a deposition method. Depositing on the substrate to form a Si-containing layer.

The method of the present disclosure includes the formation of a bimetal-containing layer on a substrate using vapor deposition, more specifically, a SiMO _x or SiMN _x film (wherein x may be 0-4, M is Ta, Also provided is the formation for deposition of Nb, V, Hf, Zr, Ti, Al, B, C, P, As, Ge, lanthanoids (such as Er), or combinations thereof.

  The method of forming a silicon-containing layer on a substrate of the present disclosure may be useful in the manufacture of semiconductors, solar cells, LCD-TFT, or flat panel type devices. The Si—H containing iodosilane of the present disclosure can deposit a Si containing film using any vapor deposition method known in the art. Examples of suitable vapor deposition methods include chemical vapor deposition (CVD) or atomic layer deposition (ALD). Typical CVD methods include thermal CVD, plasma enhanced CVD (PECVD), pulsed CVD (PCVD), low pressure CVD (LPCVD), low pressure CVD (SACVD), or atmospheric pressure CVD (APCVD), flow CVD (f-CVD). ), Metal organic chemical vapor deposition (MOCVD), hot wire CVD (also known as HWCVD, cat-CVD, where the hot wire serves as an energy source for the deposition process), radical embedded CVD, and these Combinations are listed. Typical ALD methods include thermal ALD, plasma enhanced ALD (PEALD), spatial ALD, hot wire ALD (HWARD), radical incorporation ALD, and combinations thereof. Supercritical fluid deposition can also be used. The deposition method is preferably ALD, spatial ALD, or PE-ALD to obtain appropriate step coverage and film thickness control.

  The vapor of the Si-containing film forming composition is introduced into a reaction chamber containing a substrate. The temperature and pressure inside the reaction chamber and the temperature of the substrate are maintained at conditions suitable for depositing at least a portion of the Si—H containing iodosilane onto the substrate. That is, after introducing the vaporized composition into the chamber, the conditions in the chamber are such that at least a portion of the vaporized precursor is deposited on the substrate to form a silicon-containing film. Co-reactants can also be used to assist in the formation of the Si-containing layer.

  The reaction chamber may include, but is not limited to, a parallel plate reactor, a cold wall reactor, a hot wall reactor, a single wafer reactor, a multi-wafer reactor, or other such type of deposition system, etc. It can be any housing or chamber of the apparatus in which the deposition process is performed. All of these exemplary reaction chambers can function as ALD reaction chambers. The reaction chamber may be maintained at a pressure in the range of about 0.5 mTorr to about 760 Torr. Further, the temperature in the reaction chamber may range from about 20 ° C to about 700 ° C. One skilled in the art will recognize that the temperature can be optimized by simple experimentation to achieve the desired result.

  The temperature of the reactor can be controlled by controlling the temperature of the substrate holder or by controlling the temperature of the reactor wall. Apparatus used to heat the substrate is known in the art. The reactor wall is heated to a sufficient temperature to obtain a desired film of the desired physical state and composition at a sufficient growth rate. A non-limiting exemplary temperature range in which the reactor wall can be heated includes from about 20 ° C to about 700 ° C. If plasma deposition is utilized, the deposition temperature may range from about 20 ° C to about 550 ° C. Alternatively, if a thermal process is performed, the deposition temperature may range from about 300 ° C to about 700 ° C.

  Alternatively, the substrate may be heated to a sufficient temperature to obtain a desired silicon-containing film of the desired physical state and composition at a sufficient growth rate. A non-limiting typical temperature range in which the substrate can be heated includes 150 ° C. to 700 ° C. Preferably, the temperature of the substrate is maintained at 500 ° C. or lower.

The type of substrate on which the silicon-containing film is deposited will vary depending on the intended end use. A substrate is usually defined as the material on which processing is performed. The substrate may be any suitable substrate used in the manufacture of semiconductors, solar cells, flat panels, or LCD-TFT type devices. Examples of suitable substrates include wafers such as silicon, silica, glass, Ge, or GaAs wafers. The wafer may have one or more layers on which a material different from the previous manufacturing process is deposited. For example, the wafer may be a silicon layer (crystalline, amorphous, porous, etc.), a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a carbon-doped silicon oxide (SiCOH) layer, or a combination thereof May be included. In addition, the wafer may include a copper layer, a tungsten layer, or a metal layer (eg, platinum, palladium, nickel, rhodium, or gold). The wafer may include a barrier layer of manganese, manganese oxide, tantalum, tantalum nitride, or the like. The layer may be planar or patterned. In some embodiments, the substrate may be coated with a patterned photoresist film. In some embodiments, the substrate is a layer of oxide used as a dielectric in MIM, DRAM, or FeRam technology (eg, ZrO ₂ based material, HfO ₂ based material, TiO ₂ based material, rare earth oxide based). Materials, ternary oxide-based materials, etc.), or layers derived from nitride-based films (eg, TaN) used as electromigration barriers, as well as adhesive layers between copper and low-k layers Good. The disclosed method can deposit a silicon-containing layer directly on the wafer or directly on one or more layers on the top surface of the wafer (if the patterned layer forms a substrate). Further, those skilled in the art mean that the term “film” or “layer” as used herein refers to any material thickness that is superimposed on or spread over the surface, where the surface It will be appreciated that it may be a trench or a line. Throughout this specification and claims, a wafer and any associated layers thereon are referred to as a substrate. The actual substrate utilized may also depend on the particular precursor embodiment utilized. However, in many cases, the preferred substrate utilized will be selected from hydrogenated carbon, TiN, SRO, Ru, and Si-type substrates such as polysilicon or crystalline silicon substrates.

The substrate may be patterned to include vias or trenches having a high aspect ratio. For example, a conformal Si-containing film such as SiO ₂ is deposited using any ALD technique on a through silicon via (TSV) having an aspect ratio in the range of about 20: 1 to about 100: 1. Also good.

The Si-containing film forming composition may be supplied undiluted. Alternatively, the Si-containing film forming composition may further contain a solvent suitable for use in vapor deposition. The solvent can be selected in particular from C _{1 to} C ₁₆ saturated or unsaturated hydrocarbons.

For vapor deposition, the Si-containing film-forming composition is introduced into the reactor in the form of vapor by conventional means such as piping and / or flow meters. The vapor form is such that the carrier gas is blown into the liquid by vaporizing the composition for forming a Si-containing film in a conventional vaporization process such as direct liquid injection or direct vapor extraction in the absence of a carrier gas. By evaporating the vapor in the carrier gas without blowing into the liquid, or when the precursor is a solid at room temperature, such as that disclosed in Xu et al. WO 2009/087609 It can be generated by using a sublimation device. The composition for forming a Si-containing film may be supplied in a liquid state to a vaporizer (direct liquid introduction), and the composition is vaporized and mixed with a carrier gas, and then introduced into the reactor. Alternatively, the Si-containing film forming composition may be vaporized by passing a carrier gas through a container containing the composition or by blowing a carrier gas into the composition. The carrier gas, Ar, the He, or N _2, and mixtures thereof, without limitation. The carrier gas and composition are then introduced into the reactor as vapor.

  The Si-containing film-forming composition is placed in the reactor or deposition chamber by the Si-containing film-forming composition transfer device of FIGS. 3-5 showing three exemplary embodiments of the Si-containing film-forming composition transfer device. May be carried. As detailed above and as shown in the examples below, the transfer device must be clean and dry, and made of a material that the Si-H containing film forming composition does not react with. There must be.

  FIG. 3 is a side view of an embodiment of the Si-containing film forming composition reactant transfer apparatus 101. In FIG. 3, the Si-containing film forming composition 110 of the present disclosure is contained in a container 200 having two conduits, an inlet pipe 300 and an outlet pipe 400. Those skilled in the reactant art will recognize that the vessel 200, the inlet tube 300, and the outlet tube 400 are manufactured to prevent leakage of the Si-containing film-forming composition 110 in gaseous form even at high temperature and pressure. You will recognize.

  The outlet pipe 400 of the transfer device 101 is connected to a reactor (not shown) or other components between the transfer device and the reactor, such as a gas cabinet, through a valve 700 so that fluid can flow. The Preferably, vessel 200, inlet tube 300, valve 600, outlet tube 400, and valve 700 are made of passivated 316L EP, or 304 passivated stainless steel. However, those skilled in the art will recognize that other non-reactive materials may be used in the teachings herein.

  In FIG. 3, the end portion 800 of the inlet tube 300 is located above the surface of the Si-containing film forming composition 110, while the end portion 900 of the outlet tube 400 is formed on the surface of the Si-containing film forming composition 110. Located on the lower side. In this embodiment, the Si-containing film forming composition 110 is preferably in liquid form. An inert gas (including but not limited to nitrogen, argon, helium, and mixtures thereof) may be introduced into the inlet tube 300. The inert gas pressurizes the transfer device 200, and as a result, the liquid Si-containing film forming composition 110 is pushed out through the outlet pipe 400 into the reactor (not shown). In order to carry the vapor to the substrate on which the film is formed, the reactor is a liquid Si-containing film-forming composition 110 with or without the use of a carrier gas such as helium, argon, nitrogen, and mixtures thereof. A vaporizer may be included to convert the water into steam. Alternatively, the liquid Si-containing film forming composition 110 may be directly delivered to the wafer surface as a jet or aerosol.

  FIG. 4 is a side view of the second embodiment of the Si-containing film forming composition reactant transfer apparatus 101. In FIG. 4, the end portion 800 of the inlet tube 300 is located below the surface of the Si-containing film forming composition 110, while the end portion 900 of the outlet tube 400 is the surface of the Si-containing film forming composition 110. Is located above. FIG. 2 also includes an optional heating element 140 that can increase the temperature of the Si-containing film-forming composition 110. In this embodiment, the Si-containing film forming composition 110 may be in a solid form or a liquid form. An inert gas (including but not limited to nitrogen, argon, helium, and mixtures thereof) may be introduced into the inlet tube 300. The inert gas is blown into the Si-containing film-forming composition 110 and carries the mixture of the inert gas and the vaporized Si-containing film-forming composition 110 to the outlet pipe 400 and the reactor.

  3 and 4 include valves 600 and 700. One skilled in the art will recognize that valves 600 and 700 may be set in an open or closed position so that flow can pass through conduits 300 and 400, respectively. If the Si-containing film-forming composition 110 is in gaseous form, or if sufficient vapor pressure exists above the solid / liquid phase, the transfer device 101 of either of FIGS. 3 and 4 or any solid present or Simpler transfer devices having a single conduit terminating above the surface of the liquid may be used. In this case, the Si-containing film-forming composition 110 is carried in the form of steam through the conduit 300 or 400 by simply opening the valve 600 in FIG. 3 or the valve 7 in FIG. The transfer device 101 may be maintained at an appropriate temperature, for example by using an optional heating element 140, to provide sufficient vapor pressure to the Si-containing film forming composition 110 to be carried in the form of vapor. Good.

  3 and 4 disclose two embodiments of the Si-containing film-forming composition transfer apparatus 101, those skilled in the art will recognize that the inlet tube 300 and the outlet tube 400 will not depart from the disclosure herein. Will be recognized both above or below the surface of the Si-containing film-forming composition 110. Further, the inlet pipe 300 may be a filling port.

  The vapor in solid form of the Si-containing film forming composition may be conveyed to the reactor using a sublimation apparatus. FIG. 5 shows an embodiment of a typical sublimation apparatus 100. The sublimation apparatus 100 includes a container 33. The container 33 is not limited, but may be a cylindrical container or an arbitrary shape. Container 33 is comprised of materials such as, but not limited to, passivated stainless steel, aluminum oxide, glass, and other chemically compatible materials. In some cases, but not limited to, the container 33 is composed of another metal or metal alloy. In some cases, the container 33 has an inner diameter of about 8 centimeters to about 55 centimeters, or an inner diameter of about 8 centimeters to about 30 centimeters. As will be appreciated by those skilled in the art, other structures may have various dimensions.

  The container 33 includes a sealable upper portion 15, a sealing member 18, and a gasket 20. The sealable top 15 is configured to seal the container 33 from the external environment. The sealable top 15 is configured to allow access to the container 33. Furthermore, the sealable top 15 is configured such that a conduit passes through the container 33. Furthermore, the sealable top 15 is configured to allow fluid to flow into the container 33. The sealable top 15 is configured to receive and penetrate a conduit including a dip tube 92 to keep the container 33 and fluid in contact. A dip tube 92 having a control valve 90 and a connection piece 95 is configured to flow carrier gas into the container 33. In some cases, the dip tube 92 extends below the central axis of the container 33. Further, the sealable top 15 is configured to receive and penetrate a conduit including the outlet tube 12. The carrier gas and the vapor of the Si-containing film forming composition are taken out from the container 33 through the outlet pipe 12. The outlet pipe 12 includes a control valve 10 and a connection part 5. In some cases, the outlet tube 12 is connected to a gas supply connection for guiding the carrier gas from the sublimation device 100 to the reactor so that the fluid flows.

  Container 33 and sealable top 15 are sealed by at least two sealing members 18 or by at least about four sealing members. In some cases, the sealable top 15 is sealed to the container 33 by at least about 8 seal members 18. As will be appreciated by those skilled in the art, the seal member 18 is releasably connected to the container 33 to the sealable upper portion 15 to form a gas resistant seal with the gasket 20. Seal member 18 may include any suitable means for sealing container 33 known to those skilled in the art. In some instances, the seal member 18 includes a thumbscrew.

  As shown in FIG. 5, the container 33 further includes at least one disk disposed therein. The disc includes a shelf or horizontal support for solid material. In certain embodiments, the inner disk 30 is annularly disposed within the container 33 such that the disk 30 includes an outer diameter or circumference that is smaller than the inner diameter or circumference of the container 33 to form the gap 31. . The outer disk 86 is annularly disposed within the container 33 so that the disk 86 includes an outer diameter or circumference that is the same, substantially the same as or substantially coincident with the inner diameter of the container 33. The outer disk 86 forms a gap 87 disposed at the center of the disk. A plurality of disks are disposed in the container 33. The disks are stacked in an alternating configuration, and the inner disks 30, 34, 36, 44 are stacked vertically with alternating outer disks 62, 78, 82, 86 in the container. In some embodiments, the inner disks 30, 34, 36, 44 extend annularly outward and the outer disks 62, 78, 82, 86 extend annularly toward the center of the container 33. As shown in the embodiment of FIG. 5, the inner disks 30, 34, 36, 44 are not in physical contact with the outer disks 62, 78, 82, 86.

  The assembled sublimation device 100 has inner legs 30, 34, 36 having support legs 50 arranged and connected, inner passages 51, concentric walls 40, 41, 42 and concentric slots 47, 48, 49. , 44. The inner disks 30, 34, 36, 44 are stacked vertically and are annularly oriented around the dip tube 92. In addition, the sublimation device includes outer disks 62, 78, 82, 86. As shown in FIG. 3, the outer disks 62, 78, 82, 86 need to be in close contact with the container 33 for good contact to transfer heat from the container 33 to the disks 62, 78, 82, 86. There is. Preferably, the outer disks 62, 78, 82, 86 are connected to or in physical contact with the inner wall of the container 33.

  As shown, the outer disks 62, 78, 82, 86 and the inner disks 30, 34, 36, 44 are stacked in the container 33. When assembled in the container 33 to form the sublimation device 100, the inner disks 30, 34, 36, 44 are connected to the outer gas passages 31, 35, 37, between the assembled outer disks 62, 78, 82, 86. 45 is formed. Further, the outer disks 62, 78, 82, 86 form inner gas passages 56, 79, 83, 87 together with the support legs of the inner disks 30, 34, 36, 44. The walls 40, 41, 42 of the inner disks 30, 34, 36, 44 form slotted slots for holding the solid precursor. The outer disks 62, 78, 82, 86 include walls 68, 69, 70 for holding solid precursors. During assembly, the solid precursor is placed in the annular slots 47, 48, 49 of the inner disks 30, 34, 36, 44 and the annular slots 64, 65, 66 of the outer disks 62, 78, 82, 86.

  An annular slot 47 in the inner disk 30, 34, 36, 44 with solid powder and / or granular particles of a size less than about 1 centimeter, or less than about 0.5 centimeter, or less than about 0.1 centimeter, 48, 49 and outer disks 62, 78, 82, 86 are loaded into annular slots 64, 65, 66. The solid precursor is loaded into the annular slot of each disk by any method appropriate to the uniform distribution of solids within the annular slot. Suitable methods include, but are not limited to, direct pouring, use of handle, use of funnel, automatic measurement dispensing, and pressurized dispensing. Depending on the chemical properties of the solid precursor material, the loading may be performed in an enclosed environment. Furthermore, for these toxic, volatile, oxidizable and / or air sensitive solids, an inert gas atmosphere and / or pressurization in a sealed box is performed. May be. Each disc could be loaded after setting the disc in the container 33. A more preferred procedure is to load the solid before setting the disc in the container 33. The total weight of the solid precursor loaded into the sublimation device can be recorded by weighing the sublimation device before and after the loading process. Furthermore, the consumed solid precursor can be calculated by weighing the sublimation device after the vaporization and deposition process.

  A dip tube 92 having a control valve 90 and a connecting piece 95 is located in the central passage 51 of the support leg to which the inner disks 30, 34, 36, 44 are arranged and connected. Therefore, the dip tube 92 passes through the inner passage 51 perpendicularly toward the bottom 58 of the container 33. The end of the dip tube 55 is located proximal to the gas window 52 / or above the container bottom 58. The gas window 52 is disposed on the bottom inner disk 44. The gas window 52 is configured so that the carrier gas can flow out of the dip tube 92. In the assembled sublimation device 100, the gas passageway 59 is formed by the bottom surface 58 of the container 33 and the bottom inner disk 44. In some cases, the gas passageway 59 is configured to heat the carrier gas.

  During operation, the carrier gas is preheated before being introduced into the container 33 via the dip tube 92. Alternatively, the carrier gas may be heated as it flows through the gas passageway 59 by the bottom surface 58. The bottom surface 58 is thermally integrated and / or heated by an external heater consistent with the teachings herein. Thereafter, the carrier gas passes through a gas passage 45 formed by the outer wall 42 of the inner disk 44 and the outer wall 61 of the outer disk 62. The gas passage 45 is connected to the top of the inner disk 44. The carrier gas flows continuously over the solid precursor contained in the annular slots 47, 48 and 49. The sublimated solid vapor from the annular slots 47, 48, 49 is mixed with the carrier gas and flows vertically upward through the container 33.

  Although FIG. 5 discloses an embodiment of a sublimation apparatus that can carry vapors of any solid Si-containing film-forming composition to the reactor, those skilled in the art will not depart from the teachings herein. It will be appreciated that other sublimation device designs may be appropriate. Finally, those skilled in the art will disclose the present disclosure to semiconductor processing tools that use other transfer devices, such as the ampules disclosed in Jurcik et al., WO 2006/059187, without departing from the teachings herein. It will be appreciated that a Si-containing film-forming composition can be carried.

  If necessary, the Si-containing film forming composition apparatus of FIGS. 3-5 allows the Si-containing film forming composition to be in a liquid phase and have sufficient vapor pressure. It may be heated to temperature. The transfer device may be maintained at a temperature in the range of, for example, 0 to 150 ° C. One skilled in the art recognizes that the temperature of the transfer device can be adjusted in a known manner to control the amount of the Si-containing film-forming composition that is vaporized.

In addition to the composition of the present disclosure, a reactive gas can also be introduced into the reactor. O ₂ ; O ₃ ; H ₂ O; H ₂ O ₂ ; oxidizing agent such as H ₂ O ₂ ; O · or OH ·; NO; oxygen-containing radicals such as NO ₂ ; carboxylic acids such as formic acid, acetic acid, propionic acid; It may be a radical species of NO, NO ₂ or carboxylic acid; paraformaldehyde; and mixtures thereof. Preferably, the oxidant is selected from the group consisting of O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , its oxygen-containing radicals such as O. or OH., And mixtures thereof. Preferably, when the ALD method is performed, the co-reactant is plasma treated oxygen, ozone, or a combination thereof. If an oxidizing gas is used, the resulting silicon-containing film will also contain oxygen.

Alternatively, the reaction gas may be H ₂ , NH ₃ , (SiH ₃ ) ₃ N, hydrosilanes (SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , Si ₅ H ₁₀ , Si ₆ H _12, etc. ), Chlorosilanes and chloropolysilanes (SiHCl ₃ , SiH ₂ Cl ₂ , SiH ₃ Cl, Si ₂ Cl ₆ , Si ₂ HCl ₅ , Si ₃ Cl ₈ etc.), alkyl silanes (Me ₂ SiH ₂ , Et ₂ SiH ₂₎ , MeSiH ₃ , EtSiH _3, etc.), hydrazines (N ₂ H ₄ , MeHNNH ₂ , MeHNNHMe etc.), organic amines (NMeH ₂ , NEtH ₂ , NMe ₂ H, NEt ₂ H, NMe ₃ , NEt ₃ , (SiMe _{3) 3) 2} NH, etc.), ethylenediamine, dimethylethylenediamine, diamine such as tetramethylethylenediamine S, pyrazoline, pyridine, B-containing molecules, (B 2 _{H 6,} trimethylboron, triethyl boron, borazine, substituted borazine, dialkylamino borane), alkyl metals (trimethylaluminum, triethylaluminum, dimethyl zinc, diethyl zinc, etc.) , These radical species, or a mixture thereof. If H ₂ or inorganic Si-containing gas is used, the resulting silicon-containing film can be pure Si.

  Alternatively, the reaction gas can be, but is not limited to, ethylene, acetylene, propylene, isoprene, cyclohexane, cyclohexene, cyclohexadiene, pentene, pentyne, cyclopentane, butadiene, cyclobutane, terpinene, octane, octane, or combinations thereof. Saturated or unsaturated, straight chain, branched or cyclic hydrocarbons.

The reactive gas may be treated with a plasma to decompose the reactive gas into its radical form. N ₂ can also be used as a reducing agent when processing with plasma. For example, the plasma can be generated at a power in the range of about 50W to about 500W, preferably about 100W to about 200W. The plasma may be generated in the reactor itself or may be present in the reactor itself. Alternatively, the plasma may typically be at a location exiting the reactor, such as within a remotely located plasma system. Those skilled in the art will recognize methods and apparatus suitable for such plasma processing.

  Desirable silicon-containing films may also include other elements such as, but not limited to, B, P, As, Zr, Hf, Ti, Nb, V, Ta, Al, Si, or Ge.

  The Si-containing film forming composition and one or more co-reactants may be introduced into the reaction chamber simultaneously (chemical vapor deposition), sequentially (atomic layer deposition), or in another combination. For example, the vapor of the Si-containing film forming composition may be introduced in one pulse, and the two additional metal sources may be introduced together in another pulse (modified atomic layer deposition). Alternatively, a co-reactant may already be contained in the reaction chamber before the introduction of the Si-containing film forming composition. The co-reactant may pass through a local or remote plasma system and be decomposed into radicals. Alternatively, the Si-containing film forming composition may be continuously introduced into the reaction chamber while other precursors or reactants are introduced by pulse (pulse chemical vapor deposition). In another alternative, the Si-containing film forming composition and the one or more co-reactants may be sprayed simultaneously from a showerhead with a susceptor holding a plurality of wafers rotating underneath. (Spatial ALD).

  In one non-limiting typical atomic layer deposition process, a gas phase of a Si-containing film-forming composition is introduced into the reaction chamber, which now contacts a suitable substrate. Excess composition can then be removed from the reaction chamber by purging and / or evacuating the reaction chamber. An oxygen source is introduced into the reaction chamber where it is reacted with the absorbed Si-H containing iodosilane in a self-controlled manner. Any excess oxygen source is removed from the reaction chamber by purging and / or evacuating the reaction chamber. If the target film is a silicon oxide film, this two-step process can give the desired film thickness, or this can be repeated until a film of the required thickness is obtained.

Alternatively, the target film is a metal silicon / metalloid oxide film (ie, SiMO _x , x may be 0 to 4, and M is B, Zr, Hf, Ti, Nb, V, Ta, Al , Si, Ga, Ge, or a combination thereof) after the above two-step process, a vapor of a metal-containing or semi-metal-containing precursor may be introduced into the reaction chamber. The metal-containing precursor or metalloid-containing precursor will be selected based on the nature of the deposited metal silicon / metalloid oxide film. After introduction into the reaction chamber, the metal-containing precursor or metalloid-containing precursor contacts the substrate. Any excess metal-containing or metalloid-containing precursor is removed from the reaction chamber by purging and / or evacuating the reaction chamber. Again, an oxygen source may be introduced into the reaction chamber to react with the metal-containing precursor or metalloid-containing precursor. Excess oxygen source is removed from the reaction chamber by purging and / or evacuating the reaction chamber. When the target film thickness is obtained, the process can be terminated. However, if a thicker film is desired, a total of four stages of processing can be repeated. By alternately supplying the Si-containing film forming composition, the metal-containing precursor or the semi-metal-containing precursor, and the oxygen source, a film having a desired composition and thickness can be deposited.

Further, by changing the number of pulses, a film having a desired stoichiometric M: Si ratio can be obtained. For example, a SiMO ₂ film can be obtained by having one pulse of a composition for forming a Si-containing film, one pulse of a metal-containing precursor or metalloid-containing precursor, and a pulse of an oxygen source after each pulse. . However, those skilled in the art will recognize that the number of pulses required to obtain the desired film may not be the same as the stoichiometric ratio of the resulting film.

The silicon-containing film obtained by the above-described method is SiO ₂ ; SiC; SiN; SiON; SiOC; SiONC; SiBN; SiBCN; SiCN; SiMO, SiMN (wherein M is naturally in the oxidation state of M) (Which is selected from Zr, Hf, Ti, Nb, V, Ta, Al, Ge). One skilled in the art will recognize that the desired film composition can be obtained by careful selection of suitable Si-containing film forming compositions and co-reactants.

  After the desired film thickness is obtained, the film may be subjected to additional processing such as thermal annealing, furnace annealing, rapid thermal annealing, UV or electron beam curing, and / or plasma gas exposure. Those skilled in the art are aware of the systems and methods utilized to perform these additional processing steps. For example, the silicon-containing film may have a temperature in the range of about 200 ° C. to about 1000 ° C. in the range of about 0.1 seconds to about 7200 seconds under an inert atmosphere, H-containing atmosphere, N-containing atmosphere, or combinations thereof. It may be exposed for hours. Most preferably, the temperature is 600 ° C. for less than 3600 seconds. More preferably, the temperature is less than 400 ° C. The annealing process may be performed in the same reaction chamber in which the deposition process is performed. Alternatively, the substrate may be removed from the reaction chamber and the annealing / flash annealing process may be performed in a separate apparatus. In any of the above post-treatment methods, UV curing, in particular, has been found to be effective in enhancing film integrity and cross-linking and reducing the H content of the film when the film is a SiN-containing film. . Typically, a combination of thermal annealing and UV curing up to <400 ° C. (preferably about 100 ° C. to 300 ° C.) is used to obtain the highest density film.

  The following non-limiting examples are given to further illustrate embodiments of the present invention. However, the examples are not intended to be exhaustive and are not intended to limit the scope of the invention described herein.

Example 1 9.56 g (33.7 mmol) of anhydrous lithium iodide powder (Sigma Aldrich) in a 250 mL 3-neck (24/40) European style flask containing a magnetic stirring bar coated with PTFE 99 +%) and 80 mL of anhydrous chloroform. While stirring the mixture, dichlorosilane (8.4 g; 83.2 mmol, excess) (“DCS”) was added to the reaction flask through the headspace. A color change was observed immediately (light purple). The temperature was increased from ˜22 to 29 ° C. during DCS exposure. The mixture was stirred at ambient temperature for a further 18 hours. The appearance of the solid changed from a coarse beige form to a fine white powder. At this time, the mass of the solid decreased. The solid was filtered and dried under vacuum (2.75 g recovered; calculated 3.0 g). The solvent was removed under static vacuum by condensing into a trap cooled in liquid nitrogen. The remaining purple liquid was weighed (4.54 g; calculated 10.0 g; 45%) and analyzed by GCMS: 80.5% was SiH ₂ I ₂ (“DIS”) with the balance higher The boiling point compound). Although the calculated product yield is unreliable due to the sample size and the means by which the chloroform was removed, this example shows that the halide exchange to produce the product DIS is successful.

Example 2: A similar reaction was performed using the same procedure and reagent addition amount as described in Example 1, except that toluene was used instead of chloroform. GC sample analysis of the liquid (no additional workup) revealed that DIS was the main product (sans solvent) and contained small amounts of DCS and ClSiH ₂ I.

Example 3 In a glove box purged with nitrogen, 4.25 g (31.7 mmol) of anhydrous lithium iodide was placed in a 60 cc stainless steel ampoule with a diaphragm valve and a pressure gauge. Nitrogen gas was removed under vacuum and DCS (1.60 g, 15.9 mmol) was added by condensation (−196 ° C.). The container was then closed and thawed to ambient temperature and left for 30 minutes. Volatiles were extracted with anhydrous toluene and analyzed by GCMS, revealing DCS, the intermediates ClSiH ₂ I, and DIS (main product). This example shows that the process can be completed without the use of a solvent.

  Example 4: Exposure of sodium iodide powder (10.61 g; granules, colorless, crystalline solid) to excess DCS gas in a 50 cc Schlenk tube under static vacuum with no visible signs of reaction . No change in pressure was observed. The DCS was then condensed into a Schlenk tube and thawed several times to ambient temperature, but there was no sign of reagent volume reduction, coloration, or pressure change (no reaction). The reaction with sodium iodide appeared to require a solvent (ie, methylene chloride, chloroform, acetonitrile, etc.) that showed some solubility. Lithium iodide is clearly preferred because of its higher reactivity. This example shows that the alkali metal halide reactant that is NaI is not as reactive as LiI.

Example 5: 530 g of product scale in pentane solvent: 500 g of anhydrous LiI (3.74 mol; Acros Organics, 99) in a 2 L 3-neck round bottom (RB) flask with a stir bar coated with PTFE %) And filled with anhydrous n-pentane to a 1 L scale. Most of the headspace nitrogen was removed in vacuo (to a pressure of about 600 torr) and excess DCS (492 g; 4.87 mol; 2.8-fold molar excess) was added to the flask through the headspace. The flask was periodically cooled to 5-8 ° C and completely transferred. The solids were too heavy to be stirred by using a stirrer plate / stir bar. The mixture was mixed by frequently shaking / rotating the pot manually. The flask was left at room temperature overnight with the magnetic stir bar left intact. Stirring was not possible. The solid was filtered and dried under vacuum (169 g recovered; calculated 158 g). The pale pink filtrate was distilled to remove pentane (bp = 36 ° C.). The remaining colorless liquid was distilled under reduced pressure using a receiver cooled with dry ice pellets (about 0-5 torr / 21-31 ° C.). This resulted in a colorless frozen solid in the collector, and almost no residual liquid remained in the distillation pot. The solid product was thawed and weighed (350 g; calculated 530 g; 65%). From gas chromatography / mass spectrometry, 91% (area percent) pure DIS and a small amount of DCS (0.964%), pentane (0.326%), ClSiH ₂ I (4.9533%), and perchloro / The impurities temporarily assigned as the periodododisiloxane compound were revealed (see FIG. 6).

The possible siloxane-type impurities found in Example 5 suggest that these compounds are formed by moisture from one or more of the following:
• Surface moisture from glass reactor / distillation system (less likely).
• Origin of air leakage into the system.
• Moisture in the starting lithium iodide (possibly reasonable). This may also include some level of lithium hydroxide.
• Moisture from sample preparation and manipulation (not fully optimized) for GC analysis.

  This highlights the importance of meticulous measurements to remove all possible moisture sources throughout the process. However, based on the elution time of GC, these siloxane impurities appear to be easily separated from the main product.

Example 6: 530 g of product scale in pentane solvent: 500 g of anhydrous LiI in a 2 L 3-neck RB flask with mechanical stirrer, cooling cup condenser and 1/4 "PTFE sparger tube 3.74 mol; Acros Organics, 99%) was charged and filled with anhydrous n-pentane to 1 L. Dichlorosilane (183 g; 1.81 mol) was added under the surface over 22 minutes, the temperature was 18 From 1 (cold pentane) to 31.0 ° C. The reaction mixture was stirred vigorously, some reflux was observed during the addition of DCS, the reaction mixture was stirred at ambient temperature for 3 hours and the liquid was GCMS analyzed. from the chromatographic traces of DCS, pentane, partially substituted intermediates ClSiH ₂ I, and D .. S was stirred area percent .ClSiH ₂ I and DIS revealed were respectively 6 and 13% the reaction mixture for a further 18 hours then the solid was filtered and dried under vacuum (226 g recovered; Calculated 158 g) Solvent and low boiling impurities were removed by distillation, yielding crude DIS (320 g, 89% by GC) (˜62%). It is shown that similar yields can be obtained by changing the stoichiometric ratio.

  Example 7: 500 g of LiI (3.74 mol; 99.9% City Chemical, colorless powder) was placed in a 2 L 3-neck RB flask equipped with a mechanical stirrer. A cooling cup condenser and an internal thermocouple were attached to the reactor. About 800 mL of anhydrous chloroform was added to the LiI powder. The condenser was cooled to −78 ° C., and 196 g of dichlorosilane (1.94 mol, 3.5 mol% excess) was added to the condenser (−78 ° C. dry ice, isopropyl alcohol slush bath) over 15 minutes with stirring under reduced pressure. I passed. The pressure was 680 torr at 23 ° C. Additional nitrogen gas was added to the reactor to a pressure of 780 torr. The mixture was stirred for 22 hours and exhibited a pink-purple color. The solid was filtered and dried under vacuum. The filtrate was collected in a 1 L flask. Chloroform was distilled at 61 ° C. and the remaining purple liquid was collected and weighed (148 g, 28%, unpurified DIS product after removal of solvent). This low yield suggests that pure LiI was limited to low solubility in chloroform. Hydrogenation of the reactant LiI to some extent can increase the reactivity of the salt and promote product formation with more siloxane-based impurities.

Example 8: LiI (24.8 g, 0.19 mol) was added to a 4-neck round bottom flask equipped with a mechanical stirrer, a thermocouple, and a dry ice IPA condenser while flowing nitrogen. Pentane (80 mL) was transferred by cannula. TSA-Cl ((SiH ₃ ) ₂ N (SiH ₂ Cl) 25 g, 0.18 mol) was added dropwise to the resulting mixture at room temperature over 15 minutes. There was no fever. After stirring at ambient temperature for about 90 minutes, the reaction mixture was analyzed by GC-MS and found to be 57% unreacted TSA-Cl and 39% TSA-I ((SiH ₃ ) ₂ N (SiH ₂ I)). Was shown (FIG. 4). At this point, the reaction mixture was stirred at room temperature overnight. In the GC analysis after stirring overnight, a main peak corresponding to SiH ₃ -I was obtained, and peaks corresponding to TSA-Cl and TSA-I disappeared. Optimization of reaction time is ongoing.

Example 9: Comparison of LI particle size LI of 0.5-1 mm
20 L jacket with mechanical stirrer, condenser (adjusted to -70 ° C), fixed addition port, inlet tube for addition of dichlorosilane below the surface, and inlet for liquid pentane addition 15 L of pentane was placed in the filter reactor. The temperature in the reactor jacket was adjusted to + 35 ° C and the reactor condenser was adjusted to -70 ° C. The reactor was then stirred at ~ 200 RPM and then lithium iodide (12.25 kg, 91.52 mol) was charged to the reactor under a nitrogen atmosphere. Subsequent gravimetric addition of dichlorosilane (4.52 kg, 44.75 mol) was adjusted to a rate of about 1 kg per hour. After the DCS addition is complete, leave the reactor jacket at + 35 ° C and the condenser at -70 ° C. After stirring for 16 hours, stirring was stopped and the reactor contents were discharged through a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was then washed with pentane (3 × 1 L) to give 7.19 kg of solid residue. The filtrate and washings were combined and subsequently distilled at 88 kPa to obtain unpurified diiodosilane (9.04 kg, purity 83%). The balance of the material contained 1.3% DCS; 0.6% pentane; 14.1% SiH ₂ ClI; and 0.1% SiHI ₃ as suggested by GC analysis. Further distillation of this crude material at 3.2 kPa yielded 99.6% DIS; 0.1% SiH ₃ I; 0.1% SiH ₂ ClI; 0, as suggested by GC analysis. Diiodosilane (7.39 kg, yield 58%) containing 0.15% SiHI ₃ and 0.12% other was obtained.

1-1.25mm LI
20 L jacket with mechanical stirrer, condenser (adjusted to -70 ° C), fixed addition port, inlet tube for addition of dichlorosilane below the surface, and inlet for liquid pentane addition Into the filter reactor, 15 L of unused pentane (Sigma Aldrich, purity> 99%) was added. The temperature in the reactor jacket was adjusted to + 35 ° C and the reactor condenser was adjusted to -70 ° C. The reactor was then stirred at ˜200 RPM and then lithium iodide (9.99 kg, 74.64 mol) was charged to the reactor under a nitrogen atmosphere. Subsequent gravimetric addition of dichlorosilane (3.88 kg, 38.42 mol) was adjusted to a rate of about 1 kg per hour. After the DCS addition is complete, leave the reactor jacket at + 35 ° C and the condenser at -70 ° C. After stirring for 16 hours, stirring was stopped and the reactor contents were discharged through a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was then washed with pentane (3 × 1 L) to give 4.96 kg of solid residue. The filtrate and the washing solution were combined and subsequently distilled at 88 kPa to obtain unpurified diiodosilane (8.01 kg, purity 86%). The remainder of the material was 0.1% DCS; 1.2% pentane; 0.1% SiH ₃ I; 4.5% SiH ₂ ClI; and 0.1 as suggested by GC analysis % SiHI ₃ of it contained. The crude material was further distilled at 3.2 kPa to obtain 99.7% DIS; 0.01% SiH ₃ I; 0.03% SiH ₂ ClI; and 0.1% SiHI ₃ ). Diiodosilane containing (8.16 kg, yield 77%) was obtained.

  As described above, the particle size of lithium iodide affects the isolation yield. Surprisingly, improved yields are observed when using a larger particle size lithium iodide compared to a smaller particle size.

Example 10: Effect of solvent recycling Solvent recycling Mechanical stirrer, condenser (adjusted to -70 ° C), fixed addition port, inlet tube for addition of dichlorosilane below the surface, and liquid pentane addition 15 L pentane was placed in a 20 L jacketed filter reactor equipped with an inlet for. The temperature in the reactor jacket was adjusted to + 35 ° C and the reactor condenser was adjusted to -70 ° C. The reactor was then stirred at ~ 200 RPM and then lithium iodide (12.34 kg, 92.19 mol) was charged to the reactor under a nitrogen atmosphere. Subsequent gravimetric addition of dichlorosilane (4.25 kg, 42.08 mol) was adjusted to a rate of about 1 kg per hour. After the DCS addition is complete, leave the reactor jacket at + 35 ° C and the condenser at -70 ° C. After stirring for 16 hours, stirring was stopped and the reactor contents were discharged through a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was then washed with pentane (3 × 1 L). The filtrate and the washing solution were combined and subsequently distilled at 88 kPa to obtain unpurified diiodosilane (9.26 kg, purity 82%) in the distillation pot. Distillate (11 L, 82% most pentane; 12% DCS; 4% SiH 2 ClI; and 1% DIS) was recycled back to the reactor for continuous synthesis.

Accordingly, a mechanical stirrer, a condenser (adjusted to -70 ° C), a fixed addition port, an inlet tube for the addition of dichlorosilane below the surface, and an inlet for the addition of distillate / pentane. The aforementioned 20 L jacketed filter reactor equipped with distillate (11 L, 82% most pentane; 12% DCS; 4% SiH2ClI; and 1% DIS). The temperature in the reactor jacket was adjusted to + 35 ° C and the reactor condenser was adjusted to -70 ° C. The reactor was then stirred at ~ 200 RPM and then lithium iodide (12.38 kg, 92.49 mol) was charged to the reactor under a nitrogen atmosphere. Subsequent gravimetric addition of dichlorosilane (4.17 kg, 41.28 mol) was adjusted to a rate of about 1 kg per hour. After the DCS addition is complete, leave the reactor jacket at + 35 ° C and the condenser at -70 ° C. After stirring for 17 hours, stirring was stopped and the reactor contents were discharged through a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was then washed with pentane (3 × 1 L). The filtrate and the washing solution were combined and subsequently distilled at 88 kPa to obtain unpurified diiodosilane (8.77 kg, purity 84%) as a distillation residue in the distillation pot. This crude material was further distilled at 3.2 kPa to give 99.5% DIS; 0.14% SiH ₃ I; 0.24% SiHI ₃ and others 0.12%) diiodosilane (7 .29 kg, 62% yield).

Unused solvent equipped with mechanical stirrer, condenser (adjusted to -70 ° C), fixed addition port, inlet tube for addition of dichlorosilane below the surface, and inlet for liquid pentane addition A 20 L jacketed filter reactor was charged with 15 L of unused pentane (Sigma Aldrich, purity> 99%). The temperature in the reactor jacket was adjusted to + 35 ° C and the reactor condenser was adjusted to -70 ° C. The reactor was then stirred at ~ 200 RPM and then lithium iodide (12.47 kg, 93.16 mol) was charged to the reactor under a nitrogen atmosphere. Subsequent gravimetric addition of dichlorosilane (4.85 kg, 48.02 mol) was adjusted to a rate of about 1 kg per hour. After the DCS addition is complete, leave the reactor jacket at + 35 ° C and the condenser at -70 ° C. After stirring for 16 hours, stirring was stopped and the reactor contents were discharged through a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was then washed with pentane (3 × 1 L). The filtrate and the washing solution were combined and subsequently distilled at 88 kPa to obtain unpurified diiodosilane (8.01 kg, purity 86%). This crude material was further distilled at 3.2 kPa to obtain 99.9% DIS; 0.01% SiH ₃ I; containing 0.02% SiHI ₃ ) diiodosilane (6.68 kg, yield 51 %).

  As described above, recycling often simplifies regulatory compliance and has economic and environmental benefits, but impurities can accumulate. Eliminating the recycling step and using virgin solvent for each synthesis run results in an ultra-high purity product purity level that cannot be obtained after solvent recycling.

Example 11: Material compatibility A piece of material is dipped in SiH ₂ I ₂ (synthesized by the method disclosed in US 2016/0264426) and sealed in a glass pressure tube at a specified temperature. And kept in the dark for the specified time. The analysis value of the first control was 96.9% SiH ₂ I ₂ based on GCMS peak integration, with 1.3% SiH (Me) I ₂ and 1.6% SiHI ₃ . The results are shown below and indicate that it is difficult to maintain the stability of SiH ₂ I ₂ . The applicant believes that HX or X ₂ is a reactant used in this synthetic process is the cause of instability of the reaction product SiH ₂ I _2, which is shown by the results of the lower control. As can be seen, some standard packaging materials further accelerate the decomposition of the product SiH ₂ I ₂ .

Example 11: Stability SiH ₂ I ₂ synthesized by the disclosed method was stored at room temperature in a passivated stainless steel cylinder. Analysis was performed using GCMS peak integration before and after storage in a cylinder. The table below shows that this product maintains its purity without the need for any stabilizers.

Virtual _Example: I 3 _Si-CH 2 Synthesis of _{-SiI 3 Cl 3 Si-CH 2} -SiCl 3 + 6Li-I → I 3 Si-CH 2 -SiI 3 + 6Li-Cl
Lithium iodide and pentane or other suitable solvent are added to the flask under inert and anhydrous conditions, followed by slow addition of solution or solvent free liquid bis (trichlorosilyl) methane. Stir the suspension vigorously until complete reaction is observed by disappearance of bis (trichlorosilyl) methane in a GCMS analysis of a portion of the reaction mixture. The obtained suspension is filtered on a medium glass frit packed with diatomaceous earth to obtain a pentane solution of the target product. The product bis (triiodosilyl) methane is isolated in pure form by vacuum distillation and / or sublimation.

  The reactants are commercially available, or Organomet. Chem. 92, 1975 163-168.

  While embodiments of the invention have been shown and described, modifications thereof can be made by those skilled in the art without departing from the spirit and teachings of the invention. The embodiments described herein are illustrative only and not limiting. Many variations and modifications of the compositions and methods are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited to the embodiments described herein, but the scope is limited only by the following claims, including all equivalents of the claimed subject matter.

A Si-containing film forming composition transfer apparatus, comprising an inlet pipe and an outlet pipe, and comprising a canister containing any of the Si-containing film forming compositions disclosed above A composition transfer device is also disclosed. The apparatus of the present disclosure may include one or more of the following aspects:
The end of the inlet tube is located above the surface of the Si-containing film-forming composition and the end of the outlet tube is located below the surface of the Si-containing film-forming composition;
The end of the inlet tube is located below the surface of the Si-containing film-forming composition and the end of the outlet tube is located above the surface of the Si-containing film-forming composition;
-Further comprising diaphragm valves at the inlet and outlet;
The inner surface of the canister is glass;
The inner surface of the canister is passivated stainless steel;
The canister is a light-resistant glass with a light-resistant coating on the outer surface of the canister;
The inner surface of the canister is aluminum oxide;
-Further comprising one or more barrier layers on the inner surface of the canister;
-Further comprising 1-4 barrier layers on the inner surface of the canister;
-Further comprising one or two barrier layers on the inner surface of the canister;
Each barrier layer comprises a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a silicon carbonitride layer, a silicon oxycarbonitride layer, or a combination thereof;
• Each barrier layer is 1-100 nm thick; or • Each barrier layer is 2-10 nm thick.

The Si-containing film forming composition may be supplied undiluted. Alternatively, the Si-containing film forming composition may further contain a solvent suitable for use in vapor deposition. The solvent can be selected in particular from C _{1 to} C ₁₆ saturated or unsaturated hydrocarbons.

For vapor deposition, the Si-containing film-forming composition is introduced into the reactor in the form of vapor by conventional means such as piping and / or flow meters. The vapor form is such that the carrier gas is blown into the liquid by vaporizing the composition for forming a Si-containing film in a conventional vaporization process such as direct liquid injection or direct vapor extraction in the absence of a carrier gas. By evaporating the vapor in the carrier gas without blowing into the liquid, or when the precursor is a solid at room temperature, such as that disclosed in Xu et al. WO 2009/087609 It can be generated by using a sublimation device. The composition for forming a Si-containing film may be supplied in a liquid state to a vaporizer (direct liquid introduction), and the composition is vaporized and mixed with a carrier gas, and then introduced into the reactor. Alternatively, the Si-containing film forming composition may be vaporized by passing a carrier gas through a container containing the composition or by blowing a carrier gas into the composition. The carrier gas, Ar, the He, or N _2, and mixtures thereof, without limitation. The carrier gas and composition are then introduced into the reactor as vapor.

  The Si-containing film-forming composition is placed in the reactor or deposition chamber by the Si-containing film-forming composition transfer device of FIGS. 3-5 showing three exemplary embodiments of the Si-containing film-forming composition transfer device. May be carried. As detailed above and as shown in the examples below, the transfer device must be clean and dry, and the Si-containing film-forming composition must be made of non-reactive materials. Don't be.

  FIG. 3 is a side view of an embodiment of the Si-containing film forming composition reactant transfer apparatus 101. In FIG. 3, the Si-containing film forming composition 110 of the present disclosure is contained in a container 200 having two conduits, an inlet pipe 300 and an outlet pipe 400. Those skilled in the reactant art will recognize that the vessel 200, the inlet tube 300, and the outlet tube 400 are manufactured to prevent leakage of the Si-containing film-forming composition 110 in gaseous form even at high temperature and pressure. You will recognize.

  The outlet pipe 400 of the transfer device 101 is connected to a reactor (not shown) or other components between the transfer device and the reactor, such as a gas cabinet, through a valve 700 so that fluid can flow. The Preferably, vessel 200, inlet tube 300, valve 600, outlet tube 400, and valve 700 are made of passivated 316L EP, or 304 passivated stainless steel. However, those skilled in the art will recognize that other non-reactive materials may be used in the teachings herein.

  In FIG. 3, the end portion 800 of the inlet tube 300 is located above the surface of the Si-containing film forming composition 110, while the end portion 900 of the outlet tube 400 is formed on the surface of the Si-containing film forming composition 110. Located on the lower side. In this embodiment, the Si-containing film forming composition 110 is preferably in liquid form. An inert gas (including but not limited to nitrogen, argon, helium, and mixtures thereof) may be introduced into the inlet tube 300. The inert gas pressurizes the transfer device 200, and as a result, the liquid Si-containing film forming composition 110 is pushed out through the outlet pipe 400 into the reactor (not shown). In order to carry the vapor to the substrate on which the film is formed, the reactor is a liquid Si-containing film-forming composition 110 with or without the use of a carrier gas such as helium, argon, nitrogen, and mixtures thereof. A vaporizer may be included to convert the water into steam. Alternatively, the liquid Si-containing film forming composition 110 may be directly delivered to the wafer surface as a jet or aerosol.

  FIG. 4 is a side view of the second embodiment of the Si-containing film forming composition reactant transfer apparatus 101. In FIG. 4, the end portion 800 of the inlet tube 300 is located below the surface of the Si-containing film forming composition 110, while the end portion 900 of the outlet tube 400 is the surface of the Si-containing film forming composition 110. Is located above. FIG. 4 also includes an optional heating element 140, which can increase the temperature of the Si-containing film-forming composition 110. FIG. In this embodiment, the Si-containing film forming composition 110 may be in a solid form or a liquid form. An inert gas (including but not limited to nitrogen, argon, helium, and mixtures thereof) may be introduced into the inlet tube 300. The inert gas is blown into the Si-containing film-forming composition 110 and carries the mixture of the inert gas and the vaporized Si-containing film-forming composition 110 to the outlet pipe 400 and the reactor.

  3 and 4 include valves 600 and 700. One skilled in the art will recognize that valves 600 and 700 may be set in an open or closed position so that flow can pass through conduits 300 and 400, respectively. If the Si-containing film-forming composition 110 is in gaseous form, or if sufficient vapor pressure exists above the solid / liquid phase, the transfer device 101 of either of FIGS. 3 and 4 or any solid present or Simpler transfer devices having a single conduit terminating above the surface of the liquid may be used. In this case, the Si-containing film-forming composition 110 is carried in the form of vapor through the conduit 300 or 400 by simply opening the valve 600 in FIG. 3 or the valve 700 in FIG. The transfer device 101 may be maintained at an appropriate temperature, for example by using an optional heating element 140, to provide sufficient vapor pressure to the Si-containing film forming composition 110 to be carried in the form of vapor. Good.

  3 and 4 disclose two embodiments of the Si-containing film-forming composition transfer apparatus 101, those skilled in the art will recognize that the inlet tube 300 and the outlet tube 400 will not depart from the disclosure herein. Will be recognized both above or below the surface of the Si-containing film-forming composition 110. Further, the inlet pipe 300 may be a filling port.

  The vapor in solid form of the Si-containing film forming composition may be conveyed to the reactor using a sublimation apparatus. FIG. 5 shows an embodiment of a typical sublimation apparatus 100. The sublimation apparatus 100 includes a container 33. The container 33 is not limited, but may be a cylindrical container or an arbitrary shape. Container 33 is comprised of materials such as, but not limited to, passivated stainless steel, aluminum oxide, glass, and other chemically compatible materials. In some cases, but not limited to, the container 33 is composed of another metal or metal alloy. In some cases, the container 33 has an inner diameter of about 8 centimeters to about 55 centimeters, or an inner diameter of about 8 centimeters to about 30 centimeters. As will be appreciated by those skilled in the art, other structures may have various dimensions.

  The container 33 includes a sealable upper portion 15, a sealing member 18, and a gasket 20. The sealable top 15 is configured to seal the container 33 from the external environment. The sealable top 15 is configured to allow access to the container 33. Furthermore, the sealable top 15 is configured such that a conduit passes through the container 33. Furthermore, the sealable top 15 is configured to allow fluid to flow into the container 33. The sealable top 15 is configured to receive and penetrate a conduit including a dip tube 92 to keep the container 33 and fluid in contact. A dip tube 92 having a control valve 90 and a connection piece 95 is configured to flow carrier gas into the container 33. In some cases, the dip tube 92 extends below the central axis of the container 33. Further, the sealable top 15 is configured to receive and penetrate a conduit including the outlet tube 12. The carrier gas and the vapor of the Si-containing film forming composition are taken out from the container 33 through the outlet pipe 12. The outlet pipe 12 includes a control valve 10 and a connection part 5. In some cases, the outlet tube 12 is connected to a gas supply connection for guiding the carrier gas from the sublimation device 100 to the reactor so that the fluid flows.

  The assembled sublimation device 100 has inner legs 30, 34, 36 having support legs 50 arranged and connected, inner passages 51, concentric walls 40, 41, 42 and concentric slots 47, 48, 49. , 44. The inner disks 30, 34, 36, 44 are stacked vertically and are annularly oriented around the dip tube 92. In addition, the sublimation device includes outer disks 62, 78, 82, 86. As shown in FIG. 5, the outer disks 62, 78, 82, 86 need to adhere to the container 33 for good contact to transfer heat from the container 33 to the disks 62, 78, 82, 86. There is. Preferably, the outer disks 62, 78, 82, 86 are connected to or in physical contact with the inner wall of the container 33.

  As shown, the outer disks 62, 78, 82, 86 and the inner disks 30, 34, 36, 44 are stacked in the container 33. When assembled in the container 33 to form the sublimation device 100, the inner disks 30, 34, 36, 44 are connected to the outer gas passages 31, 35, 37, between the assembled outer disks 62, 78, 82, 86. 45 is formed. Further, the outer disks 62, 78, 82, 86 form inner gas passages 56, 79, 83, 87 together with the support legs of the inner disks 30, 34, 36, 44. The walls 40, 41, 42 of the inner disks 30, 34, 36, 44 form slotted slots for holding the solid precursor. The outer disks 62, 78, 82, 86 include walls 68, 69, 70 for holding solid precursors. During assembly, the solid precursor is placed in the annular slots 47, 48, 49 of the inner disks 30, 34, 36, 44 and the annular slots 64, 65, 66 of the outer disks 62, 78, 82, 86.

  An annular slot 47 in the inner disk 30, 34, 36, 44 with solid powder and / or granular particles of a size less than about 1 centimeter, or less than about 0.5 centimeter, or less than about 0.1 centimeter, 48, 49 and outer disks 62, 78, 82, 86 are loaded into annular slots 64, 65, 66. The solid precursor is loaded into the annular slot of each disk by any method appropriate to the uniform distribution of solids within the annular slot. Suitable methods include, but are not limited to, direct pouring, use of handle, use of funnel, automatic measurement dispensing, and pressurized dispensing. Depending on the chemical properties of the solid precursor material, the loading may be performed in an enclosed environment. Furthermore, for these toxic, volatile, oxidizable and / or air sensitive solids, an inert gas atmosphere and / or pressurization in a sealed box is performed. May be. Each disc could be loaded after setting the disc in the container 33. A more preferred procedure is to load the solid before setting the disc in the container 33. The total weight of the solid precursor loaded into the sublimation device can be recorded by weighing the sublimation device before and after the loading process. Furthermore, the consumed solid precursor can be calculated by weighing the sublimation device after the vaporization and deposition process.

  A dip tube 92 having a control valve 90 and a connecting piece 95 is located in the central passage 51 of the support leg to which the inner disks 30, 34, 36, 44 are arranged and connected. Therefore, the dip tube 92 passes through the inner passage 51 perpendicularly toward the bottom 58 of the container 33. The end of the dip tube 55 is located proximal to the gas window 52 / or above the container bottom 58. The gas window 52 is disposed on the bottom inner disk 44. The gas window 52 is configured so that the carrier gas can flow out of the dip tube 92. In the assembled sublimation device 100, the gas passageway 59 is formed by the bottom surface 58 of the container 33 and the bottom inner disk 44. In some cases, the gas passageway 59 is configured to heat the carrier gas.

  During operation, the carrier gas is preheated before being introduced into the container 33 via the dip tube 92. Alternatively, the carrier gas may be heated as it flows through the gas passageway 59 by the bottom surface 58. The bottom surface 58 is thermally integrated and / or heated by an external heater consistent with the teachings herein. Thereafter, the carrier gas passes through a gas passage 45 formed by the outer wall 42 of the inner disk 44 and the outer wall 61 of the outer disk 62. The gas passage 45 is connected to the top of the inner disk 44. The carrier gas flows continuously over the solid precursor contained in the annular slots 47, 48 and 49. The sublimated solid vapor from the annular slots 47, 48, 49 is mixed with the carrier gas and flows vertically upward through the container 33.

  Although FIG. 5 discloses an embodiment of a sublimation apparatus that can carry vapors of any solid Si-containing film-forming composition to the reactor, those skilled in the art will not depart from the teachings herein. It will be appreciated that other sublimation device designs may be appropriate. Finally, those skilled in the art will disclose the present disclosure to semiconductor processing tools that use other transfer devices, such as the ampules disclosed in Jurcik et al., WO 2006/059187, without departing from the teachings herein. It will be appreciated that a Si-containing film-forming composition can be carried.

  If desired, the Si-containing film-forming composition delivery device of FIGS. 3-5 allows the Si-containing film-forming composition to be in a liquid phase and have sufficient vapor pressure. It may be heated to temperature. The transfer device may be maintained at a temperature in the range of, for example, 0 to 150 ° C. One skilled in the art recognizes that the temperature of the transfer device can be adjusted in a known manner to control the amount of the Si-containing film-forming composition that is vaporized.

In addition to the composition of the present disclosure, a reactive gas can also be introduced into the reactor. O ₂ ; O ₃ ; H ₂ O; H ₂ O ₂ ; oxidizing agent such as H ₂ O ₂ ; O · or OH ·; NO; oxygen-containing radicals such as NO ₂ ; carboxylic acids such as formic acid, acetic acid, propionic acid; It may be a radical species of NO, NO ₂ or carboxylic acid; paraformaldehyde; and mixtures thereof. Preferably, the oxidant is selected from the group consisting of O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , its oxygen-containing radicals such as O. or OH., And mixtures thereof. Preferably, when the ALD method is performed, the co-reactant is plasma treated oxygen, ozone, or a combination thereof. If an oxidizing gas is used, the resulting silicon-containing film will also contain oxygen.

Alternatively, the reaction gas may be H ₂ , NH ₃ , (SiH ₃ ) ₃ N, hydrosilanes (SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , Si ₅ H ₁₀ , Si ₆ H _12, etc. ), Chlorosilanes and chloropolysilanes (SiHCl ₃ , SiH ₂ Cl ₂ , SiH ₃ Cl, Si ₂ Cl ₆ , Si ₂ HCl ₅ , Si ₃ Cl ₈ etc.), alkyl silanes (Me ₂ SiH ₂ , Et ₂ SiH ₂₎ , MeSiH ₃ , EtSiH _3, etc.), hydrazines (N ₂ H ₄ , MeHNNH ₂ , MeHNNHMe etc.), organic amines (NMeH ₂ , NEtH ₂ , NMe ₂ H, NEt ₂ H, NMe ₃ , NEt ₃ , (SiMe _{3) 3) 2} NH, etc.), ethylenediamine, dimethylethylenediamine, diamine such as tetramethylethylenediamine S, pyrazoline, pyridine, B-containing molecules, (B 2 _{H 6,} trimethylboron, triethyl boron, borazine, substituted borazine, dialkylamino borane), alkyl metals (trimethylaluminum, triethylaluminum, dimethyl zinc, diethyl zinc, etc.) , These radical species, or a mixture thereof. If H ₂ or inorganic Si-containing gas is used, the resulting silicon-containing film can be pure Si.

  Alternatively, the reaction gas is saturated, such as, but not limited to, ethylene, acetylene, propylene, isoprene, cyclohexane, cyclohexene, cyclohexadiene, pentene, pentyne, cyclopentane, butadiene, cyclobutane, terpinene, octane, or combinations thereof. Alternatively, it may be an unsaturated, linear, branched, or cyclic hydrocarbon.

The reactive gas may be treated with a plasma to decompose the reactive gas into its radical form. N ₂ can also be used as a reducing agent when processing with plasma. For example, the plasma can be generated at a power in the range of about 50W to about 500W, preferably about 100W to about 200W. The plasma may be generated in the reactor itself or may be present in the reactor itself. Alternatively, the plasma may typically be at a location exiting the reactor, such as within a remotely located plasma system. Those skilled in the art will recognize methods and apparatus suitable for such plasma processing.

  After the desired film thickness is obtained, the film may be subjected to additional processing such as thermal annealing, furnace annealing, rapid thermal annealing, UV or electron beam curing, and / or plasma gas exposure. Those skilled in the art are aware of the systems and methods utilized to perform these additional processing steps. For example, the silicon-containing film may have a temperature in the range of about 200 ° C. to about 1000 ° C. in the range of about 0.1 seconds to about 7200 seconds under an inert atmosphere, H-containing atmosphere, N-containing atmosphere, or combinations thereof. It may be exposed for hours. Most preferably, the temperature is 600 ° C. for less than 3600 seconds. More preferably, the temperature is less than 400 ° C. The annealing process may be performed in the same reaction chamber in which the deposition process is performed. Alternatively, the substrate may be removed from the reaction chamber and the annealing / flash annealing process may be performed in a separate apparatus. In any of the above post-treatment methods, UV curing, in particular, has been found to be effective in enhancing film integrity and cross-linking and reducing the H content of the film when the film is a SiN-containing film. . Typically, a combination of thermal annealing and UV curing up to <400 ° C. (preferably about 100 ° C. to 300 ° C.) is used to obtain the highest density film.

  The following non-limiting examples are given to further illustrate embodiments of the present invention. However, the examples are not intended to be exhaustive and are not intended to limit the scope of the invention described herein.

Example 1 9.56 g (33.7 mmol) of anhydrous lithium iodide powder (Sigma Aldrich) in a 250 mL 3-neck (24/40) European style flask containing a magnetic stirring bar coated with PTFE 99 +%) and 80 mL of anhydrous chloroform. While stirring the mixture, dichlorosilane (8.4 g; 83.2 mmol, excess) (“DCS”) was added to the reaction flask through the headspace. A color change was observed immediately (light purple). The temperature was raised to about 22-29 ° C. during DCS exposure. The mixture was stirred at ambient temperature for a further 18 hours. The appearance of the solid changed from a coarse beige form to a fine white powder. At this time, the mass of the solid decreased. The solid was filtered and dried under vacuum (2.75 g recovered; calculated 3.0 g). The solvent was removed under static vacuum by condensing into a trap cooled in liquid nitrogen. The remaining purple liquid was weighed (4.54 g; calculated 10.0 g; 45%) and analyzed by GCMS (80.5% was SiH ₂ I ₂ (“DIS”) with the balance higher) The boiling point compound). Although the calculated product yield is unreliable due to the sample size and the means by which the chloroform was removed, this example shows that the halide exchange to produce the product DIS is successful.

1-1.25mm LI
20 L jacket with mechanical stirrer, condenser (adjusted to -70 ° C), fixed addition port, inlet tube for addition of dichlorosilane below the surface, and inlet for liquid pentane addition Into the filter reactor, 15 L of unused pentane (Sigma Aldrich, purity> 99%) was added. The temperature in the reactor jacket was adjusted to + 35 ° C and the reactor condenser was adjusted to -70 ° C. The reactor was then stirred at approximately 200 RPM, and then lithium iodide (9.99 kg, 74.64 mol) was charged to the reactor under a nitrogen atmosphere. Subsequent gravimetric addition of dichlorosilane (3.88 kg, 38.42 mol) was adjusted to a rate of about 1 kg per hour. After the DCS addition is complete, leave the reactor jacket at + 35 ° C and the condenser at -70 ° C. After stirring for 16 hours, stirring was stopped and the reactor contents were discharged through a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was then washed with pentane (3 × 1 L) to give 4.96 kg of solid residue. The filtrate and the washing solution were combined and subsequently distilled at 88 kPa to obtain unpurified diiodosilane (8.01 kg, purity 86%). The remainder of the material was 0.1% DCS; 1.2% pentane; 0.1% SiH ₃ I; 4.5% SiH ₂ ClI; and 0.1 as suggested by GC analysis % SiHI ₃ of it contained. This crude material is further distilled at 3.2 kPa to contain 99.7% DIS; 0.01% SiH ₃ I; 0.03% SiH ₂ ClI; and 0.1% SiHI ₃ Diiodosilane (8.16 kg, 77% yield) was obtained.

  As described above, the particle size of lithium iodide affects the isolation yield. Surprisingly, improved yields are observed when using a larger particle size lithium iodide compared to a smaller particle size.

Example 10: Effect of solvent recycling Solvent recycling Mechanical stirrer, condenser (adjusted to -70 ° C), fixed addition port, inlet tube for addition of dichlorosilane below the surface, and liquid pentane addition 15 L pentane was placed in a 20 L jacketed filter reactor equipped with an inlet for. The temperature in the reactor jacket was adjusted to + 35 ° C and the reactor condenser was adjusted to -70 ° C. The reactor was then stirred at about 200 RPM and then lithium iodide (12.34 kg, 92.19 mol) was charged to the reactor under a nitrogen atmosphere. Subsequent gravimetric addition of dichlorosilane (4.25 kg, 42.08 mol) was adjusted to a rate of about 1 kg per hour. After the DCS addition is complete, leave the reactor jacket at + 35 ° C and the condenser at -70 ° C. After stirring for 16 hours, stirring was stopped and the reactor contents were discharged through a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was then washed with pentane (3 × 1 L). The filtrate and the washing solution were combined and subsequently distilled at 88 kPa to obtain unpurified diiodosilane (9.26 kg, purity 82%) in the distillation pot. Distillate (11 L, 82% most pentane; 12% DCS; 4% SiH 2 ClI; and 1% DIS) was recycled back to the reactor for continuous synthesis.

Accordingly, a mechanical stirrer, a condenser (adjusted to -70 ° C), a fixed addition port, an inlet tube for the addition of dichlorosilane below the surface, and an inlet for the addition of distillate / pentane. The aforementioned 20 L jacketed filter reactor equipped with distillate (11 L, 82% most pentane; 12% DCS; 4% SiH2ClI; and 1% DIS). The temperature in the reactor jacket was adjusted to + 35 ° C and the reactor condenser was adjusted to -70 ° C. The reactor was then stirred at about 200 RPM and then lithium iodide (12.38 kg, 92.49 mol) was charged to the reactor under a nitrogen atmosphere. Subsequent gravimetric addition of dichlorosilane (4.17 kg, 41.28 mol) was adjusted to a rate of about 1 kg per hour. After the DCS addition is complete, leave the reactor jacket at + 35 ° C and the condenser at -70 ° C. After stirring for 17 hours, stirring was stopped and the reactor contents were discharged through a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was then washed with pentane (3 × 1 L). The filtrate and the washing solution were combined and subsequently distilled at 88 kPa to obtain unpurified diiodosilane (8.77 kg, purity 84%) as a distillation residue in the distillation pot. The crude material was further distilled at 3.2 kPa to obtain diiodosilane (7. 5% DIS; 0.14% SiH ₃ I; 0.24% SiHI ₃ , and others 0.12%). 29 kg, 62% yield).

Unused solvent equipped with mechanical stirrer, condenser (adjusted to -70 ° C), fixed addition port, inlet tube for addition of dichlorosilane below the surface, and inlet for liquid pentane addition A 20 L jacketed filter reactor was charged with 15 L of unused pentane (Sigma Aldrich, purity> 99%). The temperature in the reactor jacket was adjusted to + 35 ° C and the reactor condenser was adjusted to -70 ° C. The reactor was then stirred at about 200 RPM and then lithium iodide (12.47 kg, 93.16 mol) was charged to the reactor under a nitrogen atmosphere. Subsequent gravimetric addition of dichlorosilane (4.85 kg, 48.02 mol) was adjusted to a rate of about 1 kg per hour. After the DCS addition is complete, leave the reactor jacket at + 35 ° C and the condenser at -70 ° C. After stirring for 16 hours, stirring was stopped and the reactor contents were discharged through a reactor filter into a 22 L round bottom flask. The salt on the reactor filter was then washed with pentane (3 × 1 L). The filtrate and the washing solution were combined and subsequently distilled at 88 kPa to obtain unpurified diiodosilane (8.01 kg, purity 86%). This crude material was further distilled at 3.2 kPa to obtain diiodosilane (6.68 kg, 51% yield) containing 99.9% DIS; 0.01% SiH ₃ I; 0.02% SiHI _3. )

  As described above, recycling often simplifies regulatory compliance and has economic and environmental benefits, but impurities can accumulate. Eliminating the recycling step and using virgin solvent for each synthesis run results in an ultra-high purity product purity level that cannot be obtained after solvent recycling.

Claims (16)

formula:
Si _w H _x R _y I _z (1)
N (SiH _a R _b I _c ) ₃ (2), or (SiH _m R _n I _o ) ₂ —CH ₂ (3)
(Wherein w is 1 to 3, x + y + z = 2w + 2, x is 1 to 2w + 1, y is 0 to 2w + 1, z is 1 to 2w + 1, and each a is independently 0 to 3 Each b is independently 0-3, each c is independently 0-3, a + b + c = 3, provided that at least one a and at least one c are 1, and each m Is independently 0-3, each n is independently 0-3, each o is independently 0-3, and at least one m and at least one o is 1, m + n + o = 3 and each R is independently a C1-C12 hydrocarbyl group, Cl, Br, or ER ′ ₃ group, where each E is independently Si or Ge, and each R ′ is independently H or a C1-C12 hydrocarbyl group)
A method of synthesizing a Si-H containing iodosilane having
Formula _{Si w H x R y X z} , or _N in _{(SiH a R b X c)} 3, or _{(SiH m R n X o)} 2 -CH 2 ( wherein, X is Cl or Br, and w , X, y, z, a, b, c, m, n, and o are as defined above, and a formula MI, where M = Li, Na, K, Rb Or an alkali metal halide reactant having Cs) to produce a mixture of MX and (1), (2), or (3);
Isolated from the formula _{Si w H x R y I z} , N (SiH a R b I c) 3, or _{(SiH m} R _n I _o) said mixture said SiH-containing Yodoshiran having 2 -CH ₂ A method comprising:   The method of claim 1, wherein M = Li.   The method of claim 1, further comprising adding a non-coordinating solvent to the reaction step.   4. The method of claim 3, wherein the non-coordinating solvent is propane, butane, pentane, hexane, heptane, chloromethane, dichloromethane, chloroform, carbon tetrachloride, methylene chloride, acetonitrile, and combinations thereof. The isolation step comprises filtering the said mixture, separating MX from the SiH-containing Yodoshiran having the formula _Si w _H x _R y _{I z} or _{N (SiH a R b I c} ) 3 The method as described in any one of Claims 1-4.   The method according to claim 1, wherein the alkali metal halide reactant is LiI. The method of claim 1, wherein the halosilane reactant is SiH ₂ Cl ₂ . The method of claim 1, wherein the halosilane reactant is Si ₂ HCl ₅ . The method according to claim 1, wherein the halosilane reactant is (SiH ₃ ) ₂ N (SiH ₂ Cl). Formula Si _w H _x I _z or N (SiH _a I _c ) ₃ (where w = 1-3, x + z = 2w + 2, x = 1-2w + 1, z = 1-2w + 1, Each a is independently 0-3, each c is independently 0-3, with at least one a and at least one c being 1, a + c = 3. A method of synthesizing a containing iodosilane,
The formula Si _w H _x X _z or N (SiH _a X _c ) ₃ , wherein X is Cl or Br, and w, x, z, a, and c are as defined above. A halosilane reactant having and an alkali metal halide reactant having the formula MI (wherein M is Li, Na, K, Rb, or Cs) to produce Si _w H _x I _z or N (SiH generating a mixture of _a I _c ) ₃ and nMX;
Method comprising the step of generating the SiH-containing Yodoshiran that by filtering the mixture, having the formula _Si w _H x _{I z} or _{N (SiH a I c) 3} . The method of claim 10, wherein the halosilane reactant is SiH ₂ Cl ₂ . The method of claim 10, wherein the halosilane reactant is Si ₂ HCl ₅ . The method of claim 10, wherein the halosilane reactant is (SiH ₃ ) ₂ N (SiH ₂ Cl).   14. The method according to any one of claims 10 to 13, wherein the alkali metal halide reactant is LiI. A Si-containing film forming composition transfer device, comprising an inlet pipe and an outlet pipe, and including a canister containing the Si-containing film forming composition, wherein the Si-containing film forming composition comprises Si -H containing iodosilane and about 0 ppbw to about 100 ppbw of Ag, Au, or Sb, wherein the Si-H containing iodosilane has the formula:
Si _w H _x R _y I _z (1)
N (SiH _a R _b I _c ) ₃ (2), or (SiH _m R _n I _o ) ₂ —CH ₂ (3)
(Wherein w is 1 to 3, x + y + z = 2w + 2, x is 1 to 2w + 1, y is 0 to 2w + 1, z is 1 to 2w + 1, and each a is independently 0 to 3 Each b is independently 0-3, each c is independently 0-3, a + b + c = 3, provided that at least one a and at least one c are 1, and each m Is independently 0-3, each n is independently 0-3, each o is independently 0-3, and at least one m and at least one o is 1, m + n + o = 3 and each R is independently a C1-C12 hydrocarbyl group, Cl, Br, or ER ′ ₃ group, where each E is independently Si or Ge, and each R ′ is independently H or a C1-C12 hydrocarbyl group)
A composition transfer device for forming a Si-containing film. The composition transfer apparatus for forming a Si-containing film according to claim 15, wherein the Si—H-containing iodosilane is SiH ₂ I ₂ .

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